Structural, optical, vibrational, and magnetic properties of sol-gel derived Ni doped

ZnO nanoparticles
Gunjan Srinet, Ravindra Kumar, and Vivek Sajal

Citation: Journal of Applied Physics 114, 033912 (2013); doi: 10.1063/1.4813868

View online: http://dx.doi.org/10.1063/1.4813868
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 JOURNAL OF APPLIED PHYSICS 114, 033912 (2013)

Structural, optical, vibrational, and magnetic properties of sol-gel derived

Ni doped ZnO nanoparticles
Gunjan Srinet, Ravindra Kumar,a) and Vivek Sajal
Department of Physics and Materials Science and Engineering, Jaypee Institute of Information Technology,
Noida-201307, Uttar Pradesh, India

(Received 15 March 2013; accepted 26 June 2013; published online 18 July 2013)
With a view to study structural, optical, vibrational, and magnetic properties of solgel derived
Zn1xNixO (x ¼ 0.02, 0.04, and 0.06) nanoparticles, systematic investigations have been carried out.
The Rietveld refinement of X-ray powder diffraction data revealed a single hexagonal phase with
space group P63mc. The secondary phase of NiO appeared only in 6% Ni doped sample. Phonon
modes in Ni doped ZnO nanoparticles were studied through Fourier transform infrared
measurements. Furthermore, the enhancement in optical band gap with Ni doping from 3.29 to
3.32 eV has been observed through UV-visible spectroscopic analysis. Photoluminescence spectra
of Zn1xNixO show the UV-emission peak showing the blue shift with increase in doping
concentration followed by broad visible (blue) emission corresponding to the defect emission whose
intensity decreased with increasing Ni concentration. A clear room temperature ferromagnetism is
observed in all samples but saturation magnetization decreased with increasing Ni content. The
suitability of bound magnetic polarons (BMP) model is checked and numbers of BMPs are found to
be of the order 1015 per cm3, which is very small for the percolation in ZnO. In the present case,
oxygen rich stoichiometry with enhanced Zn-O bonding favours the indirect Ni-O-Ni ferromagnetic
exchange coupling and reduction of oxygen vacancies leading to strong hybridization of Ni in
ZnO host matrix responsible for room temperature ferromagnetism. V C 2013 AIP Publishing LLC.

[http://dx.doi.org/10.1063/1.4813868]

INTRODUCTION synthesized by pulsed laser deposition.14 Magnetic properties

of Ni-doped ZnO thin films were also reported by Wakano
In recent years, diluted magnetic semiconductors
et al.15 but ferromagnetism could only be observed below
(DMSs) have attracted the scientific community due to their
30 K. Besides, successful incorporation of Ni2þ into ZnO
potential applications in the new emerging field of optoelec-
host matrix, only paramagnetic behaviour was observed by
tronics; spin polarized Light emitting diodes (LEDs), photo-
Yin et al.16 Liu et al.17 reported that defect states are respon-
voltaic, and sensors.1,2 Also, these materials may play an
sible for the RTFM in Ni doped ZnO system. On the other
important role in future spintronic devices which manipulate
hand, Tong et al.18 explained enhancement of the RTFM by
both charge and spin.3 Investigations on DMSs were origi-
H2 annealing. Under this scenario, magnetism in Ni doped
nally inspired by Ohno et al.4 by discovering the low temper-
ZnO is still a subject of debate that demands careful investi-
ature ferromagnetism in Mn doped GaAs with the Curie
gations. In the present paper, experimental and theoretical
temperature around 110 K. The main challenge in practical
investigations on structural, optical, vibrational, and mag-
applications of these materials is the attainment of room tem-
netic properties of Ni doped ZnO nanoparticles synthesized
perature ferromagnetism (RTFM). The theoretical prediction
by the sol-gel method are presented.
of RTFM in some doped wide band gap semiconductors
(II–VI and III–V group semiconductors) has stimulated more EXPERIMENTAL
research attention on these materials.5 Among II–VI semi-
conductors, ZnO is a versatile multifunctional candidate, Ni doped ZnO nanoparticles were prepared by
with a direct wide band gap (3.37 eV at 300 K), large exci- the sol-gel route by using 2-methaxyethanol as stabilizing
tonic binding energy (60 meV), outstanding electro-optic and agent. Appropriate proportions of high purity zinc
piezoelectric properties, and excellent chemical stability acetate [Zn(CH3COO)2  2H2O] and nickel acetate
which can be useful in electronics and optoelectronics.6,7 [Ni(CH3COO)2  4H2O] were used to synthesize Zn1xNixO
After theoretical predictions of RTFM in ZnO based DMS (x ¼ 0.02, 0.04, 0.06) nanoparticles. Initially, 0.1 M zinc ace-
systems,5,8 number of groups experimentally investigated tate solution was prepared in 2-methoxymethanol. Nickel ac-
this phenomenon subsequently.9–13 From the literature, it is etate, the doping source was added to this solution to attain a
observed that there are few studies on Ni doped ZnO system, desired Zn:Ni ratio of 0.98:0.02, 0.96:0.04, and 0.94:0.06.
in which diverse magnetic properties have been reported. Liu The resulting solution was mixed overnight at 60  C using a
et al. observed the RTFM behavior in Ni-doped ZnO films magnetic stirrer to get a stable and homogeneous solution in
which no particulates or precipitates were visible. Then, the
a)
Author to whom correspondence should be addressed. Electronic mail: final solution was dried in an oven at 100  C for 24 h and
[email protected] then ground. Afterwards, the dried gel was calcined at

