v.2020.

JAN

B. Dielectric Properties of Materials

mostly organic (PET, PTFE, PP, PS …)

• Materials strong covalent interchain, weak bonds intrachains
– ceramics / polymers electronic ceramics
crystalline inorganic (Al2O3, BaTiO3, glasses …) structural ceramics
strong ionic bond (bricks…)
– solids in which outer electrons are unable to move through structure
• Functions • Properties
– energy storage – large C (freq dependent)
– insulation – high r, br
– new apps: capacitive sensing, …
• Objectives
– understand underlying energy storage mechanisms
– understand insulation breakdown mechanisms
– select proper dielectrics (from chips to high-power cables)

Reference: S.O. Kasap (4th Ed.) Chap. 7; RJD Tilley (Understanding solids, 2nd Ed) Chap. 11.
Dielectric Properties 2102308 1
 Dielectric Materials
• introduction
– relative permittivity (er), polarizability (a) er

• polarization mechanisms
– types: electronic, ionic, dipolar, interfacial e r ( )

– frequency dependency
• br (electric field strength, breakdown field)
– gas, liquid, solid
• capacitors
– ceramic, polymer, electrolytic
• nonlinear dielectrics
– piezo-, ferro-, pyro-electricity
• special cases for EE
– see brochure for EE ceramics (self-study)
Dielectric Properties 2102308 2
 7.1 Relative permittivity er also called “dielectric constant”

- dielectric is the working material (active component) in capacitors. The simplest structure is the
parallel plate capacitor (Fig. 7.1). Without the dielectric (a), the stored charge is Qo. With the
dielectric (c), the stored charge increase to Q, or by a factor of er , the relative permittivity.
- under electric field E, the constituents of the dielectric (ions, atoms, molecules) become polarized
(Fig. 11.3). Internal electric dipole moment (p) induced by E, resulting in observable
polarization (P).
Qo e o A e re o A Q C
Co = = C= ; er = =
V d d Qo Co

* i(t) is a displacement current, not conduction current.

1 V
Potential Energy: U = CV 2 = Q
2 2
Dielectric Properties 2102308 3
 - electric dipole moment (p) or dipole moment (or just dipole) is charge balanced, see A
- a mechanism that gives rise to such dipole is electronic polarization, see B
- the resulting dipole is proportional to the electric field strength E, the proportionality constant is
termed (electronic) polarizability, see C
- the relative permittivity (er) is related to the polarizability (a) of materials, see D
A. dipole moment: separation of –ve and +ve charges (equal magnitude, charge balance)

p can interacts with external 

Ex. H+-Cl−, p ~ 3.6×10−30 C.m
(unit: C·m)

B. electronic polarization (all atoms) E

C x O
Electron cloud
Qnet = 0 Qnet = 0 
p = 0 p  0
a = 0 Atomic a  0
nucleus

pinduced = a e
Center of negative ( unit: C·m = [F·m2][V/m] )
charge
(a: polarizability)
(ae: electronic polarizability)

pinduced
(a) A neutral atom in E = 0. (b) Induced dipole moment in a field
Dielectric Properties 2102308 4
 30
C. polarizability ae
fo
10
fo
with electric field  Rn
x1015 Hz
Hook’s Xe
Ze = x (restoring force) Ar Kr

2 2 1 ae ~ Z0.99
pe = Qa = (Ze )x =
Z e
  ae
ae
 x10-40 F m2
Ne

without  He Z  → large electron cloud

→ further from nucleus →
d 2x can be shifted easily → a 
 x = me Z 2 0.1
dt 1 10 100
me Z d 2 x 1 d 2 x Atomic number Z
x= =
 dt 2 02 dt 2 Electronic polarizability and its resonance frequency vs. the
number of electrons in the atom (Z). The dashed line is the best
simple harmonic equation: fit line.
1/ 2
  
 o    ~constant
 Zme 
Ze 2
, a e =
meo2

Key message: The heavier the element ( Z ), the higher the electronic polarizability (ae)
Dielectric Properties 2102308 5
 D. e r &ae Before insertion: Qo
V Q Q
= = o = o →
d Co d e o A
Bound polarization Qo = e o A 
-QP
charges on the surfaces
+QP
bound
charges
After insertion: Qp
free +Q -Q

charges
E
(b) ptotal = Q p d →
ptotal * pinduced  N  ( Ad )
Qp = =
d d
Q p = ( Na e )A 
Area = A ptotal

