Photoluminescence properties of Y0.95 − xMxBO3:Eu3+ (M = Ca,Sr, Ba,Zn, Al, 0 ≤ x ≤ 0.1) in 100–450 nm regions

The single phases of Y_0.95 − xM_xBO₃:5%Eu³⁺ (M = Ca, Sr, Ba, Zn, Al, 0 ≤ x ≤ 0.1) were synthesized successfully by solid-state reaction. Their luminescent properties were studied under UV and VUV excitation. The results indicated that with the incorporation of Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺ or Al³⁺ into the host lattice of YBO₃:Eu³⁺, the high symmetry around Eu³⁺ was destroyed and the ratio of red emission(⁵D₀–⁷F₂) to orange one (⁵D₀–⁷F₁) increased, leading to a better chromaticity. Furthermore, the co-doping ions such as Ca²⁺, Zn²⁺ and Al³⁺ were beneficial to enhance the luminescent intensity of Eu³⁺. These phenomena were evaluated, and possible explanations were proposed.     

Zinc incorporation into CdTe quantum dots in glass

We report zinc incorporation into CdTe nanoparticles grown by two-step solid phase precipitation in commercial borosilicate glass quenched from the melt, based on a co-evaluation of the results of resonant Raman and optical absorption measurements. Resonant Raman spectra display a two-peak structure at wave-number positions corresponding to ternary compound Zn_xCd_1?xTe. We attribute the higher intensity peak between 190 and 195 cm^?1 to the first harmonic of the zone-center longitudinal optical mode (LO₁) and, the lower intensity peak between 157 and 160 cm^?1 to the second harmonic (LO₂) of Zn_xCd_1?xTe crystal. The wave-number of vibrational Raman modes indicates that zinc content varies between 39 and 50% during the growth of quantum dots. The asymptotic absorption edge against heat-treatment time plot extrapolates to a bulk band gap of 1.714 eV which sets a lower limit of 31% for zinc incorporated into quantum dots which is consistent with the results of resonant Raman measurements. The energetic position of asymptotic absorption edge of 1.592 eV and an additional unresolved weak structure in Raman spectrum between 166 and 182 cm^?1 observed for as-received glass might serve as a evidence for the occurrence of a different nanocrystalline phase with 13% zinc content.     

Structural and optical studies of Zn1−xCdxS quantum dots synthesized by in situ technique in PVA matrix

Zn_1−xCd_xS (x = 0.1, 0.2, 0.3, 0.4, 0.5 … 0.9) quantum dots were synthesized successfully using novel in situ technique in polyvinyl alcohol (PVA) matrix. The PVA acted as a capping agent as well as a reducing agent. The structural and optical properties of the samples were studied by X-ray diffraction (XRD), TEM analysis, UV–Visible absorption and photoluminescence spectroscopy (PL). X-ray diffraction patterns revealed cubic zinc blende phase of the samples with lattice parameter in the range 5.47–5.75 Å. Optical band gap values were calculated from the absorption spectra and observed a decreasing band gap with increasing Cd:Zn ratio. The Raman spectra were recorded using conventional Micro Raman technique. Photoluminescence spectra showed asymmetric broad emission with multiple maxima. The concentration dependent quenching of PL intensity with increasing Cd:Zn ratio was observed along with a red shift. The nonlinear optical (NLO) and limiting properties were studied using Z-scan technique.     

Solvothermal synthesis and magnetic properties of pyrite Co1−xFexS2 with various morphologies

Ternary pyrite sulfide Co_1−xFe_xS₂ (0 ≤ x ≤ 1) with various morphologies were synthesized at low temperature via solvothermal process with ethanol as the solvent. Cobalt and iron nitrates were used as starting chemicals, and thiourea as a source of sulfur. Microstructures and magnetic properties were investigated by X-ray diffraction, scanning electron microscope and SQUID magnetization measurements. With the same synthetic condition, the morphology is strongly dependent on Fe doping level x. The grain shape varies from nanoscaled sphericity to round nanorods and finally to rectangle rods with increasing x. Magnetic measurement shows a clear ferromagnetic–paramagnetic transition for the samples with x ≤ 0.5. Broad magnetic phase transition and unsaturated magnetization under high external field are observed, which is due to small grain size. CoS₂ exhibits an effective paramagnetic moment of 1.7 μ_B per Co²⁺, indicative of spin-only electronic structure.     

