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Synthesis, structure refinement and vibrational spectroscopy studies of the

Bi1−xTa1−xTe2xO4 (0 ≤ x ≤ 0.2) solid solution with stibiotantalite type
structure

Article  in  Materials Chemistry and Physics · August 2012

DOI: 10.1016/j.matchemphys.2012.05.038

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 Materials Chemistry and Physics 135 (2012) 241e248

Contents lists available at SciVerse ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Review

Synthesis, structure refinement and vibrational spectroscopy studies of the

Bi1
xTa1
xTe2xO4 (0  x  0.2) solid solution with stibiotantalite type structure
Imane Yakine a, *, Mohamed Naji b, c, Abdeslam Chagraoui a, Abdenajib Moussaoui a, Abdelmjid Tairi a
a
Laboratoire de Chimie Analytique et Physico- chimie des Matériaux-Département de Chimie, Faculté des Sciences Ben M’sik, Université HassanII-Mohammedia Casablanca, Morocco
b
CNRS, UPR3079 CEMHTI, 1D avenue de la Recherche Scientifique, 45071 Orléans cedex2, France
c
Université d’Orléans, Faculté des Sciences, Avenue du Parc Floral, BP 6749, 45067 Orléans cedex 2, France

h i g h l i g h t s

< Synthesis and crystal structures are described for the Bi1
xTa1
xTe2xO4 solid solution with (0  x  0.2).
< The structure is formed by a three-dimensional network of octahedral (Ta/Te(2))O6 linked by the octahedral (Bi/Te(1))O6.
< The infrared spectra at room temperature showed some characteristic vibration bands assigned to BieO and TaeO vibrations.

a r t i c l e i n f o a b s t r a c t

Article history: In the present study we report the synthesis, crystal structure and vibrational spectroscopy studies of Bi1
Received 24 July 2011
xTa1
xTe2xO4 orthorhombic solid solutions (0  x  0.2). Rietveld refinements showed that this solid
Received in revised form solution is continuous adopting Pnna (no.52) space group. The structure is formed by (Bi/Te(1))O6 and
25 April 2012
(Ta/Te(2))O6 octahedra, The (Ta/Te(2))O6 octahedra linked over four comers and thus the structure can be
Accepted 10 May 2012
viewed as consisting of sheets of [(Ta/Te(2))O6]3
units separated by Bi3þ cations. The infrared spectra of
Bi1
xTa1
xTe2xO4 oxides at room temperature showed some characteristic vibration bands assigned to Bi
Keywords:
eO and TaeO vibrations. Raman spectra of this crystalline solid solution series are interpreted by means
BiTaO4
TeO2
of “internal mode” approach. Assignments of the TaeO and BieO vibrational stretching modes, as well as
Stibiotantalite some of other modes, have been made.
Crystal structure Ó 2012 Elsevier B.V. All rights reserved.
Infra-red absorption
Raman spectroscopy

1. Introduction
Naturally occurring stibiotantalite with ABO4 (where A ¼ Sb3þ
or Bi and B ¼ Ta5þ, Nb5þ or Sb5þ) structure type has ferroelectric
properties which was first discovered by Gavrilova et al. [1]. These
compounds are known to posses excellent ferroelectric and
piezoelectric properties and are important potential candidates for
device fabrication for Modern Wirelless communication. Despite,
their multiple and dielectric phase transitions, the exact nature of
these transitions as well as the mechanism of ferroelectricity, still
not completely understood. The syntheses, structural, and dielec-
tric propreties of ABO4 single crystals, have first been reviewed by
Popolitov et al. [2]. BiNbO4 has the same structure as the mineral
stibiotantalite (Sb0.9Bi0.1)(Ta0.84Nb0.16)O4 and crystallizes in the
orthorhombic space group Pnna (D62h ) with 4 formula units per unit
cell. The structure can be viewed as a pseudo-layered structure in
which layers of corner sharing NbO6 octahedra are separated along
the b-axis by Bi atoms. Very few vibrational studies have been
reported so far, the only one known to the authors for these
compounds are IR absorption and reflectivity, Raman and THZ
reported by Leonov et al. [3], Kim et al. [4] Ayyub et al. [5] and
Kamba et al. [6]. In this paper we report the synthesis, structural
refinement and Raman studies of the solid solution Bi1
xTa1
x-
Te2xO4. In-situ high temperature studies of these compounds will
be reported separately [7].
2. Experimental section
2.1. Powder synthesis

