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At least 1,765 records · Page 98
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DOE OSTI2013

Mixed metallic Ba(Co,Mn)X{sub 0.2-x}O{sub 3-{delta}} (X=F, Cl) hexagonal perovskites

We show here that the incorporation of Mn in Ba-Co-oxohalide, BaCoX{sub 0.2-x}O{sub 3-{delta}}, hexagonal perovskite stabilizes the 6H-form (stacking sequence (chhhch Prime ); c, h=[BaO{sub 3}] and h Prime =[BaOX] layers), with tetramers of face-sharing octahedra) rather than the trimeric 10H-form. On the contrary to previous results on the Fe incorporation in similar system leading to more reduced 10H-compounds, the Mn effect is to increase the mean (Co/Mn) valence better suited to the 6H form. We experienced a poor Mn/Co miscibility during our syntheses leading to great difficulties to isolate mixed Co/Mn single phase materials and/or weak reproducibility. Powder neutron diffraction data shows a mixed Mn/Co octahedral occupancy, while the tetrahedra are filled by Co{sup 3+} cations. Anionic vacancies were refined in the h Prime -[BaO{sub 1-z}X{sub 1-x}] layer and the next c-[BaO{sub 3-z}] layers, while the h-[BaO{sub 3}] layers are not oxygen deficient. Magnetic properties suggest that a part of Mn cations remain paramagnetic until low temperature, while isolated spin clusters (probably driven by AFM Co tetrahedral dimers) behave as low-dimensional AFM systems. Transport measurements reveal a transition from high-temperature metallic to low-temperature semi-conducting states that could occur from defect shallow donor upon the Mn for Co substitution. - Graphical abstract: The incorporation of Mn in Ba-Co-oxohalide, BaCoX{sub 0.2-x}O{sub 3-{delta}}, hexagonal perovskite stabilizes the 6H-form with tetrameric (Co,Mn){sub 4}O{sub 15} face sharing linear chains. This results from a oxidizing Mn effect and particular Mn/Co distribution. Highlights: Black-Right-Pointing-Pointer The incorporation of Mn in BaCoX{sub 0.2-x}O{sub 3-{delta}} (X=F,Cl) hexagonal perovskites stabilizes the 6H-form. Black-Right-Pointing-Pointer It contains tetrameric (Co,Mn){sub 4}O{sub 15} face sharing linear chains. Black-Right-Pointing-Pointer The preference for such chains better than trimeric ones is due to the Manganese oxidizing effect. Black-Right-Pointing-Pointer A particular Mn/Co distribution was evidenced. Black-Right-Pointing-Pointer Transport and magnetic properties drastically change during the Mn incorporation.

36 MATERIALS SCIENCE↗
DOE OSTI2013

BiNb{sub 3}O{sub 9}, a metastable perovskite phase with Bi/vacancy ordering: Crystal structure and dielectric properties

The perovskite, BiNb{sub 3}O{sub 9}, is a metastable phase in the Bi{sub 2}O{sub 3}:Nb{sub 2}O{sub 5} system that forms only when cooled from a liquid phase. Crystals of BiNb{sub 3}O{sub 9} prepared in this way display pseudocubic 2a×2a×2a diffraction patterns, due to non-merohedral twinning of a tetragonal a×a×2a cell, with the doubled axis oriented along all three pseudocubic axes. The structure was refined using data collected on a twinned crystal to R{sub 1}=0.034 for 318 observed reflections. BiNb{sub 3}O{sub 9} has tetragonal symmetry, P4/mmm with a=3.9459(3) Å, c=7.8919(6) Å. Partial ordering of Bi atoms and vacancies occurs, with alternate (0 0 1) planes having 28% and 42% Bi occupancies. The Bi atoms are displaced from the A-site special positions by up to 0.4 Å. The compound exhibits a relatively high permittivity value of ∼230 at room temperature, and shows a sharp increase with increasing temperature towards an apparent diffuse phase transition above ∼180 °C, with an associated frequency dependent peak in the dielectric loss. - Graphical abstract: Structure for BiNb{sub 3}O{sub 9}, showing split Bi atoms. Highlights: ► First characterisation of a new perovskite phase with potentially useful dielectric properties. ► Solving of the structure using single crystal data on a multiply twinned crystal. ► Measurement of dielectric properties that show the phase has a high dielectric permittivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

