3 Mechanical properties of thin films 3.

1 Mechanical properties of PVD films

R F Bunshah, Engineering Materials DepartmenL University of California, Los Angeles. CA 90024. U.S.A.

The mechanical properties of thin films are influenced by their structure,s, stability, internal stresses and thickness which makes the understand/ng of the mechanical behavior a complex problem. Thick films of metals and alloys seem to follow the same, well-established trends in structure and properties as bulk materials produced by more conventional wrought techniques. The state of understanding of the mechanical behavior of thick films of refractory compounds is st///in its infancy and much work remains to be done for this very important class of materials.

Introduction This paper reviews the current status of the mechanical properties of films produced by the Physical Vapor Deposition (PVD) processes of evaporation, ion plating and sputtering. The thickheSS of these films ranges from 100 ,~ to millimeters and they are used in a variety o f decorative and utilitarian applications not only as coatings but as self supported shapes, i.e., sheet, foil, tubing. Although ~ o r k in this area dates back many decades, the bulk of the papers in this field have been published only in the last 20 years. PVD technology is very versatile. It enables one to deposit films of virtually every type o f inorganic materials--metals, alloys, compounds and mixtures thereof--as well as some of organic materials. The deposition rates can be varied from 10 to 250,000 .~ rain-1 and even higher. The high deposition rates have come about in the last 15 years with the advent of electron beam heated evaporation sources. Much o f the early work (up to 1963) was carried out at low deposition rates and dealt mostly with thin films.* The work has been admirably summarized in various well-known treatises. 1-6 Review articles on mechanical properties of thin films have been written, ?-12 The work on thick films and bulk deposits has matured later and reviews on it have been given by Bunshah 13-t 6 and by Paten, Movchan and Demchishin 1~ who summarized the work done at the Paten Welding Institute up to 1973. In addition the Soviet literature has numerous references to the very extensive work on thin and thick films by Palatnik and co-workers of the K h a r k o v Polytechnic Institute although this author cannot cite a review paper from this source. The mechanical behavior of thin films is quite different from that of the bulk and is very much governed by the microstructure, impurity and imperfection content which in turn governs the residual stress in the film. In fact some of the incentive in the past for the extensive studies on thin films are the very high strengths as compared to cold worked bulk material and the implied promise for the development of high strength materials. This high strength was attributed in most cases to the high levels of imperfections and of residual stress; numerous mech-

anisms are cited in the literature for the residual stress. These deductions are often speculative because the mechanical properties of thin films are generally determined on films condensed on substrates held at low temperatures whereas the structure is studied on films condensed at high temperatures. 9 As the film gets thicker, the residual stress level decreases and the mechanical properties are very similar to those of thick films or bulk condensates. It should also be pointed out that most of the mechanical properties have been studied on films deposited by evaporation in high vacuum for the simple reason that ion plating or sputtering bring into play other process variables, such as the presence of a significant ion density in the vapor phase, electrically biased substrates, etc., which affect the structure, impurity content and residual stress levels markedly and make the correlation between structure and mechanical properties more diffcult. As a precursor to the discussion on mechanical properties, it behooves us to understand the microstructure of deposited films. M i c r m t n c t u r e of PVD condemates PVD condensates deposit as single crystal films on certain crystal planes of single crystal substrates, i.e. by epitaxial growthlS; or in the more general case the deposits are polycrystalline. In the case of films deposited by evaporation techniques, the main variables are (1) the nature of the substrate (2) the temperature o f the substrate during deposition, (3) the rate of deposition and (4) the deposit thickness. Contrary to what might be intuitively expected, the deposit does not start out as a continuous film one monolayer thick and grow. Instead, three-dimensional nuclei are formed on favored sites on the substrates, e.g. cleavage, steps on a single crystal substrate, these nuclei grow laterally and in thickness (the so-called growth stage) ultimately impinging on each other to form a continuous film. Figure 1 shows the growth of gold film on rock-salt. The average thickness at which a continuous film forms depends on the deposition temperature and the deposition rate (both of which influence the surface mobility of the adatom) and varies from 10 A for Ni condensed at 15 K to 1000 A for Au condensed at 600 K. Once a continuous film has formed, the subsequent evolution to the final structure of the thin film is poorly understood at present. It undoubtedly depends on the factors mentioned above which in turn influence the primary variables of nucleation rate, growth rate, and 353

* The thickness limits for thin and thick films are somewhat arbitrary. Thin films represent thickness up to 10,000 ,IL and thick films from 10,000 ,~ and higher. Today, another viewpoint is that a film can be considered thin or thick depending on whether it exhibits surface-like properties or bulk-like properties. Vacuum/volume 27/number 4.

