Magnesium-doped semiconductors have existing and anticipated applications in the fabrication of blue and green light-emitting diodes, blue and green laser diodes, and in microelectronics devices. At present, the area is limited by the precursor characteristics of bis(cyclopentadienyl)magnesium and substituted derivatives. We will describe our efforts to identify new magnesium source compounds that are potentially superior to magnesocenes and can be used in chemical vapor deposition processes. Monomeric three- and four-coordinate amides have been synthesized and totally characterized. These complexes are low-melting solids and are significantly more volatile than magnesocene derivatives. We will also describe the synthesis and characterization of several other classes of volatile magnesium compounds that might be useful in chemical vapor deposition processes.

Titanium nitride and ternary alloys thereof are of significant interest due to their hardness, chemical resistance, and good electrical conductivity. We report the synthesis, structure, and properties of several new precursors to titanium nitride that are based upon hydrazine-derived ligands. Application of these complexes in titanium nitride film depositions is overviewed. Film properties and characterization are presented. We also describe a new process for the preparation of titanium aluminum nitride films, and focus on how the presence of small amounts of aluminum change the properties of the material.

Vanadium nitride films reflect infrared radiation and are candidates for solar control coatings for glass. Herein we report our efforts to prepare new precursors to vanadium nitride coatings. Treatment of vanadium tetrachloride with primary alkylamines in dichloromethane affords vanadium chloride amides of the empirical formula [VCI2(NHR)2(NH2R)2]. The characterization and properties of these compounds is presented. The complexes [VC12(NHR)2(NH2R)2] can be sublimed at ca. 100°C (0.1 mmHg) and serve as single-source precursors to vanadium carbonitride films. Films have been deposited in the temperature range of 400-600°C on glass and silicon substrates. The film properties and characterization will be overviewed.

Herein we report our efforts to prepare new precursors to niobium nitride (NbN) and tantalum nitride (TAN, Ta3N5) thin films. Treatment of MC15 (M = Nb, Ta) with tertbutylamine in benzene solvent affords complexes of the formula [MCI2 (NtBu)(NHtBu)(NH2tBu)]2. The niobium complex [NbC12(NtBu)(NHtBu)- (NH2tBu)]2 affords NbN films on glass substrates between 500-600 °C, while the tantalum analog [TaC12(NtBu)(NHtBu)(NH2tBu)]2 gives films of Ta3N5 in this temperature range. Treatment of MCI5 (M = Nb, Ta) with 1,1-dimethylhydrazine in dichloromethane solvent affords complexes of the formula [MC12(NNMe2)(NHNMe2)(NH2NMe2)]n. These hydrazido complexes afford cubic MN films upon glass substrates at ≥400°C. Analyses of the films are presented.

Polycrystalline fluorine doped tungsten oxide thin films were deposited onto glass substrates by reacting tungsten hexafluoride, difluoroethane, and isopropanol. The reaction was performed in an atmospheric pressure chemical vapor deposition reactor at a temperature of approximately 400 °C. The electrical conductivity and spectral properties were suggestive of n-type substitutional doping in which oxygen is partially replaced by fluorine. Temperature dependent resistivity measurements were consistent with the presence of polarons. The films were blue in color with enhanced reflectance and absorbance in the IR. These optical characteristics are potentially useful in improving the solar control properties of glass. Scanning electron microscopy revealed a faceted surface morphology. The fluorine atom concentration decreased when the films were annealed in air.

The syntheses of the first single-source precursors to gold-colored titanium nitride films are reported. The precursors have the empirical formula [TiCl2(NHR)2(NH2R)0–2] and [TiCl4(NH3)2] and are obtained upon treatment of titanium tetrachloride with alkylamines or ammonia in nonpolar organic solvents. Both precursors sublime without decomposition between 80–120 °C and 0.01–0.1 mmHg. Deposition of titanium nitride films on glass and silicon substrates was achieved using either precursor at substrate temperatures of 475–600 °C. The films were characterized by x-ray diffraction, resistivity measurements, and X-ray photoelectron spectroscopy. In particular, low levels of carbon and chlorine contaminants were observed in the films.