A stoichiometric mixture of evaporating materials for ZnAl2Se4 single-crystal thin films was prepared in a horizontalelectric furnace. These ZnAl2Se4 polycrystals had a defect chalcopyrite structure, and its lattice constants were a0=5.5563Åand c0=10.8897Å.To obtain a single-crystal thin film, mixed ZnAl2Se4 crystal was deposited on the thoroughly etched semi-insulating GaAs(100) substrate by a hot wall epitaxy (HWE) system. The source and the substrate temperatures were 620oCand 400oC, respectively. The crystalline structure of the single-crystal thin film was investigated by using a double crystal X-ray rocking curve and X-ray diffraction ω-2θ scans. The carrier density and mobility of the ZnAl2Se4 single-crystal thin filmwere 8.23×1016cm−3 and 287m2/vs at 293K, respectively. To identify the band gap energy, the optical absorption spectra ofthe ZnAl2Se4 single-crystal thin film was investigated in the temperature region of 10-293K. The temperature dependence ofthe direct optical energy gap is well presented by Varshni's relation: Eg(T)=Eg(0)−(αT2/T+β). The constants of Varshni'sequation had the values of Eg(0)=3.5269eV, α=2.03×10−3eV/K and β=501.9K for the ZnAl2Se4 single-crystal thin film.The crystal field and the spin-orbit splitting energies for the valence band of the ZnAl2Se4 were estimated to be 109.5meVand 124.6meV, respectively, by means of the photocurrent spectra and the Hopfield quasicubic model. These results indicatethat splitting of the ∆so definitely exists in the Γ5 states of the valence band of the ZnAl2Se4/GaAs epilayer. The threephotocurrent peaks observed at 10K are ascribed to the A1-, B1-exciton for n=1 and C21-exciton peaks for n=21.

Single crystal ZnIn2S4 layers were grown on thoroughly etched semi-insulating GaAs(100) substrateat 450oC with hot wall epitaxy (HWE) system by evaporating ZnIn2S4 source at 610oC. The crystalline structureof the single crystal thin films was investigated by the photoluminescence (PL) and double crystal X-ray rockingcurve (DCRC). The temperature dependence of the energy band gap of the ZnIn2S4 obtained from theabsorption spectra was well described by the Varshni’s relation, Eg(T)=2.9514eV-(7.24×10−4eV/K)T2/(T＋489K). After the as-grown ZnIn2S4 single crystal thin films were annealed in Zn-, S-, and In-atmospheres, theorigin of point defects of ZnIn2S4 single crystal thin films has been investigated by the photoluminescence (PL)at 10K. The native defects of VZn, VS, Znint, and Sint obtained by PL measurements were classified as a donorsor acceptors type. And we concluded that the heat-treatment in the S-atmosphere converted ZnIn2S4 singlecrystal thin films to an optical p-type. Also, we confirmed that In in ZnIn2S4/GaAs did not form the nativedefects because In in ZnIn2S4 single crystal thin films existed in the form of stable bonds.