Int. J. Appl. Ceram. Technol.

, 5 [1] 101–104 (2008)

Ceramic Product Development and Commercialization

Novel Synthesis of SrBi2Nb2O9 Powders From Hydroxide

Precursors
Upendra Nath Gupta, Koteswara Rao, Sivaram Pradhan, and Ratnesh Kumar Jha
National Chemical Laboratory, Catalysis Division, Pune 411 008, India

Harries Muthurajan
Armament Research and Development Establishment, Pune 411 021, India

Venkat Ravi*
National Chemical Laboratory, Physical and Materials Chemistry Division, Pune 411 008, India

Simple hydroxide precursors were used for the first time for the synthesis of a typical Aurivillius compound (SrBi2Nb2O9
(SBN)) at a low temperature. This method is very advantageous because it circumvents the use of SrCO3 in the case of
conventional ceramics as well in the coprecipitation methods, thereby lowering the formation of the product phase. Com-
mercially purchased strontium hydroxide is mixed thoroughly with freshly precipitated bismuth and niobium hydroxides in a
stoichiometric ratio and heated at different temperatures ranging from 1001C to 7501C for 12 h. The sequence of the reaction
and evolution of the product phase was monitored by X-ray diffraction (XRD) studies by recording the XRD for samples
calcined at different temperatures. The incipient SBN phase begins to form at temperatures as low as 4001C, and phase
formation was complete only at 6501C as revealed by the XRD observations. The differential thermal/thermogravimetric
analyses) also corroborate this result. The morphology and average particle size of these powders were investigated by trans-
mission electron microscopy studies.

Introduction cycles, excellent retention characteristics, and low leak-

Recently, bismuth-based compounds with an Aur-
ivillius-type structure have attracted considerable atten-
tion because of their low operating voltage, fast
switching speed, negligible fatigue up to 1012 switching
*r.venkat@ncl.res.in
r 2008 The American Ceramic Society
age current density on Pt electrodes for integrated device
applications in nonvolatile ferroelectric random access
memories (FRAM).1–9 Large remnant polarization, a
low coercive field, and a high Curie temperature are re-
quired for better performance and reliable operation of
the FRAM devices. The early developments of FRAM
were carried out mostly using a lead zirconate titanate
(PZT) perovskite ferroelectric due to its large remnant
102 International Journal of Applied Ceramic Technology—Gupta, et al.
polarization (Pr B40mC cm 2) and well-documented
properties. However, because of the problems associated
with high leakage current, poor retention of switched
charges etc, high-density FRAM devices are not yet
commercially available. The Aurivillius family of com-
pounds is represented by the formula (Bi2O2 (An
Bn 1O3n11)) where A (Sr, Ba, Ca) is a larger cation
in a 12-fold coordination and B (Nb, Ta) is a small
cation in a sixfold environment. The lattice structure of
this kind of compound is composed of n number of
(An 1BnO3n11)2 unit cells sandwiched between
(Bi2O2)21 slabs along the pseudotetragonal c-axis, while
the A-site cation occupies the cubooctahedral sites in
perovskite layers. SrBi2Ta2O9 and SrBi2Nb2O9 (SBN)
are the most intensively studied members of this in
comparison with BaBi2Ta2O9, BaBi2Nb2O9, CaBi2-
Ta2O9, and CaBi2Nb2O9.2–5
Both traditional solid-state and wet-chemical meth-
ods are used for the preparation of these compounds.6,7
In all these techniques, the temperature for the forma-
tion of product is 47001C. The disadvantage of co-
precipitation is that barium carbonate or oxalate thus
precipitated will be decomposed only at T47501C and
hence this method also does not produce this com-
pound at low temperatures. Another major drawback of
these compounds is the difficulty in achieving homoge-
neous bulk compositions without pyrochlore-phase for-
mation at lower temperatures. The present technique,
for the first time, uses a simple hydroxide precursor for
the synthesis of these bulk compounds at very low tem-
peratures. The method is easily suitable for large-scale
production and is relatively economical. The bulk SBN
powders can be used as a target for DC sputtering and
laser ablation methods for the preparation of corre-
sponding thin films.
Experimental Procedure
For preparing SBN, niobium (V) oxide, bismuth
(III) nitrate, strontium hydroxide, and standard aqueous
ammonia were used as the starting materials and they
were of AR grade (Loba Chemie, Mumbai, India).
Firstly, Nb2O5 was dissolved in HF acid (40%) after
heating in a hot water bath for 10 h. Then, niobium
hydroxide was produced by the addition of standard
ammonia solution to aqueous niobium fluoride at pH
B9. The bismuth hydroxide was precipitated by adding
liquid ammonia to bismuth nitrate solution under basic
Vol. 5, No. 1, 2008
conditions. The precipitated niobium and bismuth hy-
droxides were filtered individually, washed free of an-
ions by distilled water, and dried in an oven at 1001C
overnight. Then, strontium hydroxide (which should be
handled cautiously because of possible carbonate for-
mation on exposure to air), purchased, and freshly pre-
pared dry bismuth and niobium hydroxides were mixed
thoroughly in a stoichiometric ratio and heated at differ-
ent temperatures from 1001C to 7501C for 10 h.
Various techniques such as X-ray diffraction
(XRD), thermogravimetric analysis(TGA)/differential
thermal analysis (DTA), and transmission electron mi-
croscopy (TEM) were used to characterize these pow-
ders. The powder XRD patterns were recorded for all
the samples using a Philips (Eindhoven, The Nether-
lands) PW-1710 model X-ray diffractometer using
CuKa at room temperature. The DTA/TGA (STA
15001, Rheometric Scientific, Piscataway NJ) curves
were recorded for these powders at a heating rate of
101C/min from room temperature to 9501C. The TEM
picture was recorded with a JEOL (Tokyo, Japan) mod-
el 1200 EX instrument at an accelerating voltage of
100 kV. The fine powders were dispersed in amyl ace-
tate on a carbon-coated TEM copper grid.
Results and Discussion
Figures 1–3 show the XRD patterns of the hydrox-
ide mixtures heated at different temperatures ranging
Cu Kα
S , B N, B
S S ,B
(c)
N S B
S
Intensity (a. u.)
(b)
(a)
20 30 40 50 60
2θ (degrees)
Fig. 1. X-ray diffraction patterns of SrBi2Nb2O9 hydroxide
precursor heated at (a) 1001C, (b) 2001C, and (c) 3001C for 10 h.
www.ceramics.org/ACT Novel Synthesis of SrBi2Nb2O9 Powders 103

