J. Mater. Sci. Technol., 2012, 28(3), 268274.

Synthesis, Crystal Structural and Electrical Conductivity Properties

of Fe-Doped Zinc Oxide Powders at High Temperatures
Hakan Colak1,2) and Orhan Trkolu1)

u g
1) Department of Chemistry, Science of Faculty, University of Erciyes, Kayseri, 38039, Turkey
2) Deparment of Chemistry, Science of Faculty, University of Cankr Karatekin, Ballca Campus, Cankr, 18200, Turkey

[Manuscript received December 31, 2010, in revised form March 5, 2011]

The synthesis, crystal structure and electrical conductivity properties of Fe-doped ZnO powders (in the range
of 0.2515 mol%) were reported in this paper. I-phase samples, which were indexed as single phase with
a hexagonal (wurtzite) structure in the Fe-doped ZnO binary system, were determined by X-ray diraction
(XRD). The solubility limit of Fe in the ZnO lattice is 3 mol% at 950 C. The above mixed phase was observed.
And the impurity phase was determined as the cubic-ZnFe2 O4 phase when compared with standard XRD data
using the PDF program. This study focused on single I-phase ZnO samples which were synthesized at 950 C
because the limit of the solubility range is the widest at this temperature. The lattice parameters a and c of
the I-phase decreased with Fe-doping concentration. The morphology of the I-phase samples was analyzed
with a scanning electron microscope. The grain size of the I-phase samples increased with heat treatment and
doping concentration. The electrical conductivity of the pure ZnO and single I-phase samples was investigated
using the four-probe dc method at 100950 C in air atmosphere. The electrical conductivity values of pure
ZnO, 0.25 and 3 mol% Fe-doped ZnO samples at 100 C were 2106 , 1.7103 and 6.3104 Scm1 ,
and at 950 C they were 3.4, 8.5 and 4 Scm1 , respectively.
KEY WORDS: II-VI semiconductors; Zinc oxide and doped zinc oxide; Four point probe method

1. Introduction
Zinc oxide (ZnO) powders are very important materials due to the many interesting properties inherent in this material, such as dielectric, piezoelectric, pyroelectric, semiconducting, acousto-optic,
optical, electro-optical, nonlinear optical, photoelectrochemical and electrical properties[1] . ZnO is
one of the most versatile and technologically interesting semiconducting materials because of its typical
properties such as resistivity control over the range of
103 105 cm, transparency in the visible range,
high electrochemical stability, direct band gap, absence of toxicity and abundance in nature[2] . ZnO normally occurs in the hexagonal wurtzite crystal structure with a=0.32488 nm and c=0.52066 nm in the
standard data (JCPDS, 36-1451). Electron doping in
Corresponding author. Assist. Prof., Ph.D.; Tel.: +90
506 9868893; Fax: +90 376 2181031; E-mail address:
hakan colak@hotmail.com (H. Colak).

nominally undoped ZnO has been attributed to Zn interstitials and oxygen vacancies[3] . High purity ZnO
crystals exhibit strong n-type conductivity with the
electrons moving in the conduction band as charge
carriers. This characteristic has traditionally been attributed to native defects such as oxygen vacancies
and zinc interstitials[4,5] .
ZnO has both good electronic and optical properties because of a stoichiometric deviation due to
the existence of intrinsic defects such as O vacancies and Zn interstitials. However, these properties
of pure ZnO are unstable due to the adsorption of
atmospheric oxygen, which decreases the conductivity, and they cannot meet the increasing needs for
present day applications. To stabilize them against
such changes and enhance the properties of the ZnO,
doping is necessary and this purpose was achieved by
adding some dopants[6,7] . Moreover, doping leads to
an increase in the conductivity of ZnO. ZnO doping
was achieved by replacing Zn2+ atoms with the atoms
of the dopant elements. The eciency of the dopant

