Appl. Phys.

A (2016) 122:740
DOI 10.1007/s00339-016-0265-7

Correlation between structural, optical and magnetic properties

of Mn-doped ZnO
Pawan Kumar1 • Bipin K. Singh1 • Bhola N. Pal2 • Praveen C. Pandey1

Received: 17 March 2016 / Accepted: 8 July 2016

Ó Springer-Verlag Berlin Heidelberg 2016

Abstract We have investigated the structural, optical and 1 Introduction

magnetic properties of Mn-doped ZnO nanoparticles with
different doping concentrations (0, 2, 4 and 6 %) synthe- Transition metal-doped semiconductors have attracted lots
sised by sol–gel method. Lattice parameters, cell volume, of attention in last few decades due to their wide variety of
atomic packing fraction, crystallite size and confirmation optoelectronic and magnetic applications. ZnO with
of hexagonal wurtzite crystal structure have been studied hexagonal wurtzite crystal structure has space group P63mc
by X-ray diffraction data. Surface morphology as well as with a wide band gap (3.36 eV) and high excitation binding
grain size and the presence of all the elements have been energy (60 meV) [1–5], which makes it one of the most
confirmed by scanning electron microscope and energy- promising materials for its potential uses in ultraviolet
dispersive X-ray spectroscopy, respectively. The decrease luminescence devices, light emitting diodes (LED), solar
in lattice parameters ratio (c/a) with Mn concentration cell, gas sensors, optical limiting applications, optical
indicates lattice distortion with the incorporation of Mn2? coatings, photo catalysts, antibacterial activity, piezoelec-
ions at Zn2? site of ZnO structure, which has been con- tric devices and transparent electrodes, etc. ZnO has
firmed by Raman analysis. It has been observed that attracted the researchers towards extensive studies of its
microstructure defects induced some extra Raman vibra- properties with different doping materials [6–9]. Rare
tion modes. Ultraviolet–visible analysis shows that earth-doped ZnO [10–12] and transition metal-doped ZnO
absorption edge lies in visible region, and encroachment in have been studied for different applications [13–21]. Dif-
visible region increases, while energy band gap decreases ferent groups have reported that Mn doping significantly
with the increase in Mn concentrations. We have recorded manipulate the magnetic properties of ZnO [22–26]. In
FTIR spectra at room temperature to study the vibrational addition to its semiconducting properties, this creates a
bands present in Zn1-xMnxO samples. The magnetic study special attention of this class of materials for the use as
of samples indicates ferromagnetic behaviour at room diluted magnetic semiconductors (DMS). Such kind of
temperature. The magnetic properties increases with dop- DMS has potential application in magneto-electronics and
ing concentration due to small lattice distortion and spintronic devices, which exploit both the electron spin in
defects. magnetic materials and the charge of electron in semi-
conductors. In case of DMS, magnetic properties can be
controlled by type of carrier, their mobility and density.
The optical and magnetic properties of the materials can be
& Praveen C. Pandey tuned by tailoring the particle size [27, 28]. Some groups
[email protected] have observed different magnetic behaviour of Mn-doped
1 ZnO due to different preparation methods [29–32]. Dietl
Department of Physics, Indian Institute of Technology
(Banaras Hindu University), Varanasi, U.P. 221005, India et al. [33] predicted ferromagnetism with a very high Curie
2 temperature in p type ZnO and GaN. The paramagnetic
School of Material Science and Technology, Indian Institute
of Technology (Banaras Hindu University), Varanasi, behaviour has been observed in Mn-doped bulk ZnO pre-
U.P. 221005, India pared by solid-state reaction technique [34]. Luo et al. [35]

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740 Page 2 of 12 P. Kumar et al.

