Structural evolution,growth mechanism and photoluminescence properties of CuWO4 nanocrystals

Copper tungstate (CuWO₄) crystals were synthesized by the sonochemistry (SC) method, and then, heat treated in a conventional furnace at different temperatures for 1 h. The structural evolution, growth mechanism and photoluminescence (PL) properties of these crystals were thoroughly investigated. X-ray diffraction patterns, micro-Raman spectra and Fourier transformed infrared spectra indicated that crystals heat treated and 100 °C and 200 °C have water molecules in their lattice (copper tungstate dihydrate (CuWO₄·2H₂O) with monoclinic structure), when the crystals are calcinated at 300 °C have the presence of two phase (CuWO₄·2H₂O and CuWO₄), while the others heat treated at 400 °C and 500 °C have a single CuWO₄ triclinic structure. Field emission scanning electron microscopy revealed a change in the morphological features of these crystals with the increase of the heat treatment temperature. Transmission electron microscopy (TEM), high resolution-TEM images and selected area electron diffraction were employed to examine the shape, size and structure of these crystals. Ultraviolet–Visible spectra evidenced a decrease of band gap values with the increase of the temperature, which were correlated with the reduction of intermediary energy levels within the band gap. The intense photoluminescence (PL) emission was detected for the sample heat treat at 300 °C for 1 h, which have a mixture of CuWO₄·2H₂O and CuWO₄ phases. Therefore, there is a synergic effect between the intermediary energy levels arising from these two phases during the electronic transitions responsible for PL emissions.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

Structure and proton conductivity of mechanochemically treated 50CsHSO4·50CsH2PO4

Mixtures of CsHSO₄ and CsH₂PO₄ were mechanochemically treated using a planetary type of ball mill. The changes in structure and proton conductivity of the solid acid compounds with the treatment have been investigated. Cs₃(HSO₄)₂(H₂PO₄) and Cs₅(HSO₄)₃(H₂PO₄)₂ were formed during milling. The mechanochemically treated composite consisting of Cs₃(HSO₄)₂(H₂PO₄) and Cs₅(HSO₄)₃(H₂PO₄)₂ showed higher conductivity than the untreated mixture. In addition, a high temperature phase of Cs₂(HSO₄)(H₂PO₄) was generated from the composite at around 100 °C on heating. Conductivity of the mechanochemically treated composite significantly increased at temperatures around 90 °C on heating. The value becomes 2 × 10^− 3 S cm^− 1 at around 180 °C. On the other hand, no steep decrease is observed on cooling. The activation energies of the mechanically milled sample with high conductivities were estimated to be about 0.3 eV for both heating and cooling processes. The relatively high proton conductivity and a low activation energy for the proton conduction should be ascribed to the presence of the high temperature phase of Cs₂(HSO₄)(H₂PO₄).     

Low-temperature synthesis of Zn2SiO4:Mn green photoluminescence phosphor

Zn₂SiO₄:Mn green phosphor having comparable photoluminescence (PL) efficiency with commercial phosphor has been synthesized at 1000 °C using solid state reactions involving ZnO, silicic acid and manganese acetate. The water of crystallization attached to SiO₂ in silicic acid whose dissociation at 1000 °C seem to promote the sintering efficiency of Zn₂SiO₄:Mn. Incremental ZnO addition and re-firing at 1000 °C promote the diffusion rate of ZnO and SiO₂. The formation of a single crystalline phase of willemite structure in the samples was confirmed by powder XRD measurements. The phosphor exhibit an intense excitation band centered around 275 nm and a relatively weak excitation centered around 380 nm while the broad band green emission peaks at 524 nm. Other parameters studied include PL spectra, grain morphology, ZnO/SiO₂ molar ratio, Mn concentration, co-dopant/flux and the effect of chemical forms of Mn dopant as well as silica on the PL efficiency.     

Structure,stability and electrical properties of the La(2−x)SrxMnO4±δ solid solution series

Single phase materials of the La_(2−x)Sr_xMnO_4±δ (0.6 ≤ x ≤ 2.0) solid solution series were prepared via solid state reaction. The structure of each material was examined at room temperature and determined to be tetragonal for all phases examined. An expansion in lattice volume was observed on increasing lanthanum content. The stability and thermal expansion of each member of the solid solution series was determined via the use of in situ high temperature X-ray diffraction. It was found that all materials remained stable up to a temperature of 800 °C. Thermal expansion coefficients were found to be in the region of 15 × 10^− 6 K^− 1 for La_(2−x)Sr_xMnO_4±δ compounds where x > 1.4. The electrical conductivity of each phase was also determined over a similar temperature range with a maximum value of ∼6 Scm^− 1 at 900 °C for the x = 1.8 phase.     