(c)
* ptot = (p / molecule) × (molecule / volume) × (volume)
(a) -QP P +QP
V

Q = Qo + Q p
d
Q Q p Na e
(a) When a dilectric is placed in an electric field, bound polarization er  = 1+ = 1+ 
charges appear on the opposite surfaces. (b) The origin of these Qo  Qo eo
polarization charges is the polarization of the molecules of the
medium. (c) We can represent the whole dielectric in terms of its More detail analysis (solid polarized by a local
surface polarization charges +QP and -QP. electric field) yields Clausius-Mossotti relation:
e r − 1 Na
= 
e r + 2 3e o
- solid must be homogeneous isotropic (no
note: ae is atomic-level , er ismaterial-level parameters
permanent dipoles, dipolar molecules)
microscopic macroscopic − a includes other polarization mechanisms
Dielectric Properties 2102308 6
Q -QP +QP

Polarization P (C/cm
(b) 2)

+Q -Q
definition
E
(b)
total dipole moment
Area = A ptotal Polarization 
volume
er (c)
Area = A ptotal Qp d Qp
= = =
p
total
a) -QP P +QP

(c)
volume Ad A
(a) -QP P +QP
Vd

ced in an electric field, bound polarization

as a (b)
osite surfaces. function of external
The origin of these electric field
polarization of the molecules surface
of the d
sent
(a) the
Whenwhole dielectric
a dilectric in terms
is placed in of
an its
charge electric field, bound polarization
escharges
+QP and -QP.on the opposite surfaces. (b) The origin of these
appear
(storage)
polarization charges is the polarization of the molecules of the
medium. (c) We can represent the wholedensity material
dielectric in terms of itsresponds
surface polarization charges +QP and -QP.
Qp  
P= = ( Na e ) = e o (e r − 1)
A
polarizability excite
(atomic/molecular)
Dielectric Properties 2102308 7
 Ex. 7.2
The electronic polarizability of the Ar atom is ae = 1.710-40 F m2. What is the static dielectric
constant er of solid Ar (below 84K) if its density is 1.8 g/cm3 and atomic mass is 39.95.

Origin of charge/energy storage:

  material develops polarization (P)  pinduced (=a) binds or draws more charges (Qp)
to the electrodes. These charges can be released to do work.
(Think of stretched strings)
Dielectric Properties 2102308 8
 7.2 (electronic) polarization in covalent solids (semiconductors)

• to shift electrons in ionic cores  need ~ 10 eV (difficult)

er EG(eV)
• to shift electrons in covalent bonds  need ~ 1-2 eV (easy)
Ge 16 0.67
• stronger bonds (EG ↑)  smaller shifts (x, ae, er) Si 11.9 1.12
C 5.7 5.5
GaAs ? 1.43
SiO2 3.9 9.00

= 13.1, but why?

Na e
e r = 1+
eo
a e : a e −core + a e −valence
✓ ✓

(a) Valence electrons in covalent bonds in the absence of an applied field. (b) When an electric field is applied
to a covalent solid, the valence electrons in the covalent bonds are shifted very easily with respect to the
positive ionic cores. The whole solid becomes polarized due to the collective shift in the negative charge
distribution of the valence electrons.
Q) why concern with er of “semiconductors”?
A1) (device) In depletion layer of p-n junctions, dielectric property (er) is more important than electrical property (s ).
A2) (circuit & system) er  C  CR  BW
Dielectric Properties 2102308 9
 7.3 Polarization Mechanisms
7.3.0 Electronic polarization: (for all neutral atoms) displacement of electrons
7.3.1 Ionic polarization: (for charged ions) displacement of ions. Example: NaCl (below)

p+ p- p = a = Qa

large
(a) x
Ð Clausius-Mossotti relation:
Cl +
Na
3e o e r −1 
ai =  
N  er + 2 
p'+ p'- usually a i  10a e

(b)

E
(a) NaCl chain in the NaCl crystal without an applied field. Average or net dipole moment per ion = 0. (b) In the
presence of an applied field the ions become slightly displaced which leads to a net average dipole moment per ion.

