Liquid crystal
Liquid crystal is a state of matter whose properties are between those of conventional liquids and those of solid crystals. For example, a liquid crystal can flow like a liquid, but its molecules may be oriented in a common direction as in a solid. There are many types of LC phases, which can be distinguished by their optical properties. The contrasting textures arise due to molecules within one area of material being oriented in the same direction but different areas having different orientations. An LC material may not always be in an LC state of matter.
Liquid crystals can be divided into three main types: thermotropic, lyotropic, and [|metallotropic]. Thermotropic and lyotropic liquid crystals consist mostly of organic molecules, although a few minerals are also known. Thermotropic LCs exhibit a phase transition into the LC phase as temperature changes. Lyotropic LCs exhibit phase transitions as a function of both temperature and concentration of molecules in a solvent. Metallotropic LCs are composed of both organic and inorganic molecules; their LC transition additionally depends on the inorganic-organic composition ratio.
Examples of LCs exist both in the natural world and in technological applications. Lyotropic LCs abound in living systems; many proteins and cell membranes are LCs, as well as the tobacco mosaic virus. LCs in the mineral world include solutions of soap and various related detergents, and some clays. Widespread liquid-crystal displays use liquid crystals.
History
In 1888, Austrian botanical physiologist Friedrich Reinitzer, working at the Karl-Ferdinands-Universität, examined the physico-chemical properties of various derivatives of cholesterol which now belong to the class of materials known as cholesteric liquid crystals. Previously, other researchers had observed distinct color effects when cooling cholesterol derivatives just above the freezing point, but had not associated it with a new phenomenon. Reinitzer perceived that color changes in a derivative cholesteryl benzoate were not the most peculiar feature. He found that cholesteryl benzoate does not melt in the same manner as other compounds, but has two melting points. At it melts into a cloudy liquid, and at it melts again and the cloudy liquid becomes clear. The phenomenon is reversible. Seeking help from a physicist, on March 14, 1888, he wrote to Otto Lehmann, at that time a Privatdozent in Aachen. They exchanged letters and samples. Lehmann examined the intermediate cloudy fluid, and reported seeing crystallites. Reinitzer's Viennese colleague von Zepharovich also indicated that the intermediate "fluid" was crystalline. The exchange of letters with Lehmann ended on April 24, with many questions unanswered. Reinitzer presented his results, with credits to Lehmann and von Zepharovich, at a meeting of the Vienna Chemical Society on May 3, 1888.By that time, Reinitzer had discovered and described three important features of cholesteric liquid crystals : the existence of two melting points, the reflection of circularly polarized light, and the ability to rotate the polarization direction of light.
After his accidental discovery, Reinitzer did not pursue studying liquid crystals further. The research was continued by Lehmann, who realized that he had encountered a new phenomenon and was in a position to investigate it: In his postdoctoral years he had acquired expertise in crystallography and microscopy. Lehmann started a systematic study, first of cholesteryl benzoate, and then of related compounds which exhibited the double-melting phenomenon. He was able to make observations in polarized light, and his microscope was equipped with a hot stage enabling high temperature observations. The intermediate cloudy phase clearly sustained flow, but other features, particularly the signature under a microscope, convinced Lehmann that he was dealing with a solid. By the end of August 1889 he had published his results in the Zeitschrift für Physikalische Chemie.
Lehmann's work was continued and significantly expanded by the German chemist Daniel Vorländer, who from the beginning of the 20th century until he retired in 1935, had synthesized most of the liquid crystals known. However, liquid crystals were not popular among scientists and the material remained a pure scientific curiosity for about 80 years.
After World War II, work on the synthesis of liquid crystals was restarted at university research laboratories in Europe. George William Gray, a prominent researcher of liquid crystals, began investigating these materials in England in the late 1940s. His group synthesized many new materials that exhibited the liquid crystalline state and developed a better understanding of how to design molecules that exhibit the state. His book Molecular Structure and the Properties of Liquid Crystals became a guidebook on the subject. One of the first U.S. chemists to study liquid crystals was Glenn H. Brown, starting in 1953 at the University of Cincinnati and later at Kent State University. In 1965, he organized the first international conference on liquid crystals, in Kent, Ohio, with about 100 of the world's top liquid crystal scientists in attendance. This conference marked the beginning of a worldwide effort to perform research in this field, which soon led to the development of practical applications for these unique materials.
