钐-富勒烯插入化合物的拉曼光谱

采用固态反应法合成了名义组分为SmxC60 (x =1 ,2 ,...,6 )的插入化合物 ,获得了具有正交结构的Sm2 .75C60 超导相和具有体心立方结构的Sm6C60 相。较高Sm浓度的SmxC60 (x≥ 3 )的拉曼谱峰的展宽与减弱可归因于C60 分子的畸变和电 -声子相互作用。拉曼光谱的结果还表明 ,尽管SmxC60 (x =2 ,3 ,4,5 )暴露空气后转变为非晶态 ,但C60 分子畸变反而减小 ;在Sm6C60 非晶态中C60 分子即使存在 ,但其畸变仍然很大 ,或C60 分子已遭到破坏并形成了某种非晶碳化物     

Raman spectra of Ba6−3xSm8+2xTi18O54 solid solution

Raman spectra of Ba_6−3xSm_8+2xTi₁₈O₅₄ solid solution were investigated as the function of x and sintering time. Reasonable explanations were provided about the Raman shifts and their intensities at 1013, 590, 751, 280, 232 cm⁻¹. 1013 cm⁻¹ demonstrates the existence of BaCO₃ phase in solid solution, 590 cm⁻¹ is the symmetric stretching mode of the basal oxygens of the octahedral; 280 and 232 cm⁻¹ are the symmetric stretching modes resulted from the tilt of octahedral when large cation sites are Sm³⁺ and Ba²⁺. The shoulder peak appearing around 302 cm⁻¹ is related to the vacancy produced by the unequal valence of Sm³⁺ and Ba²⁺.     

Effect of Dy substitution on structural,magnetic and optical properties of BiFeO3 ceramics

Bi_1−xDy_xFeO₃ (x=0.0, 0.03, 0.05, 0.07, 0.10 and 0.12) ceramics were synthesized by solid state reaction method. Effects of Dy substitution on structural distortion, magnetic and optical properties of BiFeO₃ were examined by X-ray diffraction, Raman and UV–Visible spectroscopy. The samples were found to crystallize in rhombohedral structure of BiFeO₃ with R3c space group. The reduction in lattice parameters and unit cell volume indicate the distortion in FeO₆ octahedra of the rhombohedral structure without any signature of phase transformation up to x=0.12. The predictable weak ferromagnetic hysteresis loops can be observed in the Dy doped samples with maximum remnant magnetization of 0.2103 emu/g for x=0.12. The weak ferromagnetism is ascribed to the suppressed spiral spin structure and magnetically active characteristic of Dy³⁺ ions together with ferromagnetic coupling between Dy³⁺ and Fe³⁺ ions. With optical band gap in visible region, Dy doped BiFeO₃ ceramics are potential material for optoelectronic device and solar cell applications.     

Sm富勒烯的价带光电子能谱

用紫外光电子能谱和同步辐射光电子能谱研究了Sm掺杂C₆₀薄膜的价带电子结构.Sm的价电子大部分转移给C₆₀，化学键以离子性为主.对于任何化学配比都没有观察到费米边，所以Sm富勒烯超导相在室温下为半导体性质.获得了很接近单相Sm_2.75C₆₀的样品在费米能级附近的电子态密度分布.固溶相的光电子发射与Sm_2.75C₆₀有明显区别.Sm_xC_{60关键词： 60}的Sm填隙化合物')" href="#">C₆₀的Sm填隙化合物 价带光电子能谱 电子结构     

X-ray diffraction and magnetic susceptibility of sodium fullerides NaxC60

The X-ray diffraction (XRD), magnetic susceptibility and electron spin resonance (ESR) measurements have been carried out for Na_xC₆₀. The XRD profiles with x<4 can be assigned to a face-centered cubic (fcc) lattice, while those with 4≦x to a hexagonal one. The temperature dependence of magnetic susceptibility χ for Na_xC₆₀ using SQUID was fitted to the Curie law, and estimated temperature-independent component χ₀. The composition x dependence of the χ₀ for Na_xC₆₀ shows two maxima at around x=3 and x=10, and minimum at x=6. The absence of Pauli contribution at x=6 was confirmed using ESR. A trace of superconducting transition at 14 K has been found for some Na_xC₆₀ specimens with 8<x<9.     