The site-selective excitation and the dynamical electron–lattice interaction on the luminescence of YBO₃: Sb³⁺

The phosphor of YBO₃: Sb³⁺ was synthesized by solid state reaction. Its crystal structure was examined by using X-ray diffraction analysis. The morphology and particle size were characterized with a scanning electron microscopy. The properties of YBO₃: Sb³⁺ luminescence was systematically studied by exciting borate host, the ¹P₁ and ³P₁ levels of Sb³⁺ at the Cᵢ and C₁ sites with 168, 203, 218, 252 and 262 nm, respectively, measured on the synchrotron radiation instruments. The different configurations of emission spectra excited with variant wavelengths show the character of wavelength-selective excitation, which was attributed to different occupations of the Sb³⁺ site in the YBO₃ crystal lattice. Moreover, strong electron–lattice interaction (i.e., the Jahn–Teller effect) between Sb³⁺ and YBO₃ host was discriminated by comparing low temperature and room temperature spectra. The site-selective luminescence was confirmed by YBO₃ activated with multiple Sb³⁺concentrations. The spectral assignment was verified with fluorescence lifetime achieved by using the Time-Correlated Single-Photon Counting method. - Graphical abstract: The dynamical Jahn–Teller effect (electron–lattice interaction) between Sb³⁺ and YBO₃ host was revealed from hyperfine structure in excitation spectra measured on the synchrotron radiation instruments combined with cryogenic technique. Highlights: • The site-selective excitation of YBO₃: Sb³⁺ was demonstrated. • The temperature-dependent luminescence of YBO₃: Sb³⁺ was observed. • Strong electron–lattice interaction between the Sb³⁺and YBO₃ host was revealed. • Superposition of the Jahn–Teller effect and site-selective excitation was discriminated. • Optical parameters were calculated by using a molecular orbital approximation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Site preference, magnetism and lattice vibrations of intermetallics Lu₂Fe 17–x T x (T=Cr, Mn, Ru)

We present an atomistic study on the phase stability, site preference and lattice constants of the rare earth intermetallics Lu₂Fe 17–x T x (T=Cr, Mn, Ru). The calculated preferential occupation site of ternary element T is found to be the 4f site. The order of site preference is given as 4f, 12k, 12j and 6g for Lu₂Fe 17–x T x . The calculated lattice parameters are corresponding to the experimental results. We have calculated the magnetic moments of Lu₂Fe 17–x T x compounds. Results show that the calculated total magnetic moment of Lu₂Fe₁₇ compound is M=37.34 μ B /f.u. In addition, the total and partial phonon densities of states are evaluated first for these complicated structures. - Graphical abstract: The vibrational modes are mostly excited by Fe atoms, Lu contributes to the lower frequencies modes, and the contribution of Ru atoms is the same as Fe atoms. Highlights: • There are no reports on lattice vibrations of Lu₂(Fe, T) 17–x (T=Cr, Mn, Ru) compounds. • The phase stability and site preference are evaluated first for the complex structures of Lu₂(Fe, T) 17–x (T=Cr, Mn, Ru) compounds. • The lattice inversion method to obtain the interatomic pair potential is the unique one.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Crystal and electronic structures of the new quaternary RCr₃Si₂C (R=Y, Gd–Tm, Lu, U) compounds

Nine new quaternary intermetallic RCr₃Si₂C (R=Y, Gd–Tm, Lu, U) compounds have been synthesized and characterized by both powder and single-crystal X-ray diffraction. These compounds crystallize in the hexagonal system with space group P6/mmm and lattice parameters a~9 Å and c~4 Å. Single-crystal X-ray diffraction refinement evidences a new type-structure closely related to the YCo₃Ga₂-type. Electronic structure properties and crystal stability of real YCr₃Si₂C against hypothetical YCr₃Si₂ are discussed in view of the Korringa–Kohn–Rostoker calculations, accounting for models with different atomic occupancy on selected sites as well as emphasizing the role of carbon in stabilization of YCr₃Si₂C compound. Highlights: • Crystal structure determination of the new intermetallic YCr₃Si₂C compound. • New type-structure closely related to the YCo₃Ga₂-type. • Theoretical study of the structural stability by electronic structure calculations. • Crystal structure characterization of the entire RCr₃Si₂C series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis, crystal structure and properties of Mg{sub 3}B{sub 36}Si{sub 9}C and related rare earth compounds RE{sub 3−x}B{sub 36}Si{sub 9}C (RE=Y, Gd–Lu)

