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Undoped and Sm3+-doped BaAl2S4 and BaAl2Se4 single crystals were grown by the chemical transport reaction method. The optical energy band gaps of the BaAl2S4 and BaAl2Se4 were found to be 4.10 and 3.47 eV, respectively, at 5 K. In their photoluminescence spectra measured at 5 K, broad emission peaks at 459 and 601 nm appeared in the BaAl2S4 and at 486 and 652 nm in the BaAl2Se4. These emissions are assigned to donor–acceptor pair recombinations. Sharp emission peaks were observed in the Sm3+-doped BaAl2S4 and BaAl2Se4 single crystals at 5 K. Taking into account the ionic radii of the cations and Sm3+, these sharp emission peaks are attributed to the electron transitions between the energy levels of Sm3+ substituting with the Ba site.
We investigated the photoluminescence as well as the crystal structure and optical energy gaps of the Zn1-xCdxAl2Se4-4xS4x solid solution system based on the Al-related compounds of ZnAl2Se4, ZnAl2S4, CdAl2Se4, and CdAl2S4. The single crystals of the system with 0.0 ≤ x ≤ 1.0 were grown by the chemical transport reaction technique. The Zn1-xCdxAl2Se4-4xS4x crystallizes in a defect chalcopyrite structure for a whole composition and has an optical energy gap ranging from 3.525 to 3.577 eV at 13 K. The photoluminescence spectra at 13 K showed a strong emission band in the blue spectral region and a weak broad emission band in the visible region due to donor–acceptor pair recombination. The composition and temperature dependence of these bands were examined in the investigated regions. The simple energy band scheme for the radiative mechanisms of the Zn1-xCdxAl2Se4-4xS4x is proposed on the basis of our experimental results along with photo-induced current transient spectroscopy measurements.
We investigated the photoluminescence spectra as well as the crystal structure and optical energy gaps of the Zn1-xCdxAl2Se4 single crystals grown by the chemical transport reaction method. It was shown from the analysis of the observed x-ray diffraction patterns that these crystals have a defect chalcopyrite structure for a whole composition. The lattice constant a increases from 5.5561 A for x = 0.0 (ZnAl2Se4) to 5.6361 A for x = 1.0 (CdAl2Se4) with increasing x, whereas the lattice constant c decreases from 10.8890 A for x = 0.0 to 10.7194 A for x = 1.0. The optical energy gaps at 13 K were found to range from 3.082 eV (x = 1.0) to 3.525 eV (x = 0.0). The temperature dependence of the optical energy gaps was well fitted with the Varshni equation. We observed two emission bands consisting of a strong blue emission band and a weak broad emission band due to donor–acceptor pair recombination in the Zn1-xCdxAl2Se4 for 0.0 ⩽ x ⩽ 1.0. These emission bands showed a red shift with increasing x. The energy band scheme for the radiative mechanism of the Zn1-xCdxAl2Se4 was proposed on the basis of the photoluminescence thermal quenching analysis along with the measurements of photo-induced current transient spectroscopy. The proposed energy band model permits us to assign the observed emission bands.
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