Photoluminescence of nanoparticles of (Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>)<Subscript>0.95</Subscript>(Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.05</Subscript> solid solution

We have ground bulk samples to obtain nanoparticles of (Ga₂S₃)_1–x (Eu₂O₃) _x solid solutions, the sizes of which were determined using an atomic force microscope. The photoluminescence spectra of the nanoparticles were studied in the temperature interval 77–300 K. We have established the mechanisms for emission and transfer of energy from the matrix to the rare-earth ion, and we determined the Stokes shift (ΔS = 0.7 eV), the Huang–Rhys parameter (S = 16), and the optical phonon energy (ħ−ω = 23 meV).     

Shear-induced low-dimension electron transport in (LaMnO<Subscript>3</Subscript>)<Subscript>2</Subscript>/(SrMnO<Subscript>3</Subscript>)<Subscript>2</Subscript> superlattice

Effects of a mechanical shear on the electron transport properties of a (LaMnO₃)₂/(SrMnO₃)₂ superlattice are investigated using first-principle DFT calculations. While the unstrained superlattice is a 3-D conducting half metal, application of a pyramidal shear transforms it into a non-spin-polarized conductor. Depending on whether the out-of-plane component of the shear is tensile or compressive the conductivity is 1-D out-of-plane or 2-D in-plane. The shear-induced low-dimensional conductivity is also associated with the FM-AFM transition.     

Entanglement in the linear-chain Heisenberg antiferromagnet Cu(C<Subscript>4</Subscript>H<Subscript>4</Subscript>N<Subscript>2</Subscript>)(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>

Quantum correlations are generally impossible to address directly in bulk systems. Quantum measures extended only to a few number of parties can be discussed in practice. In the present work we study a cluster of spins belonging to a compound whose structure is that of a quantum magnet. We reproduce at a much smaller scale the experimental outcomes and then we study the role of quantum correlations there. A macroscopic entanglement witness has been introduced in order to reveal quantum correlations at nonzero temperatures. The critical point beyond which entanglement is zero is found at T _c = 15 K.     

A computer study of the Raman spectra of the (GaN)<Subscript>129</Subscript>, (SiO<Subscript>2</Subscript>)<Subscript>86</Subscript>, and (GaN)<Subscript>54</Subscript>(SiO<Subscript>2</Subscript>)<Subscript>50</Subscript> nanoparticles

The Raman spectra of the (GaN)₁₂₉, (SiO₂)₈₆, and (GaN)₅₄(SiO₂)₅₀ nanoparticles were calculated using the molecular dynamics method. The spectrum of (SiO₂)₈₆ had three broad bands only, whereas the Raman spectrum of (GaN)₁₂₉ contained a large number of overlapping bands. The form of the Raman spectrum of (GaN)₅₄(SiO₂)₅₀ was determined by the arrangement of the GaN and SiO₂ components in it. The nanoparticle with a GaN nucleus had a continuous fairly smooth spectrum over the frequency range 0 ≤ ω ≤ 600 cm⁻¹, whereas the spectrum of the nanoparticle with a SiO₂ nucleus contained well-defined bands caused by vibrations of groups of atoms of different kinds and atoms of the same kind.     

Improved structural stability and electrochemical performance of Na<Subscript>3</Subscript>V<Subscript>2</Subscript> (PO<Subscript>4</Subscript>)<Subscript>3</Subscript> cathode material by Cr doping

Cr-doped sodium vanadium phosphate (NVP) in the form of Na₃V_2-xCr_x(PO₄)₃ (x = 0, 0.02, 0.04, 0.08, 0.10) is synthesized via a facile sol-gel route as cathode materials for sodium ion batteries. The structure and morphology of these materials are systematically characterized by x-ray diffraction (XRD), Fourier-infrared spectra (FT-IR), and scanning electron microscope (SEM). XRD analysis reveals that with the increasing amount of Cr, the crystallographic parameters show a descending trend. Electrochemical tests show that the cycle stability and the specific capacity of the sodium ion batteries can be significantly improved by doping Cr into NVP. Among all the Cr-doped cathode materials, Na₃V_1.92Cr_0.08(PO₄)₃ achieves the highest capacity of 112.2 mAh g^?1 and the capacity retention is 97.2 % after 50 cycles. Electrochemical impedance spectroscopy measurements demonstrate that Cr doping is an effective method to reduce the contact resistance of interparticles by suppressing irreversible phase transformation at low sodium contents.     