Dielectric Properties 2102308 10

 7.3.2 Orientational polarization (or dipolar polarization): re-orienting of molecules
with permanent dipole moments.
- certain molecule has “permanent” dipole moment due to bonding (see Examples in Box)
- similar to ionic but |p+|  |p-| for each molecule
- under electric fields, molecules are re-oriented such that p align along E as much as possible
(atoms/molecules in liquid/solid phase are not free to move)

Examples (materials):
note strong
Polar liquids – water (), temperature
acetone, alcohol, electrolyte dependency
Polar gases – steam,
gaseous HCl () po = Qa
Polar solids – glasses p
2
ad = o
Examples (values): 3kT

p ~ 3.6×10−30 C.m


p ~ 6.2×10−30 C.m
Dielectric Properties 2102308 11
 7.3.3 Interfacial polarization (or space charge polarization): build-up of mobile
charges
- certain dielectric has mobile charges (electrons, holes, ions)
- though they move under electric fields, they cannot leave dielectrics, but pile-up at grain
boundaries (polycrystals), at equilibrium, internal field block further charge movement
− aif not significant in most cases, except at low frequencies

Dielectric Properties 2102308 12

 7.3.4 Total polarization
7.3.0 7.3.1 7.3.2
a  ae + ai + a d (average)

(aif is location specific)

7.3.3

dipolar
2

Dipolar solid
general trend:
1. semiconductor: concerned with parasitic capacitance ae  ai  a d
2. insulator: more concerned with breakdown field (br)
except those related to valence electrons
Dielectric Properties 2102308 13
 7.4 Frequency dependency of polarisability and relative permittivity
- capacitors are used in applications throughout the frequency spectrum: from low, power line
frequencies (50/60 Hz), to high, communications frequencies (MHz/GHz)
- dielectric materials may or maynot have time to respond to the excitation (ac frequency), this
depends on the dominant polarization mechanism(s) and the ac frequency
- generally, the mechanisms which involves heavy masses are slowest, light are fastest (Fig. 11.5)
− aif (charge switch positions at grain boundaries), upto 106 Hz
− ad (dipoles of molecules rotate in medium), upto 109 Hz
− ai (ions stretch/compress), upto 1012 Hz
− ae (electron cloud shifts around nucleus), upto 1016-1017 Hz (see slide #5)
- frequency dependency of polarisability:

a total = a if + a d + a i + a e
a dc
a ( ) =
1 + j

Dielectric Properties 2102308 14

 - when dipoles respond to electric field, there’s a delay (in the case of step function, Fig. 7.12) or
phase lag (sinusoidal function) because:
1. ions/molecules have to rotate in a viscous material (liquids, polymers, solids), this transfers
energy to medium (working principle of microwave oven, 2.45 GHz), causing energy loss
2. thermal agitation tries to randomize dipole orientation
- the dielectric response to electric field (delay, loss) is best described using a complex dielectric
function (): the real part (☺) signifies energy storage, the imaginary part () signifies loss.
Datasheet for dielectric usually state loss tangent () at frequencies of interest
- frequency dependency of complex relative permittivity in materials with
Case A: one polarization mechanism (simplest)
Case B: four polarization mechanisms (complex, hypothetical) ☺ 
 e r = e r − je r
e r
 tan  =
e r

Dielectric Properties 2102308 15

case A: material has one polarization mechanism
Na a dc
from e r = 1 + and a ( ) = the frequency dependency of real and imaginary parts
eo 1 + j
of the relative permittivity follows curves in (b)
P = Posin(t - )
out of phase
E = Eosint
er' and er''
er' e r = e r − je r
er (0) Dielectric resonance:
storage (C) • energy storage by field () =
• energy transfer to random
collisions (1/)
er''

1 loss (G)

0.01/ 0.1/ 1/ 10/ 100/
    
v = Vosint
(a) (b)
(a) An ac field is applied to a dipolar medium. The polarization P (P = Np) is
out of phase with the ac field. The relative permittivity is a complex number
with real (er') and imaginary (e r'') parts that exhibit frequency dependence.
Dielectric Properties 2102308 16
case B: material has many polarization mechanisms
e r − 1 Na a dc
from = ; a total = a if + a d + a i + a e ; a ( ) =
e r + 2 3e o 1 + j

Interfacial and
space charge

storage
Orientational,
er'
Dipolar

Ionic
Electronic
er''
loss er' = 1
a if ae
ad ai ƒ
10 2 1 102 104 106 108 1010 1012 1014 1016
Radio Infrared Ultraviolet light

The frequency dependence of the real and imaginary parts of the

dielectric constant in the presence of interfacial, orientational, ionic
and electronic polarization mechanisms.

