International Journal of Semiconductor

Science & Technology (IJSST)

ISSN(P): 2250-1576; ISSN(E): 2278-9405
Vol. 5, Issue 2, Jun 2015, 1-10
TJPRC Pvt. Ltd.

EFFECT OF NI-DOPING ON STRUCTURAL AND MAGNETIC PROPERTIES

OF ZnO NANOPARTICLES
RAMINDER PREET PAL SINGH 1, I. S. HUDIARA2,
SUDHAKAR PANDAY3 & PUSHPENDRA KUMAR4
1,3

Department of Electronics & Communication Engineering, Desh Bhagat University,

Mandi Gobindgarh, Punjab, India
2
4

Chitkara University (Punjab Campus), Chandigarh, India

Department of Chemistry, Arni University, Kangra, Himachal Pradesh, India

ABSTRACT
In the present study, Zn1-xNixO (x=0.01, 0.03, 0.05 and 0.07) diluted magnetic semiconductor (DMS)
nanoparticles have been synthesized using modified sol-gel method. The structural and magnetic properties of the
Ni-doped ZnO samples annealed at 600oC have been characterized by X-ray diffractometer (XRD), Scanning electron
microscope (SEM) and Vibrating sample magnetometer (VSM). The average crystalline size was calculated using
Debye-Scherrers formula. The particle size was found to be in the range of 36 to 42 nm. X-ray diffraction patterns
revealed that the crystal structure of samples corresponds to hexagonal wurtzite ZnO phase along with an additional
diffraction peaks linked to NiO and metallic Ni. SEM micro-image confirmed the presence of spherical Zn1-xNixO
nanoparticles. VSM measurement shows the hysteresis loop at room temperature which confirms the ferromagnetic
property of the samples. The origin of ferromagnetism in the samples could be due to the exchange interaction between
Ni2+ ions.

KEYWORDS: Zn1-Xnixo Nanoparticles, Ni-Doping, Diluted Magnetic Semiconductor, Magnetic Properties, Spintronics
INTRODUCTION
Diluted magnetic semiconductors (DMS) have attracted much attention in recent years because it is a type of
semiconductor in which fraction of host cations can be easily replaced by magnetic ions in order to achieve the objective of
fabricating spintronics devices such as spin-valve transistor.[1-4] ZnO is a group II-IV semiconductor and has become one of
the most promising candidates for DMS materials.[5] Moreover, ZnO have potential applications in optoelectronics due to
its, wide band-gap (3.3 eV) and high exciton binding energy (60 meV) properties. Scientists are investigating the effect of
doping ZnO with transition metals such as Fe, Co and Mn.

[6-13]

. A number of experiments have been carried out to

investigate the structural and magnetic properties of Ni-doped ZnO.[14-18] Experimental studies conformed that the
ferromagnetism strongly depends on synthesis techniques and environmental conditions used for the preparation of
samples. Various chemical methods have been developed to prepare nanoparticles of different materials of interest. Most
of the ZnO nanocrystals have been synthesized by traditional high temperature solid state reaction method. However this
method is time consuming and properties of the product cant be controlled. ZnO nanoparticles can be prepared on a large
scale at low cost by simple solution based methods, such as chemical co-precipitation, hydrothermal reaction, and sol-gel
synthesis.
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Raminder Preet Pal Singh, I.S. Hudiara,

Sudhakar Panday & Pushpendra Kumar

In the present work, we have synthesized Zn1-xNixO nanoparticles using modified sol-gel method. This is a simple
and low cost method and gives good yield of the end product and takes less time in preparing the nanoparticles. In this
research work we have studied the effect of dopant ion concentration on the structure and magnetic properties of Ni doped
ZnO (Zn1-xNixO (x = 0.01, 0.03, 0.05 and 0.07) annealed at 600oC.

EXPERIMENTAL PROCEDURE
Nanocrystalline Zn1-xNixO (x = 0.01, 0.03, 0.05) semiconductors were synthesized by a simple modified sol-gel
method. Zinc Acetate (Zn-(CH3COO)2 .2H2O) and Nickel Acetate (C4H6NiO4.4H2O) were taken according to the
calculated stoichiometric ratio in a beaker containing 100ml distilled water. NaOH mixed in distilled water was added
drop-wise during the experiment in order to maintain pH of the solution at 10. The solution was then stirred at room
temperature for 2 h followed by aging for 24 hrs at the same temperature. After aging, precipitate that formed was filtered.
The product obtained at this stage was mixed Zinc and Nickel hydroxide powder. This compound was annealed at 6000 C
for two hours and then grinded to obtain the final nanoparticles of Ni doped ZnO.

