Pressure and Temperature Effects on Point-Defect Equilibria and Band Gap of ZnS

The pressure (100–200 MPa) and temperature (900–1100°C) effects on the equilibria of native point defects and background impurities in Zn-enriched ZnS are studied using cathodoluminescence and transmission spectra. The optimal conditions are found under which high pressures and temperatures accelerate migration of defects and impurities. The associated structural and compositional changes are studied by scanning electron microscopy. The increase in the concentration of dissolved oxygen at high pressures and temperatures is accompanied by a reduction in the band gap of ZnS, growth and blue shift (to 395–400 nm) of the shorter wavelength component of the SA blue emission in ZnS, and quenching of the longer wavelength component (445 nm). In addition, at 300 K a free-exciton bandI ₁ emerges at 342 nm. It is shown that the data available in the literature can be used to evaluate the concentration of dissolved oxygen in ZnS · O from its band gap. The effects of different oxygen species on the transmission of ZnS are studied in the range 3.5–15 m.     

ZnSe<Cu> Luminescence at High Doping Levels

ZnSe was doped with Cu via thermal diffusion from Cu foil in the course of chemical vapor deposition. The Cu distribution over the deposit was studied, and the Cu solubility in ZnSe was determined as a function of temperature. Copper was shown to prevent oxygen incorporation from the gas phase. The microstructure and homogeneity of ZnSe were studied by scanning electron microscopy. The cathodoluminescence (CL) spectra were measured on fracture surfaces in order to elucidate the origin of the Cu-related emission centers. Heavy doping with Cu was shown to gives rise to a long-wavelength CL band, which shifts from 525 to 550 nm as the temperature is raised from 80 to 300 K. The associated changes in oxygen-related self-activated luminescence were correlated with the Cu and O concentrations. To gain more detailed insight into the origin of the green Cu-related emission in p-type ZnSe, we examined its photoexcitation spectrum, temperature-dependent peak position, quenching, and variation with excitation intensity. The conclusion is drawn that the longer wavelength CL bands are due to electron transitions from the Zn_i ^·· donor level to the impurity band. The CL spectrum of heavily doped ZnSe shows no emissions between 800 and 1400 nm, related to the V _Se and V _Zn vacancies.     

Cathodoluminescence of CuCl Powder

The cathodoluminescence behavior of CuCl powder was studied in the temperature range 80–400 K. The cathodoluminescence spectrum of CuCl was found to contain bands peaked at 393.5, 700, 780, and 830 nm and to vary significantly with temperature. An anomalous temperature-induced shift of the Z ₃ exciton emission was revealed.     

Crystal Growth and Properties of (CuInSe2) x (2ZnSe)1 – x Solid Solutions

(CuInSe₂) _x (2ZnSe)_{1 – x} crystals are grown by the horizontal Bridgman process and chemical vapor transport, and their composition and structure are determined. The transmission and reflection spectra of the crystals are measured near the intrinsic edge. The results are used to determine the band gap of the (CuInSe₂) _x (2ZnSe)_{1 – x} solid solutions, which is found to vary nonlinearly with composition.     

Sintering studies on submicrometre-sized Y-Ba-Cu-oxide powder

The isothermal sintering behaviour of submicrometre-sized (<50 nm) powders of single-phase YBa₂Cu₃O _x (123) and unreacted stoichiometric mixture of submicrometre-sized (<50 nm) powders of BaCO₃, Y₂O₃ and CuO (which on calcination at 1173 K gives YBa₂Cu₃O _x ) was investigated through dilatometry under different sintering atmospheres. The sintering rate of the powder compacts was impeded by the presence of oxygen. The activation energies,Q, of sintering were determined to be 1218 kJ mol^–1 in argon, 1593 kJ mor^–1 in air and 2142 kJ mol^–1 in oxygen. A decrease in the apparent sintered density with increasing oxygen partial pressure was also observed. X-ray diffraction and thermal analyses (thermogravimetry and differential thermal analysis) showed no reaction during sintering of the single-phase product. Pellets fabricated from uncalcined powder exhibit two stages of sintering, one between 1073 and 1173 K having an activation energyQ=627kJ mol^–1, and a second one above 1173 K withQ=383.7 kJ mol^–1. A.c. susceptibility, resistivity and critical current density were determined as a function of the temperature of the sintered samples.     