In practice: one mechanism dominates at operating frequency

Dielectric Properties 2102308 17
 - the storage and loss characters of dielectric (in parallel plates) appear in the equivalent circuit ()
as an ideal (lossless) capacitor of capacitance C (☺) in parallel with a conductance G ()
- this can be derived from the basic definition of admittance ()
- important design parameters are loss per unit volume () and loss per unit capacitance ()

 Admittance of a parallel plate capacitor:

e e A r =e r − je r e e  A e e A
Y  j o r ⎯e⎯ ⎯⎯→ j o r + o r = jC + G ideal capacitor (lossless): jC
d d d
real capacitor (lossy): jC + G
e eA e εA
where C = o r ; G = o r
d d
V2
P = Posin(t -) Conductance = Gp = 1/Rp W = GV = 2

RP
 e r

W
☺
C
e r  Wvol = =  =  2e oe r tan 
dA

W
v = V osint v = V osint  Wcap = =  = V 2 tan 
C
EE basic definitions: quantity DC ac quantity real imaginary

I/V, i/v conductance (G) admittance (Y) Y = conductance (G) + susceptance (jB)

V/I, v/i resistance (R) impedance (Z) Z = resistance (R) + reactance (jX)

Dielectric Properties 2102308 18

 Ex. 7.6-7.7

At a given voltage, which dielectric will have the lowest power dissipation per unit capacitance at 60Hz? Is this also true at 1MHz?

Calculate the heat generated per second due to dielectric losses per cm3 of XLPE (power cable insulator) and Al2O3 at 60Hz and
1MHz at a field of 100kV/cm.
(from Kasap 3rd Ed., table 7.4 p.611)
f = 60 Hz f = 1 MHz

Loss/Volume Loss/Volume -1 -1
Material er' tan 
(mW cm )
-3 er' tan  -3
(W cm )
k (W cm K )

-4 -4
XLPE 2.3 3 x 10 0.230 2.3 4 x 10 5.12 0.005

-3 -3
Alumina 8.5 1 x 10 2.84 8.5 1 x 10 47.3 0.33

Dielectric Properties 2102308 19

 7.6 Dielectric strength and breakdown
7.6.1 Dielectric strength
• dielectric materials used as insulator between two conductors at different voltages to prevent
the ionization of air
• at high fields, all dielectrics fail (breakdown, become conducting)
• critical field is called dielectric strength (br)

arcing

corona discharge

Types of pole insulators:

- glass
- ceramic
- glass-ceramic

Dielectric Properties 2102308 20

 The nature of breakdown:
• breakdowns in liquid and gaseous dielectrics are temporary; in solids, permanent
(conducting channels physically created)
• dielectric strength (br) depends on frequency: different for DC and AC fields
• br depends on molecular structure, impurities, defects (esp. voids), geometry, T,
humidity, ...

Dielectric strength (br) of typical insulators

gas
(@ 1 atm)

liquid

glass
solid
polymer

Key: air (N2/O2, lower limit), glass (SiO2, upper limit)

Dielectric Properties 2102308 21

 7.6.2 Dielectric breakdown in gases
Mechanisms:
* corona discharge -- partial breakdown of air around curved electrodes, see fig. (a)
* partial discharge -- see figs. (b,c)
Crack (or defect) at dielectric-
High voltage conductor Void in dielectric electrode interface

e1
Gas e2

Ground
(a) (b) Partial Discharge (c)
(does not connect the electrodes)
Corona and Partial Discharges: (a) The field is greatest on the
surface of the cylindrical conductor facing the ground. If the voltage
is sufficiently large this field gives rise to a corona discharge. (b) The
field in a void within a solid can easily cause partial discharge. (c)
The field in the crack at the solid-metal interface can also lead to a
partial discharge.

Gauss: e11 = e22 → voids & cracks reduce br

Dielectric Properties 2102308 22
 Mechanism (physical origin): electron avalanche effect
(similar to reverse biassed p-n junction [2102385, C5])
• always a few free electrons (due to cosmic rays)
• under high fields, these electrons can accelerate and
impact ionize neutral gas atoms, giving electrons and
ions which conduct
• process repeat → avalanche
“Spacing” matter:

Remedies:
* increase conductor spacing d (decrease electric
field, E = V/d)
* increase air pressure: pressure  → mfp & mft 
→ average kinetic energy  → breakdown 
* replace dielectric: air → SF6

Dielectric Properties 2102308 23

 7.6.3 Dielectric breakdown in liquids
• mechanisms not clear, but probably due to:
• conductive particles bridging electrodes (in impure liquids)
• gas bubbles in liquids (after partial discharge  → local temperature  → bubble size )
• electrode injection (see next slide)

7.6.4 Dielectric breakdown in solids

Caused by intrinsic properties of dielectrics and environmental factors. Five main mechanisms:

