Cubic symmetry around iron in CoSi2

The Mössbauer spectra of ⁵⁷Fe in CoSi₂ have been measured in 3.5 and 4.0 T external magnetic fields. The measured spectra showed only magnetic splitting thereby proving the cubic symmetry around ⁵⁷Fe atoms in CoSi₂ (fluorite‐type lattice). Two iron positions were found: in one the iron atoms substitute Co atoms, in the other one the iron populates the empty cubic site in the lattice. It is considered that the results may well contribute to clarifying the atomic positions and local symmetries in metastable Co‐ and Fe‐silicides forming after implantation of Co and Fe in Si at elevated temperatures.     

Comparison of the electronic structure of a thermoelectric skutterudite before and after adding rattlers: an electron energy loss study

Skutterudites, with rattler atoms introduced in voids in the crystal unit cell, are promising thermoelectric materials. We modify the binary skutterudite with atomic content Co(8)P(24) in the cubic crystal unit cell by adding La as rattlers in all available voids and replacing Co by Fe to maintain charge balance, resulting in La(2)Fe(8)P(24). The intention is to leave the electronic structure unaltered while decreasing the thermal conductivity due to the presence of the rattlers. We compare the electronic structure of these two compounds by studying the L-edges of P and of the transition elements Co and Fe using electron energy loss spectroscopy (EELS). Our studies of the transition metal white lines show that the 3d electron count is similar for Co and Fe in these compounds. As elemental Fe has one electron less than Co, this supports the notion that each La atom donates three electrons. The L-edges of P in these two skutterudites are quite similar, signalling only minor differences in electronic structure. This is in reasonable agreement with density functional theory (DFT) calculations, and with our multiple scattering FEFF calculations of the near edge structure. However, our experimental plasmon energies and dielectric functions deviate considerably from predictions based on DFT calculations.     

过渡金属掺杂钛酸纳米管的电子结构和光学性质研究

采用平面波超软赝势方法计算了过渡金属(TM)(Fe,Co或者Ru)掺杂钛酸纳米管的电子结构及光学性质.对TM取代钛酸纳米管层间间隙位H+的几何结构进行优化,发现掺杂对几何结构的影响较大,其中Co或者Ru掺杂的形成能均较低.此外,掺杂的TM与周围的O原子成键,有形成固熔体的趋势.掺杂后的能带结构分析表明:Fe,Co或者Ru掺杂导致钛酸纳米管禁带宽度减小并且于禁带中引入了新的能级,这主要归因于b1g(dx2-y2)及a1g(dz2)态的出现;部分杂质能级处于半填充状态,成为空穴的俘获中心,减少电子和空穴的复合;掺杂后,价带顶向低能方向移动,使价带中形成的空穴氧化性更强.最后,掺杂的钛酸盐纳米管的吸收光谱显示,Ru掺杂的钛酸纳米管导致其在可见光范围内有更强的吸收.     

Oxygen partial pressure dependence of in situ X-ray absorption spectroscopy at the Co and Fe K edges for (La0.6Sr0.4)(Co0.2Fe0.8)O3−δ

The oxygen partial pressure (P(O₂)) dependence of in situ X-ray absorption spectroscopy (XAS) at the Co and Fe K edges was measured simultaneously and continuously at 900 and 1000 K. These experiments, which were performed during reduction, changing P(O₂) from 1 to 10^?4 atm, were used to investigate each valence related to Co and Fe in (La_0.6Sr_0.4)(Co_0.2Fe_0.8)O_3?δ (LSCF). The absorption edge shift of the Co K edge was more than twice that of the Fe K edge at 1000 K during reduction. For quantitative analysis, X-ray absorption near-edge structure spectroscopy was carried out at the Co and Fe K edges; the results indicated that the Co valence decreased more easily than the Fe valence; that is, the oxygen preferentially left from the oxygen sites around Co.     

