The rapid solid-state synthesis of group III and transition metal nitrides at ambient and high pressures

The development and improvement of new and existing technologies requires the synthesis of ultra-pure, crystalline materials. To meet this need, new ways of synthesizing materials with specific properties that are difficult or impossible to produce using traditional methods must be developed. The research presented herein outlines various new techniques that can be effectively used to produce high quality, crystalline materials using a novel time and energy efficient process called solid-state metathesis. This process combines two or more solid, molecular precursors that react exothermically to rapidly produce crystalline refractory ceramic and electronic materials, such as binary and ternary metal carbides, nitrides, phosphides, sulfides and oxides. Several important materials, including graphite, gallium nitride, indium nitride, tantalum nitride, silicon nitride and cubic boron nitride, which had been difficult or impossible to synthesize using standard solid-state metathesis reactions, can now be synthesized using modified metathesis methods. One of the new techniques described in this thesis for the successful synthesis of materials, such as gallium nitride, is the use of high pressures (up to 80,000 atm) before initiating a solid-state reaction. New nitrogen precursors were investigated, such as lithium amide and ammonium chloride, which when combined in the proper ratios, aid in the formation of gallium and indium nitride at ambient pressures. The major focus of this work is on new synthetic techniques that rapidly produce pure, crystalline materials. Since gallium nitride is an important direct wide-bandgap semiconductor of interest for high brightness, blue light-emitting diodes, lasers and flat panel displays, a large majority of the research described has been devoted to developing more efficient methods for synthesizing and purifying high quality products. Also discussed is the importance of controlling the temperature by the addition of less reactive precursor salts to these exothermic solid-state metathesis reactions, that often can reach temperatures in excess of 1500{dollar}spcirc{dollar}C. The techniques described in this manuscript open up a new area of study that is likely to produce materials, that were previously unobtainable, and provide novel, efficient routes to materials, that are currently difficult to produce.