Pergamon Press/Printed in Great Britain

R F Bunshah: Mechanical properties of PVD films

surface mobility of the adatom. The problem has been tackled by Van der Drift '9 and is also the subject of a currently unpublished paper by Thornton. z The microstructure and morphology of thick single phase films have been extensively studied for a wide variety of metals, alloys and refractory compounds. The structural model was first proposed by Movchan and Demchishin, zl Figure 2 and was subsequently modified by Thornton z2 as shown in Figure 3. Movchan and Demchishin's diagram was arrived at from their studies on deposits of pure metals and did not include the transition zone of Thornton's model, Zone 7", which is not prominent in pure metal or single phase alloy deposits but becomes quite pronounced in deposits of refractory compounds or complex alloys produced by evaporation and in all types of deposits produced in the presence of a partial pressure of inert or reactive gas, as in sputtering or ion plating processes. The evolution of the structural morphology is as follows, as the writer sees it today: At low temperatures, the surface mobility of the adatoms is reduced, and the structure grows as tapered crystallites from a limited number of nuclei. It is not a full density structure but contains longitudinal porosity of the order of a few hundred

~ngstr6ms width between the tapered crystallites. It also contains a high dislocation density and has a high level of residual stress. Such a structure has also been called 'Botryoidal' and corresponds to zone 1 in Figures 2 and 3. As the substrate temperature increases, the surface mobility increases and the structural morphology first transforms to that of Zone 7", i.e. tightly packed fibrous grains with weak grain boundaries and then to a full density columnar morphology corresponding to Zone 2 (Figure 3). The size of the columnar grains increases as the condensation temperature increa.~. Finally, at still higher temperatures, the structure shows an equiaxed grain morphology, Zone 3. F o r pure metals and single phase alloys, TI is the transition temperature between Zone | and Zone 2 and 7"2 is the transition temperature between Zone 2 and Zone 3. According to Movchan and Demchishin's original model, 22 TI is 0.3 T,, for metals, and 0.22-0.26 7"= for oxides; whereas 7", is 0.45-0.4 7", for both as shown in Figure 4. (7". is the melting point in K.) T h o m t o n ' s modification shows that the transition temperatures may vary significantly from those stated above and in general shift to higher temperatures as the gas pressure in the synthesis process increases.

Figure 1. Sequence of micrographs illustrating the effect of increasing deposit thickness of gold on rocksalt. 8000.s 354

R F Bunshah: Mechanical properties of PVD films

Zone I

Zone 2

Zone 3
."

~~q:~..-.;;~;='.'.:'..- ....

..:..i':~".3 -. . . ~ ~ / / ~ ~ " ~ ; :''"" ' ; : : " "" "

.'..::.;.':o;-:-.

,..:..;-.:.-.: .- . . . . . j

%~,P," $ " .

~. "....

T, Ternperot'ure Metols OxiOes Zone I < 0 3 T;~ < 0 . 2 6 T~ Zone 2 0.3-045T,~ 026-045T~

T2 ,, Zone 3 >0.45T~ >045T'~

which can be operated in the electron microscope, aT'as Hoffman ~ has reviewed the test techniques and the reader could do no better than to read Hoffman's article or the original references. The basic handling problem encountered with the preparation and mechanical property testing of thin film specimens is much less severe with thick films for which many of the standard test specimens, machines and techniques can he readily used. Therefore, the spectrum of mechanical properties measured on thick films is much broader than with thin films.

Mechanical properties of thin films

T h e tensile properties o f t h i n films have been reviewed. 9, t o. 36, z~ As H o f f m a n t concludes, the data r e p o r t e d are n o t very consistent even on the same material. T h e reader is advised to consult the references f o r details. In general, the observed strength o f v a p o r - d e p o s i t e d metal films consists o f three parts:
O'OBS = O'Bulk Jr
O'lmperfcclions

Figure 2. Structural zones in condcnsates. =~

TRANSITIONSTRUCTURE CONSISTINGOF DENSELYPACKED FIBROUSGRAINS POROUSSTRUCTURE ~ ~ CONSISTINGOFTAPERED CRYSTALLITESSEPARATED ~"~ ' BY VOIDS COtUt/i~AR GRAINS

RECRYSTALLIZED GRAINSTRUCTURE

~ O-Thickne~s

~311 ~
~ ' ,I = " =.7.~ : ' . . : "~'.': "" 7 . % ~

~,.~=~:..:.,.-.=....':....~.,.~ -.~; :

~,:"%

~.~.~.

A':,f',[

ARGON PRESSURE (rnTorrl

L5 SUBSTRATE TEMPERATURE(T/TM)

