Dielectrics

1
 Electronic Conduction
electric field Ε VA 1 1
resistivity,      
current density J l I  conductivity

V = voltage; I = current; A = area; l = length

2
 Bonding in Solids

Ionic

Covalent Metallic
3
 Electron Energies in Crystals
• In general, bonding implies that the electron orbitals of adjacent atoms overlap
• Neighbouring electrons cannot posses the same energy (Pauli Exclusion Principle)
• The electrons therefore occupy a spread of energy levels or “bands”.
• Certain energies are left unoccupied – the “band gap”.

This result can also be derived by

solving Schrödinger's equation for
an electron in periodic potential

4
 Band Theory of Conduction

• This description of energy bands is used to explain conduction in

crystalline (and to some extent non-crystalline) materials
• We generally only need consider two energy bands
– The highest filled or partially filled band, often know as the valence band, as
the occupancy of this band is linked to the valency of the ions
– The next higher energy band into which electrons may be “promoted”; this is
often known as the conduction band
• It is assumed that electrons are free to move in partially filled bands
– i.e. under electric fields they will traverse the lattice
• In filled bands the electrons are not free
– They are “localized” or tied to the nearest ion

5
 Band Structures

The various possible electron band structures in solids at 0 K.

(a) The electron band structure found in metals such as copper, in which there are available
electron states above and adjacent to filled states, in the same band.
(b) The electron band structure of metals such as magnesium, wherein there is an overlap of filled
and empty outer bands.
(c) The electron band structure characteristic of insulators; the filled valence band is separated
from the empty conduction band by a relatively large band gap (>2 eV).
(d) The electron band structure found in the semiconductors, which is the same as for insulators
except that the band gap is relatively narrow (<2 eV).

6
 Intrinsic Semiconductors

• Intrinsic semiconductors are dominated by the behaviour of a “pure” crystal

• The valence band is completely full at 0 K; the conduction band is empty
• As temperature is increased, electrons gain sufficient energy to cross the band gap to the
conduction band, where they can move under an applied field.
• The conduction electrons leave “holes” in the valence band which can also move under
applied fields and contribute to the conductivity
• Concentration of electrons in conduction band (n) = conc. of holes in valence band (p)
• If we want to calculate the conductivity we need to know how many electrons are in the
conduction band
7
 Extrinsic Semiconductors
• Extrinsic semiconductors include aliovalent impurity atoms which either
put an extra electron into the conduction band (donors/n-type) or trap one
from the valence band (acceptors/p-type) leaving a hole.

• In both cases the conductivity is increased but the equality of

concentrations of conduction electrons and holes is broken: n ≠ p

8
Donor and Acceptor States
For a sufficiently large
number of impurities,
the extrinsic conduction
dominates the intrinsic

9
 Dielectrics – Basic Principles
• Initially, we consider dielectrics to be
insulators
– Later we will treat them as large band-gap
semiconductors E=0
• When an electric field is applied a
continuous current cannot flow as there are
almost no free carriers….
• …but, the fixed charges, or charge
distributions, can be distorted, resulting in a
charge on the surface of the dielectric. --------

• Also, there is a slight change in the

dimensions E≠0
– This is known as electrostriction

• It is easiest to consider the properties of

dielectrics from the point of view of a
capacitor +++++++

10
 The Parallel Plate Capacitor
• When a voltage, V, is applied across two parallel
plates in a vacuum a charge, Q, develops
• Experimentally we find that ++++++
– Q V A/d d
• The constant of proportionality is known as the - - - -Area
- -=A
permittivity of free space, e0 (= 8.845 x 10-12 F m-1)
– Q = e0 V A/d
• The capacitance, C, is the ratio of charge to voltage
– C = Q/V = e0 A/d
• Remember that the field inside the plates, E, is V/d,
hence, the surface charge density, , is given by
–  = Q/A = e0 E
• On filling the gap with a dielectric material, it is ++++++
found that the surface charge density and d
capacitance increase by a factor er, which is material - - - -Area
- -=A
specific and known as the relative permittivity*
– C = e0erA/d
– permittivity = e = e0er

*Also sometimes the “dielectric constant”

11
 Permittivity and Susceptibility
• The surface charge density of the filled capacitor comprises two contributions
– The original surface charge density of the unfilled capacitor, , ….
– ….and that contributed by the dielectric material…
– ….which is known as the polarization, P.
• P is the “electrical analogue” of strain
– i.e. it represents how much the charge distribution is distorted by the “electrical
stress” (or field)
• We define the susceptibility, c, by
– e0c = P/E
• Its relationship with relative permittivity is
– er = c + 1
• For most dielectrics of interest, er ≥ 10 we can ignore the “1”.
• When a field is applied to a dielectric we create not only the “electrical strain”
or polarization, P, but also a true elastic strain, x.
• The two are found to have a quadratic relationship
– x = Q P2
– Where Q is known as the electrostriction coefficient
• The electrostrictive strain is vanishingly small, except for materials with very
high relative permittivities

