H. S.

Leipner: Physics of materials

9. Dielectric properties

+ − + − + − + − + − + − 1. Polarization mechanisms
+ − + − + − + − + − + − 2. Dielectric constant
+ − + − + − + − + − + −
3. Piezoelectricity
+ − + − + − + − + − + −
4. Ferroelectrics
+ − + − + − + − + − + −

+ − + − + − + − + − + − 5. Dielectric breakdown
+ − + − + − + − + − + − 6. High and low-k dielectrics
 Introduction

 Electrical conductivity very small; insulators

 They are, however, affected by an electric field.
 Capacitance of a parallel plate capacitor

(vacuum/air) (with dielectric) Stored energy

Dielectric

+ − + −
− Parallel plate capacitor with plates
+ − +
+ − + − of area A and separation d. When a
− +
− dielectric material is placed
+ − +
+ − d + − between the plates, the dielectric
+ − −
+ becomes polarized.

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 2

 Design of ceramic capacitors

Examples of ceramic capacitors. Single-layer ceramic capacitor (disk capacitors)

and multilayer ceramic capacitor (stacked ceramic layers).

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 [Askeland 1994/Kasap 1997] 3
 8.1 Polarization mechanisms

Effect of an electric field on an isolated atom

G+ G−

The electron orbits of an isolated atom in an electric field are distorted. The
centroids of charge are separated by a distance d.

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 Dipole moment

 Dipole moment of one atom induced by the external electric field

Pa = qd
 Polarization of a dielectric crystal (dipole moment per unit volume)
P = Nqd
E
− +
+ −
+ − + − + − + − + − + −
+ −
+ − + − + − + − + − + −
+ + − + − + − + − + − + − −

+ + − + − + − + − + − + − − Dielectric crystal as an ensemble

+ + − + − + − + − + − + − − of atomic dipoles. As a result of
+ − + − + − + − + − + −
the application of the external
+ −
electric field, a surface charge
+ − + − + − + − + − + −
+ − appears.

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 5

 Polarizability

 Macroscopic polarization (surface charge density)

P = ε 0 χE
(χ = εr – 1, electric susceptibility)
 Similarly, the atomic dipole is proportional to the field,
Pa = αpEloc
Local electric field
 If the differences in the local field for surface atoms are not taken
into account, we get
P = NαpEloc

 The polarizability αp can be expressed with the dielectric constant εr,

taken into account the relation between the external and local electric
field

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 6

 Other polarization mechanisms

 In ionic crystals, the applied electric field pulls the kations and
anions in different directions.
 The result is an ionic contribution to the polarization, Pi.

di E Ptot = P + Pi
+ −
Na+ Na+ Na+ Pi = Nqidi

Cl− Cl− Cl−

Na+ Na+ Na+ The effect of applying an electric

field to the positions of the ions
in a NaCl crystal
Cl− Cl− Cl−

di

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 Polar molecular crystals

 Materials with molecules of a permanent dipole moment

 Dipole moment much larger than the induced dipole moment in
nonpolar molecules → much higher dielectric constant
 Normally in a solid the molecules are fixed and cannot follow the
electric field, but there are exceptions, e. g. hydrogen chloride.

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 Temperature variation of dielectric constant

εr

e−
e−
e−
e− Cl− e− H+

e− e−
e−

The HCl molecule and variation of the dielectric constant εr with temperature T for HCl.
The abrupt change corresponds to the temperature at which the molecules are no longer
able to align themselves with the external electric field.
[Turton 2000]

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 Dielectric constant HCl 9
 8.2 Dielectric constant

Time

For a slowly varying field E, the polarization P is expected to vary at the same
frequency.

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 Polarization vs time 10

 High-frequency dielectric constant

High frequencies (optical range, ν ≈ 5·1014 Hz)

 Dielectric constants from electromagnetic theory

 Speed of light

(vacuum) (inside the dielectric)

 Thus, or εopt = nˆ2 (nˆrefractive index)

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 Dielectric constant at optical frequencies

Material εs εopt

Diamond 5.68 5.66

NaCl 5.90 2.34
LiCl 11.95 2.78
TiO2 94.00 6.80
Quartz 3.85 2.13

Values of the dielectric constant in a static electric field,

εr = εs, and at optical frequencies, εr = εopt
[Turton 2000]

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 Dielectric constant

 Usually, the static dielectric constant is higher.

 Electrons can quickly follow the alternating electric field.
 However, the ionic contribution to the polarization becomes much
smaller.
 The ions cannot follow the quick change of the field.
 At high frequencies, only the induced polarization remains.