found an anti-ferromagnetic ordering in Mn-doped ZnO followed by furnace cooling to room temperature. Further,
nanoparticles prepared by a combustion method. However, pellets have been crushed to get powder sample for all
the correct mechanism of room temperature ferromag- characterisations, while EDS and SEM characterisation
netism (RTFM) is still a topic of debate. have been performed in pellets form with gold coating on
Since large amount of energy in solar radiation is consist the samples.
of visible light, in order to improve the absorption prop-
erties of ZnO, it should absorb not only UV but also visible 2.2 Characterisations
light. For this, band gap of ZnO has to be narrowed or to be
split up into several sub-band gaps, which can be achieved The phase confirmation of synthesised samples has been
by incorporation of transition metal ions. Substitution of performed by Rigaku-MiniFlex-II DESKTOP powder
transition metal ions in host semiconductor may produce X-ray diffractometer with CuKa radiation (k = 1.54 Å) at
small lattice disorder or defects, which is responsible for 30 kV and 15 mA. All patterns were recorded over the
change in structural, optical and magnetic properties of range 20 B 2h B 80 with a step size of 0.02°. The mor-
host semiconductor. phology has been investigated with scanning electron
In this paper, we present the study on structure, mor- microscope (SEM) in pellets forms. OXFORD Instrument
phology, elemental analysis, Raman scattering, FTIR, SEM EVO 18 Research has been used for SEM and EDX
optical and magnetic properties of sol–gel-derived Mn- analysis. The optical absorption spectra of the samples
doped ZnO nanopowder. UV–Vis analysis has been per- have been recorded by the Lambda-35 UV–Vis spec-
formed to know the effect of Mn concentration on trophotometer from PerkinElmer in the range of
absorption properties of ZnO. These results show strong 200–800 nm. The room temperature Raman spectrum
absorption broadening with Mn doping in UV region with ranging from 100 to 1000 cm-1 has been collected with a
absorption edge in visible region, which may have Renishaw inVia Raman spectrometer. Fourier transform
important application for photo-detector or solar cell. infrared (FTIR-8400S) spectrophotometer has been used to
RTFM is important for practical spintronic devices; obtain information about functional groups present in the
therefore, we have also studied magnetic properties of samples. Magnetic behaviour has been measured using
samples to know the effect of Mn concentration on RTFM. Quantum Design MPMS-3 magnetometer in temperature
In this study, we have tried to correlate the change in range 5–300 K.
absorption and RTFM of samples with structural change
due to Mn incorporation using an easier route of synthesis.
3 Results and discussions

2 Experimental procedure 3.1 Structural analysis

2.1 Synthesis of ZnO: Mn nanoparticles X-ray diffraction has been used to estimate structural
parameters and phase purity of ZnO and Mn-doped ZnO
The samples of Mn-doped ZnO with nominal compositions system. Figure 1 shows XRD pattern of synthesised
Zn1-xMnxO (x = 0.00, 0.02, 0.04 and 0.06) have been Zn1-xMnxO(x = 0.00, 0.02, 0.04 and 0.06) nanopowder.
synthesised by sol–gel route using high-purity analytical The sharp and intense peaks indicate that the samples are
grade acetates of Zn and Mn, i.e. Zn(CH3CO2)22H2O and highly crystallite. The XRD peaks for (100), (002), (101),
Mn(CH3CO2)24H2O, without any further purification. For (102), (110), (103) and (112) planes are found to be in a
the synthesis of the samples, we dissolved appropriate good agreement with the standard peak position of pure
amount of zinc acetate dehydrate in isopropyl alcohol ZnO (PDF: 792205). No extra peaks of impurity phases are
under magnetic stirring for 2 h and then added appropriate detected within the detection limit of the instrument (ex-
proportion of manganese acetate tetra hydrate with stirring cept x = 0.06). It indicates that all the investigated samples
until complete dissolution of the precursors. Moreover, have hexagonal wurtzite structure with a space group
urea was used as a burning agent, and then, the resultant P63mc. We have observed some traces of impurity peak of
solution was stirred until the gel was obtained. In this entire Mn3O4 for x = 0.06. We should pointed out that volume
process, the temperature was maintained at 100 °C. These fraction of Mn3O4 in doped ZnO is very small. Thus, we
gels were then heated at 500 °C for 30 min in furnace to can predict that Mn3O4 does not significantly affect the
obtain sample in powder form. An additional heat treat- properties of ZnO. Kumar et al. [14] also observed the
ment was given at 600 °C for 2 h in furnace to remove the presence of Mn3O4 in Mn-doped ZnO. It has been observed
impurities. Then, samples in pellets form were placed in that peak position of planes shifted towards higher angles
crucible for sintering in furnace at 1000 °C for 2 h and lower intensities with Mn concentration increasing,

