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  • Formation and Supercooling of AuSi Eutectic Droplets On Si Substrates: An In-Situ Study Using Synchrotron Radiation

    Transféré par

    mouchak12
    173 vues240 pages
    Semiconductor (SC) nanowires (NMs) have been identified as important components for future electronic and sensor nanodevices. They are produced using a metal catalyst (Au) that forms a low eutectic point with the SC phase (Si) and enables their nucleation and their growth at low temperatures. The aim of this study is to investigate the formation, the structure as well as the behaviour of such liquid eutectic droplets in interaction with the substrates on which the futur NMs properties will later depend. This work has been performed in-situ , using synchrotron radiation which is the perfect tool to characterize this mechanism at the atomistic scale. The eutectic droplets have been obtained through the dewetting of thin gold films. This process has been found to modify the epitaxial relationships between the gold and the silicon substrate. The obtained droplets are accompanied by a wetting layer (WL) whose conditions of formation as well as atomic structure,which turned to be a surface reconstruction, have been determined. During the cooling process, the supercooling effects in such AuSi eutectic droplets have been found to be enhanced in the presence of this reconstruction. It has been explained by its specific atomic structure which is likely to stabilize the liquid phase. Similar experiments on other systems (Au-Ge or Al-Si) were performed and a synthesis has been made in order to present the current knowledge on this topic in comparison with the results of this work.

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    Formation and supercooling of AuSi eutectic droplets on Si substrates: an in-situ study using synchrotron radiation

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    Semiconductor (SC) nanowires (NMs) have been identified as important components for future electronic and sensor nanodevices. They are produced using a metal catalyst (Au) that forms a low eutectic point with the SC phase (Si) and enables their nucleation and their growth at low temperatures. The aim of this study is to investigate the formation, the structure as well as the behaviour of such liquid eutectic droplets in interaction with the substrates on which the futur NMs properties will later depend. This work has been performed in-situ , using synchrotron radiation which is the perfect tool to characterize this mechanism at the atomistic scale. The eutectic droplets have been obtained through the dewetting of thin gold films. This process has been found to modify the epitaxial relationships between the gold and the silicon substrate. The obtained droplets are accompanied by a wetting layer (WL) whose conditions of formation as well as atomic structure,which turned to be a surface reconstruction, have been determined. During the cooling process, the supercooling effects in such AuSi eutectic droplets have been found to be enhanced in the presence of this reconstruction. It has been explained by its specific atomic structure which is likely to stabilize the liquid phase. Similar experiments on other systems (Au-Ge or Al-Si) were performed and a synthesis has been made in order to present the current knowledge on this topic in comparison with the results of this work.

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    173 vues240 pages

    Formation and Supercooling of AuSi Eutectic Droplets On Si Substrates: An In-Situ Study Using Synchrotron Radiation

    Transféré par

    mouchak12
    Semiconductor (SC) nanowires (NMs) have been identified as important components for future electronic and sensor nanodevices. They are produced using a metal catalyst (Au) that forms a low eutectic point with the SC phase (Si) and enables their nucleation and their growth at low temperatures. The aim of this study is to investigate the formation, the structure as well as the behaviour of such liquid eutectic droplets in interaction with the substrates on which the futur NMs properties will later depend. This work has been performed in-situ , using synchrotron radiation which is the perfect tool to characterize this mechanism at the atomistic scale. The eutectic droplets have been obtained through the dewetting of thin gold films. This process has been found to modify the epitaxial relationships between the gold and the silicon substrate. The obtained droplets are accompanied by a wetting layer (WL) whose conditions of formation as well as atomic structure,which turned to be a surface reconstruction, have been determined. During the cooling process, the supercooling effects in such AuSi eutectic droplets have been found to be enhanced in the presence of this reconstruction. It has been explained by its specific atomic structure which is likely to stabilize the liquid phase. Similar experiments on other systems (Au-Ge or Al-Si) were performed and a synthesis has been made in order to present the current knowledge on this topic in comparison with the results of this work.

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    THSE

    Pour obtenir le grade de

    DOCTEUR DE LUNIVERSIT DE GRENOBLE


    Spcialit: Physique de la Matire Condense et du Rayonnement
    Arrt ministriel : 7 aot 2006

    Prsente par

    Rmi DAUDIN
    Thse dirige par Gilles RENAUD et Alain PASTUREL codirige par Tobias SCHLLI prpare au sein du CEA Grenoble - Service de Physique des Matriaux et des Microstructures dans l'cole Doctorale de Physique de Grenoble

    Formation and supercooling of AuSi eutectic droplets on Si substrates: an in-situ study using synchrotron radiation
    Thse soutenue publiquement le 10 Fvrier 2012 devant le jury compos de :

    M. Jean-Marie Dubois
    Directeur de Recherche CNRS, IJL Ecole des Mines, Nancy, Prsident

    M. A. Lindsay Greer
    Professeur, University of Cambridge, MSM, Cambridge, Rapporteur

    M. Harald Reichert
    Docteur, Max Planck Institut, Stuttgart, Rapporteur

    M. Yves Garreau
    Professeur, Universit Paris-Diderot, LMPQ, Paris-7, Examinateur

    M. Jol Chevrier
    Professeur, Universit Joseph Fourier, Grenoble, Examinateur

    M. Gilles Renaud
    Docteur, CEA Grenoble, SP2M, Directeur de thse

    M. Alain Pasturel
    Directeur de Recherche CNRS, SIMaP, Grenoble, Directeur de thse

    M. Tobias Schlli
    Docteur, Responsable scientifique ligne ID01, European Synchrotron Radiation Facility, Grenoble, Co-Directeur de thse

    Merci !
    Thse : Travail prsent sous forme douvrage exposant une recherche scientifique originale est ses rsultats dans un tablissement suprieur habilit, soumis soutenance publique devant un jury pour lobtention du grade de docteur. (Source : Centre National de Ressources
    Textuelles et Lexicales : www.cnrtl.fr/definition/these)

    Loin de moi lide de porter le discrdit sur mes confrres de la linguistique mais cette dfinition, bien qulgante et synthtique, nen est pas moins incomplte. En effet, cette dernire ne dcrit quun tat final et administratif de ce quest rellement une thse, or mon humble avis, une thse cest bien plus que cela. Dans la thse, au dbut on signe un contrat, la fin on soutient (normalement). Entre les deux il se passe des trucs (Bref). Ces trucs ont t pour ma part les campagnes dexpriences synchrotron, les runions, les dpouillements des mesures, les vacances en Australie, linterprtation des rsultats, les lectures darticles, les prparations de confrences, les pauses cafs, les relectures darticles, les critures darticle, les rinterprtations des rsultats, les runions, les prparations des TD dIUT, les nouvelles expriences pour confirmer la nouvelle interprtation des rsultats, les dpouillements des nouvelles mesures, les pauses caf, les re-relectures des articles, les vacances Nouma, les modifications dans lcriture de larticle conformment aux rsultats des nouvelles mesures, les vacances en Croatie, lencadrement de stages, les demandes de simulations pour confirmer les expriences, les runions de prparation aux nouvelles expriences pour rpondre aux questions souleves par les simulations, les pauses caf, les vacances en Slovaquie, lcriture du dbut du manuscrit, le suivi des derniers cours pour obtenir tous ses crdits, la rcriture de tout le dbut du manuscrit suite aux premires corrections, les vacances en Ecosse, les rere-relectures des mmes articles quon commence enfin comprendre vraiment, lcriture de la thse, lcriture de la thse, les vacances, lcriture de la thse, lcriture de la thse, lcriture de la thse [], la correction de la thse, la correction de la thse, la correction de la thse [], le DEPOT de la thse, la fiesta, quelques 6 ou 7 rptitions de soutenance pour vacuer du discours 75% des heu, et pis et autres et bin , et enfin la soutenance ! Et, sans crier gare, cest fini, avec mme des commentaires positifs sur le travail rendu ! Mais le plus mmorable de ces trois quatre annes, au-del mme du pot de thse, ce sont surtout les personnes que lon ctoie, qui vous aident, et que je tiens remercier ici. Tout dabord, je tiens remercier les membres du jury davoir pris le temps dexaminer cette thse. Leur intrt pour ce travail a t une vraie rcompense aux efforts consentis. Je tiens adresser un grand merci mes deux principaux encadrants: Gilles Renaud et Tobias Schlli. Il est vident que cette thse naurait pas pu dbuter, se drouler ni aboutir sans eux. Dbuter grce lobtention de la bourse de thse qui ntait pas du tout acquise, se drouler grce la forme olympique de Tobias en manip synchrotron et aboutir grce au super coaching de Gilles. En effet, le changement dencadrement au cours de la thse a t au final bnfique de part leur complmentarit. Je tiens ainsi remercier Tobias qui ma accueilli et form sur mon sujet de thse. Je le remercie de son perptuel enthousiasme, de sa simplicit et de son nergie dbordante qui sont lorigine dun travail intense mais dcontract. Il est nanmoins parfois difficile de le suivre, que ce soit sur un vlo ou lorsquil se met rflchir en mode maillot jaune. Mme en manip 5h du matin, alors que mon cerveau se mettait automatiquement en mode sans chec avec une frquence douverture des paupires synchronise sur celle de lacquisition des scans, celui de Tobias affichait encore allgrement 3i.s-1 (ides par secondes) ! Je le remercie davoir partitionn son cortex et utilis la partie la moins rapide avec moi pour mviter de finir en queue de grupetto. Lors du dpart de sir Schlli pour des cieux plus clments (ou pas), cest donc Gilles qui a su faire face la rcupration dun thsard en perdition !

    Un grand merci lui, qui malgr un agenda dj bien fourni, a toujours t disponible pour moi bien quil se soit souvent excuser de ne pas lavoir t plus. En plus de toute la formation quil ma promulgu sur la manip, je tiens le remercier de mavoir coach sur dautres aspects du mtier de chercheur : crire les comptes-rendus de manip, crire un article, prsenter les rsultats, crire in-situ, ex-situ et ab-inito en italique, aller en confrences et mme celles auxquelles je ntais pas inscrit, petite anecdote : Gilles : - Hey Rmi, jai un oral une conf. Santorini, cest une petite le grecque des Cyclades super jolie. La conf est sympa ya des activits tous les soirs, malheureusement je ne vais pas pouvoir y aller car jai trop de boulot, a tennuierai de me remplacer ? Moi : - Ecoute je vrifie mon agenda car je suis pas mal occup en mai (yeeeesssss !) [] ok bon je pense que je vais russir marranger si a peut te dpanner Merci infiniment pour les heures passes corriger cette thse, pour les encouragements, les prcieux conseils, la disponibilit dans la dernire ligne droite pour prparer la soutenance. Mes remerciements sadressent bien videmment Alain Pasturel, propuls directeur de thse sans mnagement et grand manitou des simulations ralises dans ce travail. Toujours enthousiaste la vue des rsultats exprimentaux, il a la courtoisie de ne jamais traiter les exprimentateurs de fieffs ttus bien quil ne comprenne pas pourquoi lon sobstine faire des expriences reintantes sur des instruments ultra-coteux alors quil peut faire la mme chose avec un ordinateur (ou quelques dizaines de plateformes de calcul). Pour lui rien nest impossible il suffit de charger en points k . Un grand merci lui ainsi qu toute lquipe qui lentoure et qui font tout sa place Nol Jakse, Thomas Nogaret et Tuy Nguyen. Jespre vivement que cette collaboration se prolongera dans le futur. Ce travail rsulte aussi de lapport inestimable, scientifique ou non, de nombreuses personnes du laboratoire. Merci Franois Rieutord, le chef NRS, pour son accord ma venue au laboratoire. Merci Giovanni Davi et Christine Revenant pour leur pugnacit dans le traitement des donnes GISAXS et Adrien Vaysset pour ces efforts concernant la reconstruction de surface. Merci Odile, Pascal ainsi que Vincent le seul suivre rgulirement les changements dadresse des imprimantes. Merci a Carmelo et Ccile du secrtariat qui ont rsolu tous mes problmes administratifs en un tour de main. Je noublie bien videmment pas le staff bas lESRF et particulirement Olivier Geaymond, la technique, sans qui aucune des expriences naurait t possible. Pour les missions Dbuggages / Cablages / Arrangeages / Rglages / Dmontages / Remontages / Jairactualis-ton-badge / Limprimante-elle-est--ltage / et autres conseils dusage : Olivier Ulrich himself, merci lui ! Je lui dois au moins 30 cafs ! Merci aussi lhomme assis dans le fond de la salle de contrle qui code qui code qui code quand il na pas la tte dans son gonio : Sbastien Micha toujours de bonne humeur et prompt la rigolade. Un grand merci a Axel Maurice, mon tout premier esclave stagiaire, Auvergnat de surcroits, avec qui le travail ainsi que les -cts ont t dexcellents moments (il a eu 18/20 !), et merci pour les cours de LaTeX ! Je remercie de plus chaleureusement Tao Zhou (prononcez Tao Tch) pour tous les dbuggages de mon ordi et son aide prcieuse sur le MEB. Il a appris le franais en 2 mois et rflchit plus vite que son ordinateur pourtant configur pour grer en mme temps 3 parties en rseau, les tlchargements et les lignes de commande dirigeant la manip depuis son lit, impressionnant ! Merci de plus Nils et Valentina, post-docs arrivs lors de ma 3eme anne, toujours plein de conseils de sages et surtout dencouragements lors des moments un peu difficiles de la rdaction et de la prparation de soutenance. Enfin un grand merci Francesca (Madame tlou tlou !), ma co-bureau, qui a apport un vent de fraicheur tout au long de cette thse. Son dbit de parole en italien au tlphone na dgal que les dcibels qui laccompagnent mais son ton enjou a gay pendant trois ans lambiance monastique du C5 que seul le rire de Gilles venait parfois troubler.

    La russite dune thse, ce nest pas seulement les copains du boulot mais aussi ceux hors-boulot (quoi ? ya une vie en dehors de la thse ? bin sur les 30 premiers mois oui...) Merci toute la troupe du GPM2 and co. que jai rencontr par le biais de ma dou : Pinpin sur lequel il faudra un jour crire un livre (best-seller assur !), Laulau mon collgue de rdaction, de discussions matos vlo et dinventions rvolutionnaires toutes dj tombes dans le domaine publique, Malika qui ma tu lEkiden et qui participera cette anne son 30eme Raid INP, Pierrot le M. Bretzel/Fischer et sponsor officiel de bons conseils pour grer sa fin de thse, Bastien qui nous a forg un magnifique couteau, Bn qui supporte tant bien que mal cette bande de thsard, Arthur hey mon ptit vient faire la Royale, cest facile ! , Hlne jamais cours de bons plans charcute-fromage-pinard-bire, Djo dont lide rcurrente traversant son esprit est il me faudrait une slack plus longue , Sbastien Gravier qui organise des barbeuks seulement lorsquil pleut et qui utilise sont garage pour entreposer tout sauf sa voiture et Charline notre piqueuse professionnel qui nous vaccine en mme temps quelle sert lapro. Merci bien videmment aux anciens du gaz de la belle poque du 40 Foch et des parties de coinche endiables qui mont soutenu pendant cette thse. Mon bon Copla et sa Julie avec lesquels jai heureusement partag bien plus que leur 8 dmnagements (dont un frigo king-size au 5eme sans ascenseur), le vieux FlowD toujours chercher la petite bte, le Smon qui a toujours la banane, la Nono qui nous a fait dcouvrir Edinburgh by night, le TomP cuisinier hors pair et toujours fringant pour pousser la chansonnette, la Tina monte sur ressort et jamais fatigue et oui je peux le dire maintenant : Cest super Saint-Sorlin dArves ! , merci pour tous ces moments inoubliables ! Merci au Sbastien Gay mon voisin de table en CE1 venu mencourager pour mon oral, merci au zikos connus au Mans (taime la rillette ? et bin Sarthois !) Marko et Riton venus Grenoble rien que pour tre plus prs de moi de la Bobine ! Un norme merci ma famille, ma sur La (spcialiste du gteau de crme de marron) et mon frre Benot ainsi que Seb et Marie qui mont soutenu jusquau bout, je penserai eux emmitoufl dans ma doudoune de luxe ! Il est vident que rien de tout cela naurait pu se concrtiser sans le soutien inbranlable de mes parents. Je les remercie infiniment pour leurs encouragements inconditionnels dans tous les aspects de ma vie, je ne pourrais pas rver mieux. Merci mon pre pour tous ses conseils lucides et aviss ainsi que pour le show lors du pot ! Merci ma mre toujours aux petits soins et qui, lors de mes priodes dhyperactivit, sinquite souvent que je ne tire pas trop sur la corde et qui je rponds inexorablement tinquite mman ! . Une mention spciale mon pote de toujours, Pyo, avec qui je partage tout depuis la premire anne de maternelle ! Un soutient sans faille depuis tout ce temps, je le remercie de sa zen-attitude toute preuve, avec lui rien nest un problme cest tout simplement que cest a la vie ! Scandant son crdo cest cool ! qui veut lentendre, cest en grande partie grce lui si jen suis l aujourdhui et ce sera encore le cas pendant longtemps ! Et enfin un merci avec une mention bien plus que spciale et venant du fond du cur ma dou ! Passe par la case thse un an avant moi, elle a toujours su trouver les ressources ncessaires et les mots pour me supporter et me rconforter lorsque le moral ntait pas au beau fixe. Merci pour toutes ses petites attentions, ses bons petits plats (mme en rando !) et sa tolrance envers mes trop nombreux tinquite, on en reprend une et on y va . Merci pour sa motivation inaltrable et sa force de persuasion pour mentrainer dans des activits toujours plus prilleuses ou simplement aller la dchetterie. Et surtout, merci davoir t le catalyseur de notre futur projet; nos aventures de thse sont maintenant derrire nous alors que se dressent dj devant les nouvelles et qui, jen suis certain, nous rservent bien des surprises !

    Merci mes diffrents sponsors psychologiques : La Bobine, le Yassou, mon vlo, basketusa.com, ma cafetire et le SAV dOmar et Fred.

    Le luxe de demain sera la lenteur dans le silence -Anonyme-

    Contents

    French Summary - Rsum de la thse en Franais Introduction Chapter I State of the art xi

    sFI

    xnowires prodution F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F sFIFI sFIFP he pourEviquidEolid proess F F F F F F F F F F F F F F F F F F F F F woleulr fem ipitxy @wfiA nd growth modes F F F F F F F F F F F ustrtes nd surfes X ilion nd qermnium F F F F F F F F F F F F gtlysts X qold nd eluminum F F F F F F F F F F F F F F F F F F F F F F hse digrms F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F

    I I P R R U V V

    sFP

    emiEondutor sustrtes nd metl tlysts F F F F F F F F F F F F F F F F F F sFPFI sFPFP

    sFQ

    sntertions F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F sFQFI sFQFP sFQFQ sFQFR

    hepositEindued surfe reonstrutions F F F F F F F F F F F F F F F F F F IH hewetting of thin (lms X formtion of islnds F F F F F F F F F F F F F F F II etting droplet on solid surfe F F F F F F F F F F F F F F F F F F F F F IQ

    sFR sFS

    hesription of the liquid stte X the pirEorreltion funtion F F F F F F F F F F IT viquidEsolid phse trnsition F F F F F F F F F F F F F F F F F F F F F F F F F F F F IV sFSFI sFSFP uperooling X thermodynmi nd lssil model F F F F F F F F F F F F IV feyond the lssil model X the ioshedrl order F F F F F F F F F F F F PR hermodynmi nd struture F F F F F F F F F F F F F F F F F F F F F F F PV olidi(tion of euteti lloys F F F F F F F F F F F F F F F F F F F F F F F QI viquids in smll dimensions F F F F F F F F F F F F F F F F F F F F F F F F QQ
    In-situ

    sFT

    rtiulr liquid ehviour X F F F F F F F F F F F F F F F F F F F F F F F F F F F F PU sFTFI sFTFP

    sFU

    pei( fetures onerning nnowires growth F F F F F F F F F F F F F F F F F F QQ sFUFI sFUFP gEnnowires growth F F F F F F F F F F F F F F F F F F F F F F F F QS

    sFV

    viquid ehviour lose to interfes F F F F F F F F F F F F F F F F F F F F F F F F QV sFVFI viquidEpour interfes X lyering e'et F F F F F F F F F F F F F F F F F QV i

    sFVFP

    viquidEolid interfes F F F F F F F F F F F F F F F F F F F F F F F F F F F QW

    Chapter II Methods and experimental set-up

    ssFI Ery sttering y surfe F F F F F F F F F F F F F F F F F F F F F F F F F F F F RQ ssFIFI Erys refrtion t n interfe F F F F F F F F F F F F F F F F F F F F F F RQ ssFIFP fsi Erys di'rtion F F F F F F F F F F F F F F F F F F F F F F F F F F F RT ssFP ghrteriztion methods F F F F F F F F F F F F F F F F F F F F F F F F F F F F F SH ssFPFI qrzing inidene Ery ttering @qsA F F F F F F F F F F F F F F F F SH ssFPFP urfe Ery di'rtion @hA F F F F F F F F F F F F F F F F F F F F F SR ssFPFQ qrzing inidene smll ngle Ery sttering @qseA F F F F F F F F SS ssFQ ixperimentl setEup F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F SV ssFQFI he synhrotron nd the fwQP emline F F F F F F F F F F F F F F F F F SV ssFQFP
    In-situ growth of Nanostructure on Surface

    @sxA X the experimentl

    huth F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F TH ssFQFQ gorretions ftors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F TS ssFR xumeril simultions F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F TU


    Chapter III Growth of Au on Si(111)

    sssFI qse study for low overge experiments F F F F F F F F F F F F F F F F F F F TW sssFIFI qrowth t SUH u F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F TW sssFIFP heposit t nd nneling F F F F F F F F F F F F F F F F F F F F F F F UP sssFIFQ gomprison etween the two growth modes F F F F F F F F F F F F F F F UT sssFP qs study of the interfe epitxil reltionships F F F F F F F F F F F F F F F F UU sssFPFI ixperimentl results F F F F F F F F F F F F F F F F F F F F F F F F F F F F UU sssFPFP hisussion on growth nd dewetting of eu on i@IIIA F F F F F F F F F F VQ sssFPFQ etomi on(gurtions of the interfe F F F F F F F F F F F F F F F F F F F VR
    Chapter IV Au-induced reconstructions of Si(111) : (66)Au , (

    3 3)R30 Au

    sFI viterture review F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F WS sFP ixperimentl results F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F WV sFPFI gonditions of formtion of the gold reonstrution F F F F F F F F F F F F WV sFPFP tility F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IHH sFQ i@IIIAE@TTAeu struture F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IHQ sFQFI ht olletion nd symmetry verging F F F F F F F F F F F F F F F F F IHQ sFQFP wodel ivlution F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IHS ii

    Chapter V Supercooling in AuSi droplets

    FI yn i@HHIA sustrtes F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IIU FIFI i@HHIA sustrte9s struture F F F F F F F F F F F F F F F F F F F F F F F F IIU FIFP uperooling on the i@HHIA surfe F F F F F F F F F F F F F F F F F F F F IIV FIFQ olid struture F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IIW FP yn i@IIIA sustrtes F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IPH FPFI uperooling on i@IIIAE@ 3 3AQH eu reonstrution F F F F F F F F IPH FPFP uperooling on i@IIIAE@TTAeu reonstrution F F F F F F F F F F F F F IPI FQ tudy of the liquid struture F F F F F F F F F F F F F F F F F F F F F F F F F F F F IPR FQFI ixperimentl study F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IPR FQFP imultion results F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IPV FR tudy of the size e'et F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IQP
    Chapter VI Case of other systems and inert substrates

    sFI eu on qe@IIIA F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IQW sFP el on i@IIIA F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IRS sFQ gse of inert sustrtes F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F ISH sFQFI eui on iy2 F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F ISH sFQFP euqe on iy2 F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F ISP sFQFQ euqe on el2 y3 F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F ISQ
    Chapter VII Discussion and synthesis Conclusion and Perspectives Annexe : Structure factors dataset and model References 155 171 177 189

    iii

    Introduction

    xnotehnologies hve ttrted lot of ttention these pst few yersF st is minly due to the explosion of the use of eletroni devies suh s ell phones or omputersF hese produts re mde of integrted iruits with the mjor prt omposed of semiEondutor devies suh s trnsistorsF he e0ieny of n integrted iruit eing proportionl to the numer of trnsistorsD the redution of their sizes therefore inreses their performnes nd t the sme time redues the prodution ostsF wore reentlyD new interests re emerging in the use of nnoEojets in other domins suh s nnosensor in iohemistryF here re two di'erent pprohes to uild nnostruturesF he (rst one is lled the topEdown pproh nd onsists in sulpting the mteril in the desired shpe nd sizeF his pproh is however sometimes limited when one wnts to reh very smll sizes s the tehniques usedD even if they re very preiseD rete defets tht 'et the properties of the ojetF he seond pproh is lled ottomEup s the ojet is uilt lmost tom y tomF sn this seD the im is to (nd some methods whih n ledD y using wellEontrolled experimentl onditions driving the proessesD to the selfEorgniztion of the tomsF sn oth sesD the new fetures displyed y these ojets re dominted y surfe e'ets t the origin of the new propertiesF sn this ontextD semiEondutor nnowires @xsAD whih n e seen s oneEdimensionl ojets i D exhiit unique optilD mehnil or eletroni propertiesF wore preiselyD i xs re one of the most studied oneEdimensionl semiEondutors nd re expeted to e unvoiE dle omponents in new pplitions suh s solr ellsD sensors or new eletroni deviesF iven if new wys to produe them hve een disoveredD the historil nd the most studied proess remins the one proposed in IWTR y gner nd illis gner nd illisD IWTRF his proessD presented in the (rst hpter of this workD requires the help of liquid gold whih serves s tlyst to orgnize the silion toms in the form of xF iven if suh tlyti mehnisms re highly investigtedD mny fundmentl questions in rystlEgrowth ehviour remin unnswered orGnd ontroversilF es the stte of the tlyst is of prime importne to ontrol growth prmeters @kinetiD orienttionD morphologyFFFA on whih will lter depend xws propertiesD we need to investigte in detils this mehnismF his hh work hs een rried out t the PwEx i lortory of the gie qreE nole whih is in hrge of emline dedited to the hrteriztion of the growth of nnoEojets on surfes t the ip ii F st is however only reently tht the group hs een equipped with the required elements to perform the growth of xsF he work presented in this mnusript does not del with xs growthD ut results from n unexpeted mesureE ment X the existene of the tlyst in its liquid stte t unusully low temperturesF
    i. Their length is much larger than their diameter. i. Service de Physique des Matriaux et Microstructures-Nanomatriaux et Rayonnement Synchrotron. ii. European Synchrotron Radiation Facility.

    xiii

    Introduction

    he existene of n element s )uid phse in metstle liquid stte elow its melting temperture is phenomenon lled superoolingF hespite it is wellEknown phenomenonD the understnding of the mehnisms governing it is inompleteF heir re two omplemenE try theories to explin this e'etF he (rst oneD whih is often reported to e the lssil oneD dopts mrosopi point of view to desrie the superooling ehviourF sing therE modynmil oneptsD ooling down liquid elow its melting pointD in order to rystllize itD is neessry s it enles the formtion of stle solid nuleusF his nuleus serves s seed for the toms still in the liquid phse tht tth to it nd llow the growth of the solid phseF es the size of the stle nuleus is inversely proportionl to the degree of superoolingD the more the liquid is superooled the esier it solidi(esF his desription is widely used in mteril siene to predit nd ontrol solidi(tion proessesF he seond theory dopts more tomisti point of viewF st explins the superooling ehviour y the ft tht the liquid toms lolly form lusters displying strutures inomE ptile with those of solid rystlsF es onsequeneD the liquidEsolid trnsition is slowed down euse the toms re lredy orderedD presenting stle on(gurtion of low energyD nd thus hve to deeply reorgnize their rrngement to dopt the rystl strutureF hese speil lusters re ssumed to present (veEfold symmetryD suh s ioshedrD tht preE vents the formtion of n ordered rystl i F his kind of ordering in liquids hs lredy een oserved ut remins very di0ult to hrterize experimentlly ii F st is even more di0ult to mke the link etween the development of (veEfold ordering in liquids nd their superE ooling ehviourF roweverD the improvement of the hrteriztion tehniques now llows to study in more detils this still unler orgniztion whih is t the hert of n intense reserh in the (eld of ondensed mtterF he omplexity of superooling phenomen is inresed when it onerns the solidi(tion of lloysF his is however the se in this work into whih the euEi system is investigtedF woreoverD the euEi liquid lloy forms euteti liquid whih mens tht for ertin omE positionD the eui liquid phse is lredy stilize down to low temperturesF felow this euteti tempertureD the euteti liquids re expeted to undergo very smll superooling nd to rystllize fter the seprtion of the di'erent omponentsF sn the present work this is therefore the oservtion of the eui euteti liquid well elow its euteti temperture @under the form of nnoEdroplets in ontt with i sustrteA tht led us to investigte its tomi struture using surfe Ery di'rtionF he understnding of the intertions etween the eui liquid nd its sustrte re of prime importne s they re the ses of the di'erent prmeters tht govern the growth of nnowiresF
    i. A crystal presenting an order at long distances adopts a three, four or six-fold symmetry. ii. Evidences of this kind of ordering has been demonstrated by simulations.

    xiv

    he di'erent spets of this work onerning the formtion nd the superooling ehE viour of the eui euteti droplets re presented s follows in the mnusript X

    Chapter I : State of the art.

    sn this prt re presented the physil onepts required

    to understnd the following resultsF ome prtiulr fetures onerning surfe siene re desriedD the mterils used in this work nd the proess in whih they re used for the growth of nnowires re presentedF es this proess is sed on solidi(tionD lrge prt of this hpter is dedited to the struture of the liquids nd the liquidE solid trnsitionsF e rie)y rell some generl onepts on solidi(tion proesses ut linger on the spei( lloys studied in this workF ome fetures onerning these liquid lloys rought to the nnosle nd the spei( ses of nnowires growth re desriedF

    Chapter II : Methods and experimental set up.


    in-situ

    yur experiments onsist in n

    study of sustrtes9 surfesD in ltr righ uumD y the use of synhrotron

    rditionF sn this hpter re therefore relled some ses onerning surfe Ery di'rtion nd the properties of the synhrotron lightF e present in detils how the mesurements re performed s well s the experimentl set up for good understnE ding of the resultsF

    Chapter III : Growth of Au on Si(111).

    fefore investigting the liquid dropletsD

    we fous on how they form on the sustrtes vi the deposit of thin gold (lm tht turns into islnds nd then into droplets y inresing the tempertureF his hpter ims to mesure the morphologil prmeters of the islnds s well s the evolution of tomi struture of the goldEsilion interfe with nnelingF

    Chapter IV : Au-induced reconstructions of Si(111) : (66) and ( .

    3 3)R30

    he formtion of the gold islnds nd the droplets tkes ple in the presene of

    gold wetting lyer induing surfe reonstrution with very peulir strutureF sn this hpter we present our experimentl results onerning the formtion of this reE onstrution nd the determintion of its tomi strutureF

    Chapter V : Supercooling in AuSi droplets.

    sn this hh workD prtiulr suE

    perooling e'ets hve een oserved in the eui euteti droplets in intertion with di'erent strutures of the i sustrtesF his hpter is dedited to the presenttion of the results deling with the solidi(tion proesses nd the struture of the liquidF

    Chapter VI : Case of other systems and inert substrates.

    he mjor prt of xv

    Introduction

    this work onsists in the investigtion of the euEi systemF roweverD some experiments in other systems tht re used for the growth of semiEondutor nnowires hve een studied using the sme experimentl onditionsF he results otined on the euEqe nd elEi systems re presented in this hpterF

    Chapter VII : Discussion and synthesis.

    elthough this hh work is in line with

    the very intense reserh deling with the euEi systemD the onepts tkled here onern some spei( questions rised in the lst dede due to the pperne of new experimentl onditions nd new mens of hrteriztionF sn this lst hpterD we ompre our results to the reent literture nd propose n overview of the di'erent onepts tht re still under deteF

    xvi

    Chapter I State of the art


    Contents
    I.1 Nanowires production . . . . . . . . . . . . . . . . . . . . . . . . . .
    I.1.1 I.1.2 The Vapour-Liquid-Solid process . . . . . . . . . . . . . . . . . . . . . . . . . . .

    1
    1 2

    Molecular Beam Epitaxy (MBE) and growth modes

    I.2

    Semi-conductor substrates and metal catalysts . . . . . . . . . . .


    I.2.1 I.2.2 Substrates and surfaces : Silicon and Germanium . . . . . . . . . . Catalysts : Gold and Aluminum . . . . . . . . . . . . . . . . . . . .

    4
    4 7

    I.3

    Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
    I.3.1 I.3.2 I.3.3 I.3.4 Phase diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    8
    8 10 11 13

    Deposit-induced surface reconstructions

    Dewetting of thin lms : formation of islands Wetting droplet on a solid surface

    . . . . . . . . . . . . . . . . . .

    I.4 I.5

    Description of the liquid state : the pair-correlation function . . Liquid-solid phase transition . . . . . . . . . . . . . . . . . . . . . .
    I.5.1 I.5.2 Supercooling : thermodynamic and classical model Beyond the classical model : the icosahedral order . . . . . . . . . . . . . . . . . .

    16 18
    18 24

    I.6

    Particular liquid behaviour : . . . . . . . . . . . . . . . . . . . . . .


    I.6.1 I.6.2 Thermodynamic and structure Solidication of eutectic alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    27
    28 31

    I.7

    Specic features concerning nanowires growth . . . . . . . . . . .


    I.7.1 I.7.2 Liquids in small dimensions . . . . . . . . . . . . . . . . . . . . . .

    33
    33 35

    In-situ

    SC-nanowires growth

    . . . . . . . . . . . . . . . . . . . . .

    I.8

    Liquid behaviour close to interfaces


    I.8.1 I.8.2

    . . . . . . . . . . . . . . . . .

    38
    38 39

    Liquid-Vapour interfaces : layering eect . . . . . . . . . . . . . . . Liquid-Solid interfaces . . . . . . . . . . . . . . . . . . . . . . . . .

    I.1.

    Nanowires production

    his hpter presents the generl onepts tht hve een enountered during this workF his overview ontins the ses on the growth of nnowiresD the desription of the mterils used in this study s well s spei( fetures onerning the physis of surfesF e onsequent prt is dedited to the liquid stteD the solidi(tion proesses nd the prolems linked to the presene of interfesF

    I.1

    Nanowires production

    he topi of this setion is short introdution to the pourEviquidEolid @vA proess s well s some onsidertions onerning epitxil growthF sn this studyD ttention ws pid on the physil intertions of the deposited metl with the underlying sustrte to understnd the very (rst events rising in this proessF he studied systems were not exposed to vpour )ux nd no nnowire hs een formedF he v proess is however presented here euse it is t the hert of nnowire growth nd highlights the di'erent physil prmeters rising in this (eld of nnosieneF ome prtiulr fetures onerning growth will lso e introdued in this hpter to get ler understnding of the purpose of this workF por rther omplete desriptions onerning the growth of nnowiresD the reder is dvised to refer to reent reviews of ng oss
    et al. et al.

    ng

    et al.D

    PHHVD hmidt

    et al.

    hmidt

    et al.D

    PHIH nd

    ossD PHIH s well s referenes thereinF

    I.1.1 The Vapour-Liquid-Solid process


    pigure sFI illustrtes the suessive steps desriing the v mehnism X ! pirstD the metl tlyst is deposited on the sustrteD for instne t room temperture @AD in the form of thin (lmF ! henD the smple is nneledD the (lm dewets @see setion sFQFQA nd liquid droplets form t the euteti temperture e of the given system @see setion sFQFIA ! pinllyD the tlyst droplet is exposed to semiondutor @gA vpour )uxF he inE oming g toms di'use inside or t the surfe of the droplet due to onentrtion grdientsF e typil v growth experiment is performed etween UHH u nd WHH uF ith respet to the phse digrm of the onerned systemD the g toms rystllize t the dropletEsustrte interfe nd nnowires strt to growF he growth is thus perE formed y onstnt rrivl of new g toms t the interfe etween the droplet nd the newlyEformed nnowiresD its dimeter depending on the lterl size of the dropletF I

    Chapter I.

    State of the art

    Au-Si liquid alloy RT Au Si Vapour

    Te

    Vapour

    Liquid Solid 700 K 900 K


    growth

    Surface diffusion Bulk diffusion

    Si NW

    Vapour
    growth

    Figure I.1  Scheme of the Vapour-Liquid-Solid process in the case of Si nanowires growth catalyzed
    by Au islands.

    I.1.2 Molecular Beam Epitaxy (MBE) and growth modes


    es we hve just seenD the deposit of the tlyst on the sustrte is prerequisite to v experimentsF ipitxil i growth is very ommon (eld of surfe sieneD eyond the (eld of nnowires studiesF por exmpleD the growth of qe on i sustrtes hs een extensively studied oigtlnderD PHHIY hou
    et al.D

    PHIIY qossmnn

    et al.D

    IWVSY uhler

    et al.D

    IWWIF

    ypil epitxil growths re performed y woleulr fem ipitxy whih onsists in heting mteril soure whih provides )ux of toms orientted towrds the desired sustrteF hepending on experimentl prmeters ii mny tomi proesses n tke ple t the surfeD s represented in pigure sFPF gontrolling the )ux s well s the deposition time mkes possile the formtion of thin (lms of severl engstrmsF he rystlline growth performed through wfi retes solidEsolid interfeF et the thermodynmil equilirium there exists three di'erent growth modes @see pigure sFQA X ! the prnkEn der werwe modeD orresponding to omplete wetting of the suessive deposited lyersF he growth mode is thus hieved lyer y lyerF ! the trnskiEurstnow mode for solids presenting lower wettility with respet to
    i. The word Epitaxy comes from a combination of Greek words :  arrangement, respectively. ii. such as nature of materials, temperature, ux, etc...

    and   which mean on and

    I.1.

    Nanowires production

    Flux

    Step-flow (growth)
    Adsorption Desorption Diffusion Growth

    Incorporation Nucleation Complete layers Intermixing

    Substrate

    Figure I.2  Illustration of the dierent physical process that can arise during Molecular Beam
    Epitaxy.

    the sustrteF sn this se few tomi lyers n wet the sustrte @lled wetting lyers @vAAD the following toms form solid islnds on top of itF ! the olmerEeer mode for whih no wetting lyer n formF he growth onsists in the formtion of islnds diretly on the sustrteF fsillyD these di'erent growth modes depend on the di'erene etween the surfe energies of the two mterilsF por exmpleD metl toms deposited on ermi would very likely grow following the olmerEeer growth modeF rowever if the surfe energies re of the sme orderD it is quite di0ult to predit the growth modeD the di'erene etween two modes eing sometimes very smll nd the equilirium onditions rrely hievedF e more detiled disussion on growth mode is presented in ghpter sss in the se of eu on i@IIIAF reisions will lso e given onerning surfe energies when deling with wetting properties @see setion sFQFRAF
    Frank-van der Merwe

    Stranski-Krastanov

    Volmer-Weber

    Figure I.3  Presentation of the three typical growth modes. The Frank-van der Merve mode
    consisting in a layer by layer growth, the Stranski-Krastanow mode for which 3D objects form on a wetting-layer and the Volmer-Weber mode displaying direct island nucleation.

    Chapter I.

    State of the art

    I.2

    Semi-conductor substrates and metal catalysts

    sn this workD we hve studied mostly the euEi system s well s the euEqe nd elEi systemsF e quik introdution to these mterils is given in this setionF

    I.2.1 Substrates and surfaces : Silicon and Germanium


    ilion iii @aIRA is the seond most undnt element in the erth9s rust @the (rst one eing oxygenA nd is found nturlly under the form of oxides ut lso in minerlsF ure silionD esily ville ommerillyD is extrted from its oxide form y retion with grphite iv F st elongs to the semiEondutor lss @nrrow gp etween the vlene nd ondution ndsA nd its photosorption properties re used in everydy lifeD for exmple in solr pnelsF
    [001]
    a = 5.43

    [111]

    Figure I.4  Silicon crystal in its diamond-type structure consisting in two face centered cubic
    (fcc) crystals translated by a

    (1/4, 1/4, 1/4) vector. In transparency is printed the (111) plane which

    corresponds to the orientation of substrates studied in this work.

    st rystllizes in dimond struture v @see pigure sFRAD with lttie prmeter of SFRQHW D into whih eh tom is loted in the enter of tetrhedrl site nd shres four onds with the nerest neighoursF qermnium @aQPA vi is lso semiEondutor with properties very similr to the ones
    iii. The discovery of silicon is generally attributed to Jns Jacob Berzelius (in 1824), its name coming from the Latin word silicis which means int. iv. SiO2 +2CSi+2CO v. Groupe number : 227 ; Space groupe :

    F d 3m

    vi. The Germanium element was predicted by Mendeleev in 1871 and discovered by Clemens Alexander Winkler in 1886. Its name comes from Germania meaning Germany in Latin.

    I.2.

    Semi-conductor substrates and metal catalysts

    of silionF st rystllizes in the sme strutureD with lttie prmeter slightly lrger X SFTSUS @CR7 ompred to iAF st is however muh rrerF
    Top view 1st (6th) layer 2nd (3rd) layer
    3rd (4th) layer [111]

    [121]
    [101]

    Side view

    1st bilayer

    [111]

    2nd bilayer

    3rd bilayer

    Figure I.5  Top view and side view of a silicon (111) orientated substrate.

    sn surfe sieneD the interesting fetures do not relly onern the ulk ehviour of the mterilF st is therefore more relevnt to present some surfe properties enountered in this (eld nd prtiulrly in this workF yne of the most relevnt property of surfes is their possiility to rerrnge their tomi surfe struture to redue their surfe energyF he resulting struture is lled surfe reonstrutionF he i@IIIAE@UUA reonstrution is nie exmple to understnd how surfe toms hnge their on(gurtion to rete n energetilly fvourle surfe orderF st is the (rst reonstrution tht hs een imged y nning unneling wirosopy @wA finnig
    al.D et

    IWVQF e detiled desription n e found in kyngi

    et al.D

    IWVS nd oigtlnderD

    PHHIF he i@IIIA surfe reonstrution rises euse under pure onditions vii D the surfe toms of the ulkEterminted @IIIA rystl present lk of neighours nd therefore disply dngling ondsF he more dngling ondsD the higher the surfe energyD therefore surfe toms try to redue the numer of dngling ondsF row do they hieve this c pigure sFS shows tht i toms in @IIIA plnes re rrnged in iElyersF sf the surfe is omposed of the lower prt of the (rst iElyer @lue toms in (rst iElyerAD it is ler tht the surfe presents three dngling onds per surfe tomF roweverD if the rystl is terminted y the higher prt of the iElyer @red tomsAD the surfe dngling onds re redued to one
    vii. In the case of Si(111), the sample must be outgased for several hour around 900 K and then ashed at about 1500 K under Ultra High Vacuum.

    Chapter I.

    State of the art

    per surfe tomF his explins whyD experimentllyD i@IIIA surfe is lwys terminted y iElyerF sn dditionD toms of the (rst lyer lso lower the numer of dngling onds y hnging their on(gurtionF his is hieved y the retion of new onds with surfe neighours nd leds to new surfe unit ell whih is seven times lrger thn the one of the ulkEterminted @IIIA rystl @see pigure sFTAF

    dimer stacking fault

    corner hole adatom

    Figure I.6  Top-view and side-view of the Si(111)-(7x7) reconstruction structure [Voigtlnder,
    2001]. The rearrangement of atoms creates a surface unit cell seven times larger than the theoretical one.

    he rerrngement of surfe toms leds to the pperne of X ! dtomsD shring three dngling onds with underlying rest toms nd ! dimersD whih form round dtom regions @t the edges of the hlf unit ellA nd lso redue the numer of dngling ondsF he formtion of dimers retes stking fults nd yields one hlf of the unit ell tht is fulted @pA nd the other hlf tht is unfulted @AD with respet to the ulk stking sequeneF st lso retes empty sites where six @UUA unit ells meetD whih re lled orner holes viii F his rrngement llows the struture to redue its numer of dngling onds from RW to IW nd therefore to redue its surfe energy tih et
    al.D

    IWWPF es reonstrution is

    onsequene of lol eletroni density djustmentD it highly depends on the rystllogrphi orienttionF por exmpleD the i@HHIA surfe toms form @PIA surfe reonstrution nd
    viii. The complete transformation process from the unreconstructed Si(111) surface to Si(111)-(77) structure can be seen via the nice animation performed by Yan Liang from the Department of Chemical Engineering and Materials Science, University of Minnesota : http ://vimeo.com/1086112 .

    I.2.

    Semi-conductor substrates and metal catalysts

    its energy is higher thn the one of the i@IIIA surfeF pollowing the sme philosophyD non polluted qe@IIIA surfe is lso reonstrutedF urE prisinglyD lthough i nd qe re very similr mterilsD they do not present the sme surfe reonstrution X the most stle surfe struture of qe@IIIA is the @PVA reonstrution presenting dtoms nd resttoms without dimersD ornerEholes or stking fults feker
    al.D et

    IWVWF

    I.2.2 Catalysts : Gold and Aluminum


    qold @aUWA is ertinly the (rst metl studied in humn historyF xoody knows who disovered it (rst ut the reson might e tht it ws shiny ix F
    [001]

    a = 4.078

    Figure I.7  Gold crystal unit cell illustrating its fcc structure.

    qold is softD dutile metl Y good ondutor of het nd eletriity nd is inert to ir nd most regentsF st is historilly widely used in jewelery for its olorF sts ioEomptiility @mlleility nd orrosion resistne for instneA mkes it relevnt for its use in dentistryF wore reentlyD with strong dvnements mde in the (eld of nnomterilsD gold nnoprE tiles were found to e vlule ndidtes in diverse medil pplitions foisselier nd estruD PHHWF sts rystl struture is fe entered ui @fA x with lttie prmeter of RFHUVP D s represented in pigure sFUF eluminum @aIQA nd lmost ll the possile elEsed lloys were lso prone to studiesF rowever luminum ws isolted only in IVPS nd is nonmgneti nd nonsprking metlF st is not found pure in nture ut hs to e extrted from uxiteF st n esily e st nd is usedD mostly under the form of lloysD in wide rnge of pplitions @from ns or foil
    ix. The rst traces of gold manipulations go back to about 3600 BC in Egypt. x. Group number : 225 Space group :

    F m 3m

    Chapter I.

    State of the art

    to erospe industryAF vike goldD its rystl struture is f with lttie prmeter slightly smller X RFHRWS F

    I.3

    Interactions

    sn the previous setion @sFPAD we hve rie)y presented the generl properties of the mterils studied in this workF sn this setion we fous on severl phenomen tht rise from potentil intertions etween the deposited metl nd the g sustrteF

    I.3.1 Phase diagrams


    e thermodynmil phse digrm displys the di'erent domins @phsesA into whih the inry lloyD or the pure elementsD form spei( struture in the solid stteF st lso shows the domins where the lloy is liquid or where the liquid phse is in equilirium with solid phseF he di'erent domins depend on the onentrtion s well s on the temperture xi F pigure sFV displys the equilirium phse digrm of the euEi system whih is t the hert of the present workF st is rther simpleD with only S di'erent phses X the homogeneous liquid phse @ AD the two domins into whih pure solid eu @ A or i @ A oexist with liquid lloy nd the two solid euEpgg nd iEhimond struturesF

    1600

    Temperature (K)

    1400 1200

    Liquid Liquid + <Si>

    1000

    <Au> + 800 600

    Liquid

    Te=636 K 18.6 % Si_Diamond Au_FCC Si (at.%)

    10 20 30 40 50 60 70 80 90 100

    Figure I.8  Gold-Silicon phase diagram.

    wo remrkle fetures n e pointed out X ! the presene of very low euteti point @xSi aIW tF7D e aTQT uA whih shows tht for given ompositionD the lloy n sty in its liquid stte t very low temperture
    xi. [ ], ( ) and < > stand for gas, liquid and solid phases, respectively.

    I.3.

    Interactions

    ompred to the melting tempertures of eh omponent tken sepertelyF ! the sene of stle ulk rystlline lloy X silion is not solule in the eu solid phse @nd inverselyAF he study of the euEi phse digrm llows us to give here some preisions on the v proess presented in setion sFIFIF et the euteti temperture the system is omposed of droplet whih is ssumed to e t the euteti ompositionF sf one wnts to perform the growth of nnowires t UHH uD nneling the system to the desired temperture leds to dissolution of the sustrte i toms into the droplet following the i liquidus lineF et UHH u the i onentrtion in the droplet is out PI tF7 nd is lmost tntmount to the euteti one due to the very steep liquidus lineF henD when the droplet is exposed to the i vpour )uxD the i toms enter the liquid phse nd di'use to the interfeF pollowing the phse digrmD the droplet onentrtion is shifted to the right hnd side of the liquidus line nd the system enters the grey re orresponding to the twoEphses `ibC@euiA dominF pollowing the hellEqulliver rulesD the silion in exess @ompred to the liquidus omposition t UHH uA rystllizes to form the solid phseF he solidi(tion rises t the dropletEsustrte interfe euse it o'ers perfet nuletion sites to the i tomsF sdellyD the nnowire n keep growing s long s the i vpour )ux is mintinedF xote here tht the system is out of equilirium ut remins in sttionnry proess onsisting in inorportionD di'usion nd solidi(tion of the i tomsF he euEqe nd elEi phse digrmsD represented in pigure sFW@A nd sFW@AD respetivelyD lso disply euteti points whih di'er in omposition nd tempertureF he v growth n lso e performed using these systems @s well s mny others hmidt
    et al.D

    PHIHAF

    roweverD for these two systemsD smll frtion of the g phse is solule in the solid struture of the respetive metlF his is illustrted y smll domin t the left hnd side of the digrmD often noted in litertureF
    Temperature (K)
    1400
    Temperature (K) 1200

    1600

    Liquid Liquid + <Ge>

    Liquid Liquid +<Al> Liquid + <Si>

    1400 1200 1000 800 600 0

    1000 800 600

    <Au>+ Liquid

    Te=641 K 28 % Ge_Diamond Au_FCC


    Ge (at.%)
    (a)

    Te=850 K 12 % Si_Diamond Al_FCC


    10 20 30 40 50 60 70 80 90 100 Si (at.%)
    (b)

    10 20 30 40 50 60 70 80 90 100

    Figure I.9  (a) Gold-Germanium phase diagram.(b) Aluminum-Silicon phase diagram. The
    phase corresponds to the metal-SC bulk solid phase in both cases.

    Chapter I.

    State of the art

    he phse digrms presented ove re onsistent when onsidering the given systems in their ulk strutureD whih onsists in negleting surfe e'etsF es it will e presented lter @see setion sFUAD some onsiderle gps from the ulk ehviour n rise when systems re rought to the nnosle xii F sn the (eld of surfe sieneD spei( feture tht hs een intensely studied is the reonstrution of sustrte9s surfe upon deposition of smll mount of metlF

    I.3.2 Deposit-induced surface reconstructions


    e hve seen in setion sFPFID tht the toms t the surfe of the i@IIIA sustrte rerrnged themselves euse of the lk of neighoursF his reorgniztion eing men of deresing the energy per surfe tomF e similr proess tkes ple t the very erly stges of metl depositF he deposited mteril indues rerrngement of the surfe toms in surfe struture tht hs periodiity lrger thn the re surfeF pigure sFIH is n ritrry exmple of @PPA reonstrutionF he deposited toms form surfe unit ell whih is twie lrger thn the surfe unit ell of the sustrteF woreoverD some spei( reonstrutions periodiities n sometimes require to e turned with respet to the sustrte surfe lttieF he ngle is therefore dded to the nottion X for exmpleD @ 3 3AQH reonstrution would refer to surfe unit ell 3 times lrger with mesh turned y QH with respet to the sustrte oneF

    Deposit
    Substrate (2x2)

    Substrate surface lattice (1x1)


    Figure I.10  Illustration of a (22) reconstruction. The surface unit cell displayed by the deposited
    atoms (yellow) contains in this case 5 atoms (4 cell of the underlying substrate (black).

    1/4 + 4)

    and is twice as large as the surface unit

    por the metlEg systems presented in this workD severl reonstrutions re known to existF por deposited eu toms on i@IIIA sustrteD the most ommonly oserved reonsE trutions re the @SPAD the @ 3 3AQH nd the @TTA reonstrutionF e more detiled desription of these reonstrutions is given in ghpter sss F yther less studied reonstrutions
    xii. This is perfectly illustrated in the case of the carbon element : the physical properties of a single sheet of graphite (under the form of graphene or nanotube, or even fullerene) dier a lot from the ones of bulk.

    IH

    I.3.

