J Supercond Nov Magn (2013) 26:34873493

DOI 10.1007/s10948-013-2197-1

O R I G I N A L PA P E R

Effect of Annealing Temperature on Structural and Magnetic

Properties of Zn0.94Co0.05 Cu0.01 O
Z.K. Heiba L. Arda Mohamed Bakr Mohamed
Nasser Y. Mostafa N. Dogan

Received: 14 February 2013 / Accepted: 23 March 2013 / Published online: 11 April 2013
Springer Science+Business Media New York 2013

Abstract The doped ZnO system Zn0.94 Co0.05 Cu0.01 O

(ZCCO) was prepared as a nano-polycrystalline by a simple solgel process, then air annealed at different temperatures. Applying X-ray diffraction (XRD) and the Rietveld
method, structural analysis showed that Co and Cu replace
Zn substitutionally yielding ZCCO single phase. The refined u-fractional coordinate of Zn increases monotonically
by an annealing temperature from 0.3546 at 500 C reaching 0.3722 at 800 C, very near from the ideal value 0.375.
The Zn tetrahedrons become more symmetric and the distortion is gradually relieved by annealing up to 800 C. Annealing at 900 C introduces tetrahedron distortion in an
opposite way. The zero field cooled (ZFC) and field cooled
(FC) magnetization versus the temperature at different applied fields and the magnetization versus the applied field
at different temperatures were carried out. The system exhibits a ferromagnetic behavior at room temperature. As the
annealing temperature increases from 550 to 900 C, the
saturation magnetization at 300 K increases from 0.0507 to
0.1088 emu/g.

Z.K. Heiba N.Y. Mostafa

Faculty of Science, Taif University, P.O. Box 888, Al-Haweiah,
Taif, Saudi Arabia
Z.K. Heiba M.B. Mohamed ()
Faculty of Science, Physics Department, Ain Shams University,
Cairo, Egypt
e-mail: mbm1977@yahoo.com
L. Arda
Faculty of Arts and Sciences, Bahcesehir University,
Besiktas 34100, Istanbul, Turkey
N. Dogan
Physics Department, Gebze Institute of Technology,
Gebze 41400, Kocaeli, Turkey

Keywords Nanostructures Magnetic properties

Microstructure

1 Introduction
ZnO is an interesting direct wide bandgap semiconductor
that is being explored for numerous applications [1]. Transition metal doped ZnO is a promising candidate material
for the field of spin-electronics. Spin-electronics (or spintronics) is based on concepts that utilize the quantum mechanical spin properties of carriers in addition to the carrier charge in realizing electronic functionality [2, 3]. There
are several theoretical arguments as well as experimental
reports, which predict that Co doped ZnO (ZCO) may be
the most promising diluted magnetic semiconductor material for room temperature ferromagnetism [4, 5]. One of the
key questions is whether the resulting materials is indeed a
single phase alloy of ZCO; and if it is so, are the Co ions
incorporated substitutionally for Zn2+ or interstitially with
uniform distribution or clusters keeping the ZnO structure.
In a previous study [6], we prepared nano-Zn1x Cox O as
a powder and thin film applying a solgel technique and
found that up to x 0.12, Co replaces Zn substitutionally
yielding ZCO single phase. The adding of a small amount
of Cu to Co-doped ZnO helps to achieve ferromagnetism by
creating additional carriers [7]. It has been found that the
magnetism observed in ZnO materials is due to the presence of lattice defects such as oxygen and zinc vacancies.
These vacancies in cluster form give rise to magnetic moment [8, 9]; the oxygen vacancies migrate and formed clusters on annealing as it reduces the bond energy that favors
a decrease in the strain field energy [9]. Annealing could
improve the structural and physical properties of ZnO films
doped with transition metals. Hsu et al. [10] investigated