Na1−xLixNbO3 ceramics studied by X-ray diffraction, dielectric, pyroelectric, piezoelectric and Raman spectroscopy

Na_1−xLi_xNbO₃ ceramics with composition 0.05≤x≤0.30 were prepared by solid-state reaction method and sintered in the temperature range 1100-1150 °C. These ceramics were characterised by X-ray diffraction as well as dielectric permittivity measurements and Raman spectroscopy. Dielectric properties of ceramics belonging to the whole composition domain were investigated in a broad range of temperatures from 300 to 750 K and frequencies from 0.1 to 200 kHz. The Rietveld refinement powder X-ray diffraction analysis showed that these ceramics have a single phase of perovskite structure with orthorhombic symmetry for x≤0.15 and two phases coexistence of rhombohedral and orthorhombic above x=0.20. The evolution of the permittivity as a function of temperature and frequency showed that these ceramics Na_1−xLi_xNbO₃ with composition 0.05≤x≤0.15 present the classical ferroelectric character and the phase transition temperature T_C increases as x content increases. The polarisation state was checked by pyroelectric and piezoelectric measurements. For x=0.05, the piezoelectric coefficient d₃₁ is of 2pC/N. The evolution of the Raman spectra was studied as a function of temperatures and compositions. The results of the Raman spectroscopy study confirm our dielectric measurements, and they indicate clearly the transition from the polar ferroelectric phase to the non-polar paraelectric one.     

Temperature and composition dependence of vibrational modes in Sm1−xLaxAlO3

At room temperature and for x₀ ～ 0.43, the system Sm_1?xLa_xAlO₃ undergoes a first order phase transition in which an orthorhombic structure transforms into a rhomboedral structure as x increases. This phase transition was investigated by Raman scattering experiments on polycrystalline compounds in the range 0 ? x ? 1. The dependence of low frequency modes on x is reported and compared with their well known temperature dependence. Soft modes have been observed in the orthorhombic (D_2h¹⁶) and rhomboedral (D_3d⁶) phases. It was found that the first order phase transition is probably driven by a double degenerate mode whose two components in the low symmetry phase display a linear composition dependence of their squared frequencies. The source of anomalous behaviour of Raman bands near the phase transition is discussed.     

Optical properties of samarium doped zinc-phosphate glasses

Samarium doped zinc-phosphate glasses having composition Sm₂O_{3 (x)}ZnO_(60−x) P₂O_{5 (40)} (where x=0.1-0.5 mol%) were prepared by melt quenching method. The density of these glasses was measured by Archimedes method; the corresponding molar volumes have also been calculated. The values of density range from 3.34 to 3.87 gm/cm³ and those of molar volume range from 27.62 to 31.80 cm⁻³. The optical absorbance studies were carried out on these glasses to measure their energy band gaps. The absorption spectra of these glasses were recorded in UV-visible region. No sharp edges were found in the optical spectra, which verifies the amorphous nature of these glasses. The optical band gap energies for these glasses were found to be in the range of 2.89-4.20 eV. The refractive index and polarizability of oxide ion have been calculated by using Lorentz-Lorentz relations. The values of refractive index range from 2.13 to 2.42 and those of polarizability of oxide ion range from 6.51×10⁻²⁴ to 7.80×10⁻²⁴ cm³.     

Coexistence of superconductivity and magnetism in the La0.87−xLnxSr0.13FeAsO (Ln=Sm, Gd, Dy) system

The interplay between the superconducting phase and spin density wave order phase was studied. We report the magnetic and superconducting properties of the hole-doped FeAs-based superconducting compound La_0.87−xLn_xSr_0.13FeAsO (Ln=Sm, Gd, Dy; 0≤x≤0.06). Both resistivity and magnetic susceptibility measurements show that the superconducting transition temperature decreases with increase in composition of magnetic ions. The hysteresis loop of the La_0.87−xLn_xSr_0.13FeAsO sample shows a superconducting hysteresis in addition to a paramagnetic background. The experiment demonstrates that the magnetism and superconductivity coexist in hole-doped FeAs-based superconducting compounds. Among these three magnetic rare-earth elements, the influence of Dy³⁺ doping on superconductivity is more evident than that of Gd³⁺ doping, while the influence of Sm³⁺ doping is the weakest. The trend is consistent with the variation of the lattice parameter along c-axis.     

Structure and phase transitions in chloroantimonate(V) crystals: [(C2H5)3NH]SbCl6 and [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl

New triethylammonium salts: [(C₂H₅)₃NH]SbCl₆ (TCA) and [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl (TCAT) have been synthesized. The compounds crystallise in monoclinic symmetry: space groups P2₁/n and P2₁/c, for TCA at 293 K and TCAT at 100 K, respectively. The crystal structure of [(C₂H₅)₃NH]SbCl₆ consists of discrete ionic pairs—triethylammonium cations and hexachloroantimonate anions—linked via the bifurcated N-H?Cl hydrogen bonds. The crystal structure of [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl is composed of three symmetrically independent triethylammonium cations, chlorine anion and two symmetrically independent hexachloroantimonate anions. TCA undergoes a structural phase transition at 336 K (on heating) into the orthorhombic C222 space group, whereas TCAT reveals a structural phase transition at 332 K. The phase transitions are of the first order type. TCA shows a ferroelastic domain structure below 336 K. Differential scanning calorimetry, dilatometric, dielectric dispersion and Raman scattering measurements have been used to study the phase transition mechanisms in these triethylammonium salts.     