D.6

Figure 3. Structural zones in condensates. 2~ It should be emphasized that : I. The transition from one zone to the next is not abrupt but smooth. Hence the transition temperatures should not he considered as absolute but as guidelines. 2. All zones are not found in all deposits. For example, Zone T is not prominent in pure metals but becomes more pronounced in complex alloys, compounds or in deposits produced at higher gas pressures. Zone 3 is not seen very often in materials with high melting points. Figure 4 shows scanning electron micrographs of Zones 1, T, and 2 in TiC deposits. Other examples may be seen in the illustrations in ref ~a-16 Most thick deposits exhibit a strong preferred orientation (fiber texture) at low deposition temperatures and tend towards a more random orientation with increasing deposition temperature. Figure 5 shows the evolution of a large grained columnar morphology in a Be deposit from a much larger number of fine grains which were originally nucleated on the substrate. As growth proceeds, only those grains with a preferred growth direction survive, presumably due to considerations of the minimization of surface energy. Mechanical property determination A number of testing techniques have been used to determine the strength properties of thin films. They include the high speed rotor test 23 the bulge test 2`-2a microtensile testing machines of the 'soft '29-32 and the 'hard' categories a3-36 and even fixtures

where aau~k is the inherent strength level of bulk polycrystailine material in the annealed state, al,,,,,f,c,~,, , is the contribution due to point and line defects resulting from the deposition process in excess of those normally found in the bulk annealed state and oth~=k,,,, is the contribution arising from the smallest dimension of the film and its limiting effect on grain size such that dislocation multiplication and migration are impeded. ~I Table I gives the strength properties of thin films of some metals and compares them to bulk values. 10 In many cases the strengths are about 200 times those of annealed bulk samples and 3 to 10 times those of hard drawn samples. The tensile strength values are given numerically as well as by fractions of the shear modulus. The ductility of the high strength films is very limited which is similar to the behavior of high strength fibers or whiskers. A principal point of contention is whether the ultimate tensile strength is a function of the film thickness or not. The discrepancy also appears to he dependent on the test method used, i.e. between the bulge test and tensile test. In many cases it appears that the strength decreases as the film thickness increases from approximately the 2(X)-300 A. range to about 2000--4000 A range. At the greater thickness the strength is about the same as that of heavily worked bulk material. There are several papers relating the strength properties of thin films to the 'crystallite size' and 'block structure' as influenced by the deposition temperature, stress, recovery and recrystallization process. '*-49 One manifestation of this is the phenomenon of creep or plasticity in room temperature tensile tests as exhibited by an irreversible initial loading curve but almost reversible unloading and reloading curves as long as the previous stress level is not exceeded. An example of this is shown in Figure 6 from Neugebauer 3 as the change in slope of the stress--strain curve. The possibility of this change in slope being related to an elastically soft measurement or to creep in the cement of the grips altogether be discarded. Long term creep rates have been measured and for gold they vary from 10 -7 to lO"-4 min -~ depending on load, dimensions and the amount of prestrain. 3 The estimates of the relative elastic and plastic extension at fracture vary from completely elastic to an almost even mixture of elastic and plastic deformation. Fracture in ductile gold single crystal filmsa6 results from a localized plastic deformation with resultant thinning of the film

355

R F Bunshah: Mechanical properties of PVD films

OlI~IIT ~ Iunli~lCl
y ~ ' ~,' -. ..~ . , -

FRACTURE

CROB S~CTION

DEPOSITION TEMPERATURE

MICRONARDNIF,B$ Ir~ I LOAD lOIN

~,.

.'

...:

{',;

'

,;'

52O

ZONE 1

3OOO

.11=o ZONE T

~4

i ! " '~,
~OO0 tk~o ZONE2

~; - - i

:'{l~ i

'

"

_!
Figure 4. Structure and microhardncss of TiC deposits at various substrate temperatures.T M and a rise in stress level. Eventually the smaller cracks formed in this manner join to cause fracture. The dislocations necessary for the deformation are not the grown-in dislocations but those which nucleate and multiply in discontinuous regions. Most observations show no necking prior to fracture. The maximum stress appears to correspond to that needed to propagate cracks from flaws existing in the specimen, in polycrystalline nickel, the fracture is the 'clean-cleavage' type. 3~ Medm~c=l ~ of tldck comle~ates and Imlk depz~ts
heat t r e a t m e n t .

ZONE 3

showing yield strength, ultimate tensile strength, hardness and ductility as a function of grain size, deposition temperature and test temperature. One of the features of the d a t a is that the properties of thick deposits of metals and alloys are very similar to those of wrought materials which are produced by the conventional processes of melting, casting, mechanical working and We will consider each type of material separately since the behavior of metals and alloys is vastly different from that of refractory compounds. The early work in this area was that of Bunshah, 53.s4 Bunshah and Juntz "*s and Smith ~6 who deposited thick films of Be, Ti and Cu respectively and measured mechanical properties. In 1965, Palatnik and co-workers published a paper

Table 2 lists the mechanical properties of thick deposits ofmetals, alloys, refractory compounds and laminated structures. In many cases, the mechanical test data are quite extensive 356

R F Bunshah: Mechanical properties of PVD films

Table !. Strength properties of thin films. ' Maximum tensile strength Shear
Material Au Structt=re Bulk hard-drawn (l I I) crystal film (100) crystal film (ll0) (l I I) polycrystalline lilm Polycrystalline film (100) crystal film Polycrystalline film Bulk hard-drawn Polycrystalline fihn Polycrystalline film Bulk hard-drawn Polycrystalline film Polycrystalline film Rolled foil Bulk cold-rolled Polycrystalline film Bulk cold-rolled Polycrystalline film kg/mm z 28? 81 27 49 55 26 32 371" 59 42 49 93 88 19 modulus* G/114 G/36 G/I l0 G/59 G/54 G/I 15 G/92 G/75 G/47 G/68

