Dielectric and Optical Behavior of ‘Ba’ substituted Lead

reducing Double Perovskite

Rajib Padhee

School of Physics
Sambalpur University, Burla, Sambalpur

1
 Introduction
Ceramic Materials
• Ceramic materials can be broadly
considered to be inorganic non-
metallic materials.
• However, it is more useful to
classify them as polycrystalline
non-metallic materials.
• The inherent physical properties of
ceramics has made them desirable
for use in wide range of industries,
with their first applications in the
electronics sector.

2
 Dielectrics

Dipole moment or polarisation can be induced by

the application of suitable electric field

Polar Non-Polar

Permanent or spontaneous No permanent or spontaneous

polarisation exist in the polarisation exist in the
absence of an electric field absence of an electric field

Ferroelectrics
Permanent or spontaneous
polarisation can be reversed by the
application of an electric field. 3
 Why ferroelectric oxides ?

Tailoring of Materials Properties Viable as

per Specific Application

 Stability of Ferroelectric Oxides over

Wide Range of Conditions

4
 Classification of ferroelectric oxides

Bismuth oxide
layer structure

Perovskite-type

Pyrochlore -type

Tungsten Bronze-type
5
 Ferroelectric Material Devices

FRAM
Multi layered capacitors (Varistors)

Piezoelectric Ceramics

Capacitors
Pyroelectric sensor
6
Some previous works on Double perovskites
• General chemical formula: A2BB’O6, where A= Alkaline earth
elements (Ba,Ca,Sr); While B site occupied by 1st row of 3d
magnetic element in the periodic table and B’ site is occupied by
4d non-magnetic elements with oxygen atom located in
between forming alternate BO6 and B’O6 octahedra.
• The wide range of these compounds is due to variation at the
magnetic and non-magnetic B and B’ elements as well as A-site
cations.
• First reported: Ba2LnSbO6 and Sr2LnSbO6 (Ln= Dy,Ho,Gd).
• Ca2CeNbO6 synthesized by solid state reaction technique.
• No magnetic ordering is found.
• Some work on thin films of double perovskite have also been
reported.
• These are having high-symmetry Tetrahedral structure.
• The present work is motivated with the idea of having a
perovskite oxide with a high symmetry Orthorhombic structure.
• Presence of Bi3+ and Pb2+ at the A site favours formation of polar
structure .
A2BB’O6

Where A stands for alkaline earth metal and B transition metal

BO6

Orthorhombic Double perovskite A2BB’O6

8
Pb2BiNbO6 (PBN): crystalline structure
Double-perovskite cell

Pb2+

Bi3+

Nb5+

O2-

• Two interpenetrating FCC sublattices

• Strong polarity by Bi3+, Pb2+ and Ba2+ creates non-
centrosymmetric enviroment
Lead reducing double perovskite
synthesis
Lead reducing double perovskite
Pb2-x BaxBiNbO6 (x=0, 0.5, 1.0, 1.5, 2.0 )

1 Pb2BiNbO6
2 Pb1.5Ba0.5BiNbO6
3 Pb1Ba1BiNbO6
4 Pb0.5Ba1.5BiNbO6
5 Ba2BiNbO6

Calcination = 900oC

10
Some Instruments Used

11
 10
(1 2 0) Intensity (Arb. Unit)
(0 3 1)

20
( 1 1 2)
(0 7 0)
(1 7 1)
(0 8 1)

30
(0 7 2) (1 6 2)(2 1 2)

(3 0 0)

40
(1 9 2)
(1 11 1)
(1 8 3)
(0 11 2)

50
Cal

(4 6 1) (0 1 5)
Bkg
Obs

(0 5 5) (0 15 0)

Bragg Angle(2)
(3 9 3)
(2 6 5)

60
(2 17 0)
(3 12 4)

70
(1 16 2)
c=9.0207
a=8.2576

SD=0.0047
o
o

Pb1.5Ba0.5BiNbO6
b=26.2839

V=1957.89
o

• Orthorhombic structure
80 Intensity (Arb. Unit)
0
200
400
600
800
1000

10

(0 1 0)
(a)

(3 0 0)
(2 1 0)
(0 0 2)
20

(5 1 0)
(5 1 1 )
(6 0 1) (1 2 0 )
(020) (512)
30

(5 2 1) ( 2 2 2 )
(7 1 1)
(0 3 1) (6 2 0)
Structural Analysis

(0 3 2)
40

(0 2 4)
(7 2 3) (1 4 1)
(10 1 2)
b=7.9713

SD=0.0078

(8 3 1)
o

c=10.3497
a=21.5798

V=1780.35

50
o
o

(12 0 0)
o
Bragg's Angle (2 )

(9 3 2)(10 3 1)
(8 1 5) (6 2 5)
Indexed XRD pattern at room temperature

(1 5 0)
60

(14 0 1)
(2 4 3)
Cal

(4 5 2)
Diff.