* Corresponding author. Well-crystallized powder samples of Bi1
xTa1
xTe2xO4 were

E-mail address: imane.yakine85@gmail.com (I. Yakine). synthesized by mixing reagents of high purity Bi2O3, Ta2O5 and

0254-0584/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2012.05.038
242 I. Yakine et al. / Materials Chemistry and Physics 135 (2012) 241e248

TeO2 in an agate mortar. The solid state reaction takes place in the
following steps: appropriate stoichiometric amounts of the
precursors were finely ground for several minutes, preheated in air
at 700  C for 24 h, in order to prevent melting of Bi2O3, and were
then heated at successively higher temperatures (700 and 850  C
for 24 h) in air with several intermediate grindings. The positions of
the chemical compositions under study inside the system
Bi2O3eTa2O5eTeO2 are shown in Fig.1. The quality and formation of
the compound are checked by X-ray diffraction (XRD) technique.

2.2. Instrumental methods

2.2.1. X-ray diffraction

The final products of Bi1
xTa1
xTe2xO4 (0 x 0. 2) have been
monitored by X-ray powder diffraction using a Bruker D8 Advance
diffractometer and Cu Ka (l ¼ 1.5406Å) radiation. The structural Fig. 2. X-ray powder diffraction patterns for Bi1
xTa1
xTe2xO4 (0  x  0.2).
refinements were undertaken from the powder data. The patterns
were scanned through steps of 0.02 (2q), between 10 and 100
first 20 peak positions, with a maximal absolute error of 0.03 (2q),
(2q) with a fixed-time counting of 100 s. Rietveld’s profile analysis
were used as input data. The X-ray diffraction pattern for all the
method was employed for refinements using the FULLPROF
compositions was assigned to an orthorhombic structure. The
program [8].
lattice parameters were refined using the complete powder
diffraction data sets and the complete powder diffraction data are
2.2.2. Spectroscopy studies
given in Table 1. All the observed reflections for the compositions
The infrared spectrum in the spectral range between 1000 and
could be indexed in the space group Pnna. Fig. 3 shows the cell
400 cm
1was recorded using a Biorad FT-IR spectrometer FTS-40A
parameter variations as a function of x for Bi1
xTa1
xTe2xO4
using KBr pellets. The Raman characterizations were performed on
(0  x  0.2), where progressive substitution of bismuth and
Jobin Yvon T64000 spectrometer; coupled with an optical micro-
tantalum by tellurium provokes an increase of the unit cell
scope (x100 objective) and a CCD detector in a backscattering
parameters a, b, c and V Table 2 The increase is due to the substi-
geometry. The l ¼ 514.5 nm line was used as excitation source.
tution of Bi3þ (ri ¼ 1.03 Å, coordination 6) and Ta5þ(ri ¼ 0.64Å,
Rejection of the elastic peak was achieved using a holographic
coordination 6) by Te4þ (ri ¼ 0.97 Å, coordinence 6) [32] R.D.
notch filter, which resulted in a cutting of the scattered signal
Shannon, Acta Crystallogr. Sect. A 32 (1976), p. 751. Full Text via
below 100 cm
1. The laser power on the sample was maintained 3
CrossRef [10]. The linear increase of the lattice parameters when
at mW mm
2. The acquisition time was 30 s (3accumulations).
bismuth and tantalum is replaced by tellurium shows that Vegard
law is verified and indicates clearly that there is a complete solu-
3. Results and discussion bility and so that these compounds from a solid solution in which
a given proportion of Te4þ replaces an equal proportion of Bi3þ and
3.1. X-ray diffraction study Ta5þ [(Xr Bi 3þ)þ(XrTa 5þ) < (2XrTe 4þ)].