12
 tan d
• In practice, most dielectrics are not perfect insulators
– They allow some charge transport or loss of energy
– They are termed as being lossy
• A lossy capacitor is usually represented by a capacitor and resistor in parallel
R
V
i

i
V

• In AC circuits the current and voltage in a purely capacitive circuit are 90o or
p/2 radians, out of phase
• For a lossy capacitor the phase angle is p/2 – d
• Where tan d = 1/(w R C)
– Note: w = 2pf

13
 Complex Permittivity
• Not all energy losses in dielectrics are due to conductivity
• We can envisage some parts of the polarization process that do not exactly
follow the applied ac field (i.e. there is a phase lag)
• We could think of these processes as being due to some type of dielectric
“friction”
• We can therefore represent these processes by allowing part of the permittivity
to lag by 90o
• This is equivalent to saying that the permittivity has real (e/) and imaginary
(e//) parts
– e* = e’ + i e’’
• The imaginary part is the lossy part and it can be shown that
– tan d = e’’/e’

14
 Polarization Mechanisms
• When a field is applied to a dielectric there are a
number of charge displacement mechanisms which
contribute to the polarization
• These are generally distinguished by the speed with
which they can follow an AC field
• The most prevalent are:
• Electronic
– Orbitals are distorted by the field
– Can respond up to optical frequencies
• Ionic
– Positions of ions are shifted changing the length of
dipoles
– Responds up to the microwave region
• Molecular/Dipolar/Orientation
– Distortion and rotation of molecules e’’
– e.g. water
• Space charge
– Charge carriers become immobilised at interfaces or
potential barriers

• Each mechanism “relaxes” at a different frequency,

– with the appearance of a step change in the real part and
a peak in the imaginary part of permittivity

15
 Debye Relaxation

Debye relaxation is the most common form of frequency dependence of

permittivity for non-electronic polarization mechanisms

es  e
e   e +
1 + w 2 2
w
e  e s  e  

1 + w 2 2

es is the static permittivity

e∞ is the high frequency permittivity
 is the relaxation time
16
 Defect Chemistry
• Most insulators are considered as wide band-gap semiconductors
• Defect species can act as donors, acceptors or charge carriers
• Example: titanium dioxide (TiO2)
– Titanium vacancy
– For a titanium ion (4+) to leave the lattice it must take 4 electrons with it
• Ti4+ + 4e = Ti
– However this leaves 4 holes in the valance band; hence the vacancy could act as an
acceptor
– Similarly an oxygen vacancy leaves two electrons behind
• O2- = ½ O2 + 2e
– N.B. removing a single TiO2 unit leaves the crystal neutral as the electrons and
holes cancel out
– The details of the lattice will determine whether these charges are localised or free
to move
– In the case of the oxygen vacancy, the electrons generally add to the conductivity
– However, the vacancy itself looks like a charge carrier
• Compared to the normal oxygen site (O2-) in the neutral crystal the vacancy has a relative
charge of 2+
• At elevated temperatures, the vacancy can move through the lattice under applied fields
and so adds to conductivity

17
 Kroger and Vink Notation
• The creation of defect species are described using the Kroger and Vink
notation:
– Defect reactions are described using equations
– The equations must balance in terms of
• The number of atoms/ions of each element
• The number of lattice sites
• The total charge
– Elements are denoted by their chemical symbol; a vacancy is denoted by the letter
V; electrons by “e” and holes by “h”
– The site of a species in the lattice are demoted by a subscript showing the normal
element occupying that site
– Charges are shown as a superscript relative to the normal charge on the lattice site in
the defect fee crystal; negative charges by the oblique superscript “ / ”; positive
charges by a dot “ · ” and neutral by a cross “ x ”
– Unchanged species are not shown on both sides of the equation
• Example: oxygen vacancy creation in TiO2:

OOX  12 O2  +VO + 2e/

18
 Dopants and Impurities
• The same type pf notation is used to examine what happens when we have
impurities or dopants
– E.g. niobium in TiO2

Nb2O5  2NbTi + 4OOx + 12 O2  +2e/

• More examples:
//
CoO  CoTi + OOx + VO
//
CoO + 12 O2  CoTi + 2OOx + 2h 
• Even though we may be able to write a correctly balanced equation, it
doesn’t mean that the mechanism actually happens
• We need to study the thermodynamics of the mechanisms
• In oxides this is often done by measuring the conductivity as a function of
temperature and the partial pressure of oxygen.

