Materials Letters 110 (2013) 42–44

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Effect of cobalt doping on structural and thermoelectrical power of zinc

allu chromites synthesised by sol–gel auto-combustion method
P.P. Hankare a,n, K.R. Sanadi a,n, A.V. Mali a, K.M. Garadkar a, S.D. Delekar a, I.S. Mulla b
a
Solid State Research Laboratory, Department of Chemistry, Shivaji University Kolhapur, Maharashtra 416004, India
b
Centre for Materials for Electronics and Technology (C-MET), Panchavati, Pune 411008, India

art ic l e i nf o a b s t r a c t

Article history: Nanocrystalline cobalt doped zinc allu-chromites (Zn1
xCoxAlCrO4, where x ¼0.0, 0.25, 0.50, 0.75 and 1.0)
Received 22 June 2013 were prepared by sol–gel auto-combustion method. These synthesised materials were characterised by
Accepted 23 July 2013 XRD, EDAX, SEM, TEM and TEP. XRD pattern shows formation of single cubic spinel phase only. The
Available online 31 July 2013
crystallite size and lattice parameters decrease with increasing cobalt content in zinc allu-chromites. The
Keywords: crystallite size lies in the range between 16 and 21 nm. Elemental analysis was carried out by using
Sol–gel preparation EDAX. The surface morphology of prepared sample is amorphous in nature which was investigated by
Nanoparticles SEM. Particle size obtained from TEM analysis was found to be 20 nm. The TEP studies of the samples
XRD reveal their semiconducting nature which was measured by using two probe methods.
EDAX
& 2013 Elsevier B.V. All rights reserved.
SEM
TEM

1. Introduction 2. Experimental

The study of transition metal oxides, particularly spinel ferrites
in the nanoregime, assumes significance from of a fundamental
point of view as well as an applied perspective. In recent years
attention has been devoted to nanostructured metal oxides
because of their unique properties and potential applications in
variety of fields [1–4]. Nanostructured mixed metal oxide materi-
als have received broad attention due to their distinguished
performance in electronics, optics, photonics and has various
catalytic activity such as water gas shift reaction, combustion of
halogenated hydrocarbons, alkylation of phenol, dehydrogenation
and hydrogenation [5–6].
Recent interest in the study of several spinel type chromites is
in terms of the synthesis of their nanoparticles at low tempera-
tures by different techniques. In view of the potential applications
of these nanosized magnetic materials in different technological
areas, as well as to study the intriguing magnetic properties
of the nano-chromite materials [7–11], aim of the present
work was to study the structural, surface and thermoelectric
power of a powder with the composition prepared by sol–gel
autocombustion.
n
Corresponding authors. Tel.: +91 231 2609381.
E-mail addresses: p_hankarep@rediffmail.com (P.P. Hankare),
sanadikishor@gmail.com (K.R. Sanadi).
Polycrystalline powder of Zn1
xCoxAlCrO4 was prepared by
sol–gel auto-combustion method. The A.R. grade citric acid
(C6H8O7  2H2O), cobalt nitrate [Co(NO3)2  6H2O], zinc nitrate
[Zn(NO3)2  4H2O], alluminium nitrate [Al(NO3)3  6H2O], and chro-
mium nitrate [Cr(NO3)3  9H2O] were used as starting materials.
The samples were prepared by sol–gel autocumbustion method as
prepared in our previous work [12].
3. Results and discussion
XRD analysis: The typical X-ray diffraction patterns of the sample
Zn1
xCoxAlCrO4 with x¼0.0, 0.25, 0.50, 0.75 and 1.0 are shown in
Fig. 1. This pattern corresponds to diffraction peaks of (220), (311),
(400), (422), (511) and (440). All the samples of nanoparticles
exhibit single cubic spinel structure only. The average crystallite
size (D) was calculated from the full width at half maximum
(FWHM) of the most intense peak (311) by using the Scherrer′s
formula [13].
D ¼ 0:9λ=β cos θ
where β is the FWHM of the most intense peak (311) and θ is the
Bragg angle for the (311) peak. The crystallite size of the samples
which was evaluted from the Scherrer′s equation lies between 16
and 21 nm. The lattice parameter ‘a’ was calculated by the least
square method. The lattice parameter, crystal size, and bulk density