Fig. 2 shows the X-ray powder diffraction patterns of Bi1
x-

Ta1
xTe2xO4 (0  x  0.2), the patterns are very similar. Indexing of
X-ray powder diffraction patterns for these compositions was
performed by means of the computer program DICVOL91 [9]. The
Fig. 1. Positions of the Bi1
xTa1
xTe2xO4 with x ¼ 0.05, 0.1, 0.15 and 0.2 inside the
Bi2O3eTa2O5eTeO2 system.
3.2. Refinement of the structure
The full pattern refinements were carried out by means of the
Rietveld method using the FULLPROF program integrated in WIN-
PLOTR pack [8]. The space group (Pnna, no. 52) and the atomic
positions of the structure BiTaO4 [11] was used as starting model in
the refinement procedure for the samples Bi1
xTa1
xTe2xO4
(0  x  0.2).. In this model the histogram or phase fraction scale
factors, background coefficients, sample displacement error, unit
cell parameters, and Lorentzian components of the pseudo-Voigt
coefficients adjusted for strain broadening and peak asymmetry
were refined first (pattern matching). The results show good
agreements in the considered space group. The atomic positions
and the isotropic thermal parameters of all the atoms were then
refined freely.
In the second step, the structural parameters of BiTaO4 in the
Pnna space group were used as starting parameters for the Rietveld
refinement of the solid solution. Structural refinement of Bi1
x-
Ta1
xTe2xO4was realized by adopting two principal hypothesis. In
the first one, Ta4þ and Te5þ ions are supposed to occupy statisti-
cally 4d site whereas Bi3þ cations occupy the 4c position. After
several cycles of least-squares refinements, the reliability factors
were very high. In the second step of refinements, the Ta5þ/Te4þ (2)
cations occupy the 4c position and the Bi3þ/Te4þ (1) cations were
allowed to residein the 4d site. The reliability factors, crystal data
 I. Yakine et al. / Materials Chemistry and Physics 135 (2012) 241e248 243

Table 1
X-ray powder diffraction data observed and calculated for Bi1
xTa1
xTe2xO4 (0  x  0.2).

Bi0.95Ta0.95Te0.1O4 Bi0.90Ta0.90Te0.2O4 Bi0.85Ta0.85Te0.3O4 Bi0.80Ta0.80Te0.4O4

hkl dobs Å dcalc Å Iobs Icalc dobs Å dcalc Å Iobs Icalc dobs Å dcalc Å Iobs Icalc dobs Å dcalc Å Iobs Icalc
020 4.61 4.59 6 5 4.56 4.58 8 6 4.57 4.58 3 6 4.53 4.58 8 5
101 3.75 3.74 5 6 3.71 3.74 6 5 3.72 3.74 3 4 3.72 3.74 6 4
111 3.57 3.56 21 24 3.54 3.56 21 21 3.56 3.56 17 21 3.53 3.56 23 22
121 3.16 3.15 100 100 3.14 3.15 100 100 3.15 3.15 100 100 3.13 3.15 100 100
040 2.96 2.94 28 28 2.93 2.92 26 27 2.95 2.92 29 28 2.93 2.92 29 28
200 2.83 2.83 11 11 2.81 2.83 11 10 2.82 2.83 9 11 2.80 2.83 11 13
210 2.75 2.75 10 11 2.73 2.75 10 11 2.74 2.75 8 10 2.72 2.75 10 12
220 2.55 2.54 7 5 2.53 2.55 8 7 2.54 2.55 8 7 2.53 2.55 8 7
002 2.49 2.48 8 6 2.47 2.48 13 9 2.48 2.48 12 8 2.47 2.48 8 8
022 2.31 2.31 13 11 2.28 2.29 4 3 2.29 2.29 3 13 2.28 2.29 14 12
112 2.29 2.24 4 4 2.29 2.23 4 9 2.23 2.23 1 4 2.29 2.23 4 4
240 2.04 2.04 5 4 2.03 2.03 8 4 2.04 2.03 5 5 2.02 2.03 9 5
151 1.99 1.98 9 9 1.98 1.98 4 8 1.99 1.98 4 9 1.98 1.98 5 9
042 1.90 1.89 4 4 1.89 1.89 17 2 1.90 1.89 11 4 1.89 1.89 18 4
202 1.86 1.86 17 16 1.86 1.87 6 17 1.86 1.87 4 17 1.85 1.87 6 16
212 1.84 1.85 9 10 1.83 1.84 8 9 1.84 1.85 5 9 1.83 1.84 9 4
222 1.77 1.78 7 7 1.77 1.77 7 6 1.77 1.75 4 7 1.77 1.77 6 5
301 1.76 1.72 9 9 1.75 1.76 9 9 1.76 1.76 6 9 1.75 1.76 10 9
161 1.74 1.73 4 5 1.73 1.73 14 4 1.74 1.73 19 4 1.73 1.73 25 4
232 1.68 1.67 7 6 1.68 1.68 8 9 1.68 1.65 8 7 1.67 1.68 9 7
152 1.63 1.64 2 2 1.63 1.63 2 2 1.63 1.65 2 2 1.63 1.63 2 2
260 1.61 1.60 26 22 1.60 1.60 4 24 1.61 1.60 2 26 1.62 1.60 2 24
242 1.57 1.56 15 11 1.57 1.57 8 15 1.57 1.56 5 15 1.56 1.57 7 13
123 1.53 1.54 9 9 1.53 1.53 14 9 1.53 1.53 10 9 1.52 1.53 12 9
341 1.51 1.54 3 2 1.50 1.51 5 3 1.51 1.53 4 3 1.50 1.51 9 3
133 1.47 1.48 4 3 1.47 1.47 6 4 1.47 1.44 3 4 1.46 1.47 5 4
322 1.46 1.45 2 2 1.45 1.45 4 2 1.45 1.45 2 2 1.45 1.45 4 3
270 1.44 1.43 1 2 1.44 1.44 1 1 1.44 1.44 1 1 1.44 1.44 1 2
332 1.41 1.45 <1 <1 1.40 1.40 3 <1 1.41 1.40 <1 <1 1.41 1.40 <1 <1
181 1.37 1.34 2 2 1.36 1.36 6 2 1.37 1.34 3 2 1.36 1.36 2 2