    Interactions

    of gold on i@IIIA suh s @PPA eifert et al.D PHHID @2 32 3A or @2 212 21A10.9 E


    ki IWWV hve so een reportedF sn the sme wyD eu forms @ 3 3AQH reonstrution on the qe@IIIA sustrte
    et al.D et al.D

    whih is supposed to e similr to the one on i@IIIA rowes

    IWWQF xote here

    tht no @TTA reonstrution is known to form in the euEqe@IIIA systemF es fr s el is onernedD pioneering work of vnder nd worrison reveled the formtion of surfe reonstrution of el on i@IIIA for sumonolyer rnge nd t high tempertures vnder nd worrisonD IWTRF he i@IIIAE@ 3 3A Eel reonstrution ws susequently studied in more detils y severl tehniques xorthrupD IWVRY md rorioD IWWW urfe reonstrutions re therefore most of the times twoEdimensionl strutures nd re studied for overges of the order of one monolyer xiii F por higher overgesD typilly ove P wvD the formtion of thin rystlline (lms @or islnds depending on the growth modeD see setion sFIFPA strts to e fvouredF hese thin epitxil solid (lms n undergo morphologil trnsformtions tht turn them into islndsF his is the topi of the next setion @sFQFQAF
    et al.D

    IWVRY rung

    et al.D

    IWWHY

    I.3.3 Dewetting of thin lms : formation of islands


    hroughout the litertureD it is often mentioned tht the liquid tlyst droplets re oE tined y inresing the tempertureD whih indues the dewetting of the solid (lm previously deposited t y wfiF his preision is useful euse the droplets ould hve een oE tined using other methodsF por instneD deposit performed t higher temperture n led to diret islnding ording to the olmerEeer or the trnskiEurstnow growth modesF st is even possile to diretly ly down eu mirodroplets on the sustrte perrlis
    et al.D

    PHHVF sf the dewetting proess is often usedD it is rrely desried in detilsF fefore
    i. e.

    the eu deposit trnsforms into liquid tlyst droplets tht n e used for the growth of nnowiresD the solid (lm (rst dewets in the solid stteD it undergoes struturl hnges upon nneling leding to the retion of solid islndsF e give here rief desription of this proess to introdue the results presented in ghpter sssF ioneering work of yleigh yleighD IVUVD s well s following studies of wullins wulE linsD IWSU llowed more reent uthors to derive models onerning the dewetting proess through the study of the stility of thin solid (lms rolovitz nd frnD IWVTY IWVTY tirn nd hompsonD IWWPF hese solid (lms present high surfeEtoEvolume rtio so tht the system tries to redue its surfe reF his redution n e hieved vi di'usion of toms whih tend to gglomerteF yviouslyD the gglomertion is esier t high temperture
    xiii. The case of Ge-(2N) reconstruction on Si(001), with N depending on the coverage (1-3 ML) has been reported [Zhou et al., 2011].

    II

    Chapter I.

    State of the art

    s tomi di'usion is enhnedF he dewetting is therefore onsequene of nneling ut nneling is not the driving fore @whih is the redution of the surfe energyAF pigure sFII illustrtes the dewetting proess whih ours in two steps X the retion of voids in the (lm @@AD @AA nd their susequent growth @@AD @dAAF
    Grain boundary Intersection with substrate Contact angle - Diffusion - Propagation

    Film
    Substrate
    (a) (b)

    (c)

    (d)

    Figure I.11  Side view illustrating the two steps dewetting process. (a) The polycrystalline lm
    is at with the presence of a grain boundary. (b) Fluctuation due to thermal activation sets in at the position of the grain boundary (c) The created voids is large enough to create a contact angle (d) The void starts to grow.

    sf stle thin solid (lm is nneledD smll mplitude )ututions pper Xi.

    e.

    the (lm

    gets rougherF he retion of voids is the onsequene of )ututions lrge enough to rete deep groove tht n reh the sustrteF sn polyrystlline (lmsD it is resonly ssumed to rise t grin oundries @pigure sFII@AD @AAF e ontt ngle is reted etween the sustrte nd the solid if the groove intersets the surfeF henD mss trnsfers our vi surfe di'usion to redue the urvture of the (lm edge resulting in the growth of the voids @pigure sFII@AD @dAAF hue to n inhomogeneous reprtition of the removed toms @see pigure sFIPAD some regions re thiker @eA thn others @fAF es onsequeneD the void grows fster in front of f res nd the result is nonEplnr propgtion of the voidsF et some point the thik re of type e dethes from the (lm nd solid islnd reminsF

    B
    Void A

    Islands

    Film

    Figure I.12  Top view showing the non-planar propagation of the void. This results in the presence
    of thicker areas (A) which detach from the solid lm and become islands.

    his simple model well desries the generl trends onerning the dewetting of solid (lmsF e nie exmple onerning the dewetting of eu (lms n e found in h0r een derived ng nd hfD PHIIY ierreEvouis IP
    et al.D et al.D

    PHHWF rowever for the desription of more omplex phenomenD more preise models hve PHHW @nd referenes thereinAF

    I.3.

    Interactions

    I.3.4 Wetting droplet on a solid surface


    feuse of the dewetting proessD thin metl solid (lms form solid islnds on the unE derlying g sustrteF hen the system temperture is inresed up to the euteti oneD the solidEliquid trnsition tkes ple nd liquid droplet reminsF he morphologil equiE lirium linking the droplet to the sustrte n e expressed using the oung9s eqution presented herefterF
    a Young's equation

    he wetting properties of liquid droplet @i. proposed in IVHS oungD IVHS X

    e.

    its shpeA in intertion with solid

    sustrte depends on n energeti equilirium desried y the wellEknown oung9s eqution

    liqvap cos() = solvap solliq

    @sFIA

    with liqvap D solvap nd solliq the liquidEvpourD solidEvpour nd solidEliquid surfe tensionsD respetively nd the ontt ngle @mesured in the liquid phseAD s represented in pigure sFIQF roweverD lthough ontt ngle is quite esy to mesureD the three surfe energy termsD whih re fundmentl prmeters in mteril siene s they re relted to the inding fore etween tomsD re di0ult to otin experimentllyF he study of surfe energies is sienti( (eld deling with mny fets of mteril siene nd n not e introdued hereF roweverD severl spei( fetures onerning the present work re presented rie)y herefterF

    vap-liq vap-sol

    Vapour-Vacuum
    Liquid

    liq-sol
    Solid

    Figure I.13  Scheme representing the wetting of a liquid droplet in interaction with a solid
    substrate.

    Precisions relative to surface energies

    e (rst remrk hs to e mde here on the de(nitions used for the surfe energies tht re surfe stressD surfe free energy or surfe tensionF por lrityD we only remind here tht IQ

    Chapter I.

    State of the art

    surfe stress is quntity desried y tensor nd is relted to the work needed to deform solid surfe elstillyD wheres surfe energy is relted to the work needed to rete new surfe re @in tFm2 AF he surfe tension term is the liquid nlogue of the surfe energy for solidF sn mteril siene it is ommon to use the surfe tension or the surfe energy term eqully for oth phsesF sn this studyD ttention ws pid on the wetting ehviour of eui droplets on i suE strtesF st is therefore importnt to hve n ide of the di'erent surfe energy vlues onerE ning this system for whih the surfe energy of solid i needs to e known s well s the di'erent surfe tension terms of goldF
    Si substrate surface energy

    sing experimentl levge tehniques todineD IWTQ orD more reentlyD indenttion tehniques oupled to moleulr dynmi simultions nk
    et al.D

    PHHT s well s theoreE


    et al.D

    til lultion using the wodi(ed imedded etom wethod @wiewA hng

    PHHQ

    it is possile to evlute the i rystl surfe energyF he surfe energy of solid silion depends on its rystllogrphi orienttion with the low index plnes presenting the lowest energies nd X

    Si(111) 1.2 tFm2 < Si(110) 1.5 tFm2 < Si(100) 1.9 tFm2
    Gold surface energies

    @sFPA

    he se of gold seems to e it more omplexD s illustrted y le sFI whih gthers the di'erent vlues enountered in litertureF st revels tht for the liquidEvpour nd solidEliquid energiesD the omprison etween the di'erent ppers re in good greement nd provides the ommonly used vlues X ! liqvap 1.2 tFm2 nd ! solliq 0.13 tFm2 F por the vlue of the solidEvpour surfe energy solvap D the dispersion is lrger nd must rise from the di'erent ssumptions used in the simultion tehniques s well s the experimentl unertintiesF sn dditionD solvap is temperture dependent ndD s for iD rystllogrphi orienttions lso in)uene the resultF roweverD in most metlD the di'erene in solvap etween H u nd the melting temperture m do not exeed IH 7 yson nd willerD IWUUD the error thus remins quite lowF he men vlue of ll the solvap of le sFI is IFSR 0.19 tFm2 F st ompres well with the vlue of the studies tht do not tke into ount rystllogrphi orienttions e'ets yson nd willerD IWUUY wezey nd qierD IWVPF yne n lso note here thtD s for IR

    I.3.

    Interactions

    Table I.1  Surface energy values found in literature for pure gold. The temperature and the method
    are indicated when explicitly mentioned.

    (Au) Au(111) Au(001) Au(110) Au(111) Au(001) Au(110) Au(111) Au(001) Au(110) solvap

    inergy @tFm2 A IFPV @H uA IFTQ @H uA IFUH @H uA IFQV @H uA IFRW @H uA IFVS @H uA IFTI @H uA IFUI @H uA IFUW @H uA IFPS @H uA IFS @H uA IFQS @IQQT uA IFTP @QHH uA IFQT @WHH uA IFIS IFIV IFQ @QHH uA HFIQ HFIQ

    ehnique hp ight inding totlEenergy method


    Ab-initio

    eferene itos
    et al.D

    IWWV

    wehl nd ponstntopoulosD IWWT kriver nd osengrdD IWWP xeeds nd wns(eldD IWVW yson nd willerD IWUU wezey nd qierD IWVP inet et al.D PHHP hnD PHIH igry et al.D IWWS inet et al.D PHHP urnullD IWSH

    solvap

    solvap liqvap liqvap liqvap solliq solliq

    seudopotentil energy method urfe entropy estimtion glultion from enthlpy of tomiztion hermodynmi model vevitted droplet hermodynmi model hroplets on glss

    ll f metlsD lose pked surfes @low indexes plnesA of the rystl re the most stle X

    Au(111) < Au(001) < Au(110) F


    feyond pure goldD the interest of this work lies in the euEi lloyF es it hs een shown oveD surfe energies of pure elements re lredy di0ult to evluteF yviouslyD it is even hrder in the se of lloys nd very few studies del with themF es pointed out y hmidt et
    al.

    in their reent review on nnowiresD the wetting properties of the tlyst strongly in)uene

    the shpe of the nnowiresF st is therefore relevnt to ttempt n evlution of the di'erent energy terms in the se of the eui lloyF king solvap = 1.25 tFm2 for the i@IIIA surfe energyD liqvap = 0.85 tFm2 for the eui liquid lloy xidih
    et al.D

    IWUSD nd RQ s ontt ngle essel


    et al.D

    et al.D

    PHHQD the

    oung9s eqution provides n evlution of the interfe energy etween the droplet nd the sustrte @<Si>(AuSi) A of HFTP tFm2 hmidt PHIHF
    et al.

    sn the se of droplet t the tip of nnowire nd for whih wetting properties re di'erentD the thermodynmil proess proposed y oper yields liqvap = 0.91 tFm2 IS

    Chapter I.

    State of the art et al.D et al.

    nd solliq = 0.8 tFm2 oper

    PHHUF his grees well with the proposed vlues of xeolsin nd hhetininD PHHQF

    solliq = 0.75 tFm2 y xeol9sin


    llowed uim et
    al.

    woreoverD the oservtion of the melting proess of pure gold y inorportion of i toms to lulte the interfe energy etween the solid eu nd the eui liquid
    et al.D

    lloy X <Au>(AuSi) = 0.3 tFm2 D t VHH u uim

    PHHWF

    I.4

    Description of the liquid state : the pair-correlation function

    he study of liquids requires to devise mthemtil onepts in order to desrie the toms ehviour in this stte of mtterF he (rst piture tht omes in mind is tht in liquidD the toms re distriuted rndomlyF rowever some sttistis n e derived to piture the rrngement t given timeF his stti desription n e done through the use of the pir orreltion funtion whih desries the vrition of the tomi density s funtion of the distne from distint prtileF his funtion is importnt in the studies of liquids s it n e determined using Ery or neutron sttering tehniquesF his funtionD usully noted g(r)D is plotted on the grph in pigure sFIRF sn this se is represented the rdil orreltion funtion whih mesures the independene etween the positions of the prtilesF he funtion equls zero t the origin @where n tom is pledA euse of eletroni repulsions nd then presents severl mxim orresponding to the difE ferent groups of toms de(ned s (rstD seondD thirdD etFFF neighoursF por lrge vlues of

    rD the funtion tends to unity s the liquid is disordered t long rnge X the position of the
    tom loted t lrge r is not in)uened y the position of the referene tomF sing simple ideD the orreltion funtion n e seen s the proility of (nding n tom in ring of (nite thikness r entered on the referene prtileF st is given y X

    g(r) =

    V n(r) N 4r2 r

    @sFQA

    with N the numer of identil prtiles loted in spe of volume V nd n(r) the numer of toms loted etween r nd r + rF st therefore llows one to lulte the men numer of toms present t distne R round the tom t the originD whih is lled the oordintion numer N X
    R2

    N = 4
    R1

    r2 g(r)dr ,

    for r limited to the shell of (rst nerestEneighours

    @sFRA

    N orresponds to the red re under the urve of g(r [R1 , R2 ]) nd is of the order of
    IT

    I.4.

    Description of the liquid state : the pair-correlation function

    3 2 g(r) 1 0

    R1

    R2

    2nd nearest neighbours

    1st nearest neighbours

    Figure I.14  Pair correlation function g(r) and the corresponding groups of nearest neighbours
    responsible for the dierent peaks.

    IP for most liquidsD whih is omptile with ompt rrngementF huring n Ery or neutron experiment for hrterizing liquidsD the mesured quntity is the struture ftor @A @with the momentum trnsfer de(ned in setion ssFIFPAD whih is relted to g(r) y X

    S(Q) = 1 +
    0

    (g(r) 1)e iQr dr

    @sFSA

    e simple pourier trnsform of @A therefore llows us to dedue the experimentl pir orreltion funtionF IU

    Chapter I.

    State of the art

    I.5

    Liquid-solid phase transition

    xow tht we hve seen wht is liquid nd how it is possile to desrie itD we will disuss some theoretil spets of the solidi(tion proessD i.
    e.

    the retion of solid phse from

    liquid phseF en importnt onept in the study of liquidEsolid trnsitions is the ft tht liquid does not trnsform into solid s soon s the melting point is rehedF e liquid needs to e ooled elow its melting point in order to form stle ggregteF his phenomenon is lled superooling or underoolingF his ehviour ws pointed out y phrenheit in IUPR who reorded the (rst superooling experiment on liquid wter xiv phrenheitD IUPRF st hs een lerly shown tht liquid needs to overome n energeti rrier to trnsform into solid phseF his is desried within the lssil nuletion theory rie)y presented herefterF his theoryD sed on erly works of feker feker nd horingD IWQSY fekerD IWQVD hs een developed further y urnull urnull nd pisherD IWRWY urnullD IWSHd in the se of metls y desriing the onditions of formtion of solid lusters from the melt nd how the size of these lusters evolves with timeF

    I.5.1 Supercooling : thermodynamic and classical model


    e phse trnsitionD solidi(tion for instneD of pure element is driven y the vrition of the free enthlpy G given y xv X

    Gs = Hs T Ss

    @sFTA

    with T the temperture @uAD H the enthlpy vrition @relted to the energy of the hemil ondsA nd S the entropy vrition @relted to the struturl orgniztionAF et the melting temperture Tm D the ontinuity of the funtion G implies tht Gsolid = Gliquid nd it omes X

    Gs = 0 Ss =
    oD the eqution @sFTA eomes for T = Tm X

    Hs Tm

    @sFUA

    Gs = Tm

    Hs Hs Hs T Gs = T , Tm Tm Tm

    with T the superooling vlueF

    @sFVA

    xiv. It is worth mentioning here that even for water, the most common liquid, the solidication process in not completely understood. xv. the index 's' stands for solidication

    IV

    I.5.

    Liquid-solid phase transition

    e quik look t the sign of Gs llows us to know whether or not the trnsition n e hievedF ith Ss negtive for solidi(tion proess @retion of orderA X

    T > Tm T < 0 Gs > 0 solidi(tion impossile T < Tm T > 0 Gs < 0 solidi(tion possile

    @sFWA

    he (rst thing to note hereD is tht the liquid must e superooled to hve hne to solidifyF xeverthelessD the thermodynmi only quints the possile existene of the solid phse ut does not explin how this ltter is reted from mirosopi point of viewF por T < Tm D the vrition of free enthlpy G of group of tom whih is out to form spheril solid nuleus of rdius r depends on the energeti ompetition etween the retion of solidGliquid interfe solliq nd the vrition of free enthlpy per volume unit

    gV @aT Hs /Tm A X
    Gvolume Gsurf ace

    Gnucleus

    4 = r3 gV + 4r2 solliq 3

    @sFIHA

    his eqution shows the di'erent fores driving the solidi(tion proessF e now present the results deriving from this sttementD whih onern the potentil formtion nd the stility of reted nuleus in two di'erent ses X homogeneous nd heterogeneous nuletionF
    a Homogeneous nucleation Thermodynamics of nucleation

    he proess of homogeneous nuletion onsists in the retion of stle nuleus y ggregtion of toms somewhere in the liquid phseF iqution @sFIHA shows tht the stility of this nuleus depends on its size rF sn pigure sFIS@A re plotted the surfe nd the ulk prt of the free enthlpy s funtion of the rdius r to highlight their respetive ontriution to the totl vritionF his ltter presents mximum t r D lled the ritil rdiusD orresponding to the energeti rrier tht hs to e overome to rete stle nuleusF sf r < r D the r2 surfe term domintes @reting surfe osts too muhA nd the solid returns in the liquid stteF sf

    r > r the ulk term is preponderntD the nuleus is stle nd the solid n strt to growF
    his proess is illustrted in pigure sFIS@A for the se r = r F sn this on(gurtionD there re equl hnes for the nuleus to e stle or notF he lultion of the vlue of r is done for X

    dG 2solliq 2solliq Tm 2 = 0 so it omes X r = = = , dr gV T Hs T

    @sFIIA IW

    Chapter I.

    State of the art

    Gsurf . 4 sol liq r 2

    Liquid

    r = r*
    r

    t=0

    r*

    Nucleus
    1

    t + t

    04 Gvol. TS s r 3 3

    r > r*
    r

    r < r*
    r

    r
    (a)

    Solidification
    (b)

    Dissolution

    Figure I.15  (a) Plot of


    of

    r.

    The maximum of

    Gvolume and Gsurf ace as well the Gnucleus function is obtain for

    as their sum (Gnucleus ) as a function a nucleus of size

    r .

    (b) Illustration of

    two scenarios 1 (starting growth) and 2 (returning to liquid state) that can follow when a nucleus reaches a size of

    (at t=0).

    with = solliq Tm /Hs eing the qis prmeterF sn the se of pure goldD with

    solliq = 0.13 tFm2 @see setion sFQFRAD Hs aEIPFS ktFmol1 aEIFPP 109 tFm3 nd Tm aIQQT uD
    the qis prmeter is IFRS 107 uFm xvi F herefore the more the liquid is superooled @lrge

    T AD the smller the ritil rdius is hene the esier it is for the liquid to solidifyF he riE
    til rdius s funtion of the superooling vlue is plotted on the grph in pigure sFITF

    1E-7

    r* (m)

    1E-8

    1E-9 0 50 100 150 200 250 300

    T
    Figure I.16  Supercooling dependence of the critical size of a forming nucleus for pure Au.
    xvi.

    107

    K.m for most metals.

    PH

    I.5.

    Liquid-solid phase transition

    Kinetics of nucleation

    sn the se of luster of ritil size r @i. e. ontining n tomsAD the ddition of nother struturl unit will lower its free energy @see previous setionAF st is however resonle to ssume tht there exists n energeti rrier tht hs to e overome due to the inorportion proess @Ginc AD s illustrted in pigure sFIUF

    Liquid
    Rejection Ginc

    Solid

    Free energy G
    is thus X

    Incorporation

    Figure I.17  Plot of the free energy variation undergone by a solid which grows by addition of a
    structural unit. An energetic barrier has to be overcome for each new addition.

    he nuletion rte orresponding to the inorportion of new toms in the solid luster

    J = Ae

    G +Ginc kB T

    @sFIPA

    with e term enompssing the shpe ftor of the nuleusD the numer of ville nuletion sites t the liquidEsolid interfe nd the virtionl frequeny of the prtiles tht try to overome the rrierF he onditions of formtion of stle nuleus s well s its pity to grow in the liquid therefore depend on thermodynmil onditions ut lso on di'usion proessesF his is why for exmpleD it is possile to form solids presenting no rystlline struture @glssesA y quenhing themF he ooling rte eing very highD the toms do not hve enough time to di'use nd form rystl X these prtiulr solids n e seen s frozen piture of the liquid stte in (rst pproximtionF ntil the IWSHsD no lrge superooling tendeny hd een oserved in monotomi liquid metlsD most of them presenting solidi(tion temperture Ts redued y IS to PH7 omE PI

    Chapter I.

    State of the art

    pring to Tm urnullD IWSHF his suggested tht the energeti rrier for nuletion ws smllF his ssumption ws supported y the ft tht the oordintion numer for n tom in the liquid is 12 @see setion sFRA nd hene led to the ide tht the liquid phseD of similr densityD presented short rnge order very similr to the future rystl strutureF sn other words X the liquid ws supposed to e redy to rystllizeF roweverD urnull himself showed tht the supposed smll rrier tully me from the heterogeneous nuletion X the formtion of the solid phse is tlyzed y the presene of wlls whih serve s seed @i.
    e.

    s nuleusA urnullD IWSHF he quntittive in)uene

    of these seeds on the nuletion proess is explined in the next setionF hey n e for instne impurities or more generlly the inner wll of ruileF por exmpleD urnull showed tht the superooling of merury droplets n rnge from IH to VH u depending on the mteril used for the ruile urnullD IWSPF

    Heterogeneous nucleation

    sn the se of heterogeneous nuletionD the nuleus is represented y spheril p in ontt with prtile @i.
    e.

    the sustrteA nd the liquid phse @see pigure sFIVAF

    liq-sol liq-sub
    Solid

    Liquid

    sol-sub
    Substrate

    Figure I.18  Picture of a solid spherical cap in contact with a substrate and its liquid.

    he vetors in pigure sFIV represent the surfe energies @in the sme wy s in seE tion sFQFRA rising with the retion of the solidEliquid @solliq AD the solidEsustrte @solsub A nd the liquidEsolid @liqsub A interfesF he vrition of free enthlpy of the nuleus needs in this se to ount for these di'erent surfe terms X

    Gnucleus = Gvolume + Gsurf ace with Gsurf ace = f (solliq , solsub , liqsub )

    @sFIQA

    he importnt feture is to ompre how the retion of the nuleus is in)uened y the presene of the solid sustrteF iqution sFIQ desriing how the vrition of free enthlpy of the nuleus in the heterogeneous se @Gnucleus (het)A is relted to the one of the homogeE neous se @Gnucleus (hom)A through the funtion f tht only depends on the wetting ngle PP

    I.5.

    Liquid-solid phase transition

    X 1 Gnucleus (het) = Gnucleus (hom) f () with f () = (2 3 cos + cos3 ) 4


    @sFIRA

    por heterogeneous nuletionD the vlue of the ritil rdius r is still 2solliq /T Ss @due to its de(nitionA ut the numer of toms in the nuleusD nd even more importnt the nuletion rteD hve hnged in the sme proportion s GF ith n nd J the numer of toms present in the nuleus nd the nuletion rte for the homogeneous seD the numer of toms nd the nuletion rte in the heterogeneous se for the sme vlue of r re

    nhet = n f () nd Jhet = J f ()F


    1.0 0.8

    0.020 0.015 0.010 0.005 0.000


    0 30 60

    f()

    0.6 0.4 0.2 0.0

    (a)

    90

    120

    150

    180

    f()

    10

    15
    (b)

    20

    25

    30

    35

    Figure I.19  (a) Plot of the function


    Zoom on the low

    f (),

    the contact angle

    is taken in the solid phase. (b)

    values highlighting the large inuences undergone by good wetting solids.

    he vrition of the funtion f () is plotted on the grphs in pigure sFIWF his ftor n extremely derese the numer of toms of the nuleus s well s the nuletion rte needed to form stle struture when the solid wets the sustrte X f () = 1.3 102 for

    = 30 AF he se = 180 D orresponds to nonEwetting solid nd thus the homogeneous


    se @f () = 1A is reoveredF sn the light of these onsidertions on heterogeneous nuletionD experimentl setEups were devised to void heterogeneous nuletionF his ould e hieved y the emulsi(tion tehnique in whih the liquid metl is seprted into multiple droplets surrounded y n inert liquid @orgni )uidA or through mgneti levittion @ontinerless tehniqueA erepezko nd ikD IWVRF fy use of these proessesD it ws found tht liquid metls ould e superooled down to PHQH7 of their melting tempertures efore rystllizingF he thermodynmi models desried ove @very rie)yA re widely used to understnd solidi(tion proesses or phse trnsitionGequilirium from mrosopi point of viewF PQ

    Chapter I.

    State of the art

    hey n lso e extended for exmple to the se of lloys nd predit phse formtions y the explortion of the phse digrmF roweverD it is the oservtions of lrge underooling of some elements tht solidify into loseEpked strutures s well s the existene of intermetlli eutetis tht led pFgF prnk to propose tht the liquid struture itself must e responsile for its metstle ehviourF

    I.5.2 Beyond the classical model : the icosahedral order


    a Frank hypothesis

    he prnk postulteD expressed in IWSP prnkD IWSPD pointed out tht there exist three possile wys to put IP spheres in ontt with ommon IQth F he (rst two tomi rrngeE ments re the wellEknown loseEpked rystl strutures @f nd hpAF he third oneD whih he thought ws even more trivil s he suggested tht it  comes
    schoolboy D to the mind of any good e.

    onsists in pling the toms t the enter of eh fe of dodehedronD i.

    the vertex of n ioshedron @see pigure sFPHAF ith this ssumptionD prnk proposed tht s metlli liquids oolD lol tomi strutures ontining ioshedrl short rnge order @syA develop in the liquid phseF ith desription using this sy modelD the liquid presents n verge oordintion numer of IP ut is it denser xvii inditing tht the liquid stte isD t lest lollyD more stleF his energetilly fvorle environment ws on(rmed y moleulr dynmi simultion t the eginning of the IWVHs y teinhrdt simple vennrdEtones potentil teinhrdt
    et al. et al.D

    in simulted superooled liquid with IWVIY IWVQF usequently to the work

    of prnkD wky wkyD IWTP developed this ideF re showed tht n ssoition of disE torted f tetrhedr n uild ioshedron lusters @of more thn IQ tomsA presenting PH externl {III} fetsF he reltion etween the numer of shells @LA in the luster nd the numer of toms N is given y N = (10/3)L3 + 5L2 + 3L + 1F por L = 1D we otin the IQ toms ioshedron @pigure sFPH shows the ses for L = 2AF hese lusters hve lredy een oserved experimentlly esenio
    et al.D

    IWWVF rowever their stility with inresing

    numer of toms remins unler nd strongly depends on the mterilF he model proposed y prnk therefore devites from the lssil theory y the ft tht the energy of the liquid is lolly minimized y the formtion of lusters with (vefold symE metryF woreoverD this pentgonl order xviii is inomptile with trnsltionl periodiity so tht long rnge order n not e hieved X it is impossile to tile Ph spe with pentgons nor Qh spe with ioshedron without reting defets @see pigure sFPIAF es onsequeneD
    xvii. It is known that the mean distance between neighbouring atoms is slightly smaller in the liquid than in the solid phase xviii. An icosahedron belongs to the

    m35

    point group.

    PR

    I.5.

    Liquid-solid phase transition

    FCC close-packed environment

    HCP environment

    Icosahedral environment
    N=55

    Mackay clusters

    Figure I.20  Top : Representation of two atoms (black) in dierent local atomic packings (red).
    Both are surrounded by 12 other atoms but one is in a FCC close-packed structure (left) and the other in a hexagonal close-packed environment. Both present a three-fold symmetry. Bottom : (left) In this case the black atom is also surrounded by 12 neighbours but is located in an icosahedral environment which presents ve-fold symmetry highlighted by the two pentagons plotted in red. (right) Illustration of the Mackay cluster for L=2.

    if lrge numer of toms in the superooled liquid re rrnged in n ioshedrl environE mentD the liquidEsolid trnsition n tke ple only through deep on(gurtionl hnges ting s nturl energeti rrier nd the liquid stte is fvouredF he pperne of this new onept for the desription of mtter led xelson nd hdev to propose mthemtil

    Figure I.21  The tilling of the sheet plane with pentagonal pieces (in red) cannot be performed
    without the creation of empty areas (in white).

    PS

    Chapter I.

    State of the art

    theory to model pentgonl order nd defets in liquids nd glsses xelsonD IWVQF his desE ription led to the onlusion tht for liquid presenting pronouned syD its lssi pir orreltion funtion should e modi(ed y presenting shoulder on the seond pek hdev nd xelsonD IWVRF he desription of this short rnge order lso soon required prtiulr frmework to distinguish etween severl lol environmentsF his n e hieved y the use of four integers proposed y roneyutt nd endersen in IWVU roneyutt nd endersenD IWVUF
    b Description of short range order (SRO) :

    he desription of the short rnge order onsists in nlyzing the distriution of the neighours surrounding referene tomF hese lusters n hve di'erent geometries nd the method onsists in nomenlture omposed of four indexesF st llows one to distinguish etween vrious lol strutures suh s fD hpD nd ioshedrl environments y trnsE lting into numers how two toms re relted to eh other in group of tomsF he four indexes re expressed s follows X ! the (rst indites whether or not toms omposing the pir studied re nerEneighoursD ! the seond one orresponds to the numer of ommon nerest neighours shred y the referene pirD ! the third one is the numer of onds etween ommon nerest neighoursD ! nd the lst one is used to distinguish strutures with the sme (rst three indexes ut hving di'erent topologiesF gonsidering thisD the f struture is desried y pirs with IRPI indies wheres ITTI nd IRRI pirs re typil of on(gurtionsF pive fold symmetries re represented for exmple y pirs noted ISSI or ISRI nd IRQI @for distorted struturesA @see pigure sFPPAF

    1441

    1551

    1541

    Figure I.22  Schemes of dierent local atomic structure using the Honeycutt and Andersen indexes.
    1441 (bcc), 1551 (pentagon) and 1541 (distorted pentagon).

    he ioshedrl order nd ommonEneighour nlysis hve een t the hert of mny


    ab-initio

    moleulr dynmis simultions studies to understnd the struture of underooled


    et al.D

    metlli liquids tnsson nd endersenD IWVVY tkse nd sturelD PHHQY ng PT

    PHHRY

    I.6.

    Particular liquid behaviour :

    gelino

    et al.D

    PHHUY uim nd ueltonD PHHU nd more reently the struture of metlli


    et al.D

    glsses heng

    PHHTY tkse nd sturelD PHHVF xowdysD these models sed on


    et al.D

    syD lredy oserved in metlli solid lloy elwn hehtmn in metlsF

    IWVR nd eing

    si element of qusiErystl desriptionD re widely epted s the origin of superooling roweverD experimentl evidenes of their existene in metlli liquid phse only rose fter long e'orts s they re rndomly orientted nd re thus hrd to revel with stteE ring tehniquesF pormtion of pentgonl lusters hs (rst een oserved in liquid led t the interfe with silion sustrte eihert uelton ton et
    et al. et al.D

    PHHHF sn PHHPD henk

    et al.

    reveled PHHPF

    their existene in levitted xiD pe nd r liquids y neutrons sttering henk

    et al.D

    on(rmed this y the use of Erys nd mde the link etween the inresing

    numer of pentgonl lusters nd the degree of superoolingD on(rming prnk9s theory uelE
    al.D

    PHHQY PHHTF eentlyD simultions showed tht in dditionD ioshedrl lusters n


    et al.D

    selfEssemle in orgnized rrngements leding to the formtion of defets in the growing rystl uryinnis PHIIF

    he liquid stte s well s the solidi(tion proesses presented in this setion from generl point of view re phenomen tht ply signi(nt role in the growth of g nnowires nd hve to e ontrolled to rete the desired ojetF sndeed the v growth is sed on the use of metl tlyst tht n form liquid lloy with the gF sing the prtiulr properties of the metlEg lloys forming n eutetiD it is possile to grow nnowires t very low temperturesF roweverD the simple ide tht the growth is only governed y the thermodynmi equilirium omposition given y the liquidus line xix D whih is very ttrtive nd true from mrosopi point of viewD seems to e muh more hllenging to understnd when looking it loserF he next setion presents the di0ulties enountered in the studies onerning the formtion of eutetis nd their use in g growthF

    I.6

    Particular liquid behaviour :

    wixing two di'erent mterils n led to mny di'erent phsesF hese di'erent phses depend on the onentrtion of eh element s well s the temperture nd n e represenE ted using phse digrmF e good exmple of the omplexity rising from the study of lloys is given in pigure sFPQ whih displys the phse digrm of the extensively studied peEpe3 gF his system presents lrge vriety of di'erent ompounds with lots of prtiulr points nd equilirium lines seprting the di'erent phses @nd only for pe3 g onentrtion rnging
    xix. at constant temperature.

    PU

    Chapter I.

    State of the art

    from H to U 7A xx

    Figure I.23  Fe-Fe3 C phase diagram [Pollack, 1988].

    rereD we re not going to present ll the fetures tht n e present in phse digrmD s it ould (ll n entire ookF rowever the prtiulr euteti point lredy mentioned is of high importne in this study nd is presented elow in the se of the studied systemsF

    I.6.1 Thermodynamic and structure


    st hs lredy een introdued tht the systems studied in this work @mostly eui ut lso euqe or eliA disply phse digrms tht re t the sme time very simple nd very omplitedF por instneD the eui phse digrm @pigure sFVAD is simple euse it is only omposed of (ve phses X ! the @euiA liquid phseD ! two domins into whih the solid `eub or `ib nd liquid @euiA oEexistD ! nd the two distint f `eub nd dimondElike `ib phsesF snterestingly no eui solid lloy exists in the ulk xxi F sn the euEqe nd elEi system hoE weverD rystlline lloys for smll onentrtion rnges of the g element n form @often noted phseAF heep euteti in liquid lloys ttrted lot of ttention euse of their surprisingly low melting temperture ompred to the ones of the pure elementsF sn sense they n lmost e seen s very underooled liquidsF es we hve seenD studying the strutures of monotomi liquids is lredy very omplitedF st therefore seems to e even more omplited to del with suh prtiulr euteti lloysF he entrl question whih still remins unnswered in
    xx. Interactive binary phase diagrams can be found on this web page : http ://www.crct.polymtl.ca/fact/Documentation/SGTE/SGTE_Figs.htm . xxi. There is no mutual solid solubility of the two materials in bulk structure.

    PV

    I.6.

    Particular liquid behaviour :

    the se of glssEforming metlli lloys is whether or not the liquidGglss struture di'ers signi(ntly from rystlline phses qskellD PHIIF wny studies tried to nswer this triky question sine the disovery of ulement who otined the (rst metlli glss y quenhing the eui euteti liquid ulement
    et al.D

    IWTHF

    rumeEothery nd enderson rumeEothery nd endersonD IWTH were the (rst to proE pose n explntion for the ompositions oserved in euteti lloysF he rumeEothery phsesD ssumed to form in the lloysD depend on the numer of eletron of eh omponent y de(ning the eletron tom rtio etween the two speiesF sn the IWUHsD thermodynmil studies strted to set the (rst idesF glultions tE king pure elements s strting points showed tht the oserved euteti diverged lot from predition nd this ws explined using the ssumed existene of the eu3 i rumeEothery phse gstnet
    et al.D

    IWUVF rowever the generl theory proposed y rumeEothery

    et al.

    hs enountered quite mny exeptions in the desription of eutetis n thus n not e tken s previling riterion even if in ertin ses their ssumption seems to e veriE (ed si
    et al.D

    PHIHF

    wodels nd experiments were omined to desrie the toms intertions nd it ws proposed tht metlEg onds were preferred to metlEmetl onds nd gEg onds E ghorne
    et al.D

    IWUTF hey lso pointed out tht other models tht tried to extrpolte solid

    strutures to predit the liquid one were indequte s they filed to reprodue the density vrition etween the two sttesF his desription is supported y reent ab-initio simultions showing the iElloying e'et in the liquid t the euteti omposition nd the inrese of the sy in the underooled regionF e potentil orreltion etween sy nd the derese of di'usivity would lso exE plin the tendeny for the euEi euteti to rete n morphous lloy sturel et
    al.D

    PHIHF

    sn dditionD Ery di'rtion experiments yield the pir orreltion funtion whih ws (tE ted y reverse monte rlo nlysis highlighting the reking of the euEeu onds round the euteti temperture nd the inrese of the density of the liquid with deresing temE perture ked
    et al.D

    PHHUF sing omplementry neutron di'rtion experiments nd


    et al.D

    numeril simultionsD it ws lso found tht the men distne in euEi ond for its respeE tive euteti onentrtion is PFR ghirwtkul PHIIF wore reentlyD the strutures of egEqeD egEiD euEqe nd euEi euteti liquids hve een explined through vritions of the eletril resistivity whih is elieved to rise euse of onentrtion )ututionsF hese results were otined onsequently to the study of q nd snn liquid lloys with the sme tehnique eoki
    et al.D

    PHHPF pigure sFPR represents the

    homogeneous euteti lloy @QA into whih onentrtion )ututions of the metl @IA nd the g @PA phses re supposed to formF rereD i nd i re the resistivity nd the volume PW

    Chapter I.

    State of the art

    frtion of domin iD respetivelyF essuming tht domins I nd P re very smllD the relE tion etween their volume frtion nd the mesured resistivity n e ddressed t given onentrtion of the lloy stmi
    et al.D

    PHHU X

    1 + 2 =

    3 /3

    @sFISA

    with the di'erene etween the referene resistivity for the homogeneous liquid @meE sured t high D when no onentrtion )ututions riseD for given onentrtionA nd the mesured resistivity t lower temperture @for the sme onentrtionAF

    (1,1) (3,3)

    (2,2)
    Figure I.24  Illustration of the concentration uctuations that are supposed to arise in eutectic
    liquids from resistivity measurement. The major part of the liquid is composed of an homogeneous metal-SC liquid but some regions present variation of concentration into which pure metal or pure SC phases develop. The concentration uctuations are larger near the eutectic composition.

    epeting the mesurements for severl lloy onentrtionsD it is possile to plot the vrition of 1 + 2 s funtion of the lloy onentrtion for ertin tempertureF his is done for the euEi lloy t the euteti temperture in pigure sFPS@A whih highlights tht the onentrtion )ututions re mximum for the euteti ompositionF roweverD lthough onentrtion )ututions re lwys mximum t the euteti ompositionsD they lso our in wide rnge of temperture even if they re smller fr from the euteti tempertureF his ehvior is not fully understood to dteF st lso seems tht onentrtion )ututions strongly depend on the shpe of the euteE tiF pigure sFPS@A displys the onentrtion )ututions vlues t the euteti point for seveE rl system s funtion of the prmeter hosen y sked et al. sked et al.D PHHP XT /2 xF

    T is the di'erene etween the g melting temperture nd the euteti temperture Te D x orresponds to the euteti onentrtion with the g phse tken s referene @HFVI for
    euEi nd HFUP for euEqeAF st shows tht deep euteti point @suh s in the euEi systemA presents lrger onentrtion )ututions thn other systems @lmost twie the mount of the euEqe systemAF his desription therefore lrgely supports tht segregtion proess @see next setionA tkes ple round the euteti point nd lims for supposed poor tenE deny of these lloys to e superooled elow their euteti pointD s reported for the xiEx QH

    I.6.
    7 6

    Particular liquid behaviour :

    7
    Au-Si

    1+ 2 (%)

    1+ 2 (%)

    5 4 3 2 1 0 50
    eut. comp.

    5 4
    Au-Ge

    3 2 1
    Ag-Ge

    Ga-Sb In-Sb Ag-Si

    60 70 80 Au concentration (at.%)

    90

    0 400

    600

    800

    1000

    (a)
    Figure I.25  (a) Plot of the variation of
    parameter [Itami

    T/x (K) (b)


    as a function of the gold content at Te : maximum

    1200

    1400

    1600

    1 +2

    for the eutectic concentration. (b) Plot of the variation of

    et al., 2007] (see text).


    PHIHF

    1 + 2

    as a function of Ikeda

    et al.

    system stmi

    et al.D

    hrough the di'erent spets desried in this setionD one n see tht the struture of euteti lloys is very omplex nd still hllenges tomisti desriptions s strong lloying is known to rise in prllel to onentrtion )ututions tken s the strting point of the solidi(tion proess xxii F

    I.6.2 Solidication of eutectic alloys


    he understnding of the solidi(tion proess in eutetis nd more generlly in liquid lloys is very omplex ndD depending on the prmeters xxiii s well s on the di'erent omponentsD n led to mny di'erent struturesF hetiled studies n e found in uurz nd pisherD IWWV nd the referenes thereinF rere we will very rie)y present the sis of the theory to introdue the prmeters tht in)uene the solidi(tionF he solidi(tion of eutetis nd their susequent morphologies re prtiulr euse of the simultneous solidi(tion of the di'erent omponents present in the liquidF vet inry euteti lloy e solidi(ed from its liquid phse into two lmellr nonEmisile solid phses

    nd vi therml grdient @see pigure sFPT@AAF he resulting solidi(tion is equivlent


    to moving the solidEliquid interfe t rte v through the liquidF his situtionD ompred to the growth of single phse tht would led to solute di'usion nd superooling uurz nd pisherD IWWVD is fvourle sine the unneeded toms rejeted y one phse serve for the growth of the other phse y the estlishment of di'usion (elds
    xxii. In addition, recent simulations led to the discovery of a potentially stable AuSi solid phase [Tasci et

    al., 2010].
    xxiii. such as the composition or the cooling rate.

    QI

    Chapter I.

    State of the art

    T Te

    /2 v T (a)
    L

    L
    L

    (b)
    /2.
    The solid-liquid interface, moving at a speed

    Figure I.26  (a) Picture of a solidication process from an homogeneous eutectic liquid into
    two distinct solids separated by

    presents a

    temperature of solidication Ts diering from Te . (b) The supercooling values arises from diusion eects in the liquid in front of the interface and capillary eects at the

    solid interface.

    @see pigure sFPT@AAF his lerly highlights the ft tht euteti growth is governed y mss trnsport in lrge solidi(tion proessesF ithout going too muh into detils hereD it is worth to sy tht the growth rte v D the lmellr sping nd the di'usion oe0E ients of the di'erent omponents led to di'erent on(gurtions of the liquidEsolid interfe s well s onentrtion vritions long the interfeF he di'usion nd the pillry efE fets @represented y di'erent vetors in pigure sFPT@AA re t the origin of underooling @T = Tdif f + Tcap AF roweverD their e'ets vry in opposite diretions so tht the resulE ting T vlue n e onsidered s onstnt for given lloyF his kind of models s well s more re(ned ones hve een used in mny studies to understnd the sting of lloysD espeilly in the peEg nd elEsed system tht present gret prtil usesF roweverD despite the possiility of tking dvntges of the omposite properties of euteE ti metlEg lloys nd the understnding we hve so fr on their sting ehviourD mny fundmentl questions remin unnsweredD espeilly in their use in new (elds suh s in nnosiene mong whih unexpeted e'ets riseF he se of elEsed lloys upon underooling nd glss forming ility hs een stuE died hs
    et al.D

    PHHIF viu

    et al.

    reported the mirostruturl hnges of the elEqe euteti


    et al.D

    for di'erent solidi(tion pth viu

    PHHQ s well s solidi(tion proess in the elEi


    al.D

    system underooled y levittion tehnique viu et

    PHHRF iswrmoorthy et

    al.

    desried PHHUF

    the symmetril onentrtion hnges rising etween the solid nd the liquid phse in n eliEsed ommeril lloy melted in n ethnol solution iswrmoorthy QP
    et al.D

    I.7.

    Specic features concerning nanowires growth

    sn the se of euEi nd euEqe lloysD strong interests rise in the (eld of metlli glsses sine their disovery y ulement ulement et
    al.D

    IWTHD ut lso euse of their use in nnoE

    mterils prodution gner nd illisD IWTRF qrvity segregtion experiments illustrted the seprtion of the elements nd the susequent rystlliztion t the euteti temperE ture endersen
    et al.D

    IWUIF

    roweverD ghen nd urnull studied the het pity nd the enthlpy of the eui euteti system ooled in fused sili to reprodue homogeneous onditions nd reported n underooling vlue @etween Te nd oserved Ts A of UH uF hey lso oserved the tendeny of the liquid to e denser thn the solid phse X when the liquid ws quenhed to rete n morphous lloyD the ruile remined intt wheres it ws found roken when slowly ooled down due to the extension of the sEreted rystlF et this time ghen nd urnull lredy ttriuted the deepElying euteti of this system to the tendeny for unlike toms to ssoite when in the melts ghen nd urnullD IWTUD in ontrst with their seprtion to form the solid owing to the high stility of silion in its ovlent rystlline stteF his generl pproh however seems to e (ne to desried ulk proessesD wheres unexpeted phenomen disovered reently nd desried in the next setion seem to need further studies to e fully understoodF

    I.7

    Specic features concerning nanowires growth

    elthough this work does not diretly del with nnowires growthD the study of their growth enles the oservtion of the liquid stte in very smll liquid droplets s these ltter re required to grow smllEdimeter nnowiresF sn dditionD severl peulir fetures re typil of nnowire growth nd hve to e presented here s their existene nd their potentil in)uene n e disussed throughout this mnusriptF

    I.7.1 Liquids in small dimensions


    a Surface eects in small dimension

    hesigning ojets t the nnometer sle leds to n inrese of the surfeEtoEvolume rtioF gonsequentlyD surfe e'ets n our nd modify the properties of the mterilF sn our seD the importnt prmeter is the equilirium etween the liquid nd the solid phse for given lloyF his is reveledD in the se of ulk lloysD y the phse digrms presented in setion sFQF roweverD it is possile to lulte how the size of the droplet modi(es the euteti temperture of the onsidered lloyF his size in)uene is presented in the work of hmidt et
    al.

    who inluded surfe qis free energy in thermodynmil lultions hmidt

    et al.D

    QQ

    Chapter I.

    State of the art

    PHIHF heir resultsD in the se of the euEi systemD shows tht shift towrds the low tempertures of more thn IS u n e expeted for droplets smller thn PH nm in dimeter @for exmple X Te = 30 u for IH nm dropletAF he unertinty of their expettions is however quite lrge s the experimentl prmeter vluesD used in the lultionD re di0ult to mesureF st is nevertheless ommonly ssumed tht size e'ets hve to e onsidered for systems presenting typil sizes of IH nm or less hwlh nd oorheesD PHHVF
    b Experimental observations

    sn reent pperD edhikri

    et al.

    presented oth theoretil nd experimentl work


    et al.D

    onerning the in)uene of size in the euEqe system edhikri

    PHHUF heir lulE

    tions predited lowering of the euteti temperture of RH u for IH nm dimeter euqe droplet t the tip of qe nnowireF roweverD their experimentl oservtions reveled tht the droplets ould e superooled out IHH u elow the euteti pointF heir experimentl results re omprle to those otin y uodmk s those presented y utter
    et al. et al.

    who reported the growth of qe

    nnowires through eu tlyst well elow the euteti point uodmk et al.D PHHUD s well desriing the modi(tion of the euEqe phse digrm
    et al.

    for growth t nnosle utter nd utterD PHHVF he explntions re however di'erent from study to notherF uodmk edhikri
    et al.

    lim for thermlEhistory ndGor gs pressure

    dependene s well s possile growth with solid gold tlyst @see next setionA wheres ssumed tht the qe supersturtion needed to drive the qe solidi(tion t the interfeD omined with n eu energeti homogeneous nuletion rrier due to size n e responsile for lrge underoolingF sn the se of the euEi systemD uim rne uim
    et al.D et al.

    studied the growth kinetis of solid i y

    oversturting n @euiA liquid droplet t onstnt temperture on n morphous memE PHHVF sn this studyD they onluded tht i nuletion is heterogeneous proessD ourring t the edge of the droplet with no oservle size e'et down to IP nmF sn similr susequent studyD QS nm gold prtiles were exposed to disilne gs nd the trnsformtion of pure `eub system into the twoEphses `eubC@euiA system ws folloE wed uim
    et al.D

    PHHWF sn this se size e'ets were pointed out y the oservtion of quite

    instnt shrink of the `eub phse s soon s this ltter rehed size of out V nmF hrough these few exmplesD one n see tht size e'ets hve to e onsidered when exmining phse trnsitions t the nnosleF roweverD it is importnt to note here tht they re studied most of the time in the prtiulr se of nnowires growth nd represent only the tip of the ieergF fsillyD these e'ets hve to e studied in prllel with other modi(ed prmeters suh s for exmple pillry e'ets or modi(tion of the energy of the liquidGsolid interfeF he following rief presenttion of speil fetures out nnowire QR

    I.7.

    Specic features concerning nanowires growth

    growth serves s n illustrtion to show the di0ulties enountered in this (eld s well s sis for further disussionF

    I.7.2
    a

    In-situ

    SC-nanowires growth

    Case of the Vapour-Solid-Solid process

    Temperature (K)

    1200 1000
    800 600 0 10 20 30 40 50 60 70 80 Ge (at.%)

    Figure I.27  Illustration of the domain where VLS ans VSS process can occur in the case of the
    Au-Ge system phase diagram.

    es lredy mentionedD it hs een oserved tht qe nnowires n grow elow the euteti temperture in the presene of solid tlyst uodmk
    et al.D

    PHHUF his suggests the PHHT s well s for the

    existene of pourEolidEolid proess @AF his prtiulr proess ws lso supposed to rise during i nnowires growth using n el tlyst ng et tlyst en
    et al.D al.D

    triky formtion of shrp iEqe interfes in nnowires heterostrutures vi inry eleu PHHWF he v proessD simply uses the peulir shpe of the phse digrm tht is the phse oundry etween the @metlEgA liquid phse nd the @metlE gAC`gbF sn the sme wyD the proess is relted to the possile g soluility in the solid metlD
    i. e.

    the existene of `metlEgb solid phse X inresing the g ontent in

    the solid solution modi(es the equilirium nd leds to the preipittion of the g in exess @see pigure sFPUAF es no soluility of i exists in solid `eubD these proesses n not tke ple in this peulir systemF he dvntges of the proess is the lowering of the growth temperture s well s the lowering of the soluility of the g in the tlyst prtile leding to the slowing down of the growth proessF
    b Equilibrium changes during growth

    pigure sFPV displys very ommon oservtion tht is the expnsion of the nnowire9s dimeter t its seF his ehviour whih seems to e rther insigni(nt t (rst glneD QS

    Chapter I.

    State of the art

    Figure I.28  SEM picture of a Si nanowire grown on a Si(111) substrate through an AuSi liquid
    droplet and exposed to disilane. The scale bar is 100 nm [Zhou, 2011]

    highlights n importnt hrteristi X the interfe energy equilirium is not the sme for liquid tlyst droplet in ontt with the sustrte nd with the nnowireF his phenomenon is esy to oserve y ompring the wetting ngle presented y the E tlyst droplet efore growth nd fterF he tlyst droplet in ontt with the )t sustrteD in the se of the euEi systemD displys wetting ngle @mesured in the liquid phseA of out RQ essel
    et al.D

    PHHQ wheres it presents muh more spheril shpe t the top of

    nnowireF his is due to suessive equilirium vritions undergone y the interfe s soon s the nnowire strts to growF his is illustrted in pigure sFPW whih shows the evolution of the ontt etween the droplet nd the growing nnowireF his e'et is ler exmple of the di'erene tht hs to e ounted when ompring physil properties of tlyst droplet t the tip of nnowire nd on )t sustrteF

    time
    (AuSi) (AuSi) (AuSi) <Si> <Si>

    <Si>

    Figure I.29  Scheme illustrating the change in surface energies during the growth of a nanowire,
    which can inuence the physical behavior of the liquid catalyst.

    QT

    I.7.

