FERROELECTRIC

CERAMICS:
properties, processing
and applications
 Introduction
 A ferroelectric ceramic mixes the smartness of a
ferroelectric material and the tailoring
possibilities of ceramics.
 Since both kind of materials exhibit many
interesting properties, the mixture should be
good…
 Ferroelectrics: ferroelectric domains
 Ferroelectric domains are generated by coupling between dipole
moments of atoms.
 When subjected to electric field, the domains pointing towards its
direction start to grow over its neighbouring domains.
 Ferroelectrics: hysteresis loop
 Saturation and remanent
polarization
 Coercive field
 Possibility to reverse the
polarization
 Smart material: it keeps
information (remanent
poalrization)
 Ferroelectrics: phase transition
 Ferroelectricity is a phase transition (Curie point)
 Ferroelectric phase has always lower symmetry
 Example: BaTiO3 (cubic changes into tetragonal)
 Ferroelectrics: summary
 Present spontanous polarization
 Polarization can be inversed
 Ferroelectric domains
 Hysteresis loop
 Ferroelectricity is a phase transition
 Piezoelectric and pyroelectric effect
 Ceramics is a wide term…
 The term ceramics
covers all inorganic non-
metallic materials whose
formation is due to the
action of heat.
 So you could think
something like this…
 …but we are dealing with
ADVANCED ceramics!

We can control, modify

and optimize its
properties by tailoring
the material!
 Properties of ceramics
 Mechanical: poor toughness (under study)
 Electrical: semiconductors, superconductors,
piezoelectrics, pyroelectrics, ferroelectrics
(BaTiO3, PZT…)
 High resistance to abrasion
 Excellent hot strength
 Chemical inertness
 We can tailor properties for specific applications
 Why are ferroelectric ceramics so
important?
FERROELECTRICS
 High permittivities
 Spontaneus polarization
 Electric conducticity can be
controlled
 Piezoelectric and pyroelectric
effect
 Optical anisotropy,
electrooptic an
photorefractive deffect
CERAMICS
 Broad range of chemical
composition
 Control of grain size,
porosity…
 Possibility of varying its
shape and size.
 High resistance to abrasion
 Excellent hot strength
 Chemical inertness

All this properties lead to a lot of potential

applications!
 1. General Procedure of Processing
 Raw
Materials
 Mixing
 Calcining
 Character
 Milling
-ization  Poling
 Sintering

 Binder
Burnout
 1. raw materials
Weighing the raw materials
according to the stoichiometric
formula of the ferroelectric
ceramic desired .
 2. Mixing
Mixing the powders
either mechanically or
chemically
 Mechanical mixing is usually done by either ball milling or
attrition milling for a short time.
 Chemical mixing on the other hand is more homogeneous as
it is done by precipitating the precursors in the same container.
 3.Calcination
The solid phase reaction takes
place between the constituents
giving the ferroelectric phase
during the calcination step
 4. Milling
The lumps are ground by
milling after calcining.
 5. binder burnout

After shaping, the green bodies are

heated very slowly to between
500-600° C in order to remove
any binder present.
 6.Sintering
 Afterthe binder burnout is over,
the samples are taken to a
higher temperature for sintering
to take place.
 7.Poling
 it does not show any piezoelectricity when the
ferroelectric ceramic is cooled after sintering .
Piezoelectric behavior can be induced in a
ferroelectric ceramic by a process called
"poling" .
 In this process a direct current (dc) electric field
with a strength larger than the coercive field
strength is applied to the ferroelectric ceramic at
a high temperature, but below the Curie point.
 8.Characterization
On the application of the external dc
field the spontaneous polarization
within each grain gets orientated
towards the direction of the applied
field. This leads to a net polarization in
the poling direction
Two special important methods
widely uses in the labs .
1. Metal Organic Decomposition
(MOD)
2. (2)hot-pressed solid-state
sintering method
 1. MOD
 MOD:Metal Organic
Decomposition
1. spin-coat the solution on a bulk Si wafer at
4000 rpm, 20 seconds .
2. the film is baked on hot plate at 150 for 10
minutes to remove the solvent .
3. then the film is given a pyrolysis heat
treatment in a furnace at 470 ℃for 30
minutes to remove the residual organics
and promote chemical reaction

