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At least 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Charge ordering and multiferroicity in Fe{sub 3}BO{sub 5} and Fe{sub 2}MnBO{sub 5} oxyborates

The comparison of Fe{sub 3}BO{sub 5} and Fe{sub 2}MnBO{sub 5} reveals that the 2Fe{sup 2+}: Fe{sup 3+} charge ordering of the former is suppressed in the latter. Spin dynamics probed by ac susceptibility are strongly affected by the substitution, inducing superparamagnetism at low temperature in Fe{sub 2}MnBO{sub 5}. Interestingly, for both oxyborates, glassiness is observed in the dielectric properties at low temperature, but only Fe{sub 3}BO{sub 5} shows a magnetodielectric effect close to its lower magnetic transition. A change in the electrical polarization, measured by pyroelectric current integration, is observed in Fe{sub 3}BO{sub 5} and is even more pronounced in Fe{sub 2}MnBO{sub 5}. Such results suggest that these oxyborates behave like antiferromagnetic relaxor ferroelectrics. These features are proposed to be related to the distribution of the species (Fe{sup 3+}, Fe{sup 2+} and Mn{sup 2+}) over the four transition metal sites forming the ludwigite structure. - Graphical abstract: 90 K [010] electron diffraction patterns of Fe{sub 3}BO{sub 5}. The yellow arrows in the pattern indicate the extra-spots corresponding to the superstructure induced by the charge ordering. - Highlights: • The TEM (ED) study of the Fe{sub 3}BO{sub 5} oxyborate at 90 K reveals a superstructure related to a Fe{sup 2+}/Fe{sup 3+} ordering. • The Fe{sub 2}MnBO{sub 5}, Mn-substituted counterpart, does not show such ordering. • Our magnetic and electric measurements demonstrate that these magnetic ferrites exhibit glassiness in their charges (relaxor-type) with additional superparamagnetism at low T for Fe{sub 2}MnBO{sub 5} and magnetodielectric coupling near T{sub N2}=72 K in Fe{sub 3}BO{sub 5}. • The pyroelectric measurements confirm the existence of a ferroelectric behavior in these antiferromagnets. Accordingly, our results open the route to the study of other large class of the M{sub 2}{sup 2+}M’{sup 3+}BO{sub 5} ludwigites and to their complex magnetism and its relationship to relaxor ferroelectricity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Introducing Eu{sup 2+} into yellow phosphor LiBaB{sub 9}O{sub 15}:Ce{sup 3+}, Dy{sup 3+} as blue emitting source to realize white emission

A series of Dy{sup 3+}, Ce{sup 3+}/Dy{sup 3+}, Eu{sup 2+}/Dy{sup 3+} and Ce{sup 3+}/Eu{sup 2+}/Dy{sup 3+} doping LiBaB{sub 9}O{sub 15} (LBB) phosphors were synthesized via a high temperature solid-state method. LBB:Dy{sup 3+} cannot create light under ultraviolet radiation, however, LBB:Ce{sup 3+}, Dy{sup 3+} can produce yellow emission under 295 nm excitation. The energy transfer occurs from Ce{sup 3+} to Dy{sup 3+} ions via electric dipole-dipole interaction and the critical distance is estimated to be 21.15 Å based on concentration quenching model. Generally, Eu{sup 2+} ion is a sensitizer to Dy{sup 3+} ion, however, there is only the emission of Eu{sup 2+} in LBB:Eu{sup 2+}, Dy{sup 3+}, which means there is no energy transfer from Eu{sup 2+} to Dy{sup 3+} ions. Interestingly enough, when doping Eu{sup 2+} ion into LBB:Ce{sup 3+}, Dy{sup 3+}, white emission can be achieved by increase the blue (350–425 nm) emission intensity. The spectral property, quantum efficiency, CIE chromaticity coordinates and thermal quenching property of LBB:Ce{sup 3+}, Eu{sup 2+}, Dy{sup 3+} are investigated. The results indicate that LBB:Ce{sup 3+}, Eu{sup 2+}, Dy{sup 3+} may be a potential application to white light emitting diodes. - Graphical abstract: LBB:Ce{sup 3+}, Dy{sup 3+} can create white emission by doping Eu{sup 2+} ions. - Highlights: • LBB:Ce{sup 3+}, Dy{sup 3+} can produce white emission by doping Eu{sup 2+} ion. • There is no energy transfer from Eu{sup 2+} to Dy{sup 3+} ions. • Energy transfer occurs from Ce{sup 3+} to Dy{sup 3+} ions. • LBB:Ce{sup 3+}, Eu{sup 2+}, Dy{sup 3+} may be a potential application for white LEDs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

