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i KristaZZund Technik I 11 1 7 1 1976 i 686-697 1

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I.MARKOV,R. KAISCHEW
Institutc of Physical Chemistry, Bulgarian +4cademyof Sciences, Sofia

Influence of the Supersaturation


on the Mode of Thin Film Growth

The thermodynamic criterion of the mechanism of growth of thin films is reconsidered.


It is shown t h a t the supersaturation plays a significant role in determining the growth
mode in addition t o already discussed interrelation between the specific surface energies
of the substrate, deposit and the substrate-deposit interface. The conclusions are in good
agreement with experimental observations in deposition of f.e.c. metals on f.c.c. metal
substrates t h a t a t positive surface energy change the island growth is favoured a t super-
saturations lower than some critical one while a t higher supersaturations a layer growth
takes place. The STRANSKI-KRASTANOV mechanism consisting in formation of three-
dimensional nuclei on top of previously deposited layers of the overgrowth is considered
in more details. It is concluded t h a t its occurrence depends on the sign and the value of the
lattice misfit between the substrate and the overgrowth, on the interaction forces between
them and on the thermodynamic stability of the deposit. The validity of the classical
nucleation theory for explanation of the growth mode transition is also discussed.
Das thermodynamische Kriterium fur den Wachstumsmechanismus von diinnen
Schichtcn wurde nachgepriift. Es wurde gezeigt, daR neben den schon diskutierten Zu-
sammenhiingen zwischen den spezifischen Oberfliichenenthalpien der Unterlage, des
Niederschlags und der Phasengrenze Niedcrschlag-Unterlage such die tfbersiittigung bei
der Bestimmung des Wachstumsmechanismus eine bedeutcnde Rolle spielt. Die SchluB-
folgerungen sind in guter Ubereinstimmung mit den experimentellen Befunden im Falle
der Abscheidung von k.f.2.-Metallen auf k.f.z.-Metallunterlagen, wonach boi positiven
Anderungen der Oberfliichenenthalpie bei fibersattigungen niedriger als die kritische
das Inselwachstum, und bei obersiittigungen hoher als die kritische das Schichtenwachs-
tum bevorzugt wird. Der STRANSKI-KRASTANOV Mechanismus, gekennzeichnet durch
Bildung dreidimensionaler Keime auf zuvor abgeschiedenen Schichten, wurde ausfiihr-
licher betrachtet. Es wurde die SchluBfolgerung gezogen, daR seine Verwirklichung von
dem Vorzeichen und der GroBe des relativen Unterschieds der Gitterkonstanten der Metalle
der Unterlage und des Niederschlags, von den Wechselwirkungskraften zwischen ihnen
und von der thermodynamischen Stabilitiit des Nicderschlags abhiingig ist. Die qiiltigkcit
der klassischen Keimbildungstheorie wurde in Hinblick auf die Deutung der f ' b e r g h g e
der Wachstumsmechanismen ineinander diskutiert.

1. Introduction
Structure and properties of thin films are strongly connected with t h e mechanism
of t h e crystallization process. In this respect the study of t h e influence of the super-
saturation no thin film growth mode is of great interest.
On t h e base of detailed thermodynamic analysis BAUERestablished some years
ago that if on chemical reactions, alloying, interdiffusion or other changes of the
surfaces t a k e place, the mechanism of the crystallization process on a foreign sub-
strate is only governed by the interrelation of the specific surface energies of the
686 I. MARKOV.R. KAISCHEW

su%&rzs#eu,, deposit a a d the suMm6sdeposit interface a*.Three different cases


-7 be
1. The q5Wz8ticm pfooess poceede by formation and growth of three-dimen-
sional nuclei (VOLMER-WEBER mechanism) when
0, <a + at. (1)
2. The process proceeds b y formation and spreading of two-dimensional nuclei
(FRANK-VAN DER MERWEmechanism) when