Luminescence and defect studies of YAlO3:Dy3+, Sm3+ single crystals exposed to 100 MeV Si7+ ion beam

Ionoluminescence (IL) and photoluminescence (PL) spectra for different rare earth ions (Sm³⁺ and Dy³⁺) activated YAlO₃ single crystals have been induced with 100 MeV Si⁷⁺ ions with fluence of 7.81×10¹² ions cm^?2. Prominent IL and PL emission peaks in the range 550–725 nm in Sm³⁺ and 482–574 nm in Dy³⁺ were recorded. Variation of IL intensity in Dy³⁺ doped YAlO₃ single crystals was studied in the fluence range 7.81×10¹²–11.71×10¹² ions cm^?2. IL intensity is found to be high in lower ion fluences and it decreases with increase in ion fluence due to thermal quenching as a result of an increase in the sample temperature caused by ion beam irradiation. Thermoluminescence (TL) spectra were recorded for fluence of 5.2×10¹² ions cm^?2 on pure and doped crystals at a warming rate of 5 °C s^?1 at room temperature. Pure crystals show two glow peaks at 232 (Tg₁) and 328 °C (Tg₂). However, in Sm³⁺ doped crystals three glow peaks at 278 (Tg₁), 332 (Tg₂) and 384 °C (Tg₃) and two glow peaks at 278 (Tg₁) and 331 °C (Tg₂) in Dy³⁺ was recorded. The kinetic parameters (E, b s) were estimated using glow peak shape method. The decay of IL intensity was explained by excitation spike model.     

Anionic conductors Ln2/3[Bi12O14](MoO4)5 with Ln = La,Nd, Gd,Ho, Yb. Synthesis–spark plasma sintering–structure–electric properties

A new series of columnar phases Ln_2/3□_1/3[Bi₁₂O₁₄](MoO₄)₅ (□ vacancy) with Ln = La, Nd, Gd, Ho and Yb have been synthesized and structurally characterized. They feature the same formula as the molybdate phase Bi_2/3□_1/3[Bi₁₂O₁₄](MoO₄)₅ and crystallize in the monoclinic system, space group P2/c. These phases are isostructural with the prototype structure Bi[Bi₁₂O₁₄](MoO₄)₄(VO₄). Pellets of this rare-earth series obtained by spark plasma sintering and measured by impedance spectroscopy show a good anionic conductivity with a parabolic evolution whose maximum is raised by the Gd species at a determined value σ = 6.6 × 10^− 3 S cm^− 1 at 980 K.     

Preparation of proton conductive composites with CsHSO4/CsH2PO4 and phosphosilicate gel

New composite materials were prepared using cesium hydrogen sulfate (CsHSO₄) or cesium dihydrogen phosphate (CsH₂PO₄) and phosphosilicate gel (P₂O₅–SiO₂ gel). In X-ray diffraction patterns of these composites, diffraction peaks due to Cs₂H₅(SO₄)₂(PO₄) and CsH₅(PO₄)₂ were observed for CsHSO₄–(P₂O₅–SiO₂ gel) composites and CsH₂PO₄–(P₂O₅–SiO₂ gel) composites, respectively. These composites showed high conductivities in the order of 10^− 3 S cm^− 1 at 150 °C due to melting of Cs₂H₅(SO₄)₂(PO₄) or CsH₅(PO₄)₂ in the composites. In the cooling process, the CsHSO₄–(P₂O₅–SiO₂ gel) composites kept relatively high conductivity to 110 °C where solidification of Cs₂H₅(SO₄)₂(PO₄) occurs, whereas CsH₂PO₄–(P₂O₅–SiO₂ gel) composites showed relatively high conductivity continuously to ambient temperature.     