“Ni{sub 5}TiO{sub 7}” is Ni{sub 5}TiO{sub 4}(BO{sub 3}){sub 2}

It is shown that the compound known as Ni{sub 5}TiO{sub 7} and considered as a promising catalyst and oxidation product of alloys does not exist and its XRD pattern actually corresponds to Ni{sub 5}TiO{sub 4}(BO{sub 3}){sub 2} - Graphical abstract: XRD pattern of “Ni{sub 5}TiO{sub 7}” (top) is identical to that for Ni{sub 5}TiO{sub 4}(BO{sub 3}){sub 2} (bottom) based on single-crystal structural data. - Highlights: • Popular catalyst known as Ni{sub 5}TiO{sub 7} is actually Ni{sub 5}TiO{sub 4}(BO{sub 3}){sub 2}. • B{sub 2}O{sub 3} came from the flux used for crystal growth. • Some authors reporting this phase did not use any boron compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Refining whisker size of 2024Al/Al18B4O33w composite through extrusion and its effects on the material's micro-structures and mechanical properties

Highlights: • The nonuniform distributions of stress and velocity along whisker lead to whisker breakage. • The microcrack between broken whiskers can propagate into interface or matrix, related to the wedge angle of broken whisker. • The whisker breakage and staggered result in the decreasing distance between neighboring whiskers. • The smaller distance between neighboring whiskers reduces the resistance to the propagation of crack resulting in the lower ultimate tensile strength of extruded composite. - Abstract: Hot extrusion is used to improve the distribution of whiskers and refine the whisker sizes of 2024Al/Al{sub 18}B{sub 4}O{sub 33}w composite. The grain size and the ultimate tensile strength of the extruded 2024Al/Al{sub 18}B{sub 4}O{sub 33}w composite are analyzed. The results show that the average length of whiskers decreases due to the whisker breakage. The nonuniform distributions of stress and velocity along the whisker lead to whisker breakage. The microcrack between the broken whiskers can propagate into the interface or the matrix, related to the wedge angle of the broken whisker. The extrusion is beneficial to the whisker staggered and makes it easy for the microcracks filled with matrix. The whisker breakage and the whisker staggered result in the decreasing distance between the neighboring whiskers. Due to the dislocation motion constrained by matrix and the overlap of the deformation areas, the decreasing distance between the neighboring whiskers promoting the recrystallization results in the smaller grain size. During tensile tests, due to the smaller resistance with the smaller distance between the neighboring whiskers, the cracks between the progressive broken whiskers are easy to coalesce resulting in the lower ultimate tensile strength of the extruded composite.

