A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication' described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .'whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.'" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.
Late in 1944 a group of petroleum and coal technologists was organized in Washington under the sponsorship of the Petroleum Administration for War and the U. S. Bureau of Mines. This group, known as the Technical Oil Mission, was placed under the authority of the Technical Industrial Intelligence Committee of the Joint Chiefs of Staff, which was then promoting the organization of other missions to be sent to Germany to obtain technical information regarding various industries in that country. The objective of the Tehnical oil Mission was to obtain technical data on German production of synthetic oil from coal and all other commercial practices and research projects connected with the oil industry. The primary purpose was to obtain such data as were immediately essential to assist the war against Germany and Japan, with secondary emphasis on technical information that would assist American industry after the end of the war. since oil-production facilities in Germany and the occupied countries controlled by Germany were the top targets for strategic bombing, the Technical Oil Mission was the first group under the Technical Induslrial Intelligence Com,mittee to enter Germany. A few members of the group flew to London in February 1945 and the majority of the remainder followed in March. In London they were joined by an equal number of British investigators and the combined mission was then sent into Germany under the authority of the Combined Intelligence Objectives Subcommittee (CIOS). A summary of the more important information gained by this combined British and American mission is presented below. German Oil Production The oil available to Germany, both natural and synthetic, and including production from occupied countries, reached a peak in late 1943 and early 1944 Production at this time was at the rate of 1,200,000 metric tons Per month, equivalent to 100,000,000 bbl. per year, or about 7 per cent of the wartime production in the United States. Of this production, jo per cent was crude oil from Romania and Hungary, 12 Per cent was crude oil from Germany itself, including Austria, 9 per cent cumprised coal-carbonization products, that is, tar and light oil, and only the remaining 29 per cent was synthetic liquid fuel made from coal or tar. Synthetic liquid fuel made in Germany was equivalent therefore to less than 2 per cent of wartime production of crude oil in the United States. The success of the strategic bombing campaign against German oil-production facilities is demonstrated by the fact that by September 1944 the Ploesti fields of Romania and much of the syrlthetic oil production had been eliminated, so that the amount of oil available to the German war machine was only 25 per Cent of the peak qualltity mentioned above. By early 1945, when the combined British and American oil mission was entering
Late in 1944 a group of petroleum and coal technologists was organized in Washington under the sponsorship of the Petroleum Administration for War and the U. S. Bureau of Mines. This group, known as the Technical Oil Mission, was placed under the authority of the Technical Industrial Intelligence Committee of the Joint Chiefs of Staff, which was then promoting the organization of other missions to be sent to Germany to obtain technical information regarding various industries in that country. The objective of the Tehnical oil Mission was to obtain technical data on German production of synthetic oil from coal and all other commercial practices and research projects connected with the oil industry. The primary purpose was to obtain such data as were immediately essential to assist the war against Germany and Japan, with secondary emphasis on technical information that would assist American industry after the end of the war. since oil-production facilities in Germany and the occupied countries controlled by Germany were the top targets for strategic bombing, the Technical Oil Mission was the first group under the Technical Induslrial Intelligence Com,mittee to enter Germany. A few members of the group flew to London in February 1945 and the majority of the remainder followed in March. In London they were joined by an equal number of British investigators and the combined mission was then sent into Germany under the authority of the Combined Intelligence Objectives Subcommittee (CIOS). A summary of the more important information gained by this combined British and American mission is presented below. German Oil Production The oil available to Germany, both natural and synthetic, and including production from occupied countries, reached a peak in late 1943 and early 1944 Production at this time was at the rate of 1,200,000 metric tons Per month, equivalent to 100,000,000 bbl. per year, or about 7 per cent of the wartime production in the United States. Of this production, jo per cent was crude oil from Romania and Hungary, 12 Per cent was crude oil from Germany itself, including Austria, 9 per cent cumprised coal-carbonization products, that is, tar and light oil, and only the remaining 29 per cent was synthetic liquid fuel made from coal or tar. Synthetic liquid fuel made in Germany was equivalent therefore to less than 2 per cent of wartime production of crude oil in the United States. The success of the strategic bombing campaign against German oil-production facilities is demonstrated by the fact that by September 1944 the Ploesti fields of Romania and much of the syrlthetic oil production had been eliminated, so that the amount of oil available to the German war machine was only 25 per Cent of the peak qualltity mentioned above. By early 1945, when the combined British and American oil mission was entering
Institute of Metals Division - The Vapor- Liquid-Solid Mechanism of Crystal Growth and Its Application to Silicon