a, = a oi. + (2)
In principle this growth mode may be realized if the deposit and the substrate
are of one and the same substance (BAITER). I n such a case a, = 0 and a, = a. This
limitation is connected with the requirement the above equation to be fulfilled with
respect t o the formation of each new monolayer.
3. The beginning of the process is connected with the formation of one or several
monolayers. After that three-dimensional nuclei are formed on top of them (STRANSKI-
KRASTANOV mechanism) under the condition
a, >a + at. (3)
It follows from the above criterion that if the temperature change of the surface
energies or the kinetic factors are negligible in a narrow temperature intervalone mode
of growth is only possible for a given substrate-deposit system. However, some recent
experimental data concerning deposition of f.c.c. metals on f.c.c. metal substrates
show a transition from island growth to layer-by-layer one as the substrate tempera-
ture decreases or the evaporation rate increascs (JESSER, MATTHEWS) ; HORNG,
VOOK1974; GRADMANN 1975; GRADMANN, KUMMERLE, TILLMANNS). Obviously, the
supersaturation may play a significant role with respect to the determination of the
growth mode. So the aim of the present paper is to explain the effect mentioned above
on the base of the classical nucleation theory.
It must be noted that the thermodynamics of crystallization on foreign substrates
has been an object of intensive studies (STRANSKI, KRASTANOV; KAISCHEW, BLIZNAKOV;
KAISCHEW;LACMANN ; KLEBER;TOSCHEV, PAUNOV, KATSCHEW; BLIZNAPOV, DELI-
NESHEV). The island-layer-by-layer growth mode transition is generally considered
by KLEBER and by TOSCHRV et al. The calculations are performed using a simple
cubic lattice deposit on a structureless substrate as a model with the help of the
method of the mean works of separation (STRANSKI,KAISCHEW;HONIGMANN). On
Figure 1 the dependence of the Gibbs free energies of formation of both three-dimen-
sional nuclei AGs, E and two-dimensional nuclei AGz,p on the supersaturation A p for
the three possible surface energy relations (1)- (3) is schematically shown. The figure
is based on the results of TOSCHEV et al. As is seen when the surface energy change is
negative or zero the formation of two-dimensional nuclei is only possible irrespective
of the value of the supersaturation. However, when the surface energy change is
positive three-dimensional nucleation is energetically favoured at supersaturations
lower than some critical one Apcr, a t which the nuclei have a monolayer height. At
higher supersaturations three-dimensional nuclei have no physical sense, as their
height is smaller than that of a monolayer, and two-dimensional nucleation would
only take place. Obviously, the classical nucleation theory is capable a t least qualitati-
vely of explaining the growth mode transition.
In the present paper the calculation of Apcr for the growth mode transition to
occur in the case of positive surface energy change is made by equalization of the
Gibbs free energies of formation of three- and two-dimensional nuclei as in the paper
of TOSCHEV c t al. For the sake of comparison of the results with experimental data
Influence of the Supersaturation on the Mode of Thin Film Growth 687

c- -A JJ 0 A PL AJJcr + A P __c

Fig. 1. Dependence of the Gibbs free energies for formation of three-dimensional nuclei AG3, k
and two-dimensional nuclei 4 7 2 ,k on the supersaturation d p at different surface e n e m changes

the calculations are made for f.c.c. lattice deposit with (100) and (111) orientations
on a substrate with the same structure. It has been also accepted that the overgrowth
is pseudomorphic to the substrate, the strain energy having been included in t h e
interfacial surface energy term. Moreover, the energetic influence of the substrate
has been assumed t o be limited within one monolayer of the deposit. Thus, the cal-
culations have been considerably simplified. Then, on the base of the results obtained
a more general criterion of the film growth mode has been derived.

2. Critical supcrsaturations
The equilibrium form of a f.c.c. crystal is a truncated octahedron (Fig. 2 ) with equal
lengths of the edges of the cubic and octahedral faces if the first ncighbour model
ratio is accounted for : t ~ ~ = ~J3/2~ (MACEENZIE
/ t ~ ~et al.
~ 1962). The three-dimensional
nucleus with (100) orientation just before the transformation to a two-dimensional
momolayer square one has the form of a truncated square pyramid represented by
sect,ion 1. The corresponding nucleus with (111) orientation before transformation
t o a hexagonal monolayer nucleus has the form of a truncated hexagonal pyramid -
section 2.
2.1. (100) orientation
I n this case the surface energy increase CJJ connected with the formation of three-
dimensional nucleus with the above form is
+ + +
v = G%o -t f i w 3 p h ) 01, (1, $ 7 4 2 (G - a,) (4)
where h and I , are the height and the lenght of the upper edge of the nucleus, re-
spectively.
The volume V of the nucleus is
V = [(Z3 + 1 2 7 ~-) ~2:1/3 1/2 . (5)
688 I. MARKOV,
R. KAISCHEW

