SolGel

September2000

YVO4:Ln(Ln=Eu,Nd)luminescentnanoparticles
by
ArnaudHuignard*,ThierryGacoinandJeanPierreBoilot
SolidStateChemistryGroup,LaboratoryofPhysicsofCondensed
Matter,
EcolePolythechnique,Palaiseau,France
*Contactaddress:ah@pmc.polytechnique.fr
Thisisasummaryoftheresultspresentedatthe"18thworkshopofFrench

LuminophoresGroup"March2000,UniversityofLyonI Thecompletelistof
presentationscanbefoundonlineatthefollowingaddress:http://www.univ
bpclermont.fr/LABOS/lmi/gfl/gfl18.htm

Introduction
Inorganicluminescentmaterialshavepracticalapplicationsinavarietyofdevices
fromconventionalTVtoelectroluminescent,plasmaorfieldemissiondisplays.
Moreover,theexplosivegrowthofopticalcommunicationsincreasedthedemandfor
highperformingluminescentmaterialsintheareaofsolidstatelasers.
Traditionaltechniquesmakeuseofhightemperaturessolidstatereactionsforthe
obtentionofluminescentmaterialsandleadstoagglomeratesof5to20minsize.
SolGelandcolloidalchemistryprovestobeapowerfultechniquetocontrolthesize
oftheultimategrainsofthematerialgivingthefreedomtotheresearchertotailorand
bettercontrolthefinalstructuralparameterswhichhaveanimpactontheluminescent
efficiency.
Bulkmaterialswithstrongluminescentpropertiesareusuallyoxidesdopedwith
lanthanidesortransitionelements:
Y2O3:Eu3+,Y3Al5O12:Nd3+(YAG),Al2O3:Cr3+
Recentlyanintensiveresearcheffortwasdirectedtowardschalcogenidescoreshell
nanostructuresordopedsemiconductornanoparticleswithanarrowparticles
distributionandhighluminescentquantumyield.
CdSe/ZnS(13),ZnS/Mn(4),CdS/Mn(56)
Advantagesofusingnanoparticles

1.Theycanreplaceinmostofthecaseinstableorganicchromophoresusedas
luminescentprobesinavarietyofapplications(biology).
2.Theycanbeincorporatedinasolidmatrix(hybrid,solgel,etc)andusedfor
opticaldeviceasbulkorfilms

3.Hightransparentmaterialcanbemadebytheappropriatechoseofthe
nanoparticlessizeandrefractiveindex.
4.Surfacechemistry,dopingandsizecontrolshouldleadtoimprovedluminescent
performances.

BulkYVO4
DopedYVO4(78)exhibitsahighluminescentefficiencyanditremainsagood
exampleforcomparison.
Thetablebelowshowsthewavelengthofemissioninrespecttothedopantsused:

Lanthanides
Eu
Dy
Nd

Emissionwavelength
(nm)
614617
572
1060

Application
Luminophore
Luminophore
Lasers

YVO4Structure
ThestructureofOrthovanadatesisofZircontype(Quadratic(a=b=7,23,c=6,29
))

YVO4:LnSynthesis
YVO4wassynthesizedbyaqueouscoprecipitationreactionsfromY3+Ln3+and
VO43saltsinwater(Figure1).Thedetailsoftheprocedurecanbefoundin(9)


Figure1:Aqueouscoprecipitation

ThecolloidalsuspensionsofLn:YVO4nanoparticleswasobtainedbydispersingthe
precipitateusingsonificationandstabilizationoftheparticleswithsodium
hexametaphosphate.

Toachievepurificationandimproveitsstability,theobtainedcolloidalsuspensionis
thendialyzedinpurewaterfor12hours.

TheColloidalsolutionsthosepreparedremainstableforseveralmonthsinalargepH
range(4<pH<12)

Nanoparticlesstructure

Highresolutiontransmissionmicroscopyshowsanellipsoidalgeometrywith
characteristicdimensionsofaround15and30nm.

