Liquid Crystals for Large Display

&
Basic Theory
Dr. Md. Lutfor Rahman
FIST, UMP
Introduction
LCDs based on the twisted nematic (TN) mode are the
most common flat panel displays.

The conventional TN LCDs utilized in wristwatches or
desk calculators can only contain a small number of matrix
segments (e.g. 8 X 8), and therefore cannot be applied for
displays with high information content.

Further development of the TN cell resulted in thin film
transistor (TFT) LCDs.
This technology enables active switching of a large number of
segments (e.g. 640 X 1024) by integrated TFTs.

Even though TFT LCDs made a great leap forward in
performance compared to the conventional TN LCDs, they
kept their advantages like low weight, low space requirement
and low power consumption.

Based on the unique combination of properties of LCs and
TFTs, a totally new product, the notebook came up in the
beginning of the 1990s.

The display performance and size of TFT LCDs had been
dramatically improved since that time as a consequence of the
continuous development of electronics and materials.


Whereas in the first half of the 1990s the cursor could not follow
fast movement of the mouse, multimedia applications were
realized for the first time by the introduction of fast switching 15
inch TFT LCDs in 1998.

As the visible area of a 15 inch TFT LCD corresponds to that of a
17 inch cathode ray tube (CRT) it was obvious to consider use in
desktop monitors.

However, for this application the viewing angle dependency of the
optical effect, especially contrast and colour shift, had to be
improved.

This was possible by the introduction of optical
compensation films. Even better optical performance is
possible after the development of new switching modes,
the so-called in plane switching (IPS) and the vertically
aligned (VA) mode in the end of the 1990s.

Computer monitors using these techniques have already
replaced CRT monitors to a large extent.

However, the hurdles of LCDs for TV use were far higher
than for notebooks and monitors, because for the first
time the display of full moving pictures had to be
realized.







Therefore a switching time under the so-called frame time
(vide infra) of 16 ms is required. This one frame
switching time should be achieved together with high
brightness, high contrast and good colour quality.

Before reviewing the LCDs material development we
give an overview on basic requirements of the TV
application and the essential physical properties of liquid
crystals.


Basic requirements and physical properties
The prerequisite for commercial LCs is a broad nematic phase
range of -40 to 100C in order to guarantee the so-called
Operating temperature range of LCDs.

The clearing point of a liquid crystal is the temperature at
which the liquid crystal phase vanishes.

It has to be at least 10C higher than the operating temperature
of the device.
In order to respond to an applied switching voltage LCs must
exhibit a dielectric anisotropy (), defined as the difference
of the dielectric constants parallel and perpendicular to the
director of the nematic phase.
Depending on the molecular structure the dielectric anisotropy
can be positive (molecular dipole parallel to the long axis of
the molecule) or negative (molecular dipole perpendicular to
the long axis of the molecule).

Elastic constants K
i
are the proportional constant between the
force (the electric field in case of LCDs) and the deformation
of director fields.

There exist three K
i
(i = 1.2.3) dependent on the deformation of
the director (splay, twist, bend).

The operating voltage is proportional to the square root of the
fraction between elastic constants and dielectric anisotropy.
The reorientation of the LCs upon switching depends on the
configuration of the display and the switching mode.

The basis of the visible electro-optical effect is the
birefringence (n), which is defined as the difference between
the extraordinary refractive index (light propagation parallel to
the director) and the ordinary refractive index (light propagation
perpendicular to the director).

Upon switching the reorientation of the LC molecules leads to
an effective change of the optical path which is defined as dn
(d = cell gap).
This results in a change of the transmission of the display
between 0 and 100%.
The switching time of an LCD is proportional to the
rotational viscosity (l) of the liquid crystal.

Low l is an absolute perquisite for the TV application. Each
pixel in a display is driven by a TFT charging the pixels by
signal pulses.

The voltage has to be sustained till the next refresh signal
pulse arrives (this time is one frame time).

