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ALLOYS
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Journal of Alloys and Compounds 237 (1996) 1-5

Growth of cerium(IV) oxide films by the electrochemical generation

of base method
Y a n c h u n Z h o u a, J a y A . S w i t z e r b
alnstitute of Metal Research, Academia Sinica, 72 # Wenhua Road, 110015 Shenyang, China
bGraduate Center for Materials Research, University of Missouri-Rolla, Rolla, MO 65401-0249, USA
Received 1 July 1995; in final form 18 August 1995

Abstract

Cerium(IV) oxide films were deposited electrochemically on 430 stainless steel and (100)-oriented highly doped degenerate
p-type single-crystal silicon in aqueous solution by the electrogeneration of base method. The as-prepared films were
characterized by X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The results demonstrated that
the as-deposited material was faceted cerium oxide with the fluorite structure. Grain size of the film was found to increase from
6 to 16 nm when the bath temperature varied from 26 to 80 C, but to decrease from 18 to 6 nm when the applied current
density increased from 0.5 to 3.0 mAcm 72. The films were observed to have no preferred orientation.
Keyword,:: Cerium oxide; Thin films; Electrochemical deposition

1. Introduction

Cerium oxide is a promising material that has

potential use as a solid oxide fuel cell electrolyte [1,2].
It can also be used as promoter of automotive exhaust
catalysts because it possesses an excellent high oxygen
storage capacity [3,4]. Recent work has shown that
cerium oxide films with ultrafine grain size can greatly
improve the resistance of metals and alloys to high
temperature oxidation [5]. Thus, low cost methods for
making cerium oxide need to be developed.
Several ways have so far been used to make cerium
oxide films, including vapour deposition processes, i.e.
reactive sputtering [6], electrochemical vapour deposition [7], and the aqueous precipitation method, i.e.
sol-gel [8] and spin coating [9]. Electrodeposition in
aqueous solution has recently been recognized as an
attractive method for making thin oxide ceramic films
[10] because it offers the advantages of low temperature processing, low cost, and high purity [11,12]. In
addition, the structure and phase composition of the
electrodeposited oxide ceramic films can be easily
controlled by adjusting the electrochemical parameters
because the driving force for the reaction is precisely
known In the electrochemical synthesis of oxide
ceramics, both anodic (redox change) and cathodic
0925-8388/96/$15.00 1996 Elsevier Science S.A. All rights reserved
SSDI 0925-8388(95)02048-9

methods can be employed. In the redox change method, a metal ion or complex is oxidized at the electrode
surface, the pH of the solution is adjusted so that the
initial oxidation state is stable, and then the higher
oxidation state undergoes hydrolysis to a metal hydroxide or oxide. We have used the redox change
method to grow nanoscale ceramic superlattices in the
T I - P b - O system [13,14] and defect chemistry TI203
superlattices [15]. In the cathodic generation of base
method, base is formed at an electrode surface by a
cathodic process and metal ions or complexes are then
hydrolysed by the electrogenerated base. We have
used the cathodic electrogeneration of base method to
synthesize nanoscale ZrO 2 [16] and CeO 2 powders
with high sintering ability [17]. Since the electrochemical reactions produce hydroxide ion and hydrogen gas
by the reduction of water, at similar experimental
conditions the morphology of C e O 2 formed at the
electrode surface depends on the applied current
density, i.e. CeO 2 films can be formed at low current
density and CeO 2 powders can be produced at high
current density. In the present paper, we report, for
the first time, the synthesis of CeO 2 films using
the electrogeneration of base method. The microstructural features of the CeO 2 films are also
presented.

Y. Zhou, J.A. Switzer / Journal of Alloys and Compounds 237 (1996) 1-5

2. Experimental details

10.

In this work, CeO 2 films were produced by the

cathodic electrogeneration of base method, in which a
cathodic current was used to generate base at an
electrode surface and metal ions or complexes are
then hydrolysed by the electrogenerated base. The
starting materials for the preparation of CeO 2 films
were cerium(III) nitrate hexahydrate, Ce(NO3) 3.
6H20 (99.9%), and ammonium nitrate (99.999%),
both from Aldrich Chemical Company Inc., Milwaukee, WI, USA. The nanoscale CeO 2 films were
prepared in the cathode compartment of a divided
electrochemical cell. The anode, which acts as a
counterelectrode, was a platinum mesh. The cathode,
which acts as the working electrode, was a 430 stainless steel disk, or (100)-oriented highly doped degenerate p-type single-crystal silicon. The cathode compartment in the divided cell contained 0.1M
cerium(III) nitrate and 0.l M ammonium nitrate, and
the anode compartment contained 0.1 M of ammonium nitrate. The two compartments were separated
by a medium porosity glass frit. Since high current
density would favour the production of powders, CeO 2
films were formed at current densities ranging from 0.5
to 4.0 mA cm -2. The bath temperature was adjusted
from room temperature (26 C) to 80 C. The deposits
were dried for 24 h in air at room temperature.
The nanoscale CeO 2 films were characterized by
X-ray diffraction (XRD), scanning electron microscopy, and atomic force microscopy (AFM). XRD
patterns were obtained with a Scintag 2000 diffractometer using CuKet radiation at a scan rate in 2 0 of
2 min-l. The crystallite sizes were estimated from the
line broadening of the (111) peak obtained using a
scan rate in 2 0 of 0.5 min -1. The crystallite size D
was calculated from the Scherrer equation:
D = 0.9Mfl cos O

