Pergamon

Materials Research Bulletin 36 (2001) 2119 2126

Effects of precursors on hydrothermally synthesized

SrTiO3 powders
Changlong Chen, Xiuling Jiao, Dairong Chen*, Yuting Zhao
Department of Chemistry, Shandong University, Jinan 250100, P.R. China
(Refereed)
Received 14 December 2000; accepted 30 May 2001

Abstract
SrTiO3 powders with different particle sizes from 50 to 100 nm have been hydrothermally prepared
from different Ti and Sr precursors and characterized with XRD, TEM, and other techniques. The
effects of strontium and titanium precursors on the formation of SrTiO3 powders and the reaction
conditions such as alkali concentration were studied. Furthermore, the effects of precursors on SrTiO3
particle size have been studied in detail. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: A. Structural materials; A. Inorganic compounds; B. Chemical synthesis; C. X-ray diffraction

1. Introduction
SrTiO3 is an important component of the SrTiO3 grain boundary layer capacitor (SrTiO3GBBLC) ceramics materials [1]. It is traditionally prepared by solid-state reaction [2,3],
oxalic coprecipitate method [4,5] and the sol-gel technique [6], which can be regarded as the
improved solid-state method. The resulting powders by the traditional methods usually have
a high agglomeration and inhomogeneous particle size as a result of the high-temperature
treatment required for the formation of SrTiO3 powders. As a novel method to prepare oxide
powders, the hydrothermal technique [2,7] became attractive in the last decade for its mild
reaction conditions, regular particle morphology, and homogeneous particle size distribution
of the prepared powders. In recent years, several papers reported on the hydrothermal

* Corresponding author.
E-mail address: cdr@sdu.edu.cn (C.L. Chen).
0025-5408/01/$ see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 2 5 - 5 4 0 8 ( 0 1 ) 0 0 6 9 4 - 8

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synthesis of SrTiO3 powders, including the preparation from TiO2 gel powders [8,9] and the
synthesis of its nanoparticles from TiO2 nanoparticles and Ti(OC4H9)4 [10,11]. More
recently, Xu et al. hydrothermally prepared SrTiO3 particles coated with a layer of dodecylbenzenesulphonic using TiCl4, Sr(NO3)2, KOH, and dodecylbenzenesulphonic as reagents [12]. In the present study, fine SrTiO3 powders are obtained under mild conditions
using TiCl4 or TiOSO4H2O and Sr(OH)2nH2O as titanium and strontium sources, which
may be suitable for the industrial synthesis, and the effects of the precursors on the prepared
products are studied in detail for the first time.

2. Experimental
2.1. Preparation of the precursors
2.1.1. Ti precursors
TiCl4 (Tianjin 4th Chemical Plant, Tianjin, P.R. China) was dissolved in deionized water
to form a TiOCl2 solution, in which the Ti concentration was 2.0 moldm3. Under stirring,
an NaOH solution (12.0 moldm3) was added dropwise to the TiOCl2 solution until the pH
value of the mixture was about 7. The white precipitate obtained was named as Ti precursor
A. TiOCl2 solution, which was prepared as that in precursor A, was refluxed for 1-1/2 hours.
After cooling to room temperature, H2TiO3 was obtained by filtration, washed with deionized water, and then dried at 70C, which was labeled as Ti precursor B.
TiOSO4H2O (Shanghai 4th Reagent Plant, Shanghai, P.R. China) was dissolved in
deionized water to form the TiOSO4 solution (3.0 moldm3). The subsequent process was
the same as the preparation of the Ti precursor A and the Ti precursor C was obtained. Using
the above TiOSO4 solution, the Ti precursor D was obtained through the process for
preparing the Ti precursor B.
Rutile TiO2 and anatase TiO2 (synthesized by a hydrothermal process in our laboratory)
were used as Ti precursors E and F, respectively.
2.1.2. Sr precursors
SrCl26H2O (Chongqing Beipei Chemical Reagent Plant, Chongqing, P.R. China) was
dissolved in deionized water and mixed with a stoichiometric amount of NaOH solution
(12.0 moldm3) to form Sr(OH)2nH2O by precipitation, which was then filtered and
washed by deionized water to obtain Sr precursor A.
SrCl26H2O solution was mixed with a stoichiometric amount of NaOH solution (12.0
moldm3) to form Sr(OH)2nH2O precipitation, the suspension solution was called Sr
precursor B.
2.2. Synthesis of SrTiO3 powders
Stoichiometric amounts of the Sr and Ti precursors were mixed and stirred to form a
homogeneous slurry. Then, an amount of solid NaOH was added in while magnetically
stirring. Afterwards, 15.0 cm3 of the homogeneous slurry was poured into a 20.0-cm3

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stainless steel autoclave with a Teflon liner. After heating under the autogeneous pressure for
several hours at the designed temperatures, the product was obtained by filtration, washed
with deionized water and dried at 70C.
2.3. Characterization
The X-ray diffraction (XRD) patterns of the products were recorded on a Rigaku D/MAX
2200 PC X-ray diffractometer using CuK radiation and a graphite monochromator. A
Hitachi-800 transmission electron microscope (TEM) was used to observe the particulate
properties of the prepared powders and a Zetasize 3000 laser scattering size distribution
instrument (Malvern Co.) was applied to measure the distribution of the particles.