Fig. 3. Cell parameter variations as a function of x for Bi1
xTa1
xTe2xO4 (0  x  0.2), where progressive substitution of bismuth and tantalum by tellurium provokes an increase of
the unit cell parameters a, c and V.
244 I. Yakine et al. / Materials Chemistry and Physics 135 (2012) 241e248

Table 2 and details of refinement for Bi1
xTa1
xTe2xO4 are shown in Table 3.

Unit-cell dimensions of Bi1
xTa1
xTe2xO4 (0  x  0.2). Fig. 4 shows the agreement between the calculated and observed
Formula Bi1
xTa1
xTe2xO4 a (Å) b (Å) c(Å) V(Å3) diffraction profiles for Bi1
xTa1
xTe2xO4 with different concentra-
x ¼ 0.05 Bi0.95Ta0.95Te0.1O4 5.627(1) 11.764(3) 4.952(2) 327.8(1) tion. The atomic positions and important interatomic distances in
x ¼ 0.10 Bi0.90Ta0.90Te0.2O4 5.628(2) 11.765(1) 4.953(2) 327.9(2) the structure (for x ¼ 0.15 as an example) are given in Table 4 and
x ¼ 0.15 Bi0.85Ta0.85Te0.3O4 5.629(3) 11.767(2) 4.954(3) 328.2(1) Table 5, respectively. The refinement in the second hypothesis was
x ¼ 0.20 Bi0.80Ta0.80Te0.4O4 5.630(2) 11.777(1) 4.955(2) 328.5(3)
confirmed to be very appropriate.
The crystal structure of Bi1
xTa1
xTe2xO4 (0  x  0.2) is shown
in Fig. 5. The (tantalum/tellurium) atoms are octahderally coordi-
nated by oxygen atoms and are linked at four corners along the ac-

Table 3
Reliability factors, crystal data and details of refinement f for Bi1
xTa1
xTe2xO4.

Formula Bi0.95Ta0.95Te0.1O4 Bi0.90Ta0.90Te0.2O4 Bi0.85Ta0.85Te0.3O4 Bi0.80Ta0.80Te0.4O4