The voltage drop during one frame time is characterized by the
voltage holding ratio (VHR), which is defined as the ratio of
the voltages at a pixel at the end and the beginning of the
frame time.
A high VHR is important for a flicker free picture.

All structural elements (side chain, rings, linking groups,
terminal groups) of a liquid crystal molecule contribute to the
physical properties (Table 1).

For example benzene rings with polar substituents contribute
to the dielectric aniosotropy significantly.

In addition the aromatic ring contributes to higher values of
the optical aniosotropy compared to a cyclohexane ring.

n

1
0.15 0.26 8 35
-2- (-7)

80 260

0.23 0.28 15 20 250 500
Z
Table 1: Characteristic n, and 1 ranges for different core
structures with polar substitutions. Z can be a COO group, a
CF
2
O group, a CH
2
CH
2
group or a single bond.
As a consequence we empirically find limitations for high
polar liquid crystals with low n values.

Other contradictory requirements are the coexistence of high
clearing point and low viscosity.

Thus, it is very difficult to achieve LCs with a high clearing
point (broad operating temperature range) and low viscosity
(fast switching) or LCs with high polarity (low operating
voltage) and low viscosity.

However, these are the decisive LC properties for LCD
products (Table 2). It means that we have to achieve
breakthroughs to overcome these phenomenological
limitations of LC material properties.
In Table 1 characteristic property combinations for the most
important LC parameters n, and l for different core
structures are shown.

Additional properties like solubility etc. play a decisive role
for practical use.

Moreover liquid crystals must be chemically, photochemically
and electrochemically stable.

Empirically VHR values decrease with increasing dielectric
anisotropy of the LCs.
The combination of high polarity with high VHR is therefore
another usually contradictory material requirement.

Only few super fluorinated materials (SFM) have suitable
property combinations.

The main material research target is synthesis and
identification of compounds with lower viscosity maintaining
or even improving the other properties.
Computer simulations for the calculation of , n based on
molecular properties such as dipole moments and
polarizabilities are often in good agreement with measured
values of LCs.
Calculated electrostatic potentials give a very useful hint for
the so-called reliability parameters.

Computer simulation of bulk properties like elastic constants,
viscosities and melting points on the other hand are still in an
early stage.

A single liquid crystal compound cannot fulfill the complex
requirements of the displays.

The wide operating temperature range in combination with
other properties requires mixtures of typically 10 to 20
compounds.




Nevertheless melting points of LC mixtures are not
thermodynamically defined phase transitions but metastable
states with a very long lifetime.



Technology Material
requirements
Characteristics
VA TFT -3 ~ -4
n ~ 0.08
1 ~ 100
Low rotational viscosity difficult to achieve for
lateral highly flourinated compounds
IPS 7 11
n 0.09 0.12
1 ~ 70
Inter digital electrodes / high aperture ratio
requires high values
TN TFT 5 6
n 0.09 0.10
1 ~ 70
Low n values difficult to combine with high
positive and low rotational viscosity
Projection ~ 8
n 0.21
1 200
High n materials with very high light stability
required
Table 2: Overview material requirements for the most
important active matrix addressed LCDs use in LCD TVs
The Nematic Director n
n
The local average axis of the long molecular axis
director
n
Temperature
Smectic C Smectic A Nematic
n
z
u
n
Other Liquid Crystal Phases
u
n
The Order Parameter


n
2
2
1
(cos ) (3 cos 1)
2
u u = = S P
2
2
2
cos
1
cos
3
cos ( 0 ) 1
u
u
u
O
O
O
= =
O
= =
}
}
o
d
d

no order


perfect order
2
2
(cos ) 1
(cos ) 0
u
u
= =
= =
S P
S P
perfect crystal

isotropic fluid
The Order Parameter
It is sometimes difficult to determine whether a
material is in a crystal or liquid crystal state.

Crystalline materials demonstrate long range
periodic order in three dimensions.

