Crystal structure and thermal expansion of LaCr1−xMgxO3, 0 < x ≤ 0.25

Solid solution LaCr_1?xMg_xO₃, 0 < х ≤ 0.25 was prepared by heating stoichiometric amounts of appropriate oxides in air at 1400 °C, 48 h. At room temperature it crystallizes in orthorhombically distorted GdFeO₃-type structure (a ≈ √2 × a_per; b ≈ √2 × a_pe; c ≈ 2 × a_per, where a_per – perovskite subcell parameter). High-temperature X-ray powder diffraction (HT XRPD) and dilatometry revealed first order phase transition to rhombohedral perovskite phase (R-3c, a ≈ √2 × a_per, c ≈ 2√3 × a_per) at 260–311 °C (OR phase transition). Crystal structures of room-temperature orthorhombic and high-temperature rhombohedral phases for LaCr_0.75Mg_0.25O₃ were refined using HT XRPD data. Temperature of OR phase transition increases gradually with increasing of magnesium content. Low-temperature orthorhombic phase exhibits TEC lower in comparison with high-temperature rhombohedral one (e.g. for LaCr_0.85Mg_0.15O₃ TEC(O) = 8.8 ppm K^?1; TEC(R) = 11.6 ppm K^?1). TEC for rhombohedral phase increases with increasing magnesium content from 10.4 ppm K^?1 for LaCr_0.95Mg_0.05O₃ to 12.1 ppm K^?1 for LaCr_0.75Mg_0.25O₃.     

First observation of the reversible O3 ↔ P2 phase transition: Crystal structure of the quenched high-temperature phase Na0.74Ni0.58Sb0.42O2

According to thermal expansion data, O3-type phase Na_xNi_(1+x)/3Sb_(2−x)/3O₂ (x ≈ 0.8) undergoes at ca. 1270 K a reversible transition to a less dense form. The high-temperature phase quenched to liquid nitrogen belongs to P2 type, space group P6₃/mmc (no. 194), a = 3.0123 Å(2), c = 11.2264 Å(7) for x ≈ 0.74 at 298 K. The stabilisation of P2 versus O3-type structure at high temperatures seems to be due to alkali distribution over greater number of sites thus increasing entropy and decreasing Na⁺–Na⁺ repulsion.     

Temperature dependent transport properties in molybdenum oxide doped α-NPD

The temperature dependent transport properties of molybdenum oxide (MoO₃) doped N,N′-di(1-naphthyl)-N,N′-diphenylbenzidin (α-NPD) were studied over a frequency range of 100 Hz to 1 MHz. The value of trap density and mobility calculated by detailed analysis of current–voltage (I–V) characteristics are 9.43 × 10²⁶ m^?3 and 1.23 × 10^?6 cm² V^?1 s^?1, respectively. The relaxation time for the carriers in the bulk and in the interface region decreases with temperature. The Cole–Cole plot indicates the device can be modeled as the combination of two parallel resistor–capacitor (R–C) circuits with a series resistance of around 70 Ω. The dc conductivity shows two different regions in the studied temperature range with activation energy of E_a ～ 0.107 eV (region I) and E_a ～ 52 meV (region II), respectively. The ac conductivity follows the universal power law and the onset frequency increases with increase of temperature. The temperature dependent conduction mechanism can be explained by correlated hopping barrier (CBH) model.     

Apatite-forming ability and magnetic properties of glass-ceramics containing zinc ferrite and calcium sodium phosphate phases

