EPR study of copper ions in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The EPR spectra of Cu²⁺ ions (² D _5/2) located at two structurally nonequivalent positions Cu1 and Cu2 in crystals of lithium heptagermanate Li₂Ge₇O₁₅ are recorded. The angular dependences of the EPR spectrum are measured in the paraelectric phase of the Li₂Ge₇O₁₅ compound (T = 300 K). The components of the g factor and the hyperfine interaction tensor A are determined, and the orientation of the magnetic axes with respect to the crystallographic basis is established. The EPR spectra are recorded in the temperature range in the vicinity of the temperature T _C = 283 K of the transition from the paraelectric phase to the ferroelectric phase. The position symmetry of the Cu1 and Cu2 centers is determined at temperatures above and below the phase transition temperature T _C . The localization of paramagnetic centers in the structure is discussed, An analysis of the results obtained demonstrates that the Cu1 and Cu2 centers in the Li₂Ge₇O₁₅ crystal lattice replace lithium ions located at two structurally nonequivalent positions with the symmetries described at temperatures above T _C by the triclinic C _i and monoclinic C ₂ point groups, respectively.     

Influence of heat treatment process in In<Subscript>2</Subscript>O<Subscript>3</Subscript>-MWCNTs as photoanode in DSSCs

Indium oxide-multi-walled carbon nanotubes (In₂O₃-MWCNTs) were prepared by sol-gel method for DSSCs. The synthesis of indium oxide (In₂O₃) was carried out by dissolving indium chloride (InCl₃) in a solvent of 2-methoxyethanol. Different annealing temperatures of 400, 450, 500, 550, and 600 °C were proposed in this study. The changes in the structural properties were analyzed by means of X-ray diffraction (XRD) and atomic force microscopy (AFM) analysis. The XRD spectrum estimated the average crystallite sizes of 3 nm for each sample. AFM results indicated very rough surface area of the films where it increased linearly from 1.8 to 11 nm as the annealing temperature increases. The In₂O₃-MWCNTs-based DSSC exhibited good photovoltaic performance with power conversion efficiency (η), photocurrent density (J _sc ), open circuit voltage (V _oc ), and fill factor (FF) of 1.13 %, 5.5 mA/cm², 0.53 V, and 0.42, respectively. Even though the film annealed at 450 °C exhibited low τ _eff, it achieved the greatest D _eff of 29.67 cm² s^?1 which provides an efficient pathway for the photogenerated electrons with minimum electron recombination loss that increased the J _sc and V _oc in the DSSC. The obtained structural and electron transport analysis was proposed as a suitable benchmark for In₂O₃-MWCNTs-based dye-sensitized solar cell (DSSCs) application. Hence, this study suggests that the optimum temperature for In₂O₃-MWCNTs is at annealing temperature of 450 °C prepared via sol-gel method.     

Raman scattering spectroscopy of inclusions of carbon in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> films and its solid solutions with HfO<Subscript>2</Subscript>

We apply Raman scattering spectroscopy to study the nature of carbon inclusions in Al₂O₃ and (HfO₂) _x (Al₂O₃)_{1 ? x} films deposited using volatile complex compounds. Raman spectra of the films under investigation contain D and G vibrational modes, which indicate that carbon clusters of the sp ² configuration tend to form in the films. We estimate the size of clusters from the integrated intensity ratio I _D /I _G and find it to be in the range of 14–20 Å. The content of hydrogen in carbon clusters is calculated from the height of the photoluminescence pedestal and is found to vary from 14 to 30 at % depending on the regime of the film’s synthesis.     

Correction of the band gap of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Submicron samples of Y₂O₃:Eu³⁺ phosphor with elevated photoluminescence (PL) efficiency and activator concentration of 9 at % obtained by the sol–gel method were investigated by diffuse reflection spectroscopy and PL spectroscopy. It is found that the diffuse reflection spectrum in the vicinity of the fundamental absorption edge (<300 nm) is distorted by the superposition of the PL of Eu³⁺ ions, as a result of which the calculated value of optical band gap E _g of the Y₂O₃ matrix is overestimated. An algorithm for eliminating the PL influence on the absorption edge is proposed, and the correct E _g values are found to be 4.61 ± 0.12 and 4.50 ± 0.12 eV for annealing at 700 and 1300°C, respectively.     

