PEG-300 assisted hydrothermal synthesis of 4ZnO·B2O3·H2O nanorods

4ZnO·B₂O₃·H₂O is commonly used as a flame-retardant filler in composite materials. The microstructure of the powder is of importance in its applications. In our study, for the first time, one-dimensional (1D) nanostructure of 4ZnO·B₂O₃·H₂O with rectangle rod-like shape has been synthesized by a hydrothermal route in the presence of surfactant polyethylene glycol-300 (PEG-300). The nanorods have been characterized by X-ray powder diffraction (XRD), inductively coupled plasma with atomic emission spectroscopy (ICP-AES), thermogravimetry (TG) and differential thermal analysis (DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) equipped with selected area electron diffraction (SAED) as well as high-resolution transmission electron microscopy (HRTEM). These nanorods are about 70 nm in thickness, 150-800 nm in width and have lengths up to a few microns. 4ZnO·B₂O₃·H₂O nanorods crystallize in the monoclinic space group P2₁/m, a = 6.8871(19) Å, b = 4.9318(10) Å, c = 5.7137(16) Å, β = 98.81(21)° and V = 191.779(71) Å³.     

Luminescent properties of long lasting phosphor Ca2MgSi2O7:Eu

Long afterglow phosphors (Ca_1−xEu_x)₂MgSi₂O₇ (0.002 ≤ x ≤ 0.02) were prepared by solid-state reactions under a weak reductive atmosphere. X-ray diffraction pattern, photoluminescence spectra, decay curve, afterglow spectra and thermoluminescence curves were investigated. The phosphors showed two emission peaks when they were excited by 343 nm, due to two types of Eu²⁺ centers existing in the Ca₂MgSi₂O₇ lattice. However, only one emission peak can be found in their afterglow spectra. Energy transfer between Eu²⁺ ions in inequivalent sites was found. A possible mechanism was presented and discussed. The afterglow decay time of Ca_1.998MgSi₂O₇:Eu_0.002 was nearly 12.5 h which means it was a good long lasting phosphor.     

Effect of doping with Nd ions on the structural and ferroelectric properties of Ca0.28Ba0.72Nb2O6 single crystal

The crystal structure of Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystal with Nd-doping has been determined from X-ray single crystal diffraction data, in the tetragonal system with space group P4bm and the following parameters: a = b = 12.458 Å, c = 3.954 Å, V = 613.688 Å³, and Z = 5. X-ray diffraction results on a Nd-doped CBN-28 single crystal also have demonstrated that Nd³⁺ and Ca²⁺ occupy the same site in the crystal structure. Dielectric and ferroelectric measurements have been performed. Transition from ferroelectric to paraelectric at around 223 °C has been observed. The Nd-doped crystal has a lower Curie temperature (T_m) than that of undoped CBN-28 crystal. The spontaneous polarization (P_s) and coercive electric field (E_c) also decrease compared with their values in the undoped CBN-28 crystal.     

Novel Dy-doped Ca2Gd8(SiO4)6O2 white light phosphors for Hg-free lamps application

The luminescent properties of Ca₂Gd_8(1−x)(SiO₄)₆O₂:xDy³⁺ (1% ≤ x ≤ 5%) powder crystals with oxyapatite structure were investigated under vacuum ultraviolet excitation. In the excitation spectrum, the peaks at 166 nm and 191 nm of the vacuum ultraviolet region can be assigned to the O²⁻ → Gd³⁺, and O²⁻ → Dy³⁺ charge transfer band respectively, which is consistent with the theoretical calculated value using Jφrgensen's empirical formula. While the peaks at 183 nm and 289 nm are attributed to the f-d spin-allowed transitions and the f-d spin-forbidden transitions of Dy³⁺ in the host lattice with Dorenbos's expression. According to the emission spectra, all the samples exhibited excellent white emission under 172 nm excitation and the best calculated chromaticity coordinate was 0.335, 0.338, which indicates that the Ca₂Gd₈(SiO₄)₆O₂:Dy³⁺ phosphor could be considered as a potential candidate for Hg-free lamps application.     

