An emission band that appears in the high energy side of the photoluminescence spectra of a modulation doped multiple quantum well structure was investigated by means of magneto‐photoluminescence and photoluminescence excitation spectroscopy. We show that this emission band is related to the Al0.36Ga0.64As layers of the structure. We analyze the data within the framework of the configuration coordinate model and attribute this photoluminescence band to the recombination of electrons trapped to a new deep center in the alloy and the photogenerated holes. ©1995 American Institute of Physics.