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Liquid Crystal Materials

Broad Classification
Lyotropics
amphiphilic molecules, polar and non-polar
parts form liquid crystal phases over certain
concentration ranges when mixed with a
solvent

hydrophobic
non-polar tail

+
-

hydrophilic
polar head

Thermotropics
molecules consisting of a rigid core and
flexible tail(s) form liquid crystal phases
over certain temperature ranges.

flexible tail

rigid core

The Lyotropic Phases

micelle

cross section

reverse
micelle
cross section

The Thermotropic Liquid Crystal Molecule


Chemists
View

CN

Physicists
Engineers
View

Shape Anisotropy
Length > Width

The molecule above (5CB) is ~2 nm 0.5 nm

Geometrical Structures of
Mesogenic Molecules
Low Molecular Weight

High Molecular Weight


(polymers)

disk-like

rod-like

(
most practical applications

)n
)n

The Liquid Crystal Phase

Crystal

Nematic LC Isotropic
Temperature

The Nematic Director n


n
H

Long
Molecular
Axis

H H

C
H

C
H H

C
H H

H H

director

H H

The local average axis


of the long molecular axis

Other Liquid Crystal Phases

Smectic C

Smectic A
Temperature

Nematic

Chirality
The methyl group on the 2nd carbon atom
on the alkyl chain of the molecules extends
out of the plane of the paper and the hydrogen atom extends into the plane of the paper.
Therefore the 2nd carbon can be thought of
as a right or left handed coordinate system

left-handed right-handed H H H H H
mirror images
C N

H-C-C-C-C-C
H H H H H

non-chiral

H H H
H

C N

H-C-C-C-C-C
non-superimposable

CH3
H H H
H

chiral (RH)

The Chiral Nematic


Ordinary Nematic
CN

Chiral Nematic
CN

director

pitch

The Chiral Doped Nematic


You can create a cholesteric material by doping a conventional
nematic with a chiral dopant.

1
HTP
Pc

Chiral Dopant
S-811
IS-4651

For dilute solutions

HTP (m)-1
-14
-13.6

- indicates left twist sense

For a 10% doping of S-811


1
P
HTP c
1

0.71 m
1
14 m 0.1

The Chiral Smectic C: Ferroelectrics


C10H21 O

CH3
COO CH2 CH C2H5

Eye- dipole moment


fin - chiral
ferroelectric LC has a
dipole moment perpendicular to its long
axis, and is chiral.

The Chiral Smectic: TGB


Twisted Grain Boundary (TGB)

A twisted grain boundary smectic A phase (frustrated) - TGBA*

Discotic Liquid Crystal

O
C

C
R

O
O

example: R=OCOC11H23

O
C
R

C
O

Discotics Liquid Crystals


n
n

Columnar, columns of molecules


in hexagonal lattice

Nematic discotic phase

Polymer Liquid Crystals


Combining the properties of liquid crystals and polymers
Main Chain
mesogenic moieties are
connected head-to-tail

rigid

semi-flexible

Side Chain
mesogenic moieties
attached as side chains
on the polymer backbone

Polymer Liquid Crystals


forming nematic liquid crystal phases

main-chain

side-chain

Example of Side-Chain Polymer LCs


R1
-(-CH2-C-)XO C-O-(CH2)n-O

O
CO

R2

Too slow for display applications (switching times ~ 0.5-1 s


Useful for other applications such as:
Optical filters
Optical memory
Alignment layers for low molecular weight LCs
Non-linear optic devices (optical computing)

The Order Parameter


n

1
2
S P2 (cos ) (3 cos 1)
2

cos
2

2
cos
d

no order
3

cos2 ( 0o ) 1

perfect order

S P2 (cos ) 1

perfect crystal

S P2 (cos ) 0

isotropic fluid

Maier-Saupe Theory - Mean Field Approach


Interactions between individual molecules are represented by a
potential of average force
n

V cos vP2 cos P2

{V: minimum} when phase is ordered (-P2(cos))


{V: V=0} when phase is disordered (<P2(cos)>)
factor for intermolecular strength ( )
From Statistical Mechanics (Self Consistency)