Electron paramagnetic resonance of Cr<Superscript>3+</Superscript>-Li<Superscript>+</Superscript> centers in (Cr,Li): Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> synthetic forsterite

Synthetic single crystals of chromium-and lithium-doped forsterite, namely, (Cr,Li): Mg₂SiO₄, are studied using electron paramagnetic resonance spectroscopy. It is revealed that, apart from the known centers Cr³⁺(M1) and Cr³⁺(M2) (with local symmetries C_i and C_s, respectively), these crystals involve two new types of centers with C₁ symmetry, namely, Cr³⁺(M1)′ and Cr³⁺(M2)′ centers. The standard parameters D and E in a zero magnetic field [zero-field splitting (ZFS) parameters expressed in GHz] and principal components of the g tensor are determined as follows: D=31.35, E=8.28, and g=(1.9797, 1.9801, 1.9759) for Cr³⁺(M1)′ centers and D=15.171, E=2.283, and g=(1.9747, 1.9769, 1.9710) for Cr³⁺(M2)′ centers. It is found that the lowsymmetric effect of misalignment of the principal axes of the ZFS and g tensors most clearly manifests itself (i.e., its magnitude reaches 19°) in the case of Cr³⁺(M2)′ centers. The structural models Cr³⁺(M1)-Li⁺(M2) and Cr³⁺(M2)-Li⁺(M1) are proposed for the Cr³⁺(M1)′ and Cr³⁺(M2)′ centers, respectively. The concentrations of both centers are determined. It is demonstrated that, upon the formation of Cr³⁺-Li⁺ ion pairs, the M1 position for chromium appears to be two times more preferable than the M2 position. Reasoning from the results obtained, the R₁ line (the ²E → ⁴A₂ transition) observed in the luminescence spectra of (Cr,Li): Mg₂SiO₄ crystals in the vicinity of 699.6 nm is assigned to the Cr³⁺(M1)′ center.     

In-plane torque and gap symmetry of untwinned YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7</Subscript> crystals

The reversible magnetic torque of untwinned YBa₂Cu₃O₇ single crystals shows the four-fold symmetry in thea-b plane. The irreversible torque indicates evidence for a novel intrinsic pinning along thea andb axes. These facts mean that the free energy of the four-fold symmetry has a minimum when the field is applied along thea orb axis. The results are consistent with those expected from thed _x ²?y ² symmetry and rule out the possibility of thed _xy symmetry. The Fermi surface anisotropy is not responsible for the observed anisotropy. This is firstbulk evidence for thek-dependent gap anisotropy on the Fermi surface. The two-fold anisotropy parameter is found as\(\gamma _{ab} = \sqrt {{{m_a } \mathord{\left/ {\vphantom {{m_a } {m_b }}} \right. \kern-\nulldelimiterspace} {m_b }}} = 1.18 \pm 0.14\).     

High-frequency EPR of Cr<Superscript>2+</Superscript> ions in CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>

High-frequency broad-band (65–240 GHz) EPR is used to study impurity centers of bivalent chromium in a CdGa₂S₄ crystal. It is found that the EPR spectra correspond to tetragonal symmetry. The spin Hamiltonian H = βB · g · S + B ₂ ⁰ O ₂ ⁰ + B ₄ ⁰ O ₄ ⁰ + B ₄ ⁴ O ₄ ⁴ with the parameters B ₂ ⁰ =23659±2 MHz, B ₄ ⁰ =1.9±1 MHz, |B ₄ ⁴ |=54.2±2 MHz, g_‖=1.93±0.02, and g_⊥=1.99±0.02 is used to describe the observed spectra. It is concluded that chromium ions occupy one of the tetrahedrally coordinated cation positions.     

