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Novel Ammonium Acetate Fuel Based Autocombustion Method for the Preparation of
Nickel Doped Zinc Oxide Nanoparticles

Article in Advanced Science Engineering and Medicine · June 2014

DOI: 10.1166/asem.2014.1545

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Vanga Rajendar Kalagadda Venkateswara Rao

Yeungnam College of Science and Technology Jawaharlal Nehru Technological University, Hyderabad
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 Article
Advanced Science,
Copyright © 2014 American Scientific Publishers
Engineering and Medicine
All rights reserved Vol. 6, 1–5, 2014
Printed in the United States of America www.aspbs.com/asem

Novel Ammonium Acetate Fuel Based Autocombustion

Method for the Preparation of Nickel Doped
Zinc Oxide Nanoparticles
V. Rajendar1 , N. Prudhvi Raju2 , and K. Venkateswara Rao1
∗
1
Centre for Nano Science and Technology, Jawaharlal Nehru Technological University Hyderabad,
Kukatpally, Hyderabad 500085, India
2
Department of Nano Technology, Acharya Nagarjuna University, Guntur, A.P, India

A novel approach for the synthesis of nickel doped zinc oxide dilute magnetic semiconductors has
been discussed in this paper. The use of fuels such as ammonium acetate and urea were used in
this paper in order to produce zinc oxide nanoparticles of very small size ranges with nickel content
varying from 2 to 10 percent. The produced particles were observed to be single phase materials
which were confirmed by evident ferromagnetic properties of these particles in the absence of
individual nickel or nickel oxide phases. The synthesized particles were also tested for their optical
emission properties which yielded in the emission peaks related to the nickel doped zinc oxide
compound instead of individual phases confirming the earlier processed information.
Keywords: Dilute Magnetic Semiconductors, Nickel Doping, Auto Combustion Method,
Photoluminescence.

1. INTRODUCTION urea), versatility of the process and single phase formation

The semiconductor industry has grown leaps and bounds in
the past decade due to the advent of dilute magnetic semi-
conductors. Their applications range from usage in photo-
catalytic devices to spintronic applications.1–7 Introduction
of a magnetic material into a semiconducting material has
brought about these changes with iron doped zinc oxide
being the first of the kind. Further studies on the introduc-
tion of other magnetic materials such as cobalt and nickel
are being envisaged. Out of the three magnetic materials
discussed above nickel doped zinc oxide is the most stable
Ni2+ state.
Multiple studies on the synthesis routes of nickel doped
zinc oxide nanomaterials have been discussed in the
past where these materials have been produced by ther-
mal evaporation, metal organic chemical vapor deposition
(MOCVD),8–10 template method,11 hydrothermal method,12
aqueous chemical growth (ACG).13
14 The advent of solu-
tion combustion method as a synthesis technique has
shown importance in the facile production of nanomateri-
als. The use of simple ingredients (ammonium salts and
∗
Author to whom correspondence should be addressed.
of complex compound oxides has ensured the increased
use of solution combustion method as a rapid nanoma-
terial formation method in the case of dilute magnetic
semiconductors.
In this paper, a novel and reliable method of synthesis
for preparing nickel doped zinc oxide DMS using solution
auto-combustion method has been discussed. This particu-
lar procedure of synthesis, with emphasis on the fuels used
has never been used prior to this paper for the preparation
of nickel doped zinc oxide dilute magnetic semiconduc-
tors. The procedure of synthesis has been modified and
improved compared to the method discussed in our ear-
lier method to make cobalt doped zinc oxide. A validation
of this procedure of synthesis was done by characterizing
the materials using a scanning electron microscope (SEM–
FEI company), X-ray diffraction system (XRD-Bruker D8)
and a vibrating sample magnetometer (VSM-Lakeshore,
Model no.: 7410) and photoluminescence spectroscopy
(PL). These validations were done in order to prove the
successful preparation of nickel doped zinc oxides in their
nano form while retaining its magnetic and semiconduct-
ing properties.