P cos exp vP cos P )d cos


2

P2

exp vP cos P d cos


2

=(kT)-1

Maier-Saupe Theory - Mean Field Approach

n
Order Parameter, S

1.0

Isotropic
Fluid
0.0

Nematic
Liquid
Crystal

-0.6

Temperature

Landau-de Gennes Theory


1 2 1 3 1 4 1
2
f f 0 aS bS cS L(S ) GS ( z )
2
3
4
2
a=(T-T*), , b, c, T*, L are phenomenological constants

Good near NI transition

surface

Order Parameter, S

G is a surface interaction strength

Temperature

Predicts order near


surface

The Order Parameter:


How does it affects display performance ?
The order parameter, S, is proportional to a number of important
parameters which dictate display performance.
Parameter
Elastic Constant
Birefringence
Dielectric Anisotropy
Magnetic Anisotropy
Viscosity Anisotropy

Nomenclature
Kii
n

proportional to

S2
S
S
S

Example: Does the threshold switching voltage for a TN increase


or decrease as the operating temperature increases.

VTH

K
S2
Scales as the square root of S

S
therefore lowers with increasing temperature

Anisotropy: Dielectric Constant


Off-axis dipole moment, angle with molecular axis

NhFS
2F
2


3 cos 1

o
2k BT

N:
h,f:
S:
:
:
k B:
T:

number density
reaction field, reaction
cavity parameters
order parameter
anisotropy in polarizability
molecular dipole moment
Boltzman constant
Temperature

For values of the angle , the


dipolar term is positive, and for
values , the dipolar term is
negative, and may result in a
materials with an overall -.

Anisotropy: Dielectric Constant


++
+++

positive

- ---

negative

- +
- +
- +
- +

E
all angles in
the plane
to E are
possible for the
- materials

Anisotropy: Duel Frequency

low frequency, >0

high frequency, <0

MLC-2048 (EM Industries), Duel Frequency Material


Frequency (kHz)
0.1
1.0
10
50
Dielectric Anisotropy ()
3.28 3.22 0.72 -3.0

100
-3.4

Dielectric Constants (@20oC, 1kHz)


*Mixture
BL038
MLC-6292
ZLI-4792
TL205
18523
95-465
*EM Materials

Application

PDLCs
TN AMLCDs
TN AMLCDs
AM PDLCs
Fiber-Optics
- material

16.7
7.4
5.2
5
2.7
-4.2

21.7
11.1
8.3
9.1
7
3.6

5.3
3.7
3.1
4.1
4.3
7.8

Materials
Vacuum
Air
Polystyrene
Polyethylene
Nylon
Water

Dielectric Constant
1.0000
1.0005
2.56
2.30
3.5
78.54

Dielectric Constants:
Temperature Dependence

16

CH3-(CH2)4

S(T )

14
Dielectric Constant

4-pentyl-4-cyanobiphenyl

12

Temperature Dependence

Extrapolated from isotropic phase

is

10


8
6

1
2 //
3

25

30
T-TNI (C)

C N

S(T )
Average Dielectric Anistropy

35

1
2 //
3

Magnetic Anisotropy: Diamagnetism


Diamagnetism: induction of a magnetic moment in opposition
to an applied magnetic field. LCs are diamagnetic due to the
dispersed electron distribution associated with the electron
structure.
Delocalized charge makes
the major contribution to
diamagnetism.
Ring currents associated with
aromatic units give a large
negative component to for
directions to aromatic ring
plane. is usually positive since:

ll 0

ll

Magnetic Anisotropy: Diamagnetism


/109 m3 kg 1

Compound
C5H11

CN

1.51

C7H15

CN

1.37

CN

0.46

CN

0.42

C5H11
C7H15
CN
C7H15

-0.38

Optical Anisotropy: Birefringence


ordinary ray (no, ordinary index of refraction)

extraordinary ray (ne, extraordinary index


of refraction)

Optical Anisotropy: Birefringence


n no

ordinary wave
extraordinary wave

1 cos 2 sin2

2
2
2
n
no
ne
optic
axis

For propagation along the optic


axis, both modes are no

Optical Anisotropy: Phase Shift


analyzer

liquid
crystal

polarizer

light

= 2dno,e/
e=2dn/
n = ne - no
0 < n < 0.2

depending on deformation

380 nm < < 780 nm


visible light

Birefringence (20oC @ 589 nm)