0021-8979/2013/114(3)/033912/6/$30.00 114, 033912-1 C 2013 AIP Publishing LLC

V

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 033912-2 Srinet, Kumar, and Sajal J. Appl. Phys. 114, 033912 (2013)

FIG. 2. FESEM image of 2% Ni doped ZnO.

(weighted profile R-value) and v2 (goodness-of-fit quality

factor) obtained after the final cycle of refinement for all
FIG. 1. Reitveld refined XRD patterns of Zn1xNixO (inset shows the
doping-induced peak shift). samples are presented in Table I. Low values of v2 and pro-
file parameters (Rp and Rwp) suggest that derived samples
are of good quality and refinements are effective. Observed
600  C for 2 h. Further, samples were compacted into pellets and calculated values were perfectly matching as can be seen
and sintered at 950  C. from figures. There is no detectable impurity peak up to the
X-ray diffraction (XRD) of sintered pellets was carried 4% of Ni doping but a few traces of NiO (200) phase around
out by a X-ray diffractometer (Shimadzu XRD-6000 with 42 , were detected for x > 0.04 which shows that nickel con-
CuKa (k ¼ 1.5406 Å) radiation). XRD data was analyzed by tent x > 0.04 is beyond the solid solubility limit of Ni in
Full Proof Software (Rietveld Methods). A Field emission ZnO. Lattice parameters slightly decreased with increase in
scanning electron microscopy (FESEM) was used to deter- Ni concentration, which can be assigned to a smaller ionic
mine the morphology of the sample. Fourier transform infra- radius of Ni2þ (0.55 Å) than that of Zn2þ (0.60 Å) which
red spectroscopy (FTIR) measurements were done by using shows the incorporation of Ni ions on Zn sites.19 A doping
Perkin Elmer BX-II spectrophotometer through KBr pellet induced peak shift (101) toward higher values (inset of
technique in the range 400–4000 cm1. Absorption spectra Figure 1) is also observed. The average bond length shows a
were carried out by a Perkin Elmer Lambda-35 UV–visible continuous decrease with doping concentration confirming
spectrometer in the wavelength range of 300–800 nm. the substitution of Ni on Zn sites. Average crystallite sizes
Photoluminescence spectra of samples were acquired using determined by Scherer’s formula vary from 45 to 48 nm,
xenon flash lamp as excitation source by Perkin Elmer which is dependent on the increasing broadening of peaks
Lamda luminescence spectrophotometer (LS-55). The mag- with doping concentration.
netic properties of samples were carried out by vibrating
sample magnetometer (VSM) (EV9). SEM
Figure 2 shows the FESEM image of 2% Ni doped ZnO
Structural properties sample, which shows accurately separated grains with
XRD hexagonal structure on the surface.

Rietveld refined XRD patterns of Ni doped ZnO samples

FTIR studies
are shown in Figure 1 in which all Bragg peaks are indexed
in the wurtzite type hexagonal structure with space group To study the composition, quality, and molecular struc-
P63mc. Parameters Rp (profile fitting R-value), Rwp ture of samples, FTIR spectra were performed in the range

TABLE I. Calculated parameters from Rietveld refinement.