Physical and optical properties of Co2+, Ni2+ doped 20ZnO + xLi2O + (30 − x)K2O + 50B2O3 (5 ≤ x ≤ 25) glasses: Observation of mixed alkali effect

Co²⁺ and Ni²⁺ ions doped 20ZnO + xLi₂O + (30 ? x) K₂O + 50B₂O₃ (5 ≤ x ≤ 25) mol% glasses are prepared using melt quenching technique. Structural changes of the prepared glasses by addition of transition metal oxides, CoO and NiO are investigated by UV–vis–NIR, FT-IR spectroscopy and XRD. The XRD pattern indicates the amorphous nature of prepared glasses. FT-IR measurements of the all glasses revealed that the network structure of the glasses are mainly based on BO₃ and BO₄ units placed in different structural groups in which the BO₃ units being dominant. The optical absorption spectra suggest the site symmetry of Co²⁺ and Ni²⁺ ions in the glasses are near octahedral. Crystal field and inter-electronic repulsion parameters are also evaluated. The optical band gap and Urbach energies exhibited the mixed alkali effect. Various physical parameters such as density, refractive index, optical dielectric constant, polaron radius, electronic polarizability and inter-ionic distance are also determined.     

Microwave dielectric ceramics in (Ca1− xBax)(Zn1 / 3Nb2 / 3)O3 system

(Ca_1−xBa_x)(Zn_1 / 3Nb_2 / 3)O₃ (x = 0–1.0) microwave dielectric ceramics were prepared and investigated. The Ba(Zn_1 / 3Nb_2 / 3)O₃-based solid solution was observed for x = 0.9, and the compositions with x = 0.1–0.7 resulted in the mixture of two phases. Dielectric constant ε_r and temperature coefficient of resonant frequency τ_f of the present ceramics varied anomalously and reached their maximum at x = 0.7–0.9, and these phenomena were originated from the partial substitution of small Ca²⁺ ions for larger Ba²⁺ at A-site. On the other hand, a good combination of microwave dielectric properties (ε_r = 36, Qf = 16,170 GHz, τ_f = − 12 ppm/°C) were obtained at x = 0.1, while the decreased Qf value was observed in other compositions.     

Optical studies on X and γ irradiated vacuum grown CsBrI:Eu2+ crystals

CsBr_0.9I_0.1:Eu²⁺ crystals were grown by Bridgman technique. Optical absorption spectrum of the unirradiated CsBr_0.9I_0.1:Eu²⁺ crystals show absorption bands at 270 nm and 340 nm. Irradiated CsBr_0.9I_0.1:Eu²⁺ shows single F band for F(Br⁻) and F(I⁻) centers at 730 nm. Conversion of Eu²⁺ to Eu³⁺ after irradiation is confirmed by optical absorption technique. Sharp and single Photoluminescence (PL) emission band is observed at 440 nm for CsBr_0.9I_0.1:Eu²⁺ crystals. Photostimulated Luminescence (PSL) emission band observed for CsBr_0.9I_0.1:Eu²⁺ crystals at 442 nm due to excitation at 730 nm shows that the F centers are photostimulable. PSL emission intensity increases linearly with irradiation dose up to 2.5 Krad.     