19
Ferroelectrics

20
 Ferroelectrics
• Ferroelectric materials exhibit a polarization, even in
zero field
– They are self-polarizing: they exhibit a “spontaneous
polarization”
– The spontaneous polarization can be reversed by the
temporary application of a sufficiently high field
• The perovskite barium titanate (BaTiO3) is a typical
example
• It can be seen from the crystal structure that the centre
of positive charge does not coincide with the centre of
negative charge

21
 Landau Theory of Phase Transitions
• To describe ferroelectric phase transitions P 1.0
we need a free energy function (G),
for which DG becomes < 0 at 0.8

non-zero P, for T < Tc.

0.6

0.4
• This works for
DG   P 2 +  P 4
0.2

with    T  TC  0.2 0.4 0.6 0.8 1.0 1.2

T/Tc

• Stable solutions exist when

T > Tc
DG 0.30
dDG T = Tc
 0  2P + 4 P 3  0 0.25

dP 0.20

 T < Tc
 P  0 or P  0.15

2 0.10

0.05

0.5 0.5

0.05
P

22
 Curie-Weiss Law
• Also
d 2 DG 1
  2 + 12  P 2

dP 2 e
1 1 C
e T TC    ; the Curie  Weiss law
2 2 T  Tc  TC  T
and
1 1
e T T  
C
4 4 T  Tc 

1/e e
2.0

1.5

1.0
4

0.5
2

0.8 1.0 1.2 1.4 0.8 1.0 1.2 1.4

T/Tc T/Tc

23
 1st and 2nd Order Transitions
• The above is true for continuous or 2nd order transitions (no jump in P at TC)
–  is positive
• For first order (discontinuous) transitions  is negative,
necessitating a term in P6 0.25

DG   P 2 +  P 4 + P 6 0.2

C m- 2
where    T  T0  0.15

P /
0.1
• Similar solutions exist, but TC< T0
0.05

0.0008 0
300 350 400 450 500
T / K
0.0006 14000
12000
1/ er

0.0004 10000
er 8000
6000
0.0002
T0 4000
2000
0
0
380 400 420 440 380 400 420 440
T / K T / K
T0 Tc
These graphs are the model data for barium titanate BaTiO3
24
 Ferroelectric Domains
• In most “as-prepared” ferroelectric materials, the
direction of polarization is not homgeneous.
• The material partitions into domains in which the
directions of polarization represent the possible variants
of polarization in the crystal
– e.g. in a tetragonal perovskite there are 6 possible directions
– How many are there in a rhombohedral perovskite ?
• There are two driving forces for the creation of domains:

1. On cooling through Tc the polarization, P, is 2. The change of lattice parameters at Tc results in

established, creating surface charge, which in turn stresses being placed on a clamped crystal (e.g. in a
creates the depolarization field, Ed. The crystal ceramic). The crystal partitions into ferroelastic
partitions into 180o domains to minimize the domains to minimize the shape strain and reduce
depolarization energy (= P. Ed), effectively elastic stress. In a tetragonal system these are 90o
eliminating the surface charge. domains
+++++++
P P

Ed
- - - - - - -
25
 Domain Images
• Images of domains can be observed using SEM n polished and etched sections,
or with TEM on thin sections

10 m

26
 Domain Switching
• After cooling through Tc there is zero net polarization due
to domain formation
• The process of polarization reversal, as manifest in the E=0
hysteresis loop, proceeds via the movement of domain
walls not by simultaneous polarization reversal throughout
the cystal a c a
• If a constant field, of sufficient magnitude, is applied
parallel to one of the principle axes of the crystal then a
permanent* rearrangement of the domains is achieved, to
provide a remanent polarization
• Poling is the means by which randomly oriented ceramics
can exhibit macroscopic polarization

E
a
c
a
*domain walls are subject to
slow relaxation effects which
result in ageing of the
ferroelectric properties

27
 Perovskites
• The family of materials with the perovskite
structure represent one of the more
commercially important groups of
ferroelectrics, accounting for the majority of
applications
• The formula is ABO3, where A and B can be
a wide variety of metals and where the
valence of A and B must add up to +6

A+ B5+ State at RT A2+ B4+ State at RT A3+ B3+ State at RT

KNbO3 Ferroelectric BaTiO3 Ferroelectric BiFeO3 Ferroelectric

Ferromagnetic
NaNbO3 Antiferroelectric BaZrO3 Paraelectric LaAlO3 Paraelectric

KTaO3 Paraelectric PbTiO3 Ferroelectric BiScO3 Ferroelectric ?