Cell parameters

% of Ni a (Å) c (Å) V (Å3) Bond length R-factors D (nm)

2 3.253 5.203 47.63 1.978 Rp ¼ 9.84, Rwp ¼ 16.2 48

Rexp ¼ 12.4, v2 ¼ 1.7
4 3.251 5.202 47.61 1.977 Rp ¼ 10.6, Rwp ¼ 18.0 47
Rexp ¼ 13.2, v2 ¼ 1.8
6 3.250 5.201 47.58 1.976 Rp ¼ 10.8, Rwp ¼ 16.7 45
Rexp ¼ 16.7, v2 ¼ 1.9

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 033912-3 Srinet, Kumar, and Sajal J. Appl. Phys. 114, 033912 (2013)

FIG. 3. (a) The full range transmit-

tance spectra of Zn1xNixO (x ¼ 0.02,
0.04, and 0.06). Inset shows the varia-
tion of IR bands corresponding with Ni
content. (b) FTIR absorbance spectra
corresponding to Zn-O bonds with
gaussian fitting.

of 400 to 4000 cm1 at room temperature. Figure 3(a) shows induced structural changes on doping.22 The average bond
the full scan transmittance spectra of Zn1xNixO (x ¼ 0.02, length of Zn(Ni)-O in Zn1-xNixO system is determined from
0.04, and 0.06) nanoparticles. The broad absorption peak the band position of E1(TO) and by the relation
around 3500 cm1 represents the stretching vibration of the  1=2
1 k
 ¼ 2pc l , where  is the wave number, c is the velocity
O-H group. Absorption peaks observed at around 2350 are
assigned to the CO2 mode which may be due to atmospheric of light, k is the average force constant of the Zn(Ni)-O
CO2.20 The absorption peak at 1420 cm1 corresponds to bond, and l is the effective mass of the bond, given by:
symmetric stretching ts (COO) vibrations of acetate species M ½xM þð1xÞM 
l ¼ Mo þ½xMNi þð1xÞMZn , where Mo, MZn, and MNi are atomic
Zn 
but the absorption peak (1580 cm1) corresponding to asym-
o Ni
weights of O, Zn, and Ni, respectively, and force constant is
metric stretching tas (COO) (Ref. 21) may have merged related to the average Zn(Ni)-O bond length (Å) by the equa-
with the principle absorption peak at 1620 cm1 correspond-
tion k ¼ 17
r 3 (Ref. 23). Calculated values of effective mass,
ing to bending vibrations of the interlayer water molecule.
force constant, and bond length are summarized in Table II.
The IR active characteristic broad band (optical phonon
The effective mass of Zn (Ni)-O bond decreased with Ni
modes) of ZnO is observed in the spectral range
substitution because of the lower atomic weight of Ni than
400–600 cm1. Absorption bands are found to blue shift with
Zn. Also, decrease of the average force constant is observed
increasing Ni doping which reflects that the Zn-O-Zn net-
with substitution of Ni which results in an increment in the
work is perturbed by the presence of Ni in its environment.
average Zn (Ni)–O bond length. The variation of the bond
To locate exact positions of Zn-O bands, IR band in the
length due to Ni substitution is consistent with the trend
region 400-600 cm1 is shown in the Figure 3(b) fitted by
observed by Rietveld analysis.
the Gaussian and showing three bands X1, X2, and X3. The
band X1 at around 445 cm1 corresponds to E1 (TO) mode.
Bands at 484 cm1 (X2) and 533 cm1 (X3) are surface pho- Optical properties
non modes (SPMs) and named as SPM [A1 (TO)] and SPM UV-VIS spectroscopy
[E1(TO)], respectively, generally appear when the size of
prepared particles is smaller than the incident IR wave- Optical properties of samples were studied by
length.22 These IR bands corresponding to Zn show a varia- UV-visible spectroscopy in the range 300–800 nm. The posi-
tion in vibrational frequencies with Ni concentration, as tion of the absorption edge is observed to be shifting towards
shown in the inset of Figure 3(a), which may be due to the lower wavelength side with increase in Ni concentration in
difference in ionic radii of Zn and Ni as well as due to ZnO (Figure 4), indicating an increase in the band gap with
Ni doping. The band gap was estimated by extrapolation of
linear portion of (ah)2 versus h curve (Figure 4(b)) by
TABLE II. The IR band and local structure data of Zn Ni-O bonds of
Zn1xNixO.
using the Tauc plot relation a / ðh  Eg Þ1=2 for the direct
band gap semiconductor between the absorption coefficient
Samples Wavenumber Effective mass Force constant Bond (a) and the energy band gap (Eg), where h is the planck’s
(Zn1xNixO) (cm1) (atomic weight) (N m1) length (Å) constant and  is the frequency of the incident photon. Band
gaps are observed to vary from 3.29 to 3.32 eV with increase
x ¼ 0.02 445 12.8426 150.11 2.2457
x ¼ 0.04 448 12.8327 152.15 2.2356
of the nickel concentration as shown in the inset of Figure
x ¼ 0.06 451 12.8322 154.07 2.2263 4(b). This optical energy band gap widening and the absorp-
tion edge blueshift can be attributed to an increase in the