Fine particles of zinc ferrite (ZnFe₂O₄) and calcium sodium phosphate [NaCaPO₄] were crystallized in bulk x(ZnO, Fe₂O₃)(65?x)SiO₂20(CaO, P₂O₅)15Na₂O (6 ≤ x ≤ 21 mol %) glassy matrix by heat treatment. Initial magnetization curves reveal that samples with x = 6 and 9 mol % zinc–iron oxide exhibit both ferrimagnetic and paramagnetic contributions, whereas, samples with x > 9 mol % zinc–iron oxide exhibit only ferrimagnetic contribution. This observation is supported by the disappearance of the electron paramagnetic resonance (EPR) absorption line centered at g ≈ 4.3 in samples with x > 9 mol % zinc–iron oxide. Apatite-forming ability of the glass-ceramic samples was investigated by examining apatite formation on the surface of the samples treated in simulated body fluid (SBF). Increase in apatite-forming ability was observed with an increase in zinc–iron oxide content. The results obtained have been used to understand the evolution of the apatite surface layer as a function of immersion time in SBF and glass-ceramic composition. A good correlation has also been observed between the magnetic nature of the samples and their apatite-forming ability. These materials are expected to find application as thermo-seeds in hyperthermia treatment of bone cancer.     

Temperature dependence of spectral positions and widths of 5DJ → 7FJ fluorescence lines originating from Sm2+ ions in SrFCl crystals

The temperature dependence of the spectral positions and widths of the photoluminescence lines corresponding to the ⁵D₀ → ⁷F₀, ⁵D₀ → ⁷F₁ and ⁵D₁ → ⁷F₀ electronic transitions in Sm²⁺-doped SrFCl crystal was measured between 87 and 625 K at ambient pressure. The temperature dependence of the homogeneous line width Γ_h(T) for all these transitions in the whole temperature range used can be described by the two-phonon Raman scattering of acoustic phonons with the Debye temperature T_D ≈ 230 K. Comparison of the temperature- and pressure-induced shifts revealed why all the emission lines studied show the blue temperature shifts. It is so because a greater part of the line shift is caused by the thermal expansion of the host crystal and not by enhancement of the electron–phonon coupling with increasing temperature.     

Optical constants and crystal chemical parameters of Sc2W3O12

The refractive indices of Sc₂W₃O₁₂, measured at wavelengths of 435.8–643.8 nm, were used to calculate n_a = 1.7331, n_b = 1.7510, n_c = 1.7586 at λ = 589.3 nm and n_∞ values at λ = ∞ from a one-term Sellmeier equation. Mean refractive indices, 〈n_D〉, and mean dispersion values, 〈A〉, are, respectively, 1.7475 and 110 × 10^?16 m². Total electronic polarizabilities, α_obs, were calculated from n_∞ and the Lorenz–Lorentz equation. The unusually large difference between the observed polarizability of 28.415 Å³ and the calculated total polarizability α_T of 26.74 Å³ (Δ = +6.3%) is attributed to (1) a large M–O–W angle, and (2) a high degree of W 5d–O 2p and Sc nd–O 2p hybridization, where n signifies unspecified Sc d orbitals.     

Fluorescence properties and relaxation processes of Tb3+ ions in ZnCl2-based glasses

60ZnCl₂–20KCl–20BaCl₂–xTbCl₃ glasses (x = 0.10, 0.25, 0.50, 0.75, 1.00, and 1.25) were prepared by melt-quenching method, and Tb³⁺ fluorescence properties were investigated under 355 nm excitation. Regardless of x values, the electrons that were relaxed from the ⁵D₃ to ⁵D₄ level of Tb³⁺ ions by the multiphonon relaxation, were repressed to 28% of all the excited electrons because the ZnCl₂-based glass had much lower phonon energy than oxide glasses. For 0 < x ≤ 0.34, the cross relaxation, (⁵D₃ → ⁵D₄) → (⁷F₀ ← ⁷F₆), was repressed, and consequently 72% and 28% of all the excited electrons were radiatively relaxed by the ⁵D₃ → ⁷F_J (J = 6, 5, 4, 3, and 2) and ⁵D₄ → ⁷F_J (J = 6, 5, 4, and 3) transitions, respectively. The lifetimes of the ⁵D₃ and ⁵D₄ initial levels were obtained to be 1.1 and 2.1 ms, respectively.     