H. Colak et al.: J. Mater. Sci. Technol., 2012, 28(3), 268274.

element depends on its electronegativity and the difference between its ionic radius and the ionic radius
of zinc[8] . Extensive studies have been carried out
to modify the properties of ZnO for dierent applications. Doping with transitional metal elements leads
to many interesting properties of ZnO[9] . In addition, thermal annealing is a widely used method to
improve crystal quality and to study structural defects
in materials. For semiconductors, thermal annealing
is also used to activate dopants. During the annealing
process, dislocations and other structural defects will
move in the material and adsorption/decomposition
will occur on the surface, thus the structure and the
stoichiometric ratio of the material will change, which
inuences the electrical and optical properties of ZnO.
The structural, electrical and optical properties are
vital for semiconductor devices. It is necessary to investigate how these properties are aected by thermal
annealing[10] .
Although there are a few reports on the doping elements in the ZnO varistor, the eects of some dopants,
such as Fe, on the electrical conductivity of the ZnO
varistor still remain unclear. This is because doping
eects have been studied in quite dierent systems under dierent experimental conditions[11] . In this work,
metallic iron-doped ZnO powders were synthesized at
high temperatures by using the solid state reaction
method. Then, their structural properties were studied and the dc electrical conductivity of the ZnO solid
solution samples was measured at high temperatures.
The solid state reaction was chosen because of its reproducibility, easy control and sucent products for
measurement[12] .
2. Experimental
Synthesized iron (Fe) doped ZnO powders at high
temperatures were measured by using the standard
solid state reaction method. At rst, solid mixtures
of Fe-ZnO (0.25 x 15 mol%) were prepared by mixing and homogenizing with stoichiometric amounts of
pure ZnO and metallic Fe in an agate mortar. As
starting materials, commercially pure ZnO powders
(99.9% Fluka) and metallic iron powders (99.5% Alfa
Aesar) were used. The powder mixtures were rst
calcined at 600 and 650 C for 24 h. After grinding
and homogenization, the pre-annealed mixtures were
heat treated at 700, 750, 800, 850, 900 and 950 C,
respectively. All these heat treatments were made
in air atmosphere for 48 h, in alumina crucibles and
without any compaction procedure. At the end of
each heat treatment procedure, the annealed powders
were slowly cooled in the furnace by switching it o
(uncontrolled). Before and after heat treatment, each
of the samples was ground in an agate mortar to homogenize powder size. The samples were then analyzed with X-ray powder diraction (XRD). The XRD
data of the samples were recorded on a computerinterfaced Bruker AXS D8 advanced diractometer
operating in BraggBrentano geometry (CuK radi-

269

ation, graphite monochromator, 40 kV and 40 mA)

over a 10 deg.290 deg. angular range. The divergence and receiving slits of 1 and 0.1mm, respectively,
were located on the diractometer. The diraction
patterns were scanned in 0.002 deg. (2) steps and the
diracted beams were counted with a NaI(Tl) scintillation detector. The Dirac Plus and Win-Index programs were used to obtain information about the crystal structures of the samples. Then, for a comparison
with standard data, the PDF program (Maint Powder
Diraction Database Manager Software) was used. In
all cases, the XRD patterns of the samples, which were
obtained as single phase, could be indexed on the basis of a hexagonal cell in the FeZnO system. The
single phase was named as I-phase. The other samples which were not indexed with a hexagonal crystal structure were named as II-phase. Samples which
were out of the solubility range were heterogeneous
solid mixtures (I+II). The morphologies of both annealed (950 C) and non-annealed undoped ZnO samples and I-phase samples (950 C) were observed by
scanning electron microscopy (SEM, LEO 440) operated at 20 kV. Before SEM measurement, the I-phase
samples in the FeZnO system were pressed into pellets of 0.1 cm in thickness (t) and 1.3 cm in diameter
(d) under 5 ton pressure (369 MPa) and were calcined at 950 C for 24 h in air. After heat treatment,
the XRD measurements showed that no phase change
in the hexagonal samples was observed. The average
grain sizes of the I-phase samples were calculated by
the image-pro plus 5.0 program from the SEM micrographs.
The electrical conductivity (dc ) measurements of
the I-phase samples (950 C) were made using the
standard four-probe dc method. The circular samples
with a hexagonal structure, which were mentioned
above as the pelleted samples, were used for the electrical conductivity measurements. To reduce contact
resistance, ne platinum wires were directly attached
to the surface of the samples. The ohmic character of
the wire contacts was checked prior to each measurement. The contacts were positioned symmetrically
with respect to the center of the circular pellet and the
contact separations (s) were 0.2 cm. The conductivity
measurements were made between 100 and 950 C for
I-phase samples synthesized at 950 C. The increase
in furnace temperature was initial in 100 C (in the
range 100400 C) steps, then in 50 C (450950 C)
steps in air. During the measurements, the sample
temperature was determined by a thermocouple located 5 mm away from the sample. This thermocouple had a cold (0 C) junction. All experimental data
were recorded by a Keithley 2400 sourcemeter and a
Keithley 2700 electrometer which were controlled by
a computer.
3. Results and Discussion
3.1 Structural properties
Because data on the solubility of Fe ions in ZnO

