Influence of electromagnetic radiation on the phase composition of clustered CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films

The effect of white and UV radiation on the phase composition of amorphous CN _x films are studied by X-ray diffraction analysis and visible-range spectroscopy. The films have variable-range atomic order and consist of amorphous graphite clusters (30 Å) crystalline clusters (50–100 Å) of graphite, diamond, and carbon nitride phases; and intercluster medium with long-range (1–2 Å) atomic order. It is shown that irradiation of the films by white light facilitates the growth of fine graphite clusters. Irradiation by UV light suppresses the growth of the graphite and carbon nitride phases, favoring the growth of the diamond phase (1.5%). It is demonstrated that a change in the mesoscopic phase composition of the CN _x films causes a change in the energy gap width in the visible range from E _g = 0.75 eV for the films irradiated by white light to E _g = 1.75 eV for those exposed to UV radiation.     

Role of the Cluster Structure of Amorphous Fe<Subscript>67</Subscript>Cr<Subscript>18</Subscript>B<Subscript>15</Subscript> Alloy in Magnetism and in the Changing of Electron Scattering Mechanisms under the Influence of Ion (Ar<Superscript>+</Superscript>) Irradiation

The contribution of clusters of different sizes to magnetism and the switching of electron scattering mechanisms in amorphous Fe₆₇Cr₁₈B₁₅ alloy during ion Ar⁺ irradiation is studied. The cluster magnetism is found to be related to the presence of clusters of the following two types: large α-(Fe, Cr) clusters of size D = 150–250 Å and small (D = 40–80 Å) clusters in a random intercluster medium. The generation of small ferromagnetic and antiferromagnetic clusters during ion irradiation leads to the formation of cluster glass, which affects the electrical properties of the alloy and causes a magnetic frustration. The temperature dependence of the barrier height is shown to characterize the magnetic state of the alloy in low fields. On the whole, the temperature dependence of the order parameter is a universal characteristic of the system. The temperature dependence of resistivity of initial alloys in the temperature range 98–300 K (ρ(T) ∝ T²) is determined by electron scattering by quantum defects, and the transition into a ferromagnetic state is revealed when the derivative ?ρ/?T ∝ T is analyzed. The increase in resistivity and the relation ρ ∝ T^1/2 in strongly inhomogeneous samples after irradiation at a dose Φ = 1.5 × 10¹⁸ ions/cm² are caused by weak localization effects, and the transition to a ferromagnetic state becomes obvious when the derivative ?ρ/?T ∝ T^–1/2 is considered. Irradiation by fluence Φ = 3 × 10¹⁸ ions/cm2 induces a giant (twofold) increase in the alloy density, restores the ferromagnetism of large clusters, decreases the resistivity by 37%, and restores the relation ρ(T) ∝ T², which results from the overlapping of the irradiation-induced small clusters when their concentration increases and from an increase in the alloy density. The overlapping of clusters lowers the barrier height and decreases the sensitivity of the alloy to an applied field. The relation ρ(T) ∝ T² is valid for the entire temperature range T = 2–300 K because of the partial screening of the magnetic moments of large clusters by a medium having the properties of cluster glass.     

Magnetic properties of the Gd<Subscript>2</Subscript>V<Subscript>0.67</Subscript>Mo<Subscript>1.33</Subscript>O<Subscript>7</Subscript> and Y<Subscript>2</Subscript>VMoO<Subscript>7</Subscript> pyrochlore compounds

It is demonstrated that 50% substitution of vanadium for molybdenum in the pyrochlore lattice of the complex oxide Y₂(V _x Mo_{1 ? x} )₂O₇ results in a transition from the spin-glass ground state (at x = 0) to the ferromagnetic state in Y₂VMoO₇ (a = 10.1645(2) Å, T _C = 55 K). The Gd₂V_0.67Mo_1.33O₇ compound (a = 10.2862(3) Å) is a ferromagnet with T _C (84 K) exceeding that of undoped Gd₂MnO₂O₇.     

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.     

Structural transformations of K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals with variations in temperature

Single crystals of the K₃H(SO₄)₂ compound are investigated using X-ray diffraction on Xcalibur S and Bruker diffractometers. The structure of the low-temperature monoclinic phase is refined (space group C2/c, z = 4, a = 14.698(1) Å, b = 5.683(1) Å, c = 9.783(1) Å, β = 103.01(1)°, T = 293 K, Bruker diffractometer), the structural phase transition is revealed, and the structure of the high-temperature trigonal phase is determined (space group R \(\bar 3\) m, z = 3, a = 5.73(1) Å,c = 21.51(1) Å,T = 458 K, Xcalibur diffractometer).     