3488

systematically the effect of annealing on structure and magnetism for Co-doped ZnO films under air, Ar, and Ar/H2
atmospheres at 523 K. They found that the ferromagnetism
of the films was strongly correlated with the oxygen vacancies in the ZnO lattice. Annealing the Al doped ZnO films
in oxygen, air, or nitrogen would improve the crystallinity,
but also could induce oxygen or nitrogen to be incorporated
into the films, which degraded the electrical properties [12].
Cho et al. [11] heat-treated CoFe doped ZnO films at 823 K
for 10 min by rapid thermal annealing under vacuum. They
found that, upon rapid thermal annealing, a remarked increase in the magnetization and the electron concentration
of the films. Khare et al. [13] observed that the magnetization of annealed Zn0.98 Co0.02 O films decreased after annealing at 673 K regardless of reducing or oxidizing atmosphere.
Huang et al. [14] reported that for the Co-doped ZnO films
annealed in air the saturation magnetization decreased with
increasing annealing temperature. Mingpeng et al. [15] annealed Ni and Al codoped ZnO films in a vacuum at 673 K
for 2 h under a magnetic field of 4.8 104 A/m applied
along the film plane. The annealing enhances the room temperature ferromagnetism of the films. Liu et al. [16] sputterdeposited Ni doped ZnO films and heat-treated them by
rapid thermal annealing at 1073 K for 10 min in Ar gas
environment. They found that the heat-treatment increased
markedly the magnetization of the films and destroyed the
ZnO crystallinity. In the present study, we investigate the effect of air annealing on the structure and magnetic properties
of Zn0.94 Co0.05 Cu0.01 O at different temperatures.

2 Sample Preparation and Characterization

The system Zn0.94 Co0.05 Cu0.01 O was prepared as polycrystalline nanoparticle powders using the solgel technique.
The appropriate weighed amounts of the precursor materials zinc acetate dihydrate (Fluka), cobalt acetate tetrahydrate
(Alfa Easer) and copper acetate tetrahydrate (Alfa Easer)
were dissolved in methanol at room temperature. Acetyl
acetone and triethanolamin were added to the solution and
the mixture was stirred several hours to get clear and transparent solution. Viscosity of the solutions was controlled by
the addition of methanol. Powder samples were prepared by
gelling and drying of solgel derived precursors solutions in
a beaker. The gels were first dried using a magnetic stirrer
and the resulting powders were pre heated at various temperatures between 200 C and 400 C for 5 min under air
to burn all the solvent. After that the powders were ground
and then annealed at 550, 600, 700, 800, and 900 C for
30 min under air in a box furnace. X-ray diffraction patterns
of Zn0.94 Co0.05 Cu0.01 O powder samples were recorded using a Rigaku difractometer with Cu K radiation. The surface morphology, and stoichiometry of the powders were determined by using Scanning Electron Microscopy (SEM).

J Supercond Nov Magn (2013) 26:34873493

Magnetic measurements were carried out with the Quantum Design Model 6000 Vibrating Sample Magnetometer
(VSM) option for the physical properties measurement system (PPMS) in the temperature interval from 5 K to 300 K
under a magnetic field of up to 6 T.

3 Results and Discussions

3.1 XRD Structural Analysis
The XRD patterns of the system Zn0.94 Co0.05 Cu0.01 O annealed at different temperatures are shown in Fig. 1. The
effect of annealing is readily clear; the diffraction intensity increases indicating better crystallization and the peaks
become narrower indicating increasing crystallite size. All
samples are single phase, with ZnO wurtzite hexagonal
structure of space group P63 mc. Applying the MAUD program [17], Rietveld analysis showed that the occupation
number of the CoCu ions in the position 2b ( 13 23 u) is
in good accordance to the intended value during preparation, indicating that Co and Cu ions are incorporated substitutionally in the ZnO lattice replacing the Zn ions in
the position 2b. The site 2b occupancy shared by Zn and
Co/Cu ions was set free in a subsequent refinement after refining all other structural parameters. Figure 2 shows
the SEM micrographs of Zn0.94 Co0.05 Cu0.01 O nanoparticles. The particle sizes at low temperatures (550600 C)
are small and at temperatures greater than 600 C, particle sizes of samples seem to be increasing as seen in
SEM micrographs. These results are compatible with Rietveld analysis. Also, agglomeration between nanoparticles
is predominant as seen in Fig. 2. The composition of the
Zn0.94 Co0.05 Cu0.01 O nanoparticles is investigated by EDS.
EDS spectrum of Zn0.94 Co0.05 Cu0.01 O nanoparticles after

