The dynamic processes of the free excitonic transitions in GaN grown by metal‐organic chemical‐vapor deposition (MOCVD) have been studied. The recombination lifetimes of the A and B excitons have been measured at different temperatures and excitation intensities, from which radiative recombination lifetimes of about 0.35 and 0.3 ns for the A and B excitons, respectively, have been obtained. An increase in excitation power has resulted in a drastic enhancement in the radiative decay rate as well as in the exciton photoluminescence quantum yield, suggesting the excitonic transitions may provide gain for laser actions in GaN. The high quality as well as high purity of the investigated MOCVD sample has been demonstrated by the observations of (1) the free A‐ and B‐excitonic transitions, (2) excited states of the free excitons, (3) narrow free excitonic emission linewidths (1.7 meV at 10 K), (4) low electron concentration, and (5) high electron mobilities (∼600 cm2/V s).

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