70
Obs

(12 1 5)
Pb2BiNbo6

(13 4 2)
(4 6 3)
80

12
 Comparison of XRD data of
Pb2-xBaxBiNbO6(x=0, 0.5, 1.0, 1.5, 2.0)
1400

yobs.A1
1200
E2
E3
Intensity(Arb. Unit)

1000 E4
E5
800

600

400

200

0 10 20 30 40 50 60 70 80 90
Angle(2)
Table1 Comparison of cell parameters (in Å), volume (V in Å3), average
particle size (P in nm), average grain size (G in μm) and orthorhombic
distortions (D in %) of Pb2-xBaxBiNbO6 (x=0,0.5,1.0,1.5) compounds.

Compounds a b c V P G D

Pb2BiNbO6 13.8165 16.5918 7.9460 1821.56 75 1.81 0.091

Pb1.5Ba0.5BiNbO6 28.1768 11.0739 4.8465 1512.24 63 1.75 0.436

PbBaBiNbO6 9.2698 22.0729 6.2573 1280.32 101 1.21 0.409

Pb0.5Ba1.5BiNbO6 13.6008 16.2553 8.2375 1821.20 80 1.17 0.089

Ba2BiNbO6 7.7842 14.7776 15.7690 1813.936 52 1.05 0.310

• Most of the reflection peaks are shifted and their intensities get changed
without following any specific trend.
• The cell parameters get slightly changed but do not exhibit any definite
relationship.
• Particle size also changes significantly.
• The orthorhombic distortion of the compounds are significant without
following any specific order.
 SEM micrograph of PBBN(Lead Barium Niobate)
at room temperature by HITACHI S3400N scanning electron microscope

Pb2BiNbO6 Pb1.5Ba0.5BiNbO6

PbBaBiNbO6 Ba2BiNbO6
 EDX For sample
Pb2BiNbO6 Pb1.5Ba0.5BiNbO6

PbBaBiNbO6 Ba2BiNbO6
Pb0.5Ba1.5BiNbO6 • Grains with distinct grain
M boundaries
I • BaCO3 reduces oxygen
C
R vacancy and grain growth
O • Small nucleation results in
-
S bigger grains
T • No presence of external
R
U elements
C
T
Pb0.5Ba1.5BiNbO6 U
R
E
-
E
D
X
SEM Micrograph and EDX pattern
17
 Structural Analysis
10

Pb0.5Ba1.5BiNbO6 • Peaks (850-400cm-1) – lattice

8
vibrations
6 • Symmetric stretching mode of
Transmittance(T%)

Nb-O: 847cm-1

413
4
• Anti-symmetric stretching mode

847
2 of the octahedra NbO6 and BiO6:
709cm-1and 571cm-1
1637

571
709
0
1431
• O-C-O bending modes: 413cm-1
-2 • C=O stretching vibrations:
-4
1637cm-1
• Overtones of sustained vibration:
4000 3500 3000 2500 2000 1500 1000 500
-1
1431cm-1
Wave number (cm )
• With increase of Ba+2
concentration the hygroscopic
nature disappears
Room temperature FTIR data
18
 Dielectric parameters for sample PBBN
1 kHz
10 kHz
16000
100 kHz eps1kHz
14000 Pb2BiNbO6 x=0
1 MHz
14000
Pb1.5Ba0.5BiNbO6 eps10kHz
(b)
4 eps100kHz
12000 25
eps1MHz
12000
3 Tand1k
20 TanD10k
10000 TanD100k
1 kHz 10000 TanD1M

Tan 
2
15 10 kHz
8000 100 kHz
Tan

8000 1
10 1 MHz

r
r

6000 6000 0
5
0 100 200 300 400 500

4000 4000 0
Temp( C)
0

0 100 200 300 400 500 2000

2000
0
Temp( C)
0
0
0 100 200 300 400 500 600
0 50 100 150 200 250 300 350 400 450 500 550 0
0 Temp( C)
Temp( C)
20000
1 kHz 2.5
10 kHz Ba2BiNbO6 1 kHz
10000 (PbBa)BiNbO6 10 kHz 18000 100 kHz 10 kHz
2.0 1 MHz
100 kHz 100 kHz
1 MHz 16000
1.5 1 MHz

Tan
8000 14000
1.5 1.0

10 kHz
12000 0.5
100 kHz
6000 1.0 1 MHz
0.0
10000
tan

0 100 200 300 400 500

r

8000 o
r

0.5 Temperature( c)

4000
6000
0.0
4000
2000
0 100 200 300 400 500
o 2000
Temperature( C)

