Thermochimica Acta, 64 (1983) 259-265 259

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

SOME PHYSICO-CHEMICAL PROPERTIES OF PURE AND DOPED

NICKEL OXIDE. THERMAL ANALYSES AND X-RAY DIFFRACTION
STUDIES

Z.M. HANAFI, F.M. ISMAIL and S.M. ELOUI

Inorganic Chemistry Department, National Research Centre, Dokki, Cairo (Egypt)
(Received 2 November 1982)

ABSTRACT

In this investigation pure and doped NiO with different concentrations of AI, Ga or In are
thermally analysed. The results indicate the presence of two endothermic peaks at about 120
and 250°C which were attributed to the loss of adsorbed water and phase change, respec-
tively.
X-Ray data indicated that all samples belong to the cubic system. In the case of samples
doped with high concentrations of Ga or In, a new line is observed which may be due to the
formation of a spinel form. There is no systematic change between the calculated values of
lattice parameters, a, of doped samples and the type or concentration of dopant. This change
has been related to the difference in the values of the ionic radii of Ni 2+ and those of dopant
elements.

INTRODUCTION

The electronic properties of semiconductors can be modified by introduc-

ing v a r i o u s a d d i t i v e s into the p a r e n t lattice. Such m o d i f i c a t i o n s p l a y a
p r o m i n e n t role in the s t u d y o f several p r o p e r t i e s . N i c k e l o x i d e d o p e d with
m o n o v a l e n t e l e m e n t s h a s b e e n studied extensively. V e r y little w o r k c o n c e r n -
ing the g r o u p I I I A e l e m e n t s w a s f o u n d in the literature. T h r e e d o p a n t s were
c h o s e n , n a m e l y , A1, G a or I n in d i f f e r e n t c o n c e n t r a t i o n s .
T h e a i m w a s to o b t a i n s o m e i n f o r m a t i o n c o n c e r n i n g the influence o f
d o p a n t t y p e o n the t h e r m a l p r o p e r t i e s a n d s t r u c t u r e o f N i O .

EXPERIMENTAL

T h e d i f f e r e n t s a m p l e s o f nickel o x i d e were p r e p a r e d as described.

0040-6031/83/$03.00 © 1983 Elsevier Science Publishers B.V.

260

Undopedsamples
The method applied in the preparation of nickel oxide was devised by
Francois [1] where nickel carbonate was heated at 400, 550 and 1000°C for
3 h to produce black, gray and green nickel oxide, respectively.

Doped samples
The method used by Deren et al. [2] in doping with gallium was adopted
in the preparation of all samples containing the three dopant atoms AI, Ga
or In. The concentrations of the additives were 0.1, 0.5 and 1.0 at.% of A1,
Ga or In.
Three undoped samples and nine differently doped samples were ob-
tained. In this investigation the samples were subjected to thermal analysis
using a derivatograph in the temperature range 25- - 950°C. X-Ray diffrac-
tion studies were conducted using CuK~ radiation and a Ni filter. All
samples were analysed under the same instrumental conditions.

RESULTS AND DISCUSSION

The results of thermal analysis of the three undoped and nine doped
samples are shown in Fig. 1. The positions of the peaks are listed in Table 1.
From Table 1 it is observed that the DTA curves of undoped samples
prepared at 400 and 550°C contain an endothermic peak at about 120°C.
This peak may be attributed to a loss of adsorped water. The other
endothermic peak, which occurs at about 250°C in all samples, may be due
to a phase transformation from a cubic structure with a slight rhombohedral
deformation to a perfect cubic structure [3-6].
The X-ray diffraction patterns obtained show that all samples belong to
the cubic system. There are no lines corresponding to a rhombohedral
modification of NiO. This result indicates that the amount of this form in
the prepared samples is not in the X-ray limit.
In the case of undoped samples, the breadth of diffracted lines decreases
when the temperature of preparation increases. This decrease was attributed
to a decrease in the lattice defects [7]. Therefore, the undoped samples
prepared at 1000°C represent the most stoichiometric composition of nickel
oxide, NiO.
For Al-doped samples, no new lines are observed in the charts up to 1.0
at.% A1. But in the case of Ga-doped samples, a new line appears at
d = 2.48 A for the samp.le doped with 1.0 at.% Ga. This value may be
correlated with d = 2.49 A for the line corresponding to 80 or 100% intensity
in the A.S.T.M. cards of Ga203 or NiGa204 spinel, respectively. To detect
which of these two compounds has contaminated this Ga-doped sample, the
 261

0.1 0.1

OJ
0J
dm 0.5 dm
d---t-- d t 05
1.0
1.0

0:I ~ 0:1
&m 0.5 Am
1.0__oQt, % G~
1.0 Qt.Olo At

I 1 1 I I I I I I I I I l I I I I

4 0 0 *C

At 550 C
100 *C 0.1

4 0 0 °C 0.5
D.T.G &t
dm ~
~-- ~, ,. 550 "C
dt 1000"C- ='

0.1 D.T.G
dm 0.5
T.G. dt
1.0

OJ
T,G
,&m _ _ 0.5
1,0 at ~'IoI n

~ , , z , , , , , i J ,, J ,7~a~o~
1 0 200 300 400 500 600 700 800 900"C 100 200 300 400 500 600 O. O'C

Fig. 1. TG, D T G and DTA curves of undoped and doped samples of NiO.

