CHEM. RES.

CHINESE UNIVERSITIES 2010, 26(2), 185188

Synthesis and Characterization of Cubic Zinc Titanate

Doped with Lithium
YU Ran-bo1, ZHENG Ming-zhen1, CHEN Jun1, DENG Jin-xia1, LIU Gui-rong1 and XING Xian-ran1,2*
1. Department of Physical Chemistry, 2. State Key Laboratory for Advanced Metals and Materials,
University of Science and Technology Beijing, Beijing 100083, P. R. China
Abstract Cubic (Zn,Li)TiO3 powders were synthesized through a modified sol-gel route including the Pechini
process via a three-step heat treatment. The as-synthesized (Zn,Li)TiO3 could be stable up to 1000 C. The dielectric
constant and dielectric loss tangent of all the synthesized (Zn,Li)TiO3 samples at different measurement frequencies
showed the similar tendency. At the same frequency, the dielectric constant and the dielectric loss tangent of
(Zn,Li)TiO3 samples decreased and increased, respectively, with the lithium doping content increase. The as-prepared
(Zn,Li)TiO3 showed improved microwave dielectric properties, and its maximum value of quality factor could reach
34000 GHz.
Keywords Cubic zinc titanate; Lithium doping; Sol-gel preparation; Pechini process; Microwave dielectric property
Article ID 1005-9040(2010)-02-185-04

Introduction

As the most important functional materials, complex metal oxides have received considerable attention.
With the rapid growth of wireless communication industries, microwave devices with high performance
and miniaturized size have become increasingly important. Thus hexagonal ZnTiO3 ceramics have recently drawn much attention of researchers due to
their excellent dielectric properties in the microwave
range[1] and low-temperature sintering application[13].
But there has not been much work on cubic ZnTiO3,
which can be used as dielectric materials for microwave device and more preferably for low-temperature
co-fired ceramics(LTCCs)[4,5]. Metal cations, such as
Pb2+, Bi3+, and Ni2+, were doped into the cubic ZnTiO3
and the photoluminescence characteristics of the cubic
ZnTiO3 were studied in recent work[68]. Li+ with the
radius similar to that of Zn2+ is a promising candidate
for doping ZnTiO3. Additionally, there were many
researches about the synthesis of ZnSnO3 from
Li2SnO3 through low-temperature ion exchange[9],
which revealed that Li+ might replace Zn2+ in the cubic ZnTiO3. To our known, there has not been reported
about cubic(Zn,Li)TiO3 solid solution so far.
Various synthetic methods were effective for the

preparation of functional complex oxide materials[1017]. In this work, we synthesized cubic

(Zn,Li)TiO3 by a modified sol-gel method including
the Pechini process[10], followed by heat treatments.
The phase distribution, thermal stability, crystal morphology, dielectric properties and microwave dielectric properties were investigated.

Experimental

The cubic (Zn,Li)TiO3 samples were prepared in

the light of (Zn1xLi2x)TiO3 with 0.1x0.4 by a solgel route including the Pechini process[10]. The commercial Zn(NO3)26H2O(A. R. grade), Li2CO3(A. R.
grade), tetrabutyl titanate(C16H36Ti)(A. R. grade),
ethylene glycol (HOCH2CH2OH)(A. R. grade) and
citric acid monohydrate(C6H8O7H2O)(A. R. grade)
were used as the starting materials. Zn(NO3)26H2O
and Li2CO3 were dissolved in deionized water at 60
C, to which the aqueous solutions of HOCH2CH2OH
and C6H8O7H2O were added and stirred until the solution was clarified. This solution was poured into the
ethanol with C16H36Ti that was stirred to get a solution,
which was evaporated at 80 C to form a precursor gel.
According to the thermal analysis[1115] the precursor
gel was then heated at 600 C for 3 h and at 800 C for

*Corresponding author. E-mail: xing@ustb.edu.cn

Received April 2, 2009; accepted May 19, 2009.
Supported by the National Natural Science Foundation of China(Nos.20731001, 20871015 and 50725415), the Program for
New Century Excellent Talents in University, China(NCET), the National Basic Research Program of China(No.2007CB613601)
and the Program for Changjiang Scholars and Innovative Research Team in University, China(No.IRT0708).