36 MATERIALS SCIENCE↗
DOE OSTI2018

High elongation achieved by band-like distribution of reinforcements in aluminum matrix composites

Highlights: • The high elongation of composites with high reinforcement content has been achieved by band-like distribution of ABO. • The band-like distribution of ABO could lead to more homogenous strain distribution by scattering the damages. • The cracks played a key role in the strain non-localization process, but have negligible contribution to the tensile strain. • A model of the relationship between the ductility enhancement and the band-like distribution of ABO was established. • The residual stresses induced by band-like distribution of ABO were theoretically calculated and experimentally measured. - Abstract: Ductile aluminum matrix composites reinforced by Al{sub 18}B{sub 4}O{sub 33} whisker (ABO) with band-like distribution (Band-like Aluminum Matrix Composites, BAMCs) were fabricated by powder metallurgy and extrusion followed by annealing. The cracks tend to nucleate in the ABO-rich bands, but the band-like structure induces compressive residual stress then suppresses the crack propagation and improves the strain transferring ability in the BAMCs. The denser and smaller cracks formed in the BAMCs with higher ABO volume fraction during tensile test. These cracks play an important role in the strain non-localization process, but have negligible contribution to the tensile strain.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Single-crystal oxoborate (Pb{sub 3}O){sub 2}(BO{sub 3}){sub 2}WO{sub 4}: Growth and characterization

Highlights: ► (Pb{sub 3}O){sub 2}(BO{sub 3}){sub 2}WO{sub 4}, has been prepared by solid-state reaction methods below 620 °C. ► Single-crystal XRD analysis showed that it crystallizes in the orthorhombic group. ► The crystal structure is composed of one-dimensional 1/∞ [Pb{sub 3}O]{sup 4+} chains. ► BO{sub 3} and WO{sub 4} groups are located around the chains to hold them via Pb-O bonds. ► The IR spectra further confirmed the presence of BO{sub 3} groups. -- Abstract: An oxoborate, (Pb{sub 3}O){sub 2}(BO{sub 3}){sub 2}WO{sub 4}, has been prepared by solid-state reaction methods below 620 °C. Single-crystal XRD analysis shows that it crystallizes in the orthorhombic group Cmcm with a = 18.480(4) Å, b = 6.3567(13) Å, c = 11.672(2) Å, Z = 4. The crystal structure is composed of one-dimensional 1/∞ [Pb{sub 3}O]{sup 4+} chains formed by corner-sharing OPb{sub 4} tetrahedra. BO{sub 3} and WO{sub 4} groups are located around the chains to hold them together via Pb-O bonds. The IR spectra further confirmed the presence of BO{sub 3} groups. Furthermore we have performed theoretical calculations by employing the all-electron full potential linearized augmented plane wave (FP-LAPW) method to solve the Kohn Sham equations. Starting from our XRD data we have optimized the atomic positions by minimizing the forces. These are used to calculate the electronic band structure, the atomic site-decomposed density of states, electron charge density and the chemical bonding features. The calculated electronic band structure and densities of states suggest that this oxoborate possesses a wide energy band gap. The valence band maxima and the conduction band minima are located at Y point in the Brillouin zone resulting in a direct energy band gap of 2.3 eV using the local density approximation and 2.6 eV for the Engel–Vosko generalized gradient approximation. This compares well with our experimentally measured energy band gap of 2.9 eV. From our calculated electron charge density distribution, we obtain an image of the electron clouds that surround the molecules in the unit cell of the crystal. The chemical bonding features were analyzed and the substantial covalent interactions are observed between Pb and O, B and O and W and O atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis of nano-sized amorphous boron powders through active dilution self-propagating high-temperature synthesis method

Graphical abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed. Highlights: ► Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis method. ► The morphology, particle size and purity of the samples could be effectively controlled via changing the endothermic rate. ► The diluter KBH{sub 4} played an important role in active dilution synthesis of amorphous nano-sized boron powders. ► The active dilution method could be further popularized and become a common approach to prepare various inorganic materials. - Abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method at temperatures ranging from 700 °C to 850 °C in a SHS furnace using Mg, B{sub 2}O{sub 3} and KBH{sub 4} as raw materials. Samples were characterized by X-ray powder diffraction (XRD), Laser particle size analyzer, Fourier transform infrared spectra (FTIR), X-ray energy dispersive spectroscopy (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission TEM (HRTEM). The boron powders demonstrated an average particle size of 50 nm with a purity of 95.64 wt.%. The diluter KBH{sub 4} played an important role in the active dilution synthesis of amorphous nano-sized boron powders. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Anisotropic lattice thermal expansion of PbFeBO{sub 4}: A study by X-ray and neutron diffraction, Raman spectroscopy and DFT calculations