EM Industry
Mixture
BL038
TL213
TL205
ZLI 5400
ZLI 3771
ZLI 4792
MLC-6292
ZLI 6009
MLC-6608
95-465
MLC-6614
MLC-6601
18523
ZLI 2806

0.2720
0.2390
0.2175
0.1063
0.1045
0.0969
0.0903
0.0859
0.0830
0.0827
0.0770
0.0763
0.0490
0.0437

ne
1.7990
1.7660
1.7455
1.5918
1.5965
1.5763
1.5608
1.5555
1.5578
1.5584
----------------1.5089
1.5183

no
1.5270
1.5270
1.5270
1.4855
1.4920
1.4794
1.4705
1.4696
1.4748
1.4752
----------------1.4599
1.4746

Application

PDLC
PDLC
AM PDLC
STN
TN
AM TN LCDs
AM TN LCDs
AN TN LCDs
ECB
- devices
IPS
IPS
Fiber Optics
- device

Birefringence: Temperature
Dependence
1.8

Index of Refraction

Average Index

ne

1.7

1
ne 2 2n02
3

1 2
2
ne 2n0
3

niso

Extrapolated from isotropic phase

1.6

no

Temperature
Dependence

1.5

n S(T )

1.4
50

40

30
T-TNI (C)

20

10

Birefringence Example: 1/4 Wave Plate


What is minimum d for
liquid crystal 1/4 wave plate ?

circular polarized
linear polarized

Unpolarized

polarizer

d LC: n=0.05

1
Ne No
4
Takes greater number of e-waves
ned nod 1
than o-waves to span d, use

n=0.05

4
1
589nm
d

2,950 nm 2.95 m
4 n 4 0.05

Nematic Elasticity: Frank Elastic Theory


1
2
2
2

{
K
(
n
)
K
(
n
n
)
K
(
n
n
)
} dV
11
22
33

2V
1
{ K 24 ( n n + n n ) K 13 ( n n )} dV
2V

1
1
2
Fe o ( E n ) dV o
( B n ) 2 dV
2V
2 V o

Fd

1
Fs W0 sin 2 0 dS
2
s

Splay, K 11

Twist, K 22

Bend, K33

Surface Anchoring
Alignment at surfaces propagates over macroscopic distances
microgrooved surface homogeneous alignment (//)
rubbed polyimide

ensemble of chains homeotropic alignment ()


surfactant or silane

Surface Anchoring
N

fa
ce

polar
anchoring
W

su
r

azimuthal
anchoring
W

Strong anchoring
Weak anchoring

10-4 J/m2
10-7 J/m2

W, is energy needed to
move director n from
its easy axis

Creating Deformations with a


Field and Surface - Bend Deformation

E or B

Creating Deformations with a


Field and Surface - Splay Deformation

E or B

Creating Deformations with a


Field and Surface - Twist Deformation

E or B

Magnitudes of Elastic Constants


EM Industry
Mixture

K11
(pN)

K22
(pN)

K33
(pN)

Application

BL038
TL205
ZLI 4792
ZLI 5400
ZLI-6009

13.7
17.3
13.2
10
11.5

----------6.5
5.4
5.4

27.7
20.4
18.3
19.9
16.0

PDLC
AM PDLC
TN AM LCD
TN
AM LCD

Order of magnitude estimate of elastic constant

U 1014 ergs
6
11
K ii

10
dynes

10
N 10 pN
8

10 cm
U: intermolecular interaction energy
: molecule distance

Elastic Constant K22:


Temperature Dependence
K S 2 (T )

K22 (x 10-12 Newton)

7
6
5
4
3
2
-30

-20
-10
T-TNI (C)

The Flexoelectric Effect


+

Undeformed
state of banana
and pear shaped
molecules

Polar structure
corresponds to
closer packing
of pear and
banana molecules

Splay

Polar Axis

Bend

Effects of an Electric Field


n

n sin x cos y
E Eo y

1
1
2
2
fe o E n o Eo cos2 Electric Free Energy Density
2
2
df
1
2
Electric Torque Density
e e o Eo sin 2
d 2