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6 h, then at 850 C for 4 h. The final powder was

milled again with a 3%(mass fraction) polyvinyl alcohol(PVA) solution, and then pressed into discs with
a diameter of about 10 mm. Then the pellets covered
with the same powders were sintered at 900 C for 4 h
and cooled to room temperature in the furnace for the
measurement of dielectric properties.
Phase identification and structural characterization were performed on an X-ray diffractometer
(Model M21XVHF22, MAC Science Co., Ltd.,
Yokchama, Japan) with Cu K radiation. The thermal
behavior of the precursor powder and the final products were examined by thermogravimetry-differential
thermal analysis(Model Q600 SDT-DSC, TA Company, USA). The dielectric constant and loss tangent of
the product were measured on a multi-frequency meter(Model HP-4275A, Agilent Technologies Inc., Melrose, MA). The relative permittivity and dielectric
loss at microwave frequencies were characterized at
room temperature by the Hakki-Coleman DR method
and cavity method[18,19] on a network analyzer(HP
8270ES Agilent Technologies Inc., Santa Rosa, CA).
The temperature coefficients of resonant frequencies(f) were measured in a temperature range of
2580 C.

Results and Discussion

To obtain the final product, the suitable heating

temperature of the precursor should be determined.
The TG-DTA curves of precursor powder with starting
Li molar ratio of 2x=0.2(Fig.1) were measured. A continuous mass-loss occurred from 100 C to 600 C due
to the water and excess organic substance losses. The
DTA curves exhibit a slightly endothermic peak at
about 100 C, which should be attributed to the evaporation of the water. And the two exothermic peaks
at about 200250 C and 300350 C may be
caused by the burning of organic compositions. The

Fig.1 TG-DTA curves of the precursor powder with

starting Li molar ratio of 0.2

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DTA curve in a range of about 230280 C shows a

endothermic peak due to the vigorous evolution of
citric acid decomposed to aconitic acid(C6H4O6) and
itaconic acid(C5H4O4) as represented by the following
reactions[1114]:
(Zn, Li)Ti(C6H6O7)3(s)
(Zn,Li)Ti(C6H4O6)3(s)+3H2O(g)
(1)
(Zn,Li)Ti(C6H4O6)3(s)
(Zn,Li)Ti(C5H4O4)3(s)+3CO2(g)
(2)
And the exothermic peak in a higher temperature
range of about 420600 C was probably related to
the two process: (1) burnout of organic compounds;
(2) formation of (Zn,Li)2Ti3O8 and (Zn,Li)TiO3 phases[15]. Therefore, to obtain the final (Zn,Li)TiO3
product, the precursor powder should be pre-heated at
600 C for several hours to facilitate the formation of
cubic phase and then re-heated at a temperature higher
than 600 oC to crystallize completely.
The XRD patterns of as-synthesized (Zn,Li)TiO3
products derived from the precursors undergoing the
three-step heat treatment are shown in Fig.2. The
evolution of phase distribution in the (Zn,Li)TiO3 specimens was clear. With the starting materials of
(Zn1-xLi2x)TiO3, when 0.1x0.3 cubic (Zn,Li)TiO3
could form but coexisted with minor Li2ZnTi3O8.
Moreover, the mixture of Zn2Ti3O8 and Li2TiO3 rather
than (Zn,Li)TiO3 was obtained when x0.4. It is well
known that Li2TiO3 exists three phases, , and [20,21],
and -Li2TiO3 is stable at temperature about 850 C,
which is close to the formation temperature of ZnTiO3.
Moreover, -Li2TiO3 and ZnTiO3 have the similar lattice parameters and topologically identical structure,
and the radius of Zn2+ and that of Li+ are similar(Zn2+:
0.0740 nm; Li+: 0.0760 nm). Hence it is possible to
form a (Zn,Li)TiO3 solid solution with x=01.0 via a
topotactic transformation. In our synthesis, (Zn,Li)
TiO3 could be obtained in a range of 0.1x0.3

Fig.2 X-ray diffraction patterns of (Zn,Li)TiO3

products with starting Li molar ratio of 2x
x: a. 0.1; b. 0.2; c. 0.3; d. 0.4.

