Surface Technology, 14 (1981) 25 - 39

25

ADHE SION *

H. K. PULKER and A. J. PERRY

Balzers AG, FL-9496 Balzers (Liechtenstein)

R. BERGER lnstitut fi~r Experimental-Physik, University of Innsbruck, A-6020 Innsbruck (Austria) (Received February 17, 1981)

Summary A d h e s i o n is defined as the w o r k n e c e s s a r y to s e p a r a t e the c o a t i n g - s u b s t r a t e i n t e r f a c e ; most available m e t h o d s m e a s u r e the load required to strip off the coating. The m a n y q u a n t i t a t i v e and q u a l i t a t i v e m e t h o d s used are presented and the origins of adhesion are discussed. The p a r a m e t e r s influencing the adhesive s t r e n g t h are reviewed: s u b s t r a t e p r e p a r a t i o n , c o a t i n g technique, residual pressure in the v a c u u m c h a m b e r and s u b s t r a t e t e m p e r a t u r e are all found to be significant, and a g i n g effects w h i c h can raise or lower the a d h e s i o n can also be observed. M a n y variables affect the m e a s u r e d a d h e s i o n and m e a n t h a t only a partial analysis is possible in genera] at the present time. This leaves a wide field open for f u r t h e r studies.

1. I n t r o d u c t i o n

and definition

The problems of a d h e s i o n of c o a t i n g s with t h i c k n e s s e s between 0.05 and 50 um are discussed in this paper. In most a p p l i c a t i o n s these c o a t i n g s are not self-supporting but r a t h e r are applied to the surface of a solid body. This solid either can simply f u n c t i o n as a s u b s t r a t e or can have specific properties w h i c h are improved in some w a y by the a p p l i c a t i o n of the coating. I m p r o v e m e n t of the surface is thus defined as an i n t e n t i o n a l and e x a c t a l t e r a t i o n of the optical, electrical, chemical or m e c h a n i c a l properties of the solid surface.

* Invited paper given at a Seminar on Surfaces and Interfaces, Bern, Switzerland, December 3, 1980, which was organized by the Swiss National Science Foundation. 0376-4883/81/0000-0000/$02.50 ~ Elsevier Sequoia/Printed in The Netherlands

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In all these cases sufficiently good a d h e s i o n b e t w e e n the p a r t n e r s is of' p a r a m o u n t i m p o r t a n c e to the u s e f u l n e s s of such a system. These c o a t i n g s c a n be p r o d u c e d by v a r i o u s t e c h n o l o g i e s such as p h y s i c a l v a p o u r d e p o s i t i o n (PVD) in a v a c u u m or c h e m i c a l v a p o u r d e p o s i t i o n (CVD) from the g a s e o u s phase. The p r e p a r a t i o n and the p r o d u c t i o n t e c h n o l o g y c a n g r e a t l y influence the w a y i n ' w h i c h the m a t e r i a l s adhere. W h a t t h e n e x a c t l y is adhesion'? N e w e r physics, c h e m i s t r y and t e c h n i c a l d i c t i o n a r i e s define a d h e s i o n as " . . . the b o n d or the s t r e n g t h of the bond b e t w e e n two m a t e r i a l s or two bodies; also the bond of i n d i v i d u a l m o l e c u l e s to the i n t e r f a c e s u r f a c e s " [1 -:3]. The A S T M defines a d h e s i o n as the " C o n d i t i o n in which two s u r f a c e s are held t o g e t h e r by e i t h e r v a l e n c e forces or by m e c h a n i c a l a n c h o r i n g or by b o t h t o g e t h e r . " [4]. T h e s e b o n d i n g forces could be v a n der W a a l s ' forces, elect r o s t a t i c forces a n d / o r c h e m i c a l b o n d i n g forces which are effective across the interface. In this p a p e r the word a d h e s i o n will be used as a s y n o n y m for " t h e a d h e r e n c e " of a film to its s u b s t r a t e and, in its b r o a d e r sense, for the " a d h e s i v e s t r e n g t h " . A d h e s i o n is defined by the w o r k n e c e s s a r y to s e p a r a t e a t o m s or m o l e c u l e s at the interface. A d i s t i n c t i o n c a n be m a d e b e t w e e n the m a x i m u m possible a d h e s i o n (basic a d h e s i o n ) of a s y s t e m w h i c h r e p r e s e n t s the m a x i m u m a t t a i n a b l e v a l u e on the one h a n d a n d the e x p e r i m e n t a l l y m e a s u r e d a d h e s i o n [5, 6] on the other. T h e m a c r o s c o p i c e x p e r i m e n t a l l y m e a s u r e d a d h e s i o n v a l u e s are det e r m i n e d by the basic adhesion, the m e c h a n i c a l p r o p e r t i e s of the fihn and the f r a c t u r e m e c h a n i s m in the s e p a r a t i o n p r o c e s s [7, 8]. The r e l a t i o n b e t w e e n the e x p e r i m e n t a l l y m e a s u r e d a d h e s i o n EA and the basic a d h e s i o n BA is g i v e n by
EA = BA -

