GENERAL I ARTICLE Liquid Crystals - The 'Fourth' Phase of Matter Shruti Mohanty The remarkable physical properties of liquid crystals have been exploited for many uses in the electronics industry_ This article summarizes the physics of these beautiful and I • complex states of matter and explains the working of a liquid crystal display. Shruti Mohanty has worked What are Liquid Crystals? on 'thin film physics of free standing banana liquid The term 'liquid crystal' is both intriguing and confusing; while crystal films' as a summer it appears self-contradictory, the designation really is an attempt student at RRI, Bangalore. to describe a particular state of matter of great importance She is currently pursuing her PhD in Applied Physics today, both scientifically and technologically. TJ!e[:w:odynamic at Yale University, USA. phases of condensed matter with a degree of order intermediate Her work is on supercon­ between that of the crystalline solid and the simple liquid are ductivity, particularly on called liquid crystals or mesophases. They occutliS Stable phases superconducting tunnel 'junctions and their for many compounds; in fact one out of approximately two applications. hundred synthesized organic compounds is a liquid crystalline material. The typical liquid crystal is highly ani'sotropic - in some cases simply an anisotropic liquid, in other cases solid-like in some directions. Liquid-crystal physics, although a field in itself, is often in­ cluded in the larger area called 'soft matter', including polymers, colloids, and surfactant solutions, all of which are highly de­ formable materials. This property leads to many unique and exciting phenomena not seen in ordinary condensed phases, and possibilities of novel technological applications. Liquid crystalline materials have been observed for over a cen­ tury but were not recognized as such until the 1880s. The most Keywords significant breakthrough came in 1888 when an Austrian bota­ Phase transition, birefringence, nist named Friedrich Reinitzer (credited for the first systematic polarisation, defects in liquid report of the phenomenon) observed that a material known as crystals, liquid crystal displays. cholesteryl benzoate had two distinct melting points. In his ________L~A~A~, __ ---- __ 52 v V VV V v RESONANCE I November 2003 GENERAL I ARTICLE experiments, Reinitzer increased the temperature of a solid sample and watched the crystal change into a hazy liquid at l4S.SoC. As he increased the temperature further, the material changed into a clear, transparent liquid at l78.SoC. The color of the turbid liquid also changed from red to bright blue-violet to pale blue, and the whole process was reversible. Reinitzer sent his early work to Otto Lehmann, a professor of natural philoso­ phy (physics) in Germany. Lehmann had constructed a polariz­ ing micros~ope with a stage to control precisely the temperature of his samples. He examined Reinitzer's substance with his microscope and noticed its similarity to other samples he was studying then. The term 'liquid crystal' was coined by him in 1900 (although at first he called them 'flowing crystals' (1889) and 'crystalline solids' (1890)). Slowly the study of this phase spread to all the continents and there was an explosive growth during the 1970s and 1980s. Theories for the liquid crystal phases added a new dimension of study and the invention of liquid crystals displays gave the field a practical dimension. Scientific studies of liquid crystals in­ volve both the chemistry and physics of this state, being concerned with liquid crystal synthesis and investigation of structure-property relationships. Technologically, liquid crys.:. tals have become a part of our lives, first showing up in wrist­ watches and calculators, but now being used for all kinds of advanced instrumentation, including laptops and futuristic flat panel displays. Their advantage was first their low power con­ sumption and small size; now they are competitive with other technologies for attractiveness, ease of viewing, cost and dura­ bility. Classification of Liquid Crystals The distinguishing characteristsics of phases of condensed mat­ ter are • Positional order • Orientational order. -R-ES-O-N-A-N--C-E-I-N-o-v-e-m-b-e-r-2-00-3--------~~~------------------------------5-3 GENERAL I ARTICLE te mer at u re crystal Uquid crystal (mesophases) liquid • 3-D lattice • 1- (2-)D lattice • no lattice • no lattice • orientation • orientation • orientati on • no orientation • solid • fluid -fluid - fluid ~ anisotropic ~ anaotropic ~ anaotropic ~ aotropic Figure 1. Solids, liquid crys­ Positional order refers to the extent to which molecules or tals and liquids - the mo­ groups of molecules, on average, show translational symmetry. lecular picture. Orientational