Materials Letters 59 (2005) 2908 2910

www.elsevier.com/locate/matlet

A solvothermal route to crystalline lithium niobate

Meinan Liu, Dongfeng Xue*
State Key Laboratory of Fine Chemicals and School of Chemical Engineering, Dalian University of Technology, 158 Zhongshan Road, Dalian 116012, China
Received 11 February 2005; accepted 10 April 2005
Available online 31 May 2005

Abstract
A solvothermal route for the preparation of crystalline state lithium niobate using Li2CO3 and Nb2O5 is developed. Oxalic acid is
employed as solvent, which coordinates with niobium oxide to stimulate the main reaction. Scanning electron microscopy images show that
the as-prepared sample displays a cubic morphology. X-ray diffraction and IR spectrum of the as-prepared sample indicate that the sample is
well crystalline.
D 2005 Elsevier B.V. All rights reserved.

1. Introduction
Lithium niobate LiNbO3 (LN), as an excellent functional
material, exhibits outstanding chemical and physical properties such as good ferroelectric, pyroelectric, piezoelectric,
electro-optical, photo refractive and nonlinear optical
behaviors [1 3]. It has valuable applications for the light
modulation, holographic memory devices, second harmonic
generation devices and optical parametric oscillation devices, etc. However, all these applications demand the
production of LN powders with the highest possible purity,
well-defined particle morphology, and small particle size
distribution. It is expected that specific crystal morphologies
enhance the performance and allow a fine-tuning of various
properties of LN [4].
In recent years, there are several methods for the
synthesis of LN powders, including solid-state reactions,
sol-gel, metal alkoxides, and hydrothermal processes as well
as the peroxide route [5 7]. Moreover, Kakihana et al. has
synthesized LN powders from the water-soluble DL-malic
acid complex [8]. It has been known that to prepare LN
powders by solid-state reactions (between Nb2O5 and
Li2CO3) needs high temperature above 1200 -C. Singlephase stoichiometric materials with a reproducible Li / Nb

ratio are however difficult to obtain by solid-state synthesis.

Reaction in 1 : 1 mixture of Li2CO3 and Nb2O5 powders
may yield not only LiNbO3 but also Li3NbO4 and LiNb3O8
[9]. In contrast, wet chemical routes are a promising
alternative, since they can well control the whole process
from the molecular precursor to the final material to give
Li2CO3
0.1334 g

Oxalic
acid
Stirring at room temperature

Clear colorless solution 33 ml

Nb2O5 0.48 g
Mixture
Calcination at 340C
White precipitate

filtration

Calcination at 60C

LiNbO3 powders
* Corresponding author.
E-mail address: dfxue@chem.dlut.edu.cn (D. Xue).
0167-577X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2005.04.041

Fig. 1. Flowchart for preparing LN powders by the solvothermal method, in

which oxalic acid is employed as the solvent.

012

M. Liu, D. Xue / Materials Letters 59 (2005) 2908 2910

2909

40

Number of particles

208
1010

214
300

116
122
018

024

006
113
202

110

104

Intensity (arbitrary unit)

35
30
25
20
15
10
5
20

30

40

50

60

70

80

2 (degree)
Fig. 2. XRD pattern of the LN powders synthesized at 340 -C by the
solvothermal route. The solid circles stand for the orthorhombic phase of
Nb2O5 powders.

highly pure and homogeneous materials. On the other hand,

wet routes allow low reaction temperature, so that the size
and morphology of the synthesized particles may be well
controlled, and the desired phase can be prepared [10].
In this work, the synthesis of LN powders by solvothermal route is studied. Oxalic acid is employed as solvent,
which plays an important role to coordinate with niobium
oxide. Furthermore, LN powders are obtained in a uniformly
cubic shape, which is not yet available in the literature. Xray powder diffraction and IR spectrum are employed to
characterize the quality of the synthesized LN powders.

2. Experimental
The flowchart depicting the synthesis of LN powders by
solvothermal method is shown in Fig. 1. Li2CO3 (A.P.),
Nb2O5 (ultra-purity, 99.99%), and oxalic acid (A.P.) are used
without further purification. In a typical synthesis of LN
powders, 133.4 mg of Li2CO3 is added into 33ml of oxalic
acid (0.35 mol L
1). The solution is stirred until a clear
colorless solution is obtained. 480 mg Nb2O5 powders are
then added. The obtained mixture is transferred into a Teflon

0
0.0

0.5

1.0

1.5

2.0

2.5

Cubic edge length (m)

Fig. 4. The edge length distribution (sample size 90 cubes) of the asprepared LN powders.

cup of 50 ml inner volume, which is slid into a steel autoclave

and carefully sealed. The autoclave is heated in furnace at
340 -C for 10 h and then cooled down to room temperature
naturally. The synthesized precipitate is filtered and thoroughly washed with distilled water. Ammonia solution (NH3
28%) is used to remove the included impurities. The
precipitate is subsequently dried in air at 60 -C.
Phase composition and crystallinity of the as-synthesized powders are characterized using X-ray powder
diffraction (XRD, D/Max 2400, Rigaku equipped with
the graphite monochromatized CuKa radiation) in the 2h
angles ranging from 15- to 80-. Scanning electron microscopy (SEM, JSM-5600LV, JEOL) investigations are
performed on microstructure of the LN powders. The
infrared spectra (FTIR) of the prepared LN powders are
measured by the KBr pellet method (NEXUS, Nicolet) in
the range of 400 4000 cm
1.

