Magnetic and Electrical Characteristics of Nd3+ and Mn2+-Co-doped Calcium Molybdato-Tungstates Single Crystals.

Single crystals of Ca1-3x-yMny□xNd2x(MoO4)1-3x(WO4)3x molybdato-tungstates (□ denotes vacant sites) with a scheelite-type structure have been successfully grown by the Czochralski technique in an inert atmosphere. This paper presents the results of structural, optical, magnetic, and electrical properties, as well as the broadband dielectric spectroscopy measurements of single crystals with different Nd3+ ion concentrations, i.e., when x = 0.0050 or x = 0.0098, and with constant content of Mn2+ ions, i.e., when y = 0.0050. Our magnetic studies have shown that substitution of diamagnetic Ca2+ ions in the CaMoO4 matrix with paramagnetic Nd3+ ones with a content not exceeding 0.02 and having a screened 4f-shell revealed a significant effect of orbital diamagnetism and Van Vleck's paramagnetism. Both single crystals have revealed residual electrical conductivity without an intrinsic region and a change of sign of the Seebeck coefficient at ca. 230 K. Dielectric spectroscopy measurements have shown constant values of relative permittivity (εr ∼ 8) and loss tangent (tan δ ∼ 0.01) both up to 400 K and up to 1 MHz, as well as the Fermi energy (∼0.04 eV) and the Fermi temperature (∼500 K) determined for both crystals from the diffusion component of thermopower. These results suggest the presence of shallow acceptor and donor levels in the studied crystals.

Experimental validation of energy dependences of YALO3:Mn TL detectors: irradiation to ISO radiation qualities.

The effect of application of filters, made of different materials and various thickness, is studied by Monte Carlo calculations using MCNP6.2 code. The calculated data were validated by experimental studies (benchmark tests). Experimental results obtained for YAlO3:Mn high-Z TL detectors irradiated to different standard ISO radiation qualities (X-ray series N-40, N-60, N-80, N-100, N-120, N-150 and N-200 as well as isotopic series S-Cs) modified by various metal (copper and aluminum) filters of thickness of 0.5, 0.8 and 1 mm. The experimental results are compared with results of Monte Carlo simulations done for the same 'radiation-attenuator-detector' combinations and geometry. Obtained results show good consistence between the experimental and calculated data that testifies adequacy of the used calculations and their applicability to modeling of modification of an output from the high-Z detectors exposed to photons of various energies.

Exploring Structure-Sensitive Factors Relevant to Cryogenic Laser Operation in Oxide Crystals Doped with Er3+ Ions.

Crystals of Gd3Al2.5Ga2.5O12:Er3+, (Lu0.3Gd0.7)2SiO5:Er3+ and LiNbO3:Er3+ compounds differing in origin and the nature of their inherent structural disorder were crystalized. Optical absorption and luminescence spectra for transitions between the 4I15/2 and the 4I13/2 multiplets of Er3+ ions for the crystal samples were recorded versus temperatures in the region of 80-300 K. Gathered data were analyzed thoroughly providing the in-depth knowledge of the effects of temperature on intensities, wavelengths and bandwidths of Er3+ transitions. The information acquired together with the knowledge of significant structural dissimilarities of the host crystals chosen made it possible to propose an interpretation of the impact of a structural disorder in Er3+-doped crystals on their spectroscopic properties, and to determine their lasing ability at cryogenic temperatures upon resonant (in-band) optical pumping.

Magnetic and Electrical Characteristics of Nd3+-Doped Lead Molybdato-Tungstate Single Crystals.

Single crystals of Pb1-3x▯xNd2x(MoO4)1-3x(WO4)3x (PNMWO) with scheelite-type structure, where ▯ denotes cationic vacancies, have been successfully grown by the Czochralski method in air and under 1 MPa. This paper presents the results of structural, optical, magnetic and electrical, as well as the broadband dielectric spectroscopy measurements of PNMWO single crystals. Research has shown that replacing diamagnetic Pb2+ ions with paramagnetic Nd3+ ones, with a content not exceeding 0.01 and possessing a screened 4f-shell, revealed a significant effect of orbital diamagnetism and Van Vleck's paramagnetism, n-type electrical conductivity with an activation energy of 0.7 eV in the intrinsic area, a strong increase of the power factor above room temperature for a crystal with x = 0.005, constant dielectric value (~30) and loss tangent (~0.01) up to room temperature. The Fermi energy (~0.04 eV) and the Fermi temperature (~500 K) determined from the diffusion component of thermopower showed shallow donor levels.