Crystallographic data
Symmetry Orthorhombique Orthorhombique Orthorhombique Orthorhombique
Space group Pnna Pnna Pnna Pnna
Lattice parameters:
a(Å) 5.627(1) 5.628(2) 5.629(3) 5.630(2)
b(Å) 11.764(3) 11.765(1) 11.767(2) 11.777(1)
c(Å) 4.952(2) 4.954(3) 4.954(3) 4.955(2)
Volume (Å3) 327.8(1) 327.9(2) 328.2(1) 328.5(3)
Z 4 4 4 4
Experimental conditions for data collection
Wavelength (Å) 1.5406e1.54426 1.5406e1.54426 1.5406e1.54426 1.5406e1.54426
2q rang ( ) 10e100 10e100 10e100 10e100
Step ( 2q) 0.02 0.02 0.02 0.02
Integration time(s) 100 100 100 100
Rietveld data
Program for Rietveld analysis Fullprof Fullprof Fullprof Fullprof
Number of independent parameters 81 81 81 81
Pseudo-Voigt function h 0.00409 0.001487 0.005808 0.000597
Caglioti parameters:
U 0.050664 0.029591 0.014915 0.098710
V
0.036279
0.014749
0.003521
0.05514
W 0.021821 0.018824 0.008803 0.23211
RF 2.20 2.10 1.71 2.60
RB 3.45 1.63 1.94 3.53
RP 5.21 5.00 4.12 5.26
RWP 6.65 6.74 5.49 6.96
c2 0.889 0.831 1.09 0.899
Rexp 7.06 7.39 5.46 7.34

Fig. 4. Final Rietveld plots of Bi0.95Ta0.95Te0.1O4 (a), Bi0.90Ta0.90Te0.2O4 (b), Bi0.85Ta0.85Te0.3O4 (c) and Bi0.80Ta0.80Te0.4O4 (d). The upper symbols illustrate the observed data (cross) and
the calculated pattern (solid line). The vertical markers show calculated positions of Bragg reflexions. The lower curve is the difference diagram.
 I. Yakine et al. / Materials Chemistry and Physics 135 (2012) 241e248 245

Table 4
Atomic coordinates and isotropic temperature factors with their estimated standard
deviation. Bi0.95Ta0.95Te0.1O4.

Atome Site x y z Biso(Å2) OCC

Bi0.95Ta0.95Te0.1O4
Bi 4c 0.25000 0.00000 0.7223(3) 0.60(4) 0.95000
Te(1) 4c 0.25000 0.00000 0.7223(3) 0.60(4) 0.05000
Ta 4d 0.3609(2) 0.25000 0.25000 0.39(4) 0.95000
Te(2) 4d 0.3609(2) 0.25000 0.25000 0.39(4) 0.05000
O(1) 8e 0.138(2) 0.3069(10) 0.511(2) 1.0(3) 2.00000
(2)
O 8e 0.597(2) 0.9077(11) 0.595(2) 0.5(3) 2.00000
Bi0.90Ta0.90Te0.2O4
Bi 4c 0.25000 0.00000 0.7222(3) 0.61(5) 0.90000
Te(1) 4c 0.25000 0.00000 0.7222(3) 0.61(5) 0.10000
Ta 4d 0.3607(3) 0.25000 0.25000 0.45(5) 0.90000
Te(2) 4d 0.3607(3) 0.25000 0.25000 0.45(5) 0.10000
O(1) 8e 0.138(3) 0.3074(12) 0.509(3) 1.6(4) 2.00000
(2)
O 8e 0.593(2) 0.9059(12) 0.584(2) 0.1(4) 2.00000
Bi0.85Ta0.85Te0.3O4
Bi 4c 0.2500 0.0000 0.7225(2) 2.31(4) 0.85
Te(1) 4c 0.2500 0.0000 0.7225(2) 2.31(4) 0.15
Ta 4d 0.3620(19) 0.2500 0.2500 2.05(4) 0.85
Te(2) 4d 0.3620(19) 0.2500 0.2500 2.05(4) 0.15
