Journal of Alloys and Compounds 441 (2007) L7–L9

Letter

Combustion synthesis and photoluminescence of

perovskite PbTiO3 nanopowders
Suwen Liu ∗ , Zhiliang Xiu, Jian’an Liu, Fengxiu Xu,
Weina Yu, Jie Pan, Xiaopeng Cui, Jiaoxian Yu
Department of Material Science and Engineering, Shandony Institute of Light Industry, Jinan 250353, PR China
Received 8 June 2006; received in revised form 16 September 2006; accepted 26 September 2006
Available online 22 November 2006

Abstract
Perovskite PbTiO3 nanopowders were synthesized by citric acid sol–gel combustion method using citric acid (CA) as a reductant/fuel and
nitrate as an oxidant at 700 ◦ C. The particle sizes were in the range of 40–50 nm observed by transmission electron microscopy (TEM). The
photoluminescence (PL) spectrum revealed that an intense emission at 415 nm was ascribed to the Pb2+ ion 3 P1 –6 S0 transition.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Combustion; Photoluminescence; Nanopowders

1. Introduction scintillators [11–13]. The luminescence of Pb2+ ion is generally

Lead titanate in its perovskite structure is of great interest
for many applications, such as non-volatile memories, actuators
and transducers due to their excellent piezoelectric and electro-
optic properties [1,2]. Many methods have been applied to
prepare lead titanate powders, such as sol–gel method [3], co-
precipitation [4] and hydrothermal synthesis [5], besides the
traditional solid-state reaction of mixed oxides [6].
The citric acid sol–gel combustion method is one kind of
non-alkoxide sol–gel method and can synthesize nanomaterials
with high purity, better homogeneity and high surface area in a
single step [7–9]. In the combustion process, the exothermic heat
generated by thermally induced redox reaction involving citrate
and nitrate anions in the gel precursor, where citric acid acts as
a fuel and strong reductant and nitrate act as a strong oxidant.
Its key feature is that the heat required to drive the chemical
reaction and accomplish the compound synthesis is supplied by
the reaction itself and not by an external source [10]. This method
has the advantages of low processing cost, energy efficiency and
high production rate.
Lead ions Pb2+ (6 S2 ) are well known as effective activators
of luminescence, such as in sun-tan lamps, X-ray phosphors or
∗ Corresponding author.
E-mail address: liusw@sdili.edu.cn (S. Liu).
ascribed to the 1 S0 –3 P0,1 transitions originating from the
6s2 –6s6p interconfigurational transition [14]. The luminescence
properties of Pb2+ ion are strongly dependent on the host lattice
for its s2 outer electron configuration [15,16].
In this paper, we have synthesized PbTiO3 nanopowders by
citric acid sol–gel combustion method and investigated their
photoluminescence properties.
2. Experimental
All the reagents used were of analytical purity and used without further
purification. The schematic flow chart of the synthesis process is shown in Fig. 1.
TiO(NO3 )2 used as the source of titanium was prepared according to Fig. 1.
Citric acid was used as a reductant/fuel because it not only can form stable
water-soluble complexes with Ti and Pb ion but is also a rich fuel. Citric acid
and Pb(NO3 )2 were dissolved in distilled water and mixed with the TiO(NO3 )2
solution. The molar ratio of Pb:Ti:CA:NO3 − was 1:1:2:0.56. Then the pH value
of the solution was adjusted to be 6–7 by 25% NH3 ·H2 O and heated at 60–70 ◦ C
under vigorous stirring until a brown gel formed. The gel was dried in an oven at
90 ◦ C for 12 h. Finally, the xerogel was placed in a muffle furnace preheated at
700 ◦ C and sharply burnt and gave out bright flame and large amount of gases.
The whole combustion process was lasted for 30 min and puffy powders were
finally obtained.
Thermogravimetric/differential thermal analysis (TG/DTA) experiments
were performed on a TGA/SDTA 851e instrument, in a Pt crucible at heating rate
of 25 ◦ C/min, from 20 to 800 ◦ C at nitrogen atmosphere. The X-ray diffraction
(XRD) pattern of the powder was examined using Japan RigaKu D/max-␥ X-
ray diffractometer system with graphite monochromatized Cu K␣ radiation

