GaN nucleation layer (NL) decomposition was measured using optical reflectance over a wide range of pressure P, temperature T, and H2/NH3 gas mixture. The GaN NLs show measurable decomposition above 800 °C and do not significantly roughen until above 960 °C. The NL decomposition rates increase with increasing P, increasing T, and decreasing NH3 flow. An activation energy EA of 2.68 eV was measured (from 820 to 960 °C) for NL decomposition and an EA of 2.62 eV was measured (from 900 to 1075 °C) for decomposition of thick, high-T bulk GaN films. Depending on P, the pre-exponential factor A0 was four to nine times larger for NL decomposition compared to bulk GaN decomposition. The EA measured for both NL and bulk GaN decomposition in mixed H2 and NH3 flows is similar to the EA for Ga desorption, suggesting that the rate-limiting step for both NL and bulk GaN decomposition is Ga desorption. © 2003 American Institute of Physics.