Phase relations of the Li2O-Ta2O5-B2O3 and Li2O-WO3-B2O3 systems and promising nonlinear optical compounds in K2O-Ta2O5-B2O3 system

The subsolidus phase equilibria of the Li₂O-Ta₂O₅-B₂O₃, K₂O-Ta₂O₅-B₂O₃ and Li₂O-WO₃-B₂O₃ systems have been investigated mainly by means of the powder X-ray diffraction method. Two ternary compounds, KTaB₂O₆ and K₃Ta₃B₂O₁₂ were confirmed in the system K₂O-Ta₂O₅-B₂O₃. Crystal structure of compound KTaB₂O₆ has been refined from X-ray powder diffraction data using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pmn2₁ (No. 31), with lattice parameters a = 7.3253(4) Å, b = 3.8402(2) Å, c = 9.3040(5) Å, z = 2 and D_calc = 4.283 g/cm³. The powder second harmonic generation (SHG) coefficients of KTaB₂O₆ and K₃Ta₃B₂O₁₂ were five times and two times as large as that of KH₂PO₄ (KDP), respectively.     

A yellow-emitting Ca3Si2O7: Eu phosphor for white LEDs

A series of yellow-emitting phosphors based on a silicate host matrix, Ca_3 − xSi₂O₇: xEu²⁺, was prepared by solid-state reaction method. The structure and photoluminescent properties of the phosphors were investigated. The XRD results show that the Eu²⁺ substitution of Ca²⁺ does not change the structure of Ca₃Si₂O₇ host and there is no impurity phase for x < 0.12. The SEM images display that phosphors aggregate obviously and the shape of the phosphor particle is irregular. The EDX results reveal that the phosphors consist of Ca, Si, O, Eu and the concentration of these elements is close to the stoichiometric composition. The Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be excited at a wavelength of 300-490 nm, which is suitable for the emission band of near ultraviolet or blue light-emitting-diode (LED) chips. The phosphors exhibit a broad emission region from 520 to 650 nm and the emission peak centered at 568 nm. In addition, the shape and the position of the emission peak are not influenced by the Eu²⁺ concentration and excitation wavelength. The phosphor for x = 0.045 has the strongest excitation and emission intensity, and the Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be used as candidates for the white LEDs.     

Electronic structure and photoluminescence properties of Eu-activated Ca4Si2O7F2

The blue-emitting phosphors Ca_(4−x)Eu_xSi₂O₇F₂ (0 < x ? 0.05) have been prepared by solid-state reaction and the photoluminescence properties have been studied systematically. The electronic structure of calcium fluoride silicate Ca₄Si₂O₇F₂ was calculated using the CASTEP code. The calculation results of electronic structure show that Ca₄Si₂O₇F₂ has an indirect band gap with 5 eV. The top of the valence band is dominated by O 2p and Si 3p states, while the bottom of the conduction band is mainly composed of Ca 3d states. Under the 350 nm excitation, the obtained sample shows a broad emission band in the wavelength range of 400-500 nm with peaks of 413 nm and 460 nm from two different luminescence centers, respectively. The relative intensity of the two peaks changes with the alteration of the Eu²⁺ concentration. The strong excitation bands of the powder in the wavelength range of 200-420 nm are favorable properties for the application as lighting-emitting-diode conversion phosphor.     

New lead vanadium phosphate with langbeinite-type structure: Pb1.5V2(PO4)3

The new lead vanadium phosphate Pb_1.5V₂(PO₄)₃ was synthesized by solid state reaction and characterized by X-ray powder diffraction, electron microscopy, and magnetic susceptibility measurements. The crystal structure of Pb_1.5V₂(PO₄)₃ (a = 9.78182(8) Å, S.G. P2₁3, Z = 4) was determined from X-ray powder diffraction data and belongs to the langbeinite-type structures. It is formed by corner-linked V³⁺O₆ octahedra and tetrahedral phosphate groups resulting in a three-dimensional framework. The lead atoms are situated in the structure interstices and only partially occupy their positions. An electron microscopy study confirmed the structure solution. Magnetic susceptibility measurements revealed Curie-Weiss (CW) behavior for Pb_1.5V₂(PO₄)₃ at high temperature whereas at around 14 K an abrupt increase on the susceptibility was observed.     