3. Results and discussion

3.1. Effects of precursors on the formation of SrTiO3
To investigate the effects of the precursors on the formation of SrTiO3 powders, the
following experiments were carried out. First, the powders were prepared from different Ti
precursors using Sr precursor A as Sr source while other conditions were held constant. XRD
patterns of the as-prepared products are shown in Fig. 1. It can be seen that pure SrTiO3
powder could be obtained from Ti precursors A, C, D, and F, while the Ti precursors B and
E gave SrTiO3 powders with an impurity of rutile titania. In light of the above findings, the
Ti precursors were analyzed using XRD patterns. Fig. 2 shows the XRD patterns of the Ti
precursors A, B, C, D, E, and F. It indicates that precursors A and C were amorphous, which
had been assumed to be H4TiO4 from their preparation process, while Ti precursors B and
D, which were assumed to be H2TiO3 from their preparative method, had some rutile and
anatase titania, respectively, as deduced from the corresponding XRD patterns. The results
indicate that the formation of SrTiO3 powder was greatly affected by the nature of the Ti
precursor. Anatase and amorphous TiO2nH2O rather than rutile favor the formation of
SrTiO3. Pure SrTiO3 powder could be obtained using anatase or amorphous TiO2 as the Ti
precursor. To investigate why the amorphous H4TiO4 favors the formation of SrTiO3,
H4TiO4 from both TiOCl2 and TiOSO4 solution were hydrothermally treated under the same
conditions as used for the preparation of SrTiO3. As a result, anatase TiO2 formed from both
solutions. Therefore, it can be concluded that anatase structure rather than the rutile aids in
the formation of purer SrTiO3 powders by the hydrothermal process. This result can be
explained as the similarity between the TiO6 octahedron of anatase TiO2 and SrTiO3. The
TiO bond distances are 0.194(4 TiO) and 0.198(2 TiO) nm in the TiO6 octahedron of
rutile [13] and those are 0.191(2 TiO) and 0.195(4 TiO) nm in TiO6 octahedron of
anatase [14 16]. The bond angles are 90.0, 80.8 and 99.2 in TiO6 octahedron of rutile,
while those in TiO6 of anatase are respectively 90.7, 83.7, and 96.3 [17,18]. It is also
known that the bond distances and bond angles are 0.195 nm and 90.0 in TiO6 octahedron
of SrTiO3 [19]. It seems that the TiO6 octahedron of SrTiO3 is more similar to that of the
anatase than rutile, and only a small distortion is needed to transform from anatase TiO6 to

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Fig. 1. XRD patterns of the products prepared from different Ti precursors. Sr source: Sr precursor A; reaction
temperature:200C; reaction time: 4 h; a, b, c, d, e, f, respectively, from Ti precursors A, B, C, D, E, and F.

Fig. 2. XRD patterns of Ti precursors A (a), B (b), C (c), D (d), E (e), and F (f).

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Fig. 3. XRD patterns of SrTiO3 powders prepared from Ti precursor A and Sr precursor A at different NaOH
concentrations. Reaction temperature: 200C; reaction time: 4 h; NaOH concentration: a. 0.2 moldm3; b. 0.5
moldm3; c. 0.7 moldm3; d. 1.1 moldm3.

SrTiO3 TiO6. Because of the similarity between the TiO6 of anatase and SrTiO3, a smaller
energy barrier is needed to form SrTO3 from anatase than that from rutile.
Further experiments in which Sr precursor B was used as Sr source with different Ti
precursors showed a similar result to that using Sr precursor A as Sr source, which indicates
that filtration or not of Sr(OH)2 precipitation did not affect the formation of SrTiO3.
To find the optimal reaction conditions for the formation of SrTiO3 powders from
different precursors and study the reactive activities of the precursors, different reaction
conditions including reaction temperature, time, and the NaOH concentration were studied.
Fig. 3 shows the XRD patterns of the products from Ti precursor A and Sr precursor A
treated at 200C for 4 h at different NaOH concentrations. Fig. 3 shows that the crystallinity
of the prepared SrTiO3 powders increased with increasing NaOH concentration from 0.1 to
0.7 moldm3, where the crystallinity reached a plateau. Thus, a NaOH concentration of 0.7
moldm3 or higher is necessary for preparing well-crystallized SrTiO3 powders from Ti
precursor A and Sr precursor A. Similar experiments were carried out using other precursors
and the optimal reaction conditions for preparing well-crystallized SrTiO3 powders from
different precursors are listed in Table 1. They show that the reactivity of Ti precursors is
similar. For example, the borderline reaction conditions were similar to preparing wellcrystallized SrTiO3 powder from different Ti precursors at 200 C using Sr precursor A as
a Sr source. On the other hand, Sr precursor A had a higher reactive activity than Sr precursor
B. Well-crystallized SrTiO3 powder could be prepared at 200C for 4 h in 0.7 moldm3
NaOH solution from Ti precursor A and Sr precursor A, while a NaOH concentration higher
than 5.0 moldm3 was necessary to obtain well-crystallized SrTiO3 powder from Ti
precursor A and Sr precursor B under the same reaction conditions.

