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Stoichiometric gadolinium oxide thin films have been grown on silicon (100) substrates with a low-energy dual ion-beam epitaxial technique. Gadolinium oxide shares Gd[sub 2]O[sub 3] structures although the ratio of gadolinium and oxygen in the film is about 2:1 and a lot of oxygen deficiencies exist. Photoluminescence (PL) measurements have been carried out within a temperature range of 5–300 K. The detailed characters of the PL emission integrated intensity, peak position, and peak width at different temperature were reported and an anomalous photoluminescence behavior was observed. The character of PL emission integrated intensity is similar to that of some other materials such as porous silicon and silicon nanocrystals in silicon dioxide. Four peaks relative to α band and β band were observed also. Therefore we suggest that the nanoclusters with the oxygen deficiencies contribute to the PL emission and the model of singlet-triplet exchange splitting of exciton was employed for discussion. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]