Memorandum 6M=4809

Division 6 - Lincoln Laboratory

Massachusetts Institute of Technology
Lexington 73, Massachusetts
SUBJECT: PARAMErERS OF THE THIN FnM DEPOSITION PROCESS
To:
Professor EwanWo Fletcher
From:
Peter Fowler

Page 1 of 37
The formation and nature of thin films is considered from the
point of view of molecular kinetics of film and 5ubstrate
o
General
briteria for control of some.properties of films are discussedo
Distribution List&
To receive complete memorandumg
J 0 Goodenough Lo Harri:s" Room
Do Smith p. Fowler remainder of Group 63 Staff to
J e Raffel Haq,Room 6=031 recei va abstract <?n1y
Guditz
Ko Shoulders
Eo Fletcher
10 Loeb
Wo d tR\;ghl'el!@n
This docUD1ent is issued for internal distribution and use only by and for Lin-
coln Laboratory personnel. It should not be given or shown to any other in-
dividualsor groups without express authorization. It may not be reproduced
in whole or in part without permission in writing from Lincoln Laboratory.
The research reported in this document was supported
jointly by the Department of the Army. the Depart-
mentor the Navy. and the Department of the Air Force
under Air Force Contract No. AF 19(IZZ)-458.
6M=4809 Page 2 of37
The memorandum has been divided into the following sectiono
TOPIC

Section A.o
Section
Section C.o
Section Do
Section E.o
Section
Section G.o
Section
Section 1.0
Section Jo
Forces of Adsorption
Molecular Adsorption Kinetics
Lateral Interaction and Molecular, Mobility
Molecular Velocity
Rate of Evaporation
Film Thickness
Lattice Fit
Electron Diffraction
Cleaning of Substrate Using Particle Beams
Condensation Coefficients
.c It!hemically Bonded Films
MatJi:.Bmblh:tog}."aphY
i
. c, ..
Supplementar.y Bibliogra phy:I

Bibliographical Abbreviations
PAGE
----
33
S
8
13
14
17
20
21.


25"
27
333
" f'
34
37
6M-4809
Page :3 ot 37
INTRODUCTION
A problem exists as to what materials, structure, geometr.y,
are reqtti..red for the optimum thin film componento It is known that various
solids with particular crystal orientations will have to be firmly de=
posited on different substrateso Reliable means for control ot any comb-
ination of desired properties must be developedo
EXperimentation to the present bas shown that the difficulties
attendant in just getting a vapor to deposit and remain on a surface are
numerous 0 The first and foremost problem, then, in connection with
attraction and the macroscopic phenomenon of adsorptiono
Since Langmuir published his Nobel Prize winning theory13J ot monomeleeular
theoretical
coverage of the phenomenon of multimolecular
Assuming that the deposit has been accomodated by the substrate,
the question then arises as to what the structure of the deposit i5
9
and
how we control ito A unified theor.y describing the prooess of cr.ystal
growth proceeding from multimolecular adsorption has not been published
as yet,9 although et alia, have given some rate equations
volving few unknown parameters,o
This paper discusses observations made upon deposition of vapors
of normal solids in relation to the forces involved and the molecular
kinetics of the oCri teria for the choioe of
parameters which effect various properties are implied to some extent
o
Section Ao FORCES OF "ADSORPTION
The forces entering into physioa1 adsorption are
1
,2,14,24risted
belowo The dependence of energy of interaction on separation, of two
particles is given in each case as r:no In general when one molecule is
considered as interactingwitliasnrfaee composed of molecules of the
other type in question the dependence o interaction energy varies as r
10 (London)3$)129 fluctuating multipoles .... Always
attractive and orients molecules with greatest numbers of
nearest neighborso*
* This force is the reason for different heats of adsorption on different
crystal faces (varying surface density of molecules)o Germer
31
endorses
this viewlJ but i,n 1,9 PPo Rhodin states objections 0
6M.,,4809 Page 4 of 37
a o Dipole - dipole" proportional to r=6(by far the most
important term at film equilibrium distances except for
spme polar substrateso) . .
. -8
Dipole - proportional to ro
c!' Quadrupole - quadrupole J' p;roporti onal to r -10
0
,
20 Repulsive (Exchange or Valenee)9 proportional to.e=r/r
o
, or
r=n, with n taken equal to 9 to 100 for various caseso
29
3.0 Vibration of solidlatt-:i.6eo
Vibra tion of adsorba te 0 .
50 Internuclear molecular vibrationo
In addition to these, polar substrates have forces acting which cause
molecules to orient in a especiall:r ;tn the case of p03f'at-
ornie molecules 0 These are predominant in some cases 4) .
60 Orientation mutual attraction between permanent di-
poles;; proportional. to r =60 CD Attractive or repulsiye depending on orient=-
ation whep adsorbedo
. 128 5
70 Ipduction (Debye)' <=> Always attractiveo
a o M.utual attraction permanent dipole and induced
d;i.pole$' proportional tor-6o
b o Mutual between permanent quadrupole and
dJ1ced tor -80
Co Mutual between permanent quadrupole and in=
. -10
duced quadrupole* proportional to r 0
In the case of ionic s'ubstrates, the surface energy for an
bate has been calculated. as. a;function of distance from the adsorbent, in=
eluding the effects of lJ 7 above, using a summation process up
to a distance r = f =1(3, where f is the number of lattice
points per um t volume and; contlnuopscenergy
per un;i.t volumeo Other cases have been' calculated also, especially by
deBoero 29 The minimum'll the curve obtained gives the energy required to
take the adsorbate from this equilibrium. position to ipfini ty with tbe,ej-
ception of the effects of Vbration (3.94,9 and 5 above)o The physical sur-
face is thus described by a 3 dimensional potential surface
70
,913
0
which
gives us the heat of adsorption at every point for a molecule at
6M=48 09
Page of 37
its equilibrium position, being a periodic function for a perfect qr.r-
stalo This is ,.the type of model used in the study of api 0 tie ef""
fects of surface heterogeni ties (cracks, dislocations!J etc 0.) has bEfen
investigate9 by deBoer and Custers
24
and polyani
68
0 The find thal the
variation of energy of adsorption for topographies varying from ne,dles
28 \
to needle-ltke carl ties is of one order of magnitude and thus c0'tld ..:..
