The Nucleation, Growth, and Structure of

Electroless Copper Deposits

Richard Sard*
Bell Telephone Laboratories, Incorporated, Murray Hill, New Jersey

ABSTRACT
A n electron microscopic investigation has revealed that the electroless
deposition of copper occurs by repeated t h r e e - d i m e n s i o n a l nucleation at cata-
lytic sites on a substrate. The n a t u r e of the catalytic sites formed by i m -
mersion in the standard stannous and p a l l a d i u m chloride solutions was ob-
served and found to influence the structure of the s u b s e q u e n t l y deposited
metal. Initially, copper nuclei about 25A in d i a m e t e r form aggregates an order
of m a g n i t u d e larger. As the autocatalytic reduction reaction continues the
aggregates increase in size u n t i l they become energetically unstable; t h e n
recrystallization occurs. The resulting continuous copper films exhibit a
heterogeneous microstructure with grain size variations of more t h a n an order
of m a g n i t u d e and also n u m e r o u s t w i n faults.

There exists at present a considerable a n d rapidly the substrate; second, the sensitization of the sub-
growing interest in the electroless deposition of strate with stannous chloride; third, the activation of
metallic films onto n o n c o n d u c t i n g substrates. Although the sensitized substrate with p a l l a d i u m chloride;
m a n y chemical systems for metal deposition have been finally, the deposition of a metallic copper film. The
developed (1), relatively little is k n o w n about the formulations of the various solutions are given in
mechanisms which govern the behavior of these com- Table I. Initially, solutions were prepared using dis-
plex systems. Recently, however, some progress tilled w a t e r of c o n v e n t i o n a l purity. Subsequently,
toward this goal has been made b y Okinaka (2) and however, deposition experiments were carried out
P a u n o v i c (3) who employed electrochemical methods with a higher regard for purity. For example, these
to study the kinetics of the electroless copper plating experiments were conducted in a l a m i n a r flow work
reaction. station and solutions were prepared with w a t e r 1 that
A n i m p o r t a n t property of electroless systems is was twice distilled in a quartz apparatus. The water
their ability to deposit metals selectively. This prop- used for the r i n s i n g operations after each stage of the
erty, which depends critically on the structure of the process was of the same type used for solution prep-
sensitized substrate, has been demonstrated b y Sharp aration. Reagent grade chemicals were used without
(4), who desensitized portions of a surface with u.v. f u r t h e r purification.
radiation, and also by T u r n e r (5), who used a p r i n t - The electron microscopic techniques which were
ing technique to apply a sensitizer selectively. used to investigate the structures present at each
A f u n d a m e n t a l aspect of this type of deposition,
l A n a n a l y s i s c a r r i e d o u t b y D. L. M a i m , of B e l l T e l e p h o n e L a b o -
about which very little is known, concerns the basic r a t o r i e s , u.~ing s p a r k s o u r c e m a s s s p e c t r o s c o p y i n d i c a t e d t h a t this
s t r u c t u r a l mechanisms responsible for the nucleation w a t e r c o n t a i n e d f r o m I to 10 a t o m i c p p m of t o t a l r e s i d u a l i m p u r i -
ties.
and growth of metallic films. These factors are i m -
p o r t a n t because they will u l t i m a t e l y determine the Table I. Solution formulations
properties and consequently the technological useful-
ness of the films. Interest in magnetic thin films has Constituents Quantity Concentration
led to several studies dealing with the structure of
electroless nickel (6-8) and cobalt (9-12) deposits Sensitization*
that were chemically reduced from solutions c o n t a i n - A. SnC12 92H.~O 16 g/1 0.07 M
ing hypophosphite. However, there appears to be Conc. HC1 30 m l / 1 0.62 M
v i r t u a l l y no data available on the growth and struc- B. SnCI~ - 2H20 30 g/1 0.13 M
ture of other electroless deposits including copper, Conc. HC1 10 ml/1 0.27 M
which is of considerable technological importance. Activation*
Also, there is very little direct evidence (6, 9) con- A. PdCI.~ 0.1 g/1 0.0006 M
cerning the structures which exist prior to the f o r m a - Conc. HC1 8 ml/1 0.22 M
tion of a continuous metal deposit. One reason for this B. PdCI~ 0.75 g/1 0.004 M
lack of direct evidence is that electron microscopes Conc. HC1 10 m l / 1 0.27 M
capable of resolving information on the order of 10A Electroless Copper
are needed. While such i n s t r u m e n t s are available, they A. S a u b e s t r e ' s s o l u t i o n (22) 170 g/1 0.60 M
KNaC4H40~ 9 4 H 2 0 (Ro-
have not yet been employed to study the process of c h e l l e salt) 50 g/1 1.25 M
electroless deposition. NaOH 35 g/1 0.14 M
CuSO~ 9 5H~O 30 g/1 0.28 M
The present study has been p r i m a r i l y concerned EDTA 10 g/1 0.03 M
with the nucleation and growth of electroless copper I m m e d i a t e l y p r i o r to u s e f i v e p a r t s of t h i s solution are
deposits. However, some of the results, p a r t i c u l a r l y c o m b i n e d w i t h o n e p a r t H C H O (37%).
those p e r t a i n i n g to the sensitization and activation B. O k i n a k a ' s m e t h a n o l s o l u t i o n (23)
t r e a t m e n t s which precede metal deposition, are u n - Part 1
doubtedly of a more general n a t u r e and can therefore CuSO4 * 5H'~O i0 g / l 0.04 M
H C H O (37%) 60 m l / 1 0.78 M
be applied to other e]ectroless deposition systems. CHsOH 300 ml/1 30%