Ab initio calculations of structural,electronic, optical and thermodynamic properties of alkaline earth tellurides BaxSr1−XTe

Structural, electronic and thermodynamic properties of SrTe and BaTe compounds and their ternary mixed crystals Ba_xSr_1−xTe in the rock-salt structure have been studied with density functional theory (DFT), whereas the optical properties have been obtained by using empirical methods such as the modified Moss relation. The exchange-correlation potential was calculated using the generalized gradient approximation (GGA) of Perdew–Burke–Ernzerhof (PBE) and the local density approximation (LDA) of Teter–Pade (TP). In the present work, we used the virtual-crystal approximation (VCA) to study the effect of composition (x). The calculated lattice parameters at equilibrium volume and the bulk modulus for x=0 and x=1 are in good agreement with the literature data. Furthermore, the Ba_xSr_1−xTe alloys are found to be an indirect band gap semiconductor. In addition, we have also predicted the heat capacities (C_V), the entropy(S), the internal energy (U) and the Helmholtz free energy (F) of the parent compounds SrTe and BaTe.     

Annealing of thin Zr films on Si1−xGex(0≤x≤1): X-ray diffraction and Raman studies

X-ray diffraction experiments have been combined with Raman scattering and transmission electron microscopy data to analyze the result of rapid thermal annealing (RTA) applied to Zr films, 16 or 80 nm thick, sputtered on Si_1−xGe_x epilayers (0≤x≤1). The C49 Zr(Si_1−xGe_x)₂ is the unique phase obtained after complete reaction. ZrSi_1−xGe_x is formed as an intermediate phase. The C49 formation temperature T_f is lowered by the addition of Ge in the structure. Above a critical Ge composition close to x=0.33, a film microstructure change was observed. Films annealed at temperatures close to T_f are continuous and relaxed. Annealing at T>T_f leads to discontinuous films: surface roughening resulting from SiGe diffusion at film grain boundaries occurred. Grains are ultimately partially embedded in a SiGe matrix. A reduction in the lattice parameters as well as a shift of Raman lines are observed as T exceeds T_f. Both Ge non-stoichiometry and residual stress have been considered as possible origins for these changes. However, as Ge segregation has never been detected, even by using very efficient techniques, it is thought that the changes originate merely from residual stress. The C49 grains are expected to be strained under the SiGe matrix effect and shift of the Raman lines would indicate the stress is compressive. Some simple evaluations of the stress values indicate that it varies between −0.3 and −3.5 GPa for 0≤x≤1 which corresponds to a strain in the range (−0.11, −1.15%). X-ray and Raman determinations are in good agreement.     

Low-field magnetic properties of LaMnO3+δ with 0.065≤δ≤0.154

In a weak magnetic field LaMnO_3+δ exhibits at δ=0.065 below the paramagnetic-to-ferromagnetic (FM) Curie temperature, T_C, a mixed (spin-glass and FM) phase followed by a frustrated FM phase at δ between 0.100 and 0.154. The same behavior is observed in La_1−xCa_xMnO₃ with x between 0 and 0.3. This can be understood by the similar variation of the Mn⁴⁺ concentration, c between ≈0.13 and 0.34, in both materials when x or δ is increased. On the other hand, considerable differences are found between these compounds in the values of the magnetic irreversibility, in the dependencies of T_C(c) and the magnetic susceptibility, χ(c), as well as in the critical behavior of χ(T) near T_C. These differences can be explained by distortions of the cubic perovskite structure, by the reduced lattice disorder and by the more homogeneous hole distribution in LaMnO_3+δ than in La_1−xCa_xMnO₃.     

Magnetism on Mg1−xZnxCyNi3

The magnetic phase diagram for Mg_1−xZn_xC_yNi₃ has been tentatively constructed based on magnetization and muon spin relaxation (μSR) measurements. The superconducting phase was observed to fade as x (y) increases (decreases). The low y samples show early stages of long-range ferromagnetism, or complete long-range ferromagnetism. In the phase diagram, the ferromagnetic phase exists in addition to the superconducting phase, suggesting that there is some correlation between superconductivity and ferromagnetism, even though the coexistence of ferromagnetism and superconductivity is not observed from the μSR measurements down to 20 mK for the superconducting sample (T_c=2.5 K, (x, y)=(0, 0.9)).     