IS M S M

( 1)

w h e r e IS is the i n t e r n a l m e c h a n i c a l stress a n d M S M is the method-specific e r r o r of m e a s u r e m e n t . The basic a d h e s i o n c a n n o t u s u a l l y be d e t e r m i n e d b e c a u s e the size of the m e a s u r e m e n t e r r o r c a n seldom be estimated. T h e e x p e r i m e n t a l l y m e a s u r e d a d h e s i o n is given in u n i t s of force or e n e r g y per u n i t s u r f a c e area. A r e l a t i o n b e t w e e n the e n e r g y Waa of a d h e s i o n a n d the force of a d h e s i o n c a n only be d e r i v e d w h e n a r e a s o n a b l e a n d c o n c l u s i v e e s t i m a t e of the p a t h followed by the a d h e s i v e force F(x) o v e r the dividing d i s t a n c e x b e t w e e n the film a n d the s u b s t r a t e s u r f a c e c a n be m a d e [6]: e Wad =~ F(x) dx (2)
.y

The s t r e n g t h of the a d h e s i o n a c r o s s the i n t e r f a c e c a n be d i s t r i b u t e d v e r y u n e v e n l y b e c a u s e the s t r u c t u r e s of the s u b s t r a t e s u r f a c e and of the film are often h e t e r o g e n e o u s . C o n t a m i n a n t s c o v e r i n g v e r y small a r e a s and m o n o m o l e c u l a r c o n t a m i n a n t s on the s u b s t r a t e s u r f a c e c a n also c a u s e local c h a n g e s in the a d h e s i v e s t r e n g t h . T h u s the e x p e r i m e n t a l l y d e t e r m i n e d a d h e s i o n v a l u e s should be r e g a r d e d as a v e r a g e v a l u e s across the i n t e r f a c e surfaces investigated.

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2. M e t h o d s

of measurement

T h e i n d i v i d u a l m e t h o d s of m e a s u r e m e n t u s e d to d e t e r m i n e t h e d e g r e e of a d h e s i o n c a n be c l a s s i f i e d a n d s u b d i v i d e d a c c o r d i n g to v a r i o u s c r i t e r i a , e.g. m e c h a n i c a l a n d n o n - m e c h a n i c a l m e t h o d s . A n e x a m p l e of a s i m p l e q u a l i t a t i v e t e s t is s h o w n i n Fig. 1.

(a)

(d)

(b)

(e)

(c)

(f)

Fig. 1. Qualitative test to check film adhesion by bending. The scanning electron micrographs (a) - (f) were obtained at various magnifications. The specimen examined is an Ni-Fe substrate coated with a rhenium film 10 ~m thick which had been applied by ion plating. When the specimen is bent to a radius of 0.6 mm [9] the close-packed crystallite columns develop cracks as the substrate is stretched. The micrographs show that the film has not separated from the substrate. Therefore the adhesion is good, I n t h e p r a c t i c a l a p p l i c a t i o n of a m e a s u r i n g m e t h o d it is i m p o r t a n t to k n o w , a m o n g o t h e r t h i n g s , w h e t h e r t h e m e t h o d c a n be c a r r i e d o u t w i t h o u t

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d e s t r o y i n g t h e t e s t o b j e c t s a n d w h e t h e r it c a n p r o v i d e r e p r o d u c i b l e r e s u l t s a n d t h e size o f t h e m e t h o d - s p e c i f i c e r r o r o f m e a s u r e m e n t . T h e s i m p l i c i t y o f t h e m e a s u r e m e n t a p p a r a t u s a n d t h e t i m e n e c e s s a r y to m a k e t h e m e a s u r e m e n t s h o u l d a l s o be t a k e n i n t o a c c o u n t . A n o t h e r p r a c t i c a l c o n s i d e r a t i o n is t h e u s e o f a m e a s u r e m e n t m e t h o d t h a t s i m u l a t e s as c l o s e l y as p o s s i b l e t h e t y p e of s t r e s s to w h i c h t h e c o a t i n g / s u b s t r a t e s y s t e m w i l l be s u b j e c t e d in s e r v i c e . T a b l e s 1 a n d 2 l i s t a n u m b e r o f m e t h o d s o f m e a s u r i n g t h e a d h e s i o n o f t h i n films w h i c h h a v e a p p e a r e d in t h e literature. TABLE 1 Mechanical methods of determination

Qualitative
Scotch tape test [6, 10 - 14] Abrasion test [12, 15] Bend and stretch test [8, 16] Shearing stress test [16 - 18]

Quantitative
Direct pull-off method [8, 19 -33] Moment or topple test [3,1 37] Electromagnetic tensile test ]38] l~aser spalation test 139] Ultracentrifuge test [6, 16, 10- 4,11 Ultrasonic test ]6. 701 Peeling test [6. 45 - 48] Tangential shear test [49. 501 Scratch test [44, 46, 51 - 67]

TABLE 2 Non-mechanical methods of determination

Qualitative
X-ray diffraction test [65]

Quantitative
Thermal method [68, 69] Capacity test 16, 7l] Nucleation test [46]