Tellurium Solubility in TlGaTe<Subscript>2</Subscript> and TlInTe<Subscript>2</Subscript> and the Electrophysical Properties of Solid Solutions

The complex methods of the physicochemical analysis are used to study TlGaTe₂–Te and TlInTe₂–Te alloys in which the tellurium solubility region up to 5.0 at % is observed. The temperature dependences of the lattice parameters and the electrical conductivity of TlGaTe_{2 + x} and TlInTe_{2 + x} have been studied in different crystallographic directions. The TlGaTe_{2 + x} and TlInTe_{2 + x} solid solutions undergo a phase transition at a temperature of 498 K. The transition nature is interpreted.     

Nonstoichiometric high-pressure phase of Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

Tm _x Cu₃V₄O₁₂, a perovskite-like oxide (space group, Im-3; Z = 2; a = 7.279–7.293 Å) containing vacancies in its cationic sublattice, was obtained barothermally (P = 7.0–9.0 GPa, t = 1000–1100°C) for the first time. The temperature dependences on the electrical resistivity (10–300 K) and the magnetic susceptibility (0–300 K) were investigated. It was shown that the oxide Tm _x Cu₃V₄O₁₂ is characterized by metal-type conductivity and paramagnetic properties.     

Hydrogen solubility in amorphous Mg<Subscript>0.6</Subscript>SiO<Subscript>2.6</Subscript> at high pressure

The solubility of hydrogen in amorphous Mg_0.6SiO_2.6 at a temperature of 250°C and pressures up to 75 kbar is studied using a quenching technique. The molar ratio H₂/formula unit is found to nonlinearly increase with pressure from x = 0.12 at P = 10 kbar to x = 0.303 at P = 75 kbar. An investigation of the quenched samples by Raman spectroscopy demonstrated that hydrogen dissolves in amorphous Mg_0.6SiO_2.6 in the form of H₂ molecules. X-ray diffraction and Raman studies showed that the hydrogenation of the samples is likely to be accompanied by a phase transition in the amorphous lattice of Mg_0.6SiO_2.6 at P ≈ 52.5 kbar to a denser amorphous modification.     

The Nernst-Ettingshausen coefficient in the normal phase of doped HTSCs of the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>y</Subscript> system

The temperature dependence of the Nernst-Ettingshausen coefficient Q(T) in the normal phase of doped HTSCs of the yttrium system was studied. The main features characterizing the behavior of this coefficient were revealed, and the character and mechanism of the effect that various nonisovalent substituents exert on the Q(T) dependence were analyzed. It is shown that the narrow-band model permits one not only to describe all the specific features observed in the Q(T) curves but also to perform a simultaneous quantitative analysis of the temperature dependences of four kinetic coefficients (the electrical resistivity and the Seebeck, Hall, and Nernst-Ettingshausen coefficients) with the use of a common set of model parameters characterizing the band structure and carrier system in the normal phase of an HTSC. This approach was employed to determine the carrier mobilities and the asymmetry of the dispersion curve in the systems studied (YBa₂Cu₃O_y, y = 6.37–6.91; YBa₂Cu_3?xCo_xO_y, x = 0–0.3; Y_1?xCa_xBa₂Cu₃O_y, x = 0–0.25; Y_1?xCa_xBa_2?xLa_xCu₃O_y, x = 0–0.5) and to analyze the effect of the substitutions involved on the variation of these parameters.     

Phase separation of the spin system in the La<Subscript>0.93</Subscript>Sr<Subscript>0.07</Subscript>MnO<Subscript>3</Subscript> crystal

The magnetic state of the manganite La_0.93Sr_0.07MnO₃ in the range 4.2–290 K was studied using elastic neutron scattering. The magnetic state of this compound was found to occupy a particular place in the La_1?xSr_xMnO₃ solid-solution system, in which the antiferromagnetic type of order (LaMnO₃, T_N=139.5 K) switches to ferromagnetic ordering (La_0.9Sr_0.1MnO₃, T_C=152 K) with increasing x. In the transition state, this compound contains large-scale spin configurations of two types. A fractional crystal volume of about 10% is occupied by regions of the ferromagnetic phase with an average linear size of 200 Å, while the remainder of the crystal is a phase with a nonuniform canted magnetic structure. Arguments are presented for the phase separation of the La_0.93Sr_0.07MnO₃ spin system being accounted for by Mn⁴⁺ ion ordering.     