Crystal structure,thermal analysis and IR spectrometric investigation of l-tyrosine hydrazide diphosphate monohydrate

The monoclinic crystal structure of (C₉H₁₅N₃O₂)₂P₂O₇·H₂O denoted DLTHDP [a = 14.626(1), b = 6.1990(2), c = 14.562(1) Å, β = 97.289(3)°, Z = 2, monoclinic P2₁, D_cal = 1.508, D_mes = 1.49 g cm⁻³] has been solved using direct methods and refined to a reliability factor R = 4.37% for 2079 independent reflections. The DLTHDP structure can be described by infinite polyanions [P₂O₇·H₂O]_n⁴ⁿ⁻ organized in chains parallel to the b-direction and located at z = 1/2, alternating with organic cations associated in ribbons spreading along the a-direction. Multiple hydrogen bonds originating from amine, hydroxyl groups and water molecules donors [NH…O(N) and O(W)H…O] connect the different components of the lattice. The IR data of DLTHDP is reported and discussed according to the theoretical group analysis and by comparison with IR results of similar compounds. The coupled thermogravimetric analysis (TGA)–differential thermal analysis (DTA) thermal study shows the departure of one water molecule, confirming the hydrated character of this compound.     

Effect of heat treatment on morphology and thermal decomposition kinetics of multiwalled carbon nanotubes

High temperature treatment in inert atmosphere proved to be an effective way to improve high temperature stability of MWNTs in ambient condition. TEM analysis of heat-treated MWNTs confirmed successful removal of impurities and formation of ordered graphene layers and internal bamboo structure. TG–DTG curves indicated that decomposition range and rate of as-received MWNTs were narrow and notably higher, respectively, than heat-treated MWNTs mainly due to presence of impurities like metal nanoparticles in the former. Non-isothermal kinetic analysis revealed that the rate determining mechanism for as-received MWNTs was random nucleation and growth of active species. However, for heat-treated MWNTs, rate controlling mechanism was chemical reaction. Higher activation energies (～203 kJ mol^?1 and 280 kJ mol^?1) and reaction orders (3 and 4) of MWNTs heat-treated at 1200 °C and 1800 °C in inert, respectively, indicated delayed thermal decomposition than as-received MWNTs (E_a ≈ 178 kJ mol^?1; n = 1) even in oxidative atmosphere.     

A new indium metal-organic 3D framework with 1,3,5-benzenetricarboxylate,MIL-96 (In), containing μ3-oxo-centered trinuclear units and a hexagonal 18-ring network

A new indium trimesate In₁₂O(OH)₁₂({OH}₄,{H₂O}₅)[btc]₆·≈31H₂O, called MIL-96, (btc = 1,3,5-benzenetricarboxylate or trimesate species) was hydrothermally synthesized under mild condition (210 °C, 5 h) in the presence of trimethyl 1,3,5-benzenetricarboxylate in water and characterized by single-crystal X-ray diffraction technique. The MIL-96 (In) structure exhibits a three-dimensional metal-organic framework containing isolated trinuclear μ₃-oxo-bridged indium clusters and infinite chains of InO₄(OH)₂ and InO₂(OH)₃(H₂O) octahedra generating a hexagonal network based on 18-membered ring. The two types of indium entities are connected to each other through the trimesate species which induce corrugated chains of indium octahedra, linked via μ₂-hydroxo bonds with the specific –cis–cis–trans– sequence. The 3D framework of MIL-96 reveals three kind of cavities (two of them have estimated ≈ 400 Å³ volumes), in which are encapsulated free water molecules. The latter species are removed upon heating at 150 °C.     