2.1. Mechanical methods

I n m e c h a n i c a l m e t h o d s a d h e s i o n is m e a s u r e d b y a p p l y i n g a t b r c e to t h e coating/substrate system under examination. This force causes a mechanical s t r e s s a t t h e i n t e r f a c e w h i c h s h o u l d r e m o v e t h e film f r o m t h e s u b s t r a t e o n c e the stress has been increased to an appropriate level. The definitions given h e r e for " m e c h a n i c a l s t r e s s " a r e t h o s e c o m m o n l y u s e d in t h e field o f p h y s i c s and are thus different from those definitions which have become established in t h i n film l i t e r a t u r e . T h e s t r e s s c a n be e i t h e r t e n s i l e p e r p e n d i c u l a r to t h e i n t e r f a c e o r s h e a r i n g p a r a l l e l to t h e i n t e r f a c e . In p r a c t i c a l a p p l i c a t i o n s a c o m b i n a t i o n o f t h e s e t w o t y p e s of s t r e s s u s u a l l y o c c u r s . T h a t f o r c e o r e n e r g y a t w h i c h t h e s e p a r a t i o n o f film a n d s u b s t r a t e first t a k e s p l a c e is t a k e n as a n i n d e x o f t h e e x p e r i m e n t a l l y m e a s u r e d a d h e s i o n [6].

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In addition to the stress produced by e x t e r n a l forces, very strong i n t e r n a l stresses i n h e r e n t in the film (intrinsic stress) also affect the i n t e r f a c e and influence the e x p e r i m e n t a l adhesion m e a s u r e m e n t results in an u n d e t e r m i n e d way. In extreme cases very strong i n t e r n a l stresses alone can lead to d e t a c h m e n t of the film [72, 73] or to cohesive failures in the s u b s t r a t e [74]. In general, failure and thus s e p a r a t i o n can a p p e a r in any of five regions (Fig. 2) [75]. Region 1 is the inside of the film and region 5 is the bulk m a t e r i a l of the s u b s t r a t e which is sufficiently distant from th~ interface. If the s e p a r a t i o n occurs in one of these two regions then failure is cohesive. On an atomic scale, region 3 can be e i t h e r a very sharply defined i n t e r f a c e or a very diffuse i n t e r f a c e layer. In o r d e r to be able to m e a s u r e the adhesion, the s e p a r a t i o n must take place in this region [75, 76]. Even with a m a t e r i a l t r a n s i t i o n of the m o n o l a y e r - o n - m o n o l a y e r type, the changes in some physical c h a r a c t e r i s t i c s (e.g. elasticity and electrical i n t e r f a c e p h e n o m e n a ) t a k e place c o n t i n u o u s l y . When there is an i n t e r f a c e layer (e.g. t h r o u g h diffusion) the t r a n s i t i o n a l area increases in size. For this r e a s o n a distinction is made between the m e c h a n i c a l b e h a v i o u r of the interface layers in regions 2 or 3 and t h a t of the inner regions of film 1 or s u b s t r a t e 5 [75, 76].
Schicht 1

--j2 --3

Substrat 5

Fig. 2. The five regions [75] in which separation can take place.

A s e p a r a t i o n exclusively at the interface is assumed to be improbable a c c o r d i n g to the " w e a k b o u n d a r y t h e o r y " [77, 78]. Rather, the s e p a r a t i o n should always o c c u r in the bulk regions of coating or s u b s t r a t e (cohesive failure) or in a finitely thick " w e a k l a y e r " (interface layer) between the two substances. A failure within the weak i n t e r f a c e layer is r e g a r d e d as an adhesive failure. The weak layer can be a brittle oxide l a y e r or an absorbed and occluded l a y e r of gas a n d / o r some o t h e r kind of c o n t a m i n a t i o n . The basis of a n o t h e r t h e o r y [79] is the t r i g g e r i n g of a f r a c t u r e at preexisting cracks in the s u b s t r a t e or within the film a c c o r d i n g to the so-called G r i f f i t h - O r o w a n c r i t e r i o n [19, 80]: a2 = c o n s t a n t x

EG/l

(3)

where E is the modulus of elasticity, G is the work per unit surface area r e q u i r e d for c r a c k propagation, l is the length of the longest c r a c k s in existence and a is the force per unit surface area required for c r a c k propa-

