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I.MARKOV,R. KAISCHEW

Institutc of Physical Chemistry, Bulgarian +4cademyof Sciences, Sofia

on the Mode of Thin Film Growth

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

-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

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

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

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.

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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Authors' address :

Dr. I. MARKOV, Prof. Dr. R. KAISCHEW

Institute of Physical Chemistry

Bulgarian Academy of Sciences

1000 Sofia

Bulgaria

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