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MSE 131 Ceramics

Lecture 3

Dr. Benjamin O. Chan


Physics Department
Ateneo de Manila University
2016

Electrical Properties
Electrical Conductivity ( )
Insulators
Semi-conductors
Conductors
Superconductors

Conductivity
mho/m units

1
N = number of mobile charge carriers
q = charge per carrier
= mobility of charge carriers
Nq = charge density

Nq

Ceramics vs.
Metals/Polymers

Conducting Ceramics
Ionic Crystals
Alkali halides
Strongly bound positively charged cations and
negatively charged anions immobilized
Wide band gap = insulating
Ionic conduction possible!
Some ions can hop from lattice site to lattice site under
an applied electric field
ion

N ione

ion

where Nion = hopping ion density,

ion=

hopping ion mobility

Ionic Conduction
Ions must have sufficient energy to overcome
energy barrier
Electric field reduces energy
barrier

Neighboring site must be vacant


Schottky defect

Proceeds in a diffusion-like manner


ion

De
k BT

assuming one charge unit per atom is transported

Ionic Conductivity
Arrhenius Equation
ion

Do exp

Q
k BT

can now be written as


ion

where
o

N ione 2 Do
k BT

o exp

Q
k BT

Taking the ln of each side


yields
ln

ion

ln

Q
k BT
*slope = activation energy

Vacancy Formation
Charge neutrality maintained
Schottky defect: cation-anion vacancy pair
Frenkel defect: vacancy-interstitial pair
Charged impurity
monovalent host replaced by divalent impurity

Stoichiometric compounds
More vacancies formed at
elevated temperature
Non-stoichiometric compounds
contain a large amount of
vacancies even at low
temperatures

Covalently Bonded Ceramics


Intrinsic impurities
No such thing as pure semiconductor
Defective by nature

Doping = Intentionally Impure


Group III impurity
Missing electron = hole = p-type carrier

Group V impurity
Extra electron = n-type carrier

Group V Impurity in Si

Intentional Impurities
Usually in the ppm range
Group V
Donates an electron to the material
Impurity energy level just below conduction band

Group III
Accepts an electron from the material
Impurity energy level just above valence band

Band Representation
Fermi Energy
Conduction Band
Valence Band

Donor and Acceptor Levels

Majority and Minority Carriers


Majority carrier
Usually from dopant
Extrinsic carriers

Minority carrier
Usually from interband transitions
Intrinsic carriers

Valid for reasonably low T


The picture can change at high T
Intrinsic carriers become the majority!

Ec

Ev

Si Band Structure

GaAs Band Structure

Energy Gap at 0 K
Element

Eg (eV)

C (diamond)

5.48

Si

1.17

Ge

0.74

Sn (gray)

0.08

The Energy Gap


Decreases with atomic number
Artificial diamond: C-based IC
Ge: good IR detector
Sn easily conducts at room temperature

Wavelength equivalent

( m)

1.24
E (eV )

Temperature Dependence
E g (T )

E g ( 0)

T
T

where Eg(0) is the energy gap at 0 K


= 5 x 10-4 eV/K and
D = Debye temperature (Table 19.2)

Temperature needed to reach 96% of the final value for


heat capacity CV
T> D : classical region
T< D : QM consideration

Eg vs. T
Eg decreases with
increasing
temperature
For Si,
D=650K,

Eg reduction
= -2.4 x 10-4 eV/K

Basic Test Circuit


In general,
E= J
E = electric field across
sample (volt/m)
J = current density
(amps/m2)
= resistivity (ohm-m)

Ohms law
E

J
is constant

Measurement
V = Electric potential (volts)
I = Current (amps)

Resistance R and Resistivity


V = EL, J = I/A
L = length of sample
A = cross-sectional area

E
V
L
V
I
R

J
I
A
L
A
L
A

(ohm)

Slope of V-I graph

Problems with Resistivity Measurements


Geometrical shape required for specimen
Uniform cross-sectional area

Contact resistance
Loading effects from meter
Voltmeter: should not draw current
High impedance required

Ammeter: should not impede current flow


Zero resistance desired

Stray capacitance and inductance

Four Point Probe Technique


(ASTM F84-84, F374-84)

Suitable for wafer/thin film geometry


Rectangular/circular/cylindrical/slab

Minimizes contact resistance and loading


effects
Four probes separated equally by distance s
Outer probes: constant current supply
Inner probes: voltmeter

Sheet resistance Rs

Rs

V
(CF )
I

Four Point Probe


Correction Factors
Geometrical in
nature
Something to do with
s and how big the
sample dimensions
are with respect to it

