Electronic excitations and luminescence of SrAlF5 crystals doped with Ce3+ ions

This paper reports the results of a time-resolved photoluminescence and energy transfer processes study in Ce³⁺ doped SrAlF₅ single crystals. Several Ce³⁺ centers emitting near 4 eV due to 5d-4f transitions of Ce³⁺ ions substituting for Sr²⁺ in non-equivalent lattice sites were identified. The lifetime of these transitions is in the range of 25–35 ns under intra-center excitation in the energy region of 4–7 eV at T = 10 K. An effective energy transfer from lattice defects to dopant ions was revealed in the – 7–11 eV energy range. Both direct and indirect excitation channels are efficient at room temperature. Excitons bound to dopants are revealed at T = 10 K under excitation in the fundamental absorption region above 11 eV, as well as radiative decay of self-trapped excitons resulting in luminescence near 3 eV.     

Conductivity and dielectric relaxation phenomena in (NH4)2SO4 single crystal

AC impedance measurements have been carried out on (NH₄)₂SO₄ single crystals for the temperatures from 300 to 473 K and frequency range between 100 Hz and 4 MHz. The results reveal two distinct relaxation processes in the sample crystal. One is the dipolar relaxation with a peak at frequency slightly higher than 4 × 10⁶ Hz. The other is the charge carrier relaxation at lower frequencies. The frequency dependence of conductivity is described by the relation σ(ω) = Bωⁿ, and n = 1.32 is obtained at temperatures below 413 K. This value drops to 0.2 and then decreases slightly with increasing temperature. The dipolar response of the (NH₄)₂SO₄ single crystal under an ac field is attributed to the reorientation of dipoles. The contribution of charge carriers is increasing substantially with increasing temperature at temperatures above 413 K. The temperature variation of conductivity relaxation peaks follows the Arrhenius relation. The obtained activation energy for migration of the mobile ions for (NH₄)₂SO₄ single crystal was 1.24 eV in the temperature range between 433 and 468 K in this intrinsic region. It is proposed that the NH₄⁺ in the sample crystal has the contribution to the electrical conduction.     

Effects of Zr impurity on microscopic behavior of Hf metal

Hf metal with ∼ 3 wt% Zr impurity has been reinvestigated by perturbed angular correlation (PAC) spectroscopy using a LaBr₃(Ce)–BaF₂ detector set up to understand the microscopic behavior of this metal with temperature. From present measurements, five quadrupole interaction frequencies have been found at room temperature where both pure hcp fraction (∼33%) with 12 nearest neighbor Hf surrounding the probe ¹⁸¹Hf atom and the probe–impurity fraction (∼33%) corresponding to 11 nearest neighbor Hf plus one dissimilar Zr atom are clearly distinguished. At room temperature, the results for quadrupole frequency and asymmetry parameter are found to be ω_Q=51.6(4) Mrad/s, η=0.20(4) for the impurity fraction and ω_Q=46.8(2) Mrad/s, η=0 for the pure fraction with values of frequency distribution width δ=0 for both components. At 77 K, only 1 NN Zr impurity (∼93%) and pure hcp (∼7%) components have been found with a value of δ ∼ 10% for the impurity fraction. A drastic change in microstructural configuration of Hf metal is observed at 473 K where the impurity fraction increases to ∼ 50% and the pure hcp fraction reduces to ∼ 15% with abrupt changes in quadrupole frequencies for both components. The pure fraction then increases with temperature and enhances to ∼50% at 973 K. In the temperature range 473–973 K, quadrupole frequencies for both components are found to decrease slowly with temperature. Using the Arrhenius relation, binding energy (B) for the probe–impurity pair and the entropy of formation are measured from temperature dependent fractions of probe–impurity and pure hcp in the temperature range 473–773 K. The three other minor components found at different temperatures are attributed to crystalline defects.     

