Optical absorption spectroscopic studies on holmium(III) complexes with beta-diketone and heterocyclic amines: the environment effect on 4f-4f hypersensitive transitions

The optical absorption spectra of [Ho(acac)(3)(H(2)O)(2)].H(2)O, [Ho(acac)(3)phen] and [Ho(acac)(3)bpy] (where acac is the anion of acetylacetone; phen is 1,10-phenanthroline and bpy is 2,2'-bipyridyl) complexes in the visible region, in a series of non-aqueous solvents (methanol, ethanol, isopropanol, chloroform, acetonitrile and pyridine.) have been analyzed. The largest intensity variation was observed in the (5)G(6)<--(5)I(8) (centered at 450 nm), and (5)G(5), (3)H(5), (3)H(6)<--(5)I(8) (centered at 360 nm) transition regions. The band shape and oscillator strength of the hypersensitive transitions display pronounced changes as compared to Ho(3+) aqua-ion. The band shapes of the hypersensitive transitions show remarkable changes on passing from aqueous solution to various non-aqueous solutions which is the result of change in the environment about the Ho(III) ion in the various solutions and suggests coordination of solvent molecule(s), in some cases. The results clearly show that among the solvents studied pyridine is the most effective in promoting the 4f-4f spectral intensity. It has been inferred from this study that 2,2'-bipyridyl is a stronger ligand for heavier lanthanides. A comparative account of hypersensitivity in the present complexes with those of other adducts of Ho(beta-diketoenolate)(3) with heterocyclic amines is discussed. The TGA analyses showed that the phen complex is thermally more stable over its bpy analogue.     

Ho替代Y的YBCO外延薄膜制备及超导电性

利用直流磁控溅射技术制备了Ｈｏ替代的ＹＢＣＯ超导薄膜，Ｘ射线技术（θ－２θ扫描：θ－θ扫描及—扫描）、ＳＥＭ和电子通道花样（ＥＣＰ）测试表明，所制备的掺杂薄膜具有高平面内外延性和平面外外延性。发现掺杂薄膜的临界电流密度Ｊｃ比ＹＢＣＯ薄膜的有不同程度的提高，掺杂量ｘ＝０４时有最大值。     

Symmetry‐Breaking Transitions in HoCuAs2–xPx and ErCuAs2–xPx (x = 0–2): Crystal Structure,Application of Landau Theory,Magnetic and Electrical Properties

Crystal structures of compounds undergoing symmetry‐breaking transitions have been investigated by the X‐ray single crystal and powder methods. While the phases HoCuAs₂ through HoCuAs_1.33P_0.67 and ErCuAs₂ through ErCuAsP retain the tetragonal HfCuSi₂ structure (P4/nmm space group), the compounds HoCuAsP through HoCuAs_0.33P_1.67 and ErCuAs_0.67P_1.33 through ErCuAs_0.33P_1.67 undergo orthorhombic distortions to the GdCuAs_1.15P_0.85 structure (Pmmn space group). Further distortions follow in the phosphides: HoCuP₂ adopts a larger orthorhombic cell (Cmma, a = 5.273(3), b = 5.305(3), c = 9.645(5) Å) and ErCuP₂ has a monoclinic cell with a doubled parameter, the b parameter in the monoclinic cell (P2₁/n, a = 3.737(3), b = 19.239(15), c = 3.728(3) Å, β = 90.09(1)°). Zigzag chains are formed in the phosphorus layer of ErCuP₂. According to Landau theory the transitions from HoCuAs_1.33P_0.67 to HoCuAsP and from ErCuAsP to ErCuAs_0.67P_1.33 can be continuous, and the transitions from HoCuAs_0.33P_1.67 to HoCuP₂ and from ErCuAs_0.33P_1.67 to ErCuP₂ are necessarily first‐order. The results of magnetic and electrical measurements for HoCuAs₂ and HoCuP₂ are reported. Due to the magnetic moments localized on Ho atoms both compounds order antiferromagnetically at low temperatures. They exhibit metallic conductivity.     

