Inorg Chem. 1998 Dec 28;37(26):6638-6644. doi: 10.1021/ic981022d.

H(2)GaN(3) and Derivatives: A Facile Method to Gallium Nitride.

Inorganic chemistry

Jeff McMurran, Dingguo Dai, K. Balasubramanian, Cory Steffek, J. Kouvetakis, John L. Hubbard

PMID: 11670795 DOI: 10.1021/ic981022d

Abstract

We describe the formation and properties of H(2)GaN(3) (1), which is a very simple and stable molecular source for chemical vapor deposition (CVD) of GaN heterostructures. Compound 1 and the perdeuterated analogue D(2)GaN(3) (2) are prepared by the LiGaH(4) and LiGaD(4) reduction of Br(2)GaN(3) (3), respectively. Compound 3 is obtained from the thermal decomposition of the crystalline adduct SiMe(3)N(3).GaBr(3) (4) via loss of SiMe(3)Br. A single-crystal X-ray structure of 4 reveals that the molecule is essentially a Lewis acid-base complex between SiMe(3)N(3) and GaBr(3) and crystallizes in the orthorhombic space group Pna2(1), with a = 14.907(5) Å, b = 7.759(3) Å, c = 10.789(5) Å, V = 1248(1) Å,(3) and Z = 4. The new azidobromogallane HBrGaN(3) (5) is also prepared by reaction of appropriate amounts of 3 and LiGaH(4). Both H(2)GaN(3) (1) and D(2)GaN(3) (2) are volatile species at room temperature and can be readily distilled at 40 degrees C (0.20 Torr) without decomposition. Normal-mode analysis and ab initio theoretical calculations suggest that the vapor phase IR spectra of 1 and 2 are consistent with a trimeric (H(2)GaN(3))(3) and (D(2)GaN(3))(3) molecular structure of C(3)(v)() symmetry. On the basis of the mass spectrum, 1 is a trimer in the vapor phase and decomposes readily at low temperatures by elimination of only H(2) and N(2) to yield pure and highly stoichiometric GaN thin films. Crucial advantages of this new and potentially practical CVD method are the significant vapor pressure of the precursor that permits rapid mass transport at 22 degrees C and the facile decomposition pathway that allows film growth at temperatures as low as 200 degrees C with considerable growth rates up to 800 Å/min.

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