Dielectric Properties of Solids

Dielectric Properties of Solids

http://www.eetimes.com/document.asp?doc_id=1276895

(SDRAM = Syncronous dynamic RAM)

Prof.Shih-Ying Hsu, Department of Electrophysics, National Central University, Taiwan
 Dielectric Properties of Solids
Introduction (concept) Capacitor (condenser)

Eapp 
For some materials σ → 0 (at RT) upon E app
They are called insulators or dielectrics.
? 
Charge can not flow freely in the direction of E app , but

Dielectric 
E app can penetrate into their interiors and
affect the internal structure of such materials.

macroscopically,
εo A
i) When no dielectric, C o =
d
ε oε r A
ii) When a dielectric is inserted, C =
d
iii) The calculation of ε is an important aim of any microscopic theory
of dielectrics.
 
iv) also, their response to the AC E field reflected in

ε (ω ) and as ω → optical range

It leads to optical properties of dielectrics

 n= ε


v) In some ionic crystal, even when Eapp = 0,
there may be long-range electrostatic force between the
ions (in addition to the lattice potential)

Ex: Ferroelectricity, piezoelectricity

https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
 E

- + - - + -

+ - + + - +

Ionic polarization occurs in all ionic

solids: NaCl, MgO…

+ +

Molecular polarization, occurs in all

insulating molecules; oils, polymers,
H2O…
Review of basic formulas

In dielectrics, there are no free charges, but bound charges,

i.e. electric dipoles are present.

Definition
 
- + dipole moment p = qd (- →+)
−q d +q

qE Torque felt
+   
τ = p× E
 Potential energy

- E  
V = −p⋅ E
− qE
In discussing dielectric materials

Polarization P = # of dipole moment / unit volume

= NP the dipole moment density : units of C/m2
 Electric field inside the parallel plate :
 V0
E0 =
L


Now, insert a slab of dielectric ⇒ modify the field to a new value E

  
E0 − E ′ = E

E ′ due to polarization change
  
E0 − E ′ = E : new field inside the slab
Now,
 
Electric displacement D = ε0 E 0 (just outside the dielectric) or
  
D = ε0 E + P (inside dielectric)

  P
∴ E = E0 −
ε0
    
also, D = ε E + P = εE = ε ε E
0 0 r

ε
where ε r = Dielectric constant
ε0
All the dielectric and optical characteristics of
substances are contained in this constant.
The dielectric constant and polarizability : the local field

The polarization of a medium is produced by the field

 
Dipole moment p = αE
Polarizability
  
Polarization P = Np = NαE
    
and D = ε E + P = ε E + NαE
0 0

 Nα  
= ε 0 1 + E
 ε0 
 
Previously, D = ε 0ε r E

Nα
∴ εr = 1+
ε0
 Define electrical susceptibility χ such that
   
P = ε 0 χE cf. P = NαE

then
Nα
χ = εr = 1 + χ
ε0
In fact,

   
P = αE local instead of P = αE Maxwell

If this microscopic field is averaged, one obtains the

macroscopic or Maxwell field E .
Recap

https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
*)Soda-lime glass, also called soda-lime-silica glass, is the most prevalent type of glass, used for windowpanes, an
.
d glass containers (bottles and jars) for beverages, food, and some commodity items Source Wikipedia
https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
Local effective field at an atom or an ion in a dielectric sample :

Eloc = Eo + E1 + E2 + E3

Eo : the field produced by fixed charges external to the body

E1 : depolarization field of induced surface charges on the boundary
E2 : the field produced at the center of an imaginary cavity by the
polarization-induced surface charges over the cavity
E3 : the field produced at the center of the imaginary cavity due to
the discrete dipoles distributed over all atomic sites.
 
• What is the local field E local ?
    
E local = E0 + E1 + E 2 + E 3

depolarization dipole field inside

the cavity
Lorentz field


 P
E1 = depolarization field =−
ε0
 π P cos θ 
2
P
E2 = ∫  − 2πR sin θdθ =
2 See Kittel
 4πε 0 R  3ε 0
0 2

E 3 = 0 for the symmetric structure such as cubic
 
  P P  2 
∴ E local = E0 − + + 0 = E0 − P
ε 0 3ε 0 3ε 0
 Lorentz cavity field E2 and field of dipoles inside cavity E3

E2 from
Eo surface of
spherical cavity

E3 from dipoles inside sphere

rdθ
θ

++ +
+++ +
  
   P P
E local =  E0 −  +
 ε 0  3ε 0
Therefore,

  P
E local = E Maxwell + E local : microscopic field which
3ε 0
fluctuates within the
medium
Now,
  