1. Intrinsic (electronic) breakdown (by avalanche)

• initial electrons:
- pre-exist in CB of dielectrics
- electrode injection (see next slide)
• under br, electron move a distance l gains an energy of ebrl
• ebrl > EG → impact ionization (break valence bond)
• Ex: EG ~ 5 eV, l = 50nm → br ~ 1 MV/cm
• upper theoretical limits: occur only in high purity dielectric—e.g., SiO2 in MOSFET

Dielectric Properties 2102308 24

 Electrode Injection
= Enormous increase in the injected electrons from metal electrodes
Mechanism: electron tunnelling through thin potential barrier (Fowler-Nordheim)
Possible at: metal-air, metal-liquid, metal-solid interfaces
PE(x)
EF +  eff Vo
Grid or Anode
e- Cathode
EF EF
E

0 x
0 xF x = 0 x = xF
HV V
Metal Vacuum

(a) (dielectric) (b) (c)

(a) Field emission is the tunneling of an electron at an energy EF
through the narrow PE barrier induced by a large applied field. (b)
For simplicity we take the barrier to be rectangular. (c) A sharp point
cathode has the maximumfield at the tip where the field-emission of
electrons occurs.
Dielectric Properties 2102308 25
  Thermal breakdown  Electromechanical breakdown
• e.g., in ceramics and glasses • e.g., in polyethylene and polyisobutylene
• Two heat sources:
• Positive feedback:
1. s. finite conduction @ LF (Joules heat = s2)
F → d → C → Q → F  mechanical runaway
2. er. dielectric loss @ HF (V2 tan )
• Positive feedback: T  → (1,2)   thermal runaway  eA Q1Q2 
C = Q = CV F =k 
(Metals, r  T. Insulators, s  T)  d d2 
Two indicators/signatures of thermal breakdown • End results:
1. br depends on field duration due to heat capacity - plastic flow (viscous deformation)
(thermal lag) - cracks (electrofracture)
Example: Pyrex @ 70C
- pulse 1ms → br = 9 MV/cm - thermal breakdown (since  )
- cont. @ 30s → br = 2.5 MV/cm
+Q -Q
2. br depends on temperature:

V
polyethylene-based =
polymeric insulation d
F F

d
V

An exaggerated schematic illustration of a soft dielectric medium

experiencing strong compressive forces due to the applied voltage.

Dielectric Properties 2102308 26

  Internal discharge
Origin
• microvoids (manufacturing defects) → partial discharge (see 7.6.2) → erosion of local,
internal surfaces, then …
• voids propagate → tree branches (see next slide)
(hollow volumes in which gaseous discharge takes place and forms a conducting channel)
Remedy: prevent microvoids by improving manufacturing process
Example: Power Coax
polymer
M-S-I-S-M
M-I-M
• semi-PE surface has no
microvoids due to
PE manufacturing (extrusion
process draws sheaths and
PE at the same time)
• semiconducting →
equipotential (V) →
reduce local high field
PVC
regions () → no tree
Two types of dielectric:
1. PE, polyethylene, to maximize voltage
branches
2. PVC, polyvinyl chloride, to protect cable
(a) A schematic illustration of electrical treeing breakdown in a high voltage coaxial cable which was initiated
by a partial discharge in the void at the inner conductor - dielectric interface. (b) A schematic diagram of a
typical high voltage coaxial cable with semiconducting polymer layers around the inner conductor and around
the outer surface of the dielectric.

Dielectric Properties 2102308 27

Dielectric Properties 2102308 28
  Insulation ageing
Sources:
* physical: temp and mechanical stress variations → structural defects such as microcracks
* chemical: radiation, ambient, oxidation → deteriorate chemical structure
* electrical: dc fields dissociate & transport ion → structural change
ac fields → treeing
• in moist environment → microscopic voids containing water (or aqueous electrolyte)

Dielectric Properties 2102308 29

 Ebr
• Breakdown mechanism can change, depending on
operating conditions
SiO2, dc 10

Intrinsic • It is not possible to clearly identify a specific
Electronic
Electro-  breakdown mechanism for a material
mechanical
1 MV cm-1

  Internal discharges
and electrical trees
Thermal
100

Water trees
Air, 60 Hz
10

1 kV cm -1

1 ns 1 µs 1 ms 1s 1 min 1 hr1 day 1 mo 1 yr10 yrs

Time to breakdown
Time to breakdown and the field at breakdown, br, are interrelated and depend on the mechanism that causes
the insulation breakdown. External discharges have been excluded (based on L.A. Dissado and J.C. Fothergill,
Electrical Degradation and Breakdown in Polymers, Peter Peregrinus Ltd. for IEE, UK, © 1992, p. 63)