Ethylenediamine-assisted solvothermal synthesis of one-dimensional CdxZn(1−x)S solid solutions and their photocatalytic activity for nitrobenzene reduction

A series of one-dimensional Cd_xZn_(1−x)S semiconductor alloys were prepared via a hydrothermal method with the assistance of ethylenediamine at 180 °C for 12 h. The products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption/desorption and Fourier transform infrared techniques. With the value of x increased, the band gap of Cd_xZn_(1−x)S semiconductor alloys gradually decreased indicating that catalysts were exchanged to visible-light response. Photocatalytic reduction results showed that Cd_0.73Zn_0.27S exhibited the highest photocatalytic activity toward photo production of aniline via nitrobenzene reduction under visible irradiation respectively. The reaction mechanism was also discussed.     

High dielectric constant observed in (1 − x)Ba(Zr0.07Ti0.93)O3–xBa(Fe0.5Nb0.5)O3 binary solid-solution

Binary solid-solutions of the (1 ? x)Ba(Zr_0.07Ti_0.93)O₃–xBa(Fe_0.5Nb_0.5O₃) system, with 0.1 ≤ x ≤ 0.9,were fabricated via a solid-state processing technique. X-ray diffraction analysis revealed that all samples exhibited a single perovskite phase. The BaFe_0.5Nb_0.5O₃ also promoted densification and grain growth of the system. Dielectric measurements showed that all samples displayed a relaxor like behavior. The x = 0.1 sample presented a dielectric-frequency and temperature with low loss tangent (<0.07 at 10 kHz). For x > 0.2 samples, the dielectric data showed a broad dielectric constant–temperature curve with a giant dielectric characteristic. In addition, a high dielectric constant > 50,000 (at 10 kHz and temperature > 150 °C) was observed for the x = 0.9 sample.     

Co1−xZnxFe2O4 (0 ≤ x ≤ 1) nanocrystalline solid solution prepared by the polyol method: Characterization and magnetic properties

Highly crystalline stoichiometric Co_1?xZn_xFe₂O₄ (0 ≤ x ≤ 1) nanoparticles were successfully synthesized by the polyol process. X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), transmission electron microscopy (TEM), infrared spectroscopy (IR), zero-field ⁵⁷Fe Mössbauer spectrometry and magnetic measurements using a SQUID magnetometer were employed to investigate the effect of the substitution of Zn²⁺ ions for Co²⁺ ones on the structure, and the magnetic properties of the cobalt ferrite, CoFe₂O₄. The unit cell parameter almost increases linearly with increasing Zn concentration, x, following Vegard's law. The red and blue shifts observed for the metal-oxygen ν₁ and ν₂ IR vibration bands, respectively, were consistent with the preferential entrance of Zn²⁺ ions in tetrahedral sites. Besides, detailed magnetic investigation in correlation with the cation distribution has been reported. All the particles exhibit superparamagnetic behaviour at room temperature. In addition, the magnetic characteristics (blocking temperature, saturation magnetization, coercivity, Curie temperature) clearly depend on the chemical composition and cation distribution. Both the blocking temperature and Curie temperature decrease drastically with Zn composition, x, increase. Further, the saturation magnetization follows an almost bulk-like behaviour with values notably larger than that of the bulk, mainly attributed to cation distribution deviation.     

Spectroscopic ellipsometry and magneto-transport investigations of Mn-doped ZnO nanocrystalline films deposited by a non-vacuum sol–gel spin-coating method