Figure 1: Schematic Diagram of Modified Sol-Gel Synthesis

Technique to Prepare Ni Doped Zno Nanoparticles

RESULTS AND DISCUSSIONS

XRD Analysis
X-ray diffraction analysis of all the samples was done using Brucker AXS diffractometer. X-ray diffraction
patterns of Ni doped ZnO show exhaustive evolution of hexagonal wurtzite phase in all the samples. Initially at low
concentration no peak corresponding to Nickel oxide was observed which confirmed no phase segregation i.e. perfect
incorporation of Ni. In all the samples peak intensity is very high which confirmed good crystalline formation. The
maximum peak intensity was observed corresponding to the plane (101). Initially as the Ni was incorporated, the intensity
of peaks increased but at higher doping concentration it decreased. The maximum peak intensity was recorded in the
Impact Factor (JCC): 4.1875

Index Copernicus Value (ICV): 3.0

Effect of Ni-Doping on Structural and Magnetic Properties of ZnO Nanoparticles

Zn0.97Ni0.03O sample.

Figure 2: XRD Patterns of Pure Zno and Zn1Xnixo (X = 0.01, 0.03,

0.05, and 0.07) Nanoparticles Annealed at 600
It has been reported in literature that when any foreign particle is incorporated in the crystal lattice, it produces
strain as well as defects in the lattice which may reduce the crystal quality.[19] Figure 2, shows the shifting in peak which
was probably due to strain in the lattice. In doping, ionic radii plays an important role. If the ionic radii of foreign particle
are higher or lower than the host lattice, then lattice parameters of host expand or contract to accommodate it. Ionic radius
of Ni2+ (0.68 A) is larger than that of Zn2+ (0.60 A). So shifting of peaks towards lower angle suggests the incorporation
of Ni in the ZnO lattice.[20] The average crystalline size was calculated by using scherrers equation (1) and was found to be
in the range of 36 nm to 42 nm as shown in table 1.
= k / B Cos

(1)

Where, is grain size, B is the full width at half maxima and is the wavelength of X-ray used (1.548 ) and is
the diffraction angle.
As Ni was incorporated, the crystalline size increased but when the Ni concentration was increased to 3% the
crystalline size was decreased which correlates with the XRD pattern. Doping causes enhanced nucleation growth which
supports the crystalline growth but at higher concentration, it causes distortion in the crystal lattice resulting in reduction in
crystallinity and size. The values of lattice strain are also shown in table I and are very low. The lattice parameters were
calculated using equation (2) given below.

(2)
Where d, h, l, k, a and c are lattice constants.
The calculated values shown in table I, are very close to the reported values in literature.[21] At higher
concentration of Ni, a remarkable increase in dislocation density was also observed.

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Raminder Preet Pal Singh, I.S. Hudiara,

Sudhakar Panday & Pushpendra Kumar

Table 1: Lattice Parameters of Pure ZnO and Zn1Xnixo (X = 0.01,

0.03, 0.05, and 0.07) Nanoparticles Annealed at 600
Ni
Doping
%
0%

2.4755

Unit Cell
Parameters
A
C
3.232
5.278

1.633

Dislocation
Density(10-3)
linem-2
0.65

2.4755

3.232

5.278

1.633

0.65

2.4715

3.227

5.269

1.632

0.56

2.4755

3.232

5.278

1.633

0.62

2.4781

3.235

5.283

1.633

0.77

Scherrer
Size

Lattice
Strain

d101 ()
Spacing

39 nm

0.0027
0.0027
4
0.0025
4
0.0026
8
0.0025

1%

39 nm

3%

42 nm

5%

40 nm

7%

36 nm

c/a
ratio

Figure 3: Shifting of NiO Peak with the Doping Concentration of Zn1-Xnixo Samples Annealed at 600
On the other hand, with the increase in Ni concentration, an additional diffraction peak corresponding to NiO
(as shown in figure 3) appears at 2 = 43.2. This revealed that phase segregation has occurred in the samples. Also, with
increase in Ni concentration, the intensity of NiO peak increases and shifts to the lower angle which is an indication of
distortion of NiO to larger spacing where nickel gets oxidized and incorporated into ZnO lattice.[22] Apart from this peak,
a weak reflection at 2 = 44.3 corresponding to Ni is also obtained.[27] Thus the XRD studies clearly indicate the presence
of Ni metal, apart from NiO, in the polycrystalline samples.
Scanning Electron Microscope (SEM) Analysis
For study of surface morphology, scanning electron microscope Carl Zeiss Supras 55 was used. Figures 4(a) & (b)
show SEM images of undoped and Ni doped ZnO. The SEM image of Zn0.99Ni0.01O confirmed that as synthesized material
is in nano range and in good agreement with calculated crystalline size from XRD.