O(1) 8e 0.1421(17) 0.3024(7) 0.5078(17) 2.9(3) 2.00
O (2)
8e 0.5906(16) 0.9068(8) 0.5926(16) 2.3(3) 2.00 Fig. 5. The structure of Bi1
xTa1
xTe2xO4 showing the sheets of (Ta/Te(2))O6 octahdedra
Bi0.80Ta0.80Te0.4O4 separated by (Bi/Te(1)) atoms.
Bi 4c 0.25000 0.00000 0.7217(4) 0.58(5) 0.80000
Te(1) 4c 0.25000 0.00000 0.7217(4) 0.58(5) 0.2000
Ta 4d 0.3618(3) 0.25000 0.25000 0.07(5) 0.80000 alternation of the (Bi/Te(1))e(Bi/Te(1)) separation within the rows of
Te(2) 4d 0.3618(3) 0.25000 0.25000 0.07(5) 0.20000 (Bi/Te(1)) atoms, running along the c-axis Fig. 5, there being a short,
O(1) 8e 0.138(3) 0.3067(12) 0.518(3) 0.7(4) 2.00000 3.57A , and long, 3.94A , distance and are in good agreement with
(2)
O 8e 0.598(3) 0.9118(13) 0.600(3) 0.7(4) 2.00000
values reported previously [12].
An alternate description of the Bi coordination is with the Bi
occupying the vertex of a BiO4 square pyramid Fig. 7 Presumably
plane. The orthorhombic structure can be viewed as a pseudo- the Bi 6s2 lone pair electrons occupy the ‘‘fifth’’ coordination site of
layered structure in which layers of corner sharing (Ta/Te(2))O6 the Bi atoms in this description. These 6s electrons apparently
octahedra are separated along the b-axis by (Bi/Te(1)) atoms. occupy the area between two adjacent Bi atoms, repelling both the
The structure may be described in terms of (tantalum/tellurium) oxygen and nearby Bi atoms, hence the alternating BieBi
and oxygen atoms forming sheets of [(Ta/Te(2))O6]3
polyanions separation.
which are held together by (Bi/Te(1)) atoms with a formal valency
of þ3. The oxygen atoms (O1) which are shared by two (Ta/Te(2)) 3.3. Spectroscopy studies
atoms form a square gird when viewed along the y direction. Only
every other square of the O(1) atoms is occupied by (tantalum/ 3.3.1. IR study
tellurium) atoms Fig. 6.
The infrared spectra of Bi1
xTa1
xTe2xO4 oxides at room
The coordination around (Bi/Te(1)) is also octahedral (highly temperature are shown in Fig. 9. All samples show characteristic
distorted) Fig. 7 and are edge shared to form chains along the a- vibration bands between 400 and 1000 cm
1, which are assigned to
direction Fig. 8 projecting along the ac-plane. Six oxygen atoms in
a distorted octahedral geometry surround the (Bi/Te(1)) atoms, with
two of the (Bi/Te(1))eO distances being very much longer than the
other four (2.75A ), Table 5. A feature of the structure is the