Effects of magnetic field on shape evolution of Fe–Co particles in a Cu matrix

The effects of magnetic field on the shape evolution of ferromagnetic fcc Fe–Co particles in Cu–0.83 at.% Fe–1.37 at.% Co alloy single crystals were examined using magnetic anisotropy measurements. The Cu–Fe–Co single crystals were aged at 993 K for 2 h to 24 h under a magnetic field of 10 T parallel to either the [001] or [011] direction. The magnetic anisotropy was examined by measuring magnetic torque around the (100) plane. It was found that the fcc Fe–Co particles are elongated in the direction parallel to the magnetic field. Furthermore, the elongation along [001] is more remarkable than that along [011]. The results are explained quantitatively by considering the minimization of the sum of the interface energy, elastic strain energy and magnetostatic energy of spheroidal particles.     

Co[V2]o4: a spinel approaching the itinerant electron limit

Studies of the structure, magnetization, and resistivity under pressure on stoichiometric normal spinel Co[V(2)]O(4) single crystals show (i) absence of a structural distortion, (ii) abnormal magnetic critical exponents, and (iii) metallic conductivity induced by pressures at low temperatures. All these results prove that Co[V(2)]O(4) sits on the edge of the itinerant-electron limit. Compared with similar measurements on Fe[V(2)]O(4) and other A[V(2)]O(4) studies, it is shown that a critical V-V separation for a localized-itinerant electronic phase transition exists.     

过渡金属原子掺杂的锯齿型磷烯纳米带的磁电子学特性

利用基于密度泛函理论的第一性原理方法,研究了掺杂铁、钴和镍原子的锯齿型磷烯纳米带(ZPNR)的磁电子学特性.研究表明,掺杂和未掺杂ZPNR的结构都是稳定的.当处于非磁态时,未掺杂和掺杂钴原子的ZPNR为半导体,而掺杂铁或者镍原子的ZPNR为金属.自旋极化计算表明,未掺杂和掺杂钴原子的ZPNR无磁性,而掺杂铁或者镍原子的ZPNR有磁性,但只能表现出铁磁性.处于铁磁态时,掺杂铁原子的ZPNR为磁性半导体,而掺杂镍原子的ZPNR为磁性半金属.掺杂铁或者镍原子的ZPNR的磁性主要由杂质原子贡献,产生磁性的原因则是在ZPNR中存在未配对电子.掺杂位置对ZPNR的磁电子学特性有一定的影响.该研究对于发展基于磷烯纳米带的纳米电子器件具有重要意义.     

Study on B2 structure epitaxial Fe/Co superlattice

The B2 structure Fe₅₀Co₅₀ alloy is very attractive material as a large spin conductance asymmetry. In this study, we have tried to fabricate epitaxial Fe/Co superlattice with B2 structure. In order to investigate the relationship between the film structure and the substrate temperature, the films were prepared at different substrate temperature. The film structure of Fe/Co was evaluated by reflection high energy electron diffraction (RHEED). The in-plane lattice spacing gradually decreased to that of a bulk Fe₅₀Co₅₀ as increase in the number of layers. The B2 structure ordered phase of Fe/Co superlattice was successfully confirmed by RHEED and X-ray diffraction (XRD).     

Existence, character, and origin of surface-related bands in the high temperature iron pnictide superconductor BaFe(2-x)Co(x)As2

Low energy electron diffraction (LEED) experiments, LEED simulations, and finite slab density functional calculations are combined to study the cleavage surface of Co doped BaFe(2-x)Co(x)As2 (x = 0.1,0.17). We demonstrate that the energy dependence of the LEED data can only be understood from a terminating 1/2 Ba layer accompanied by distortions of the underlying As-Fe2-As block. As a result, surface-related Fe 3d states are present in the electronic structure, which we identify in angle resolved photoemission spectroscopy (ARPES) experiments. The close proximity of the surface-related states to the bulk bands inevitably leads to broadening of the ARPES signals, which excludes the use of the BaFe(2-x)Co(x)As2 system for accurate determination of self-energies using ARPES.     