0
0
0 100 200 300 400 500
0 100 200 300 400 500 
Temperature( c)
o
Temperature( C)
 Temperature Dependence of Dielectric
parameters - Pb0.5Ba1.5BiNbO6
10000 4
1kHz
1kHz
• Relaxor type
• Pb and Bi : High value
10kHz

3
100kHz 10kHz
1MHz
100kHz dielectric- due to their
2
1MHz volatile nature
• Moderate loss
Tan 

1
• Ba doping lowered the Tc
may be due increase in
r

0
symmetry, but not all
0 100 200 300 400 500 compounds have Tc
0
Temperature( C) • Dielectric constant higher
1000 without lead
• Can be used in phase-
shifters, oscillators,
microwave tunable circuits,
0 100 200 300 400 500 resonators, capacitors, etc.
0
Temperature( C)

20
Comparison of dielectric properties at 1 kHz of
Pb2-x BaxBiNbO6 (x=0,0.5,1.0,1.5,2.0)

Compounds εRT εmax tanδRT tanδmax Tc ( oC )

Pb2BiNbO6 490 --- 0.59 1.95 -----

Pb1.5Ba0.5BiNbO6 650 14000 0.12 0.72 480

PbBaBiNbO6 710 ------ 0.025 1.54 -----

Pb0.5Ba1.5BiNbO6 760 16200 0.051 1.08 430

Ba2BiNbO6 858 17340 0.088 4.5 350

 Temperature dependence of Polarization -
Pb0.5Ba1.5BiNbO6

2
4 2Pr=1.44, 1.24 and 0.85 C/cm

3 • High volatility of Pb and Bi

2 results in rounded corner
1 • Ba reduced oxygen
P(C/cm )
2

0 vacancies and increased

o
-1 25 C
o
the ferroelectric property
50 C
-2 o
100 C in comparison to PBN
-3

-4

-3 -2 -1 0 1 2 3
E(kV/cm)

22
 UV –Vis spectra - Pb0.5Ba1.5BiNbO6
• Does not absorb strongly
1.2 (a) 50
(b)
Absorbance
1.1 Absorbance

1.0
40
Eg=2.08 eV
in UV
0.9 30
• Visible Absorbption: 400-
Absorption

665nm
(h)2
0.8
20

• Eg from Tauc plot

0.7

UV Range 10
0.6

0.5
Visible Range 0
(absorption): 2.08eV
0.4
200 300 400 500 600 700 1 2 3 4 5 6 7 • Eg from refelctance:
40
Wave length ()(nm) h(eV) 2.1eV
(c)
R% 500 (d) • Smaller band gap
30 Reflectance indicates possibility of
2
(ln[{h (Rmax-Rmin)}/(R-R min)])

400
Eg=2.1 eV utilizing more visible light
300
for photocatalytic
R%

20
200 devices
10 100 • Band gap increases
0 systematically with
0
200 300 400 500 600 700
1 2 3 4 5 6 7 increase in Ba doping
h(eV)
Wavelength()(nm)
23
Table 2 Comparison of energy band gap (Eg) calculated from absorbance
and reflectance spectroscopy for the studied samples.

Compounds Eg (eV) Eg (eV)

(Absorbance) (Reflectance)

Pb2BiNbO6 2.17 2.18

Pb1.5Ba0.5BiNbO6 1.62 1.78

PbBaBiNbO6 1.98 2.08

Pb0.5Ba1.5BiNbO6 2.1 2.2

Ba2BiNbO6 2.40 2.37

24
 PL : Variation of Intensity with Wavelength

- Pb 0.5Ba1.5BiNbO6

20
• Blue emission due to
ground state transition of

600 nm
ex=400 nm Ba2+: 462-500nm
15
• Yellow emission due to
optical transition of Ba2+:
Intensity (AU)

10
595-602nm
• Yellow emission
dominate: Ba2+ ions
5 occupies the non-centro-
460-520 nm 490 nm
460-480 nm 470 nm

symmetric site in the

590-605 nm

host PBN
0
• Useful for LED
400 450 500 550 600 650 700

Wave length (nm)

 Variation of Z’ with Z’’ at different temperatures
70
65 70
o 65
60 225 C fig.5(b)
o
55 250 C
o

o
Pb2BiNbO6 60
55
225 C
o
250 C Ba2BiNbO6
50 275 C o
o 50 275 C
45 300 C o
o 45 300 C
40 325 C o
40 325 C
35
Z''(k)

35

Z''(k )
30
30
25
25
20
20
15 15
10 10
5 5
0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Z'(k) Z'(k)
 Z’ vs Frequency
400
z'375c
350 Pb2BiNbO6 z'400c 500 z'350c
z'425c z'375c
300 z'450c z'400c
z'475c 400 z'425c
250 z'450c
z'500c
200 300
Z'(K)