Dielectric Properties 2102308 30

 7.7 Dielectric Materials
Fundamental trade-offs:
• selection criteria: C, f, max. volt, acceptable loss
C-Vmax
• large C more easily obtained at low frequency (interface & dipolar polarizations) freq-loss

electrolytic

ceramic

polymer

ceramic

polymer

electrolytic

Dielectric Properties 2102308 31

 source: Wiki
Dielectric Properties 2102308 32
 Ceramic capacitors (high-er)
Non-polar

e r = 10 d = 10 m Metal termination Class 1 (low loss)

resonant, tuning
Epoxy A = 1cm2
Ceramic → C = 885 pF

Leads

Metal electrode

source: Wiki
A → C  100 F

(a) Single layer ceramic capacitor (b) Multilayer ceramic capacitor

(e.g. disk capacitors) (stacked ceramic layers)
Class 2 (volume efficiency)
Single and multilayer dielectric capacitors
buffer, coupling
MLCC status ferroelectric (doped)
2005: 100s F, 1,400 layers BaTiO3 (er ~ 100s – 1,000s)
2013: d = 0.5 m

Dielectric Properties 2102308 33

 Polymer film capacitors (low-er)
Polymers: low er but wide frequency response (low tan )
er  2 − 3
Al metallization
slightly offset to provide
means for connections
(a)

Polymer film

Polymers
(b) Market share: er @ 1 kHz:

50% (PP) 2.2

40% (PET) 3.3

(PEN) 3.0
(PPS) 2.0

Two polymer tapes in (a) each with a metallized film electrode on the
surface (offset from each other) can be rolled together (like a Swiss roll-
cake) to obtain a polymer film capacitor as in (b). As the two separate
metal films are lined at oppose edges, electroding is done over the whole source: Wiki
side surface.

Dielectric Properties 2102308 34

 electrolyte: ionic conducting liquid/solid
Electrolytic capacitors: (high-C)
Liquids er  9 Solids
by electrolysis * paper-soaked e r = 28
grown electrolytically, * conducting solid electrolyte
thin (0.1m), * makes good Epox y
responsible for large C contact with Al2O3 Ag paste
Silver paint

Ta 2 O 5 Graphite
Electrolyte Ta M nO 2 Silver paste
Al2 O3 Ta
Al foils Anode Cathode
50-100m

Al Al

Al case Lads

(a) (b)

(a) (b) Solid electrolyte tantalum capacitor. (a) A cross section without
Capacitive behaviour due to fine detail. (b) An enlarged section through the Ta capacitor.
Al/Al2O3/electrolyte
etched to make surface porous Polarity is important because Al/Al2O3 and Ta/Ta2O5 are
(A) before forming Al2O3 rectifying contacts → need to be reverse biased; otherwise,
 : liquids dry the structures conduct! (no longer insulate / store energy)
Dielectric Properties 2102308 35
 Comparison of dielectrics for capacitor applications
low C high C
7.7.2 high frequency low-medium frequency
Capacitor name Polypropylene Polyester Mica Aluminum, Tantalum, High-K ceramic
electrolytic electrolytic,
(C3H6)n (C10H8O4)n KAl3Si3O10(OH)2 solid (ferroelectric)

Dielectric Polymer film Polymer film Mica Anodized Al2O3 Anodized X7R
film Ta2O5 film BaTiO3 base
(see 7.8.3)
er 2.2 – 2.3 3.2 – 3.3 6.9 8.5 27 2000
tan 4  10-4 4  10-3 2  10-4 0.05 - 0.1 0.01 0.01
Ebr (kV mm-1) DC 100 - 350 100 - 300 50 - 300 400 - 1000 300 - 600 10

d (typical minimum) 3 - 4 µm 1 µm 2 - 3 µm 0.1 µm 0.1 m 10 µm

 Cvol (µF cm-3) 2 30 15 7,500a 24,000a 180

Rp = 1/Gp; C = 1 F; 400 kW 40 kW 800 kW 1.5 - 3 kW 16 kW 16 kW
1000 Hz

 Evol (mJ cm-3)b 10 15 8 1000 1200 100

Polarization Electronic Electronic and Ionic Ionic Ionic Large ionic
Dipolar displacement

