A. Zhuk

Role of paramagnetic defects in light emission processes in Y-doped ZrO2 nanopowders

Luminescence and structural properties of pure and Y-doped ZrO2 nanopowders with different Y content synthesized by co-precipitation of Zr and Y salts were investigated by x-ray diffraction, transmission electron microscopy, electron paramagnetic resonance (EPR) and photoluminescence (PL) methods. It was found that at constant calcination temperature (700 °С), the increase of Y content stimulates the transformation of crystalline phase from monoclinic through the tetragonal to the cubic one. Generally, room temperature PL emission was found to be similar for the samples with different Y content, demonstrating the same overlapped PL components in visible spectral range under extrinsic excitation. The relative contribution of each PL component was found to be affected by calcination time. In EPR spectra of as-prepared samples no signals were observed. The annealing in N2 or H2 flow results in the appearance of the signal from surface Zr3+ defects. In the latter the signal assigned to F-center also arises. The anti-correlation observed between the PL intensity and the value of the Zr3+ EPR signal allows us to conclude that the Zr3+ center is the center of fast non-radiative recombination. At the same time, interrelation between the intensity of the EPR signal assigned to F-centers and observed PL bands was not found.

Features of ZnS-powder doping with a Mn impurity during synthesis and subsequent annealing

Luminescence, electron spin resonance, and X-ray diffraction (XRD) methods were used to investigate the features of ZnS-powder doped by Mn impurity during self-propagating high-temperature synthesis and subsequent annealing. The obtained powder consists of ZnS microcrystals with mainly hexagonal phase (80 ± 5)%. It was found, that after synthesis Mn presents not only in the form of non-uniformly distributed microscopic impurities in ZnS, but also in the form of Mn metal nanocrystals. Thermal annealing at 800°C leads to the additional doping of ZnS from metallic Mn, to the redistribution of the embedded Mn in the volume of microcrystals, and to the ZnS oxidation. At the same time, the ratio between the cubic and hexagonal phases does not change. It was shown that annealing causes a decrease in the concentration of the defects responsible for the luminescence-excitation bands, which correspond to transitions from the ground to the excited states of the Mn2+ ion. As a result of annealing, there is also a change in XRD coherent domain size. Simultaneously, the intensity of peaks in the luminescence-excitation spectrum with wavelengths of 375 and 395 nm was changed. The causes of these changes and the nature of the corresponding bands are discussed.

New insight on the interaction of self-activated and Mn-related emission centers in ZnS

The photoluminescence (PL) and PL excitation (PLE) spectra of undoped and thermally doped with Mn ZnS single crystals are studied. In the PL spectra, the bands caused by Mn-related and self-activated (SA) emission centers were observed. A number of narrow peaks whose intensity enhanced with increasing Mn content were found in the PLE spectra of SA emission. The same peaks were present in the PLE spectra of the Mn-related emission band. Some of these peaks were previously observed in the absorption spectra and attributed to Mn2+ ions. The appearance of Mn-related peaks in the PLE spectra of SA emission is explained by excitation transfer from the Mn2+ ions to SA emission centers. The conditions required for this transfer and possible mechanisms of the process are discussed.

Elemental composition and luminescent characteristics of Zns:Cu powders, obtained by self-propagating high-temperature synthesis using Nacl as a flux

This work was devoted to ultrafine ZnS:Cu powders obtained by self-propagating high-temperature synthesis (SHS) using NaCl as a flux. Powder particles size and morphology were characterized by scanning electron microscopy (SEM). Elemental composition was measured by local energy-dispersive X-ray spectroscopy (EDS). Photoluminescence (PL) and luminescence excitation (PLE) spectra were studied. The influence of different amount of NaCl as a flux in synthesis of ZnS:Cu on its elemental composition and luminescent characteristics was investigated.

Structural transformations in ZnS:Cu in the course of thermal annealing

The influence of annealing at 800°C on the photoluminescence, electron spin resonance, and X-ray diffraction spectra of powder-like ZnS:Cu, obtained by the self-propagating high-temperature synthesis of a charge, consisting of Zn, S, and CuCl, is studied. It is shown that variation in the material’s heating rate up to the annealing temperature leads to a nonmonotonic variation in the spectral location and full-width at half-maximum of the photoluminescence band in the blue-green spectral region, as well as in the Mn2+ paramagnetic center concentration. It is established that the cubic and hexagonal ZnS phases, as well as the ZnO and CuZn phases, are present in the powder after synthesis. It is shown that annealing of the obtained powder at 800°C leads to three processes: the transformation of the hexagonal ZnS phase into the cubic phase, the oxidation of ZnS and CuZn, and the diffusion of Cu into the bulk of the ZnS microcrystals from the CuZn phase. A model attributing the observed variations in luminescence and electron spin resonance spectra to the diffusion of Cu and Mn impurities into the microcrystal bulk, particularly from the CuZn phase, and to their accumulation at extended defects is suggested.