Акцепторное легирование мышьяком при осаждении слоев CdTe из диметилкадмия и диизопропилтеллура

The incorporation and activation of arsenic from tris(dimethylamino)arsine in CdTe layers grown by metalorganic chemical vapor deposition with dimethylcadmium and diisopropyltellurium on GaAs substrates are investigated. Arsenic incorporation into CdTe to depend on the crystallographic orientation of the layers and increases in the order (111)B<(100)<(310). Arsenic concentration in the CdTe layers is proportional to the tris(dimethylamino)arsine flow rate to the power of 1.4 and an increase with decrease of the diisopropyltellurium/dimethylcadmium ratio from 1.4 to 0.5. The as-grown CdTe:As layers had p-type conductivity with arsenic and hole concentrations of 1·1017–7·1018 and 2.7·1014–4.6·1015 cm–3, respectively, but the arsenic activation efficiency not exceeding 0.3%. After annealing in argon flow (250–450 ° C) the highest hole concentration and arsenic activation efficiency were 1·1017 cm–3 and ~4.5 % respectively. The ionization energy of arsenic determined from the temperature dependence of the hole concentration was in the range of 98–124 meV. Low-temperature photoluminescence spectra of the layers showed an emission peak with energy of 1.51 eV, which can be attributed to donor-acceptor recombination, where the acceptor is AsTe with ionization energy about 90 meV.

Dissolution and Solubility of the Synthetic Natroalunite and the Arsenic-Incorporated Natroalunite at pH of 2.00–5.60 and 25–45°C

Arsenic is very harmful to most living organisms. The solubility data of As-containing compounds are significant in geoscience and environmental science. The arsenic-incorporated natroalunite precipitation has been proposed to eliminate arsenic from water, both for industrial practice and remediation of polluted areas. Unfortunately, only few works have been made on partial arsenic incorporation in natroalunite and the thermodynamic data for natroalunite and arsenic-incorporated natroalunite now are still lacking. Moreover, the dissolution mechanisms of arsenic-incorporated natroalunites have never been studied. In the present work, the dissolution of the synthetic natroalunite [Na0.93(H3O)0.61Al2.82(SO4)2(OH)6] and the synthetic arsenic-incorporated natroalunite [Na0.88(H3O)2.44Al2.35(AsO4)0.38(SO4)1.62(OH)6] at 25°C, 35°C, and 45°C was experimentally examined in HNO3 solution (pH of 2.00 and 4.00) and pure water. The characterizations confirmed that the solids showed no recognizable change after dissolution. All dissolutions underwent a pH variation, which was caused by a great depleting of H3O+/OH− ions, typically at the reaction beginning. The dissolution in H3O+ medium proved to be near-stoichiometric within the short beginning period, and the dissolved Na+, Al3+, SO42−, and AsO43− concentrations were stoichiometric according to the initial solids and then appeared to be nonstoichiometric with the Na/SO4 mole ratios higher and the Al/SO4 and AsO4/SO4 mole ratios lower than the stoichiometry until the experimental end, indicating that the components were released from solid to solution preferentially after the following order: Na+ (H3O+) > SO42− > AsO43− > Al3+. From the experimental results under the condition of initial pH 2.00 and 25°C, the solubility products [Ksp] and the Gibbs free energies of formation [ΔGf°] were calculated to be 10−81.02±0.33∼10−81.04±0.27 and −4713 ± 2 to −4714 ± 1 kJ/mol for the natroalunite and 10−92.30±0.30∼10−92.41±0.37 and −5078 ± 2 to −5079 ± 2 kJ/mol for the arsenic-incorporated natroalunite, respectively. The thermodynamic quantities, ΔG°, ΔH°, ΔS°, and ΔCp°, were determined to be 462303.43 J/K·mol, 122466.83 J/mol, −1140.39 J/K·mol, and 4280.13 J/K·mol for the natroalunite dissolution reaction at initial pH 2.00 and 25°C and to be 526925.48 J/K·mol, 159674.76 J/mol, −1232.38 J/K·mol, and 1061.12 J/K·mol for the dissolution of the arsenic-incorporated natroalunite at initial pH 2.00 and 25°C, respectively.