order refers to the extent to which the molecules align along a specific direction on a long-range basis. In a crystalline solid, molecules are ordered in both the above ways, i.e. they are constrained to occupy specific sites in a lattice and to point their molecular axes in specific directions. On the other hand, molecules in a liquid diffuse randomly throughout the sample without any orientational order. Thus, a crystal has orientational and three-dimensional positional order, whereas a liquid has none. In contrast, liquid crystal phases have long range orientational order, but their long range positional order is generally at most two dimensional, although some exotic, very anisotropic three­ dimensionally ordered structures such as the smectic B and the twist-grain boundary phase are included in this family. Depending on the degree of positional order, different liquid crystal phases arise, e.g. • no positional order, giving rise to the nematic phase; ________LAAAAA, __ ------ 54 v V VV V v RESONANCE I November 2003 GENERAL I ARTICLE • one dimensional positional order, giving rise to smectic phases; • two dimensional positional order, giving rise to the columnar phase. Additionally, liquid crystals are also classified into: Thermotropics: These have small organic molecules, usually rod-like or disk-like, which show mesomorphic behaviour as a function of temperature. Lyotropics: These contain mixtures of organic molecules which show mesomorphic behaviour as a function of concentration of one or more of the molecular species in the mixture, as well as temperature. Liquid crystalline phases occur most readily in systems whose molecules have shapes that favors parallel packing. A few repre­ sentative shapes are shown in Figure 2. Experimental Identification of Liquid Crystals Liquid crystal phases can be identified by a variety of tech­ niques like optical polarizing microscope, differential scanning calorimetry, X-ray analysis, miscibility studies, neutron scatter­ Figure 2 . Shape anisotro­ ing studies and nuclear magnetic resonance. A few of these are pies of liquid crystalline described here. molecules. 20 - 30 A Rods(Calamitic) 1~_)-5A Disks/Cones [Stacks of these form columns] [ 1 (Discotic) '------ !J __________ ----=---::1 Boards ~I============~I_~- -R-ES-O--N-A-N-C-E-I--N-ov-e-m-b-e-r-2-0-0-3-----------~--------------------------------5-5 GENERAL! ARTICLE Box l. Polarization Light Passing Through Crossed Polarize,. Normal (unpolarised) optical radiation has Polarizer 1 Polarizer 2 I~ __.. light waves whose electric field vectors vi­ CVeftlcaJ) " (Horizontal)-~~.... __ brate in all perpendicular planes with respect Incident 8Hm (Unpolartzed) to the direction of propagation. When the \ electric field vectors are restricted to vibrate in a single plane by polarizing filters, then the Iight is said to be plane polarized with respect to the direction of propagation. Differential Scanning Calorimetry (DSC) Heat is needed to melt a crystalline solid to a liquid crystalline phase. The heat is measured using a DSC instrument. Although DSC cannot identify the type of phase, it provides valuable information like the exact transition temperatures and the en­ thalpies of the different phases. Polarizing Microscope In a polarising microscope, the light is polarized (Box 1) by passing it through a polarizing filter. It then passes through the sample, and then through a second polarizing filter called the analyzer. When a liquid crystal material is placed on a micro­ scope slide with a cover slip and the slide is heated and viewed using a polarizing microscope, textures characteristic of each type of liquid crystal can be seen. Cooling the liquid can also yield these textures when liquid crystal phases are present. X-ray Crystallography This can be used to study the extent of translational or posi­ tional order, and thus infer the type of liquid crystal phase. -56-------------------------------~-----------R-E-S-O-N-A-N-C-E-I---N-ov-e-m-b-e-r-2-o-o-3 GENERAL I ARTICLE The Thermotropic Mesophases Friedel (1922) classified thermotropic liquid crystals broadly I \ , into nematic, cholesteric, and smectic. As time went on, more /1, II and more complex, exotic phases were discovered. n The nematic phase is the simplest liquid crystalline phase ex- I I \ hibited by long rod-like organic molecules. The word nematic L-________-.--.J stems from the Greek word vT7J.1a (nema) which means 'thread' Figure 3. Nematic phase. referring to the thread-like structures seen in this phase when viewed through the polarizing microscope. This phase possesses orientational order of the long axes of the molecules about a particular direction referred to as the director n. The director is apolar in nature (n is physically indistinguishable