Adv. Sci. Eng. Med. 2014, Vol. 6, No. xx 2164-6627/2014/6/001/005 doi:10.1166/asem.2014.1545 1

Novel Ammonium Acetate Fuel Based Autocombustion Method
2. EXPERIMENTAL DETAILS
The Zn1−x Nix O (i.e., x = 0, 0.02, 0.04, 0.06, 0.08 and 0.1)
nano powders have been synthesized through a modified
auto combustion method using fuel to oxidizer equal to
one ( = 1). Zinc nitrate hexahydrate Zn(NO3 2 · 6H2 O,
nickel acetate Ni (NO3 2 · 6H2 O were used as precursor
materials while ammonium acetate and urea were used as
fuel. All the chemicals were purchased from Merck chem-
icals. All of the chemical reagents used in this experiment
are analytical grade and used without further purification.
Stoichiometric proportions of all the chemicals were dis-
solved in 100 ml of distilled water. Polyethylene glycol
was added under constant stirring until a highly viscous
gel was formed. The reaction was then carried out in a
hot oven in order to complete the combustion reaction.
Fine powders were obtained after 5 min of heat treat-
ment. Un-doped and other nickel doped samples were
then sent for material characterization without further
treatment.
3. RESULTS AND DISCUSSION
3.1. Morphological Studies
The particle size evaluation for samples with nickel con-
tent 0.02, 0.04, 0.06 and 0.08 were done. The SEM results
Figure 1. SEM images of all the samples of nickel doped zinc oxide nanoparticles of different concentrations.
2 Adv. Sci. Eng. Med. 6, 1–5, 2014
Rajendar et al.
for the same can be seen in Figure 1. Intermittent samples
were analyzed in order to check the behavior of particle
growth with increasing concentration of nickel in the sam-
ple. The sample with no nickel content has a hexagonal
to triangular shape in the size range of 100–150 nm. Pure
zinc oxide is known for its hexagonal wurtzite structure.
Here it can be observed that without any addition of nickel
to the crystal structure, zinc oxide takes it native hexagonal
shape. This points to the fact that the followed synthesis
procedure is indeed viable for preparing zinc oxide.
The sample with 0.04 nickel also has an evident hexago-
nal shape with a grainy surface unlike pure zinc oxide sam-
ple which has a smooth finish. The sizes of the hexagonal
particles are similar to its predecessor at 150 nm although
the smaller grains that form them are in the size range of
20–30 nm. This could be due to the breaking of the long
range morphological order of zinc oxide by nickel oxide
which has an octahedral shape. Particle size is seen to
decrease to 50 nm with an irregular shape for samples with
0.1 nickel in them. The particle shape is undefined and the
size range varies in the range of 40–60 nm. This can be
explained using the same analogy used earlier where the
increase in nickel oxide content has completely broken the
morphological ordering of zinc oxide.
Rajendar et al.
From all the SEM images it is clear that the addition
of nickel has shown a known effect on the morphology of
zinc oxide evidencing the formation of nickel doped zinc
oxide using this novel auto-combustion method.
3.2. X-Ray Diffraction Studies
XRD on all the samples were done in order to method-
ically check for the change in the crystal structure of
zinc oxide with addition of nickel to the system. The
analysis was done in order to prove that the synthe-
sis method explained earlier is able to produce sin-
gle phase zinc nickel oxide instead of separate phases.
A stack figure of all the XRD patterns can be seen in
Figure 2.
All the patterns match with zinc oxide standard diffrac-
tion data JCPDS 36-1451. The most significant point to be
noted in these patterns is the emergence of two peaks at
2 values 36.9 and 43.1 in samples with nickel content
exceeding 0.06 molar ratios. These two peaks belong to
zinc nickel oxide JCPDS 80-0075 of these peaks, the peak
at 36.9 can be seen as an addition peak, which broad-
ens the zinc oxide peak at 36.1 . It is made clearly visible
only through de-convolution of the graph. The emergence
of these peaks implies the higher formation of the zinc
nickel oxide phase with concentrations exceeding 0.06
nickel.
The crystallite sizes for all the samples have been cal-
culated using Debye Scherrer’s formula in order to look
for any change in lattice parameters due to the inclusion
of nickel into zinc sites. Table I and Figure 3 represent the
change in crystallite size with increasing nickel content in
the prepared samples.
The graph clearly shows that the crystallite size of the
sample at 0.02 concentration of nickel is smaller and then
jumps to a crystallite size of 50 nm when the concentration
of nickel is increased to 0.04 and then slowly decreases
Figure 2. XRD Patterns of all the samples of nickel doped zinc oxide
nanoparticles of different concentrations. The pointers mark the emer-
gence of zinc nickel oxide peaks.
Adv. Sci. Eng. Med. 6, 1–5, 2014
Novel Ammonium Acetate Fuel Based Autocombustion Method