    Specic features concerning nanowires growth

    Coarsening, tapering and faceting eects during growth

    es the topi of this work only onerns the very (rst events of the intertions etween the metl tlyst nd its underlying g sustrteD we will only mention here some remrE kle fetures rising during growthF sing eletron mirosopyD rnnon
    et al.

    oserved

    orsening proessD sed on the mehnism of ystwld9s ripenningF he surfe di'usion of the gold toms from smll to lrge droplets present t the top of i nnowires leds to di'erent sizes nd shpes of the nnowires @see pigure sFQHA rnnon in the middle of pigure sFQH uodmk et
    al.D et al.D

    PHHTF

    enother ommon oservtion is the tpering of nnowires during growthD s represented PHHTF e tpered nnowire is the onsequene of tomi di'usion of the metl tlyst t the surfe of the nnowireF hereforeD the diE meter of the droplet dereses s well s the one of the nnowireF pinllyD pigure sFQH @ottomA illustrtes the feting ehviour ourring on the nnowires sides oss
    et al.D

    PHHSY hvid

    et al.D

    PHHVF his e'etD mostly studied in the euEi systemD

    onsists in swEtooth feting of the nnowires sides X the nnowires sides perpendiulr to the < 112 > sustrte diretion present lterntive ( nd ( orientted fetsF hese 111) 113) preferred orienttions re supposed to depend on geometry nd surfe energies s well s on the droplet dimeter nd gold overgeF
    Vapour Coarsening Vapour

    growth
    Au surface diffusion
    200 nm

    Tapering
    40 nm

    100 nm

    Faceting

    Figure I.30  Schemes representing dierent processes inuencing the shape of the nanowires. Top :
    the coarsening, middle : the tapering and bottom : the faceting. The associated pictures illustrating each process are taken from [Hannon respectively.

    et al., 2006],[Kodambaka et al., 2006] and [Ross et al., 2005],

    QU

    Chapter I.

    State of the art

    I.8

    Liquid behaviour close to interfaces

    I.8.1 Liquid-Vapour interfaces : layering eect


    he lyering phenomenon in liquids onsists in the orgniztion in the form of lyers of the toms just elow the surfe of liquidF st hs een (rst oserved in omplex liquids ontining highly nisotropi moleules or liquid rystls nd is supposed to rise euse of the high length of the strutures omposing the liquidF sn metlsD surfe melting @liquid forE mtion t the surfe of ulk solid elow Tm xxiv A is quite ommon phenomenon prenken nd vn der eenD IWVSD wheres formtion of solid t the liquidGvpour interfeD theoreE tilly predited in IWVI h9ivelyn nd ieD IWVID is more reently disovered fetureF he lyering of liquid metls nd lloys n e deteted y Ery re)etivity whih disE plys pek hrteristi of the formtion of orgnized lyers perpendiulr to the interfeF sn the se of q egn et n nd fi liquids ershn
    et al.D al.D

    IWWSD sn ostmnn et
    et al.D

    al.D

    IWWWD rg wgnussen et

    al.D

    IWWSD

    et al.D

    PHHW s well s in euteti liquid lloys fin hpyrko PHHWD re)etivity experiments reveled tht the two

    PHHS nd euqe ershn

    to three (rst liquid lyers re well de(ned suh s those t the surfe of their respetive rystlsF por ll these ses howeverD no long rnge order prllel to the surfe hs een reportedF sn the se of the prtiulr eui systemD it hs een reently reported tht the lyering e'et is muh more pronouned nd ours in the (rst seven to eight lyersD s represented in pigure sFQI hpyrko
    et al.D

    PHHTF

    Figure I.31  Representation of the electronic density variations reecting the layering eect arising
    at a vapour-liquid interface and decaying with depth. It is enhanced in the case of metals and alloys (comparing the two rst images) and even more pronounced in the case of the Au-Si liquid alloy [Shpyrko

    et al., 2006].

    sn dditionD ontrry to other metls nd lloys studied to dteD the topmost lyer exhiits lterl longErnge rystlline order @Ph rystlA @see pigure sFQPA wheres the underneth
    xxiv. This phenomenon arises for example at the surface of ice makes it (more) slippery.

    QV

    I.8.

    Liquid behaviour close to interfaces

    lyers lterl order is liquidlikeF his Ph rystlD )oting on the lyered liquidD is found to e stle up to UHH u nd undergoes solidEsolid trnsition t TRH u etween low temperture @TQH uETRH uA nd high temperture @TRH uEUHH uA phse hpyrko
    et al.D

    PHHUF purther experiments using synhrotron rdition nd more preise model tht tkes into ount surfe sti'ness reveled tht the lowE phse is ilyer whih trnsforms into the monolyer highE phse wehler
    et al.D

    PHIHF

    7.386

    Si
    Au

    9.386
    Figure I.32  Unit cell of the low temperature 2D Au-Si crystal phase existing at the surface of
    the eutectic AuSi liquid [Shpyrko

    et al., 2007].

    st is worth mentioning here tht other euEg lloys studiedD suh s euEn nd euEqeD do not present Ph surfe rystl struture nor enhned lyeringF his on(rmed the ide tht lthough qe is very similr to iD euEqe nd euEi re very di'erent lloysF his is lredy highlighted y the ft tht in spite of similr euteti tempertureD the euteti omposition di'ers lot nd tht smll frtion of qe is solule in solid euF e omprle sitution hs to e studied in the se of the liquid struture nd onerns the solidEliquid interfeF his is the topi of the next setionF

    I.8.2 Liquid-Solid interfaces


    sn this setionD proesses tht re known to rise t the interfe etween liquid nd solid re presented from n tomisti point of viewF heses onepts will e very useful to understnd the in)uene of the sustrte9s struture on the liquid droplet struture disussed in the lst hpter of this mnusriptF sn IWUSD pepen ws the (rst who tried to estlish theory for the in)uene of the solid9s struture on the liquidF ris work ws sed on modeling of hrd spheresF essuming tht ertin topologil ontinuity must exist etween the solid nd the liquid nd tht the liquid must present mximum of density vi loseEpkingD he predited the onditions for pling toms t the interfe in the (rst two djent liquid lyersF ris results predited QW

    Chapter I.

    State of the art

    (a)

    (b)

    Figure I.33  (a) Simulation results showing the variation of the planar-averaged density as a
    function of the distance from the solid phase revealing a kind of transition slice of liquid into which the atoms are ordered. The ordering being lost with the distance from the solid [Curtin, 1987]. (b) Corresponding phenomenon in liquid Ga in contact with a diamond substrate [Huisman

    et al., 1997].

    tht the mximum of density found in the liquid nd onsistent with long rnge order n e hieved y (lling the (rst two liquid lyers with equl quntity of tringulrD retngulr nd pentgonl struturl units pepenD IWUSF ithout regrding the ordering prllel to the solid surfeD simultions hve predited tht trnsition re should exist etween the perfetly ordered rystl nd the disordered liquid gurtinD IWVUF es shown in pigure sFQQ@AD this trnsition n extend over severl tomi lyersF roweverD it hs only een demonstrted experimentlly in IWWU y ruismn et
    al.

    ruismn

    et al.D

    IWWUF fy hoosing low temperture liquid metl @qA on @IIIA

    dimond sustrte whih is trnsprent to EryD re)etivity mesurements reveled the orgniztion of the toms lose to the surfe into iElyers @see pigure sFQQ@AAF e very nie workD performed y yh s shown in pigure sFQR yh et RH
    al.D et al.

    with eletron mirosopy tehniquesD mde

    possile diret oservtions of the ordering of liquid el toms in ontt with el2 y3 solid PHHSF his density )utution phenomenon is now widely

    I.8.

    Liquid behaviour close to interfaces

    epted to our nd even if further studies re requiredD it seems resonle to think tht this ordering triggers nuletion proessesD the liquid phse strting to dpt the struture of its respetive rystl qreerD PHHTF

    Figure I.34  Transmission Electronic Microscopy image revealing the layering of the rst layers
    in liquid Al in contact with the Al2 O3 substrate [Oh

    et al., 2005]

    roweverD despite ontinuous improvements of hrteriztion tehniques it is still hrd to depit lerly the tomi orderD if it existsD within liquid lyer or wht hppens if the liquid mteril is di'erent from the underlying sustrteF eihert strte eihert
    et al.D et al.

    reported the (rst


    et al.

    mesurement of pentgonl lterl ordering t the interfe of liquid led nd i@HHIA suE PHHHF sing extensive wonte grlo simultionsD reni studied the in)uene of the sustrte interfe on the pentgonl short rnge order tht n exist in liquid phse s presented in setion sFSFP reni nd vowenD PHHPF hey report tht n ttrtive surfeD leding to strong ttrtion etween the toms of the two phsesD n lolly inrese the density nd therefore promote (veEfold symmetryF hese results therefore suppose tht if the ordering lose to the interfe is inomptile with rystl strutureD the liquid phse ould still e stilized wheres solid in ontt with the liquid is ommonly ssumed to trigger heterogeneous solidi(tionF

    In this chapter, we have presented the dierent elements constituting the scientic framework of this study. Before investigating the specic behaviour of Au on Si substrates towards growth and dewetting (Chapter III), formation of reconstruction (Chapter IV) and solidication (Chapter V and VI), we described in the next chapter (Chapter II) the technical aspects constituting the experimental framework.

    RI

    Chapter II Methods and experimental set-up


    Contents
    II.1 X-ray scattering by a surface
    II.1.1 II.1.2

    . . . . . . . . . . . . . . . . . . . . .

    43
    43 46

    X-rays refraction at an interface . . . . . . . . . . . . . . . . . . . . Basic X-rays diraction . . . . . . . . . . . . . . . . . . . . . . . .

    II.2

    Characterization methods
    II.2.1 II.2.2 II.2.3

    . . . . . . . . . . . . . . . . . . . . . . .
    . . . . . . . . . . . . .

    50
    50 54 55

    Grazing incidence X-ray Scattering (GIXS)

    Surface X-ray diraction (SXRD) . . . . . . . . . . . . . . . . . . . Grazing incidence small angle X-ray scattering (GISAXS) . . . . .

    II.3

    Experimental set-up . . . . . . . . . . . . . . . . . . . . . . . . . . .
    II.3.1 II.3.2 The synchrotron and the BM32 beamline . . . . . . . . . . . . . .

    58
    58

    In-situ growth of Nanostructure on Surface (INS) : the experimental


    hutch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60 65 Corrections factors . . . . . . . . . . . . . . . . . . . . . . . . . . .

    II.3.3

    II.4

    Numerical simulations . . . . . . . . . . . . . . . . . . . . . . . . . .

    67

    II.1.

    X-ray scattering by a surface

    he im of this hpter is to explin the si onepts tht re essentil to understnd the tehniques presented nd used lter in this workF feyond the results desried in the following hptersD it is importnt to know how they re otined s well s under wht kind of experimentl onditionsF sn (rst setionD we present some generl hrteristis on the use of Ery nd give some preisions onerning the investigtion of reiprol spe in this prtiulr frmework @see setion ssFIAF sn seond oneD the di'erent tehniques using Ery sttering to proe the mtter re desried @see setion ssFPAF he experimentl setEup is presented in the lst setion @see setion ssFQAF

    II.1

    X-ray scattering by a surface

    e)etion nd refrtion phenomen of n eletromgneti wve t n interfe re omE mon for ll wvelengths nd re desrie y nell9s lw nd presnel equtionF hese phenoE menD rising t the interfe etween two mediD result from their di'erene of refrtive indexesD whih themselves depend on the wvelengthF otl re)etion hppens when the inE oming wve trvels from medium with higher index to medium with lower index of refrtionF sn the se of visile lightD most of mterils hve refrtive index lrger thn the one of irD thereforeD totl re)etion hppens t the mterilGir interfe inside the mterilF his is lled totl
    internal

    re)etion nd is widely usedD for exmpleD to trnsmit

    informtion through optil (ersF sn the se of Erys @shorter wvelengthAD the refrtive index of most mterils eE omes slightly smller thn tht of ir so tht totl re)etion n ourF e will see here how proing surfes ndGor interfes with Erys justi(es the use of grzing inideneF

    II.1.1 X-rays refraction at an interface


    es we hve seenD the importnt prmeter is the index of refrtion nF por Erys in ondensed mtterD n is written X

    n = 1 + i
    with X

    @ssFIA

    1 e2 Na 2 mc2

    i (Zi

    fi ) 2 i Ai

    nd

    1 e2 Na 2 mc2

    fi 2 i Ai
    i

    @ssFPA

    where Na is the evogdro9s numerD the density @gFm3 A nd the wvelength @AF por eh tomi speies iD Ai @gFmol1 AD Zi D fi nd fi re the tomi mssD the sttering ftor @equivlent to fj in setion ssFIFPAD the dispersion ftor nd the sorption ftorD respetivelyF RQ

    Chapter II.

    Methods and experimental set-up

    Ei

    Er

    kr

    ki

    r t

    Et kt

    Figure II.1  Scheme of the refraction of X-rays at an interface (with the polarization in the
    incident plane)

    ypil orders of mgnitude re 105 for nd 106 for whih implies tht the rel prt of n is slightly smller thn I for ErysF sf we pply the lssil nellEhesrtes lw to the on(gurtion presented in pigure ssFID it omes X

    n cos t = cos i

    2 2 whih eomesD for smll i nd t : t = i 2 + 2i

    @ssFQA

    he ritil ngle c is peulir vlue of i elow whih totl externl re)etion oE urs @i.
    e.

    t aHAF prom eqution @ssFQAD we n dedue X c = 2


    e.

    @ssFRA on the

    hereforeD c s well s D depend on the mteril nd on the photon energy @i.

    wvelength s 1/E AD its vlue eing of the order of few tenth of degreeF vet us now hve look t the ehviour of the trnsmitted em whih serves to proe the smpleF sts wve vetor tkes the form X
    kt = k0 cos i 0
    with

    k0 =

    (II.5)

    A iB

    withD in the smll ngle pproximtion X


    1 A= 2
    1/2 2 (i

    2 c )2

    4 2

    2 i

    2 c

    1 ;B= 2

    1/2 2 (i

    2 c )2

    4 2

    2 c

    2 i
    (II.6)

    he mplitude of the trnsmitted wve @At A t point r is proportionl to e ikt r X

    At e ik0 (x cos i +AziBz) e ik0 (x cos i +Az) e k0 Bz e iRe(kt )r e k0 Bz


    RR

    @ssFUA

    II.1.

    X-ray scattering by a surface

    e n thus write the expression of the trnsmitted intensity It X

    It = At A e i2Re(kt )r e 2k0 Bz e i2Re(kt )r e z/l t

    with l =

    1 = 2k0 B 4B

    @ssFVA

    he trnsmitted intensity dereses exponentillyD with l its penetrtion depthF pigure ssFP@A shows the vrition of the penetrtion depth for di'erent energiesF por i `c D l is no longer energy dependentD ut only mteril dependentF
    10
    4

    22 keV
    10
    4

    f=3c
    10
    3

    11 keV

    ()

    10

    ()

    7 keV

    f = c
    2

    10
    10
    2

    f=0.5c
    0.6 0.8 1.0

    i/c
    (a)

    1.2

    1.4

    1.6

    1.8

    i/c
    (b)

    Figure II.2  Variations of the scattering depth (a) as a function of the incident angle for three
    dierent energies, (b) as a function of the incident angle for exit angles equal to half, one and three time the critical angle for a Si surface and an incident wavelength of 1.1 (

    8 ). and =5.04 10

    i. e. 11 keV, =4.03 106

    roweverD s the sttered intensity is mesured outside the mterilD the sme proedure must e pplied to the wve whih goes through the mteril to the irF he relmotz9s reiproity priniple ensure symmetril solution so tht i n e reple y f for identil formultionsF he sttering depth therefore eomes X

    4(Bi + Bf )

    @ssFWA

    where i nd f indite the use of i ndGor f in ll the previous formulF he vrition of the sttering depth s funtion of the inident ngle for severl vlues of the exit ngle is plotted in pigure ssFP@AF e onvenient wy to illustrte the propgtion of Ery in the mteril lso onsists in negleting the sorptionD whih mens tht aH in the equtionsF ith this ssumptionD for

    i < c D the rel prt of kz equls zero @i.

    e.

    i eomes imginry in eqution @ssFTA for AAD

    therefore k hs rel omponent only long xF his mens tht the wve propgtes only long the interfe with n mplitude deresing quikly perpendiulr to the interfeF por RS

    Chapter II.

    Methods and experimental set-up

    inident nd exit ngles with vlues lose to the ritil ngleD the propgtion tkes ple from IH to IHH elow the interfe @pigure ssFP@AAF till in the smll ngle pproximtionD we rell here the equtions for the mplitude re)etion r @|Er | = r |Ei |A nd trnsmission t @|Et | = t |Ei |A oe0ients X

    r=

    2 i 2i A + A2 + B 2 2 i + 2i A + A2 + B 2

    1/2

    t=

    2 (i

    2i 2i A + A2 + B 2 )1/2

    @ssFIHA

    he squre of these oe0ients @ar2 D at2 A illustrte the intensity vrition during the proessF heir vritions s funtion of the inident ngle re plotted in pigure ssFQF
    10
    0

    4
    T = t
    0 1 2 3

    R = r

    3 2

    10

    -1

    10

    -2

    1
    10
    -3

    i/c
    (a)

    i/c
    (b)

    Figure II.3  (a) Reection and (b) transmission coecients for the intensity as a function of the
    incident angle for a Si surface and 1.1 wavelength (11 keV).

    por i f D RaI whih orresponds to totl externl re)etionF et the sme timeD the trnsmission oe0ient rehes mximum X taP @when negleting sorptionA for i = f whih mens tht the mplitude of the trnsmitted wve is twie its mplitude in vuumF ell these onsidertions lim for the use of grzing inideneF hen working with i ndGor f very lose to the ritil ngleD the sttering y the surfe toms is enhned while the ulk signl is redued to its minimumF ith this tehniqueD the toms tht re proed re those ontined etween the surfe nd depth of the order of F

    II.1.2 Basic X-rays diraction


    sn this setionD we simply rell the si equtions governing the intensity sttered y threeEdimensionl rystlF e lso present some spei( fetures enountered in the spei( se of surfe di'rtionF e detiled desription of Ery di'rtion is ville in stndrd textooks rrenD IWTWY tmesD IWVPF RT

    II.1.

    X-ray scattering by a surface

    Diraction by a 3D crystal

    he intensity sttered y solid struture into whih the toms re distriuted in N1 D N2 nd N3 unit ells long the three rystl diretions de(ned y the vetor a1 D a2 nd a3 is given y X
    2 2 2 I(Q) = CF 2 (Q)SN1 (Q a1 )SN2 (Q a2 )SN3 (Q a3 )

    @ssFIIA

    where C is onstnt nd X
    N 1

    SN (Q aj ) =
    n=0

    e iQaj n ,

    j = 1, 2, 3

    @ssFIPA

    he struture ftor F (Q) is expressed s X

    F (Q) =
    j unit cell

    fj e iQrj

    @ssFIQA

    where rj indites the tomi position within the unit ell nd fj is the sttering ftor of tom j F woreover the interferene funtion of Nj di'rting units is given y X
    2 SNj (Q aj ) =

    sin2 (Nj Q aj /2) , sin2 (Q aj /2)

    j = 1, 2, 3

    @ssFIRA

    he intensity is therefore the omintion of the struture ftor whih only depends on the positions of the toms within the unit ellD nd the form ftor representing the shpe of the rystlF ith this desriptionD it eomes ler tht the intensity funtion I @QA presents mxim @i. onditions X
    e.

    existene of frgg peksA for prtiulr vluesD whih re lled the vue

    Q a1 = 2h Q a2 = 2k Q a3 = 2l

    where hD k nd l Z

    @ssFISA

    he intensity is therefore equl to zero unless Q is vetor of lttie de(ned y si vetors @b1 Db2 Db3 A into whih Q = hb1 + kb2 + lb3 F he di'rtion proess re thus mesured in the reiprol spe desried y this new lttie lled the reiprol lttieD relted to the rel lttie @a1 Da2 Da3 A y X

    b1 =

    a2 a3 ; a1 a2 a3

    b2 =

    a3 a1 ; a2 a3 a1

    b3 =

    a1 a2 a3 a1 a2

    @ssFITA

    ith this de(nition X Q = hb1 + kb2 + lb3 = Qhkl F por Qh in(nite rystl without defetD the reiprol spe is thus omposed of @hD k D lA points of intensity @lled frgg RU

    Chapter II.

    Methods and experimental set-up

    re)etionsA forming periodi networkF ih @hD k D lA reiprol re)etion orresponds to fmily of periodi tomi plnes omposing the rystl whih interfere with the inoming wve in onstrutive wy i F he distne dhkl etween two @hD k D lA plnes of this fmily is given y dhkl = 2/ |Qhkl |F woreoverD Qhkl is perpendiulr to the @hD k D lA plne nd its length is |Qhkl | a 4 sin()/ i F prom this we n extrt the well known frgg9s lw X

    2dhkl sin() =
    hen the vue onditions re ful(lled @i. thus given y X
    2 2 2 2 Ihkl = CFhkl N1 N2 N3

    @ssFIUA

    e.

    t the position of re)etionAD the intensity is @ssFIVA

    nd the struture ftor tkes the form X

    Fhkl =
    j unit cell

    fj e 2i(hxj +kyj +lzj ) e Mj

    @ssFIWA

    where xj D yj nd zj re the frtionl oordintes of the onsidered tom j in the unit ell nd Mj its heyeEller ftorF
    b Diraction by a reconstructed surface : rods of scattering

    sn the se of surfe reonstrution @see setion sFQFPAD the rystl is qusi Ph struture with (nite thiknessF king the vetor a3 equl to this thikness orresponds to set N3 equl to I in eqution ssFIVF hereforeD in the vue ondition Q a3 = 2lD l is now ontinuous vrile s the intensity is no longer equl to zero for nonEinteger vlue of lF he intensity eomes X
    2 2 2 Ihkl = CFhkl N1 N2

    @ssFPHA

    he vrition of the intensity long the rod gives informtion on the struture in the z direE tionF he modultion period is relted to the thikness wheres the modultion mplitude indites the norml tomi displementsF he di'rted signl reorded in the presene of surfe reonstrution is therefore mesh of rods perpendiulr to the surfe nd loted t frtionl order in etween the ulk frgg peks @see pigure ssFRAF he distriution of the rods depends on the periodiity of the reonstrution ompred to the unreonstruted surfeF por exmpleD the i@IIIAE@UUA reonstrution displys T rods @U intervlsA etween
    i. We note here that the existence and the construction of the reciprocal lattice is not a mathematical creation as often presented in many school courses but arises from physical process and describes the scattered intensity distribution in space. i. With

    the scattering angle.

    RV

    II.1.

    X-ray scattering by a surface

    two frgg peks @or rystl truntion rodAF

    Diraction by an ideal surface : Crystal Truncation Rods (CTR)

    e semiEin(nite rystlD

    i. e.

    in(nite rystl trunted y shrp interfeD n e seen

    s in(nite rystl with one hlf of its volume presenting n eletron density equls to zeroF he di'rtion pttern therefore onsists in the onvolution of the Qh reiprol lttie with the pourier trnsform of the step funtionF his onvolution leds to nonEzero intensity distriution etween the frgg peks long the l diretion @see pigure ssFRAF hese rystl truntion rods extend perpendiulrly to the surfe nd onnet ulk frgg peksF

    Q z (or l)

    2D ROD

    CTR

    Bulk Bragg peak

    Q|| (or h)
    Figure II.4  Schematic representation of the continuous rods (shaded red) arising from a reconstructed surface and the crystal truncation rods arising from a crystal truncated by a surface (black), the maximum intensity is at the bulk Bragg positions and quickly decreases in between. From [Renaud, 1998].

    he intensity is given y repling SN3 (Q3 a3 ) y gives X

    n3 =0 n3 =

    e iQ3 a3 n3 iqution @ssFIIA whih

    Ihkl (CT R) = C |F (Q)|2

    sin2 ( 1 N1 Q a1 ) sin2 ( 1 N2 Q a2 ) 1 2 2 2 1 2 1 1 sin ( 2 Q a1 ) sin ( 2 Q a2 ) 2 sin( 2 Q a3 )

    @ssFPIA

    es the g therefore re)ets the tomi orgniztion t the surfe of the rystlD n urte study of their intensity distriution gives importnt informtion on the surfe struture suh s surfe roughnessD surfe relxtion or the formtion of lyer during growthF RW

    Chapter II.

    Methods and experimental set-up

    II.2

    Characterization methods

    sn the previous setions we hve seen how Erys intert with mtter nd the sis of the di'rtion phenomenF sn this setion we will now fous on prtiulr use of this onept in order to extrt struturl informtion on surfes nd interfesF

    II.2.1 Grazing incidence X-ray Scattering (GIXS)


    pigure ssFS is sheme showing the qrzing snidene Ery ttering geometry where i nd f re the inident nd exit nglesD respetivelyF sn this on(gurtion is the projetion of the sttering ngle P @etween ki nd kf A nd orresponds to the rottion of the smple round its surfe normlF he totl momentum trnsfer Q is omposed of n inEplne Q i nd outEofEplne Q ii omponentF hereforeD in the grzing inidene geometryD Q is lmost to Q @@Q A is very smllA nd 2F

    Surface

    Q QII Q

    i
    Figure II.5  Scheme of the GIXS geometry. The grey surface intersects the rst atomic layer.

    Denitions of the dierent scans

    pigure ssFT@A represents wht is usully lled the sphere of re)etion @the iwld9s sphereAF sts onstrution llows n esy visuliztion of the onditions of di'rtionF he little grey sphere orresponds to n @hklA nodes of the reiprol lttieF his node hs ertin size due to the (nite size of the di'rting ojetF he diretion of the inident em is given y the vetor ki whih termintes t the origin of the reiprol speF sts length

    2/ de(nes the rdius of the sphere whih psses through the originF he di'rted em
    @represented y kf A is lso represented so tht Qakf Eki n e de(ned X it is thus hord
    i. ii.

    Q =(4/) sin(/2). Q =k0 (sin i + sin f )

    SH

    II.2.

    Characterization methods

    of the sphereF his onstrution immeditely implies tht the @hklA nodes interseted y the sphere stisfy the frgg9s lw @see ssFIFPAF

    hkl node
    Ewald sphere

    hkl nodes

    l-scan

    kf ki i

    CTR Rocking-scan

    h
    Radial-scans

    QII
    Origin of the reciprocal space

    k
    (b)

    (a)

    Figure II.6  (a) Construction of the Ewald's sphere.(b) Sketch representing several Bragg reections (and one CTR) composing the reciprocal space. The arrows illustrate typical scans performed in this work and are commented in the text.

    he mesurement of re)etion during n experiment is possile under two onditions X ! the iwld9s sphere hs to interset the re)etionF por given i D this is done y turning the rystl round its surfe norml @rottion of AF st n lso e done y hnging the energy @the rdius of sphere is hngedA ut it is rrely done due to tehnil onsidertions on our emlineF ! the detetor hs to e pled t the right positionF his is done y hnging the ngles

    nd f F
    he pek intensity in the reiprol spe n therefore e mesured long di'erent diretionsF his is illustrted in pigure ssFT@A whih presents typil sns performed in this workD whih re X !
    radial-scans

    X whih onsists in snning reiprol spe in rdil diretion y vrying

    the length of QD s onventionl E2 sn in whih here 2 = nd = ( 0 )F sn this studyD ll the radial-scans re performed in the plne @long Q A long n zimuth spei(ed for eh sn Y !
    l-scans

    X orresponding to outEofEplne sns long Q Y performed t onstnt |Q| y rotting the smple round its surfe

    ! nd

    rocking-scans

    normlF SI

    Chapter II.

    Methods and experimental set-up

    Shape of a diraction peak

    he (nite size of the rystl in the surfe plne leds to the ft tht the frgg peks re not perfet hir funtions ut present (nite widthF he pull idth t rlf wximum @prwA of frgg pek @see pigure ssFUAD is diretly relted to the verge size D of the sttering dominsF sn terms of vrition of the momentum trnsferD the prw for
    scansD l-scans radial-

    nd rocking-scans re Q D Q nd D respetivelyF e good pproximtion

    of the domin size i in the diretion of the mesurement is given y X

    Dradial =

    2 ; Q

    Dl =

    2 ; Q

    Drocking =

    2 Q

    @ssFPPA

    Intensity (arb. u.)

    FWHM

    Figure II.7  Illustration of the FWHM measurement of a Bragg peak.

    he pproximtion on the vlue of the size omes from the ft tht D orresponds to the domins whih stter oherentlyF he mesurement is therefore limited y the oherent length of the inident em in the diretion prllel to the surfeF he desription of the pek shpe n e re(ned using orreltion funtion g@rA whih tkes into ount the proility of oherent sttering etween two toms seprted y r X Cr0 aID Cr aHF he intensity distriution of the pek n therefore e seen s the onvolution of the theoretil perfet hir funtion rry nd the pourier rnsform @pA of the orreltion funtionF
    c In-plane reciprocal space map

    es presented in setion sFPFID silion hs the dimondErystl struture so tht the i@IIIA surfe presents n hexgonl geometry @pigure ssFV@AAF
    i. The potential mosaic spread () has to be included in the estimation of domain sizes in rocking-scans by :

    (Q/Q)2 + 2 .

    can be estimated by measuring several orders of a reection.

    SP

    II.2.

    Characterization methods

    [010]s [121]b ks (242)b


    2/3(242)b

    Bragg reflection CTR


    [110]s [110]b

    (030)s

    (020)s

    (220)s

    (440)b

    a2 a3
    a1

    1/3(242)b

    (010)s

    (110)s

    (220)b
    hs [100]s [211]b

    --

    [001]s

    [111]b

    (100)s
    1/3(422)b

    (200)s
    2/3(422)b

    (300)s
    (422)b

    --

    --

    --

    (a)

    (b)

    Figure II.8  (a) Image of the rst layer of the Si(111) surface illustrating the hexagonal geometry.
    (b) Representation of 60

    of the in-plane reciprocal lattice for the Si(111) surface, the relationship

    between experimental surface indexes and conventional bulk indexes are indicated.

    sn surfe sieneD it is the onvention to de(ne two of the primitive lttie vetors prllel to the surfe nd the lst vetor perpendiulrF sn the se of @IIIA orientted surfe of dimondElike rystl @suh s i@IIIAA the primitive lttie vetor @with the ulk willer indexA re @see pigure ssFV@AA X

    a1 =

    1 1 0 1 b; 2

    a2 =

    1 0 1 1 b; 2

    a3 =

    1 [1 1 1]b 3

    @ssFPQA

    he orresponding reiprol lttie @b1 Db2 Db3 A n thus e lulted using eqution @ssFITAF st omes X

    b1 =

    2 2 1 1 b; 3

    b2 =

    2 1 2 1 b; 3

    b3 = [1 1 1]b

    @ssFPRA

    huring the experiments it is even more onvenient to de(ne reiprol surfe lttie X @[h 0 0]s D [0 k 0]s D [0 0 l]s AF he orrespondene etween the ulk nd the surfe indexes is given in pigure ssFV@A whih depits TH of the reiprol spe for the i@IIIA surfe t laHF sn this studyD most of the
    radial-scans

    @or

    l-scans A

    re presented s funtion of

    the momentum trnsfer so tht only the reiprol diretion expressed in ulk oordinte is givenF rowever in ghpter s we present the sns s funtion of the surfe reiprol lttie unit s it llows to quikly remrk the periodiity of speil fetures suh s gs or reonstrution peksF he synhrotron powerful em @see setion ssFQFIA llows the quisition of mny sns in short period of time ii F e n therefore perform wht we ll extended reiprol spe
    ii. compared to laboratory sources such as rotating anode.

    SQ

    Chapter II.

    Methods and experimental set-up

    mps whih onsist in mpping prt of reiprol speF his is hieved y performing mny
    rocking-scans

    t di'erent vlues of the momentum trnsferF lotting them together

    provides qulittive oservtion of the sttering distriution in reiprol speF he green re in pigure ssFW illustrtes reiprol spe mp for vrition of of TH D three di'erent rocking-scans re representedF he durtion of quisition nd the ury of these kinds of mps depend on the ounting rte nd the step etween two Q vluesF sn generl mp overing QH degrees for Q rnging from HFS 1 to V 1 is reorded in out V hoursF
    [121]b ks Rockingscan [110]b

    (440)b

    (220)b hs [211]b

    --

    Figure II.9  Illustration of the acquisition of an extended reciprocal space map. The green area
    corresponds to the recorded surface by the acquisition of many

    rocking-scans.

    II.2.2 Surface X-ray diraction (SXRD)


    urfe Ery hi'rtion onsists in quntittive pproh of qsF he im is to determine the positions of the toms of the studied strutureD s presented in ghpter s onerning the determintion of the i@IIIAE@TTAeu reonstrutionF he struturl inforE mtion is ontined in the struture ftors whih re otined y mesuring the integrted intensity of eh re)etionF
    a Integrated intensity

    righly resolved

    rocking-scans

    re performed on eh re)etionF he M points omposing

    the sn re seprted in Mn points ontining the noise @Nj A nd Ms points ontining the signl @Si AF gonsidering onstnt noiseD the integrted intensity is given y X
    Ms

    I =
    i=1

    Ms Si Mn

    Mn

    Nj
    j=1

    @ssFPSA

    sn dditionD severl orretions hve to e pplied to tke into ount the errors generted y the pprtus nd the mesurement itselfF hey re presented in setion ssFQFQ fter the presenttion of the experimentl setEupF por detiled desription of these orretionsD the SR

    II.2.

    Characterization methods

    reder n refer to liegD IWWUY oh et

    al.D

    PHHHF e omplete set of mesurements onsist

    in integrting ll the essile re)etionsF he systemti error eing dedued y reording severl equivlent re)etions relted y symmetry @see setion sFQFIAF
    b Structure factor analysis

    prom the mesured struture ftorsD stndrd methods i n e pplied to otin simple struture whih n serve s strting pointF he theoretil struture ftor of the proposed model n e lulted nd ompred to the experimentl onesF he lssil wy to re(ne the model onsists in minimiztion of funtions ompring the experimentl nd the lulted struture ftorsF he funtions tht hve to e minimized re X

    1 = N p
    2

    hkl

    exp calc |Fhkl | Fhkl 2 exp

    nd R =

    hkl

    exp calc |Fhkl | Fhkl exp hkl |Fhkl |

    @ssFPTA

    2 where N is the numer of mesured re)etionsD p the numer of prmeter nd exp

    the experimentl unertintiesF R is lled the reliility ftorF sn this studyD minimizE tions hve een performed @see setion sFQFPA using the yh softwre for surfe struture nlysis liegD PHHHF st onsists in (nding the smllest vlue of 2 y (tting severl prmeE ters i F wore detils on surfe struture determintion methods nd exmples n e found in peidenhns9lD IWVWF

    II.2.3 Grazing incidence small angle X-ray scattering (GISAXS)


    qse is qs exept tht ll the onsidered ngles re tken less thn few degreesF he reiprol spe nd the ngulr oordintesD represented in pigure ssFIH re linked y X

    qx qy qz

    0 euse of smll nglesD the iwld9s sphere urvture n e negleted k0 sin(2) k0 f k0 2


    @ssFPUA

    with k0 a2/F sn this on(gurtion the sttered intensity is mesured very lose to the origin of the reiprol speF et this positionD the sttering omes from inEhomogeneities of eletron density X roughE ness or presene of islnds for instneF he sttering intensity nd shpe depend on the morphology nd the topogrphy of the sttering ojetF st is therefore wy to study themF qse hrteriztion hs eome very powerful tehnique these pst few yers nd
    i. Such as Patterson or electron-density dierence maps. i. Typically : symmetry, domains, atomic positions, Debye-Waller factors and occupancy.

    SS

    Chapter II.

    Methods and experimental set-up

    qz

    qy kf

    ki

    Figure II.10  Illustration of the GISAXS technique.

    llows urte studies in surfe sieneF sn this workD qse experiments were used to hrterize the verge morphologil prmeters @interEislnds distneD inEplne size nd heightA of gold nnoEislnds spred on the silion sustrteF rere will e presented the essenE til sis to ess these prmeters from the study of the di'rtion ptternF he omplete theoretil nd experimentl detils of the qse tehnique re desried in enud
    al.D et

    PHHWF wo dimensionl qse ptterns re reorded with Ph detetor pled perpendiulr

    to the inident em @see pigure ssFIHAF he intensity for n homogeneous group of nnoE ojets on surfe n e writtenD in (rst pproximtion X

    I(Q) = F (Q) S(Q)

    @ssFPVA

    with S the pourier trnsform of the islndEislnd pir orreltion funtion @lso lled the interferene funtionA nd F the pourier trnsform of the islnd shpe @the form ftorAF he intensity is therefore omintion of signl ontining informtion on the verge shpe of the ojets @F A nd seond one @S A desriing how these ojets re distriuted on the surfeF @QA ontins the informtion on the lterl positions of the islnds X

    S(Qxy ) = 1 + s

    [g(r) 1] e iQxy r dr

    @ssFPWA

    with s the prtile men density nd g(r) the islndEislnd pir orreltion funtionF he form ftor of n islnd n e written s the pourier trnsform of the eletron density (r) over the islnd9s volume X

    F (Q) =
    V

    (r)e iQxy r dV

    @ssFQHA

    ST

    II.2.

    Characterization methods

    rowever etter desription is given using the historted ve forn epproximtion @hfeA into whih the form ftor is the oherent sum of four terms tking into ount the di'erent sttering pths represented in pigure ssFII usher
    et al.D

    IWWWF

    ki

    kf Substrate

    Figure II.11  Illustration of the four scattering paths involved in the DWBA for X-rays interacting
    with islands on a surface.

    e quik nlysis of the Ph qse pttern llows one to otin the lterl sizes d nd the height h of the islnds X these prmeters re inversely proportionl to the spred of the intensity long Qy nd Qz D respetively @see pigure ssFIPAF he men distne D etween two islnds is given y the inverse of the distne seprting the min orreltion peks long the prllel diretionF sn prtieD to perform quntittive nlysisD we will see in setion sssFI tht we n use the ssqse progrm vzzriD PHHPF

    f (q ) d 2/D h D

    2/d

    2/h

    2 (qII)
    Figure II.12  Example of a 2D GISAXS pattern (right) onto which several information on the
    droplets morphology (left) can be measured.

    st inludes (tting proedure of prllel nd perpendiulr ross setions of the Ph pttern to dedue the morphologil prmetersF he softwre provides mny nnoprtile shpes s well s severl theoretil interferene funtions tht re used to lulte the theoretil qse ptternGrossEsetion nd ompre it to the experimentl oneF SU

    Chapter II.

    Methods and experimental set-up

    II.3

    Experimental set-up

    he experiments relized for this present work were rried out t the iuropen ynhroE tron dition pility in qrenoleD prneF wost of the experiments were performed on the fwQP emline nd some others on the shHQ emlineF foth llow
    in-situ

    hrteriztion

    of surfes nd growth of nnoojet in ultrEhighEvuumF sn this setionD rief desription of the synhrotron is givenD the fwQP emline will e presented s well s the experimentl setEupF

    II.3.1 The synchrotron and the BM32 beamline


    a The European Synchrotron Research Facilities

    e present here only very short desription of the min qulittive fetures of the synE hrotron rditionF por dditionl informtionD the reder n refer to the ip wesite ii or to textooks suh s elsExielsen
    et al.D

    ynhrotron rdition is the eletromgneti (eld tht is emitted y reltivisti elerE ted hrged prtilesF he elertion is hieved y the use of the well known vorentz fore nd onsists in pplying stti mgneti (eld to the hrged prtile iii F por non reltivisti elerted hrgesD the rdited )ux is isotropilly spred round the elertion @see left hnd side of pigure ssFIQAF por reltivisti prtilesD their energy is given y X E = mc2 with >> 1D with c the speed of light nd m the rest mssF heir veloity is v = c with

    = (1 1/ 2 )1/2 whih gives v c for >> 1F sn this se the rdition is emitted in the
    diretion of the motion due to the reltivisti speEtime vorentz trnsformtions @see right hnd side of pigure ssFIQAF
    Electron Orbit Acceleration
    Arc viewed by observer

    Electron Orbit

    Acceleration ~1/

    v/c <<1

    v/c~1

    Figure II.13  Illustration of the radiation emission of electrons in circular motion. Left : nonrelativistic case, right : relativistic case. From [Als-Nielsen
    ii. http ://www.esrf.fr iii.

    et al., ].

    F=evB, with F the Lorentz force, B the magnetic eld, e the charge and v the speed of the particle.

    SV

    II.3.

    Experimental set-up

    he light rdited t n ngle with respet to the trjetory of the hrge in its ssoited frme is seen y the oserver in the lortory frme t n ngle given y the reltion X

    tan

    1 tan

    @ssFQIA

    por = 90D tan 1/ F he opening ngle of the rdition is thus of the order of 1/ F et the ipD the eletrons re elerted to T qeD s = 1957 i qeD the typil perture of the soure is VH rdF pigure ssFIQ @rightA shows the intertion etween the hrged eletron nd stedy elertion @perpendiulr to the motionA provided y ending mgnet @fwAF sn this seD the ollimtion is onserved only in the vertil diretionF here re emlines using ending mgnet t the ipF o improve the olletion of the synhrotron rditionD the other emlines use wht is lled multipole insertion devies @shAF sn this seD the eletrons re sumitted to suessive opposite mgneti (elds orientted perpendiulrly to the diretion of motionF hereforeD the eletrons osillteD the ollimtion is onserved in oth diretions whih inreses the photon )ux i @see pigure ssFIRAF
    1/ 1/
    <1/

    1/

    Figure II.14  Schematic illustration of the undulator regime. From [Als-Nielsen

    et al., ].

    wore thn the photon )uxD the relevnt prmeter when using the synhrotron light is the photon density in the imge spotD in unit of solid ngle nd in nrrow energy ndwidthF his is ll the rillineD its evolution over the yers nd the tehnologil dvnements is shown in pigure ssFISF e high rilline o'ers gret signlEtoEkground rtio nd is thus perfet tools to proe ojet t the nnosleF
    b The BM32 beamline

    he white em reted in the synhrotron y the intertion etween the eletrons nd the ending mgnet is (rst ollimted y mirror oted with iridiumF hen the em propgtes through doule i@IIIA rystl X the (rst rystl enles to hoose the em energy @i.
    e.

    wvelengthA from U to QH keD the seond one fouses the em in the horizontl

    diretionF e seond mirror is then used to fous the em vertillyF ith this on(gurtionD the resulting em size would e HFPS mm horizontlly nd HFIS mm vertilly t the smple lotion with )ux of 5 1011 phFs1 @t PH keAF st is then etter de(ned y the use of set of vertil nd horizontl slitsF he vertil slits llows to otin em size of typilly
    i. If the angular deviation

    is less than

    1/ ,

    the dierent pulses interfere.

    SW

    Chapter II.

    Methods and experimental set-up

    log Brilliance (ph/sec/mm /mrad /0.1%BW)

    22 20 18 16 14 12 10 8 6 1940 1960 1980 2000 2020 2040 2060


    Rotating anode
    X-ray tube ESRF 2m Undulator APS RIKEN ESRF 10 Pole Wiggler

    8 Pole Wiggler
    Bending magnet

    Year

    et al., ].

    Figure II.15  Historical evolution of the brilliance with X-ray photon sources. From [Als-Nielsen

    HFQ mm nd the horizontl ones eliminte the sttering signl oming from the (rst slitsF he em then goes through set of (lters nd upton foil whih serves s monitor s it is onneted to two diodes mesuring its stteringF he sEde(ned inident em n then e used for the experiment whih tkes ple in the r hmerF

    II.3.2

    In-situ growth of Nanostructure on Surface

    rimental hutch

    (INS) : the expe-

    he r hmerD oupled to di'rtometerD is dedited to in-situ hrteriztion of surfesGinterfesF st onsists in omplete equipment to prepreD ontrol nd study surfes nd is fully desried in enud et
    al.D

    PHHRF roweverD tehnil omponents re in onstnt

    evolution so tht some detils n di'er from the desription nd the existing setEupF rere re presented the generl omponents illustrting the prinipl hrteristis of the setEup used in the present workF
    a The chamber

    he ultr high vuum is mintined in the hmer y PHH lFs1 turomoleulr pump omined with RHH lFs1 ion pump nd vx2 @liquid nitrogenAEooled titnium sulimtion pumpF he keEout of the whole pprtus t ITH g enles se pressure of IH11 mrF he min hmer is oupled to lodElok system omposed of two prts X one prt llowing the introdution of the smpleD seond in r equipped with furne used for long degzing tretment without polluting the min hmerF he smple is trnsfered in the TH

    II.3.

    Experimental set-up

    GIXS

    Diffractometer Be window

    GISAXS

    x RHEED screen
    z

    X-rays

    Pyrometer

    Effusion cell

    Figure II.16  Experimental set-up on BM32

    Ery hmer vi trnsfer rodF he molydenum smple holderD onto whih the smple is stukD is held on the furne vertillyF st n e heted y rdition @up to IHHH uA nd y eletron omrdment @up to IUHH uAF e nrrow input fe window @for Ery trnsprenyA llows the entrne of the inident em whih interts with the smpleD wide prt of the sttered intensity n e olleted thnks to the lrge output windowF por wfi depositD the hmer is equipped with severl evportion unudsen ell whih re lirted using qurtz mirolneF he lening of surfes n e rried out with ion omrdmentF sn the present setEupD e)etion righEinergy iletron hi'rtion @riihA is used for fst nd qulittive hrteriztion of the surfes @roughness nd reonstrutionA X the resulting di'rtion ptterns n e visulized on the )uoresent sreenF e qudrupole mss nlyzer llows the detetion of residul gses or even potentil leksF he temperture of the smple is mesured thnks to sgyx infrEred pyrometers pled outsideD ehind spphire viewportF heir lirtions for urte temperture ontrol re detiled in the next setionF es lredy mentioned in ghpter sD the sx sienti( interests re moving towrd the hrteriztion of nnoEojets grown through the gh tehniqueF he hmer hs thus een reently equipped with gze soures of disilne nd digermneF es the fe windows nd emline omponents @slits nd windowsA indue kground stteringD severl tools hve to e pled to suppress this e'etF o do soD ntiEsttering TI

    Chapter II.

    Methods and experimental set-up

    slits @of HFPSD HFQ nd HFQS mmA re dded in r just ehind the entrne fe windowF e set of horizontl nd vertil slits re lso pled outside the hmer etween the exit fe windows nd the detetor @Hh or IhA for the qs hrteriztion for the sme purposeF sn dditionD s the smple is pled vertilly nd the inident ngle is very lowD the horizontl em size is lrger thn the projeted smple sizeD mjor prt of the intensity must e removed in this diretionF he prt on the k side is suppressed y the molydenum smple holder nd the prt on the front side is stopped y tungsten knifeEedgeF he Ph hrgeEouple devie @gghA mer is pled in the diretion of the low nglesD t vrile distne from the smple @etween HFS m nd R mAF o protet it from the inident nd speulrly re)eted emD tungsten em stop is pled just efore the exit windowsF o void sttering from the ir reE(lled tue is lso present etween the exit window nd the ggh merF

    GIXS
    Detector Slits

    GISAXS
    CCD Output beryllium windows RHEED gun

    In-situ MBE (up to 6 sources) Ion bombardment Temperature : RT to 1700 K Auger electron spectroscopy Residual gases analysis

    UHV Load-lock
    Sample Beam-stop Sample

    Anti-scattering slits Input slits

    RHEED screen

    X-rays
    Input beryllium windows

    Sample

    Load lock system

    Deposition sources

    UHV chamber

    Figure II.17  Scheme of the experimental set-up on BM32

    TP

    II.3.

    Experimental set-up

    Temperature control

    fsed on the lnk reltion desriing the rdition of lk ody i nd the ien eqution i D fundmentl reltion in pyrometry n e ddressed X

    1 1 k = ln( ) T T hc

    @ssFQPA

    where k D hD nd c re the foltzmnn onstntD the lnk onstntD the speed of light nd the wvelength of the rdition emitted y the ojetD respetivelyF

    is the spetrl emissivity

    nd T the rightness temperture whih is mesured y the pyrometerF yn pigure ssFIV@A we n see tht when the smple is heted t high tempertureD its emission is in the orngered rngeF o lirte the pyrometer for the silion sustrte we need to known its emissivity in the experimentl onditionsF o do so wire of ultr pure led hs een (xed on the wolylokD next to the i smpleD in wy tht the shdow of the wire n e seen on the riih sreenF he smple ws heted very slowly while the temperture ws mesuredF he emissivity ws then (xed t vlue for whih the pyrometers displyed the melting temperture of ultr pure led @THH uA s soon s the led wire ws oserved to meltF his typil temperture ws hosen to insure n urte mesure in this rnge of temperture @round the eui euteti tempertureAF he ury of the temperture mesurement is evluted to 5 K F rowever the importnt prmeter in this study is more the reltive temperture @for mesuring superooling for instneA thn the solute oneF
    c Substrates preparation

    he sustrte preprtion is n importnt step s we need to work with very len surfesF he IHIH mm2 i@IIIA smple is stuk on the smple holder y the use of very thin lyer of liquid indiumF he smple holder @wolylokA is mde in molydenum whih hs een previously hemilly lened i nd outgssed on the furne in the lodElok systemF he ensemle is then pled in the preprtion hmer nd outgssed t SHH u during PR hours to remove orgnis impurities efore eing trnsferred into the growth hmer under
    i. A black body is an ideal object that would absorb all the electromagnetic radiations without transmitting nor reecting them. The Planck's law states that the spectral brightness depends on the wavelength

    and the temperature as : l0 (, T )

    = (C1

    )/(e

    C2 /T

    l0 of the black body only 1), with C1 = 2hc2 and

    C2 = hc/k .
    i. The Wien's law derives from the Planck's law and stipulates that the wavelength for which the highest energy radiation is emitted by the black body is inversely proportional to the temperature :

    Emax = hc/4.965kT ,

    with

    in meters and T in K.

    i. The Molyblock is placed in a bath of trichloroethane with ultrasonic sound and then washed with acetone, then in ethanol. A chemical etch (in aqua Regia ) may also be used to remove possible metallic contaminants.

    TQ

    Chapter II.

    Methods and experimental set-up

    Si sample

    Sample holder (Mo)

    (a)

    (b)

    Figure II.18  (a) Picture of the sample stuck on the sample holder and heated for de-oxidation.
    (b) Picture of the RHEED screen for a Si(111) surface reconstructed (77) : between two Bragg reection, six fractional order reections can be counted.

    rF he smple is then slowly heted to IPHH u @pigure ssFIV@AA to e deoxidized for out IH minutesF pon ooling riih hrteriztions re performed X the di'rtion pttern revels the formtion wellEde(ned i@IIIAE@UUA surfe reonstrution @pigure ssFIV@AAD typil sign for len i@IIIA surfe wrk
    et al.D

    IWUUF

    he proedure to prepre i@HHIA nd qe@IIIA re quite similrD the purity eing ontrolE led y the presene of @PIA surfe reonstrution riih ptternF
    d The diractometer

    he r hmer desried in the previous setion is mounted on TEirle di'rtoE meter presenting zExis geometry with the smple positioned vertilly @see pigure ssFIWAF his on(gurtion hs een hosen to void signl extintion due to polriztion ftors equl to zero for sttering ngles of the order of WH in the horizontl plne @see setion @ssFQFQAA he inident ngle i n e set y rottion of the whole ensemle round the vertil xis X F he two rdles 1 nd 2 llow rottion of the smple round X nd Y @3 with 0.001 resolutionA to set its surfe perpendiulrly to the Z xisF he positioning of the smple in the em is done vi trnsltion long Z with n ury of IH mF he detetor position in the @X DY D0A nd @0DY DZ A plnes re enle y rottions of nd f D respetivelyF he ngle orresponds to the frgg ngle projetion prllel to the surfe nd the f ngle to its perpendiulr projetionF e rottion of QTH of the smple round its surfe norml @rottion of A is llowed y the rottion the whole goniometri hed thnks TR

    II.3.

    Experimental set-up

    X Cradles Sample X-Ray beam

    CCD camera for GISAXS

    Y Detector for diffraction

    Figure II.19  Schematic representation of the main motions of the INS-Diractometer. The
    dierent colors refer to dierent part that can move independently from each other. All the angles and axes are dened in the text.

    to di'erentilly pumped rotry feedthroughF

    II.3.3 Corrections factors


    sn setions ssFI nd ssFQD we foused on theoretil spets of surfe di'rtionF e disE uss now the ftors tht re generted y the experimentl mesurements @oming from the detetorD smpleD etFFFA nd hs to e orreted for quntittive study ndGor to ompre di'erent experimentsF hese orretions depend on the hrteristis of the inident rdiE tionD on the di'rtometer geometry nd even lso on the smple usedF hey re presented here in the se of synhrotron rdition provided y ending mgnet nd the zExis di'rtometer geometry presented in the previous setionF
    a The resolution function

    hen performing snD it is useful to know wht is the ury of our mesurementF his is done y determining the resolution funtion whih depends on the ngulr divergene of the inident emD the energy resolution @E/E a k/k A nd the ngulr eptne of the detetorF he inEplne divergene of the em on fwQP is HFIQ mrd wheres the ngulr eptne depends on the perture of the slits used during the experimentF rowever the ngulr eptne is lrger thn the inEplne divergene of the em nd results in highly symmetri resolution funtion presenting prllelepiped shpe tngent to the iwlE TS

    Chapter II.