Strain at
fracture, ~/o ~. 1.2 0.5 I 0.7 3.5 2.3 0.7 0.3-0.4

Thicknessdependent Reference

No Yes No Yes No No -Yes --

36 25 30 24 32 32 -24 50

Ag

Cu

G/98
G/51 G/54 G/256 G/67 G/40 G/171 G/66

-1.8 -10-15 -1.8 -0.5-0.8

-Yes No No -Yes

-51 37 52 -3I -50

Ni AI

1251"
2 I0 16"t" 42

* Shear moduli from AlP Handbook, t957. 1" Bulk tensile strength from Handbook of Chemistry and Physics, 42nd ed., 1961. Fracture strain not quoted for hulk material.

on mechanical properties of AI condensates: ~ It is impossible to review in detail all the papers. The pertinent data are shown in Table 2 and the discussion below will concentrate on the highlights. Metals and alloys. Movchan and Dcmchishin studied the tensile properties and microhardness of Ni, Ti and W condensates produced at various deposition temperatures. No tensile tests were performed on specimens deposited in Zone ] (Figure 2). Tests on specimens deposited in Zone 2 showed high strength and low ductility at low deposition temperature. The strength decreased and the ductility increased with deposition temperature. The strength and ductility values of specimens deposited in Zone 3 showed approximately the same values as for rccrystallized specimens produced from wrought material, The microhardness variation with deposition temperature for Ni, Ti and W is shown in Figure 7. The tapered crystallite morphology in Zone I showed a high hardness much greater than that of annealed metal. The hardness decreased rapidly with increasing deposition temperature to a fairly constant value for Zone 3 morphology which corresponds to the hardness
o f recrystallized metals.
's=

Figure 5. Photomicrograph of a Be deposit showing the evolution of large columnar grains.

i !

~ I=J 2 0 Z ).. Q C~

Gold

W guo[ E E 72o -

~o
~E E
480 c~

9
*=l 1.0 n)..

~. 58o
420~20 Ti ~ 0 05 I 1.0 ,00 / ' 200 ~ 400 ' 600 800 I I000 ' )200 . 1400 )600

Bose t e m p e r o t u r e C PER CENT

STRAIN

Figure 6. Typical stress-strain curve for thin film. s

Figure 7. Variation of microhardness with deposition temperature for metals.2.

357

R F Bunshah: Mechanical properties of PVD films

Table 2. Mechanical properties of thick films or bulk condensates.

0.2 ~, Yield stress (kg/mm 2)

Ultimate
tensile strength 5/. Elong (or ~ RA) Microhardness

Deposition

Grain
size (tzm) Thickness (~m) 40

Test
temp (C) 25 Refer. ence 57

Material AI

(kg/mm')
200 160 80 8 Knoop at 0.5 g toad

temp (C) 200 300 4OO 250-350

1-2 1 0.7 0.1 0.07 4--10

25 25

67 63

Cu

15 28 40 45 18-22 35 240 170 50 2.38 16 0.27 (annealed 500C) 60 40 400-800 120 180

1000 > 15 3-20

25 25 25

17 68 69

0.1 0.6 1 0.1

0.5 3-5 5-20 20 1000

25 25 25 25

70 63 71 72

Ag

10 35 45 20 15 66-72 46 35 25 140 281 316 295 62 (bend test) 47 (bend test) 4 20 18 0.I 0.3 0.45 1.0 > 4 (bend test) >5.2 (bend test) 0.3 250 450 600 96.6 109 104 125 91 400-420 260 220 554 425 329 260 250 120 90 75 240(Knopp) 215 168 170 400 550 700 350---425 480--550 625-685 760--790

Fe

Be

75-100

25

72

100 0.2

1000 0.2-2 20

25 25 25

54 73 74

Ni

115 66-74

129 135 155 247 140(melted and wrought)

338 336 366 403 407 138

39(20) 32(20) 35(21) 21(21) 44(30) 0.6

26 19 12.7 3.7 18 620 420 380

275 375 375 375 357 2.6 I000

25

59

28 38 Ti 189 225 436 189 (melted and wrought) 295 302 471 302

20 12 25(66) 20(38) 3(25) 40f61 ) 560 200 130

250 400 600 400 800 800 600 450 200 400 500

25 25

27 21

1000 32 8 I 50 250 250 250 250 1000 100-250

25 25 25 25 25 25 25 200

17 58

21 75 76

280--420 141)-280
Mo

20 35 19 28 44 (5.3 (0.8) (1.0) 7.3 22 191 169 186 112 I 15 720 460 300 990 704 804 745 540 600 1000 1000 530 85 19 I0 0.7