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Table 1
Optimal reaction conditions for preparing SrTiO3 powders from different precursors
Ti precursor

Sr precursor

C
D
D

B
A
B

Temperature
(C)

Reaction time
(h)

NaOH concentration
(mol dm3)

150
200
240
200
150
200
240
240
200
200

6
4
2
4
7
4
4
4
4
4

0.8
0.7
0.7
5.0
1.0
0.8
0.7
3.0
0.7
3.0

Fig. 4. TEM graphs of SrTiO3 powder particles prepared from different precursors. Reaction temperature: 200C;
Reaction time: 4 h; NaOH concentration: 0.7 moldm3 (a, b, c) and 5.0 moldm3 (d). a. From Sr precursor A
and Ti precursor A, b. From Sr precursor A and Ti precursor C, c. From Sr precursor A and Ti precursor D, d.
From Sr precursor B and Ti precursor A.

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Fig. 5. Laser-scattering size distribution of the products prepared from Ti precursor A and Sr precursor A (a), Ti
precursor A and Sr precursor B (b). Reaction temperature: 200C; reaction time: 4 h; NaOH concentration: a. 0.7
moldm3; b. 5.0 moldm3.

3.2. Effects of precursors on the particulate properties

Fig. 4 shows the TEM photographs of the SrTiO3 powders prepared from different Ti and Sr
precursors. It indicates that SrTiO3 particles from Ti precursor A and Sr precursor A have a grain
size of 100 nm or so (Fig. 4a). As for the particles from Ti precursor C and Sr precursor A, the
size ranges from 100 to 120 nm (Fig. 4b), while the particles from Ti precursor D and Sr
precursor A have a mean size of 100 nm (Fig. 4c). In summary, the particle size of the SrTiO3
powders from Sr precursor A was about 100 nm regardless of whether Ti precursor A, C, or D
was used. However, from Sr precursor B, in which the Sr(OH)2nH2O was not filtered, the
particles size was about 30 50 nm regardless of which Ti precursor was used as the Ti source.
Fig. 4d shows the TEM photographs of the SrTiO3 particles prepared from Ti precursor A and
Sr precursor B, which were obtained by reaction in a 5.0 moldm3 NaOH at 200C for 4 h. It
can be seen that smaller SrTiO3 particles could be obtained when Sr precursor B replaced Sr
precursor A as the Sr source. The prepared SrTiO3 powders may form through two processes:
nucleation and grain growth. When the rate of nucleation was faster than that of grain growth,
small particles formed, while large particles could be obtained with a slow nucleation rate and a
fast grain growth rate. In the present hydrothermal synthesis, the Sr precursor B might favor the
nucleation process, and the small particles formed.

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The particle size distribution of the prepared powder was also characterized using the laser
scattering method shown in Fig. 5. It clearly indicates that the particle size has a narrow
distribution, although the mean size was different from that observed on the TEM photographs. The mean size of the particles was about 200 nm from the laser scattering size
distribution, while a value is about 100 nm from the corresponding TEM graphs. For the
50-nm particles from TEM images, the mean size was about 195 nm from the laser scattering
size distribution. It is known that the TEM image gives the real particle size, while laser
scattering size distribution gives the average size of crystallite agglomerates. This result
reveals that about 2 4 particles aggregated with each other and larger SrTiO3 particles have
lower agglomeration than the smaller ones.

4. Conclusions
SrTiO3 powders were synthesized hydrothermally using NaOH as mineralizer from
different Ti precursors such as H4TiO4 from both TiCl4 and TiOSO4 solution, H2TiO3 from
TiOSO4 solution, anatase TiO2 and Sr precursors including filtered and unfiltered
Sr(OH)2nH2O. The nature of Ti precursors greatly affected the crystallization of SrTiO3
powders with the anatase form of TiO2 favoring the formation of SrTiO3 during the
hydrothermal reaction, while the nature of Sr(OH)2nH2O precursor did not. The crystallization of the product depends on the reaction time, temperature, and NaOH concentration.
The size of the SrTiO3 particles was affected greatly by the Sr precursors, with the filtered
Sr(OH)2nH2O favoring the formation of larger SrTiO3 particles.
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