Nanocrystalline Zn_1?xMn_xO films (x = 0, 0.05, 0.1, 0.15, and 0.2) were deposited onto corning glass substrates by a non-vacuum sol–gel spin coating method. All of the films were annealed at 450 °C for 2 h. The structural, optical and magneto-transport properties were investigated by X-ray diffraction, spectroscopic ellipsometry and a system for the measurement of the physical properties. X-ray diffraction analysis of the films reveals that the Mn-doped ZnO films crystallize in the form of a hexagonal wurtzite-type structure with a crystallite size decreases with an increase of the Mn concentration. It was also found that the microstrain increases with the increase of the Mn content. Evidence of nanocrystalline nature of the films was observed from the investigation of surface morphology using transmission, scanning electron microscopy and atomic force microscopy. The optical constants and film thicknesses of nanocrystalline Zn_1?xMn_xO films were obtained by fitting the spectroscopic ellipsometric data (ψ and Δ) using a three-layer model system in the wavelength range from 300 to 1200 nm. The refractive index was observed to increase with increasing Mn concentration. This increase in the refractive index with increasing Mn content may be attributed to the increase in the polarizability due to the large ionic radius of Mn²⁺ compared to the ionic radius of Zn²⁺. The optical band gap of the nanocrystalline Mn–ZnO films was determined by an analysis of the absorption coefficient. The direct transition of the series of films was observed to have energies increasing linearly from 3.17 eV (x = 0) to 3.55 eV (x = 0.2). Magnetoresistance (MR) was measured from 5 K to 300 K in a magnetic field of up to 6 T. Low-field positive MR and high-field negative MR were detected in Mn-doped ZnO at 5 K. Only negative MR was observed for temperatures above 200 K. The positive MR in Mn-doped ZnO films was observed to decrease drastically when the temperature increased from 5 K to 100 K. The isothermal MR of Zn_1?xMn_xO films with different Mn concentrations at 5 K reveals that the increase of the Mn content induces a giant positive MR above x = 0.05 and reaches up to 55% at an applied field of 30 kOe for x = 0.2.     

Influence of Ga3+ ions on spectroscopic and dielectric features of multi component lithium lead boro bismuth silicate glasses doped with manganese ions

Multi-component glasses of the chemical composition 19.5Li₂O–20PbO–20B₂O₃–30SiO–(10 − x)Bi₂O₃–0.5MnO:xGa₂O₃ with 0 ≤ x ≤ 5.0 have been synthesized. Spectroscopic (optical absorption, IR, Raman and ESR) and dielectric properties were investigated. Optical absorption and ESR spectral studies have indicated that managanese ions do exist in Mn³⁺ state in addition to Mn²⁺ state in the samples containing low concentration of Ga₂O₃. The IR and Raman studies indicated increasing degree of disorder in the glass network with the concentration of Ga₂O₃ up to 3.0 mol%. The dielectric constant, loss and ac conductivity are observed to increase with the concentration of Ga₂O₃ up to 3.0 mol%. The quantitative analysis of the results of dielectric properties has indicated an increase in the insulating strength of the glasses as the concentration of Ga₂O₃ is raised beyond 3.0 mol%. This has been attributed to adaption of gallium ions from octahedral to tetrahedral coordination.     

XPS and Mössbauer studies on BaSn1−xNbxO3 (x ≤ 0.100)

A few compositions of perovskite oxide BaSn_1?xNb_xO₃ (with x ≤ 0.10) system, prepared by solid state ceramic method, have been studied employing XPS and Mössbauer spectroscopy techniques. Mössbauer spectra of these compositions in the temperature range of 78–300 K reveal that the oxidation state of Sn is +4. In XPS measurements, compositions with x ≤ 0.010 show no evidence of Nb⁵⁺ signal whereas the compositions with x ≥ 0.050 show clear evidence of Nb⁵⁺ signals indicating some unreacted Nb₂O₅ component in the system. This confirms the earlier report where presence of small amount of unreacted Nb₂O₅ was predicted.     

Mixed alkali effect in Li2O–Na2O–B2O3 glasses containing Fe2O3—An EPR and optical absorption study