Yellow-emitting (Ca2Lu1−xCex)(ScMg)Si3O12 phosphor and its application for white LEDs

Luminescence properties of the yellow-emitting (Ca₂Lu_1?xCe_x)(ScMg)Si₃O₁₂ (CLSM:xCe³⁺ x = 0.01–0.15) phosphor are investigated for various Ce³⁺ concentrations. Different Ce³⁺ emission sites and energy transfers between them are observed, resulting in a red shift of the emission spectra from 530 to 575 nm with increasing x from 0.01 to 0.15. Combining with blue (460 nm) InGaN LEDs, CLSM:Ce³⁺ shows excellent performances for phosphor-converted white LEDs with higher color rendering index R_a of 87.4–87.9 and lower color temperature T_C of 5034–5814 K, especially for warm pcWLEDs with a high color rendering (R_a > 80) and a low color temperature (T_C < 4000 K). Thermal quenching behaviors depending on Ce³⁺ concentrations and temperatures are discussed.     

Both initial concentrations of Fe(II) and monovalent cations jointly determine the formation of biogenic iron hydroxysulfate precipitates in acidic sulfate-rich environments

In order to accurately predict the types of biogenic iron hydroxysulfate precipitates in acidic, sulfate-rich environments facilitated by Acidithiobacillus ferrooxidans, different initial concentrations of Fe^2 +, K⁺, Na⁺, and NH₄⁺ are selected and tested in batch experiments for the formation of the precipitates. The critical equations of jarosite formation in FeSO₄–K₂SO₄–H₂O system or FeSO₄–(NH₄)₂SO₄–H₂O system could be described as Y = ? 22120.8077 ? 0.04257x + 0.006170x² (R² = 0.9979) or Y = 0.03540 ? 0.002950x + 7.407E ? 5x² (R² = 0.9934), respectively, where Y is the threshold or critical values of the molar ratio of Fe/K or Fe/NH₄ for jarosite formation, and x (mmol/L) is the initial concentration of Fe(II). Schwertmannite is the sole biogenic secondary ferric mineral when molar ratio of Fe/K or Fe/NH₄ is higher than Y in the system with a given initial Fe(II) concentration. The precipitates are an admixture of schwertmannite and jarosite, or pure jarosite when the Fe/M molar ratio is lower than Y. The crystallinity of the secondary ferric minerals increased with the increase of initial Fe(II) concentration in the medium with a fixed K⁺ concentration. It is observed that the capacity of monovalent cation in promoting jarosite formation is K⁺ > NH₄⁺ > Na⁺, as exhibiting that the capacity of K⁺ in this process is about 75 and 200 times greater than NH₄⁺ and Na⁺, respectively. Obviously, both the initial concentration of Fe(II) and molar ratio of Fe to monovalent cation determine the types of biogenic iron hydroxysulfate precipitates.     

Growth and characterization of (Pb,La)TiO3 films with and without a special buffer layer prepared by RF magnetron sputtering

The (Pb, La)TiO₃ (PLT) ferroelectric thin films with and without a special buffer layer of PbO_x have been deposited on Pt/Ti/SiO₂/Si(100) substrates by RF magnetron sputtering technique at room temperature. The microstructure and the surface morphology of the films annealed at 600 °C for 1 h have been investigated by X-ray diffraction (XRD) and atomic force microscope (AFM). The surface roughness of the PLT thin film with a special buffer layer was 4.45 nm (5 μm × 5 μm) in comparison to that of 31.6 nm (5 μm × 5 μm) of the PLT thin film without a special buffer layer. Ferroelectric properties such as polarization hysteresis loop (P–V loop) and capacitance–voltage curve (C–V curve) of the films were investigated. The remanent polarization (P_r) and the coercive field (E_c) are 21 μC/cm² and 130 kV/cm respectively, and the pyroelectric coefficient is 2.75 × 10^− 8 C/cm² K for the PLT film with a special buffer layer. The results indicate that the (Pb, La)TiO₃ ferroelectric thin films with excellent ferroelectric properties can be deposited by RF magnetron sputtering with a special buffer layer.     