Table 5
Selected interatomic distances and angles for Bi1
xTa1
xTe2xO4 (x ¼ 0.15).

Bi/Te(1) O1 (1)
O2 (1)
O3 (2)
O4 (2)
O5 (2)
O6 (2)
Vij
O1 (1) 2.750(8) 4.807(12) 4.691(13) 2.673(12) 3.488(12) 4.493(12) 0.16
O2 (1) 121.9(5) 2.750(8) 2.673(12) 4.691(13) 4.493(12) 3.488(12) 0.16
O3 (2) 136.3(6) 63.2(4) 2.301(9) 4.41813() 2.587(13) 2.960(13) 0.55
O4 (2) 63.2(4) 136.3(6) 147.5(7) 2.301(9) 2.960(1) 2.587(13) 0.55
O5 (2) 90.8(5) 134.9(6) 71.7(5) 84.2(5) 2.108(9) 2.834(13) 0.92
O6 (2) 134.9(6) 90.8(5) 84.2(5) 71.7(5) 84.5(6) 2.108(9) 0.92
P
Vij 3.27

hBi/Te(1)
Oi ¼ 2.386Å
O1 (1) 1.883(9) 2.837(12) 2.816(14) 3.947(13) 2.928(13) 1.883(9) 1.13
O2 (1) 97.78(7) 1.883(9) 3.947(13) 2.829(12) 1.883(9) 2.928(13) 1.13
O3 (1) 90.6(7) 171.6(8) 2.075(9) 2.698(12) 2.816(14) 2.673(12) 0.67
O4 (1) 171.6(8) 90.6(7) 81.1(6) 2.075(9) 2.673(12) 2.820(13) 0.67
(2)
O5 97.1(7) 92.8(6) 87.0(6) 81.5(6) 2.021(9) 4.006(13) 0.78
(2)
O6 92.8(6) 97.1(7) 81.5(6) 87.0(6) 164.8(8) 2.021(9) 0.78
P
Vij 5.17
hTa/Te(2)
Oi ¼ 1.993Å
Fig. 6. (Tantalum/tellurium)-oxygen octahderal network along the ac-plane.
246 I. Yakine et al. / Materials Chemistry and Physics 135 (2012) 241e248
Fig. 7. Coordination of (Ta/Te(2)) and (Bi/Te(1)) in Bi1
xTa1
xTe2xO4 (Bond distances are given in Table 6).
BieO and TaeO vibrations [13e15]. As shown in Fig. 9, the band-
widths and positions are quite similar from one compound to the
next (0  x  0.2). Therefore, it can be inferred from IR spectra that
the these compounds have similar structural models, in agreement
with the result getting from X-ray diffraction patterns.
3.3.2. Raman spectra
3.3.2.1. Room temperature Raman spectroscopy. The room temper-
ature phase of BiTaO4 belongs to the Pnna (D62h ) space group. Since
it is believed and as the Rietveld structural refinement (this work)
shows to be isostructural to BiNbO4, where the four Bi3þ ions
occupy D62h sites and the four Ta4þ ions occupyD62h. Two distinct sets
of eight O2- ions are all in general C1 positions. The primitive unit
cell contains four structural units, giving a total of 72 normal modes
at the center of the Brillouin zone (q ¼ 0). The nuclear site group
analysis, leads to the classification of the optic phonons into the
following irreducible representation:
G ¼ 8Ag þ 8Au þ þ9B1g þ 8B1u þ 10B2g þ 9B2u þ 9B3g þ 8B3u
(1)
The presence of the inversion center of symmetry of the lattice
causes a mutual exclusion of the Raman and Infra-red modes which
implies that all gerade modes are Raman active and all ungerade
modes except Au are Infra-red active.
According to XRD investigations reported in this work, the
structure remains similar for all the compositions, which should
result in the same number of Raman and infra-red active bands
Fig. 8. Chains of (Bi/Te(1))eO edge-shared distorted octahedra in Bi1
xTa1
xTe2xO4.
within the series. Fig. 10 shows Raman spectra of the Bi1
xTa1
x-
Te2xO4 series. In practice, and in the absence of single crystal data, it
would be impossible to observe all the predicted modes in poly-
crystalline samples due to several reasons among them the overlap
of incompletely resolved modes, the low polarizability of some of
these modes.
In the absence of other descriptions of the vibrational spectra for
these complexes, and as TaO6 octahedra are not greatly distorted
from the ideal Oh symmetry, one can adopt the description repor-
ted by Pushan Ayyub [5] for BiNbO4 and BiSbO4 based on the
“internal mode” approach, where he interpret the vibrational
spectra as arising from the vibration of an isolated BO6. The
vibrational modes of an isolated BO6 octahedron and the correla-
tions that they bear to D2h symmetry (as in BiTaO4) are reported
elsewhere [5]. In A3þB5þO4, the n1 (A1g) Raman mode arises from
the symmetric BeO stretching vibration and is normally the
strongest among the highest-frequency modes. In our case, this
band at 600 cm
1 arises is the n1 mode. The n2 mode is weaker in
such systems; so it can be assigned to the peak at around 540 cm
1.
It is expected that the weak bands at frequencies above 670 cm
1
arise from stretching vibrations of the A3þ ions in their highly
distorted octahedral coordination. The symmetry assignments for
the observed frequencies are displayed in Table 6.
Fig. 9. IR transmission spectra of Bi1
xTa1
xTe2xO4 (0  x  0.2).
 I. Yakine et al. / Materials Chemistry and Physics 135 (2012) 241e248 247

1,0 [Sum]
[Exp]
[Exp]-[Sum]

Intensity normalized
0,8
Intensity (arb.units)

0,6

0,4
x=0.2

x=0.15 0,2

x=0.1
0,0
x=0.05
200 400 600 800 1000
x=0 -1
Stokes shift [cm ]
200 400 600 800 1000
Fig. 11. Experimental Raman spectrum of BiTaO4 and best fit using the causal Voigt
-1
Stokes shift(cm ) model.

Fig. 10. Raman spectra of solid solution Bi1
xTa1
xTe2xO4.