The Influence of Immersion of Porous Silicon in Aqueous Solutions of Fe(NO<Subscript>3</Subscript>)<Subscript>3</Subscript> on Photoluminescence during Long Storage

The interaction of porous silicon (PS) with aqueous solutions of Fe(NO₃)₃ with different molar (M) concentrations causes introduction of iron ions into silicon pores (PS–Fe), formation of adsorbed iron coatings with different thicknesses, and an increase in the stability of PS layers, which is important for development of device structures based of PS. To treat PS layers with solutions by the immersion method, it is necessary to determine how this affects the spectral composition and intensity of photoluminescence (PL), as well as the kinetics of PL changes during long storage under atmospheric conditions. Upon treatment of freshly prepared PS by immersion into in a Fe(NO₃)₃ aqueous solution, it was found that, after short-term storage (up to 5 days) of the PS samples, the PL intensity increases by 7.5 and 3–3.6 times at low (0.2 M) and high (0.7–0.8 M) concentrations of Fe(NO₃)₃, respectively, compared to the PL intensity of an untreated PS layer. After long-term storage (4 months), the PL intensity of PS–Fe samples with concentrations of 0.1–0.2 and 0.7–0.8 M was observed to considerably increase (by 8–18 times) with unchanged position of the PL peak with respect to untreated PS. However, at the Fe(NO₃)₃ concentration of 0.3 М, the PL intensity decreases and the PL peak shifts to the blue, which is explained by incomplete coverage of the PS surface by an adsorbed iron layer. The kinetics of PL spectra during long-term storage is analyzed, and a model is proposed to explain the PL intensity and spectral composition.     

Quasi-one-dimensional quantum spin liquid in the Cu(C<Subscript>4</Subscript>H<Subscript>4</Subscript>N<Subscript>2</Subscript>)(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> insulator

We analyze measurements of the magnetization, differential susceptibility and specific heat of quasi-onedimensional insulator Cu(C₄H₄N₂)(NO₃)₂ (CuPzN) subjected to magnetic fields. We show that the thermodynamic properties are defined by quantum spin liquid formed with spinons, with the magnetic field tuning the insulator CuPzN towards quantum critical point related to fermion condensation quantum phase transition (FCQPT) at which the spinon effective mass diverges kinematically. We show that the FCQPT concept permits to reveal and explain the scaling behavior of thermodynamic characteristics. For the first time, we construct the schematic T–H (temperature-magnetic field) phase diagram of CuPzN that contains Landau–Fermi-liquid, crossover and non-Fermi liquid parts, thus resembling that of heavy-fermion compounds.     

Acoustic emission and thermal expansion of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> and Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> crystals

The temperature dependence of the elongation per unit length for Pb(Mg_1/3Nb_2/3)O₃ crystals unannealed after growth and mechanical treatment is investigated in the course of thermocycling. It is revealed that this dependence deviates from linear behavior at temperatures below 350°C. The observed deviation is characteristic of relaxors, is very small in the first cycle, increases with increasing number n of thermocycles, and reaches saturation at n≥3. In the first cycle, a narrow maximum of the acoustic emission activity is observed in the vicinity of 350°C. In the course of thermocycling, the intensity of this maximum decreases and becomes zero at n>3. For (1?x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ crystals, the dependence of the temperature of this acoustic emission maximum on x exhibits a minimum. It is assumed that the phenomena observed are associated with the phase strain hardening due to local phase transitions occurring in compositionally ordered and polar nanoregions.     

Vibrational spectra of disordered oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>WO<Subscript>3</Subscript>F<Subscript>3</Subscript>

Comparative analysis of the IR absorption and Raman scattering spectra of a polycrystalline sample of perovskite-type oxyfluoride (NH₄)₃WO₃F₃ has been performed in the frequency range 370–4000 cm^?1 at temperatures from 92 to 303 K, including the transition between the orientationally disordered cubic and low-symmetry phases. The conformation of WO₃F₃ octahedral groups is established and transitional anomalies of the internal modes of these groups and ammonium ions are revealed. Comparative analysis of the IR and Raman spectra suggests that the phase transition under study is mainly related to the ordering of octahedral groups and formation of W-O…H-N hydrogen bonds.     

Comparative Study of the Magnetoelectric Effect in HoAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and HoGa<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Single Crystals

The comparative study of the magnetoelectric properties and magnetostriction of HoGa₃(BO₃)₄ and HoAl₃(BO₃)₄ single crystals has been carried out. The investigated compounds exhibit qualitatively similar magnetodielectric and inverse magnetoelectric ME _E effects with the close absolute values, which is indicative of the weak effect of a nonmagnetic metal ion. On the contrary, the magnetostriction of the galloborate has been found to be threefold higher than that of the alumoborate. In addition, the difference between the qualitative behaviors of magnetostriction has been established: the magnetic-field dependence of magnetostriction for the alumoborate has the maximum near 70 kOe at T = 4.2 K, while the galloborate magnetostriction has no maximum and does not saturate in a field of 140 kOe.     

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.     