EPR and optical absorption studies of Cr3+ doped lithium potassium sulphate single crystals

X-band electron paramagnetic resonance (EPR) studies of Cr³⁺ doped lithium potassium sulphate single crystals have been done at room temperature. The Cr³⁺ crystal field and spin Hamiltonian parameters have been evaluated by employing resonance line positions observed in the EPR spectra for different orientations of external magnetic field. The evaluated g, D and E values are: g_x = 2.0763 ± 0.0002, g_y = 1.9878 ± 0.0002, g_z = 1.8685 ± 0.0002 and D = 549 ± 2 × 10^?4 cm^?1, E = 183 ± 2 × 10^?4 cm^?1. Using EPR data the site symmetry of Cr³⁺ ion in the crystal is discussed. Cr³⁺ ion enters the lattice substitutionally replacing K⁺ site. The optical absorption study of the single crystal is also done in 195–925 nm wavelength range at room temperature. By correlating optical and EPR data the nature of bonding in the crystal is discussed. The calculated values of Racah parameters (B and C), crystal field parameter (D_q) and nephelauxetic parameters (h and k) are obtained as: B = 697, C = 3247, D_q = 2050 cm^?1, h = 1.146 and k = 0.21.     

Stoichiometric and non-stoichiometric films in the Si–O–N system: mechanical,electrical, and dielectric properties

A novel low-temperature (600–850 °C), chemical vapor deposition method, involving a simple reaction between disiloxane (H₃Si–O–SiH₃) and ammonia (NH₃), is described to deposit stoichiometric, Si₂N₂O, and non-stoichiometric, SiO_xN_y, silicon oxynitride films (5–500 nm) on Si substrates. Note, the gaseous reactants are free from carbon and other undesirable contaminants. The deposition of Si₂N₂O on Si (with (1 0 0) orientation and a native oxide layer of 1 nm) was conducted at a pressure of 2 Torr and at extremely high rates of 20–30 nm min⁻¹ with complete hydrogen elimination. The deposition rate of SiO_xN_y on highly-doped Si (with (1 1 1) orientation but without native oxide) at 10⁻⁶ Torr was ∼1.5 nm min⁻¹, and achieved via the reaction of disiloxane with N atoms, generated by an RF source in an MBE chamber. The phase, composition and structure of the oxynitride films were characterized by a variety of analytical techniques. The hardness of Si₂N₂O, and the capacitance–voltage (C–V) as a function of frequency and leakage current density–voltage (J_L–V) characteristics were determined on MOS (Al/Si₂N₂O/SiO/p-Si) structures. The hardness, frequency-dispersionless dielectric permittivity (K), and J_L at 6 V for a 20 nm Si₂N₂O film were determined to be 18 GPa, 6 and 0.05–0.1 nA cm⁻², respectively.     

Spectroscopic investigations on Eu3+ ions in Li–K–Zn fluorotellurite glasses

Eu³⁺ ions incorporated Li–K–Zn fluorotellurite glasses, (70 − x)TeO₂ + 10Li₂O + 10K₂O + 10ZnF₂ + xEu₂O₃, (0 ⩽ x ⩽ 2 mol%) were prepared via melt quenching technique. Optical absorption from ⁷F₀ and ⁷F₁ levels of the Eu³⁺-doped glass has been studied to examine the covalent bonding characteristics, energy band gap and Judd–Ofelt intensity parameters. The emission spectra (⁵D₀ → ⁷F_0,1,2,3,4) of the glasses were used to estimate the luminescence enhancement, asymmetric environment in the vicinity of Eu³⁺ ions, stimulated emission cross section and branching ratios. The phonon side band mechanism of ⁵D₂ level of the Eu³⁺ ions in the prepared glass was examined by considering the excitation and Raman spectra. The radiative lifetime calculated using Judd–Ofelt parameters was compared with the experimental lifetime to estimate the quantum efficiency of ⁵D₀ level of Eu³⁺ ions in Li–K–Zn fluorotellurite glass.     