Luminescentproperties

UnderUVexcitation,thecolloidalsolutionshowsabrightemissionat615nmwhichis
associatedtothe5D07F2transitionoftheEu3+ions(figure2)

Figure2:ColloidalsolutionofY0.95Eu0.05VO4(5*104mol.l1)beforeandafter
UVexcitation
Quantumefficiency
Measuredquantumefficiency(15%)remainshoweverfarbelowthebulkmaterial.
ThislowQEispresumablyduetothehighwaterpresenceattheparticlessurface.
OHgroupsarewellknownluminescencequenchercenters.
QuantumyieldwasfoundtoincreasewithbothD2O<>H2Oexchangeand
hydrothermalannealing.BothluminescenceQEandlifetimeeffectsareshownbelow

Quantumefficiency

Lifetime


Surfaceeffects
OHimpactontheluminescencepropertiesofnanoparticleswasevaluatedby
consideringacoreshellmodelwheretheshellisfullyhydratedandtherefore
completelyquenched(QEofshell=0).AssumingthattheCorequantumefficiencyis
similartotheoneobtainedwithDeuteratedsamples(CoreQE=QE(D2O))thenone
cancalculatethat50%oftheEuatomsarein3nmfullyhydratedshelland
completelyquenched.

YVO4:NdCase
ColloidalsolutionofY0.98Nd0.02VO4
(0,2mol.l1)

Surfaceeffects


ThesemeasurementshavebeenmadeincollaborationwithP.AschehougetB.
Viana,
ofSolidStateAppliedChemistryLaboratory,ENSCP,Paris

Nanocompositesmaterials
NanocompositesmaterialscanbeeasilypreparedbyincorporatingtheYVO4:Ln
stabilizednanoparticlesonasilicasolgelmadeprecursor.Bothdiporspincoating
techniquescanbeused.


Summary
Averysimpleandefficientchemicalroutetopreparehighluminescentcolloidswith
controlledcompositionhasbeenpresented.Nanoparticlesthoseformedcaneasily
assembledasthinfilmsbydiporspincoatingtechniques.Theyarewatersolubleand
biocompatible.IncomparisonwithorganicdyesandsemiconductorQD,theyare
narrowerinspectrallinewidthandprobablymorestableagainstphotobleaching.
Furtherstudiesaredirectedtowardsbettersize,crystallinityandsurfacemolecular
graftingcontrol.
References
1.A.R.Kortan,R.Hull,R.L.Opila,M.G.Bawendi,M.L.Steigerwald,P.J.Carrol,L.E.Brus
J.Am.Chem.Soc.,112,1990,1327
2.M.A.Hines,P.J.GuyotGenest
J.Phys.Chem.100,1996,468
3.X.Peng,M.C.Schalamp,A.V.Kadavanish,A.P.Alivisatos
J.Am.Chem.Soc.,119,1997,7019
4.R.N.Bhargava,D.Gallagher,X.Hong,A.Nurmikko
Phys.Rev.Lett.72,1994,416
5.G.Counio,S.Esnouf,T.Gacoin,JP.Boilot
J.Phys.Chem.B100,1996,20021
6.G.Counio,T.Gacoin,JP.Boilot
J.Phys.Chem.B102,1998,5257
7.A.K.Levine,F.C.Palilla
Appl.Phys.Lett.,5(6),1964,118
8.R.C.Ropp
LuminescenceandtheSolidState,Elsevier,1991
9.A.Huignard,T.Gacoin,JP.Boilot
Chem.ofMaterials,12(4),2000,1090

SelectedbibliographyonsemiconductorsQuantumDots

YVO4
Wetchemicalsynthesisofdopedcolloidalnanoparticles:YVO4:Ln(Ln=Eu,Sm,Dy).
Riwotzki,K.,Haase,M.,J.Phys.Chem.B102(50):1012935(1998).

CdX,ZnX
SynthesisandcharacterizationofCuxSnanoparticles:natureoftheinfraredbandandchargecarrier
dynamics
M.C.Brelle,C.L.TorresMartinez,J.C.McNulty,R.K.Mehra,andJ.Z.Zhang,
PureandAppl.Chem.72,101,2000.