We report on the synthesis and characterisation of Mg{sub 3}B{sub 36}Si{sub 9}C. Black single crystals of hexagonal shape were yielded from the elements at 1600 °C in h-BN crucibles welded in Ta ampoules. The crystal structure (space group R3{sup ¯}m, a=10.0793(13) Å, c=16.372(3) Å, 660 refl., 51 param., R{sub 1}(F)=0.019; wR{sub 2}(F{sup 2})=0.051) is characterized by a Kagome-net of B{sub 12} icosahedra, ethane like Si{sub 8}-units and disordered SiC-dumbbells. Vibrational spectra show typical features of boron-rich borides and Zintl phases. Mg{sub 3}B{sub 36}Si{sub 9}C is stable against HF/HNO{sub 3} and conc. NaOH. The micro-hardness is 17.0 GPa (Vickers) and 14.5 GPa (Knoop), respectively. According to simple electron counting rules Mg{sub 3}B{sub 36}Si{sub 9}C is an electron precise compound. Band structure calculations reveal a band gap of 1.0 eV in agreement to the black colour. Interatomic distances obtained from the refinement of X-ray data are biased and falsified by the disorder of the SiC-dumbbell. The most evident structural parameters were obtained by relaxation calculation. Composition and carbon content were confirmed by WDX measurements. The small but significant carbon content is necessary by structural reasons and frequently caused by contaminations. The rare earth compounds RE{sub 3−x}B{sub 36}Si{sub 9}C (RE=Y, Dy–Lu) are isotypic. Single crystals were grown from a silicon melt and their structures refined. The partial occupation of the RE-sites fits to the requirements of an electron-precise composition. According to the displacement parameters a relaxation should be applied to obtain correct structural parameters. - Graphical abstract: Single crystals of the new boridesilicide Mg{sub 3}B{sub 36}Si{sub 9}C were obtained from the elements in a Si-melt. Besides B{sub 12}-icosahedra and ethan-like Si{sub 8}-units it contains a disordered SiC-dumbbell. Correct distances were obtained by relaxation calculation based on the X-ray data. Highlights: • Black single crystals of Mg{sub 3}B{sub 36}Si{sub 9}C were yielded from the elements at 1600 °C. • The rare earth compounds RE{sub 3–x}B{sub 36}Si{sub 9}C (RE=Y, Gd–Lu) are isotypic. • Correct structural parameters result from X-ray data and subsequent relaxation.

36 MATERIALS SCIENCE↗
DOE OSTI2013

The Y{sub 5−x}Mg{sub 24+x}(1.08(4)≤x≤1.30(1)) series and a ternary derivative Ce{sub 6.9}Y{sub 12.5(7)}Mg{sub 92.2}: A comparison of their crystal and electronic structures

The Y{sub 5−x}Mg{sub 24+x} series and a ternary derivative, Ce{sub 0.36}Y{sub 0.64(2)}Mg{sub 4.76}, have been synthesized using high-temperature methods and characterized by both powder and single crystal X-ray diffraction. The Y{sub 5−x}Mg{sub 24+x} series upon quenching from 580 °C crystallizes over the range 1.08(4)≤x≤1.30(1) in the cubic α-Mn structure type (I4{sup ¯}3m, Z=2, Pearson symbol cI58) with mixed occupancy of Y and Mg at the 8c site. As Mg content increases, the corresponding lattice parameter a increases from 11.2337(6) Å for Y{sub 3.92(4)}Mg{sub 25.08} to 11.256(2) Å for Y{sub 3.70(1)}Mg{sub 25.30}. Attempts to replace Y atoms with larger, isovalent Ce atoms yielded Ce{sub 6.9}Y{sub 12.5(7)}Mg{sub 92.2}(=Ce{sub 0.36}Y{sub 0.64(2)}Mg{sub 4.76}), which adopts a defect Sm{sub 11}Cd{sub 45} structure type (F4{sup ¯}3m, Z=8, Pearson symbol cF446.4), with a lattice parameter a=22.443(2) Å that is nearly twice larger than those of the Y{sub 5−x}Mg{sub 24+x} series. The complex crystal structure of this ternary derivative can be described as an ordered, body-centered cubic packing of four chemically and structurally distinctive “nested-polyhedra,” two 27-atom and two 29-atom, α-Mn units. Electronic structure calculations show nearly free electron like behavior, but with a distinctive pseudogap in the density of states curve for the ternary system. - Graphical abstract: Reported is the Mg-rich intermetallic compounds Y{sub 5−x}Mg{sub 24+x} series adopting the cubic α-Mn type structure and its complex ternary derivative Ce{sub 6.9}Y{sub 12.5}Mg{sub 92.2} crystallized in a defect Sm{sub 11}Cd{sub 45} type structure with a nearly twice larger lattice parameter than those of the Y{sub 5−x}Mg{sub 24+x} series. Electronic structure calculations show nearly free electron like behavior, but with a distinctive pseudogap in the density of states curve for the ternary system. Highlights: • The Y{sub 5−x}Mg{sub 24+x} series and Ce{sub 6.9}Y{sub 12.5}Mg{sub 92.2} have been synthesized. • Ce{sub 6.9}Y{sub 12.5}Mg{sub 92.2} is seen as a body-centered cubic packing of “nested-polyhedra”. • Electronic structures show nearly free electron like behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Crystal structure, magnetism and transport properties of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10}

