Fundamental optical transitions in hexagonal boron nitride epilayers

Fundamental optical transitions in hexagonal boron nitride (h-BN) epilayers grown on sapphire by metal–organic chemical vapor deposition (MOCVD) using triethylboron as the boron precursor have been probed by photoluminescence (PL) emission spectroscopy. The low temperature (10 K) PL spectrum exhibits two groups of emission lines. The first group includes the direct observation of the free exciton and impurity bound exciton (BX) transitions and phonon replicas of the BX transition, whereas the second group is attributed to the direct observation of the band-to-band transition and its associated phonon replicas. The observations of zero-phonon lines of the band-to-band and exciton transitions, which are supposedly forbidden or “dark” in perfect h-BN crystals, result from a relaxed requirement of momentum conservation due to symmetry-breaking in the presence of high concentrations of impurities/defects and strain, which in turn provided more deterministic values of the energy bandgap (Eg), exciton binding energy (Ex), and binding energy of impurity bound excitons (EBX) in h-BN epilayers. Excitonic parameters of h-BN epilayers grown by MOCVD, carbon-free chemical vapor deposition, and high purity h-BN bulk materials are compared and discussed. The present results, together with available information in the literature, represent a significant improvement in the understanding of the fundamental optical properties and excitonic parameters of h-BN ultrawide bandgap semiconductors.