This paper reports the interesting results on mixed alkali effect (MAE) in xLi₂O–(30-x)Na₂O–69.5B₂O₃ (5 ≤ x ≤ 28) glasses containing Fe₂O₃ studied by electron paramagnetic resonance (EPR) and optical absorption techniques. The EPR spectra in these glasses exhibit three resonance signals at g = 7.60, 4.20 and 2.02. The resonance signal at g = 7.60 has been attributed to Fe³⁺ ions in axial symmetry sites whereas the resonance signal at g = 4.20 is due to isolated Fe³⁺ ions in rhombic symmetry site. The resonance signal at g = 2.02 is due to Fe³⁺ ions coupled by exchange interaction. It is interesting to observe that the number of spins participating in resonance (N) and its paramagnetic susceptibility (χ) exhibits the mixed alkali effect with composition. The present study also gives an indication that the size of alkali ions we choose in mixed alkali glasses is also an important contributing factor in showing the mixed alkali effect. It is observed that the variation of N with temperature obeys Boltzmann law. A linear relationship is observed between 1/χ and T in accordance with Curie–Weiss law. The paramagnetic Curie temperature (θ_p) is negative for the investigated sample, which suggests that the iron ions are antiferromagnetically coupled by negative super exchange interactions at very low temperatures. The optical absorption spectra exhibit only one weak band corresponding to the transition ⁶A_1g(S) → ⁴A_1g(G); ⁴E_g(G) at 446 nm which is a characteristic of Fe³⁺ ions in octahedral symmetry.     

Nanocrystalline spinel Ni0.6Zn0.4Fe2O4: A novel material for H2S sensing

Nanocrystalline powders of Ni_1?xZn_xFe₂O₄ (0 ≤ x ≤ 0.5) mixed ferrites, with cubic spinel structure and average crystallite size ranging from 28 to 42 nm, were synthesized by the ethylene glycol mediated citrate sol–gel method. The structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and microstructure by transmission electron microscopy (TEM). The response of prepared Ni_1?xZn_xFe₂O₄ mixed ferrites to different reducing gases (liquefied petroleum gas, hydrogen sulfide, ethanol gas and ammonia) was investigated. The sensor response largely depends on the composition, temperature and the test gas species. The Zn content has a significant influence on the gas-sensing properties of Ni_1?xZn_xFe₂O₄. Especially, Ni_0.6Zn_0.4Fe₂O₄ composition exhibited high response with better selectivity to 50 ppm H₂S gas at 225 °C. Incorporation of palladium (Pd) further improved the response, selectivity and response time of Ni_0.6Zn_0.4Fe₂O₄ to H₂S with the shift in the operating temperature towards lower value by 50 °C. The enhanced H₂S sensing properties can mainly be attributed to the selectivity to oxidation of H₂S and noble metal additive sensitization. Furthermore, the sensor exhibited a fast response and a good recovery.     

Growth of the Zn1−xMnxO alloy by the MOCVD technique

Single-phase thin films of the diluted magnetic semiconductor Zn_1−xMn_xO have been grown by the MOCVD technique. Depositions have been done at T = 450 °C on fused silica and (0 0 0 1) sapphire substrates. Layers on silica exhibit polycrystalline structure with [0 0 1] preferential orientation while Zn_1−xMn_xO films are (0 0 0 1) epitaxially grown on c-sapphire with the epitaxy relation: 30° rotation of the Zn_1−xMn_xO [1 0 0] direction with respect to the [1 0 0] of the substrate. The manganese content varies in the (0–30%) range and is always higher in samples grown on sapphire substrates under the same conditions. Variations of a and c lattice parameters, assessed by X-ray diffraction, follow Vegard's law and attest to the incorporation of substitutional Mn²⁺ ions. Hall effect measurements show a decrease of the mobility with the incorporation of manganese in ZnO, and optical transmission results present the shift of the absorption edge towards higher energies.     

Multicolor-emitting Ca3 -x-ySry(PO4)2:xEu2 + (0 ≤ x ≤ 0.075, 0 ≤ y ≤ 2.2) phosphors for light-emitting diodes