Microstructural effects on the superionic conductivity of a lithiated glass-ceramic

Three different formulations of 14 Li₂O·9 Al₂O₃·38 TiO₂·39 P₂O₅ composition (LATP) were melted, cast and crystallized. As-cast glass was characterized by differential scanning calorimetry which exhibited a distinct and strong exothermic peak around 680 °C. The peak was attributed to the crystallization of the glass. The crystallized glass (glass-ceramic) was further characterized by X-ray diffraction which showed the existence of Li_1 + xAl_xTi_2 − x(PO₄)₃ (x ⋍ 0.3)as the primary phase mixed with a small concentration of AlPO₄ and an unidentified phase. The scanning electron micrographs revealed the presence of the primary crystalline phase with an average grain size of 1 μm. Electrical characterization by AC impedance spectroscopy revealed grain and grain boundary contributions to the total conductivity. The effect of specimen processing parameters on conductivity is also investigated and discussed.     

Magnetic properties of nanocrystalline Fe86.7Zr3.3B4Ag6 thin film

The changes of magnetic properties with annealing temperature were studied in the amorphous Fe_86.7Zr_3.3B₄Ag₆ thin film. The thin films were deposited by a DC magnetron sputtering method, annealed at 300–700°C for 1 h in vacuum under a field of 1.5 kOe parallel to the film plane, and then furnace-cooled. As a result, it has been found that the Ag addition to Fe–Zr–B amorphous thin films resulted in the decrease of crystallization temperature to 400°C due to promoted crystallization ability. Also, it gave rise to formation of fine BCC α-Fe crystalline precipitates with a grain size smaller than 10 nm in the amorphous matrix near 400°C, and led to prominent enhancement in the magnetic properties of the Fe_86.7Zr_3.3B₄Ag₆ thin films. Significantly, excellent magnetic properties such as a saturation magnetization of 1.7 T, a coercive force of 1 Oe and a permeability of 7800 at 50 MHz were obtained in the amorphous Fe_86.7Zr_3.3B₄Ag₆ thin film containing 7.2 nm-size BCC α-Fe, which was annealed at 400°C. Also, core loss of 1.4 W cm⁻³ (B_m=0.1 T) at 1 MHz in the thin film was obtained, and it is a much lower value than had been obtained in any existing soft magnetic materials. Such excellent properties are inferred to originate from the uniform dispersion of nano-size BCC α-Fe in the amorphous matrix.     

Hydrothermal synthesis of self-emitting Y(V,P)O4 nanophosphors for fabrication of transparent blue-emitting display device

Self-emiting Y(V_x,P_1?x)O₄ blue nanophosphors with various compositons (x=0.1–0.9) were synthesized by a facile hydrothermal route and subsequently annealed at different temperatures of 800–1100 °C for 2 h. A higher content of vanadate in Y(V,P)O₄ nanophosphors resulted in a larger particle growth upon annealing. The blue luminescence under a vacuum ultraviolet excitation increased with an increasing phosphate content. Considering the size and luminescence, Y(V_0.1,P_0.9)O₄ nanophosphors annealed at 800, 1000, and 1100 °C were used for the formation of transparent blue emissive layer. Nanophosphor layer was uniformly deposited on glass substrate by a screen-printing. ～0.9 μm thick nanophosphor layer that was prepared with 1000 °C-annealed Y(V_0.1,P_0.9)O₄ nanophosphor showed a high visible transmittance value of 78%. Transparent blue-emitting test panel of plasma display was simply fabricated using nanophosphor layer/glass as a rear panel and combining it with the front panel used in the current plasma display panel, and their discharge luminance properties were discussed.     

Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)

Phase transformations in squaric acid (H₂C₄O₄) have been investigated by thermogravimetry and differential scanning calorimetry with different heating rates β. The mass loss in TG apparently begins at onset temperatures T_di=245±5 °C (β=5 °C min^?1), 262±5 °C (β=10 °C min^?1), and 275±5 °C (β=20 °C min^?1). A polymorphic phase transition was recognized as a weak endothermic peak in DSC around 101 °C (T_c⁺). Further heating with β=10 °C min^?1 in DSC revealed deviation of the baseline around 310 °C (T_i), and a large unusual exothermic peak around 355 °C (T_p), which are interpreted as an onset and a peak temperature of thermal decomposition, respectively. The activation energy of the thermal decomposition was obtained by employing relevant models. Thermal decomposition was recognized as a carbonization process, resulting in amorphous carbon.     