prove to be a great effect in adsorptiono *
Section B<t . MOLECULAR ADSORPTION KINETICS
We have then that when a molecule strikes the a
solid
9
(the height of the surface dependent on the energy of the
ecule)!J it Jlay transfer some of its energy to the solid. lattice, a thus
be left wi th than enough energy' to escape the A would
thus remain 1n this site if not energizedo This is the $,ituation we hgve
at low temperatureso The well that the molecule may be in thQugh pos=
sibly not the deepest one that the surface offers and th, bi:nd=
ing of the molecule is not as strong:as might be is we get
ecule to 1ll.lgrate over the surfac80 ** The process that:Qceurs to allOw
such lateral motion of the molecules is the quantized en,rgy transfer
"",
the solid lattice vibrationso . These vibrations are on tae
temperature and thus we see how temperature enters as a inlhe
sticking of'filmso We may also see that this energy in op};)osition
to the Van well and thus the heat of adsorptiqnwil1 be the
depth of the well as we go to higher temperatures but according
* The effect of electrostatic attraction and repulsiQ:n ions
and ionic substrates, tending to localize action over ion of latt1pe, has
been neglected in the foregoing 0 This is of some importance in a ;f'ew . ,
'
** A cluster of molecules that may by chance aggregate at some spot'
will undoubtedly become unstableand:form a crystal structure in an at';'
tempt to get in a lower energy stateo The absence of migration however
9
will not allow any sort of eCntinnity of the film (ioeo, any long distance
ordering) but rather may have a layer of random crystals 0 The acti ve
sites thus presented will be of great adsorptive ability but we must
balance this gain against our requirement, in some cases, for unifornnty
of structureo
6M=4809
Page 6 of 37
to some lawo Lateral motion due to incomplete transference of the kin-
etic energy of the arriving molecule is of importance a1s0
69
0
Asswning we know the potential variation of the surface due to
multipole effects and repulsive forces, we are thus led to consider the
process or surface diffusion which is required to si tua te molecules in
preferred siteso The motivating forces is as noted above = solid lat=
tice vibrationso Volmer and others
B
,9,71,9l3l showed conclusively that
under certain circumstances, surface diffusion does take placeo A famous
experiment due to Volmer, is tne formation of crystals of Hg from vaporo
The crystals grew out of the substrate at a rate more than 1000 times that
calculated to be possible the basis of direct addition of molecules
of the vapor to the crystalso Since we may assume that during a suf=>
ficiently long period of time during _. the experiment, the atomic beam
deposits atoms uniformly over the surface then there is little question
as to the necessity of surface migration for the occurrence of this efQ
fecto Yang'O that When some area of nuclei is presented
9
direct impingement of atoms becomes an part of the nucleation
processo
The quantum mechanics of the migrational process were investigated
for the case of gases by Lennard=Jones and assuming the
Langmuirian model of adsorptiono They treat the vibration of the solid
lattice as the perturbation (derived-from expansion of a Morse potential)
causing a surge of energy to and from the solido The surges cause trans=
itions of the atoms to various energy stateso Calculations made place the
time that a molecule will remain in such a on the order of 10=
12
seoo
Let us assume that an adsorbed atom (Becker coined nadatomQ21922)
held by some potential well is given a quantum of solid vibrational
The atom may then be excited to a higher bound level in the well or into
the continuum where it is either captured by another well or leaves the
surface completeiYo (Lennard=Jones
56
points out that a mobile atom may
also lose energy by collision with another mobile atom or bound atomo
If the energy of activation for migration is small compared with k'r9 then
collisions will be rare and it the concentration is not too large so that
migration is not prevented by other adatoms then theory that the
. 1
mean life of activation will be nearly independent of terperatureo)
6M=4809
Page r of 37
We may assume that the momentum transfered to the adsorbate i$
dependent on the type of substrate and cr.ystal face presento since
the fact that whether migration or evaporation takes place is dependent
on the direction and magnitude of then we should have certain
substrates causing more migration, or evaporation, than others at the
same temperatureo The macroscopic parameters here are specific heat and
total energy 0
In addition, there w:tllbe a temperature dependence (of exci tat"",
ion) of both the number of quanta transferred per second and the energy
of these quanta 0 There is a :ti-ni te probability of 2 or 3 quanta being C
transferred simultaneously, but it is found to be negligible in our ca$eo
A possible mechanism for evapdrationis the second order process of an ad=
ditional quanta being transferred to" the molecule while it is an excited
stateo
It is onthis latter basis that Lennard-Jones calculated the mean
=12
life of the adatom in an axci ted state to be approximately 10 sec o 'He
further calculated the time that a gas atom is expected to be in an
bed state and found it to be on the order of 10=5 seconds o This result is
in agreement will the mean life1::"of an ada tom found experimentally on
the basis of Langmuirus theoryo This carries the implication that the
turbation used in Lennard=Jones theor,y is by far the most important effect
in the range of temperature arid pressure used for confirming experiments
o
The possibility that substrates rich in conduction electrons c
could cause excitations by means of the electron motion was investigated
by Lennard=Jones o In metals we have approximately 10
15
co10/seco of sur"""
face atoms wi th electrons so there is ample reservoir of energy for tran=
sitionBo The calculation of mean time of transition is again approximately
10=12 and the electrons are 1% efficient in this transfer 0 This _
then is not as large an effect as the former effects discussed but it is
interesting that it will be independent of temperature and thus may be a
dominant factor for transitions at low temperature
o
6M=4809 Page 8 of 31
Section Co LATERAL INTERACTION AND MOLECULAli MOBILITY
,
The foregoing theor,y was developed for the explanation of gaseous
adsorption 0 It is obvious that we must make some changes to apply these
results to the adsorption of molecules of substanc,s that are normally
solido (eogo
9
metals)o A.. gas is clBracterized by "light attraction at large
separation and by large repulsion at small S3paration9 whereas normal solids
have quite strong attraction at small s eparationo We cone>
cern ourselves with lateral interactions 0 (Lennard"",
Jones has given a good qualita-tive description of molecular cohesion
23
)o
gaseous adsorption9 then,' lateral interaction is negligible
and$ in fact, theories of monolayer coverage by adsorbed gases postulate
that it is However, the process of aggregation of
from vapors of normal solids will make a continually decreasing portion
of the surface available for true Langmuirian adsorptiono In addition to
the variation of the number of substrate adsorption sites we see that there
will be attraction (or possible repulsion) due to the presence of the
adsorbate itselfo This situation then is not as simple to treat as gaseous
adsorption9 for instead of th-amolecples playing a more or less
part in the adsorption9 now each molecule is a source of energy, 10e
09
tre
molecule being adsorbed takes over the role of the subs.}rat&J but with (in
general) different adsorptive abill tyo ":1
This adsorbate=adsorbate interaction will lead to the formation
of crystals while the crystal growth will be modified by
interaction (termed lattice fit)- and enhanced (or not) by
activated migrationo The lateral interaction
9
if negatives just com=
pensate for the positive vibrational energy thus 'giving the depth of the
I I
multipole well (page 5) its physical meaning ot. heat of That
lateral interaction is important is apparent from the marked rise of heat
of adsorption and peak at monolayer coverage lateral interaction is ex=
pected to be pronounced when each molecule hitting the surface must find
itself confronted wi th several nearest neighbors26
s
27
o
The general process of migration and evaporation of adatoms due to
Lennard<=Jones as described in Section B is undoubtedly that occuring with
the adsorption of vaporized solids 0 We may a conclusion from the first
6Mc::a4809 .
Page 9 of 37
second order processes of energy transfer noted in that section, namely 8
there should be ? discreteness in the phenomena of adsorbed films in the
following mannero Assume an atom'to be captured by a well of depth Wand
further imagine the transfer to the, atom of a quanta of energy E corres.-
ponding to the existing temperature e If E > W the goes to the contin-
uumo If E <. w the atom goes to an excited bound stateo In this case, the
second order process is required to excite to t he continuum and this will
occur if 2E >W& Now, if 2E ,W but 3E / W (it is unknown whether the
third order process process is
required for excitation to the continuumo Now on the assumption that
migration is required for orientation of an adsorbed film,9 we see that as
W DE n will have critical points for orientation phen-
omena 0 Since E f(T) there should be critical points for these phenomena
dependent on temperatureo
There are experimental effects that may be explained on this basis
9
for example, RhodinRsxoorientation of aluminum films whereby the atoms
quire sufficient mobility (energy E above) to aggregate into cr,ystals
o
10
That is, as Rhodin states,9 many deposited films are unstable in the sense
that a cluster of adatoms will aggregate in to cr.ystal(s) provided that
the atoms have sufficient mobilitYo'Brunauer (refo 2,9 Po472) states that
kT must be raised So that it is as great as the energy difference between
the minimum and maximum potential
Further
9
Rhodinu s investigation of Aluminum deposition showed that
at lower temperatures, the (110) Aloplane was preferentially deposited
parallel to the mica backingo However, as the temperature of the substrate
is there comes a point where the (111) plane deposited parallel
to the backingo It appears that fit orientation must be modified
somewhat 0 On the lattice fit basis
9
the (110) plane should always be found
parallel to the substratso We see than that a "critical
u
temperature ex=
iats above which the effects of the lattice fit are overcome by some other
force{s}0
The above effect brings to mind the theory of Dixit
30
0 He gives
a classical theory for such orientatrhan based on the Van der Waallls equa=
tion of state for a 2 dimensional gas (n1 :: RT) and the Ramsey"",Shields'J
equation (which gives surface tension as a function of temperature)o
6M=4809 Page lOot 37
This argument shows that a given temperature corresponds to a
area .;:per adsorbed atom and thus. to crystal planes of varying. densi tyo
Assuming an amorphous substrate J Dint was able to predict "6ri tical re-
orientation for the deposition of varioue".p,!anes parallel
to the 'substrateo The surface-.can be represented in our potential

surface picture as a planeo Why notJ then assume that our crystalline' :.
structure approaches a fiat potential surface with increasing temperature?
