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Single crystal CuAlSe2 layers were grown on thoroughly etched semi-insulating GaAs(100) substrate at 410℃ with hot wall epitaxy (HWE) system by evaporating CuAlSe2 source at 680℃. The crystalline structure of the single crystal thin films was investigated by the photoluminescence(PL) and double crystal X-ray diffraction (DCXD). The carrier density and mobility of single crystal CuAlSe2 thin films measured with Hall effect by van der Pauw method are 9.24×1016 cm-3 and 295 cm2/V․s at 293K, respectively. The temperature dependence of the energy band gap of the CuAlSe2 obtained from the absorption spectra was well described by the Varshni's relation, Eg(T) = 2.8382 eV - (8.86 × 10-4 eV/K)T2/(T + 155K). After the as-grown single crystal CuAlSe2 thin films were annealed in Cu-, Se-, and Al-atmospheres, the origin of point defects of single crystal CuAlSe2 thin films has been investigated by PL at 10 K. The native defects of VCd, VSe, Cdint, and Seint obtained by PL measurements were classified as donors or acceptors. And we concluded that the heat-treatment in the Cu-atmosphere converted single crystal CuAlSe2 thin films to an optical n-type. Also, we confirmed that Al in CuAlSe2/GaAs did not form the native defects because Al in single crystal CuAlSe2 thin films existed in the form of stable bonds.

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