X-ray emission study of the electronic structure of nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Valence states of metal ions and the phase composition of nanocrystalline Al₂O₃ (of the original oxide and the oxide irradiated by high-energy Fe⁺ ions) are studied by using x-ray emission Al L_{2, 3} and O Kα spectra. It is established that the shape of the Al L_{2, 3} spectra strongly changes as one goes from the original (bulk) Al₂O₃ to nanocrystalline oxide, while the O Kα spectra remain practically unchanged. Moreover, irradiation by high-energy Fe⁺ ions results in slight additional changes in the x-ray spectral characteristics of the aluminum oxides under study. The obtained experimental data are compared with the results of theoretical calculations of the electronic structure of α and γ phases of Al₂O₃ performed using the LDA formalism. Using the results of x-ray spectral studies, electronic structure calculations, and x-ray diffraction analysis, it is shown that the revealed spectral differences between the nanocrystalline state of aluminum oxide and the bulk material can be interpreted as a phase transition from the α phase to the γ phase of Al₂O₃ with an addition of bayerite.     

Electronic excitations and defects in nanostructural Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A time-resolved cathodo-and photoluminescence study of nanostructural modifications of Al₂O₃ (powders and ceramics) excited by heavy-current electron beams, as well as by pulsed synchrotron radiation, is reported. It was found that Al₂O₃ nanopowders probed before and after Fe⁺ ion irradiation have the same phase composition (the γ-phase/δ-phase ratio is equal to 1), an average grain size equal to ～17 nm, and practically the same set of broad cathodoluminescence (CL) bands peaking at 2.4, 3.2, and 3.8 eV. It was established that Al₂O₃ nanopowders exhibit fast photoluminescence (PL) (a band at 3.2 eV), whose decay kinetics is described by two exponential stages (τ₁ = 0.5 ns, τ₂ = 5.5 ns). Three bands, at 5.24, 6.13, and 7.44 eV, were isolated in the excitation spectrum of the fast PL. Two alternate models of PL centers were considered, according to which the 3.2-eV luminescence either originates from radiative relaxation of the P^? centers (anion-cation vacancy pairs) or is due to the formation of surface analogs of the F⁺ center (F _S ⁺ -type centers). In addition to the fast luminescence, nano-Al₂O₃ was found to produce slow luminescence in the form of a broad band peaking at 3.5 eV. The excitation spectrum of the 3.5-eV luminescence obtained at T = 13 K exhibits two doublet bands with maxima at 7.8 and 8.3 eV. An analysis of the luminescent properties of nanostructural and single-crystal Al₂O₃ suggests that the slow luminescence of nanopowders at 3.5 eV is due to radiative annihilation of excitons localized near structural defects.     

Charge storage behavior of nanostructures based on SiGe nanocrystals embedded in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> matrix

The charge storage behavior of nanostructures based on Si_1?x Ge _x (0 ≤ x ≤ 1) nanocrystals (NCs) in an Al₂O₃ matrix was investigated. The structures have been grown by RF magnetron sputtering and subsequently annealed at temperatures ranging from 700 °C to 1000 °C for 30 min in nitrogen ambient. The stoichiometry of the SiGe NCs and the alumina crystalline structure were found to be significantly dependent on the RF power and the annealing temperature. The sizes of the SiGe NCs and their distribution were investigated by grazing incidence small angle X-ray scattering (GISAXS). The capacitance-voltage (C-V) and conductance-voltage (G-V) measurements were performed to investigate the charge trapping characteristics of the memory structures. The C-V hysteresis width depends on variations in the crystalline structure resulting from different annealing temperatures. It is also shown that charge injection is governed by the Fowler-Nordheim tunnel mechanism for higher electric fields.     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Phase transitions of SC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript> ferroelectrics in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-based nanoporous matrices

Temperature dependences of the linear permittivity ε' and the third harmonic amplitude γ_3ω of composites prepared by introducing ferroelectrics SC(NH₂)₂ into matrices of porous aluminum oxide Al₂O₃ with pore sizes 60 and 100 nm are determined. It is found that temperature T _c of the ferroelectric phase transition and the temperature T _i of the phase transition from incommensurable phase to the paraphrase increase significantly. The transition shifts increase as pore diameters decrease.     