14 24 38 19 37

300

Nb V
W

300 300 1000 1000 1000 25 25 25

76 76 21

358

R F Bunshah: Mechanical properties of PVD films

Table 2.--continued 0.2~ Yield

Material Ni-20Cr stress (kg/mm 2) 337 577 752 1195 393 (melted

Ultimate
tensile strength 540 780 871 1223 569 49 60 1068-1195 35--45 40-55 27-42 180 150 ~ Elong (or % RA) 26(27) 21(26) 18(19) 6(8) 37(31 ) 25(21) 53(41) 1-12 8-25 5-20 10-30 650 250 380 80 200 1000 500-800 450 350 400 1000 384 256 331 320 360 502 960-1960 700--2015 300 1907-2440 1800-2400 3500--4000 2710 2955 2955 4110 4160 2400 2500-2800 2700-3030 2350 2300 LAMINATES Microhardness (kg/mm z) 80 112 131 180 78

Deposition
temp

Grain
size (o,m) 13 2.6 1.8 0.5 10.4 13 1.8 Thickness (/,m) 375 375 375 375 325 375 375 79 375 375 375

Test
temp CC) 25 25 25 25 25 1000 1000 25 1000 1000 1000 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 Reference 60

("C)
950 780 680 427

and wrought)
25 40.9 970-1195 950 680 4(X)--800 400-800 4130-800 200 400 400 600 1000 1400 I 100 400 600. 11300 1400 120 210 304 416 538 721 750 1100 500 500 520 730 830 1080 1120 550 550 550 550 2.6 50 50 50 50 50 5 50-75 50-75 50-75 50-75

Ti-6AI--4V 80Ni-20Cu 50Ni-50Cu 20Ni-80Cu 80Ni-16Fe (permalloy) A1203

65 17

74 21

ZrO2

Y203

248 226 215 208 205 198

3.2 5 8 14 21 58

300 300 300 300 300 300 300 300 300 100 100 100 100 100 100

81 21

78

Ti~O Tie SiO2 Ta:C TaC SiC (rf sputter) TiC (ARE process)

82 83 84 85 79

10

ZrC
(Hf-3Zr)C VC NbC

80 92 95

C u - N i laminate C u - F e laminate Cu-Ni laminate C u - F e laminate N i - F e laminate Ni-SiO

35-70

Ti-TiC

35-55 110 80 125 150 150 105 95 80 251

13 4(30-800 1.8 0.88 0.45 300 300 300 200 1.8 500 240-360 300 150 150

2 15-25 0.1 0.04 0.04 20 20 20 20 250

25 25 25 25 25 25 200 400 600

86 87 88

89

90

359

R F 8unshah: Mechanical properties of PVD films

Bunshah and co-workers studied the effect of deposition temperature on the grain size, tensile properties and hardness of Ti,SS. ss Ni,Se Nb, V, Mo 76 and Ni-20 Cr 6 alloys for deposits made in Zones 2 and 3. They found that increasing deposition temperature produced larger grain size, low strength, higher ductility, and low hardness. Even at the lowest deposition temperature in Zone 2, the ductility was good ( > 2 0 % RA for I t,m grain diameter Ti at a yield strength of 56,000 psi). Moreover, they found that both the yield strength and hardness varied as the inverse square root of grain diameter, i.e. followed the HalI-Petch relationship,6t, 6, which is

a.

ao +

k d - t/2

where ,7,, is the yield strength; d is the grain diameter and; So, k are constants. Figure 8 shows an example of this relationship for Ni-20 Cr alloy.
Groin d i o m e t e r , /~m 5 2 I I I 1

properties of dispersion-strengthened alloys. For Ni-NbC alloys, the yield strength increases with volume fraction of the dispersed phase and decreases with an increase of deposition temperature which in turn increases the particle size and interparticle spacing. They also studied the steady-state creep rate of NI-ZrO2 dispersion strengthened alloys which is very low at a very high temperature. The same authors t7 also showed that it is possible to produce thick deposits of all the alloys across the C u - N i system and that the mechanical properties vary systematically with composition as would be expected. Movchan, Demchishin and Kooluck ~6 studied Fe, F e - N b C , and F e - N i - N b C alloys. Their results indicate that NbC increases the strength of Fe at 25 and 700C. Alloying the Fe matrix with Ni produces additional strengthening at both temperatures thus showing the possibility of combining solid solution strengthening and dispersion strengthening.

2OO

tO I

O5 l

Refractory compo~KIs

160 v ~..-120 --

~_ 8o
o_
>.