The Bi1
xTa1
xTe2xO4 compounds were found to form solid
solutions over a very narrow range of concentrations (0  x  0.2),
with all the compositions belonging to the orthorombic class. The
dependence of Raman frequencies on x for the different modes is
indicated in Table 6. All the simulations presented in this paper
have been performed with Focus which is curve fitting software
freely available on the web [16] for non-commercial purposes.
Fig. 11 shows a best fit for BiTaO4 using a causal Voigt model.
Some observations may be made regarding the general features
of the spectra. Most of the Raman peaks in these mixed systems are
appreciably broadened as compared to the pure end member
(x ¼ 0) Fig. 12. An increase of the width (as shown in the Fig. 12) is
the result of an overlapping of different stretching MeO modes.
Such broadening would have indicated strong disorder effects due
to the absence of long-range translational symmetry [17,18]. A weak
mode at 970 cm
1 is observed in one of this solid solution. This
mode may be identified as a local (impurity) mode since its
frequency is much higher than the maximum vibrational frequency
of the perfect host lattice. Same mode has been observed in BiNbO4
and SbNbO4 [5].
The lattice vibrations and soft modes are not discussed in this
paper, since it requires probing the optical modes at very low
frequencies (below 100 cm
1).
4. Conclusions
In this paper we reported the results of the synthesis, crystal
chemistry, Rietveld refinements and IR and Raman spectroscopy
studies of a new solid solution series, Bi1
xTa1
xTe2xO4. The exis-
tence of a continuous solid solution is confirmed by X-ray diffrac-
tion as well as IR and Raman spectroscopy. These materials
crystallise in the orthorombic system with the Pnna (D62h ) space
group. The structure consists of a three-dimensional framework of
(tantalum/tellurium) and oxygen atoms forming sheets of [(Ta/
Te(2))O6]3
polyanions which are held together by (Bi/Te(1)) atoms
with a formal valency of þ3. The oxygen atoms (O1) which are
shared by two (Ta/Te(2)) atoms form a square gird when viewed
along the y direction. Only every other square of the O(1) atoms is
occupied by (tantalum/tellurium) atom. The infrared spectra of
Bi1
xTa1
xTe2xO4 oxides at room temperature showed some char-
acteristic vibration bands assigned to BieO and TaeO vibrations.
Vibrational Raman spectra of this crystalline solid solution series
are interpreted by means of “internal mode” approach. Assign-
ments of the TaeO and BieO vibrational stretching modes, as well
0
100 12,50

25,00

37,50
Table 6
50,00
Vibrational spectra of Bi1
xTa1
xTe2xO4 and assignment of the observed peaks. 80
62,50
Symmetry 75,00
Bi1
xTa1
xTe2xO4 assignment [5] 87,50

x¼0 x ¼ 0.05 x ¼ 0.1 x ¼ 0.15 x ¼ 0.2 60 100,0

143,044 142,849 142,724 143,032 142,761
151,388 152,334 152,974 152,636 152,483 5
Sp

180,816 181,427 179,877 182,072 181,466 F2u(n6) 40 4

ec

207,123 206,64 206,552 206,669 206,62 3

tra

234,554 233,02 232,378 233,226 232,47

2
267,413 267,04 265,655 268,146 267,574 F2g(n5)
20
319,529 320,956 321,733 321,021 321,633 1
381,375 381,607 381,225 381,444 381,623
401,977 402,871 403,856 402,863 403,386 700 750 800
5000 550 600 650
425,578 425,805 427,388 426,648 426,162 -1
541,081 541,31 542,72 540,473 542,041 Eg(n2) Raman shift (cm )
595,582 594,718 593,738 595,268 594,546 A1g(n1)
620,373 619,517 619,883 619,762 619,53 Fig. 12. 3D image of the Raman spectra of the Bi1
xTa1
xTe2xO4. The x-axis is the Stokes
670,065 667,993 664,807 669,198 667,383 shift from 500 to 800 cm
1. Y-axis is the number of spectra from 1 to 5 corresponding
745,864 743,278 743,428 743,602 742,636 respectively to x ¼ 0; 0.05; 0.1; 0.15 and 0.2. Z-axis or the color scale corresponds to the
normalized Raman intensity. Double arrow indicates the broadening.
248 I. Yakine et al. / Materials Chemistry and Physics 135 (2012) 241e248
as some of the other modes, have been made. Most of the Raman
peaks in these mixed systems are appreciably broadened as
compared to the pure end member (x ¼ 0). Such broadening would
have indicated strong disorder effects due to the absence of long-
range translational symmetry.
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