Crystal structure and properties of the new complex vanadium oxide K2SrV3O9

The new complex vanadium oxide K₂SrV₃O₉ has been synthesized and investigated by means of X-ray powder diffraction (XPD), electron microscopy and magnetic susceptibility measurements. The oxide has an orthorhombic unit cell with lattice parameters a = 10.1922(2) Å, b = 5.4171(1) Å, c = 16.1425(3) Å, space group Pnma and Z = 4. The crystal structure of K₂SrV₃O₉ has been refined by Rietveld method using X-ray powder diffraction data. The structure contains infinite chains built by V⁴⁺O₅ square pyramids linked to each other via VO₄ tetrahedra. The chains form layers and potassium and strontium cations orderly occupy structural interstices between these layers. Electron diffraction as well as high resolution electron microscopy confirmed the structure solution. Magnetic susceptibility measurements revealed an antiferromagnetic interaction with J of the order of 100 K inside the chains and no long-range magnetic order above 2 K. The origin of the magnetic exchange is likely a result of super-exchange interaction through the two VO₄ tetrahedra linking the polyhedra with the magnetic V⁴⁺ cations.     

Structural and electrical properties of HfO2/Dy2O3 gate stacks on Ge substrates

In the present work we report on the structural and electrical properties of metal-oxide-semiconductor (MOS) devices with HfO₂/Dy₂O₃ gate stack dielectrics, deposited by molecular beam deposition on p-type germanium (Ge) substrates. Structural characterization by means of high-resolution Transmission Electron Microscopy (TEM) and X-ray diffraction measurements demonstrate the nanocrystalline nature of the films. Moreover, the interpretation of the X-ray reflectivity measurements reveals the spontaneous growth of an ultrathin germanium oxide interfacial layer which was also confirmed by TEM. Subsequent electrical characterization measurements on Pt/HfO₂/Dy₂O₃/p-Ge MOS diodes show that a combination of a thin Dy₂O₃ buffer layer with a thicker HfO₂ on top can give very good results, such as equivalent oxide thickness values as low as 1.9 nm, low density of interfacial defects (2-5 × 10¹² eV^− 1 cm^− 2) and leakage currents with typical current density values around 15 nA/cm² at V_g = V_FB − 1V.     

The preparation,characterization and optical properties of Cd2V2O7 and CdCO3 compounds

Cadmium vanadium oxides (Cd₂V₂O₇) and Cadmium carbonates (CdCO₃) were synthesized via a facile hydrothermal method. X-ray diffraction (XRD), Raman spectroscopy, infrared spectrometer (IR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the structure, morphology and chemical state of the samples, respectively. The photoluminescence (PL) properties of the as-synthesized Cd₂V₂O₇ and CdCO₃ were measured at room temperature using an excitation wavelength of 325 nm. The Cd₂V₂O₇ shows two visible light emission centers located at 589 and 637 nm, which are supposed to be relevant to local defects in Cd₂V₂O₇. The CdCO₃ shows three emission centers located at 408, 530 and 708 nm, which are supposed to be relevant to the electron transition from the conduction band to valence band and defect related energy level.     

Crystal growth and structure of R2Ir2O7 (R = Pr, Eu) using molten KF

Single crystals of R₂Ir₂O₇ (R = Pr, Eu) have been synthesized using molten KF at 1373 K. The pyrochlore compounds crystallize in a cubic space group (No. 227, origin choice 2), with Z = 8. At room temperature, the lattice parameters are a = 10.3940(4) Å, V = 1122.92(7) Å³ and a = 10.274(3) Å, V = 1084.5(6) Å³ for Pr₂Ir₂O₇ and Eu₂Ir₂O₇, respectively. In this paper, we report the crystal growth of R₂Ir₂O₇ (R = Pr, Eu) and their structure determinations from single crystal X-ray diffraction experiments at temperatures of 110, 115, and 298 K.     

Synthesis and photoluminescence of Ca-(Sn,Ti)-Si-O compounds

The phase relation of the compounds prepared in the CaO-SnO₂-SiO₂ system at 1673 K and in the CaO-TiO₂-SiO₂ system at 1573 K was investigated in order to explore new Ti⁴⁺-activated stannate phosphors. Solid solutions of Ca(Sn_1−xTi_x)SiO₅ and Ca₃(Sn_1−yTi_y)Si₂O₉ were synthesized at x = 0-1.0 and y = 0-0.10, respectively, and their crystal structures were analyzed by powder X-ray diffraction. Photoluminescence of these solid solutions was observed in a broad range of a visible light wavelength region under ultraviolet (UV) light excitation. The peaks of the emission band of Ca(Sn_0.97Ti_0.03)SiO₅ and Ca₃(Sn_0.925Ti_0.075)Si₂O₉ were at 510 nm under excitation of 252 nm and at 534 nm under excitation of 258 nm, respectively. The absorption edges estimated by the diffuse reflectance spectra were at 300 nm (4.1 eV) for CaSnSiO₅ and at 270 nm (4.6 eV) for Ca₃SnSi₂O₉, suggesting that the excitation levels in Ca(Sn_1−xTi_x)SiO₅ were above the band gap of the host, although the levels in Ca₃(Sn_1−yTi_y)Si₂O₉ were within the band gap and near the conduction band edge.     

