Liquid Crystal - History

History

In 1888, Austrian botanical physiologist Friedrich Reinitzer, working at the Charles University in Prague, 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 145.5 °C (293.9 °F) it melts into a cloudy liquid, and at 178.5 °C (353.3 °F) 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 name coined by Otto Lehmann in 1904): 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 (sample holder equipped with a heater) 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 20th century until his retirement 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 topic of research into 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 (now known as Williams 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. Unfortunately 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 used to this very day to tailor materials to meet specific applications.

In 1969, Hans Kelker succeeded in synthesizing a substance that had a nematic phase at room temperature, MBBA, 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 (cyanobiphenyls) with low melting temperatures by George Gray. That work with Ken Harrison and the UK MOD (RRE Malvern), in 1973, led to design of new materials resulting in rapid adoption of small area LCDs within electronic products.

In 1991, when liquid crystal displays were already well established, Pierre-Gilles de Gennes 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".