Band Gap Engineering and Trap Depths of Intrinsic Point Defects in RAlO3 (R = Y, La, Gd, Yb, Lu) Perovskites.

The possibility of band gap engineering (BGE) in RAlO3 (R = Y, La, Gd, Yb, Lu) perovskites in the context of trap depths of intrinsic point defects was investigated comprehensively using experimental and theoretical approaches. The optical band gap of the materials, E g, was determined via both the absorption measurements in the VUV spectral range and the spectra of recombination luminescence excitation by synchrotron radiation. The experimentally observed effect of E g reduction from ∼8.5 to ∼5.5 eV in RAlO3 perovskites with increasing R3+ ionic radius was confirmed by the DFT electronic structure calculations performed for RMIIIO3 crystals (R = Lu, Y, La; MIII = Al, Ga, In). The possibility of BGE was also proved by the analysis of thermally stimulated luminescence (TSL) measured above room temperature for the far-red emitting (Y/Gd/La)AlO3:Mn4+ phosphors, which confirmed decreasing of the trap depths in the cation sequence Y → Gd → La. Calculations of the trap depths performed within the super cell approach for a number of intrinsic point defects and their complexes allowed recognizing specific trapping centers that can be responsible for the observed TSL. In particular, the electron traps of 1.33 and 1.43 eV (in YAlO3) were considered to be formed by the energy level of oxygen vacancy (VO) with different arrangement of neighboring YAl and VY, while shallower electron traps of 0.9-1.0 eV were related to the energy level of YAl antisite complexes with neighboring VO or (VO + VY). The effect of the lowering of electron trap depths in RAlO3 was demonstrated for the VO-related level of the (YAl + VO + VY) complex defect for the particular case of La substituting Y.

The crystal structure and thermal expansion of novel substitutionally disordered Ca10TM0.5(VO4)7 (TM = Co, Cu) orthovanadates.

The whitlockite-related materials have attracted researchers' attention because of their potential application in various fields, especially in optoelectronics. In the present work, the structure of novel whitlockite-related oxides Ca10TM0.5(VO4)7 (TM = Co, Cu) is studied at room and high temperatures, using X-ray powder diffraction. These compounds form by fractional substitution of divalent transition metal atoms into the Ca3(VO4)2 lattice. Rietveld refinements provided the structural details. The lattice parameters are a = 10.78074(6) Å, c = 37.8196(2) Å, and V = 3806.67(4) Å3 for Ca10Co0.5(VO4)7 and a = 10.78710(7) Å, c = 37.8997(3) Å, and V = 3819.23(4) Å3 for Ca10Cu0.5(VO4)7. Structure refinement results show that among the five available sites (M1-M5), the M2+ ions select the M5 site. This finding is confirmed by analysis of interatomic distances: due to the difference in size between TM and Ca ions sharing the M5 site, the M5-O distance shortens by about 5.0% for Ca10Co0.5(VO4)7 and 2.7% for Ca10Cu0.5(VO4)7 with respect to the unsubstituted parent compound, Ca3(VO4)2. The observed trends in the crystallographic properties of the studied crystals are in line with those of previously reported structurally related phosphates, Ca10.5-xMx(PO4)7 (M = Mg or divalent transition metal). Moreover, the observed tendency for occupation of M5 by small divalent ions follows the earlier theoretical results. For cobalt and copper substituted orthovanadate and orthophosphate whitlockite related materials, a linear variation in the unit cell size is demonstrated. The common equation for evaluation of volume is applicable to the substitution of the two transition metals in orthovanadate and orthophosphate whitlockite related materials. Thermal expansion is investigated for both compounds. The variations of the lattice parameters and the thermal expansion coefficient with temperature are determined in the 300-810 K range. The lattice parameter, a, expands by 0.80% for Ca10Co0.5(VO4)7 and 0.74% for Ca10Cu0.5(VO4)7 in this range. The lattice parameter, c, enlarges by about 0.70% for both samples. In the studied temperature range, the volume thermal expansion coefficient of Ca10Co0.5(VO4)7 increases from 37.2 to 44.8 MK-1 and for Ca10Cu0.5(VO4)7, it increases from 35.1 to 45.2 MK-1; the observed expansion anisotropy is smaller than those of other related compounds.

Exploring the Impact of Structure-Sensitivity Factors on Thermographic Properties of Dy3+-Doped Oxide Crystals.