Analysis of temperature-dependent electrical resistivity of ZnO nano-structures

The temperature–dependent electrical resistivity ρ(T) in metallic and semiconducting phase of ZnO nanostructures is theoretically analysed. ρ(T) shows semiconducting phase in low temperature regime (140 K<T<180 K), shows an absolute minimum near 180 K and increases linearly with T at high temperatures (200 K<T<300 K). The resistivity in metallic phase is estimated within the framework of electron–phonon and electron–electron scattering mechanism. The contributions to the resistivity by inherent acoustic phonons (ρ_ac) as well as high frequency optical phonons (ρ_op) were estimated using Bloch–Gruneisen (BG) model of resistivity. The electron–electron contributions ρ_e?e=BT² in addition with electron–phonon scattering is also estimated for complete understanding of resistivity in metallic phase. Estimated contribution to resistivity by considering both phonons, i.e., ω_ac and ω_op and the zero limited resistivity are added with electron–electron interaction ρ_e–e to obtain the total resistivity. Resistivity in Semiconducting phase is discussed with small polaron conduction (SPC) model. The SPC model consistently retraces the low temperature resistivity behaviour (140 K<T<180 K). Finally the theoretically calculated resistivity is compared with experimental data which appears favourable with the present analysis in wide temperature range.     

Near-infrared photoluminescence and thermally stimulated current in Cu3Ga5Se9 layered crystals: A comparative study

Near-infrared photoluminescence (PL) and thermally stimulated current (TSC) spectra of Cu₃Ga₅Se₉ layered crystals grown by Bridgman method have been studied in the photon energy region of 1.35–1.46 eV and the temperature range of 15–115 K (PL) and 10–170 K (TSC). An infrared PL band centered at 1.42 eV was revealed at T = 15 K. Radiative transitions from shallow donor level placed at 20 meV to moderately deep acceptor level at 310 meV were suggested to be the reason of the observed PL band. TSC curve of Cu₃Ga₅Se₉ crystal exhibited one broad peak at nearly 88 K. The thermal activation energy of traps was found to be 22 meV. An energy level diagram demonstrating the transitions in the crystal band gap was plotted taking account of results of PL and TSC experiments conducted below room temperature.     

Giant magnetic refrigerant capacity in Ho3Al2 compound

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Ho₃Al₂ compound are investigated by magnetization and heat capacity measurements. Two successive magnetic transitions, a spin-reorientation (SR) transition at T_SR=31 K followed by a ferromagnetic (FM) to paramagnetic (PM) transition at T_C=40 K, are observed. Both magnetic transitions contribute to the MCE and result in a large magnetic entropy change (ΔS_M) in a wide temperature range. The maximum values of ?ΔS_M and adiabatic temperature change (ΔT_ad) reach 18.7 J/kg K and 4.8 K for the field changes of 0–5 T, respectively. In particular, a giant value of refrigerant capacity (RC) is estimated to be 704 J/kg for a field change of 5 T, which is much higher than those of many potential refrigerant materials with similar transition temperatures.     

A.c. conductivity and relaxation in LiCoVO4 ceramics

The LiCoVO₄ compound is synthesized by solution-based chemical method. X-ray diffraction analysis exhibits a single phase nature of the compound with cubic structure. The dielectric constant (ε_r), tangent loss (tanδ) and a.c. conductivity (σ_ac) have been studied as a function of frequency and temperature using complex impedance spectroscopy (CIS) technique. The variation of (ε_r and tanδ) with frequency at studied temperatures shows a dispersive behavior at low frequencies. Frequency dependence of σ_ac at different temperatures obeys Jonscher’s universal power law governed by the relation: σ_ac = σ_dc + Aωⁿ, where n is the frequency exponent in the range of 0 ⩽ n ⩽ 1 and A is a constant that depends upon temperature.     

Raman studies of phase transitions in ferroelectric [C2H5NH3]2ZnCl4

The present paper accounted for the synthesis, differential scanning calorimetric and vibrational spectroscopy of [C₂H₅NH₃]₂ZnCl₄grown at room temperature. Differential scanning calorimetric (DSC) disclosed five phase transitions at T₁=231 K, T₂=234 K, T₃=237 K, T₄=247 K and T₅=312 K. The temperature dependence of the dielectric constant at different temperatures proved that this compound is ferroelectric below 238 K. Raman spectra as function temperature have been used to characterize these transitions and their nature, which indicates a change of the some peak near the transitions phase. The analysis of the wavenumber and the line width based on the order–disorder model allowed to obtain information relative to the thermal coefficient and the activation energy near the transitions phase.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

