chapter 2: liquid crystals states between crystalline and isotropic liquid
TRANSCRIPT
Chapter 2: Liquid CrystalsStates between crystalline and
isotropic liquid
Liquid Crystals, 1805-1922. Before discovery of LC, Lehmann designed a microscope that could be used to monitor phase transition process.
1888 by Prof. Reinitzer, a botanist, University of Prague, Germany
C11H23O CO2H
C S N I
84.5o 128o 139.5o
Phase Transition first defined by Georges Freidel in 1922
The ordering parameterS=1/2<3cos2-1>
S=0, isotropicS=1, OrderedNematic, S=0.5-0.6
Classification of Smectic Liquid Crystals
A type: molecular alignment perpendicular to the surface of the layer, but lack of order within the layer.
B type: molecular alignment perpendicular to the surface of the layer, having order within the layer.
C type: having a tilted angle between molecular alignment and the surface of the layer.
Smectic B Liquid Crystals
Smectic C Liquid Crystals
Smectic A Liquid Crystals
More Detailed Classification of Smectic Phases
Nematic Liquid Crystals
Cholesteric Phase Liquid Crystals
Polymeric Liquid Crystal
Advantages of Nematic Phase and Cholesteric Phase LC
For Display Propose
Low ViscosityFast Response Time
Discotic Liquid Crystals
Response to Electric and Magnetic Fields
External Electric Field and Dielectric Properties of LC molecules
Dielectric Constant
L = C = q/V
Flow of ions in the presence of electric field
Internal Field Strength E = E0 – E’
S = 0 1 > S > 0
Alignment of LC molecules in Electric Field
Dielectric Anisotropy and Permanent Dipole Moment
Dielectric Anisotropy and Induced Dipole Moment
easily polarized
Molecular axis
induced is large is large
induced is small
is small
+ -r//
+
-
r
dielectric constant along the direction perpendicular to the molecular axis
dielectric constant along the direction parallel to the molecular axis
Light is a high frequency electromagnetic wave and will only
polarize electron cloud.
In general, = > 0 or
Positive> 0 (10 to 20) Negative < 0 (-1 to -2)
For high electrical resistance materials, n is proportional
to 1/2
n = n n > 0 in general
n is a very important parameter for a LC device. Larger the n value, thinner the LC device and faster the response time
O
S C N
C5H11
= +33
C - N - I76 98
O
O C7H15
C
N
C5H11 = - 4.0
C - N - I45 101
Examples
Magnetic Susceptibility and Anisotropy
Most of the organic molecules have closed-shell structure which is diamagnetic. In particular, the aromatic component will lead to a ring current that against the external magnetic field. Therefore the magnetic susceptibility is negative
//
large
small
Light as Electromagnetic Wave
Plane Polarized light can be resolved into Ex and Ey
Birefringence
Ordinary light travels in the crystal with the same speed v in all direction. The refractive index n0=c/v in all direction are identical.
Extraordinary light travels in the crystal with a speed v that varies with direction.The refractive index n0=c/v also varies with different direction
Generation of polarized light by crystal birefringence
Interaction of Electromagnetic Wave with LC Molecules
E field
Induced dipole by electromagnetic wave
Propagation of the light is hindered by the molecule
Speed of the light is slowed down
= C ///
//
E field
Induced dipole by electromagnetic wave
Propagation of the light parallel to the molecular axis
Change of the speed is relatively small
// = C// /
//
Circular Birefringence
Reflection of Circular Polarized Light
Devices for Liquid Crystal Display
Designs of LC cell
Electronic DriveAM: active matrix; TFT: thin film transistor; MIM: metal-insulator-metal
Alignment of LC molecules in a Display Device
Dynamic Scattering Mode LCD Device
Twisted Nematic (TN) Device 1971 by Schadt
Optical Response of a Twisted Nematic (TN) Device
Applied voltages and optical response
Super Twisted Nematic (STN) LC Device 1984 by Scheffer
By addition of appropriate amounts of chiral reagent
Twisted by 180-270 o
N:Number of row for scanningVs: turn on voltageVns:turn off voltage
Sharp change in the voltage-transmittance curve
Electrically Controlled Birefringence (ECB) Device (DAP type)
Black and White RF-STN Device
Optical response of Nematic LC in a Phase-ChangeGuest-Host Type Device (by G. Heilmeier)
Phase Change (PC) in a Guest Host (GH) LC Device
In-Plane Switching (IPS) type LC Device
Polymer Dispersed Liquid Crystal (PDLC) Device
Polymeric Nematic LC Materials
Active Matrix LCD
Structure of a typical LC Display
Hybrid Aligned Nematic (HAN) type
Fast response time,Upto ms scale.