LuminescecedecaykineticsofMn2+dopedZnSnanoclustersgrowninreversemicelles,
B.A.Smith,J.Z.Zhang,A.Joly,andJ.Liu,
Phys.Rev.B,62,20212028,2000.
InorganicQuantumDotOrganicDendrimerNanocompositeMaterials,
K.Sooklal,J.Huang,C.J.Murphy,L.HanusandH.J.Ploehn,
Mater.Res.Soc.Symp.Proc.1999,576,439.
LuminescenceofCdSNanoparticlesDopedandActivatedwithForeignIons,
J.M.HuangandC.J.Murphy,
Mater.Res.Soc.Symp.Proc.1999,560,33.
LuminescenceSpectralPropertiesofCdSNanoparticles,
J.R.Lakowicz,I.Gryczynski,Z.Gryczynski,andC.J.Murphy,
J.Phys.Chem.B1999,103,7613.
LayerbylayerassemblyofthinfilmZenerdiodesfromConductingPolyelectrolytesandCdSe
Nanoparticles.
T.Cassagneau,T.E.Mallouk,J.H.Fendler,
J.Am.Chem.Soc.,120(31),78487859(1998).
TheEffectofCadmiumIonAdsorptionontheGrowthofCdSNanoparticlesatColloidalSilicaParticle
InterfacesinBinaryLiquids
I.Dkny,L.Turi,G.Galbcs,andJ.H.Fendler,
J.Coll.Interf.Sci.,195,307315,(1997).
CoupledCompositeCdSCdSeandCoreShellTypesof(CdS)CdSeand(CdSe)CdSNanoparticles
YongchiTian,TheresaNewton,NicholasA.Kotov,DirkM.Guldi,andJanosH.Fendler,
J.Phys.Chem.,100,89278939(1996)
HighTemperatureOpticalStudiesofCdSNanoparticles
HYkseliciandPDPersans,
JNonCryst.Sol.,vol.203,206(1996)
OpticalstudiesofthegrowthofCd[1x]Zn[x]Snanocrystalsinborosilicateglass,
H.Yukselici,P.Persans,andT.Hayes,
Phys.Rev.B,vol.52,pp.11763,1995.
UnusualPhotoluminescenceofPorousCdS(CdSe).
R.Tenne,V.Nabutovsky,E.Lifshitz,andA.F.Francis,
SolidStateCommun,82,651(1992).
PhotochemistryofColloidalSemiconductors.OnsetofLightAbsorptionasaFunctionofSizeof
ExtremlySmallCdSParticles
H.Weller,H.M.Schmidt,U.Koch,A.Fojtik,S.Baral,A.Henglein,W.Kunath,K.Weiss,E.Diemann
Chem.Phys.Lett.124(1986)557560
PhotochemistryofColloidalMetalSulfides.
8.PhotoPhysicsofExtremlySmallCdSParticles:QStateCdSandMagicAgglomerationsNumbers
A.Fojtik,H.Weller,U.Koch,A.Henglein
Ber.Bunsenges.Phys.Chem.88(1984)969977

RELATEDLINKS
Moreonlinepapersfromthesameworkshoponluminescentsolgelmadematerials
LuminescencepropertiesoptimizationofPrinCatiO3(pdffile)
byP.T.Diallo,P.Boutinaud,R.Mahiou,J.C.Cousseins
InfluenceofOHgroupsonthespectralcharacteristicsofEudopedSolGelhybrids(pdffile)
byA.C.Franville,D.Zambon,R.Mahiou
ReferencematerialonYVO4

NeodymiumDopedYttriumOrthvanadate(Nd:YVO4)
Crystalpropertiesandluminescentperformances
fromCASIX
Nd:YVO4energylevels
fromNASA
Eu:YVO4energylevels
fromNASA
SellmeierCoefficientsTableforrefractiveindexcalculationsofYVO4
FromNasa
Nd:YVO4advantagesoverNd:YAGcrystallasers
FromITIElectrooptics
Helpusimprovethispage

Pleasetakeafewmomentstogiveusyourfeedbackandwhatfeaturearticlesyouwouldliketoseeinthenearfuture.