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Fig. 1 XRD pattern of Zn1-xMnxO (0.00, 0.02, 0.04 and 0.06)

sintered at 1000 °C

which causes small variation in lattice parameters. Fig-

ure 2a–c shows peak position of (100), (002) and (101)
planes, which confirm the agreement with the statement.
The lattice constants (a and c) and volume of unit cell of
ZnO:Mn have been calculated with unit cell software.
Values of a and c are listed in Table 1. The lattice constant
‘a’ of Mn-doped ZnO is slightly larger than that of un-
Fig. 2 a–c Peak position of (100), (002) and (101) planes,
doped ZnO because the ionic radius of Mn2? (0.80 Å) is respectively
slightly larger than that of Zn2? (0.74 Å) ions [23]. The
variation of c/a ratio with Mn concentration is shown in concentration confirms the incorporation of Mn2? ion at
Fig. 3, which indicates that c/a ratio decreases with the Zn2? site of ZnO structure.
increase in Mn concentration. This indicates the occurrence The volume of the unit cell has been calculated using the
of lattice distortion with Mn concentration. equation [36].
For HCP structure a = b = c and c/a = 1.633, when pffiffiffi
Mn2? of higher ionic radius substituted at the place of 3 2
V¼ a c
Zn2? ions, the lattice parameter ‘a’ as well as ‘b’ increases, 2
which causes decrease in ‘c’ in order to maintain distorted The values of unit cell volume are listed in Table 1,
HCP structure. Thus, c/a ratio decreases with increase in which shows that volume changes with Mn concentration.
Mn concentration. This indicates that crystal structure shift It may be due to variation in lattice constants (a and c) with
towards higher symmetry. The change in c/a ratio with Mn Mn concentration.

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740 Page 4 of 12 P. Kumar et al.

Table 1 Lattice parameters,

Composition Lattice parameter Crystallite size (nm) Cell volume (Å)3 APF
crystallite size, cell volume and
atomic packing fraction of the a (Å) c (Å)
samples
ZnO 3.2533 5.2093 49.76 47.7470 0.7548
Zn0.98Mn0.02O 3.2529 5.2091 47.88 47.7346 0.7547
Zn0.96Mn0.04O 3.2671 5.2105 52.17 48.1646 0.7578
Zn0.94Mn0.06O 3.2644 5.2055 54.35 48.0403 0.7579

Fig. 3 Variation of lattice parameters ratio (c/a) with Mn

Fig. 5 Change in crystalline size with Mn concentration
concentration
value of APF is approximately 75 %, while APF of bulk
ZnO is nearly 74 %, which indicates that APF of investi-
gated samples are slightly larger than bulk ZnO. It may be
due to size effect in nanocrystal samples. APF increases
with the increase in Mn concentration, which may be
because of decrement of voids in the samples. The same
pattern has also been reported by Mote et al. [36]. The
crystallite size of pure and Mn-doped ZnO has been cal-
culated using Scherer’s formula [4].
0:9k
D¼
b cos h
where k is wavelength of X-rays (1.54 for Cu Ka), h is
Bragg’s angles, and b is the full width at the half
maximum.
The crystallite size of un-doped sample is higher ini-
Fig. 4 Variation of APF with Mn concentration tially, and latter, it decreases for Mn (2 %) doping as the
lattice easily accept Mn2? ions without affecting ZnO
structure. As Mn concentration starts increasing, crystallite
Atomic packing fraction has been calculated using for- size increases as shown in Fig. 5. The same behaviour has
mula [36]. been obtained by Dole et al. [1]. Change in crystallite size
with Mn concentration attributed to substitution of Mn2?
2pa
APF ¼ pffiffiffi ion in Zn2? site of ZnO structure, as incorporation of Mn2?
3 3c ions (having higher ionic radius than Zn2?) in ZnO struc-
where a and c are lattice parameter. ture can create some strains–stress, which in turn can
Figure 4 shows the variation of APF with Mn concen- promote both densification and grain growth and can
tration, and its values are listed in Table 1. The observed increase grain boundaries or surface diffusion.