Single crystals of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10} were obtained from a process in which a polycrystalline sample of CeRu{sub 2}Al{sub 2}B was annealed in an excess of a Ni–In flux. The initial phase, CeRu{sub 2}Al{sub 2}B, does not recrystallize, instead, crystals of a new phase, Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10}, could be isolated once the flux was removed. The title compound crystallizes in the tetragonal space group P4/nmm (No. 129) with a=1139.02(8), c=801.68(6) pm (c/a=0.70) in the Nd{sub 3}Ni{sub 29}Si{sub 4}B{sub 10} structure type. Electrical resistivity measurements reveal metallic behavior with a minimum of 700 µΩ cm and a small residual resistivity ratio of RRR=1.4 indicating a large amount of disorder scattering. The cerium atoms are either in the 4+ or an intermediate valence state with a valence fluctuation temperature far above room temperature. - Graphical abstract: Single crystals of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}A{sub l4.1}B{sub 10} were obtained using a process in which a polycrystalline sample of CeRu{sub 2}Al{sub 2}B was annealed in an excess of a Ni–In flux. Electrical resistivity measurements reveal metallic behavior with a minimum of 700 μΩ cm and a small residual resistivity ratio of RRR=1.4 indicating a large amount of disorder scattering. The cerium atoms are either in the 4+ or an intermediate valence state with a valence fluctuation temperature far above room temperature. Display Omitted - Highlights: • Flux synthesis of high quality single crystals of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10} is presented along with the crystal structure, magnetic and transport properties. • The compound is isostructural to Nd{sub 3}Ni{sub 29}Si{sub 4}B{sub 10} but is first of this structure type showing mixed occupancies of d-elements. • This is an intermetallic phase with Ce in either the 4+ or an intermediate valence state. • The fact that this structure with mixed occupied transition metal sites exists suggests that more compounds of this type should be accessible and the physical properties tuned.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Two-dimensional titanium carbonitrides and their hydroxylated derivatives: Structural, electronic properties and stability of MXenes Ti{sub 3}C{sub 2−x}N{sub x}(OH){sub 2} from DFTB calculations

The structural, electronic properties and stability of the new MXene compounds—two-dimensional pristine carbonitrides Ti{sub 3}C{sub 2−x}N{sub x} and their hydroxylated derivatives Ti{sub 3}C{sub 2−x}N{sub x}(OH){sub 2} are studied by means of DFTB calculations. The genesis of the properties is discussed in the sequence: binary MXenes Ti{sub 3}C{sub 2} (Ti{sub 3}N{sub 2})→hydroxylated forms Ti{sub 3}C{sub 2}(OH){sub 2} (Ti{sub 3}N{sub 2}(OH){sub 2})→pristine MXene Ti{sub 3}C{sub 2−x}N{sub x}→hydroxylated Ti{sub 3}C{sub 2−x}N{sub x}(OH){sub 2}. All examined materials are metallic-like. The most favorable type of OH-covering is presented by the occupation of the hollow sites between three neighboring carbon (nitrogen) atoms. Two-dimensional MXene carbonitrides with random distribution of C and N atoms are found to be thermodynamically more favorable. - Graphical abstract: The side views of the optimized atomic structures of some examined hydroxylated derivatives of MXene Ti{sub 3}CN and their electronic band structures. Display Omitted - Highlights: • Very recently 2D titanium carbonitrides have been synthesized. • Structural, electronic properties and stability for these materials were evaluated. • The hydroxylated derivatives of 2D titanium carbonitrides are examined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis and structural and magnetic characterization of the frustrated magnetic system La{sub 2}Ni{sub 4/3−x}Co{sub x}Sb{sub 2/3}O{sub 6}