2D-network of inorganic-organic hybrid material built on Keggin type polyoxometallate and amino acid: [L-C2H6NO2]3[(PO4)Mo12O36]·5H2O

A new inorganic-organic hybrid material based on polyoxometallate, [L-C₂H₆NO₂]₃[(PO₄)Mo₁₂O₃₆]·5H₂O, has been successfully synthesized and characterized by single-crystal X-ray analysis, elemental analysis, infrared and ultraviolet spectroscopy, proton nuclear magnetic resonance and differential thermal analysis techniques. The title compound crystallizes in the monoclinic space group, P2₁/c_, with a = 12.4938 (8) Å, b = 19.9326 (12) Å, c = 17.9270 (11) Å, β = 102.129 (1)°, V = 4364.8 (5) Å³, Z = 4 and R₁(wR₂) = 0.0513, 0.0877. The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like (2D/∞ [(PO₄)Mo₁₂O₃₆]³⁻) which forming via weak Van der Waals interactions along the z axis. The characteristic band of the Keggin anion [(PO₄)Mo₁₂O₃₆]³⁻ appears at 210 nm in the UV spectrum. Thermal analysis indicates that the Keggin anion skeleton begins to decompose at 520 °C.     

Synthesis, crystal structure and thermal decomposition of [La2(CH3CH2COO)6·(H2O)3]·3.5H2O precursor for high-k La2O3 thin films deposition

Lanthanum acetylacetonate La(C₅H₇O₂)₃·xH₂O has been used in the preparation of the precursor solution for the deposition of polycrystalline La₂O₃ thin films on Si(1 1 1) single crystalline substrates. The precursor chemistry of the as-prepared coating solution, precursor powder and precursor single crystal have been investigated by Fourier Transformed Infrared Spectroscopy (FTIR), differential thermal analysis coupled with quadrupole mass spectrometry (TG-DTA-QMS) and X-ray diffraction. The FTIR and X-ray diffraction analyses have revealed the complex nature of the coating solution due to the formation of a lanthanum propionate complex. The La₂O₃ thin films deposited by spin coating on Si(1 1 1) substrate exhibit good morphological and structural properties. The films heat treated at 800 °C crystallize in a hexagonal phase with the lattice parameters a = 3,89 Å and c = 6.33 Å, while at 900 °C the films contain both the hexagonal and cubic La₂O₃ phase.     

Alanine-assisted low-temperature combustion synthesis of nanocrystalline LiMn2O4 for lithium-ion batteries

Nanocrystalline LiMn₂O₄ powders have been synthesized by combustion process in a single step using a novel fuel, l-alanine. Thermogravimetric analysis and differential thermal analysis of the gel indicate a sharp combustion at a temperature as low as 149 °C. Quantitative phase analysis of X-ray diffraction data shows about 97% of phase purity in the as-synthesized powder, which on further calcination at 700 °C becomes single phase LiMn₂O₄. High Brunauer, Emmett, and Teller surface area values obtained for ash (53 m²/g) and calcined powder (23 m²/g) indicate the ultrafine nature of the powder. Average crystallite size is found to be ∼60-70 nm from X-ray diffraction analysis and transmission electron microscopy. Fourier transformed infra-red spectrum shows two strong bands at 615 and 511 cm⁻¹ originating from asymmetrical stretching of MnO₆ octahedra. A nominal composition of Li_0.88 Mn₂O₄ is calculated from the inductive coupled plasma analysis. From UV-vis spectroscopy, an optical band gap of 1.43 eV is estimated which is assigned to a transition between t_2g and e_g bands of Mn 3d. Electrochemical charge-discharge profiles show typical LiMn₂O₄ behavior with a specific capacity of 76 mAh/g.     