Co+离子注入单晶TiO2铁磁性来源与微结构研究

在室温下,将能量为80 keV, 注量分别为1×1016和1×1017ions/cm2的Co+离子注入到10 mm×10 mm×0.5 mm的单晶TiO₂样品。在氮气保护下, Co+离子注量为1×1017 ions/cm2时样品在温度为900 ℃的条件下退火30 min。 利用超导量子干涉仪 （SQUID）测量样品磁性, 并应用X射线衍射（XRD）和扩展边X射线吸收精细结构谱（EXAFS）研究Co+离子注入后样品的微观结构。 样品磁性测量结果表明:Co+离子注入后的样品具有室温铁磁性, 并且其饱和磁化强度的大小与Co+离子注量及样品是否经退火处理有关。 EXAFS研究表明: Co元素在Co+离子注量为1×1017ions/cm2的样品中主要以团簇形式存在;样品经退火处理后, Co团簇消失, 并发现Co部分替代TiO₂单晶中的Ti。Co+离子注入后, 在样品中形成Co团簇与否受离子注量的影响。 阐述了样品微观结构与铁磁性来源之间的关系。 At room temperature, monocrystalline plates of rutile (TiO₂) were implanted with cobalt ions of an energy of 80 keV to fluences of 1×1016 and 1×1017 ions/cm2 respectively . The 1×1017 ions/cm2 Co implanted samples were annealed in nitrogen at 900 ℃ for 30 min. The magnetic properties of Co implanted samples were measured with a superconducting quantum interference device magnetometer (SQUID) at room temperature. Furthermore, the X ray diffraction (XRD) and Extended X ray Absorption Fine Structure (EXAFS) were applied to investigate the structural and compositional properties of Co implanted samples. The magnetic measurements of samples showed that the size of the saturation magnetization of the Co implanted samples were related to the fluence of ions, and the saturation magnetization of the sample after annealed decreased significantly. The EXAFS measurements showed the presence of cobalt metallic clusters in the sample implanted to ion fluence of 1×1017 ions/cm2. The Co metallic clusters disappeared in the sample after annealed, and resulted in the oxidized Co, which is presumed to substitute into the Ti site. The formation of Co clusters or not was determined by the ion fluence. The relation between ferromagnetic behavior and microscopic structure of the Co implanted samples is discussed.     

Study of metglas 2605 CO by extended and near edge X-ray absorption fine structure

Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) studies of the transition metal sites in Metglas 2605 CO (Fe₆₇Co₁₈B₁₄Si₁) illustrate differences in the two sites. The average transition metal distance, obtained by standard EXAFS analysis, is larger for iron than for cobalt sites in this material. The XANES for Co and Fe are nearly identical except for a shift of the Co fine structure to high energy relative to that of Fe; the sign and magnitude of this shift is commensurate with the EXAFS results. Finally, there was no detected polarization dependence of the EXAFS, indicating that the structural manifestations of the magnetic anisotropy in this material are smaller than the detection limits of these experiments.     

Deformation-induced texture in nanocrystalline 2:17, 1:5 and 2:7 Sm-Co magnets

The effect of crystal structures on texture induced by hot plastic deformation was studied for Sm-Co, Sm-Zr-Co, Sm-Zr-Co-Fe and Sm-Co-Fe-Mn nanocrystalline alloys with 9-22 at% Sm. Nanocrystalline precursors were obtained via high-energy ball milling and subsequent hot consolidation; deformation was carried out at 800-1150 °C. The analysis of X-ray diffraction and magnetic measurements showed that the degree of the axial [0 0 1] texture after deformation was negligible for the ordered 2:17 structure, but became increasingly noticeable for the disordered 2:17 (“1:7”), 1:5 and 2:7 structures. Because of interplay of several factors including the [0 0 1] texture, saturation magnetization and magnetocrystalline anisotropy, there was no universal trend in the hard magnetic properties with the Sm content. Optimum compositions for the maximum energy product varied from Sm₁₁(Co, Fe, Mn)₈₉ in the Sm-Co-Fe-Mn series to Sm₁₁Zr₂(Co, Fe)₈₇ in the Sm-Zr-Co-Fe series to Sm₁₇(Co, Fe)₈₃ in the Sm-Co-(Fe) series. Iron substitution for cobalt strongly suppresses the 1:5 structure, whereas the Fe-free magnets based on the SmCo₅ compound showed by far the highest room-temperature coercivity.     