270

H. Colak et al.: J. Mater. Sci. Technol., 2012, 28(3), 268274.

Table 1 Observed phases in the binary system of Fe-doped ZnO (in the range of 0.2515 mol%)
x (Fe addition)/mol%
0.25 0.50 0.75 1
2
3
4
5
6
7
8
9
10
11
12
13
14
I
I
I I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II
I
I
I I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II
I
I
I I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II
I
I
I
I I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II
I
I
I
I
I I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II
I
I
I
I
I
I I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II I+II
IFe-doped ZnO (hexagonal structure), IIcubic-ZnFe2 O4 , I+IIheterogeneous solid mixtures

Temp./ C
700
750
800
850
900
950
Notes:

Fig. 1 XRD patterns of Fe-doped ZnO: (a) undoped

ZnO (950 C), (b) 0.25 mol% Fe-doped ZnO, (c)
3 mol% Fe-doped ZnO, (d) 6 mol% Fe-doped ZnO,
(e) 15 mol% Fe-doped ZnO (950 C) (: the peaks
of II-phase, ZnFe2 O4 )

are not known, annealing experiments at varying temperatures were performed[13] . Fig. 1 shows the XRD
patterns of pure ZnO (950 C, 48 h), 0.25, 3, 6 and
15 mol% Fe-doped ZnO samples (950 C, 48 h). In
this gure, all the XRD patterns show typical peak
patterns, which can be indexed as the ZnO wurtzite
structure. The peak appears at 2=34.44 deg., which
corresponds to the (002) directions of the ZnO hexagonal wurtzite structure[14] . For 6 and 15 mol% Fedoped ZnO samples, XRD patterns show extra peaks,
which indicate ZnFe2 O4 , (PDF No. 011108)[1518] .
The XRD patterns of other single I-phase samples,
which were synthesized at other temperatures, were
quite similar to the patterns of the I-phase samples
given in Fig. 1. At 950 C, the XRD measurements
revealed that doping with more than 3 mol% caused
the coexistence of the I and II phase. No indication of
iron metal impurities was observed in the samples. In
the FeZnO binary system, the observed single phases
and heterogeneous solid mixtures depending on the
reaction temperature and amounts of Fe doping are
presented in Table 1. The widest range solubility
in the ZnO lattice of Fe ions is at 950 C, and at
this temperature the solubility limit is 3 mol%. At
lower temperatures the solubility range is lower than

15
I+II
I+II
I+II
I+II
I+II
I+II

950 C. The low solubility of Fe may be satisfyingly

explained by the heterovalence of the Fe ions in the
ZnO host lattice[13] . The mobility of Fe ions which
diuse in ZnO tetrahedral sites increases with temperature. Heat treatment temperature was found to
have an eect on the solubility of Fe ions in ZnO[19] .
In addition, both the ionic radii and the valence state
are important factors in determining the solubility of
the dopants. A smaller deviation of these factors from
those of Zn2+ would be favorable for the dopants to
have a higher solubility. This study focused on single
I-phase ZnO samples synthesized at 950 C due to
the limit of the solubility range, which is the widest
at this temperature. The other I-phase samples synthesized at temperatures lower than 950 C, and the
multiphase samples (I+II) were excluded from this
study.
For the wurtzite ZnO structure, the lattice constants determined at room temperature by various experimental measurements and theoretical calculations
were in good agreement. The lattice constants of the
samples mostly ranged from 0.32483 to 0.32501 nm for
the a parameter and from 0.52023 to 0.52050 nm for
the c parameter. The deviation from that of the ideal
wurtzite crystal is probably due to lattice stability
and ionicity[20] . Table 2 shows the dependence of the
Table 2 Unit cell parameters of I-phase ZnO samples at 950 C
x (Fe addition)/mol%
0.25
0.50
0.75
1
2
3