Fig. 1 X-ray Diffraction patterns of the system Zn0.94 Co0.05 Cu0.01 O

annealed at different temperatures

J Supercond Nov Magn (2013) 26:34873493

3489

Fig. 2 SEM micrographs of the

Zn0.9 Co0.05 Cu0.01 O
nanoparticle with different
magnification (a and b) 550 C,
(c and d) 600 C, (e and f) 700,
and (g and f) 800 C
temperatures

annealing at 600 C is seen in Fig. 3. Zn, Co, and Cu peaks

are clearly seen. The content of Zn, Co, and Cu are consistent with preparation of samples. Table 1 gives the refined
structural parameters obtained from Rietveld analysis. Inspecting this table, we notice that the lattice parameters first
decrease by annealing up to 600 C then increase. The reduction with annealing can be explained in view of reducing
the lattice defects, which are built during seeding and crys-

tal growth. At lower temperatures 600, the grain size is

still small but at higher temp of annealing >600, the grains
become much bigger resulting in increasing the lattice parameters. An obvious increase in crystallite size is observed
with a reduction in lattice microstrain upon increasing the
annealing temperature. A small anisotropy was found in
crystallite size and microstrain for all samples. As a general remark for all samples, the microstrain along the direc-

3490

J Supercond Nov Magn (2013) 26:34873493

Fig. 3 EDS spectrum of

Zn0.94 Co0.05 Cu0.01 O
nanoparticles annealing at
600 C

Table 1 The refined lattice

parameters (a and c) (),
z-fractional coordinate of Zn,
average ZnO bond lengths
dZnO  (), average bond angle
OZnO (deg.), anisotropic
crystallite size D nm and
microstrain e 104 obtained
from Rietveld analysis of the
powder XRD patterns of
Zn0.94 Co0.05 Cu0.01 O system

Zn0.84 Co0.05 Cu0.01 O

550 C

600 C

700 C

800 C

900 C

3.2549(4)

3.2544(3)

3.2575(2)

3.2567(2)

3.2569(3)

5.2123(9)

5.2121(9)

5.2157(5)

5.2136(4)

5.2134(5)

c/a

1.6014

1.6016

1.6011

1.6009

1.6007

u(Zn)

0.3546(18)

0.3657(11)

0.3689(12)

0.3722(11)

0.3771(14)

dZnO 

1.982

1.980

1.982

1.981

1.981

Ob ZnOb 

111.96

110.44

109.98

109.51

108.81

Oa ZnOb 

106.87

108.49

108.95

109.43

110.12

D(100)

49

92

147.5

208

211

104

16.3

13.3

11.8

8.1

8.6

D(001)

51

98

165.8

190

201

e(001) 104

17.6

14.3

15.0

9.1

10.5

e(100)

tion 0001 is less than along the basal directions 1010.

This can be attributed to the high density of Zn population in the basal ab-plane (001), which when replaced by
CoCu ions produces Frankel defects which results in high
microstrain along this plane. Each atom in ZnO is tetrahedrally coordinated to the four nearest neighbors of the
other atomic kind, with two independent distances per tetrahedron. An ideal value for a single position parameter u
of 3/8 = 0.375 is expected for a true tetrahedral nearestneighbor atom environment
around each atom in a unit cell

having c/a = 2 2/ 3 = 1.63299. Inspecting Table 1, we
find that the refined u-fractional coordinate increases monotonically, by annealing temperature, from 0.3546 at 500 C
reaching 0.3722 at 800 C, which is very near from the
ideal value, 0.375. With annealing temperature 900 C, it
becomes 0.3771, a value greater than ideal value. Refinements were tested for a false minimum near u 0.3546
by starting with different u values in the range 0.373-0377 but convergence back to u 0.355 was always rapid.
The corresponding changes in the Zn/CoCu tetrahedron dimensions are shown in Table 1. As shown in Fig. 4, the

Fig. 4 A Zn4O tetrahedron with three basal oxygen atoms at c = 0.5

and apex atom at c = 0.0

Zn/Co tetrahedrons have a base in the ab-plane and apex

along the c-direction. Increasing the annealing temperature
from 550 to 800 C decreases the average basal bond an-

