ZnS:Tm and ZnS:Tm,Cl thin films were grown by metalorganic chemical vapor deposition (MOCVD), using diethylzinc, H2S, Tm(thd)3(thd=2,2,6,6-tetramethyl-3,5-heptanedione), and HCl. The ZnS:Tm did not contain oxygen which might be introduced through the thd-radical. It thus has only codopant-free Tm3+luminescent centers probably associated with native defects. The electroluminescence (EL) spectrum of the ZnS:Tm,Cl showed three satellite emission lines in addition to the original emission of the ZnS:Tm, indicating the existence of Tm–Cl complex centers. In contrast, the photoluminescence (PL) spectrum of the ZnS:Tm,Cl under host excitation showed no discernible satellite emission lines. Hence, though the Tm ions in the Tm–Cl complex centers are expected to be charge compensated by Cl or a certain Cl-induced defect, they are rather inactive in the PL excitation while active in the EL excitation. The same properties were observed for the MOCVD-grown ZnS:Sm and ZnS:Sm,Cl [A. Kato, M. Katayama, A. Mizutani, N. Ito, and T. Hattori, J. Appl. Phys.77, 4616 (1995)], and therefore they probably occur for other rare-earth luminescent centers with Cl codopant. ©1997 American Institute of Physics.