Cu Kα Cu Kα
(115)

(008)
(315)
(200)

Intensity (a. u.)

Intensity (a.u.)

(b) (11.11)
(0210)
(01.11)
(b) (113) (202)
(124) (131) (317)

(a)
(a)

20 30 40 50 60 20 30 40 50 60
2θ (degrees) 2θ (degrees)

Fig. 2. X-ray diffraction patterns of SrBi2Nb2O9SBN hydroxide Fig. 3. X-ray diffraction patterns of SrBi2Nb2O9 hydroxide
precursor heated at (a) 4001C and (b) 5001C for 10 h. precursor heated at (a) 6501C and (b) 7001C for 10 h.

from 1001C to 7501C for 10 h. When To3001C, the but without many distinct crystalline peaks as illustrated
XRD shows (Fig. 1) reactant phases (‘‘S’’ for Sr(OH)2, in Fig. 2a. The trend was similar even at 5001C without
JCPDS No. 74-0407, ‘‘B’’ for Bi2O3, JCPDS No. 78- a significant change in the XRD pattern (Fig. 2b). How-
1793, and ‘‘N’’ for Nb2O5, JCPDS No. 30-0872), in- ever, the formation of an SBN phase at 6501C was
dicating the initial stages of the reaction occurring in the confirmed by XRD studies (Fig. 3). All the d- lines were
samples. The incipient product phase, Aurivillius com- indexed in accordance with the reported pattern
pound, begins to form at temperatures as low as 4001C (JCPDS No. 86-1191).

5.775e-4 101
100

– 0.05
95

– 0.10
Derivative Weight (mg/min)

90

– 0.15
Weight % (%)

85

– 0.20

80
– 0.25

75
– 0.30

70
– 0.3457 69
0 100 200 300 400 500 600 700 800 900 950
Temperature (°C)

Fig. 4. The differential thermal analysis/thermogravimetric analysis curves recorded for SrBi2Nb2O9 precursor powders at a heating rate of
101C/min.
104 International Journal of Applied Ceramic Technology—Gupta, et al.
Fig. 5. Transmission electron microscopy image of SrBi2Nb2O9
powders formed at 6501C.
These experiments also indicate that no major in-
termediate phases were formed during the course of the
reaction. This is the lowest temperature reported6,7 so
far for the preparation of this compound. In general, a
pyrochlore phase was found to be formed along with the
product in the traditional solid-state method.6,7 But in
this method no pyrochlore phase was produced, possibly
due to the low temperatures at which its product phase
was formed, and it could be directly related to the
application of hydroxide precursors. Hence, it is very
advantageous to use this technique to prepare a single-
phase Aurivillius compound at low temperatures.
Figure 4 depicts the DTA/TGA curves for these
powders heated at a rate of 101C/min from room tem-
perature to 9501C. The first endotherm observed at
lower temperatures indicates removal of hydroxyl ion,
whereas the endotherm at 6501C–7001C implies the
formation of an SBN phase. There is not much litera-
ture on thermal studies for these compounds and hence
no reference can be obtained. The average particle size
and morphology of these powders were investigated by
Vol. 5, No. 1, 2008
TEM studies. Figure 5 depicts the typical micrograph
for these powders. The average crystallite size (t) of these
powder particle sizes was calculated using Scherrer’s
formula (t 5 Kl/B Cos yB), assuming particles are
spherical, K 5 0.9; l, the wavelength of X-ray radia-
tion; B, the full-width at half-maximum of the diffract-
ed peak, and yB, the angle of diffraction, is 90 nm.
Conclusions
A typical member (SBN) of the Aurivillius family
of compounds was synthesized at a relatively low tem-
perature using novel hydroxide precursors. This method
does not involve any carbonate and hence a product
phase is formed at a lower temperature as compared
with other procedures reported in the literature. This
technique is very simple, economical, and suitable for
large-scale production. The phase contents and mor-
phology of these powders were investigated using XRD
and TEM techniques.
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