Volume efficiency:
 Capacitance per unit volume Max energy per
 unit volume

Dielectric Properties 2102308 36

 
7.8 Nonlinear dielectrics
- normal dielectric materials are polarized
(polarization P) under electric fields (field
strength E): zero E, zero P (see )
- some dielectrics have non-zero P even at zero E

due to pressure (piezoelectric, ), or heat
(pyroelectric, )
- some (pyro & ferroelectric) even have 7.8.1
permanent or spontaneous polarization Ps (no
fields, pressure, heat required, )
- the direction of Ps in pyro cannot be switched 
(), in ferro can be switched () by E 

7.8.3
materials respond to:

dielectric
electric field

piezo
pressure

pyro
ferro 
heat

7.8.2
-

Dielectric Properties 2102308 37

 7.8.1 Piezoelectricity
- Piezoelectricity comprises a direct and a converse effect (Fig. 7.40)
- piezoelectric crystals must be non-centro symmetric (Figs. 11.7, 7.42)

(direct) piezoelectric effect converse piezoelectric effect

(a) P=0 (c) V

Pi = d ijT j S j = d ij Ei
Force
l
stress T =
F strain S =
A l
(b) P V (d) V

dij: piezoelectric coefficient

(or piezoelectric modulus)
PThe piezoelectric effect. (a) A piezoelectric
i = induced polarization along i
crystal with
Sj = induced no strain
mechanical
Tapplied stress or field. (b) The crystal isEstrained
j = applied mechanical stress along j
by an applied
i = applied electric field
force which induces polarization in the crystal and generates
surface charges. (c) An applied field causes the crystal to become
strained. In this case the field compresses the crystal. (d) The
strain changes direction when the field is reversed, and now the
Dielectric Properties
crystal is extended. The dashed
2102308
rectangle is the original sample 38
 - of the possible 32 point groups (Appendix), only 20 are non-centrosymmetric (Fig. 11.7)
- when centrosymmetric crystals are under pressure, the dipole changes cancel out (Fig. 7.41)
- when non-centrosymmetric crystals are under pressure, the dipole changes do not cancel,
resulting in net polarization P (Fig. 7.42)
- non-centrosymmetric requirements → only piezo crystals, not polycrystals or amorphous
- examples of piezo crystals and associated coefficients (Table 7.8)
- applications: (Fig. 7.43) direct and converse piezoelectric effects are complementary and
often used together in a transducer

Dielectric Properties 2102308 39

 Centrosymmetric crystals:
CoM of –ve & +ve charges coincide,
Force
even with external forces

O P=0 P=0

(a) (b)

A cubic unit cellA has a center of symmetry.

Non-centrosymmetric crystals: y force the centers
(a) In the absence of an applied A' of mass for positive
* CoM of –ve & +ve charges shifted and negative ions coincide. (b) This situation does not change when
under stress → P the crystal is strained by an applied force.
x
* Direction of P can be different from O P=0 P
those of applied force
B'
B A''

(a) P=0 (b)

B''
Dielectric Properties 2102308 (c) 40
 1

PbZrO3 + PbTiO3

0. standard piezo crystals (large d but ceramics cannot be bent)

1. most widely used: a quartz (Figs. 11.9-11.10)
2. light/flexible: polymers (Fig. 11.12)

Dielectric Properties 2102308 41

 a quartz
- chemically SiO2; structurally, not amorphous, not single crystal, but ...
− a helix: helices () of distorted corner connected SiO4 tetrahedra (Fig. 11.10a)
- tetrahedral unit (Fig. 11.9): internal dipoles cancel, but when force F applied, net dipole p results
- quartz unit cell (Fig. 11.10): internal dipoles cancel, but when force F applied, net dipole p results

helix double helix

 a helix

Dielectric Properties 2102308 42

 polymers
- rely on permanent dipoles on polymer chains: strong polar bonds (C—F, C—Cl, C—N), H-bonds
- example units, chains: PVF (Fig. 11.12a, c); PVDF (Fig. 11.12b, d)—to form isotactic chains
(maximum dipoles) the polymers must be poled during cooldown
- without poling, polymer crystallizes into centrosymmetric form (Fig. 11.14a), thus nonpiezoelectric
- with poling, polymer crystallizes into non-centrosymmetric form (Fig. 11.14b), thus piezoelectric

Dielectric Properties 2102308 43

 Applications
Applications involve (electrical  mechanical): ultrasonic transducer, microphone, oscillator,...