We report the synthesis of double perovskites La{sub 2}Ni{sub 4/3−x}Co{sub x}Sb{sub 2/3}O{sub 6} with x=0, 1/3, 2/3 and 1 by a solid state method. Rietveld refinements of X-ray and neutron powder diffraction data show that all samples crystallize in space group P2{sub 1}/n, with almost perfect occupation of the 2d octahedral site with the transition metals, while all Sb{sup 5+} are randomly distributed in a 2c octahedral site. The saturation magnetization in hysteresis loops indicates that the samples are ferrimagnetic throughout all the series. Virgin magnetization curves lie outside hysteresis loops at low temperatures and thermal evolution of H{sub m} – defined as the inflection point of these curves – follows the de Almeida–Thouless dependence for x≠0. This spin glass like behavior below 30 K is also supported by thermal evolution of the coercivity, which follows an exponential law typical of magnetic clusters, not found in the pure Ni{sup 2+} perovskite, x=0 extreme. - Graphical abstract: Display Omitted - Author-Highlights: • We synthesized new double perovskites: La{sub 2}Ni{sub 4/3−x}Co{sub x}SbO{sub 6} (x=1/3, 2/3, 1). • The cations occupying octahedral sites are highly ordered in all samples. • Magnetic transition occurs as a consequence of superexchange paths. • Frustration is found and attributed to competition between different interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Influence of yttrium content on the location of rare earth ions in LYSO:Ce crystals

Single-crystal X-ray diffraction (SCD), X-ray fluorescence (XRF), inductively coupled plasma optical emission spectroscopy (ICP-OES) and X-ray excited luminescence (XEL) measurements were performed to investigate structure details and segregation coefficients of (Lu{sub 1−x}Y{sub x}){sub 2}SiO{sub 5}:Ce (x=0 at%, 8.7 at%, 25.7 at%, 44.7 at%, 65.7 at%, 87.9 at% and 100 at%). Y{sup 3+} cations were found to have a preferential occupation for RE1 site (7-oxygen-coordinated) over RE2 site (6-oxygen-coordinated), which results in a greater increase of cell parameter c than that of a with increase in Y content due to LYSO's microstructure characteristics. Results presented here revealed that the less the difference in electronegativity and effective ionic radius between the two ions, the easier substitution of one ion by the other, and hence the higher segregation coefficients. Besides, the contribution of luminescence of Ce1 and Ce2 in the whole XEL was evaluated, and the location of Ce{sup 3+} ion was discussed. - Graphical abstract: Segregation coefficients of (Lu{sub 1−x}Y{sub x}){sub 2}SiO{sub 5}:Cce:italic> at RT/ce:italic>. Display Omitted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Cation substitution in β-tricalcium phosphate investigated using multi-nuclear, solid-state NMR

The substitution of aluminium, gallium and sodium cations into β-tricalcium phosphate (β-TCP; Ca{sub 3}(PO{sub 4}){sub 2}) has been investigated, and the Ca sites involved successfully determined, using a combination of 1D {sup 31}P, {sup 27}Al, {sup 71}Ga, {sup 23}Na and {sup 43}Ca (natural abundance) NMR and 2D {sup 27}Al({sup 31}P), {sup 71}Ga({sup 31}P) and {sup 23}Na({sup 31}P) rotary-resonance-recoupled heteronuclear multiple-quantum correlation (R{sup 3}-HMQC) NMR. Over the compositional range studied, substitution of Ca{sup 2+} by Al{sup 3+} or Ga{sup 3+} was observed only on the Ca(5) site, whilst substitution by Na{sup +} was confined to the Ca(4) site. Some AlPO{sub 4} or GaPO{sub 4} second phase was observed at the highest doping levels in the Al{sup 3+} and Ga{sup 3+} substituted samples. - Graphical abstract: 2D contour plots with skyline projections showing recoupling of {sup 27}Al, {sup 71}Ga and {sup 23}Na to different {sup 31}P sites. - Highlights: • β-Ca{sub 3}(PO{sub 4}){sub 2} has been prepared pure and also with Al{sup 3+}, Ga{sup 3+} and Na{sup +} substituents. • Multi-nuclear 1D NMR and heteronuclear X({sup 31}P) recoupling have been used. • Models for substitution correctly predict site preference and occupancy. • Progressive changes in {sup 31}P spectra have been explained. • Al{sup 3+} and Ga{sup 3+} substitute onto the Ca(5) site, and Na{sup +} onto the Ca(4) site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Yb{sub 14−x}Tm{sub x}MnSb{sub 11} (0<x<0.5): Structure and magnetic properties