Highlights: • Mullite-type PbFeBO{sub 4} shows uni-axial negative coefficient of thermal expansion. • Anisotropic thermal expansion of the metric parameters was modeled using modified Grüneisen approximation. • The model includes harmonic, quasi-harmonic and intrinsic anharmonic contributions to the internal energy. • DFT calculation, temperature- and pressure-dependent Raman spectra help understand the phonon decay and associated anharmonicity. - Abstract: The lattice thermal expansion of mullite-type PbFeBO{sub 4} is presented in this study. The thermal expansion coefficients of the metric parameters were obtained from composite data collected from temperature-dependent neutron and X-ray powder diffraction between 10 K and 700 K. The volume thermal expansion was modeled using extended Grüneisen first-order approximation to the zero-pressure equation of state. The additive frame of the model includes harmonic, quasi-harmonic and intrinsic anharmonic potentials to describe the change of the internal energy as a function of temperature. The unit-cell volume at zero-pressure and 0 K was optimized during the DFT simulations. Harmonic frequencies of the optical Raman modes at the Γ-point of the Brillouin zone at 0 K were also calculated by DFT, which help to assign and crosscheck the experimental frequencies. The low-temperature Raman spectra showed significant anomaly in the antiferromagnetic regions, leading to softening or hardening of some phonons. Selected modes were analyzed using a modified Klemens model. The shift of the frequencies and the broadening of the line-widths helped to understand the anharmonic vibrational behaviors of the PbO{sub 4}, FeO{sub 6} and BO{sub 3} polyhedra as a function of temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Luminescence improvement in Pr{sup 3+} and Gd{sup 3+} activated Sr{sub 2}Mg(BO{sub 3}){sub 2} inorganic phosphor

Highlights: • Sr{sub 2}Mg(BO{sub 3}){sub 2} doped Gd{sup 3+} and Pr{sup 3+} have been synthesized by solution combustion synthesis technique. • Effect of doping concentration of Gd{sup 3+} and Pr{sup 3+} on the luminescence of synthesized material is discussed. • Effect of charge compensation by Li{sup +}, Na{sup +} and K{sup +} on emission intensity is studied in detail. • Efficient energy transfer from Pr{sup 3+} to Gd{sup 3+} in Sr{sub 2}Mg(BO{sub 3}){sub 2} was observed. • Optimum concentration and critical transfer distance for optimum concentration have been determined. - Abstract: The photoluminescence properties of (Sr{sub 1−x}Pr{sub x}){sub 2}Mg(BO{sub 3}){sub 2}; (Sr{sub 1−2x}Pr{sub x}M{sub x}){sub 2}Mg(BO{sub 3}){sub 2,} (M = Li, Na, K); (Sr{sub 1−x}Gd{sub x}){sub 2}Mg(BO{sub 3}){sub 2}; (Sr{sub 1−2x}Gd{sub x}M{sub x}){sub 2}Mg(BO{sub 3}){sub 2}, (M = Li, Na, K) and (Sr{sub 1−4x}Pr{sub x}Gd{sub x}Na{sub 2x}){sub 2}Mg(BO{sub 3}){sub 2} inorganic phosphors prepared by solution combustion synthesis technique are discussed. The structure of the prepared phosphor characterized using Thermogravimetric–differential thermal analysis, X-ray diffraction and fourier transform-infrared. Scanning electron microscopy images of the prepared materials show irregular grains with agglomerate phenomena. Photoluminescence properties were studied at room temperature. Optimum concentration and critical transfer distance of the synthesized phosphors were determined.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+}: A novel blue emitting phosphor for white LEDs

