Optical properties of ordered Ga0.5In0.5P epitaxial layers grown by metalorganic vapor phase epitaxy are investigated by photoluminescence (PL) in a temperature range of 10–200 K using excitation power densities between 0.35 W/cm2 and 20 W/cm2. It is found that the intensity of the highest‐energy PL peak of the ordered Ga0.5In0.5P epilayer decreases first, then increases and finally goes down again with increasing temperature. A model of ordered Ga0.5In0.5P epitaxial layers is proposed, in which the ordered Ga0.5In0.5P epilayer is regarded as a type‐II quantum well structure with band‐tail states, and the dependence of PL spectra on the temperature and excitation intensity is reasonably explained.

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