Vol. 130, No.

4 THERMODYNAMICS OF AQUEOUS SULFUR 869

REFERENCES 7. D. J. Turner, in "Thermodynamics of Aqueous Sys-

1. "Water Chemistry of Nuclear Reactor Systems 2,"
British Nuclear Energy Society, London (1981).
2. R. J. Biernat and R. G. Robins, Electrochim. Acta,
14, 809 C1969).
3. J. W. Cobble, R. C. Murray, Jr., P. J. Turner, and
K. Chen, "High Temperature Thermodynamic
Data for Species in Aqueous Solution," EPRI Re-
port NP 2400, Electric Power Research Institute,
Pals Alto, CA (May 1982).
4. D. D. Wagman, W. H. Evans, V. B. Parker, I.
"Halow, S. M. Bailey, and R. H. Schumm, "Se-
lected Values of Chemical Thermodynamic Prop-
erties," NBS Technical Note 270-3, U.S. Dept. of
Commerce, Washington, DC (1968).
5. Revision to Ref. 4 in Appendix of NBS Technical
Note 270-8, 1981.
6. R. C. Murray and J. W. Cobble, in "Proceedings of
the 41st International Water Conference," p. 295,
Pittsburgh, Pennsylvania (1980).
tems with Industrial Applications," S. A. New-
man, Editor, pp. 653-679, ACS Symposium Series
133, American Chemical Society, Washington,
DC (1980).
8. JANAF Thermochemical Tables, National Bureau
of Standards, NSRDS-NBS 37, U.S. Govt. Print-
ing Office, Washington, DC (1971).
9. M. Pourbaix, "Atlas Of Electrochemical Equilibria
in Aqueous Solutions," "Sulfur," Section 19.2,
National Association of Corrosion Engineers,
Houston, TX (1974).
10. W. M. Latimer, "The Oxidation States of the Ele-
ments and their Potentials in Aqueous Solution,"
2nd ed., Prentice-Hall, Inc., Englewood Cliffs,
NJ (1952).
11. A. J. Ellis and W. Giggenbach, Geochim. et Cosmo-
chim. Acta, 35, 247 (1971).
12. W. Giggenbach, Inorg. Chem., 13, 1724 (1974).

Electrodeposition of Conducting Transition Metal Oxide/Hydroxide

Films from Aqueous Solution
Dennis Tench and Leslie F. Warren
Rockwell International, Microelectronics Research and Development Center, Thousand Oaks, California 91360

Metal oxide/hydroxide films formed by electrochem- The current then increases on each cycle as new Ni ~+
ical or chemical growth on the corresponding metal is oxidized and deposited, and the oxide deposit is
electrode have been investigated extensively. Many of cycled between NiO (OH) and Ni (OH) 2
these oxy-hydroxides are of considerable practical in- Nickel oxy-hydroxide films prepared by this poten-
terest because of their charge storage capabilities tial cycling technique appear to be uniform and smooth,
(Ni, Mn), electrochromic activity (Ni, Rh, Ir), electro- are electrically conducting, and exhibit electrochromic
catalytic properties (Ru), and photoelectrochemical properties, rapidly turning from transparent to dark
activity (Cu, Ni, Fe), A simple method for the con- brown at well-defined potentials. Figure 2 shows a
trolled application of such films onto substrates other linear plot of film thickness, measured by ellipsometry,
than the metals themselves (e.g., onto semiconductors) vs. the integrated peak charge. Approximate calcula:
does not appear to have been developed. We report tions of the film thickness based on the voltammetry
here our preliminary results describing a general tech- peak charge (Fig. 1), assuming a cubic lattice and Ni-O
nique for the electrochemical deposition of oxide/ bond distance of 4.2A, gave comparable numbers to
hydroxide films of copper, nickel, cobalt, iron, and those derived from the ellipsometry measurements.
manganese from aqueous solution. The general prop- Electrochemically, the electrodeposited films resemble
erties of these materials, some of which are new, are
also discussed.
Films were typically deposited on a 0.5 cm~ rotat- I I I
•ng platinum disk electrode (400 rpm), either by
g
voltage cycling (50 mV/sec) or at constant electrode -0,6
potential from buffered solutions (pH 6.5-7.5). A s o -
d i u m acetate buffer was used since, at the metal ion
concentrations employed (0.10-0.25M), other common -0.4
buffering agents either precipitate the metal hydroxide
or strongly complex the metal ion (increase the over-
I
potential for deposition). All potentials are given rela- ~'E -0.2
1,2 /
tive to the saturated calomel electrode (SCE). <
E
Figure 1 shows voltarnmograms associated with
o
nickel oxy-hydroxide deposition. On the first anodic
sweep (dashed line), only a slowly increasing anodic
current is evident. On each subsequent cycle, beginning ~ +0.2
at the positive limit, corresponding reduction and oxi-
dation peaks, for which the associated (equivalent)
charge increases with each cycle, were observed. The O
+0.4
cathodic/anodic peaks correspond to reduction/oxida-
tion of the nickel oxy-hydroxide film, which is de-
posited by oxidation of Ni 2+ to Ni 8+ and precipitates +0.6