(1)

where a is the wavelength of the X-rays, O is the

diffraction angle, and fl is the corrected full width, at
half-maximum of the peak given by
fl =f12m - f l ~

(2)

where tim is the measured half-width, and fls is the

half-width of a standard CeO 2 sample with a grain size
larger than 1 ixm. The microstructural features of
CeO z films were observed in a JSM-T310A scanning
electron microscope and in a Nanoscope II scanning
tunnelling microscope (Digital, Santa Barbara, CA)
fitted with AFM equipment.

3. Results and discussion

Fig. 1 shows the pH change of the solution as a

function of charge passed during the electrochemical

9.

8.
jIu

7:

7.

III

6.

5.

1'000

2000

3000

4000

5000

6000

Coulombs
Fig. 1. Change in pH as a function of charge passed during
electrochemical growth of CeO2 films.
synthesis. The starting pH of the solution was 4.5. In
the initial stage of electrochemical synthesis, the pH of
the solution increased rapidly to a value of about 7.3,
and the precipitated product appeared on the electrode surface. The pH value remained between 7.3 and
7.8 until a charge of 3000 C was passed and began to
drop to a value of 4.2, after which no precipitated
product was observed although the cathodic reduction
continues. Similar phenomena were observed in the
previous work by Chen et al. [8] where they made
ultrafine CeO 2 powders by adding hexamethylenetetramine to Ce(NO3) 3 solution. They attributed the
drop in pH to the formation of H3 O+ by the following
reaction:
Ce(H20)x(OH)(y4-y)+ + H20--+ CeO2 n H 2 0 + H3 O+

(3)
We must emphasize that we are generating Ce(IV)
oxide starting with Ce(III) in solution and using an
electrochemical reduction reaction. The mechanism
for the oxidation of Ce 3+ to Ce 4+ is not understood.
Chen et al. [8] demonstrated that Ce 3 oxidized to
Ce 4+ in the initial stage of synthesis where the pH of
the solution increased rapidly. The Ce 4+ ions underwent strong hydration and were in the form of
C e ( H 2 0 ) x ( O H ) ~ 4-y)+. After the oxidation of C e 3+
ions finished, the precipitation of CeO2" n i l 2 0 began.
In our present work, the electrochemical reaction
produces a high concentration of hydroxide ion at the
surface of the electrode by the reduction of water to
hydrogen gas. The surface pH is a strong function of
the applied cathodic current, and it is certainly much
higher than the pH which we measure for the solution.
As the pH of the solution dropped to 4.2, the rate of
CeO 2 formation is too low to be taken account of. In

Y. Zhou, J.A. Switzer / Journal of Alloys and Compounds 237 (1996) 1-5

our previous paper [17], we assumed that the Ce(III)

ions in the solutions were hydrolysed by the electrogenerated base to form colloidal particles of
Ce(III) hydroxide or hydrous oxide. This colloidal
material was possibly oxidized to Ce(IV) oxide during
the drying process. However, neither Chen et al. [8]
nor our work [17] gave a satisfying explanation of the
complex change in pH. It is apparent that more
investigation of the precise chemistry is helpful in
understanding mechanisms of formation of CeO 2 films
by the electrochemical generation of base method.
The films deposited by the cathodic electrogeneration of base method were identified by XRD to be
cerium oxide with the cubic fluorite structure. No trace
of cerium(III) oxide was detected by X R D analysis.
Fig. 2 shows the XRD pattern of a CeO 2 film deposited on a 430 stainless steel substrate using a
current density of 0.5 mA cm -2. The lattice parameter
was 0.5419 nm. We would like to emphasize that no
subsequent heat treatment was used to induce crystallinity in the electrochemically produced cerium
oxide film. The effect of the current density on the
composition and grain size of the deposits was also
investigated. Fig. 3(a) shows the X R D patterns of
CeO 2 films deposited on stainless steel substrate using
different current densities. It shows that the full width
at half-maximum of the (111) CeO 2 peaks increases
with the increase in the applied current density. It also
shows lhat the intensity of the (111) CeO 2 peaks
decreases with the increase in the applied current
density, indicating that the crystallite size of the
deposits decreased with the increase in current density. Fig. 3(b) summarizes the crystallite size data

(ltl)

(220)
ss(llO) I

~ 11
30

40

(311)

11t

1[ It

]1(222)
50

60

(400)

.(420)[

70

80

(422)
90

2
Fig. 2. X R D pattern of CeO 2 film deposited on stainless steel
substrate using a current density of 0.5 m A c m 2 (ss, stainless steel).