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 Survey of polarization mechanisms
E

Polarization mechanisms in
E – + materials: (a) electronic, (b)
– +
– + ionic, (c) high-frequency
– + dipolar or orientation
– +
(present in ferroelectrics), (d)
E low-frequency dipolar
(present in linear dielectrics
and glasses), (e) interfacial
space charge at electrodes,
and (f) interfacial space
charge at heterogeneities
(c) (f) such as grain boundaries.
E E
hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 [Askeland 1994/Hench, West 1990] 14
 Frequency dependence

Polarization
Molecular

Ionic

Electronic

104 108 1012 1016 1020

Frequency (Hz)

Frequency dependence of polarization mechanisms

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 15

 8.3 Piezoelectricity

 In certain dielectric materials, the application of an external stress

produces electrical charges on the surface.

F F

 Converse piezoelectric effect: A piezoelectric material becomes

strained when placed in an electric field.
Δl

E
hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 16
 Dielectric effects

 When any material undergoes polarization, its ions and electronic

clouds are displaced, causing the development of a mechanical strain
in the material. This effect is seen in all materials subjected to an
electric field and is known as the electrostriction.
 Piezoelectrics – materials that develop voltage upon the application
of a stress and develop strain when an electric field is applied.
 Pyroelectric – the ability of a material to spontaneously polarize and
produce a voltage due to changes in temperature.
 Ferroelectric – a material that shows spontaneous and reversible
dielectric polarization.

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 Piezoelectric crystals

Inversion center

−
−

3+
3+
− −
− −

When a stress is applied to a crystal structure with three-fold symmetry and zero
polarization, the symmetry is altered and the material acquires a non-zero
polarization even without an electric field.

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 Piezoelectric coefficients

~ ~g (mV m/N)
Material d (pC/N)
Quartz 2.3 50
BaTiO3 190 12
PZT 268 to 480 12 to 35
PbNb2O6 80
PbTiO3 47
LiNbO3 6
LiTaO3 5.7

[Askeland 1996]

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 Design of a spark igniter

 Example: A PZT spark igniter is made using a disk that has a 5 mm

diameter and 20 mm height. Calculate the voltage generated
if the ~g coefficient for PZT used is 35 mV m/N. Assume that
a compressive force of 10 kN is applied on the circular
face.
 Solution:
Definition of the g~ coefficient
Stress σ = F/A = 5.09 MN/m2
Therefore, the electric field is E = g~σ =1.78·105 V/m
U = E d = 3565 V.

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 20

 8.4 Ferroelectrics

 Material with a finite polarization even in the absence of any

external electric field or applied stress
 Name misleading: nothing to do with iron; properties resembles
those of ferromagnetic solids
 Hysteresis of polarization

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 21

 Hysteresis
P
Ps

Pr

Ec

Hysteresis curve as the polarization versus the electric field. Characteristic values are
the saturation polarization Ps, the remanent polarization Pr, and the coercive field Ec.

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 22

 Microscopic properties of ferroelectrics

 Neighboring dipoles are aligned in mutual interaction.

 Arranged dipoles form domains
(compare the magnetic domains in ferromagnets).
 Characteristic transition temperature, where the alignment of the
dipoles is destroyed (ferroelectric Curie temperature)
 Typically, material with complicated crystal structure of low
symmetry
 Finite polarization even without external electric field
 All ferroelectrics are also piezoelectric materials
 Ferroelectric materials have a very high dielectric constant
(as large as several thousand).
 Permanent polarization can be used to store non-volatile digital
information.

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 Ferroelectric domains

Ferroelectric domains in BaTiO3 shown by imaging with crossed polarizers

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 24
 Alignment of dipoles

The ferroelectric hysteresis loop

and the alignment of the dipoles

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 [Askeland 1996] 25

 Hysteresis loop of barium titanate
P

E E

Ferroelectric hysteresis loop of single-crystalline BaTiO3 and a BTO polycrystal (right)

[Askeland 1996]

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 26

 Dielectric constant vs. temperature

The effect of temperature and grain size on the

dielectric constant in barium titanate. Above
the Curie temperature, the spontaneous
polarization is lost due to a change in crystal
structure and barium titanate is in the
paraelectric state. The grain size dependence
shows that the dielectric constant is a
microstructure sensitive property.
[Askeland 1996/Moulson, Herbert 1990]

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 27

 Barium titanate structure

Ti4+

O2−

Ba2+

Compared to the ideal cubic

d arrangement the positive and
negative ions are displaced
by a distance d ≈ 0.01 nm.

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 28

 Ferroelectric perovskite phase

Tetragonal perovskite phase:

each titanium atom is bonded to
six nearest-neighbor oxygen
atoms, but is not exactly in the
centre of the octahedron. This
offset means that tetragonal
BaTiO3 is ferroelectric. The
electrical polarization may be
reversed by applying an external
electric field.

Single crystals of BaTiO3 generally

contain many domains,
corresponding to different
directions of Ti off-centering. The
net effect of the different domain
orientations is to cancel out any
macroscopic polarisation.