Bulk and surface properties of ionic salt CsH5(PO4)2

We report a comparative study of transport and thermodynamic properties of single-crystal and polycrystalline samples of the ionic salt CsH₅(PO₄)₂ possessing a peculiar three-dimensional hydrogen-bond network. The observed potential of electrolyte decomposition ≈ 1.3 V indicates that the main charge carriers in this salt are protons. However, in spite of the high proton concentration, the conductivity appears to be rather low with a high apparent activation energy E_a ≈ 2 eV, implying that protons are strongly bound. The transport anisotropy though is not large, correlates with the crystal structure: the highest conductivity is found in the [001] direction (σ_130 °C ∼ 5.6 × 10^− 6 S cm^− 1) while the minimal conductivity is in the [100] direction (σ_130 °C ∼ 10 ⁻⁶ S cm^− 1). The conductivity of polycrystalline samples appears to exceed the bulk one by 1–3 orders of magnitude with a concomitant decrease of the activation energy (E_a ≈ 1.05 eV), which indicates that a pseudo-liquid layer with a high proton mobility is formed at the surface of grains. Infrared and Raman spectroscopy used to study the dynamics of the hydrogen-bond system in single-crystal and polycrystalline samples have confirmed the formation of such a modified surface layer in the latter. However, no bulk phase transition into the superionic disordered phase is observed in CsH₅(PO₄)₂ up to the melting point T_melt ∼ 151.6 °C, in contrast to its closest relative compound CsH₂PO₄.     

Oxygen diffusion studies on (Y2O3)2(Sc2O3)9(ZrO2)89

The oxygen tracer diffusion coefficient (D?) has been measured for 9 mol% scandia 2 mol% yttria co-doped zirconia solid solution, (Y₂O₃)₂(Sc₂O₃)₉(ZrO₂)₈₉, using isotopic exchange and line scanning by Secondary Ion Mass Spectrometry, as a function of temperature. The values of the tracer diffusion coefficient are in the range of 10^? 8–10^? 7 cm² s^? 1 and the Arrhenius activation energy was calculated to be 0.9 eV; both valid in the temperature range of 600–900 °C. Electrical conductivity measurements were carried out using 2-probe and 4-probe AC impedance spectroscopy, and a 4-point DC method at various temperatures. There is a good agreement between the measured tracer diffusion coefficients (D?, Ea = 0.9 eV) and the diffusion coefficients calculated from the DC total conductivity data (D_σ, Ea = 1.0 eV), the latter calculated using the Nernst–Einstein relationship.     

Synthesis,crystal structure,spectroscopic characterization and optical properties of bis(4-acetylanilinium) tetrachlorocobalt (II)

The chemical preparation, crystal structure, spectroscopic investigations and optical features are given for a novel organic–inorganic hybrid material [C₈H₁₀NO]₂CoCl₄.The compound is crystallized in the orthorhombic space group Cmca, with the following unit cell parameters: a=19.461(2) Å, b=15.523(2) Å, c=13.7436(15) Å, and Z=8. The atomic arrangement shows an alternation of organic and inorganic layers along the b-axis. The cohesion between these entities is performed by N–H…Cl and N–H…O hydrogen bonds and π–π stacking interactions.Infrared and Raman spectra at room temperature are recorded in the 4000−400 and 4000−0 cm⁻¹ frequency regions, respectively and analyzed on the basis of literature data. This study confirms the presence of the organic cation [C₈H₁₀NO]⁺ and of the [CoCl₄]²⁻ anion. UV–vis spectroscopy results showed the indirect transition with band gap energy 2.98 eV.     

Electrical,magnetic and magnetocaloric properties of polycrystalline Pr0.63A0.07Sr0.3MnO3 (A=Pr,Sm and Bi)

We studied the effects of the partial substitution (10%) of praseodymium by samarium and bismuth, on the structural, magnetic, magnetocaloric and electrical properties of the Pr_0.63A_0.07Sr_0.3MnO₃ (A=Pr, Sm and Bi) manganites prepared using the solid state reaction. Refinement of the X-ray diffraction patterns shows that all our samples are single phase and crystallize in the orthorhombic structure with Pnma space group. Magnetic studies indicate that all the samples exhibit a ferromagnetic–paramagnetic transition with increasing temperature. Curie temperature T_C decreases by substitution. M(H) curves indicate the presence of some antiferromagnetic domains in the substituted samples testifying the phase-separated nature of these samples. The magnetic entropy curves –ΔS(T) show a maximum in vicinity of T_C. Important values of maximum of −ΔS are recorded for our compounds. For the parent compound, we found 4.59 J/kg K for an applied magnetic field of 2 T at T_C=266 K which raises the possibility of using this compound as a magnetic refrigerant. The temperature dependence of the electrical resistivity ρ(T) indicates that all compounds exhibit a metal-insulator transition with increasing temperature. Electrical study suggests the presence of a correlation between electrical and magnetic properties.     