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3.2 Morphological analysis

We have done SEM characterisation to study the mor-

phology (texture), crystallite structure, grain size and ori-
entation of materials making up the sample. SEM
micrographs of samples under investigation are shown in
Fig. 6a–d, which confirms the crystallite structure of
Zn1-xMnxO (x = 0.00, 0.02, 0.04 and 0.06) nanopowder.
From image analysis, it has been observed that crystallites
are fused to form grains. The grain size calculated by SEM
micrograph indicates that most of the grains are in the
range of 200–300 nm for all samples under investigation.

3.3 EDX (elemental) analysis

Energy-dispersive X-ray spectroscopy has been used for

qualitative and quantitative analysis of the entire element
present in the samples. Image of SEM micrograph shows
particular region of EDX analysis. Elemental mapping for
distribution and relative proportion of Zn0.98 Mn0.02O over
the scanned area is shown in Fig. 7. Same process has been
used for all the samples. The ratio of Zn:Mn:O is given in
Table 2, which confirms the presence of Mn in ZnO
structure. It has been observed that atomic and weight
percentage of Mn within the scanned area increases with
increase in doping concentration.

3.4 Optical properties

Absorption spectroscopy is a powerful technique to explore

the optical properties of nanoparticles. The absorption
spectra that measured in the range of 200–800 nm of the
ZnO and Mn-doped ZnO nanoparticles at different con-
centration of Mn (0, 2, 4 and 6 %) are presented in Fig. 8.
The absorption curves exhibit an intensive absorption in
200–380 nm wavelength range, with the absorption edge
between 400 and 550 nm. From this result, it is clear that
absorption edge shifted towards higher wavelength with the
increase in Mn concentration. In best of our knowledge, no
one has reported encroachment in visible region up to
550 nm with Mn-doped ZnO nanoparticles without sec-
ondary phase formation. Abdel-Galil et al. [37] reported
absorption in visible region due to formation of flower-like
structure. Omri et al. [38] reported absorption edge between
300 and 370 nm. Lotfi Orimi and Khosravi [39] have
observed absorption in visible region due to secondary
phase formation. Some authors have reported blue shift [40]
in Mn-doped ZnO due to quantum confinement or orbital’s
hybridization. The absorption edge shift in the considered
samples may be due to surface effect–average crystallite
size or morphology. This indicates substitution of Mn ions
into the Zn site of ZnO lattice. The change in band gap is Fig. 6 SEM image of a ZnO, b Zn0.98Mn0.02O, c Zn0.96Mn0.04O and
also responsible for absorption edge shift of samples. d Zn0.94Mn0.06O nanopowders, respectively

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740 Page 6 of 12 P. Kumar et al.

Fig. 7 EDX spectra of Mn-

doped ZnO nanopowder

Table 2 Atomic and weight percentage of all the samples

Mn % Zn Mn O
at.% wt% at.% wt% at.% wt%

0 49.50 80.02 0 0 50.5 19.98

2 56.77 83.48 1.11 1.37 42.12 15.16
4 51.09 79.33 2.25 2.93 46.66 17.73
6 50.92 78.15 3.74 4.82 45.34 17.03

In order to find the effect of Mn concentration on band

gap, we made use of Tauc relation to calculate optical band
gap [36].
ðahmÞ1=m ¼ cðhmEg Þ ð1Þ
where a is absorption coefficient given by a = -A/d (d is Fig. 8 Absorption spectra of Zn1-xMnxO nanopowder
the thickness of sample cell and A is the absorbance), hm is
photon energy, c is a constant, and Eg is the energy band Omri et al. [38] also observed decrease in band gap with
gap of the material. The value of ‘m’ depends on the type increase in Mn concentration. It may be due to the sp–
of the transitions. m = 1/2, 2, 3/2 for allowed, indirect and d exchange interaction between transition metal ions and
forbidden transition, respectively. Zn or due to Mn clustering, changing in average crystallite
From Eq. (1), a Tauc plot [(ahm)2 vs. hm] can be drawn. size and surface area-to-volume ratio. The band gap of
The point of the extrapolation of the linear part that meets Zn1-xMnxO (x = 0.00, 0.02, 0.04 and 0.06) has been in the
the abscissa will give the value of the band gap energy (Eg) range of 3.00–2.85 eV. The variation of band gap with Mn
of the materials [41]. Tauc plot to calculate band gap of concentration is shown in Fig. 10. The ferromagnetism in
individual samples is shown in Fig. 9a–d. It has been found Mn-doped ZnO is due to localised magnetic moments
that the band gap energy decreases with the increase in mediated by free charge carriers. The magnetisation curve
doped Mn concentration up to 4 %. Mote et al. [36] and shows magnetic behaviour increases with Mn