The model that must be assumed contains no new forces but rather only the
effect that vibrational pushes the potential wells up until we have
effectively a plane surfaceo EXperiments like. those of Dixit.on several
substrates could prove the correctness of this 0 Rhodin states that the '.
maximum orientation and rate at wpich orientation increases with temper=
ature is typical of the substrateo This is what we would expect, since the
potential surfaces of various substrates at the same temperature are cer=
taiIlly different and the effect of heating of these different substances
should not give the. same rate of increase of vibrational energy (flatten-
ing of the surface)o
Dixit rr S. shows that as temperatpre increases, each atom requires
more areai ioeo,9 less dense of the cry.stal are deposited para-
llel to :the backingo If we assume,Sl as is logical, that at the temperatures
involved, formation of a will proceed (migration is talti.ng place
and&crystal is a lower energy state than an amorphous cluster)s then the
mechanism that seems to determine is, that the surface is pushing
as many atoms away from it as possibleo That is, would
appear to be repulsing more adatoms as the temperature is increased and
repulSing in such a manner as :to allow only a low density of atoms to re=
main parallel to t he substrate 0 When enough atoms to form a unit cell
aggregate these atoms will form into their crystal state with a plane par-
allel to the substr?te corresponding to the density of atoms by
the above mechanismo Carry;i.ng this to its logical conclusion, we should
have all molecules repulsedo The evidence for this is in the phen=
omenon of evaporation at sufficiently high temperatureso
has that for highe;r substrate temperatures
more oriented films are producedo We therefore, that since the
of temperatJ[re is to increase mobility, then with more mobility the atoms
6M-4809 Page 11 of 37
are able to reach more stable positionso This is in with the
earlie;r conclusion that for more mobile adatomic motiol'l on a crystal subCl:t
strate,9 the temperature must be such as. to give the adatoxns mo-
bility to get out of the potential well& The smaller.orle:h.ting forces
(less stable orientations). should require lOW'F for such
orientations to take place" This is a minimum 1fr
is required for a particular orientation, K9fdg-h6 showed. that germari:ium
films appa .. , continuous when deposited a substrate held at room
tempera:ture, but granular when t:qe suljstrate is heated during dep""
ositiono Sennett and. Scott47 57 found from ,lectron microscopy that
silver deposited at 70 to 300
0
C atomic aggregation than
when deposited at room temperatureo !feating of (2 Sec"'"
onds) films produced the same Bannon and CurneyS3 found that
CaF
2
, crystals grew ,from 170 i to 2.50 i as the was increased
from 100
0
to 30QO C, necessitating atomic mobilityo They noted different
orientations appearing as the temperature. was. increased just as did Kupo
and Miyake.54 in their investigation of Ca, and Ni on PbS"
Levinstein
32
investigated the deposition of 3.5 metals(. Results show ....
ed decreased orientation for substances of increasingly higher melting
point 0 This is in agreement with Rhodin for if' the substrate (amorphous)
temperature kept constant and substances of varying melting points are
the metals of lower melting point will have more mobility than
those o:f the h;tgher melting point,9 (the closer to, the melting point'..;. the
more mobility)o His results predipt that a greater observed orientation
should occur for. more mobile atomBo If we were to raise the temperature
of the we expect the metals of higher melting point to become
moreorientedo Experimentation for proof of this effect was carried
out by LeVinsteino
When we speak of mo'DilitY.9 it must be remembered that the motion will
not of a perfect fluid, but rather more like that of a viscous
fluid
j
ioeo, mobility is characterized by short. distance motions <> That
mobility is limited is pointed. out by Schultz,2o He shows that for an
atomic beam obliquely incident, crystals grow inclined somewhat toward
the axis of the beam thus demonstrating that the dts.tance of mobile
Page 12 of 37
motion is of the order of magnitude of the size of crystallites grown by
him 0 Schultz also argues that aince all crystallites at aQY time during
deposition ane of the same approximate height (even those from
projections of the substrate) there/ore mobility is else one
might expect some. crys.talli tes to be towering over others 0 The la t ter
argument, however, is not sufficient to validate limited mobility since
if one allowed completely free motion of all molecules one would expect
something like a distribution of crystal heights which may be
the distribution Cockcroft
37
showed experimentally the idea
of sbme limited mobility by placing a wire near the substrate and noting
that a aggregates of the condensed vapor appear in the region of the
wirens shadowo
In addition to the former effect, we would. also expect the metals;
of higher melting point, if given enough mobility,to form more.strofiglY
oriented films since a high melting point implies a stronger bond=
ing or cohesive force" Uo Semenoff
33
has showthe relationship of the
energy of cohesion, U" (eftectively the latent heat and
the energy of adhesiong fI to the problems of deposi tioD. ot filmso He
:Sl1ows the critical pressure to be a fll11ction ottemperatureg
p := ! exp( =A/I!.f) where .A =. U .. 6 and ! is a constant which depends on
the geometry of the system,9 . tpe . Size of condensing and a
linear temperature correctiono The quantity A is said by Rhodin to be
the Van der Waal
8
s energy between adatom.and substrate. and experi-
mentally found by him for aluminum films o We see then, of
the attractive forces acting on an a datom increase, then the of
impinging atoms need not be as, great for condensation to occuro Rhodin
also foundg as we could expect9 tpat orientation is greater for
pairs of materials with greater A() Thus, in general, we might expect a
)
more oriented crystalline film to be fonned from of sub
ea
stances of higher melting point, dependent, of course, on the mobility
imparted by substrate vibrationo
6M",,4809 Page 13 of 37
Section De MOLIDULAR VELOCI'lI
The effect of yarying velocity of atoms being deposited was inves-
tigated by Levinstein
p
Using a velocity selector apparatus, he was able
to find no difference in the size or structure of aggregates of the de=
posited meta1s e . In the case of Antimony, a variation of size of aggre=
gates was found,9 but further investigation showed that this was due to
the presence of some polyatomic molecules of Antimony which naturally
would a different crystal size or structure than the monatomic
molecules 0
Bateson and BaChemeyer
51
attempted to on the
fact that slow atoms were used However, it would seem
that the velocity-would be an indirect effect the true factor being the
mobility of the atoms was so low that at concentrations (pressure) \lsed
by them, well oriented aggregates could not be The randomly or=
iented crystal atructure resulting "WO\ll.d naturally provide for or ...
i .
ientation in. later layers than would a well crystallized formationo
Beeck$ and Smith?4 investigated in gaseous
(0005 = 10 Memo Hgo ). atmosphereo* The collisions of beam atoms in tran-
sit form clouds and clusters of slow atoins before reaching the substratee
The randomly oriented wh;ich formed in the:tr experiments when
higher gas pressures (2=10 memo I:ig& l were used c01l1d be explained by the
low mobility argument of the preeeeding paragraphlO ?ddi:liion, it is
notised that the presence of a gas of pressure 05-2 moM" Hgo induces the
deposition of planes of low density parallel to the s,ubstrate implying
that this is the. lower energy configuration rather than the planes de-
posited in vacuoo that. there is no apparent reason
why this should take placeo Beeck
s
et alia" suggest that the presence
of adsorbed gas would the vapor atoms into corresponding
to planes of least densityo 'Theygo onto say that the low density plane.
phenomena occurs under conditions for which a complete surface layer is
highly improbable and thus the effect of gases on orientation tnust be
. . . \
* See also references 55,86,.88-90,162-4 for other experiments on de-
position in gaseous atmosphereo
6M-4809 Page 14 of 31
purelY'" kinetic fl. ei through dissipating the condensation potential
energy ot the surface, by effecting the distribution of the
metal atoms. they reach the substrateo The answer to this problem
can be partly answered when we know the .,meohanism that orient.,.,
ation of vapor deposits in vacuoo A good start would be constructive or
destructive proof of Dixitns theor,yo
gave a theory which a dependence of sublimation
and condensation on the, velocity of atoms;" However, there appears to be
an incorrectassumptiono He postulated a potential barrier" for sublim-
ation ( transition to continuUlll) much as was shown at 'the beginning of thi s
paper but then goes on to postulate ? barrier for condensation without
giving the physics of such a Since the forces an atom is sub-
jected to on approach to the surface are attractive and not until adsorb=
ed doe,S it meet the repulsive effects of vibratio:m.,9 and other
forces, this assumption would seem fals80 The atom which is adsorb-
ed (for aperiod,as given by Lennard-Jones theory) comes to equilibrlum
with the, surfa.ce, and in this state its velocity of approach is completely
obscured 0 Th,e deciding factor of the effect of velocity is
evidence and Levenst'ein IT s conclusion is that veloei ty is of no effecto
Section Eo RATE OF EVAPORATION
The fact that experimentali,sts may have concluded that velocity
is a factor, is probably because veloeityand rate of evaporation are
independent 0 The effect of one could be for that of the othero
Levinstein!s investigation and qualitative theor,r shown the effect of rate
of evaporationo That a "critical" pressure exists,below which condensation
does not take place has been shown by severa1
35
""'38
o
It is the pressure
at which point the rate of evaporation of adatoms is greater than their
rate of arrival thus being due to the that substrate-adsorbate force
is lowo It is found in many cases that i t presence of adsorbed
impurities partially satisfy and thus lower the substrates attract-
ive potential
o
Frazer
16
.5 says that if a surface is completely the va ....
