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CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 53075311
www.elsevier.com/locate/ceramint

Preparation, dielectric property and infrared emissivity of Fe-doped ZnO


powder by coprecipitation method at various reaction time
Xiaolei Sun, Yan Jia, Xiaoqin Liu, Junbo Wang, Jie Xu, Xinhai He, Chong Fu, Songtao Liu
College of Mechanical & Electronic Engineering, Xi'an Polytechnic University, Xi'an Shaanxi 710048, China

Received 12 August 2013; received in revised form 14 October 2013; accepted 23 October 2013
Available online 1 November 2013

Abstract

Fe-doped ZnO powders have been synthesized by the coprecipitation method at 600 1C with various reaction time, using zinc nitrate as the
staring material, urea as the precipitator, and ferric nitrate as the doping source, respectively. The phase and morphology of the prepared powders
have been characterized by X-ray diffraction and scanning electron microscopy, respectively. It was found that the prepared product synthesized
for 1 h had a pure ZnO wurtzite structure and was a ZnO(Fe) solid solution powder. The real part, imaginary part, and dielectric loss of complex
permittivity of prepared powders in the frequency range of 8.212.4 GHz decreased with increasing reaction time. The average infrared
emissivities of prepared powders at the waveband range of 814 m increased with extending reaction time.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: ZnO; Dielectric property; Infrared emissivity

1. Introduction () of complex permittivity of the prepared AZO powders have


been improved in the frequency range of 8.212.4 GHz due to
Zinc oxide (ZnO) is one of the most important and versatile the generation of AlZn defects. Zhou et al. [7] prepared
semiconductors with a direct wide band gap of 3.37 eV microwave absorption coating using tetra-needle-like ZnO
at room temperature. It has also many excellent properties, whiskers as the main functional agent. It showed the excellent
such as, nontoxic, cheap, unique optical, and electrical proper- microwave absorption property in the frequency range of 8
ties, which has wide applications in the solar cells, sensors, 18 GHz because of the formation of semi-conductive networks,
photocatalysis, transparent thin lm transistors [13]. In diffuse reections, multipoles, and the multi-interfaces.
recently years, ZnO has recently attracted increasing interest In addition, ZnO shows also the low infrared emissivity at
due to its remarkable microwave absorbing property and the waveband range of 814 m. Yao et al. [8] synthesized
infrared shielding property. Zn0.99  xMn0.01CoxO (x 0.00, 0.01, 0.03, and 0.05) powders
Zhuo et al. [4] synthesized intriguing ZnO dendritic nanos- at different calcination temperatures by a solid-state reaction
tructures by a two-step chemical vapor deposition (CVD) and the best infrared emissivity value was 0.754. Dongmei
process. The RL (reection loss) value of the composite with et al. [9] fabricated AZO thin lms by a sol-gel method and
50 vol% ZnO dendritic nanostructures reached  42 dB at studied the effect of Al concentration and temperature on the
3.6 GHz with a thickness of 5.0 mm. Chen et al. [5] fabricated infrared emissivity of AZO lms at the waveband range of
the tetrapod-like ZnO nanostructures by rapid heating metal Zn 814 m. The prepared AZO lm showed the low infrared
pellet at 900 1C in air, which showed the good microwave emissivity. Zhang et al. [10] synthesized the Co-doped ZnO
absorption property in the frequency range of 218 GHz. Wang powder by the conventional solid state reaction. The prepared
et al. [6] synthesized Al-doped ZnO (AZO) powders by a powders presented the low infrared emissivity at the waveband
coprecipitation method. The real part () and imaginary part range of 35 m and 814 m and the excellent microwave
absorption property in the frequency range of 8.212.4 GHz.
n
Corresponding author. Tel.: 86 29 62335812; fax: 86 29 62335812. Therefore, because the Fe element belongs also to the VIII
E-mail address: suxlei@163.com (X. Su). group, it presents the same effects on the microstructure,