Fig. 2. Equilibrium form of f.c.c. crystal - truncated


octahedron. Section 1 - equilibrium form of f.c.c. crystal
with (IOO)-orientationon a substrate before transformation
to monolayer square nucleus. - Section 2 - equilibrium
ioim of f.c.c. crystal with (111)-orientation on a substrate
before transformation to monolayer hexagonal nucleus

Under the conditions dg, = 0 and d V = 0 the following expression for the equili-
brium form ratio h/l, is obtained:
fi +
hll, = ( ~ 1 0 0 ai - loo - (6)
The Gibbs free energy change for the formation of the nucleus is given b y
AG, = a, + VAp/v (7)
u being the molar volume.
The Gibbs free energy AG3,k of formation of a critical nucleus is calculated in the
usual way consisting in determination of an extremum value. Then, the following
expression is obtained:
d G 3 , ~= (Sv2/3Ap2)[(fianl -k - ad3 - ( $ k 1 - %d31 . (8)
If we apply again the above relation between a, and a,, and taking into account
t h a t of is smaller enough than a and a, the above expression niay be simplified to the
form
+
AG3,b = (2$dOO/Ap2) (aim 61. - 0s) * (9)
The Gibbs free energy increase AG, connected with the formation of a two-dimen-
sional square nucleus with a edge length I , is given by
+ +
AG, = 4 ( ~ , , 01.- 0,) 4&$1o - (G/b2)A P (10)
where xlo is the specific edge energy and b is the first neighbour distance of the sub-
strate, b2 being then the area occupied by one atom of the deposit in the (100) contact
plane.
Using the same procedure the following expression for the Gibbs free energy AG2,
of formabion of critical two-dimensional nucleus is obtained :
AG2,r = 4 b a 4 o / [ d p- b2(a1, + - as)] . (11)
Taking into account the connection between the edge energy qoand thc surface
energy ~1,
xlo = , (12)
Influence of the Supersaturation on the Mode of Thin Film Growth 689

valid for f.c.c. lattice for dG2,k one obtains:


AG2,k = b4400/4[Ap - b2(a1, +- a,)] . (13)
Finally, under the condition dG3,k = dG2,k the critical supersaturation Apcr is
expressed by the equation
+
Apcr = 262(al, at - a,) * (14)
It is worth noting that the same equation may be derived starting from the ex-
pression (6) for the equilibrium form of the three-dimensional nucleus after sub-
stituting the height h by the one of a monolayer h-, = b / @ and expressing the edge
lenght I, through the Kelvin-Gibbs equation 13,E = a1,b3/ApL,,.

2.2. (111)orientation
In the other case of (111)orientation the following expressions for the surface energy
increase p, the volume V , the equilibrium form ratio h/l, and for the Gibbs free energy
for formation of a critical nucleus are obtained :
+
9 = [ ( 3 1/T/2) 1; (9/2 h ( z 3 -t h ( i 3 / 2jz))] + (3 z3h6100 f
+ +
( i q 4 ) C(3& h(fl/fi))2 - 3%1(ac - 0 8 ) (15)
+ +
V = ( 3 0 1 2 ) Zih ( 9 / 4 @) Z3h2 (1/3/8)h3 (16)
= (1/3/J% (%l
J 4 3 + Of - % ) / ~ l l l (17)
AGs,k = ( 4 1 / 3 ~ ? 1 1 0 ~ / A +
( 0 1p1 ~ .
1 ) (Ti - a,) (18)
The corresponding expression for the two-dimensional hexagonal nucleus are as
follows (xu= a1,b/2):
AG2 = ( 9 m ) +
w,,, - 0,) + 612% - ( 9 / 4 )( 4 / b ) 2d p (19)

