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Chapter 2: Liquid Crystals States 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 Phase Transition first defined by Georges Freidel in 1922 C CO2H S 84.5o N 128o I 139.5o The ordering parameter S=1/2<3cos2Q-1> S=0, isotropic S=1, Ordered Nematic, 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 Viscosity Fast Response Time Discotic Liquid Crystals Response to Electric and Magnetic Fields External Electric Field and Dielectric Properties of LC molecules Dielectric Constant ke0L = C = q/V Flow of ions in the presence of electric field Internal Field Strength E = E0 – E’ Alignment of LC molecules in Electric Field S=0 1>S>0 Dielectric Anisotropy and Permanent Dipole Moment m m Dielectric Anisotropy and Induced Dipole Moment easily polarized + minduced is large r// eis large - + r Molecular axis - minduced is small eis small e dielectric constant along the direction perpendicular to the molecular axis e 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, e = ee> 0 or ee Positivee> 0 (10 to 20) Negative e< 0 (-1 to -2) For high electrical resistance materials, n is proportional to e1/2 n = nn > 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 Examples S C N C5H11 e = +33 C - N - I 76 98 O N C O C5H11 O C7H15 e = - 4.0 C - N - I 45 101 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 Propagation of the light is hindered by the molecule E field e// Induced dipole by electromagnetic wave Speed of the light is slowed down = C /e// Propagation of the light parallel to the molecular axis E field Induced dipole by electromagnetic wave e // Change of the speed is relatively small // = C// /e Circular Birefringence Reflection of Circular Polarized Light Devices for Liquid Crystal Display Designs of LC cell Electronic Drive AM: 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 scanning Vs: turn on voltage Vns: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-Change Guest-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 rigid Linker: 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 Common components for LC molecules Core Group Linker A, B -(CH=N)-; -(N=N)-(N=NO)-; -(O-C=O)Terminal Group X, Y Non-polar flexible groups -R, -OR, -O2CR Polar rigid group -CN, -CO2H, -NO2, -F, -NCS 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 like structure upon heating (5) Chemically stable. (6) Phase transition temperature is determined by H and S. At TCN or TNI, Go = Ho –TSo= 0. Therefore TCN= HoCN/SoCN and TNI= HoNI/SoNI L D n L/D > 4 Ti > Tm (nematic) No. of Phenyl ring 2 3 4 5 6 L/D 2 3 3.9 4.8 5.5 Ti 77 213 320 445 565 Tm 388 438 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. 67 o O 6-10 o O Flexible linker O O L n D Nematic phase could not be observed until L/D >4 n 1 2 3 L/D 3 .8 5 .1 6 .4 Ti 132 254 464 Tm 176 220 6-10 o 67 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: Crystal TC-N T Nematic LC TN-I Isotropic Liquid 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. (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. O HO R R OH O R = C5H11 R = C8H17O R = C10H21O TCN = 88; TNI=126.5 TCS = 101; TSN = 108; TNI=147 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 C8H17O N C H X Terminal group for nematic Short chain MeO N C H X 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 Tm 84 Ti Ti 127 3.5 68 130 95 24 35 204 130 34 239 71 (52) Stereochemistry of alicyclic systems H R NC H H H NC R No LC phase Tm C N Ti C5H11 CN 48 61 C5H11 CN 24 35 C5H11 CN 31 55 C5H11 CN 62 100 I 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. Heteroatom effects 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. MM2 space-filling models Flat molecule TNI = 55 oC Unsymmetrical TNI = 19 oC Symmetrical but rings are perpendicular TNI = 28 oC The TCN and TNI orders: dicyclooctane > cyclohexane > phenyl MM2 calculation Linear structure 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. R (CH2)n R where R= N C H OCH3 n 0 1 2 3 4 5 Tm 266 171 156 - Ti >390 312 270 - 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. O C5H11 O CN Tm Ti 48 79 30 51 C5H11 CN 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. X C8H17O CO2H Not quite linear for some substituents Electronic effects arising from the lateral groups Mixing of two Components may generate a LC phase RO CO2H R = Me or Et Doesn't show LC properties O HO OR or R' RO OH O LC Mixture of two Components RO N C4H9 MBBA R = Me EBBA R = Et A mixture of MBBA (60%) and EBBA (40%) would lead to LC at room temperature Temperature Dependent Rotation of the Cholesteric Phase Left Cl H Right CH3(CH2)12CO2 H Main Chain Liquid Crystal Polymer mesogenic unit flexible linker Side Chain Liquid Crystal Polymer Polymer Backbone Polymer Backbone Laterally attached Terminally attached Combined Liquid Crystal Polymer Lyotropic Liquid Crystal Polymers Fairly rigid rod like polymers; but soluble in certain solvents to form a LC phase O HN O O NH Kelver HN PBA Dissolve and LC formation Fiber formation to give high tensile strength fibers Common Components for Lyotropic Liquid Crystals N O N S O N S N Examples N S S N n Poly(p-phenylenebenzobisthiazole) PBT Soluble in PPA or H2SO2 and could be fabricated as high tensile strength polymeric wires N O O N n