Brightness waves of different activators in ZnS single crystals

The brightness waves of ZnS single crystals with copper and manganese activators have been examined. The measurements were made on single emitting spots of the crystals with time resolution. It could be ascertained that the single spots act independently and that the copper and manganese centres show different electroluminescent properties. The observed phenomena have been investigated in connection with recent electroluminescence theories.     

Low-voltage cathodoluminescence of ZnS single crystals

Bright blue and green cathodoluminescence from low resistivity ZnS crystals has been observed under the excitation of low-energy electron beams of several tens of volts; i.e., 40 fL at 50 V. Properties of the surface of the crystals are studied by the dependence of current and brightness on applied voltage and by the spectra of cathodoluminescence and photoluminescence.     

Quenching of photoluminescence in ZnS:Cu single crystals

Experiments on the quenching of photoluminescence in ZnS:Cu single crystals by secondary radiation are reported. Quenching of emission at photon energies of 1.4, 1.7, 2.4 and 2.75 eV by photons at 0.93, 1.6, 2.0, 2.4 eV is found, with a possible fifth peak at 2.7 eV. The effect of each secondary band on each emission band is found to be equivalent. This is explained in terms of a model in which all quenching transitions effectively fill a common ground state for the green/blue emission.     

Polarisation of the IR luminescence of cubic ZnS single crystals

The polarization of the IR luminescence of oriented ZnS crystals has been measured. None of the three main emission bands shows measurable polarization after excitation with polarized or unpolarized light. This result supports centers with symmetryT _d because they do not require any selection rules for the polarization of optical dipole transitions.     

Oxygen-phase-state changes in ZnS single crystals annealed in vapors of the constituents

Exciton reflection and emission spectra and edge emission have been investigated in ZnS sinle crystals grown from the melt and containing oxygen and then subjected to annealing in vapors of the constituents. The study of optical properties of the crystals cooled to 77°K were conducted in parallel with structural investigations of the crystals using proton and x-ray diffraction analyses. Based on the experimental data it was concluded that in the ZnS lattice, oxygen exists in a number of phase states: as part of a ZnS·O solid solution in the host lattice; as a precipitate from the saturated solid solutionβ=ZnS·O_sat; as an impurity atmosphere in the vicinity of packing faults; as ZnO precipitated on dislocations. The effect of oxygen in these various phase states on the exciton spectra and edge emission of ZnS was investigated. It was shown that oxygen is not very mobile in ZnS crystals annealed in sulfur vapor and it becomes concentrated mainly at packing defects. This leads to an increase in the concentration of packing defects and makes possible a transition from the cubic to the hexagonal modification of ZnS. The concentration of oxygen at packing defects leads to the appearance in reflection spectra and in the edge emission spectra ofα-ZnS of an additional hexagonal band located on the long wavelength side which is caused by the formation ofβ-ZnS·O solid solution. Oxygen diffuses quite rapidly through ZnS which has been annealed in zinc vapor and it precipitates from the crystals as the distinct phases ZnO orβ-ZnS · O_sat, and as a result the defect content of the hostα-ZnS lattice decreases. The concentration of the ZnO-phase is quite small and its exciton bands do not appear in the reflection spectra. The precipitation of the solid solution in the form of the phaseβ-ZnS · O_sat leads to the appearance of an additional long wavelength absorption edge in the 334 to 335 nm region (at 77°K). In addition, because single crystals of ZnS annealed in zinc vapor contain a large concentration of sulfur vacancies, there occurs a rather rapid formation of the solid solution on the layers ofα-ZnS close to the surface; this leads to a broadening and a shift toward longer wavelengths of the sphalerite exciton spectra. A similar shift is observed for the edge emission band ofα-ZnS. When the crystals are aged, theα-ZnS·O solid solution decomposes and the bands assume the standard sphalerite positions. Changes in the intensity of edge and exciton emission were investigated taking into account changes in the phase state of oxygen in the crystals.     

Infra-red enhancement and quenching of photoconductivity in sulfur-annealed ZnS single crystals

Infra-red (IR) enhancement and quenching of photoconductivity has been observed in S-annealed ZnS single crystals. These effects are studied as a function of the wavelength and the intensity of both types of radiation. Some interesting new properties are found, e.g. the decrease of a quenching effect at a constant intensity of the ultra-violet (UV) light with an increasing IR-light intensity and the existence of two opposite quenching curves depending on the UV-light intensity. These properties are explained by the appearance, in the investigated crystals, of an ambipolar conductivity state in a certain UV-light intensity range.     

Study of the trapping states in ZnS single crystals grown from gallium melt

The trapping levels in zinc sulphide single crystals grown from gallium melt have been investigated using thermoluminescence techniques. The observed peak at 175° K consists of two overlapping components at 173 and 200° K respectively. Thermal activation energies and frequency factors were calculated for both traps. The dependence of glow curve shape on excitation conditions is caused by the retrapping by non-filled 200° K traps of electrons freed from 173° K traps in the course of the glow curve run. In addition to the results on “pure” crystals, measurements were made on samples grown with chlorine, oxygen and copper impurities, as well. Although no positive identification of the chemical nature of the 173 and 200° K trapping centers has been possible, we find that our results are not inconsistent with a previously suggested model in which the traps are identified as complex defects. Comparison is also made with trap spectra observed earlier in gallium-doped zinc sulphide samples prepared by the usual methods.