The compounds, Yb{sub 14−x}Tm{sub x}MnSb{sub 11} (0<x<0.5), were synthesized as single crystals via Sn flux. The maximum amount of Tm was determined from wavelength dispersive microprobe analysis to be x=0.45 (1). Single crystal data are consistent with the Ca{sub 14}AlSb{sub 11} structure type and one formula unit can be described as consisting of 14 Yb{sup 2+} cations, MnSb{sub 4} tetrahedron, Sb{sub 3} linear anion and 4 Sb{sub 3}{sup -} anions. The site occupancy of the Tm atom was not determined because of the small amount and small difference in scattering between Tm and Yb. The difference in bond lengths or angles between the solid solution and pristine Yb{sub 14}MnSb{sub 11} is less than 1%. The magnetic susceptibility of samples prepared by Sn flux with the nominal composition of Yb{sub 14−x}Tm{sub x}MnSb{sub 11} (x=0.1, 0.2, 0.3, and 0.4), show that these phases are ferromagnetic at low temperature with the T{sub C} decreasing from 56 to 39 K with increasing x. Magnetic saturation for the x=0.4 composition at 5 K is consistent with Tm being present as Tm{sup 3+} and a negative magnetoresistance ratio (MR=[(ρ(H)−ρ(0))/ρ(H)]×100%) of 18% at 3 T is observed. -- Graphical abstract: Magnetic susceptibility (χ) for Yb{sub 14−x}Tm{sub x}MnSb{sub 11} at H{sub a}=0.01 T as a function of temperature along with a view of the structure. Highlights: • New rare earth containing transition metal Zintl phase. • Control of magnetic properties through aliovalent substitution. • Magnetic ordering due to both d and f electrons. • Large magnetoresistance at low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Structure and photoluminescence properties of Na{sub 2}Y{sub 2}B{sub 2}O{sub 7}:Ce{sup 3+},Tb{sup 3+} phosphors for solid-state lighting application

Novel phosphors of Na{sub 2}Y{sub 2}B{sub 2}O{sub 7}:Ce{sup 3+} and Na{sub 2}Y{sub 2}B{sub 2}O{sub 7}:Ce{sup 3+},Tb{sup 3+} were synthesized by a solid-state process and characterized with X-ray diffraction, photoluminescence (PL), PL excitation (PLE), and fluorescence decay time. The relationship between the observed Ce{sup 3+} emission properties and the crystal structure of Na{sub 2}Y{sub 2}B{sub 2}O{sub 7} is built and the result shows that Ce{sup 3+} ions occupy two non-equivalent Y{sup 3+} sites in the host. The codoping of Tb{sup 3+} in Na{sub 2}Y{sub 2}B{sub 2}O{sub 7}:Ce{sup 3+} can tune the emitting colour from blue to green and increase the luminescence quantum efficiency to 75.2% by the energy transfer of Ce{sup 3+}→Tb{sup 3+}. The energy transfer processes of Ce{sup 3+}–Ce{sup 3+} and Ce{sup 3+}–Tb{sup 3+} are analysed and determined to be electric dipole–dipole and dipole–quadrupole, respectively. The broad PLE spectra of Na{sub 2}Y{sub 2}B{sub 2}O{sub 7}:Ce{sup 3+} and Na{sub 2}Y{sub 2}B{sub 2}O{sub 7}:Ce{sup 3+},Tb{sup 3+} are well matched with the emission from near UV LED chips, which indicates that they are promising blue and green phosphors for phosphor-converted white LEDs. - Graphical abstract: Colour-tunable phosphors Na{sub 2}Y{sub 2}B{sub 2}O{sub 7}:Ce{sup 3+},Tb{sup 3+} with optimal quantum yield of 75.2% are synthesized and the phosphors can be served as n-UV pumped materials for LEDs. - Highlights: • Green phosphor Na{sub 2}Y{sub 2}B{sub 2}O{sub 7}:Ce{sup 3+},Tb{sup 3+} with quantum efficiency of 75.2% for n-UV application is synthesized. • The site occupation of Ce{sup 3+} in Na{sub 2}Y{sub 2}B{sub 2}O{sub 7} is investigated with the crystal structure and photoluminescence spectra. • The energy transfer of Ce{sup 3+}–Ce{sup 3+} and Ce{sup 3+}–Tb{sup 3+}, which is responsible to the tunable emitting colour of the phosphor, is demonstrated and the mechanism is studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Keggin (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}H]·xH{sub 2}O: Characterization and crystal structure

