title: Chemical vapor deposition of gallium nitride from the GaCl(3)+NH(3) system. Theoretical study of the structure and thermodynamics of potential intermediates formed in the gaseous phase.
abstract: Quantum chemical calculations at the B3P86/6-311G(d,p) level have been performed on potential intermediate molecules in the chemical vapor deposition (CVD) of GaN from the GaCl(3) + NH(3) system. The investigated molecules included the monomer (Cl(x)GaNH(x), x = 1-3) and oligomer species (Cl(2)GaNH(2))(n) with n = 1-3 and (ClGaNH)(n) with n = 1-4 as well as the respective chain dimers and trimers. The calculations revealed the importance of intramolecular Cl...H hydrogen bonding and dipole-dipole interactions in determining the conformational properties of the larger species. Except for the ClGaNH monomer, the Ga[bond]N bonding has a single bond character with a strong ionic contribution. Our thermodynamic study of the composition of the gaseous phase supported the predominance of the Cl(3)GaNH(3) complex under equilibrium conditions. Additionally, the calculated Gibbs free energies of various GaCl(3) + NH(3) reactions imply the favored formation of "saturated" chain and cyclic oligomers below 1000 K.
authors.affiliation: Research Group for Technical Analytical Chemistry of the Hungarian Academy of Sciences at the Institute of General and Analytical Chemistry, Technical University of Budapest, H-1111 Budapest, Szt. Gellért tér 4, Hungary. akovacs@mail.bme.hu
authors.forename: Attila
authors.initials: A
authors.lastname: Kovács