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according to the reactant molar ratio from the formula

(Zn1xLi2x)TiO3. The lattice parameters and crystal
unit volume of the as-synthesized (Zn,Li)TiO3 solid
solution were obtained by Powder X-ray diffraction
and TREOR software(Fig.3). It is obvious that the a
axis and crystal unit volume increased with the increasing lithium amount due to the larger size of lithium ion than that of zinc ion.
Fig.4 TG-DSC curves of final(Zn,Li)TiO3 products
with starting Li molar ratio of 0.4

Fig.3 Lattice parameters and unit cell volume of

as-synthesized (Zn,Li)TiO3 powder

Because of the evaporation of lithium during

the heat treatment and the valence difference between lithium and zinc, the starting molar ratio of
[Zn2+]/[Li+]=(1x)/2x was adopted in the process of
synthesis. The ICP results for the three products
are (Zn0.89Li0.06)TiO2.92, (Zn0.81Li0.12)TiO2.87 and
(Zn0.72Li0.22)TiO2.82, which agreed with the formula of
ABO3.
To investigate the thermal stability of the
as-synthesized product, the TG-DSC measurement of
final product (Zn,Li)TiO3 with starting Li content of
2x=0.4 was performed(Fig.4). From the TG curve we
could observe a slight mass loss in the whole temperature range due to evaporation of the water and partial lithium atoms. And a change existed at about

750800 C in the DSC curve may be drawn by the

phase transition of (Zn,Li)2Ti3O8 into cubic
(Zn,Li)TiO3. This agrees with the result that Yamaguchi et al. reported[15]. When the temperature reached
about 1000 C, an obvious increase of heat flow in the
DSC curve could be detected, which could be assigned to the decomposition of (Zn,Li)TiO3 into
(Zn,Li)2TiO4 and TiO2 at this temperature[15]. Apparently, lithium doping made the as-synthesized
(Zn,Li)TiO3 exhibiting better thermal stability than
ZnTiO3, but probably because the evaporation of the
lithium atoms at a high temperature, the improvement
of the thermal stability is not much.
The morphologies of the as-synthesized
(Zn,Li)TiO3 samples were homogeneous and were
influenced by lithium doping. Fig.5 shows the
FE-SEM micrographs of the three (Zn,Li)TiO3 samples. The average grain sizes of the (Zn,Li)TiO3
powders were about 200300 nm, which was similar
to that of ZnTiO3. With the lithium doping content
increase, the uniformity of the grain size became
worse.

Fig.5 Field-emission scanning electron micrographs of as-synthesized (Zn,Li)TiO3 products with

starting Li molar ratio of 2x
(A) x=0.1; (B) x=0.2; (C) x=0.3.

The dielectric constant of the (Zn,Li)TiO3 products were measured at ambient temperature in a
range of 60 kHz40 MHz[Fig.6(A)]. At the same
frequency, the dielectric constant of (Zn,Li)TiO3 decreased with lithium doping content increasing, which

may be due to the smaller ionic polarizability contribution to the dielectric constant of Li+ than Zn2+[22].
For the same x value, the dielectric loss tangent increased with increasing measurement frequency. And
when lithium doping content increased, the dielectric

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Vol.26

as-synthesized (Zn,Li)TiO3 showed better thermal

stability and improved the microwave dielectric properties.
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Fig.6

Dielectric properties of as-synthesized (Zn,Li)TiO3

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about 34000 GHz, which is larger than that of
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Table 1

Microwave dielectric properties of (Zn,Li)TiO3

powders with different starting Li molar ratios
of 2x

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In summary, cubic (Zn,Li)TiO3 ceramic products

were synthesized via a modified sol-gel route including Pechini process. With the lithium doping the

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