Magnetic phase diagrams of the CrB- and FeB-type HoSi compounds

The temperature magnetic phase diagrams of the dimorphic HoSi compound were studied by neutron diffraction. The sample comprises 35.5% CrB- (Cmcm) and 64.5% FeB-type (Pnma) of structure. Both phases order antiferromagnetically below T_N=25 K and undergo first-order magnetic transitions at T_ic=16.5 K. Their T-phase diagrams comprise a low temperature (LT) 2.7 K−T_ic and a high temperature (HT) range T_ic−T_N with distinct wave vectors.The LT magnetic ordering of the CrB-type HoSi with the wave vector q₁=(1/2, 0, 1/2) corresponds to a uniaxial magnetic structure, with the Ho moments along the shortest axis c. At 2.7 K the ordered moment value is 8.6(2) μ_B/Ho atom. The HT ordering, described by the wave vector q₂=(q_2x, 0, q_2z) with a T-variable length, corresponds to an amplitude modulated structure.The magnetic ordering of the FeB-type HoSi requires two symmetry independent vectors q₃=(0, q_3y, q_3z) for the LT- and q₄=(q_4x, q_4y, 0) for the HT range. Both vectors correspond to sine wave modulated structures with the Ho magnetic moments confined along the shortest axis b. The q₃ vector has an almost invariable length vs. T close to ≈(0, 9/17, 1/11). At 2.7 K the amplitude of the wave is 10.9(1) μ_B/Ho atom. At T_icq₃ jumps to the wave vector q₄=(q_4x, q_4y, 0) with a T-variable length. At 17 K q₄=(0.092(1), 0.538(3), 0). Around T_ic there is a narrow coexistence range of the q₃ and q₄ competing phases. Various models are discussed and compared with the isomorphic RSi (R=rare earth) compounds counterparts of HoSi, a comparison that has led us to briefly review the magnetic structures available in the literature for this interesting class of compounds.     

纳米晶HoFeO3的合成及其气敏性能研究

为开发新型具有高性能的气敏材料 ,以Ho2 O3 、Fe(NO3) 3·9H2 O、硝酸 (1∶1)为原料 ,在柠檬酸体系中 ,用溶胶凝胶法合成了具有钙钛矿结构的稀土复合氧化物HoFeO3;用XRD、TEM对产物的组成、粒径大小、形貌进行了表征 .结果表明 ,产物为纳米颗粒 ,平均粒径为 2 5nm左右 ,且为颗粒均匀的圆球形 .另外 ,在最佳工作温度为3 10℃时 ,采用静态配气法测试了材料的气敏性能 ,发现HoFeO3 对体积分数为 0 .5 的乙醇的灵敏度高达 10 3 ,高出其它被测气体 5倍以上 ,因此 ,HoFeO3 对乙醇有较好的灵敏度和抗干扰能力 .且元件的响应恢复特性良好 ,响应时间和恢复时间分别为 12和 7s     

High-pressure rare earth silicates: Lanthanum silicate with barium phosphate structure, holmium silicate apatite, and lutetium disilicate type X

The phase relations of a wide selection of rare earth disilicates have been investigated up to 10 GPa and 1700 °C using piston cylinder and multi-anvil equipment. Single-crystal X-ray structures have been obtained for the following high-pressure phases: (1) La_2.67(SiO₄)₂: monoclinic, space group C2/m, Z=2, a=9.419(2), b=5.445(1), c=7.214(1) Å, β=115.71(3)°, R=0.042; disordered Ba₃(PO₄)₂ structure type, with 3×b and 7×b superstructures identified. (2) Ho_8.67(SiO₄)₆(OH)₂: hexagonal, P6₃/m, Z=1, a=9.3221(4), c=6.7347(2) Å, R=0.026; silicate hydroxyapatite. (3) Lu₂Si₂O₇: tetragonal, P4₁2₁2, Z=4, a=6.5620(2), c=11.9535(4) Å, R=0.023; type X diorthosilicate structure, and the silicate analogue of tetragonal Er₂Ge₂O₇.     