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 033912-4 Srinet, Kumar, and Sajal J. Appl. Phys. 114, 033912 (2013)

401 nm corresponds to Oi, emission band at 434 nm to the

Zni, blue emission bands centred at 462 and 487 nm corre-
spond to the VZn, and the low intensity green emission band
at 518 nm is attributed to oxygen and zinc vacancies.28 Thus,
we conclude that Ni doping leads to an increase in electron
concentration and decrease in the intrinsic defect density.

Magnetic properties
Field dependent magnetization (M-H) curves recorded
at room temperature are shown in Figure 6. All samples
show the RTFM behaviour. A decrease in the saturation
magnetization with increase in the doping concentration is
observed and values of remnant polarization and coercivity
FIG. 4. (a) Absorption spectra of Zn1xNixO (Ni ¼ 2%, 4%, 6%). (b) Tauc are approximately same for 2% and 4% Ni doped ZnO
plot of the samples. Inset shows the variation of band gap with Ni doping. samples but slightly decreased for 6%.
The origin of RTFM in oxide based DMSs is still not
carrier concentration and in principle be explained by the clear as there is an incomplete understanding whether it is an
Moss-Burstein band filling effect, which is frequently extrinsic effect due to direct interaction between the local
observed in n-type semiconductors.24,25 moments in magnetic impurity clusters or is indeed an intrin-
sic property caused by exchange coupling between the spin
of carriers and local moments. There are various theories
Photoluminescence spectroscopy
proposed in the literature to explain the mechanism of the
The intrinsic and extrinsic defects and the change in the origin of magnetism in DMSs.29–31
optical band edge are also examined from the PL spectros- As oxygen vacancies are inherently present in our sam-
copy. Room temperature PL (RT PL) spectra of Ni doped ples due to the stabilization of the structure, it can be pre-
ZnO nanoparticles excited at 325 nm are shown in (Figure dicted that oxygen vacancy defect constituted bound
5(a)), which show the near band edge (NBE) UV emission magnetic polarons (BMPs) are promising candidates for the
around 375 nm, slightly shifting to the longer wavelength origin of RTFM in this system. According to the BMP
with increase in Ni concentration (inset of Figure 5(a)), model, bound electrons in defects, like oxygen vacancies
which is in good agreement with the absorbance spectra and (Vo), can couple with Ni ions and cause ferromagnetic
further confirms the substitution of Ni2þ ions on Zn2þ sites. regions to overlap giving rise to long range ferromagnetic
The UV emission is followed by the high intensity broad ordering. According to this theory of defect mediated
visible band in the range 400–520 nm. The origin of the visi- RTFM, the large density of oxygen vacancy help to provide
ble emission in ZnO is still a controversial issue as it is not more BMPs and enhancing FM. The evolution observed in
easy to separate the produced emissions by different type of our case is decrease in magnetization with decrease in oxy-
defects. For instance, it was suggested by Zhao et al.26 that gen vacancies, indicating that percolation of BMPs may be
violet emission originates from an electronic transition responsible for ferromagnetism.32
between the interstitial-zinc (Zni) level and the valence band The suitability of BMP model is checked by fitting the
or between the bottom of the conduction band and the M-H data to the following equation:30
Zn-vacancy level (VZn). However, green luminescence of
ZnO being mediated by oxygen vacancy (Vo) and defect M ¼ Mo LðxÞ þ vm H;
states.27 Thus as shown in Figure 5(b), the broad visible
emission is deconvoluted for different defect states with the where the first term is to account for the BMP contribution
help of Gaussian fitting. The defect level emission band at and the second term is due to the observed paramagnetic

FIG. 5. (a) PL spectra of Ni doped ZnO

samples. (b) PL spectra of Zn0.98Ni0.02O
along with the Gaussian fit.