Optical and dielectric studies of phase transitions in single crystals of NaNbO<Subscript>3</Subscript>-Gd<Subscript>1/3</Subscript>NbO<Subscript>3</Subscript> solid solutions

The temperature dependences of the permittivity ? and the false-color image patterns obtained by the rotating polarizer method for single crystals of (1 ? x)NaNbO_3?x Gd_1/3NbO₃ (x = 0.003, 0.090) solid solutions with different degrees of diffuseness of the phase transition are investigated. A multifractal analysis of the false-color images has revealed anomalies in the temperature dependences of the parameter ?_∞ of the multifractal spectrum. For a sample with a sharp phase transition (x ≈ 0.003), the temperature of this anomaly is in good agreement with the temperature of the jumps in the permittivity ?(T) and birefringence. For an NNG crystal with x ≈ 0.09, which exhibits a diffuse maximum of ?(T), the temperatures of the anomalies of ?_∞(T) differ in the central and peripheral regions, which correlates with the distribution of Gd over the crystal.     

Inverse magnetoresistance in (FeCoB)-(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) magnetic granular composites

The magnetoresistance, magnetization, and microstructure of granular composites with the general formula (Fe₄₀Co₄₀B₂₀)_x(Al₂O₃)_100?x were studied for contents of the amorphous metallic component both above and below the percolation threshold (x≈43). The low-temperature transverse magnetoresistance of the composites is negative at x=41 and practically zero for x=49. For metal contents below the percolation threshold (x=31), a noticeable (7–8%) positive magnetoresistance, reached in magnetic fields of about 17 kOe, was observed. Possible mechanisms of the generation of inverse (positive) magnetoresistance are discussed.     

Spin-dimerization in rare-earth substituted La<Subscript>2</Subscript>RuO<Subscript>5</Subscript>

The Ru-Ru spin-singlet formation in La_2 ? x L n _x RuO₅ (Ln = Pr, Nd, Sm, Gd, Dy) was investigated by measurements of the specific heat and magnetic susceptibility. After subtraction of the lattice contribution from the specific heat (C _p ), similar excess entropy values were obtained for all compounds. These entropies can be explained by the formation of antiferromagnetic Ru-spin dimers at low temperatures and provide a lower estimate for the intradimer exchange strength. Pronounced changes in the transition temperatures and a broadening of the corresponding peak in C _p were observed. These changes depend on the rare-earth element and are due to local structural changes and heterogeneities caused by the substitution. The magnetic susceptibilities can be described by the sum of a rare-earth paramagnetic moment and the susceptibility of the unsubstituted La₂RuO₅. Density functional theory (DFT) calculations were performed for various compounds to investigate the origin of the magnetic transition and the relationship between structural changes and the spin-dimerization temperature. The combination of the present results with previous structural investigations supports the model of a spin-pairing of the Ru moments which occurs as a reason of the structural phase transition in La_2 ? x L n _x RuO₅.     

Magnetorefractive effect and giant magnetoresistance in Fe(<Emphasis Type="Italic">t</Emphasis><Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)/Cr superlattices

The magnetorefractive effect in Fe(t _x , Å)/Cr(10 Å) samples grown by molecular-beam epitaxy with a variable thickness of the iron layer (superlattices, cluster-layered nanostructures) has been studied in the IR region (λ = 2–13 µm) in s and p polarizations of light. The magnetoresistive effect in a dc magnetic field, H ≤ 32 kOe, has been measured on the same samples. The iron layer thickness required for the magnetorefractive response to appear has been found to be t _Fe ≥ 3 Å. The correlation between the magnitude of the magnetorefractive effect in the mid-IR region and magnetoresistance has been discussed.     