Liquid crystal materials became a focus of research in the development of flat panel electronic displays beginning in 1962 at RCA Laboratories. When physical chemist Richard Williams applied an electric field to a thin layer of a nematic liquid crystal at 125 °C, he observed the formation of a regular pattern that he called domains. This led his colleague George H. Heilmeier to perform research on a liquid crystal-based flat panel display to replace the cathode ray vacuum tube used in televisions. But the para-azoxyanisole that Williams and Heilmeier used exhibits the nematic liquid crystal state only above 116 °C, which made it impractical to use in a commercial display product. A material that could be operated at room temperature was clearly needed.
In 1966, Joel E. Goldmacher and Joseph A. Castellano, research chemists in Heilmeier group at RCA, discovered that mixtures made exclusively of nematic compounds that differed only in the number of carbon atoms in the terminal side chains could yield room-temperature nematic liquid crystals. A ternary mixture of Schiff base compounds resulted in a material that had a nematic range of 22–105 °C. Operation at room temperature enabled the first practical display device to be made. The team then proceeded to prepare numerous mixtures of nematic compounds many of which had much lower melting points. This technique of mixing nematic compounds to obtain wide operating temperature range eventually became the industry standard and is still used to tailor materials to meet specific applications.
In 1969, Hans Keller succeeded in synthesizing a substance that had a nematic phase at room temperature, N--4-butylaniline, which is one of the most popular subjects of liquid crystal research. The next step to commercialization of liquid-crystal displays was the synthesis of further chemically stable substances with low melting temperatures by George Gray. That work with Ken Harrison and the UK MOD, in 1973, led to design of new materials resulting in rapid adoption of small area LCDs within electronic products.
These molecules are rod-shaped, some created in the laboratory and some appearing spontaneously in nature. Since then, two new types of LC molecules have been synthesized: disc-shaped and cone or bowl shaped.
In 1991, when liquid crystal displays were already well established, Pierre-Gilles de Gennes working at the Université Paris-Sud received the Nobel Prize in physics "for discovering that methods developed for studying order phenomena in simple systems can be generalized to more complex forms of matter, in particular to liquid crystals and polymers".
Design of liquid crystalline materials
A large number of chemical compounds are known to exhibit one or several liquid crystalline phases. Despite significant differences in chemical composition, these molecules have some common features in chemical and physical properties. There are three types of thermotropic liquid crystals: discotic, conic, and rod-shaped molecules. Discotics are disc-like molecules consisting of a flat core of adjacent aromatic rings, whereas the core in a conic LC is not flat, but is shaped like a rice bowl. This allows for two dimensional columnar ordering, for both discotic and conic LCs. Rod-shaped molecules have an elongated, anisotropic geometry which allows for preferential alignment along one spatial direction.- The molecular shape should be relatively thin, flat or conic, especially within rigid molecular frameworks.
- The molecular length should be at least 1.3 nm, consistent with the presence of long alkyl group on many room-temperature liquid crystals.
- The structure should not be branched or angular, except for the conic LC.
- A low melting point is preferable in order to avoid metastable, monotropic liquid crystalline phases. Low-temperature mesomorphic behavior in general is technologically more useful, and alkyl terminal groups promote this.
Liquid-crystal phases
The various liquid-crystal phases can be characterized by the type of ordering. One can distinguish positional order and orientational order. Liquid crystals are characterized by orientational order, but only partial or completely absent positional order. In contrast, materials with positional order but no orientational order are known as plastic crystals. Most thermotropic LCs will have an isotropic phase at high temperature: heating will eventually drive them into a conventional liquid phase characterized by random and isotropic molecular ordering and fluid-like flow behavior. Under other conditions, a LC might inhabit one or more phases with significant anisotropic orientational structure and short-range orientational order while still having an ability to flow.The ordering of liquid crystals extends up to the entire domain size, which may be on the order of micrometers, but usually not to the macroscopic scale as often occurs in classical crystalline solids. However some techniques, such as the use of boundaries or an applied electric field, can be used to enforce a single ordered domain in a macroscopic liquid crystal sample. The orientational ordering in a liquid crystal might extend along only one dimension, with the material being essentially disordered in the other two directions.