    Methods and experimental set-up

    d9s sphere @see pigure ssFPHAF es onsequeneD the resolution of rocking-scan is etter thn the one of
    radial-scan

    whih is proportionlly linked to the perture of the detetion slitsF


    rocking-scansF

    his is the reson why the olletion of the dt for quntittive nlysis @see setion sFQFIA is done y mesuring the reonstrution rods through highly resolved

    Ewald sphere
    Resolution function

    acceptance

    kf

    /2

    Q= QII ki

    Figure II.20  Sketch of the in-plane projection of the Ewald's sphere construction and the resolution function

    Sample correction

    he integrted intensity must lso e orreted from geometril ftor orresponding to the surfeF he illuminted prt is lled the tive surfe nd n e de(ned with the opening of the slits pled efore the smple nd etween the smple nd the detetor position @see pigure ssFPIAF he inEplne illuminted surfe re A i is given y A = di do / sin()F
    Output slits do
    Sample

    Input slits

    di

    Incoming beam

    Active area
    Figure II.21  Illuminated area dened by the two sets of slits

    i. This is not valid for small values of

    for which better corrections must be applied.

    TT

    II.4.

    Numerical simulations

    Polarization factor

    he polriztion ftor P is de(ned y the squre osine of the ngle etween the diretion of oservtion nd the polriztion diretionF por synhrotron rditionsD the polriztion is lmost ompletely horizontl @WS% for ending mgnetA nd we use zExis di'rtometer so tht the vertil polriztion n e negletedF he horizontl polriztion is given y X

    Ph = 1 (sin i cos cos f + cos i sin f )2 1 sin2 f = cos2 f


    @sin i 0 nd cos i 1 for grzing inideneA

    @ssFQQA

    por inEplne re)etions @f 0AD P is lmost equls to one so tht no polriztion orretions re neededF
    d Lorentz factor

    he vorentz ftor ounts for the snning di'erenes tht rise in proing re)etions t di'erent positions in the reiprol speF nning re)etion mens moving the smple nd the detetor so tht the re)etion rosses the iwld9s sphereF roweverD depending on the re)etionD the time for this ltter to rosses the iwld9s sphere hngesF o ompre the integrted intensity mesured t di'erent lotions in the reiprol speD the mesured intensity must e multiplied y ftor L whih represents the integrted volume @s funtion of the di'rtometer nglesA in the diretion of the snF por
    rocking-scan

    X @ssFQRA

    Lrockingscan =

    1 sin cos i cos f

    por more detils onerning the vorentz ftorD the reder n refer to liegD IWWUY oh
    et al.D

    PHHH

    II.4

    Numerical simulations

    sn prllel to the experimentl results otined thnks to the omintion of the r hmer nd the synhrotron lightD
    ab-initio

    simultions hve een performed on the euE

    i system in the frme of ollortionF his prt of the work hs een mnged y elin sturelD homs xogret nd xoel tkse from the sweEvwwg i lortoryD oE direted y the niversit tosephEpourier @tpA de qrenole nd the gentre xtionl de l eherhe ienti(que @gxAF por the
    Condenss.

    ab-initio

    moleulr dynmis simultionsD nonil

    i. Science et Ingnieurie des MAtriaux et Procds - Laboratoire de Physique et Modlisation des Milieux

    TU

    Chapter II.

    Methods and experimental set-up

    x @onstnt numerD volumeD tempertureA ensemles were used using the ienn ab-initio simultion pkge uresse nd touertD IWWWF rojeted ugmented plne wves @esA with the erdewEng exhngeEorreltion potentils hve een dopted ng nd erdewD IWWIY uresse nd purthmullersD IWWTY uresse nd purthmullerD IWWTF he vlene stte of eh element hs een previously de(ned in the provided e potentilsF e do not desrie here further tehnil detils onerning the simultion method s the lrge mjority of this work is experimentlF he simultion results re simply displyed in ddition to the experimentl ones to disuss the di'erent key points so tht tehnil detils re not mndtory to understnd the purpose of this workF

    TV

    Chapter III Growth of Au on Si(111)


    Contents
    III.1 GISAXS study for low coverage experiments . . . . . . . . . . . .
    III.1.1 Growth at 570 K . . . . . . . . . . . . . . . . . . . . . . . . . . . . III.1.2 Deposit at RT and annealing . . . . . . . . . . . . . . . . . . . . .

    69
    69 72 76

    III.1.3 Comparison between the two growth modes . . . . . . . . . . . . .

    III.2 GIXS study of the interface epitaxial relationships

    . . . . . . . .

    77
    77 83 84

    III.2.1 Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . III.2.2 Discussion on growth and dewetting of Au on Si(111) . . . . . . . . III.2.3 Atomic congurations of the interface . . . . . . . . . . . . . . . .

    III.1.

    GISAXS study for low coverage experiments

    e importnt prt of this thesis is the study of the intertions etween the eui liquid droplets nd the sustrtes to improve our knowledge of the v proessF roweverD key prmeter is to understnd in detils how these droplets hd formed on the sustrteF o do soD we present in this hpter the results onerning the deposition proess nd the nneling of the smple to the euteti tempertureF sn setion sssFID we fous on the morphologil pE rmeters of the smll deposits @P wvA using the qse tehnique wheres in setion sssFP we present the struturl informtion otined y qs mesurements for thiker deposits @U wvAF e speil ttention hs een pid on the struture of the euGi interfe nd its evolution with inresing tempertureF

    III.1

    GISAXS study for low coverage experiments

    e hve performed qse mesurements to shed light on the morphologies of gold islnds tht form on the i@IIIA sustrtesF he growth of gold nnoEislnds ws hieved y two di'erent wys X IF suessive eu deposits @1.4 2.2 wvA t onstnt temperture of SUH uD whih is TH u elow Te F PF single deposit of P wv t progressively nneled up to Te F qse proes regions with di'erent eletroni density thn tht of i sustrteF he qsE e ptterns re hrterized y two loes originting from the onstrutive interferenes etween the wves sttered y nery prtilesF he width W nd the height H of the isE lnds re derived from the width nd height of the loesD respetively @see pigure ssFIPAF he interEislnd distne D is derived from the distne etween the loes long the diretion prllel to the surfe qy F e quntittive qse nlysis ws performed with the ssqse softwre vzzriD PHHPF he interferene funtion ws modeled with the prrystl theory mking the link etween regulr lttie nd fully disordered struturesF

    III.1.1 Growth at 570 K


    pigure sssFI shows the suessive qse ptterns reorded t SUH u for inresing gold depositF et IFR wvD the presene of ssymetril loes n e ttriuted to experimentl issuesD however the intensity long qz is quite low nd is ssumed to e due to the retion of the wetting lyer t this overgeF sndeed the imge t P wv shows n inrese of intensity long qz s well s hnge in the loes shpe inditing the formtion gold islndsF prom qse imgesD prllel nd perpendiulr uts were extrted t positions mrked y the dotted lines on the lst piture of pigure sssFI nd (tted with the ssqse softE TW

    Chapter III.

    Growth of Au on Si(111)

    2.2
    qz (nm-1)

    1.4 ML

    2 ML

    0 -1 0 qy (nm-1) 1

    Figure III.1  Evolution of the GISAXS pattern coming from Au deposit at 570 K with increasing
    coverage.

    wre vzzriD PHHPF pigure sssFP displys the two uts for the deposit thikness of P wvF sn the w study of ot
    et al.

    D gold islnds were elorted under similr onditions @ut on


    et al.D

    viinl surfeA nd were found to e Qh ot

    PHHTF o ompre to the experimentl

    mesurementsD the hosen model is thus n verge islnd shpe eing trunted sphere on top of wetting lyerF he greement etween the model nd the experimentl urve is very good nd llows the extrtion of the di'erent morphologil prmeters presented in le sssFI for IFR wv nd P wvF IFR wv P wv P wv

    D@nmA W @nmA H @nmA @ A iquF thikF @nmA ixpF thikF @nmA SP5 IPFH1.2 PFS0.2 QUFR4 HFQH HFQP QP3 IPFS1.2 PFU0.3 QVFU4 HFRS HFRS QP W E E E E
    D, W
    and

    Table III.1  Average morphological dimensions of Au islands on Si(111) at 570 K for 1.4 and 2
    ML. The dimensions

    are obtained from a quantitative GISAXS analysis and represent

    the inter-islands distance, width and height of the structures, respectively. The contact angle experimental deposited Au thickness (Exp. thick.) is indicated for comparison.

    and

    the equivalent thickness (Equ. thick.) are calculated from the morphological dimensions and the

    [Rota

    et al., 2006].

    he interEislnd distne dereses from SP nm to QP nm from IFR to P wv while the islnds size remins quite the smeF his orresponds to the nuletion of new eu prtiles on the vD etween the islnds tht hve formed (rstD s previously oserved y w ot
    et al.D

    PHHTF he verge shpe is trunted sphere with ontt ngle in the islnd of

    pproximtely QV F snterestinglyD the overge of the surfe y the islnds n e estimted from the interEprtile distne nd the islnd widthF por exmpleD t P wvD the overge of the v y the islnds is IQ7 of the totl surfeF sn dditionD the equivlent thikness UH

    III.1.

    GISAXS study for low coverage experiments


    3

    10

    log10(I) (counts/pixel)

    Best fit Experiment

    Best fit Experiment

    10

    10

    0.2

    0.4

    0.6

    qy (nm )

    -1

    0.8

    1.0

    0.5

    1.0

    qz (nm )

    -1

    1.5

    2.0

    (a)

    (b)

    Figure III.2  GISAXS cut extracted along the dotted lines in Figure III.1 for the 2 ML deposit
    (a) parallel to the surface at of maximum intensity,

    i. e.

    qz = 0.85 nm1 and (b) perpendicular 1 for 2 ML at 570 K. at qy = 0.15 nm

    to the surface at the position The black (open circles) lines

    correspond to the experimental data and the red (no symbols) line to the best t with the IsGISAXS software. The intensity is represented on a logarithmic scale.

    of the islnds n e dedued from the morphologil dimensions otined y qseF he totl thikness of the islnds plus the I wv v well grees with the experimentl deposited thikness @le sssFIAF woreoverD the morphologil dimensions n e ompred with those otined y wD when ville ot et al.D PHHTF et P wvD there is very good greement for the interEislnd distne nd the islnds widths otined y w nd y qse re similr y tking into ount the error rsF hespite the lk of quntittive informtion for lower overge @etween H nd I wvAD the growth of gold on i@IIIA thus seems to follow trnskiEurstnow mode t reltively high temperture @SUH uAD onsisting in (rst the growth of I wvEthik eu wetting lyer nd then in islnds nuletion on top of it y gglomertion of the following deposited tomsF por P wv the islnds re PFS nm0.2 nm highD IP nm1 nm wide nd seprted y QP nm2 nm @see pigure sssFQAF

    32 nm 2.5 nm
    12 nm
    Figure III.3  Illustration of the gold islands morphology at 570 K for a 2 ML deposit.

    e now fous on the nneling of P wv deposit performed t to ompre with the results otined in the se desried oveF UI

    Chapter III.

    Growth of Au on Si(111)

    III.1.2 Deposit at RT and annealing


    a Morphological evolution with annealing

    qse imges were reorded during the nneling of the depositF pigure sssFR displys them t RVH uD STH uD THH u nd TQH u to qulittively illustrte the dewetting proessF felow RVH uD no mesurement of the ext temperture is ville i nd the qse imges from to RVH u do not present ny di'erene unless slight derese of the intensity long

    qz whih my indite tht the thin deposited (lm hs lredy strted to dewetF eove
    RVH uD the ontinuous shrinkge of the intensity long qz re)ets the inresing height of the eu prtilesF sn this experimentD prllel nd perpendiulr uts were extrted nd (tted from RVH u to TQH u @every IH uA with the forming islnds still modeled y trunted spheresF
    2.2
    qz (nm-1)

    480 K

    560 K

    600 K

    630 K

    0 -1 0 qy (nm-1)
    Figure III.4  Evolution of the GISAXS pattern of a 2 ML-thick Au deposit on Si(111) performed
    at RT, for increasing temperatures between 480 K and 630 K.

    pigure sssFS@A shows thtD from SRH u to TQH uD the interEislnd distne linerly inreses from PS to SH nmD inditing either the olesene of the islnds or the gglomertion of toms from potentil residul thin (lm leving wider re in etweenF he islnd width (rst inresesD efore eing pproximtely onstnt from RWH u to TQH u while their height inreses from QFU nm to TFP nm @pigure sssFS@AAF he ontt ngle inreses from SQ to UQ @pigure sssFS@AA F et e D the melting of the system leves droplets presenting n verge seprtion of RV nmD width of IU nmD height of T nmD ontt ngle in the liquid phse of UQ F he dewetting proess thus implies tht the prmeters W D H nd inrese with temE pertureF woreoverD loser look to the slope of the urves in pigure sssFS@AD @A @nd @AA revels tht this inrese n shemtilly e seen s two regimes proessF sndeedD eE low STHSUH uD the vrition of eh prmeter is very smllD lmost onstntD wheres the
    i. The lowest accessible temperature of the pyrometers being about 470 K.

    UP

    III.1.

    GISAXS study for low coverage experiments

    slope eomes steeper ove this tempertureF sn other words the deweeting proess is enE hned ove STH uF his ssumption is further supported y qs mesurements during the nneling of U wv @see setion sssFPFIA nd will e disussed in setion sssFPFPF
    (a)
    Size (nm)
    20

    50

    (b)

    Distance (nm)

    15

    40

    10

    30
    5

    540

    560

    580

    600

    620

    540

    560

    580

    600

    620

    T (K)
    (c)
    Contact angle ()
    70

    T (K)
    0.6

    (d)

    Thickness (nm)
    540 560 580 600 620

    0.5

    60

    0.4

    50

    0.3 540 560 580

    T (K)

    T (K)

    600

    620

    Figure III.5  Morphological parameters deduced from the ts of GISAXS data for increasing
    annealing temperatures, from 540 K to 630 K of a 2 ML-thick Au deposit. (a) the inter-island distance, the dashed-red line is a linear t illustrating the coalescence process (b) the width (red/open circles) and height (black/squares) of the islands and (c) the aspect ratio as a function of the temperature. (d) Calculated equivalent thickness for each t in comparison with the experimental one (dashed-blue line). The vertical green-dashed line marks the supposed critical temperature separating the two dewetting regimes (see text). The arrows are guides to the eyes showing the abrupt change of the slope.

    Estimation of the interface energy at

    Te

    sn ghpter sD we hve seen tht the oung9s eqution desries the reltionship etween the ontt ngle nd the di'erent surfe energiesD whih re key prmeters to model the epitxil growth of xs y the v proess @see setion sFQFRAF por mirometerEsized dropletsD the ontt ngle is pproximtely RQ essel
    et al.D

    PHHQD while in the present studyD the

    ontt ngle is UQ for droplet width of IU nm t Te F st therefore on(rms tht the ontt UQ

    Chapter III.

    Growth of Au on Si(111)

    ngle is inversely proportionl to the luster size viD IWWTF reneD the ontt ngle of nnometerEsized droplet mesured here n e used for n urte determintion of the interfe tension leding to proper model of epitxil x growthF sing the sme surfe energy vlues s in ghpter sD
    i. e.

    solvap = 1.25 tFm2 nd

    liqvap = 0.85 tFm2 D yields the liquidEsolid interfe tension of IFH tFm2 for ontt
    ngle of UQ t e F es expetedD this vlue is lrger thn tht of HFTP tFm2 otined for mirometerEsized droplet hmidt
    c
    et al.D

    PHIHF

    Discussion on the calculated equivalent thickness

    he equivlent thikness of the prtiles vries with the nneling tempertureF st inE reses ove STH u nd is even lrger thn the experimentl eu thikness etween SUH u nd TPH u @pigure sssFS@dAAF e suggest tht this vrition ould e linked to n euEsiliide on the surfe of the islndsF sndeedD surfe enrihment in i my e driven y the lower surfe energy of i reE ltive to euF he euEsiliide formtion in similr experiments fed n intense dete in literture eh
    et al.D

    IWWQF glliri

    et al.

    pplied sptilly resolved euger line shpe nE IWVRF essel


    et al.

    lysis to QH wv euGi@IIIA nneled up to UUH u nd onluded to n intermixed iEeu skin on top of the islnds glliri
    et al.D

    studied mirosopi liquid


    et al.D

    droplets of the euGi@IIIA system with photoemission spetrosopy nd showed tht the surfe of the liquid euEi droplets is enrihed with i essel PHHHF Ery photoeE
    e.

    mission spetrosopy @A supports the ide tht for smll deposit of euDi.

    elow P wvD
    et al.D

    n euEi lloy (lm is formed t room temperture @AF usequent deposition leds to the nuletion of gold elow the lloy with n rupt euGi@IIIA interfe eh roshino et
    al.D

    IWWQY

    PHHVF his oservtion is supported y our qs experiment presented in the

    next setion @setion sssFPAD whih highlights preferred epitxil orienttions of the eu@IIIA rystl plne with respet to i@IIIA nd thus lims for the presene of shrp interfeF sn dditionD ove Te D Ery di'rtion reveled similr Ph rystlline gold siliide s presented in ghpter sD )oting elow the surfe of the liquid euteti eu81 i19 lloy with i tomi omposition of pproximtely UH tF7 in the topmost surfe lyer hpyrko wehler
    et al.D et al.D

    PHHTY

    PHIHF
    radial-scans

    huring the qse experiment presented hereD some qsh mesurements were lso performedF sn prtiulrD t QHH u during the deposition @see pigure sssFTAF por HFT wvD the sn displys no ler di'rtion signl from eu ut the i@IIIAE@UUA reonsE trution peks re reordedF his my rise euse in the suEmonolyer rngeD the gold toms oupy some speil sites of the i reonstrution whih onserves its struture u
    et al.D

    PHIHF por P wvD the sustrte reonstrution peks vnish nd the eu@IIIA pek

    UR

    III.1.

    GISAXS study for low coverage experiments

    10

    0.6 ML 2 ML

    (7x7)

    C.T.R.

    Intensity (cps)

    (111)

    10

    2.2

    2.4

    2.6

    2.8

    3.0

    3.2

    3.4

    3.6

    3.8

    4.0

    Q ( )
    Figure III.6 

    -1

    Radial-scans

    along the Si[1 21] azimuth for 0.6 ML and 2 ML Au deposits at 300 K.

    The peaks marked with a circle are Si-(77) reconstruction peaks, the ones marked with # are unassigned peaks.

    emergesF snterestinglyD we oserve the pperne of three unssigned peks @mrked with 5A X two peks sitting t the @UUA positions @t PFIS nd QFPS 1 A ut tht re not suppoE sed to e reonstrution peks i D s well s less intense one t PFSQ 1 F hese peks might indite the formtion of eui rystlline ompound @see setion FP nd sFIAF sndeedD in his hh thesisD egnus qF studied the selfEorgnized growth of eu on i@IIIA egnusD PHHUF yne of his interesting results onerns iw pitures of some islnds displying tomi plne sping tht do not orrespond to ny interEplnr distne in f goldF he uthor explins this y the formtion of islnds omposed of goldEsiliidesF le sssFP hs een tken from egnusD PHHU nd lists some goldEsiliide ompounds reported in literture nd supposed to e metstleF he diversity of these strutures is however not very helpful s mny interEplnr distnesD from severl ompounds ould e t the origin of the unssigned peksF por exmpleD the est interEplnr distnes orresponding to the 5 peks t PFIVD PFSQ nd QFPP D re the eu0.77 i0.23 @QIIAD the eu7 i@RHHA nd the eu2 i@VHHAD respetivelyF sn dditionD qsh inEplne nd outEofEplne mesurements were rried out t TPH u nd yield n verge width nd height of IS nm nd R nm respetivelyF hese vlues orrespond to the lrgest rystllites in the islndsF he orresponding qse mesurements yield n verge width nd height of IUFVIFV nm nd TFUHFU nm respetivelyF hese vlues orrespond to the whole islnd whtever its rystlline stteF he omprison etween the
    i. Their shape are dierent than typical reconstruction peaks.

    US

    Chapter III.

    Growth of Au on Si(111)

    gompound eu0.77 i0.23 eu5 i2 eu5 i eu2 i eu7 i eu3 i eu4 i


    therein.

    ymmetry etrgonl rexgonl etrgonl etrgonl etrgonl yrthorhomi etrgonl

    vttie prmeters in aWFT aWFQV Y aISFRT aTFUS aIWFSH aUFVR aUFVP Y aSFSS Y aIIFIT aSFSS

    Table III.2  Crystal structure of some gold-silicide compounds, from [Agnus, 2007] and references

    two vlues lims for the mjor prt of the islnds eing singleErystlF he di'erene might rise from the formtion of the eui shell t the surfe of the islnds resulting from the gglomertion of the toms tht ompose the euEsiliide thin (lm tht n potentilly forms t F he di'erene of sizes otined y qse nd qsh yields the mximum thikness of the eui shell iFeF pproximtely P nmF e omined nd medium energy ion sttering study estimted thikness of QER wvD iFeF pproximtely I nmD t the surfe for nominl P wv overge t roshino
    et al.D

    PHHVF pinllyD the upper limit of P nm

    t TPH u is of the sme order s the estimtion of I nm t F

    III.1.3 Comparison between the two growth modes


    D @nmA qrowth QP3 hewetting QI3 W @nmA H @nmA IPFS1.2 PFU0.3 ITFI1.6 RFI0.4 @ A QVFU4 SRFS4

    Table III.3  Morphological characteristics of the 2 ML Au/Si(111) at 570 K obtained either by


    successive deposits at constant temperature (growth) or by a deposit followed by successive thermal annealing (dewetting).

    sn the (rst euGi@IIIA seriesD the growth is mde up to P wv t SUH uF sn the seond seriesD the dewetting of the P wv deposit is performed t inresing tempertures with one hrteriztion step t SUH uF sn oth sesD the islnds re trunted spheresF emrklyD in spite of di'erent elortion methodsD the interEislnd distne of oth smples is the sme @le sssFQAF his is thus stle on(gurtionD whih minimizes the energy of the systemF roweverD the islnd size otined y dewetting is lrger thn tht otined y growthF huring the dewettingD i toms my gglomerte in the islnds nd get lloyed with eu tomsF he di'erene in sizes etween oth proesses is likely to e ttriuted to the minimum thikness of the eui shellD pproximtely I nm t SUH uF woreoverD the ontt ngle is lrger in se of dewettingF e higher ontt ngle in the se of dewetting my rise euse this proess UT

    III.2.

    GIXS study of the interface epitaxial relationships

    tends to redue the surfeEtoEvolume rtio nd therefore leds to more roundEshped islndsF

    III.2

    GIXS study of the interface epitaxial relationships

    sn the previous setionD the qse study imed t getting some morphologil inforE mtion on the shpe of the prtiles during the growthGnneling of eu on i@IIIAF sn this setionD we fous on how thiker gold (lms ndGor islnds re relted to the sustrte from n tomisti point of viewF sn other wordsD qs experiments here mke possile the study of the interfe struture etween the two solidsF

    III.2.1 Experimental results


    a Deposition at room temperature

    e (rst step onsists in hrterizing the system fter the gold deposit t F o do so radial-scan is performed long the i[1 zimuth just fter deposit of U wv of gold 10] @pigure sssFU@AAF es expeted it displys the two frgg peks of the silion single rystl found in this diretionF sn dditionD ll the llowed frgg peks of gold re reordedD whih indites tht the deposited thin (lm is polyrystlF elong this diretionD these peks n e gthered into three fmilies orresponding to three types of interfe orienttion perpendiulr to the surfe X ! eu@IIIA i@IIIA @type e in redAD ! eu@110A i@IIIA @type f in greenAD ! nd eu@001A i@IIIA @type g in lueAF
    (111) (110) (001) (220) Si(440)

    Si(220)

    Si(220) Si(7x7)

    (220) 2 ML 5 ML 7 ML 20 ML

    Intensity (arb. u.)

    Intensity (arb. u.)

    (200)

    (111) (200)

    (111) (331) (113) (222) (400) (420)

    (242)

    (333)

    -1 6 Q ( )

    2.5

    3.0

    Q ( )

    -1

    3.5

    4.0

    4.5

    (a)

    (b)

    Figure III.7  (a)


    (b)

    Radial-scan

    Radial-scan
    [1 10]

    along the

    [110]

    azimuth performed at RT after a deposit of 7 ML,

    along the

    azimuth performed at RT after deposits of 2, 5, 7 and 20 ML.

    UU

    Chapter III.

    Growth of Au on Si(111)

    yviouslyD some of them n elong to more thn one type ut it is impossile to distinE guish etween two types for single pekF rereD we tke the eu(220)D eu@IIIA nd eu@PHHA peks s signture of types eD f nd gD respetivelyF e n lso notie tht the (lm is very texturedD the eu(2 pek eing y fr the most intenseF sn pigure sssFU@A is plotted the 20) sme
    radial-scan

    s in the pigure sssFU@A ut for di'erent deposited mount X PD SD U nd

    PH wvF ht is importnt here is to oserve the evolution of the three outEofEplne epitxil reltionships with the depositF por P nd S wvD only the eu(2 pek is present whih 20) mens tht the gold rystllites present the e type epitxy onlyF por U wvD the eu@IIIA nd the eu@PHHA peks show up @iFe f nd g types pperA ut the eu(220) pek is still the most intense @i.
    e.

    epitxy e is preponderntAF por higher overge @PH wvA the three

    modes oexist with still mjority of the gold strutures in eEtype epitxyF his shows tht the outEofEplne epitxy type depends on the overge ut with dominnt type eF he ritil overge t whih epitxies f nd g pper ould not e determined urtely s they were oserved sometimes even t S wvF st is lso importnt to note here tht iE@UUA reonstrution pek is still reorded for smples onto whih P nd S wv were depositedF his ehvior n hve di'erent origins X either the surfe is not ompletely overed y the gold (lmD or the gold toms sit on peulir @UUA reonstrution sites whih preserve the positions of the silion toms in the (rst lyer of the sustrte u
    b Evolution upon heating
    et al.D

    PHIHF

    st is now interesting to hve look on how the epitxil reltionships evolves if we het the smpleF
    Si(7x7)

    2 ML

    RT 600 K

    10

    Si[110], 620 K Si[121], 620 K (111)

    Si(220)

    (220)

    Intensity (arb. u.)

    Intensity (cps)

    10

    (200)

    (111)

    (200)

    (220)

    CTR

    5 ML

    10

    2.5

    3.0

    Q ( )
    (a)

    -1

    3.5

    4.0

    4.5

    2.5

    3.0

    3.5
    -1

    4.0

    Q ( )
    (b)

    Figure III.8  (a)

    Radial-scans along the [1 azimuth for a 2 ML and a 5 ML deposit at RT and 10] 600 K,(b) Radial-scans along the [1 10] and [1 azimuths for a 5 ML deposit at 620 K. A radial-scan 21]
    performed at 630 K displaying a liquid structure signal is also plotted.

    UV

    III.2.

    GIXS study of the interface epitaxial relationships

    yn the radial-scans plotted in pigure sssFV@A for P @topA nd S wv @downA t QHH uD only the e epitxy is lerly identi(edF he orresponding t THH u @QT u elow the euEi euteti pointA show thtD in oth sesD the eu@IIIA nd the eu(2 peks intensity 20)
    radial-scans

    inrese nd tht for S wvD the eu@PHHA pek ppersF enneling of the smples thus indues etter rystllinity nd modi(tion of the epitxil reltionshipF st is lso interesting to ompre the di'erene etween two sns performed long di'erent i zimuthsF his is done in pigure sssFV@A whih ompresD for S wvD the sns long the i[1 nd the 10] i[1 diretionsF he intensities of the peks vry lrgely with the zimuthD reveling n 21] inEplne texture of the grinsF sndeed untextured polyristlline gold omposed of rndomly orientted grins would led to onstnt intensity long the heyeEherrer rings @iFe with rottion of the smple round its surfe normlAF he suspeted spei( inEplne orienttions for the di'erent outEofEplne epitxies n e found nd highlighted with reiprol spe mp suh s tht reorded t TPH u nd plotted in pigure sssFW@AF st hs een reorded just efore meltingD y reording the intensity in setor loted etween the i[1 nd i[1 xesF he i(2 frgg pek is lerly 10] 21] 20) visileD together with heyeEherrer rings of the polyrystlline gold @eu@IIIAD eu@PHHA nd eu@PPHAAF he intensity of the eu@PPHA ring presents mxim for di'erent inEplne direE tions reveling texture with dditionl fvorle inEplne orienttions with respet to the ones oserved y ompring the two i zimuths in pigure sssFV@AF his indites tht for the dominnt e type epitxy @eu@IIIA i@IIIAAD di'erent inEplne orienttion reltionships @ysA n e foundF es fr s the two other rings re onernedD orresponding to the other outEofEplne epitxies @f nd gAD the mp lso revels intensity vritions with F roweverD

    l-scan

    Si[111]

    (220) (200) (111)

    Si[121]
    Au(311)

    OR2 OR3
    Au(111) Au(200)

    Si[110]=OR1
    Si(220)

    Au(220)

    Si(220) radialscan
    (b)

    Si[110]

    Qll

    rockingscan

    (a)

    Figure III.9  (a) In-plane Reciprocal Space Map covering 30 of the reciprocal space (red : high
    intensity, blue : low intensity, yellow : intermediate) at 620 K. The white ring corresponds to a loss of the synchrotron beam during the acquisition time. (b) Scheme of the measurements performed in reciprocal space around the Au(2 20) peak.

    UW

    Chapter III.

    Growth of Au on Si(111)

    the inEplne orienttion reltionships for type f nd g were oserved only few timesD with no ler reproduile trend from one experiment to notherF es it ppers tht the strongly dominnt outEofEplne epitxy is y fr of type eD we thus fous on the e epitxy s the mesurements reveled systemti ehvior of the evolution of its inEplne y with temE pertureF fy mesuring the eu@PPHA ring in severl wys @see pigure sssFW@AA for di'erent tempertures upon nnelingD it hs een possile to follow severl prmeters suh s the solid dewetting or the inEplne orienttion hngesF
    Gold thermal expansion

    pigure sssFIH@A shows the rdil evolution of the eu(2 pek with tempertureF et 20) QHH uD the pek is t Q = 4.36 1 in reiprol speD whih is equivlent to @PPHA dEsping of its theoretil position lulted y Q = (2 h2 + k 2 + l2 )/a2 with aAu the Au lttie prmeter of gold t QHH u @RFHUW A nd @h,k,l A the willer9s indexes @@PD2DHA in this seAF he orresponding eu rystls re thus not strinedF pon hetingD the pek shifts from RFQT 1 to RFQQ 1 t TPH u illustrting the expnsion of gold with inresing tempertureF e vlue of Au = 15.106 u1 is dedued for the liner therml expnsion oe0ient of goldD in very good greement with literture xix nd wxirD IWRIF he eu pek lso nrrows nd inreses in intensity with inresing temperturesD re)eting the growth of the rystllites thnks to higher tomi moilityF
    Following the dewetting

    @long Q A t the Q vlue of the eu(2 pek re reported in pigure sssFIH@AF 20) e pek round Q = 2.5 1 is foundD orresponding to the eu(3 frgg positionD whih 11)
    l-scans

    10

    10

    Intensity (cps)

    Intensity (cps)

    300 K 520 K 580 K 620 K

    300 K 470 K 550 K 620 K


    10
    4

    10

    3
    3

    10

    4.25

    4.30

    4.35

    Qll ( )
    (a)

    -1

    4.40

    4.45

    4.50

    0.5

    1.0

    1.5 2.0 -1 Q ( )
    (b)

    2.5

    3.0

    Figure III.10  (a)

    Radial-scans

    on the Au(2 20) peak along the Si[1 direction at 300 K, 520 K, 10]

    580 K and 620 K, the shift of the peak shows the expansion of gold with annealing. (b)

    ) crossing the

    Au(3 11)

    l-scans (along

    Bragg peak at 300 K, 470 K, 550 K and 620 K

    VH

    III.2.

    GIXS study of the interface epitaxial relationships

    on(rms tht the eu@IIIA plnes re prllel to the i@IIIA plnesF et QHH uD the pek width @prwa0.37 1 A nd the osilltion period orrespond to (lm thikness of ITFV @U wvA with low roughnessF et inresing temperturesD the osilltions dispper nd the eu(3 pek eomes nrrowerD re)eting tht the (lm (rst roughens efore the dewetting 11) proess tkes ple X the (lm turns into islndsF et TPH u the prw of the pek is HFHW 1 D whih orresponds to n verge islnd9s height of out UH F
    Evolution of the in-plane epitaxial relationships

    he rocking-scans on the eu@PPHA heyeEherrer ring provide informtion on the inEplne rystllogrphi orienttion of the grins omposing the gold (lm ndGor the gold islndsF es shown in pigure sssFIID t QHH u the sn displys lrge nd rod pek entered on the i[1 diretion nd two nrrow stellites peks @whih re equivlent euse of sixE 10] fold symmetryA t 19.1 orresponding to the i[2 inEplne diretionF his revels two 31] preferred inEplne orienttions of the gold strutures with respet to the sustrte t QHH uF he (rst orienttion reltionship @yIA relted to the entrl pek is [1 eu@IIIA [1 i@IIIA 10] 10] nd orresponds to identil orienttion of the eu rystls nd the i sustrteF he seond orienttion reltionship @yPAD rotted in the plne y IWFI D is [2 eu@IIIA [1 i@IIIAD 31] 10] for whih the [2 rows of eu re prllel to the i[1 xisF et QHH uD mjority of the 31] 10] grins @WP7A re in yI on(gurtion s dedued from the integrted intensityF yI is thus the preferred orienttionF efter nneling the smple t TPH u nd dewetting of the (lm into islnds @still solidAD new pek shows up t 11.9 @pigure sssFIIA ttesting the emergene of third epitxil
    OR2 300 K 620 K 300 K after melting and solidification OR1

    10
    Intensity (cps)

    19.1

    10.9 OR3

    10

    -20 -15 -10


    Figure III.11 

    -5

    (deg)

    10

    15

    20

    Rocking-scans

    on the Au(220) ring at 300 K, 620 K and again at 300 K after

    melting and subsequent cooling. The peaks correspond to the directional relationships in the plane between the gold and the silicon substrate

    VI

    Chapter III.

    Growth of Au on Si(111)

    orienttion @lled yQA of gold islnds with the silion sustrteF his epitxil orienttion ould e either the [792]eu@IIIA [1 i@IIIA reltionship lredy reported y ghen et al. 10] ghen nd ghenD IWWT whih would yield pek t IPFPI or the [4 eu@IIIA [1 i@IIIA 51] 10] whih would yield pek t IHFVW F e will see lter tht the ltter is the orret oneD nd tht it should e reEwritten [121]eu@IIIA [2 i@IIIAF e n lso notie tht t TPH uD 31] the entrl pek is nrrower nd less intense thn the IWFI oneF prom the integrted pek intensityD we dedue tht hlf of the islnds now dopt the yP on(gurtionF reneD the dewetting proess tking ple from to TPH u is ompnied y hnge in the epitxil reltionships from yI to yPD s represented in pigure sssFIPF
    Si[111] 300 K ~1.5 nm
    Side view

    Polycrystalline, textured: OR1 predominant


    Top view

    620 K

    Dewetting + in-plane rotation: three different ORs


    Top view Side view

    Figure III.12  Illustration summarizing the evolution of the system : the deposit of 7 ML at
    300 K forms a thin lm with a cube on cube epitaxy. Heating induces a dewetting and the islands appears with a change in epitaxial relationship.

    st is interesting to note hereD tht in the se of P wv depositD the yI ws found to e the dominnt inEplne orienttionD even fter nneling t TPH uF his is shown in pigure sssFIQ whih displys more intense pek for the yI for the two temperturesF es smller mount of deposited mteril logilly leds to smller islnds with the dewetting @see setion sssFIFPAD possile link etween the size of the islnds nd the inEplne orienttions n not e exludedF he potentil onnetion etween the two s well s with the rystlline struture is disussed t the end of this hpter @see setion sssFPFPFdA
    OR1
    10
    3

    500 K 580 K

    OR2

    Intensity (cps)

    OR3
    10
    2

    -20

    -10

    ()

    10

    20

    Figure III.13 

    Rocking-scans

    on the Au(220) ring at 500 K, 580 K, for a 2 ML deposit.

    VP

    III.2.

    GIXS study of the interface epitaxial relationships

    III.2.2 Discussion on growth and dewetting of Au on Si(111)


    he l-scan plotted in pigure sssFIH@A shows tht the U wv deposit of gold t onsists in )t (lm whih turns into islnds with inresing tempertureF he dewetting proess is driven y the minimiztion of the surfeEtoEvolume rtio nd is di'usion limited proess @see ghpter sD setion sFQFQAF es onsequeneD the tomi moility o'ered y the nneling llows the system to redue its surfe re through gglomertion of the toms tirn nd hompsonD IWWPF sn the se of eu growth on i@IIIAD s the surfe energy of gold @Au aIFS tFm2 A yE son nd willerD IWUU is higher thn the i@IIIA plne energy @Si aIFP tFm2 A nk
    et al.D

    PHHTD growth mode is expeted fuer nd oppD IWUPF roweverD the growth of eu on i@IIIA sustrtes is known to follow u mode @IwvEhigh wetting lyer C Qh growthA t reltively high temperture @ove SHH uA fuer nd oppD IWUPY wieh kosin
    et al.D et al.D

    IWWIY

    riino nd tneD PHHSY puhigmi nd shimiyD IWWT ut lso sometimes t uirE PHHIF e qusiEprnkEvn der werwe @pwA growth mode @lyer y lyer growth on severl disordered lyersA hs lso een reported for deposits performed t low tempeE rture @IHH uA tlohowski nd fuerD IWVV nd Qh or Ph growth hs een oserved t depending on the sustrte qulity utzel nd weinelD IWVWF st is lso known tht eu grows in lyer y lyer mode t on the low density plne i@HHIA uim et
    al.D

    IWWTF he

    di'erent oserved growth modes in this peulir system my rise euse of the reltively lose vlues of the surfe energies s well s the unertinty tht seems to exist on the Au vlue @see ghpter sD setion sFQFRAF he interfe energy etween the sustrte nd the growing (lm depends on the interE tion energy etween the two rystlsF pollowing vojkowski
    et al.

    vojkowski nd pehtD

    PHHHD the interfe energy @I A etween gold nd silion is given y X

    I = Si + Au adh ,

    @sssFIA

    where adh is the dhesion energyF hereforeD the most stle interfe @smll I A orresponds to smll Si nd Au vlues nd lrge adh onesF por iD the @IIIA plne hs the lowest surfe energy s it is the densestD whih explinsD for exmpleD tht i nnowires nturlly grow long this diretionF por f metls suh s goldD the low energy surfes re losely pked plnesD with Au(111) < Au(001) < Au(011) itos
    et al.D

    IWWVF st therefore explins why the

    eu@IIIA i@IIIA epitxy @type eAD whih is energetilly fvouredD is the prominent epitxyF sn ddition to surfe energies of eu nd iD two other prmeters n in)uene the growth mode X the lttie mis(t s well s the interfil ondingF sn some wysD they re relted to adh X adh inreses @i.e. I deresesA when the interfil onding is stronger VQ

    Chapter III.

    Growth of Au on Si(111)

    thn the onding in the deposit itself nd when the mis(t etween the two mterils is low @see next setionAF por P wv deposit t D pigure sssFV@A@eA nd sssFU@A disply gold peks of very low nd rod intensity reminding more n morphous signtureF rowever they n lso e due to very smll rystl grinsF hese mesurements lim for gold (lm with poor rystllite qulity into whih euEi onds my e preferred to euEeu ondsD thus lowering I F his oservtion grees well with the proess proposed y eh eh
    et al.D et al.

    s well s roshino

    et al.

    who

    mesured tht for smll deposits of eu @elow PQ wvAD n euEi lloy (lm n form t IWWQY roshino
    et al.D

    PHHVF por susequent depositionD their studies pointed

    out tht the nuletion of the gold (lm ours elow the lloy with n rupt euGi@IIIA interfeF he pperne of the eu(2 peks for S wv @pigure sssFU@AA nd the presene 20) of potentil rystlline euEi phses in the experiments performed with P wv @setion sssFIFPA support this ideF hen nneling t inresing temperturesD tomi di'usion inreses nd the dewetting proessD whih is ssumed to strt t the grin oundries of the (lm tirn nd hompsonD IWWPD tkes ple @pigures sssFIH@AAF he inrese withe temperture of the gold frgg peks intensity in pigure sssFV@A revels the hnges tht tke ple in hemil ondings to form euEeu insted of euEi ondsF he dewettingD whih ours in the solid stteD leds to rystlline islnds distriuted on wetting lyer rnnon dispperne of the osilltions t SVH u in the
    l-scan et al.D

    PHHTF emrklyD the

    lerly underlines the destrution

    of the (lm t this tempertureF his grees very well with the ssumption tht SUH u is ritil temperture ove whih the dewetting proess is enhnedF sn ddition to the morphologil spets desried previously @setion sssFIFPAD we hve shown tht the dewetting proess is ompnied y hnges in the inEplne epitxil relE tionships etween the emerging islnds nd the i sustrteF o explin this ehviourD the next setion @setion sssFPFQA fouses on the tomi desription of the proess tht rises t the interfeF

    III.2.3 Atomic congurations of the interface


    a Coincidence Site Lattice theory

    vet us simply ssume tht the dhesion energy is linerly linked with the onding energy

    EAuSi etween i nd eu toms in position of good mthing s follows vojkowski nd pehtD PHHH X EAuSi adh = 2/3 , @sssFPA
    VR

    III.2.

    GIXS study of the interface epitaxial relationships

    here is the verge tomi volume nd represents the frtion of perfet onds nd n thus e seen s the degree of good mthing etween the two plnesF iqution sssFP mens tht the etter the mthingD the higher adh D the lower the interfe energy @eqution @sssFIAAF his sttement hs to e linked to ommon geometril riterion proposed y follmn et
    al.

    follmnn nd xissenD IWTVF he riterionD lled oinidene site lttie @gvAD onsists

    in ringing the two di'erent ltties into prtil self oinideneF he ommon lttie sites form the nodes @the HEpointsA of superElttieF he preferred orienttion reltionship @yA orresponds to the mximum density of pproximte gv nodes @H lttie nodesAD iFe to lrge in eqution @sssFPA nd therefore to low interfe energyF roweverD despite mny experimentl studies on surfeGinterfe nd other theoretil modelshhmenD IWVPY utoD IWVWY skuhr nd irouzD IWWTD to dteD no simple riterion exists to predit epitxil on(gurtionF roweverD uto et
    al.utoD

    IWVW onluded tht the y hosen y system is


    et al.skuhr

    more ditted y the lowering of the elsti strinF skuhr

    nd irouzD IWWT

    proposed lever geometril methodD similr to follmnnD to desrie epitxil reltionship X y lulting the overlp of the reiprol lttie points @represented y spheresA of oth rystls X the on(gurtion tht mximizes the overlpped volume gives the most expeted orienttion reltionshipF
    b Evolution of the mismatch with T

    es the interfe etween eu nd i@IIIA is known to e shrp @iFe without intermixingAeh


    et al.D

    IWWQY roshino

    et al.D

    PHHVY ghen nd ghenD IWWT t lest well elow the euteti temE

    pertureD let us fous on the wy the eu@IIIA plne is relted to the sustrte for the three epitxil y in terms of tomi mthing in rel spe nd pply follmnn9s riterionF he lttie prmeters of the two rystls @aSi = 5.431 nd aAu = 4.079 D t QHH uA di'er lrgely resulting in lrge mis(t given y X = |aAu aSi | /aSi = 0.25 nd hene in poor tomi mthingF he three epitxil on(gurtions reveled y Ery re represented in rel spe in pigure sssFIR y superposing the eu@IIIA plne @yellow tomsA with the i@IIIA plne @lk tomsA t QHH uF pigure sssFIR@A orresponds to the yI on(gurtion in whih the [1 rows of the two rystls re prllelF sn this on(gurtionD eh fourth tom of the 10] eu[1 row oinides with the third tom of the i[1 oneF st revels n hexgonl gv 10] 10] @highlighted in redGdshedA of periodiity L1 @IIFSP AF he rottions y IWFI nd IHFW of the eu@IIIA plnes round the III xis ringing the system into yP nd yQ on(gurE tions re represented in pigure sssFIR@A nd sssFIR@AD respetivelyF he yP on(gurtion leds to gv of periodiity L2 @UFTVA X the (rst tom of the eu[2 row flling in good 31] oinidene on the seond of the i[1 rowF he gv periodiity of the yQ is L3 @IHAD the 10] VS

    Chapter III.

    Growth of Au on Si(111)

    (a)
    Au[110] // Si[110]

    OR1

    (b)
    Au[231] // Si[110] Au[110] 19.1

    OR2

    (c)
    Au[110] Si[110]

    OR3
    Au[121] // Si[231]

    10.9

    L1
    Au[112] // Si[112]

    L2

    L3

    Si[111] Si[111]

    Si[111]

    Si

    Au

    Figure III.14  Plane view of the interface represented by the superposition of the Au(111) plane
    above the Si(111) plane, the lattice parameters values are taken at 300 K. The Au(111) plane is rotated around the Si[111] axis by (a) 0 (OR1), (b) 19.1 (OR2) (c) and 10.9 (OR3). The atoms marked with a black cross are in perfect coincidence. For each case, the Coincidence Site Lattice is plotted in red (dashed) and the periodicity (Lx ) is indicated. It reveals that :

    L2 < L3 < L1 .

    oinidene eing lmost hieved for the seond tom of the eu[1 row with the (rst of the 21] i[2 rowF xote tht the third epitxy is identil to tht lredy reported y ghen et al. 31]

    written [792]eu@IIIA [1 i@IIIAF yur nottion [1 eu@IIIA [2 i@IIIA emphsizes the 10] 21] 31]
    prllel rows of the two rystl long whih the oinidene sites re foundF hereforeD ording to the H lttie riterion of follmnn nd the relted interfe energyD the yP should e fvoured with respet to the yQD itself more fvorle thn the yI @L2 < L3 < L1 AF ixperimentllyD if yP is indeed the preferred orienttion reltionship t TPH uD this is not the se t D where the yI is more fvourleF reneD the H lttie theory hs to e re(ned y tking the y mismth into ountF sndeedD to understnd this e'etD one must tke loser look to wht extent the good mthing relly is nd how it evolves with tempertureF he mismth of the y [hkl]eu@IIIA [h k l ]i@IIIA represents the reltive error etween the theoretil perfet oinidene point nd the rel ples where the gold toms re lotedF st n e expressed s X

    ORx =

    i dAu[hkl] j dSi[h k l ] , x (1, 2, 3) (j dSi[h k l ] )

    @sssFQA

    where dAu[hkl] nd dSi[h k l ] re the distnes etween two toms in the gold hkl nd silion h k l rowsD respetively @for exmple dSi[1 =QFVR t QHH uAF i is the ith tom of 10] VT

    III.2.

    GIXS study of the interface epitaxial relationships

    1.8 1.6
    Mismatch (%)

    OR1 OR2 OR3

    (4/3) (1/2) (2/1)

    1.4 0.6 0.4 0.2 300 350 400 450 500 550 600 Temperature (K)

    Figure III.15  Temperature dependence of the mismatch value


    tionships. The ratio

    for the three orientation rela-

    m/n

    is given in the caption next to the concerned epitaxy.

    the onsidered gold row tht lmost mthes the j th tom of the i rowF sn this rnge of tempertureD the therml expnsion oe0ients of the two mterils n e onsidered s onstnt ut hve very di'erent vlues X Au aIRFS106 K 1 nd

    Si aPFT106 K 1 F es onsequeneD gold expnds muh more thn silion nd the misE
    mth vlues re modi(ed upon heting @see pigure sssFISAF et QHH uD OR1 = 0.13% nd

    OR2 = 0.63%D the shortest periodiity is thus o'ered y the yP reltionship ut the est
    mthing is hieved y the yI oneF es fr s the yQ is onernedD its mismth vlue is so high @OR3 = 1.7%A tht no grin presents this epitxil orienttionF ith inresing temperture OR2 dereses @s well s OR3 A nd OR1 inresesD rossover is found round SHH uF et TPH u X OR1 = 0.53% nd OR2 = 0.23%D the yP on(gurtion is therefore preE

    Au[110] II Si[110]

    OR1 -

    Au[231] II Si[110]

    -OR2 -

    OR1 = 0.12% RT

    OR2 = 0.63%

    620 K OR1 =0.53 %


    OR2 = 0.23%

    Figure III.16  Scheme summarizing the mismatch dierence between RT and 620 K for the OR1
    and the OR2. The origin and the rst coincidence site are represented along the parallel Au and Si rows recalled above. At RT the smallest mismatch is provided by OR1 whereas OR2 is more favourable at higher temperatures.

    VU

    Chapter III.

    Growth of Au on Si(111)

    ferred to the yI nd the yQ emerges euse its mismth vlue is reduedF rereD the experimentl mesurements lerly underline tht the previling riterion for the euGi@IIIA interfe in this experiment is the mthing qulityDi. of the mismthD s repitulted in pigure sssFITF
    e.

    the minimiztion

    Energetic information provided by simulations

    he three ys were lso studied y ab-initio lultionsF he simultion ells re onstiE tuted of IH vuum lyer nd R lyers eu sl on top of T i@IIIA ilyers whose ottom lyer dngling onds re hydrogented y r tomsF he lulted eu nd i equilirium lttie prmeters provided y the simultions re RFIQU nd SFRTQ F es onsequeneD yID yP nd yQ hve lttie mismth of CIFH7D CHFP7 nd EHFV7 ompred to the i sustrteD nd the eu lyers re strined euse of the simultion ell periodiityF he lultion of the formtion energies Ef is otined y X

    Ef = [Etot (nSi Si nAu Au nH H )] /Asurf ESiH


    where Etot is the totl energy of the systemD n nd represent the numers of toms nd the tomi ohesion energies of iD eu nd rF Asurf is the unit ell surfe nd ESiH is the hydrogented i surfe energyF he three ys hve formtion energies round HFW tFm2 F es the relxed i@IIA nd i@IIIAE@UUA he surfe energies re IFSUQ nd IFPIW tFm2 D the eu deposition dereses the surfe energy of the systemD whih is in greement with the experimentlly oserved good eu wettilityF sn le sssFR re gthered the formtion energies of the three ys with yP presenting the lowest oneF st thus on(rms the rguments of lower oinidene site lttie nd mismth we proposedF rowever these rules do not work for the reltive formtion energies etween yI nd yQF his vision is thus good strting guide to serh for good yD ut it is t the moment too simple for urte qunti(tionsF he reson might e tht ll the eui ondsD not only the eui with perfet site oinideneD need to e tken into ount to study in detil the reltive stility of the vrious ysF y yI yP yQ pormtion energy @tFm2 A HFVVT
    0.857

    HFWHV

    Table III.4  Formation energies obtained by

    ab-initio

    calculations for the dierent ORs.

    VV

    III.2.

    GIXS study of the interface epitaxial relationships

    Discussion on size-dependent atomic structure.

    et the end of setion sssFPFID it ws pointed out tht for P wv depositD the yI pek in the rocking-scan t TPH u @pigure sssFIQA ws more intense thn the two others @orresponding to yP nd yQAF st thus suggests tht in the se of smller depositD whih leds to smller islnds upon dewettingD the yI is fvouredF sn other wordsD it seems tht smll islnds do not need to hnge their inEplne y to ompenste the therml expnsionF his ehviour n e explined when one looks t the vrition of the mismth vlue long single rystllogrphi rowF sn pigure sssFIS nd sssFIT D the vlues of the mismth re given for the losest oinidene site from the tom tken s originF roweverD for the other oinidene sites @long the sme rowAD the mismth vlues re lrger nd inrese proportionlly with the distne from the originF hereforeD t TPH uD for whih OR1 is lrger thn OR2 D lrger islnds re likely to fvour the yP wheres smller islnds n remin with yIF his ssumption is further supported y the ft tht the yQ presents the lrgest mismth vlue in ny seD with orresponding pek displying the lrgest prw @i. struturesAF roweverD the ove desription is vlid only if we ssume tht islnds hve singleErystl struturesF sndeedD the mesurement of the prw in pek only gives informtion on the grin sizesF he question rised here is therefore to know whether the islnds hve single or polyErystlline strutureF por P wvD the lterl sizes of the grins extrted from the prw in the rocking-scans in pigure sssFIQ t SVH u re IR nm nd IV nm for the yI nd yP peksD respetivelyF sn dditionD the prw of
    radial-scan e.

    the smllest

    on the eu@PPHA pek gives IS nmF hese lterl size

    vlues re remrkly lose to the ones otined in setion sssFIFP y qse mesurements @ IT nmAF es qse mesurements re relted to the shpe of the islndsD these results lim for islnds with singleErystl strutures i D the lrgest displying the yP nd the smllest the yIF roweverD for thiker depositsD it seems it more trikyF sn the se of U wv depositD the men lterl size of the grins t TPH uD extrted from pekD is QH nmF prom the
    rocking-scans radial-scan

    on the eu@PPHA

    in pigure sssFIID it omes PPFSD IUFS nd Q nm for

    yPD yI nd yQD respetivelyF e reltive omprison etween these vlues supports the ssumption tht the size of the grin is relted to the yF roweverD their solute vlue seem to e very underestimtedF he errors on the lterl size of the grins n e ttriuted to low point density in the snsD the miss of the mximum ring intensity or the presene of mosi termF edditionl informtion n e otined y mesuring the grin size thnk to the investigtion of outEofEplne sns in the di'erent orienttionsF o do soD
    i. with a possible formation of a AuSi shell (see section III.1.2(c)).

    l-scans

    similr

    VW

    Chapter III.