NaTaO3 Ferroelectric PbZrO3 Antiferroelectric

AgNbO3 Ferroelectric SrTiO3 Paraelectric

28
 Ferroelectric-Ferroelectric Phase Transitions

• Often, and particularly in the case of

perovskites, there are transitions between
different ferroelectric phases

Cubic Tetragonal

Orthorhombic Rhombohedral

29
 Applications of Ferroelectrics
• Ferroelectrics are used for a wide variety of applications
• This is due to the fact that the polarization can influence, or be influenced by, a
variety of external inputs or outputs
• Each application requires a specifically optimised material
• There are a limited number of variables, or design elements, that may be
manipulated in ferroelectric ceramics to achieve a tailored material solution
– Can be used as a model for other types of electroceramic

Property Coupling Devices

Polarization reversal Electric field Memories
Permittivity Electric field Capacitors
Piezoelectricity Pressure Sensors
Field Actuators, resonators
Pyroelectricity Temperature IR imaging
PTC effects Conductivity Thermistors
Electro-optic effect Light Modulators

30
 Electroceramics Design Features
• The wide variety of applications for ferroelectrics and other ceramics
demands that we have methods to modify their properties.
The features over which we have some control and which can be
used to tailor the properties are summarised below.

Intrinsic
• Crystal Chemistry
– Structure, ionic radii, polarizability
– Isovalent substitutions, solid solutions, phase transitions

Extrinsic
• Defect chemistry
– Equilibrium defect concentrations
– Kinetic factors; diffusion coefficients

• Microstructure
– Grain size, grain boundaries
– Domains (ferroelectric, ferroelastic, ferromagnetic)
– Micro-heterogeneity

• Nanostructure
– Defect clusters
– Lattice ordering
– Nano-domains

31
 Crystal Chemistry - Structural Phase Transitions
• Perovskite structure accommodates large range of ions
• Distortions from cubic include:
(rA + rO )
– Distortion of oxygen octahedron t
– Displacement of central ion 2 (rB + rO )
– Tilting of octahedra
Goldschmidt tolerance factor

Cubic Tetragonal

Orthorhombic Rhombohedral
e.g. BaTiO3

32
 Crystal Chemistry - Solid Solutions
e.g. BaTiO3

Hennings, Schnell & Simon

(1982)

Jaffe, Cook & Jaffe (1971)

33
 Microstructure
• Major extrinsic influence on functional properties
– Grain
• size
• shape
• orientation

– Grain boundary
• composition
• width

– Domains
• size
• morphology
• mobility

34
 Microstructure - Textured Ceramics
• Ferroelectric crystals are anisotropic; most ceramics are isotropic with
randomly oriented grains
• Correctly “textured” polycrystalline materials can have enhanced
properties compared to randomly oriented materials
• Methods of orientation include:
– Mechanical orientation of acicular particles – tape-casting, extrusion
– “Seeding” with large acicular crystals – “templated grain growth”
– Field-orientation
• Shape anisotropy of perovskite powders is small
• Electrical anisotropy is high

Example: PbNb2O6 produced by templated grain growth

35
Ceramic Capacitors

36
 Ceramic Capacitors
A
• €200 billion sales, > 1012 units, p.a. world-wide
t
• Requirements for minimum component size
– large capacitance per unit volume εo εr A
C
t

• Specification a multilayer capacitor C  εo εr

V t2
– high permittivity dielectric (er = 4000) e.g. BaTiO3
• but with < 15% variation from –55 to +125oC
– ceramic layer thickness 5 to 50 m – lower limit is breakdown dependent
– electrode thickness 1 to 3 m
– > 50 layers per part
– > 99% density => high breakdown voltage
A
– co-sintering of ceramic and metal layers C m  εo εr  n2C
– volume > 10 million units per day t
n
– unit cost < 1p

37
 Multilayer Capacitors

1206: 3.2 x 1.6 x 1.5 mm

0402: 1.0 x 0.5 x 0.6 mm
0201: 0.5 x 0.25 x 0.3 mm !!