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.07.087

(311)
(220)
(400) (422)
Relative Intensity (A.U)
20 40
2θ
Fig. 1. XRD patterns of the system (Zn1
xCoxAlCrO4, where x ¼0.0, 0.25, 0.50, 0.75
and 1.0).
Fig. 2. EDAX pattern for the sample Zn1
xCoxAlCrO4 (x¼ 0.50).
of the sample decrease with decreasing cobalt content which is
shown in Supplementry data. This can be attributed to the differ-
ence in ionic radius of Co2+, Zn2+, Cr2+.
EDAX and SEM analysis: It was essential to check the chemical
composition of the each annealed sample. One representative
pattern of Energy dispersive analysis of X-rays (EDAX) for
x ¼0.50 composition is shown in Fig. 2. The EDAX result clearly
shows that, Zn0.50Co0.50AlCrO4 contains Zn, Co, Al and Cr without
any impurity. The SEM micrograph of Zn0.50Co0.50AlCrO4 sample is
shown in Fig. 3. The composition shows more interconnected
reticulated mesh like morphology.
P.P. Hankare et al. / Materials Letters 110 (2013) 42–44 43
(511) (440)
X = 1.0
X = 0.75
X = 0.50
Fig. 3. SEM photographs of Zn1
xCoxAlCrO4 (x¼ 0.50).
X = 0.25
X = 0.0
60 80
Fig. 4. TEM micrograph of Zn1
xCoxAlCrO4 (x ¼0.50).
Transmission electron microscopy analysis: TEM was used to
investigate the morphology and micrographs of the sample. The
micrograph of the nanoparticles of Zn0.50Co0.50AlCrO4 sample is
shown in Fig. 4. The image shows the co-existence of spherical
particles with an average particle size of 20 nm and which is in
good agreement with the XRD result.
Thermoelectric power measurement study: The variation of the
Seebeck coefficient as a function of temperature is shown in Fig. 5.
As the amount of cobalt increases, the n-type semiconducting
nature of sample also increases. A negative value of α confirms
n-type charge carriers [14–16]. The most probable mechanism
for n-type conduction is electron hopping between Cr3+ and Cr2+
ions such as,
Cr2þ 2Cr3þ þ e

4. Conclusions
Cobalt substituted zinc allu chromites were prepared by simple
sol–gel auto-combustion method. XRD analysis shows simple
cubic spinel structure with average crystalite size 20 nm. The
lattice parameter and particle size decrease with increasing cobalt
content. EDAX analysis confirms that the material is composed of
Zn, Co, Al, and Cr without any impurity. Particle size obtained from
TEM analysis was found to be in good agreement with the value
obtained from XRD pattern. TEP measurement shows n-type
semiconducting nature.
44 P.P. Hankare et al. / Materials Letters 110 (2013) 42–44

0
-20
-40
-60
-80
-100
-120
-140
ΔV
-160
-180
-200 X = 0.0
-220 X = 0.25
-240
X = 0.50
X = 0.75
-260
X = 1.0
-280
-300
-320
400 450 500 550 600
ΔT
Fig. 5. Variation of Seebeck coefficient of (Zn1
xCoxAlCrO4, where x¼ 0.0, 0.25, 0.50, 0.75 and 1.0) with temperature.

Acknowledgement [3] Iglesias O, Labarta A, Batlle X. Journal of Nanoscience and Nanotechnology

One of the authors thankfully acknowledges the University Grants
Commission, Government of India, for their financial support.
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.matlet.2013.07.087.
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