Using = 5 and E=0.5 V/m

2
1
1
2
12
2
2
6
o Eo 8.85 10 C / N m 5 0.5 10 V / m 5.5 N / m 2
2
2

Effects of an Magnetic Field


n

n sin x cos y
B Bo y

1
2
1 2
fe
Bo cos2
B n
2 o
2 o
dfb 1 2
e

Bo sin 2
d 2 o

Magnetic free energy density

Magnetic torque density

Using = 10-7 m3kg-1 and B= 2 T = 20,000 G

1 2 1
2
7
7
3
1
Bo 4 10 N / A 10 m kg 2T 0.2 N / m 2
2 o
2

Surface

Deformation Torque


2
exp
x

2 4
d

tan

Orientation of molecules obeys this eq.

1
fd K cos2
2 x
dfd 1 2
d
K
d 2 d

Free energy density from elastic theory

sin 2 K

2
d

Torque density

Surface

Deformation Torque
2

2
d K
d

2
K
d
Material
Steel
Silica
Nylon

3
8

10 N 2

5 10
11

6 2

15N / m 2 15Pa

Shear Modulus
3
100 GPa
Shear modulus Youngs modulus
8
40 GPa
1 GPa

Coherence Length: Electric or Magnetic


Surface

1 2
d e K
2 d

1
sin 2 o E 2 sin 2
2

K 1
d 2

o E

Balance torque

Find distance d

K 1
d

o E

10

Coherence length
N

Using E = 0.5 V/m


1

1.5 m
6
12 2
2
and = 20
8.85 10 C / N m 20 0.5 10 V / m
11

Viscosity: Shear Flow Viscosity Coefficient

n v

n v

shear stress ( )

velocity gradient (v )

n v
n v

Typically >
>

Viscosity: Flow Viscosity Coefficient


LC specification sheets give
kinematic viscosity in mm2/s

Dynamic Viscosity
1 kg/ms = 1 Pas
0.1 kg/ms = 1 poise

Kinematic Viscosity
1 m2/s

Approximate density
kg
1000 3
m

Viscosity: Flow Viscosity Coefficient

1m
ii 20 mm 2 / s 20 mm 2 / s

3
10 mm
Typical
Flow
Viscosity

10

Conversion

EM Industry
MIXTURE

CONFIGURATION

ZLI-4792
ZLI-2293
MLC-6610
MLC-6292
18523
TL205
BL038

TN AM LCDs
STN
ECB
TN AM LCDs (Tc=120oC)
Fiber Optics (no=1.4599)
PDLC AM LCD
PDLCs (n=0.28)

kg / m 3 0.02 kg / ms 0.2 poise

Density

Conversion
0.1 kg/ms = 1 poise

Kinematic ()
(mm2/s)

Dynamic ()
(Poise)

15
20
21
28
29
45
72

0.15
0.20
0.21
0.28
0.29
0.45
0.72

Viscosity: Temperature Dependence


N

H3CO

C4H9

1.0

For isotropic liquids

K
T
B

0.7
0.4
0.2
0.1
20

iso 0 exp

E is the activation energy for


diffusion of molecular motion.

3
1
TNI

30
40
50
Temperature (C)

60

Viscosity: Rotational Viscosity Coefficient


n

Time

Rotation of the director n bv external


fields (rotating fields or static).
Viscous torque's v are exerted on a liquid
crystal during rotation of the director n
and by shear flow.

d
v 1
dt
rotational viscosity coefficient

Viscosity: Rotational Viscosity Coefficient


n

EM Industry
MIXTURE
ZLI-5400
ZLI-4792
ZLI-2293
95-465
MLC-6608

CONFIGURATION
TN LCDs
TN AM LCDs
STN
- Applications
TN AM LCD

Viscosity
(mPa s)
109
123
149
185
186

Viscosity
(Poise)
1.09
1.23
1.49
1.85
1.86

1 Pa
0.109 Pa s 0.109 kg / m s 1.09 poise

3
10 mPa

1 109 mPa s 109 mPa s

Viscosity: Comparisons

Material

Viscosity (poise)

Air
Water
Light Oil
Glycerin

10-7
10-3
10-1
1.5

LC-Rotational (1)
LC-Flow (ii)