gation. The c r a c k thus !brined grows in a direction normal to t h a t of the applied m e c h a n i c a l stress. The actual fl'acture is assumed to be a t r a n s f o f m a t i o n of e n e r g y either" into dissipative e n e r g y (e.g. heat) stored as elastic d e f o r m a t i o n or supplied externally, It must also be assumed that an energy t r a n s % r takes place from the area a r o u n d the f r a c t u r e to the f r a c t u r e zone. F r a c t u r e can also extend across several of the given regions. If the s e p a r a t i o n of the c o a t i n g from the s u b s t r a t e takes place inside or a r o u n d the interface layer, the force or e n e r g y n e c e s s a r y for the s e p a r a t i o n is a m e a s u r e of the e x p e r i m e n t a l l y m e a s u r e d adhesion [76]. However, if the s e p a r a t i o n takes place deep inside the film or substrate, it is a cohesion fracture, i,c. the adhesion forces are s t r o n g e r t h a n the cohesion forces. From a q u a l i t a t i w , point of view, the adhesion is considered to be bad if a s e p a r a t i o n in the interface l a y e r can be caused. However, if a s e p a r a t i o n occurs in the bulk. the adhesion is good. Q u a n t i t a t i v e values can only be obtained when the force used to lift the c o a t i n g can be measured. Individual m e a s u r e m e n t m e t h o d s are distinguished from one a n o t h e r by the way the load is coupled to the sample system and then by the way in which it is applied. These criteria allow a division into m e t h o d s which can remove the c o a t i n g t h r o u g h (a) a force applied p e r p e n d i c u l a r l y to the interface layer or (b) a tbrce applied at v a r i o u s angles to the interface layer. An upper limit of the t r a n s f e r a b l e force, and thus a m a x i m u m measurable adhesion value, results from the fact that in almost all the m e a s u r i n g m e t h o d s (with the exception of', for example, u l t r a c e n t r i f u g e or heat expansion methods) a t r a c t i o n piece must be a t t a c h e d m e c h a n i c a l l y . Thus this limit is d e p e n d e n t on the load c a p a c i t y or degree of fixation of the methodspecific a t t a c h m e n t (e.g. gluing or soldering). B e c a u s e of the v a r y i n g a t t a c h m e n t t e c h n i q u e s and the individual t r a n s f e r devices (Scotch tape, needles for s c r a t c h i n g etc.) f u r t h e r uncontrolled stresses can be caused in the interface layer in addition to the c o n t r o l l e d m e c h a n i c a l stress p r o d u c e d externally. Such additional stress ('an be caused, for example, by drying, p o l y m e r i z i n g or stiffening of the glue l a y e r or the solder l a y e r used for the t r a c t i o n piece. It can also o c c u r b e c a u s e of p l a s t i c - e l a s t i c d e f o r m a t i o n of the t r a c t i o n piece itself d u r i n g a test. The e x p e r i m e n t a l l y d e t e r m i n e d a d h e s i o n values are thus not free from effects due to the m e a s u r e m e n t m e t h o d used. Therefore it is u n f o r t u n a t e l y n o t a l w a y s possible to c o m p a r e m e a s u r e m e n t s obtained by different methods.

2.2. Non-mechanical methods

With the exception of the n u c l e a t i o n method, n o n - m e c h a n i c a l m e t h o d s to m e a s u r e adhesion are not very well developed, and their field of applic a t i o n is severely limited. These m e t h o d s can, in a n y case, be used for basic i n v e s t i g a t i o n s . Even the n u c l e a t i o n m e t h o d is too complicated for use for t e c h n o l o g i c a l applications b e c a u s e it requires too m u c h e q u i p m e n t and t a k e s too m u c h time. F o r this r e a s o n we shall not discuss it in more detail here.

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3. C a u s e s o f a d h e s i o n

3.1. Interface layer

The quality of adhesion between solids, e.g. between a film and its substrate, depends to a large extent on the microstructure of the interface layer that is being formed. The following types of interface layers can be distinguished [8, 69, 81].

3.1.1. Mechanical interface layer

This type of interface layer forms on rough porous substrates. The film material fills the pores and o.ther morphologically advantageous places when there is sufficient surface mobility and wetting, and a mechanical anchor is formed. The adhesion depends on the physical characteristics (particularly the shear strength and the plasticity) of the combination of materials.

3.1.2. Monolayer on monolayer

This interface is characterized by an abrupt transition from the film material to the substrate material. The transition region has a thickness 2 5 A. Interfaces of this type form when no diffusion occurs; there is little or no chemical reaction and the substrate surface is dense and smooth.

3.1.3. Chemical bonding interface layer

This type of interface layer is characterized by a constant chemical composition across several lattices. The formation of the interface layer results from the chemical reactions of film atoms with substrate atoms which may also be influenced by the residual gas. A distinction is made between intermetallic bonds and alloys and chemical bonds such as oxides, nitrides etc.

3.1.4. Diffusion interface layer

This interface layer is characterized by a generalized constant change in the lattice and the composition in the film-substrate transition area. At least partial solubility is required for diffusion between the film and the substrate material to take place. The necessary energy (1 - 5 eV) must be supplied from elsewhere, e.g. when copper is evaporated onto an unheated gold substrate the heat of condensation is sufficient for diffusion to take place. Diffusion layers have advantageous characteristics as transitional layers between very different materials, e.g. for reducing mechanical stresses resulting from thermal expansion.

3.1.5. Pseudodiffusion interface layer

This type of layer can be formed by implantation at high particle energies or by sputtering and ion plating of the substrate materials with simultaneous condensation of the film material. Pseudodiffusion interface layers have the same advantageous characteristics as diffusion interface layers, but in contrast with the latter they can be formed from

m a t e r i a l s t h a t do not m u t u a l l y diffuse, ion b o m b a r d m e n t before c o a t i n g can i n c r e a s e the " s o l u b i l i t y " in the i n t e r f a c e layers, t h u s i n c r e a s i n g the diffusion by p r o d u c i n g a h i g h e r c o n c e n t r a t i o n of point defects [82] and stress g r a d i e n t s [83]. One type of i n t e r f a c e l a y e r seldom o c c u r s alone. In n o r m a l practice. c o m b i n a t i o n s of the v a r i o u s types of i n t e r f a c e layers often o c c u r simultaneously.