Graphical abstract: Under the 350 nm radiation excitation, Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+} has a broad blue emission band. When the temperature turned up to 150 °C, the emission intensity of Ba{sub 1.97}B{sub 2}O{sub 5}:0.03Ce{sup 3+} is 63.4% of the initial value at room temperature. The activation energy ΔE is calculated to be 0.25 eV, which prove the good thermal stability of Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+}. All the properties indicate that Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+} may have potential application in white LEDs. - Highlights: • Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+} has a broad blue emission band under the 350 nm radiation excitation. • Emission intensity of Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+} is 63.4% (150 °C) of the initial value (30 °C). • The activation energy ΔE for thermal quenching is 0.25 eV. - Abstract: A novel blue emitting phosphor Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+} is synthesized by a high temperature solid state method. The luminescent property and the thermal stability of Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+} are investigated. Under the 350 nm radiation excitation, Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+} has a broad blue emission band, and the peak locates at 417 nm which is assigned to the 5d{sup 1}–4f{sup 1} transition of Ce{sup 3+}. It is further proved that the dipole–dipole interaction results in the concentration quenching of Ce{sup 3+} in Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+}. When the temperature turned up to 150 °C, the emission intensity of Ba{sub 1.97}B{sub 2}O{sub 5}:0.03Ce{sup 3+} is 63.4% of the initial value at room temperature. The activation energy ΔE is calculated to be 0.25 eV, which prove the good thermal stability of Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+}. All the properties indicate that Ba{sub 2}B{sub 2}O{sub 5}:Ce{sup 3+} may have potential application in white LEDs.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Synthesis and structural characterization of a new rubidium borosulfate, Rb{sub 5}BS{sub 4}O{sub 16}

Highlights: • Rb{sub 5}BS{sub 4}O{sub 16} has been synthesized using (NH{sub 4}){sub 2}SO{sub 4} as a source of sulfate ions for the first time. • Zero-dimensional anion groups, [B(SO{sub 4}){sub 4}]{sup 5−}, exist in the title compound. • Spectral properties and thermal analysis of Rb{sub 5}BS{sub 4}O{sub 16} were reported. - Abstract: A new rubidium borosulfate, Rb{sub 5}BS{sub 4}O{sub 16}, has been synthesized using (NH{sub 4}){sub 2}SO{sub 4} as a source of sulfate ions for the first time. The compound crystallizes in the space group P4{sub 3}2{sub 1}2 (No. 96) of the tetragonal system with a = 10.148(4) Å, c = 16.689(14) Å, V = 1718.8(17) Å{sup 3}, and Z = 4. Zero-dimensional anion groups, [B(SO{sub 4}){sub 4}]{sup 5−}, a central BO{sub 4} tetrahedron sharing all its four vertices with neighboring sulfate tetrahedra, exist in the title compound, and then the rubidium atoms are situated in the voids of the resulting structure. The IR spectrum confirms the presence of BO{sub 4} and SO{sub 4} units. The UV–vis-NIR diffuse reflectance spectrum exhibits a band gap of about 3.99 eV. The TG-DSC analysis suggests that Rb{sub 5}BS{sub 4}O{sub 16} is an incongruent melting compound.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Fluorescence properties of Tb{sup 3+} and Sm{sup 3+} activated novel LiAl{sub 7}B{sub 4}O{sub 17} host via solution combustion synthesis

