Thermostimulated surface autosegregation in bismuth ferrite single crystals

The chemical and phase composition and morphological features of the surface nanostructure have been studied by the methods of high-resolution scanning electron microscopy, X-ray microprobe analysis, and atomic force microscopy in bismuth ferrite single crystals. This structure was formed as a result of the thermostimulated surface segregation after annealing in air or vacuum at the pressure of 10⁻⁴ Pa. It has been experimentally found that, at temperatures less than 500°C, Bi₂F₄O₉ nanoparticles were formed due to the selective diffusion of iron atoms to the surface. Starting from 300°C in vacuum and 450°C in air, the segregating atom type changed and nanophases with high bismuth concentration (sillenites Bi_{26 − x} Fe _x O₃₉ and Bi₂O₃ appeared in some regions. The partial orientation of new phases has been observed in some surface regions. A probable mechanism of the described phenomenon that represents a combination of selective intrinsic mass-transport of atoms from the bulk to the surface and their thermal evaporation has been discussed.     

Oriented surface autosegregation in the lead germanate single crystals

High-resolution raster electron microscopy, X-ray phase analysis, and atomic force microscopy were used to study the phase composition and morphological features of Pb₅Ge₃O₁₁ surface nanostructure formed as a result of thermostimulated surface segregation. It was experimentally established that, at some temperature, oriented Pb₃GeO₅ nanoparticles of 10–50 nm in size appeared. A probable mechanism of this phenomenon (which can be attributed to a new type of epitaxy implemented by selective intrinsic mass transfer to the surface) was discussed.     

Thermostimulated surface autosegregation in bismuth titanate single crystals

High resolution scanning electron microscopy (HRSEM), atomic force microscopy (AFM), and electron microprobe X-ray analysis (EPMA) were used to study the morphology and local phase composition of (001) faces in single crystals of bismuth titanate Bi₄Ti₃O₁₂ formed as a result of thermostimulated surface segregation (TSAS). One possible mechanism for this phenomenon, generated by the selective internal mass transfer of the matrix’s own atoms to the surface in competition with the processes of selective component evaporation, is discussed.     

Low-temperature luminescence and thermally stimulated luminescence of BeO: Mg single crystals

Luminescence and thermally stimulated luminescence (TL) of BeO: Mg crystals are studied at T = 6–380 K. The TL glow curves and the spectra of luminescence (1.2–6.5 eV), luminescence excitation, and reflection (3.7–20 eV) are obtained. It is found that the introduction of an isovalent magnesium impurity into BeO leads to the appearance of three new broad luminescence bands at 6.2–6.3, 4.3–4.4, and 1.9–2.6 eV. The first two are attributed to the radiative annihilation of a relaxed near-impurity (Mg) exciton, the excited state of which is formed as a result of energy transfer by free excitons. The impurity VUV and UV bands are compared with those for the intrinsic luminescence of BeO caused by the radiative annihilation of self-trapped excitons (STE) of two kinds: the band at 6.2–6.3 eV of BeO: Mg is compared with the band at 6.7 eV (STE₁) of BeO, and the band at 4.3–4.4 eV is compared with the band at 4.9 eV (STE²) of BeO. In the visible region, the luminescence spectrum is due to a superposition of intracenter transitions in an impurity complex including a magnesium ion. The manifestation of X-ray-induced luminescence bands at T = 6 K in BeO: Mg indicates their excitation during band-to-band transitions and in recombination processes. The energy characteristics of the impurity states in BeO: Mg are determined; the effect of the isovalent impurity on the fluctuation rearrangement of the BeO: Mg structure in the thermal transformation region of STE₁ → STE₂ is revealed.     

Kinetics of thermally stimulated recombination processes in lithium borate crystals

This paper reports on the results of the experimental and theoretical investigations of thermally stimulated recombination processes in crystals of the lithium borates Li₂B₄O₇ and LiB₃O₅. For both types of crystals, the measurements of thermally stimulated luminescence curves, spectra, and temperature dependences of the intensities of steady-state X-ray luminescence have been performed in a single experimental cycle. In the framework of a unified model for the Li₂B₄O₇ and LiB₃O₅ crystals, the thermally stimulated recombination processes have been calculated and the obtained results have been interpreted talking into account all available experimental data.     