Experimental Part 2
NaOH 40 g/1 1.0 M
Four aspects of the o v e r - a l l process of electroless KNaC,H40~ - 4H20 (Ro-
deposition were investigated: first, the influence of chelle salt) 26 g / l 0.1 M
P a r t s 1 a n d 2 are m i x e d i n e q u a l v o l u m e s Drior to use.
* Electrochemical Society Active Member.
Key words: electroless deposition, copper, n u c l e a t i o n and growth,
s t r u c t u r e of t h i n films, e l e c t r o n m i c r o s c o p y . * B a s e d o n B e r g s t r o m ' s p a t e n t (21).

864

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 Vol. 117, No. 7 ELECTROLESS COPPER DEPOSITS 865

stage of the process were bright-field and dark-field

imaging combined with selected-area electron diffrac-
tion, as well as direct carbon or two-stage surface
replicas shadowed with a P t - P d alloy. These investi-
gations were carried out with a Siemens Elmiskop
i n s t r u m e n t operated at 100 kV.
In order to s t u d y the initial stages of the process,
prior to the formation of a continuous, self-supporting
deposit, an e l e c t r o n - t r a n s p a r e n t substrate is required.
Evaporated carbon films, about 200 to 400A thick,
were used, and suitable substrates were prepared by
c o n v e n t i o n a l techniques employing either plastic-
coated microscope grids or glass slides as the original
substrate materials.
Continuous copper films, 500-1000A thick, were de-
posited onto glass slides, evaporated carbon, K a p t o n
(a polyimide film), and freshly cleaved mica sub-
strates. The structures of these films were studied by
the electron microscopic techniques m e n t i o n e d p r e -
viously, which required stripping of the deposits from
all b u t the carbon substrates. Continuous copper de-
posits were also e x a m i n e d b y reflection electron dif-
fraction while t h e y were still a d h e r e n t to their s u b -
strates in order to d e t e r m i n e w h e t h e r the different
substrates exerted a n y influence on their orientation
a n d structure.