Effect of chromium substitution in Ca4Mn3O10

Ca₄Mn_3−xCr_xO₁₀ compounds were synthesized in order to investigate the role of an isoelectronic substitution in the layered manganite. Induced structural changes are mainly described as a distortion of the two types of octahedra in the n=3 RP structure. The results indicate that Cr³⁺ is not the only significant valence state for chromium ions. Electrical and magnetic characterization allow to conclude that chromium does not favour the double exchange mechanism in these compounds.     

Curie temperatures and crystallization behavior of amorphous Fe81−xNixZr7B12 (x=10, 20, 30, 40, 50, 60) alloys

Curie temperature, crystal structure and crystallization behavior of amorphous alloys with the stoichiometry Fe_81−xNi_xZr₇B₁₂ (x=10–60) have been studied by X-ray diffractometry (XRD), differential scanning calorimetry (DSC) and AC-magnetization (TMAG) measurements as functions of temperature. The thermal stability of long-range magnetic order, T_C vs. Ni content in as-quenched amorphous alloys exhibits maximum at 352 °C for x=40. The primary crystallization has been detected during annealing at the first crystallization stage of all ribbons investigated.     

Raman scattering from electronic excitations of samarium in semiconducting and metallic Sm1−xYxS

The Raman spectra of Sm_1?xY_xS for $\text{x?0.4}$ have been measured. Electronic scattering between the J = 0 ground state and the J = 1 and 2 excited states of Sm²⁺ is observed. The singlet-triplet transition is observed on both sides of the black to gold phase transition in Sm_1?xY_xS.     

Low field AC susceptibility study of intergranular critical current density in Mg-substituted CuBa2Ca3Cu4O12−y high temperature superconductors

Measurements of the a.c.susceptibility (χ=χ′+iχ″) have been made on the Mg substituted high T_C superconducting system, CuBa₂(Mg_xCa_1−x)₃Cu₄O_12−y (Cu-1234) with x=0, 0.10 & 0.20, at different values of the a.c.field amplitude. Estimates of the intergranular critical current density(J_C) made from the field dependent χ″-T curves show an improvement in the Mg-substituted Cu-1234 system. Results have been analysed in the light of the crystal structure and the superconducting anisotropy factor (γ=ξ_ab/ξ_c) of the Cu-1234 system. Lower superconducting anisotropy emanating from Mg substitution has been found to be significant, resulting in better superconducting properties.     

Thermal stability of A-site ordered PrBaMn2O6 manganites

The crystal structure and electromagnetic properties as well as thermal stability of the A-site ordered PrBaMn₂O₆ manganites have been investigated. These samples have been prepared by using ‘two-steps’ synthesis mode. They have tetragonal structure with no tilt of MnO₆ octahedra and show ferromagnetic metal to paramagnetic semiconductor transition. The most significant structural feature of the A-site ordered manganites is that the MnO₂ sublattice is sandwiched by two types of rock-salt layers PrO and BaO. The different degree of Pr and Ba ions in the A-sublattice is revealed. The A-site ordered PrBaMn₂O₆ sample with maximum degree of the A-site order demonstrates ferromagnetic metallic to paramagnetic insulating transition with the Curie point ∼320 K. The A-site disordered Pr_0.50Ba_0.50MnO₃ sample is ferromagnetic metal below T_C≈140 K. The cation order in these compounds is stable in air up to 1300 °C. For the partly A-site ordered samples the magnetic and electronic phase separation is observed. The magnetotransport properties of the A-site ordered manganites treated under different conditions are discussed in terms of the superexchange interactions and A-site order degree.     

On the criteria of formation and lattice distortion of perovskite-type complex halides

The famous Goldschmidt's tolerance factor gives us a necessary but not sufficient condition for the formation of perovskite-type compounds (ABX₃). In this work, computerized data analysis has been used to find some complementary criteria for the formation and lattice distortion of perovskite-type complex halides. It has been found that the radius ratio (R_A/R_X) and (R_B/R_X), affecting the stability of BX₆ octahedra and AX₁₂ cubo-octahedra (they are basic units of perovskite structure), are also dominating factors for the formation and lattice distortion of perovskite-type compounds. Besides, it has been found that the transition between the perovskite structure (with corner-sharing BX₆ octahedra) to BaNiO₃ structure (with face-sharing BX₆ octahedra) can be predicted by a criterion based on the relative magnitude of ionic radii and electronegativity. Based on multivariate data analysis, several complementary criteria for the formation and lattice distortion of perovskite-type complex halides have been obtained, and some empirical equations expressing the relationships between the ionic radii (R_A,R_B,R_X) and the lattice constants of perovskite-type complex halides have been found. The physical meaning of these empirical relationships has been discussed based on Pauling's rules of the crystal lattice stability of complex ionic compounds.