Studies on organolanthanide complexes : LXIII. Synthesis, spectroscopic and X-ray crystallographic characterization of new early organolanthanide, organoyttrium hydride and organoholmium hydroxide complexes

Organolanthanide chloride complexes [(CH₃OCH₂CH₂C₅H₄)₂Ln(μ-Cl)]₂ (Ln = La, Pr, Ho and Y) react with excess NaH in THF at 45°C to give the dimeric hydride complexes [(CH₃OCH₂CH₂C₅H₄)₂Ln(μ-H)]₂, which have been characterized by IR, ¹H NMR, MS and XPS spectroscopy, elemental analyses and X-ray crystallography. [(CH₃OCH₂CH₂C₅H₄)₂Y(μ-H)]₂ crystallizes from THF/n-hexane at −30°C, in the triclinic space group P1 with a = 8.795(2) Å, b = 11.040(1) Å, c = 16.602(2) Å, = 93.73(1)°, β = 91.82(1)°, γ = 94.21(1)°, D_c = 1.393 gcm⁻³ for Z = 2 dimers. However, crystals of [(CH₃OCH₂CH₂C₅H₄)₂Ho(μ-OH)]₂ were obtained by recrystallization of holmium hydride in THF/n-hexane at −30°C, in the orthorhombic space group Pbca with a = 11.217(2) Å, b = 15.865(7) Å, c = 17.608(4) Å, D_c = 1.816 gcm⁻³ for Z = 4 dimers. In the complexes of yttrium and holmium, each Ln atom of the dimers is coordinated by two substituted cyclopentadienyl ligands, one oxygen atom and two hydrogen atoms (for the Y atom) or two hydroxyl groups (for the Ho atom) to form a distorted trigonal bipyramid if the C(η⁵)-bonded cyclopentadienyl is regarded as occupying a single polyhedral vertex.     

Effects of multi-dopants (Zn and Ho) in stabilizing spinel structure for cathode materials in lithium rechargeable batteries—Novel chelated sol–gel synthesis

Multi-doped spinels, namely LiMn₂O₄ and LiZn_xHo_yMn_2−x−yO₄ (x = 0.10–0.18; y = 0.02–0.10), for use as cathode materials for lithium-ion rechargeable batteries were synthesized via sol–gel method, using lauric acid as the chelating agent, to obtain micron-sized particles. The physical properties of the synthesized samples were investigated using differential thermal analysis, Fourier-transform infrared spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy, energy-dispersive X-ray analysis, and electrochemical methods. XRD showed that LiMn₂O₄ and LiZn_xHo_yMn_2−x−yO₄ have high degrees of crystallinity and good phase purities. The SEM images of LiMn₂O₄ showed an ice-cube morphology with particles of size 1 μm. Charge–discharge studies showed that undoped LiMn₂O₄ delivered the discharge capacity of 124 mA h/g with coulombic efficiency of 95% during the first cycle, whereas doped spinels delivered discharge capacities of 125, 120, and 127 mA h/g in the first cycle with coulombic efficiencies of 96%, 91%, and 91%, respectively.     

Room Temperature Ferromagnetism in Ga1-xHoxN (x=0.0 and 0.05) Diluted Magnetic Semiconductor Thin Films

Holmium doped GaN diluted magnetic semiconductor thin films have been prepared by thermal evaporation technique and subsequent ammonia annealing. X-ray diffraction mea-surements reveal all peaks belong to the purely hexagonal wurtzite structure. Surface mor-phology and composition analysis were carried out by scanning electron microscopy and energy dispersive spectroscopy respectively. The room temperature ferromagnetic proper-ties of Ga_1-xHo_xN(x=0.0, 0.05) films were analyzed using vibrating sample magnetometer at room temperature. Magnetic measurements showed that the undoped films (i.e. GaN) exhibited diamagnetic behavior, while the Ho-doped (Ga_0.95Ho_0.05N) film exhibited a ferro-magnetic behavior.