Graphical abstract: - Highlights: • New LiAl{sub 7}B{sub 4}O{sub 17}:Tb{sup 3+}, Sm{sup 3+} phosphors were synthesized first time by solution combustion method. • The LiAl{sub 7}B{sub 4}O{sub 17}:Tb{sup 3+} emissions; 489, 544, 586 and 623 nm (λ{sub ex} = 234 nm). • Also for LiAl{sub 7}B{sub 4}O{sub 17}:Sm{sup 3+}; 564, 601 and 649 nm (λ{sub ex} = 403 nm). • Synthesized materials were characterized by powder XRD, FE-SEM. • Concentration quenching mechanism and critical transfer distance of Tb{sup 3+} and Sm{sup 3+} in the prepared sample has been investigated. - Abstract: Novel LiAl{sub 7}B{sub 4}O{sub 17} (LABO) phosphor activated with trivalent rare earth ions (RE = Tb, Sm) was synthesized by using solution combustion synthesis. The powder X-ray diffraction (XRD), field emission-scanning electron microscope (FE-SEM), photoluminescence (PL), critical transfer distance (R{sub c}) and quenching mechanism studies were employed to characterize the samples. Under ultraviolet irradiation of the LiAl{sub 7}B{sub 4}O{sub 17}: Tb{sup 3+}, Sm{sup 3+} phosphors exhibit the typical green ({sup 5}D{sub 4} → {sup 7}F{sub j} = 6, 5, 4 and 3) emission band of the Tb{sup 3+} ions, as well as an orange-red and red ({sup 4}G{sub 5/2} → {sup 6}H{sub J=5/2,} {sub 7/2,} {sub 9/2}) emission bands of the Sm{sup 3+} ions. These results suggest that Tb{sup 3+} and Sm{sup 3+} activated LABO phosphor could be promising in vision of the necessity for solid state lighting applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

A novel single-phase white phosphor NaBaBO{sub 3}:Dy{sup 3+},K{sup +} for near-UV white light-emitting diodes

Highlights: • A white phosphor NaBaBO{sub 3}:Dy{sup 3+},K{sup +} with CIE coordinate (0.301, 0.308) was synthesized. • The optimum doping concentration of Dy{sup 3+} ions was found. • The effect and mechanism of K{sup +} ion as a charge compensator were discussed. • Temperature-dependent PL property of NaBaBO{sub 3}:Dy{sup 3+},K{sup +} was studied. • PL decay and quantum efficiency behaviors of the samples were investigated. - Abstract: A novel Dy{sup 3+}-doped NaBaBO{sub 3} white-emitting phosphor has been prepared by high temperature solid-state reaction method. The phase structure and luminescence properties of NaBaBO{sub 3}:Dy{sup 3+},K{sup +} samples were investigated. Photoluminescence results show that the as-prepared samples could be effectively excited by near-ultraviolet (NUV) light and generate white light emission due to the {sup 4}F{sub 9/2} → {sup 6}H{sub 15/2} (blue) transition and {sup 4}F{sub 9/2} → {sup 6}H{sub 13/2} (yellow) transition of Dy{sup 3+} ions, respectively. The optimum doping concentration of Dy{sup 3+} ions in the NaBaBO{sub 3} host was determined to be 5.0 mol% and the CIE chromaticity of the sample was determined to be (0.301, 0.308). Moreover, the mechanism of K{sup +} ion as a charge compensator on the improvement of photoluminescence property and the effect of temperature on the photoluminescence property of NaBaBO{sub 3}:Dy{sup 3+},K{sup +} were investigated. Furthermore, photoluminescence decay and quantum efficiency behaviors of NaBaBO{sub 3}:Dy{sup 3+},K{sup +} were also studied. The present work demonstrates that the NaBaBO{sub 3}:Dy{sup 3+},K{sup +} phosphor is a potential candidate for NUV white light emitting diodes.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Crystal and electronic characterization of Nd{sub x}Ti{sub 1−x}BO{sub 2+d} semiconductors