+
Apcr = 1/5wJ,ll ai - 4 * (22)
The same expression may be obtained starting from (17) and substituting h = h1 =
= (15/i$) b and l 3 , k = (2 f i / 3 ) OiiiV/Apcr.
Considering equations ( 1 3 ) and (21) it is seen that when da = a ai - a, + 0 >
two-dimensional nucleation is possible in the supersaturation interval A p L A p <
where A ~ = L SJa, S , being the area occupied by an atom in the corresponding
contact plane. In the case of zero surface energy change (deposition onto the same
substrate, ac = 0, a, = a) two-dimensional nucleation is possible at positive super-
saturations. However, when Ao < 0, AG2,k occupies finite positive values also a t
negative supersaturations or a t undersaturations, respectively. This means that if
the deposit-substrate interaction is stronger than the deposit-deposit one the first
layer may be formed in an undersaturated system (STRANSKI, KRASTANOV).
Moreover, i t is clear that in the case of positive surface energy change (a, a at) < +
three-dimensional nuclei may be formed at supersaturations lower than the critical
one. Two-dimensional nucleation is favoured energetically a t higher supersaturations.
Hence, the following criterion for the growth mode may be written:
1. Island growth connected with the formation of three-dimensional nuclei is
possible when
0s < ahkl + ai - Ap/21Chk1b~ (23)
690 I. MARXOV,
R. KAISCHEW

2. Layer growth connected with the formation and spreading of two-dimensional


nuclei is favoured when
as > ahkl f 04 - A@ki,kib2 . (24)
The constant khkl depends only on the orientation, k,,klba being the area occupied
by an atom of the deposit in the contact plane (klw = 1, k,,, = (512).
It is noteworthy that the above criterion is valid not only for positive surface energy
change, but also for any change of the surface energy. Obviously, if Aa < 0 the sign
of the second inequality is independent of the value of the supersaturation term,
i.e. if (3) holds (24) is also fulfilled.
It is interesting now to compare the BAUER’Scriterion with the results obtained in
the present paper. I n order to derive the criterion BAUER has started from the ex-
pression for the equilibrium form of a cubic nucleus
+
hll, = (a q - a,)/2a (25)
assuming an independence of the surface energies of the size of the nucleus. Practically,
this is the same formula for the equilibrium form derived by KAISCHEW(1950, 1952,
1960)
h/l, = 1 - P/2a (26)
in terms of the specific adhesion energy P between the deposited cubic crystallite
and the structureless substrate. The identity of the two formulae is immediately
seen if the definitive equality for /? is written
=a + a, - a $ . (27)
The last expression is valid not only in the case of structureless substrate, but also
in the case of crystalline one with a lattice inisfit between the substrate and the
overgrowth. In the first case /? and a, are determined only by the interaction forces
between the atoms of the two partners. I n the second one the strain energy has t o by
accounted for as this is done by VAN DER MERWE(1Yg3, 1963a) upon calculating the
interfacial energy of a bicrystal system.
If the height h in (25) is substituted by the thickness of the inonolayer and the edge
lenght I, is expressed through the Kelvin-Gibbs equation the result will be identical
to equation (14) of the present paper as well as to the result obtained by TOSCHEV
et al. Obviously, the condition h = 0 used by BAUERleads t o elimination of the
volume term in the expression for the Gibbs free energy change. I n t,his respect his
result may be considered as a first approximation.
Finally, i t is interesting to point out that the criteria (23) and (24) may be written
in terms of the works of separation as this is done by KLEBERand by TOSCHEV,
YAUNOVand KAISCHEW. Then, (23) and ( 2 4 ) will have the following form:
Y’ < Y - ACLP (23a)
Y’ > Y - 4 1 2 (244
where y and y’ are the worksof separation of two atoms of the deposit and of a deposit
atom from the substrate, respectively.
On one hand, the above form of presentation has the advantage to be more suitable
for numerical calculations. On the other hand, the comparison of the experimental
data would be easier with the criteria (23) and (24), bearing however in mind all the
uncertainties connected with the values of the surface energies of the metals measured
experimentally. Obviously, the choice of the form of the criterion depends on the
particular aim of the given investigation.
Influence of the Supersaturation on the Mode of Thin Film Growth 691