By definition, an isotropic liquid has no orientational
order.

Substances that aren't as ordered as a solid, yet
have some degree of alignment are properly called
liquid crystals.
The Order Parameter
To quantify just how much order is present in a
material, an order parameter (S) is defined.

Traditionally, the order parameter is given as follows:
The Order Parameter
where theta is the angle between the director and
the long axis of each molecule.

The brackets denote an average over all of the
molecules in the sample.

In an isotropic liquid, the average of the cosine
terms is zero, and therefore the order parameter is
equal to zero.

For a perfect crystal, the order parameter evaluates
to one.
The Order Parameter
Typical values for the order parameter of a liquid
crystal range between 0.3 and 0.9, with the exact
value a function of temperature, as a result of kinetic
molecular motion.


Interactions between individual molecules are represented by a
potential of average force
( ) ( )
2 2
cos cos V vP P u u = < >
Maier-Saupe Theory - Mean Field Approach
{V: minimum} when phase is ordered (-P
2
(cosu))
{V: V=0} when phase is disordered (<P
2
(cosu)>)
factor for intermolecular strength ( v)
u
n
|

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 Nomenclature
Elastic Constant K
ii
S
2
Birefringence An S
Dielectric Anisotropy Ac S
Magnetic Anisotropy A_ S
Viscosity Anisotropy Aq S
Example: Does the threshold switching voltage for a TN increase
or decrease as the operating temperature increases.

Scales as the square root of S
therefore lowers with increasing temperature
2
TH
K S
V S
S c
=
A
proportional to
Anisotropy: Dielectric Constant
|
Off-axis dipole moment, angle | with molecular axis
( )
2
2
3cos 1
2
o B
NhFS F
k T

c o |
c
(
A = A +
(

N: number density
h,f: reaction field, reaction
cavity parameters
S: order parameter
Ao: anisotropy in polarizability
: molecular dipole moment
k
B
: Boltzman constant
T: Temperature
For values of the angle |<54.7
o
, the
dipolar term is positive, and for
values |>54.7
o
, the dipolar term is
negative, and may result in a
materials with an overall -Ac.
Anisotropy: Dielectric Constant
++
++
+
- -
- -
-
E
c
c
Ac = c c > 0
E
Ac = c c < 0
positive
negative
all angles in
the plane
to E are
possible for the
-Ac materials
E
Dielectric Constants (@20
o
C, 1kHz)
*Mixture Application Ac c

BL038 PDLCs 16.7 21.7 5.3
MLC-6292 TN AMLCDs 7.4 11.1 3.7
ZLI-4792 TN AMLCDs 5.2 8.3 3.1
TL205 AM PDLCs 5 9.1 4.1
18523 Fiber-Optics 2.7 7 4.3
95-465 -Ac material -4.2 3.6 7.8
Materials Dielectric Constant
Vacuum 1.0000
Air 1.0005
Polystyrene 2.56
Polyethylene 2.30
Nylon 3.5
Water 78.54
*EM Materials
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. A_ is usually positive since:
0
ll ll
_ _ _ _ _

A = > >
Magnetic Anisotropy: Diamagnetism
C
5
H
11
C
7
H
15
CN
CN
CN
C
5
H
11
CN
C
7
H
15
C
7
H
15
CN
9 3 1
/10 m kg _

A
1.51
1.37
0.46
0.42
-0.38
Compound
Optical Anisotropy: Birefringence
ordinary ray (n
o
, ordinary index of refraction)
extraordinary ray (n
e
, extraordinary index
of refraction)
Optical Anisotropy: Birefringence
ordinary wave
u
extraordinary wave
o
n n =
2 2
2 2 2
1 cos sin
o e
n n n
u u
= +
For propagation along the optic
axis, both modes are n
o

optic
axis
Birefringence (20
o
C @ 589 nm)
EM Industry An n
e
n
o
Application
Mixture