Single crystals of the potassium salt (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}H]·xH{sub 2}O of the vanadium tri-substituted α-Keggin dodecatungstosilicate were prepared and analyzed by vibrational, EPR and {sup 51}V NMR spectroscopy. Varying the synthesis conditions allows crystallization of partially reduced anions. The crystal structure was determined for both oxidized (V{sup 5+}) and partially reduced (V{sup 4+/5+}) potassium salts. Single crystal X-ray diffraction data and solid state {sup 51}V-NMR spectra confirm the occurrence of a single vanadium site in a cubic structure due to rotational disorder of the Keggin ion. Partially reduced compounds crystallize within the same structure as fully oxidized ones. EPR experiments confirm strong interaction of V{sup 4+} with two V{sup 5+} ions, in accordance with insertion of a V{sub 3} subunit into the lacunary Keggin ion as designed in the synthesis method. The 3D-edifice is composed of K{sup +}/H{sub 2}O counter-sublattice with evidence of tunable water occupancy. - Graphical abstract: Relative arrangements of HPA clusters in (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}]·xH{sub 2}O. - Highlights: • We prepared single crystals of the potassium salt (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}H]·xH{sub 2}O. • The synthesis was designed to give the α-1,2,3-[SiV{sub 3}W{sub 9}O{sub 40}] Keggin ion. • Strict pH control was necessary to avoid vanadium partial reduction. • Reduced compounds crystallize within the same structure as fully oxidized ones. • EPR confirms strong interaction of V{sup 4+} with two V{sup 5+} ions in a V{sub 3} subunit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Perovskite LaPbMSbO{sub 6} (M=Co, Ni): Structural distortion, magnetic and dielectric properties

The B-site ordered double perovskite oxides LaPbMSbO{sub 6} (M=Co, Ni) have been synthesized via the modified Sol–Gel precursor two-step route. Rietveld refinements reveal strong abnormal structural distortion and BO{sub 6} octahedral deformation appearing along the ab plane. Owing to the cooperative Jahn–Teller effect of Co{sup 2+} and Pb{sup 2+} ions, the Co-related compound exhibits almost complete Co{sup 2+}–Sb{sup 5+} order. For magnetic properties, spin-canted antiferromagnetic state with high extent of magnetic frustration is confirmed. The Ni-related compound presents heavier magnetic frustration for introducing tiny disorder on site occupation accompanied with valence state and further enhancing the complexity of magnetic competition. Dielectric measurements present a considerable temperature dependent dielectric relaxation with great dc-like loss feature in the LaPbCoSbO{sub 6}. For LaPbNiSbO{sub 6}, however, the permittivity with low dielectric loss is shown to be insensitive to either temperature or frequency. The corresponding electronic active energy manifests that the weakly bounded 3d-electron is prone to hop in a more distorted Co–Sb sublattice. - Graphical abstract: XRD Rietveld refinement result of LaPbCoSbO{sub 6} presented a large BO{sub 6} octahedral distortion along the ab plane. Based upon the variations from Co–O–Sb bond angles, a fierce competition from many extended magnetic coupling routes (M–O–O–M) would induce a considerably large magnetic frustration and electron hopping restriction. - Highlights: • Highly ordered LaPbMSbO{sub 6} (M=Co, Ni) were synthesized. • Abnormal structural distortion appeared in the ab plane. • Strong magnetic frustration was confirmed via M{sup 2+}–O–O–M{sup 2+} route. • Dielectric measurements presented a large difference between Co and Ni samples. • 3d-electronic structure determines lattice distortion and physical properties.

