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Photoluminescence (PL) and photoluminescence excitation (PLE) spectroscopies are used to track the temperature dependence of the A exciton energy (EXA) in undoped bulk ZnO crystals grown by the seeded-chemical-vapor-transport method. For T150 K, the edge emission becomes broad as the A exciton recombination and its longitudinal-optical (LO) phonon replica become superimposed. We use PLE to determine the temperature dependence of EXA by monitoring the broad green emission commonly observed in as-grown ZnO crystals, and thus have established the energy difference between the EXA and PL emission peak energies. The PL emission at 3.26 eV at room temperature is shown to be offset by about 50 meV to lower energy than the actual EXA transition. The temperature dependence of the energy difference between the EXA and PL peaks is compared with predictions based on the lineshape function for the EXA– LO recombination. At 300 K, the PL is predominantly composed of EXA– LO recombination. Further, the temperature dependence of the EXA transition energy can be described using standard expressions and the Debye and Einstein temperatures are found to be 700±30 and 240±5 K, respectively. The slope of the EXA versus T curve for ZnO approaches a constant value of dEXA/dT=−0.35 meV/K near room temperature.
Wang et al. (Mon,) studied this question.