Impact Factor (JCC): 4.1875

Index Copernicus Value (ICV): 3.0

Effect of Ni-Doping on Structural and Magnetic Properties of ZnO Nanoparticles

Figure 4: SEM Image of (A) Pure Zno and (B) Zn0.99Ni0.01O Nanostructures
Ni incorporation was also confirmed by the EDAX analysis. The estimated values of Ni in ZnO are shown in table
2. From the table, it can be observed that %age of Ni incorporated in the samples is lower than their actual composition
incorporated during the synthesis process.
Table 2: EDAX Data of Ni-Doped ZnO Nanoparticle
Sample
ZnO (Pure)
Zn0.99Ni0.01O
Zn0.97Ni0.03O
Zn0.95Ni0.05O
Zn0.93Ni0.07O

Ni %
-0.54
2.11
4.12
6.99

Zn %
66.81
61.98
72.81
70.56
64.35

O%
15.44
12.31
11.94
9.09
12.59

C%
17.75
24.92
11.38
16.23
16.07

Vibrating Sample Magnetometer (VSM) Analysis

Magnetization measurements on the synthesized nanoparticles were carried out using Microsense E29 vibrating
sample magnetometer. All the measurements were made at room temperature. Pure ZnO sample shows no hysteresis curve
as shown in figure 5 (a), confirmed the diamagnetic property. Diamagnetic nature of pure ZnO has also been reported in
literature.[23]

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Raminder Preet Pal Singh, I.S. Hudiara,

Sudhakar Panday & Pushpendra Kumar

(a)

(b)

(c)

(d)

(e)

Figure 5(A-E): Room Temperature Ferromagnetism of Undoped ZnO and

Doped Zn1Xnixo (X = 0.01, 0.03, 0.05, and 0.07) Nanoparticles
Whereas, from the magnetic hysteresis loops (MH curve) for Ni doped samples i.e. Zn1-xNixO (x=0.01, 0.03,
0.05 and 0.07) it is clear that all samples exhibit ferromagnetic behavior at room temperature. However, some researchers

Impact Factor (JCC): 4.1875

Index Copernicus Value (ICV): 3.0

Effect of Ni-Doping on Structural and Magnetic Properties of ZnO Nanoparticles

observed ferromagnetism only at lower doping concentration (x < 0.05) but paramagnetic behavior for higher doping
concentration.[21] The values of saturation magnetization (Ms) and coercive field (Hc) of our Ni doped ZnO samples are
shown in the table 3.
Table 3: Magnetic Properties of Zn1-Xnixo (X=0.01, 0.03 0.05 and 0.07) Nanoparticles
Sample
Zn0.99Ni0.01O
Zn0.97Ni0.03O
Zn0.95Ni0.05O
Zn0.93Ni0.07O

Hc (Oe)
74
127
120
84

So far, different models have been proposed

[24-26]

Ms (emu/g)
0.0216
0.0135
0.0157
0.0145
to explain mechanism responsible for the origin of

ferromagnetism in diluted magnetic semiconductors, but still this issue is controversial. Carrier-mediated ferromagnetism
can be possible model in order to explain the observed ferromagnetism in our samples. The origin of ferromagnetism might
be due to the formation of Ni-related secondary phase such as metallic nickel and NiO. From XRD pattern, it can be seen
that intensity of NiO peak increases with the increase in Ni concentration. Possibility of ferromagnetic behavior of samples
due to secondary phase NiO is ruled out as we know that bulk NiO is anti-ferromagnetic in nature above Neel temperature
of 520 K.[27]
From table 3, it is clear that the coercivty increases upto 127 Oe for 3% Ni-doped ZnO sample and for 5 and 7 at
% concentration value decreases to 120 Oe and 84 Oe which shows reduction in ferromagnetism. When the concentration
of Ni increases, carrier density decreases due to the compensation of oxygen vacancies, and as a result, ferromagnetism
decreases.[28] This fact revealed that Ni metal cluster as a secondary phase is not responsible for ferromagnetic behavior in
our samples. Thus, possibility of origin of ferromagnetism due to secondary phases in our samples is ruled out.
However, intrinsic defects such as oxygen vacancies and Zn interstitials, can usually act as shallow donors in
ZnO. Therefore, the room-temperature ferromagnetism in our samples could originate from the long-range Ni2+Ni2+
ferromagnetic coupling mediated by shallow donor electrons.[22]

CONCLUSIONS
In the present study, Ni doped ZnO (Zn1-xNixO (x=0.01, 0.03 0.05 and 0.07)) diluted magnetic semiconductor
nanoparticles were successfully synthesized via simple modified sol-gel method. X-Ray diffraction pattern show formation
of hexagonal wurtzite structure in all samples of Ni doped ZnO along with secondary phases of metallic nickel an NiO. All
the samples of Zn1-xNixO (x=0.01, 0.03 0.05 and 0.07) shows room temperature ferromagnetic behavior as observed from
the M-H curves. Long-range Ni2+Ni2+ ferromagnetic coupling mediated by shallow donor electrons could be the possible
reason for room temperature ferromagnetic behavior. The Ni doped ZnO nanoparticles of the present work having room
temperature ferromagnetism could be the suitable diluted magnetic semiconductors for Spintronic device applications.

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