pors of most normal solids should experience no -critical point" even
6M=4809 Page 15 of 37
with the weakest of substrate attractive forcese> Many theories have been
given covering "critical pressure" with referenpe to its, tem-
perature dependence including those of Frepkel
35
, FOJorler
41
,9Semenoft;-126
Peier1s
42
fi Devons hi re
43
:j and reference variatipn witb
atu.re is quite amenable to experiment (eogo., references 8,936-38,9104-106)0
All such theories depend in essence on the presence and magnitude*
of the forces of physical 'adsprption discussed earlier although various
methods of treatment are usedo A high rate of evaporation however should
be expected to have the same effect as a dense atomic beam of slow atoms,
for both processes have the effect of putting atoms on the surface in .
great enough quantities for them to atgregate during their meart life
Levinstein
9
s work shows that slow evaporation produces (for Antimony)'large
patches which have diffuse diffraction patterns whereas rapid
gives ISmaller patches with sharp diftr..acti:en patterns (crystalline form-
ation)0 He interprets. the diffuse- pattern as showing the Antimony to be
in the amorphous phase" Levinsteinfurther<hblds that we caa.not expect
\1
this to occur in general since the of many sub$tances is
not found probably because crystallization takes place sofasto
found that slow evaporation gives diffuse electron.
t
diffract1Dn rings whereas fast evaporation gives sharp patternso
ion in gaseous atmosphere produced the same resultso The rate ofevapor=
ation then effects the structure of the deposit, by effecting the manner
in which the molecular aggregates form and grow
o
Sennett and Scot%7
9
57
showed that rapidly evaporated (2 seconds) films tend to remain thin and
cover the substrate more continuously as compared to slow evaporated (2Q
minutes) films which grow thick in aggregates before
They concluded from their experimepts that normal migration time is intep.
upted by the arrival of more The ensuing collisions are the means
for nuclei formationo In Lennard-Jones
56
predicted a shorter mi=
gration time for gaseous adsorption than is given by his earlier quantum
mechanicairesults o His conclusion, was based on the fact that mobile at=
oms, when present in great numbers, will collide otten leading to trans"'"
i tions to excited states or the continuum (whereas in the case of l;,
'* For example:; the statistical mechanical theory shows"'that as ;a greater
lateral interaction (reaching to far:bhest neighbors) is assumed, the more
definite is the critical temperatureo
6M=4809 Page 16 of 31
adatoms of normal solids, nucleation may take place instead)o Their eon=
clusion in terms of experimental parameters is that migration is a func=
tion of beam intensitY9 in our earlier conclusion that i' is
a function of substrate temperatureo
Levinstein explains the preceeding phenomena as follows: The nftm-
ber of a toms in motion on the is proportional to the rate of
arrival of atoms and these adatoms will move qver the surface until they
collide with other atoms and form_ patches (depelldent on subetrat!3 tbrees
especially the presence of cracks, implirities, dislocations,
Assuming evaporation has been in progress for a while with some patches
the atoms arriving suqaequently co11tbde with each to fom
new patches or with old patches to inOrease their sizeo With a
high rate of the former event place since there is
er probability of hitting other adatoms than the relatively few patcheso
With a slow rate of arri,al, the latter evetftt$kes place since
greater probabilij}y that the mobile atoms'WiIT, strlki":-;e. patch before thEfT
leave the surface and thus make fewer but larger patches 0 Carrying this
to logical end, there will be a rate, of a rrip'al whereby the mean lli.fe
!J \
'L of an a tom in the adsorbed state,? is shorter than the reciprocal
of this ratetand thus condensation practically stop except for
some direct additions to the nucleio .Levinstein's experiment was con=
fined to Antimony and show.d we use a less -mobile 8nbstahh$, the same ef=
- \. - .
fect might not-be obse;rvedo By increasing-the temperature, the mobility
.could be increased the noted for An= -
timony-might occur for these other substances also
o
Sennett and Scott varied the evaporation rate-of their deposition
by a factor pf 2000 and yet ,the thickness of the film only changed by a
factor of 100 Evaporation rate then appear to be a valuable para-
meter for varying the properties of filmsb
6M-4809 Page 17 of 37
Section FG FiLM THICKNl!SS '
was
48
concluded that thin metal films are amorphous up to a cer-
tain thickness somewhere in the range 50 i to 200 i and at this
crystallization takes place if temperature conditions are favorableo.
His argument is based ong
(1) the increase in conductivity of at this point which he
says follows from cryst,allization
9
(2) the fact that adhesive forces are than cohesive for-
ces in very thin and thus the substrate forces prevent
formation of
In reference to point (1) W'e may conSider Sennett. and Scott R sin:",
vestigation' of the growth of metal films and in, the region of 50=200 io
Electron micrographs shpw th?t the phenomenon that is taking place is
.
that small aggregates (0001=<>01 microns) are joining togethero We con=
elude that this is the phenomena that was called crystallizationo Sen=
nett and Scott found that adsorption of light at this point-where
the aggregates begin to joino The voids that exist between aggregates
when the film is thin would be detrimental to and thus as more
aggregates join together conduction would increaseo Repeating Was
9
ex-
periment and using electron microscopy could clear up the pointo
Concerning point (2), agree that the first few atom layer;s of
film are strongly influenced by the substrate put contend that after
several atoms are deposited in close proximity, the lateral interaction
will lead to a ggregation, (granting that there must be sufficient mobility
allowed) 0 Yang
j
et 801i8949950in developing their thermodynamic""'statist=
ica1 theory of nucleation from the -vapor pp.ase concluded that a unit cell
aggregation is required for crys tal growtho The unit eell is < 10 atoms
for many substances and thus we see that only very .. ll aggregates are
required before we could expec-.t; the transition of the film to go from
amorphous to crystal struetureo Sennett c:tnd Scott did not define the
state of the aggregates that were present before the joining process at
.50=200.i but we would conclude that they were crystallineo Was
u
con
cO
elusion that the films changed from amorphous to crystalline then is
thought to be in error although the joining of aggregates may change the
6M=4809 Page 18 of 37
type of crystal structure perhaps leading to long, chains of oriented
crystals 0
As a confirmation of the state of very thin films we have the re-
sults of Germer and White
161
who show transmission patterns of
films. in random crystal struct-
ure=strong apparent even at 30 i thickness o Schultz52, investigating
kali Halides,'-'was unable to get reflection patterns for films thinner than
100 i9 but transmission patterns showed random crystals with (100) planes
parallel to the sUbstrateo (The explanation for (100) orientation is giv-
en as the result of cube faces lying on a smooth surfaee
o
) Thicker films
showed (Ill) orientationo Harris, et investigating thermal sta"",
bilization of gold smoke deposits (prepared in inert gas atmosphere) sug-
gest three possible structures for the filmsg
10 Each aggregate consists of a number of crystallites surrounded
by disordered regionso
20 .Each aggregate consists of a large number of smaller nuclei o
30 Each aggregate consists of a single crystallite having a non-
equilibrium latticeo From energy considerations, an excess of
vacant sites is the most probable type of lattice
o
They point out (1), which is the probable structure at very low tem=
peratures (/'IV 20
o
K) is untenable from the point of view of rate of approach
to equilibrium and that diffraction rules out (2) in favor of (3)0
Other structures that one might have to consider might be
10 random crystal structure with non-equilibriym latticeo
20 amorphous throughouto
An example of 2 in the literature is Levinsteings work noted on page 15
of this papero Antimoqy was fOUlld to be one of the substances for which
the amorphous phase can be formed during slow evaporationo We might take
this substance as representative of one end of the scale of
thin filmso Next on this scale would come the randomly oriented films
I
and thence to the well-oriented films and this whole scale verying with
film thickness as notedo An important here would be an arg-
ument, pointing toward the relation between this scale and a scale of
molecular orbital shapes and energies or some other microscopic quality
of the deposito
6M=4809 Page 1<9 of 37
Rhodinus
10
investigation of thin aluminum films sh9WS a variation
of observed percentage of orientation with film thickness o He graphed
thickness against and found maximum orientation to occur for
a small thickness, the films becoming less oriented as more atoms
are depositedo We 1IlUst keep in mind that temperature is a big factor in
the orientation and
9
in theory," proper temperature can produce maximum .
orientation even to a single crystal throughout the thickness ofa
It is reasonable to believe that the maximum. conductivity point9
maximum adsorption maximum orientation point, and joining of the
small aggregates in the. experiments of Sennet and Scott" and Rhodin
are all closely related" To compare Was' and Sennett and ScottUs
we might vary the evaporation rate and measure conductivity at the same
" thickness for fast and slow evaporated films o Sennett and Scott srlft'
that the aggregates donatjoin for slower evaporation rates until a
greater thickness of deposit is obtained and thus at a given thickness
the 90nductivity could be expected to be lower for the slowly evaporated
filmo
An account of the probable kinetics of very thip deposits during
the period in which nuclei form is given has
wri ttenin the kinetics of the formation of 11'll01e1o McLauchlin,9 Scott'
and Sennett
l
5'8 have. watched the formation of nuclei and "aggregates in an
electron microscopeo
It is possible that as separate patches of cf __ growing" o:ut
over the substrate will have boundary when they jo1n.9' un"'"
less we provide the atoms with sufficient mobili tyo . tt has been
1" '.
that long distance ordering of structure can be promPted very thin .