Synthesis of thermally evaporated ZnSe thin film at room temperature

Zinc selenide (ZnSe) thin film on glass substrates were prepared by thermal evaporation under high vacuum using the quasi-closed volume technique at room temperature (300 ± 2 K). The deposited ZnSe properties were assessed via X-ray diffraction, atomic force microscope (AFM), UV-Vis specrophotometry, Raman spectroscopy, photo-luminescence, Fourier transform infrared spectroscopy (FT-IR) and spectroscopic ellipsometry. The X-ray diffraction patterns of the film exhibited reflection corresponding to the cubic (111) phase (2θ = 27.20°). This analysis indicated that the sample is polycrystalline and have cubic (Zinc blende) structure. The crystallites were preferentially oriented with the (111) planes parallel to the substrates. The AFM images showed that the ZnSe films have smooth morphology with roughness 6.74 nm. The transmittance spectrum revealed a high transmission of 89% in the infrared region (≥ 600 nm) and a low transmission of 40% at 450 nm. The maximum transmission of 89.6% was observed at 640 nm. Optical band-gap was calculated from the transmission data of specrophotometry, photo-luminescence and ellipsometry and was 2.76, 2.74 and 2.82 eV respectively. Raman spectroscopic studies revealed two longitudinal optical phonon modes at 252 cm ^-1 and 500 cm ^-1. In photoluminescence study, the luminescence peaks was observed at 452 nm corresponding to band to band emission. FT-IR study illustrated the existence of Zn-Se bonding in ZnSe thin film. The optical constants were calculated using spectroscopic ellipsometry and were determined from the best fit ellipsometric data in the wavelength regime of interest from 370-1000 nm. These results manifested excellent room temperature ZnSe synthesis and characteristics for opto-electronics technologies.     

Structural,electrical and optical properties of copper selenide thin films deposited by chemical bath deposition technique

A low cost chemical bath deposition (CBD) technique has been used for the preparation of Cu_2–xSe thin films on glass substrates. Structural, electrical and optical properties of these films were investigated. X-ray diffraction (XRD) study of the Cu_2–xSe films annealed at 523 K suggests a cubic structure with a lattice constant of 5.697 Å. Chemical composition was investigated by X-ray photoelectron spectroscopy (XPS). It reveals that absorbed oxygen in the film decreases remarkably on annealing above 423 K. The Cu/Se ratio was observed to be the same in as-deposited and annealed films. Both as-deposited and annealed films show very low resistivity in the range of (0.04–0.15) × 10^–5 -m. Transmittance and Reflectance were found in the range of 5–50% and 2–20% respectively. Optical absorption of the films results from free carrier absorption in the near infrared region with absorption coefficient of 10⁸ m^–1. The band gap for direct transition, E_g.dir varies in the range of 2.0–2.3 eV and that for indirect transition E_g.indir is in the range of 1.25–1.5 eV.     

Optical,infrared and electrical conductivity of glasses in the TeO2-B2O3 system

Infrared (IR) and optical absorption spectra were measured in order to study the structure of some tellurite glasses containing boric oxide. The compositions (mol%) were (100-X) TeO₂,XB₂O₃ whereX=5, 10, 20, 25, 30. The optical spectra were measured at room temperature in the wavelength range 350–450 nm, and the results show that the fundamental absorption edge is a function of composition, with the optical absorption due to indirect transitions. The optical band gap increases with increasing B₂O₃ content. The validity of the Urbach rule was investigated. The IR results prove the distribution of the TeO₄ polyhedra which determines the network and the basic oscillations of the building units in the tellurite glasses. The IR results also prove the distribution of the boroxal group. The electrical conductivity was measured as a function of temperature in the temperature range (300–573 K). Both the conductivity and activation energy were found to be a function of added oxide type.     