    Growth of Au on Si(111)

    s in pigure sssFIH@A were performedD t the eu@PPHA Q position nd for three di'erent

    vlues orresponding to the three ysD t SPH uD SVH u nd TPH uF por eh yD the
    height of the strutures n e extrted t eh tempertureD their evolution re plotted in pigure sssFIUF
    12
    From Lscan Au220

    OR1 OR2 OR3

    h (nm)

    520

    540

    560

    580

    600

    620

    T (K)
    Figure III.17  Evolution of the height (h) of the structures as a function of the temperature, for
    the three dierent ORs.

    et SPH uD the height sizes re equivlent for eh y nd equl PFS nmF he deposit is still under the form of rough (lmD on(rming the results otined in setion sssFIFP@A tht limed for ritil dewetting temperture of STH uF roweverD the three ys re lredy presentD whih mens tht grins re likely to strt to turn to djust their inEplne orienttionF ith further nnelingD di'erent heights re ttriuted to eh y with IPFSD WFR nd RFV nm t TPH u for yID yP nd yQ respetivelyF essuming tht the height is proportionlly linked to the lterl sizeD these results support the sizeEdependene of the dopted y y the rystllitesF purthermoreD the size of the islnds n e studied
    ex-situF

    pigure sssFIV@A shows iw

    imge orresponding to smple onto whih deposit of out U wv of gold ws performed t D followed y nneling t TPH uD elow the euteti tempertureD to void the melting of the islnds pigure sssFIV@AF he extrtion of the size distriution from the piture is shown in pigure sssFIV@A nd rnges from PH nm to ISH nmF woreoverD quik nlyzis revels slight iEmodl distriution with smll nd lrge islnds displying men sizes of SS nm nd

    IPP nmD respetivelyF rowever the stndrd devition is lrge for oth hrteristi sizesF
    his oservtion lso supports the ide of sizeEdependent yF roweverD the sizes extrted from the iw imge do not mth the sizes determined y qs mesurements whih provide signi(nt smller vluesF gompred to the P wv smple seD one would rther onlude here to polyrystlline islndsF sn dditionD pigure sssFIW present the epw study rried out on the smple of the iw imgeF he extrted pro(les on lrge islnds @IA gives X H 20 nm WH

    III.2.

    GIXS study of the interface epitaxial relationships

    2 m

    100

    Number of particles

    80 60 40 20 0 20 40 60 80 100 120 140 160

    Diameter (nm)
    (a) (b)

    extracted from the SEM image displaying two characteristic sizes.

    nd W 150 nmF fy modeling the shpe of the islnd y trunted sphereD rough i estimtion of the ontt ngle is given y = acos(1 (H/0.5W )) nd gives RS D in good greement with essel
    et al.

    Number of particles

    Figure III.18  (a) SEM image of

    ML sample annealed at 620 K.(b) Lateral size distribution

    essel

    et al.D

    PHHQF por the smller islnd @PA we otin X

    H = 8 nmD W = 90 nm nd thus vlue of QU F his result vries in opposite wy with


    the sttement tht smller islnd should disply lrger ontt ngle @see setion sssFIFPAF 50 100 150 200 250 rowever this result only quints for one islnd nd is supposed to e within the error rF st is therefore more relevnt exmple of the lrge distriution of the morphologil prmeters in the selfEorgniztion of eu islnds on i@IIIA egnusD PHHUF
    8 7 6 5 4 3 2 1 0 150 0 20
    Lateral size (nm)

    2
    H (nm)

    20 15 10 5 0 0 50 100 x (nm)

    40 60 x (nm)

    80

    Figure III.19  AFM image of a reduced area of the same sample presented in Figure III.18(a)
    and the two correponding two proles.

    sn the light of these experimentl resultsD it is likely tht smll islnds otined with P wv deposit re singleErystl islndsF sn the se of lrger islnds otined with U wv
    i. We neglect here the convolution with the AFM tip.

    WI

    Chapter III.

    Growth of Au on Si(111)

    depositD polyrystlline struture is mye more onlusiveF sn dditionD the reltionship etween the size of the grins nd their preferentil y seem to e resonle ssumptionF roweverD further experiments re lerly needed to get more preise informtion on the isE lnds9 strutureF
    In this chapter we have described in a rst part the morphological parameters of the golds islands in the case of Au growth for small deposits. In a second part, we have presented the dewetting process undergone by a thicker gold lm when the temperature is increased as well as the modications of the interface relationship between the two crystal lattices. In addition, we have mentioned the presence of a wetting layer together with the islands. The next chapter present the results obtained on the study concerning the formation and the atomic structure of this wetting layer which has been found to undergone surface reconstructions.

    WP

    III.2.

    GIXS study of the interface epitaxial relationships

    Summary of Chapter III


    Study of small deposits (2 ML) :

    he growth of eu on i@IIIA t SUH u follows trnskiEurstnow mode nd results in


    islnds of PFU nm in height nd of IPFS nm in widthD seprted y out QP nmF

    he islnds otined y dewetting from to SUH u present the sme interEislnds distne
    @QI nmA ut re it lrger with men height of RFI nm nd men width of IT nmF

    he omprison etween the morphologil prmeters otined y qse nd the sizes


    of the grins otined y qs lims for islnds with singleErystl strutureF

    sn the se of dewettingD the omprison etween the qse model nd the experimentl
    deposit mkes elieve tht eui shell n form t the surfe of the islndsF he qs mesurements support this ide with the presene of unssigned peks in the sns tht ould e ttriuted to eui metstle phsesF et lest they show n lloying e'et t for smll depositsF

    et Te D the nnosized droplets otined y dewetting present ontt ngle of UQ whih


    is muh lrger thn the one of mirosopi droplets @RQ AF
    Study of larger deposits (7 ML) :

    he deposit of out U wv of eu on i@IIIA t results in )t polyrystlline (lmF et D the mjority of the [1 eu@IIIA [1 i@IIIA @yIAF 10] 10]
    grins present the orienttion reltionship X

    ith the inrese of the tempertureD the (lm roughensF he formtion of the voids is
    supposed to tke ple round STH uD the ritil temperture t whih the (lm turns into islndsF

    huring the dewetting proessD the inEplne epitxil reltionships re found to hnge
    euse of di'ering therml expnsion of the two mterilsF his e'et modi(es the misE mth vlue t the interfe nd the most stle inEplne orienttion reltionship t TPH u eomes X [2 eu@IIIA [1 i@IIIA @yPAF 31] 10]

    he three di'erent oserved orienttion reltionships re explined using the gv theory


    nd the qulity of the mthingF he simultion results support tht the three ys re energetilly fvourle in terms of surfe energies presenting the sme rnkingF roweverD the lulted dhesion energies vries in the other wy with the yQ tht would present the most fvourle interfe energy reveling the limits of the gv theoryF

    he size of the grins is likely to e relted to its epitxil reltionship with the sustrteF
    he islnds re supposed to e polyrystlline for suh islndsF WQ

    Chapter IV Au-induced reconstructions of Si(111) : (66)Au , ( 3 3)R30Au


    Contents
    IV.1 Literature review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV.2 Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . .
    . . . . . . . . .

    95 98
    98 100

    IV.2.1 Conditions of formation of the gold reconstruction

    IV.2.2 Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    IV.3 Si(111)-(66)Au structure . . . . . . . . . . . . . . . . . . . . . . . 103


    IV.3.1 Data collection and symmetry averaging . . . . . . . . . . . . . . . IV.3.2 Model Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 105

    IV.1.

    Literature review

    sn setion sFQFP the surfe reonstrutions tht n form in the euEi@IIIA system hve een rie)y presentedF e mjor prt of this work dels with the understnding of the formE tion of the i@IIIAE@TTAeu reonstrutionD its stility nd its strutureF sn the pstD this reonstrution hs een mostly studied in the suEmonolyer regime wheres it is studied here in the presene of islnds @or dropletsA tht form for deposits lrger thn P wv s explined in the previous hpterF sn this hpter we (rst present literture review @setion sFIA to get n overview of the knowledge on the surfe reonstrutions in the euEi@IIIA systemD then we desrie our experimentl results onerning its formtion nd its stility @setion sFPAF pinllyD we present the prtiulr tomi struture of the @TTA reonstrution nd how this ltter hs een re(ned @setion sFQAF

    IV.1

    Literature review

    es lredy mentioned in ghpter s gold is metl known to indue mny surfe reonsE trutions when it is deposited on i@IIIA sustrteF por overge rnging from H to P wvD the @SxPAD @ 3 3AQH nd the @TTA reonstrutions re the most ommon nd hve een intensively studied over the lst two dedesF wny ttempts hve een mde to drw orret piture of the phse digrm presenting the di'erent reonstrutions s funtion of overge nd tempertureF lss qroze
    et al.D et al.

    lss nd wrksD IWWU proposed sumonolyer


    et al.

    phse digrm of the system nd their work ws then further developed y qroze PHHH to extend the digrm up to P wv overge @see pigure sFIAF
    (5x2)

    900 +3D (6x6) (6x6) + (6x6)+3D

    Temperature (K)

    (7x7)+(5x2) 700 (5x2) +

    500

    0.4

    0.8

    ML

    1.2

    1.6

    Figure IV.1  Simplied surface reconstruction phase diagram of Au on Si(111), taken from [Grozea

    et al., 2000]. and

    are two dierent (

    3 3)R30

    reconstruction.

    WS

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , (

    3 3)R30 Au

    heir work illustrtes the omplexity of this system in whih the domins of existene of the reonstrution re di0ult to de(ne preisely s they depend over wide rnges on the mount deposited nd on the tempertureF sn dditionD the phse trnsitions re still unler due to the di0ulties to get the detiled tomi strutures of eh phseD whih re still under deteF his is even more omplited onsidering tht smll eu prtiles n nulete nd grow t vrious tempertures in prllel to the di'erent reonstrutions wieh
    et al.D

    IWWIY

    xkjim et al.D IWWUF he @SPA reonstrution is known to form in the sumonolyer regime in quite wide overge rnge t low temperture @RHH uA from HFI wv up to HFU wvD whih nrrows with inresing temperture @only up to HFS wv t IHHH uAF he @ 3 3AQH surfe reonstrution n e found in wide rnge of overge nd tempertureF woreoverD it is neessry to distinguish etween the two phses E@ 3 3AQH @HFSEI wvD RHHEWHH uA nd E@ 3 3AQH @IEP wvD TSHEVHH uAF hese two struturesD whih hve the sme perE iodiityD seem to di'er in their hemil environment nd in the density of their domin wlls ykud
    et al.D

    IWWTF he @TTA is known to form generlly ove I wv nd is stle

    up to out UHH uF ell these reonstrutions were found to e stle ove the euteti temE perture @e aTQT uAD suggesting potentil stiliztion of euEi onds y surfe proessesF yther reonstrutions were lso reported suh s @PPA eifert et al.D PHHID @2 32 3A nd @2 212 21A10.9 ki et al.D IWWVF xoteD tht the ltter is relted to the inE plne orienttion reltionship reported in this work in ghpter sssF he (rst oservtion of the @TTA reonstrution ws reported y vnder vnderD IWTRF st hs een studied using snning tunneling mirosopy @wA hit et
    et al.D al.D

    IWWPY kmi

    IWWRY rigshiym
    et al.D

    et al.D

    IWVTY PHHIY xgo

    et al.D

    IWWVD trnsmission eletron difE IWWIY qroze


    et al.D et al.D

    frtion @ihA khshi lvn

    et al.D

    IWWIY lss nd wrksD IWWSD euger eletron spetrosopy


    et al.D

    IWVSD Ery di'rtion @hA hornish


    al.D et al.D

    IWWVD low
    al.D

    energy eletron di'rtion @viihA xkjim et rigshiym IWVTY PHHIY lvn


    et al.D

    IWWUY vnderD IWTRY kmi et

    IWWRY

    IWVSY xogmi

    IWWH D imptEollision

    ionEsttering spetrosopy @sgsA rung nd illimsD IWVV nd re)etion high energy eletron di'rtion @riihA ki
    et al.D

    IWWVY uhrmtsov nd shimiyD IWWVY uhrmtE

    sov et al.D IWWWF heling with the @TTA reonstrution n not e done without mentioning the @ 3 3AQH s mny studies revel ler link etween the two struturesF he viih study of rigshiym et al. rigshiym et al.D IWVT reports trnsition from @TTA pttern into @ 3 3AQH C ring like pttern y nneling t high tempertureD the trnsiE tion eing reversileF his grees well with ih mesurement khshi et al.D IWWI whih reveled tht the @TTA pttern n rise from the low temperture @ 3 3AQH Cstr pttern y inresing overge or y deresing the temperture t high overge from the @ 3 3AQH C ringGhexgon ptternF he retion of the @TTA reonstrution y ooling WT

    IV.1.

    Literature review

    the smple from higher tempertures whose the reonstrution is @ 3 3AQH indites
    need of tivtion energy ut t the sme timeD the @TTA ws lso found to e instle ove THH u liming for wek inding energy in this studyF he ooling rte ws lso reported to in)uene the resulting surfe struture xgo
    et al.D

    IWWVF w oservtions performed

    t room temperture nd reported y xogmi et al. xogmi et al.D IWWH lso reveled ontinuous trnsition from @ 3 3AQH to @TTA X the @ 3 3AQH domins @with domin wll running long the `IPIb sustrte diretionsA derese in size with inresing overge to form well ordered @TTA strutureF sn this study the trnsition ws not found to e reversileF e omplementry wGviih study kmi et al.D IWWR lims for the oEexistene of two @ 3 3AQH domins @one ordered nd one disorderedA t HFU wvF ith inresing overgeD the ordered domins dispper nd viih mesurements show tht disordered doE mins turn into @TTA struturesF et the sme timeD the @TTA unit ell is not visile y w wheres retngulr rrys of protrusion with smller periodiity thn the @TTA re seenF he uthors onluded tht the @TTA struture onsists in network whih omposes the domin wlls tht seprte the @ 3 3AQH dominsF enother omined viihGw study from lvn et al. lvn et al.D IWVS reports the oservtionD t I wv eu overgeD of @ 3 3AQH viih pttern ut with w imges displying lol @TTA strutures X the proposed model onsists in @TTA struture omposed of struturl units of 3 periodiE ityF hnks to the sgs tehniqueD study rung nd illimsD IWVV proposed model of the @TTA onsisting of omintion of simple honeyom nd entered hexgons with no position vritions of the underlying i toms s well s no mixing etween the speiesF he @ 3 3AQH strutureD with empty hexgons presenting no long rnge orderD is seen s preursor of the @TTA whih forms y (lling the hexgons with dditionl eu tomsF hornish
    et al.

    hornish

    et al.D

    IWWI used inEplne surfe Ery di'rtion whih is very

    suitle tehnique to solve the tomi strutureF heir study on(rmed the trimer model for the @ 3 3AQH previously proposed y yur et al. yur et al.D IWVSF hey lim tht the @TTA is not superstruture of the @ 3 3AQH ut tht the toms deeply rerrnge themselves in struture omposed of two sixfold twinned dominsF he gold toms rrnge themselves in turned trimer triplets with dditionl eu sites in etweenF prom tterson funtionD the euEeu distne ws found to e PFV F his trimer orgniztion is lso supE ported y ih nd riw mesurements from lss rigshiym
    et al.D et al.

    lss nd wrksD IWWS nd

    reent wCviih study in whih prtil disorder in the @TTA struture ws oserved PHHIF
    et al.

    e more omplex model hs een suggested y qroze

    qroze

    et al.D

    IWWV y

    reEnlyzing the surfe Ery di'rtion dt of hornish et al. using diret method qilE WU

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , ( et al.D

    3 3)R30 Au

    more

    et al.D

    IWWUY wrks

    IWWV to determine the surfe strutureF hey proposed tht

    the @TTA tomi struture n e desried s omintion of pentgonl units nd trimers with (xed euEeu distneF sn the next setion @sFPA of this ghpterD we (rst fous on the onditions of formtion of the i@IIIAE@TTAeu reonstrution @s well s on the i@IIIAE@ 3 3AQH eu A in the experimentl onditions of the present studyF sn this workD we investigte the reonstrutions tht pper for thik deposited gold (lms tht dewet with nneling nd form islndsGdroplets in oexistene with wetting lyer of the order of one monolyer thiknessF

    IV.2

    Experimental results

    IV.2.1 Conditions of formation of the gold reconstruction


    e stndrd experiment onsists in depositing gold (lm of severl wv @typilly U wvA t followed y nneling of the smple @s detiled in ghpter sssAF et the euEi euteti tempertureD the i toms di'use into the islnds whih hve formed during the dewetting of the (lmD nd the system meltsF

    (6x6) (1x1)

    Scans in Figure IV.3

    Si[121]

    (3x3)R30

    Si[110]

    Figure IV.2  Reciprocal space map covering 30 of the reciprocal space (between the silicon

    [1 10] azimuths) recorded in the solid state at RT after a 7 ML deposit performed at RT, annealed and [121]
    at 700 K (liquid) and subsequent cooling. The red colors correspond to high intensities whereas blue ones correspond to low intensities and yellow to intermediate. This map clearly shows the Si monocrystal Bragg peaks (A :(2 ), B :(4 ), C :(2 )) together with the Au polycrystalline Debye20 40 42 Scherrer rings (symbol) as well as the mesh of thin peaks corresponding to the (66) reconstruction.

    he system ws nneled t out UHH uF efter the return t D reiprol spe mpD plotted in pigure sFPD ws reordedF st ws otined y plotting together RVH WV
    rocking-scansD

    IV.2.

    Experimental results

    eh performed t di'erent vlueF his mp displys three ulk frgg peks together with powder di'rtion rings from polyrystlline goldF sn dditionD mesh of smller peks n lerly e seenD orresponding to @TTA surfe periodi superstruture s the smllest unit of the mesh is six times smller thn the one omposed y the i surfe frgg peks in reiprol speF he orresponding struture in rel spe is therefore T times lrgerF yn the mp is lso plotted the reiprol spe unit ell of the @ 3 3AQH reonstrution @ 3 times smllerAF he peks form mesh turned y QH nd re ommon with some of the @TTA reonstrution peksF sn our experimentsD nneling the smple ove e ws found to e neessry step to otin the @TTA reonstrution whih forms upon susequent ooling round TUH uF sf the smple is not nneled high enoughD only @ 3 3AQH reonstrution remins upon ooling hlli
    720 K 680 K 570 K
    Intensity (arb. u.)
    et al.D

    PHIHF
    680 K 710 K 720 K
    Intensity (arb. u.)

    Upon cooling

    Upon heating

    1.3

    1.4

    1.5

    h (r. l. u.)
    (a)

    1.3

    1.4

    1.5

    h (r. l. u.)
    (b)

    Figure IV.3 

    Radial-scans

    performed along the Si[1 21] azimuth at the location highlighted in

    Figure IV.2 on the rst maximum of the liquid signal crossing two (66) peaks. (a) For a 5 ML deposit, annealed at 720 K, 680 K and 570 K. (b) upon heating at 680 K, 710 K and 720 K.

    is

    given in terms of reciprocal lattice unit (r.l.u) dened in the basis of the unreconstructed surface unit cell (see Figure II.8). The two recorded (66) reconstruction peaks are thus located at 1.33 (8/6) and 1.5 (9/6).

    pigure sFQ@A illustrtes this sttement X the radial-scans reorded on the (rst mximum of the liquid signlD long the i[1 zimuthD revel no @TTA peks t UPH uF hey only 21] pper t TVH uF pon further oolingD their intensity inreses to reh mximum t SUH u in the superooled regimeF sf the smple is heted ginD the @TTA reonstrution vnishes round TVH u s it is illustrted in pigure sFQ@AF he @ 3 3AQH to @TTA trnsition is thus found to e reversile nd tkes ple t TVH uF st is however importnt to keep in mind here tht the pperne of the @TTA peks overlp the ones of the @ 3 3AQH reonstrutionF e therefore oserve the formtion of the @TTA reonstrution ut it is WW

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , (

    3 3)R30 Au

    10

    CTR

    *
    Intensity (cps)

    570 K, annealed at 720 K 650 K, annealed at 920 K

    10

    * * * * * *

    10

    CTR

    *
    1.4 1.6 1.8 2.0 2.2

    1.0

    1.2

    2.4

    2.6

    2.8

    h (r. l. u.)
    Figure IV.4 
    and 920 K).

    Radial-scans

    along the Si[1 21] azimuth highlighting the liquid structure factor and

    the (66) signature (stars) for a 30 ML deposit of gold annealed at dierent temperature (720 K

    impossile to know whether or not the @ 3 3AQH is still presentF st is possile tht oth
    re present t the sme time elow TVH uF he sme experimentl proedure ws pplied to smple onto whih QH wv of gold were depositedF efter nneling t UPH u nd ooling down to SUH uD the smple presents nie liquid signl together with lssil @TTA peks s plotted in pigure sFRF hen the smple is nneled t higher temperture @iFe WPH uD elow the gold evportion temperture of IPHH u essel
    et al.D

    PHHQAD highly enhned @TTA signl is mesured upon oolingD

    even t reltively high temperture @TSH uAF nssigned peks @5A re lso reorded nd re ssumed to rise euse of the presene of the Ph eui rystl disovered y hpyrko et
    al.

    hpyrko

    et al.D

    PHHTF he presene of these strutures is disussed in more detils in

    the next hpterF purthermoreD the domins re wider s the prw of the reonstrution peks deresesF sn dditionD the intensities of the rystl truntion rods @whih re)et the i surfe qulityA inrese when the smple is nneled t higher temperture suggesting tht gold n hve potentil in)uene on the tomi orgniztion of the sustrteF his question will e disussed in more detils in the light of dditionl experiments presented herefterF

    IV.2.2 Stability
    huring the sme experimentD ion omrdment @sfA ws performed on the smple in the superooled regime @t THH uAF he @TTA reonstrution peks disppered in only IH s of omrdment @see pigure sFSAD whih implies tht the longErnge ordering of the reonstruE tion ws destroyed in etween the dropletsF he smple ws then kept t onstnt tempeE IHH

    IV.2.

    Experimental results

    Intensity (cps)

    600 K 600 K, 10 s IB 600 K, 6h later 10


    4

    10

    1.3
    Figure IV.5 

    1.4 h (r. l. u.)

    1.5

    Radial-scans

    performed on the rst maximum of the liquid signal and crossing two

    (66) reconstruction peaks (same azimuth as in Figure IV.3) at 600 K : before proceeding to IB, after 10 seconds of Ar+ bombardment and six hours later. Between the three scans, the temperature was kept constant.

    rture @THH uA for round six hoursF efter this period the radial-scan shows the repperne of the reonstrutionF he peks re smller nd widerD inditing tht the reonstrution is less strutured nd presents smller dominsF hese oservtions highlight di'erent fts X IF the system hs to e nneled t lest t TWH uDi.
    e.

    TH u ove Te to form the @TTA lrger

    upon oolingF he @TTA reonstrution is found to pper round TVH u Y PF the higher the smple is nneledD the etter the reonstrution is de(ned @i. domin sizesA Y QF the reonstrution n reEform even t low temperture @THH uA in the presene of gold liquid droplet whih seem to serve s reservoirD s suggested in pigure sFTF
    At 600 K Ar+
    e.

    Au-Si liquid alloy 6 hours later (6x6) reformation

    (6x6) reconstruction
    Destruction of the (6x6)

    Gold diffusion

    Figure IV.6  Scheme illustrating the reformation of the (66) reconstruction at 600 K. Before
    bombardment the droplets of AuSi alloy are surrounded by the wetting layer reconstructed (66) , the reconstruction is then destroyed by ion bombardment, the (66) wetting layer re-forms by diusion of gold atoms.

    IHI

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , (

    3 3)R30 Au

    e similr experiment hs een performed ut in this se the system ws in the solid stteF he ion omrdment ws performed t fter nneling t UPH uF pigure sFU@A displys the radial-scans performed long the i[1 diretion efore nd fter the omrdmentF he 21] omprison of the two sns revels tht the gold peks remin the sme showing tht the gold islnds re un'eted y the sf wheresD s for sf performed in the superooled regimeD the @TTA peks dispper due to the destrution of the surfe strutureF he interesting feture in this se onerns the oservtion of the g evolution s their intensity @nd shpeA yields informtion on the surfe roughness @see ghpter ssAF pigure sFU@A shows n lmost omplete dispperne of the g with the omrdE mentF his mens thtD in ddition to the destrution of the @TTA D the omrdment lso roughens the sustrte surfeF sf the smple is nneled gin t THH uD whih is still elow e D the g intensity is reovered @see pigure sFU@AA X the sustrte9s smoothness improves with nnelingF roweverD the temperture is too low to o'er to the i toms the neessry moility to re(ne the surfeF es we hve seen tht t THH u the eu toms di'use from the droplets to the sustrte surfe nd n reform the @TTA reonstrutionD it is likely tht the smoothing of the sustrte surfe is due to the surfe di'usion of the gold toms whih intert with the i surfe toms nd mke their displements possileF sndeedD it hs lredy een reported tht gold is n e'etive surftnt for the homoepitxil growth of i on i@IIIA sustrtesF e temperture of t lest WPH u is required to form i thin (lms of high qulity on re surfess ellen nd usperD IWVVF roweverD using viih nd utherford ksttering spetrometry @fAD ilk
    et al.

    reported the formtion of

    homoepitxil i (lms through n overlyer of eu t lower tempertures @UPHEUUH uA ilk

    CTR

    Before bombardment After bombardment (111) (200) 9/6

    10

    10

    Before bombardment - RT After bombardment - RT After bombardment - 600 K

    Intensity (cps/s)

    10

    CTR

    8/6

    Intensity (cps/s)

    7/6

    10/6

    10

    10

    *
    1.0 1.2 1.4 1.6

    *
    1.8 2.0

    1.85

    1.90

    1.95

    2.00

    2.05

    h (r. l. u.)
    (a)

    h (r. l. u.)
    (b)

    Figure IV.7  (a)


    (b)

    Radial-scans

    Radial-scans

    performed along the Si[1 21] azimuth, at RT, before and after IB.

    on the Si substrate CTR at RT before IB, at RT after IB and annealed at 600 K.

    IHP

    IV.3. et al.D

    Si(111)-(66)Au structure

    IWWRF imilr results were otined y winod

    et al.

    y depositing the i toms on

    i@IIIAE@SPAeu reonstruted surfe winod

    et al.D

    IWWPF he goldEovered surfe ws

    found to reple the twoEdimensionl growth of i @whih only ours t the domin wlls of the reonstrutionA y the formtion of thin i (lm etween the gold reonstrution nd the i surfeF e similr experiment hs een performed in this workD nd is desried in the setion ssF st shows the lyer y lyer growth of i in the presene of i@IIIAE@TTAeu reonstrution t TPH uF e few ppers hve studied the eui droplets in prllel with the surfe reonstrutionF wieh et
    al.

    wieh et

    al.D

    IWWI pointed out tht the eui droplets re very moile even t

    low temperture @ut ove SSH uAF heir displements were found to leve trks on the sustrte whih prevent the formtion of the @TTA F gonverselyD the @TTA formtion ws oserved to strt t the edges of ig prtilesF he trks formtion hs een explined lter onD thnks to the iw tehnique essel
    et al.D

    PHHQF pon oolingD the i present in exess

    in the droplet is deposited on the sustrteD the prtile migrtes leving trk of i ehind it with horizontl fets orientted @IIIAF he liquidGsolid interfe is therefore ssumed to e very )tF everselyD upon hetingD the prtiles move y dissolution of the i into the dropletsF xow tht the @TTA reonstrution formtion nd stility onditions hve een desriedD we fousD in the next setionD on its tomi strutureF

    IV.3

    Si(111)-(66)Au structure

    IV.3.1 Data collection and symmetry averaging


    a Data collection

    e thin (lm of gold @out U wvA ws deposited t D nneled t UPH u nd susequently ooled down k to F he remining system onsists in polyrystlline gold islnds toE gether with euE@TTA reonstrution s presented in setion sFPFI in pigure sFPF he olletion of the set of dt onsisted in performing highly resolved

    rocking-scans

    on eh

    @TTA re)etionD over IPH segment of reiprol speF ell re)etions were integrted nd monitorD reD vorentz nd polriztion orretions were pplied @see ghpter ssAF he suE strtes9 frgg re)etions nd gs were removed to void ulk ontriutionsD the remining set of dt thus onsists in WUT inEplne reonstrution struture ftors represented in piE gure sFV@AF his (gure lerly revels rottionl nd mirror symmetries whih mens tht equivlent re)etions were reordedF IHQ

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , (

    3 3)R30 Au

    [0 k]

    P3

    [0 k]
    [h k]

    [h k]

    [h 0] -10

    [h 0] 0 10 20 Reconstruction reciprocal lattice units


    (b)

    0 10 20 Reconstruction reciprocal lattice units


    (a)

    30

    30

    [h k] P3m1 Grozea et. al.

    [h k]

    [h 0] 0 4 12 20 8 16 24 Reconstruction reciprocal lattice units


    (c)

    [h 0] 0
    4 12 20 8 16 24 Reconstruction reciprocal lattice units
    (d)

    28

    28

    Figure IV.8  (a) Experimental structure factors. (b) Averaged experimental structure factors
    using

    p3

    symmetry.(c) Averaged experimental structure factors using

    structure factor used in Grozea (66) reconstruction.

    et al.

    [Grozea

    et al., 1998] in p6mm


    h and k

    p3m1

    symmetry. (d) Averaged

    symmetry. The surface of the

    circle is proportional to the reection's intensity.

    are expressed in the reciprocal units of the

    Symmetry and averaging

    he mesurement of equivlent re)etions is not wste of time ut n improvement of the dtset qulity s it llows redution of the systemti error y verging of the equiE vlent intensities peidenhns9lD IWVWF he use of progrm lled ei liegD PHHH mkes possile the verging in di'erent symmetry groupsF pigure sFV@A shows our dt verged in
    p3

    symmetryF st lerly displys mirror plne suggesting tht the dt n e verged

    using more symmetril groupF he ei progrm provides n verge greement ftor orresponding to mesure of the systemti error in the dtsetF his ftor representsD for given symmetry groupD the di'erene etween theoretilly perfetly equivlent re)etions for the reorded dtF por our dtsetD the lowest verge greement ftor is otined for IHR

    IV.3.

    Si(111)-(66)Au structure

    the

    p3m1

    symmetryF he ompiltion of our dt set in this symmetry group redues the


    p3m1

    numer of independent re)etions to RRI with men systemti error of QFW 7F he result is plotted in pigure sFV@A for the symmetryF ell independent experimentl struture ftors re listed in le ss in ennexeF he errors i re lso given together with the theoretil struture ftors dedued from the re(ned model presented in setion sFQFPF he omprison with the experimentl ones is provided y the prtil 2 F

    IV.3.2 Model Evaluation


    a Thickness and domain size

    e quik nlysis of severl @TTA peks yields informtion on the verge domin sizeF sn pigure sFW@A is plotted
    rocking-scan

    performed on one of the most intense frtionlE


    e.

    order @TTA pek for whih vorentzin (t provides prw of HFIHP @i.

    HFHHIV rdF t

    aPFVW 1 AF he verge size of the domin of this reonstrution is thus of IIP nm @expoE nentilly deying orreltion length of ST nmAD whih shows tht the @TTA reonstrution is of high qulityF
    Experiment Fit
    Experiment Fit

    Intensity (x10 cps)

    20

    FWHM ~ 0.102

    0 21.8 22.0 22.2 22.4 22.6 22.8

    Intensity (arb. u.)


    0.5

    40

    1.0

    (deg)

    Qz( )
    (b)

    -1

    1.5

    2.0

    2.5

    (a)

    Figure IV.9  (a)

    Rocking-scan

    performed on the (8/6 ,2/6, 0.096) reconstruction peak.(b) Repre-

    sentative out-of-plane scans performed along the (2/6 ,1/6, l) reconstruction rod.

    pigure @A displys

    l-scan

    performed on @TTA pek @the @2/6 D1/6D lAA nd revels

    slow derese in intensity perpendiulr to the surfeF his is typil for rodElike shpe of signls rising from surfe struturesD the prw @mesured on severl @TTA rodsA indites tht the thikness of this reonstrution is of the order of one monolyerF
    i.

    2F 2 hkl

    2 + stat. ,

    with

    stat.

    the statistical error of the considered reection.

    IHS

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , (

    3 3)R30 Au

    Patterson map

    sn Ery sterringD only the intensity of the re)etions is mesured X the phse is lostF his is the wellEknow phse prolem whih mkes the re(nement of the struture more di0ultF roweverD informtion on the tomi struture n e otined y use of the tterson mpF sn surfe Ery di'rtionD we use the plot of the twoEdimensionl tterson funtion P (x, y) given y X

    P (x, y) =
    h,k

    |Fhk0 |2 cos 2(hx + ky)

    @sFIA

    es lredy mentioned our dtset only ontins frtionlEorder re)etions of the @TTA struture so tht the tterson mp only revels the tomi order of the surfe reonstruE tionF he tterson otined with our dtset is plotted in pigure sFIH with its symmetri unit highlighted in redF he ontour plot revels positive peks orresponding to intertomi vetors of the rel struture peidenhns9lD IWVWF

    Figure IV.10  Experimental fractional-order Patterson function plotted on the (66) unit cell.
    The three arrowed peaks are known to be due to trimer of Au.

    sn le sFI re shown the reltive weights in intertomi distne vetors in the eui system hornish et
    al.D

    IWWI whih indites tht the most intense peks re due to distne

    etween two gold tomsF prom tterson mpD one n therefore derive set of intertomi vetors to uild tril model from whih lulted struture ftors n e otined nd ompred to the experiment @see setion ssFPFPAF eording to our tterson mpD the strongest pek in the irreduile unit orresponds to euEeu distne of out PFV F he three rrows point out three equivlent intertomi vetors of similr lengthF hornish et IHT
    al.

    showed tht they re due to eu trimers tht re the

    IV.3.

    Si(111)-(66)Au structure

    prominent struturl elements of the i@IIIAEeu@ 3 3AQH nd of the i@IIIAEeu@TTA


    strutures hornish et al.D IWWIF sndeedD eu trimers orrespond to three intertomi vetors of sme length rotted y IPH F rowes
    et al.

    lso reported the formtion of eu trimers eing

    t the origin of the sme ontour plot in the tterson mp in the se of the formtion of euE@ 3 3AQH reonstrution on qe@IIIAF rowever the re(ned model proposed y hornish et
    al.

    ws still inompleteF sndeedD using

    lssil methods to determine spei( strutureD one requires to hve strting model lose to the rel oneF his onditionD whih is y the wy quite strongD ensures tht the ssumed phses @impliitly imposed y the tril modelA re lose to the rel onesF e strting model n for exmple e extrted from w mesurementsF woreoverD our tterson mp @see pigure sFIHA displys dditionl peks whih mens tht some other representtive intertomi distnes hve to e onsidered in the modelF hespite the pprent simpliity of the tterson mp nd mny e'orts to propose tril struture sed on eu trimers ompleted with either eu or i toms to (t the other intertomi distnesD no stisftory model ould e deduedF sf proper model from tterson mp n not e proposedD other pprohesD lled diret methodsD n e ppliedF hese diret methods re sed on the lultion of physil properties helping to (nd the most plusile strting modelsF por exmpleD with method sed on the lultion of entropyD qilmore
    et al.

    were le to diretly determine the iE


    et al.D et al.

    @UUA reonstrution from dtset of struture ftors qilmore sme method pplied to the h dt of hornish
    et al.

    IWWUF sing the hve een le to


    al.D

    D qroze

    propose model of the tomi struture of the euE@TTA reonstrution qroze et


    c Direct method renement : Grozea's model

    IWWVF

    frie)yD their method onsists in djoining set of phses to the mesured set of intensitiesF he proposed phses re estimted to e selfEonsistent with (gure of merit orresponding to the most plusile strutureD this ltter eing determined y minimum reltive enE tropy method qilmore
    et al.D

    IWWUF he resulting phsing mpsD lssi(ed ording to the


    i. e.

    greement with the (gure of meritD re the imges of the hrge density

    of the tomi
    e.

    strutureF roweverD in prtieD in the initil stgeD only prtil phsing mps @i.

    only

    Table IV.1  Relative weight of interatomic distance vectors in the Au-Si system [Dornisch
    1991].

    et al.,

    histne vetor euEeu euEi iEi

    Z1 Z2 TPRI IIHT IWT

    elF weight I HFIV HFHQ IHU

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , ( e.

    3 3)R30 Au

    prtil struturesA n e otined nd new toms @i. the est prtil phsing mp hs in pigure sFIIF
    11 2 12 13 14 14

    hrge densityA re dded in the


    et al.

    struture through itertive proesses ontrolled t eh stepF sn the work of qroze


    p3

    symmetry nd revels PH eu tomsF he ompletion

    of the struture y their itertive method resulted in the hexgonl unit lttie represented
    5

    3 6
    1

    11 2

    3 6
    1

    5 9 3

    12

    13

    5 9
    3

    14 2
    14

    1 13 13 12
    2 14

    12
    11

    1
    13

    12 11

    B
    4 7

    10

    4
    8

    13

    14 1

    10

    12 2 10 11

    8 10

    11 6
    5

    7 8 10
    4

    6
    5

    3
    10

    8 4
    9

    3 6

    A
    5 9

    11 2

    11 2

    12

    13 14

    6 1 9

    5 3

    12

    13 14

    3 12 11 7 4
    8

    14 2
    1

    12
    11

    14
    1

    12

    13
    13 14 1

    10

    10

    13 4
    8 13 14 1

    12 2 10
    11

    12 2 10 11

    Figure IV.11  Scheme of the Au-(66) hexagonal lattice (dashed-black line). It is composed of
    45 atoms : 14 independent sites (grey atoms in dashed-blue hexagonal primitive lattice) from which the 28 others can be deduced by the

    p3

    symmetry (the equivalent atoms have the same number).

    The 3 other atoms (green) are the special sites partially occupied (see text). The structure is also completely described by tiling the plane with the highlighted A and B rings which are formed by sub-structural trimers (red) and pentagons (blue)

    he resulting surfe struture otined y qroze et struture with


    p3

    al.

    therefore onsists in hexgonl

    symmetry @lmost

    p31m AF

    sn pigure sFIID the grey toms re the IR


    p3

    independent sitesD the equivlent toms relted y y their nlysisF sn dditionD qroze
    et al.

    symmetry hve the sme numerF sn

    green re highlighted the sites on the symmetry xis hving prtil oupny s reveled mention the presene of twin dominsF wore interestingly this struture is omposed of two kinds of ring sites X the sites e whih re prtilly oupiedD nd the sites f whih present two rottionl vrintsF e omintion of pure empty e rings nd f rings orresponds to struture with 3 periodiityF es mentioned y qroze
    et al.

    D this reonstrution is stonishingly simpleD nd t the

    sme time omplitedF imple euse it displys suEstruturl units omposed of gold triE IHV

    IV.3.

    Si(111)-(66)Au structure

    mers in greement with the struture proposed y hornish

    et al.

    nd omplited euse

    it forms inomplete nd omplete pentgons @pigure sFIIAF sf ll the e sites would e (lledD only omplete pentgons would formF sn ddition to the positions of the gold toms presented in pigure sFIID qroze
    et al.

    lso proposed the re(nement of the i tomi struture in the

    (rst lyers whih were found to e neessry to improve the greement etween the model nd their experimentF heir results pointed out tht the i positions in the (rst lyer di'er lot from their positions in the ulkF sndeedD with only the eu toms tken into ountD with two domins ut without inluE ding speil site tomsD the 2 vlue otined y qroze
    et al.

    is still QPD very fr from the

    idel vlue of IF he ddition of two doule i lyers redued this vlue to VF pinllyD they otined their est greement @2 aQFVA y inluding the gold toms with prtil ouptions @green toms in pigure sFIIA nd strin (eld in the sustrte whih strongly disples the i toms in the (rst lyersF he model of qroze
    et al.

    is ttrtive euse it o'ers tril model for stndrd

    struture re(nement omposed of eu trimers s well s other struturl units tht ould not hve een dedued from the tterson funtion nlysisF sndeedD the presene of the pentgon units n explin why it hs een impossile for hornish
    et al.

    hornish

    et al.D

    IWWI to

    determine the @TTA struture with lssil methods sine ny model tking into ount only trimer units would e too fr from the rel struture nd thus onvited to filF iven if the diret method is very powerfulD severl wek points hve to e mentioned onerning their studyF pirstD their experimentl struture ftors dtset ontins muh less re)etions thn our dtset @out ftor four D see pigure sFV@dAAF eondD their systemE ti unertinty in their mesurements @ IH 7 hornish
    et al.D

    IWWIA is muh higher thn

    our nd despite thtD their 2 vlue remins rther high i F woreoverD the redution of the

    2 hs een otined only through strong ssumptionsF pinllyD the experimentl onditions
    imposed trnsfert of the smple into y hmerD whih ould hve in)uened the resultsF hereforeD in the following we present our struture re(nement of the @TTA reonstruE tionF ith the help of qroze9s model s strting strutureD we onfront this ltter to our own set of Ery dt whih ontins more re)etions @i.
    e.

    less unertintiesAF en importnt

    point is tht our dt were olleted under ompletely di'erent experimentl onditionsD it is thus even more interesting to ompre the two @TTA struturesF

    i. The

    value is inversely proportional to the uncertainty value so that a high uncertainty lowers the

    IHW

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , (

    3 3)R30 Au

    Determination of the structure of the (66) reconstruction Without the Si substrate

    sn the (rst 2 minimiztion ttemptsD only the eu toms were tken into ountF he model used in the (rst evlution simply onsisted in the hexgonl lttie @dshedElkA presented in pigure sFII with RS gold tomsF ell toms were ssumed to hve the sme heyeEller @hA s well s the sme oupny prmeter @even for the speil sitesAF heir displements were llowed with respet to the
    p3

    symmetry whih mens tht the

    speil toms were ssumed to e immoile nd tht the di'erent sets of three relted toms were onstrined in diretions respeting the imposed symmetryF he evlution of this model gives 2 vlue of IHFI whih is very good vlue regrding the simpli(tion imposed in our modelF his greement on(rms tht the struture proposed y qroze quite surprising t (rst sightD is the rel one nd forms in our experimentF ithout giving mny detilsD the pper of qroze
    et al. et al.

    D whih is

    mentions tht the struture

    displys twin dominsF he twin domin n e dedued y mirror pled long the long digonl of the primitive p3 unit ell highlighted in pigure sFII y dshedElue linesD whih is the short digonl of the @TTA unit ellF pigure sFIP shows domin I in whiteD whih orresponds to the struture presented in pigure sFIID nd its twin domin P in yellow through the mirror mF
    11 13 10 7 4 8 10
    7 11

    14 13 14 1 1

    12 3 9 5 6 2 3 5 5 6

    1 14 12 13

    12 2

    2
    4 8 7 11

    11 10

    8 10

    7 4

    6 5

    11

    3 2 13 6 1

    m
    9 6 12 14 2 1

    9 6 3 7 2 12

    10

    8 4 13

    5 9 3

    14

    1 10 13 11 7

    14

    12

    Figure IV.12  Unit cell of domain 1 (in white) and the corresponding unit cell of the twin domain
    (2 in yellow) deduced through a mirror m placed along the long diagonal of the primitive unit cell. Other mirrors can be deduced from the

    p3

    symmetry and correspond to the edges of the unit lattice.

    he other mirrors re dedued y the

    p3

    symmetry nd orrespond to the edges of the


    et al.

    unit lttieF he ddition of n inoherently sttering seond domin in the (t proedure redued the 2 to SFVD on(rming the results desried y qroze F his resultD lredy
    al.

    very goodD n e improved y fousing on the speil sitesF sndeedD qroze et

    pointed out

    tht the gold toms loted on the symmetry xis disply prtil oupny of HFSHRHFHHRF IIH

    IV.3.

    Si(111)-(66)Au structure

    sn our previous (t proessD this e'et hs not een reveled s ll the toms in the model were ssumed to hve the sme oupny vlueF o tke into ount this potentil di'ereneD distint oupny s well s h prmeters were ttriuted to the speil tomsF his led to derese of the 2 vlue down to QFID nd the oupny vlue of the speil toms droped to HFRWHFHISD wheres the oupnies of other toms remined equl to IF hese results demonstrte tht with only gold tomsD the model proposed y qroze
    al. et

    is lredy in very good greement with our h dtF he 2 vlue is even muh etter
    et al.

    in our seD despite the muh lower unertinties in our dtsetF roweverD to improve their

    2 vlueD qroze

    hd to inlude severl i doule lyers sujeted to strin (eld tht

    disples the toms fr from their ulk positionsD espeilly in the (rst lyerF e will see elow if the ddition of i toms in our model n in)uene the 2 minimiztionF
    With a Si substrate

    fy simply dding silion doule lyer elow the gold reonstrutionD t the ulk positionD with n oupny ssumed to e equl to ID the 2 vlue deresed to IFVS with the i toms slightly displed from their originl positionsF his result does not support qroze
    al. et

    9s model s the i toms re not strongly displed from their ulk onesF rowever the

    redution of the 2 vlue shows tht the i toms ontriute to the di'rted signlD even if their ontriution remins wekF e lst (t ws performed with i doule lyer with the positions given y qroze
    et al.

    D in this seD with the oupnies of the euD speil eu nd i toms ssumed to e ID HFRW nd I respetivelyD the (nl 2 vlue is IFQD with still very slight displements with respet to qroze9s positions oserved during the (ttingF roweverD the smll di'erene etween the two

    2 vlues @IFVS nd IFQA does not llow to de(nitely hoose this lst model whih seems to
    e less physil euse of the lrge displements of the i toms with respet to their ulk vluesF hespite the ft tht the eu toms seem to hve n in)uene on the position of the i toms in the (rst lyer of the sustrteD our experimentl dt would mke us elieve tht the preferred solution is the one for whih the i ulk positions re onservedF he tomi positions otined in the lst two (ts n e found in le P nd Q in ennexeF he (nl inEplne h vlue of nonEspeil surfe gold toms ws found to e IFQ0.04 2 whih is twie its ulk vlue @HFT 2 ers nd helleyD IWWIAF emrklyD the inrese y ftor of two to three times of the ulk h term for surfe toms hs lredy een oserved during the nlysis of the euE@ 3 3AQH reonstrution lss nd wrksD IWWSF st hs een ttriuted to the lk of neighours providing dditionl degrees of freedom to the toms to virteF roweverD the h term for speil eu toms nd i toms ould not e re(nedD presenting very low @ H 2 A i nd very high @ P 2 A h termsD respetivelyF
    i. This very low value might be implied by the 3-fold symmetry axis onto which these atoms sit.

    III

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , (

    3 3)R30 Au

    [h h]
    Exp.

    Mod.

    [h 0] 0

    12 20 4 8 16 28 24 Reciprocal lattice units of the (6x6) reconstruction

    Figure IV.13  Experimental structure factors (in black), together with the nal model structure
    factors (in white). The circles are of same sizes ( nal agreement

    i. e. same intensity) for all reection illustrating the

    of 1.3.

    hrough this model evlution we hve thus shown tht the struture proposed in the pper of qroze
    et al.

    grees very well with our mesurement @see pigure sFIQAF st is prtiE

    ulrly interesting to note tht prtil oupnies of speil toms s well s twin domins re fully on(rmed y our nlysisF woreoverD it mens tht this prtiulr struture lso forms in our experimentl onditions whih onsist in thik deposit t nneled nd then ooled downF wo spei( fetures hve however to e disussed here in more detilsF st onerns the positions of the i toms nd the prtil oupnyF es the experimentl investigtion hve shown to reh their limits onerning these questionsD they re disussed in the light of the simultion results whih o'er the possiility to go eyondF sndeedD the simultions support the ft tht the i toms of the (rst lyer re strongly displed in the presene of the @TTA reonstrutionF woreoverD wheres the y were found to form in the se of thik eu rystl in ontt with i sustrte terminted y i doule lyerD the @TTA struture is found to form through deep reErrngement of the (rst lyerF his ltter looses its surfe ulk struture nd form distorted trimers distriuted in n orgnized mnner within the @TTA unit ell xogretD to e pulishedF he prtil oupny @ HFSA of the speil toms requires more ttention tooF sndeedD this vlue needs to e relted to physil mening nd indites tht eu tom n e present or not t this speil position in equl proportionF his vlue is not ttriuted to the presene of vny in one of the speil site in the struture s (t performed with this onstrin results in the inrese of the 2 vlueF st rther indites the oexisteneD in equiE proportionD of @TTA ells with the speil sites fully oupiedD nd @TTA ells with speil sites unoupiedF his ssumption hs een on(rmed y the energeti study of the @TTA IIP

    IV.3.

    Si(111)-(66)Au structure

    reonstrution performed y

    ab-initioF

    he lultions point out tht the overll struture

    is mix of n unfulted struture with H7 oupny nd fulted struture with IHH7 oupny for speil tomsD the surfe energy of the fulted struture @HFRHT tFm2 A eing higher y only PP mtFm2 ompred to the unfulted one @HFQVR tFm2 A xogretD to e pulishedF st is worthwhile to mention tht the euE@TTA reonstrutionD omining gold trimer nd pentgon unitsD hs een oserved y w during the study of the lotion of sorption site on this struture tlohowskiD PHHQF his study on(rms ll the min fetures desried in the model presented ove with nune onerning the speil sites t the orner of the unit ell whih re supposed to e sent of the strutureF his is however surprising s the 2 inreses y ftor three if their oupny is (xed t H in our model evlutionF xevertheless the energy of this unexpeted struture whih looks more like twoEdimensionl pseudoEglss hs een lulted in our
    ab-initio

    simultions nd found to e energetilly

    fvorle with HFRI tFm2 ompred to the IFS tFm2 for the nominl i@IIIA surfeF
    e Discussion on the (66)

    ( 3 3)R30

    transition

    hespite wide literture overing the reonstrutions in the euEi@IIIA system @see seE tion sFIA nd the results presented in this hpterD there re still open questions onerning the potentil reltionships etween the @TTA nd the @ 3 3AQH reonstrutionsF e remind here tht the trnsition etween the @TTA nd the @ 3 3AQH reonstrution is reversile nd ours round UHH uF roweverD elow UHH u we n not onlude tht the @ 3 3AQH hs disppered euse its reonstrution peks re overlpped y those of the @TTA F woreoverD the tomi proesses governing the trnsition etween the two struE tures re unknownF huring our experimentsD peulir sttering signl tht seems to e relted to oth reonstrutions hs een reordedF pigure sFIR is zoom on the low Q vlues of the solid mp plotted in pigure sFPF wo rrows highlight the presene of some kind of di'use rings tht surround the @ 3 3AQH reonstrution peksF heir rdius is of the length of the @TTA reiprol unit ell nd their intensity is orientted towrd the origin of reiprol speF his kind of rings hve lredy een oserved in viih studies khshi
    et al.D

    IWWIY rigshiym

    et al.D

    IWVT ut t

    high tempertures @round THH uA so tht they were ttriuted to kind of disorder implied y the ompetition etween the @TTA nd @ 3 3AQH struturesF roweverD in our seD they were reorded fter the return t D the system ws therefore lredy solidi(ed nd the tomi di'usion very lowF woreoverD if one looks it loserD they re tully not rings of onstnt intensity ut more omposed of di'use intensity linking two @TTA peks with mximum in etweenF et the momentD no ler struture n e proposed to explin this IIQ

    Chapter IV.