Results and Discussion

Sensitization.--Evaporated carbon substrates were
immersed in stannous chloride solutions, rinsed in
distilled water, dried, and e x a m i n e d electron micro-
scopically.2 It was found that the product of this
sensitization t r e a t m e n t exists as particulate m a t t e r on
an e x t r e m e l y fine scale. Particles of the order of 10A
were resolved, and these tended to agglomerate into
dense clumps an order of m a g n i t u d e larger. High
resolution bright-field and dark-field micrographs
which illustrate these results are shown in Fig. l a and
lb, respectively.
Figure la represents the structure present after
immersion of a carbon substrate for 3 sec in stannous
chloride solution A. The darker regions are in diffrac- Fig. 1. Sensitization of carbon substrates: a (top) bright-field
tion contrast a n d correspond to the deposited m a - image, 3 sec in SnCI2-A; b (bottom) dark-fleld image, 10 sec in
terial. These regions appear to be clumps that are SnCI2-B.
about 100-250A in size and are comprised of smaller
particles about 25A in size. The coverage in this
field of view is a p p a r e n t l y less t h a n 25%. I n d a r k -
field micrographs at higher magnifications (Fig. l b )
the smallest resolvable particles are a p p r o x i m a t e l y
10-20A in size. Images of this type reveal only a por-
tion of the deposited m a t e r i a l as most of the diffracted
electrons are stopped by the objective aperture.
The electron diffraction p a t t e r n shown is Fig. 2 is
typical of those observed after sensitization in either
solution for periods up to 1 m i n and water rinsing.
This p a t t e r n corresponds to the oxide phase, SnO2
(ASTM Data Card 5-0467). The analysis 3 of n u m e r o u s
similar diffraction p a t t e r n s confirmed this result. It is
i m p o r t a n t to remember, however, that these experi-
ments were not performed in situ and the deposits
were exposed to an air e n v i r o n m e n t for at least 10
rain prior to examination, d u r i n g which time oxida-
tion u n d o u b t e d l y occurred.
The breadths of diffraction lines, as d e t e r m i n e d
from microdensitometer traces, yielded an i n d e p e n -
dent calculation of the particle size. Both the integral Fig. 2. Typical selected-area electron diffraction pattern of
b r e a d t h and the peak w i d t h at half m a x i m u m were sensitized carbon substrate.
determined from several typical patterns. Breadths of
1 to 2 x 10 -8 radians were found, which correspond Increasing either the concentration of stannous
to calculated values of the particle sizes in the range chloride or the i m m e r s i o n time resulted i n a n i n -
from about 30 to 15A, to a first approximation (14). creased coverage of the adsorbed sensitizing species.
However, on a microscopic scale the coverage was
2 One series of t h e s e e x p e r i m e n t s w a s c a r r i e d o u t i n c o l l a b o r a t i o n heterogeneous, p a r t i c u l a r l y w h e n distilled w a t e r of
w i t h I:L D. H e i d e n r e i c h u s i n g a m o d i f i e d S i e m e n s E i m i s k o p t h a t is
c a p a b l e o f 2A r e s o l u t i o n u n d e r o p t i m u m c o n d i t i o n s (13). I t is u n - o r d i n a r y p u r i t y was used. The results obtained from
l i k e l y , h o w e v e r , t h a t f e a t u r e s s m a l l e r t h a n 10A c o u l d b e r e s o l v e d h i g h - p u r i t y solutions showed a m a r k e d i m p r o v e m e n t
i n t h e p r e s e n t s a m p l e s d u e t o t h e b a c k g r o u n d " n o i s e " f r o m ~he
substrates. with respect to u n i f o r m i t y and reproducibility. Figure
z These measurements were facilitated by graphically recording 3 illustrates the effect of increasing the immersion
m a n y of the p a t t e r n s w i t h a J a r r e l l A s h mierodensitometer, E v a p o -
r a t e d TIC1 w a s u s e d f o r a c a l i b r a t i o n s t a n d a r d . time from 5 to 30 sec, as coverage increases from ap-

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 866 J. Electrochem. Soc.: ELECTROCHEMICAL SCIENCE July 1970
at the surface. I n this regard, the pH at the surface is
a n i m p o r t a n t factor which has been found (4) to
d e t e r m i n e which compounds are formed. Recent work
by Sharp and co-workers (4) has shown that t i n must
be present as S n +2 and not Sn +4, otherwise activation
and electroless deposition will not occur. Diffraction
patterns indicating the presence of the b i v a l e n t oxide,
(SnO)160 (ASTM Data Card 13-111) were observed
on samples subjected to a very mild rinse, i.e., 10 sec
immersion without turbulence. Although no systematic
s t u d y of r i n s i n g was conducted, this t r e a t m e n t i n -
fluenced the structure observed d u r i n g activation and
electroless deposition.
Activation.--A surface c o n t a i n i n g only an adsorbed
sensitizer is inactive in an electroless solution(17).
Hence, the presence of a suitable catalyst is essential
if that surface is to receive a n electroless deposit.
P a l l a d i u m chloride solutions are most f r e q u e n t l y used
to provide the catalyst. The reaction m e c h a n i s m for
this process is generally thought (24) to be:
Sn +2 + Pd +2 ~ P d 0 § Sn +4, which m e a n s that the
adsorbed stannous ions provide the sites and electrons
for the adsorbing palladium ions. When excess sensi-
tizer is dragged through into PdC12 solutions due to
i n a d e q u a t e rinsing, the reduction to metallic Pd occurs
adjacent to the interface and in the bulk of the solu-
tion. In such cases, metallic Pd particles, 50-1O0A in
size, become adsorbed on the surface. The set of
arrows shown in Fig. 4 refers to corresponding regions
in bright and dark-field micrographs w h e r e these
particles are clearly seen.
The m a n n e r in which r i n s i n g was carried out after
the sensitization and activation t r e a t m e n t s was found
to affect the configuration of the adsorbed material.
In contrast to the previous results for r e l a t i v e l y mild
r i n s i n g by immersion, the structure shown in Fig. 5