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 033912-5 Srinet, Kumar, and Sajal J. Appl. Phys. 114, 033912 (2013)

FIG. 6. M-H curves of Zn1xNixO samples (a) x ¼ 0.02, (b) x ¼ 0.04, and (c) x ¼ 0.06. Insets (i) in a, b, and c show the initial portion of the M-H curve fitted
with BMP model, and inset (ii) zoomed M-H curves.

contribution at higher field. According to the above equation, Table III. The spontaneous moment per BMP is found to be
the samples are predicted as a mixture of BMPs where local- of the order of 1015 emu and the number of BMPs which
ized charge carriers strongly interact with the doped transi- were determined from Mo and meff values are of the order of
tion element over the Bohr radius and the paramagnetic 1015 per cm3, which is very small to the concentration neces-
matrix.32 Here, the spontaneous moment of the system is sary for percolation in ZnO. The required concentration for
given by Mo ¼ N  ms, where N is the number of BMPs percolation of BMPs is in the range of 1020 per cm3, which
involved and ms is the spontaneous magnetic moment per is five orders larger than observed value.31 Thus BMP model
BMP. L(x) ¼ coth(x) – (1/x) is the Langevins function with alone is insufficient to explain RTFM in the Ni doped ZnO
x ¼ meffH/(kBT), where meff is the true spontaneous moment system.
per BMP. At high temperature, the interaction between We further try to explain the FM on the basis of
the BMPs can be ignored and ms ¼ meff can be taken. vm is Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction, which
the susceptibility of the matrix. Parameters Mo, meff, and vm explains the magnetic phases on the basis of concentration of
are variables during the fit. It can be clearly seen from the fit- free carriers apart from the concentration of magnetic ions.
ting (inset of Figure 6(i)) that fitted data closely follow To achieve ferromagnetism in Ni doped ZnO, the electron
the experimental data and fitted parameters are listed in concentration must be low,5,33 as ZnO is a native n-type

TABLE III. List of parameters obtained from experimental M-H curve along with the fitted data in BMP model.

Samples Experimental data Fitting parameters extracted from BMP model

Zn1xNixO Mr  104 (emu/g) Hc (Oe) S Mo  103 (emu/g) meff  1017 (emu) vm  106 (egs) N  1015 (cm3)

x ¼ 0.02 2.51 53 3/2 3 1.5 0.4 1.1

x ¼ 0.04 2.52 54 3/2 2.3 1.5 9.9 0.86
x ¼ 0.06 2.06 49 3/2 2.1 1.32 1.5 0.89

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 033912-6 Srinet, Kumar, and Sajal J. Appl. Phys. 114, 033912 (2013)

material. Furthermore, the addition of electrons to the system ACKNOWLEDGMENTS

will move the Fermi energy level up, resulting a decrease in
hole density and a reduction in magnetization. In our case, One of the authors, R.K., is thankful to Mr. Jitendra
oxygen rich stoichiometry with increased Zn-O bonding Singh (CEERI Pilani, India) for experimental support.
favours the indirect Ni-O-Ni ferromagnetic exchange cou- 1
C. Klingshirn, J. Fallert, H. Zhou, J. Sartor, C. Thiele, F. M. Flaig, D.
pling. Furthermore, the enhanced Zn-O bonding in 2% and Schneider, and H. Kalt, Phys. Status Solidi B 247, 1424 (2010).
4% in turn reduces the Vo (donors) and leads to strong 2
M. D. McCluskey and S. J. Jokela, J. Appl. Phys. 106, 071101 (2009).
3
hybridization (p-d exchange coupling) of Ni in ZnO host ma- D. Wu, Q. Y. Xu, F. M. Zhang, X. S. Liu, and Y. W. Du, AAPPS Bull. 18,
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4
H. Ohno, Science 281, 951 (1998).
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