2 May 2007 Development of hot-pressed and chemical-vapor-deposited zinc sulfide and zinc selenide in the United States for optical windows
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By the mid 1950s, there was a need for infrared-transmitting materials with improved optical and mechanical characteristics for military and commercial instruments. The newly invented "heat-seeking" missile also required a more durable infrared-transmitting dome. Some properties of ZnS were known from studies of natural minerals. More properties of pure ZnS and ZnSe were measured with single crystals grown in Air Force and industrial laboratories in the 1950s. In 1956, a team led by William Parsons at the Eastman Kodak Hawk-Eye Works in Rochester, New York began to apply the technique of hot pressing to make infrared-transmitting ceramics from powders. This work led to commercial production of six materials, including ZnS (IRTRAN® 2) and ZnSe (IRTRAN® 4) in the 1960s. Because the hot pressed materials could not be made in very large sizes and suffered from undesirable optical losses, the Air Force began to look for alternative manufacturing methods around 1970. Almost immediately, highly successful materials were produced by chemical vapor deposition under Air Force sponsorship by a team led by James Pappis at the Raytheon Research Division in Waltham, Massachusetts. Chemical-vapor-deposited materials replaced hot pressed materials in most applications within a few years. From a stream of Air Force contracts in the 1970s and early 1980s, Raytheon produced two different grades of ZnS for windows and domes, one grade of ZnSe for high-energy CO2 laser windows, and a composite ZnS/ZnSe window for aircraft sensor pods. In 1980, a competitor called CVD, Inc., was formed by Robert Donadio, who came from the Raytheon Research Division. CVD began with a license from Raytheon, but soon sued Raytheon, arguing that the license violated the Sherman Antitrust Act. Raytheon countersued for breach of employment contracts and misappropriation of trade secrets. In 1984, a jury ruled in favor of CVD, which went on to build a lucrative business in ZnSe and ZnS. CVD was eventually purchased, first by Morton, and later by Rohm & Haas. II-VI, Inc. was formed in 1971 by Carl J. Johnson and James E. Hawkey to produce CdTe optics for industrial CO2 lasers. When Raytheon introduced ZnSe into the market in 1974, it was obvious that ZnSe was superior to CdTe, so II-VI purchased ZnSe from Raytheon to produce optical components. The supply of ZnSe was never stable enough for II-VI, which therefore began its own effort to deposit ZnSe in 1975. In 1980, II-VI became an investor in and customer of CVD, Inc., buying a substantial portion of the ZnSe that could be supplied by both Raytheon and CVD. Still pressed to meet customer demand, II-VI built its first ZnSe production furnace in the period 1983-1986. A second furnace came on line in 1988 and two more were operational by 1990. Finally attaining excess capacity, II-VI became a supplier of ZnS as well as ZnSe. In 1990, Raytheon exited the ZnS and ZnSe business, leaving it mainly to CVD and II-VI.
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Daniel C. Harris, Daniel C. Harris, "Development of hot-pressed and chemical-vapor-deposited zinc sulfide and zinc selenide in the United States for optical windows", Proc. SPIE 6545, Window and Dome Technologies and Materials X, 654502 (2 May 2007); doi: 10.1117/12.716808; https://doi.org/10.1117/12.716808

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