Ion diffusion-controlled thermally stimulated processes in x-ray irradiated halide crystals

The ionic and ion diffusion-controlled thermally stimulated relaxation (TSR) processes in CaF₂, BaF₂, LiBaF₃ and KBr crystals were investigated above 290 K by means of the ionic conductivity, ionic thermally stimulated depolarisation current (TSDC) and thermal bleaching techniques. Under a DC field the halide crystals store large ionic space charge. We were able to detect in CaF₂, BaF₂, LiBaF₃ and KBr in the extrinsic ionic conductivity region a series of the ionic defect (the interstitial anion and/or anion vacancies - in fluorides; the cation vacancies - in KBr) release stages: 3-6 wide and overlapping ionic TSDC peaks. The correlated data of the ionic TSDC and the F band thermal show that above 290 K the TSR processes are initiated and controlled by the ionic defect thermal detrapping, migration and interaction with the localised electronic and ionic charges and colour centres. The ion diffusion-controlled TSR processes take place in the above halide crystals.     

Ion diffusion-controlled thermally stimulated processes in X-ray irradiated halide crystals

The ionic and ion diffusion-controlled thermally stimulated relaxation (TSR) processes in CaF 2 , BaF 2 , LiBaF 3 and KBr crystals were investigated above 290 v K by means of the ionic conductivity, ionic thermally stimulated depolarisation current (TSDC) and thermal bleaching techniques. Under a DC field the halide crystals store large ionic space charge. We were able to detect in CaF 2 , BaF 2 , LiBaF 3 and KBr in the extrinsic ionic conductivity region a series of the ionic defect (the interstitial anion and/or anion vacancies - in fluorides; the cation vacancies - in KBr) release stages: 3-6 wide and overlapping ionic TSDC peaks. The correlated data of the ionic TSDC and the F band thermal evidence that above 290 v K the TSR processes are initiated and controlled by the ionic defect thermal detrapping, migration and interaction with the localised electronic and ionic charges and colour centres. The ion diffusion-controlled TSR processes take place in the above halide crystals.     

Effects of exposure temperature on thermally stimulated currents in InSe single crystals

The thermally stimulated currents (TSC) in InSe single crystals are investigated as a function of initial temperature T₀ at which the samples examined are excited. In particular, experiments show that the peak at low temperature increases considerably in height and shifts markedly to lower temperatures as T₀ is reduced. A kinetic model is proposed for the interpretation of the results.     

Thermoluminescence and thermally stimulated currents in PbMoO4 crystals

Thermally stimulated depolarization (TSD) currents have been studied in the range from 4 K to room temperature by utilizing direct contacts as well as blocking contacts. Charge carrier injection and subsequent trapping seem to be responsible for internal electric fields. A glow peak near 186 K arises from a dipolar relaxation. The results of additional optical excitation during polarization provide some more information on charge transport involved in relaxation processes. The correlation to the results of photoconductivity and annealing procedure leads to the assumption of oxygen vacancies as the dominant defect centres. The study of thermoluminescence (TL) after X-irradiation gives evidence on defect states in question. In addition, from the results quasi-free charge carriers are assumed to be thermally generated above 100 K.     

Thermally stimulated surface segregation in sodium chloride crystals

Abstract-Using the methods of X-ray microanalysis (XRMA), Auger electron spectroscopy (AES), highresolution scanning electron microscopy (HRSEM), atomic-force microscopy (AFM), IR specular reflection spectrometry (IRSRS), and quadrupole mass-spectrometry (QMS), the chemical and phase composition, as well as the morphology of the cleaved surfaces of sodium chloride crystals formed as a result of thermally stimulated surface autosegregation (TSAS), is studied. A super-stoichiometric increase in the sodium content in the surface nanolayers with an increase in temperature up to 600 K and a decrease in this content upon further heating is established experimentally. A decrease in the sodium content in the nanolayers virtually in the entire range of annealing temperatures for the reversible segregation process, as well as a decrease in this content on the surface with increasing annealing time under conditions of medium vacuum, is also been found. In addition, we observe the selective sublimation of sodium in the nanolayers at temperatures above 400 K and in the microlayers at temperatures above 600 K.     

