Low-temperature solvothermal synthesis of nanocrystalline indium nitride and Ga–In–N composites from the decomposition of metal azides

Nanocrystalline InN powders have been synthesized through metal azide decomposition in superheated toluene and refluxing hexadecane solvents near 280 °C. The metal azide intermediates were formed in situ through the metathesis reaction of InBr3 and NaN3. The InN products from toluene consist of ∼10 nm hexagonal (wurtzite) structured crystallites in aggregated arrangements. InN from hexadecane and lower temperature toluene reactions produced more poorly crystalline InN that appears to contain a cubic (zinc blende) component. Coordinating amine solvents led to decomposition of the nitride to indium metal. Several reactions were undertaken to produce mixed metal nitrides of the form Ga1−zInzN where z is 0.5 and 0.75. The mixed metal nitride products are analytically consistent with composite versus solid-solution formation, however some metal mixing is observed. Data from X-ray diffraction, electron microscopy, thermal analysis, elemental analysis, and several spectroscopic methods are combined to form a consistent picture of the bulk and surface structures for these nanocrystalline InN materials.