3. Stranski-Krastanov mechanism
We shall now consider in more details the condition for two-dimensional nucleation -
inequality (24) - which is strictly valid for the first monolayer of the deposit. Ac-
cording to BAUER after several monolayers deposited three-dimensional nuclei can be
formed on top of them if Aa < 0. This means that a change of the inequality sign
is t o be expected after some film thickness. However, the formation of each new
monolayer leads to rearrangement of the previously formed ones because of the
tendency of the system towards a state with a minimum free energy (VAN DER MERWE
1949). Besides, the elastic strains become negligible after some film thickness (VAN DER
MERWE1963, 1963a). Hence, during the film growth each new monolayer would
change the conditions for the formation of the next one in such a way that u, -+0 and
at --f 0. Then, after some thickness the film growth would proceed by formation and
spreading of two-dimensional nuclei.
It is noteworthy that the same conclusion is drawn by STRANSKI and KRASTANOV
themselves. They have found that the growth of a monovalent ionic crystal K-A’
on the surface of an isomorphic divalent substrate K**A’occurs initially by formation
of a monolayer. After that the formation of two-dimensional two ions high nuclei
on the first monolayer is found to be more probable than of three-dimensional ones.
After three monolayers deposited in such a way the energetic influence of the sub-
strate becomes negligible, i.e. adis practically zero. It is clear that the two-dimensional
two layers thick nuclei can not be considered as three-dimensional ones although their
height might be comparable with the other dimensions. As two-dimensional nuclei
they grow laterally with no energetic threshold in contrast to the three-dimensional ones.
It may be concluded that the layer growth can take place by formation of mono-
layer or polylayer two-dimensional nuclei. Moreover, depending on the experimental
conditions and on the material properties of the system under investigation the layer
growth process may be either mononuclear one (layer-by-layer growth) (KAISCHEW
1957) or polynuclear one (HILLIG). I n any case it is a layer growth connected with a n
energetic barrier for formation of two-dimensional nuclei.
As is seen the term ,,STRAKSKI-KRASTANOV mechanism” is not suitable for des-
cription of the process involving formation of three-dimensional nuclei on top of one
or several monolayers deposited on the substrate through layer growth mode. However,
since it has already been widely accepted in the literature (BA‘CTER, POPPA; VENABLES,
PRICE) it will be also used here in the above sense.
As was mentioned above STRANSRI and KRASTANOV have considered a substrate-
deposit system with no misfit. Besides, the deposit is assumed to be thermodynamically
stable under the experimental conditions. If this is not the case a formation of three-
dimensional nuclei onto the layers of the deposit may be expected.
We shall discuss first the case of thermodynamically stable overgrowth. If the
lattice spacing of the deposit a is sufficiently smaller than that of the substrate b,
i.e. in the case of negative misfit, the first layer is stretched out t o fit the substrate.
Then, the surface energy of the new substrate is smaller than of the bulk deposit.
Taking also into account the interfacial surface energy due t o the misfit it becomes
clear that a positive surface energy change will accompany the next step of the
deposition process. If now the supersaturation is lower than the critical one three-
dimensional nuclei can be formed on top of the first layers. The deposition of Ag on
(100)-Mo ( ( u - b ) / b = - 8.25%) (HAKTIG)and of Cu on (111)-Au ((a- b ) / b =
= - 11.5%) (VOOK, HORNG, MACKJR) may be considered as an example of the above kind.
If the misfit is positive and sufficiently large the atoms of the deposit occupy every
second trough of the substrate. The distance between the troughs taking part in
the process become twice larger and the real misfit gets a negative value. Then, this
692 I.MARKOV,R. KAISCHEW