Highlights: • Crystal and electronic structure properties of Nd{sub x}Ti{sub 1−x}BO{sub 2+d} structure were investigated. • New crystal structures for Nd–Ti complexes are determined. • Distortions in the crystal structure were observed as a result of Boron shortage. • Prominent change in electronic properties of the samples with the increasing Nd amount. - Abstract: Neodymium substituted TiBO{sub 3} samples were investigated according to their crystal, electric and electronic properties. Studies were conducted by X-ray absorption fine structure spectroscopy (XAFS) technique for the samples with different substitutions in the preparation processes. To achieve better crystal structure results during the study, XRD pattern results were supported by extended-XAFS (EXAFS) analysis. The electronic structure analysis were studied by X-ray absorption near-edge structure spectroscopy (XANES) measurements at the room temperatures. Due to the substituted Nd atoms, prominent changes in crystal structure, new crystal geometries for Nd-Ti complexes, phase transitions in the crystals structure were detected according to the increasing Nd substitutions in the samples. In the entire stages of the substitutions, Nd atoms were observed as governing the whole phenomena due to their dominant characteristics in Ti geometries. Besides, electrical resistivity decay was determined in the materials with the increasing amount of Nd substitution.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Concentration quenching of Eu{sup 2+} doped Ca{sub 2}BO{sub 3}Cl

Highlights: • Ca{sub 2}BO{sub 3}Cl doped with Eu{sup 2+} prepared by solid state reaction. • Concentration quenching studied by intensity and lifetime measurements. • Accurate determination of the critical transfer distance. • Interaction mechanism verified to be dipole–dipole interactions. - Abstract: With the aim of determining the concentration quenching mechanism of Eu{sup 2+} doped Ca{sub 2}BO{sub 3}Cl, a series of phosphors with a varied Eu{sup 2+} concentration (Ca{sub 2−x}BO{sub 3}Cl:xEu{sup 2+}) was synthesized by the solid state reaction method. The phase structure was determined by X-ray diffraction. Photoluminescence (PL) measurements showed broad excitation and emission signatures of the allowed f–d transition of Eu{sup 2+} ions. The PL emission intensity was found to be increased by increasing the concentration of Eu{sup 2+} ions up to x = 0.03 and then decreased as a result of the concentration quenching effect. The lifetime of the emission from the Eu{sup 2+} ions was measured and the decrease in the lifetime with increasing Eu{sup 2+} concentration confirmed that non-radiative energy transfer occurred between Eu{sup 2+} ions. From the luminescence data, the value of the critical transfer distance was calculated as 1.5 nm and the corresponding concentration quenching mechanism was verified to be a dipole–dipole interaction.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Luminescence properties of Eu{sup 2+} doped SrB{sub 4}O{sub 7} phosphor for radiation dosimetry

Highlights: • Report TL/OSL properties of SrB{sub 4}O{sub 7}:Eu{sup 2+} under beta irradiations. • OSL Sensitivity was about 33% than that of commercially available α-Al{sub 2}O{sub 3.} • TL glow peaks was appear at 305° C and TL sensitivity about 200 times higher than TLD-500. • OSL decay pattern was faster than α- Al{sub 2}O{sub 3}:C and dose response was linear nature. - Abstract: In this report, we presented the TL/OSL properties of Eu doped SrB{sub 4}O{sub 7} phosphor under β-irradiation. This phosphor was synthesized by using solid state method. The phosphor shows OSL sensitivity about 33% than that of commercially available α-Al{sub 2}O{sub 3}: C phosphor. CW-OSL curve possess two components having photoionization cross-sections 0.707 × 10{sup −17} and 18.58 × 10{sup −17} cm{sup 2} respectively and TL sensitivity about 200 times higher than TLD-500. The kinetic parameters such as activation energy, frequency factor and order of kinetics of TL curve were calculated by using peak shape method. In TL/OSL mode dose-response was almost linear in the range of measurements. The MDD was found to be 1.26 mGy with 3σ of background. Also reusability studies showed the phosphor can be reused for 10 cycles with 1% change in the OSL output. The PL spectra of SrB{sub 4}O{sub 7} showed emission in NUV region when excited with 318 nm under UV source.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Luminescent properties and energy transfer studies of color-tunable LuBO{sub 3}: Ce{sup 3+}/Tb{sup 3+}/Eu{sup 3+} phosphors