Unit cell parameters/nm

a
c
0.32501
0.52050
0.32499
0.52047
0.32493
0.52033
0.32488
0.52026
0.32488
0.52025
0.32483
0.52033

lattice parameters a and c, respectively, on the addition ratio of metallic Fe. The lattice parameters of
the Fe-doped ZnO system are smaller than those of
pure ZnO, both a and c parameters decrease with the
substitution of Fe ions with Zn ions. Fe ions are substituted with Zn2+ ions which are in the tetrahedral
sites of the wurtzite structure of ZnO. It is considered
that valence state of Fe in ZnO is both +2 and +3,
namely Fe in the ZnO matrix exists in a mixed valence state. It has been reported that local magnetic
probes like electron paramagnetic resonance and

H. Colak et al.: J. Mater. Sci. Technol., 2012, 28(3), 268274.

271

Fig. 2 SEM images of I-phase samples for pure ZnO (non-annealed) (a), pure ZnO (annealed) (b), 0.25 (c),
0.50 (d), 0.75 (e), 1 (f), 2 (g) and 3 mol% (h) Fe-doped ZnO samples at 950 C

Mssbauer spectroscopy indicate the presence of Fe

o
in ZnO in both valence states, Fe2+ and Fe3+ . And
the presence of Fe3+ in ZnO is due to possible hole
doping in the system by cation (Zn) vacancies[21] . It
has also been reported in another study[22] that usually, if Fe is present in the substitutional site in a
defect-free ZnO crystal, the valence state of Fe will
be +2. In this report, also, the X-ray photoelectron
spectroscopy (XPS) result conrmed the presence of
uncoupled Fe3+ within the sample. In the FeZnO
binary system, Fe3+ ions are present due to the existence of cation vacancy. Cation vacancy near Fe
can promote Fe2+ into Fe3+ and also mediate the
Fe2+ Fe2+ exchange interaction. Since the transi-

tion metal (TM) doping percentage is slightly on the

higher side toward the cationic percolation threshold, Fe2+ Fe3+ exchange, although being less in number in comparison to the Fe2+ Fe2+ interaction, may
also be possible[22] . However, the ionic radius (fourcoordinated) of the Fe2+ ion is 0.074 nm and that
of the Fe3+ is 0.064 nm while the ionic radius of the
Zn2+ is 0.074 nm[23] . Therefore, the decrease in the
lattice parameters a and c can be explained by the
ionic radii dierence[24] .
Fig. 2 shows the SEM micrographs of both annealed (950 C) and non-annealed undoped ZnO and
I-phase ZnO samples (950 C). In the SEM micrographs of undoped ZnO samples (Fig. 2(a) and (b)),

272

H. Colak et al.: J. Mater. Sci. Technol., 2012, 28(3), 268274.

there is a homogeneous grain distribution. From these

images the average grain sizes were calculated and
were found to be 0.63 and 1.03 m, respectively[19] .
The grain sizes of the annealed sample are obviously
larger than those of the non-annealed samples, which
could be caused by strain relaxation. The annealing process clearly produces a recovery of the crystal
structure and an increase in the grain size[1,25] . As
can be seen in the SEM micrographs, the grains of
the I-phase samples are homogeneously distributed.
The grain size of all synthesized Fe-doped ZnO
samples are given in Table 3. From the SEM images,
Table 3 Grain size values of I-phase ZnO samples
at 950 C
x (Fe addition)/mol%
ZnO
ZnO
0.25
0.50
0.75
1
2
3
Note: non-annealed

Grain size/m
0.67
1.03
1.32
1.46
1.73
1.93
2.51
2.60

Znx Zn + e
i
i

3.2 Electrical properties

The total electrical conductivity is calculated using the following equation:
I 1
G
V