40 ~f

~'~:~
j

o Deposited
o Wilcox eta/. Webster

,b

2o
Grolfl d i a m e t e r

30
"1/2 ,

~
ram-I/2

~o

Deposits of refractory compounds, oxides, nitrides and carbides are very important for wear resistant applications in industry. Their structure and properties are strongly dependent on the deposition process. Their behavior is very different from metals and alloys. It is also very hard to measure the mechanical properties of ceramics by tensile tests similar to those used for metals and alloys because of their brittle nature. A very good test to measure the fracture stress of such brittle coatings is the Hertzian fracture test which measures the fracture stress and the surface energy at the fracture surface. 7~ Colen and Bunshah 7s used to measure the fracture behavior of YzO~ deposits of various grain sizes. Figure 9 shows the variation in microhardness with deposition temperature for AIzO3 and ZrO2 from the work of
uE 12OO

Figme g. Variation of yield strength with grain-size for Ni-20 Cr."" For all these metals and alloys the yield strength, ductility and hardness values correspond to those of the same materials produced by casting, mechanical working and recrystallization. The variation of yield-strength and hardness with grain-size, i.e. HalI-Petch type relationships were also very similar between the deposited and wrought materials, small variations being ascribable to differences in grain morphology and preferred orientations. The Ni-20 Cr alloy showed good strength at 1000C and also obeyed the Hall-Perch relationship. The HalI-Petch relationship is also obeyed by thick films of Cu and Ag to grain-sizes as small as 0.05 t~m as shown by Nenioto, Jumbou and Suto. 63 Thus, these thick deposits behave as true engineering materials. Chambers and Bower 6'~ studied the mechanical properties of 18-8 stainless steel, gold and magnesium and showed that their tensile properties were very similar to their wrought counterparts. Smith, Kennedy and Boericke 6s studied the (r, -i /9) type Ti-6AI-4V alloy. They showed that the tensile properties are very similar to the wrought material except for a much smaller value in per cent elongation due to premature onset of plastic instability in a tensile test at pinholes in the deposited samples. The bend ductility was however superior to the wrought material. Paton, Movchan and Demchishin ~7 studied the mechanical
360

E
tO00 --

o'
r~4 8 0 0 0 ~' 6 0 0

o
_~ :E

400
200

AL~O~
400 600 800 I000
t200

200

1400

t60C

Substrote temper0ture,

Figure 9. Variation of microhardness with deposition temperature for AI203 and ZrO~. 2' Movchan and Demchishin, z' shuwing that the behavior of these oxide deposits is quite different in one respect from that of metals (Figure 8). The hardness falls when the structure changes from tapered crystallites (Zone I) to columnar grains (Zone 2) as with metals. However, unlike metals the hardness increases markedly as the deposition temperature rises from 0.3 T,, to 0.5 7",. The authors attribute this to a more 'perfeet' material produce at the higher deposition temperatures due to 'volume processes of sintering'. A similar hardness curve was obtained for Y20~ deposits. TM

R F Bunshah: Mechanical properties of PVD films

Figure 10 from the work of Raghuram and Bunshah 79 also shows a very marked increase in microhardness of TiC deposits on going from 0.15 7", (500 C) to 0.3 7", (1000' C). The hardness increases for the oxides and TiC with increasing deposition temperature. Both these sets of results may be explained by the following concept. Since the strength of ceramics is very
GO00

capacity owing to the relaxation processes associated with large angle grain boundaries. Below 180 K, the damping is equal for single crystal and polycrystalline films? ~

Summary and conclusions

Physical Vapor Deposition (PVD) te~:hniques are a powerful way to produce thin films, thick films and bulk deposits of a variety of materials. The mechanical properties of thin films are influenced by their structure, stability, internal stresses and thickness which makes the understanding of the mechanical behavior a complex problem. Thick films of metals and alloys seem to follow the same, well established trends in structure and properties as bulk materials produced by more conventional wrought techniques. The state of understanding of the mechanical behavior of thick films of refractory compounds is still in its infancy and much work remains to be done for this very important class of materials.

o KHN

......... LoOO

"E E

509 5000

' ..y..' ........"""I T

C. 40oo
E

o
.u :~ 300O -

Acknowledgements
2000 0 ] 500 Substrete : JO00 'temperoture, C tSO0

The support of the National Science Foundation under Grant DMR 75-13347 is gratefully acknowledged.