Effect of low-temperature annealing on the magnetization curve of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + <Emphasis Type="Italic">x</Emphasis></Subscript> ceramics

The effect of low-temperature annealing on the magnetization curve of YBa₂Cu₃O_{6 + x} ceramics in the superconducting state (x ≈ 0.9) is investigated. When the annealing time is fairly long, the field dependence of magnetic moment M exhibits a feature in the form of a plateau, where the value of M remains almost constant. The evolution of this feature in the magnetization curves of annealed samples with annealing time and temperature is studied. It is assumed that low-temperature annealing gives rise to metastable ferromagnetic clusters in YBa₂Cu₃O_{6 + x} ceramics, the contribution of which to the magnetic moment accounts for the feature in the magnetization curves of the annealed samples.     

Experimental Study and Analysis of Absorption Spectra of Ni<Superscript>2+</Superscript> Ions in Nickel Orthoborate Ni<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>2</Subscript>

The results of studies of the absorption spectra of nickel orthoborate Ni₃(BO₃)₂ in the range of electronic d–d-transitions are reported. The obtained data are analyzed in the framework of the crystal field theory. The Ni²⁺ ions are located in two crystallographically nonequivalent positions 2a and 4f with point symmetry groups C_2h and C₂, respectively, surrounded by six oxygen ions forming deformed octahedra. The absorption spectra exhibit three intense bands corresponding to spin-resolved transitions from the ground state of nickel ion ³A_2g (³F) to the sublevels of the ³T_2g (³F), ³T_1g (³F) and ³T_1g (³P) triplets split by the spinorbit interaction and the rhombic component of the crystal field. At temperatures below 100 K, the spectra exhibit a thin structure, in which phonon-free lines can be distinguished. Comparison of the calculated frequencies of the zero-phonon transitions with the experimental data allows estimating parameters of the crystal field acting on the nickel ions in the 2a- and 4f-positions, as well as the parameters of electrostatic interaction between the 3d electrons and spin-orbit interaction constants.     

Optical studies of phase transitions in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Ti(O<Subscript>2</Subscript>)F<Subscript>5</Subscript> crystal

Polarization-optical study of twinning and measurements of the Raman spectra and birefringence in oxyfluoride (NH₄)₃Ti(O₂)F₅ were carried out over the temperature range 90–350 K. Phase transitions were detected at temperatures T ₀₁ = 266 K (second-order transition) and T ₀₂ = 225 K (first order). It is assumed that the crystal symmetry is changed as follows: Fm3m ? I4/mmm ? I4/m. Anomalies of the spectral parameters are established in the frequency range of internal vibrations of ammonium ions and Ti(O₂)F₅ complexes. An analysis of the results shows that the transition at T ₀₁ is likely due to small shifts of the tetrahedral groups from their position on the triad axis and that the transition at T ₀₂ is due to fluorine-oxygen ordering of Ti(O₂)F₅ complexes.     

Luminescence characteristics of the Pr<Superscript>3+</Superscript> ion in SrB<Subscript>4</Subscript>O<Subscript>7</Subscript> and SrB<Subscript>6</Subscript>O<Subscript>10</Subscript>

Spectral and kinetic characteristics of the luminescence and luminescence excitation spectra of polycrystalline SrB₄O₇:Pr (1%) and SrB₆O₁₀:Pr (1%) samples are studied at 150–170 K. The samples show an intense luminescence band in the vicinity of 405 nm (¹ S ₀→¹ I ₆ transitions of Pr³⁺) and shorter wavelength bands also assigned to transitions from the ¹ S ₀ level. The main luminescence decay constant is ～2×10^?7 s. The excitation spectra of the ¹ S ₀ luminescence in these crystals are significantly different. The SrB₄O₇:Pr crystal shows three well-resolved bands at 6.14, 6.55, and 6.91 eV in the region of the 4f ²→4f ¹5d transitions and a complex structure in the region of interband transitions (7.1–20 eV), whereas the SrB₆O₁₀:Pr crystal shows a weakly structured band at 6.31 eV and no excitation in the region of the interband transitions. The physical mechanisms that may be responsible for the observed features of the spectra are discussed.     