(1)

where G is the geometric resistivity correction

factor[27] . Both the values and the variation of the
electrical conductivity of the pelleted powder ZnO
samples are in connection with their structure and its
changes. On the other hand, thermal treatments of
the respective samples modify their structural characteristics and consequently, their electrical properties.
On this basis, the study of the temperature dependence of the electrical properties of ZnO samples, may
oer useful information about the possible changes of
the structural characteristics of ZnO samples[28] .
The temperature dependence of electrical conductivity (dc ) of the I-phase ZnO pelleted powder samples at 950 C was studied in the temperature range of
100950 C. log T 103 /T graphs were drawn in order
to show the conductivity change with respect to temperature. The graphs were compared with each other

(3)

Zn
i

the grain size of the Fe-doped ZnO samples slightly

increases with the addition of Fe because the substitution of Fe2+ and Fe3+ for Zn2+ increases the activity of ZnO by means of distortion of the ZnO lattice,
which is benecial to grain growth in Fe-doped ZnO
samples[26] . The grains are regular in size and shape.
Some pores can be noticed in the photographs. When
increasing the dopant concentration to 3 mol%, the
porosity increased[24] . In addition, the surface of the
samples is smooth.

T =

and the conductivity characteristics of the samples

were evaluated. The electrical conductivity plots vs
temperature of undoped ZnO, 0.50, 0.75 and 2 mol%
Fe-doped ZnO (950 C) samples are given in Fig. 3.
The graphic curves of the other single I-phase samples
were quite similar to the curves of the single I-phase
samples given in this gure. As seen in Fig. 3, the electrical conductivity of I-phase samples increases with
increasing temperature and shows the semiconducting behavior of pure and Fe-doped ZnO samples. It
is well known that the electrical conductivity of ZnO
samples is controlled by intrinsic defects (oxygen vacancy and interstitial zinc atoms) generated at high
temperature[11] .
Also, for ZnO samples, increasing electrical conductivity with temperature can be explained by the
following:
ZnO Znx + 1/2O2 (g)
(2)
i
(4)

Zn
i

+e

After ionization, carrier concentration is increased

by two extra electrons[29] . The electrical conduction
of the doped ZnO follows a mechanism in which the
electron or hole hops from one localized site to the
next. Whenever it is transferred to another site, the
surrounding molecules respond to this perturbation
with structural changes and the electron or hole is
temporarily trapped in the potential well leading to
atomic polarization. The electron resides this site until it is thermally activated to migrate to another site.
Another aspect of this charge hopping mechanism is
that the electron or hole tends to associate with local
defects[30] .
It is observed that conductivity slightly decreases
with increasing Fe concentration (Fig. 4). It is well
known that the electrical conductivity of ZnO samples at room temperature is due to intrinsic defects
created by oxygen vacancies. These defects introduce
donor states in the forbidden band slightly below the
conduction band and hence result in the conducting
behavior of ZnO. The electrical conductivity is controlled by the intrinsic defects generated during synthesis and by the presence of dopants. It is known that
during the sintering process at high temperature, oxygen vacancies will be produced which are responsible
for electrical conductivity. From the observed result of
decrease in conductivity of ZnO on Fe doping, it seems
that the Fe-doping aects the defect chemistry of the
ZnO. Therefore, It is believed that Fe in ZnO acts as
a deep donor and decreases the concentration of intrinsic donors. This reduction in intrinsic donor concentration increases with increasing Fe content, which
in turn decreases the electrical conductivity[31] .
Many researchers have studied the eects of 3d
transition metal impurities on the electrical conductivity of the ZnO varistor. They investigate that 3d
transition metals could enhance the excess oxygen
concentration in the grain boundary region and a

273

H. Colak et al.: J. Mater. Sci. Technol., 2012, 28(3), 268274.

0.8
(a)

0.0
-1

log ( /S cm )

-1

/S cm )

-0.8

log

(b)

0.6

0.0

-1.6

-2.4

-3.2

-0.6

-1.2

-1.8

-4.0

-2.4

-4.8

-5.6

-3.0
0.8

1.0

1.2

1.4

1.6

1/

1.8
3

10

2.0

2.2

2.4

0.8

2.6

1.0

1.2

1.4

1.6

-1

1/

/ K

1.8
3

2.0

2.2

2.4

2.6

-1

10 / K

1.6
(c)