3.2. Types of bonding

A d h e s i o n forces lying b e t w e e n 0.1 and 10 eV can be classified as follows: p h y s i s o r p t i o n , c h e m i s o r p t i o n and c h e m i c a l bonding. T h e c h a r g i n g effect [37] c a n also be classified as p h y s i s o r p t i o n . When two m a t e r i a l s with v e r y different e l e c t r o n affinities are combined, an e l e c t r i c a l double l a y e r forms which also c o n t r i b u t e s to the adhesion. P h y s i s o r p t i o n c o n t r i b u t e s up to a p p r o x i m a t e l y 0.5 eV to the adhesion. The force lies b e t w e e n 10 ~ and 10 s dyn cm 2 The i n t e r a c t i o n b e t w e e n film and s u b s t r a t e a t o m s which is described as c h e m i s o r p t i o n c a n r e s u l t in s t r o n g bonds w h e n e l e c t r o n s are shifted or e x c h a n g e d . In t r u e c h e m i c a l b o n d i n g s u c h as c o v a l e n t and ionic b o n d i n g as well as in m e t a l b o n d i n g the b o n d i n g forces are very strong, d e p e n d i n g on the degree of e l e c t r o n t r a n s f e r . In c o v a l e n t and ionic b o n d i n g the r e s u l t i n g bonds tend to be brittle, w h e r e a s in m e t a l b o n d i n g ductile alloys are often produced. The e n e r g y c o n t r i b u t e d to the a d h e s i o n from chemical bonds r a n g e s from 0.5 to a b o u t 10 eV. The forces are g r e a t e r t h a n or equal to 10 L1 dyn cm 2 This a p p a r e n t l y c l e a r p i c t u r e of differing i n t e r f a c e l a y e r s and types of i n t e r a c t i o n is c o m p l i c a t e d by the fact t h a t s u r f a c e s do not. b e h a v e u n i f o r m l y b e c a u s e t h e y are u n d e r the influence of the so-called a c t i v e and passive centres. A c t i v e c e n t r e s include g r a i n b o u n d a r i e s , dislocations, v a c a n c i e s or c r y s t a l l i t e faces with v a r y i n g free e n e r g i e s and a c t i v a t i o n energies of' c h e m i s o r p t i o n . P a s s i v e centres, w h i c h are a n a l o g o u s to a c t i v e centres, are s u r f a c e a r e a s w h i c h h a v e a l r e a d y been c o v e r e d with foreign m a t e r i a l so t h a t little or no c h e m i s o r p t i o n c a n t a k e place. It should be n o t e d t h a t the q u a l i t y of a d h e s i o n i m p r o v e s w i t h t i m e in some cases (e.g. silver on glass). This p h e n o m e n o n c a n be e x p l a i n e d in t e r m s of the slow (diffusion) formagion of an o x y g e n - b o n d e d i n t e r f a c e layer. O t h e r i n v e s t i g a t i o n s m a d e u s i n g the s c r a t c h test [82, 84] of the c h a n g e s in adh e s i o n t h a t t a k e place w i t h t i m e for m e t a l films on p o l y m e r s u b s t r a t e s h a v e s h o w n t h a t t h e r e is a m a r k e d i m p r o v e m e n t in the a d h e s i o n of the gold film o v e r a period of time. In this case the m a j o r p a r t of the i m p r o v e m e n t in a d h e s i o n was a t t r i b u t e d to the slow f o r m a t i o n of an e l e c t r o s t a t i c double layer. This was p r o v e d by b o m b a r d i n g t h e film with ions from a glow d i s c h a r g e w h i c h b r o k e d o w n the double layer, w h e r e u p o n the a d h e s i o n r e t u r n e d to its o r i g i n a l l o w e r v a l u e [82]. This series of e x p e r i m e n t s showed t h a t the e l e c t r o s t a t i c c o m p o n e n t s c o n t r i b u t e significantly to adhesion.

33

This observation confirms that adhesion seldom comes about only t h ro u g h reciprocal action but r at her that it is determined by the combined effects of various intermolecular atomic interactions.

4. P a r a m e t e r s influencing adhesion
The adhesion of thin films is influenced by a large number of parameters. Some of these are defined by the choice of materials for the coating and the substrate. The others are influenced by the preparation of the substrate, the coating process and the handling of the film-substrate combination after the coating process is completed. 4.1. Coating and substrate materials In most cases the substrate is given and fixed, and the coating is applied to change certain of its characteristics, e.g. antireflection coating of lenses, corrosion protection of a metal or improvement of hardness. The choice of material combinations in each case is often quite limited because of the application for which the system is intended. The choice of the combination of substances (if the film is to be evaporation coated) determines whether the interface layer will be of the diffusion type or the chemical bond type, or whether weak reciprocal action forces will be effective across the interface. If it is expected that the adhesion between the chosen materials will be weak, then the adhesion can be improved by the addition of an appropriate intermediate layer (compound system). The most common application of intermediate layers is to improve the adhesion of gold films on oxide substrates, e.g. glass. Metals such as chromium which oxidize and alloy easily are usually used as the intermediate layer. The chromium adheres very well to the substrate because of oxidation, and the chromium and gold form a diffusion interface layer which also has very good adhesion [85]. The adhesion of evaporated aluminium films on glass can be greatly improved by using nickel or chromium in a similar way [56]. The evaporation coating of metal alloys with low internal stresses (e.g. 75(~o Ti and 25% Cr) is a special case whereby the components of the alloy themselves often have a very high internal stress [86]. 4.2. Substrate preparation The formation of an interface layer and thus the adhesion are greatly influenced by the physical and chemical structure of the substrate surface and the neighbouring areas as well as by the morphology of the surface (planicity, waviness and roughness). The chemical composition of a surface itself is almost always different from that of the bulk of the material. Prior treatment of the surface, e.g. cutting and polishing, changes not only the mechanical structure but also the chemical structure of the surface. This can have both positive and negative effects on adhesion. For example, a layer comprising the polishing