Seiko Astron 35SQ

World's first Quartz watch
December 1969

Elastic
Mechanical
waves in the
vibrations
solid
Piezoelectric
transducer

A B

Oscillator Oscilloscope

Dielectric Properties 2102308 44

 Ex. 7.13
Given piezoelectric coefficient d = 25010-12 m/V and er = 1000, piezoelectric cylinder has a
length of 10mm and diameter of 3mm. Spark gap is in air and has a breakdown voltage of about
3.5kV. What is the force required to spark the gap? Is the force realistic?

soln F

F
P = dT = d  F
A
A
P ⎯(⎯ ⎯→ Q ⎯(⎯
Q = AP )
⎯→ V
Q = CV )
Piezoelectric

F = L Piezoelectric V

Piezoelectric

F
F
(a) (b)
The piezoelectric spark generator

note: J = W.s = N.m

Dielectric Properties 2102308 45
 7.8.2 Ferroelectric
- ferroelectric crystals have spontaneous or permanent polarization (even without applied field)
- example: perovskite BaTiO3 where small cation (Ti4+) displaced from the center of unit cell, thus
internal dipole, results in increased overall stability (Fig. 7.46, next slide)
- origin of ferroelectricity comes from long-range dipolar interactions (vs short-range chemical
bonds between atoms). If the interaction results in parallel internal dipoles, we have ferroelectric
(Fig. 11.5), but if antiparallel we have antiferroelectric materials (Fig. 11.10), Table 11.2
- the long-range dipolar interactions (resulting polarization) is reduced by increasing temperature.
At the Curie temperature TC, the dipole orientations are random and the material becomes
paraelectric (Fig. 11.21)
- ferroelectric is a subset of piezoelectric: it responds to external force F which causes change of
polarization P (Fig. 7.47)
- ferroelectric is a subset of dielectric: it responds to electric field E which causes change of
polarization P. The P-E characteristic is hysteresis (Fig. 18.35). (hysteresis = “to lag bebind”)
- “ferro-” in analogy to ferromagnetic (such as Fe) that posses permanent magnetization
- ferroelectric, ferromagnetic are ferroic materials (that exhibit hysteresis and domain structure)

Dielectric Properties 2102308 46

 BaTiO3 (Curie temperature = 130C)

c/a = 1.01
a = 4Å

For BaTiO3: er along

a axis = 4,100
c axis = 160

Perovskite (ABO3)
think of cubic lattice with
Ba at corners of cube (sc)
O at every face center (fcc)
Ti at body center (bcc)

- practical ceramic ferroelectrics are polycrystalline; internal dipoles in different domains sum to zero, hence
no ferroelectricity unless they are poled
- Poling: manufacturing process whereby electric field is applied during crystal cooling which leads to well-
defined polarization direction at T < TCurie
Dielectric Properties 2102308 47
 ferroelectric antiferroelectric

ferroelectric paraelectric

Dielectric Properties 2102308 48

Dielectric Properties 2102308 49
 Ferroelectric ⊆ Piezoelectric

y P

x
P

Ferroelectric ⊆ Dielectric
P-E characteristic
p =a
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson

P Np
Learning™ is a trademark used herein under license.

field (V/m)
polarizability (F.m2)
P dipole moment (C.m)
molecules/volume (/m3)
 polarization (C/m2)

P = a
P = a
a = e 0 (e r − 1)
Figure 18.35 Ferroelectric hysteresis loops
Dielectric Properties 2102308 50
 7.8.3 Pyroelectricity LiTaO3 pyroelectric heat detector

“Pyro” = fire, heat

- pyroelectric crystals must be noncentro-symmetric + have unique polar axis (internal dipoles
spontaneously lie parallel to this axis)
- Examples i) BaTiO3 under heat yields measurable voltage proportional to heat (Fig. 7.48), due
to T → Ti4+ shifted → Ps. ii) LiTaO3 operates similarly (above). iii) wurtzite ZnS (Fig. 11.8)
- the sensitivity of pyroelectric crystals is reflected by the pyroelectric coefficient p: the ratio
between the change in permanent polarization Ps to the change in temperature T
Temperature change = T
Ps
p=
T

Heat

P V

Dielectric Properties 2102308 51

 pyroelectric material used in human/animal intruder detector systems

Ex. For PZT, how much voltage is generated over a 0.1mm gap when the temperature change is 1mK?

Dielectric Properties 2102308 52

 self-study

https://th.mouser.com/new/Kemet-
Electronics/kemet-pyroelectric-sensor-modules/

Dielectric Properties 2102308 53

Dielectric Properties 2102308 54