    Au-induced reconstructions of Si(111) : (66)Au , (

    3 3)R30 Au

    (6x6) Diffuse rings

    Si[121]

    (3x3)

    Si[110]
    A
    Figure IV.14  Zoom on the map plotted on Figure IV.2 highlighting the orientated diuse rings
    surrounding the common (66) and (

    3 3)R30

    reconstruction peaks.

    kind of intensity distriutionD howeverD it might e relted to unexplined fetures lredy reportedF ome studies report viih di'rtion ptterns tht do not orrespond to w imges lvn
    et al.D

    IWVSY kmi

    et al.D

    IWWR whih implies tht some re of the smples

    n lolly present frustrted struturesF sn our seD it ould orrespond to domins ompoE sed of @TTA unit ells turned y QH with respet to the i@IIA strutureDi. e. prllel to the @ 3 3AQH unit ellF wye some kind of domin wlls etween remining @ 3 3AQH domins nd @TTA dominsF
    In this chapter are described the experimental results concerning the conditions of formation of the (66) reconstruction as well as its stability. It is found to form around 680 K upon cooling and its structure has been determined using quantitative SXRD with important precisions brought by the simulations. Interestingly the (66) reconstruction has been found to re-form at 600 K by surface diusion of the Au atoms of the droplets. It means that the AuSi droplets can be supercooled at least down to 30 K below the eutectic temperature. The next chapter describes the dierent observations concerning the AuSi droplets and their tendency to supercooling depending on the substrate's structure.

    IIR

    IV.3.

    Si(111)-(66)Au structure

    Summary of Chapter IV
    Experimental results :

    he @TTA reonstrution is found to form during the ooling proess round TVH uF he
    proess is reversile X if the smple is heted ginD the @TTA disppers round UHH uF

    he higher the smple is nneledD the etter the reonstrution is de(nedF efter hving een destroyed y ion omrdment in the superooled regime @THH uAD the
    @TTA reonstrution reforms thnks to the di'usion of eu toms from the droplets to the re sustrteF

    he reovering of the i surfe y nneling only to THH u shows tht the wetting lyer
    of gold improves the moility of the i tomsF
    Determination of the (66) structure :

    he olletion of the dt hs een performed t nd onsists in WVH re)etions inteE


    grted nd orretedF

    he verging of the dt results in systemti error of QFW 7 in the


    group reduing the numer of independent re)etion to RRIF

    p3m1

    symmetry

    he study of severl @TTA rods shows tht this reonstrution is I wv thik with domins
    of out TH nmF

    he tterson mp shows the hrteristi peks relted to the trimer unitsF he other
    peks re impossile to ddress with simple modelF

    he determintion of the struture is done with strting model proposed y qroze


    al.
    2

    et

    who hd very high unertinty on their dtD minimiztion of the vlue thnks

    to strong ssumptions nd ompletely di'erent experimentl onditionsF

    he resulting gold struture onsists in two dominsD omposed of trimer nd pentgonl


    unitsD relted y mirrorF ome speil sites present prtil oupny of HFS implying tht they re present in one domin ut not in the otherF

    yur experimentl dt do not provide enough detils to hoose etween the two est models
    di'ering in the positions of the i toms @ulk position X 2 aIFVD position of qroze
    al. et

    X aIFQAF
    2

    he simultion results tend to on(rm tht the i toms of the (rst lyer re strongly
    displed from the ulk positions nd form distorted trimers displying long rnge orderF

    IIS

    Chapter V Supercooling in AuSi droplets


    Contents
    V.1 On Si(001) substrates . . . . . . . . . . . . . . . . . . . . . . . . . . 117
    V.1.1 V.1.2 V.1.3 Si(001) substrate's structure . . . . . . . . . . . . . . . . . . . . . . Supercooling on the Si(001) surface . . . . . . . . . . . . . . . . . . Solid structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 118 119

    V.2

    On Si(111) substrates . . . . . . . . . . . . . . . . . . . . . . . . . . 120

    V.2.1 V.2.2

    Supercooling on Si(111)-(

    3 3)R30 Au

    reconstruction

    . . . . .

    120 121

    Supercooling on Si(111)-(66)Au reconstruction

    . . . . . . . . . .

    V.3

    Study of the liquid structure . . . . . . . . . . . . . . . . . . . . . . 124


    V.3.1 V.3.2 Experimental study Simulation results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 128

    V.4

    Study of the size eect . . . . . . . . . . . . . . . . . . . . . . . . . 132

    V.1.

    On Si(001) substrates

    hroughout the two previous hptersD we hve seen tht the dewetting of thin gold (lm leds to the formtion of islnds nd then to droplets when pssing through Te F sn dditionD the @TTA reonstrution n form upon ooling if the system is nneled high enoughF sn our experimentsD when ooling down the smplesD di'erent solidi(tion tempertures were reorded depending on the experimentl onditionsF his hpter presents the di'erent reE sults onerning the superooling e'et mesured for eui droplets on i@HHIA @setion FIAD i@IIIAE@TTAeu nd i@IIIAE@ 3 3AQH eu surfes @setion FPAF xote here tht in lE most ll the ses the solidi(tion proess is found to extend in given rnge of tempertureF he solidi(tion is found to strt t given temperture @i.
    e.

    some of the droplets hve

    solidi(edA nd to e ompleted t lower temperturesF sn eh seD we desrie the ppeE rne of the (rst grins nd the reorded omplete solidi(tionF por omprison etween the di'erent experiments the solidi(tion temperture Ts is tken s the lowest oneD for whih ll the droplets re solidi(edF

    V.1

    On Si(001) substrates

    V.1.1 Si(001) substrate's structure


    es it hs een done for the i@IIIA sustrteD we present in pigure FI the i@HHIA sustrteF his orienttion yields four fold symmetry t the surfeD with the surfe unit vetors eing [100] nd [010]F hue to the de(nition of the reiprol lttieD the determintion of the reiprol surfe unit ell in the se of ui symmetry is simple s it leves ll vetors unhnged through the trnsformtion @ut their lengthAF
    Si(001) surface lattice [010]
    a = 5.4903

    Si(001) reciprocal lattice [010]


    [110]

    [110] (040)
    (440)

    (220) (400) [001] [100] [001] [100]

    Figure V.1  Scheme of the atomic arrangement in a the cubic symmetry of the Si(001) plane.
    The surface unit vectors are represented in red (plain).

    i@HHIA sustrtes thus di'er t the tomi sle from the i@IIIA leding to severl IIU

    Chapter V.

    Supercooling in AuSi droplets

    physil di'erenes etween the two orienttionsF por exmpleD the tomi density is di'erent etween the two orienttionsD thus they do not present the sme eletroni densityF es onsequeneD the rerrngement of the surfe toms is only omposed of dimersD leding to @PIA reonstrution on i@HHIA insted of @UUA on i@IIIAF he surfe energy of i@HHIA is higher thn tht of i@IIIA @see ghpter sAD the growth of gold is therefore expeted to e di'erent s well s the wetting onditions essel
    et al.D

    PHHQF enother di'erene lies in the

    sene of euEindued surfe reonstrutions of i@HHIAF o ompre with the extensively studied euEi@IIIA system presented lterD we performed typil experiment on the i@HHIA sustrte y deposit t of out V wv nd susequent nneling to form eui droplets through dewetting nd melting t the euteti tempertureF he superooling ehviour nd the solidi(tion struture hve een investigted s presented herefterF

    V.1.2 Supercooling on the Si(001) surface


    efter the oservtion of the melting proess y the formtion of the eui euteti liquidD the smple ws nneled RH u ove Te D i.
    e.

    t TUH uF st ws then ooled down to reord the

    temperture t whih the solidi(tion proess tkes pleF he radial-scans performed long the iIIH zimuth t TUH uD SVH u nd SSH u re plotted on the grph in pigure FP@AF et TUH u it displys liquid struture with the pperne of the (rst grins of gold @the eu@PPHA pek strts to growA t SVH uF he omplete solidi(tion proess is then oserved t SSH uD whih is VH u elow Te D with the pperne of the eu@IIIAD eu@PHHA nd eu@PPHA peks supporting the retion of polyrystlF
    670 K 580 K 550 K Si(220) (220)
    10
    4

    Si(220)

    (220)

    670 K 640 K 600 K

    Intensity (cps)

    (111)
    10
    4

    Intensity (cps)

    (111)
    10
    3

    (200)

    (311)

    (200)

    (222)
    2

    10
    10
    3

    2.5

    3.0

    Q ( )
    (a)

    -1

    3.5

    4.0

    4.5

    2.5

    3.0

    3.5

    Q ( )
    (b)

    -1

    4.0

    4.5

    5.0

    Figure V.2 
    720 K.

    Radial-scans

    along the [110] azimuth (a) at 670 K, 580 K and 550 K, for a 8 ML

    deposit, annealed at 670 K and (b) at 670 K, 640 K and 600 K, for the same deposit annealed at

    hen the smple ws heted ginD ut this time the mximum nneling temperture IIV

    V.1.

    On Si(001) substrates

    ws UPH uF pigure FP@A shows the

    radial-scans

    still performed long the iIIH diretion

    during ooling down of the smple from this tempertureF snterestinglyD in this se the solidi(tion tkes ple t THH u whih is only QH u elow e F

    V.1.3 Solid structure


    efter return t D the system is in the solid stte nd reiprol spe mp ws reordedF hue to the sustrte symmetryD the mp overs in this se RS of reiprol spe nd is plotted in pigure FQF gompred to the solidi(tion of eui lloy onto i@IIIA sustrte @see pigure sFPAD the solid gold is found to e very textured on the i@HHIA with ler ue on ue epitxy X the eu@PPHA ring intensity is onentrted on the iIIH diretion while the mjority of the eu@PHHA intensity @s well s the of eu@RHHAA is loted on the iIHH zimuthF herefore the lerly preferred y etween the solidi(ed eu nd the i@HHIA surfe is X IHHeu@HHIA IHHi@HHIAF
    [110] Au(420) Au(331) Au(222) Au(311) Au(220) Si(220)

    [100] Au(111) Au(200) Si(400)

    Au(400)

    Figure V.3  Reciprocal space map of solidied Au on Si(001) substrate.

    hese results show tht in the se of the i@HHIA sustrteD the higher the nneling the lower the superooling nd the resulting solid islnds re mde of grins displying prllel inEplne epitxil reltionship with the surfeF e higher nneling leds to onentrtion hnges in the droplets s well s in their sizeF he in)uene of the nneling temperture relted to the droplet size thus seems to e prmeter tht hs to e tken into ountF st is disussed in the next setion in the light of the results otined on i@IIIA sustrtesF IIW

    Chapter V.

    Supercooling in AuSi droplets

    V.2

    On Si(111) substrates

    pigure FR is guide to the eyes for ler overview of the di'erent signls enountered during the mesurementsF sn the previous hpter @ghpter sAD the grphs were plotted s funtion of the reiprol lttie units to simplify the indextion of the reonstrution peks tht re loted on frtionl ordersF sn this hpter s well s in the next oneD grphs re plotted s funtion of the momentum trnsfer @1 A whih llows omprisons in more generl sesF
    _ [121]

    Si Bragg Au rings (3x3)R30 (6x6)

    CTR

    Si-(1x1)

    5.66
    _ (242)

    3.78

    5.38 5.06 4.74 4.42 4.1

    3.49 3.17 2.85 2.53 1.89 2.21

    1.6 1.28 0.96 0.64 0.32 0.55 1.09 1.65

    2.18
    (111)

    2.75
    (200)

    _ (220)

    3.85
    (220)

    4.36

    4.95
    (311)

    5.45

    6.05

    _ (440)

    _ [110]

    2.66

    3.08

    3.27

    4.35

    5.10

    6.54

    Figure V.4  Scheme representing the 30 (between the Si[1 and Si[1 azimuth) of reciprocal 10] 21]
    space required to get a clear overview of the dierent signals encountered during the measurement (see Figure IV.2). The positions of Si Bragg peaks, CTRs, (66) or (

    3 3)R30

    reections and

    1 ). Au Debye-Scherrer rings are given in the space of momentum transfer Q (

    he mp of pigure FR therefore llows to quikly visulize the di'erent signls reorded in the snsD espeilly the numerous reonstrution peksD long the i[110] nd i[1 21] zimuthsF his highlightsD for exmpleD tht the @ 3 3AQH reonstrution peks n only e reorded long the [1 diretionF elong the other diretionsD they overlp with the 10] gs nd the frgg peksF

    V.2.1 Supercooling on Si(111)-(

    3 3)R30 Au

    reconstruction

    sn ghpter s we hve seen tht on i@IIIAD eui droplets oexist with wetting lyer reonstruted either @ 3 3AQH or @TTA F sn the se of gold deposits of the order of T wvD we hve seen tht neessry step to form the @TTA reonstrution during the ooling down ws minimum nneling of out TH u ove Te D otherwise only the @ 3 3AQH IPH

    V.2.

    On Si(111) substrates

    (111)

    Si(220)

    (220)

    (111)

    Intensity (arb. u.)

    690 K 660 K

    530 K 500 K

    Intensity (arb. u.)

    (200)
    (3)

    640 K 560 K 540 K

    * *

    (3)

    (200) (220) (CTR)

    2.5

    3.0 -13.5 Q(A )


    (a)

    4.0

    4.5

    2.5

    3.0 3.5 -1 Q ( )
    (b)

    4.0

    4.5

    Figure V.5  (a)


    (b)

    Radial-scans

    performed along the

    [110]

    azimuth (along which the (

    3 3)R30

    peaks can be observed) at 640 K, 560 K and 540 K, for a 5 ML deposit after annealing at 640 K.

    Radial-scans

    along the

    (66) reconstruction

    [121] azimuth at 690 K, 660 K, 530 K and 500 K for a 6 ML deposit. The peaks are marked by .

    reonstrution is otinedF sn the followingD we ompre the superooling ehviour of the eui droplets in presene of either @ 3 3AQH or @TTA reonstrutionF huring the mjority of the ooling experimentsD the temperture ws redued y steps of IH u nd meE surementsD suh s tion of the proessF sn (rst experimentD deposit of S wv of gold ws performed nd nneled only IH u ove Te to prevent the formtion of the @TTA upon oolingF pigure FS@A presents three radial-scans reorded long the [110] zimuth t TRHD STH nd SRH u during the ooling proE essF yn eh sn the @ 3 3AQH peks re visile nd no @TTA peks re oservedF et TRH uD the system is in the liquid stte nd the (rst solid grins pper t STH uF he omplete liquidEsolid trnsition of the droplet sets in t SRH u whih is WH u elow Te F
    radial-scansD

    were reorded t eh tempertureF roweverD for lrityD the

    grphs disply only spei( tempertures whih re elieved to e essentil for the desripE

    V.2.2 Supercooling on Si(111)-(66)Au reconstruction


    sn nother experimentD T wv were deposited t nd nneled t TWH uF his nneling temperture ws hosen euse it ws found to e the lowest vlue to form the @TTA upon oolingF his hoie therefore redues potentil e'et due to the di'erene in the nneling nd llows loser omprisons with the previous experimentF pigure FS@A gthers radialscans reorded long the [1 21] zimuth during the ooling proessF his diretion hs een hosen in order to see the @TTA peks @mrked with strA nd t the sme time to void IPI

    Chapter V.

    Supercooling in AuSi droplets

    Solid
    Intensity (arb. u.)

    (6x6) (3x3) Si(001)

    Liquid
    480 520 560 600 640 680 720 Temperature (K)
    Figure V.6  Schematic evolution of the Bragg intensity highlighting the solid-liquid-solid phase

    transition cycles for Si(001), Si(111)-(

    3 3)R30 Au

    and Au on Si(111)-(66)Au substrates.

    the i@PHA frgg pekF et TWH uD ll the droplets re in the liquid stte s on(rmed y the 2 sene of gold peksF et TTH uD the formtion of the @TTA reonstrution tkes ple nd on(rms the results presented in ghpter sssF et SQH uD whih is IH u nd PH u elow the solidi(tion tempertures with the @ 3 3AQH reonstrution nd the i@HHIA surfeD the pperne of the (rst grins hppensF woreoverD the intensity of the @TTA reonstrution peks hs lso inresedF pinllyD the omplete rystlliztion of the system ws otined only when it ws ooled down to SHH uD
    i. e.

    IQH u elow Te

    snterestinglyD the overll proess s well s the di'erent remrkle temperture vlues were found to e reproduile when strting over solidEliquidEsolid trnsition yleF st is therefore possile to represent these results y plotting the eu@PPHA re)etion intensity s funtion of temperture @see pigure FTAF he urves present n hysteresis shpeD the width of the loop illustrting the superooling pityF woreoverD for the ses investigted so frD
    i. e.

    T wv nneled t di'erent tempertures on di'erent surfesD the hysteresis urves

    show liquidEsolid trnsition tht extend over rnge of temperture of out RH uF his point will e disussed in setion FR in terms of droplets9 size nd reonstrution qulityF roweverD pigure FT lerly indites tht the superooling ehviour of the eui euteti droplets is in)uened y the sustrte orienttion ndGor reonstrution typeF sn ddition to the superooling mesurements desried oveD some remrkle fetures were reorded during the ooling down of the smplesF st hs een presented if ghpter s tht eui Ph rystl hs een reported to form t the surfe of the eui euteti liquid lloy hpyrko
    et al.D

    PHHTY wehler

    et al.D

    PHIHF pigure FU@A is grph on whih re


    et al.

    superposed our liquid struture ftor mesurement in the underooled regime @round THH uA nd the ones @t low nd high tempertureA performed in the work of hpyrko for low

    Q vlues hpyrko
    IPP

    et al.D

    PHHUF yur sn in this se is reorded outside symmetry xis to

    V.2.

    On Si(111) substrates

    void reonstrutions or frgg peksF yur reorded peks re t the positions of the ones mesured y hpyrko
    et al.

    D orresponding to low temperture Ph rystl phse )oting

    t the surfe of the eui euteti liquid @see setion sFUAF st thus seems here tht this two dimensionl rystl is lso present t the surfe of the liquid droplets in our seF sn dditionD in the following grphs plotted in the next setion the pek t QFPU 1 D highlighted with little tringle ove itD should not e tken s reonstrution pekF his pek is present even t high tempertures nd lso orresponds to surfe Ph rystl phse i F
    This study

    Intensity (arb. u.)

    [Sphyrko et al.] low T phase [Sphyrko et al.] high T phase


    2

    Intensity (.10 cps)

    720 K 630 K 610 K 590 K 570 K

    1.0

    Q(A )
    (a)

    -1

    1.5

    2.0

    2.2

    2.4

    2.6 2.8 -1 Q ( )
    (b)

    3.0

    3.2

    Figure V.7  (a) Superposition of our experimental liquid structure factor and the ones extracted
    from the paper of Shpyrko

    et al.

    [Shpyrko

    arising from a 2D AuSi crystal.(b)

    on the Si[1 21] azimuth and focusing on the rst order of the liquid structure. The narrowing of the peak indicates a decrease in the standard deviation of the mean inter-atomic distance in the liquid and thus illustrates the ordering of the liquid.

    et al., 2007] revealing the correspondence between peaks Radial-scans for several temperatures upon cooling, performed

    enother speil feture onerns the evolution of the liquid nd the @TTA reonstrution signls with the derese of the tempertureF pigure FU@A shows sns performed on the (rst order of the liquid struture ftor for di'erent tempertures during ooling nd efore solidi(tion @long the i[1 zimuthAF st revels tht the liquid pek gets nrrower nd 21] inreses in intensity with deresing tempertureF he nrrowing of the liquid is due to less dispersed vlue of the men distne etween two (rstEneighour toms nd thus unE derlines the ordering of the toms in the liquidF et the sme timeD the @TTA reonstrution peks re lso found to inrese in intensity illustrting the improvement of the qulity of the reonstrutionF
    i. It is however impossible to distinguish between the low T or the high T structure as in the work of Shpyrko, two peaks can be found at this position, each one corresponding to a dierent phase.

    IPQ

    Chapter V.

    Supercooling in AuSi droplets

    sn this setionD very importnt results were otinedF pirstD for similr mount of gold depositedD the resulting eui liquid droplets re found to present muh lrger superooE ling ehviour in the presene of @TTA reonstrution @Ts aSHH uA ompred with the @ 3 3AQH reonstrution @s aSRH uA or the i@HHIA sustrte ii @s aSSH uAF sn ddiE tionD two dimensionl eui rystl is ssumed to e )oting on the surfe of the liquid dropletsF pinllyD the ordering of the toms in the liquid upon ooling is reorded in prllel with the improvement of the reonstrution qulityF es the superooling e'et is lrger in presene of the @TTA reonstrutionD we elieve tht it n in)uene the liquid ehviour nd thus the solidi(tion proessF he next setion is therefore devoted to the study of the liquid struture in the presene of the @TTA reonstrutionF

    V.3

    Study of the liquid structure

    e hve seen in ghpter s @setion sFVFPA tht solid n in)uene liquid9s strutureD t lest in the (rst lyersF he @TTA reonstrution presents trimers of pentgons nd is found to e very stle @see ghpter sAF es it hs een shown tht the superooling ehviour of liquid n e in)uene y the pperne of the ioshedrl short rnge order @see setion sFSFPAD the underlying ide ppering here is tht the reonstrutionD due to its spei( strutureD n in)uene the formtion of (vefold lusters into the eui dropletsF he retion or the inrese of this order would led to the stiliztion of the liquid phseF o see whether or not this ide is relevntD experimentl mesurements nd simultions were performed to get more informtion on the inner struture of the liquidF

    V.3.1 Experimental study


    sn pigure FV is plotted the reiprol spe mp of the eui system in the liquid stte in the superooled regime fter nneling t UPH uF st displys the i frgg peksD the @TTA reonstrution peks nd three rings tht orrespond to the (rst three essile mxim of the essile liquid struture ftorF he rdil struture ftor of the liquid is extrted y performing the ngulr verge of the experimentl liquid intensity whih is similr to the pir orreltion funtion @see setion sFRAF e (rst step to know whether or not the liquid struture n e ompred to the @TTA struture is to derive the men struture ftor of this ltterF o do soD the intensities of ll mesured @TTA di'rtion peks ontined in HFHS 1 intervls of the reiprol mp were summed upF he result of this opertion is represented y the lk rosses in pigure FW@A in wy tht eh ross orresponds to
    ii. onto which no gold reconstruction is reported.

    IPR

    V.3.

    Study of the liquid structure

    Angular average
    a

    Si(242)

    Si(440) Si(220)
    and

    Si(111) Au(6x6)
    [110]

    Figure V.8  Reciprocal space map covering 30 of reciprocal space (between the silicon

    [1 21]

    azimuth) recorded in the supercooled state. The red colors correspond to high intensities

    whereas blue correspond to low ones and yellow to intermediate ones. This map displays the Si monocrystal Bragg peaks and a mesh of thin peaks corresponding to the (66) reconstruction already observed in the previous chapter. The three intense rings correspond to rst, second and third order of the liquid structure factor which can be extracted by an angular average of the intensity.

    the totl @TTA intensity enountered in the hosen intervlF he smoothening of the disrete hrteristis of the signl is performed y fst pourier trnsform whih lowers the high frequeny omponents nd results in representtive urve of the rdil intensity distriutionF he extended shoulder on the seond order is hrteristi of the pentgonl order present in the reonstrution hdev nd xelsonD IWVRY uelton
    et al.D

    PHHTF

    Experimental: liquid at 560 K Simulated: liquid at 600 K Averaged (6x6)

    S(Q)
    1 0 2 3 4

    Q ( )
    (a) (b)

    -1

    Figure V.9  (a) Summation of all the measured intensity arising from the (66) reconstruction (black crosses) and result of the Fourier transform illustrating its radial intensity distribution (red) (b)Plot of the structure factor of the experimental liquid, simulated liquid and a hypothetical structure factor by averaging the (66) reconstruction peaks.

    IPS

    Chapter V.

    Supercooling in AuSi droplets

    Weak liquid signal

    Intense (6x6) peaks


    Scanned part at different Q values in Fig.V.11

    Strong liquid signal

    Figure V.10  Zoom on the rst order of the liquid structure factor. The intensity increases in the
    vicinity of intense (66) reconstruction peaks reecting local similarities between the two structures.

    he experimentl liquid struture ftor in its superooled stte is plotted on the grph in pigure FW@A together with the theoretil struture ftor of the simulted liquid t THH u provided y
    ab-initio

    lultions performed y eF sturelF he two liquid struture

    ftors re in very good greement whih on(rms the ury of the moleulr dynmis simultions of this systemF sn ddition is plotted the rdil intensity distriution of the @TTA reonstrutionF st ompres well to the experimentl nd theoretil struture ftors pointing out the presene of similr intertomi distnes in the @TTA reonstrution nd the liquidF hen looking loser t the (rst order of the liquid in the mp of pigure FV we remrk n inEplne nisotropy of the intensity distriution from the liquid @see pigure FIHAF iven more interestingD the liquid signl is enhned in the viinity of the strongest @TTA reonstruE tion peksF his oservtion suggests tht struturl similrities etween the reonstruted interfe nd the djent liquid lyers my exist in wy tht the liquid tends to dopt the struture of the reonstrutionF he dshed rrow in pigure FIH indites the diretion of the reiprol spe long whih the sns presented in pigure FII@A nd @A re performedF wore preiselyD it orresponds to the sn noted 1D performed long this diretion nd in the plneD
    i. e.

    t Q 0 1 F he sns 2 D3 nd 4 re performed long the sme inEplne

    zimuth ut t di'erent vlues of Q X IFQRD P nd PFTV 1 D respetivelyF he @TTA reonstrution is I wv thik surfe strutureD its di'rted intensity thus orresponds to mesh of rods perpendiulr to the surfe in the reiprol speF he vertiE l dshed lines in pigure FII@A represents two intense rods existing on the diretion onto whih the sns re performedF elong eh sn of pigure FII@AD the intensity of the two @TTA rods re therefore reordedF es fr s the liquid droplets re onernedD the resulting di'rted signl is di'erentF sn reiprol speD the di'rted intensity of n isotropi liquid is distriuted t the surfe of sphere hving rdius inversely proportionl to the men distne etween two nerest neighour tomsF his spheril intensity distriution hs (nite thikness due to the deviE IPT

    V.3.

    Study of the liquid structure

    Q
    3 2.68

    (-1)

    Intensity distribution

    Measurements

    (a)
    4

    (b)

    1.24 1

    2 Isotropic liquid Interfacial liquid (6x6)

    ~0 0

    1 1 Q|| ( )
    -1

    2.4

    2.6

    2.8
    -1

    3.0

    Q|| ( )

    Real space

    (c)

    Si(111)

    Si(111)

    Figure V.11  (a) Scheme of the distribution of the intensity in the (Q ,Q ) plane in the direction
    of the dashed arrow in Figure V.10. (b) Scans corresponding to the arrows plotted in (a), performed in the plane (scan (scans

    1) and parallel to it for several values of out-of-plane momentum transfer,

    2, 3 and 4). (c) Representation of the system with equivalent colors between the diracting

    structures and the corresponding intensities.

    tion of the men interEtomi distneF st is represented in pigure FII@A y the yellow re whih is the utD in the studied plneD of one fourth of the liquid sphereF n 1D performed in the plneD therefore displys the liquid signl in the middle of the two @TTA reonstruE tion peksF n 2D reorded t Q = 1.24 1 D lso displys the @TTA signl euse of their rod shpe distriutionD ut the liquid signl is shifted to the left in greement with its spheril shpeF sn sns 3 nd 4D the @TTA reonstrution signl is still mesured wheres the mximum of the liquid intensity is no longer within the snned rngeF roweverD in sns 2D 3 nd 4D n unexpeted ump of intensity is still reorded etween the two @TTA reonstrution peksD t the inEplne position of the (rst mximum of the liquid struture ftorF e remining intensity t this inEplne position tht does not vnish long Q highlights the presene of rod t the position of the liquidF st therefore revels IPU

    Chapter V.

    Supercooling in AuSi droplets

    the presene of strutured interfil liquid in the droplet @liquid rod in pigure FII@A nd @AA whose lterl short rnge order is in)uened y the @TTA reonstrution @see piE gure FIHAF sn other wordsD the system seems to orrespond to liquid droplets in the presene of @TTA reonstrution tht n in)uene the struture of the liquid t the solidEliquid interfe s represented in pigure FII@AF st hs een shown in ghpter s tht the @TTA reonstrution is omposed of trimers of pentgonsF e thus propose tht the in)uene of this reonstrution on the struture of the liquid onsists in helping the formtion of Eor stilizing preEexistingE (veEfold lusters tht fvor the liquid stte nd prevent the solidi(tion proess @see setion sFVFPAF yur mesureE ments lerly reveled the existene of strutured liquid t the interfe with the sustrte in the presene of the @TTA reonstrutionF roweverD it ws not possile to mesure experiE mentlly the retion of (veEfold sy in the superooled dropletsF sn order to on(rm to wht extend our proposed proess n e vlidtedD simultions on the liquid were performedF

    V.3.2 Simulation results


    he im of these simultions is to explore the struture of the liquid t temperture ove Te @t UHH uA nd in the superooled regime @THH nd SHH uA to detet potentil hnges during the ooling proessF o do soD PST toms with proportion of eu nd i toms orresponding to the euteti omposition re rrnged in ui ox with periodi oundry onditionsF he side ox length is ITFS nd the durtion of the run is QH ps with time step of Q fsF sn pigure FIP is plotted the menEsqure displement < r2 (t) > dedued from the simultionsF he three tempertures disply similr evolution presenting distintive regimesF he (rst one onerns the short times with llisti motion of the toms with n mplitude evolving s t2 F st is then followed y rossover region where the slope wekensF he slowing down of the motion rises when the toms ome ross their (rst neighours nd rrnge in oordintion polyhedr suh s those presented in pigure sFPPF et longer timeD the menEsqure displement grows linerly with time orresponding to the di'usive regimeF he extrtion of the selfEdi'usion oe0ients yields HFHUSD HFHRT nd HFHPH 2 Fps1 t UHHD THH nd SHH uD respetivelyD nd on(rms the liquid ehviour for the three temperturesF por eh tempertureD neighor nlysis of the simulted euteti liquid ws rried outF he detiled threeEdimensionl piture of the lol struture ws extrted ndD using the roneyuttEendersen indies presented in setion sFSFPD the perentge of lusters with (veE fold symmetries @represented y ISSID IRSI nd IRQI pirsA in the liquid ould e lultedF yn the grph in pigure FIQ is plotted the vrition of the perentge of eh onsidered IPV

    V.3.

    Study of the liquid structure

    10

    <r (t)> ( )

    10 10 10 10 10

    700 K 600 K 500 K

    t t
    2

    -1

    -2

    Diffusive regime Crossover Ballistic regime

    -3

    -4

    0.01

    0.1

    10

    t (ps)
    Figure V.12  Mean-square displacement
    500 K.

    < r2 (t) >

    deduced from the simulations at 700, 600 and

    pir s well s the one of the totl (veEfold symmetry pirsF he shortErnge order displys n ppreile proportion @RT 7A of pirs in lol (veEfold rrngement t UHH uF huring the ooling down to the superooled regimeD this proportion inreses to reh SI 7 nd SR 7 t THH nd SHH uD respetivelyF hese results therefore revel thtD (rstD (veEfold sy n develop in the eui euteti liquid nd seondD tht the superooling proess enhnes its

    Content of each pair (%)

    1431
    20

    Total

    52

    15

    1451

    50

    48 10

    1551
    700 650 600 550 500 Decreasing temperature (K)

    Figure V.13  Percentage of the 1551, 1451, 1431 ve-fold clusters present in the simulated liquid
    (referring to the left axis) and of the total ve-fold symmetry pairs (referring to the right axis) as a function of decreasing temperature.

    Total five-fold symmetry pairs (%)

    54

    IPW

    Chapter V.

    Supercooling in AuSi droplets

    formtionF en interesting informtion onsists in the omprison of the intertomi distnes found in the di'erent struturesF his done in pigure FIR showing the surfe unit ell of the @TTA reonstrution @with the extended trimers of pentgons surrounding itAD the ISSI luster found in the simulted liquid nd the fFFF gold struture t SSH uF emrklyD the nerestEneighour distne in the pentgons is PFVT t room tempertureD denser thn for gold in its ulk fFFF struture @PFWH t SSH uAD ut lose to the intertomi distne @PFVR A in ioshedrl eu lusters in the superooled liquidD s dedued from the simultionsF woreoverD the (veEfold lusters found in the simulted liquid nd the pentgons of the @TTA reonstrution present very similr topologyF hereforeD the @TTA surfe struture o'ers perfet sites to stilize the (veEfold lustersD whih in turn stilize the superooled metlF

    1551

    FCC (550 K)

    23

    (6x6)

    2.84 2.86

    2.90

    Figure V.14  Image of the Si(111)-(66)Au reconstruction surface leading to enhanced supercooling with the unit cell highlighted by the black line (only the Au atoms are shown). Out of 45 atoms in the unit cell, 30 are in a pentagonal environment (green lines). In insets are shown a gold pentagonal cluster (1551) present in the simulated liquid and the fcc gold lattice at 550 K. The cluster has similar topology and bond length (2.84 ) as the surface structure (2.86 ), both denser than the Au fcc lattice at this temperature (2.90 ).

    hroughout the investigtions presented ove in this setionD severl key points hve een highlighted nd show tht the @TTA struture hs n in)uene on the liquid nd ply role in the enhnement of the superooling e'et oserved in the eui liquid droplets X ! he ordering of the toms in the liquid is reorded in prllel with the improvement of the qulity of the @TTA reonstrutionF ! he verge rdil struture ftors of the experimentl nd simulted @presenting IQH

    V.3.

    Study of the liquid structure

    syA liquids s well s tht of the @TTA reonstrution disply similritiesF ! he (rst mximum of the liquid struture ftor presents n inEplne nisotropy of the intensity distriution X it is more intense in the diretion of the strong @TTA peks re)eting the liquid lterl short rnge order in)uened y the reonstrutionF ! e rod of intensity is reorded long Q t the inEplne position of the liquid reveling the ordering of the liquid lose to the dropletGsustrte interfeF ! he nlysis of the simultions performed on the liquid t di'erent tempertures shows tht the sy n develop in the eui liquid nd is enhned in the superooling regimeF ! he men intertomi distne in the (veEfold lusters is smller thn tht in the fFFF gold struture nd t the sme time disply pentgons of similr topology @nd sizeA thn those present in the @TTA reonstrutionF sn the light of ll these resultsD it is therefore proposed tht the euEindued i@IIIAE @TTA reonstrutionD whih present very unusul pentgonl rrngementD promote ndGor enhne the nuletion of (veEfold lusters in the liquidF he retion of the sy in the eui droplets thus stilize the liquid stte nd enhne the superooling ehviour @see pigure FISAF
    700 K

    Au-Si liquid alloy

    650 K

    ISRO

    520 K

    (3x3)R30 reconstruction

    the Si(111)-(

    (6x6) reconstruction

    Figure V.15  Schematic illustration of the proposed process. At 700 K the AuSi droplet forms on

    3 3)R30

    surface. Upon cooling, at 650 K, the (66) reconstruction is formed and

    inuences the liquid's structure. With still decreasing temperature, the ISRO develop in the droplet and stabilize the liquid down to 520 K.

    sn pigure FISD the imges suppose tht the reonstrutions extend ll over the surfeD even t the dropletsGsustrte interfeF roweverD on the fwQP emlineD the wide size of the em prevents preise mesure nd only provides n verge over lrge surfe of the smpleF sn dditionD the islnds over few perent of the totl re so tht it is not stritly possile to onlude the existene of longErnge ordered reonstrution t the sustrteE droplet interfeF es the @TTA reonstrution is very stle nd energetilly fvourleD it is however possile to think tht similr struture n form lollyF he question of the interfe9s struture is disussed in ghpter ssF he enhnement of the superooling y the @TTA reonstrution is however otined IQI

    Chapter V.

    Supercooling in AuSi droplets

    if the smple is nneled t lest TH u ove Te F gompred with the results otined in the se of the i@HHIA sustrte for whih higher nneling led to lower superoolingD one would thus expet solidi(tion proess tht tkes ple t higher temperture thn the one mesured with the @ 3 3AQH reonstrution @nneled lowerAF st seems therefore unvoidle to fous on the e'et of the nneling proess tht is responsile of three e'ets tht ould in)uene the solidi(tion X ! pollowing the phse digrm of the eui systemD higher nneling leds to lrger i ontent in the dropletsF ! he higher the nneled tempertureD the lrger the dropletsF ! he qulity of the @TTA reonstrution is improved with lrge nnelingF gonerning the onentrtion of the dropletsD it ould not e determined experimentlly in this workF st is thus resonly ssumed tht it follows the equilirium phse digrm s the droplet is in ontt with the i sustrte reservoir nd n djust the i ontent with the temperture vritionsF hereforeD whtever the mximum nneling temperture isD upon ooling to Te D the onentrtion follows the liquidus line nd hs the euteti vlue t Te F he proess governing the i onentrtion djustments is disussed in ghpter ssF st is ssumed in this work tht the size of the droplets @even for deposits of P wvA re too lrge to indue surfe e'ets nd thus hve n in)uene on the superooling e'etF hereforeD the presenttion of the size e'ets does not im to show potentil fetures rising t the nnosle ut onsists in the study of the in)uene of the @TTA nd @ 3 3AQH reonstrutions on droplets of di'erent sizesF he underlying ide eing the inrese of the surfeEtoEvolume rtio for whih the in)uene of the surfe @reonstrutionA on the volume @liquidA is ssumed to e enhnedF st is possile to in)uene the size of the droplets y hnging the deposited mount ndGor the nneling temperture @orsening proessAD the formtion of the reonstrutions eing t the sme time dependent on the nneling temE pertureF hereforeD y performing severl experiments with di'erent mounts of gold nd di'erent nneling temperturesD it hs een possile to study in prllelD the formtion of the reonstrutions @s well s its qulity in the se of the @TTA reonstrutionA nd their in)uene on liquid droplets of di'erent sizes @i.
    e.

    of di'erent surfeGvolume rtiosAF

    V.4

    Study of the size eect

    sn (rst experimentD three di'erent experiments with P wvD IH wv nd QH wv of gold were performed y nneling t the sme temperture of UPH uF e lrger deposit leds to lrger islnds nd then to lrger droplets for equivlent nneling temperture whih t the sme time llows the formtion of the @TTA reonstrution upon oolingF IQP

    V.4.
    (111)

    Study of the size eect

    Intensity (arb. u.)

    Intensity (arb. u.)

    * *

    (200) (220) (CTR)

    720 K 530 K 510 K

    (111)

    720 K 630 K
    (200) (220)

    550 K 510 K

    * *
    (CTR)

    * * *
    2.5 3.0 -1 3.5 Q ( )
    (a)

    4.0

    4.5

    2.5

    3.0 3.5 -1 Q ( )
    (b)

    4.0

    4.5

    Figure V.16 

    Radial-scans

    along the

    [121]

    azimuth (a) at 720 K, 530 K and 510 K, for a 2 ML

    deposit and (b) at 720 K, 630 K, 550 K and 510 K, for the same sample onto which were added 8 ML to reach a total of 10 ML.

    pigure FIT@A shows the solidi(tion sns for the P wv smpleF et SQH u upon oolingD the sn only displys @TTA reonstrution peksD the rystl truntion rod nd the Ph )oting rystl pekF he droplets re thus still liquid t SQH u nd disply shrp liquidE solid trnsition tht tkes ple t SIH uF yn the sme smple ws dded V wv of gold to reh totl deposit of IH wv nd seond nneling t UPH u ws performedF sn this seD the solidi(tion of the system rises t SIH u s for the P wv depositD with the very (rst grins oserved to pper t SSH u @see pigure FIT@AAF he mjor prt of the droplets in this se thus turn into solid islnds t similr temperture thn for P wvF eginD
    (111) (200)

    (220)

    720 K 570 K 540 K

    Intensity (arb. u.)

    * * * *
    2.0 2.5
    along the

    (CTR)

    3.0

    Q ( )

    -1

    3.5

    4.0

    4.5

    Figure V.17 
    deposit.

    Radial-scans

    [121]

    azimuth at 720 K, 570 K and 540 K, for a 30 ML

    IQQ

    Chapter V.

    Supercooling in AuSi droplets

    630 K 570 K 540 K

    Si(220)

    (220)

    (111) (200)

    820 K 620 K
    (220)

    560 K 520 K

    Intensity (arb. u.)

    (200) (111)

    Intensity (cps)

    * * * *
    (CTR)

    * *

    2.5

    3.0 3.5 -1 Q ( )
    (a)

    4.0

    4.5

    2.5

    3.0 -1 3.5 Q ( )
    (b)

    4.0

    4.5

    Figure V.18 

    Radial-scans

    for a 30 ML deposit (a) along the

    [110]

    azimuth at 630 K, 570 K and

    540 K and (b) along the

    [1 21]

    azimuth at 820 K, 620 K, 560 K and 520 K, in this case the sample

    was previously annealed at 940 K

    the proedure ws performed for QH wv depositF pigure FIU shows tht in this se the solidi(tion proess initites t SUH u with the emergene of very wek eu@PPHA pekF et SRH uD the liquidEsolid trnsition sets inF yn the one hndD the P wv nd IH wv smplesD oth nneled t UPH u to get the retion of @TTA reonstrutionD present the sme order of superooling ompred to the T wv smple in the previous setion @even nneled it lowerD t TWH uD with @TTA reonstrutionA X in these ses the solidi(tion is reorded t SHHSIH uF his oservtion lims for sizeEindependent superooling ehviour or more preisely tht the di'erene in the surfeGvolume rtios etween the two experiment does not in)uene the development of the syF yn the other hndD the QH wv smpleD lso nneled t UPH u in presene of @TTA reonstrutionD displys lowered superooling e'et @s aSRH uA X this lims for t lest some sizeEdependene of the superooling ehviour with the ide tht lrger volume is less in)uened y the surfe strutureF sn order to onlude whether or not the size e'et is prominent nd on(rm the in)uene of the @TTA reonstrutionD QH wv deposit ws nneled t the euteti temperture wheres nother one ws nneled well ove Te D t WRH u i F he smple nneled t WRH u formed muh lrger droplets euse of the orsening proess wieh
    et al.D

    IWWIF

    he ooling experiment shows tht the QH wv smple nneled t e @see pigure FIV@AAD only presents prtil @ 3 3AQH reonstrution nd tht most of the grins re lredy formed t SUH u @very intense eu@PPHA pekA with omplete solidi(tion tht sets in when SRH u is rehedF he QH wv smple nneled t very high temperture @WRH uA nd therefore
    i. We paid attention not to heat the sample higher in order to avoid gold evaporation.

    IQR

    V.4.

    Study of the size eect

    * *
    Intensity (arb. u.)
    (111) (200)

    950 K 650 K 550 K 490 K


    (220)

    * *
    (CTR)

    2.5

    3.0

    Q ( )

    -1

    3.5

    4.0

    4.5

    Figure V.19 
    2+8 ML sample.

    Radial-scans

    along the

    [1 21]

    azimuth at 950 K, 750 K, 650 K and 490 K, for the

    omposed of lrger droplets with ler @TTA reonstrution solidi(es t lower temperture X SPH u @see pigure FIV@AAF prom these omprisonsD two key points n e expressed X IF he S wv nd QH wv smplesD oth nneled only slightly ove e with two di'erent sizes of droplets nd ooled down in the presene of the @ 3 3AQH reonstrution disply the sme solidi(tion temperture X SRH uF PF he QH wv smple nneled t WRH u nd the QH wv smple nneled t UPH u were oth ooled down with the @TTA reonstrutionF rowever the former hs lrger droplets s well s etter @TTA reonstrution nd solidi(ed t lower tempertures @s aSPH uA thn the ltter @s aSRH uAF he sme trend hs lso een oserved for the IH wv deposit fter nneling t WSH uD whih presented nier @TTA reonstrution nd solidi(tion temperture shifted y EIH u @s aRWH uA @see pigure FIWAF hroughout these mesurements rried out on di'erent sustrtes nd experimentl onditions @deposited mountsD nneling temperturesD reonstrutionsAD severl ssumpE tions were on(rmedF htever the deposited mount isD the presene of the @TTA reonsE trution enhnes the superooling ehviourD the @ 3 3AQH reonstrution lwys leE ding to lower superoolingF woreoverD if lrge mount of gold is deposited @QH wvAD the in)uene of the @TTA reonstrution on the superooling ehviour is weker euse the surfeGvolume rtio is smller unless su0ient nneling is pplied to promote the retion of @TTA reonstrution of high qulityF
    The aim of this chapter was to present the dierent results concerning the supercooling phenomena arising in AuSi liquid droplet in contact with Si substrates. We have seen that a low supercooling is recorded on Si(001) substrates

    IQS

    Chapter V.

    Supercooling in AuSi droplets

    whereas it is enhanced on Si(111) substrate. The maximum supercooling value has been observed in the case of the Si(111)-(66)Au surface for which a signal corresponding to an ordering of the liquid at the liquid-solid interface has been recorded. As the structure of the (66) reconstruction is locally formed with pentagonal units, we believe that this particular surface can favour the presence of clusters presenting ve-fold symmetry and stabilize the liquid phase. The simulation results performed on the system tend to conrm this explanation. In the next chapter, we investigate other systems that are used to grow nanowires through the VLS process.

    IQT

    V.4.

    Study of the size eect

    Summary of Chapter V
    Supercooling in the Au-Si(001) system :

    por eui droplets solidifying on i@HHIA sustrteD it is found tht the higher the smple
    is nneledD the smller the superooling isF

    he inEplne orienttion reltionship etween the solidi(ed gold nd the i@HHIA sustrte
    is strongly dominted y the ue on ue epitxyF
    Supercooling in the Au-Si(111) system :

    T wv of eu nneled IH u ove Te followed y ooling down results in the solidi(tion of the eui droplets in the presene of @ 3 3AQH reonstrution WH u elow Te F por similr mount of gold nneled TH u ove Te D the solidi(tion tkes ple in the
    presene of the @TTA reonstrution IPHIQH u elow Te F

    pon oolingD the presene of the eui Ph rystl phse is oserved s well s the ordering
    of the liquid in prllel to the ordering of the @TTA reonstrutionF
    Investigation of the liquid's structure :

    he rdil struture ftors of the experimentl nd simulted liquids (t very well ttesting
    the ury nd reliility of the simultions for the liquid stte in this systemF

    he (rst order of the liquid signl is enhned in the viinity of the most intense @TTA
    peks inditing struturl similrities etween the twoF

    e rod of intensity is reorded t the inEplne position of the liquid reveling the ordering
    of the liquid lose to the dropletGsustrte interfeF

    he neighor nlysis of the simulted euteti liquid shows n ppreile inrese of the
    mount of (veEfold lusters with the derese of the tempertureF

    he men intertomi distne in the (veEfold lusters is smller thn tht in the fFFF
    gold struture nd t the sme time disply pentgons of similr topology @nd sizeA thn those present in the @TTA reonstrutionF
    Size eect :

    he omprison of severl experiments rried out with di'erent mounts of gold nd


    di'erent mximum nneling tempertures on(rmed tht the superooling ehviour is in)uened y the surfe reonstrution X the @TTA reonstrution tends to lower the solidi(tion tempertureF

    he @TTA in)uene is redued with the inrese of the sizes of the droplets inresing the
    surfeEtoEvolume rtioDi.
    e.

    for lrge droplets prt of the liquid do not feel the surfeF

    he in)uene the @TTA is gin inresed when this ltter is of high qulityF
    IQU

    Chapter VI Case of other systems and inert substrates


    Contents
    VI.1 Au on Ge(111) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139 VI.2 Al on Si(111) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145 VI.3 Case of inert substrates . . . . . . . . . . . . . . . . . . . . . . . . 150
    VI.3.1 AuSi on SiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VI.3.2 AuGe on SiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150 152 153

    VI.3.3 AuGe on Al2 O3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    VI.1.

    Au on Ge(111)

    sn ghpter D we hve disussed the solidi(tion proesses of eui droplets on i suE strtesF wny e'orts were put in this system whih reveledD depending on the sustrte9s strutureD unexpeted ehviour upon oolingF sn order to ttempt omprison with the results otined with euEiD similr experiments were performed on the euEqe nd elEi whih re supposed to hve reltively lose properties s they lso omine metl nd semiEondutor nd n e used for v growthF sn ddition to the study of the solidi(E tion pthD some results onerning growth nd dewetting re presented nd ompred to the se of eu on i@IIIAF he eui nd euqe superooling ehviour ws lso studied on inert sustrtes Y hene onstituting losed systems s opposed to opened when on the g sustrstesF

    VI.1

    Au on Ge(111)

    es it hs een done in the se of the euEi system in ghpter @see pigure FRAD sheme of the reiprol spe is plotted in pigure sFID whih llows to esily distinguish etween the sustrteD the solid islndsD the liquid droplets nd the reonstrutions di'rtion signlsF
    _ [121]

    Ge Bragg Au rings (3x3)R30

    CTR

    Ge-(1x1)

    5.43
    _ (242)

    3.63

    1.81

    1.05

    2.09
    (111)

    (200)

    _ (220)

    4.19
    (220) (311)

    5.23

    _ (440)

    _ [110]

    2.66 3.08 3.14

    4.35 5.10
    3 3)R30

    6.28
    reections and Au

    Figure VI.1  Scheme representing the 30 (between the Ge[1 10] and Ge[1 azimuth) of the 21]
    reciprocal space. The positions of the Ge Bragg peaks, CTR , (

    1 ) values. rings are given in momentum transfer Q (

    IQW

    Chapter VI.

    Case of other systems and inert substrates

    Layer by layer deposit


    pigures sFP gthers the radial-scans performed during the deposition of severl wv of eu on qe@IIIA sustrteF et HFS wvD oth sns only disply the qe sustrte fetures @frgg peks nd gsA without ny gold rystlline signlF he sn long the [1 diretionD 10] howeverD revels the presene of the @ 3 3AQH reonstrution rowes et al.D IWWQF hen I wv is rehedD the eu peks pperD their intensity inreses s long s the deposition proess is mintined nd depends on the inEplne orienttion @i. e. on the zimuthAF he eu@PHHA pek is lredy very intense for only I wv long the [110] diretion wheres its signl long the [1 xis ppers only t Q wv nd is very lowF he eu@PPHA re)etion ppers on 21] oth xes t I wv nd lso inreses with inresing depositionF he eu@IIIA pek remins quite low on oth xes even for Q wvF he presene of well de(ned eu frgg peks s well s @ 3 3AQH reonstrution peks for Q wv deposit seem to indite tht the growth of eu on qe@IIIA is hieved y the formtion of Qh rystlline strutures together with reonstruted wetting lyer in this experimentF his result is it surprising s the surfe energy of qe@IIIA is smller thn the one of i@IIIAF es the unertinty on the temperture elow RSH u is lrgeD we elieve tht we did not wit long enough efore proeeding to the eu deposit so tht it hd een performed ove F sn ddition to the eu frgg peksD two re)etions @t 2.15 1 nd 2.5 1 A re present on oth xes nd do not orrespond to ny lttie sping in goldF hey re ssumed to ome from the formtion of euqe rystlline phse nd re disussed in detils lterF
    -

    10

    0.5 ML 1 ML 1.7 ML (200) 3 ML

    Ge(220)

    (220)
    10
    4

    0.5 ML 1.7 ML

    1 ML 3 ML

    Ge(242)

    CTR (220) (111)

    Intensity (cps)

    Intensity (cps)

    10

    R3

    R3
    10
    3

    10

    (311)

    (111)

    (200)
    10
    2

    10

    10

    10

    2.0

    2.5
    Hh0 at RT

    3.0

    3.5
    -1

    4.0

    4.5

    2.0

    2.5

    3.0

    3.5

    4.0
    -1

    4.5

    5.0

    5.5

    Q ( )
    (a)

    Q ( )
    H00 at RT
    (b)

    Figure VI.2 
    peaks.

    (a) the Ge[1 10] azimuth and (b) the Ge[1 azimuth. 21]

    Radial-scans performed at RT for a total deposit of 0.5, 1.7 and 3 ML of Au, along 1,
    R3 stands for (

    3 3)R30

    reconstruction

    IRH

    VI.1.

    Au on Ge(111)

    Annealing and melting


    HH0 melting = R3xR3 reconstruction

    H00 melting

    10

    (200) (220)

    590 K 650 K

    630 K 660 K

    10

    (111)
    4

    590 K 650 K CTR

    630 K 660 K

    Ge(242)

    Intensity (cps)

    R3
    10
    3

    (111)

    Intensity (cps)

    10

    R3

    R3

    10

    (222) (220)

    10

    (222)
    10
    2

    (200)

    (311)

    10

    10

    10

    2.0

    2.5

    3.0

    3.5
    (a)

    4.0
    -1

    4.5

    5.0

    5.5

    2.0

    2.5

    3.0

    3.5
    (b)

    4.0
    -1

    4.5

    5.0

    5.5

    Q ( )

    Q ( )

    Figure VI.3 
    the Ge[1 10]

    azimuth and (b) along the Ge[1 21] azimuth.