case may be considered as the previous one. For instance, this is the case of deposition
of K on (100)-W (MAYER).The misfit calculated using the bulk lattice spacings is
+65%. However, taking into account the larger radius of the potassium atoms the
real misfit is -17.5% and three-dimensional nuclei have been observed to grow
on top of a potassium-tungsten transition layer. It is interesting to point out that the
same conclusion is drawn by HALICIOGLU on the base of a numerical analysis of the
structure of the overgrowth as a function of the misfit and the substratedeposit inter-
action energy ratio.
The case of thermodynamically unstable overgrowth may be considered as follows.
If the surface energy of the bulk stable deposit is larger than the one of the strained
unstable one serving as a substrate and formed through layer growth three-dimen-
sional nuclei can be formed. Otherwise, if the unstable phase has a more close packed
lattice than the stable one three-dimensional nuclei may be observed as in the case of
formation of or-Fe nuclei (b.c.c.) on top of strained y-Fe film (f.c.c.) 20 k thick (JESSER,
MATTREWS 1967; GRADMANN 1975; GRADXAKNet al.). Conversely, if the stable
phase is the more close packed one layer growth would proceed. In such a case the tran-
sition of the unstable to the stable one occurs by rearrangement of the crystal planes.
For instance, such a case is established upon deposition of p-Co (f.c.c.) on (100)-Cu
(JESSER, MATTHEWS 1968a) where the unstable-stable phase transformation (P-Co to
or-&) is due to the misfit dislocations and the associated stacking faults.
I n conclusion, it may be thought that the STRANSKI-KRASTANOV mechanism is
consisted in two alternating stages: the first one determined by the condition (24) and
the second one connected with (23). Moreover, the realization of this growth mode
depends on some particular properties of the system under study such as the sign and
the value of misfit, the thermodynamic stability of the overgrowth as well as the
structures of the two phases.

4. Comparison with experimental data


Experimental observations of the crystallization mode transitions itre presented in
Table 1. It is seen that an island growth (IG) is observed at higher substrate tem-
peratures or at lower evaporation rates. At lower substrate temperatures or at higher
incidence rates, i.e. at higher supersaturations, respectively, a layer growth (LG) is
established. It is clearly seen that the data are in very good qualitative agreement
with the predictions of the classical nucleation theory.
For the sake of quantitative comparison the following must be taken into account :
1. The experimental data for the surface energies of the metals and their tem-
perature dependence are not reliable.
2. There are no experimental data for the surface energies of crystal faces with
different crystallographic orientations.
3. The calculation of the supersaturation in high vacuum systems under dynamic
conditions is uncertain because of the lack of data for the accomodation coefficient,
film temperature etc.
4. The foreign atoms adsorbed on both the substrate and the deposit may change
the surface energies and the shape of the nuclei.
On the other hand, an exact theory has to take into account: (i) the formation of
the nuclei on growth steps of the substrate surface or on other active, energetically
preferred sites, (ii) the kinked structure of the surfaces and the edges of both three-
dimensional and two-dimensional nuclei, respectively, (iii) the dependence of the
surface interfacial energy on the size and thickness of the nuclei or on the super-
saturation, respectively, (iv) that the influence of the substrate force field is not
restricted within one monolayer of the overgrowth.
Influence of tho Supersaturation on the Mode of Thin Film Growth 693