Ba2BiNbO6

Z'
150
200
100

50 100

0
0
-50
1 10 100 1000
1 10 100 1000
logf(KHz)
logf(khz)
 Z” vs Frequency
-250
-140 z''375c
z''375c
z''400c z''400c
-120 z''425c -200 z''425c
z''450c z''450c
-100
-150
-80
Pb2BiNbO6
Z''(k)

z''(k)
-60 -100
Ba2BiNbO6
-40

-50
-20

0
0
1 10 100 1000
logf(khz) 1 10 100 1000
logf(khz)
 Variation of Z’’ and M’’ with frequency at different
temperatures
Pb2BiNbO6
Ba2BiNbo6
0.0014 0.0006
200
(a)
x=0 8
0.0012 180
Z''
M'' 160 o
425 C -1
0.0010 o
425 C o
140 6
450 C 0.0004
o
450 C
0.0008 120 M'' -1

M'''

lnM & lnZ

Z''(k )
o
425 C

Z''(k)
100 o
450 C
4
M''

0.0006 -1
80 0.0002
0.0004 60 -1
40 2
0.0002 Z'' -1
20
425 C
o
0.0000
o
450 C 0 0
0.0000
1 10 100 1000
-20
1 10 100 1000 log f(kHz)
log(f)(kHz)
 σac with frequency at different temperature of PBBN(Lead Barium Niobate)
substituted by Ba

      0  a n
0.012 0.010
o
175 C Fig.8(b)
0.009
0.010 o
Pb2BiNbO6 0.008
o
200 C
o
Ba2BiNbO6
325( C) 225 C
o o
350( C) 0.007 250 C
o
0.008 o
375( C) 275 C
0.006 o
o 300 C
400( C) o

ac( m )
325 C

-1
o 0.005
0.006 425( C) Fit data


o
450( C) 0.004
ac

fit data
0.004 0.003

0.002

0.002 0.001

0.000
0.000
1 10 100 1000
Log(f)(kHz)
1 10 100 1000
Frequency (kHz)
 Variation of fitting parameter (A and n) with temperature for
0.0000035
0.007
3.5 A 0.9
Ba2BiNbO6 A
0.0000030 0.006
0.8
3.0
0.0000025 0.005
0.7
2.5 n
0.0000020 0.6 n 0.004

2.0 Pb2BiNbO6 0.5 0.003

0.0000015
n

n
A
Fig.9(b)

A
0.4
1.5 0.002
0.0000010
0.3
1.0 0.001
0.0000005
0.2
0.000
0.5 0.0000000 0.1

250 300 350 400 450 500 -0.001

o
200 250 300 350 400 450 500
Temperature( C) o
Temperature( C)
 Variation of σdc with inverse of temperature of PBBN(Lead Barium Niobate)
substituted by Ba
0.01
Data
Fit linear

data
Ea=1.07 eV Linear fit
1E-3 Ea=0.88 eV
Ea=0.57 eV
1E-4
dc( m )
-1

dc( m )
Pb2BiNbO6

-1
Ba2BiNbO6
-1

-1
1E-4

1E-5
1E-5
1.2 1.4 1.6 1.8 2.0 1.5 1.6 1.7 1.8
3 -1 3 -1
10 /T(K ) 10 /T(K )
 I~ V characteristics - Pb0.5Ba1.5BiNbO6
(a)
0.010
o 0.1
(b)
200 C Ea =0.74 eV
o
225 C
0.008 o
250 C
o
275 C data
o fit data
300 C
Current(I)(Amp)

0.006 o
325 C

R ( )
-1
o
350 C

-1
0.004

0.002

0.000
1E-11
1.2 1.6 2.0 2.4 2.8 3.2 3.6
0 20 40 60 80 100
3 -1
10 /T(K )
Voltage(V)(volt)

• Deviation from Ohm’s law: Semiconducting nature

• Ea from R-1 vs 103/T = 0.74eV
• Leakage current can be neglected at higher temperature as oxygen
vacancy and space charge polarisation are dominating features.
 Conclusions
• Orthorhombic crystal structure.
• FTIR data confirms, in addition to different types of vibration in the
compounds.
• EDS analysis shows the absence of any foreign atoms.
• Ferroelectricity in the studied samples has been confirmed from dielectric
anomaly and polarization plots.
• The optical band gap calculated by UV-vis confirms the usefulness of the
materials for photo catalytic application.
• Emission band of photo luminescence plot indicates the materials is useful
for blue/yellow LED.
• I~V characteristics show the NTCR and semiconducting behaviour of the
samples.
35