Optical absorption spectra and luminescence spectra were recorded as a function of temperature between 295 K and 800 K for single crystal samples of Gd2SiO5:Dy3+, Lu2SiO5:Dy3+, LiNbO3:Dy3+, and Gd3Ga3Al2O12:Dy3+ fabricated by the Czochralski method and of YAl3(BO3)4:Dy3+ fabricated by the top-seeded high temperature solution method. A thermally induced change of fluorescence intensity ratio (FIR) between the 4I15/2→ 6H15/2 and 4F9/2 → 6H15/2 emission bands of Dy3+ was inferred from experimental data. It was found that relative thermal sensitivities SR at 350 K are higher for YAl3(BO3)4:Dy3+ and Lu2SiO5:Dy3+than those for the remaining systems studied. Based on detailed examination of the structural peculiarities of the crystals it was ascertained that the observed difference between thermosensitive features cannot be attributed directly to the dissimilarity of structural factors consisting of the geometry and symmetry of Dy3+ sites, the number of non-equivalent Dy3+ sites, and the host anisotropy. Instead, it was found that a meaningful correlation between relative thermal sensitivity SR and rates of radiative transitions of Dy3+ inferred from the Judd-Ofelt treatment exists. It was concluded that generalization based on the Judd-Ofelt parameters and luminescence branching ratio analysis may be useful during a preliminary assessment of thermosensitive properties of new phosphor materials.

High-Pressure Low-Temperature Optical Studies of BaWO4:Ce,Na Crystals.

We report detailed optical studies of BaWO4:Ce and BaWO4:Ce,Na single crystals. The material does not emit any luminescence at ambient pressure under near-UV (325 nm) excitation. Efficient green light is emitted only at high pressure (HP) and low temperature (LT). The luminescence is of excitonic character, since the lowest Ce3+ 5d level is degenerate with the conduction band also under hydrostatic pressures. To explain these phenomena, absorption measurements were made together with powder X-ray diffraction (XRD) and confocal micro-Raman and Fourier transform infrared (FTIR) spectroscopy. Raman experiments confirm the existence of a metastable phase, induced by certain nonhydrostatic conditions, before the reversible transition at a high-pressure range above 9 GPa, where efficient photoluminescence (PL) occurs. Although the phase transition is reversible, it proceeds with a prominent hysteresis observed in luminescence and Raman experiments. FTIR focuses on the existence of Ce3+ multisites observed during LT measurements.

EMR studies of the internal motion of Mn(4+) ions in the Sr overdoped (La(1-x)Sr(x))(Ga(1-y)Mn(y))O3 (x/y up to 8) supplemented by magnetic and optical spectroscopy measurements.

The effect of the Sr doping on electronic structure in single crystals of (La(1-x)Sr(x))(Ga(1-y)Mn(y))O3 solid solutions (LSGM) is investigated by means of electron magnetic resonance (EMR). The EMR results are supplemented by magnetic susceptibility and optical spectroscopy measurements. The compositions with small concentration of Mn doping (y<1%) and overdoped content of Sr (the ratio x(Sr)/y(Mn) up to 8) are used to maximally enhance the role of divalent doping. The experimental results provide evidence of the holes delocalization in the overdoped compound (x(Sr)/y(Mn)>1). This delocalization is accompanied by appearance of the new charge transfer transitions in the optical spectrum and dynamical valence change of manganese atoms. Additionally we observe the thermally activated narrowing of resonance EMR lines due to the internal motion, which is characterized by the energy barrier depending strongly on the ratio x(Sr)/y(Mn). The energy barrier is found to be associated with the charge carrier (hole) self-trapped energy. Fitting the EMR spectra in three orthogonal planes to an orthorhombic spin Hamiltonian enables extracting the zero-field splitting (ZFS) parameters and the Zeeman g-factors for Mn(4+) (S=3/2) ions in LSGM. The experimental ZFS parameters are modeled using superposition model analysis based on an orthorhombic symmetry approximation.

A combined study of the equation of state of monazite-type lanthanum orthovanadate using in situ high-pressure diffraction and ab initio calculations.

Lanthanum orthovanadate (LaVO4) is the only stable monazite-type rare-earth orthovanadate. In the present paper the equation of state of LaVO4 is studied using in situ high-pressure powder diffraction at room temperature, and ab initio calculations within the framework of the density functional theory. The parameters of a second-order Birch-Murnaghan equation of state, i.e. those fitted to the experimental and theoretical data, are found to be in perfect agreement - in particular, the bulk moduli are almost identical, with values of 106 (1) and 105.8 (5) GPa, respectively. In agreement with recent reported experimental data, the compression is shown to be anisotropic. Its nature is comparable to that of some other monazite-type compounds. The softest compression direction is determined.