Analysis of electronic structures of 3d transition metal-doped TiO2 based on band calculations

The electronic structures of titanium dioxide (TiO₂) doped with 3d transition metals (V, Cr, Mn, Fe, Co and Ni) have been analyzed by ab initio band calculations based on the density functional theory with the full-potential linearized-augmented-plane-wave method. When TiO₂ is doped with V, Cr, Mn, Fe, or Co, an electron occupied level occurs and the electrons are localized around each dopant. As the atomic number of the dopant increases the localized level shifts to lower energy. The energy of the localized level due to Co is sufficiently low to lie at the top of the valence band while the other metals produce midgap states. In contrast, the electrons from the Ni dopant are somewhat delocalized, thus significantly contributing to the formation of the valence band with the O p and Ti 3d electrons. Based on a comparison with the absorption and photoconductivity data previously reported, we show that the t_2g state of the dopant plays a significant role in the photoresponse of TiO₂ under visible light irradiation.     

Magnetic structure and preferential occupation of Fe in the composite compound Nd2Co6Fe

The crystal and magnetic structures of the composite compound Nd₂Co₆Fe have been investigated by high-resolution neutron powder diffraction and X-ray powder diffraction. The compound crystallizes in the hexagonal Ce₂Ni₇-type structure consisting of Nd(Co,Fe)₂ and Nd(Co,Fe)₅ structural blocks alternately stacked along the c-axis. Multi-pattern Rietveld refinement of neutron diffraction and X-ray diffraction data at room temperature reveal that substitution of Fe for Co occurs exclusively in the Nd(Co,Fe)₅ structural blocks. The preferential occupation of the Fe atoms in the structure is discussed based on the mixing enthalpy between Nd and Fe atoms and on the lattice distortions. In agreement with the reported magnetic phase diagram of the Nd₂Co_7−xFe_x compounds, magnetic structure models with the moments of all atoms in the ab plane at 300 K and along the c-axis at 450 K provide a satisfactory fitting to the experimental neutron diffraction data. The refinement results show that the atomic moments of (Co,Fe) atoms within the Nd(Co,Fe)₅ blocks decrease slightly with temperature, whereas the atomic moments of Nd in the compound and of (Co,Fe) atoms at the interface between the Nd(Co,Fe)₂ and Nd(Co,Fe)₅ blocks are reduced significantly.     

Local structure and optical absorption characteristic investigation on Fe doped TiO_2 nanoparticles

The local structures and optical absorption characteristics of Fe doped Ti O2 nanoparticles synthesized by the sol-gel method were characterized by X-ray diffraction(XRD), X-ray absorption fine structure spectroscopy(XAFS) and ultraviolet-visible absorption spectroscopy(UV-Vis). XRD patterns show that all Fe-doped Ti O2 samples have the characteristic anatase structure. Accurate Fe and Ti K-edge EXAFS analysis further reveal that all Fe atoms replace Ti atoms in the anatase lattice. The analysis of UV-Vis data shows a red shift to the visible range. According to the above results, we claim that substitutional Fe atoms lead to the formation of structural defects and new intermediate energy levels appear, narrowing the band gap and extending the optical absorption edge towards the visible region.     

