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Abstract:
In ZnTe:V bulk crystals with nominal vanadium concentrations between 1000 and 7000 ppm three vanadium-ion states V+, V2+, and V3+ were found in low-temperature optical measurements. No-phonon lines of the internal emissions were detected for the 5E(D)→5T2(D) transition of V+(d4) at 3401 cm−1 (0.422 eV), for 4T2(F)→4T1(F) of V2+(d3) at 4056 cm−1 (0.503 eV), and for 3T2(F)→3A2(F) of V3+(d2) at 4726 cm−1 (0.586 eV). The energies of the internal transitions are reduced with respect to the corresponding transitions in ZnS:V and ZnSe:V. The respective excitation spectra display, in addition to broad charge-transfer bands, higher excited levels of the individual charge states. Crystal-field calculations of the detected transition energies based on the Tanabe-Sugano scheme are presented. With the help of sensitization experiments, a one-electron model is designed, in which the donor level (V2+/V3+) is situated 12 500 cm−1 (1.55 eV) below the conduction-band edge and the acceptor level (V2+/V+) 9400 cm−1 (1.17 eV) above the valence-band edge. The dynamical behavior of the three infrared lurainescence bands was measured. Decay time constants of 43 μs (V+), 120 μs (V2+), and 420 μs (V3+) were found. Electron-paramagnetic-resonance (EPR) results measured on the same samples are presented in an accompanying paper and confirm the optical detection of isolated substitutional V2+(d3) and V3+(d2) ions. Relations between the EPR and optical results are discussed.