(d)

0.8

0.8

0.0
-1

log ( /S cm )

-1

log ( /S cm )

0.0

-0.8

-1.6

-2.4

-0.8

-1.6

-2.4

-3.2

-3.2

-4.0

-4.0

0.8

1.0

1.2

1.4

1.6

1/

1.8
3

2.0

2.2

2.4

2.6

0.8

1.0

1.2

1.4

1.6

-1

10 / K

1/

1.8
3

2.0

2.2

2.4

2.6

-1

10 / K

Fig. 3 Electrical conductivity plots for undoped ZnO (a), 0.25 (b), 0.75 (c) and 2 mol% (d) Fe-doped ZnO (950 C)

is expected between the nearest donors at low temperatures. The total electrical conductivity can be
expressed as follows;

3
2

-1

log ( /S cm )

dc = 0 exp(Ea /kT )

0
-1
Conductivity at 100

-2

Conductivity at 500

-3

Conductivity at 950

-4
-5
-6
0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Fe / mol%

Fig. 4 Electrical conductivity variation for Fe-doped

ZnO I-phase ZnO samples (950 C)

potential barrier is formed preferentially. Therefore,

the electrical conductivity of Fe-doped ZnO samples
is apparently lower than that of undoped ZnO samples, and the grain boundary is more resistive than
the grain[3234] . Also, it was observed from the SEM
micrographs that Fe-doping produces a large number
of pores which may be the main reason for the significant decrease in the conductivity of the considered
samples[35] .
In general, for a semiconducting material, dc conductivity increases exponentially with temperature indicating that conductivity is a thermally activated
process. For doped semiconductors with low concentration of donors, the hopping transport of carriers

(5)

where dc is the electrical conductivity at any temperature, Ea is the activation energy, which corresponds
to the energy dierence between the donor level and
the conduction level, 0 is the pre-exponential factor,
k is the Boltzmann constant, and T is the absolute
temperature[8,11,30,36] .
The activation energy can be calculated from the
conductivity equation shown below,
Ea 1
+ ln 0
(6)
k T
The slope of the linear part of the Arrhenius curve
of the lnT 1/T graph is equal to Ea /k. For the
temperature range the I-phase ZnO samples have
Arrhenius-type electrical conductivity. From these
curves, drawn for all I-phase ZnO samples, the activation energies Ea were calculated (Fig. 5).
The increase in the activation energy of Fe-doped
ZnO can be explained as follows: when ZnO is substituted with Fe ions which are in the 3+ ion valence
state, they replace the Zn2+ ions and occupy zinc interstitial sites. The substituted Fe atoms cannot be
easily ionized like zinc atoms because of their higher
ionization potential (2 eV). Hence, the donor concentration is lowered by the addition of Fe which results
in the decrease of electrical conductivity. Thus, a
ln T =

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H. Colak et al.: J. Mater. Sci. Technol., 2012, 28(3), 268274.

0.63

0.54

0.36

/ eV

0.45

0.27

0.18

0.09
0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Fe / mol%

Fig. 5 Eect of doping concentration on activation energy for I-phase ZnO samples (950 C)

higher value of activation energy (Ea ) is found for Fedoped ZnO samples and it increases with increasing
iron concentration (x)[31] .
4. Conclusion
Fe-doped ZnO powders were synthesized by using the solid state reaction method with metallic Fe
powder and commercially pure ZnO powder. The
XRD analysis results indicated that all powder samples in the FeZnO binary system (0.25x3 mol%,
at 950 C) had a wurtzite structure, namely the solubility limit of Fe in the ZnO lattice at this temperature
was 3 mol%. The lattice constants of the I-phase ZnO
samples decreased with Fe doping concentration. The
grain size of the I-phase ZnO samples increased with
both heat treatment and the amount of Fe doping.
For pure and Fe-doped ZnO samples (950 C), electrical conductivity increased with heat treatment and
decreased with increasing doping concentration. In
addition, the activation energy of I-phase ZnO samples increased with increasing dopant concentration.
Acknowledgement
This work was nancially supported by the Research
Foundation of Erciyes University (Kayseri, Turkey).
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