Computing
resistivity

Rs w
w=sample thickness

Correction Factor Limit


Rs formula valid for w a or d

In the limit as ds, we can show that


CF = ( /ln 2) = 4.54

Carrier Type Determination


Is the material n-type or p-type?
Seebeck Effect
Double thermocouple

Works for
Bulk material
Films on high resistivity material
Films on opposite type substrate

Hot Probe (ASTM F42-77(87))

Voltmeter/Ammeter

How it works
Hot probe has greater carrier concentration
Positive terminal of meter must be on the hot
probe
If p-type, electrons flow from cold to hot junction:
meter records positive reading
If n-type, electrons from flow from hot to cold:
meter records negative reading

If the tester leads are inverted, the deflections


will be inverted! (this can be confusing!?)

Another Way to Determine Resistivity and


Carrier Type
Hall Effect Apparatus
Can measure concentrations down to 1012
electrons/cm3
Sensitivity is several orders of magnitude better
than any chemical analysis
Applies to bulk material
Pass a current in a material
immersed in a magnetic field

Hall Effect
Consider a rectangular block of n-type
semiconductor immersed in a magnetic field
with a magnetic induction B in the z-direction
Let a current density j flow through the
material in the +x direction
Flowing electrons
experience a Lorentz
force deflecting them
from their path

qv B

Hall Effect
Lorentz force makes the electrons drift to one side of
the material
Accumulation of charge sets up an electric field
Hall field

eE

Hall field builds up until it balances the Lorentz force

Ey

vx Bz

The current density j in the material is

Nv x e

N and the Hall Coefficient


We can calculate the number of conduction
electrons N (per unit volume)

j x Bz
N
eEy
Define the Hall constant/coefficient

RH

1
Ne

coefficient is inversely proportional to N


sign indicates carrier type

Limitations of the Hall Technique


Heating Effects
An electromagnet is usually used
Current required is in the AMPS range
typically

Do the measurements quickly


Demagnetization is necessary when
repeating the experiment

Non-Linear Response
Diode
Rectifying effect
Conducting under forward bias
Non-conducting under reverse bias

Thermal effects
Resistance increases with temperature
Resistance decreases with temperature

Diode I-V Characteristic

Temperature Dependence of

o 1 T

Superconductors
Resistivity drops to zero at low
temperatures

Critical Temperatures

Ceramic Superconductors
YBa2Cu3O7-x (YBCO)
Orthorhombic layered
perovskite containing
periodic O vacancies

Drawbacks
Brittleness
Cannot carry high current
densities
Environmental instability

Cooper Pair Formation


Electron drifts through crystal generating temporary
perturbations along its path
Displaced ion can be set oscillating by perturbation
generating a phonon
Phonon interacts quickly with a second electron
lowering its energy due to lattice deformation
Second electron emits phonon which interacts with
first electron
Phonon is passed back and forth, coupling the
electrons together, bringing them into a lower energy
state

Cooper Pairs and


Fermi Surfaces
All electrons on a Fermi surface having
opposite momentum and spin form Cooper
pairs
Cloud of Cooper pairs is formed
Cooperative drifting through the crystal proceeds
This is an ordered state of the conduction
electrons!
Ordering eliminates scattering by lattice atoms,
resulting in zero resistance!

Fermi Energy
EF lower in superconducting state
Superconducting state is separated from the
normal state by an energy gap Eg
Energy gap stabilizes Cooper pair against
small changes of net momentum
they wont break apart!

Eg ~ 10-4eV
Observed via IR absorption measurements at
T<Tc

DOS Superconductor

Josephson Effect
Another way to measure Eg
Two pieces of metal
One in superconducting state, the other in normal state

Energy bands in superconductor are raised by an


appropriate voltage
If the applied voltage is big enough, filled states in
superconductor are opposite empty states in normal
conductor
Cooper pairs can tunnel through

Eg is determined from the threshold voltage for


tunneling

Josephson Junction

Optical and Dielectric Properties


Optical properties = response of
materials to electromagnetic radiation
Dielectric properties = response to
electric fields of insulators
Both properties (including magnetic
properties) depend to large extent on
the polarization of the material

Electromagnetic Spectrum

MECHANISMS OF
POLARIZATION

ELECTRONIC POLARIZATION
External electric field shifts the electron cloud
of an atom
Electric field arises from an applied potential
difference (volts) across the material

Temporary or induced dipole results


Polarization vanishes when the electric field is
removed

Can occur in all types of material regardless


of the type of bonding

IONIC/ATOMIC POLARIZATION
Applied electric field causes charge
separation
Cations move toward negative electrode
Anions move toward positive electrode

Important for ionic materials


Example 11.2-2
Calculate the increase in separation of Cs+
and Cl- when an ionic polarization of 4 10-8
C/m2 is achieved by the application of an
electric field.