Fig. 3. Effect of time on sensitization of carbon substrates in

SnCI~,-A (high purity): a (top) 5 sec immersion, b (bottom) 30 sec
immersion.

p r o x i m a t e l y 30 to 75%. Although these fields of view

are r e p r e s e n t a t i v e and appear to have u n i f o r m
coverage, the results must be considered qualitative
as other samples subjected to similar t r e a t m e n t s oc-
casionally exhibited different configurations. Hence, a
considerable a m o u n t of statistical data would have
to be obtained and analyzed, together with m e a s u r e -
ments on a more macroscopic scale, in order to d e -
scribe and i n t e r p r e t the adsorption kinetics of this
system quantitatively.
The above results confirm some of the deductions
which were made recently b y other workers who have
studied the nucleation, growth, and structure of
electroless nickel (6) a n d cobalt (9, 1O) deposits.
Marton and Schlesinger (6) were u n a b l e to resolve
the products of stannous chloride sensitization, prior to
activation and nickel deposition. By e x t r a p o l a t i n g a
plot of particle size vs. time (back to t = 0) for grow-
ing N i - P islands, assuming a constant microscopic
growth rate, the catalytic sites were estimated to be
less t h a n 10A in diameter. On the basis of the present
results, it appears that the most i m p o r t a n t sites for
f u r t h e r n u c l e a t i o n and growth are the densest regions
of the deposit.
Several i m p o r t a n t aspects regarding the sensitiza-
tion with stannous chloride solutions r e q u i r e f u r t h e r
study. Although the presence of S,nO2 is indicated by
electron diffraction, this analytical method is obvi-
ously not well suited to a direct study of hydrolyzed Fig. 4. Activation of carbon substrate in PdCI2-A after sensitiza-
species and therefore cannot identify which of the tion in SnCI2-A (high purity, S sec each) with incomplete rinse.
m a n y possible (15,16) stannous or stannous chloro- Arrows indicate Pd particles, a (top) Bright-field image; b (bottom)
hydroxides, oxyhydroxides, or h y d r a t e d oxides forms dark-field image of same region.