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Fig. 10 Energy band gap versus Mn concentration of Zn1-xMnxO

nanopowder

concentrations; this indicates increase in the charge carriers

with Mn doping. This increase in charge carriers affects the
sp–d exchange interactions by increasing d electron
moments of Mn ions, which could result the red shift in the
band gap. Thus, the magnetic behaviour of samples also
affects the band gap of materials. The blue shift in the band
gap has been explained with the help of Burstein–Moss
effect [4, 7]. In case of Burstein–Moss effect, Fermi level
merges into conduction band due to increase in carrier
concentration. But in our observation, band gap decreases
up to 4 % doping and then a small increase for 6 % doping.
This type of behaviour has also been observed by Bhat
et al. [42]. The initial decrease in band gap followed by an
increase is termed as band gap ‘Bowing’. This type of band
gap bowing has also been observed in Mn-doped ZnO thin
film, nanocrystals and Mn-doped CdS [43]. The band gap
bowing has been theoretically explained using second-
order perturbation theory [44]. Shi and Duan [45] observed
that bowing parameter for ZnBeO and MgBeO alloys is
large and dependent on composition. Therefore, observed
variation of band gap may be due to sp–d exchange
interactions affected by the composition.

3.5 Raman analysis

Raman spectra are recorded at room temperature to

investigate microstructural and vibrational properties of
ZnO wurtzite structure. The optical phonon irreducible
representation is given by Zhang and Xie [46], Vijaya-
prasath et al. [47] as
Copt ¼ A1 þ 2B1 þ E1 þ 2E2
where A1 and E1 are polar modes. These modes can split
Fig. 9 (ahm)2 versus photon energy of a ZnO, b Zn0.98 Mn0.02O, into transverse optical (TO) and longitudinal optical (LO)
c Zn0.96Mn0.04O and d Zn0.94Mn0.06O nanopowders phonon, while B1 mode is Raman inactive. Non-polar

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740 Page 8 of 12 P. Kumar et al.