" .
(discontinuous) films by means of deposition in an atmosphere of gaso
For light vacuum deposition the. thicker films begin to show long dis-
tame order At liquid ai;r temperatures:"hN.e probab=
ly occur but as is more crystalline structure
of very long distance order should appearo
A phenomena probably allied to specific heat has been noted by
some in that certain substances can not be, deposited beyond a certain
thickness em let us say in the niicr9n range, yet other substances can be
deposited. to millimeter thicknesso If we imagine a molecule strlking
6H=4809
.Page ot 37
a deposit of some insulator whereby the energy transferred is not
\
pated by conduction
j
then we expect an elastic collision resulting
in the repulsion of the moleculeo That a, sink: for the energy
is' requirep. ,has been rtumerous tim.es in the MoI-o To film
laboratory, iSrotesso;r*o Harris o A good electron conductor is used
for a backing for the film and !ood deposits are formed hut if the back-
ing is not a good then it is in many cases impossible
the vapor to sticko
Section Go LATTICE- FIT,
The effects mentioned on page g of the of the
ited material, with the $upstrate cOIl:cernesi many. (eogo, references -1$1
79 37, 49, 50, 58=67.9 l07
i
116.9 1$5, 156, 159; 169)&, Basically we re
quire a t to have a complementary to that of the
subs trate 0 Naturally the spacing required "aecomodation is not
that of the substrate1 but t. that
is of greatest effect in adsorption of the particular adsorbateo As
examplefj _strong dispersion force will the molecule with the tnO$*,.
neigbborsj an ion will be attracted to a lattice ion (if the
strate is ionic)o The best fit of an adsorbate lattice then could be with
a spaCing different from the of the substrateo There-
fore:; ,in considering lattice fit, we may not say (wi inyestigation
ot'the forces acting,in'Jl particular an adsorbate, deposited
on, a substrate with identidallattiee' will be easily accomodatede
Some have concluded that the maximum difference of lattice spacings
that still of a deposited film is
This again is dependent on the strength of forces of
eogo
9
",the adhesion of an ion to a metal substrate is very and .y
accomtnoq,tlte a pair of materials with much greater than 1,% differenceo
An example of the determining f?ctors of lattice fit is seen in the adsor-
ption of aluminum on 'Aluminum.,(llO) plane will fit within a.
few percent in"the plane of the atoms residing in
ions of maximum Van der': ' Wail H s attrac:tion6 It seems likely that if we
were to ionize alumin1.lm and proceed with deposition there wo uld be much
6M=4809
Page 21 of 37
less accomodation due to electrostatic attraction of Aluminum to the
opposing the position With most number of nearest neighbors, etco
Due to the fact that the alvminun lattice is so distorted in such a
ion, little if any crystal would be expected at normal
(The situation for higher temperatures is discussed ear=
lier with reference to theory)o Each case of lattice fit orient=
. . ;'
ation must be judged on its own basis using as cr;tteda the relative
nitude of the various of adsotption, such as have been calculated
by
Sect:J..on Ho ELECTRON DIFFRACTION
There is some dispgreement as to the effect of the electron
diffraction process on films o Definite evidence has been given that
the crystal (or amorphous) is changed by the electron
and other equally evidence shows no change in the films so
6 64 '.
treated
7
,91 $ The variable that must Ibe taken into account when com=
paring the results of variQ:ps' experiments are}
10 Pensity of
20 Energy of electronso
30 Adhesive force of deposit to substrateo
40 Cohesive forees of deposit()
With regard to (3) we must realize thlt eleotron bombardment
of a physically adsorbed film may require very little energy to break th e
bonding and allow mobility of the atoms, whereas the energy required tor
disrupting a chemically bonded film may be considerable
o
et alia
162
.9 provide ,an example of (4) in their 'Work on
the sintering of gold blacks o Gold being heated stabilize and
change optical and electrical characteristicso The energy required
diffusion of a lattice atom to the surface of the smoke is found to be
about 1/3 of the 2705 kcalo/gmo atom for diffusion in massive goldo We
expect that the transfer of electrons should produce the same effects
as heating did in this caseo
We must make a careful comparison of the parameters noted above
when conSidering the results of electron diffraction experiments
o
For
6M=4809 Page 22 of 37
instance, the experimenter with a high energy, high density im-
I
pinging on aphysically Adsorbed,thermodynamically unstable film will more
than li:kely report structural changes in t he film or at Ie , a change in
optical and electrical
Wright and WOOds
167
' investigated the decomposition thin films
of various salts and oxides under slow electron bombardment o Decomposition
was measured by the chahge in secondary emission:which after
bombardment 0 It was foUnd that the energy required for did
not agree with the 'heat of formation of the compound as predicted by some o
The energy for decompositipn t&nded to ;gree the optical qbsorption
energy 0 The mechanism o-f some qases\ras c0I19luded to be
the of free and electrons which to the surface
where thay may release atoms from the compound thus change the cathodic
emission propertieso In this article, the work of
ists in this particular fiel.d are discussed 0 Bombardment of Barium 'Oxide
films is covered by lmai an' '!f1zushima
171
0
i
The use of 'electron diffraction for investigating crystalstruc=
ture of films is covered in references 61, 77=83,87, 1240
Section 10 CLEMJING OF StJBSTRATE USING PARTICLE BEAMS
The preparation of substrate utilizing electronic or ionic beams
is found to be helpful91-93.9166o The 'desired effect of these beams is to
drive off chemisorbed material such as gases, whose masking of surface for=
ces is well 0 Yang was to have investigated the effects
of such forces in 1954 but no data has been published as yeto In the
course of a symposium on vacuum evaporated films
97
at least 10 methods for
"
cleaning substrates were presented and all agreed that the final' step should
be cleaning with a beam of charged particles 0 Possi ble mech cmisms for the
process of this cleaning may beg (1) Local intense heating by the beam causes
a surge of energy ejecting the or (2) Direct satisfaction ,of a
chemisorption bondo Experimentation with variable density and particle en-
ergy beams could clear up this pointo
The use of electron beams is said to be superior to the use of
beams of other particleso An ion beam could be detrimental in some cases
Page 23 of 37
due to its reactive effecto Protons of sufficient velocity could form By=
drogeno energy of is generally low enough so that
heating drives it off quite readilyo However, if one must wait for the subc:o
strate to cool before proceeding with deposition, the cleansed surface has
time to become dontaminated againo
Carr
93
describes the effects of treatment of Gold,
\
which could be detrimental to vapor depositiono When Mercury vapor is de=
posited on such a surface it is adsorbed to all but points where the
tron beam had falleno Mro Ko Ro Shoulders gives the interpretation that
the beam had reduced various organic substrates pre sent 9 possibly to
thus presenting a low adsorptive spot compared to the gold surfaceo
A recent book by Holland
166
gives mUch good discussion of the
cleaning proce'sses o An important point that he discusses is the requirement
for a relatively high pressure to exist in order for glow discharge clean-
ing to be used
9
this paradox leads us back to the requirement for particle
bombardment as a final step in the cleaning processo*
Dro Ao Lo Loeb describes a method for post mortem investigation
of cleanliness of the substrate surface o Visible radiation is made incid=
ent on the film and the optical cons'tants are from transmission
and reflection experimentso The system is then reversed so the light is
incident on the backing and the optical constants recalculatedo Disagree=
ment of the 2 sets of optical obtained implies the presence of
impurities at the interfaceo The theory of reflection and transmission of
radiation by thin films and methods for analysis sre"given in the two art=
icles by Harrisj) 'Beasley and Loebo168Jl169
Section J o CONDENSATION COEFFICIENTS
now bring into the discussion the coefficient describing the
ability of a film to be depositedo Knudseri
lOl
,102 a Thermal
odation Coefficient as a = (8
3
"""E:i)!(E
2
wher$ Er is the energ1
! .