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 Vol. I17, No. 7 ELECTROLESS
Fig. 5. Effect of severe agitation during rinsing of carbon-coated
glass substrate. Sensitization and activation far 30 sec each in
SnCI2-A and PdCI2-A. a (top) Bright-field image, b (bottom)
shadowed, carbon replica showing surface morphology.
resulted from a more severe rinse, i.e., holding the
carbon-coated glass substrate u n d e r r u n n i n g distilled
water. The transmission micrograph in Fig. 5a i n -
dicates that the active m a t e r i a l covers only a r e l a -
tively small fraction of the surface in an island n e t -
work. The morphology of this s t r u c t u r e is visible in
carbon replicas (Fig. 5b). Based on the shadowing
geometry and Fig. 5b, these islands are estimated to
be a p p r o x i m a t e l y 40A in elevation.
The structures a n d diffraction patterns observed
after activation of sensitized surfaces that received
adequate rinsing were quite similar to those obtained
prior to the activation treatment. The n e t w o r k - l i k e
clumps of adsorbed sensitizer persisted and the dif-
fraction patterns became more diffuse which suggests
that the activation process consists of the adsorption
of very small a m o u n t s ( p r o b a b l y less t h a n about 20A)
of Pd onto the sensitized regions. Direct evidence of
metallic P d in diffraction patterns of these samples
was observed w h e n e l e c t r o n - b e a m induced recrystalli-
zation resulted in particles 100-150A in size. Also,
regions exhibiting dense coverage f r e q u e n t l y gave
diffraction patterns with extra lines corresponding to
PdO.
The following qualitative results on the effect of the
deposition variables were obtained. Increased concen-
tration (solution B) resulted in increased Pd coverage.
With respect to activation time, it appeared t h a t most
of the sensitized regions became covered after about
10-20 sec and that prolonged immersion had little
effect. These effects were only observed w h e n other
factors, such as rinsing, did not interfere.
Electroless copper deposition.--The electroless dep-
osition of copper from solution occurs only at
catalytic regions on a surface. The initial stage in this
process is represented b y Fig. 6, which corresponds to
a 3-sec i m m e r s i o n in solution A. The copper particles,
which appear dark in Fig. 6a, n u c l e a t e d at t h e most
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COPPER DEPOSITS 867
Fig. 6. The initial stage of copper deposition after 3 sec in
solution A. Carbon substrate sensitized and activated for 3 sec
each in SnCI2-A and PdCI2-A. Twinned crystallite denoted by "T."
a (top) Bright-field image, b (bottom) dark-field image of same
region.
favorable catalytic sites. These sites correspond to
the densest regions of the active material, which ap-
pear in gray contrast in Fig. 6a against the lighter,
inactive regions on the substrate. It is interesting to
note t h a t the copper particles, which range up to
about 300A in size, are not single crystals b u t consist
of aggregates of smaller crystallites. This observation
is confirmed by the dark-field micrograph (Fig. 6b),
which shows that the larger aggregates c o n t a i n
r a n d o m l y oriented crystallites that are less t h a n 50A
in diameter. The streaks associated with the bright,
diffracting crystallites in Fig. 6b are due to spherical
aberration, i.e., the objective aperature was positioned
off the optical axis, and are w i t h o u t s t r u c t u r a l signifi-
cance. The feature denoted b y the letter "T," which
consists of two regions in diffraction contrast
separated by a small dark b a n d with parallel sides, is
believed to represent a t w i n n i n g fault. The formation
of twins d u r i n g electroless copper deposition is an
i m p o r t a n t part of this process and is discussed below.
As the process continues autocatalytically, copper
deposits on the originally formed nuclei. After about
10 sec in solution A, the largest aggregates exceed
500A in size, yet all of these features consist of
smaller crystallites as seen in Fig. 7. Crystallites as
small as 25-50A across are resolved, although some
coherently diffracting regions larger t h a n 100A are
p l a i n l y visible. Close e x a m i n a t i o n of this as well as
n u m e r o u s similar samples revealed that the twin
fault density at this stage is about 10TM c m - 2 which
corresponds to a p p r o x i m a t e l y 1% of the deposited
nuclei. The diffraction patterns obtained from these
deposits indicate that the copper is r a n d o m l y oriented
and possesses the lattice p a r a m e t e r of b u l k material.
It appears, therefore, that the deposition process from
solution is r a n d o m with respect to orientation. Thus,
the formation of t w i n faults can occur w h e n e v e r ad-
jacent crystallites are in t w i n orientation across a
c o m m o n {111} boundary.
 868 J. Electrochem. Soc.: E L E C T R O C H E M I C A L
Fig. 7. Copper deposit after 10 sec in solution A. Carbon sub-
strate sensitized and activated for 10 sec each in SnCI2-A and
PdCI2-A. a (top) Bright-field image, b (bottom) dark-field image
of same region.
Several i m p o r t a n t aspects of the electroless deposi-
tion of continuous films are illustrated in Fig. 8, which
represents the structure formed w h e n an activated
substrate similar to Fig. 5 was plated for 1 m i n in
solution A. The bright and dark-field pair of t r a n s -
mission micrographs (Fig. 8a and 8b, respectively)
reveal that the grain size of this structure varies by
more t h a n a n order of magnitude. The largest grains
are 800-1000A across, which corresponds to the esti-
m a t e d film thickness. It is noted that these larger
grains tend to form continuous chains that are sepa-
rated by regions consisting of much finer crystall.ites.
The surface morphology of this deposit (Fig. 8d) con-
firms the existence of large elevated chains separated
b y regions where the film is t h i n n e r . The large-
grained regions u n d o u b t e d l y correspond to the active
sites on the substrate where copper deposition orig-
inated.
With the exception of the chainlike n e t w o r k of
larger grains, the basic s t r u c t u r a l features that are
visible in Fig. 8 were common to all continuous de-
posits regardless of pretreatment. The microstructures
were all qualitatively similar with respect to the
grain-size variations and the existence of n u m e r o u s
t w i n faults. (The parallel fringes which extend across
m a n y of the larger grains in Fig. 8a are due to micro-
t w i n faults.) Typically, t w i n fault densities in excess
of 101~ cm -2 were observed. 4 Moreover, all deposits
were r a n d o m l y oriented. This result was d e t e r m i n e d
from transmission p a t t e r n s (e.g., Fig. 8c) of detached
films and confirmed from reflection patterns of de-
posits still adherent to their substrates. The substrates
activated for use in the reflection experiments were
glass, freshly cleaved mica, and the polyimide m a -
terial, Kapton.
The rate of electroless copper deposition is depen-
dent on the n a t u r e of the catalytic surface as well as
S i m i l a r t w i n f a u l t densities h a v e b e e n o b s e r v e d f o r b o t h single
c r y s t a l (18) a n d p o l y c r y s t a l l i n e (19) copper electrodeposits a n d also
f o r e v a p o r a t e d films (20).
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SCIENCE J u l y 1970