Desired thickness of the film is achieved

Ferroelectric BST-thick film ceramic on an
alumina substrate
2. hot-pressed solid-state
sintering method
 SEM micrograph
of a cross section
of PLZT
transparent
ferroelectric
ceramics.
hot-pressed solid-state sintering method
 PbO, La2O3, ZnO, Nb2O5, ZrO2, and TiO2 with
purity of 99.4–99.8% and micrometer particle size were
used as starting materials. The stoichiometric mixture
was ballmilled in a plastic container with zirconia
grinding media in alcohol solution, then dried and
ground. The ground mixture powders were pressed
under 80 kg/pressure into a cylindrical bar of 60 mm in
diameter and 60 mm in height.
hot-pressed solid-state sintering method
During a sintering process, an oxygen flow of 3 L/min
was passed through the oven. The sintering
temperature was elevated to 950 °C at a rate of 200
°C/h and kept for 1⁄2 h, then pressure was gradually
applied to the sample until 480 kg/ while the oven
temperature was increased to 1200 °C at the same
time.
hot-pressed solid-state sintering method
The temperature and pressure were kept for 6 h before
the pressure was released. Subsequently, the
temperature was continuously increased to 1250 °C in
1⁄2 h and kept for 10 h. After sintering, the oven was
cooled down to 950 °C at a rate of 140 °C/h and
then cooled naturally until room temperature. The
sintered specimen was cut and polished to obtain the
required size for different measurements.
 Applications of
Ferroelectric Ceramics
( general overview )
 background
 Ferroelectric ceramics are used in a very broad
range of functional ceramics and form the
materials base for the majority of electronic
applications. These electronic applicators
account for more than 60% of the total high
technology ceramics market worldwide
 Capacitors
 Basic principle
( 0 r A)
C
t
 'C' is the capacitance, 0 is the permittivity of free
space,  r is the relative dielectric permittivity, 't' is
the distance between the electrodes, 'A' is the
area of the electrodes.
 multilayer ceramic (MLC)
 The volumetric efficiency can be further
enhanced .
 consists of alternate layers of dielectric and
electrode material.

(n 0 r A)
C
t
 Ferroelectric Memories
 FRAM (Ferroelectric Random Access Memory)
is a non-volatile memory combining both ROM
and RAM advantages in addition to non-
volatility features. It has higher speed in write
mode, lower power consumption and higher
endurance
Overview of FRAM
 Advantages over EEPROM
 Transaction Time
- 30,000 times faster than EEROM
 Energy Consumption
 200 times lower power consumption compare to
EEPROM
 1 FRAM Cycle is just Reading
 1 EEPROM Cycle consists of erasing , writing and
reading
 Endurance
 100,000 times higher endurance over EEPROM
and the energy consumption is at 64Byte every
write cycle
 Electro-optic Applications
 Ferroelectric Thin Film Waveguides. An optical
waveguide controls the propagation of light in a
transparent material (ferroelectric thin film) along a
certain path
 Ferroelectric Thin Film Optical Memory Displays .
 Other Ferroelectric Thin Film
Applications
 Pyroelectric Detectors :Pyroelectric detectors are
current sources with an output proportional to
the rate of change of its temperature
 Surface Acoustic Wave Substrates
 An elastic wave generated at the input
interdigital transducer (IDT) travels along the
surface of the piezoelectric substrate and it is
detected by the output interdigital transducer.
These devices are mainly used for delay lines and
filters in television and microwave
communication applications
Most Common Commercial
Ferroelectric Ceramic
 Lead Zirconate Titanate (PZT)
 Chemical formula Pb Zrx Ti1-x O3
 “Perovskite” ABO3
 A and B are different in size
A cation is at centre
B cation is at the corner
O atom are at centre of unit cell faces.
 Lead Zirconate Titanate (PZT)
 generates a voltage when some mechanical stress
is applied … piezoelectric effect
 useful for sensor and actuator application
 Doping
Acceptor doping internal friction losses piezoelectric constant

Donor doping internal friction losses piezoelectric constant

 Lead Zirconate Titanate (PZT)
 Poling
High Temperature
High Voltage
 Repeat to achieve high piezoelectric constant
 PZT Thin Films
 Used in number of devices
 Thickness of 90nm
 low crystallization temperature
 good surface morphology
 high remnant polarization
Application of PZT

Acoustic Device for underwater

Application
 Acoustic Device for underwater
Application
 Ultrasonic Sensors
 Commercial sound waves generating devices use
PZT thin films
 Bulky ferroelectric ceramic sensors
 Acoustic Device for underwater
Application
 Hence
Thin films are used
Low fabrication cost
 Film deposition techniques
Electron beam evaporation [1]
Rf diode sputtering [2]
Ion beam deposition [3]
RF planar magnetron sputtering [4]
MOCVD [5]
ECR [6]
laser ablation [7]
and sol-gel
[8]
 Fabrication
 0.25µm oxide layer
 0.3µm Pt. electrode
 PZT thin film deposition for 2 hours at 350˚C
 Annealing at 650˚C for 20 minutes
 Cooled to room temperature
 Fabrication
 SEM patterns of deposited PZT thin film

 PZT thin film annealed at 850˚C for 5 minutes

 Fabrication
 Lithography used to form a window in silicone
substrate
 Oxide layer is removed
 100µm diaphragm was created by etching
 Successive layers of Pt, PZT and Pt deposited
 poling under an electric field of 10kV per cm at
a temperature of 130˚C
 Results
 Improved ferroelectric property
 Improved accuracy
 Economical sensor
 Very small and light weight
 Can be used for application underwater
 Results
 Senstivity
 Applications
 Ultra Sonic Cleaners
 SODAR
 SONAR
 Medical Diagnostics
 Printer Heads
 Gas Lighters
 Micro Positioners
 Actuators
 Annunciators
 Sensors
 Capacitors
 FRAM
 Ceramic resonators
 Memory devices in thin film form
References of all material and
diagrams are given in report
Thankyou for your kind
attention !!