Physicochemical Properties of (CuAlSe2)x(2ZnSe)1 – xSolid Solutions

(CuAlSe₂) _x (2ZnSe)_{1 – x} solid solutions were prepared by a single-zone method. According to x-ray diffraction characterization, the solid solutions had the chalcopyrite structure for x> 0.7 and sphalerite structure for x< 0.7. CuAlSe₂, ZnSe, and (CuAlSe₂) _x (2ZnSe)_{1 – x} crystals were grown by chemical vapor transport and were used for microhardness tests and transmission measurements near the fundamental edge. The results demonstrate that the microhardness and band gap of the solid solutions pass through a maximum and minimum, respectively.     

Synthesis of Superconducting 2212 Phase in the Bi–Pb–Sr–La–Cu–O System

There have been no report about synthesis of the Bi-2212 compound in the Bi–r–La–Cu–O system. We have succeeded in synthesizing the Bi-2212 compound by partial substitution of Pb for Sr and/or Bi in the Bi–Sr–La–Cu–O system. Two samples of nearly the single 2212 phase have been obtained at a nominal composition of Bi_1.5Pb_0.5Sr_2.5La_0.5Cu₂O _z . Both of the samples crystallize in a psedotetragonal lattice, and their lattice parameters are a = 0.5476 nm and c = 3.085 nm or a = 0.5479 nm and c = 3.055 nm. They are both superconductors. The sample with longer lattice parameter c shows an onset of the resistivity drop and zero resistivity at higher temperatures of about 40 K and about 13 K, respectively. This sample also shows a diamagnetic signal starting at about 35 K with lowering temperature.     

The use of de-aggregating agents in ZnSe mechanochemical synthesis

Conventional mechanochemical synthesis of zinc selenide, ZnSe nanoparticles was performed in a planetary ball mill by high-energy milling of zinc (Zn) and selenium (Se) powders with the de-aggregating agents ZnCl₂ and phthalic acid (aromatic dicarboxylic acid, C₈H₆O₄). Physical–chemical and optical properties of the prepared ZnSe nanoparticles were studied and compared. The mechanochemically synthesized products were characterized by X-ray diffraction analysis (XRD) that confirmed the presence of cubic-Stilleite and hexagonal ZnSe phases after 18, 25, 30, 40, 45 and 50 min of milling with various amounts of the added de-aggregating agents. Size of crystallites calculated from XRD patterns was from 20 to 31 nm for cubic ZnSe prepared with ZnCl₂. For ZnSe synthesized with phthalic acid the crystallite size ranged from 16 to 73 nm. Size, phase composition, morphology, and crystallinity of ZnSe nanoparticles were studied by transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Photoluminescence spectra (PL) at room temperature have shown a broad red emission bands, and the presence of de-aggregating agent has altered the intensity of the PL signal as well.     

Physical properties of transparent conducting Cd–Te–In–O thin films: Outlining a thermodynamic system for transparent conducting oxides

Cd–Te–In–O thin films are grown by pulsed laser deposition using a composite target of CdTe powder embedded in an indium matrix. Oxygen pressures range from 2.00 to 6.67 Pa at a substrate temperature of 420 °C. The structure, optical transmission and sheet resistance of the films are measured. Substitutional compounds with In_2 − 2x(Cd,Te)_2xO₃ stoichiometry are found at high oxygen pressures. A ternary phase diagram of the CdO–In₂O₃–TeO₂ system shows the relationship between the structure and the stoichiometry of the films. To evaluate film performance, a figure of merit is proposed based on the relationship between the integral photonic flux and the sheet resistance. The best figure of merit values corresponds to a sample prepared at 3.8 Pa O₂ that consists of (In₂O₃)_0.3(CdTe₂O₅)_0.7 and exhibits an optical band gap of 3.0 eV. This sample is a suitable substrate for electrodeposition due to its good electrochemical stability.     