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.10.107
5308 X. Su et al. / Ceramics International 40 (2014) 53075311

dielectric property and infrared emissivity of ZnO powder as samples were prepared by mixing the produced powders with
the Co element possibly. Compared with Co-doped ZnO parafn in a mass ratio of 10:90.
powder, Fe-doped ZnO powder has the good magnetic
property and optical property besides microwave wave absorp- 3. Results and discussion
tion property and infrared shielding property, which is a
multifunctional material [11]. In addition, because the density The XRD patterns of prepared Fe-doped ZnO powders at
of Fe element is lower than that of Co element, the Fe-doped 600 1C with various reaction time are shown in Fig. 1. It can
ZnO powder become a lighter mass shielding material than be seen that the synthesized powders had a hexagonal wurtzite
Co-doped ZnO powder possibly. structure belonging to the C46v space group (P63mc) according
In the paper, Fe-doped ZnO powders have been synthesized to the standard JCPDS card. When the reaction time is 1 h, no
by coprecipitation method at 600 1C with various reaction impurity phase is observed and the prepared product is a ZnO
time, using zinc nitrate as the staring material, urea as the (Fe) solid solution powder. However, when the reaction time is
precipitator and ferric nitrate as the doping source, respec- up to 2 h, ZnFe2O4 impurity phase appeared. The reason is that
tively. The dielectric property in the frequency range of the more and more Fe atoms entering ZnO crystal and
8.212.4 GHz and the average infrared emissivity at the substituting Zn atoms of ZnO lattice precipitated from ZnO
waveband range of 814 m have been determined. The lattice with increasing reaction time. Therefore, the Fe con-
effects of Fe-doping on the microstructure, dielectric property centration is higher than the solubility limit of Fe in ZnO in
and infrared emissivity of ZnO powder have been studied. some areas of ZnO crystal [13]. The ZnFe2O4 impurity has
been generated by the following reactions:
2. Experimental 4Fe(precipitated) 3O2-2Fe2O3 (1)

2.1. Sample preparation Fe2O3 ZnO-ZnFe2O4 (2)

In addition, the main peak intensities of ZnO phase at


Fe-doped ZnO powders were synthesized by the coprecipi-
2 31.781, 34.381, and 36.281 increase with extending
tation method, using zinc nitrate (Zn(NO3)2  6H2O) as the
reaction time, indicating that the prepared Fe-doped ZnO
staring material, urea (CO(NH2)2) as the precipitator and ferric
powder presents the better crystallization. According to related
nitrate (Fe(NO3)3  9H2O) as the doping source, respectively.
study [14], Fe doping can inhibit ZnO crystallization. Con-
All the chemical reagents were analytical grades and were used
versely, the precipitation of Fe atoms from ZnO lattice leads to
without further purication.
the better crystallization.
First, Zn(NO3)2  6H2O, Fe(NO3)3  9H2O and CO(NH2)2
The lattice constants a and c calculated by Bragg formula of
were separately dissolved in de-ionized water. Second, appro-
all samples corresponding to ZnO doped by Fe are shown in
priate amounts of Fe(NO3)3  9H2O solutions were added into
Table 1. According to related study [14], when the Fe atoms
the Zn(NO3)2  6H2O solution according to the experimental
entered ZnO lattice, the Fe atoms occupied Zn site in ZnO
design. In our study, the molar ratio of Fe to (Zn Fe),
lattice and substituted Zn ions preferentially. Because the ion
nFe/(nFe nZn), was 0.06. Finally, CO(NH2)2 solution was
radius of Fe3 (0.645 ) is smaller than that of Zn2 (0.74 ),
slowly added into above mixture solutions. The as-prepared
the decrease of lattice constant of ZnO is caused by the
solutions were continually stirred at 100 1C for 1 h to yield
substitution of Zn atoms of ZnO lattice by Fe atoms. So the
precipitates. After ltration, the precipitates were washed with
distilled water and ethanol for several times, and then dried in
air at 120 1C in stove. Fe-doped ZnO powders were obtained
after the calcination of precipitates at 600 1C for 1 h, 2 h, 3 h,
and 4 h, respectively.

2.2. Microstructure, infrared emissivity and dielectric


property characterization

The phases of the as-prepared powders were identied by


X-ray diffraction (XRD, X'Pert PRO MPD, Cu K). The
99.99% Si (a 5.43088 ) was used as an inner standard. The
morphology of the prepared powders was investigated by
scanning electron microscope (SEM, JSM-6360LV, JEOL,
Tokyo, Japan). The average infrared emissivities of prepared
powders at the waveband of 814 m were determined by the
reference's method [10]. The permittivities of prepared pow-
ders in the frequency range of 8.212.4 GHz were determined Fig. 1. XRD patterns of the prepared Fe-doped ZnO powders at 600 1C with
by the reference's method [12], in which the measuring various reaction time.
X. Su et al. / Ceramics International 40 (2014) 53075311 5309