J Supercond Nov Magn (2013) 26:34873493

3491

gle Ob ZnOb , from 111.96 to 109.51, and increases

the average base-apex angle Oa ZnOb , from 106.87 to
109.43. Inspecting these values carefully, we notice that
tetrahedrons become more symmetric and the distortion is
gradually relieved by annealing up to 800 C. Annealing at
900 C introduces tetrahedron distortion in opposite way,
the base-apex angle Oa ZnOb  becomes greater than the
basal bond angle Ob ZnOb . The internal tetrahedral distortion and the spontaneous polarization in Zn1x Cox O can
be assessed using the atomic position parameter u [18, 19].
The four nearest cation-anion pairs are equidistant if u =
1 a 2
1
3 ( c ) + 4 , whereas the charge separation in each tetrahedral
unit will vanish if u = 3/8 (0.375). The Rietveld refined ufractional coordinate monotonously increased with annealing temperature indicating that ionic polarization of ZCO
should decrease with annealing. Similar results were obtained for Zn1x Mgx O applying pair-distribution-function
studies [20], where a slight increase in the average ZnO
distance in tetrahedrons is observed.
3.2 Magnetic Susceptibility
It is well established that the carriers and defects play important roles for appearance of ferromagnetism in transition
metal doped ZnO bulk, films, and nanoparticles [2125].
Ferromagnetism in dilute magnetic semiconductors is considered to originate from the exchange interaction between
free carrier delocalized carriers (holes or electrons) and localized d spins on the TM ions [26]. For the magnetic
properties of the Co-doped ZnO, different experimental results were obtained by different research groups. Many authors reported a ferromagnetism in a ZnO doped Co system at or above room temperature [2730], but the magnetic moment is much smaller than expected. Moreover, the
adding of dopants was also used in order to increase the
concentration of carriers mediating the interaction between
the magnetic moments and, therefore, enhance the ferromagnetism [3133]. In the other hand, other authors [34]
found no indication of ferromagnetism in this system; depending on the method of preparation. Therefore, the presence of free carriers and localized d spins is a prerequisite for the appearance of ferromagnetism [35]. Figure 5a
shows the plot of MT under a field cooled (FC) and a
zero-field cooled (ZFC) condition, with an applied field of
50 Oe for Zn0.94 Co0.05 Cu0.01 O annealed at 900 C. There is
a negligible splitting between FC and ZFC indicating a large
paramagnetic contribution. Also, Fig. 5b presents MT
curves under the FC condition for Zn0.94 Co0.05 Cu0.01 O
samples annealed at different temperatures, where similar
behavior is obvious with an increase in magnetic moment
value at lower temperatures. Figure 6 reveals the magnetic
properties measured at 10, 50, 100, 200, and 300 K for
Zn0.94 Co0.05 Cu0.01 O annealed at different temperatures. No

Fig. 5 MT curves of Zn0.94 Co0.05 Cu0.01 O (a) under 50 Oe of FC

and ZFC for a sample annealed at 900 C, (b) under 100 Oe of FC for
samples annealed at different temperatures

saturation magnetization signal is obtained within a magnetic field up to 30 000 Oe. This trend clearly suggests
the ferromagnetic behavior. Figures 6f and 6e present the
magnetization (M) versus magnetic field (H ) at 300 K for
Zn0.94 Co0.05 Cu0.01 O sample. These figures show a hysteresis at a low field indicating the presence of weaker ferromagnetism and greater paramagnetism. Inspecting Fig. 6,
one can notice that the hysteresis loops became smaller and
smaller as the annealing temperature is decreased, and the
room-temperature FM was gradually suppressed, and finally
completely removed for the sample annealed at 550 C.
The adding of a small amount of Cu to the Co-doped
ZnO helps to achieve ferromagnetism [36]. The reason for
adding a small amount of Cu to the Zn0.95 Co0.05 O system is to create additional carriers, and the magnetization
would therefore be greatly enhanced in bulk samples [37].
Conversely, extra doping with Cu would also be expected
to create a secondary phase (CuO), and thereby decrease
the carrier concentration with the result that the magnetization would decrease. The authors suggested a mechanism in which a bound magnetic polaron was responsible
for magnetic ordering in the Co/Cu co-doped films. In addition, the Zn0.94 Co0.05 Cu0.01 O sample treated at a higher
temperature exhibits a higher magnetization than the sam-

3492

J Supercond Nov Magn (2013) 26:34873493

Fig. 6 MH curves, measured at different temperatures, of Zn0.94 Co0.05 Cu0.01 O system annealed at: (a) 550 C, (b) 600 C, (c) 700 C,
(d) 800 C, and (e) 900 C, (f) enlarged part of hysteresis at room temperature for samples annealed at different temperatures

ple prepared under moderate thermal conditions, and is

consistent with the Zn0.95 Cu0.02 Cr0.03 O system [38]. From
Fig. 7, one can find that the saturation magnetization (Ms ),
at room temperature increases from 0.0507 to 0.1088 emu/g
when the sample annealing temperature increases from 550
to 900 C. This could be attributed to the existence of
more oxygen vacancies, which mediate a greater exchange
of ferromagnetism acting as the bound magnetic polarons
[39, 40].

