A comprehensive study is reported of the photoluminescence properties of ZnS thin films between 1.6 and 320 K grown by metalorganic molecular beam epitaxy and chemical beam epitaxy on GaAs substrates. Both heavy- and light-hole free excitons were observed at low temperatures with linewidths of 7.0 and 5.3 meV, respectively, as well as donor- and acceptor-bound excitons and free-to-bound recombination along with their longitudinal optical (LO) phonon replicas. The free exciton emission was observed up to 320 K, and enabled the room temperature band gap of ZnS to be unambiguously determined as 3.723 eV. The temperature dependence of the peak position, intensity, and linewidth was well described by the conventional empirical relations and by Toyozawa’s exciton line shape theory. The bound exciton peak positions were found to follow the temperature dependence of the band gap whereas the free-to-bound recombination feature was displaced by (1/2)kT above the band gap energy. Thermal quenching of the donor-bound exciton was described by a one-step quenching process with an activation energy of 14.4 meV. The self-activation (SA) center was also observed at 2.846 eV with a linewidth of 410 meV. The temperature dependence of the SA emission was well described by the configuration coordinate model. From the thermal broadening of the SA emission, an average phonon energy of 47.5 meV was determined, in good agreement with the LO phonon energy.

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