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," tems with Industrial Applications," S. A. New-
British Nuclear Energy Society, London (1981). man, Editor, pp. 653-679, ACS Symposium Series
2. R. J. Biernat and R. G. Robins, Electrochim. Acta, 133, American Chemical Society, Washington,
14, 809 C1969). DC (1980).
3. J. W. Cobble, R. C. Murray, Jr., P. J. Turner, and 8. JANAF Thermochemical Tables, National Bureau
K. Chen, "High Temperature Thermodynamic of Standards, NSRDS-NBS 37, U.S. Govt. Print-
Data for Species in Aqueous Solution," EPRI Re- ing Office, Washington, DC (1971).
port NP 2400, Electric Power Research Institute, 9. M. Pourbaix, "Atlas Of Electrochemical Equilibria
Pals Alto, CA (May 1982). in Aqueous Solutions," "Sulfur," Section 19.2,
4. D. D. Wagman, W. H. Evans, V. B. Parker, I. National Association of Corrosion Engineers,
"Halow, S. M. Bailey, and R. H. Schumm, "Se- Houston, TX (1974).
lected Values of Chemical Thermodynamic Prop- 10. W. M. Latimer, "The Oxidation States of the Ele-
erties," NBS Technical Note 270-3, U.S. Dept. of ments and their Potentials in Aqueous Solution,"
Commerce, Washington, DC (1968). 2nd ed., Prentice-Hall, Inc., Englewood Cliffs,
5. Revision to Ref. 4 in Appendix of NBS Technical NJ (1952).
Note 270-8, 1981.
6. R. C. Murray and J. W. Cobble, in "Proceedings of 11. A. J. Ellis and W. Giggenbach, Geochim. et Cosmo-
the 41st International Water Conference," p. 295, chim. Acta, 35, 247 (1971).
Pittsburgh, Pennsylvania (1980). 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).
Downloaded on 2014-05-08 to IP 221.5.4.203 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 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 ~

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

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.
Downloaded on 2014-05-08 to IP 221.5.4.203 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 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).
Downloaded on 2014-05-08 to IP 221.5.4.203 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 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 April 1983

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 Publication costs of this article wer.e assisted by
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. Rockwell Intern(~tional.
The good conductivity of the film is also evident from
t h e reversible Fe (CN) ~ - / 4 - r e d o x wave. REFERENCES
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 1. B. MacDougall and M. J. G r a h a m , This Journal,
films of copper, nickel, cobalt, iron, and m a n g a n e s e can 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
b e electrodeposited onto conducting substrates from (1981).
acetate-buffered aqueous solutions. The a s - f o r m e d 3. J. L. Ord, Sur]. Sci., 56, 413 (1976).
copper oxide films exhibit p - t y p e photoactivity. In most 4. L. D. B u r k e and T. A. M. Twomey, J. Electroanal.
cases, the o t h e r electrodeposited o x i d e / h y d r o x i d e films Chem., 134, 353 (1982).
are e l e c t r i c a l l y conducting, especially those of m a n g a - 5. S. H. G l a r u m and J. H. Marshall, This Journal, 129,
n e s e a n d cobalt. The nickel o x y - h y d r o x i d e exhibits 535 (1982).
electrochromic behavior. 6. R. E. Carbonio, V. A. Macagno, M. C. Giordano, J. R.
Vilche, and A. J. Arvia, J. Appl. Electrochem., 12,
Acknow:ledgment 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
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 of the Elements," Vol. I, A. Bard, Editor, p. 349,
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 Marcel Dekker, N e w York (1973).
S u b c o n t r a c t No. XG-O-9276. 8. E. Barchese, H. C. Chagas, and S. Wolynec, An.
Acad. Brasil. Ci~nc., 53, 309 (1981).
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 - 9. M. Cohen, D. Mitchell, and K. Hashimoto, This
script received ca. Dec. 7, 1982. Journal, 126, 442 (1979).
A n y discussion of this p a p e r will a p p e a r in a Dis- 10. G. N a g a s u b r a m a n i a n , A. S. Gioda, and A. J. Bard,
cussion Section to be p u b l i s h e d in the D e c e m b e r 1983 ibid., 128, 2158 (1981).
JOURNAL. A l l discussions for the D e c e m b e r 1983 Dis- 11. L. D. Burke. M. E. Lyons, a n d O. J. Murphy, J. Elec-
cussion Section should be s u b m i t t e d b y Aug. 1, 1983. troanal. Chem., 132, 247 (1982).

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 Experimental

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 - 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
t a n t role in m a n y i n d u s t r i a l applications. The physics
F i s h e r or Canlab and were used without f u r t h e r p u r i -
and c h e m i s t r y of the processes involved, however, still fication.
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 Sensitizer.--The stock solution we used was m a d e
difficult to f u l l y u n d e r s t a n d is photoselective deposi- by dissolving 10g SnCI~-5H20 in 12.5 ml concen-
tion. In a series of publications (1, 2, 3) from our r e - trated HCI. To prepare a sensitizer bath 2.5 ml of this
search group in W i n d s o r w e showed that aged Sn (IV) stock solution was diluted to 200 ml using distilled
chloride solution can serve as a sensitizer for electro- water.
less copper p l a t i n g and for nickel p l a t i n g from an A g i n g of the sensitizer solution w a s m o n i t o r e d using
acidic bath. F o r nickel (or cobalt) p l a t i n g from an optical absorption. W h e n the optical density r e a c h e d
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 - D ---- 0.I cm -1 at ~. : 5200A the aging process was com-
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 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
and the last rinse. at its best ( u s u a l l y after about 24 h r ) . It was possible
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 ) 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
sensitization and P d (II) a c t i v a t i o n was shown to have 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
a m a r k e d effect on subsequent m e t a l plating. In a to m a i n t a i n the optical d e n s i t y at its stated value.
copper b a t h p l a t i n g was f o u n d to occur only on the 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
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 HC1 a n d I0 mI H20. A f t e r complete dissolution we
the photomask. In an acidic n i c k e l bath p l a t i n g was diluted 1 ml of the above in 50 m l of H~O. This 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 the stock solution. A n y of the following 3 activators
p r o d u c i n g a s h a r p positive image. It was found pos- w o r k e q u a l l y well. They differ o n l y in the ensuing
sible to achieve a positive i m a g e of the p h o t o m a s k deposition rate.
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. deposition rate of No. 1 < deposition r a t e of No. 2
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 < deposition r a t e of No. 3
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 - A c t i v a t o r b a t h No. 1 : 5 ml stock + 95 ml H20
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 A c t i v a t o r b a t h No. 2 : 1 0 ml stock + 90 m l H20
possible mechanisms for the influence of u l t r a v i o l e t A c t i v a t o r b a t h No. 3 : 1 5 m l stock 4- 85 ml H20.
i r r a d i a t i o n on subsequent m e t a l deposition.
Alkaline nickel and cobalt baths.--The composition
* Electrochemical Society Active Member. 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

Downloaded on 2014-05-08 to IP 221.5.4.203 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).