a g e n t (usually an oxide), r e a c t i o n products, w a t e r and glass particles (Beilby film) forms on the s u b s t r a t e surface w h e n glass is polished [87]. Therefore the s u b s t r a t e should be prepared in such a way as to provide a defined and r e p r o d u c i b l e surface. There are m a n y physical and chemical c l e a n i n g and p r e p a r a t i o n m e t h o d s t h a t are capable of doing this. The desired c l e a n i n g is often a c h i e v e d by using a c l e a n i n g process w h i c h has a c o m b i n a t i o n of individual steps. W h e n w o r k i n g out a c l e a n i n g process it must be remembered w h i c h c o n t a m i n a n t s are to be cleaned from w h i c h surface m a t e r i a l s (metal, ceramic etc.).

4.3. Influence of the coating method

The f o r m a t i o n of the interface l a y e r is very s t r o n g l y influenced by the c o a t i n g process. In the case of films deposited by physical v a p o u r deposition a d i s t i n c t i o n is made b e t w e e n three different m e t h o d s of a p p l y i n g the c o a t i n g ( e v a p o r a t i o n in a h i g h v a c u u m , s p u t t e r i n g and ion plating), and the f o r m a t i o n of an i n t e r f a c e layer and the a d h e s i o n are influenced by the energy of the v a p o u r particles c o n d e n s i n g on the s u b s t r a t e as well as by the residual gas pressure (see Fig. 3).

_.1 ~, L

(a)

{b)

(c)

Fig. 3. Schematic diagram of the principle {}f physical coating processes [18]: {a) evaporation coating in a vacuum: (b) cathode sputtering; {{9 ion plating. P, tromping system; V, evaporator: S, snbstratc: T, target: E, energy supply to e v a p o r a t o r : P1, plasma: G, controlled gas supply; UT, negative target w~ltage (cathode voltage): Us , substrate voltage. The a v e r a g e kinetic e n e r g y of the v a p o u r particles on e v a p o r a t i o n is 0.1 - 0.2 eV. From this low e n e r g y it must be c o n c l u d e d t h a t only lightly adsorbed foreign m a t e r i a l films with a b s o r p t i o n energies of less t h a n 0,1 eV can be removed in this process and that wq)our particles c a n n o t in general be implanted u n d e r the s u b s t r a t e surface. Therefore the nuclei generally form on or in an a b s o r p t i o n layer a d h e r i n g to the s u b s t r a t e w h i c h can f u n c t i o n b o t h as a weak b o u n d a r y layer and as an adhesion layer t h r o u g h chemical bonding. In c a t h o d e s p u t t e r i n g the film m a t e r i a l e n e r g y is r a t h e r h i g h e r (1 - 10 eV) [ 7 ] . In ion plating a c o m b i n a t i o n of e v a p o r a t i o n (because of the high deposition rate) and s p u t t e r i n g (because of the high particle energy) allows particle energies g r e a t e r t h a n 100 eV to be obtained [88], Here c o n d e n s a t i o n on the s u b s t r a t e takes place u n d e r the s i m u l t a n e o u s influence of ions and

35

highly energized n e u t r a l particles (plasma) at pressures between 10 3 and 10-2 mbar. The highly energized particles can r e m o v e most of the a b s o r p t i o n l a y e r w h e n t h e y arrive at the surface. In addition, s p u t t e r i n g of the subs t r a t e surface ( p a r t i c u l a r l y for ion plating) and i m p l a n t a t i o n of particles of the film m a t e r i a l can also occur. Thus a reciprocal action between the film and the s u b s t r a t e m a t e r i a l is possible, e.g. a chemical reaction, or perhaps forced diffusion (pseudodiffusion). These are the reasons why films deposited by s p u t t e r i n g and ion plating generally a d h e r e m u c h b e t t e r t h a n e v a p o r a t e d films. In addition to the kinetic e n e r g y level of the film material, the pressure and composition of the residual gas in the coating e q u i p m e n t also d e t e r m i n e the c h a r a c t e r i s t i c s and adhesion of the film. If the film is produced by e v a p o r a t i o n in a high vacuum, the pressure should be k e p t below 10 5 _ 10 6 mbar. If this is not done the low e n e r g y v a p o u r particles will be dispersed too m u c h in the residual gas at the usual distance between e v a p o r a t o r and s u b s t r a t e (0.5 m). A l t h o u g h 0.5 m corresponds to a m e a n free path ). at a pressure of 10 4 mbar, c a l c u l a t e d from the simplified e q u a t i o n