1< 1 < 2
0.2< ii<1.0

Relaxation from Deformation


Surface

field on state

Surface

Relaxation when field is turned off


Relaxation time

zero field
state

d visc
2
K

Balance viscous/deformation torque

d
1
dt

o exp t /
10

10

1d 2
where
2
K 2

kg / ms 10 m

(10
1

Assume small deformations

11

N ) 2

(10

N ) 2

Solution

2.5 s

kg / ms 5 10 m
6

11

S u rfa c e

Relaxation from Deformation

For 100 m cell

6 ms

For 5 m cell

Freedericksz Transition The Threshold I


y

z
E
x

Ec

At some critical E
field, the director
rotates, before Ec
nothing happens

z ,0
n cos z ,sin
1
2
2
2
Fd K11 n K 22 n n K 33 n n dV
2 VOL

d
K 22
dz

Freedericksz Transition The Threshold II


2
2
1
1
Fe o E n dV o E sin2 dV
2 VOL
2 VOL

1
d
F Fd Fe K 22

2 0
dz

o E sin dz

F d F

dz d
dz

Minimize free energy with


Euler Equation

E-field
free energy

total
free energy

Freedericksz Transition The Threshold III


d 2
2
K 22

E
sin cos 0
o
2
dz

soln.
10 11 N
12
2
2
8.85

10
C
/
Nm

(10) small

V
V
200,000 0.2
m
m

VTH

V
ETH d 0.2
m

5 m 1volt

mid-layer tilt (deg)

ETH

K 22

d o 5 10 6 m

differential equation

threshold

1.0

E/Ec

Defects
s=1/2

s=+1

s=3/2

s=-1/2

s=+1

s=+2

s=-1

s=+1

The singular line


(disclination) is pointing
out of the page, and director
orientation changes by
2s on going around the
line (s is the strength)

Estimate Defect Size


core

planar radial alignment

R
l

rc
radius of core

The simplest hypothesis is that the core or defect


or disclination is an isotropic liquid, therefore the
core energy is proportional to kBTc. Let M be the
molecular mass, N Avogadadros number and
the density of the liquid crystal.
l 2 R
R
R
1
2
dr
Fe K11 n rdrd dz lK11
lK11 ln
2 z 0 0 r rc
r
rc
rc
F Fe Fcore

R
N
lK11 ln k B Tc rc2l

r
M

F
0 rc
rc

1 M K11

2 N k B Tc

1
10 11 N
26
2

10 m

23
10 J / K 10K
2

rc 3 108 m 30 nm

Microscopic Fluttering and Fluctuations


Characteristic time of
Fluctuations:
1

2
Kq

Thermally induced
Deformations

1
2
K

0.1kg / m s

10

11

N
9
589

10
m

100 s

Can see fluctuations with


microscope:
Responsible for opaque
appearance of nematic LC

General Structure
Z

Z
Y

Aromatic or saturated ring core

X & Y are terminal groups


A is linkage between ring systems
Z and Z are lateral substituents
CH3 - (CH2)4

C N

4-pentyl-4-cyanobiphenyl (5CB)

Common Groups
Mesogenic Core
Ring Groups

Linking Groups

phenyl

N
pyrimidine
N

cyclohexane

biphenyl
terphenyl
diphenylethane
stilbene
tolane
schiffs base
azobenzene
azoxybenzene
phenylbenzoate
(ester)
phenylthiobenzoate

CH2 CH2
CH CH
CH CH
CH N
N N
O

N N
O
CO
O
CS

Nomenclature
Mesogenic Core

terphenyl

biphenyl

phenyl
benzyl
benzene

phenylcyclohexane (PCH)
3

1 1

4
5

4
6

cyclohexane
cyclohexyl
Ring Numbering
Scheme

Terminal Groups
(one terminal group is typically an alkyl chain)

CH2

CH2
CH2

CH3
CH2
CH3

CH2
C*H

straight chain

branched chain
(chiral)

CH3
Attachment to mesogenic ring structure
Direct
alkyl (butyl)
Ether
-O- alkoxy (butoxy)