Full color reflective display
References(1) Liquid Crystals, P. J. Collings, Princeton(2) Introduction to liquid crystals, P. J. Collings and M. Hird, Taylor and Francis(3) Flat Panel Displays, J. A. Connor, RSC.
Structure of rigid rod like liquid crystal molecules
Core group: usually aromatic or alicyclic; to make the structure linear and rigidLinker: maintaining the linearity and polarizability anisotropic.Terminal Chain: usually aliphatic chain, linear but soft so that the melting point could be reduced. Without significant destroy the LC phase. Note that sometimes one terminal unit is replaced by a polar group to provide a more stable nematic phase.Side group: to control the lateral interaction and thereore enhance the chance for nematic. Note that large side groups will weaken the lateral interaction
Linker A, B -(CH=N)-; -(N=N)--(N=NO)-; -(O-C=O)-
Terminal Group X, YNon-polar flexible groups
-R, -OR, -O2CRPolar rigid group
-CN, -CO2H, -NO2, -F, -NCS
Core Group
Common components for LC molecules
Side Branch-F, -Cl, -CN, -CH3
Character of LC molecules
(1) Rod like or Discotic(2) Empirical Length/Diameter parameter for LC phase
4 (Flory theory predicted critical L/D ratio = 6.4; Onsager theory predicted critical L/D ratio = 3.5)
(3) Having polar or highly polarizable moiety(4) Large enough rigidity to maintain the rod or discotic l
ike structure upon heating(5) Chemically stable.(6) Phase transition temperature is determined by H an
d S. At TCN or TNI, Go = Ho –TSo= 0. Therefore TCN= Ho
CN/SoCN and TNI= Ho
NI/SoNI
n
L/D > 4 Ti > Tm (nematic)
L
D
No. of Phenyl ring L/D Ti Tm2 2 773 3 2134 3.9 3205 4.8 445 3886 5.5 565 438
When the length of the molecules increases, van der Waal’s interactions that lead to thermal stability of the nematic phase increases. When L/D goes over the critical value, nematic phase appears.
In the above examples, the critical L/D is around 4. When L/D = 1, 2, or 3, no LC phase was observed.
O
O
O
O
n DL
n L/D Ti Tm
1 3.8 1322 5.1 254 1763 6.4 464 220
Nematic phase could not be observed until L/D >4
Flexible linker
6-10 o67 o
6-10 o67 o
This type of linker group is more flexible. Entropy gain is more effective in isotropic liquid state. Therefore SN-I is relatively large, leading to a low Ti. In the presence case, even for the LC molecules having the L/D upto 5.1, the Ti is only 254 oC
Other Options for the core group.
Thermal Stability:
Low TC-N; high TN-I
larger T = TN-I - TC-N , higher the stability of the LC state
In general, shorter the LC molecule, lower the phase transition temperature it has.For LC molecule contains more polarizable aromatic cores, or longer the body, Vander Waals interactions between LC molecules will increase. This will lead to higher thermal stability.
Crystal Nematic LC Isotropic LiquidTC-N
TN-I
T
(1) Nematogenic: structures that lead to nematic phase as the only LC phase
(2) Smectogenic: smectic phase is the only mesophase exhibited
(3) Calamitic: Both nematic and smectic phases would exhibited.
Smectic Phase
Smectic LC phase: Lamellar close packing structure are favored by a symmetrical molecular structure; Wholly aromatic core-alicyclic core each with two terminals alkyl/alkoxyl chains compatible with the core ten to pack well into a layer-like structures and generates smectic phase.
Long alkyl/alkoxyl chain would lead to strong lateral interactions that favors lamellar packing smectic phase formation.
RO
OHR
O
HO
R = C5H11 TCN = 88; TNI=126.5
R = C8H17O TCS = 101; TSN = 108; TNI=147
R = C10H21O TCS = 97; TSN = 122; TNI=142
Terminal groups for smectic phase
(1) Salts from RCO2H/RNH2
(2) Terminal groups contain -CO2R, -CH=CHCOR, -CONH2, -OCF3, -Ph, -NHCOCH3, -OCOCH3
N CH
C8H17O X
N CH
MeO XShort chain
Terminal group for nematic
For Smectic Phase
NHCOCH3 > Br > Cl > F > NMe2 > RO > H > NO2 > OMe
For nematic Phase
NHCOCH3 > OMe > NO2 > RO > Br~ Cl > NMe2 > Me >F > H
-CN,-NO2 -MeO are nematogen: poor smectic/good nematic-NHCOCH3, halogen, -NR2, good smectic/nematic
Nematic Phase.