BaT2As2 single crystals (T = Fe,Co, Ni) and superconductivity upon Co-doping

The crystal structure and physical properties of BaFe₂As₂, BaCo₂As₂, and BaNi₂As₂ single crystals are surveyed. BaFe₂As₂ gives a magnetic and structural transition at T_N = 132(1) K, BaCo₂As₂ is a paramagnetic metal, while BaNi₂As₂ has a structural phase transition at T₀ = 131 K, followed by superconductivity below T_c = 0.69 K. The bulk superconductivity in Co-doped BaFe₂As₂ below T_c = 22 K is demonstrated by resistivity, magnetic susceptibility, and specific heat data. In contrast to the cuprates, the Fe-based system appears to tolerate considerable disorder in the transition metal layers. First principles calculations for BaFe_1.84Co_0.16As₂ indicate the inter-band scattering due to Co is weak.     

Magnetic properties of RPdIn (R=Gd–Er) compounds

AC susceptibility and DC magnetization measurements were performed for the RPdIn (R=Gd–Er) compounds both in the paramagnetic and in the ordered state. In opposite to GdPdIn, which is a ferromagnet (T_c=102 K), the other samples show a complex ferrimagnetic behavior with the additional transition at T_t<T_c. In the high-temperature phase (for T_t<T<T_c), a ferromagnetic interaction dominates, while in the low-temperature phase (for T⩽T_t) antiferromagnetic interactions with the magnetocrystalline anisotropy, especially strong for TbPdIn, come into play. The ordering temperatures are T_c=70, 34, 25 and 12.3 K for Tb-, Dy-, Ho- and ErPdIn respectively, while transition temperatures are T_t=6, 14 and 6 K for Tb-, Dy- and HoPdIn respectively. TbPdIn reveals an additional transition at 27 K connected with the intermediate ferrimagnetic phase. The critical fields for the magnetization process of the low-temperature phase are high (52 and 150 kOe for TbPdIn and 32 kOe for DyPdIn at T=4.2 K) yet these values decrease remarkably with increasing temperature. Results of the study are compared with magnetic and neutron diffraction data hitherto available. We state that irreversibility of the zero-field cooled–field cooled magnetization is not connected with the spin-glass phase claimed elsewhere.     

Synthesis,crystal growth and characterization of a semiorganic material: Calcium dibromide bis(glycine) tetrahydrate

Single crystals of semiorganic material calcium dibromide bis(glycine) tetrahydrate were grown from aqueous solution. The crystal belongs to monoclinic system, with a = 13.261(5) Å, b = 6.792(2) Å, c = 15.671(9) Å and β = 91.68(4)°. The presence of the elements in the title compound was confirmed by energy dispersive X-ray analysis. The solubility and metastable zone width were found. The grown crystals were tested by powder XRD, FTIR, Thermo Gravimetric and Differential Thermal Analysis, UV–vis–NIR analysis, dielectrical and mechanical studies. The transmittance of calcium dibromide bis(glycine) tetrahydrate crystal has been used to calculate the refractive index n, the extinction coefficient K and both the real ɛ_r and imaginary ɛ_i components of the dielectric constant as functions of wavelength. The optical band gap of calcium dibromide bis(glycine) tetrahydrate is 3.23 eV.     

Powder synthesis and electrical,dielectric spectroscopic characterization of rare earth disilicates (D-Er2Si2O7): Transistor scaling-22 nm or beyond

Rare earth disilicates are now a day's being analyzed as a dielectric layer for transistor scaling for the advanced 22 nm regime or beyond. So to explore these materials, the polymorphic powdered Er₂Si₂O₇ (D phase) is synthesized by solid state double sintering method to study its characteristics. Structural characterization has been performed by X-ray diffraction. SEM and EDX results shows the rods like morphology of particles and composition. The dc electrical properties are evaluated by two probe method as a function of temperature. The dielectric spectroscopic measurements of D-Er₂Si₂O₇ are performed in the temperature range 300–420 K and frequency range 1 kHz to 1 MHz. The dc electrical transport phenomenon is analyzed using Mott’s variable-range hopping approach. The ac conductivity σ_ac(ω) is obtained through the dielectric spectroscopic measurements.