Characterization of phases in a Mg–6Gd–4Sm–0.4Zr (wt.%) alloy during solution treatment

Phases in as-cast and solution-treated Mg–6Gd–4Sm–0.4Zr (wt.%) alloy have been characterized using transmission electron microscopy in this paper. The intermetallic phase in as-cast microstructure has a face centered cubic crystal structure (a = 2.2879 nm) with a composition of Mg_6.2(Sm_0.56Gd_0.44) and was dissolved after solution treatment. A particulate phase with a face centered cubic crystal structure (a = 0.5502 nm) was found in the solution-treated microstructure and suggested to already exist in as-cast sample as the nucleus for its further growth during solution treatment.     

Electrical properties and deep traps spectra of a-plane GaN films grown on r-plane sapphire

Electrical properties, deep traps spectra and luminescence spectra were studied for two undoped a-plane GaN (a-GaN) films grown on r-plane sapphire using metalorganic chemical vapor deposition and differing by structural perfection. For sample A, the a-GaN film was directly deposited on AlN buffer. A two-step growth scheme was implemented for sample B, including an initial islanding growth stage and a subsequent enhanced lateral growth. Preliminary detailed X-ray analysis showed that the stacking faults density was 8 × 10⁵ cm^?1 for sample A and 1.7 × 10⁵ cm^?1 for sample B. Electrical properties of a-GaN films were largely determined by deep traps with a level near E_c ?0.6 eV, with other prominent traps having the activation energy of 0.25 eV. The Fermi level was pinned by the E_c ?0.6 eV deep traps for sample A, but shifted to the vicinity of the shallower 0.25 eV traps for sample B, most likely due to the reduced density of the 0.6 eV traps. This decrease of deep traps density is accompanied by a very pronounced improvement in the overall luminescence intensity. A correlation of the observed improvement in deep traps spectra and luminescence efficiency with the improved crystalline quality of the films is discussed.     

Low temperature synthesis,crystal structure and thermal stability studies of nanocrystalline VN particles

The simultaneous thermal decomposition and nitridation of [VO(NH₂O)₂Gly]·H₂O complex in NH₃ atmosphere at 723–973 K gives the nanocrystalline vanadium nitride (VN) having crystallite size of 8–32 nm. It shows cubic NaCl structure with lattice parameter of a = 4.137 nm. XRD pattern Rietveld analysis program for crystal structure of VN shows the space group-Fm3m. The particle sizes measured by BET and SEM techniques are in the range of 26–100 nm. The particles are spherical and distributed homogeneously and found larger than XRD crystallite size because of agglomeration of crystallites. The fundamental IR absorption of VN material is found at 995 cm⁻¹ which gives the force constant of 634.3 Nm⁻¹. The electrical resistivity and magnetic studies show the superconducting to normal transition (T_c) at 9.2 K. Thermal decomposition of VN is carried out in O₂ atmosphere which goes through the formation of an oxynitride (V–N_p–O_q) intermediate phase up to 913 K. Finally, nanocrystalline V₂O₅ is formed at 973 K. The V₂O₅ has orthorhombic structure with lattice parameters of a = 11.537, b = 3.568 and c = 4.380 Å and the XRD crystallite size of 10 nm.     

High pressure neutron diffraction study of the magnetoresistive 1222-type ruthenocuprate,RuSr2Nd0.9Y0.2Ce0.9Cu2O10

The crystal structure of the 1222-type ruthenocuprate RuSr₂Nd_0.9Y_0.2Ce_0.9Cu₂O₁₀ has been studied by time-of-flight neutron diffraction at temperatures 100–160 K and pressures up to 5 GPa. The structure has tetragonal I4/mmm symmetry throughout (e.g. a = 3.8104(2) Å and c = 28.125(3) Å at 160 K and 5.1 GPa) with no significant distortions observed at the 140 K Ru spin ordering transition. The strongly bonded Cu–O and Ru–O network leads to a bulk modulus of 145 GPa which is high for layered cuprates, with a low anisotropy in the cell compressibility (k_c/k_a = 1.32). The Cu–O–Cu buckling angle and the tilting of the CuO₅ square pyramids decreases with pressure, but the in-plane rotation of the RuO₆ octahedra increases.