State of the art 2001

K  2800; 10µF /1206
300 layers @ 3 µm
E > 1 kV mm-1

Courtesy of Philips Components

38
0201 MLCs

39
 Z5U Capacitors
• The temperature dependence of
permittivity of pure barium titanate is
unsuitable for the majority of
electronic applications
• The electronics industry calls for
standards on temperature variation of
capacitance
– e.g.
DT / °C DC / %

Z5U +10 to +85 +22, -56

X7R -55 to +125 +/- 15

• Phase transitions can be modified by

solid solution to meet Z5U
– Shifts peak in permittivity due to
isovalent substitution of Ti4+ by Zr4+

40
 X7R Capacitors
DT / °C DC / % • For the more demanding X7R specification,
-55 to +125 +/- 15
two effects are used simultaneously
– Intra-grain heterogeneity flattens temperature
dependence
– Grain size dependent permittivity increases
permittivity

Room temperature permittivity

of >4000 can be achieved
41
 “Core-Shell” Behaviour in X7R Dielectrics
• About 1 at % of Nb5+ is substituted for Ti4+
• This segregates to the grain boundaries and acts as a grain
growth inhibitor
– In very fine grains (~ 1m) the stresses due to the
ferroelectric phase transition cannot be completely relieved
by 90o domain formation
– The internal stress increases the permittivity
• Also the Nb5+ decreases the phase transition temperature
in a similar way, but more powerfully than Zr4+
– At the grain boundary Tc < room temperature, but Tc
increases towards the grain centre, where as pure BaTiO3 Tc
= 130oC
– The radius at which Tc = room temperature can be seen as
the boundary of the domain structure
• Nb5+ acts as a donor in BaTiO3
• To avoid high conductivity and high dielectric loss, the
material is doped with an acceptor dopant to create holes
Bi3+ substituted for Ba2+
which trap the donor conduction electrons
has a similar effect to Nb5+
– Normally Co2+ is substituted for Ti4+ to act as the acceptor

42
 Manufacture - Tape-Casting
• Doctor Blade moves relative to carrier Reservoir
Blades
– Flat bed => stationary carrier (glass, steel) adjustable height
– Continuous => stationary blade
(carrier = polymer or steel band)
– Speed > 1 cm s-1
• Tape thickness
– 5 to 1000 m
– Dependent on blade height,
casting speed and rheology
• Rheology
– Shear-thinning preferred Casting slip
with viscosity at low
Carrier
shear > 4000 mPa s

Slip Components
powder
binder
solvent
plasticiser
dispersant
drying aids
de-foamers

43
 Powder Production
• Requirements • Conventional process
– Fine particle size (~ 0.7 m) – Mixed oxide route from commodity
• Rapid sintering, high permittivity chemicals
– Tight size distribution 1100oC
• Control of sintering, avoid pore – BaCO3 + TiO2 => BaTiO3 +CO2
entrapment – Mill-calcine-mill
– Low cost • Disadvantages
• Raw materials, energy costs
– Particle size – 1 to 2 m
– Poor purity – pick-up from mills and
furnace
• Interference with doping levels
– Poor stoichiometry & homogeneity
control (Ba/Ti ratio)

44
 Oxalate Process
• Precursor salt precipitated by the addition of oxalic acid to an aqueous chloride solution
•
BaCl2 + TiCl4 + 2H2C2O4
=> BaTiO(C2O4)2.4H2O + 6HCl + 6H2O

– Precipitation conditions can be controlled (temperature, concentrations) etc, to control

precipitate size
– High pH keeps impurities (e.g. Al, Fe) in solution

• Pyrolysis of oxalate at 700oC results in formation of BaTiO3

BaTiO(C2O4)2.4H2O +1/2 O2
=> BaTiO3 + 4H2O + CO + 3CO2

• Low processing temperature

– Maintains fine particle size
– Aids sinterability/reactivity
– Reduces cost

45
 Dry Stack Process - 1
• Stacking of printed green sheets
– mix casting-slip
– tape-cast
– (strip)*
– print internal electrodes (Pd or Ni)
Component Role Vol %
– (strip)* barium titanate ceramic 28.0
* alternative positions depending upon method acry lic emulsion binder 6.7
– stack/laminate methy l ethy l ketone solvent 33.0
• pressure + heat ethanol solvent 16.0
– dice p oly ethy lene gly col 400 p lasticiser 6.7
buty l benzy l p hthalate p lasticiser 6.7
– binder burn-out (400 - 600oC)
fish oil disp ersant 1.7
– fire cy clohexanone dry ing aid 1.2
– apply external metallisation 100.0
• Features
– most common multilayer process
– lab-scale (100 mm wide) to large scale (1 m wide)
– flexible, accommodates different prints/materials
– alignment is important
• variety of registration techniques
– excessive tape-handling can impact on quality

46
Dry Stack Process - 2

47