Conductivity and dielectric relaxation phenomena in (NH4)2SO4 single crystal

AC impedance measurements have been carried out on (NH₄)₂SO₄ single crystals for the temperatures from 300 to 473 K and frequency range between 100 Hz and 4 MHz. The results reveal two distinct relaxation processes in the sample crystal. One is the dipolar relaxation with a peak at frequency slightly higher than 4 × 10⁶ Hz. The other is the charge carrier relaxation at lower frequencies. The frequency dependence of conductivity is described by the relation σ(ω) = Bωⁿ, and n = 1.32 is obtained at temperatures below 413 K. This value drops to 0.2 and then decreases slightly with increasing temperature. The dipolar response of the (NH₄)₂SO₄ single crystal under an ac field is attributed to the reorientation of dipoles. The contribution of charge carriers is increasing substantially with increasing temperature at temperatures above 413 K. The temperature variation of conductivity relaxation peaks follows the Arrhenius relation. The obtained activation energy for migration of the mobile ions for (NH₄)₂SO₄ single crystal was 1.24 eV in the temperature range between 433 and 468 K in this intrinsic region. It is proposed that the NH₄⁺ in the sample crystal has the contribution to the electrical conduction.     

Preparation and properties of transparent SnO–P2O5 glasses

Colorless, transparent SnO–P₂O₅ (SP) glasses with 60–70 mol% SnO compositions were prepared by melting at 880–1000 °C in Ar atmosphere using commercial SnO and P₂O₅ powders as raw materials and vitreous carbon crucibles. SP glasses are characterized by glass transition temperature, onset of crystallization, thermal expansion coefficient and weight loss after immersion test. The viscosity of 67SnO–33P₂O₅ glass was measured by a penetration method in the range of 10^7.9–10^10.5 Pa s at 267–290 °C. The results of optical properties show that the transparent SP glasses have high refractive indexes over 1.75 and high transmission over 80% in the visible and IR region of 380 and 2700 nm.     

Thermoluminescence studies of thermally treated CaB4O7:Dy

Borate based thermoluminescence dosimeters (TLD) show high sensitivity and good TL characteristics. One of the promising material amongst the dosimeters is Dy doped CaB₄O₇. Spectrally resolved thermoluminescence of Dy doped CaB₄O₇ shows three glow peaks at about 50 °C, 240 °C and 380 °C, the intensity of the 240 °C glow peak being the maximum. All TL experiments were conducted on a high sensitivity TL spectrometer at Sussex University with a heating rate of 50 °C min^?1. Two main emissions associated with the Dy dopant are observed at ～480 and 580 nm. The samples were subjected to a series of treatments including excitation by X-rays and UV laser radiation. As part of the present research CaB₄O₇:Dy materials were subjected to two different heat treatments; quenching and slow cooling in order to investigate the changes in TL characteristics.     

Conductivity of SnP2O7 and In-doped SnP2O7 prepared by an aqueous solution method

SnP₂O₇ and In-doped SnP₂O₇ have been prepared by an aqueous solution method using (NH₄)₂HPO₄ as phosphorous source. It was found that the solid solution limit in Sn_1 ? xIn_x(P₂O₇)_1 ? δ was at least x = 0.12. All pyrophosphates in the Sn_1 ? xIn_x(P₂O₇)_1 ? δ (x ≤ 0.12) series exhibit 3 × 3 × 3 superlattice structures. The conductivities of Sn_0.92In_0.08(P₂O₇)_1 ? δ in air are 6.5 × 10^? 6 and 8.0 × 10^? 9 S/cm at 900 and 400 °C, respectively, when prepared by an aqueous solution method and annealed at 1000 °C. The conductivity of undoped SnP₂O₇ is slightly lower. However, it was also found that the low-temperature conductivities of pyrophosphates annealed only at 650 °C are several orders of magnitude higher than those annealed at 1000 °C, which could be related to a trace amount of an amorphous secondary phase. The peak conductivity was in this case observed at around 250 °C, which is the same temperature as previously observed in In-doped SnP₂O₇ although the conductivity is still three orders of magnitude lower in the present study. These differences can be related to large differences in particle size and morphology, and all in all, the conductivities of SnP₂O₇-based materials are very sensitive to the synthetic history.     