On the electrode surface, presumably as NiO (OH). Al-

though the equations are not balanced, the overall re- +0.8
action can be schematically represented a s
i
+1,0 I r I r
Ni2+ Ni 3+ ------> NiO (OH) Ni(OH)2 +1.2 +1.0 +0.8 +0,6 +0.4 +0.2
ELECTRODE POTENTIAL (V vs SCE)
~e~
[I1 Fig. 1. Cyclic voltammograms (50 mV/sec) for a rotating Pt disk
Key words: metal oxides/hydroxides, electrodeposition PrOced-
electrode (400 rpm) in an aqueous solution containing 0.13M
ures, electrochemical properties. NiSO4, 0.1M Na2SO4, and 0.13M sodium acetate (pH 7.1).
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 870 J. Eleetrochem. Soe.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY Apri[ 1983

a i ! t

140
r t
120 ~-
-4
-1
-2
~ 1110

so

i ~
v
'7 60
~2
g
40
4

20 9

6 ~ ~l --

0,4 0.8 1.2 1.6

INTEGRATED PEAK CHARGE (mC)

Fig. 2. Plot of the thickness of electrodeposited nickel oxy- _______A__L l [ I ~

hydroxide films measured by ellipsometry
area (form Fig. i1.
the thick anodic hydrous oxide films grown on nickel
electrodes in neutral or basic electrolytes (1), rather
than the passive film (2). Films having similar elec-
trochemical properties have been prepared by cathodic
deposition from aqueous nickel nitrate solutions (3-5),
where nitrate reduction to form hydroxide seems to be
involved. The structures of nickel oxy-hydroxides have
been previously investigated (3, 4, 6).
The good electrical conductivity of the nickel oxy-
hydroxide films prepared by anodic' electrodeposition
is evident from the voltammograms in Fig. 3. Note that,
in this basic electrolyte, the redox properties of the
film, as reflected in the general shape of the voltam-
mograms, changes somewhat with potential cycling
(4). The current waves corresponding to ferri-ferro-
cyanide reduction/oxidation on the oxkie-covered elec-
trode in this system (onset at 0.1V) are virtually
identical to those observed for the bare platinum
electrode.
Other oxide/hydroxide films prepared by electro-
deposition from acetate-buffered solutions and the
deposition conditions are listed in Table 1. At a poten-
tial of 1.1V, manganese oxy-hydroxide can also be de-
posited from acidic electrolytes (0.2M H2SO4). It should
be noted that manganese oxide for use in dry batteries
has been prepared by anodic deposition for some time
(7, 8), but the deposition potential at higher pH with
the acetate buffer is considerably lower. Passivating
Table I. Deposition conditions for metal oxide/hydroxide films
+ 0.6 + 0.4 + 0,2 0.0 -0.2
vs. the integrated peak
ELECTRODE POTENTIAL (V vs SCE)
Fig. 3. Cyclic voltammograms at 50 mV/sec for a stationary
electrodeposited nickel oxy-hydroxide film (100A) on Pt in 0.1M
NaOH with (solid curve) and without (dashed curve) added ferro-
cyanide (0.01M).
iron oxy-hydroxide films prepared anodically from
Fe 2+ solutions have also been described previously (9).
Film thicknesses reported below were derived from
calculations similar to those used for nickel oxy-hy-
droxide films.
Copper oxide films deposited cathodically at con-
stant Potential under the conditions given in Table I
are orange and can be grown to a nominal thickness
of about 5000A; above this limit, the deposition current
rapidly decays. The film structure was investigated by
x-ray diffraction which yielded a sharp peak corre-
sponding to a lattice spacing of 2.468 nm and two
smaller peaks (2.137 and 1.510 nm), suggesting a struc-
ture of Cu20 with a preferred orientation. The deposi-
tion process probably involves reduction of Cu 2+ in
solution and dehydration of the deposited oxide, which
can be represented schematically as
+e- --H20
Cu 2+ ) CuOH ) Cu20 [2]
OH-
Consistent with other work (10), these films were
found to undergo oxidation/reduction and to gradually