BL038 0.2720 1.7990 1.5270 PDLC
TL213 0.2390 1.7660 1.5270 PDLC
TL205 0.2175 1.7455 1.5270 AM PDLC
ZLI 5400 0.1063 1.5918 1.4855 STN
ZLI 3771 0.1045 1.5965 1.4920 TN
ZLI 4792 0.0969 1.5763 1.4794 AM TN LCDs
MLC-6292 0.0903 1.5608 1.4705 AM TN LCDs
ZLI 6009 0.0859 1.5555 1.4696 AN TN LCDs
MLC-6608 0.0830 1.5578 1.4748 ECB
95-465 0.0827 1.5584 1.4752 -Ac devices
MLC-6614 0.0770 --------- --------- IPS
MLC-6601 0.0763 --------- --------- IPS
18523 0.0490 1.5089 1.4599 Fiber Optics
ZLI 2806 0.0437 1.5183 1.4746 -Ac device

Birefringence Example: 1/4 Wave Plate
Unpolarized
linear polarized
circular polarized
polarizer
LC: An=0.05
d
What is minimum d for
liquid crystal 1/4 wave plate ?
( )
1
4
1
4
1 589
2,950 2.95
4 4 0.05
e o
e o
N N
n d n d
nm
d nm m
n

= +
= +
= = = =
A
Takes greater number of e-waves
than o-waves to span d, use
An=0.05
Surface Anchoring
microgrooved surface -
homogeneous alignment (//)
rubbed polyimide
ensemble of chains -
homeotropic alignment ()
surfactant or silane
Alignment at surfaces propagates over macroscopic distances
Surface Anchoring
|
u
N
n
polar
anchoring
W
u

azimuthal
anchoring
W
|
Strong anchoring 10
-4
J/m
2

Weak anchoring 10
-7
J/m
2
W
u,|
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 K
11
K
22
K
33

Mixture (pN) (pN) (pN) Application

BL038 13.7 ------ 27.7 PDLC
TL205 17.3 ------ 20.4 AM PDLC
ZLI 4792 13.2 6.5 18.3 TN AM LCD
ZLI 5400 10 5.4 19.9 TN
ZLI-6009 11.5 5.4 16.0 AM LCD
Order of magnitude estimate of elastic constant



U: intermolecular interaction energy
o: molecule distance
14
6 11
8
10
10 10 10
10
ii
U ergs
K dynes N pN
cm o

~ ~ = = =
Elastic Constant K
22
:
Temperature Dependence
7
6
5
4
3
2
-30
-20 -10
0
T-T
NI
(C)
K
2
2

(
x

1
0
-
1
2

N
e
w
t
o
n
)
P
-
a
z
o
x
y
p
h
e
n
e
t
o
l
e
P
-
a
z
o
x
y
a
n
i
s
o
l
e

(
P
A
A
)
2
( ) K S T
Viscosity: Shear Flow Viscosity Coefficient
n
Vv
Vv
n v
n
Vv
n
v
q
11

q
33

q
22

Typically q
22
> q
33
>q
11

( )
( )
shear stress
velocity gradient
t
q =
Vv
n
n
n
Viscosity: Flow Viscosity Coefficient
Dynamic Viscosity (q)
1 kg/ms = 1 Pas
0.1 kg/ms = 1 poise
Kinematic Viscosity (v)
1 m
2
/s

q
v

=
3
1000
kg
m
~
LC specification sheets give
kinematic viscosity in mm
2
/s
Approximate density
Viscosity: Flow Viscosity Coefficient
( ) ( ) ( )
2
2 2 3 3
3
1
20 / 20 / 10 / 0.02 / 0.2
10
ii
m
mm s mm s kg m kg ms poise
mm
q
| |
~ = = =
|
\ .
Typical Conversion Density Conversion
Flow 0.1 kg/ms = 1 poise
Viscosity
EM Industry Kinematic (v) Dynamic (q)
MIXTURE CONFIGURATION (mm
2
/s) (Poise)