TABLE 1
Peak positions obtained from thermal analysis of doped and undoped NiO samples

Sample Peak position

(°C)

Undoped NiO
N i O prepared at 400°C 120, 260
N i O prepared at 550°C 115, 250
N i O prepared at 1000°C 250
Doped NiO
N i O doped with AI (0.1, 0.5 or 1.0 at.%) 250
N i O doped with Ga (0.1, 0.5 or 1.0 at.%) 255
N i O doped with In (0.1, 0.5 or L 0 at.%) 250
262

Go In

I I I I I I I i I I I
1400 1000 700 500 1400 1000 700 500
Wove number cm - 1

Fig. 2. IR absorption spectra. For Ga: (a) pure NiO (1000°C); (b) NiO+0.1 at.% Ga; (c)
NiO+0.5 at.% Ga (d) NiO+ 1.0 at.% Ga; (e) Ga203. For In: (a) pure NiO (1000°C); (b)
NiO+0.1 at.% In; (c) NiO+0.5 at.% In; (d) NiO+ 1.0 at.% In; (e) In203.

TABLE 2
Values of a calculated for doped and undoped NiO samples

Sample a(.~)

Undoped NiO
NiO prepared at 400°C 4.1790
NiO prepared at 550°C 4.1771
NiO prepared at 1000°C 4.1768
Doped NiO
NiO doped with A1
0.1 at.% 4.1740
0.5 at.% 4.1774
1.0 at.% 4.1699
NiO doped with Ga
0.1 at.Sg 4.1755
0.5 at.% 4.1757
1.0 at.% 4.1759
NiO doped with In
0.1 at.% 4.1745
0.5 at.% 4.1801
1.0 at.% 4.1735
 263

infrared absorption spectra were investigated using a technique previously

described [8]. Figure 2, curve l, shows the IR absorption spectra of a
Ga-doped sample (1.0 at.% Ga). A new band at 665 c m - 1 c a n be observed.
This band is not detected in the spectra of undoped samples (1000°C) or
that of Ga203. Therefore, it may be due to the formation of NiGa204.
Rooksby and Vernon [9] reported that when firing 3% Ga20 a with NiO, a
compound with the formula NiGa204 is formed.
Similarly, a new line appears for the 0.5 and 1.0 at.% In-doped samples at
d--2.93 A. This line also represents the formation of In203 or NiIn204
spinel. This new line is more intense for the sample doped with 1.0 at.% In.
The IR spectra of these samples show a band around 700 c m - 1 . This band is
not observed in the spectra of pure NiO or In203. Thus the 1.0 at.%
In-doped sample may be contaminated with NiIn 204 ..
The a values of all samples were calculated from the experimental data
[10] assuming that samples possess perfectly cubic structures. These values
are listed in Table 2 and represented in Fig. 3. It is clear that the relation
between the dopant concentration and a value is not a linear one, except in
the case of undoped and Ga-doped samples. Values of the ionic radii of
different ions are listed in Table 3.
The value of the ionic radius of Ga 3÷ is nearly the same as that of Ni 2+.

4.18
(a) ~ . X ~

(cl

~ (d)
.g
o 4.17

4.1 6 I I
0 0.5 1.0 ( a t . * / . )
I I l I ! I
1000 go0 800 700 600 500 400
P r e p a r a t i o n t e m p e r a t u r e °C (undoped samples)

Fig. 3. Values of a for (a) undoped samples; (b) samples doped with AI; (e) samples doped
with Ga; (d) samples doped with In.
264

TABLE 3
Ionic radii values

Ion 'Ni 2+ Ni 3+ A13+ Ga 3+ In3+

Ionic radius (,~,) 0.69 0.62 0.50 0.62 0.81

This may lead one to assume that Ga 3+ can replace Ni 2+ in the NiO lattice
with a very small change in the lattice parameter. In the case of A1 and
In-doped samples, the change in the lattice parameter may be due to the
lattice deformation [10]. These results are in harmony with those obtained by
Mehandjiev [11].
To see if the addition of A1, Ga or In has led to the formation of a solid
solution, the change in the lattice parameter as a function of the at.% of
these added dements is calculated according to Vegard's law [12] which is

4.5

4.4- )

4.3

4,2 1

~ 4.1-
(b)

4.0-

3.9-

3.8 - (a)
I I
0 0.5 1.0
Dopant content °1o
Fig. 4. Values of a as deduced from Vegard's law for samples doped with (a)AI; (b) Ga; (c)
Ill.
 265

given as
a = 2rx

where a is the change in the lattice parameter (sample prepared at 1000°C as

standard), r is the difference in the ionic radii between Ni 2÷ and each of
A13÷, G a 3+ or In 3÷, and x is the at.% of the oxide dissolved. The results are
represented graphically in Fig. 4. It is observed that these values deviate
considerably from the present experimental values, indicating that the pre-
paration containing A1, G a or In m a y be considered as a solid solution.
In conclusion, doping NiO with A1, G a or In does not affect the thermal
behaviour, but it changes the lattice parameters. This change depends greatly
on the type and concentration of dopant and may be due to lattice defects.

REFERENCES

1 J. Francois, C. R., Acad. Sci., 230 (1950) 1282.

2 J. Deren, K. Dyrek, J. Pozniczek, M. Rekas, G. Rog and E. Wenda, Bull. Acad. Pol. Sci.
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