this means t h a t only 40% of the v a p o u r atoms r e a c h the s u b s t r a t e w i t h o u t collisions with the residual gas particles which result in a r e d u c t i o n of e n e r g y and a c h a n g e of d i r e c t i o n [89]. F u r t h e r m o r e , the n u c l e a t i o n b e h a v i o u r depends on the composition of the residual gas a b s o r p t i o n layers ( p a r t i c u l a r l y condensed w a t e r vapour) on the s u b s t r a t e surface which affects the adhesion. It should be noted that, in addition to the m i c r o s t r u e t u r e and the m o l e c u l a r s t r u c t u r e of the e v a p o r a t e d films, the adhesion is also influenced by the angle at which the v a p o u r particles hit the substrate. No difference in adhesion can be observed for p e r p e n d i c u l a r angles of incidence 0 between 0 and a b o u t 4 8 , but at values of 0 of 60 the film m i c r o s t r u c t u r e becomes porous and the adhesion is g r e a t l y reduced [48]. When the pressure is high (10 2 . 10 1 mbar) during e v a p o r a t i o n coating the p r o p o r t i o n of v a p o u r particles r e a c h i n g the s u b s t r a t e and c o n d e n s i n g t h e r e is so small, because of the s c a t t e r i n g resulting from collisions with residual gas molecules, t h a t the adhesion is bad. In contrast, a sufficient n u m b e r of highly energized v a p o u r particles r e a c h the s u b s t r a t e and condense t h e r e despite multiple collisions when s p u t t e r i n g or ion plating is used. S p u t t e r i n g gold films onto glass s u b s t r a t e s using oxygen as the s p u t t e r i n g gas is a special case. If a r g o n is used as the noble gas atmosphere, t h e n the adhesion of the gold is only m a r g i n a l l y b e t t e r t h a n t h a t of e v a p o r a t e d fihns. If a m i x t u r e of oxygen and a r g o n is used, the adhesion improves in p r o p o r t i o n to the oxygen c o n t e n t of the s p u t t e r i n g gas mixture. When the o x y g e n c o n t e n t of the gas m i x t u r e is only 20'I/o, the film adheres so

36

s t r o n g l y t h a t it can no longer be r e m o v e d from the s u b s t r a t e w i t h o u t d e s t r o y i n g it [51]. H o w e v e r , good a d h e s i o n is o b t a i n e d w h e n gold fihns are ion plated o n t o glass in an a r g o n a t m o s p h e r e [90]. The s u b s t r a t e t e m p e r a t u r e h a s a very s t r o n g effect on adhesion. T h u s the r e - e v a p o r a t i o n rate. the s u r f a c e mobility, the diffusion and the prop e n s i t y of the a t o m s to c h e m i c a l r e a c t i o n s are s t r o n g l y affected by the s u b s t r a t e t e m p e r a t u r e . This i n d i c a t e s t h a t the v a r y i n g a d h e s i o n v a l u e s o b t a i n e d are d e p e n d e n t on the s u b s t r a t e t e m p e r a t u r e , and this can be e x p l a i n e d in t e r m s of r e a c t i o n s b e t w e e n the film and the s u b s t r a t e m a t e r i a l [27], which in t u r n are d e p e n d e n t on the s u b s t r a t e t e m p e r a t u r e .

4.4. Aging
In m a n y cases the f i l m - s u b s t r a t e s y s t e m is not t o t a l l y stable once the c o a t i n g process h a s ended, and it c o n t i n u e s to c h a n g e p h y s i c a l l y and c h e m i c a l l y until it r e a c h e s a stable c o n d i t i o n [88]. The a d h e s i o n of' the film to its s u b s t r a t e often u n d e r g o e s m a r k e d c h a n g e s d u r i n g this time. T h r e e processes, which g e n e r a l l y p r o g r e s s slowly, are r e s p o n s i b l e tbr this aging: c h e m i c a l r e a c t i o n s in the i n t e r f a c e l a y e r a r e a : solid body diffusion across the i n t e r f a c e l a y e r ; c h a n g e s in the c r y s t a l s t r u c t u r e ( r e c r y s t a l l i z a t i o n t h r o u g h self-diffusion). T h e s e processes are s t r o n g l y d e p e n d e n t on t e m p e r a t u r e . T h e i r speed u s u a l l y i n c r e a s e s with i n c r e a s i n g t e m p e r a t u r e [55, 58, 91].