Probable film
Metal Solution c o m p o s i t i o n pH Electrodeposition conditions composition

Ni 0.13M NiSO4 9 6H~O 7.14 P o t e n t i a l c y c l e d b e t w e e n +0.3 a n d Ni(OH)~/NiO(OH)

0.13M N a O A c + 1.1V a t 50 m V / s e c ; a n o d i c d e p o s i .
0.1OM Na2SO, tion
Cu 0.1M C u ( O A c ) 9 . 2 H ~ O 6.45 C o n s t a n t potential at 0.0V; cathodic Cu=O
O.8M N a O A c deposition
(Nitrogen saturated)
Co 0.1M CoSO, 9 6I-LO 7.52 Constant potential at 1.0V; anodic H y d r o u s CoO= ( z < 2)
0.1M N a O A c deposition
0.1M Na2SO4
Fo 0.1M F e ( N H D ~ ( S O D ~ 9 6H~O 6.80 C o n s t a n t potential at -0.1V; anodie Hydrous FeOz ( z < 1.5)
0.2M N a O A c deposition
9.1M N a ~ O ,
(Nitrogen saturated)
Mn 0.1M M n ( O A c ) ~ 9 4H=O 7.50 C o n s t a n t potential at +0.4V; anodic Hydrous MnO= ( x < 2)
0.1M NaaSO4 deposition

Where A c = acetate.
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 VoL 130, No. 4 TRANSITION" METAL OXIDE F I L M S 871
dissolve during potential cycling in aqueous solutions. r r--T--l---.-
However, electrodeposited copper oxide films appear
to be stable in acetonitrile electrolytes, where oxida-
tion/reduction of the film itself is not observed, but
the ferrocene/ferricenium redox reaction (E ~ =
+0.4V) occurs reversibly on the film-covered elec-
trode. /'-%\
Under illumination, electrodeposited copper oxide

!,,%,,..1__.\
_i I
films exhibit p-type semiconducting behavior. The
electrolyte used to demonstrate this effect was the
acetonitrile-phthalonitrile (o-C6H4 (CN) ~) system util- i
ized with p-type Cu20 by Nagasubramanian, et al,
(10). Figure 4 shows the current-potential character-
istics of the film-covered electrode under illumination E
with chopped light (tungsten-halogen lamp, 80 roW/
cm2). Note that photocurrents in the 100 ~A/cm2 range
were observed, a remarkable result considering the 6
unoptimized nature of these as-formed films. The p- ! ./ / N
~
~ WITH ADDED
FERROCYANIDE
type behavior observed for the electrodeposited mate- +2
rial substantiates the assignment of Cu20 as its struc-
ture.
Cobalt oxy-hydroxide films anodically deposited at
constant potential under the conditions given in Table I +3

are deep yellow (thinner films exhibit interference

colors) and appear to have high electrical conductivity.
Black films approaching a nominal thickness of 1 #m
can be deposited with no observable decay in the depo-
sition current. Deposits formed at +0.8V appear to be + 0.6 + 0.4 + 0.2 0.0
much less conducting, which suggests that a Co (IV) ELECTRODE POTENTIAL (V vs SCE)
species may be responsible for the high conductivity of
films deposited at more positive potentials (11). X-ray Fig. 5. Cyclic voltammograms at 50 mV/sec for a stationary
diffraction studies indicated that such films are amor- electrodeposited cobalt oxy-hydroxide film (600A.) OR Pt in 0.1M
phous. As shown by the voltammograms in Fig. 5, in NaOH, with (solid curve) and without (dashed curve) added terra-
the presence of ferrocyanide, reversible Fe (CN)6 ~-/4- cyanide (0.0]M).
redox waves are superimposed on the voltammetric
features corresponding to oxidation/reduction of the thicknesses approaching the 1 ~m range. X - r a y diffrac-
cobalt oxy-hydroxide film in alkaline solution. The tion studies indicated an amorphous film structure.
voltammograms shown are stable, but slow changes are Under potential cycling, these films slowly di.~solve in
observed for sweeps to more negative potentials. acidic or basic electrolytes, but are apparently stable
Iron o x y - h y d r o x i d e films anodically deposited at in neutral 0.1M Na2SO4 (pH 7.5) at potentials between
constant potential under the conditions given in Table +1.0 and 0.0V. Figure 6 shows voltammograms ob-
I are pale yellow and can be grown to a nominal thick-
ness of ,-, 300A, above which the deposition current de- I 1 I I I I
cays. On films below this apparent limiting thickness,
the ferro-ferricyanide reaction proceeds reversibly,
whereas thicker films appear to be insulating. Stable -1.5
voltammograms with potential cycling between +0.6
and --0.8V were obtained for thinner films in 0.1M
NaOH. No photoresponse was observed for electrode-
posited iron oxy-hydroxide in any of various electro- -1.0

lytes tested. The film thickness was apparently too

small to permit determination of the structure by
x-ray diffraction. -0.5
Like cobalt oxy-hydroxide, manganese oxy-hydrox-
ide films (orange) anodically deposited under the con- E
< /
ditions given in Table I are highly conducting, as I
I
I
evidenced by the stable deposition currents at film Z~ 0.0
!
I
/
I 6
+ 0.5