4 Conclusions
In summary, we prepared a nano-Zn0.94 Co0.05 Cu0.01 O sample as a single phase with ZnO wurtzite hexagonal structure, by a solgel method. Upon annealing, an obvious increase in crystallite size is observed accompanied with an
increase in lattice parameters. The microstrain along the di
rection 0001 is less than along the basal directions 1010
due to Frankel defects produced by Co and Cu substitution.

J Supercond Nov Magn (2013) 26:34873493

Fig. 7 The saturation magnetization for Zn0.94 Co0.05 Cu0.01 O annealed at different temperatures

Up to 800 C, the u-fractional coordinate of Zn ion increases

monotonically indicating that ionic polarization of ZCCO
should decrease with annealing temperature. Also, the internal tetrahedral distortion in ZCCO is gradually relieved
by annealing up to 800 C. The magnetic properties are enhanced as the annealing temperature increases.

References
1. Pearton, S.J., Norton, D.P., Ip, K., Heo, Y.W., Steiner, T.: Superlattices Microstruct. 34, 3 (2003)
2. Wolf, S.A., Awschalom, D.D., Buhrman, R.A., Daughton, J.M.,
Von Molnar, S., Roukes, M.L., Chtchelkanova, A.Y., Treger,
D.M.: Science 294, 1488 (2001)
3. Pearton, S.J., Norton, D.P., Frazier, R., Han, S.Y., Abernathy, C.R.,
Zavada, J.M.: Spintronics device concepts. IEE Proc., Circuits Devices Syst. 152, 312 (2005)
4. Sato, K., Katayama-Yoshida, H.: Jpn. J. Appl. Phys. 2(39), L555
(2000)
5. Das, G.P., Rao, B.K., Jena, P.: Phys. Rev. B 69, 214422 (2004)
6. Heiba, Z.K., Arda, L.: J. Mol. Struct. 1022, 167 (2012)
7. Xu, H.Y., Liu, Y.C., Xu, C.S., Liu, Y.X., Shao, C.L., Mu, R.: Appl.
Phys. Lett. 88, 242502 (2006)
8. Ghosh, B., Sardar, M., Banerjee, S.: arXiv:1010.2381 (2010)
9. Banerjee, S., Mandal, M., Gayathri, N., Sardar, M.: Appl. Phys.
Lett. 91, 182501 (2007)
10. Hsu, H.S., Huang, J.C.A., Huang, Y.H., Liao, Y.F., Lin, M.Z., Lee,
C.H., Lee, J.F., Chen, S.F., Lai, L.Y., Liu, C.P.: Appl. Phys. Lett.
88, 242507 (2006)
11. Cho, Y.M., Choo, W.K., Kim, H., Kim, D., Ihm, Y.: Appl. Phys.
Lett. 80, 3358 (2002)
12. Ye, J.D., Gu, S.L., Zhu, S.M., Qin, F., Liu, S.M., Liu, W., Zhou,
X., Hu, L.Q., Hu, L.Q., Zheng, R., Shi, Y., Zheng, Y.D.: J. Appl.
Phys. 96, 5308 (2004)

