University of Chemical Technology and Metallurgy,
8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Microstructure, electrical properties and application of
bismuth titanate ceramics and glass-ceramics for lowenergy electronic devices
Stanislav S. Slavov, Elena P. Kashchieva, Svetlin B. Parvanov, Yanko B. Dimitriev
e-mail: [email protected]
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Aurivillius family oxides including Bi4Ti3O12 are of great
interest in the last years due to their potential for:
- applications as tranducers, capacitors, and acoustic
piezo-sensors with high temperature piezoelectric
properties;
- ferрoelectrics with high Curie temperature;
- high temperatute glasses with various refractive index;
- electro-optical modulators and deflectors for lasers and
high power light beams;
- glasses with various polarization, based on diffusion of
titanium layers;
- cackade piroelectric devices up to 3 kW/kg and 20%
thermo efectivity;
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Applications of bismuth-based feroelectics are strongly
influenced by the method of preparation.
Different methods of synthesis leads to the generation of
different microstructures and specific electrical properties.
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Purpose
The purpose of the present work is the
preparation of composite materials in the
system Bi2O3-TiO2-SiO2-Nd2O3 obtained by melt
quenching method and the study of their
electrical properties depending on composition
and temperature.
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Experimental
The samples are synthesized by melt quenching method at
fast cooling at room temperature, performed by pouring of
the melts between two cooper plates. The melting is made in
alumina crucibles at 1250 and 1500oC depending of
compositions.
The phase formation has been studied through x-ray
diffraction analysis (XRD - TUR M62, Cu-Kα radiation).
Measurements of the electrical conductivity, capacitance and
dielectric losses of selected samples are performed by DC
resistible bridge and digital capacity meter E8-4 using twoterminal method and a suitable sample holder with graphite
electrodes.
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
SiO2
50
TiO2
Bi2O3
20% SiO2
10% SiO2
5% SiO2
0% SiO2
Nd2O3
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
0% SiO2
Results
SiO2
TiO2
Bi2O3
Nd2O3
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
5% SiO2
Results
SiO2
TiO2
Bi2O3
Nd2O3
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
5% SiO2
Results
SiO2
TiO2
Bi2O3
Nd2O3
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
10% SiO2
Results
SiO2
TiO2
Bi2O3
Nd2O3
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
20% SiO2
Results
SiO2
TiO2
Bi2O3
Nd2O3
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
0% SiO2
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
0% SiO2
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
5% SiO2
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
10% SiO2
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
Sample
1
2
3
4
5
6
7
8
9
10
11
12
4A
4B
4C
4D
4E
Starting composition (mol %)
Bi2O3
TiO2 Nd2O3 SiO2
40
25
35
30
30
40
50
60
70
60
50
21
63
56
36
32
40
50
65
60
50
50
40
30
20
20
30
40
72
18
16
45
40
50
10
10
5
10
20
20
20
20
10
10
10
7
10
20
10
20
5
---10
--------9
8
9
8
5
Indentified
phases XRD
Bi4, Bi12
Bi4
Bi4
Bi4
Bi4, Bi12
Bi4, Bi12, δ
Bi4, Bi12, δ
Bi4, Bi12, δ
Bi4, Bi12, δ
Bi4, Bi12, δ
Bi4, Bi12, δ
P
δ
δ
Bi4
Bi4
Bi4
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
ln σ ,(Ω . cm)− 1
00,00
30Bi2 O 3 .50 TiO 2 .20 SiO 2
-02,00
-04,00
-06,00
-08,00