Fig. 8. Continuous copper deposit formed in solution A after
pretreatment equivalent to that of Fig. 5. a, Bright-field image;
b, dark-field image of same region; c, selected area diffraction
pattern characteristic of copper and Cu20; d, shadowed, carbon
replica of surface.
the composition of the solution. Solution A, which is
relatively unstable, deposits copper at an average rate
of 25 ~/hr (70 A/sec), whereas solution B, which is
more dilute and contains a stabilizer, is slower by a
factor of about twenty. Despite this difference, it was
found that both solutions yielded deposits with similar
s t r u c t u r a l characteristics. I n fact, by altering the
catalyst coverage and immersion times it was possible
to obtain v i r t u a l l y identical deposits. F i g u r e 9 illus-
trates this point. The deposit in Fig. 9a received a
5-sec sensitization and activation prior to electroless
deposition for 10 sec in solution A. When solution B
was used with the same p r e t r e a t m e n t relatively few
nuclei were deposited and these required several
m i n u t e s to grow into large aggregates. However, in-
creasing the p r e t r e a t m e n t times to 30 sec prior to
deposition in solution B for an equivalent d u r a t i o n
resulted in the structure shown in Fig. 9b.
Several stages in the development of a copper de-
posit from solution B w h e n the surface concentration
of catalyst is low can be seen in Fig. 10. I n these ex-
periments glass slides were used as substrates and
ultrasonic agitation d u r i n g r i n s i n g reduced coverage
to b e t w e e n 10 and 20%. The copper deposits together
with their evaporated carbon supports were re-
moved from the glass in 10% HF. This t r e a t m e n t ac-
counts for the replicalike effect in Fig. 10a, where the
outline of the deposit present at 30 sec is visible
although the copper has dissolved and also accounts
for the u n d e r c u t t i n g on the l - r a i n deposit (Fig. 10b).
The other bright-field micrographs in Fig. 10c and 10d
represent the structures developed after deposition for
3 and 5 min, respectively. The deposits obtained u n d e r
these conditions, i.e., low catalyst concentration and
stabilized solution, differ from the one in Fig. 9b in
that there are fewer aggregates and these grow to
several thousand angstroms in size before e n c o u n t e r i n g
other similar features. The dark-field image (Fig. 10e)
and diffraction p a t t e r n (Fig. 10f) confirm that the
basic m i c r o s t r u c t u r a l characteristics of these deposits
 Vol. 117, No. 7 ELECTROLESS
Fig. 9. Discontinuous copper deposits obtained from different
solutions on glass substrates, a (top) Solution A, 10 sec after
S sec each in SnCI2-A and PdCI2-A; b (bottom) solution B, 30 sec
after 30 sec each in SnCI2-A and PdCI2-A.
Fig. 10. Several stages in the formation of a copper deposit in
solution B on a glass substrate with low catalyst concentration.
Sensitization and activation for 30 sec each in SnCI2-A and
PdCI2-A with ultrasonic agitation during rinsing, a-d, Bright-field
images, 30 sec, 1, 3, and 5 min, respectively; e, dark-field image
of region shown in d; f, selected area electron diffraction pattern.
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COPPER DEPOSITS 869
are no different from those discussed previously.
The above results indicate that the structure of
continuous electroless copper deposits is a direct con-
sequence of the nucleation a n d growth p h e n o m e n a
which occur d u r i n g the initial stages of the process.
I n i t i a l l y t h r e e - d i m e n s i o n a l nucleation occurs at cata-
lytic sites on a surface. These nuclei form aggregates
which become larger due to the continued depositon
of m a t e r i a l from solution u n t i l they become e n e r -
getically unstable. At this stage a recrystallization
process occurs which eliminates the i n t e r i o r b o u n d -
aries and transforms the u n s t a b l e aggregates into
larger, single grains. Therefore, the conventional de-
scriptions of m e t a l deposition processes w h e r e i n n u -
cleation is followed by t w o - d i m e n s i o n a l growth via
surface diffusion are not applicable to electroless dep-
osition due to the chemical reduction reaction at the
surface. The m e c h a n i s m of this reaction is of great
importance and has recently been studied using elec-
trochemical techniques (2, 3). It appears that a de-
tailed u n d e r s t a n d i n g of both the physical and the
chemical aspects of this complex system will have to
be obtained before a complete q u a n t i t a t i v e description
can be given.
Summary
High resolution electron microscopy provides an
e x t r e m e l y powerful method for elucidating the struc-
t u r a l p h e n o m e n a associated with the electroless
process for m e t a l deposition on n o n c o n d u c t i n g sub-
strates. Application of this method has resulted in the
following description of this process.
The products of the s t a n d a r d stannous chloride
sensitization t r e a t m e n t exist as adsorbed clumps of
m a t e r i a l that are several h u n d r e d angstroms across
and are comprised of particles 10 to 30A in size.
Activation with p a l l a d i u m chloride results in the
adsorption of catalytic m a t e r i a l onto the sensitized
regions. The configuration of these active regions can
be altered b y rinsing. This alteration is reflected in
the structure of the s u b s e q u e n t l y deposited metal.
The s t r u c t u r a l mechanisms which govern the elec-
troless deposition of copper were deduced by follow-
ing the stepwise development of metallic films. This
process proceeds by repeated t h r e e - d i m e n s i o n a l n u -
cleation from solution at catalytic sites on the surface.
The copper nuclei, which are about 25A in diameter,
form aggregates an order of m a g n i t u d e larger. Since
the reduction reaction is autocatalytic, the size of the
aggregates increases d u r i n g growth u n t i l they be-
come energetically unstable. Then a recrystallization
process takes place and the u n s t a b l e aggregates are
t r a n s f o r m e d into relatively large grains several h u n -
dred angstroms across. Continuous copper films ob-
tained by this process exhibit a heterogeneous micro-
structure with grain size variations of more t h a n one
order of magnitude. This v a r i a t i o n is a t t r i b u t e d to the
repeated nucleation and recrystallization process.
These deposits also contain n u m e r o u s (>1010cm-2)
t w i n faults. T w i n faults can form w h e n e v e r adjacent
nuclei are in t w i n orientation and possess a common
{111} boundary. This situation a p p a r e n t l y occurs quite
f r e q u e n t l y d u r i n g the initial stages of the process
w h e n the r a n d o m l y oriented copper nuclei form on
the substrate.
A n i m p o r t a n t first step toward the goal of eluci-
dating the physical aspects of electroless copper de-
posits has been achieved. However, a more q u a n t i t a -
tive description encompassing both the physical and
chemical aspects of the system is u r g e n t l y needed.
Acknowledgment
Thanks are due to R. D. Heidenreich who made the
electron microscope facilities available to the author
and also assisted in the high resolution study of the
sensitization process which resulted in Fig. l a and lb.
The efforts of G. W. K a m m l o t t who obtained the re-
 870 J. Electrochem. Soc.: ELECTROCHEMICAL S C I E N C E J u l y 1970