Thermally stimulated recombination processes and luminescence in Li<Subscript>6</Subscript>(Y,Gd,Eu)(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystals

The thermally stimulated recombination processes and luminescence in crystals of the lithium borate family Li₆(Y,Gd,Eu)(BO₃)₃ have been investigated. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence spectra), the temperature dependences of the X-ray luminescence intensity, and the glow curves for the Li₆Gd(BO₃)₃, Li₆Eu(BO₃)₃, Li₆Y_0.5Gd_0.5(BO₃)₃: Eu, and Li₆Gd(BO₃)₃: Eu compounds have been measured in the temperature range 90–500 K. In the X-ray luminescence spectra, the band at 312 nm corresponding to the ⁶ P _J → ⁸ S _7/2 transitions in the Gd³⁺ ion and the group of lines at 580–700 nm due to the ⁵ D ₀ → ⁷ F _J transitions (J = 0–4) in the Eu³⁺ ion are dominant. For undoped crystals, the X-ray luminescence intensity of these bands increases by a factor of 15 with a change in the temperature from 100 to 400 K. The possible mechanisms providing the observed temperature dependence of the intensity and their relation to the specific features of energy transfer of electronic excitations in these crystals have been discussed. It has been revealed that the glow curves for all the crystals under investigation exhibit the main complex peak with the maximum at a temperature of 110–160 K and a number of weaker peaks with the composition and structure dependent on the crystal type. The nature of shallow trapping centers responsible for the thermally stimulated luminescence in the range below room temperature and their relation to defects in the lithium cation sublattice have been analyzed.     

Polar Fe(IO<Subscript>3</Subscript>)<Subscript>3</Subscript> nanocrystals as local probes for nonlinear microscopy

We have investigated nanocrystals of Fe(IO₃)₃ by polarization-sensitive second harmonic generation (SHG) microscopy. As the nonlinear optical properties of this material were only poorly characterized, we have first determined the relative values of the elements of its second-order susceptibility tensor, by the global fitting of the polarization-resolved SHG response of an ensemble of nanocrystals. This information allows one to optically retrieve the orientation of individual particles in the sample. The high SHG efficiency measured for nanocrystals of Fe(IO₃)₃ and their polar nature could make them very attractive for nonlinear microscopy of biological samples. PACS 42.70.Mp; 78.67.Bf     

Thermal sensors based on Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> and (Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>70</Subscript>(Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>30</Subscript> thin films

Thin films of Sb₂Te₃ and (Sb₂Te₃)₇₀(Bi₂Te₃)₃₀ alloy and have been deposited on precleaned glass substrate by thermal evaporation technique in a vacuum of 2?×?10^?6 Torr. The structural study was carried out by X-ray diffractometer, which shows that the films are polycrystalline in nature. The grain size, microstrain and dislocation density were determined. The Seebeck coefficient was determined as the ratio of the potential difference across the films to the temperature difference. The power factor for the (Sb₂Te₃)₇₀ (Bi₂Te₃)₃₀ and (Sb₂Te₃) is found to be 19.602 and 1.066 of the film of thickness 1,500 Å, respectively. The Van der-Pauw technique was used to measure the Hall coefficient at room temperature. The carrier concentration was calculated and the results were discussed.     

Magnetic properties of DyFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The magnetic properties of an easy-axis trigonal DyFe₃(BO₃)₄ antiferromagnetic crystal have been theoretically studied. On this basis, recent experimental data [1] on the field and temperature dependences of magnetization and the temperature dependence of the initial magnetic susceptibility for three crystallographic directions in this antiferromagnet have been interpreted. The characteristics of the trigonal crystal field for the rare earth ion and the parameters of the Fe-Fe and Fe-Dy exchange interactions are determined. Limitations imposed by features of the magnetic characteristics (anisotropic magnetization in the three crystallographic directions, Schottky-type anomalies in the magnetic susceptibility, etc.) on the possible splitting of the ground-state multiplet in the crystal field and the splitting of the lowest doublet due to the f-d interaction for Dy³⁺ ions are established.     

Growth and characterization of a LaCa<Subscript>4</Subscript>O(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystal

The non-linear optical (NLO) crystal LaCa₄ O(BO₃)₃ (LaCOB ) has been grown by the Czochralski method. X-ray diffraction experiments show that LaCOB crystal possesses the space group Cm, and its unit cell constants have been measured to be a=0.8168(3) nm,b=1.6081(7) nm and c=0.3630(6) nm, with an angle =101.39°. The thermal properties of LaCOB have been studied; the specific heat of the crystal is 321.9 J/molK at 330 K, and the three principal coefficients of thermal expansion of the principal axes have been calculated from the measured data to be 5.61×10^-6 K^-1, 7.21×10^-6 K^-1 and 11.01×10^-6 K^-1, respectively. The transmission spectrum shows that LaCOB crystal has a wide transparency wavelength range, and may be used as a NLO crystal. PACS 81.10.Fq; 65.40.Ba; 65.40.De     

Green emission of Ca<Subscript>3</Subscript>La<Subscript>3(1-x)</Subscript>Tb<Subscript>3x</Subscript>(BO<Subscript>3</Subscript>)<Subscript>5</Subscript> under VUV-UV excitation

A series of phosphors Ca₃La_3(1-x)Tb_3x(BO₃)₅ were synthesized by using a high-temperature solid-state reaction technique, and their VUV-vis luminescence properties were investigated. Strong host-related absorption is observed in the VUV region, and the f–d transitions of Tb³⁺ in the host lattice are assigned and discussed. The influence of both the doping concentration and the temperature on the spectroscopic properties that include the relative emission intensity and the decay time is investigated. PACS 61.72.Ww; 78.55.-m; 78.47.+p