International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016)
Synthesis, Characterization and Properties of Mn-doped ZnO
Nano- Composite
Saroj D. Patil #1, Rajendra B. Waghulade *2,
#1
Godavari College of Engineering , Jalgaon, 425001, Maharashtra, INDIA.
*2
D.N.C.V.P’s Arts, Commerce and Science College, Jalgaon, 425 001, Maharashtra, INDIA.
Abstract — This paper reports the synthesis,
Zinc oxide (ZnO), a direct wide band gap
characterization and properties of nano-sized Mn-
(3.4 eV at Room temperature) II-VI compound n-type
doped ZnO. A simple chemical co-precipitation
semiconductor, has a stable wurtzite structure with
method is used for the synthesis of Mn-dpoed ZnO
lattice spacing a = 0.325 nm and c = 0.521 nm and
nano-sized powder. Zinc Acetate (Zn(C2H3O2)2),
composed of a number of alternating planes with
Manganese acetate (Mn(CH3COO)2 ·2H2O) and the
tetrahedrally-coordinated O2- and Zn2+ ions, stacked
sodium hydroxide (NaOH) were used as a starting
alternately along the c-axis. It has attracted intensive
materials and double distilled water as a carrier. The
research effort for its unique properties and versatile
resulting nano-sized powder was characterized by x-
applications in transparent electronics, ultraviolet (UV)
ray diffraction (XRD) measurements, transmission
light emitters, piezoelectric devices, chemical sensors
electron microscopy (TEM) and energy dispersive x-
and spintronics [5-14]. It is well known that doping a
ray (EDX). The XRD studies revealed that the Mn-
selective element into ZnO is the primary method for
doped ZnO had wurtzite structure (hexagonal).The
controlling the properties of the semiconductor such as
crystalline size was found to be smallest for nano
band gap or electrical conductivity, and to increase the
sized Mn-doped ZnO when the as prepared powder
carrier concentration for electronic applications.
0
was cacinated at 400 C for 2 hr. The composition
Recently, many studies have focused on the
analysis by EDX indicated the presence of small
doping of transition metals (TMs) such as Mn, Ni, Fe,
amounts of Mn.
Co and Cr into ZnO due to the potential applications
Keywords — Nano-sized Zno,
precipitation, XRD, TEM, EDX
in spintronics [15]. Based on these properties, the
Doping,
Co-
doped and undoped ZnO nanostructures have the
possibility of being applied for nanodevices to detect
Introduction
chemical and gas because the response to different
In recent years, the synthesis of nano-materials has
gases is related to a great extent to the surface state
been a focal point of research and development
and morphology of the material. Moreover, to
activities in the area of nano-materials. Several
overcome the limitations of sensors with micrometer
methods have been developed for the preparation of
dimensions such as limited surface-to-volume ratio
nano-materials. Among the various methods, sol-
determines a limited gas response to low concentration
gel[1], spray pyrolysis, hydrothermal route[2], freeze-
of
drying, gel combustion route etc. are popular[3,4].
temperatures for operation to reach a desired gas
Chemical co-precipitation has been widely used in the
response, nanostructured materials and approaches
tested
gases
and
requirement
of
elevated
industry and in research to synthesis complex powders. have been investigated for their gas response,
selectivity and possible application in sensors with
This is because of its low cost and mass production.
better characteristics [16–20].
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International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016)
Experimatal –
The structure of the calcined powder was
investigated by using X-ray diffraction
Undoped
and
Mn-doped
zinc
oxide
nanocrystals have been synthesized in aqueous
solutions
by
(CH3COO)2
using
·
zinc
2H2O),
acetate
manganese
(Zn
acetate
(XRD) technique. The X-ray diffraction patterns were
recorded with a Rigaku diffractometer (Miniflex
Model, Rigaku, Japan) having Cu K
nm).
(Mn(CH3COO)2 2H2O) and sodium hydroxide
(NaOH) as the starting materials. Aqueous solution of
zinc
acetate
and
manganese
acetate
at
room
temperature was stirred using a magnetic stirrer. Then
the NaOH solution was added slowly drop wise up to
aqueous solution of zinc acetate and manganese
acetate under constant stirring until the final solution
pH value of about 8 was achieved.