Luminescence and microstructures of Eu-doped in triple phosphate Ca8MgR(PO4)7 (R = La, Gd, Y) with whitlockite structure

Eu³⁺-doped triple phosphate Ca₈MgR(PO₄)₇ (R = La, Gd, Y) was synthesized by the general high temperature solid-state reaction. This phosphor was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and emission spectra. XRD and FT-IR analysis indicated that Ca₈MgR(PO₄)₇ (R = La, Gd, Y) crystallized in single-phase component with whitlockite-like structure (space group R3c) of β-Ca₃(PO₄)₂. Under the excitation of UV light, the phosphors show bright red emission assigned to the transition (⁵D₀ → ⁷F₂) at 612 nm. The crystallographic sites of Eu³⁺ ions in Ca₈MgR(PO₄)₇ (R = La, Gd, Y) host were discussed on the base of site-selective excitation and emission spectra, luminescence decay and its host crystal structure.     

Preparation of Bi2S3 nanorods via a hydrothermal approach

Large-scale bismuth sulfide (Bi₂S₃) nanorods with uniform size have been prepared by hydrothermal method using bismuth chloride (BiCl₃) and sodium sulfide (Na₂S·9H₂O) as raw materials at 180 °C and pH = 1-2 for 12 h. The powder X-ray diffraction (XRD) pattern shows the Bi₂S₃ crystal belongs to the orthorhombic phase with calculated lattice constants a = 1.1187 nm, b = 1.1075 nm and c = 0.3976 nm. Furthermore, the quantification of X-ray photoelectron spectra (XPS) analysis peaks gives an atomic ratio of 1.9:3.0 for Bi:S. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopic (TEM) studies reveal that the appearance of the as-prepared Bi₂S₃ is rod-like with typical lengths in the range of 2-5 μm and diameters in the range of 10-30 nm. Finally the influences of the reaction conditions are discussed and a possible mechanism for the formation of Bi₂S₃ nanorods is proposed.     

Microstructure and electrical properties of Sm2O3 doped Bi2O3-based ZnO varistor ceramics

The dependence of the bulk density, microstructure and dc electrical properties of bismuth oxide (Bi₂O₃)-based zinc oxide (ZnO) varistor ceramics for various samarium oxide (Sm₂O₃) contents was investigated. The value of bulk density was found to 5.43-5.50 g cm⁻³ with Sm₂O₃ (mol%) content. The maximum value of bulk density is observed to be 5.50 for 0.30 mol% Sm₂O₃ containing varistor ceramics. The grain sizes for all the samples calculated from the scanning electron micrographs were found to decrease as Sm₂O₃ increases. The presence of ZnO phases, Bi-rich phases, spinel phases and Sm₂O₃ phases were observed in the samples by the energy dispersive X-ray analysis and X-ray diffraction analysis. As the Sm₂O₃ amount increased in the Bi₂O₃-based ZnO varistor ceramics, the nonlinear coefficient, α increased up to 0.10 mol%, reaching a maximum value of 58 and then decreased. The breakdown electric field, E_b, increased with the increase of Sm₂O₃ content with a maximum value of 3220 V cm⁻¹ for the 0.75 mol% Sm₂O₃ doped ZnO varistor ceramics. The leakage current, I_L, showed a minimum value of 1.10 μA for the composition of 0.30 mol% Sm₂O₃ doped Bi₂O₃-based ZnO varistor ceramics. The 0.30 mol% Sm₂O₃-doped Bi₂O₃-based ZnO varistor ceramics sintered at 1200 °C exhibited a good stability for dc accelerated aging stress of 0.90 V_1 mA/90 °C/12 h.     

Crystal growth and structure determinations of potassium hafnates: K2Hf2O5 and K4Hf5O12

Crystals of K₂Hf₂O₅ and K₄Hf₅O₁₂ were grown from molten potassium hydroxide flux. The crystal structures were determined by single-crystal X-ray diffraction. K₂Hf₂O₅ crystallizes in the space group Pnna of the orthorhombic system, with unit cell dimensions of a = 5.780(1) Å, b = 10.640(2) Å, and c = 8.666(2) Å. This compound contains infinite chains of HfO₆ octahedra that form a channel structure. K₄Hf₅O₁₂ crystallizes in the space group of the trigonal system, with unit cell dimensions of a = 5.7877(2) Å and c = 10.3693(7) Å. This compound possesses a layered structure with six-coordinate Hf in three different coordination environments (trigonal prismatic, distorted octahedral, and regular octahedral).