Terminal Groups
CH3-

methyl

CH3-O-

methoxy

CH3-CH2-

ethyl

CH3-CH2-O-

ethoxy

CH3-(CH2)2-

propyl

CH3-(CH2)2-O- propoxy

CH3-(CH2)3-

butyl

CH3-(CH2)3-O- butoxy

CH3-(CH2)4-

pentyl

CH3-(CH2)4-O- pentoxy

CH3-(CH2)5-

hexyl

CH3-(CH2)5-O- hexoxy

CH3-(CH2)6-

heptyl

CH3-(CH2)6-O- heptoxy

CH3-(CH2)7-

octyl

CH3-(CH2)7-O- octoxy

Second Terminal Group and


Lateral Substituents (Y & Z)
H
F
Cl
Br
I
CH3
CH3(CH2)n
CN
NH2
N(CH3)
NO2

flouro
chloro
bromo
iodo
methyl
alkyl
cyano
amino
dimethylamino
nitro
phenyl
cyclohexyl

Odd-Even Effect
Clearing point versus alkyl chain length
O
CH3-(CH2)n-O

CO

O-(CH2)n-CH3

clearing point

18
16
14
12
10
0 1 2 3 4 5 6 7 8 9 10 11
carbons in alkyl chain (n)

Nomenclature
Common molecules which exhibit a LC phase

CH3-(CH2)4

C N

4-pentyl-4-cyanobiphenyl

CH3-(CH2)4-O

C N

4-pentoxy-4-cyanobiphenyl

Structure - Property
vary mesogenic core
CH3-(CH2)4

C N

C-N (oC)

N-I(oC)

22.5

35

0.18

11.5

71

52

0.18

19.7

31

55

0.10

9.7

N
N

Structure - Property
vary end group

COO

CH3-(CH2)4

X
H
F
Br
CN
CH3
C6H5

C-N (oC)

N-I (oC)

87.5
92.0
115.5
111.0
106.0
155.0

114.0
156.0
193.0
226.0
176.0
266.0

Lateral Substituents (Z & Z)


Z
X

Z
A

Z and Z are lateral substituents

Broadens the molecules


Lowers nematic stability
May introduce negative dielectric anisotropy

Why Liquid Crystal Mixtures


Melt Temperature:
Liquid Crystal-Solid

Temperature

Isotropic Liquid
Liquid
Crystal

ln i = Hi(Teu-1 - Tmi-1)/R
E
eutectic
point

Solid
0

50
Concentration ( 2), %

100

H: enthalpies
Teu: eutectic temperature
Tmi: melt temperature
R: constant
Nematic-Isotropic
Temperature: TNI
TNI = iTNIi

EM Industry Mixtures
S-N

<-40 C

solid nematic transition (< means supercools)

Clearing

+92 C

nematic-isotropic transition temperature

Viscosity (mm2 /s)


+20 C
0C

15
40

flow viscosity, some materials may stipulate the


rotational viscosity also. May or may not give
a few temperatures

K33/K11

1.39

ratio of the bend-to-splay elastic constant

5.2

dielectric anisotropy

0.0969

optical birefringence (may or may not give ne, no)

dn (m)

0.5

product of dn (essentially the optical path length)

dV/dT (mV/oC)

2.55

how drive voltage changes as temperature varies

V(10,0,20)
V(50,0,20)
V(90,0,20)

2.14
2.56
3.21

threshold voltage (% transmission, viewing angle,


temperature)

EM Industry Mixtures
Property
S-N

ZLI 4792
<-40 C

MLC 6292/000
<-30 C

MLC 6292/100
<-40 C

Clearing

+92 C

+120 C

+120 C

Viscosity (mm2 /s)


+20 C
0C
-20 C
-40 C

15
40
160
2500

28
95
470
7000

25
85
460
7000

K33/K11

1.39

-------

------

5.2
0.0969

7.4
0.0903

6.9
0.1146

dn (m)
dV/dT (mV/C)

0.5
2.55

0.5
1.88

0.5
1.38

V(10,0,20)
V(50,0,20)
V(90,0,20)

2.14
2.56
3.21

1.80
2.24
2.85

1.38
2.25
2.83

Summary of Fundamentals
Thermotropic Liquid Crystal
Anisotropy
Nematic phase
Chirality
Order parameters
Dielectric Anisotropy
Diamagnetism
Birefringence
Elastic constants
Surface Anchoring
Viscosity
Threshold
Defects
Eutectic Mixture

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