In this paper, a series of Ca_3 -x-ySr_y(PO₄)₂:xEu^2 +, (0 ≤ x ≤ 0.075, 0 ≤ y ≤ 2.2) phosphors were prepared by flux assisted solid-state reaction method, and their photoluminescence properties were investigated. The β- to β′-phase transition of Ca_3 -ySr_y(PO₄)₂ for high Sr^2 + content was observed from the XRD patterns, and the corresponding optical bandgaps were obtained experimentally. Various Eu^2 + emission centers were found, which generate tunable emission depending on the Sr^2 + concentration. Broad and intense excitation bands exist in Eu^2 + activated Ca₃(PO₄)₂, and the introduction of Sr^2 + further extends and enhances the excitation bands beyond 350 nm, which is beneficial to the applications on near ultraviolet LEDs. The morphology measurement reveals that the average size of particles with smooth surface is about 11.2 μm, which is suitable for the practical applications. These results indicate that the Ca_3 -x-ySr_y(PO₄)₂:xEu^2 + phosphors could be promising candidates for LEDs.     

Preparation and structure of carbonated calcium hydroxyapatite substituted with heavy rare earth ions

Calcium hydroxyapatite (CaHap) particles substituted five types of heavy rare earth ions (Ln: Y³⁺, Gd³⁺, Dy³⁺, Er³⁺ and Yb³⁺) were synthesized using a precipitation method and characterized using various means. These Ln ions strongly affected the crystal phases and the structures of the products. With increasing Ln/(Ln + Ca) in the starting solution ([X_Ln]), the length and the crystallinity of the particles first increased and then decreased. The rare earth metal-calcium hydroxyapatite (LnCaHap) solid solution particles were obtained at [X_Y] ≤ 0.10 for substituting Y system and at [X_Ln] ≤ 0.01–0.03 for substituting the other Ln systems. LnPO₄ was mixed with LnCaHap at higher [X_Ln] for all Ln systems. A series of yttrium-calcium hydroxyapatite (YCaHap) solid solutions with [X_Y] = 0–0.10 were investigated using XRD, TEM, ICP-AES, IR and TG–DTA in detail.     

Purification of Cd0.9Zn0.1Te by physical vapor transport method

In this experiment physical vapor transport (PVT) method had been successfully applied to purify Cd_0.9Zn_0.1Te, and the concentration of impurities, Ag, Cu, Al, Fe, Na, Au and Ni decreased remarkably. The determination of two main processing parameters, the source end temperature and temperature gradient, had a strong effect on purification time, the furnace capacity and the physical and chemical properties of the impurities. In this experiment the relationship between the vapor pressure of Ag, Cu, Al, Fe, Na, Au and Ni and temperature were analyzed and the source end temperature was confirmed at 1173 K in the vacuum of 1.5 × 10^− 2Pa. The mechanism of PVT was discussed and the process of PVT can be described by W. Palosz's thermochemical model [W. Palosz, S.L. Lehocaky, F. R. Szofran, Thermochemical model of physical vapor transport of cadmium-zinc telluride. Journal of Crystal Growth 148, 1995, 49–55]. The transport time dependence on gradient temperature was given. Considering purification time and the furnace capacity, temperature gradient of 13 K/cm were chosen.     

Phase relations and high temperature-XRD studies of Gd2−xNdxTi2O7 solid solutions

A series of compositions with the general formula Gd_2−xNd_xTi₂O₇ (0.0 ≤ x ≤ 2.0) was prepared by ceramic sintering and characterized by powder XRD. Nd³⁺ has been used as a surrogate for Am³⁺, an actinide found in spent nuclear fuel. One end member, Gd₂Ti₂O₇, had the pyrochlore structure and formed solid solutions with Nd₂Ti₂O₇ up to the nominal composition Gd_1.2Nd_0.8Ti₂O₇. An increase in lattice parameter was observed as a function of x in the series Gd_2−xNd_xTi₂O₇ in the composition range 0.0 ≤ x ≤ 0.8. Compositions Gd_2−xNd_xTi₂O₇ in the range 0.8 ≤ x ≤ 1.4 were biphasic. From x ≥ 1.6, the solid solutions are monoclinic, isotypic with Nd₂Ti₂O_7. These results were explained based on the radius (r_A/r_B) ratio of the cations. High temperature-XRD studies on cubic pyrochlores showing thermal expansion are reported.