lattice constant of the Fe-doped ZnO powder synthesized for the frequency range of 8.212.4 GHz for the prepared
1 h is less than the standard lattice constant values (a 3.2524 Fe-doped ZnO powders at 600 1C with various reaction time.
and c 5.2071 ) of ZnO. According to above analysis, It can be seen that dielectric properties of prepared powders
because the more and more Fe atoms precipitated from ZnO decreased with increasing reaction time. Because the Fe atom
lattice with extending reaction time, the increase of lattice presents trivalent state usually and Fe3 is a stable state, there
constant of prepared Fe-doped ZnO with increasing reaction are three electrons bonded with the other elements. Synchro-
time is expected. nously, when the Fe atoms entered the ZnO lattice, the Fe
Fig. 2 shows SEM photos of the prepared Fe-doped ZnO atoms substituted Zn atoms in ZnO crystal preferentially and
powders at 600 1C with various reaction time. It is observed the FeZn defects have been generated. Therefore, there are
that the synthesized ZnO powders have ne spherical particles bound electrons around ZnFe defects in the ZnO crystal. Under
and present narrow particle size distribution. The average sizes the alternating electromagnetic eld, these bound electrons will
of Fe-doped ZnO powders synthesized at 600 1C for 1 h, 2 h, migrate to and fro to form relaxation polarization and loss,
3 h, and 4 h are about 300 nm, 800 nm, 1.5 m, and 2 m, thus leading to the higher and tg, respectively. The more
respectively, showing that the powder size increases gradually the substitutions have been generated, the higher the and
with increasing reaction time. The reason is that the precipita- tg are.
tion of Fe atoms from ZnO lattice improves the grain growth Additionally, impurity at interfaces is another important factor
of ZnO. affecting loss tangent of Fe-doped ZnO powders. Because the
Fig. 3 shows real part , imaginary part , and dielectric high surface area supplies opportunities for impurities to be
loss tg of complex permittivity as a function of frequency in distributed, the additives are mostly positioned at grain bound-
aries or crystal surfaces in crystal materials [15]. Some impurity
atoms congregated near the grain boundary also, which may
Table 1
cause impurity conduction. Interfacial conduction and impurities
lattice constant and infrared emissivity of prepared Fe-doped ZnO powders at
600 1C with various reaction time. play an important role in increasing the and tg of the
prepared Fe-doped ZnO powders. Additionally, the charge
Samples Reaction time/(h) Lattice constant/() Infrared emissivity accumulation at materials interfaces induced the interfacial
a b c
polarization, MaxwellWagner effects [16], which may partly
explain the phenomena observed above. Interfacial polarity
(a) 1 3.24024 5.17431 0.840 causes a build-up of charges near heterogeneities and grain
(b) 2 3.24108 5.19858 0.858 boundaries in polycrystalline materials. This kind of polarity
(c) 3 3.24222 5.20299 0.903
(d) 4 3.24394 5.25097 0.924
may contribute also to the and tg. Because the Fe-doped
ZnO powder synthesized for 1 h has the most amounts of FeZn

Fig. 2. SEM photos of the prepared Fe-doped ZnO powders at 600 1C with various reaction time; (a) 1 h; (b) 2 h; (c) 3 h; (d) 4 h.
5310 X. Su et al. / Ceramics International 40 (2014) 53075311

Fig. 3. Real part , imaginary part , and dielectric loss tg of complex permittivity as a function of frequency in the frequency range of 8.212.4 GHz for the
prepared Fe-doped ZnO powders at 600 1C with various reaction time.

defects, the most amounts of bound electrons and the highest Acknowledgement
surface area, the , , and tg have the highest values, E3.3,
E0.82, and tgE0.25. Therefore, the Fe-doped ZnO powder The authors gratefully acknowledge the support of the National
synthesized at 600 1C for 1 h shows the best dielectric property Natural Scientic Foundation of China (Grant No. 51002113), the
in the frequency range of 8.212.4 GHz. Natural Science Basic Research Plan in Shaanxi Province of China
In addition, the average infrared emissivities of Fe-doped (Grant No.2012JQ6021) and Foundation of Shaanxi Educational
ZnO powders prepared at 600 1C with various reaction time at Committee (Grant No. 2013JK0932).
the waveband range of 814 m have been presented, as
shown in Table 1. It can be seen that the infrared emissivities
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