3. Results and discussion

Lithium carbonate can be easily dissolved in oxalic acid
solution at room temperature according to Eq. (1). However, for

Fig. 3. SEM images of the as-prepared LN powders synthesized at 340 -C: low magnification view (A) and high magnification view (B).

M. Liu, D. Xue / Materials Letters 59 (2005) 2908 2910

688.24

1635.75

3474.44

Transmittance (a. u.)

2910

3000

2000

1500

1000

800

600

Wavenumbers (cm )
Fig. 5. FTIR spectra of the obtained LN powders. The data indicate the
location of the absorption bands.

niobium oxide, such a dissolution is difficult to reach. On the other

hand, high temperature and pressure in the oxalic acid solution
may lead to a strong driving force to precede the dissolution
reaction of Nb2O5 (Eq. (2)) [11]. The involved reactions in
synthesizing LN powders can be described as follows:
Li2 CO3 C2 H2 O4 I2H2 O Y C2 Li2 O4 3H2 O CO2

Nb2 O5 6C2 H2 O4 I2H2 O Y 2NbC2 O4 3 
17H2 O2H

4NbC2 O4 3 
14H2 O 2C2 Li2 O4 Y 4LiNbO3

14H2 C2 O4 O2

XRD pattern of the as-synthesized LN powders is shown in Fig.

2. The sharp reflections can unambiguously be assigned to the
hexagonal LN structure (JCPDS No. 20-0631). Each peak is
assigned as corresponding crystallographic plane by using its d and c = 13.8400
spacing value. The lattice constants a = 5.1430 A
are well consistent with the literature value a = 5.149 A
and
A
(JCPDS No. 20-0631). However some unindexed
c = 13.86 A
diffraction peaks could be attributed to the raw material Nb2O5,
which may be caused by the poor reactivity of normal Nb2O5
powders.
Representative SEM images of the as-prepared LN powders are
shown in Fig. 3. An overview image (Fig. 3(A)) at low
magnification illustrates that the obtained samples are quite
uniform in shape. A closer examination of these samples indicates
that our synthesized powders have a cubic morphology (Fig. 3(B)).
The cubic edge length distribution is depicted in Fig. 4. The
general edge length of the synthesized cubes is in the 0.4
2.1 Am
range, with an average size of 1.13 Am and a standard deviation of
0.52 based on the count of 90 particles.
Fig. 5 shows IR spectra of the as-prepared samples. The
absorption bands observed at 3474.44 and 1635.75 cm
1 are

attributed to OH vibrations due to water contamination at the

surface of the as-prepared LN samples. The absorption band at
688.24 cm
1 is attributed to Nb O vibration in the crystalline
state LN [5]. It should be noted that our present LN samples
possess a Li / Nb ratio close to the stoichiometry, such a route may
provide us a useful route to synthesize stoichiometric LN samples
and a novel way to further understand various properties of
stoichiometric LN.
In conclusion, the solvothermal synthesis of LN powders has
been successfully developed. The synthesis strategy is based on a
complex process involving the chemical reaction between niobium
oxide and oxalic acid. The avoidance of halide precursors and any
additional surfactants limits possible impurities in the final
powders. The current process is very simple, which may be
generally applicable to chemical synthesis of a wide variety of
ceramic materials. The as-prepared LN cubes may perform better
in optical and electric devices, due to the novel morphology.

Acknowledgements
The financial supports from the National Natural Science
Foundation of China (Grant No. 20471012), a Foundation
for the Author of National Excellent Doctoral Dissertation
of P. R. China (Grant No. 200322) and the Research Fund
for the Doctoral Program of Higher Education (Grant No.
20040141004) are greatly acknowledged.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]

D. Xue, K. Kitamura, J. Cryst. Growth 249 (2003) 507.

H. Akazawa, M. Shimada, J. Cryst. Growth 270 (2004) 560.
D. Xue, K. Kitamura, J. Wang, Opt. Mater. 23 (2003) 399.
N. Pinna, G. Garnweitner, M. Antonietti, M. Niederberger, Adv.
Mater. 16 (2004) 2196.
Z. Cheng, K. Ozawa, A. Miyazaki, H. Kimura, Chem. Lett. 33 (2004)
1620.
C. An, K. Tang, C. Wang, G. Shen, Y. Jin, Y. Qian, Mater. Res. Bull.
37 (2002) 1791.
D. Dey, M. Kakihana, J. Ceram. Soc. Jpn., Int. Ed. 112 (2004) 368.
E.R. Camargo, M. Kakihana, Chem. Mater. 13 (2001) 1905.
V.T. Kalinnikov, O.G. Gromov, G.B. Kunshina, A.P. Kuzmin, E.P.
Lokshin, V.I. Ivanenko, Inorg. Mater. 40 (2004) 411.
M. Niederberger, N. Pinna, J. Polleux, M. Antonietti, Angew. Chem.,
Int. Ed. Engl. 43 (2004) 2270.
E.R. Camargo, M. Kakihana, Solid State Ionics 151 (2002) 413.