I n such a case the quantitative experimental verification of the criteria (23) and
(24) as well as the evaluation of the surface interfacial energies using equations (14)
and (22) have t o be considered as illustrative only.
First, a n attempt will be made for the temperature dependence of the surface
energies of the metals under study to be accounted for. The most of the available
values have been measured a t temperatures near to the melting points. For instance,
the value 1140 erg/cma is obtained for polycrystalline Ag in He-atmosphere a t 900 "C
(FUNK, UDIN, WULFF). The data obtained at room or near room temperature are
much higher than the quoted above. So DE PLANTA, GHEZ,PIUZhave estimated the
value 5960 erg/cm2 at 80 "C as a result of measurements of the lattice parameter
change of small Ag particles. As a result of experimental study of the equilibrium of
the reaction AgJ + 1/2 H, = H J +
Ag BORELhas found the value 5500 erg/cma at
25 "C. Theoretical calculations of FRICKE have resulted the values 1920 erg/cma and
1650erg/cma for (100) and (111) faces, respectively, at 25 "C. In the case of poly-
crystalline Cu the values obtained are 1370 erg/cm2 at 1050 "C (UDIN, SHALER,
WULFF)and 1670 erg/cm2 a t 1050 "C (UDIN,1952). For Fe and Co the values 2150 erg/
om2 (PRICE,HOLL, GREENOUCH) and 1880 erg/cm2 (UDIN, SHALER, WULFF), re-
spectively, are found a t temperatures near the melting points. It seems from subli-
mation energy data that the value of Co would be higher with about 20%. Measure-
ments at room temperature are carried out for Au and the value 1837 erg/cma is
obtained (BETTNER, UDIN, WULF)in contrast to the high temperature value 1018 erg/
cma (1120 "C) (SMITH).Theoretical calculations of HACL performed for (111) face
of Au give a higher value 2150erg/cma at room temperature in comparison with
1868 erg/cm2 a t the melting point.
Summarizing it may be drawn the conclusion that the values of the surface energies
at the temperatures used in the vapour deposition experiments are higher than the
measured ones near the melting points with a factor varying in average from 1.5 to 2.
This means that if we assume the same temperature dependence for the surface inter-
facial energy the supersaturation term in (23) and (24) has t o be divided by this
factor or that the critical supersaturation must be effectively lower if we use the high
temperature values for u.
On the other hand, calculating the supersaturation we must take into account
that the temperature of the film is usually higher than the substrate one. As is shown
by BELOUS and WAYMAN the temperatures of Au and Ag films deposited on Au-Ni
thin film thermocouples on a mica substrate are higher than the substrate temperature.
This effect is attributed to the exothermic heat of condensation and radiation heating
from the evaporation source. The higher the substrate temperature and the eva-
poration rate the higher the film temperature. Differences of about 400 "C and 500 "C
are measured at evaporation rates 10 Alsec and lOQ A/sec, respectively. It could be
expected that in the case of deposition of metal vapours onto thin metal film substrates
with a rate of about 1&sec and a t room temperature the film one will be higher with
a t least 100-200 "C. Finally, bearing also in mind a possible incomplete thermal
accomodation of the vapour atoms (SEARS,CAHN)it may be concluded that the
actual supersaturation would be lower than the calculated one using the experimental
values for the substrate temperature and for the evaporation rate. Rough estimations
show that the real supersaturation will be lower than the apparent one by a factor
between 0.5 and 0.7.
Taking all that into account we will compare the experimental data with the
equations :
dpcr = 2b2w(u,, +
ut - 0,) (14a)
dpcr = fi b z ~ ( u m+ ut - 0,) ma)
Table 1
_ _ _ ~ _ _ _ _ __-__
substrate evaporation growth
deposit substrate temperature rate mode reference
________- - ( “C) -(&sec) -_
400 -1 IG JESSER, (1967)
MATTHEWS
20 -1 LG JESSEB, (1968) b
MATTHEWS
100 0.01 IG GRADMANN (1976, 1976)
100 0.30 LG GRADMANN (1975, 1976)
200 0.30 IG GRADMANN (1975, 1976)
p-co (001)-cu 350 -1 IG JESSER,
MATTHEWS(1968) a
20 -1 LG JESSER,
MATTHEWS(1968) a
Cu (111)-Ag 210 -0.10 IG VOOH (1974)
HORNG,
25 -0.10 LG VOOH (1974)
HORNO,
able 2
_._ - ~ _ _ _
Apcr x 1OI2 U Oi
bstrate “8
erg/cm2 erg/cm2 erg/cm2
erg theor.
-____ ____ ____ __
01)-cu 3.02 5.10 4.06 1670 2150 1030 550 600 48
11)-cu 4.09 I 4.63 4.36 1670 2150 1280 800 600 48
11)-cu 4.45 4.63 4.54 1670 2150 1330 850 600 48
01)-cu 4.56 3.55 1670 1880 910 700 -
1l)-Ag i:: 1 3.88 3.38 1140 1670 780 250 160 ii
325
Influence of tho Supersaturation on the Mode of Thin Film Growth 695