Adsorptive and Electrical Properties of InSb–ZnSe Films

The band gap and electrical conductivity of InSb–ZnSe films are measured. Their composition dependences, as well as x-ray diffraction data, point to the formation of substitutional solid solutions. The effect of CO adsorption on the conductivity of InSb, ZnSe, and (InSb) _x (ZnSe)_{1 – x} solid solutions is studied. The results demonstrate that the temperature, pressure, and time dependences of conductivity, as well as those of adsorption, follow classical laws. The correlation between the adsorptive and electronic properties of the films confirms that adsorption centers and surface states have the same origin. The materials exhibiting high CO selectivity and sensitivity are used to produce solid-state gas sensors.     

YBa2Cu3O7 ? x 240 K Phase Transition

YBa₂Cu₃O_{7 – x} ceramic samples have been investigated simultaneously by the thermal expansion and the acoustic emission methods during thermocycling through 200–300 K into liquid nitrogen steam. No jumps in the dilatation curves but change in the slope of one has been found at 228 and 234 K on heating and cooling respectively. These points are accompanied by the acoustic emission signals, a small value testifying for oxygen atoms displacement into the crystal lattice. On the basis of these measured experimental data, a thermal expansion coefficient and a specific capacity c _m have been calculated. By this c _m value an oxygen atom activation energy E = 0.15 eV has been calculated. It is shown that an isostructural oxygen-displacement second-order phase transition takes place between certain orthorhombic phases in YBa₂Cu₃O_{7 – x} near 240 K.     

YBa2Cu3O7?X 500–600 K Isostructural Phase Transition and Its Influence on Critical-Current Value

YBa₂Cu₃O_7–X ceramic samples voltage–current characteristics at 77 K and acoustic emission activity during thermocycling 500–600 K region have been studied. Partial oxygen sorption by these samples through heating has been established by critical-current value and acoustic emission activity at 540–550 K. During thermocycling an acoustic emission maximums have been observed on 3rd and 6th thermocycles, and these maximums correlate with some decrease of the critical-current value. It is shown that observed acoustic emission maximums are because of a phase-work hardening during thermocycling of these samples. A mechanism of this phase-work hardening influencing the critical-current value in YBa₂Cu₃O_7–X ceramic samples is discussed.     

Properties of cu-doped low resistive ZnSe films deposited by two-sourced evaporation

Two-sourced evaporation technique is used to prepare hard ZnSe films by controlling the evaporation rates of both Zn and Se at substrate temperature of 400 °C. The films are doped with Cu by immersion in the Cu(NO₃)₂-H₂O solution for different periods of time. The XRD has not shown a drastic change in the film structure while the electrical resistivity of the deposited film dropped from 10⁹ Ω-cm to about 1.6 Ω-cm for solution immersed films after heat treatment. Optical properties of deposited and doped films, such as film thickness, absorption coefficient and optical band gap have been calculated from the normal transmission spectra in the range of 300-2200 nm.The optical results show a decrease of the transmission and an increase of the refractive index and a slight shift in the optical band gap. Chemical composition of the Cu is determined by using absorption of immersed films. The composition of Cu is also compared with the composition detected by electron microprobe analyzer (EMPA).     