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L8 S. Liu et al. / Journal of Alloys and Compounds 441 (2007) L7–L9

Fig. 3. XRD pattern of the xerogel calcined at 700 ◦ C.

structure (JCPDS file no.: 06-0452). No peak corresponding

Fig. 1. Schematic flow chart of the combustion synthesis process.
to any of the source materials or allotroptic forms is found,
suggesting that a pure crystalline compound exists.
(λ = 1.5418 Å). The transmission electron micrograph (TEM) was taken using The typical TEM image of the PbTiO3 powders calcined at
a JEM-100CX instrument running at an accelerating voltage of 100 kV. The
700 ◦ C is presented in Fig. 4. It can be seen that most particles
excitation and emission spectra of the samples were measured using Hitachi
F-4500 Fluorescence Spectrometer. are fine and nearly spherical with some agglomeration and their
sizes are in the range of 40–50 nm.
Fig. 5 gives the excitation spectrum taken at the peak emission
3. Results and discussion
of 415 nm, which reveals a strong line of excitation, λ = 302 nm.
It is ascribed well to the transitions to the 1 P1 level of Pb2+ ions.
Fig. 2 presents the TG/DTA curves of the xerogel. The DTA
Fig. 6 presents the emission spectrum excited by the
curve reveals one endothermic peak at 100–200 ◦ C and two
wavelength 300 nm. A sharp emission peak at 415 nm can be
exothermic peaks at 200–300 ◦ C and 600–700 ◦ C, respectively.
seen. The ground state is 1 S0 , and the excited states are the
Accordingly, three weight loss stages can be observed from TG
triplets 3 P1,2,3 and the singlet 1 P1 [17]. H.F. Folkerts has pointed
curve. In the first stage below 200 ◦ C with little weight loss
out that the Pb2+ ion emission band near the ultroviolent spectral
is due to the loss of the residual water in the gel. The second
region originates from the s2 –sp interconfigurational transition
stage with larger weight loss that occurs in the temperature range
from the 3 P1 level at higher temperature. After excitation at
200–300 ◦ C results from the combustion reaction of citrate and
room temperature, the 3 P1 level is thermally populated and the
nitrate anions. The final weight loss at 600–700 ◦ C indicates the
decay time becomes much shorter, since the 3 P1 –1 S0 emission
crystallization of tetragonal PbTiO3 .
is allowed by spin–orbit coupling [18]. So the intense 415 nm
XRD pattern of the xerogel calcined at 700 ◦ C is shown in
emission can be ascribed to the Pb2+ ion 3 P1 –6 S0 transition.
Fig. 3. All peaks can be indexed to the PbTiO3 with a perovskite

Fig. 2. TG/DTA curves of the xerogel. Fig. 4. TEM image of the PbTiO3 powders calcined at 700 ◦ C.
 S. Liu et al. / Journal of Alloys and Compounds 441 (2007) L7–L9
Fig. 5. Excitation spectrum of PbTiO3 nanopowders taken at the emission of
415 nm.
Fig. 6. Emission spectrum of PbTiO3 nanopowders excited by the wavelength
300 nm.
L9
4. Conclusions
PbTiO3 nanopowders have been synthesized by the sol–gel
combustion method using citric acid as a reductant/fuel and
nitrate as an oxidant. Pure tetragonal phase PbTiO3 with
perovskite structure was formed at 700 ◦ C. The calcined powders
showed a nano-scale microstructure and the particle size was
in the range of 40–50 nm. The intense 415 nm emission was
ascribed to the Pb2+ ion 3 P1 –6 S0 transition.
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