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Dramatic enhancements of over 300× in the room temperature photoluminescence signal obtained from high purity GaAs epitaxial layers were recorded after a brief heat treatment in tertiarybutylphosphine vapor. Low temperature photoluminescence spectra indicate that, unlike other passivation techniques, the surface layer formed during this simple treatment does not induce any appreciable strain on the underlying epilayer. The increases in photoluminescence intensity are indicative of a reduction in surface recombination brought about by the formation of a very thin GaP layer that protects against surface oxidation.