Crystal growth and characterization of a new co-ordination complex—barium tetrakis(maleate) dihydrate

Crystals of barium tetrakis(maleate) dihydrate [Ba₄(C₄H₂O₄)₄]^?2H₂O are grown in gelated hydrosilica matrix. Single crystal X-ray diffraction studies show that the crystal system is monoclinic with space group P2₁/c. The unit cell dimensions are a=9.3721(2)  Å, b=20.5880(7)  Å, c=14.0744(4) Å, α=γ=90°, β=90.289(2)°. Powder XRD studies confirmed the single phase nature of the grown crystals. The FTIR data is in conformity with the XRD results. The TG–DTA curves of the material indicate a three-step thermal decomposition. The response of the dielectric properties in the temperature range 30 °C to 500 °C is correlated with the TG–DTA results.     

Structural and magnetic properties of thin epitaxial Fe films on (1 1 0) GaAs prepared by metalorganic chemical vapor deposition

Iron films have been grown on (1 1 0) GaAs substrates by atmospheric pressure metalorganic chemical vapor deposition at substrate temperatures (T_s) between 135°C and 400°C. X-ray diffraction (XRD) analysis showed that the Fe films grown at T_s between 200°C and 330°C were single crystals. Amorphous films were observed at T_s below 200°C and it was not possible to deposit films at T_s above 330°C. The full-width at half-maximum of the rocking curves showed that crystalline qualities were improved at T_s above 270°C. Single crystalline Fe films grown at different substrate temperature showed different structural behaviors in XRD measurements. Iron films grown at T_s between 200°C and 300°C showed bulk α-Fe like behavior regardless of film thickness (100–6400 Å). Meanwhile, Fe films grown at 330°C (144 and 300 Å) showed a biaxially compressed strain between substrate and epilayer, resulting in an expanded inter-planar spacing along the growth direction. Magnetization measurements showed that Fe films (>200 Å) grown at 280°C and 330°C were ferromagnetic with the in-plane easy axis along the [1 1 0] direction. For the thinner Fe films (⩽200 Å) regardless of growth temperature, square loops along the [1 0 0] easy axis were very weak and broad.     

Influence of the selenium content on thermo-mechanical and optical properties of Ge–Ga–Sb–S chalcogenide glasses

A number of Ge₁₇Ga₄Sb₁₀S_69−xSe_x (x = 0, 15, 30, 45, 60, and 69) chalcogenide glasses have been synthesized by a melt-quenching method to investigate the effect of the Se content on thermo-mechanical and optical properties of these glasses. While it was found that the glass transition temperature (T_g) decreases from 261 to 174 °C with increasing Se contents, crystallization temperature (T_c) peak only be observed in glasses with Se content of x = 45. It was evident from the measurements of structural and physical properties that changes of the glass network bring an apparent impact on the glass properties. Also, the substitution of Se for S in Ge–Ga–Sb glasses can significantly improve the thermal stability against crystallization and broaden the infrared transmission region.     

Bulk and surface properties of ionic salt CsH5(PO4)2

We report a comparative study of transport and thermodynamic properties of single-crystal and polycrystalline samples of the ionic salt CsH₅(PO₄)₂ possessing a peculiar three-dimensional hydrogen-bond network. The observed potential of electrolyte decomposition ≈ 1.3 V indicates that the main charge carriers in this salt are protons. However, in spite of the high proton concentration, the conductivity appears to be rather low with a high apparent activation energy E_a ≈ 2 eV, implying that protons are strongly bound. The transport anisotropy though is not large, correlates with the crystal structure: the highest conductivity is found in the [001] direction (σ_130 °C ∼ 5.6 × 10^− 6 S cm^− 1) while the minimal conductivity is in the [100] direction (σ_130 °C ∼ 10 ⁻⁶ S cm^− 1). The conductivity of polycrystalline samples appears to exceed the bulk one by 1–3 orders of magnitude with a concomitant decrease of the activation energy (E_a ≈ 1.05 eV), which indicates that a pseudo-liquid layer with a high proton mobility is formed at the surface of grains. Infrared and Raman spectroscopy used to study the dynamics of the hydrogen-bond system in single-crystal and polycrystalline samples have confirmed the formation of such a modified surface layer in the latter. However, no bulk phase transition into the superionic disordered phase is observed in CsH₅(PO₄)₂ up to the melting point T_melt ∼ 151.6 °C, in contrast to its closest relative compound CsH₂PO₄.