Properties of an Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Si interface

The phase chemical composition of an Al₂O₃/Si interface formed upon molecular deposition of a 100-nm-thick Al₂O₃ layer on the Si(100) (c-Si) surface is investigated by depth-resolved ultrasoft x-ray emission spectroscopy. Analysis is performed using Al and Si L_{2, 3} emission bands. It is found that the thickness of the interface separating the c-Si substrate and the Al₂O₃ layer is approximately equal to 60 nm and the interface has a complex structure. The upper layer of the interface contains Al₂O₃ molecules and Al atoms, whose coordination is characteristic of metallic aluminum (most likely, these atoms form sufficiently large-sized Al clusters). The shape of the Si bands indicates that the interface layer (no more than 10-nm thick) adjacent to the substrate involves Si atoms in an unusual chemical state. This state is not typical of amorphous Si, c-Si, SiO₂, or SiO_x (it is assumed that these Si atoms form small-sized Si clusters). It is revealed that SiO₂ is contained in the vicinity of the substrate. The properties of thicker coatings are similar to those of the 100-nm-thick Al₂O₃ layer and differ significantly from the properties of the interfaces of Al₂O₃ thin layers.     

Preparation,Structure, and Dielectric and Magnetic Properties of SrFe<Subscript>2/3</Subscript>W<Subscript>1/3</Subscript>O<Subscript>3</Subscript> Ceramics

Polycrystalline samples of SrFe_2/3W_1/3O₃ (SFWO) ceramic were obtained by solid-phase reactions with subsequent sintering using conventional ceramic technology. X-ray diffraction analysis showed that at room temperature, the SFWO ceramic is single-phase and has a perovskite-type structure with tetragonal symmetry and parameters a = 3.941(9) Å, c = 3.955(6) Å, and c/a = 1.0035. In studying the magnetic properties and the Mössbauer effect in SFWO ceramics, it is found that the material is a ferrimagnet, and the iron ions are only in the valence state of Fe³⁺. It is suggested that in the temperature range of T = 150–210°C, a smeared phase transition from a cubic (paraelectric) phase to a tetragonal (ferroelectric) phase takes place in SFWO with decreasing temperature.     

Multiphonon mechanism of the ionization of traps in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>: Experiment and numerical simulation

Charge transfer in Al₂O₃ has been investigated experimentally and theoretically. The experimental results are in qualitative agreement with the theory of the multiphonon ionization of deep centers. The thermal (W _T = 1.5 eV) and optical (W _opt = 3.0 eV) energies of the deep centers have been determined. It has been found that the experimental data are unsatisfactorily described by the Pool-Frenkel mechanism, which provides a non-physically small frequency factor and anomalously large effective tunneling mass.     

Exchange Bias in Layered GdBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript> Cobaltite

It is established that excess oxygen content δ influences the exchange bias (EB) in layered GdBa-Co₂O_{5 + δ} cobaltite. The EB effect arises in p-type (δ > 0.5) cobaltite and disappears in n-type (δ < 0.5) cobaltite. The main parameters of EB in GdBaCo₂O_5.52(2) polycrystals are determined, including the field and temperature dependences of EB field H _EB , blocking temperature T _B , exchange coupling energy J _i of antiferromagnet–ferromagnet (AFM–FM) interface, and dimensions of FM clusters. The training effect inherent in systems with EB has been studied. The results are explained in terms of exchange interaction between the FM and AFM phases. It is assumed that the EB originates from the coexistence of Co³⁺ and Co⁴⁺ ions that leads to the formation of monodomain FM clusters in the AFM matrix of cobaltite.