Figure 10. Variation o f microhardne~s with deposition temperature for TiC. ~

References
' L Holland, Vacuum Deposition of Thin Films, Chapman & Hall, London (1956). L Maissl and R H Clang (editors), Handbook of Thin Film Technology, McGraw-Hill, New York 0970). 3 C A Neugebauer, J B Newkirk and D A Vermilyea (editors), Structure and Properties of Thin Films, Wiley, New York (1959). 4 R W Hoffman and H G F Wilsdorf (editors), Thin Films, American Society for Metals (1964). s R Niedemeyer and H Mayer (editors), Basic Problems in Thin Film Physics, Vandenhceck and Ruppercht, Gottengen (1966). 6 Physics of Thin Films, Academic Press, New York 0963) (onwards--in multiple volumes). J A Allen, Re~' Pure Appl Chem, 4, 1954, 133. 8 G A Bassctt and D W Pashley, J lnst Metals, 87, 1958, 449. '~ R W Hoffman, Thin Films, p 99, American Society for Metals (1964). Jo R W Hoffman, Physics of Thin Fihns, 3, 1966, 246, Academic Press, New York. , i W Buckel, J Vac Sci Technol, 6, 1969, 696. ~2 K Kinosita, Thh~ Solid Films, 12, 1972, 17. ~3 R F Bunshah, Proc 4th lnt Canton Vacuum Metallurgy, p 17, Iron and Steel Inst Japan (1973). ~4 R F Bunshah, J Vac Sci Technol, 11, 1974, 633. as R F Bunshah, J Vac Sci Technol, 11, 1974, 814. 6 R F Bunshah, New Trends in Materials Processing, p 200, American Society for Metals (1976). ~ B E Paton, B A Movchan and A V Demchishin, Proc 4th lnt Con.[ on Vacuum Metallurgy, p 251, Iron and Steel lnst Japan (1973). ~s D W Pashley, Adv Phys, 5, 1956, 173. ~9 A Van der Drift, Phillips Res Rep, 22, 1967, 267. 2o j A Thornton, Ann her Mater Sci, 1977, to be published. 2~ B A Movchan and A V Demshishin, Fizika Metall, 28, 1969, 83. 22 j A Thornton, J Vac Sci Technol, 11, 1974, 666. 2~ j W Beams, J B Breazeale and W L Bart, Phys hey, 100, 1955, 1657. z,,j W Beams, Structure and Properties of Thin Films, p 183, Wiley, New York (1959). z5 A Catlin and W P Walker, JApplPhys, 31, 1960, 2135. 26 S Jovanovic and C S Smith, J Appl Phys, 32, 1961, 121. 2, p I Krukover and V A Buravikhin, Fizika Metall, 22, 1966, 144. ~s D G Brandon and Z Bauer, israelJ Technol, g, 1970, 247. ~9 D M Marsh, J Sci lnstrum, 38, 1961, 229. 50 C A Neugebauer, J Appl Phys, 31, 1960, 1096. 3a C D'Antonio, J Hirschorn and L Tarshis, Trans AIME, 227, 1964, 1346.
361

adversely effected by growth defects and at the higher deposition temperatures, the occurrence of these defects is markedly reduced, the hardness (or strength) increased very significantly. However, it should be noted that the absolute value of the hardness of the oxides is much lower than that of the carbides. Thus the possibility of a different explanation for the 'similar" behavior of these materials, i.e. the hardness increase with deposition temperature needs to be investigated. The hardness data on sputtered TiC and TiN coatings are quite similar to those produced by evaporation techniques?

Laminates Laminate composites are very attractive because of the uniform properties in the plane of the sheet. In comparison to mechanical methods of producing laminate composites, e.g. bonding of sheets, physical vapor deposition techniques are very suited to the production of such composites particularly if each lamellae is to be very thin (---4).1 ~m) in order to improve the strength and toughness of the composite. It also gives us the opportunity to have a high strength ceramic as one of the phases. Work to date has been very limited. In one investigation of the C u - N i laminates, no improvement in strength was found? 6 It is not an ideal system to investigate. In the F e - C u sT'hs and Ni-SiO s9 composites, the strength increased significantly. The Ni-SiO system was notable for the fact that the composite retained its high strength up to 700C, which is reminiscent of the dispersion strengthened SAP alloys. This appears to be a most fruitful field for future research.

Damping capacity
As a final note, it may be mentioned that fine-grained films of AI and Cu have been found to have a much higher damping

R F 8unshah: Mechanical properties of PVD films

3z j M Blakely, J AppiPhys, 35, 1964, 1756. 33 D Kuhlmann-Wilulorf and K S Rashavan, Rev Sci lnstrum, 33, 1962, 930. 3,t A Lawicy and S Schuster, Rev Sci lnstrum, 33, 1962, 1178. 35 E Orowan, ZPhys, 82, 1933, 235. 36 j W Menter and D W Pashley, in Structures and Properties of Thin Films, p 111, Wiley, New York (1959). 37 H G F Wilsdoff, Rev Sci lnstrum, 29, 1958, 323. 3. D W Pashley, Proc R Soc Lond, A225, 1960, 218. 39 C A Neugebauer, in Physics of Thin Films, Vol 2. (Edited by G Hass and E Thun), Academic Press, New York 0964). o L S Palamik, A I lll'inski, G V Federov and V S D'yachenko, lzvestra VUZ. Fizlka (Soviet Physics Journal), 1, 1966, 122. t R L Grunes, C D'Antonio and F K Kies, J Appl Phys, 36, 1965, 2735. z M Ya Fuks, V V lklozerov and Yu F Boyko, Fizika Metall, 33, 1972, 571. 3 K Kinosita, K Maki, K Nakamizo and K Takenchi, Japan J Appl Phys, 6, 1967, 42. "* M Ya Fuks, V V Belozero and Yu F Boyko, Fizika Metall, 33, 1972, 571. ,~5 F A Doljack and R W Hoffman, Thin Solid Films, 12, 1972, 71. 6 M Ya Fuks, L S Palatnik, V V Belozerov, Yu V Zolomitsky and S T Roshchenko, Fizika Metail, 36, 1973, 316. ,7 B Y Pines and N S Tan, Fizika Metall, 19, 1965, 899. " ' I T Aleksanyan, Fizika Metaii, 25, 1968, 947. 9 R W Hoffman, Thin Solid Films, 34, 1976, 185. so L S Palatnik, M Ya Fuks, B T Boiko and A T Pugacheu, Soviet Physics Dokl E~lish Translation, 8, 1964, 713. 5t A Odin8 and I T Aieksanyass, Soviet Phys Dokl, 8, 1964, 818. sz A Lawley and S Schuster, Trans AIME, 230, 1964, 27. s~ R F Btmshah, Proc A S M Golden Gate Conf, p 31, 1962. 5, R F Bunshah, Metals Eng Q, 6, 1964, 8. s5 R F Bunshah and R S Juntz, Trans Vac Met Conf, p 200, American Vacuum Society (1965). 56 H R Smith Jr, Proc ASM Golden Gate Conj', p 569. 1962. 57 L S Palatnik, G V Federov, A I Prokhavulov and A I Federenko, Fizika Metali, 20, 1965, 574. 5. R F Bunshah and R S Juntz, Met Trans, 4, 1973, 21. 59 N Kane and R F Bunshah, Proc 4th lat Conj" Vacuum Metallurgy, p 242, Iron and Steel Inst Japan 0973). 6o N Agarwal, N Kane and R F Bunshah, J Vac Sci Technol, 22, 1975, 619. 6 t E O Hall, Proc Phys Soc Lond, B64, 1951,747. 6z N J Petch, J lron Steel lnst, 174, 1951, 25. e3 M Nenioto, R Jumbou and H Suto, Trans Japan Inst Metals, 12, 1971, 113. 6, D L Chambers and W K Bower, J Vac Sci Technoi, 7, 1970, $62.