fiection diffraction patterns are also acknowledged.
Finally, considerable insight regarding the chemistry
of the electroless process was provided b y Y. Okinaka,
who, along with D. R. T u r n e r participated in helpful
discussions d u r i n g the course of this work.
Manuscript submitted Jan. 19, 1970; revised m a n u -
script received March 13, 1970.
A n y discussion of this paper will appear in a Dis-
cussion Section to be published in the J u n e 1971
JOURNAL.
REFERENCES
1. W. Goldie, "Metallic Coating of Plastics," Electro-
chemical Publications Ltd., Middlesex, E n g l a n d
(1968).
2. Y. Okinaka, Paper 144 presented at the Detroit
Meeting of the Society, Oct. 5-9, 1969.
3. M. Paunovic, Plating, 55, 1161 (1968).
4. D. J. Sharp, J. Henrickson, J. D'Amico, and J.
Kenney, Paper 136 presented at the Detroit
Meeting of the Society, Oct. 5-9, 1969.
5. D. R. Turner, Paper 137 presented at the Detroit
Meeting of the Society, Oct. 5-9, 1969.
6. J. P. Marton and M. Schlesinger, This Journal, 115,
16 (1968).
7. M. Schlesinger and J. P. Marton, J. Phys. Chem.
Solids, 29, 188 (1968).
8. A. H. Graham, R. W. Lindsay, and H. J. Read,
This Journal, 112, 401 (1965).
9. A. S. Frieze, R. Sard, and R. Weil, ibid., 115, 586
(1968).
10. A. S. Frieze, M. S. Thesis, Stevens Institute of
Technology (1966).
I i. M. G. Miksic, R. Travieso, A. Arcus, and R. H.
Wright, This Journal, l l 3 , 360 (1966)
12. L. Cadorna, P. Cavallotti, and G. Salvago, Electro-
chem. Metallorum., I, 177 (1966).
13. R. D. Heidenreich, W. M. Hess, and L. L. Ban,
J. Appl. Cryst., I, 1 (1968)
14. See, for example, J. T. Randall, "The Diffraction of
X-Rays and Electrons b y Amorphous Solids,
Liquids and Gases," Chap. 3, J o h n Wiley & Sons,
Inc., New York (1934).
15. J. D. Donaldson, Prog. Inorg. Chem., 8, 287 (1967).
16. J. D. Donaldson and W. Moser, J. Chem. Soc, 117,
835 (1961).
17. W. Goldie, Plating, 51, 1069 (1964).
18. R. Sard and R. Weil, To be published in Electro-
chim. Acta. P a p e r presented at C.I.T.C.E. Meet-
ing, Detroit, 1968.
19. E. M. Hofer and H. E H i n t e r m a n n , This Journal,
112, 167 (1965).
20. See, for example, D. W. Pashley, Advanc. Phys.,
14, 827 (1965).
21. I. A. Bergstrom, U. S. Pat. 2,702,253.
22. E. B. Saubestre, Proc. AES., 46, 264 (1959).
23. Y. Okinaka, P a p e r in preparation.
24. W. Goldie, op. cit., p. 50.