One-step synthesis of water-soluble ZnSe quantum dots via microwave irradiation

A facile strategy has been developed for the synthesis of glutathione-capped ZnSe quantum dots (QDs) in aqueous media. The reaction was carried out in air atmosphere with a single step by using Na₂SeO₃, a stable and commercial Se source, to replace the commonly adopted NaHSe or H₂Se. Moreover, microwave irradiation improved the photoluminescence quantum yield (PLQY) as well as lowered the trap emission of as-prepared ZnSe QDs. The obtained QDs performed strong band-edge luminescence (PLQY reached 18%), narrow size distribution (full width at half maximum was 26-30 nm) and weak trap emission without post-treatments. The results of transmission electron microscopy and X-ray diffraction demonstrated the small particle size (2-3 nm), good monodispersity and ZnSe(S) alloyed structure of as-prepared QDs. The experimental variables including precursors and stabilizer amounts as well as pH value had significant influence on the PL properties of the ZnSe QDs.     

The stability and a.c. electrical characteristics of composites containing YBa2Cu3O7−x and alumina at elevated temperatures

Samples of a high-temperature superconductor YBa₂Cu₃O_7–x (orthorhombic phase) showed no significant weight loss in nitrogen up to 1173 K; however, differential thermal analysis measurements show that restructuring/decomposition begins around 1121 K. No reaction with alumina was found after prolonged heating at 1073 K. Electrical properties between 100 Hz and 1 MHz were generally stable at high temperatures, with little variation in properties at 1 MHz in inert and oxidizing atmospheres. Surface oxygen can be removed at high temperatures in flowing argon causing erratic electrical behaviour at lower frequencies and lower temperatures, which can be associated with changes in the oxygen content, x, and partial quenching to the high-temperature tetragonal phase. Stability and electrical tests after pretreatment of YBCO-alumina composites at 933 K in CO₂ or steam showed partial decomposition to BaCO₃, CuO and Y₂Cu₂O₅ and a phase transition from orthorhombic to tetragonal in the YBa₂Cu₃O_7–x . The original state could be retrieved by calcination in air at73 K.     

Influence of gamma radiation on the optical properties of ZnSe nanocrystalline thin films

The effect of gamma (γ) irradiation on the absorption spectra and the optical energy bandwidth of ZnSe nanocrystalline thin films have been studied. Thin films of different thicknesses from 20 to 120 nm were deposited by Inert gas condensation technique at constant temperature of 300 K and under pressure 2 × 10⁻³ Torr of Argon gas flow. The optical transmission (T) and optical reflection (R) in the wavelength range 190–2,500 nm of ZnSe nanocrystalline thin films were measure for unirradiated and irradiated films. The dependence of the absorption coefficient α on photon energy hν was determined for different γ-doses irradiated films. The ZnSe thin films show direct allowed interband transition by γ-doses. Both the absorption coefficient (α) and optical energy bandwidth were found to be γ-dose dependent. The optical energy band width has been decreased by irradiated of γ-doses. The E_gn values of irradiated thin films by 34.5 Gy of γ-doses were recovered to nearly their initial values after 100 days at 300 K.     

Luminescent Properties of Activated CdI2Crystals

Data are presented on the luminescent properties of melt-grown CdI₂crystals activated with anion (I, S) and cation (Cd, Tl, Sb, Pb, Sn, Mn) impurities. The measured spectral and temporal responses of roentgeno- and thermoluminescence, in conjunction with earlier kinetic, optical, and photoelectric data for nominally pure and activated CdI₂crystals, indicate that, under x-ray excitation at temperatures between 85 and 295 K, intracenter transitions of impurity ions occur only in CdI₂:Mn crystals. The low-temperature roentgenoluminescence spectra of CdI₂activated with Cd, Pb, Sn, and Sb show, along with the anion-exciton emission at 530–575 nm, a band at 640–700 nm related to associates of native defects and impurities. In the 85-K electroluminescence spectra of CdI₂:Cd and CdI₂:Pb, the relative intensity of the shorter wavelength emission increases with increasing electric field, which is probably due to recombination at V _khole centers with different depths. The trapping levels in the crystals studied are mainly due to intrinsic defects and have a low retrapping efficiency. The radiative recombination and trapping processes are shown to occur at different centers.