ln σ ,(Ω . cm)− 1
-10,00
-12,00
-14,000,50
30Bi2 O3 .50 TiO2 .20 Nd 2 O 3
00,00
1,00
1,50
2,00
2,50
3,00
3,50
-02,00
3
10
−1
,K
T
ln σ ,(Ω . cm)− 1
30Bi2 O3 .50 TiO2 .10 SiO 2 .10 Nd2 O 3
-04,00
-06,00
-08,00
00,00
-10,00
-02,00
-12,00
-04,00
-14,000,50
-06,00
1,00
1,50
2,00
2,50
3,00
3,50
3
10
−1
,K
T
-08,00
-10,00
-12,00
-14,000,50
1,00
1,50
2,00
2,50
3,00
3,50
3
10
−1
,K
T
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
ln σ ,(Ω . cm)− 1
40Bi2 O 3 .50 TiO 2 .10 SiO2
00,00
-02,00
-04,00
-06,00
-08,00
ln σ ,(Ω . cm)− 1
-10,00
00,00
-12,00
-14,000,50
40Bi2 O3 .50 TiO 2 .10 Nd 2 O 3
1,00
1,50
2,00
2,50
3,00
3,50
-02,00
3
10
−1
,K
T
-04,00
-06,00
ln σ ,(Ω . cm)− 1
00,00
40Bi2 O3 .50 TiO 2 .5 SiO2 .5 Nd 2 O3
-08,00
-10,00
-02,00
-12,00
-04,00
-14,000,50
-06,00
1,00
1,50
2,00
2,50
3,00
3,50
3
10
−1
,K
T
-08,00
-10,00
-12,00
-14,000,50
1,00
1,50
2,00
2,50
3,00
3,50
3
10
−1
,K
T
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
Sample
Visual observation
Black with milky regions
30Bi2O3.50TiO2.10SiO2.10Nd2O3
4
30Bi2O3.50TiO2.20Nd2O3
40Bi2O3.50TiO2.10SiO2
40Bi2O3.50TiO2.5SiO2.5Nd2O3
Fast Cooling
40Bi2O3.50TiO2.10Nd2O3
Fast Cooling
Fast Cooling
1,21
1,29
1,38
0,42
1,19
7,09
1,23
6,19
1,14
4,63
1,18
0,63
1,37
Tm=1450 оС
Dark yelow with silver additives
33,10
0,75
Tm=1450 оС
Milk silver
1
Fast Cooling
ΔE
eV
0,67
Tm=1260 оС
Black with milky regions
4E
Fast Cooling
σ , 10 -7
(Ω.cm )-1
1,59
Tm=1500 оС
Milk silver with yelow additives
B
Fast Cooling
Tm=1450 оС
Dark silver
5
d, 10 -3 m
Tm=1400 оС
30Bi2O3.50TiO2.20SiO2
A
Method of
cooling
0,89
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Results
εr
Sample
14000,00
12000,00
10000,00
8000,00
A
30Bi2O3.50TiO2.20SiO2
4
30Bi2O3.50TiO2.10SiO2.10Nd2O3
5
30Bi2O3.50TiO2.20Nd2O3
B
40Bi2O3.50TiO2.10SiO2
4E
40Bi2O3.50TiO2.5SiO2.5Nd2O3
1
40Bi2O3.50TiO2.10Nd2O3
A
4
5
6000,00
4000,00
2000,00
00,00
0
100
200
300
400
500
600
700
t , Co
εr
8000,00
7000,00
6000,00
5000,00
B
4E
1
4000,00
3000,00
2000,00
1000,00
00,00
0
100
200
300
400
500
600
700
t , Co
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University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd, 1756 Sofia, Bulgaria
Results
tan δ
Sample
0,1200
0,1000
A
30Bi2O3.50TiO2.20SiO2
4
30Bi2O3.50TiO2.10SiO2.10Nd2O3
5
30Bi2O3.50TiO2.20Nd2O3
B
40Bi2O3.50TiO2.10SiO2
4E
40Bi2O3.50TiO2.5SiO2.5Nd2O3
1
40Bi2O3.50TiO2.10Nd2O3
0,0800
A
4
5
0,0600
0,0400
0,0200
0,0000
0
100
200
300
400
500
600
700
t,C
o
tan δ
0,1200
0,1000
0,0800
B
4E
1
0,0600
0,0400
0,0200
0,0000
0
100
200
300
400
500
600
700
t , Co
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Conclusion
1. The investigation carried out confirms that depending on
the condition of the melting of the super-cooled melt
different poly-phase glass-ceramic materials with various
microstructure could be obtained containing mainly the
bismuth titanate phase in the system Bi2O3-TiO2-SiO2-Nd2O3.
2. Addition of Nd2O3 in the samples leads to increase of the
melting themperature and decrease of glass-formation
tendensy.
3. It is established that all investigated samples are
-9
dielectric materials with conductivity between 10 -10-13 (Ω
cm)-1 at room temperature, dielectic permetivity near 1000 to
3000 and dielectric losses tagδ between 0,0002 – 0,1.
4. Addition of SiO2 in the samples leads to increasing of
dielectric losses and conductivity.
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Thanks for your attention
IInnovation Week on Renewable Energy Systems A series of events towards a European Summer School on: “PV
systems engineering and the other R.E.S.” Innovation and Intelligent Applications
1- 12 July 2012, Patras, Greece