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Ammonothermal synthesis of nitrides is reviewed, with an emphasis on gallium and aluminum nitrides due to their important applications as direct wide band gap semiconductors. Since the crystallization process of nitrides involves the formation of some intermediate compounds during ammonothermal synthesis where a mineralizer is used, some ternary amides and ammoniates of aluminum and gallium with alkali metals or halides are also reviewed briefly. The ammonothermal crystallization of GaN and AlN bulk crystals, which is analogous to the hydrothermal growth of oxides, is introduced. Retrograde solubility, mineralizers, pressure-temperature-volume-concentration (PTVC) relations, phase relations, and transport growth of GaN in alkaline solutions are discussed in detail. Recent progress of GaN single-crystal growth by the ammonothermal technique is reported. We have grown GaN bulk single crystals up to 10 mm 2 by 1-mm thick. Issues such as ammonia breakdown, impurity incorporation, and scale-up of the ammonothermal growth of III-nitrides and perspectives on the method are also discussed.

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An intense infrared absorption band has been observed in a hydrothermally grown ZnO crystal. At 12K, the band peaks near 3577.3cm−1 and has a half width of 0.40cm−1, and at 300K, the band peaks at 3547cm−1 and has a half width of 41.3cm−1. This absorption band is highly polarized, with its maximum intensity occurring when the electric field of the measuring light is parallel to the c axis of the crystal. Photoinduced electron-paramagnetic-resonance experiments show that the crystal contains lithium acceptors (i.e., lithium ions occupying zinc sites). Lithium and OH− ions are present in the crystal because lithium carbonate, sodium hydroxide, and potassium hydroxide are used as solvents during the hydrothermal growth. In the as-grown crystal, some of the lithium acceptors will have an OH− ion located at an adjacent axial oxygen site (to serve as a passivator), and we assign the 3577.3-cm−1 band observed at 12K to these neutral complexes. Our results illustrate the role of hydrogen as a charge compensator for singly ionized acceptors in ZnO.

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