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BaIn2S4, BaIn2S4:Ho3+, BaIn2S4:Er3+, BaIn2S4:Tm3+, BaIn2Se4, BaIn2Se4:Ho3+, BaIn2Se4:Er3+, and BaIn2Se4:Tm3+ single crystals were grown by the chemical transport reaction method. The optical energy gap of the single crystals was found to be 3.057, 2.987, 2.967, 2.907, 2.625, 2.545, 2.515, and 2.415 eV, respectively, at 11 K. The temperature dependence of the optical energy gap was well fitted by the Varshni equation. Broad emission peaks were observed in the photoluminescence spectra of the single crystals. They were assigned to donor–acceptor pair recombination. Sharp emission peaks were observed in the doped single crystals. They were attributed to be due to radiation recombination between the Stark levels of the Ho3+, Er3+, and Tm3+ ions sited in C1 symmetry.
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.
The optical absorption spectra of AgInS2:Co2+ single crystals grown by chemical transport reaction using iodine as a transporting medium have been studied at 6 K. The peaks can be explained by the transitions of Co2+ in the Td symmetry with the spin-orbit coupling, which means that the deviations of the atomic sites from those of the ideal wurtzite structure can be considered negligibly small. The consideration of both the crystal field parameters and the electronegativity difference between atoms may indicate that Co atoms substitute In atoms.
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.
MgxZn1-xSi: Ho3+, MgxZn1-xSe: Er3+, and MgxZn1-xSe: Tm3+ single crystals were grown by the closed-tube sublimation method. The single crystals crystallized into a zincblende structure at the composition x = 0.11 and a wurtzite structure at the composition x = 0.25, 0.32, and 0.41. The trivalent ions (Ho3+, Er3+, and Tm3+) of the rare-earth elements Ho, Er, and Tm site in Td and C3v symmetries in the single crystals with zincblende and wurtzite structures, respectively. Sharp emission peaks appeared in the photoluminescence spectra of the single crystals. These emission peaks are identified to originate from the radiation recombination between the energy levels of the trivalent ions sited in Td and C3v symmetries.
Melt-grown crystals of HgS and HgS : Co2+ were used to measure their optical absorption spectra. The optical energy band gaps of these crystals were 2.030 eV and 1.870 eV at room temperature, respectively. The impurity optical absorption peaks of Co2+ were observed at 4030, 5988, 12285, 12672, and 12905 cm−1. These peaks can be attributed to the electronic transitions between the split energy levels of Co2+ ion located at the Td symmetry site, where the crystal field, Racah, and spin-orbit coupling parameters were given by Dq = 403, B = 427, and Λ = −155 cm−1, respectively.
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