Local Structure and Raman Spectrum of
Na0.5Bi0.5TiO3
M. K. Singh
Laser Materials Development and Devices Division
Raja Ramanna Centre for Advanced Technology
Indore 452 013 (INDIA)
Sodium Bismuth Titanate
(Na0.5Bi0.5TiO3)
Structure: Perovskite
Crystal Class: Rhombohedral
Space Group: R3c (at 300K)
Lattice Parameter: a=5.48, c=13.42 (R3cH)
Structural Transitions in NBT:
Pm3m
P4bm (P4/mbm)
R3c
(>540oC)
(540-500oC)
(500oC- 400oC)
(< 300oC)
Dielectric Anomalies in NBT:
o
o
o
T
=
300
C,
T
=
275
C,
T
=
180
C,
m
RT
d
G. O. Jones and P. A. Thomas, Acta Cryst. (2002). B58, 168-178
Y. Hiruma, H. Nagata, and T. Takenaka, J. Appl. Phys. 104 (2008) 124106
(400-300oC)
Literature
Group
Method
System
Space
group
J. A. Zvirgzds (1982)
X-ray diffraction
Rhom.
R3m
S. B. Vakhrushev (1983)
Neutron diffraction
Rhom.
R3c
Soukhojak et al. (2000)
Electron diffraction
Tetra.
-----
Jones et al (2000)
Neutron diffraction
Tetra.
P4bm
Jones et al (2002)
Neutron diffraction
Rhom.
R3c
A. Pietraszko et al (2006)
X-ray diffraction
Rhom.
R3c
Balagurov, A. M. (2006)
Neutron diffraction
Rhom.+Tetra.
----------
E. Aksel et al (2011)
X-ray diffraction
Monoclinic
Cc
Group
Space
group
Rp
Rwp
Jones et al
(2000)
P4bm
5.01
6.47
Jones et al
(2002)
R3c
5.90
7.80
E. Aksel
(2011)
Our result
Cc
R3c
5.87
9.30
8.09
11.40
In ten sity (a rb . u n its)
Observed
Calculated
Difference
x=0.00
In te n s ity ( a r b . u n its )
Ambiguity in structure, calculated
from X-ray/Neutron Diffraction
38
20
30
40
Ab-initio calculation will provide better understanding
of crystal structure
40
2
50
60
70
Objective
Calculation of local structure of
NBT using ab-initio method and
comparison with Raman and
XRD data
Structure modeling of
NBT
NBT constitutes a complex perovskite
structure with two different ions Na+ and Bi3+
occupy at A site.
Na 0.5 Bi 0.50
In R3c structure, we argued that two different
ions at A-site cant occupy the symmetrically
equivalent position. It suggests that the
structure should be lower that R3c.
Ti
Computational Details
First-principles calculations have been performed within the generalized gradient
approximation (GGA) using PW91 exchange-correlation functional to density
functional theory as implemented in CRYSTAL09 code.
Tight convergence criteria are used to obtain fully relaxed total energy
calculations.
We used following norm-conversing pseudo-potentials for Bi, Na , Ti and O.
Bi: 5d10 6s2 6p3,
Na:2p6 3s1, Ti: 3s2 3p6 4s2 3d2 and O:2s2 2p4
An 8x8x8 Monkhorst-Pack k-point mesh for the primitive cell is used for Brillouin
zone integration.
In all the calculation plane-wave energy cutoff is set to be 770 eV resulting in a
numerical error of less than 1meV/atom.
We converted the structure in P1 symmetry
and the resulting configuration is structurally
optimized. R3 or R3m structures are
obtained from the optimized structure.
In R3 structure
In R3m structure
Raman scattering intensities
Raman scattering is the inelastic scattering of photons. The monochromatic
laser light interacts with molecular vibrations (i.e. phonons), resulting in the
energy of the laser photons being shifted up or down. This shift of energy gives
crucial information about the vibrational modes in the system.
Using Raman intensity
calculation, it is possible to
identify the symmetry and
chemical structure of the system.
Calculation of Raman scattering
intensities of NBT in R3 and R3m
structures
1.2
R3
1.0
Intensity (arb. units)
Intensity (arb. units)
1.2
0.8
0.6
0.4
0.2
0.0
200
400
600
-1
Wavenumber (cm )
800
1000
R3m
1.0
0.8
0.6
0.4
0.2
0.0
200
400
600
800
-1
Wavenumber (cm )
Vibration modes exist between 80 930cm -1
1000
Calculation of Raman scattering intensities
for R3c structure
Intensity (arb. unit)
Na0.5Bi0.5TiO3
Na+ 0.5
Bi3+ 0.5
0.5x1+0.5x3=2
Ba2+ 1.0
For BiFeO3 having R3c symmetry
the vibration modes predicted
between 95 590cm-1
H. M. Ttnca and G. P. Srivastava, JAP, 1 03 (2008) 083712
100
200
300
400
500
Wavenumber (cm-1)
Vibration modes exist between 120 500cm -1
Raman spectrum of NBT
Intensity (arb. units)
24000
12000
0
150
300
450
600
-1
Wavenumber (cm )
750
900
Vibrational modes at higher
frequency
Bi-O bond length
2.273
In R3c structure Bi-O bond lengths all greater than 2.53 . However the
experimentally measured shortest bond length from EXAFS study is 2.2 .
Our calculated value of the shortest bond length (Bi-O=2.25 ) in R3 structure
is in good agreement with the experimental value.
Intensity (arb. units)
0.85NBT-0.15BiCrO3
18000
9000
0
150
300
450
600
750
-1
Wavenumber (cm )
900
Conclusion
Local
structure of NBT is R3/R3m or
lower symmetry.
The high frequency modes in Raman
spectrum are intrinsic feature of NBT.
Thank You