ZLI-4792 TN AM LCDs 15 0.15
ZLI-2293 STN 20 0.20
MLC-6610 ECB 21 0.21
MLC-6292 TN AM LCDs (T
c
=120
o
C) 28 0.28
18523 Fiber Optics (n
o
=1.4599) 29 0.29
TL205 PDLC AM LCD 45 0.45
BL038 PDLCs (An=0.28) 72 0.72
Viscosity: Temperature Dependence
For isotropic liquids
0
exp
iso
B
E
K T
q q
| |
=
|
\ .
E is the activation energy for
diffusion of molecular motion.
H
3
CO
N
C
4
H
9

1.0
0.7
0.4
0.2
0.1
20 30 40 50
60
q
2
q
3
q
1
T
NI
V
i
s
c
o
s
i
t
y

(
p
o
i
s
e
)
Temperature (C)
n
Viscosity: Rotational Viscosity Coefficient
T
i
m
e

n
n
Rotation of the director n bv external
fields (rotating fields or static).

Viscous torque's I
v
are exerted on a liquid
crystal during rotation of the director n
and by shear flow.
1 v
d
dt
u
I =

1
: rotational viscosity coefficient
n
Viscosity: Rotational Viscosity Coefficient
n
n
EM Industry Viscosity Viscosity
MIXTURE CONFIGURATION (mPas) (Poise)

ZLI-5400 TN LCDs 109 1.09
ZLI-4792 TN AM LCDs 123 1.23
ZLI-2293 STN 149 1.49
95-465 -Ac Applications 185 1.85
MLC-6608 TN AM LCD 186 1.86
1
3
1
109 109 0.109 0.109 / 1.09
10
Pa
mPa s mPa s Pa s kg m s poise
mPa

| |
= = = = =
|
\ .
Viscosity: Comparisons
Material Viscosity (poise)

Air 10
-7

Water 10
-3

Light Oil 10
-1

Glycerin 1.5

LC-Rotational (
1
) 1<
1
< 2
LC-Flow (q
ii
) 0.2< q
ii
<1.0
S
u
r
f
a
c
e

x
Relaxation from Deformation
E
S
u
r
f
a
c
e

x
field on state
zero field
state
Relaxation when field is turned off
Relaxation time t
Defects
s=+1
s=+1
s=+1
s=1/2
s=-1/2
s=-1
s=3/2
s=+2
The singular line
(disclination) is pointing
out of the page, and director
orientation changes by
2ts on going around the
line (s is the strength)
A
X
Y
Z
Z
Aromatic or saturated ring core
X & Y are terminal groups
A is linkage between ring systems
Z and Z are lateral substituents
CH
3
- (CH
2
)
4
C N
4-pentyl-4-cyanobiphenyl (5CB)
General Structure
Mesogenic Core Linking Groups
Ring Groups
N
N
phenyl
pyrimidine
cyclohexane
biphenyl
terphenyl
diphenylethane
stilbene
tolane
schiffs base
azobenzene
azoxyben-
zene
phenylbenzoate
(ester)
phenylthio-
benzoate
CH CH
2 2
= CH CH
CH CH
= CH N
= N N
= N N
O
C O
C S
O
O
Common Groups
Nomenclature
Mesogenic Core
phenyl
benzyl
benzene
biphenyl
terphenyl
phenylcyclohexane (PCH)
cyclohexane
cyclohexyl
Ring Numbering
Scheme
3 2
1
6 5
4
3 2
1
6 5
4
Terminal Groups