Tl2Ba2Ca2Cu3O10的化学键性质和同质异能位移研究

在Tl2Ba2Can-1CunO2n 4(n=1,2,3,4)系列超导性氧化物中,Tl2Ba2Ca2Cu3O10具有最高Tc值(125 K)．利用电介质的平均能带模型计算了Tl2Ba2Ca2Cu3O10的局域化学键参数,得到Cu(1)-O键的共价性为0．561,Cu(2)-O键的平均共价性为0．296．应用化学环境因子计算了57Fe在Tl2Ba2Ca2Cu3O10中的穆斯堡尔同质异能位移,证实了57Fe在低掺杂时以Fe3 和Fe4 离子形式占据Cu(1)位置,而在高掺杂时以Fe3 和Fe4 离子形式分别占据Cu(1)和Cu(2)位置．结果表明,化学键理论计算有助于复杂晶体的穆斯堡尔谱的正确分析．     

The influence,on lithium electrochemical intercalation,of bond ionicity in layered chalcogenophosphates of transition metals

In the course of lithium electrochemical intercalation in the host structure of layered M∥PX₃ phases (M = V, Mn, Fe, Co, Ni, X = S, Se), it was shown that the best energy yield was obtained from low ionicity bond materials. The absorption edge energy, along with the free energy of the intercalation reactions have been correlated in a satisfactory way to the ionicity fi of the M-X bonds. These diagrams indicate which phases have to be looked at to obtain the maximum electrochemical yields.     

Magnetic characteristics of R2(Fe, Co)14B systems (R = Y, Nd and Gd)

R₂(Fe, Co)₁₄B compounds (R = Y, Nd and Gd) were prepared in high purity. The magnetic behavior of R₂(Fe, Co)₁₄B compounds is reported over the temperature range 4 to 300 K. The effects of Fe substitution by Co on the saturation magnetization, Curie temperature and anisotropy are presented. The spin-reorientation temperature is lowered as Co replaces Fe. This also results in a reduced cone angle.

The R₂Fe_14−xCo_xB alloys crystallize in the tetragonal structure over the entire concentration range of 0 x 14. When Fe is substituted by Co, the Curie temperature increases significantly, the saturation magnetization increases to a maximum value around x = 2, and the anisotropy becomes planar for R = Y and Gd. The Nd₂(Fe, Co)₁₄B systems all exhibit uniaxial anisotropy at room temperature and Nd₂Co₁₄B is strongly uniaxial at 77 K. The Nd₂(Fe, Co)₁₄B systems are conical at 77 K.     

First principles study on the electronic structure of the two chain compounds of [ M(N3)2(HCOO)][(CH3)2NH2] (M=Fe and Co)

First principles calculations have been performed to study the electronic structure and the ferromagnetic properties on the two chain compounds of [M(N₃)₂(HCOO)][(CH₃)₂NH₂] (M=Fe and Co). The relative stability of the ground state, the density of states and the electronic band structure are examined. The results reveal that antiferromagnetism (AFM) state is the ground state and ferromagnetism (FM) state is the metastable one for both of them. The two compounds exhibit semiconductor character with small gap in the FM state, while metallic in the AFM state. In the FM state, the magnetic moments mainly arise from the Fe and Co ions with little contribution from the nearest-neighboring N and O atoms due to the hybridization between the Fe or Co 3d states and the nearest-neighboring N and O 2p states.     

Structural,magnetic and XPS studies of Sn0.95Co0.05O2-0.05 and Sn0.95Fe0.05O2-0.05 nanoparticles

Structural, microstructural, X-ray photoemission spectra (XPS) and magnetic properties of transition metal ion [5 mol% of Co (SC5) and Fe (SF5)]-doped SnO₂ nanoparticles have been studied. The SC5 and SF5 nanoparticles were synthesized by a chemical route using polyvinyl alcohol as surfactant. The doped SnO₂ crystallites were found to exhibit a tetragonal rutile structure and the average grains size was measured by the Scherer relation of X-ray diffraction. Transmission electron micrographs showed that the average grain size of SC5 is smaller than SF5. SC5 nanoparticles showed strong ferromagnetic behaviour but SF5 exhibited an F-centre exchange (FCE) mechanism. Temperature-dependent magnetization showed the values of phase transition temperature. XPS confirmed the presence of Sn–O–Co and Sn–O–Fe bonds in these SC5 and SF5 nanoparticles. The oxidation states of Sn, Co and Fe were found to be +4, +2 and +2, respectively, while the core level XPS peaks of Sn 3d, O 1s, Co 2p and Fe 2p were analyzed.