* An analogous paradox has been suggested by Shoulders o One must keep
I
in mind when using 'getters" that their vapor pressure may be greater
than the amount of vacuum
6M-4809 Page 24 of 37
the molecule possesses before striking the surface,9 E2 is the energy it I,
would have if it were in thermodynamic equilibrium with the surface, and
its energy after it leaves the surfaceo MUch data is available
giving the accomodation coefficients for gases on solids (eog
o9
see ref=
erence 99)0 The simplicity of the process of gaseous adsorption compared
to that of evaporated solids due to the relative absence of .attractive
interaction between gas molecules makes the definition and measurement of
accomodation coefficients quite
For the chemisorption of
is defined, it being
chemisorbed (by forces of about 10
gases, a sticki:Qg ,probability (or ;
the ratio. ot, thirnumber of molecules ,
, '
times those of physical adsorption)
the number of molecules physically adso:Ubedo Since the molecule is defi':'
nitely bound in such a case, rather than hopping around as does a physicr
ally adsorbed particle, and since the activation energies for evaporation
and chemisorption are amenable to experiment, therefore, this coefficient
can be found 0 Becker
100
has given an, expression for its temperature de-
pendence which agrees with experimento .Becker and Hartman 21 have qual-
itatively interpreted the coefficient to })e the probability that the
physically molecules will dissociate into its constituent atotnS9
This interp:retation can be seen to hold only forpolyatomicmolecules 0
For any molecule the qualitative statement should be that S is the prob- ,
ability that the physically adsorbed molecule form a chemisorption bond
with the The monatomoc gases are then accounted foro In the
case of polyatomic gases it is necessary to break the molecule into its.
constituent atoms before chemisorption takes placeo Therefore, we see . .l
from Becker and Hartmans statement that they assume that once the mole""
cule is broken up into atoms the probabili ty for chemisorption of the ate>
onus is 10 This is reasonable since when the molecule is present in the
form of its separated constituent atoms there are strong unsatisfied bonds
for the substrate to satisfyo
For the case of deposition of solids,a6ondensation Coefficient
is postulated, defined as the ratio of the number of molecules
on the substrate to the number of molecules striking the The
complexity of the' events occuring and the fact that simplifying assumptions
(such as homogenous or periodic surface characteristics) do not closely
6M-4809 Page 25 of 37
enough describe the surfaces investigated, does not allow as yet explicit
expressions involing only known parameters 0 Devienne has made many meas ....
urements of the coefficients using radioactive tracer studies o Ai short
summar" with bibliography is given in reference 1030 Continued experimen-
tation along this' line combined with study of crystal nucleation and
will lead to the determination reproducibility
of results as is now possible with Accomodation Coefficients
o
"
Yang,? ey a1ia
49
.950}l have studied crystal nucleation and
sation Coefficients 0 In addition to the rate 'equation for nucleation which
,
\
they derive,. they give data on varying condensation coeff;tcientso Ref ....
erence 155 gives a plot of lattice fit against condensation coefficient.-
which turns out to be linear and for 15 to 20% lattice fit the condensation
coefficient is almost zero for' their particular experimental conditionso
The increase of condensation coefficient for increasing thickness of de=
posit is explained as due to the increasing availability of
1t
sinks u for
crystallization after nuclei have formedo As was noted earlier, another
effect present after a rmono1ayer or so coverage is the fact that usually
the cohesive force (which is prominent at this stage) is much greater than
On page 473 of Reference 155 it is shown that the con-
densation oefficient is greater for an increased crucible temperatureo
This is quite in line with Levinstein.vs conclusions , given earlier,-where-
by at low evaporation rates, the molecules have a greater probability of
evaporating'before aggregatingo Yang discusses this effect throughout
from the standpoint of supersaturation of the atomic base
o
Section Ko CHEMICALLY BONDED . FnMS
I. !
Throug}:lout this paper the retention of the adsorbate by the sub ....
strate by chemical means has been little more than hinted at& This is due
to the fact that references to this effect in the literature are scaIfceG
In the course of conversation with thin film experimentalists:; it has been
noted that examples of probable chemical bonding are sometimes lllQre!.ap.par-
ent than the literature implies o This bonding is thought not to be the
chemisorptive type whereby the adsorbent and adsorbate atoms retain their
identity but rather the formation of a compound at the interface that acts
6M=-4809 Page 26 of,: 37
analogously to an "impedance match" between substrate and adsorbat9o An
example of this bonding is Chromium or Aluminum deposition on glass which
is believed to form a metal oxide at the interfaceo The adhesion of these
films to glass is far greater than that of the metals which would
not be expected to form a compound at the interfaceo A simple quantitative
measure of film adhesion is the "strip test" whereby an adhesive tape is
plac ed on the film and being stripped off the ease of removal of
film from substrate is notedo Aluminum and Chromium are effected less by
the stripping than are the noble metals o
A more precise qualitative measure of film binding is that used by
Rhodin
5
C) The critical pressure (lowest pressure required for films to
form on substrate) for a temperature T is, as stated in Section 0,
p 1: ! 6) IKT We make a plot of lilip versus l/KT 0 s,lope of
the curve then gives (U+4), the binding energy of the film
(including the effects of impurities adsorbed at-the interface)o It is
questionable whether this experiment would show .p the binding energy for
all "r any) chemically bonded' films however, since the atoms may be adsorb-
ed at first by physical adsorption means and possible after some finite
time the chemical The slope of the l/KT would
not therefore indicate the chemical bondingo
It would be of great assistance in discussing the possible forces
acting to bind the film and in predicting film qualities such reflect-
ance,9 resistance$ etco to know the 'binding energy for e,ach pair of mat-
erials C) An experimenter in the optical properties of films would have an
advantage if he knew that possiblY an oxide or other compound existed at
the film-substrate interfaceo The distribution of electrons and space
charge which exists is intimately connected with the surface boundary con-
ditions as is shown by Skinner
i7
00 A few binding energies are given by
Wexler
112
, having been compiled from the few references that the literature
.
holds 0 A project which would possible be of great worth would be a more
complete of such data and an attempt at a classifying anal-
ysis of the aata
o
signed: -P.duv
PF/gk Peter Fowler
6M-4809
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71, po 476, (1947)0
Was, 390 (1939)0
74.0 Kramer,9 Zo Foro )..06, po. 675 (1937) 0 ..
755' Krautkramer, Ao d.e Po 32, po. 537. 0
76.0 Sennett and Scotts o.SeA.40
9
P() 206, (1950) 0
Page 29 or 11>
770 Tbeory and Practice of Electron Diffraction, Thompson and Cochrane,
. MacMillan and CO o .9.Lopdop.., {1939).0 ...
785' apd Wposte;r, Ao .. Co , 6, po 543 (1953)0
799 A& Co, 5, ppo 626,9634, 782$ ()"952).. .
80p Picard and Duffendack9 JO.AOP09 14, po 291, (1943)0
8I.1t .Matthews and Wilman, I3ri:\io.Jour.o App1oPhys,o 6, p0277 (1955) 111
82.0 Newman. and Pas}:tleY5)Pp M.o 46, PC) 927 [1955.)0
8 3.0 Bryant , Webe;r 0 J" A 0 . P. ?5, .p 0 1343 (1954) 0
84.0 Winke1mann$ Zo 7 J p,o
85,0 Ansbacher. an9 EPrenberg, Po Po .. So, Lo., 64 po 362 (1951)'.
86.0 Nelson, Jo CG Po 5, po 252 .. (1937)0 .
. 87.0 Finch, Q.ua rre 1)... and. Wi).man, T G F 0 $G 31,ppo 1049-80 (1935)0
88,0 Reynolds $ Po Ro" 24" ()..924)p
89.0 SnQ.th,. 10c() 9ito, po 451.()
90!t Rhodin" DG Fo 5, po,221 (j.949)o
Strong,. in. ExpO' .Phys 0 f1 po 166 .(1948) (I
925' Duslunan, VacoTe9hniques, (1949)0
93.B Carr, Ro SoIo 1, po .724. (1930) o.