(a)

26

(b)

~~ ~1)

28

30

32

34

20

20.
18.

E
o~q

16.
14.
12108

015

110

115

210

215

310

Current Density ( m A / c m 2)
Fig. 3. (a) X R D patterns of CeO 2 film deposited on stainless steel
substrate at different current densities. (b) Effect of current density
on the crystallite size of CeO 2 films.

obtained from the line broadening analysis of the

(111) peak in the XRD patterns as a function of
current density. It was assumed that the line broadening was caused entirely by particle size. No attempt
was made to consider the effect of strain or disorder
on the line broadening. Fig. 3(b) shows that the
crystallite size decrease from 18 nm in the film deposited at a current density of 0.5 mA cm -2 to 6 nm in
the film deposited at a current density of 3.0 mA cm -2.
The systematic dependence of the crystallite size on
the current density has been observed in another
system [18] and can be attributed to the fact that the
number of the nuclei changes with the current density
[18]. In the initial stage of deposition, the nucleation
and the growth of nuclei compete with each other. In
the case of high current density, the generation reaction rate is high, and the rate of nucleation exceeds
that of growth of nuclei, while, in the case of low
current density, the rate of growth of nuclei predominates [18]. As the individual nuclei grow, their diameters become equal to the average distance between the
nucleation sites and form a continuous film. Thus the
grain size in the films that are deposited at high
current densities is smaller than that in the films

Y. Zhou, J.A. Switzer / Journal of Alloys and Compounds 237 (1996) l - 5

deposited at low current densities. No structural

change of the deposits was detected by X R D analysis.
The effect of bath temperature on the crystallite size
of the CeO 2 films was also investigated. Fig. 4(a)
shows the X R D patterns of CeO 2 films deposited on
stainless steel at different bath temperatures. In all
experiments the current density was kept at
3.0 m A cm -2. We can see from Fig. 4(a) that, as the
bath temperature increases, the intensity of the (111)
CeO 2 peaks increases while the full width at halfmaximum of (111) CeO 2 peaks decreases. Fig. 4(b)
summarizes the crystallite size data obtained from the
line broadening analysis of the (111) CeO 2 peaks in
the X R D patterns as a function of bath temperature.
Again, no attempt was made to consider the effect of
strain or disorder on the line broadening. Fig. 4(b)

(111)

(a)

Fig. 5. AFM image of CeO2 film deposited on (100)-oriented highly

doped degenerate p-type silicon.

A /

(200)
80C

26

28

30

32

34

20
(b)

18
1614-

12-

*"

10"

8"

shows that the crystallite size increased from 6 nm in

the film that was made at room temperature (26 C) to
16 nm in the film that was deposited at 80 C. We
attribute the dependence of crystallite size on the bath
temperature to the fact that the base generation
reaction rate is constant in all runs (since the cathodic
current density is the same), while the rates of the
subsequent hydrolysis, condensation, and crystallization reactions would all increase with increasing temperature.
The microstructure of the CeO 2 films was analysed
by scanning electron microscopy and AFM. The surfaces of the films are smooth and crack free. Fig. 5
shows the A F M image of a CeO 2 film deposited on
(100)-oriented highly doped degenerate p-type silicon.
The current density used was 0.5 m A cm -2. It reveals
that the CeO2 grains on the silicon surface have a
faceted polyhedral morphology with good connectivity, and grain sizes are uniform within the observed
region. Work is at present under way on the electrochemical deposition of doped cerium(IV) oxide films.

4. Concluding remarks

6"
36

40

56

66

70

86

Temperature(C)
Fig. 4. (a) XRD patterns of CeO2 films deposited at different bath
temperatures. (b) Effect of bath temperature on the crystallite size
of CeOz films.

Polycrystalline cerium(IV) oxide films were deposited electrochemically on 430 stainless steel and (100)oriented highly doped degenerate p-type single-crystal
silicon substrates in aqueous solution by the electrogeneration of base method without subsequent heat
treatment. The as-produced material was identified as

Y. Zhou, J.A. Switzer / Journal of Alloys and Compounds 237 (1996) 1-5

faceted cerium oxide with the cubic fluorite structure.

The crystallite size of the electrochemically deposited
CeO2 films can be controlled by changing the bath
temperature and/or current density. The grain size
increased from 6 to 16 nm when the bath temperature
varied from 26 to 80C, and decreased from 18 to
6 nm when the cathodic current density increased from
0.5 to 3.0 m A cm

-2

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