Monocrystalline GaN(0001) thin films have been grown at 950°C on high-temperature, 100 nm thick, monocrystalline AIN(0001) buffer layers previously deposited at 1100°C on α(6H)-SiC(0001)si substrates via MOCVD in a cold-wall, vertical, pancake-style reactor. AlxGa1−xN films (0≤x≤1) were grown directly on the same SiC surface at 1100°C. Abrupt heterojunctions among the alloy composition were demonstrated. All films possessed a smooth surface morphology and were free of low-angle grain boundaries and associated oriented domain microstructures. Double-crystal x-ray rocking curve measurements for the GaN(0004) reflection for simultaneously deposited 1.4 μm films revealed FWHM values of 58 and 151 arcsec for materials grown on on-axis and off-axis material, respectively. The corresponding values for the AIN(0004) buffer layers were ≈ 200 and ≈400 arc sec, respectively. A similar relationship was found for the alloys for 0≤x≤0.2. The PL spectra of the GaN films deposited on both vicinal and on-axis substrates revealed strong bound exciton emission with a FWHM value of 4 meV. The spectra of these films on the vicinal substrates were shifted to a lower energy, indicative of films containing residual tensile stresses. A peak believed to be associated with free excitonic emission was also observed in each on-axis spectrum. Rutherford backscattering, Auger depth profiling and energy dispersive analysis were used to determine the AIN/GaN ratios in the alloys. Cathodoluminescence of solutions with x<0.5 exhibited strong near band edge emission with a FWHM as low as 31 meV. The band gaps were determined via spectral ellipsometry. Undoped GaN and A1xGa1−xN films were too resistive for accurate Hall-effect measurements. Controlled n-type Si-doping in GaN and AlxGa1−xN (for x≤0.4) was achieved for net carrier concentrations ranging from approximately 2×1017 cm−3 to 2×1019 (AlxGa1−xN) or to l × 1020 (GaN) cm−3. Mg-doped, p-type GaN was achieved with nA−nD = 3 × 1017 cm−3, p ≈ 7 Ω cm and μ ≈ 3 cm2/V·s.