(1) Due to its fast response time, the nematic LC phase is technologically the most important of the many different types of LC phase
(2) The smectic phases are lamellar in structure and more ordered than the nematic phase.
(3) The smectic phases are favored by an symmetrical molecular structure.
(4) Any breaking of the symmetry or where the core is long relative to the overall molecular length tends to destabilized the smectic formation and facilitate the nematic phase formation.
(1) At least two rings are required to enable the generation of LC phase.
(2) The nematic phase tends to be the phase exhibited when the conditions for the lamellar packing (smectic) cannot be met.
(3) Molecular features for nematic phase: (a) breaking of the symmetry or (b) short terminal chain.
C N TiTm Ti
24 35
130 239
84 127
68 130
71 (52)
204
95
3.5
34
NC R
H
H
NC H
H
R
No LC phase
Stereochemistry of alicyclic systems
CNC5H11
CNC5H11
CNC5H11
CNC5H11
C N ITm Ti
48
24
31
62
61
35
55
100
Change in the core structure of one phenyl ring for a range of non-aromatic rings only leads to increasing Tm and Ti, indicating that packing effect is more important than the polarizability effect for nematic phase. The ring functions in a space-filling manner, preventing the molecule form tumbling and maintaining the orientational ordering.
Heteroatomeffects
The heteroatoms enhances the polarity and higher melting point are seen. Nematic phase transition temperature is low than the melting point. The large sulfur atom further disrupts the nematic packing. The flexible sulfur containing ring gains more entropy from N to I and therefore lead to lower TNI.
UnsymmetricalTNI = 19 oC
Flat moleculeTNI = 55 oC
Symmetrical but rings are perpendicularTNI = 28 oC
MM2 space-filling models
The TCN and TNI orders: dicyclooctane > cyclohexane > phenyl
MM2 calculation
Linearstructure
Bent structure
Extending the number of the rings
Linking group:
Linking groups are used to extend the length and polarizability anisotropy of the molecular core in order to enhance the LC phase stability by more than any increase in melting point, producing wider LC phase ranges.
(A) Linking group should maintain the linearity of the molecule.
(CH2)nR R
R = N CH
OCH3
where
n Tm Ti
0 266 >390
1 - -
2 171 3123 - -
4 156 2705 - -
Odd number of CH2: Bent
Even number of CH2: Linear
(b) Linker groups that connect aromatic core units with the conjugation extended over the longer molecules. This could enhance the polarizability anisotropy.
Other common linker groups
O
O
O O
O
e.g.
C5H11
O CN
O
C5H11
CN
Tm Ti
48
30
79
51
Amide linker cannot be used due to the strong hydrogen bond interactions that lead to high melting temperature
Terminal Flexible Long Chain:
The function of the terminal flexible long chain is to suppress the melting point without serious destroying the LC phase.
Lateral Substitution
Lateral substitution is important in both nematic/smectic systems. However, because of the particular disruption to the lamellar packing, necessary for smectic phases, lateral substitution nearly always reduces smectic phase stability more than nematic phase stability except when the lateral substitutions lead to a strong dipole-dipole interaction.
CO2HC8H17O
X Not quite linear for some substituents
Electronic effects arising from the lateral groups
CO2HRO
R = Me or Et
Doesn't show LC properties
RO
O
OH
OR or R'
O
HO
LC
Mixing of two Components may generate a LC phase
Mixture of two Components
N C4H9
RO
MBBA R = MeEBBA R = Et
A mixture of MBBA (60%) and EBBA (40%) would lead to LC at room temperature
Cl
H
CH3(CH2)12CO2
H
Left
Right
Temperature Dependent Rotation of the Cholesteric Phase
Main Chain Liquid Crystal Polymer
mesogenic unit flexible linker
Side Chain Liquid Crystal Polymer
Polymer Backbone
Polymer Backbone
Terminally attached
Laterally attached
Combined Liquid Crystal Polymer
Lyotropic Liquid Crystal Polymers
Fairly rigid rod like polymers; but soluble in certain solvents to form a LC phase
NHHN
O O
Kelver
HN
O
PBA
Dissolve and LC formation
Fiber formation to give high tensile strength fibers
Common Components for Lyotropic Liquid Crystals
N
ON
O N
SN
S
Examples
N
SN
S nPoly(p-phenylenebenzobisthiazole) PBT
Soluble in PPA or H2SO2 and could be fabricated as high tensile strength polymeric wires
N
ON
O n