 
P = NαE local E local = E Maxwell +
P
3ε 0


   P   Nα 
P = Nα  E +  = NαE + P
 3ε 0 3ε 0
 Nα
∴ P=
 Nα   1 − 3Nεα
P 1 −  = NαE
 3ε 0
0
By the way,
     Nα   
D = ε0E + P = ε0E + E = ε 0ε r E
1 − N α 
 3 ε  0


(
ε 0 1 −Nα
3ε 0
)
+ Nα   
 E = ε 0ε r E εr =
1+ 2 Nα
3ε 0


Nα
1 − 3ε 0  1 − 3Nεα
0

 Nα  2 Nα
εr 1 −  = 1+
 3ε 0  3ε 0
Nα
3ε 0
(ε r + 2) = ε r − 1

ε r − 1 Nα 1
= = χ
Clausius-Mosotti relation ε r + 2 3ε 0 3
Sources of polarizability (Mechanism)
Different types of physical processes gives rise to polarizability
ex) dipolar(orientational), ionic, electronic polarizability

a) Dipolar (orientational) polarizability

•molecules with permanent dipole moment are present with
random orientation.
 
Upon E , those dipoles align with E f(θ)
 
potential V = − P ⋅ E = − PE cos θ 1
Probability of finding it along θ direction
π/2 π
f = e −V kT = e PE cos θ kT 0

E= 0 E≠0
Average value of P, now only considering Px
∫ Px f (θ )dΩ
Px =
∫ f (θ )dΩ
π
∫0 P cos θ ⋅ e PE cos θ kT ⋅ 2π sinθdθ
= π PE cos θ kT
∫0 e ⋅ 2π sinθdθ
1 PE
= PL(u ) where L(u ) = coth(u ) − , u=
u kT
Langevin function

Paraelectricity
For small E field,
p2 pE orientational E
Px = E ~ p ⋅ = p ⋅
3k BT 3k BT thermal E

Thus, the dipolar (orientational) polarizability is

p2
α0 =
3k BT
Substitute this into the Clausius-Mosotti equation
εr − 1 N  p2 
=  α ei +  αei- induced polarizability
ε r + 2 3ε 0  3k BT 
 
ρ
or N = NA Number of dipoles in unit volume
M
M: molecular weight

M  εr − 1  N A  p2 
  =  α ei + 
ρ  
 ε r + 2  3ε 0  3k BT 
 P2
αd = applicable in solids ?
3kT

in solids

cf. jumping frequency

ν = ν e −φ kT
D

cf. relax time E
1 φ kT
τ ≅ e
νD

Probability of leftward orientation : Ω

Probability of rightward orientation : 1 – Ω

finally:
2P 2
∴ αd =
kT
  M  ε r − 1  vs. 1
If we plot the 
ρ  ε + 2 
  r  T
M  ε r −1  N A  P2 
  =  α ei + 

ρ  ε r + 2  3ε 0  3k BT 

M. A. OMAR, ELEMENTARY SOLID STATE PHYSICS: Principles and Applications ADDISON-1993

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The dipole moments for various molecules,

1 debye = 3.33 × 10-30 C·m

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b) Dipolar dispersion (frequency dependence of orientational polar)
For AC applied field

The equation to describe the motion of dipole polarization

dPd (t ) P0 − Pd (t )
=
dt τ
Since P = αE , P0 = α d (0 ) Ae − iωt (equilibrium moment)

dPd (t ) Pd (t ) α d (0 ) − iωt
+ = Ae
dt τ τ
Let’s try a solution of the form
Pd (t ) = α d (ω ) E (t ) = α d (ω ) Ae − iωt
α d (ω ) − iωt α d (0 ) − iωt
α d (ω ) Ae − iωt (− iω ) + Ae = Ae
τ τ
α d (ω ) α d (0 )
(1 − iωτ ) =
τ τ
α d (0)
∴ α d (ω) = α d (0) : static polarizability
(1 − iωτ)
⇒ The polarization is no longer in phase with the field
(This gives rise to energy absorption)

E = Ae − i ωt

P = Be −i ( ωt −ϕ )
To derive the expression for εr(ω)
ε r (ω ) = 1 + χ e (ω ) + χ d (ω )
where ionic concentration assumed negligible

Now, in microwave region, the electronic susceptibility is

constant (e- light, respond to E (ω ) instantaneously)

Then, ε r (ω ) = n 2 + χ d (ω ) where n2 = 1 + χ e

χ d (ω ) = ε r (ω ) − n Not follow the E (ω ) instantaneously
2

a phase lag is expected.