6s H R Smith, K Kennedy and F J Boericke, J Vac Sci Technol, 7, 1970, $48. 66 B A Movchan, A V Demichishin and L V Kooluck, J Vac Sci Technol, 11, 1974, 869. 67 H Yamamoto and G Kamoshita, Trans Japan lnst Metals, 12, 1971, 12. 6, L S Palatnik, M Ya Fuks, A 1 II'yinskiy and O G Alaverdova,

Fizika Metali, 22, 1966, 744.

69 C A O Henning, F W Boswell and J M Corbett, Acta Met, 23, 1975, 177. 70 K K Ziling, L D Pokrovskiy and V Yu Pohelkin, Fizika Metall, 29, 1970, 1112. 7t L S Palatnik, A I I'lyinskiy and A G Ravlik, Fizika Metall, 19, 1965, 310. 72 G Mah and C W Nordin, Proc 16th Annual ConfSoc of Vacuum Coaters, p 103, Chicago (1973). 73 C A O Henning, F W Boswell and J M Corbett, Acta Met, 23, 1975, 187. 74L S Palamik, A I II'yinskiy, A G Ravhk, A A Nechitayls and G Ye Lyakh, Flzika Metall, 27, 1969, 1114. 7s C D Turk and H L Marcus, Trans Met Soc AIME, 232, 1968, 2251. ~6 M A Sherman, R F Bunshah and H A lkale, 12, 1975, 697. 77 F C Frank and B R Lawn, Proc R SOc Lond, 299A, 1967, 291. 7s M Colen and R F Bunsheh, J Vac Sci Technol, 13, 1976, 536. ~9 A C Raghuram and R F Bunshah, J Vac Sci Technol, 9, 1972, 1389. 80 G Mah, C W Norden and J F Fuller, J Vac Sci Technol, 11, 1974, 371. 8, R F Bunshah and R J Schramm, iThin Solid Films, 41, 1977, in press. ,2 W Grossklaus and R F Bunshah, J Vac Sci Technol, 12, 1975, 593. s3 S Furuuchi, H Sakata and K Aiwaka, Japan J Appi Phys, 13, 1974, 1905. .4 W Grossklaus and R F Bunshah, J Vac Sci Technol, 12, 1975, 811. .5 K Wasa, T Nagai and S Hayakowa, Thin Solid Films, 31, 1976, 235. .s C A O Henning, F W Boswell and J M Corbett, Acta Met, 23, 1975, 193. ,7 L S Palatnik, A I l'lynskiy and N P Sapelkin, Soviet Phys Solid St, 8, 1967, 2016. .s I I Solonovich and V I Startsev, Problemy Prochn. 1, 1973, 28. s9 L S Palatnik, A I l'lyinskiy, N M Biletchanko and R I Sinel-nikova, Fizika Metall, 32, 1971, 199. 90 R F Bunshah, Y D Gupta and A C Rashuram, unpublished data. 9t V S Postnikov, I V Zolothukhin and V K Belonsov, Fizika Metall, 26, 1968, 957. 9z A C Rallhuram, R Nimmasadda, R F Bunshah and C N J Washer, Thin Solid Films, 20, 1974, 187. 93 R F'Bunshah and A C Raghuram, J Vac Sci Technol, 9, 1972, 1385.

362