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Synthesis and properties of N 3 and CN delivery compounds and related precursors for nitride and ceramic fabrication
Author(s) -
Tice Jesse B.,
Ritter C. J.,
Chizmeshya A. V. G.,
Forrest Brandon,
Torrison Levi,
Groy T. L.,
Kouvetakis J.
Publication year - 2008
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.1422
Subject(s) - chemistry , nitride , metathesis , homoleptic , amorphous solid , reagent , ceramic , halide , crystallography , inorganic chemistry , organic chemistry , polymerization , metal , polymer , layer (electronics)
Abstract The simple azido and cyano compounds Cl 2 AsN 3 , Br 2 AsN 3 , (C 6 H 5 )SiH 2 N 3 , (C 6 H 5 )SiH 2 CN and p ‐(tolyl)SiH 2 CN have been prepared for the first time by metathesis reactions involving the corresponding halides and NaN 3 , LiN 3 and LiCN. These compounds represent a highly reactive and efficient family of delivery reagents for the preparation of N 3 and CN molecular precursors to bulk ceramics and nitride thin films. They are isolated as low volatility liquids and characterized by spectroscopic methods and chemical analysis. Ab initio simulations were used to elucidate the structural and vibrational properties of the simpler, fully inorganic Cl 2 AsN 3 and Br 2 AsN 3 species. This theoretical treatment was extended to include the hypothetical H 2 AsN 3 and HClAsN 3 derivatives which are particularly desirable as single‐source low‐temperature AsN sources for the formation of highly sought after, metastable GaAs 1− x N x materials for solar cell applications. The practical utility of the title molecules is also demonstrated by synthesizing several representative compounds of B, Be, Ga and Al, which are of interest for the development of open frameworks, optoelectronic nitrides and refractory BCN hybrids. The cyanide derivatives (C 6 H 5 )SiH 2 CN and p ‐(tolyl)SiH 2 CN react readily with Be and B halides to yield crystalline Be(CN) 2 and amorphous BCN. The latter is crystallized upon heating to form graphite‐like polymorphs with homogeneous nanoscale morphologies. The azide derivatives Cl 2 AsN 3 , Br 2 AsN 3 and (C 6 H 5 )SiH 2 N 3 react readily with GaBr 3 , GaCl 3 and BBr 3 to produce high yields of the previously reported Br 2 GaN 3 , Cl 2 GaN 3 and Br 2 BN 3 , respectively. The latter is shown to possess a trimeric molecular structure in which the α‐nitrogen of the azide group bridges the boron atoms to form cyclohexane‐like B 3 N 3 rings. Copyright © 2008 John Wiley & Sons, Ltd.