5. F i n a l c o m m e n t s

T h e r e are two i m p o r t a n t a s p e c t s of the a d h e s i o n of thin films. F r o m the a c a d e m i c a s p e c t a d h e s i o n itself' is an i n t e r e s t i n g phenomenon. Of special i n t e r e s t are the n a t u r e and degree of the forces r e a c t i n g across the i n t e r f a c e w h i c h a c t u a l l y effect this a d h e s i o n (basic adhesion). F r o m the p r a g m a t i c a s p e c t the t o t a l a d h e s i v e s t r e n g t h of the e n t i r e film to the s u b s t r a t e in a p r a c t i c a l s y s t e m has to be considered. M e c h a n i c a l m e a s u r i n g m e t h o d s tend to be d e v e l o p e d with this in mind. H o w e v e r , the r e s u l t s are influenced and falsified by a m u l t i t u d e of u n k n o w n methodspecific m e a s u r e m e n t e r r o r s so t h a t the basic a d h e s i o n c a n only be calculated a p p r o x i m a t e l y . This does not, h o w e v e r , m a k e these m e a s u r e m e n t s less v a l u a b l e for p r a c t i c a l applicaicion. Only t h r o u g h the i n t r o d u c t i o n and e x p a n s i o n of m o d e r n i n v e s t i g a t o r y m e t h o d s will it be possible to c a r r y out r e s e a r c h on m o r e c o m p l e x s u r f a c e and i n t e r f a c e processes. At p r e s e n t the difficulty lies in the fact t h a t a g r e a t deal of' i n f o r m a t i o n on the c h e m i c a l c o m p o s i t i o n and g e o m e t r y of the i n t e r f a c e layer, the b o n d i n g e n e r g y b e t w e e n film a t o m s and s u b s t r a t e atoms, the dipole m o m e n t s of a b s o r b e d complexes, the d i s t r i b u t i o n of e l e c t r i c a l conditions, oscillations, s u r f a c e a r e a diffusion and the k i n e t i c s of s o r p t i o n p r o c e s s e s and s u r f a c e r e a c t i o n s is required. A c o m p l e t e a n a l y s i s of t h e s e effects is not possible at present. This m e a n s t h a t only p a r t i a l s o l u t i o n s to the p r o b l e m s of a d h e s i o n can be m a d e

37

while certain limiting conditions are imposed. T h i s g i v e s t h e s c i e n t i s t a w i d e field t o w o r k o n b e f o r e h e c a n e x p l a i n the processes at the interface and deduce from them the laws that could lead to a n i m p r o v e m e n t o f a d h e s i o n . T h o s e w o r k i n g in p r a c t i c a l a p p l i c a t i o n s should develop more sophisticated testing methods which allow the energy a p p l i e d to b e m e a s u r e d e x a c t l y so t h a t it c a n be c o m p a r e d w i t h t h e v a l u e s deduced theoretically.

Acknowledgment
W e w i s h to e x p r e s s o u r g r a t i t u d e to M i s s K. O ' D a y for t r a n s l a t i n g t h i s paper from German.

References
1 J. Kunsemiiller, Meyers Lexikon der Technik und exakten Naturwissenschaften, B.I., Mannheim, 1971. 2 H. Franke, Lexikon der Physik, Franckh'sche Verlagshandlung, Stuttgart, 1969. 3 O.A. Neumiiller, RSmpps Chemie Lexikon, Franckh'sche Verlagshandlung, Stuttgart, 1972. 4 R . J . Good, J. Adhes., 8 (1976) 1; A S T M Definition of Term Relating to Adhesion D 907-70, ASTM, Philadelphia, PA, 1970. 5 K.L. Mittal, J. Adhes., 7 (1974) 377. 6 K . L . Mittal, Electrocomp. Sci. Technol., 3 (1976) 21. 7 D.M. Mattox, Thin Solid Films, 18 (1973) 173. 8 D.M. Mattox, Interface formation and the adhesion of deposited thin films, SC Monogr. R-65 852, 1905 (Sandia Corp.). 9 H . K . Pulker, R. Buhl and E. Moll, Vorabdrucke 9, Plansee Seminar, Reutte, 1977, Band 2, Vortrags nr. 23. 10 J. Strong, A S P Publ., 46 (1934) 18. 11 K . E . Haq, K. H. Behrndt and I. Kobin, J. Vac. Sci. Technol., 6 (1969) 148. 12 R.A. Mc. Kyton and J. J. Wallis, Thin film materials and deposition techniques for infra-red coatings, F A Tech. Rep. 74028, October 1974 (Frankford Arsenal, Philadelphia, PA). 13 E . M . Ruggiero, Proc. 14th Annu. Microelectronics Syrup., St. Louis Section, IEEE, May 24 - 26, 1965, IEEE, New York, 6B-1, 14 S. Bateson, Vacuum, 2 (1952) 365. 15 F. Schlossberger and K. D. Frankson, Vacuum, 9 (1959) 28. 16 D. Davies and B. Whittaker, Metall. Rev., 12 (1967) 15. 17 W.G. Dorfeld, Thin Solid Films, 47 (1977) 241. 18 H. Stuke and K. Wolitz, Beitrag zur Haftung yon PVD-Schichten, Seminar Deutsche
Gesselshaft fi~r Metallkunde, Bad Nauheim, 1977.

19 20 21 22 23 24

A . A . Griffith, Philos. Trans. R. Soc. London, 221 (1920) 163. H.G. Schneider and S. Meyer, Krist. Tech., 2 (1967) K15. P. Morzek, Wiss. Z. Tech. Hochsch. Karl-Marx-Stadt, 10 (1968) 175. R. Jacobsson and B. Kruse, Thin Solid Films, 15 (1973) 71. G. Katz, Thin Solid Films, 33 (1976) 99. R.B. Belser and W. S. Hicklin, Rev. Sci. Instrum., 27 (1956) 293.

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53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69

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