The resulting
precipitate was filtered and washed three to four times
using double distilled water to remove impurities. The
( = 0.1542
The crystalline size was estimated from the
broadening of Mn-ZnO (101) diffraction peak (2 =
36.310C)
using
formula.
Debye-Scherrer’s
The
transmission electron microscopy (TEM) was used to
determine the particle size and the morphology of the
nano-sized powder with JEOL 1200 EX. The
composition of elements like Zn, O and Mn is
confirmed by energy dispersive x-ray (EDX) spectra.
Result and analysis
–
hydroxide, thus formed was dried at 1000C and
The precursor was calcined in air at different
grinded into a powder, which is the precursor. The
temperatures of 4000C, 6000C, 8000C and 10000C to
precursor was calcined in air at different temperatures
produce nano-crystalline powders with different grain
0
0
0
0
of 400 C, 600 C, 800 C and 1000 C for 2 hours to
size.The XRD pattern of the calcinied powder at
produce nano-crystalline powders with different grain
4000C for 2 hour is shown in Fig.1.2.
size. Fig.1.1 is a schematic representation of the
synthesis procedure.
0.1M solution of zinc
acetate and manganese
acetate
NaOH Solution
as a
precipitating
agent
Stir the solution and add
NaOH solution drop wise
until solution pH 8 is
achieved
Fig 1.2 XRD pattern of calcinied Mn-ZnO powder at 4000C
Keep solution with
continuous stirring
for 12-15 hours
The XRD indicates the major diffraction
0
0
0
0
peaks at 2 values of 31.80 , 34.46 , 36.31 , 47.58 ,
0
0
0
56.67 , 63.01 , 68.98 ,and 76.95
Filter and wash the
resulting
precipitate and
dry it at 100° C in
air
0
etc which are
attributed to the formation of Mn ZnO. The peak
positions are agree well with cassiterite structure. The
crystallite size was calculated by using the Scherrer
formula –
Grind the resulting
powder and Calcinate
at diff.
temperatures300/400/6
00/800 ° C for 2 h
t
k
B cos
Fig. 1.1 : A schematic diagram of the synthesis
procedure.
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International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016)
where t is the average size of the crystallite, assuming
The EDX spectram of nano-sized Mn-ZnO is asd
that the grains are spherical, k is 0.9,
is the
shown in fig 1.4. The EDX analysis indicates the
wavelength of X-ray radiation, B is the peak full width
presence of signals due to the Zn (33.95%), Mn
at half maximum (FWHM) and
(5.43%), and O (60.62% ), which proves that the
is the angle of
diffraction. The crystalline size of the powder
formation
calcinied at 4000C is found to be minimum and it is
impurities.
of
the
nanocomposote
without
any
~35.31 nm.
Calcination
Temperature
Crystallite Size (nm)
0
( C)
400
35.31
600
40.25
800
40.25
1000
46.96
Table 1 : The calcination temperature and corresponding grain size
of Mn-ZnO powders
The
TEM
micrograph
of
the
powder
0
calcinied at 400 C along with the electron diffraction
Fig. 1.4 The EDX spectrum of the Mn-ZnO nanocomposite
Conclusion –
pattern is shown in Fig.1.3. The TEM micrograph
The following main findings resulted from
shows clearly that the particle size of powder calcinied
at 4000C is ~35.31 nm. This result is in well
the present investigation –
agreement with the crystallite size calculated using the
We have successfully synthesized the nano-
XRD data.
sized Mn-ZnO powder at low cost by using a
chemical co-precipitation method using zinc
acetate, managanese acetate and the sodium
hydroxide, as starting materials and water as
a carrier.
The resulting powder was characterized by
X-ray
diffraction
(XRD)
measurements,
TEM and EDX.
The crystallite size is found to be smallest when
the as-prepared powder was calcinied at 400 oC
for 2 h and it is 35.31 nm.
References –
Fig. 1.3 TEM micrograph of ZnO nano composites calcined at 8000
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