Thermodynamic calculations were carried out on chloride transport vapor phase epitaxy of GaN using GaCl3/N2 and NH3/N2. At typical growth temperature and gas flow rates, both GaN formation and gas phase etching reactions of GaN are thermodynamically favored. Under thermodynamic equilibrium, most ammonia should decompose to nitrogen and hydrogen gases and gas phase etching of GaN occurs by HCI. From experimental measurements, less than 10% of the incoming ammonia decomposes and under this condition, GaN formation from GaCl3 /N2, and NH3 /N2 is thermodynamically favored. Higher V/III ratios give a larger driving force for GaN fromation. These calculations match our experimental results. Experimentally, we have optimized the growth conditions of GaN. High crystalline quality thick GaN films (10 ˜15μm) were grown on c-Al2O3. The GaN films show band edge emission dominated PL at both room temperature and 77 K. Only one set of diffraction peaks from (1012) planes with 60° spacing in the φ-scan of X-ray diffraction are observed. This indicates that the GaN films grown on c-Al2O3 are single crystalline. Typical growth rates were about 10 ˜ I5μm/hr and typical Hall mobility values of GaN films were in the range of 3 to 40 cm2/Vsec.