Hardness of covalent crystals

Based on the idea that the hardness of covalent crystal is intrinsic and equivalent to the sum of the resistance to the indenter of each bond per unit area, a semiempirical method for the evaluation of hardness of multicomponent crystals is presented. Applied to beta-BC2N crystal, the predicted value of hardness is in good agreement with the experimental value. It is found that bond density or electronic density, bond length, and degree of covalent bonding are three determinative factors for the hardness of a polar covalent crystal. Our method offers the advantage of applicability to a broad class of materials and initializes a link between macroscopic property and electronic structure from first principles calculation.     

EPR,thermoluminescence, and thermally stimulated conductivity in BaWO4 crystals

In BaWO₄ crystals electrons and holes trapped at WO₄ complexes are identified by electron paramagnetic resonance (EPR) after X-irradiation at T = 80 K. The thermal decay of the intrinsic hole centres at about 100 K is accompanied by a simultaneous decrease of electron traps (WO₄)^3- and glow maxima of thermoluminescence (TL) and of thermally stimulated conductivity (TSC). This connection is explained by a thermally activated hopping of the $\text{(WO}{}_4\text{)}\text{3-}\text{2}$ hole centres followed by radiative recombination with electron traps (WO₄)^3-. A qualitative kinetic calculation based upon EPR data and the shift between TL and TSC glow peak confirms this model.     

Specific features in the kinetics of thermally stimulated luminescence of α-Al2O3 crystals containing defects

A study of specific features in the kinetics of thermoluminescence (TL) of defective α-Al₂O₃ crystals is reported. The TL properties are experimentally shown to be related to the presence of oxygen vacancies of thermochemical or radiation origin. It is established that the differences in the TL kinetics in α-Al₂O₃ samples grown under different conditions can be accounted for by the hypothesis that the energy spectra of the trapping levels have different widths. As is demonstrated with a titanium impurity, this broadening of the energy spectrum can originate from the presence of traces of native impurities in the α-Al₂O₃ lattice. Fiz. Tverd. Tela (St. Petersburg) 39, 1538–1543 (September 1997)     

Comparison of the spectra of a blackbody and thermally stimulated surface plasmon polaritons in the infrared range

The emission spectra of thermally stimulated surface plasmon polaritons (thermally stimulated surface plasmon polaritons) and a blackbody have been analyzed and compared, and the temperature dependence of these spectra has been studied. It has been found that the total energy of the entire ensemble of surface plasmons is proportional to the cube of temperature and their spectrum is red-shifted from the blackbody spectrum. It has been shown that the spectrum of thermally stimulated surface plasmon polaritons obeys the Wien’s displacement law, yet with another constant. The fraction of the photon energy of the conducting layer transferred to the surface plasmons has been estimated. It has been demonstrated numerically by the example of a gold layer that this fraction can exceed 10% for a layer thickness of less than 1 mm.     

Near-infrared photoluminescence and thermally stimulated current in Cu3Ga5Se9 layered crystals: A comparative study

Near-infrared photoluminescence (PL) and thermally stimulated current (TSC) spectra of Cu₃Ga₅Se₉ layered crystals grown by Bridgman method have been studied in the photon energy region of 1.35–1.46 eV and the temperature range of 15–115 K (PL) and 10–170 K (TSC). An infrared PL band centered at 1.42 eV was revealed at T = 15 K. Radiative transitions from shallow donor level placed at 20 meV to moderately deep acceptor level at 310 meV were suggested to be the reason of the observed PL band. TSC curve of Cu₃Ga₅Se₉ crystal exhibited one broad peak at nearly 88 K. The thermal activation energy of traps was found to be 22 meV. An energy level diagram demonstrating the transitions in the crystal band gap was plotted taking account of results of PL and TSC experiments conducted below room temperature.     

Hardness of covalent and ionic crystals: first-principle calculations

A new concept, the strength of bond, and a new form expressing the hardness of covalent and ionic crystals are presented. Hardness is expressed by means of quantities inherently coupled to the atomistic structure of matter, and, therefore, hardness can be determined by first-principles calculations. Good agreement between theory and experiment is observed in the range of 2 orders of magnitude. It is shown that a lower coordination number of atoms results in higher hardness, contrary to common opinion presented in general literature.     

Effects of space-charges on thermally stimulated currents

Evidence is presented of space-charge effects in thermally stimulated currents (TSC) measured at relatively high fields in homogeneous samples sandwiched between two electrodes. A new method is proposed for estimating traps depths and trap concentrations from TSC curves and the method is checked with classical SCLC and TSC results obtainded on n-GaSe samples.