Raman E2 active modes have two wave numbers namely Mn2? ions. Some additional peaks such as (138,168 and
Elow
2 and Ehigh
2 , which are associated with motion of oxygen 680 cm-1) in Mn 2 % (123, 58 and 673 cm-1) in Mn 4 %
and zinc sub-lattice, respectively. The wurtzite ZnO and (124, 163 and 673 cm-1) in Mn 6 % have been
nanoparticles have six Raman active phonon modes at observed, which may be due to the defects induced by Mn
101(Elow high
2 ), 381 (A1 TO), 407 (E1 TO), 437 (E2 ), 574 (A1 ions. The Mn2? and Zn2? induced some defects such as
-1
LO) and 583 cm (E1 LO), respectively [48]. vacancies and interstitials which activate some additional
Raman spectra of Zn1-xMnxO shown in Fig. 11 confirm vibration modes. The presence of doping vibration has also
that all the prominent peaks of ZnO are also present in Mn- observed by Wang et al. [49]. All observed Raman peaks of
doped ZnO. The two first-order modes observed at 98 and Zn1-xMnxO are tabulated in Table 3.
435 cm-1 correspond to Elow 2 and Ehigh
2 of pure ZnO
nanopowder. The mode observed at 330 and 539 cm-1 is 3.6 FTIR studies
attributed to Ehigh
2 - Elow
2 and Ehigh
2 ? Elow
2 , respectively,
-1
while 579 cm represent A1 (LO) of first order. Intensity FTIR spectroscopy technique is used to obtain information
of additional second mode at 539 cm-1 increases Mn about functional groups present in the samples, the
concentration and merges with A1 (LO) phonon. The molecular geometry and inter- or intra-molecular interac-
presence of Elow2 and Ehigh
2 in all samples under investiga- tions. We have recorded room temperature FTIR spectra to
tion confirms that Mn doping does not change wurtzite study the vibrational bands present in Zn1-xMnxO samples.
structure of ZnO. Raman scattering results are well con- Normally, we consider that the band frequencies within
sistent with those of XRD. Intensity of E2 modes decreases 1000 cm-1 are associated with the bonds between inor-
with increase in Mn concentration that indicates small ganic elements. FTIR vibrational frequencies for different
distortion in ZnO crystal structure due to incorporation of modes of Zn1-xMnxO (x = 0.00, 0.02, 0.04 and 0.06) are
shown in Fig. 12 and listed in Table 4. The FTIR vibra-
tional frequencies presenting at 588, 675, 669, and
684 cm-1 for X = 0.00, 0.02, 0.04 and 0.06 concentration,
respectively, are due to Zn–O stretching. This confirms the
wurtzite structure formation of the samples [1].
The peak observed at *1000 cm-1 can be attributed to
O–H asymmetric stretching mode. The peaks at *1410
and *1600 cm-1 are assigned to the symmetrical
stretching of C=O and asymmetric stretching of carboxyl
group, respectively. Intensity at 1600 cm-1 for Mn 2 %
and Mn 6 % is higher as compared to ZnO. The peak
around *2350 cm-1 is due to CO2 molecule present in the
acetate and in air. The peak at *2350 cm-1 is disappeared
for Zn0.96Mn0.04O. It may be possible that samples have
trapped some CO2 from atmosphere during FTIR charac-
terisation. Therefore, the presence of CO2 vibrational
modes is not serious contamination in Zn1-xMnxO
nanoparticles. Zn–O stretching modes have a blue shift
from 588 to 684 cm-1 with increase in Mn concentrations.
The blue shift observed in the samples can be explained on
the basis of atomic mass of the atom present in Zn1-x-
MnxO. Since Mn (54.93u) has less atomic mass as com-
pared to Zn (65.38u), Mn must have vibrational modes in
the higher wave number region. Hence, with increase in
Mn concentration, peak shifted towards higher wave
number, which confirms the substitution of Mn ions in Zn
site of ZnO nanoparticles.

3.7 Magnetic property

Fig. 11 Raman spectra of Zn1-xMnxO nanopowder at room Figure 13 shows the measured room temperature mag-
temperature netisation curve for the pure and Mn-doped ZnO samples.

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Table 3 Observed Raman peak

Vibration frequency (cm-1) Assignments
positions of Zn1-xMnxO
nanoparticles and their ZnO Zn0.98Mn0.02O Zn0.96Mn0.04O Zn0.94Mn0.06O
assignment
98 96 95 96 Elow
2

138 123 124 Doping related

168 158 163 Doping related
330 327 330 331 Ehigh
2 - Elow
2

384 376 384 380 A1 (TO)

435 434 435 435 Ehigh
2

539 531 523 531 Ehigh

2 ? Elow
2

579 569 566 553 A1 (LO)

680 673 673 Doping related

found that coercivity (Hc) and saturation remanence (Mrs)

for pure ZnO is 168 Oe and 0.00846, respectively. These
low values of remanence and coercivity suggest the pres-
ence of multi-domain magnetisation process. The close
scan near origin for Mn-doped ZnO shows decrease in
coercivity with increase in Mn concentration. The values of
coercivity and saturation remanence are listed in Table 5.
This decrease in the saturation magnetisation with increase
in Mn concentration can be attributed to the possible anti-
ferromagnetic order between nearest neighbour of Mn–Mn
atoms. The distance between Mn ions decreases with
increase in number of Mn atoms will lead to anti-ferro-
magnetic exchange. Figure 15 shows temperature depen-
dence of susceptibility of Mn-doped ZnO, and inset shows
ZFC–FC curve of pure ZnO.
Zero field cooling–field cooling (ZFC–FC) plots for
each sample does not show any significant differences.
ZFC–FC data lie nearly on the same point in the curve, i.e.
ZFC–FC curves are identical in nature. All samples exhibit
Curie–Weiss behaviour. Curie temperature has been cal-
culated by high-temperature linear part of 1/v versus
T curve using Curie–Weiss law. The Curie temperature of
Fig. 12 FTIR spectra of Zn1-xMnxO nanopowder Zn1-xMnxO (x = 0.00, 0.02, 0.04 and 0.06) has been found
to be 1257, 269, 111 and 80 K, respectively. This indicates
It has been observed that anti-ferromagnetic behaviour is a reinforcement of anti-ferromagnetism (AF) with increase
increasing with Mn concentration. Figure 14 shows a close in Mn concentration. Metallic Mn and all possible Mn
scan near the origin for pure ZnO nanopowder. It has been oxides phase such as MnO, MnO2, Mn2O3 are anti-