Answer
Lattice parameter of CsCl
ao

2(r R)
3

2(0.165 0.181)nm
3

0.400nm

Since there is one pair of ions per unit cell,


Z

(1dipole / cell )(1charge/ cell )


(0.400 10 9 )3 (m3 / cell )

1.56 1028 charges/ m3

Increase in separation distance


d

P
Zq

4 10 8 C / m2
8
1
.
60
10
nm
28
3
19
(1.56 10 charges / m )(1.6 10 C / charge )

Increase is less than 50 ppb

MOLECULAR/DIPOLE POLARIZATION
Alignment of permanent dipoles parallel to
the applied electric field
Common in ionic ceramics, silicates and polar
polymers
Can be retained after removal of electric field
Can freeze the aligned structure (e.g. apply field
above TG of polymer and let it cool down with the
applied field)
Electrets are polymers that retain this poled
structure for long times
Air filter: charged dust particles removed from airstream
by passing them through a web of electret fibers

INTERFACIAL POLARIZATION
Piling up of mobile charge carriers at a
physical barrier (grain boundaries,
phase boundaries, free surfaces, film
interfaces)

NET POLARIZATION
The sum of electronic, ionic, molecular
and interfacial polarization
Materials are differentiated by their level
of response from each mechanism
Ionic/molecular: type of atoms, type of
bonding
Interfacial: planar defect density

Frequency of Applied EM Field


The larger the masses involved, the slower
the response
Electrons can react to visible light ~1015 Hz
Ions can react to IR: 1012-1013 Hz
Molecules can react to sub-IR: 1011-1012 Hz
Interfaces: 10-3-103 Hz
Depends on grain size/dimension from one interface to
the next

Optical properties from Electronic and Ionic


polarization (fast processes)
Dielectric properties from Molecular and
Interfacial polarization (slow processes)

Example 11.2-4
Describe what effect, if any, each of the
following processes would have on the
net polarization of a solid: a) increase
the grain size of a ceramic polycrystal,
b) increase the concentration of network
modifiers in a silicate glass, and c)
change the frequency of the excitation
field from UV to microwave

Solution
Interfacial polarization shifts to lower
frequencies

a)

Larger grain size means more time to cross the


grain

Net polarization increases in the sub-IR


range

b)

Primary bond density decreases, number of


secondary bonds (dipoles) increases

Dominant mechanism shifts from electronic


to molecular polarization

c)

UV ~1016 Hz, microwave ~1011 Hz

Perovskite Revisited
BaTiO3
Above 120 C, cubic crystal
Below 120 C, central Ti4+ cant fit position and
displaced 0.006 nm to one side of the cell while O2- are
displaced 0.008 nm in the opposite direction
120 C = ferroelectric Curie temperature (below which
permanent polarization occurs)

Piezoelectric Effect
Mechanical deformation (e.g., uniaxial
compression) may decrease the separation
between anion and cation. The motion of the
ion produces a current and induces an
internal field.
Converse effect: application of an electric
field along the correct crystallographic
direction changes the anion-cation spacing
(Electrostriction)
An applied electric field changes the dimensions
of the material

Piezoelectric Effect
Let

= field produced by the stress. Then,

and,

d
Where g and d are constants related to the
modulus of elasticity

1
gd

Examples: quartz, various titanates, lead


zirconate, cadmium sulfide and zinc oxide.

PIEZOELECTRIC CONSTANTS

*d is in 10-12 m/V

Applications of Piezoelectrics
Usually used as a transducer
Phonograph cartridges
Convert mechanical vibrations to electrical signal to
acoustic waves

Telephones
Electrets are however taking over the telephone market
Electrets exhibit the same behavior as piezoelectrics:
applied stress cause deformation and charge motion
Poly(vinylidene fluoride) is popular choice

Pressure Gages
High frequency sound generators

Piezoelectric Materials
Quartz
One of the first piezoelectrics in common use
Precise timing of electrical circuits and watches
using vibrational frequency control

Barium Titanate
Low temperature applications

Solid solutions of PbZrO3 and PbTiO3 (PZTs)


High temperature applications (up to 490 C)

Ferroelectricity = a dipole causes neighboring


dipoles to align spontaneously (even in the
absence of an electric field)