-- -150
%
~z + 1.0
-lOO WITH ADDED
FER ROCYANIDE

~ -so
o +1.5

J ox
/ i I i + 1.0 + 0.8 + 0.6 + 0.4 + 0,2 0.0
0.0 -0.5 -1.0 -1,5
ELECTRODEPOTENTIAL(V vsSCE) ELECTRODE POTENTIAL (V vs SCE)

Fig. 4. Voltammetric behavior at 50 mV/sec of a stationary Fig. 6. Cyclic voltammograms at 50 mV/sec for a stationary
electrodeposited copper oxide film (5000A.)on p!atinum under electrodeposited manganese oxy-hydroxide film (600A) OR Pt in
illumination with chopped light (80 mW/cm 2) in acetonitrile so- 0.1M Na2S04, with (solid curve) and without (dashed curve)
lutio, containing 0.|M phthalonitrile and 0.1M NaCIO4. added ferrocyanide (0.01M).
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 872 J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
tained for m a n g a n e s e o x y - h y d r o x i d e films in the l a t t e r
electrolyte, w i t h and w i t h o u t a d d e d f e r r o c y a n i d e ion.
The good conductivity of the film is also evident from
t h e reversible Fe (CN) ~ - / 4 - r e d o x wave.
In conclusion, thin u n i f o r m m e t a l o x i d e / h y d r o x i d e
films of copper, nickel, cobalt, iron, and m a n g a n e s e can
b e electrodeposited onto conducting substrates from
acetate-buffered aqueous solutions. The a s - f o r m e d
copper oxide films exhibit p - t y p e photoactivity. In most
cases, the o t h e r electrodeposited o x i d e / h y d r o x i d e films
are e l e c t r i c a l l y conducting, especially those of m a n g a -
n e s e a n d cobalt. The nickel o x y - h y d r o x i d e exhibits
electrochromic behavior.
Acknow:ledgment
The authors g r a t e f u l l y a c k n o w l e d g e s u p p o r t of this
w o r k b y the S o l a r E n e r g y R e s e a r c h I n s t i t u t e u n d e r
S u b c o n t r a c t No. XG-O-9276.
M a n u s c r i p t s u b m i t t e d Aug. 23, 1982; revised m a n u -
script received ca. Dec. 7, 1982.
A n y discussion of this p a p e r will a p p e a r in a Dis-
cussion Section to be p u b l i s h e d in the D e c e m b e r 1983
JOURNAL. A l l discussions for the D e c e m b e r 1983 Dis-
cussion Section should be s u b m i t t e d b y Aug. 1, 1983.
Tin(IV)-Based PhotoselectiveMetal Deposition of Cobalt and Nickel
from Alkaline Baths
I. Kiflawi*
Precision Electronic Components Limited, Toronto, Ontario Canada M6M 2V6
and M. Schlesinger*
Department of Physics, University of Windsor, Windsor, Ontario Canada N9B 3P4
The electroless m e t h o d for thin m e t a l film deposition
continues to m a i n t a i n and even to e x p a n d its i m p o r -
t a n t role in m a n y i n d u s t r i a l applications. The physics
and c h e m i s t r y of the processes involved, however, still
elude e x a c t explanations. Of the aspects t h a t on the
one h a n d are easily e x p l o i t a b l e but on the other are
difficult to f u l l y u n d e r s t a n d is photoselective deposi-
tion. In a series of publications (1, 2, 3) from our r e -
search group in W i n d s o r w e showed that aged Sn (IV)
chloride solution can serve as a sensitizer for electro-
less copper p l a t i n g and for nickel p l a t i n g from an
acidic bath. F o r nickel (or cobalt) p l a t i n g from an
a l k a l i n e b a t h it was o b s e r v e d that an additional r e -
ducing b a t h is n e c e s s a r y b e t w e e n the activation step
and the last rinse.
U l t r a v i o l e t i r r a d i a t i o n of the s u b s t r a t e after S n ( I V )
sensitization and P d (II) a c t i v a t i o n was shown to have
a m a r k e d effect on subsequent m e t a l plating. In a
copper b a t h p l a t i n g was f o u n d to occur only on the