instead of equations (14) and (22) where w is a dimensionless coefficient its value
varying from 2 to 4. An average value of 3 will be accepted here bearing in mind all
the uncertainties mentioned above.
The results of the calculations are collected in Table 2. ApI and ApL are the super-
saturations at which island growth or layer growth are observed respectively. They
are calculated with the help of vapour pressure data given by NESMEYANOV. For a,,,
and a, one and the same value for the polycrystalline metal is taken which is an
additional source of error of order of about +lo0 erg/cm2. The quantity Ac = Apcr/
6khklb2is presented in column 8, Apcr being taken as the average value between ApI
and A p L . I n column 9 the values of at calculated with the help of equations (14a)
and (22a) are presented. They are compared with the ones calculated theoretically
(JESSER, MATTHEWS 1968b ; GRADMANN 1964) or given elsewhere (TAYLOR),the latter
being presented in column 10. The absolute values of the difference Ju,- uJare
given for comparison in column 11. The substrate-deposit misfit is given in column 12.
As is seen the so-calculated values of at are larger than the difference IcS- el in
the cases of y-Fe/Cu and p-Co/Cu. This means that a growth mode transition must be
observed in the opposite case of deposition of Cu on y-Fe and P-Co if this is possible
to be experimentally carried out. I n the case of Cu/Ag system the value of ci thus
found is smaller than (a, - a1 = 530erg/cni2. This leads to the conclusion that Ag
must grow on Cu through the layer mechanism only irrespective of the value of the
supersaturation. Actually, a growth mode transition is not observed for this system
(GRADMANN 1964; HORNG,VOOK)a t temperatures up to 520 "C although an evidence
for island growth also exists (VOOE,HORNG, MACUR).
Hence, the occurrence of growth mode transition may serve for rough evaluation
of ui if we accept that it occupies practically one and the same value regardless of the
order of deposition. If a growth mode transition is established in both cases of depo-
>
sition of A on B and of B on A, that, at(AB) IoA - OBI. I n the opposite case o,(AB) <
< l a A - aBl. Besides, in the first case et and w may be calculated within the accuracy
of aAand OB through measurements of the two critical supersaturations. If Apcr(AB)
and Aper(BA)are the critical supersaturations the growth mode transitions of A on
B and of B on A are observed at respectively, a mean value for w and a,(AB) = ui(BA)
may be calculated using the formulae:
w = [nll(cr(AB)/2hkibi- Apcr(BA)/2kaklb~]/2(U~
- GB) (28)

Finally, it would be emphasized that the good agreement between the values of
ci calculated theoretically and the ones extracted from the experimental data can not
be considered as an argument for the quantitative validity of the theory. This question
will be inspected in more details in the conclusion.

5. Conclusion
It is worth not,ing some points. First, it seems more reasonable the rates of formation
of both three-dimensional and two-dmensional nuclei to be compared rather than
the Gibbs free energies. However, calculations based on the classical nucleation theory
have shown that such a n approach gives rise to a negligible correction.
On the other hand, it is well known that the applicability of the classical nucleation
theory is restricted within the range of sufficiently low supersaturations. Calculations
for the number of atoms in the critical nucleus made for the particular cases quoted
above have given values between 4 and 10 if the correction coefficient w has not been
taken into account. I n the case of w being accounted for values larger than 80 have
696 I. MARKOV,R. KAISCHEW

been obtained. It is reasonable to think that the classical nucleation theory is valid
in the cascs of strong substrate-deposit interaction bonding (metals onto metals)
where lower transition supersaturations are t o be theoretically expected. Obviously,
in the case of weak substrate-deposit interaction (metals on insulators) a n atomistic
concept has to be developed for the aim of quantitative explanation of the growth
mode transition. For instance, this is the case of deposition of Ag onto vacuum cleaved
MgO where layer growth is established at -200 "C (LORD,PI~UTTON). On the other
hand, theoretical study of the interrelation between the classical and the atomistic
theories of nucleation (MILCHEV,STOYANOV, KAISCHEW) show that they both may be
considered as limit cases of a more general theory of nucleation valid for low and
high supersaturations, respectively. Taking into account that the classical theory is
in good qualitative agreement with the experimental data at higher supersaturations
(BONISSEKT, MUTAFTSCHIEV)it would be expected that the results which could be
obtained on the base of a n atomistic consideration will be very similar t o t h e ones
presented in this paper although in other terms.
Finally, we may conclude that despite of all approximations and uncertainties
mentioned above the classical nucleation theory could be accepted as a fairly good
guide for prediction of the mechanism of growth of thin films.
The authors are much indebted to Professor U. GRADMANN from the University of
Marburg for sending his experimental results prior to publication and for the helpful
discussions. The kind co-operation of Dr. C. T. Horng from the Syracuse University,
New York, who has sent the exact deposition parameters concerning the systems Cu/Ag
and Ag/Cu is also acknowledged.

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(Received November 19, 1975)


Authors' address :
Dr. I. MARKOV, Prof. Dr. R. KAISCHEW
Institute of Physical Chemistry
Bulgarian Academy of Sciences
1000 Sofia
Bulgaria

46 Kristall/Technik, Bd. 11, FI. 7