94.0 Langmui:r ap.d I3109gett,P.o R.o , 40, ppo, 7S-104 (1932).
95!tRoberts,. Po .. Ro , 129 . .A
9
. po.146 (1930)0 '
96;0 Jo Po Ro,9 l3.,. po 53 (1952)0
97 163, po (1949) 0
98 . Dunoyer, Co RoAoSo 233 pO' 9),,9 (1951).
990 Temperature dependence'of AccoCoefo on W, Ni, Pt, 1954 MIT Chem P1:iIID
Jhesis, Lo Ao
1000 Gomer and Smith, loc oci t, 0
, ).<'
6M-4809 30 of 37
.Knudsenl1 Ao Po. 34, PI) 593 (1921).0
102.0 Knudsen,. Gases,. PP.o 46052 Methuen (1934)0
103,0 Devienne,. Va9" 3,. Po. 392 (1953)0 .
104.0 Becker, Po 34, po. 13?6.. (1929) o .
105.0 Esterman., Ze f!1Po 33!1 po 320 (19?5l.o
106!1 Bikerm.an,Surfo Chem for . 219 .. (1948),.
1070 Burton, and rank, Po Ro So, 243 A, po 299 (1951)0
D )
.108,0 Frank, 0 Fo. S() 59 po 48 (1949 0
.Smoluchowski
9
trpnsfprmations .. in PPo.149-183 Wiley(1951)
llO.o Ind, and Eng, Chemo 44, PPo.1270-133a (1952)0
111,0 Turnbull and H911om?n,.Physo of Powo.Meto 109-143 McGraw-Hill (1951)
ll2.0 Quarto Rev.o 5,p.o 315 (1951) 0".
113.0 Holloman. & TurnbUll, Progoin Meto-,PhYSo.Vol- 4,. pp.,333 ... 88 (1953) 0
1140 HollolWl, Thermodynamics iti Physical Metaurgy, ppo 161-77, !mo Soco
. for Metals, Cleveland 9hip,.(19'O) 0 ".
115p Coleman. Ro65p.o 57 (1944)0
116!) Bunn, Po RQ So 141, po 567. (1933}o
117!> Frank ;md. _p. p.o Ro .. So J..98 p. 216 (1949)0
118.0 Volmer, to ;Po. 9" pe 193 (1934).
PC) 0 So 5, po 48 (1949}() .
120.0 Buerger, . 32, po 593 (1947) 0
121.0 Wells, Po Mo 379 po
122!J Gomer and cito.po 50
123,0 Cunningham, iTo ro 9& 39, 69 (1935)0
124.0 Lashkarew, To F I) So 31, ppo 1081-95 (1935)0
1250 Rideal, Introduction to Surface Chamistry, po 205 Cambridge Uo
. Press (1930)!t . . . . .' .
1260 -Semeno,ff
j
. To. Fo. 50$ 2B, po 170 (j.932)o
Becker$ 5, pp 55 (1949)0
128.0 Magnus., T.o S.o 28 P.I) 386""94 (19,32) I)
129p Zoo fio. p$.63 po 245 (1930).
Hill, J.o. Co. P.., 19,. p,o. 394. ,(1930) 0
I
LangmUir, P ..
132._ Andrade,. To. Fo. So. 31, p&,1137 (1935).
133.0 Langmuir. J 0 Ao C. 50 p .. ltJQl. (1918)._ ..
1340 Brunauer, Emmett and Teller, Jo Ao Co S. 60, po 309 (1938); 62,
P,l 1723, (1940).
6M-4809
Langmui;r.9 ;Io 1.0 0.0 So." .. p.o' 2798 .. (J.932) 0
136$) Onsager,9 Re Mo Po, 25, po 353 ..
Page 31 of 3rt
137.p Wiley (1940)0
138
9
Ono . .$! J!, Cp p.O.9' :L8.9. po, 397 _,'
139.0 OnO,9 .. Jo. Po, So, Jo,5
J
po (1959); 6; p. 10 (1951).
140,. Dole., J!, e,o Pp 16". pp25 .. (1948) o.
Hill, Jo 90 Po ;t6" (194.8)0.
1429 Fowler,)} Pp Op P!, Sp 3:1.:" po. 2,26 (1935). '
143p Po. C. O P'o S.o ppo (1940).
144p Hill, Jo 00 :Pojl.l5$ po 167 (1947)0 ,
145p Cassie
s
Tp F.o S!'9 po 450(1945) 0
146p Halsey, J 0 Ao Co 8.0 73.9 po 2693 (;t9?1) o .. '
147'0 Huttig and Theinierjl Ko PPo 69-73, 157-60 (1950); 121,9;
. pp,,50:=57
St
(;t95:t.)0 .
148
0
Ha1seY9 J o Co PO,9 16,9 po 931; .(1948)0,
149.0 ;r 0 C.o Po" 57, po 946, (1953)0
150.0 Hill.$! J.& e,G 1?!, 14$) PP.o 293, 441 (1949).
151,0 Robe;rts,9 p,(} R!t. So 141 (1937) 0
152p Hill, J.o 0 .. .9 59 po. 1065 (1955)0 .
153.p Gang11l1, 71,.ppo.275;=9 (1935).
154.9 Ha1s$y, Jo Ao. Co So 74
9
. PP.o 1082-3 (1952),0
155p Yang, et alia" A,9ta, Me:t;o 2, po 475 (1954)0
156.0 Van der Merwe, D.c- F!l" S." 5Jl p.& 291,"(1949)0 .
157.0 Egli and Zerfoss, Do F6 So 6:L (:L949). . .
158.0 McLaupb].afl, $co:t;t Senpett, Cano, J.o Res o 28, po 530 (1950) 0
159.& Thirsk"P!J Fp So 'J.o 63, po sa3 ()..950) 0 .
160.0 Engles, Uo So Bu;t"o Jo 50 ppo 2#9-61 (1953) 0
161.0 Germer, and ?& pO, Ppo. 447
Harris.jl at alia., J.o C.o IS" po. (1950) {)
HarriS., et alia., J.t) 0
9
Sp AOj) 3S, P6 582 (1948)0
Harris" et aliaj Jo Ao. P&.19
9
po 791 (1948)0
165.0 Frazer,. Molecular Rays, po 95 Yo (1931).
'1660 Holland, Vacuum Deposition. of Thin Films, po 74, Wiley (1956).
1670 and PoPoSoLo 66 Po. 1073 (1953)0
1680 Harris.}! Beasley$) and Loeb, 41, po 604 (1951)
6H-4809
1690' Harris ana Loeb, J o OoS. Ao 45, p. -179 (195')0
170
0
Skinner, J.AoP. 26, Po498 (1955)0
Page 32 of 37
171. !mai and Mizushimt, J.F oSoJ 0 9, pp. 28-1032, 1034, (1954).
1720 Wexler, Condensation CoeffieientB of Metallic A t o m s ~ held by P.Fowler.
6M-4809 Page 33 of YI
. SUPPLEMENTARY BIBLIOGRAPHY I
As a guide for continued investigation into. the properties
of thin films" the following list of .r.eferences is gi veno The work cov-
ered by these articles is less general in nature than that of the main
bibliograpw ahd should have Borne interest to those looking for thin film
components 0
1.0 Resistivity of thin films, Clark, Brito Jo Appo.Physo. 6,.po.158. (1955)
20 Electric Strength of Dielectric Films,Plessner, P. Po So Lo' 60,
po 243 (1948)0 -. . . .
30 Electron Bombardment and' Conduction of Dielectric Films, Ansbacher and
Ehrenberg, PoPoSoLo 64,.po 362 (1951}o .
4.0 Thin Film Electronic Mean Free Path,. ,Advo in Yol, ppo 1...;42
Path J.ength, of Electron Beam in Foil, Yang, Po Ro '9'0,84 po 599
6. Elect. Condo of Metal: Deposited" on Die1.ee'tiric 'in Relation to Crystal
Structure, Feldman, CoRo-.AoSo.t 0 .
70 'Relatibn between Film Res1st*o Varied by- Coverage with Diel-
ectric, ... and Vodar
1
Co R.Ao$o., .. 23$, po 414,. (1952)0
8.0 High Freqo Resistivity of Thin Films, Pj).,Ro 9l+,. pp 285 (1954) .
90 Metal Film Resistance Factors, Appleyard, PoPoS.!.,. 49, Supplo po 118
. (1937)0
100 StrUctural Changes during Growth of Metal Films, Quarrell, PoPoSoL
o
,
49, po .279 (1937)0 .... _
110 Conduction of- Thin Granulated Ag Films, Haas Scott, J o Po Ro , 11
po 394 (1950)0 . .