Oxygen isotope effect in chromium-doped Pr<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganites

The effect of oxygen isotope substitution on the properties of Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x O₃ manganites (x = 0, 0.02, 0.05) have been studied. The introduction of chromium favors (i) the decomposition of a charge-ordered state and (ii) the appearance of a ferromagnetic metallic phase in Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x ^16–18O₃. The isotope substitution ¹⁶O → ¹⁸O leads to a decrease in the content of the ferromagnetic phase, an increase in the charge-ordering transition temperature (T _CO), and a decrease in the ferromagnetic transition temperature (T _FM). The isotope mass exponent is evaluated.     

Thermophysical study of structural phase transitions in Na<Subscript>0.95</Subscript>Li<Subscript>0.05</Subscript>NbO<Subscript>3</Subscript> solid solution

Temperature dependences of specific heat C_p(T) and coefficient of thermal expansion ;(T) for Na_0.95Li_0.05NbO₃ sodium-lithium niobate ceramic samples are investigated in the temperature range of 100–800 K. The C_p(T) and α(T) anomalies at T₃ = 310 ± 3 K, T₂ = 630 ± 8 K, and T₁ = 710 ± 10 K are observed, which correspond to the sequence of phase transitions N ? Q ? S(R) ? T2(S). The effect of heat treatment of the samples on the sequence of structural distortions was established. It is demonstrated that annealing of the samples at 603 K leads to splitting of the anomaly corresponding to the phase transition Q → R/S in two anomalies. After sample heating to 800 K, the only anomaly is observed in both the C_p(T) and ;(T) dependence. Possible mechanisms of the observed phenomena are discussed.     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

Neutron-diffraction study of the crystal structure of BaTiO<Subscript>3</Subscript> ferroelectric doped with iron

The crystal structure of iron-doped barium titanate BaTi_1–x Fe _x O₃ is studied by neutron diffraction in the range of 0 ≤ x ≤ 0.12. At low concentrations of iron, x < 0.01, and at room temperature, these compounds have a polar structure with tetragonal symmetry with space group P4mm. The temperature of the transition of the tetragonal ferroelectric phase into the cubic paraelectric phase with space group Pm \(\bar 3\) m for an iron concentration of x = 0.01 is 390 K (for pure BaTiO₃, it is 410 K). At an iron concentration of x = 0.07, the crystal structure of the studied compounds varies, and it is described by the centrosymmetric hexagonal space group P6₃/mmc. The structural parameters of various phases of compound BaTi_1–x Fe _x O₃ are determined from the experimental data.     

Optical investigations of structural phase transformations in PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>-<Emphasis Type="Italic">x</Emphasis>PbTiO<Subscript>3</Subscript> single crystals located at the morphotropic phase boundary

A study has been made of the effect of a dc electric field (0 < E < 4 kV/cm) on the optical transmittance of single-crystal compounds PbMg_1/3Nb_2/3O₃-xPbTiO₃ (PMN-xPT) located at the boundaries of the morphotropic region (x = 32.0 and 36.5%) and directly at the center of the morphotropic region (x = 35%). It is shown that, at temperatures close to the morphotropic phase transition point, the electric field induces two phase transitions in PMN-32PT and PMN-35PT crystals and only one phase transition in PMN-36.5PT. The tetragonal (T) phase induced in all three compounds remains stable after the electric field is removed only in crystals with x = 35.0 and 36.5%, whereas the T phase is metastable and transforms into the monoclinic M _c phase after the field is switched off in the PMN-32PT crystals lying at the boundary of the morphotropic region on the rhombohedral side. It is found that the electric-field-induced intermediate phase M _c in PMN-35PT is inhomogeneous and that M _c transforms into the tetragonal phase in a continuous transition. It is suggested that only the presence of a third orthorhombic phase can account for the continuous character of the transition between the M _c and T phases in PMN-35PT crystals. The results obtained are interpreted in terms of the Devonshire theory for strongly anharmonic crystals. The E-T phase diagrams are constructed for all the crystals.     

Elastic properties of La<Subscript>0.82</Subscript>Ca<Subscript>0.18</Subscript>MnO<Subscript>3</Subscript> single crystal

The temperature dependences of the velocity of longitudinal sound waves and the internal friction in a La_0.82Ca_0.18MnO₃ single crystal with the Curie temperature T _C = 181 K have been studied. As temperature decreases, the single crystal is shown to undergo the transition from the pseudocubic O* to the Jahn–Teller O’ phase at T ~ 254 K and the reverse transition from O’ to O* phase at T ~ 84 K. The velocity of sound and the internal friction in the O’ phase are found to be significantly smaller than those in the O* phase.