Table I. Table showing the change in crystallite size of zinc oxide with
addition of nickel.
S. no. Ni% Crystal size
1 0.02 43
2 0.04 50
3 0.06 44
4 0.08 43
5 0.1 40
to 40 nm with further increase in the nickel concentration.
These crystallite sizes correspond well with the observed
SEM results which conclude that the individual particles
seen are single crystals.
3.3. VSM
The magnetic properties of all the samples including the
un-doped sample were done. The combined VSM graph
can be seen in Figure 4. The VSM graphs show a grad-
ual increase in the magnetic moment of the particles with
increasing concentration of nickel in the system. This is
a noted fact which concludes that the particles produced
indeed are magnetic in nature. The magnetic moment of
the samples with nickel concentrations 0.02, 0.04, 0.06,
0.08, 0.1 are 50, 76, 90, 93, 96, and 103 emu/Oe. The
increase in the magnetic strength of the particles is in
direct correlation with the increase in the nickel content in
the materials. The magnetic properties in the sample arise
due to the ferromagnetic nature of nickel occupying zinc
sites in the sample.15
Here the important part to be noted is that the emergence
of room temperature ferromagnetism and the increase in
the susceptibility of the same indicates an intrinsic mag-
netic semiconducting property of the material synthesized.
The absence of a separate nickel oxide phase can be con-
firmed using VSM. In the presence of a separate nickel
oxide phase, the overall magnetic moment would decrease
due to the antiferrromagnetic property of nickel oxide.
Figure 3. The pattern of crystallite size growth calculated from the
XRD patterns.
3
Novel Ammonium Acetate Fuel Based Autocombustion Method
(a)
(c)
Figure 4. A stack plot of all the VSM Magnetization versus Applied field loops for all the nickel doped zinc oxide samples.
The absence of this property also confirms the absence of
a separate nickel oxide phase. This suggests that the novel
synthesis route followed in this paper results in the for-
mation of single phase nanoparticulate zinc nickel oxide
DMS materials.
The intrinsic magnetic property of zinc nickel oxide can
only arise from the distribution of nickel Ni2+ ions across
the zinc oxide crystals forming defects states and con-
tributing to the anisotropic cluster formation. The presence
of these zinc vacancy based defect states can be under-
stood performing emission studies on these materials.
3.4. PL
The photoluminescence spectra for all the samples can
be seen in Figure 5. The spectra were recorded using
a fixed laser source of wavelength 325 nm. It can be
4 Adv. Sci. Eng. Med. 6, 1–5, 2014
Rajendar et al.
(b)
(d)
observed that there is a major difference between the
undoped zinc oxide sample and the doped zinc oxide. In
all the cases, a peak at 391 nm is observed which cor-
responds to native zinc oxide in the ultra violet region.
This is the only peak present in the case of undoped
sample.
The samples with nickel doping seem to have reduced
emission in the ultraviolet region and increased emission
in the visible region with additional peaks appearing at
419 nm and 452 nm.16 These peaks correspond to the
presence of oxygen vacancies and negatively charged zinc
vacancies in the samples.17 These results strong corre-
lated with the magnetic properties discussed earlier where
increased nickel content seemed to increase the magnetic
saturation and hence the susceptibility of the materials
being formed.
 Rajendar et al.
Figure 5. Graph representing the photo emission properties of nickel
doped zinc oxide.
4. CONCLUSIONS
Nickel doped zinc oxide has been synthesized successfully
using a novel auto-combustion method. The method seems
to have formed single phase zinc nickel oxides whose
purity was proven using XRD, PL and VSM data. The
particles are in the nanoparticulate form with decreasing
particle sizes with increase in nickel concentration. The
formed particles are weakly ferromagnetic in nature with
their magnetic property arising out of their intrinsic defect
states rather than nickel or nickel oxide clusters present in
the sample. Hence it can be concluded that the followed
method of synthesis is a reliable model for the develop-
ment of single phase dilute magnetic semiconducting zinc
nickel oxide nanoparticles.
Adv. Sci. Eng. Med. 6, 1–5, 2014
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Novel Ammonium Acetate Fuel Based Autocombustion Method
Acknowledgments: The authors would like to thank
the Sophisticated Analytical Instrument Facility, North-
ern Eastern Hill University for TEM. One of the
author wish to acknowledge the Department of Centre
for Nano Science and Technology (CNST), Institute of
Science and Technology, Jawaharlal Nehru Technological
University, Hyderabad for providing fellowship for meri-
torious scholars.
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Received: 30 November 2013. Accepted: 7 January 2014.
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