χ d (0 )
χ d (ω ) = : the same complex form as αd(ω)
1 − iωτ

χ d (0 ) = ε r (0 ) − n 2
 ε ( 0 ) − n 2
∴ ε r (ω ) = n 2 + r
1 − iωτ
ε ( 0 ) − n 2 ε ( 0 ) − n 2
= ε r′ (ω ) + iε r′′(ω ) = n 2 + r
+i r
ωτ
1+ω τ 2 2 1+ω τ 2 2

ε ( 0 ) − n 2
ε r′ (ω ) = n 2 + r
1 + ω 2τ 2

ε r (0 ) − n 2
ε r′′(ω ) = ωτ
1+ω τ 2 2

: Debye equations

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d) Ionic polarizability
It is related with the optical properties of lattice vibration.
The frequency dependent dielectric constant is given by
ε r (0 ) − ε r (∞ )
ε r (ω ) = ε r (∞ ) + 2
ω 
1− 
 ωt 
Since ε r (∞ ) = n 2
ε r (0 ) − n 2
ε r (ω ) = n 2 + 2
ω 
1− 
 ωt 

Dielectric constant εr(ω) versus ω, showing

dispersion in infrared region due to optical
phonons in an ionic crystal. Dashed curve
indicates removal of divergence due to
collisions of ions
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from
e) Electronic polarizability
For the e- under AC field
d2x dx
m 2 + mγ + m ω 02 x = − eE0e − iωt
dt dt
To be consistent with previous derivation

x(t ) = x0 e − iωt (can be done with x(t ) = x0 eiωt )

m(−iω ) ⋅ x(t ) + mγ (−iω ) x(t ) + mω0 x = −eE0 e − iωt

2 2

m{(ω0 − ω 2 ) − iωγ }x(t ) = −eE0 e −iωt

2

E 0 e − i ωt
x(t ) = − ⋅ 2
e k
ω0 =
(
m ω0 − ω − iγω
2
) ,
m
The polarization Pe is

(
P *e = ε 0 χE = ε 0 ε r* − 1 E0 e −iωt )
− i ωt
also P = Nα (ω ) E0 e
e
* *
e = Nex(t )
2 − i ωt
− i ωt e E0 e
α (ω ) E0 e
*
= ⋅ 2
e
(
m ω0 − ω − iγω
2
)
 e2 
 
 m
α e (ω ) = 2
*

(
ω0 − ω 2 − iγω )
and (
Nα e* (ω ) E0 e − iωt = ε 0 ε r* − 1 E0 e − iωt )
ε (ω ) =
N
*
α e (ω ) + 1
ε0
r

N e2 1
= 1+
ε 0 m (ω02 − ω 2 ) − iγω

Ne 2 ω 02 − ω 2
ε r′ (ω ) = 1 +
ε 0 m (ω 2 − ω 2 )2 + γ 2ω 2
0

Ne 2 γω
ε r′′(ω ) =
ε 0 m (ω 2 − ω 2 )2 + γ 2ω 2
0
 Ne 2 ω 02 − ω 2
ε r′ (ω ) = 1 +
ε 0 m (ω 2 − ω 2 )2 + γ 2ω 2
0

Ne 2 γω
ε r′′(ω ) =
ε 0 m (ω 2 − ω 2 )2 + γ 2ω 2
0

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Within a solid which contains permanent dipoles, all three of the above
phenomena contribute to the polarizability at low frequencies through
to high frequencies.

The dielectric constant at

optical frequencies :
electronic polarizability.
The other two contributions
are small at high frequencies
due to the inertia of the
molecules and ions.
(Ionic movements can no
longer keep up with the
alternations of the applied
field.)

Prof.Shih-Ying Hsu, Department of Electrophysics, National Central University, Taiwan

https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
 Microwave Ovens
• A microwave oven generates
electromagnetic radiation at
about 2.5 GHz. This energy
is pretty good at causing H2O
molecules to oscillate their
orientation (orientational
dielectric constant changes
greatly).
• 5 GHz - 100 GHz would be
ideal, but then most of the
energy would be absorbed
by the outermost layer of the
food, defeating the purpose.
• Ice has a low dielectric
constant, so not much
energy is absorbed by it.
Once there is a bit of melted
ice, though, then you are
really cooking.
http://home.howstuffworks.com/framed.htm?parent=micriwave.htm&url=http://www.amasci.com/weird/microexp.html
 Barium titanate BaTiO3

Below 408K, spontaneous polarization arises from

Simple cubic T > 408K coupling bet. ionic and electronic dipole moments.
Ba2+ at cube corners A displacement of Ti4+ creates an ionic dipole
moment in the direction of the displacement and
O2- at face centers associated electric field. O2- become polarized in
the opposite direction.
Ti4+ at body center
Polarization does not increase infinitely because
Paraelectric property anharmonic elastic forces limit Ti displacement.