Table 4 FTIR peak

Wave numbers (cm-1) Assignments
assignments of Zn1-xMnxO
system ZnO Zn0.98Mn0.02O Zn0.96Mn0.04O Zn0.94Mn0.06O

588 675 699 684 Zn–O stretching

896 898 900 881 Weak vibration of ZnO
1003 1008 1010 995 O–H asymmetric stretching
1410 1410 1406 1410 Symmetrical stretching of C=O
1593 1599 1609 1626 Asymmetric stretching of carboxyl group
2351 2351 2343 Co2 molecule in air

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740 Page 10 of 12 P. Kumar et al.

Fig. 13 M–H curve of pure and Mn-doped ZnO nanopowder at

Fig. 15 Susceptibility curve of Mn-doped ZnO. Inset shows ZFC–FC
300 K
curve of pure ZnO

property of system or the concentration of oxygen vacancy

is responsible for ferromagnetic exchange between Mn
ions. Other authors suggested that ferromagnetism in Mn-
doped ZnO is due to secondary phase formation [23] such
as ZnMn2O4, Mn3O4, etc. Coey et al. [50] observed that
ferromagnetic exchange in dilute ferromagnetic oxide can
be mediated by shallow donor electron. In our case, XRD
result confirms that there is no any secondary phase present
in the system except in Mn 6 %. Therefore, we believe that
ferromagnetism in our case is due to defect and incorpo-
ration of Mn in ZnO host. The connection between struc-
tural defect and RTFM has been studied by several authors
[49]. In our study, E2 mode in Raman spectra become weak
with increase in Mn concentration, which indicates that
Fig. 14 M–H curve of pure ZnO nanopowder at 300 K ZnO crystal structure is destroyed gradually by substitution
of Mn ions. XRD result also supports that lattice distortion
Table 5 Hc, Mrs and Tc values of Mn-doped ZnO nanopowder takes place with increase in Mn concentration. Thus, our
study has clearly shown that defect is an important factor
Mn (at.%) Hc Mrs Tc
affecting the RTFM as has been suggested by Wang et al.
0 168 0.0084 1257 [49].
2 149 0.0061 269
4 148 0.0037 111
6 132 0.0021 80
4 Conclusion

In this study, we combined XRD, SEM, EDS, UV–Vis,

ferromagnetic except Mn3O4, which is ferromagnetic only Raman analysis, FTIR and MPMS as reliable methods to
below 45 K. From Fig. 15, we can say that susceptibly and investigate the structural, morphology, elemental, optical
magnetisation value decrease with increase in temperature. and magnetic properties of the Mn-doped ZnO. XRD
An abrupt decrease in susceptibility value can be associ- reveals the fact that all samples have single phase and
ated with magnetic phase change. This ferromagnetic phase hexagonal wurtzite crystal structure. The shift in XRD
change is due to Mn-induced defect incorporation in the peaks towards higher angles and variation in APF, crys-
system. Although lots of theoretical and experimental tallite size, c/a ratio with Mn concentration indicate sub-
works have been done about transition metal-doped ZnO stitution of Mn ions at Zn site of ZnO lattice. The SEM
[41], the origin of ferromagnetism in Zn1-xMnxO is not images confirm the proper grain growth in all the samples.
clear yet. Some authors have reported that it is intrinsic Elemental analysis shows the presence of Zn, Mn and

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oxygen over the scanned area of the samples. UV–Vis 11. Y.H. Yang, H.G. Zhu, G.W. Yang, Appl. Phys. A 103, 73–79
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ZnO indicate small lattice distortion in ZnO crystal struc- Phys. Chem. C 116, 16700–16708 (2012)
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