Electrochemical Method to Measure

the Copper Ionic Diffusivity in a Copper Sulfide Scale
A. Etienne
Department of Metallurgy, University of British Columbia, Vancouver, British Columbia

ABSTRACT
Copper sulfides have been grown on a copper anode from an acidic solu-
tion saturated with H2S u n d e r a constant current. A theoretical model for the
scale growth has been derived for steady-state conditions. F r o m the set of
e x p e r i m e n t a l data, the cuprous ionic diffusivity of chalcocite and digenite
in the scale have been calculated in the range of t e m p e r a t u r e from 30 ~ to
73~ The measured diffusion coefficient of cuprous ion in low chalcocite was
found to be
Dcu+ = 8.1 • 10 -8 exp ( 5870
T ) (cm2sec-1)

and in low digenite

(6100)
Dc.+ = 3.6 • 10-~ exp (cm2 sec-~)
T
The calculation of the activation e n t r o p y for diffusion in both phases is a t -
tempted.

Copper sulfides can be grown on a copper anode flects the conditions imposed on the system and the
from an acidic solution saturated with H2S. If the transport properties of the scale being built. The sul-
operation is conducted at constant current, different fide activity is t a k e n as unity. I n defined geometric
sulfide layers of decreasing copper activity are built and stirring conditions, u n d e r a constant current, the
as the oxidation proceeds. If e q u i l i b r i u m is established, hydrogen sulfide and hydrogen ion activities are con-
the successive phases should be, according to the phase stant in the vicinity of the electrode. I n steady-state
d i a g r a m (1) (Fig. 1): copper, chalcocite, djurleite conditions, the activation overvoltage for a given sul-
digenite, covellite, a n d sulfur. The reaction occurring fide is a constant. Therefore, the electrode potential
at the anode is variation with time follows the evolution of the copper
activity according to the relationship [2] derived
yCu + H2S -> CuyS -~ 2H + + 2e from [1].
The electrochemical potential of such an electrode dE RT d
(Stockholm convention) is given by the following re- In Acu ~
lationship dt 2F dt
RT Acu~ AH2S dE RT d
E = Eo -- - - l n + Ea [1] = -- y - - In Acu if y = constant [2]
2F Acu~s AH+ 2 - -

dt 2F dt
The copper activity at the solid-liquid interface re- If the sulfide scale grows u n i f o r m l y on the electrode
K e y words: copper sulfides, diffusion coefficient, anodic film. surface, the copper activity at the liquid-solid i n t e r -

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