Prof.Shih-Ying Hsu, Department of Electrophysics, National Central University, Taiwan

https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
E=0 E≠0
E=0
Ferroelectrics (digression)

(1) Perovskite-type lead zirconate

titanate (PZT) unit cell in the
symmetric cubic state above
the Curie temperature.
(2) Tetragonally distorted unit cell
below the Curie temperature
A ferroelectric crystal exhibits an electric dipole
even in the absence of an external electric field.
In the ferroelectric state the center of positive
charge of the crystal does not coincide with the
center of negative charge.
A naïve picture
A naïve picture
• The local alignment of
dipoles can exist over any
length scale.
• Different regions may
exist with different
polarisation orientations:
– Call these “domains” in line
with magnetic materials.
– In contrast with magnetism,
domain walls are abrupt.
 Polarization Switching by an Electric Field

E=0

E>0

E≈EC

http://www.arne-lueker.de/Objects/work/Pb-free%20ferroelectrics/pb_free_quest.html
 Polarization Switching by an Electric Field

from Kittel

Electrical (or 1800-domains) to minimize depolarization.

Ferroelectricity
Usually ionic susceptibility is not sensitive to variation
in temperature.
However, the so called ferroelectric materials have
C
εr = B + , T > TC C- Curie constant
T − TC
: Curie-Weiss law (TC - Curie Temp.)

(Spontaneous polarization)
Static
Ferro- Para-
Dielectric
electric electric
Constant
phase phase

Ferro-electric
phase

No E applied
 potassium dihydrogen
phosphate

http://ckw.phys.ncku.edu.tw/public/pub/Notes/CondensedMatter/Powerpoint/
 Rochelle salt

BaTiO3

KDP
from Kittel
https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
 Domain Wall Movement

http://slideplayer.com/slide/4829425/

Technical Ceramics Dr. Sabar D. Hutagalung

see Electroceramics: Materials, Properties, Applications By A. J. Moulson, J. M. Herbert
see Electroceramics: Materials, Properties, Applications, By A. J. Moulson, J. M. Herbert
 see Omar

T>TC cubic
T<TC a slightly compressed cubic
~0.15Å

cf. ferroelectric domains are present(as in the case of

ferromagnetic domain in ferromagnetic materials)
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https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
https://chemistry.osu.edu/~woodward/ch754/lect2003/dielectrics_lect28.ppt
Pyroelectric Detectors/Sensors
 DRAM SEM Micrograph
Dynamic random access memory
(DRAM)

The two deep "trenches" (they

are really holes) contain the
capacitors on their walls. The
dielectric (with ~ 7 nm far too
thin to be visible) is "ONO", a
triple layer of Oxide (SiO2) –
Nitride (Si3N4)– Oxide (SiO2).
This is an “early” 64 MBit
DRAM (1996).

http://www.tf.uni-kiel.de/matwis/amat/elmat_en/kap_5/illustr/i5_1_1.html
 Hynix Announces 512Mbit Mobile DRAM
Hynix Semiconductor, a noted memory maker has said it has developed
the world's fastest and smallest 512 MBit mobile DRAM. The new DRAM
operates at 200 MHz and processes 1.6 GB of data per second. "The
product will deliver the memory capacity and speed required for third
generation mobile phones that provide new services, such as digital
media broadcast (DMB), to subscribers," the chip maker has said. It is
expected that Hynix will combine this 512Mb mobile DRAM and Nand
Flash in a multi-chip package which will allow mobile manufacturers to
make slimmer mobile phones.

http://www.tech2.com/india/news
 Non-Volatile RAMs (memory)

Smart cards use ferroelectric memories. They can hold relatively large amounts of information
and do not wear out from use, as magnetic strips do, because they use contactless radio
frequency input/output. These cards are the size and shape of credit cards but contain
ferroelectric memory that can carry substantial information, such as its bearer's medical
history for use by doctors, pharmacists and even paramedics in an emergency. Current smart
cards carry about 250 kilobytes of memory.

http://www.slideshare.net/researcher1234/ferroelectric-and-piezoelectric-materials