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 29

 Polarization

 Example: Determine the magnitude of the remanent polarization in BaTiO3.

The molar volume is 3.8·10−5 m3.
 Solution:
1 mol of BaTiO3 consists of
NA ions Ba2+, NA ions Ti4+, 3NA ions O2−
The total charge associated with 1 mol is ±6NAe
The dipole moment for 1 mol is:
Pm = 6NAed
Polarization is dipole moment per unit volume

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 30

 BaTiO3 phase transitions

Different phases of barium titanate as a function of the temperature

[Moulson, Herbert 1990]
hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 31
 BTO polymorphs

Ps Ps Ps

Cubic Tetragonal Orthorhombic Rhombohedral

130 °C 0 °C –90 °C

The polymorphs of barium titanate at different temperatures

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 32

 Magnitude of polarization

Ps

Tc

Magnitude of the polarization of the different polymorphs of barium

titanate at different temperatures. Tc is the Curie temperature.
[Moulson, Herbert 1990]
hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 33
 Dielectric constant

Dielectric constant of barium titanate as a function of the temperature

[Moulson, Herbert 1990]

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 34

 Design of a multilayer capacitor

 Example: A multi-layer capacitor is to be designed using a BaTiO3-based

formulation containing SrTiO3. The dielectric constant of the
material is 3000. Calculate the capacitance of a multi-layer
capacitor consisting of 100 layers connected in parallel using Ni
electrodes. The sides of the capacitor are 10 mm × 5 mm and the
thickness of each layer is 10 µm. What is the role of SrTiO3? What
processing technique will be used to make these?
 Solution:
Capacitance

Capacitance of one layer: 13.27 µF

Total capacitance of 100 layers connected in parallel:
1327 µF

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 35

 8.5 Dielectric breakdown

 At a critical (high) field, the dielectric material becomes a conductor.

 Increasing number of electrons by an avalanche process

e−
Conductivity

e− e−

e− e− e− e−

e− e− e− e− e− e− e− e−

Scheme of the avalanche process. The

Eb Electrical field accelerated electrons are able to excite
Conductivity against the applied electric other electrons into the conduction
field. If the field is below the breakdown band. Each of these electrons then
field then no current flows. excites another electron, and so on.

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 36

 8.6 High and low-k dielectrics

 Materials with certain dielectrical properties are important in

microelectronics
 Gate dielectrics with shrinking dimensions require high-k materials
(i. e. high dielectric constant εr)
 Static power consumption of a transistor depends on the leakage
current
 International Technology Roadmap for Semiconductors:
effective oxide thickness < 1 nm, gate leakage current < 103 A/cm2
at 100 °C (2007) in MPUs
 Standard SiO2 cannot support these requirements (high tunneling
probability through thin layer)

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 37

 Variation of the DK with the band gap

Band gap (eV)

Dielectric constant

Variation of the dielectric constant with the band gap in binary oxides
[Bersuker:2004]

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 38

 Low-k dielectric materials

 Increase in the speed of integrated circuits by reducing the size

(feature size 1 µm to 90 nm in the last decades)
 Not all IC components work faster when decreased in size:
Interconnections work slower
 Figure of merit is the product
(resistance × capacitance, in units of time)
 Shrinking cross section of wire → increase in the resistance,
reduction in wire distance → increase in the capacitance
 As a result delay increases

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 39

 Interconnections
Embedded Cu lines with interline capacitance
[Shamiryan:2004]

Cross section of
interconnections in
damascence technology
[www.tecchannel.de]
hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 40
 Dual damascence technology

1. Etch of trenches for contacts and interconnections

2. Deposition of insulating film (barrier layer) to prevent the in-diffusion
of copper in the semiconductor
3. Evaporation of a thin metal layer where the contacts and the
interconnects grow galvanically (dual damascence process)
4. When the trenches are filled the excess copper has to be removed
by chemo–mechanical polishing (similar to the intarsia in damascence
swords).
5. Deposition of a insulating oxide layer
6. Deposition of up to six additional interconnect layers

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 41

 Reduction of the dielectric constant

 Decreased polarizability with less polar bonds

 Decreased density by using of porous material

Low-k materials

Non-Si Si-based

Silica-based SSQ-based

Polymers SiOF HSSQ

Amorphous carbon SiOCH MSSQ

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 42

 Summary

 A dielectric placed in a electric field becomes polarized.

 3 factors which can contribute to polarization: induced
polarization, ionic, and permanent dipole contributions
 Specific frequency dependence of these contributions
 Requirement to control the dielectric constant in modern devices

Read about this lecture:

R. Turton: The physics of solids. Oxford University Press 2000,
chapter 10.
References to pictures and data used are given in the file
References.pdf

hsl 2006 – Physics of materials 9 – Dielectric properties 21:01 43