Highlights: • A series of color-tunable LuBO{sub 3}: Ce{sup 3+}/Tb{sup 3+}/Eu{sup 3+} phosphors were synthesized. • Phosphors exhibit strong blue/green/red emission under UV excitation. • The reason of high Tb{sup 3+} content required for Ce{sup 3+} → Tb{sup 3+} → Eu{sup 3+} energy transfer is unveiled. • Green and red LED prototypes were fabricated and characterized. - Abstract: A series of LuBO{sub 3}: Ce{sup 3+}/Tb{sup 3+}/Eu{sup 3+} phosphors were synthesized via solid state reaction. The Ce{sup 3+}/Tb{sup 3+} co-doped and Ce{sup 3+}/Tb{sup 3+}/Eu{sup 3+} tri-doped phosphors absorb near UV light through 4f-5d transitions of Ce{sup 3+}, followed by sensitized Tb{sup 3+} green and Eu{sup 3+} red emission. Decay curves investigations for samples with various Tb{sup 3+} and Eu{sup 3+} contents reveal the occurrence of Ce{sup 3+} → Tb{sup 3+} → Eu{sup 3+} energy transfer. It is found that due to relative low Tb{sup 3+} → Eu{sup 3+} energy transfer rate, a high Tb{sup 3+} content (>40%) is required for efficient Ce{sup 3+} → Tb{sup 3+} → Eu{sup 3+} energy transfer. Emission color of LuBO{sub 3}: Ce{sup 3+}, Tb{sup 3+}, Eu{sup 3+} varies from blue through green to red with Ce{sup 3+}/Tb{sup 3+}/Eu{sup 3+} ratio. The quantum efficiency of LuBO{sub 3}: Ce{sup 3+}, Tb{sup 3+} green phosphor and LuBO{sub 3}: Ce{sup 3+}, Tb{sup 3+}, Eu{sup 3+} red phosphor is 50% and 30%, respectively. Green and red LED prototypes were fabricated. The results show that the obtained phosphors are potential candidates as down-converted phosphors for NUV LEDs.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Magnetic properties of monoclinic lanthanide orthoborates, LnBO3, Ln = Gd, Tb, Dy, Ho, Er, Yb

Highlights: • Structural and magnetic properties of lanthanide orthoborates LnBO{sub 3}, Ln = Gd, Tb, Dy, Ho, Er, Yb. • LnBO{sub 3} forms a monoclinic structure with the magnetic Ln{sup 3+} forming eclipsed triangular layers. • With the exception of Gd{sup 3+} significant single-ion anisotropy is observed for all Ln{sup 3+}. • Ordering features for LnBO{sub 3}, Ln = Gd, Tb, Dy, Er between 0.4 and 2 K, onset of magnetic ordering for YbBO{sub 3} at 0.4 K, HoBO{sub 3} forms non-magnetic singlet ground state. • GdBO{sub 3} and DyBO{sub 3} are competitive magnetocaloric materials in the liquid helium temperature regime. - Abstract: The lanthanide orthoborates, LnBO{sub 3}, Ln = Gd, Tb, Dy, Ho, Er, Yb crystallise in a monoclinic structure with the magnetic Ln{sup 3+} forming an edge-sharing triangular lattice. The triangles are scalene, however all deviations from the ideal equilateral geometry are less than 1.5%. The bulk magnetic properties are studied using magnetic susceptibility, specific heat and isothermal magnetisation measurements. Heat capacity measurements show ordering features at T ≤ 2 K for Ln = Gd, Tb, Dy, Er. No ordering is observed for YbBO{sub 3} at T ≥ 0.4 K and HoBO{sub 3} is proposed to have a non-magnetic singlet state. Isothermal magnetisation measurements indicate isotropic Gd{sup 3+} spins and strong single-ion anisotropy for the other Ln{sup 3+}. The change in magnetic entropy has been evaluated to determine the magnetocaloric effect in these materials. GdBO{sub 3} and DyBO{sub 3} are found to be competitive magnetocaloric materials in the liquid helium temperature regime.

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