    Radial-scans

    performed upon annealing at 590 K, 630 K, 650 K, 660 K along (a)

    pigures sFQ shows the sme

    radial-scans

    s in the previous pigure ut for severl temE

    perture during nneling of the smpleF ynly the eu@IIIA re)etions @nd thus eu@PPPAA inrese with F et TTH uD ll the gold re)etions vnish on(rming the solidEliquid trnsiE tionF sn dditionD we note here tht the two unssigned peks mentioned ove lso dispper t Te with the pperne of the liquid droplets wheres the @ 3 3AQH reonstrution peks reminF he smple ws then nneled t mximum of UIH u nd reiprol spe mp of the liquid system ws reorded @see pigure sFQA
    _ Ge[121] _ Ge(242) Ge(111)Au(3x3)R30

    Ge-(1x1)
    1st liquid order

    _ Ge(220)

    _ Ge(440)

    _ Ge[110]

    Figure VI.4  Reciprocal space map of the Au-Ge system in the liquid state (at 670 K). The red,
    and blue colors refer to high and low intensity, respectively. The yellow colors represent intermediate intensities.

    IRI

    Chapter VI.

    Case of other systems and inert substrates

    his mp is rther simpleD displying the qe frgg peksD the qe@IIIAE@ 3 3AQH eu
    re)etions nd the (rst order of the liquid signlF he seond order of the liquid is lmost invisile @s well s on the snsAD whih my e due to the low mount of eu depositedF eove e D the system is therefore omposed of euqe liquid droplets in the presene of @ 3 3AQH reonstrutionF

    Cooling to Ts
    es for the euEi systemD we determine the solidi(tion temperture y reording radialscans

    upon ooling until the eu peks repper inditing the retion of rystl grins in

    the dropletsF his is plotted for oth xes upon oolingD t UIH uD TIH uD SWH u nd SUH u in pigure sFSF he very (rst tres of solid grins re reorded t TIH uD with the emergene
    HH0-cooling from 440C
    H00-cooling from 440C
    5

    10

    Intensity (cps)

    10

    710 K 610 K 590 K 570 K

    (220) R3 R3

    10

    (111) CTR

    710 K 590 K

    610 K 570 K

    (222)

    10

    Intensity (cps)

    R3

    (200)

    10

    10

    10

    10

    (220)

    10

    10

    2.5

    3.0

    3.5

    4.0
    -1

    4.5

    5.0

    5.5

    2.5

    3.0

    3.5

    4.0

    Q ( )
    (a)

    Q ( )
    (b)

    -1

    4.5

    5.0

    5.5

    Figure VI.5 

    the Ge[1 10] azimuth and (b) the Ge[1 azimuth. 21]

    Radial-scans

    recorded upon cooling at 710 K, 610 K, 590 K and 570 K along (a)

    of the eu@PPHA re)etion long the qe[1 zimuth ut the mjority of the droplets re still 10] in the liquid stteF he smple must e ooled down to SWH u to oserve sustntil rise of the eu peks intensityD the omplete solidi(tion of the system is otined t SUH uD WH u elow Te F woreoverD we note tht the eu@IIIA pek is now very intense on the qe[1 xes ut does not repper long the [1 diretionF he eu@PPHA intensityD in the 21] 10] ontrryD onentrtes long the qe[1 zimuthF e reiprol spe mp of the system in 10]
    i. e.

    the solid stte ws thus reorded to visulize the intensity distriution of the gold strutures @see pigure sFTAF

    IRP

    VI.1.

    Au on Ge(111)

    _ Ge(242)

    _ Ge[121]

    Au(331)
    Au(222)

    Au(311) Au(200) Au(111)

    _ Ge[110] Ge(111)-Au(3x3)R30
    Au(220) Au(420)

    Figure VI.6  Reciprocal space map of the Au-Ge system in the solid state (at RT) after melting
    and solidication. The red, and blue colors refer to high and low intensity, respectively. The yellow colors represents intermediate intensities

    Epitaxies after melting and solidication


    sn the se of eu on i@IIIAD we hve seen tht the solid reiprol spe mp presented gold rings @see pigure sFPAF his limed for the solidi(tion of gold grins in quite rndom mnner ut with the predominnt inEplne epitxil reltionships disussed in ghpter sss whih reppers fter rystlliztionF rereD the solid mp displys tres of gold rings ut with very inhomogeneous reprtition of the intensityF st therefore revels tht the grins re very textured in the plneD depending on their epitxil orienttion perpendiulr to the sustrteF he eu@PPHA rings intensity onentrtes on the qe[1 zimuthD whih therefore 10]

    Au[001] || Ge[110]

    Au

    Ge

    Au[110] || Ge[112]

    Au[110] || Ge[111]
    Figure VI.7  Top view of the interface represented by the superposition of the Au(110) plane
    above the Ge(111) plane, the lattice parameters values are taken at 300 K. The Au(110) plane is rotated around the Ge[111] axis by 30

    with respect to the parallel epitaxy.

    IRQ

    Chapter VI.

    Case of other systems and inert substrates

    orresponds to the yI presented in ghpter sss X [1 eu@IIIA [1 qe@IIIAF gonerning 10] 10] the eu@IIIA intensityD whih is onentrted on the qe[121] diretionD it orresponds to the

    [001]eu@IIHA [1 qe@IIIA epitxil reltionshipF pigure sFU illustrtes this on(gurtion in 10] the rel spe nd shows the quite perfet mthing etween the toms of the qe[1 row 10]
    nd those of the eu[001] rowD whih explin this preferred orienttionF

    Discussion on AuGe crystalline phases.


    huring the depositD we pointed out the existene of two unssigned peks whih re elieved to rise from the presene of metstle euqe solid phseF he domin present in the euEqe phse digrm orresponds to stle euqe f rystl with lttie prmeter equivlent to the one of pure goldF he di'erene only lies in sustitutions of some eu toms y qeF he phse n therefore not e distinguished from pure f `eub y di'rtion experimentsF roweverD two euqe metstle phsesD with di'erent rystl struturesD n form depending on the experimentl onditions ykmoto nd wsslskiD IWVR X ! the hexgonl lose pked Eeuqe phse @ PFW D RFU A PPFQQ AF ! nd the odyEentered tetrgonl Eeuqe phse @ IIFSS D

    hese two phses re known to rise under outEofEequilirium onditionsD y quenhing n euqe liquid lloyF he resulting phse depends on the lloy onentrtion ennthrmn et
    al.D

    IWTTY wnilD IWWWF he Eeuqe n however not e t the origin of the peks reorded gonerning the Eeuqe phseD its rystl struture nd lttie prmeters mke it more

    hereD its lttie prmeters presenting no orresponding distne to their positionsF suitle to (t the reorded peksF sndeedD the distne d(040) nd d(044) whih re equl to PFVW nd PFST D respetivelyD give the losest orresponding vlues @Q(040) aPFIU 1 nd Q(044) aPFRS 1 D respetivelyAF he di'erene etween the proposed re)etions nd the reorded ones n ome from slight di'erene in the vlue of the lttie prmetersF e re however wre tht the proposed struture is supposed to form here t during the growth of eu on qe wheres it is more likely to form during quenhing proesses in litertureF ynly one study reports its formtion in the se of the elortion of sputtered euqe (lms on qurtz sustrte t skegwD IWVVF he Eeuqe phse ws found to quikly trnsform into Eeuqe nd ui qe with soft nneling @elow QUH uAF his is not the se here s the two onerned peks remin upon nnelingD they only dispper t the solidE liquid trnsition tempertureF wore reentlyD the metstle Eeuqe phse ws oserved to form in spei( onditions during the strong underooling of euqe liquid droplet t the tip of qe nnowire utter nd utterD PHIIF sn our seD the metstle phse repper ut its signl fter the solidi(tion proess is IRR

    VI.2.

    Al on Si(111)

    very low ompred to tht reorded during the deposition proessF st is thus elieved here tht these two peks rise euse of the formtion of euqe rystlline lloy whih is suppose to e the Eeuqe phseF rowever the possiility tht this phse orresponds to nother unreported euqe phse n not e exluded s our results nd experimentl onditions do not fully gree with pulished resultsF

    VI.2

    Al on Si(111)

    eu is the historilly used tlyst for the growth of i nnowires gner nd illisD IWTRF rowever it is lso t the origin of potentil ontmintion prolems lowering the performnes of the nnowiresF el seems to e promising metl to void ontmintion nd reple goldD the most importnt prolem eing however its high retivity with oxygen nd thus the formtion of n elEoxide tht strongly lowers the e0ieny of the v proessF st is however interesting to study its ehviour under experimentl onditions similr to those used for the eu tlystF he experiment on the elEi@IIIA system ws rried out on the shHQ emlineF por given mterilD the sttering of Ery is proportionl to the squre of its tomi numer Z F ith ZAl = 13 nd ZAu = 79D the el Ery sttering is lmost RH times weker ompred to euF shHQ o'ers the possiility to perform surfe hrteriztions under r with more rillint em nd is therefore more suitle to study the elEi systemF he two experiments onsisted in nnelingD melting nd ooling IH wv nd QH wv of el deposited t on i@IIIA sustrtesF
    hh at RT

    Si(7x7)
    Intensity (cps)

    Si(220)

    Al(220)

    0 ML-RT 5 ML-RT 5 ML-750 K


    2 3 4


    Q ( )
    -1

    Figure VI.8 

    Radial-scans

    along the Si[1 10] azimuth, recorded before any deposit of Al at RT

    and after a deposit of 5 ML of Al at RT and 750 K. The peaks marked with a circle are Si-(77) reconstruction peaks.

    IRS

    Chapter VI.

    Case of other systems and inert substrates


    lscan 220

    Intensity (arb. u.)

    Intensity (arb. u.)

    RT 820 K

    RT 820 K

    19.2

    2.4

    2.6
    -1

    2.8

    3.0

    3.2

    -30

    -20

    -10

    10

    20

    30

    Qz ( )
    (a)

    ()
    (b)

    Rocking-scans

    Figure VI.9  (a)

    l-scans

    (along

    ) crossing the Al(3 11) Bragg peak at RT and 820 K and (b)

    on the Al(220) ring at RT and 820 K.

    pigure sFV shows tht s soon s IH wv re depositedD the strong iE@UUA peks dispE per nd the el di'rtion peks pperF elong the i[110] D only the el@PPHA pek is present whih is quite similr to the euEi in similr onditions @see ghpter sssAF pigure sFW@A ompres two
    l-scans

    performed on the eu@PPHA re)etion t nd

    fter nneling of the smpleF he result is omprle to wht hs een oserved for the euEi system @pigure sssFIH@AA X the pek nrrows with nneling whih orresponds to the dewetting of the (lmF he vlue of the prw t yields n estimtion of the (lm thikness of PFR nm orresponding to IH wv in greement with the deposited mountF et VPH uD the height of the strutures is out ITFS nmF et the sme timeD similr mesurements on inEplne orienttion reltionship s in the euE
    hh 220 cooling from 850 K

    Intensity (arb. u.)

    4.20 4.25 4.30 4.35 4.40 4.45 -1 Q ( )


    (a)

    Intensity (arb. u.)

    820 K 840 K

    800 K 785 K 770 K

    4.20

    4.25

    4.30 4.35 -1 Q ( )
    (b)

    4.40

    4.45

    Figure VI.10 

    Radial-scans

    on the Al(220) peak (along the Si[1 10] azimuth) (a) upon annealing

    at 820 K and 840 K and (b) upon cooling at 800 K, 785 K and 770 K .

    IRT

    VI.2.
    hh Al(220)

    Al on Si(111)
    h0 Al(220)

    Intensity (arb. u.)

    Intensity (arb. u.)

    8 ML 16 ML 23 ML 30 ML

    8 ML 16 ML 23 ML 30 ML

    4.30

    4.35 Q ( )
    (a)
    -1

    4.40

    4.45

    4.25

    4.30

    4.35 -1 Q ( )
    (b)

    4.40

    4.45

    Figure VI.11 

    and 30 ML on the Al(220) peak (a) along the Si[1 10] azimuth and (b) along the Si[1 azimuth. 21]

    Radial-scans

    performed during the deposit of Al on the Si substrate for 8, 16, 23

    i system were performed @see pigure sFW@AAF et low tempertureD rocking-scan on the el@PPHA ring displys very rod pek entered on i[1 nd hnges into nrrower pek 10] with the pperne of seond one @t IW A with nnelingF he elEi system thus presents similr dewetting proessD s desried in ghpter sss for euEiD whih is ompnied y epitxil reorgniztion upon nnelingF e n however notie here tht the entrl pek displys douleEwidth shpeF his n rise from imodl distriution of the sizes of the struturesF hen the smple is nneled t inresing tempertureD the el@PPHA pek vnishes round the elEi euteti temperture t VRH u for whih the solidEliquid trnsition tkes ple @pigure sFIH@AAF he smple n not e nneled higher otherwise el evportion n hppenF pon ooling the (rst solid grins pper t UVS u nd the solidi(tion sets in t UUH u@pigure sFIH@AAF por this smple the deposited mount of el ws too low to extrt ler liquid signlF enother experiment ws thus performed on new smple with QH wv depositF huring the depositionD radial-scans were performed on the el@PPHA signl long the i[1 nd i[1 10] 21] zimuths @see pigure sFIIAF he intensities vry in opposite wys X they inrese long the [110] xis wheres they derese long the [1 diretionD highlighting overge dependene 21] of the inEplne orienttion of the el@IIIAEi@IIIA interfe t F he smple ws then nneled nd
    radial-scans

    were quired t UVHD UWS nd VQS u

    showing progressive trnsition etween solid el frgg peks nd ler liquid signl y pprohing the euteti temperture @pigure sFIPAF pon oolingD the liquid signl trnsformed k into gold peks when the liquidEsolid trnsition tkes ple t UVH u whih is SH u elow Te F IRU

    Chapter VI.

    Case of other systems 30ML melting (Al on Si) HA and inert substrates

    (220) (111) (200)

    780 K 795 K 830 K

    (200)

    (220)

    800 K 780 K
    (311) (422)

    Intensity (arb. u.)

    Intensity (arb. u.)

    (111) (222) (400) (420)

    (311)

    (422) (420)

    Q ( )
    Figure VI.12 

    -1

    5
    -1

    Q ( )

    Radial-scans

    performed between the

    [1 10]

    and

    [1 21]

    Si azimuth upon annealing a

    30 ML Al deposit on Si(111) at 780 K, 795 K and 830 K.

    gompred to the euEi system @or euEqeAD the superooling ehviour reorded in these experiments on elEi re not very surprisingF st hs lredy een reported in literture tht lrge degree of superooling @more thn IHH uA n e hieved even for ulk studies hs
    al.D et

    PHHIF roweverD the degree of superooling nd the solidi(tion pthwys re numerousD

    very omplex nd depend on mny prmeters suh s the onentrtionD the therml historyD the ooling rte or the formtion of metstle phsesF sn the se presented hereD in the presene of i sustrte nd very smll ooling rteD it is resonly ssumed tht simple segregtion proess tkes ple resulting in the solidi(tion of seprted primry
    _ Si[121]

    _ Si(242)
    Al(311) Al(220) Al(200) Al(111)

    _ Si[110] _ Si(220) _ Si(440)

    Figure VI.13  Reciprocal space map of the Al-Si system in the solid state (at RT). The red, and
    blue colors refer to high and low intensity, respectively. The yellow colors represents intermediate intensities

    IRV

    VI.2.

    Al on Si(111)

    phses of el nd iF efter solidi(tionD the smple ws ooled down to QHH u nd reiprol spe mp ws reorded @pigure sFIQAF his mp revels solid rystlline el heyeEherrer rings tht re quite homogeneousF gontrry to the euEqe systemD the meltingEsolidi(tion yle results in n untextured solid in the se of el on i@IIIAF

    Complementary results obtained with the Al catalyst


    sn ddition to the understnding of the fundmentl spets desried throughout this mnusriptD the hllenge is to ontrol themF huring one experimentD we tried to use the lrge di'erene in the euteti tempertures etween the elEi @Te = 850 K A nd the elEqe @Te = 700 K A systems to grow qe xs on i@IIIA sustrte through n el tlystF

    Ge(220)
    Intensity (arb. u.)
    Al(200)

    Si(220)

    ref at 750 K before Ge deposition 2.5 ML Ge Al(220) 6 ML Ge 13 ML Ge

    Al(111)

    2.5
    Figure VI.14 

    3.0

    Q (A )

    -1

    3.5

    4.0

    Radial-scan

    performed along the Si[1 10] azimuth in the case of a Si(111) sample

    onto which 6ML of Al were deposited, annealed and cooled down to 750 K (black). Same

    radial-scan

    after the addition of 2.5 (red), 6 (green) and 13 ML (blue) of Ge at a constant temperature of 750 K.

    o do soD we hve nneled deposit of T wv of el on i@IIIA surfe t VUH u in order to form the eli dropletsF hen the system ws ooled down to USH u nd radial-scan long the i[110] zimuth ws reorded @see pigure sFIRAF st displys the el frgg peks nd on(rms the solidi(tion of the smple i F henD we reorded the sme sn during the ddition of qe t USH uD
    i. e.

    SH u ove the elEqe euteti tempertureF emrklyD fter

    the ddition of PFS wv of qe the intensity of the el@IIIA pek deresed wheres those of the el@PHHA nd el@PPHA inresedF efter the ddition of totl of T wvD the el@IIIA peks hs disppered leving very wek liquid signlF por IQ wv of qe dded on the smpleD
    i. The wide peak at 3.75 corresponds to the formation of small crystals of SiC.

    IRW

    Chapter VI.

    Case of other systems and inert substrates

    no more el frgg peks were reorded re)eting the melting of the systemF sn dditionD the qe@PPHA frgg pek ppered whih mens tht some qe strutures @(lmD islndsD xsFFFA hve formed in epitxy with the i@IIIA surfeF dlyD it hs een impossile to perform exsitu

    hrteriztion on this smple to see if nnowires hd een grown with suessF hese

    mesurements revel tht the ddition of qe onto the surfe omposed of eli solid islnds ove the euteti temperture of elEqe llows the melting of the system nd the potentil growth of qe xsF he presenttion of this experimentD whih is not very onlusiveD ims however to show why the knowledge of the physi of the euteti liquid droplets studied in this work is imE portnt s it ould led to etter ontrol of the growth prmeters nd should provide wide rnge of tools to design new nnoEojetsF sn ddition to the investigtions of the euEi@IIIAD euEi@HHIAD euEqe@IIIA nd elE i@IIIAD some ttempts to get more informtion on the ehviour of those metlEg liquids were rried out on sustrtes tht re supposed to e inertD t lest hemillyF o do so we hve performed similr experiments s presented ove nd in ghpter for eui on iy2 sustrte nd euqe on iy2 nd el2 y3 sustrtesF

    VI.3

    Case of inert substrates

    VI.3.1 AuSi on SiO2


    sn this experimentD wfi oEdeposit of eu nd i ws performed in required proportions to reh totl of T wv of eui lloy t the euteti ompositionF pollowing the sme experimentl proedure s in ll the previous experimentsD the smple ws heted nd radialscans

    were reorded until the dispperne of the rystlline peks vnish t the euteti

    temperture @see pigures sFIS@A nd @AAF e n note here tht the melting proess strts t TIH uD the omplete melting of the system rises t TQH uF he smple is then nneled t UPH u nd ooled downF huring the ooling proessD
    radial-scans

    re lso reorded to

    mesure the temperture t whih the liquidEsolid trnsition tkes ple @see pigures sFIS@A nd @dAAF his llows the oservtion of the (rst solid grins t SUH u @presene of the eu@PPHA pek in pigure sFIS@dAA nd very progressive solidi(tion proess tht ends when temperture of SIH u is rehedF roweverD t SQH uD the trnsition is lredy lmost ompleteF urprisinglyD one n remrk pek t PFSP 1 rising t SQH u in pigure sFIS@AD whih does not orrespond to ny f gold interplnr distneF e omprison tht n esily e mde onerns the metstle Eeuqe phse whih ws supposed to e responsile of ISH

    VI.3.

    Case of inert substrates

    pek t the sme position in setion sFIF st n lso e ttriuted to n euEi metstle phse reported in setion sssFP s the pek orresponds to the eu7 i@RHHA interplnr distne @see le sssFPAF he formtion of metstle phses in these systems however lerly requires deeper investigtionsF snterestinglyD ompred to the euEi@IIIA smplesD severl di'erenes n e oservedF he melting proess is found to strt PH u elow Te D the solidi(tion egins t SUH u nd ends round SPH u with the potentil formtion of eui metstle phsesF he superooling vlue @with Te tken s the referene pointA is di0ult to mesure ut n e roughly estimted to e IHH u with solidi(tion proess di'ering from the se of the open systemF hese results will e disussed in more detils in the next hpterF

    Intensity (cps)

    (200)

    (220)

    Intensity (cps)

    540 K 610 K 630 K

    (111)

    (111)

    540 K 610 K 630 K


    (220)

    10

    (200)

    10

    1.5

    2.0

    2.5 3.0 -1 Q ( )
    (a)

    3.5

    4.0

    4.5

    1.5

    2.0

    2.5 3.0 -1 Q ( )
    (b)

    3.5

    4.0

    4.5

    10

    (111) ? (200)

    690 K 570 K

    550 K 530 K 510 K

    10

    Intensity (cps)

    Intensity (cps)

    (220)

    690 K 570 K 550 K 530 K 510 K

    (220)

    10

    (111) (200)

    10

    10

    2.5

    3.0

    Q ( )
    (c)

    -1

    3.5

    4.0

    4.5

    2.0

    2.5

    3.0 3.5 -1 Q ( )
    (d)

    4.0

    4.5

    Figure VI.15  (a)-(b)


    610 and 630 K. (c)-(d)

    Radial-scans performed on the two substrate's axes upon heating, at 540, Radial-scans performed on the two substrate's axes upon cooling, at 690,

    570, 550, 530 and 510 K. For a eutectic AuSi deposit of 7 ML.

    ISI

    Chapter VI.

    Case of other systems and inert substrates

    VI.3.2 AuGe on SiO2


    he sme experiment ws performed ut this time with oEdeposit of T wv of euqe euteti lloy on iy2 sustrteF roweverD no solidEliquid trnsition ws oserved pssing through the euteti tempertureF et TWH uD the eu@PPHA pek ws still present in the snsD on(rming the presene of gold grinsF his oservtion ws ssumed to rise euse of onentrtion gp etween the euteti onentrtion nd the rel one with lk of qe in some islndsF o overome this issueD dditionl qe ws deposited t TWH u ndD t the sme timeD fst
    radial-scans

    were reorded on the eu@PPHA pek to follow the melting proess @see

    pigure sFIT@AAF he smple ws then ooled downD the eu@PPHA pek ppered t STH uD its intensity progressively inresed with ooling nd rehed its mximum t RWH u wheres
    Radial <100>

    before Ge deposit 0.43 0.79

    (111)

    Intensity (arb. u.)

    670 K 560 K 510 K 490 K (220)

    Intensity (cps)
    4.1 4.2
    Radial <100>

    10

    4.3 -1 Q( )
    (a)

    4.4

    4.5

    2.0

    2.5

    3.0

    3.5 -1 Q(A )

    4.0

    4.5

    Radial <100>

    (b)

    (111)

    480 K 570 K

    600 K 640 K 690 K (220)

    (111)

    670 K 620 K

    520 K 510 K 490 K (220)

    Intensity (cps)

    Intensity (cps)

    10

    10

    2.0

    2.5

    3.0 3.5 -1 Q(A )


    (c)

    4.0

    4.5

    2.0

    2.5

    3.0

    3.5 -1 Q(A )

    4.0

    4.5

    (d)

    Figure VI.16  (a) Radial-scan on the Au(220) peak during the deposition of additional Ge at 690 K
    until the disappearance of the peak due to the melting of the system. (b)

    Radial-scans

    performed performed

    at 670, 560, 510 and 490 K upon cooling from 690 K after the deposition of additional Ge. (c)

    Radial-scans
    ISP

    performed at 480, 570, 600, 640 and 690 K upon heating. (d)

    Radial-scans

    at 670, 620, 520, 510 and 490 K upon a second cooling process from 690 K.

    VI.3.

    Case of inert substrates

    the eu@IIIA pek only ppered t SIH u nd slightly inresed when the temperture ws deresed gin y PH uF o get ler mesure of the melting temperture of the systemD the smple ws heted gin @see pigure sFIT@AAF urprisinglyD t SUH u the eu@IIIA pek hs lredy disppered nd the eu@PPHA intensity strts to dereseF his ltter still presents wek intensity t TWH u suggesting tht some prts of the system remin solid even TH u ove the euteti tempertureF e susequent ooling of the system displys quite the sme solidi(tion proess s in the (rst yle @see pigure sFIT@dAA with progressive inrese of the eu@PPHA pek nd lte pperne of the eu@IIIA pek round SHH uF por this experiment the phse trnsitions were found to tke ple over wide temperture rnge with even some islnds tht ould not e meltedF st re)ets potentil heterogeneities tht will e desried lterF

    VI.3.3 AuGe on Al2O3


    imilrly to the previous experimentD oEdeposit of T wv of eu nd qe t supposed euteti omposition ws rried out on n el2 y3 F his sustrte is of prtiulr interest s it hs een reported to indue ordering in liquid el in ontt with it yh
    et al.D

    PHHSF

    eginD during the (rst heting proess of the smpleD the eu@PPHA pek ould not e remoE ved even t VPH u @see pigure sFIU@AAD suggestingD s in the previous experimentD tht the omposition ws fr from the euteti oneF o ompensteD the qe deposit ws ontinued @t VPH uA until the eu@PPHA pek vnishes nd the smple ws susequently ooled down @see pigure sFIU@AAF es for euqe deposited on iy2 D the eu@PPHA pek progressively inresed with the deresing temperture wheres the eu@IIIA pek s well s two other peks tE triuted to the phse pperedF wore interestinglyD it ws the (rst time tht g frgg peksD others thn the ulk sustrte peksD were reordedF rereD t SHH uD the qe@IIIA nd qe@QIIA frgg peks ppered nd reveled thtD s predited y the phse digrmD segregtion proess tkes ple leving eu nd qe in seprted solid phsesF eginD it ws neessry to on(rm the melting temperture of the present system so tht the smple ws heted gin @see pigure sFIU@AAF et SWH uD ll peks @from euD nd qeA were still present ut their intensities hd lredy strted to dereseF his trend ws on(rmed t TSH u for whih mjor prt of the di'rtion signl is due to the liquidF et TUH uD only the eu@PPHA pek remined nd is ttriuted to islnds with ompositions still fr from the euteti oneD
    i. e.

    presenting n exess in gold so tht only prtil melting

    ws oserved even ove the euteti tempertureF pon susequent oolingD the eu@PPHA pek reppered progressivelyD the eu@IIIA nd peks ppered t SHH u nd inresed in intensity when the temperture ws redued to RVH uD for whih the qe frgg peks risedF he investigtion of the euEqe system on the el2 y3 surfe displys similr results to ISQ

    Chapter VI.

    Case of other systems and inert substrates

    Radial <100> 820 K before Ge deposit 820 K after Ge deposit

    Radial <100>

    10

    (220)

    800 K 670 K 530 K 500 K

    (433)

    (220)

    (111) CTR

    Intensity (cps)

    Intensity (cps)

    (422)

    10

    Ge(111) Ge(311)

    10

    1.5

    2.0

    2.5
    -1

    3.0

    3.5

    4.0

    4.5

    2.0

    Q(A )
    Radial <100>
    (a)

    2.5 3.0 -1 Q(A )


    (b)

    3.5

    4.0

    4.5

    490 K 590 K 650 K 670 K

    (111)

    (433)

    (220)

    Intensity (cps)

    (422)

    Intensity (cps)

    CTR

    670 K 570 K 500 K 480 K


    (422)

    (220) (111)
    (433)

    CTR

    10

    10

    Ge(111)

    Ge(311)

    Ge(111) Ge(311)

    2.0

    2.5

    3.0 -1 Q(A )
    (c)

    3.5

    4.0

    4.5

    2.0

    2.5 3.0 -1 Q(A )


    (d)

    3.5

    4.0

    Radial-scans performed at 820 K before (black) and after (red) additional Ge deposition. (b) Radial-scans performed during the rst cooling from 820 K, at 800, 670, 530 and 500 K. (c) Radial-scans performed during the second annealing of the sample at 490 K, 590 K, 650 K and 670 K. (d) Radial-scans performed during the second cooling sequence at 670, 570, 500
    Figure VI.17  (a)
    and 480 K

    those otined for euqe on iy2 F he liquidEsolid trnsition is very progressive nd metsE tle phses re found to formF sn dditionD the formtion of very smll rystllites of pure qe re oservedF
    The results presented in this chapter as well as in the previous one, show that the supercooling behaviour of the metal-SC droplets can strongly dier from an experiment to another. At this point of this manuscript we have described our measurements and have begun to propose potential explanations to these kind of eects. However, the complexity of studying the behaviour of liquids, at the nanoscale, seems to require deeper discussion to bring a clearer point of view on what has been observed. The next chapter is dedicated to such discussion.

    ISR

    VI.3.

    Case of inert substrates

    Summary of Chapter VI
    Au-Ge(111) :

    he growth of eu on qe@IIIA is found to follow trnskiEurstnow mode in presene of @ 3 3AQH reonstrutionF he unertinty on the temperture elow RSH u mkes
    hrd to know if the deposit hs een rried out t F

    he reiprol spe mp reorded in the liquid stte does not disply nisotropi vrition
    of the intensity of the liquid signl in the (rst ring of stteringF

    pon oolingD the solidi(tion proess tkes ple WH u elow the reorded melting temE
    perture nd results in the formtion of very textured grinsF

    huring the experimentD some unssigned peks re reorded nd re ttriuted to the E


    euqe metstle phse even if we re wre tht our experimentl onditions re fr from those required to form this phseF
    Al-Si(111) :

    he elEi@IIIA system presents similr ehviour ompred to the euEi@IIIA system X the
    dewetting of the (lm is ompnied y rerrngement of the orienttion reltionshipsF

    wo smples hve een investigtedD one with S wv nd the other one with QH wvD oth
    showed liquidEsolid trnsition ourring out TH u elow Te F

    he reiprol spe mp reorded t fter solidi(tion displys reltively homogeE


    neous el heyeEherrer rings reveling the wek texture of the grinsF
    Case of inert substrates :

    AuSi on SiO2 :

    por this experimentD it ws more omplited to determine the phse

    trnsitionsF he islnds strt to melt t TIH u nd re ompletely melted t TQH uF pon ooling very progressive liquidEsolid trnsition is oserved with the pprition of the (rst grins t SUH u nd omplete solidi(tion t SIH u @IHH u elow Te AF e pek not orresponding to ny gold frgg pek is lso reordedF

    AuGe on SiO2 and Al2 O3 : sn oth sesD the unertinty on the omposition is very high

    nd we did not oserve the omplete meltingF he solidi(tion is extremely progressive ut ontinues down to very low temperture with the pperne of the phse peksF sn oth sesD the liquidEsolid nd solidEliquid trnsition tempertures re very di0ult to determineF sn the se of the el2 y3 sustrte we oserve the pprition of the qe frgg peksF ISS

    Chapter VII Discussion and synthesis

    sn ghpter sssD experimentl results hve een presented onerning the dewetting proessD whih hs een found to e ompnied y hnges in the inEplne orienttion reltionshipsF sn ghpter s we hve studied the formtionD the stility nd the tomi struture of the i@IIIAE@TTAeu reonstrution whih n oexist with either droplets or solid islndsF sn these two hptersD even if omplementry experiments n e imgined to otin more preise informtion on ritil pointsD the glol understnding of the results llows to provide stisftory explntionsF sn ghpter nd sD we strove to hrterize in more detils the tlyst liquid phse whih reveled unexpeted superooling e'ets in the euEi@IIIA systemF imilr experiments hve een performed in other systems for omprisonF he ehviour of the liquid phse in intertion with solid surfe t the nnosle is fundmentl feture in the urrent reserh onerning the growth of nnowiresF his setion therefore ims to disuss the experimentl results desried in the lst two hpters @ nd sA nd presents n overview of the di'erent physil oneptsF
    Problematics

    he superooling ehviour of given system is not esy to understndF sndeedD the geneE rl thermodynmil onepts rie)y exposed in ghpter s to explin the liquidEsolid phse trnsitionD mostly due to the erly work of urnullD were t the eginning only derived for the se of pure elementsF woreoverD the superooling phenomen in pure elements re still not ompletely eluidted inet
    et al.D

    PHHPY uim nd ueltonD PHHU nd new onepts

    on nuletion proesses re proposed uested nd qreerD PHHSF sn dditionD sed on the ssumption of prnk prnkD IWSPD the internl struture of liquids is thought to e lolly ordered in pentgonl symmetry utD despite new mens of hrteriztion nd onstnt inrese of simultion pitiesD it remins hrd to ring evidenes for this e'etF st eomes even more omplex to study superooling e'ets when deling with lloysF prom liquid lloyD numerous solid phses n form depending on the ooling prmeterD their study requires lot of ttention nd wellEde(ned experimentl onditionsF he otiE ned phse digrm n disply mny domin oundries inresing the omplexity of the study of the phse trnsitionsF woreoverD in experiments tht tke ple fr from equilirium onditionsD it is not rre to oserve the formtion of metstle phsesF rdoxillyD the solidi(tion of euteti liquids is wrongly thought to e quite esy to understnd s it is supposed to onsist in the segregtion of the two omponentsD resulting in two seprted solid phsesF woreoverD the existene of liquid eutetis is quite intriguing s the liquid phse is found t very low temperture for given omposition nd n trnsform in glss through rpid solidi(tionF iuteti liquids re lso ssumed to hve poor tenE deny to superooling ked et
    al.D

    PHHUY stmi et

    al.D

    PHIHF he mystery of their struture ISU

    Chapter VII.

    Discussion and synthesis

    remins hllenging ut reent studiesD oth experimentl nd theoretilD hve mde evident rekthroughs sked et si
    et al.D al.D

    PHHPY ked et
    et al.D

    al.D

    PHHUY stmi et

    al.D

    PHHUY sturel et

    al.D

    PHIHY

    PHIHY ghirwtkul

    PHIIF he omplexity of superooling phenomen is

    further inresed when liquid is in ontt with solidF yftenD heterogeneous nuletion is triggered nd promote solidi(tionF roweverD in some sesD spei( surfes re no good nulents for spei( liquids qreerD PHHTF he omplexity of the present work therefore lies in the study of metlEg euteti liquid @mostly euiA in intertion with its respetive g solid sustrte @iAD under the form of nnometri dropletsF hereforeD it is very hrd to use thermodynmil modelsD merely due to the ftD for instneD tht interfe energies re di0ult to mesureF woreoverD slight di'erene in one of the prmeters of the system n led to ig hnges in its solidi(tion proessF sn setion sFUFID we hve presented how the equilirium is modi(ed etween droE plet t the tip of nnowire nd one on )t sustrteF e very reent study hs reveled tht it n strongly in)uene the solidi(tion proessF sndeedD utter
    et al.

    reported the

    formtion of the metstle Eeuqe phse when ooling down euqe droplet t the tip of nnowire utter nd utterD PHIIF sn the sme studyD in the light of our results pulished one yer efore hlli
    et al.D

    PHIHD they deided to perform the sme experiment in the

    euEi systemF huring their ooling proedureD they reported tht no metstle eui phse formsD however they otined n morphous eui solidF his is therefore ompletely difE ferent result ompred to oursF sn our experimentsD the Ery mesurements lerly highlight tht the solidi(ed gold is rystlline s gold frgg peks re reorded when the solidEliquid trnsition tkes pleF hrough this simple exmpleD one n see tht there is still lot to e explined in the solidi(tion proess of these prtiulr liquidsF he experimentl onditions re thus elieved to strongly in)uene the numerous proE esses involved in the intertion etween the dropletsGislnds nd the underlying sustrteF pigure ssFI illustrtes this sttement y gthering the di'erent fetures tht hve een rised through the present studyF st shows tht the v proessD whih seems rther simple t (rst sight nd is widely used to grow nnowiresD enompss mny tomi proesses tht hve to e understood to improve our ontrol on the growth onditions nd more generlly to enlrge our knowledge of the physis t the nnosleF sn the following we ompre our (ndings to pulished results nd mke synthesis on the knowledge we hve so fr on the systems studied in this workF
    Structure of the interface and of the solidied droplets

    he knowledge of the struture of the interfe is of prime importne euse its e'et on the liquid9s struture nd the resulting islnds is ssumed to e very strongF roweverD in the ISV

    WL ? Reconstruction ?

    Contact angle ?

    Layering ?

    Si shell ?
    Surface diffusion ?

    Moving droplets ?

    Composition ?

    Ordered liquid ?

    Self-pinning / sharp interface ?


    Single / poly-crystal ? Si channel ? Si re-deposition?

    OR ?

    Size influence ?
    Figure VII.1  Scheme of the dierent features that raise questions concerning the rst stages of
    the VLS process. Some aspects concern the droplets (composition, layering, Si shell...), some others the free surface (surface diusion, WL, reconstruction...) or the interface with the substrate (interface structure, ordered liquid...). The solidication process is also concerned (phase separation, creation of Si channel, Si redeposition at the interface and amount of supercooling) as well as the resulting structure (OR, crystalline structure). The overall process being maybe dependent on the size which itself depends on the deposited amount of material as well as on the annealing temperature (and on time).

    litertureD this spet is ontroverted s )t interfes nd pinned droplets re oth reportedF en ellipsometril study hs een performed on the euGi@IIIA system y wmmler
    al. et

    who limed tht TH nm thik gold deposit forms homogeneous single rystl (lm

    t wmmler nd issmnnD IWWVF ith inresing temperturesD the (lm dewets nd turns into droplets t SWH u @RH u elow e AF he men sizes of the dropletsGislnds is out S m nd upon oolingD the solidi(tion is reorded t SRH uF his study isD to our knowledgeD the only one tht reports suh superooling ehviour @T =SH uA in the euE i@IIIA systemF he mount of superooling is equl to the one oserved in our se for the euEi@HHIA system @setion FIFPAD whih is ssumed to e lssil vlue s it hs lredy een reported y ghen
    et al.

    in IWTU ghen nd urnullD IWTUF rowever this study does

    not give ny informtion on the interfe struture whih is supposed to e one of the most relevnt prmeters to understnd the superooling e'etD s stted in ghpter F kym
    et al.

    rried out gold deposit in r t TUH u on i@IIIA sustrtesD

    resulting in diret formtion of dropletsF he iw imges reveled shrp interfe fter deposition kym nd nkD IWWUF henD one smple ws exposed to ir nd put k in r wheres the other one ws mintined in rF foth were then nneled t IHUH u for QH minF efter the ooling down to D the former smple displys gold islnds emedded ISW

    Chapter VII.

    Discussion and synthesis

    in the i sustrte wheres the ltter displys gold islnds sitting t the tip of i seF he uthors explin this e'et y ssuming tht the i equilirium onentrtion in the droplets is djusted y two di'erent proessesD depending on the nture of the free surfe @etween the dropletsAF sn the smple not exposed to irD they supposed tht the i onentrtion is ensured y the di'usion of the i surfe tomsF herefore the interfe remins shrp nd upon oolingD the i toms in exess re expelled elow the droplet nd form little i whiskerF sn the ontrryD the smple exposed to ir presents polluted free surfe whih is ssumed to prevent the surfe di'usion of i tomsF husD the i onentrtion equilirium is due to i di'usion under the droplets nd the islnds re pinnedF e similr study hs een performed y perrlis tht tkes ple under the eui droplets perrlis
    et al. et al.D

    who reported selfEpinning proess PHHVF elthough the eui droplets

    nneled only t e displyed shrp interfeD the ones nneled t higher tempertures @IIHH uA showed deep depressions one the gold islnds hd een removed fter solidi(E tionF he ssumed proess is lso the redjustment of the hemil omposition whih hs een mesured to follow the liquidus lineF he solidi(tion proess is otined y quenhingD whih prevents ny oservtion of the superooling ehviourF roweverD the uthors lso perE formed n experiment during whih the smple ws slowly ooled downF hey otin similr results with no i toms re(lling the depression nd they do not mention ny superooling e'etF sn oth ses the uthors lim for phse seprtion with i hnnels @s represented in pigure ssFIAD whih seem to e enhned in the se of ig dropletsF hese results re in ontrdition with erlier oservtions of wieh eui droplets hs lso een oserved y essel
    et al.

    who reorded the displement of IWWIF he displement of the


    et al.D

    eui droplets t high tempertures @WSH uA wieh

    et al.D

    et al.

    more reently essel

    PHHQF

    his study fouses on the vrition of the ontt ngle of the eui droplets s funtion of temperture on either i@HHIA or i@IIIAF sn ddition re reported displements of the droplets y inorportion or dissolution of the i toms t the surfeF he iw imges revel tht the droplets leve )t i@IIIA terres ehind themD whih lims for very )t interfesF enother signi(nt result is the oservtion of onstnt ontt ngle @RQ i A etween the droplets nd the i@IIIA surfe for tempertures rnging from TUH u to WPH u nd its sudden derese when the smple is heted higherF sn omprisonD it dereses linerly with inresing temperture on i@HHIAF he uthors onlude tht this peulir ehviour on i@IIIA is more onsistent with droplets presenting )t interfeF he rupt hnge in the ontt ngle s well s in the shpe of the droplet is disussed in terms of interfe energies X t the edges of the dropletsD reonstrution trnsition tkes pleD whih lolly modi(es the equiliriumF his explntion is supported y the ft tht the ontt ngle
    i. measured in the liquid phase.

    ITH

    (a)
    100 nm

    200 nm

    (b)
    200 nm

    (c)

    200 nm

    (d)

    (e)
    ii

    Figure VII.2  SEM images of a typical island present on the Si(111) substrate after a deposit of
    (a) 5 ML of Au annealed at 670 K (b) 6 ML AuSi eutectic annealed at 720 K (c) 10 ML annealed at 1055 K (d) 30 ML of Au annealed at 940 K and (e) 10 ML of Au annealed at 940 K.

    dereses linerly with temperture on the i@HHIA surfes for whih no surfe reonstruE tion is known to formF pigure ssFP ompres di'erent iw imges otined in this work in di'erent experimentl onditions @@AD @AD @dA nd @eAA to the iw imges of n islnd reported y essel
    et al.

    @@AA essel

    et al.D

    PHHQF por eh islnd i lok is present t

    its se iii F por the smple in imge @AD the ide ws to redue the potentil formtion of the depression under the droplet y oEdepositing eu nd i in euteti proportionF sn this experimentD very similr results hve een reorded ompred to pure gold deposit @in terms of surfe reonstrution nd superooling e'etAF he resulting islnd displys lrge i se with wht is supposed to e pure solid gold on top of itF sn omprisonD the islnd in imge @A otined y essel
    et al.

    D whih is y fr the lrgest oneD lso displys i se


    et al.

    ut the upper prt is omposed of two phsesF sn right is the eu phse wheres the i forms drk hnnelsF his kind of mrling solid struture hs lso een reported y perrlis
    onto which it is rather hard to distinguish.

    iii. Except for image (a), which corresponds to the smallest deposit and the lowest annealing temperature,

    ITI

    Chapter VII.

    Discussion and synthesis

    perrlis

    et al.D

    PHHVF his seems to e lso the se in our experiments when lrge islnds

    re formed @imge @dA right nd imge @eAAF herefore there might e ritil size vlue seprting two solidi(tion proessesF sf the droplet is smller thn the ritil sizeD ll the i toms solidify t the seD if it is lrgerD some of the i toms remin trpped in the liquid nd solidify in hnnelsF gonerning the struture of the interfeD our experiments support the ide of )t inE terfe etween the islnds nd the sustrte s presented y essel
    et al.

    insted of pinned

    islnds s reported y perrlis et al. F his is shown in the iw imges ut it is lso supported y Ery di'rtion resultsF sndeedD during the dewetting of the (lm we showed the hnge in the inEplne orienttion reltionship whih hs een explined using the gv theory @see setion sssFPFPAF his theory whih seems to e relevnt in the euEi se s well s in the euEqe nd elEi systems n however e pplied only if the two rystl ltties re ssumed to e prllelD i.
    e.

    the interfe is )tF sn ghpter sssD the pigure sssFII shows rocking-scan

    on the eu@PPHA ring t fter meltingEooling yle whih displys the two hrteristi peks of the two prinipl ys on(rming the )tness of the interfe fter solidi(tionF he diverging results otined in literture onerning the interfe geometry re ssuE med to rise euse of di'erenes in the preprtion of the surfeF sn the present workD the surfe preprtion is similr to tht of essel rEi@IIIA surfe perrlis
    et al.D et al.

    wheres perrlis

    et al.

    deposit gold on
    et al.

    PHHUF gonsequentlyD despite the ft tht perrlis

    suppose no di'erene etween the two proessesD we n legitimtely think tht the presene of r toms t the surfe n prevent the islnds from moving or t lest prevent the i toms of the surfe from di'usingD s stted y kym vity nd the pinned dropletF woreoverD perrlis et di'usion of the gold toms perrlis
    et al.D al. et al.

    kym nd nkD

    IWWUF he i toms re thus tken from under the droplets upon nneling resulting in the use this property to study the surfe PHHWF he removl of the r toms present etE

    ween the droplets n e done y nneling the smple t UVH uF he mesure of the gold spreding on i@IIIA is hieved y reording the formtion time of the @ 3 3AQH eu tht ours y di'usion of eu toms from the droplets to the newly re surfe similrly to wht hs een presented in the reEformtion of the @TTA reonstrution @see setion sFPFPAF enother study on(rms our ssumption X isopiello et residul y2 isopiello et
    al.D al.

    reported gold islnds emedded in

    the i@HHIA surfe when nneling thin gold (lm under )ux of x2 nd in the presene of PHHVF he resulting inEplne epitxil reltionships re totlly di'erent thn those found in the present study @see setion FIFQA whih gives evidene of ue on ue epitxyF his lso explins why in one of our experimentD rried out on the shHI emline nd for whih r onditions ould not e hievedD the surfe did not disply neither gold reonstrution nor superooling e'etsF ITP

    he )tness of the interfe implies tht upon oolingD the i toms in exess re exE pelled out of the droplets leving some )t terres onto whih the @TTA is more likely to form essel
    et al.D

    PHHQY wieh

    et al.D

    IWWIF iven if it is impossile to onlude tht the

    @TTA reonstrution n form elow the dropletsD we elieve tht the )t interfe is more fvourle to llowD t lest lollyD some similr strutures tht promote the sy in the liquidF es we hve seen tht polluted surfes suppress the surfe di'usion of goldD it seems relevnt to see if the @TTA gold reonstrutionD onsisting in thin dsored (lm spred ll over the sustrteD n lso hve n impt on the di'usion proesses of the i tomsF
    Surfactant properties of the (66) reconstruction

    [111] surface normal


    (111) _ (111)

    4x10
    Intensity (cps)

    ~ 16 min

    3x10

    [121]
    CTR _ (002)

    2x10

    10

    20 30 Time (min)

    40

    50

    Figure VII.3  left : Representation of the CTR, the red circle indicates where the intensity has
    been recorded. right : Variation of the CTR intensity as a function of time during the Si deposition.

    etullyD the question ws to know whether or not the @TTA reonstrution ould lokD in some wyD the i toms di'usion whih would thus hve n impt on the solidi(tion proessF o nswer thisD eui droplets were formed together with @TTA reonstrution s desried in previous setions nd ooled down to the superooling regime t THH uF he experiment onsisted in reording the vrition of intensity of g s funtion of time while i toms re dded y wfi @see pigure ssFQAF he reorded intensity displys periodi osilltions nd the elpsed time etween two mxim @IT minA orresponds to the ompletion of one i monolyer peidenhns9lD IWVWF pigure ssFR shows two radial-scans performed long the i[1 diretion efore nd fter the i depositF he two sns re 10] identil re)eting tht the lyerEyElyer growth of the i is possile even in the presene of the gold @TTA reonstrutionF his result is however not relly surprising s it on(rms tht eu is n e'etive surftnt for i @see setion sFPFPAF husD the liquid presents shrp interfe t the sustrtes9 surfe nd n exhnge i ITQ

    Chapter VII.

    Discussion and synthesis

    Intensity (cps)

    10

    before after Si deposition

    6/6 5/6

    10

    3/6
    2

    4/6 7/6 0.6 0.8 1.0 1.2

    8/6

    10

    0.4

    1.4

    h,k (r. l. u.)


    Figure VII.4 

    Radial-scans

    performed along the Si[1 10] azimuth before (black) and after the

    addition of Si in the presence of gold droplets together with a (66) reconstruction at 600 K.

    toms whih re ssumed to ome from the surfeF sn dditionD it is importnt to remind here tht is hs een shown in literture s well s in the present study tht Ph euEi rystls n form t the liquidEvpour interfeD either on @HHIA inrdi
    et al.D

    PHHW or

    @IIIA essel et al.D PHHHY hpyrko et al.D PHHT surfesF woreoverD we report in pigure FII the presene of liquidErod inditing the ordering of the liquid toms t the liquidEsustrte interfeF his ordering reveled similrities in its struture with the @TTA reonstrution lyer whih oexists with the eui droplets @see pigure FIHAF ith this desriptionD one esily understnds tht the liquid stteD through these experimentsD is rought in very unusul onditions nd thus revels unexpeted ehviourF he formtion of the eui shell oserved t the surfe of the droplets n e legitimtely supposed to e linked to the potentil formtion of siliides in this system prior to melting @see setion sssFIFP@A nd egnusD PHHUAF he formtion of islnds with siliide struture n not e ruled out even if no spei( metstle eui phse n e distinguished in the light of our experimentsF proesses mkes the study even more omplexF
    Size of gold islands on Si(111) bare substrates

    sn ddition

    to wht hs een presented oveD the question onerning the sizeEdependene of the di'erent

    es lredy pointed out in the se of the resulting strutures of the droplets fter solidi(E tionD it seems tht size n in)uene the di'erent physil proessesF sndeedD in our study of the epitxil reltionshipsD the dependene of the size of the grins towrd the seleted y hs een disussed @see setion sssFPFQ@dAAF sn dditionD the single or polyErystlline struture of the islnds s funtion of their size hs een reported in the hh work of egnus egnusD PHHU in good greement with our omprison etween qseD qs nd iw resultsF pinllyD in setion FRD we hve pointed out tht the in)uene of the @TTA reonstrution is ITR

    enhned when the surfeGvolume rtio is inresedD

    i. e.

    when the droplets re smllF

    he ontrol of the sizes of the tlyti droplets is hllenge s it ontrols the dimeter of the xs nd therefore their propertiesF he present work did not im to study quntiE ttively the prmeters tht ontrol the size of the dropletsF roweverD severl experiments using di'erent mounts of eu nd di'erent mximum nneling tempertures llowed us to ompreD for exmpleD the superooling e'et s funtion of the reltive sizes of the droplets @see setion FRAF pigure ssFS shows the iw imges nd the respetive size distriution t for T wv gold deposit nneled t mximum of Te @@A nd @AA nd for QH wv gold deposit nneled t mximum of WRH u @@A nd @dAA on i@IIIA surfesF

    (a)

    (b)

    1 m
    14

    10 m

    Percentage of islands (%)

    12 10 8 6 4 2 0

    Percentage of islands (%)

    (c)

    10 8 6 4 2 0

    (d)

    30 40 50 60 70 80 90 100 110 120 130

    400

    Diameter (nm)

    Diameter (nm)

    800

    1200

    1600

    Figure VII.5  SEM images of the resulting islands at RT after the deposition on Si(111) substrates
    of (a) 6 ML of Au annealed at distributions.

    Te

    (b) 30 ML annealed at 940 K. (c) and (d) Respective size

    he omprison etween this two extreme ses shows lrge di'erene of the men size of out one order of mgnitudeF hespite wide literture overing euiD it is only reently tht quntittive studies on the detils of the proess of kinetis growth hve een rried out u0no nd qrimldiD PHIHY egnusD PHHUF sn their studyD u0no et al. performed mesurement on the size of the eu islnds s funtion of the deposit nd the nneling time t VUQ u on i@IIIAF he uthors onlude tht t VUQ u the growth proess is governed y ITS

    Chapter VII.