(one terminal group is typically an alkyl chain)
CH
3
CH
2
CH
2
CH
2
CH
3
CH
2
C*H
CH
2
CH
3
straight chain



branched chain
(chiral)
Attachment to mesogenic ring structure
Direct - alkyl (butyl)
Ether -O- alkoxy (butoxy)
CH
3
-
CH
3
-CH
2
-
CH
3
-(CH
2
)
2
-
CH
3
-(CH
2
)
3
-
CH
3
-(CH
2
)
4
-
CH
3
-(CH
2
)
5
-
CH
3
-(CH
2
)
6
-
CH
3
-(CH
2
)
7
-
methyl
ethyl
propyl
butyl
pentyl
hexyl
heptyl
octyl
CH
3
-O-
CH
3
-CH
2
-O-
CH
3
-(CH
2
)
2
-O-
CH
3
-(CH
2
)
3
-O-
CH
3
-(CH
2
)
4
-O-
CH
3
-(CH
2
)
5
-O-
CH
3
-(CH
2
)
6
-O-
CH
3
-(CH
2
)
7
-O-
methoxy
ethoxy
propoxy
butoxy
pentoxy
hexoxy
heptoxy
octoxy
Terminal Groups
Second Terminal Group and
Lateral Substituents (Y & Z)
H -
F flouro
Cl chloro
Br bromo
I iodo
CH
3
methyl
CH
3
(CH
2
)
n
alkyl
CN cyano
NH
2
amino
N(CH
3
) dimethylamino
NO
2
nitro

phenyl

cyclohexyl
Odd-Even Effect
Clearing point versus alkyl chain length
0 1 2 3 4 5 6 7 8 9 10 11
carbons in alkyl chain (n)

c
l
e
a
r
i
n
g

p
o
i
n
t


18

16

14

12

10
CH
3
-(CH
2
)
n
-O O-(CH
2
)
n
-CH
3
C-O
O
CH
3
-(CH
2
)
4
C N
CH
3
-(CH
2
)
4
-O
C N
4-pentyl-4-cyanobiphenyl
4-pentoxy-4-cyanobiphenyl
Nomenclature
Common molecules which exhibit a LC phase
Structure - Property
N
N
CH
3
-(CH
2
)
4
C N
vary mesogenic core
A
A C-N (
o
C) N-I(
o
C) An Ac
22.5 35 0.18 11.5
71 52 0.18 19.7
31 55 0.10 9.7
Structure - Property
CH
3
-(CH
2
)
4
COO
vary end group
X
X C-N (
o
C) N-I (
o
C)
H
F
Br
CN
CH
3

C
6
H
5
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)
A
X
Y
Z
Z
Z and Z are lateral substituents
Broadens the molecules
Lowers nematic stability
May introduce negative dielectric anisotropy
S-N <-40 C solid nematic transition (< means supercools)

Clearing +92 C nematic-isotropic transition temperature

Viscosity (mm
2
/s) flow viscosity, some materials may stipulate the
+20 C 15 rotational viscosity also. May or may not give
0 C 40 a few temperatures

K
33
/K
11
1.39 ratio of the bend-to-splay elastic constant

Ac 5.2 dielectric anisotropy

An 0.0969 optical birefringence (may or may not give n
e
, n
o
)

dAn (m) 0.5 product of dAn (essentially the optical path length)

dV/dT (mV/
o
C) 2.55 how drive voltage changes as temperature varies

V(10,0,20) 2.14
V(50,0,20) 2.56 threshold voltage (% transmission, viewing angle,
V(90,0,20) 3.21 temperature)

EM Industry Mixtures
Property ZLI 4792 MLC 6292/000 MLC 6292/100
S-N <-40 C <-30 C <-40 C

Clearing +92 C +120 C +120 C

Viscosity (mm
2
/s)
+20 C 15 28 25
0 C 40 95 85
-20 C 160 470 460
-40 C 2500 7000 7000

K
33
/K
11
1.39 ------- ------

Ac 5.2 7.4 6.9
An 0.0969 0.0903 0.1146

dAn (m) 0.5 0.5 0.5
dV/dT (mV/C) 2.55 1.88 1.38

V(10,0,20) 2.14 1.80 1.38
V(50,0,20) 2.56 2.24 2.25
V(90,0,20) 3.21 2.85 2.83
EM Industry Mixtures