120 Some Properties Evaporated Films on Glass, Rood, Jo 00 So Ao
39, po 854, (1949)0 .. .'.'
13,0 Ther.rrmldlTl..agnetic Properties of Thin Films,. Blatt, "?o 95,. po 13,(1$4)
140 Conduction of Thin Films of Alkali Metals, Lovell, PoP oSoLo 49, po
(1937) 0 ,. .:.., ' .
150 Conduction of Thin Films of Indium, Cosslett, 49, p. 121
(1937)0 . .. '. .. '. '
160 Adhesion of Films, 00 8,0 Heavens, JoPoRo 11, p. 355 (1950).
6M-4809
Page 34 ot 37
SUPPL!m:NTARY BIBLIOGRAPHY II
The following is a listof some references oftecbniques and crit-
ical data that should be of to the experimenter investigating
vacuum evaporation of thin films o
10 Bibliography of Solid Bureau of
(1944).& . ... .-
20 Brewer, andPhys. Propo of Elemants, Rpto for Manhattan Proj-
ect MODe 438-0" Also other. reports 9f 436.serieso . .
.'
3'0' Brewer, Chern and of Misco Mato,Nuclear PbYSo Series, McGraw
._Hill Vol,. IV 19
00
Bo
4.0 Buo. Mines Vap:>r Pressures, etc.
50 Stull, '& Chem.o 39,9' po 517 (1947) Vapor Pressure of Organic
0,
6Jj Hayer"Jo.Co.Po, 1, 270 Lattice enfa;rgy of a1ko halides.
, . ," \ ,1 ."
7 Law, R&.So Io, 19, po' 920" VFlPor-
80 Barrett" Structure of- Metals', -Crystallographic' data, McGraw-Hil1(1952)
. Ta b1e pf Text, of Evap 0 'FiJ-PlB" etc Ct esp., , Po 5;1.9 .. '
90 Wexler, Condensation Coefo,. Binding Energies, and Critical
, . of Metallic Films..? held by Po. FO'JIler,o. .' " '
lOci Marshall,9Dornte, and Norton,' J o A,o C.o s., 59, po 1161 (1937) Vapor
. PressUre of Fe, .... ;
110 Schuman 'and Garrett,' JoAoCoS,9 66, PG 442 (1944); 67,po2279 (1945)
. Vapor press'ure of, Beo
12.0 Preparation of t;hin unbacked films,. Nature, 159 (1947) 0.
13.0 Yacuum symposium, Committee for Vac o TechniqJ}es (53303 L73
140 Thin films at low temperature, McLennan,'Rpt o of Prog. in Physo 1,
po 198 (1934)0 . .... '. .
15.0 Deposition at film interface, ,T.GE.$o,. 55,. po15) (1929)0
Prep." of Metal Films., Ro Io,. 21, po. 6g3 (1949)0
17<t Prepo of Unbacked Films, Carpenter and Curcio, RoSolo' 21 po675
(1950)0 ',..
180 Density Change of Rhondium Film after Evap, Stopped. Zehden, Vac, 1
PPo 38""9 (1951) 0 "" .
Tech.o for Evapo Zns :Films" Rpod, JoOoSoAo4f, p .. 291 (1951)0
20" Evapo Films on Glass, Strong, Astrophys, Jo8j,po 401 (1936).0
6M=4809 Page 35 ,01 37
. .
210 Satisf'actory Filaments for Evaporating Metals, Caldwell, J 0 Ao Po 12
, po 719 (1941) e,
220 Evapo Filaments Usedo Olsen,Smth and Crittendon, J.A-.p..
l6i p.-425 (1945}o '.
Tecp, in ,Makipg Thin Films, 2 ar:t,icles, Mar. 15, 19470
240 Rpto for Techo'of Shadow Casting, Cambridge Uo Summer School (Ref.
Vaco.lo. po 30)0'
250' Techo and Plant Set-up for Vaco Evapo,. Holland, Supp.1l. (1951), Jo
Scio Instro
26 Engineering. Index, Under 0
2.7,0 Vacuum. Metallurgy,: Elec,trochem..9" (1955)0
,28,0 Contamiilatioh,by Fllni Heavens, PofoSoLo 65B, po 788 (1952).'
29$1 Use of SiO, Labo Practice
a
, 3, po 4.41 (1'1.!:lJ)St
30.0 Molecular 18, po 300 (1946)0
310 Radioactive ShadoW' Techti, and Dep-o of Monatomic Beams, Simnad, Yangj
Pound, JoAoPo!J 25, p. 268 (1954),0
320 Soldering to- Thin FilMs, (Few. it)!) Boetticher -and Thun, Optik 11, No.1
po' 2? (1954)0 .. '--.'.. ..' . .
33.0 Prep.o Thin Filrn:!, JoioPo "?6,, po 975 (J.955)i>
Proto of Mo by SiO, Fe1dmana CoRoAoSo, 706(1952)o .
350 Contamo of Film by Source SUp}:lort Material, Heavens, Nature" 168,
po 694
36.0 Masso Evapo Formula, ;Holland, Vac-o--l,no-o. 1,p.o23-36
37.6 Thin Films on Liqu1ds, Nature 162 po 892, (1948)0
380 Effect of Deposi,tion Tempo on Magnetism of Ni Films, Fdwards, PoRo
27, po 252 (1926)0
390 Adsbrption of Sr and Ba on WaMoore, and Allison, JoCoP023, po 1609
(1955)0
400 Determination of' Object- Thickness in Electron Microscopy, Marton and
Schiff; J o Ao Po, 12,9 po 759 (1941)0
410 Silicon Monoxide Protection for Mirrors; Haas and Scott, JoOoSoAo, 39
po 179 (1949)0 " .....
42p Increasing Adhesion of Metal Films, Scott, J oOOS()Ao
9
hP, po, 804 (1950)
430 .Production of' small aperture by evaporation
. po 115 .(1951) 0 , . '. . . .
44J:1 Multiple beam interferometry, To1ansky', Vac.o 1, P.o 75 (1951)0 .
450 Preparation and Structure' of SiO- Film,. Haas', Data 16,9
. No o 4, po 21(1951) J oAoCerlt $oco . .33, P6 35.3 (1950). ".
460 MeaSuring' Film Thickness 10 i to 3r.t, Scott, McLachlan and Sennett,
JoAoPo '21, po 843, (1950)0
6M-4809 Page 36 of 37
, .
. 410 Measurement and control of thin fih thiekness, Greenland, Vaco 2,
ppo 30 ..... . . .' .
480 Prepo and properties of thin l'i02 films, Hass, Vac. 2, ppo 331-45
(1952)0 .. - .... . .
490 Preparation of thin'unbacked 810 films, Sawyer, R. S. Io, po 604
(1952)0
500 Adsorbed films of Os on W, Langmuir,PoRo 43, po 224 (1933)0
Page 37 of' 37
BIBLIOGRAPHICAL ABBR.EVIA nONS .
Abbreviations for' periodicals listed in the preceeding bibliographies areg

A.od!,P.o

.
J.oA.oC.oS o
J.o.A$)P.o
JoCoPo
0"


J ,

. .

P;oH;O . .
PpN}>A!,S!)

.
PpR.oS.o
PpT,oR.oSo
R,oM.oPp

i'.oE.oS.o
ToFpSo
V?cp .
Z!'tpp.&
ZoPoCo
Acta C1f.i.stallographica
Annalen der Physik
Academie des Sciences Comptes Rendus
Discussions of the Faraday Society
Journal of, the Am.ericanChemicalSociety
Journal of Applied Physics ..
Journal of
Journal of the of America
Journal of Physical Chemistry -
Journal de Physique et Ie Radium
Journal of Physical Society of Japan
Kolloid Zeitschrift
Proceedings of the Cambridge Philosphical Society.
Philosophical Magazine ! f I
Proceedings of the of Science"
,
Proceedings of the PhySical Soci 'ety. of London
Physical Review
Proceedings of the Royal Society of London
PIrllosopbical..Transactio.ns:of' Society
Review of Modern Physics
Review of Scientific Instruments
Transactions of the Electrochemical Society
Transactions of the Faraday SOCiety
VacuUm
Zeitschrift fur Physik
Zeitschrift fur Physikalische Chemie .