3493
13. Khare, N., Kappers, M.J., Wei, M., Blamire, M.G., MacManusDriscoll, J.L.: Adv. Mater. 18, 1449 (2006)
14. Huang, B., Zhu, D.L., Ma, X.C.: Appl. Surf. Sci. 253, 6892 (2007)
15. Yu, M., Qiu, H., Chen, X.: Thin Solid Films 518, 7174 (2010)
16. Liu, E., Xiao, P., Chen, J.S., Lim, B.C., Lia, L.: Curr. Appl. Phys.
8, 408 (2008)
17. Lutterotti, L.: Maud 2.072. http://www.mg.unitn.it/~Luttero/maud
18. Abrahams, S.C., Bernstein, J.L.: Acta Crystallogr., B Struct. Sci.
25, 1233 (1969)
19. Kisi, E.H., Elcombe, M.M.: Acta Crystallogr., Sect. C 45, 1867
(1989)
20. Kim, Y.I., Cadars, S., Shayib, R., Proffen, T., Feigerle, C.S.,
Chmelka, B.F., Seshadri, R.: Phys. Rev. B 78, 195205 (2008)
21. Jayakumar, O.D., Gopalakrishnan, I.K., Kulshreshtha, S.K.: Adv.
Mater. 18, 1857 (2006)
22. Liao, L., Lu, H.B., Zhang, L., Shuai, M., Li, J.C., Liu, C., Fu, D.J.,
Ren, F.: J. Appl. Phys. 102, 114307 (2007)
23. Sluiter, M.H.F., Kawazoe, Y., Sharma, P., Inoue, A., Raju, A.R.,
Rout, C., Waghmare, U.V.: Phys. Rev. Lett. 94, 187204 (2005)
24. Liu, X.C., Shi, E.W., Chen, Z.Z., Zhang, H.W., Xiao, B., Song,
L.X.: Appl. Phys. Lett. 88, 252503 (2006)
25. Jayakumar, O.D., Achary, S.N., Sudakar, C., Naik, R., Salunke,
H.G., Rao, R., Peng, X., Ahuja, R., Tyagi, A.K.: Nanoscale 2,
1505 (2010)
26. Alaria, J., Bieber, H., Colis, S., Schmerber, G., Dinia, A.: Appl.
Phys. Lett. 88, 112503 (2006)
27. Ueda, K., Tabata, H., Kawai, T.: Appl. Phys. Lett. 79, 988 (2001)
28. Schwartz, D.A., Norberg, N.S., Nguyen, Q.P., Parker, J.M.,
Gamelin, D.R.: J. Am. Chem. Soc. 125, 13205 (2003)
29. Maensiri, S., Sreesongmuang, J., Thomas, C., Klinkaewnarong, J.:
J. Magn. Magn. Mater. 301, 422 (2006)
30. Naeem, M., Hasanain, S.K., Kobayashi, M., Ishida, Y., Fujimori,
A., Buzby, S., Isman, S., Shah, S.: Nanotechnology 17, 2675
(2006)
31. Ndilimabaka, H., Colis, S., Schmerber, G., Muller, D., Grob, J.J.,
Gravier, L., Jan, C., Beaurepaire, E., Dinia, A.: Chem. Phys. Lett.
421, 184 (2006)
32. Yang, Z., Biasini, M., Beyermann, W.P., Katz, M.B., Ezekoye,
O.K., Pan, X.Q., Pu, Y., Shi, J., Zuo, Z., Liu, J.L.: J. Appl. Phys.
104, 113712 (2008)
33. Liu, X.J., Song, C., Zeng, F., Pan, F.: J. Phys. Condens. Matter 19,
296208 (2007)
34. Jin, Z., Fukumura, T., Kawasali, M., Ando, K., Saito, H.,
Sekiguchi, T., Yoo, Y.Z., Murakami, M., Matsumoto, Y.,
Hasegawa, T., Koinmuma, H.: Appl. Phys. Lett. 78, 3824 (2001)
35. Pei, G.Q., Xia, C.T., Cao, S.X., Zhang, J.G., Wu, F., Xu, J.:
J. Magn. Magn. Mater. 306, 340 (2006)
36. Xu, H.Y., Liu, Y.C., Xu, C.S., Liu, Y.X., Shao, C.L., Mu, R.: Appl.
Phys. Lett. 88, 242502 (2006)
37. Lin, H.T., Chin, T.S., Shih, J.C., Lin, S.H., Hong, T.M.: Appl.
Phys. Lett. 85, 621 (2004)
38. Liu, H., Fei, L., Yang, J., Jin, X., Liu, Y., Liu, X., Gao, M.: Solid
State Commun. 151, 1864 (2011)
39. Liu, Y., Yang, S.H., Zhang, Y.L., Bao, D.H.: J. Magn. Magn.
Mater. 321, 3406 (2009)
40. Kalyana Lakshmi, Y., Srinivas, K., Sreedhar, B., Manivel, M.,
Raja, M., Vithal, M., Venugopal Reddy, P.: Mater. Chem. Phys.
113, 749 (2009)