i r r a d i a t e d surface p r o d u c i n g a sharp n e g a t i v e image of
the photomask. In an acidic n i c k e l bath p l a t i n g was
o b s e r v e d to occur only on the n o n i r r a d i a t e d surface
p r o d u c i n g a s h a r p positive image. It was found pos-
sible to achieve a positive i m a g e of the p h o t o m a s k
using a n a l k a l i n e nickel (cobalt) b a t h if u l t r a v i o l e t
was a p p l i e d before the reducing bath.
The p u r p o s e of the p r e s e n t p a p e r is twofold. F i r s t
we r e p o r t t h a t the production of a n e g a t i v e p h o t o -
i m a g e using a l k a l i n e nickel or cobalt m e t a l l i z i n g baths
is also possible. Second, we a t t e m p t to f u r t h e r clarify
possible mechanisms for the influence of u l t r a v i o l e t
i r r a d i a t i o n on subsequent m e t a l deposition.
* Electrochemical Society Active Member.
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April 1983
Publication costs of this article wer.e assisted by
Rockwell Intern(~tional.
REFERENCES
1. B. MacDougall and M. J. G r a h a m , This Journal,
128, 2321 (1981).
2. S. M. W i l h e l m and N. H a c k e r m a n , ibid., 128, 1668
(1981).
3. J. L. Ord, Sur]. Sci., 56, 413 (1976).
4. L. D. B u r k e and T. A. M. Twomey, J. Electroanal.
Chem., 134, 353 (1982).
5. S. H. G l a r u m and J. H. Marshall, This Journal, 129,
535 (1982).
6. R. E. Carbonio, V. A. Macagno, M. C. Giordano, J. R.
Vilche, and A. J. Arvia, J. Appl. Electrochem., 12,
121 (1982).
7. C. C. Liang, in "Encyclopedia of E l e c t r o c h e m i s t r y
of the Elements," Vol. I, A. Bard, Editor, p. 349,
Marcel Dekker, N e w York (1973).
8. E. Barchese, H. C. Chagas, and S. Wolynec, An.
Acad. Brasil. Ci~nc., 53, 309 (1981).
9. M. Cohen, D. Mitchell, and K. Hashimoto, This
Journal, 126, 442 (1979).
10. G. N a g a s u b r a m a n i a n , A. S. Gioda, and A. J. Bard,
ibid., 128, 2158 (1981).
11. L. D. Burke. M. E. Lyons, a n d O. J. Murphy, J. Elec-
troanal. Chem., 132, 247 (1982).
Experimental
All chemicals were ACS r e a g e n t g r a d e s u p p l i e d b y
F i s h e r or Canlab and were used without f u r t h e r p u r i -
fication.
Sensitizer.--The stock solution we used was m a d e
by dissolving 10g SnCI~-5H20 in 12.5 ml concen-
trated HCI. To prepare a sensitizer bath 2.5 ml of this
stock solution was diluted to 200 ml using distilled
water.
A g i n g of the sensitizer solution w a s m o n i t o r e d using
optical absorption. W h e n the optical density r e a c h e d
D ---- 0.I cm -1 at ~. : 5200A the aging process was com-
plete and the p e r f o r m a n c e q u a l i t y of the solution was
at its best ( u s u a l l y after about 24 h r ) . It was possible
to m a i n t a i n good p e r f o r m a n c e for periods of a few
months b y p e r i o d i c a l l y adding HC1 o r w a t e r as n e e d e d
to m a i n t a i n the optical d e n s i t y at its stated value.
Activator.--To l g PdC12 we a d d e d 1 ml c o n c e n t r a t e d
HC1 a n d I0 mI H20. A f t e r complete dissolution we
diluted 1 ml of the above in 50 m l of H~O. This was
the stock solution. A n y of the following 3 activators
w o r k e q u a l l y well. They differ o n l y in the ensuing
deposition rate.
deposition rate of No. 1 < deposition r a t e of No. 2
< deposition r a t e of No. 3
A c t i v a t o r b a t h No. 1 : 5 ml stock + 95 ml H20
A c t i v a t o r b a t h No. 2 : 1 0 ml stock + 90 m l H20
A c t i v a t o r b a t h No. 3 : 1 5 m l stock 4- 85 ml H20.
Alkaline nickel and cobalt baths.--The composition
o f these are given in Table I. The m e t a l l i z i n g b a t h s