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DOE OSTI2015

Quasi-one-dimensional nanostructured cobalt (Co) intercalated vanadium oxide (V{sub 2}O{sub 5}): Peroxovanadate sol gel synthesis and structural study

Nanostructured cobalt vanadium oxide (V{sub 2}O{sub 5}) xerogels spread onto crystalline Si substrates were synthesized via peroxovanadate sol gel route. The resulting products were characterized by distinct experimental techniques. The surface morphology and the nanostructure of xerogels correlate with Co concentration. The decrease of the structural coherence length is followed by the formation of a loose network of nanopores when the concentration of intercalated species was greater than 4 at% of Co. The efficiency of the synthesis route also drops with the increase of Co concentration. The interaction between the Co(OH{sub 2}){sub 6}{sup 2+} cations and the (H{sub 2}V{sub 10}O{sub 28}){sup 4−} anions during the synthesis was suggested as a possible explanation for the incomplete condensation of the V{sub 2}O{sub 5} gel. Finally the experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5}. In this scenario two possible preferential occupation sites for the metallic atoms in the framework of the xerogel were proposed. - Graphical abstract: Quasi-one-dimensional nanostructured cobalt (Co) intercalated vanadium oxide (V{sub 2}O{sub 5}) nanoribbons synthesized by peroxovanadate sol gel route. - Highlights: • Nanostructured cobalt V{sub 2}O{sub 5} gel spread onto c{sub S}i were synthesized via peroxovanadate sol gel route. • The micro and nanostructure correlates with the cobalt content. • The efficiency of the synthesis route shows to be also dependent of Co content. • The experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5} xerogel.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Crystal structure and high-temperature properties of the Ruddlesden–Popper phases Sr{sub 3−x}Y{sub x}(Fe{sub 1.25}Ni{sub 0.75})O{sub 7−δ} (0≤x≤0.75)

Ruddlesden–Popper n=2 member phases Sr{sub 3−x}Y{sub x}Fe{sub 1.25}Ni{sub 0.75}O{sub 7−δ}, 0≤x≤0.75, have been investigated by X-ray and neutron powder diffraction, thermogravimetry and Mössbauer spectroscopy. Both samples as-prepared at 1300 °C under N{sub 2}(g) flow and samples subsequently air-annealed at 900 °C were studied. The as-prepared x=0.75 phase is highly oxygen deficient with δ=1, the O1 atom site being vacant, and the Fe{sup 3+}/Ni{sup 2+} ions having a square pyramidal coordination. For as-prepared phases with lower x values, the Mössbauer spectral data are in good agreement with the presence of both 5- and 4-coordinated Fe{sup 3+} ions, implying in addition a partial occupancy of the O3 atom sites that form the basal plane of the square pyramid. The air-annealed x=0.75 sample has a δ value of 0.61(1) and the structure has Fe/Ni ions in both square pyramids and octahedra. Mössbauer spectroscopy shows the phase to contain only Fe{sup 3+}, implying that all Ni is present as Ni{sup 3+}. Air-annealed phases with lower x values are found to contain both Fe{sup 3+} and Fe{sup 4+}. For both the as-prepared and the air-annealed samples, the Y{sup 3+} cations are found to be mainly located in the perovskite block. The high-temperature thermal expansion of as-prepared and air-annealed x=0.75 phases were investigated by high-temperature X-ray diffraction and dilatometry and the linear thermal expansion coefficient determined to be 14.4 ppm K{sup −1}. Electrical conductivity measurements showed that the air-annealed samples have higher conductivity than the as-prepared ones. - Highlights: • Ruddlesden–Popper, n=2, Sr{sub 3−x}Y{sub x}Fe{sub 1.25}Ni{sub 0.75}O{sub 7−δ}, 0≤x≤0.75, have been synthesised. • The crystal structures of the phases have been determined. • Sr{sub 2.25}Y{sub 0.75}Fe{sub 1.25}Ni{sub 0.75}O{sub 6}, made in N{sub 2}(g) has Fe{sup 3+}/Ni{sup 2+} in square pyramides. • Sr{sub 2.25}Y{sub 0.75}Fe{sub 1.25}Ni{sub 0.75}O{sub 6.4}, made in air has Fe{sup 3+}/Ni{sup 3+} in square pyramides and octahedra. • Air annealed samples have higher electrical conductivity than N{sub 2}(g) annealed.

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