MS 60003 Science and Technology of Ceramic

Electro-ceramics

S.B. Majumder
Materials Science Center
IIT Kharagpur- 721302
Insulating Oxide Electronic Materials

Acknowledgement: UCONN, IMSc

 q
Capacitance C=
V
Relative Dielectric Constant
C
ε=
CVac

Capacitance of a parallel plate capacitor

A
C = εε 0
L
 Materials already possesing
permanent dipoles, H2O, BaTiO3,
oils, waxes, amorphous
polymers,…

Displacement of ions with

respect to each other due to
external bias, only in ionic
materials

Electric Dipole Moment

p = q⋅x
Polarization
p q
P= ≡ displacement of the e- cloud with respect
V A to the core due to external bias, occurs in
ALL dielectric materials
 Ferroelectrics
Lead P Filters Oscillators
Oxygen +P E
Titanium
+P R
1 EC

0 E
-P R
Ferroelectric
or Wireless Communications Memories
-P E
 Perovskite Structure

Typical Perovskite
Ferroelectrics

•Pb(Zr,Ti)O3-PZT
•Ba(Sr,Ti)O3-BST
•KNbO3 and LiNbO3
•Pb(Ca,Ti)O3 -PCT
•Pb(Sr,Ti)O3 –PST
•Pb(Mg1/3Nb2/3)O3-PbTiO3

Properties
 Spontaneous polarization in the absence applied electrical field.
 Extremely high dielectric constant (~500-15,000).
 Strong non-linear dielectric response to an applied electrical field.
 High strain response to applied electrical field  piezoelectricity
 Strong variation in polarization with temperature  pyroelectricity
 Some Important Definitions

D: electrical displacement
ε: dielectric constant
E: electrical field
Ec: coercive field
dijk: piezoelectric coefficient (third rank tensor)
p: pyroelectric coefficient
Qijkl: electrostrictive coefficient (fourth rank tensor)

D = PS + Eε
Spontaneous Polarization and the Hysteresis
 Dielectric Constant: Slope of the P vs. E curve

Pi = ε 0ε ij E j
1200 2500
Dielectric constant ε33/ε0

Dielectric constant ε33/ε0

1000 2000

800 1500

600 1000

400 500

200 0
-300 -200 -100 0 100 200 300 -100 -75 -50 -25 0 25 50 75 100
Electric Field, E3 [kV/cm] Electric Field, E3 [kV/cm]

Paraelectric Ferroelectric

Field dependence of dielectric permittivity  TUNABILITY

 Temperature Dependence of Spontaneous
Polarization
Spontaneous Polarization (C/m2)

0.6

P
TC=490oC
0.5
E>>0
E=0
0.4

PbTiO3 T
0.3
0 100 200 300 400 500
Temperature [oC]

 ∂D  ∂P ∂ε
PYROELECTRICITY p=  = S +E
 ∂T  E ∂T ∂T
 Ferroelectric used as Pyroelectric material

Polarization
Tc Exceptional Pyroelectric
Temperature
Response

Volts

 ∂D  ∂P ∂ε
PYROELECTRICITY p=  = S +E
 ∂T  E ∂T ∂T
Electrostriction: Coupling between Polarization and Self-Strain

0.415

c aT − aC
= Q12 P02
0.410
u1 = u2 =
Lattice Parameter [nm]

TC=490oC aC
0.405
cT − aC
u3 = = Q11P02
0.400
aC
0.395 a0 u4 = u5 = u6 = 0.

0.390 a PbTiO3  for BaTiO3 and PbTiO3, |Q12|<Q11

0 100 200 300 400 500 600 and Q12<0.
Temparature [oC]
Piezoelectric effect: Strain due to an applied electric field

xij = d kij E k
Strain due to combined Electrostrictive and Piezoelectric effect

xij = d kij Ek + Qijkl Pk Pl

1
= d ε Pj + Qijkl Pk Pl
−1

ε0
kij ki

Under non-zero external stress

xij = d kij Ek + Qijkl Pk Pl + Sijkl X kl

 Polarization Switching by an Electric Field

E=0

E>0

E≈EC
Polarization Switching by an Electric Field

Applied field E and switching current

I versus time for a BaTiO3 crystal.
The curve marked A is the switching
pulse when the applied field is anti-
parallel to the polarization, and the
curve B is obtained when the field is
parallel to the polarization and no
switching occurs.
 Polarization Switching by an Electric Field

Electrical (or 1800-domains) to minimize depolarization.

 Polarization Switching by an Electric Field

Switching via Reversible Domain Wall Motion: Nucleation and Growth

Structural Aspects of Ferroelectric Phase Transformations

0.404

0.403

Lattice Parameters (nm)

0.402

0.401

0.400

0.399

0.398
R3m Amm2 P4mm Pm3m
-200 -100 0 100 200 300
Temperature (oC)
 Applications of Ferroelectrics

 Non-Volatile RAMs (memory)

 Dynamic RAMs (capacitors)
 Tunable Microwave Devices
 Pyroelectric Detectors/Sensors
 Optical Waveguides
 Piezoelectric Sensors/Actuators, MEMS
Non-Volatile RAMs (memory)
 Non-Volatile RAMs (memory)

Smart cards use ferroelectric memories. They can hold relatively large amounts of information
and do not wear out from use, as magnetic strips do, because they use contactless radio
frequency input/output. These cards are the size and shape of credit cards but contain
ferroelectric memory that can carry substantial information, such as its bearer's medical history
for use by doctors, pharmacists and even paramedics in an emergency. Current smart cards
carry about 250 kilobytes of memory.
 Dynamic RAMs (capacitors)
High dielectric constant near phase transformation from the cubic to the
tetragonal phase (500~15,000)

Tetragonal Cubic

 Proximity of the Curie temperature to the room temperature yields

large dielectric constant in BaxSr1-xTiO3 (x=0.5-0.7).
 Tunable Microwave Devices / Optical Waveguides
Dielectric constant ε33/ε0

∆ε
tunability = Φ =
2500

2000
ε (E = 0)
1500
∆ε
1000

500
Filters Oscillators
0 ε(E=0)
-100 -75 -50 -25 0 25 50 75 100

Electric Field, E3 [kV/cm]

Phase Delay
shifters lines
Pyroelectric Detectors/Sensors
Piezoelectric Sensors/Actuators, MEMS
Piezoelectric Sensors/Actuators, MEMS
Piezoelectric Sensors/Actuators, MEMS