Example 11.2-5
A compressive force of 5N (~1 lb) is applied to
a slice of quartz with dimensions 3 mm x 3
mm x 0.25 mm. If the elasticity modulus for
quartz is 70 GPa, calculate the voltage
created by the stress.
Solution
F
A

5N
(3 10 3 m) 2

5.56 105 Pa

Determine g so E can be calculated


g

1
Ed

and

Ed

Solution
5.56 105 Pa
(70 109 Pa)(2.3 10 12 m / V )

3.5 106V / m

The voltage developed is quite large


El

(3.5 106V / m)(0.25 10 3 m)

875V

Small loads can be easily detected


Phonograph cartridge

Capacitance*
Investigate the ability of a material to polarize
and hold charge
Capacitance, C
C

Q
V

Q = charge stored
on either plate
V = applied voltage
C units: Farad (C/V)
*Review Chapter 24 of University Physics by
Young and Freedman, 11th ed.

Capacitance
Material factor = permittivity,
Reflects the ability of the material to be polarized
by the electric field

Geometric factor = area/plate separation


C

Dielectric = vacuum

Co

A
o
d

= 8.85

10-12 F/m

Polarization and Dielectric Constant


Polarization and permittivity

where

= electric field strength

Dielectric constant
that of vacuum

= permittivity normalized to

Usually a function of frequency (polarization is!)

Dielectric
Constants

Example 11.3-1
Polyethylene has a polarization of 5.75
x 10-8 C/m2 in a field of 5000 V/m.
Calculate the dielectric constant of this
polymer.
Solution
P
1
o

5.75 10 8 C / m2
(8.85 10

12

F / m)(5000V / m)

2.3

Example 11.3-2
A simple parallel plate capacitor that can
store a charge of 10-4 C at 3 kV is required
for a particular application. The thickness of
the dielectric is 0.020 cm. Calculate the area
of the plates if the dielectric is vacuum, PTFE
(Teflon), BaTiO3, mica.
Solution

Q
V

10 4 C
3000V

3.33 10 8 F

Solution
A

Cd

Cd
o

(3.33 10 8 F )(0.02cm)
(8.85 10 14 F / cm)

Vacuum, =1 and A = 7525 cm2

PTFE, =2 and A = 3763 cm2


BaTiO3,
Mica,

= 3000 and A = 2.5 cm2


= 7 and A = 1075 cm2

7525cm 2

Dielectric Strength and Breakdown


The maximum electric field to which a
dielectric material can be subjected to without
breaking down or discharging
max

V
d

max

Dielectric breakdown is the electrical


equivalent of mechanical failure
Pits, holes, channels bridging conductors are
formed
Dependent on the thickness of the material

Dielectric Strength
Determined by the probability of finding
a critical flaw in the test region
Strength increases with decreasing
thickness!

Maximum charge storage: high


dielectric constant and high dielectric
strength required
Mica (+ good thermal stability)

Dielectric
Strength

Example 11.3-3
Which material (vacuum, PTFE (Teflon),
BaTiO3, mica) may be used for a simple parallel
plate capacitor that can store a charge of 10-4 C
at 3 kV? The thickness of the dielectric is 0.02
cm.
Solution
The applied field strength is

3kV
0.02cm

150kV / cm

Compared to the dielectric strengths given in the


previous table, Teflon and mica are usable although
the capacitor will be significantly large

Example 11.3-4
Suggest an alternative design for the
capacitor needed to fulfill the requirements of
storing a charge of 10-4C at 3 kV, assuming
that the raw material for the dielectric is 0.020
cm-thick sheets of BaTiO3.
Solution
Applied field strength must be reduced below
dielectric strength of 120 kV/cm corresponding to
a minimum dielectric thickness of

3kV
120kV / cm

0.025cm

Solution
BaTiO3 sheets must be stacked together to achieve a
total dielectric thickness of 0.040 cm. The required
area for the capacitor is calculated

Cd

Cd
o

For BaTiO3,
that

= 3000 and C = Q/V = 3.33x10-8 F so


8

(3.33 10 F )(0.04cm)
(3000)(8.85 10 14 F / cm)

5.02cm2

Surface Breakdown
Breakdown due to high fields may occur at
the surface (and not exclusively to the bulk) of
the material
Can be aggravated by surface moisture and
contamination

E.g., spark plugs should withstand high


temperature, high fields
Fabricated from ceramic steatite (SiO2 + MgO +
Al2O3) coated with a glassy silicate (ceramic
glaze)
Most ceramics are porous and hygroscopic