    Discussion and synthesis

    10

    25

    Percentage of droplets (%)

    Percentage of islands (%)

    8 6 4 2 0

    20 15 10 5 0

    20

    40

    60 80 100 Diameter (nm)


    (a)

    120

    20

    40

    60 80 Diameter (nm)
    (b)

    100

    120

    Figure VII.6  Size distribution of gold islands performed by the annealing at 670 K of (a) 5 ML
    on Si(111) and (b) 4 ML on Ge(111) [Porret

    et al., 2011]

    surfe di'usion limited ripening with surfe di'usion oe0ient of 8.2 1016 m2 Fs1 in good greement with the mesures of perrlis et
    al.

    t this temperture perrlis et

    al.D

    PHHWF

    st is however worth to mention tht the sizes nd the formtion proesses n e strongly modi(ed on viinl surfes s the tomi steps o'er nuletion sites to the islnds uirkosin
    et al.D

    PHHIY riino nd tneD PHHSY egnusD PHHU F

    hue to the ft tht i nd qe re very similr elementsD the euEi nd euEqe systems re often thought to e similr s wellF snterestinglyD gold islnds otined y the dewetting of thin (lm deposited on qe@IIIA disply sizes similr to those otined on i@IIIA surfeF his n e seen in pigure ssFT whih ompres the size distriutions of gold islnds otined on i@IIIA in this work nd of gold islnds otined on qe@IIIA in similr experimentl onditions orret
    et al.D

    PHIIF his simple oservtion is not insigni(nt s severl reent

    results give signs of lrge di'erenes etween the two euteti systems s desried elowF
    Cases of Au-Ge and Al-Si systems

    es lredy presented in pigure sFPSD the euqe liquid lloy displys smller onentrtion )ututions thn the eui liquidF herefore weker tendeny of the euqe lloy to unmixing ould e expeted so tht lrger superooling vlues should e oservedF sn this workD the lrgest mesured superooling in the se of euEqe@IIIA is WH u @see setion sFIA wheres it is IQH u in the se of euEi@IIIA @see setion FPFPA for similr experimentl onditionsF purthermore men superooling vlue of SH u @see setion FIFPA ws found in the se of the euEi@HHIA systemF hese omprisons lerly highlight tht the stiliztion of the eui liquid on spei( i@IIIA surfe down to very low tempertures is surprisingF gontrry to the euEi systemD unexpeted superooling nd solidi(tion ehviour of ITT

    the euqe lloy hs een reported in literture ut the resons of suh ehviour still remin ontroversil edhikri
    et al.D

    PHHTY uodmk

    et al.D

    PHHUF roweverD in these studiesD the


    e.

    droplets re studied in the se of nnowires growthD i.

    under )ux of qer4 or qe2 r6 gsD

    the stiliztion of the liquid stte seems to e due to the growth )ux itself tht hnges the equilirium onditionsF herefore diret omprison with our experiments hs to e done very refullyF ome other di'erenes in physil properties etween the two lloys were lso pointed out in reent study of ershn et
    al.

    ershn et

    al.D

    PHHWF heir study onerned

    the sene of Ph rystl )oting t the surfe of the respetive liquid @in ontrry to the eui liquidAF he uthors disuss this feture y investigting the in)uene of the di'erene in enthlpy of mixing of the two lloys @EQH ktFmol1 for eui nd EPIFS ktFmol1 for euqeA ut n not onlude with stisftory explntionF sn ddition the eui euteti liquid is known to form morphous strutures y quenhing ulement
    et al.D

    IWTH wheres the euqe

    liquid rther forms metstle strutures ykmoto nd wsslskiD IWVR re)eting quite di'erent solidi(tion proessesF hereforeD even if it seems ttrtive t (rst glneD the omprison etween the two systems remins quite risky nd requires further experimentsF he study of the elEi system hs een motivted y its potentil sustitution to eu s tlystF he report of the growth of i nnowires with el under the euteti temperture hs een reported to e proess ng et
    al.D

    PHHTF roweverD more reent studies report

    tht i nnowires n e grown through v proess down to UWH u ut spei( therml history @pregrowth nnelingA s well s spei( growth )ux hve to e respeted ser
    et al.D

    PHHWY ghoi

    et al.D

    PHIIF sn the present workD the experiments performed on the elE

    i@IIIA systemD ompred to euEi@IIIAD led to similr results in terms of dewetting ut the reorded superooling vlue is of TH u for this systemF elthough it hs een reported tht the interfe etween the eli liquid nd i@IIIA surfe exhiits n tomilly )t trnsition lyer eri et
    al.D

    PHHHD suh ordering n not e sid to our in our experimentsF

    he eli euteti liquid n thus e signi(ntly superooledD however to ompre to the eui systemD it is rther relevnt to use normlized superooling vlue X Tn = T /Te F por eli Tn = HFII wheres it omes Tn = HFPI for euiF gomprtivelyD the superooling e'et is therefore muh lrger in the eui systemF sn the this mnusript we hve presented the superooling e'et y giving the solidi(tion temperture Ts F por omprisons within severl experiments on the sme systemD we hve used the euteti temperture Te s referene temperture nd in extensionD expressed in ertin ses the superooling vlue s T = Te Ts F he normlized vlue given just ove ws lso expressed using the euteti point s the refereneF roweverD even if the solute vlue of the lowest reorded solidi(tion temperture @SHH uA is very low nd unexpeted for the euEi systemD Tn of HFPI is importnt ut not extrordinry inet
    et al.D

    PHHPF ITU

    Chapter VII.

    Discussion and synthesis

    hereforeD if one relly wnts to relize in wht extend the superooling mount reorded in this work in the euEi system is importntD study of the suEeuteti region is neessryF
    The sub-eutectic region and the real supercooling value

    sn pigure ssFU is plotted n extrt from the ulk euEi phse digrm with represenE ttions of the melting nd solidi(tion yles of the eui islnds in the se of i@IIIAE @TTAeu reonstruted smpleF

    Temperature (K)

    T = ~360 K

    TE

    Ts

    ~0.15 ~0.186

    Si atomic content
    Figure VII.7  Extract from the bulk Au-Si phase diagram together with representations of the
    melting and solidication cycles of AuSi islands on an Si(111)-(66)Au reconstructed surface. The numbers 1 to 5 refer to successive experimental steps, and the large black arrows indicate the pathways followed by the islands during heating/cooling cycles.

    he numers I to S refer to the suessive experimentl steps studied throughout this work iv F eove Te D either on heting or oolingD the liquid is expeted to follow the i liquidus lineF sf the smple is nneled t UPH u for instneD the mximum i ontent in the droplets rehes PP tF7F pon oolingD the i toms re expelled from the droplets nd t Te D the onentrtion rehes the euteti oneF felow Te D the onentrtion is ssumed to follow the metstle i liquidus represented y the extrpolted dotted lineF hereforeD t the lowest
    iv. Deposit, dewetting, melting, cooling down, solidication.

    ITV

    reorded solidi(tion temperture @Ts SIH uAD the omposition of the droplet orresponds to

    IS tF7 i nd the degree of superooling represented y the red rrow hs to e mesured


    etween the solidi(tion point nd the eu liquidus ove Te F he superooling vlue is therefore QTH u nd orresponds to Tn of HFRP whih is very lrge vlue highlighting one gin the prtiulr ehviour of the eui euteti liquid in this workF
    Complementary information provided by closed systems

    sn the mjor prt of this workD the experiments on euEiD euEqe nd elEi lloys hve een performed in wht n e lled open systemsD
    i. e.

    in ontt with g reservoirF

    st underlines the ft tht the mount of the g phse @i or qeA in the droplets n evolve with temperture @nd timeA nd lso modify the equilirium onditions suh s the struture nd the energy of the surfesGinterfesF xivelyD we deided to perform the sme kind of experiments on inert sustrtes to suppress these e'ets y working with losed systemF sn the se of eui on iy2 surfeD the most interesting result onerns the very wide temperture rnge into whih the solidi(tion or the melting proess tke ple @see setion sFQFIAF sndeedD depending on the eu pek under onsidertionD the superooling vlue vries from TH u to IPH uF sn dditionD unssigned peks re reorded fter the solidi(tion proess whih might orrespond to the pperne of siliide phsesF por euqe on either iy2 or el2 y3 D we hd to fe prolem of onentrtion whih n not e ensured to e the euteti oneF sn oth experiments we hd to proeed to the ddition of qe t temperture higher thn the euteti one nd reord the dispperne of the eu peks t the sme timeF sn the se of el2 y3 it even seems tht not ll the islnds hve een meltedF rowever on the iy2 sustrtesD the pperne nd the dispperne of the eu@PPHA pek re reorded over wide temperture rnge wheres the eu@IIIA pek @s well s the peksA ppers t very low temperture of SHH u ut lso disppers well elow e @t SUH uA upon hetingF yn el2 y3 D the eu@PPHA intensity vries with temperture ut is still present even when heting the smple TH u ove e D the study of the other peks @eu@IIIA nd A ould mke us onlude to superooling vlue of PPH uD with segregtion proessF glerly these experiments disply superooling nd solidi(tion proesses tht re not fully understoodF he importnt prolem seems to e the ontrol of the onentrtion whih n led to di'erent ehviour for the di'erent droplets on the sme sustrteF e strong temperture grdient over the el2 y3 surfe n lso not e exluded s this prtiulr smple hd to e mounted in spei( wyF sn dditionD the lirtion tehnique of the pyrometer on this surfe n e t the origin of lrger unertinties on the temperture vluesF ITW

    Chapter VII.

    Discussion and synthesis

    AuSi / SiO2

    Au / Si(111)
    280 nm

    20 nm 28 nm

    Figure VII.8  Left : SEM picture of the resulting islands that formed during the experiment
    presented in section VI.3.1 concerning the 6 ML AuSi deposit on SiO2 substrates annealed at 690 K. Right : SEM picture of the resulting islands that formed during a typical experiment with a deposit of 6 ML of Au on a Si(111) surface annealed at 720 K. The scale bar is the same for the two images to highlight the size dierence between the two experiments.

    he left hnd side of pigure ssFV shows iw piture of the resulting islnds formed during the experiment of eui on iy2 F he men size of the islnds is PH nmF urprisingly it is out ten times smller thn typil islnd tht forms on i@IIIA sustrte in similr onditions @right hnd side of pigure ssFVAF he sizes re of the sme order for euqe islnds on iy2 nd even smller on el2 y3 @round IH nmAF es the di'usion length is ssumed to e lrger on perfetly len oxide surfesD this result my rise euse of not properly prepred surfes X there must e defets suh s gy or ry dsored speies preventing the surfe di'usionF he di'erene in size oserved etween the open nd losed system might explin the di'erene in superooling ehviour s it n modify the ontt ngle @see setion sssFIFPA nd thus the solidi(tion proess @see pigure sFIWA v F st n lso e t the origin of the melting the eui islnds elow e @see pigure sFIS@AAF sndeedD very smll rystllites re known to melt elow their theoretil melting pointF his e'et ould not e studied in more detils here ut further experiment following this ide would e interesting to omplete the study of these intriguing euteti liquidsF rowever the importnt spets of this work remin the liquid nd surfeGinterfe strutures tht re elieved to e the key prmetersF sndeedD the relevnt question is not to know whether or not the struture of the sustrte hs n in)uene on the liquid stte nd the solidi(tion ut rther t THH uD in the superooled stteF
    v. The alumina substrates were historically used to increase the contact angle and get closer to homogeneous nucleation conditions [Turnbull and Cech, 1950; Perepezko and Paik, 1984].

    how

    it in)uenes themF

    pigure ssFW is the reiprol spe mp of the euqe liquid on the el2 y3 sustrte reorded

    IUH

    Au(111)

    Ge(311)

    Ge(111)

    _ (3030)

    1st liquid order Unmelted Au(220)

    _ (1120)

    _ (2240)

    Figure VII.9  Reciprocal space map covering 30 of reciprocal space recorded for AuGe on Al2 O3
    at 600 K. The red colors correspond to high intensities whereas blue correspond to low ones and yellow to intermediate ones. This map displays the Al2 O3 monocrystal Bragg peaks and CTRs. The intense ring corresponds to the rst order of the liquid structure factor. The inset represents the sector surrounded with the white-dashed line in the solid state after solidication.

    por this liquidD no lterl vrition of the intensity is reorded whih indites norml isotropi struture of the liquidF sn inset is plotted the prt of the mp surrounded y the whiteEdshed line ut t D fter solidi(tion of the systemF gompred to the solid mp reorded in the se of eu on qe@IIIA @see pigure sFTAD the heyeEherrer rings disply perfetly onstnt distriution of the intensity @oth for eu nd qeAF his revels tht the resulting solid eu @nd qeA onsists in untextured polyrystlline grins @i.
    e.

    powderAF sn

    other wordsD the solidi(tion of euqe on n el2 y3 surfe whih seems to undergo very lrge superoolingD results in solid struture tht does not shre strong epitxil reltionE ship with the sustrteF sn omprisonD the weker superooling ehviour of the sme liquid reorded on qe@IIIA ws followed y solid struture tht displyed strong inEplne orienE ttion reltionshipsF sn the light of these numerous experimentsD there is no dout tht the liquid struture nd the superooling ehviour strongly depends on the struture of the sustrte9s surfeF e surfe n t s nulent while nother do not help solidi(tionF por the euEi systemD it is even more relevnt when ompring the two di'erent open systems tht re eu on i@HHIA nd eu on i@IIIAF he i@HHIA sustrteD onto whih very low IUI

    Chapter VII.

    Discussion and synthesis

    superooling ws reordedD presents ler prllel inEplne epitxy fter solidi(tion of the droplets @see pigure FQAF st revels tht the i@HHIA sustrte is good nuletion surfe for oth i @whih is not surprisingA nd euD the eui lloyed droplets undergoing unmixing due to onentrtion )ututionsF yn the i@IIIA sustrteD the superooling e'et is enhned nd the study of the inEplne orienttion reltionships etween the solidi(ed islnds nd the i surfe shows tht it is less esy for the two rystls to mth their respetive struturesF woreoverD the superooling e'et is even more enhned in the presene of the @TTA surfe reonstrutionD nd t the sme timeD the ordering of the liquid lose to the interfe is oservedF he prllel studies of this i@IIIAE@TTAeu reonstrution whih lolly displys pentgonl rrngementD the ordering of the liquid nd the simultion results mke us elieve tht the )t interfe etween the liquid nd the i@IIIA surfe promote ioshedrl short rnge order tht would e t the origin of the lowering of the onentrtion )ututions nd the stiliztion of the liquid phseF

    IUP

    Conclusion and Perspectives

    he im of this hh ws to hrterize the ehviour of the eui euteti liquid droplets in intertion with i@IIIA sustrtesF he prolem hs een tkled y studyingD in-situ nd using the synhrotron rdition mostly in the qs geometryD the di'erent steps omposing the overll proess X the depositD the dewettingD the meltingD the nnelingD the formtion of surfe strutures nd the solidi(tionF e hve shown tht t D the deposition of severl monolyers @U wvA results in the formtion of )t polyrystlline gold (lmD with mjority of the grins displying however n epitxil reltionship with eu nd i ltties eing prllelF he very few experiments rried out with smll deposits @P wvA showed tht t the gold n e ssumed to e lloyed to the sustrte with the possiility of forming some eui phsesF ith further depositionD the (lm grows with the pperne of rystlline gold grins forming shrp interfe with the i sustrteF sf the deposit is rried out t higher temperturesD typilly SUH uD the equilirium onditions re modi(ed nd the growth follows trnskiEurstnow modeF ith the inrese of the tempertureD the (lm is sujeted to smll mplitude )ututions roughening its surfeF he dewetting proess is found to tke ple when the temperture of STH u is rehed X the (lm trnsforms into islndsF et the sme timeD due to di'ering therml expnsions of the two mterils with the nnelingD the mismth vlues etween the two ltties evolve nd the epitxil reltionships re found to hngeF his e'et hs een explined using the gv theoryF he most stle on(gurtion experimentlly mesuE red round THH u orresponds to the eu@IIIA plnes prllel to the i@IIIA sustrte turned y IW with respet to the prllel epitxyF his on(gurtion is reovered fter melting nd solidi(tion of the dropletsF hen the temperture equls the euteti temperture Te we oserve the melting of the islnds ttesting of the di'usion of the i toms to djust the onentrtion with respet to the euteti oneF sn our experimentsD the i toms needed to djust the droplets9 onentrtion re elieved to e provided y surfe di'usionF sndeedD severl mesurements show tht the surfe di'uE sion of i is enhned due to the surftnt properties of the wetting lyer of goldF woreoverD this wetting lyer is found to indue two surfe reonstrutions X the i@IIIAE@TTAeu nd the i@IIIAE@ 3 3AQH eu F he trnsition etween the two is reversile nd tkes ple round UHH uF he quntittive nlysis of the @TTA reonstrution hs reveled tht this ltter presents very spei( struture whih is omposed of two domins nd ontins triE mers nd pentgonsF sn ddition to the formtion of eui Ph rystl t the surfe of the dropletsD the ooling experiments hve reveled tht the superooling ehviour is in)uened y the orienttion of the sustrtes s well s y the surfe reonstrutionsF he lrgest superooling vlue hs IUQ

    Conclusion and Perspectives

    een mesured with i@IIIAE@TTAeu reonstruted smpleD the smllest on the i@HHIA sustrteD the i@IIIAE@ 3 3AQH eu eing intermediteF sn dditionD in the se of the i@IIIAE@TTAeu reonstruted surfeD the eui liquid reveled n ordering t the interfe with the sustrteF his liquid lso seems to present struturl similrities with the @TTA reonstrutionD the pentgonl rrngementD tht ould stilize the liquid stte down to very low temperturesF he euEqe@IIIA nd elEi@IIIA systems hve lso een studiedF elthough the temperE ture ontrol elow RSH u is quite unesyD it seems tht the growth of eu on qe@IIIA follows trnskiEurstnow mode with the wetting lyer induing @ 3 3AQH reonstrutionF he inEplne orienttion reltionships di'er from those mesured in the euEi@IIIA system ut n lso e explined using the gv theoryF he elEi@IIIA se is more similr to the euEi@IIIA in terms of dewetting proess nd epitxil reltionships ut no surfe reE onstrution hs een reordedF gonerning the superooling ehviour of oth systemsD the mesured vlues re not s surprising s in the euEi@IIIA systemF woreoverD it is elieved tht the omprison etween the di'erent systems onerning the liquid ehviour is still premture nd requires further experiments s well s some simultion investigtionsF he role of simultions is supposed to e key point in our understnding of these euteti lloys in the futureF

    his investigtion of the euEi system nd more generlly of metlEg systemsD even if it is restrined to the se of nnometri dropletsD hs rought nswers to severl questions onerning the struture nd the ehviour of liquid tlystsF here re however still some spets tht re elieved to require further studies to go eyond the urrent knowledgeF he most importnt one seems to e y fr the question onerning the existene or not of longErnge ordered reonstrution t the sustrteEdroplet interfeF he est wy to nswer this question would e the investigtion of single islndF his ould e done using nnoE sized emF sndeedD with em of the order of the islnd9s sizeD y pling the detetor on @TTA re)etion nd t the sme time snning the smpleD one ould reord the intensity vrition s funtion of the position of the em on the surfeF he position of the islnds t the surfe ould lso e determined using similr ide y pling the detetor on gold frgg pek or y using the )uoresene signlF ith still the sme ideD it would e possile to study the epitxil reltionships or the rystlline strutures of the islnds s funtion of their sizesF roweverD the will of hrterizing the in)uene of the size on the struturlGmorphologil fetures omes from the ft tht the dewetting of thin gold (lm on nominl i sustrte results in prtiles with hrteristis presenting lrge distriutionF sdellyD solution is IUR

    to (nd wy to form very identil prtiles homogeneously spred over the sustrteF sn this wyD the hrteriztion of spei( feture n e done using wide spot tht lights severl prtiles whih re ssumed to ehve in the sme wyF e nie smple to do so is the use of ptterned sustrtes tht llows to hoose the size s well s the position of the prtiles on the sustrteF he use of ptterned sustrtes omined to in-situ studies of the growth of nnowires @through ghA is the next step to go further in the understnding of suh systemsF e nie experiment would e the study of the superooling in eui droplets t the tip of nnowires grown on ptterned sustrteF sn the one hndD these kinds of experiments re performed in onstrined environment ut in the other hndD they ensure etter reproduiility s well s stronger ontrol of the prmetersF sn ddition to ll thisD very importnt spet still remins our inpity to mesure the onentrtion in the dropletsF eove Te D it is resonly ssumed to follow the i liquidus lineD however the question remins open when ooling down elow Te in the superooling regime into whih the formtion of metstle solid phses n not e exludedF feyond the improvement of our knowledge on the ehviour of superooled liquidsD the understnding of the physil proesses rising in euteti liquid is very importnt to hve etter ontrol on the tlyti retionsF he improvement of the ontrol of the growth prmeters would led to the possiility of reting more omplex ojetsF woreoverD s the hrteristis of the g nnowires strongly depend on the experimentl onditions suh s the tempertureD the omposition nd the deposition )uxD the possiility of growing nnowires well elow the euteti temperture thus llows to imgine the growth of nnowires with new morphologies nd strutures nd thereforeD new propertiesF

    IUS

    Annexe : Structure factors dataset and model

    Annexe : Structure factors dataset and model

    Table 1  List of the experimental structure factors of the reections (using the Miller indexes in the reciprocal unit cell of the (66) reconstruction), the total error .

    h
    5 5 5 6

    k
    4 4 5 1 1 2 2 3 3 4 4 5 5 0 0 1 1 2 2 3 3 4 4 5 5 6 6 7 0 0 1 1 2 2 3

    l
    -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096

    Fdata
    24.17 23.67 152.17 46.55 47.24 47.13 45.92 129.66 130.89 69.83 68.13 90.98 90.01 15.59 13.06 73.45 72.71 239.07 246.57 170.73 169.45 79.50 71.11 107.89 107.91 41.84 42.77 66.72 113.77 111.09 242.16 252.36 252.16 255.23 78.65

    3.61 3.90 7.55 2.62 2.88 2.83 3.05 6.44 7.05 4.09 4.39 5.29 5.23 5.04 5.68 3.83 4.12 11.76 13.13 8.44 9.09 5.25 5.58 6.07 6.09 4.36 4.25 3.82 5.71 6.08 12.16 13.68 12.39 13.59 8.95

    Fmodel
    26.45 26.45 154.97 43.75 43.75 41.81 41.81 134.13 134.13 69.29 69.29 84.16 84.16 13.56 13.56 78.85 78.85 269.82 269.82 175.29 175.29 75.35 75.35 99.96 99.96 33.63 33.63 64.32 115.41 115.41 252.27 252.27 191.91 191.91 37.56

    2
    0.40 0.51 0.14 1.14 1.47 3.54 1.82 0.48 0.21 0.02 0.07 1.66 1.25 0.16 0.01 1.99 2.22 6.84 3.14 0.29 0.41 0.62 0.58 1.71 1.71 3.54 4.62 0.40 0.08 0.50 0.69 0.00 23.64 21.71 21.08

    the corresponding calcu-

    2 lated structure factor values and the partial

    h
    1 2 2 2 2 3 3 3 3 3 3 3 4 4 4 4 4 4 4 4 4 5 5 5 5 5 5 5 5

    k
    1 1 1 2 2 0 0 1 1 2 2 3 0 0 1 1 2 2 3 3 4 0 0 1 1 2 2 3 3

    l
    0.096 -0.096 0.096 0.07 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096

    Fdata
    22.49 12.39 13.82 167.74 185.62 21.95 22.60 30.02 29.52 25.71 24.72 73.46 12.91 14.03 69.23 67.27 17.66 19.07 121.37 123.30 72.80 16.35 17.76 46.58 46.34 48.41 48.57 92.95 91.78

    1.11 1.06 1.11 7.46 8.43 1.12 1.31 1.53 1.61 1.58 1.57 3.49 1.74 1.66 3.44 3.35 2.07 2.07 6.01 6.10 3.54 2.02 2.11 2.36 2.50 2.63 2.87 4.66 5.01

    Fmodel
    21.24 12.07 12.07 169.76 169.75 20.96 20.96 29.68 29.68 24.53 24.53 74.31 13.65 13.65 66.27 66.27 22.28 22.28 131.13 131.13 66.42 17.79 17.79 45.58 45.58 51.87 51.87 87.85 87.85

    2
    1.26 0.09 2.48 0.07 3.54 0.78 1.57 0.05 0.01 0.56 0.02 0.06 0.18 0.05 0.74 0.09 4.99 2.41 2.64 1.65 3.25 0.51 0.00 0.18 0.09 1.73 1.32 1.20 0.62

    6 6 6 6 6 6 6 6 6 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 8 8 8 8 8 8 8

    IUV

    h
    8 8 8 8 8 8 8 8 8 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 10 10 10 10

    k
    3 4 4 5 5 6 6 7 7 0 0 0 0 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8 9 9 0 0 1 1

    l
    0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 -0.07 0.07 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 0.07 0.096 -0.096 0.096 -0.096 0.096

    Fdata
    68.64 37.84 37.22 39.75 37.65 30.06 29.99 34.00 38.88 198.74 178.59 178.45 196.82 109.44 108.84 62.75 63.86 26.69 22.38 54.19 48.48 27.06 28.95 42.47 44.69 198.48 203.89 59.63 58.67 80.06 88.24 60.58 59.12 73.34 72.38

    7.47 3.88 4.33 4.07 4.12 4.87 4.92 5.63 5.06 9.79 8.81 8.81 10.52 5.57 6.03 3.71 4.05 4.67 6.23 3.89 3.84 5.09 4.79 4.46 4.32 11.46 11.63 4.70 4.66 3.93 4.86 3.74 4.03 4.02 4.32

    Fmodel
    37.56 42.52 42.52 39.82 39.82 28.48 28.48 43.17 43.17 198.79 198.80 198.80 198.79 113.26 113.26 60.72 60.72 26.93 26.93 53.54 53.54 30.07 30.07 44.92 44.92 182.99 182.99 56.77 56.77 81.99 81.98 62.46 62.46 75.73 75.73

    2
    17.31 1.45 1.50 0.00 0.28 0.11 0.09 2.65 0.72 0.00 5.26 5.33 0.04 0.47 0.54 0.30 0.60 0.00 0.53 0.03 1.73 0.35 0.05 0.30 0.00 1.83 3.23 0.37 0.17 0.24 1.66 0.25 0.69 0.35 0.60

    h
    10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11

    k
    2 2 3 3 4 4 5 5 6 6 7 7 8 8 9 9 10 0 0 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8

    l
    -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096

    Fdata
    30.08 32.57 46.83 42.64 58.06 61.79 69.33 71.50 116.25 115.76 108.08 110.67 57.31 57.39 76.57 75.52 67.49 34.69 35.10 55.00 52.82 40.50 40.80 43.83 43.04 58.12 60.54 139.02 141.64 88.53 89.66 83.70 85.08 31.48 31.19

    4.21 4.17 3.50 3.82 4.06 4.13 4.59 4.64 6.80 6.77 6.21 6.34 4.82 4.71 5.31 5.23 4.26 3.58 3.87 3.50 3.81 3.89 3.90 4.07 4.14 4.61 4.58 7.71 7.84 5.43 5.51 5.34 5.32 7.50 7.11

    Fmodel
    35.49 35.49 44.18 44.18 59.03 59.03 73.71 73.71 115.97 115.97 110.07 110.07 56.86 56.86 80.66 80.66 55.72 31.84 31.84 53.82 53.82 44.57 44.57 41.90 41.90 56.81 56.81 150.14 150.14 85.62 85.62 82.38 82.38 31.39 31.39

    2
    1.65 0.49 0.58 0.16 0.06 0.45 0.91 0.23 0.00 0.00 0.10 0.01 0.01 0.01 0.59 0.97 7.63 0.63 0.71 0.11 0.07 1.10 0.93 0.23 0.08 0.08 0.66 2.08 1.18 0.29 0.54 0.06 0.26 0.00 0.00

    IUW

    Annexe : Structure factors dataset and model

    h
    11 11 11 11 11 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 13 13 13 13 13 13 13 13 13 13 13 13

    k
    9 9 10 10 11 1 1 2 2 4 4 5 5 7 7 8 8 9 9 10 10 11 11 0 0 1 1 2 2 3 3 4 4 5 5

    l
    -0.096 0.096 -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096

    Fdata
    61.10 61.60 42.54 41.27 55.06 38.23 37.55 28.04 31.34 46.90 46.35 88.06 86.87 23.04 26.16 63.97 63.30 36.39 35.64 59.34 59.13 33.76 24.12 30.95 30.68 37.68 40.89 123.74 124.16 94.73 94.69 55.36 56.43 58.48 77.22

    4.90 4.77 5.46 5.48 4.52 4.12 4.20 5.69 5.12 4.86 4.83 5.44 5.33 11.93 8.88 4.98 4.82 6.27 6.09 5.29 5.22 9.71 11.64 5.04 5.07 5.20 4.91 6.97 7.00 5.64 5.63 4.85 4.71 15.79 10.19

    Fmodel
    61.82 61.82 39.06 39.06 51.58 38.18 38.18 33.55 33.55 48.76 48.76 85.35 85.35 31.55 31.55 68.85 68.85 37.72 37.72 52.43 52.43 32.03 32.03 26.06 26.06 45.09 45.09 126.22 126.22 93.71 93.71 56.44 56.44 53.34 53.34

    2
    0.02 0.00 0.41 0.16 0.59 0.00 0.02 0.94 0.19 0.15 0.25 0.25 0.08 0.51 0.37 0.96 1.32 0.04 0.12 1.71 1.65 0.03 0.46 0.94 0.83 2.03 0.73 0.13 0.09 0.03 0.03 0.05 0.00 0.11 5.49

    h
    13 13 13 13 13 13 13 13 13 13 13 13 13 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14

    k
    6 7 7 8 8 9 9 10 10 11 12 12 13 0 0 1 1 2 2 2 2 3 3 4 4 5 6 6 7 7 8 8 9 9 10

    l
    0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 -0.07 0.07 0.096 -0.096 0.096 -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096

    Fdata
    32.96 47.14 51.16 78.80 77.47 84.11 82.24 15.60 23.20 4.11 47.36 37.95 74.87 110.61 109.53 121.19 121.71 128.19 115.12 109.02 119.76 93.50 90.73 75.65 76.70 19.92 79.03 80.04 91.78 93.71 94.79 100.39 45.49 44.35 14.49

    9.54 5.35 5.01 5.34 5.23 5.55 5.44 11.09 12.40 15.62 7.75 9.22 4.89 6.47 5.80 6.80 6.82 7.17 5.95 5.69 6.73 5.70 5.55 5.61 5.46 16.64 5.27 5.22 5.76 5.77 5.88 6.07 6.16 6.16 11.40

    Fmodel
    34.03 40.13 40.13 77.04 77.04 73.41 73.41 25.65 25.65 39.36 48.27 48.27 61.01 117.99 117.99 130.98 130.98 111.58 111.58 111.58 111.58 95.38 95.38 80.59 80.59 9.93 73.15 73.15 101.65 101.65 76.53 76.53 46.75 46.75 23.21

    2
    0.01 1.72 4.85 0.11 0.01 3.72 2.64 0.82 0.04 5.09 0.01 1.25 8.03 1.30 2.13 2.07 1.85 5.37 0.35 0.20 1.48 0.11 0.70 0.77 0.51 0.36 1.24 1.74 2.93 1.89 9.64 15.45 0.04 0.15 0.58

    IVH

    h
    14 14 14 14 14 14 14 14 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15

    k
    10 11 11 12 12 13 13 14 0 0 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8 9 9 10 10 11 11 12 12 13

    l
    0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096

    Fdata
    18.47 47.94 50.58 43.22 46.08 32.25 35.48 20.39 87.36 85.10 81.51 80.22 50.13 56.85 31.73 28.96 101.72 102.70 63.17 66.12 70.37 71.29 62.77 69.89 52.15 51.44 45.48 46.54 93.72 85.06 33.04 36.42 37.39 38.47 54.93

    12.03 7.41 6.98 6.85 6.25 8.19 7.20 9.48 5.37 5.27 5.25 5.16 15.87 9.70 9.08 10.21 6.16 6.12 5.05 4.94 5.13 5.07 6.50 6.14 5.65 5.60 7.14 7.05 7.79 7.96 8.46 7.52 7.37 6.89 5.65

    Fmodel
    23.21 54.72 54.72 38.84 38.84 35.27 35.27 7.48 95.57 95.57 74.29 74.29 43.13 43.13 44.93 44.93 105.48 105.48 63.16 63.16 74.80 74.80 69.33 69.33 42.84 42.84 53.24 53.24 94.94 94.94 37.07 37.07 32.90 32.90 49.24

    2
    0.16 0.84 0.35 0.41 1.34 0.14 0.00 1.85 2.34 3.95 1.89 1.32 0.19 2.00 2.11 2.45 0.37 0.21 0.00 0.36 0.75 0.48 1.02 0.01 2.72 2.36 1.18 0.90 0.02 1.54 0.23 0.01 0.37 0.65 1.01

    h
    15 15 15 15 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16

    k
    13 14 14 15 0 0 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 9 9 10 10 11 11 12 12 13 13 14 14 15 15

    l
    0.096 -0.096 0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096

    Fdata
    53.61 25.91 28.76 43.66 101.38 99.85 111.16 109.73 64.81 64.43 102.10 105.32 70.07 82.82 31.04 25.08 49.72 49.57 59.76 61.84 44.85 112.04 112.30 96.53 89.42 33.90 25.67 52.03 50.48 12.34 18.65 32.38 28.13 56.24 55.17

    5.56 11.37 8.74 4.93 6.28 6.15 6.56 6.45 5.71 5.51 6.17 6.24 5.12 5.37 7.48 10.12 5.62 5.59 5.34 5.29 13.28 7.65 7.63 6.17 5.88 8.19 10.44 5.74 5.83 10.15 11.15 7.67 8.79 5.41 5.38

    Fmodel
    49.24 26.21 26.21 41.76 95.67 95.67 113.22 113.22 62.72 62.72 98.26 98.26 67.21 67.21 36.09 36.09 51.80 51.80 68.74 68.74 43.12 121.39 121.39 84.46 84.46 29.70 29.70 48.77 48.77 15.91 15.91 35.10 35.10 54.77 54.77

    2
    0.62 0.00 0.09 0.15 0.83 0.46 0.10 0.29 0.13 0.10 0.39 1.28 0.31 8.45 0.46 1.18 0.14 0.16 2.83 1.70 0.02 1.50 1.42 3.82 0.71 0.26 0.15 0.32 0.09 0.12 0.06 0.13 0.63 0.07 0.01

    IVI

    Annexe : Structure factors dataset and model

    h
    17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 18 18 18 18 18

    k
    0 0 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8 9 9 10 10 11 11 12 12 13 13 14 14 1 1 2 2 3

    l
    -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096

    Fdata
    93.86 105.00 50.39 41.69 33.71 34.99 27.14 25.49 16.61 20.02 69.88 70.53 30.99 22.32 60.94 66.15 53.48 53.32 45.55 49.74 29.57 26.76 25.44 30.14 53.25 52.79 33.76 32.97 20.28 15.16 51.70 41.96 38.75 40.39 28.56

    7.84 7.41 7.29 7.59 8.06 7.36 9.44 10.32 10.46 11.16 5.24 5.21 8.54 12.06 10.12 9.27 6.05 6.07 6.33 5.88 9.98 11.45 11.64 8.57 5.97 5.89 7.44 7.41 11.28 10.28 6.68 7.90 6.99 6.63 11.02

    Fmodel
    89.12 89.12 44.10 44.10 43.65 43.65 29.76 29.76 21.95 21.95 68.53 68.53 37.95 37.95 63.35 63.35 51.18 51.18 53.08 53.08 44.83 44.83 32.60 32.60 53.67 53.67 34.23 34.23 21.71 21.71 56.39 56.39 32.04 32.04 28.49

    2
    0.37 4.59 0.74 0.10 1.52 1.38 0.08 0.17 0.26 0.03 0.07 0.15 0.66 1.68 0.06 0.09 0.15 0.12 1.41 0.32 2.34 2.49 0.38 0.08 0.01 0.02 0.00 0.03 0.02 0.41 0.49 3.34 0.92 1.59 0.00

    h
    18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19

    k
    3 4 4 5 5 7 7 8 8 10 10 11 11 13 13 0 0 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8 9 9

    l
    0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096

    Fdata
    29.04 34.75 37.27 44.36 50.38 62.26 63.22 59.55 56.89 26.16 24.97 27.52 19.76 20.82 22.58 17.87 24.68 52.82 56.17 43.81 44.35 17.73 17.74 38.80 67.65 57.43 60.58 30.69 35.03 59.81 60.40 25.76 33.66 13.95 24.85

    9.85 7.06 6.44 6.32 5.78 5.66 5.62 5.59 5.65 11.96 12.69 16.81 15.15 11.61 11.86 11.22 9.62 7.80 7.32 5.88 5.69 10.99 10.91 17.17 10.05 9.18 8.87 9.18 7.45 5.58 5.56 15.46 13.89 10.37 11.69

    Fmodel
    28.49 35.27 35.27 42.33 42.33 63.51 63.51 51.27 51.27 27.00 27.00 18.39 18.39 14.20 14.20 15.44 15.44 50.38 50.38 45.83 45.83 15.04 15.04 49.95 49.95 53.72 53.72 38.19 38.19 66.96 66.96 25.78 25.78 17.71 17.71

    2
    0.00 0.01 0.10 0.10 1.94 0.05 0.00 2.20 0.99 0.00 0.03 0.29 0.01 0.33 0.50 0.05 0.92 0.10 0.63 0.12 0.07 0.06 0.06 0.42 3.10 0.16 0.60 0.67 0.18 1.64 1.39 0.00 0.32 0.13 0.37

    IVP

    h
    19 19 19 19 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 21 21 21 21 21 21 21 21 21

    k
    10 10 11 11 0 0 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8 9 9 10 10 0 0 1 1 2 2 3 3 4

    l
    -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096

    Fdata
    43.15 46.53 28.11 27.67 49.59 47.91 38.98 37.79 41.72 36.97 51.07 47.98 65.86 69.01 33.26 30.58 38.00 38.77 35.59 32.46 18.82 18.26 21.60 24.69 41.76 43.47 43.02 41.27 41.91 39.13 41.35 35.00 33.31 36.95 81.96

    7.23 6.63 10.02 9.75 5.44 5.48 6.42 6.35 6.59 7.20 6.09 6.31 5.48 5.42 7.83 8.77 7.35 7.19 7.72 8.55 11.39 11.11 12.09 10.82 6.79 6.27 6.41 6.65 7.06 7.38 6.67 7.76 7.72 6.77 5.68

    Fmodel
    42.20 42.20 21.52 21.52 43.26 43.26 31.14 31.14 41.84 41.84 56.30 56.30 69.35 69.35 39.34 39.34 33.96 33.96 48.12 48.12 24.10 24.10 17.59 17.59 51.64 51.64 43.27 43.27 43.29 43.29 38.89 38.89 29.12 29.12 84.45

    2
    0.02 0.43 0.43 0.40 1.36 0.72 1.49 1.10 0.00 0.46 0.74 1.74 0.41 0.00 0.60 1.00 0.30 0.45 2.63 3.35 0.22 0.28 0.11 0.43 2.12 1.70 0.00 0.09 0.04 0.32 0.14 0.25 0.29 1.34 0.19

    h
    21 21 21 21 21 21 21 21 21 21 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 23 23 23 23 23

    k
    4 5 6 6 7 7 8 8 9 9 0 0 1 1 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8 0 0 1 1 2

    l
    0.096 -0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 -0.07 0.07 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096

    Fdata
    81.37 88.88 36.27 39.63 16.95 29.94 45.14 43.97 37.21 33.50 63.57 62.85 105.95 95.42 94.62 104.88 29.17 31.83 51.86 52.89 30.78 26.02 31.57 23.22 9.88 15.33 43.71 42.58 41.23 45.35 94.59 94.68 58.54 60.99 44.10

    5.61 16.88 7.25 6.54 11.35 9.91 6.27 6.27 7.79 8.41 6.04 5.92 6.45 5.37 5.35 6.40 9.14 8.11 5.84 5.66 9.24 10.49 8.27 12.20 10.14 10.82 6.67 6.57 7.80 6.74 6.12 6.08 5.74 5.57 8.49

    Fmodel
    84.45 23.42 36.47 36.47 25.38 25.38 33.27 33.27 42.97 42.97 68.05 68.05 102.50 102.51 102.51 102.50 24.52 24.52 41.86 41.86 28.72 28.72 21.10 21.10 20.52 20.52 30.74 30.74 40.71 40.71 100.43 100.43 64.87 64.87 50.64

    2
    0.30 15.04 0.00 0.23 0.55 0.21 3.58 2.91 0.55 1.27 0.55 0.77 0.29 1.74 2.17 0.14 0.26 0.81 2.93 3.80 0.05 0.07 1.60 0.03 1.10 0.23 3.78 3.25 0.00 0.47 0.91 0.89 1.22 0.48 0.59

    IVQ

    Annexe : Structure factors dataset and model

    h
    23 23 23 23 23 23 23 23 23 24 24 24 24 24 24 24 24 24 24 25 25 25 25 25 25 25 25 26 26 26

    k
    2 3 3 4 4 5 5 6 6 1 1 2 2 3 3 4 4 5 5 0 0 1 1 2 2 3 3 0 0 1

    l
    0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096 0.096 -0.096

    Fdata
    47.67 35.82 33.76 20.51 17.29 40.19 38.99 44.96 43.10 36.03 36.29 54.71 54.19 26.40 31.71 34.34 33.90 54.40 51.29 25.30 13.99 31.49 33.26 53.32 51.92 35.52 34.05 13.62 18.87 47.30

    7.88 7.46 7.75 12.04 11.27 6.88 6.81 6.88 6.90 7.91 7.55 5.91 5.75 13.06 8.87 8.67 8.33 7.01 6.82 12.96 10.49 10.46 10.21 5.87 5.72 7.60 7.64 14.16 15.48 5.90

    Fmodel
    50.64 33.90 33.90 20.59 20.59 39.11 39.11 42.42 42.42 36.70 36.70 59.38 59.38 24.68 24.68 39.57 39.57 49.10 49.10 25.01 25.01 34.53 34.53 50.11 50.11 35.51 35.51 18.43 18.43 43.19

    2
    0.14 0.07 0.00 0.00 0.09 0.02 0.00 0.14 0.01 0.01 0.00 0.63 0.82 0.02 0.63 0.36 0.46 0.57 0.10 0.00 1.10 0.08 0.02 0.30 0.10 0.00 0.04 0.12 0.00 0.48

    IVR

    Table 2  In-plane average atomic positions of the 14 independent gold sites and two Si layers
    (12 atoms per layer) in the positions of the bulk. The other atomic positions can be deduced by

    p3

    symmetry. Values for the errors on the positions (x,

    y )

    as well as the displacements from the

    starting positions (x,

    in ) are given. Gold Debye-Waller factor : 1.10.04 . Occupancy of

    special sites : 0.490.015. Agreement factor

    : 1.8

    x
    Gold sites

    H HFQQQQQ HFTTTTU HFQHW HFIVSP HFPSRS HFRRU HFHHVW HFRSPQ HFIQQ HFPVQT HFRVRI HFIQTT HFSUUP HFRIPV HFHVSS HFPVRS

    E E E EHFHHHR HFHHIP HFHHPV HFHHII EHFHHIV HFHHIW HFHHPW EHFHHHQ HFHHHI HFHHHP EHFHHIW EHFHHPP HFHHIU HFHHPU

    E E E HFHHHRV HFHHHSQ HFHHHSI HFHHHRV HFHHHS HFHHHTQ HFHHHRT HFHHHSV HFHHHRV HFHHHRW HFHHHSP HFHHHSP HFHHHSS HFHHHSP

    H HFTTTTU HFQQQQQ HFQHIV HFIVHR HFHQIS HFQSSQ HFQSVP HFPQST HFRUTS HFSQQU HFIQSQ HFHRR HFQUPR HFSPVV HFPITV HFRIP

    E E E EHFHHIP HFHHPR HFHHP EHFHHHU EHFHHHR HFHHIP HFHHIW EHFHHIU EHFHHHS HFHHI EHFHHIT EHFHHIS HFHHHQ HFHHIU

    E E E HFHHHRW HFHHHSU HFHHHSR HFHHHRV HFHHHRW HFHHHT HFHHHSI HFHHHSV HFHHHSP HFHHHTP HFHHHSQ HFHHHSP HFHHHSR HFHHHSU

    x
    Silicon layer 1

    HFHSST HFPPPP HFQVVW HFHSST HFPPPP HFQVVW HFSSST HFHSST HFPPPP HFQVVW HFSSST HFPPPP

    HFHHUT EHFHIPW EHFHIIT HFHHRP EHFHI EHFHHQU HFHHTI EHFHHRV EHFHHVW HFHHUQ EHFHHSP EHFHHQI

    HFHHQT HFHHQP HFHHPW HFHHPW HFHHQQ HFHHQS HFHHQR HFHHQP HFHHQP HFHHQP HFHHPW HFHHQU

    HFIIII HFIIII HFIIII HFPUUV HFPUUV HFPUUV HFPUUV HFRRRR HFRRRR HFRRRR HFIIII HFTIII

    EHFHHR EHFHHTP EHFHHQ HFHIQP HFHHTV EHFHHWQ EHFHITV HFHII EHFHHI EHFHIPS EHFHITV EHFHHWI

    HFHHQP HFHHQP HFHHQ HFHHQI HFHHQQ HFHHQI HFHHQU HFHHQI HFHHQU HFHHQP HFHHQQ HFHHQU

    IVS

    Annexe : Structure factors dataset and model

    x
    Silicon layer 2

    HFIIII HFIIII HFRRRR HFTIII HFPUUV HFRRRR HFPUUV HFPUUV HFRRRR HFWRRR HFUUUV HFUUUV

    HFHHSW EHFHHPP HFHHHQ EHFHHII EHFHHPI EHFHHHV EHFHHPU HFHHRT EHFHHSI HFHHSW EHFHHPP HFHHHQ

    HFHHQT HFHHIU HFHHRI HFHHIU HFHHPI HFHHIU HFHHPR HFHHPI HFHHPP HFHHQT HFHHIU HFHHRI

    HFHSST HFPPPP HFPPPP HFQVVW HFSSST HFSSST HFPPPP HFQVVW HFQVVW HFHSST HFVVVW HFPPPP

    HFHHSW EHFHHPP HFHHHQ EHFHHII EHFHHPI EHFHHHV HFHHRR HFHHHW EHFHHHR HFHHSW EHFHHPP HFHHHQ

    HFHHQT HFHHIU HFHHRI HFHHIU HFHHPI HFHHIU HFHHPW HFHHPI HFHHP HFHHQT HFHHIU HFHHRI

    Table 3  In-plane average atomic positions of the 14 independent gold sites and two Si layers (12
    atoms per layer) in the positions given by Grozea by

    p3

    et al. . The other atomic positions can be deduced


    y )
    2
    : 1.3

    symmetry. Values for the errors on the positions (x,

    as well as the displacements from

    the starting positions (x,

    in ) are given. Gold Debye-Waller factor : 1.30.04 . Occupancy

    of special sites : 0.490.015. Agreement factor

    x
    Gold sites

    H HFQQQQQ HFTTTTU HFQHW HFIVSP HFPSRS HFRRU HFHHVW HFRSPQ HFIQQ HFPVQT HFRVRI HFIQTT HFSUUP HFRIPV HFHVSS HFPVRS

    E E E HFHHI HFHHHV HFHHPV EHFHHHI EHFHHP HFHHIR HFHHPP HFHHHT HFHHI HFHHHQ EHFHHIW EHFHHQ HFHHHW HFHHPR

    E E E HFHHHSP HFHHHSS HFHHHS HFHHHSI HFHHSI HFHHHSU HFHHHSI HFHHHSQ HFHHHRW HFHHHSQ HFHHHSP HFHHHSR HFHHHSV HFHHHSR

    H HFTTTTU HFQQQQQ HFQHIV HFIVHR HFHQIS HFQSSQ HFQSVP HFPQST HFRUTS HFSQQU HFIQSQ HFHRR HFQUPR HFSPVV HFPITV HFRIP

    E E E HFHHHP HFHHPW HFHHIV EHFHHIQ EHFHHHS HFHHHV HFHHPT EHFHHHS HFHHHI HFHHPT EHFHHIU EHFHHPI HFHHHU HFHHIU

    E E E HFHHHSU HFHHHSU HFHHHSS HFHHHSP HFHHHSI HFHHHTI HFHHHSU HFHHHSU HFHHHSV HFHHHTR HFHHHSV HFHHHSS HFHHHSI HFHHHSU

    IVT

    x
    Silicon layer 1

    HFQTVI HFQSUU HFPQTW HFIWT HFIUQV HFHWHV HFSPTI HFQWSS HFHTV HFRQQS HFPIPI HFSUHP

    HFHHQW HFHHWQ HFHHVV HFHHQS HFHIHI EHFHHI HFHHWR EHFHHRR EHFHHQI EHFHHPT EHFHHPV EHFHHUP

    HFHHRV HFHHRS HFHHRQ HFHHSR HFHHRI HFHHRP HFHHSI HFHIHI HFHIHQ HFHHRP HFHHSQ HFHHUR

    HFIHUP HFPQS HFIQW HFQHHP HFQWU HFQQWV HFRSHP HFRISP HFHWVW HFHIQQ HFSVVR HFPSSS

    HFHHSP HFHHVP HFHHSQ EHFHHUP EHFHHTP EHFHHVU HFHHPS HFHHTI HFHHSW EHFHHRS HFHHSQ HFHHPW

    HFHHTR HFHHRR HFHHRP HFHHSQ HFHHQU HFHHRT HFHHSV HFHHU HFHIQ HFHHRI HFHHSU HFHHUU

    x
    Silicon layer 2

    HFHSVP HFPPP HFPPRW HFQVVP HFQVU HFHSU HFPPII HFPIVW HFQWPT HFSSRU HFSSQI HFHRWS

    HFHHHT EHFHHHQ EHFHHWQ EHFHHPT HFHHSV EHFHHIQ EHFHHWP EHFHHHV EHFHHHW HFHHRP EHFHHPQ EHFHHSV

    HFHHWW HFHHSU HFHHRQ HFHHSR HFHHRS HFHHRP HFHHSR HFHHRQ HFHHWU HFHHUW HFHHSR HFHHRU

    HFIHWW HFTHW HFIIRR HFIIIQ HFPUST HFPVQP HFPUWR HFRQWP HFRRHV HFPURS HFIHUT HFRRHW

    EHFHHTI EHFHHSQ EHFHIHQ HFHHQI EHFHHRS EHFHHRV HFHHQV EHFHHSU EHFHIIP EHFHHWP EHFHHTI HFHIRR

    HFHIQV HFHHTR HFHHRT HFHHTU HFHHRP HFHHRW HFHHSU HFHHSI HFHHUR HFHHUV HFHHST HFHRU

    IVU

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    PHR

    Rsum:
    Les nanofils (NFs) de semi-conducteur (SC) sont des objets possdant des proprits trs intressantes pour la fabrication de futurs composants lectroniques lchelle nanomtrique. Ils sont labors grce lutilisation dun catalyseur mtallique (Au) formant un point eutectique profond en salliant la phase SC (Si) permettant la germination et la croissance du NF basses tempratures. Ce travail a pour but ltude de la formation, de la structure et du comportement de ces gouttes dalliage eutectique en interaction avec le substrat dont les proprits futures du NF vont dpendre. Ltude a t mene in-situ, par utilisation du rayonnement synchrotron qui est un outil parfaitement ddi la caractrisation de structures lchelle atomistique. Les gouttes deutectique ont t obtenues par dmouillage du film dor. Ltude de ce procd a rvl des changements dans les relations dpitaxies entre lor et le silicium. Les gouttes ainsi formes sont accompagnes dune couche de mouillage, se rvlant tre une reconstruction de surface, dont les conditions de formation ainsi que la structure atomique ont t dtermines. Lors du refroidissement, une augmentation des effets de surfusion a t observe en prsence de cette reconstruction et a t explique par la structure mme de cette dernire qui semble stabiliser ltat liquide. Des expriences similaires ont t faites sur dautres systmes (Au-Ge, Al-Si) et une synthse a t ralise pour comparer les connaissances actuelles sur le sujet avec les rsultats de ce travail. Mots cls Nanofils, croissance, or, silicium, epitaxie par jet molculaire, reconstruction de surface, eutectique, surfusion, solidification, transitions de phase, diffraction de rayon X

    Abstract:
    Semiconductor (SC) nanowires (NMs) have been identified as important components for future electronic and sensor nanodevices. They are produced using a metal catalyst (Au) that forms a low eutectic point with the SC phase (Si) and enables their nucleation and their growth at low temperatures. The aim of this study is to investigate the formation, the structure as well as the behaviour of such liquid eutectic droplets in interaction with the substrates on which the futur NMs properties will later depend. This work has been performed in-situ, using synchrotron radiation which is the perfect tool to characterize this mechanism at the atomistic scale. The eutectic droplets have been obtained through the dewetting of thin gold films. This process has been found to modify the epitaxial relationships between the gold and the silicon substrate. The obtained droplets are accompanied by a wetting layer (WL) whose conditions of formation as well as atomic structure, which turned to be a surface reconstruction, have been determined. During the cooling process, the supercooling effects in such AuSi eutectic droplets have been found to be enhanced in the presence of this reconstruction. It has been explained by its specific atomic structure which is likely to stabilize the liquid phase. Similar experiments on other systems (Au-Ge or Al-Si) were performed and a synthesis has been made in order to present the current knowledge on this topic in comparison with the results of this work. Keywords Nanowires growth, gold, silicon, molecular beam epitaxy, surface reconstruction, eutectic, supercooling, solidification, phase transition, X-ray diffraction

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