Random alloy-like local structure of Fe(Se, S)(1-x)Te(x) superconductors revealed by extended x-ray absorption fine structure

The local structure of Fe(Se, S)(1-x)Te(x) ternary (11-type) chalcogenides has been studied by temperature dependent Fe K-edge extended x-ray absorption fine structure measurements. We find that the Fe-Se and Fe-Te distances in ternary FeSe(1-x)Te(x) are closer to the respective distances in the binary systems, revealing significant divergence of the local structure from the average one. The mean square relative displacements show a systematic change with Te content, consistent with bond relaxation in the inhomogeneous ternary phases. Also, the Fe-Te and Fe-S distances in the FeS(0.2)Te(0.8) ternary system are found to be different in the crystallographically homogeneous structure. The observed features are characteristic of ternary random alloys, suggesting that a proper consideration should be given to the atomic distribution for describing the complex electronic structure of these multi-band Fe-based chalcogenides.     

Interplay between crystal field splitting and Kondo effect in CeNi(9)Ge(4-x)Si(x)

The pseudo-ternary solid solution CeNi(9)Ge(4-x)Si(x) (0?≤?x?≤?4) has been investigated by means of x-ray diffraction, magnetic susceptibility, specific heat, electrical resistivity, thermopower and inelastic neutron scattering studies. The isoelectronic substitution of germanium by silicon atoms causes a dramatic change of the relative strength of competing Kondo, RKKY and crystal field (CF) energy scales. The strongest effect is the continuous elevation of the Kondo temperature T(K) from approximately 3.5?K for CeNi(9)Ge(4) to about 70?K for CeNi(9)Si(4). This increase of the Kondo temperature is attended by a change of the CF level scheme of the Ce ions. The interplay of the different energy scales results in an incipient reduction of the ground state degeneracy from an effectively fourfold degenerate non-magnetic Kondo ground state with unusual non-Fermi-liquid features of CeNi(9)Ge(4) to a lower one, followed by an increase towards a sixfold, fully degenerate ground state multiplet in CeNi(9)Si(4) (T(K)?～?Δ(CF)).     

Site Preference of Se and Te in Bi_2Se_(3-x)Te_x Thin Films

The ternary topological insulators Bi₂Se_3-xTe_x have attracted a great deal of attention due to their exotic physical and chemical properties.While most of the studies focus on the properties of these ternary TIs,limited research was performed to investigate the dynamic atomic stack of its crystal structure.We prepared highquality Bi₂Se_3-xTe_x thin films on Ga As(111)B substrates using molecular beam epitaxy,characterized with Raman...     

Ge_(28)Sb_6S_((66-x))Se_x玻璃系统光学特性与结构

采用熔融-急冷法制备了系列Ge28Sb6S(66-x)Sex(x=0,10,20,30摩尔比)硫系玻璃样品.分别测试了样品的密度、折射率、可见-近红外透过光谱、红外透过光谱以及喇曼光谱,并分析了在Ge-Sb-S中引入Se对其物理、光学特性的影响.利用喇曼光谱讨论了玻璃的结构与特性之间的关系.结果表明:随着Se含量的增加,样品的密度和线性折射率都增大,可见和红外截止波长都发生红移,纯硫化物玻璃样品主要由GeS4四面体和SbS3三角锥组成,随着Se逐渐代替S,硫-硒混合样品中逐渐出现了GeS4-xSex结构单元以及链状和环状的Se-Se键.     

Magnetic excitations in EuCu(2)(Si(x)Ge(1-x))(2): from mixed valence towards magnetism

We report the inelastic neutron scattering study of spin dynamics in EuCu(2)(Si(x)Ge(1-x))(2) (x?=?1, 0.9, 0.75, 0.6), performed in a wide temperature range. At x?=?1 the magnetic excitation spectrum was found to be represented by the double-peak structure well below the energy range of the Eu(3+) spin-orbit (SO) excitation (7)F(0)→(7)F(1), so that at least the high-energy spectral component can be assigned to the renormalized SO transition. Change of the Eu valence towards 2?+ with increased temperature and/or Ge concentration results in further renormalization (lowering the energy) and gradual suppression of both inelastic peaks in the spectrum, along with developing sizeable quasielastic signal. The origin of the spectral structure and its evolution is discussed in terms of excitonic model for the mixed valence state.     

Origin of the tunnel anisotropic magnetoresistance in Ga(1-x)Mn(x)As/ZnSe/Ga(1-x)Mn(x)As magnetic tunnel junctions of II-VI/III-V heterostructures

We investigated spin-dependent transport in magnetic tunnel junctions made of III-V Ga(1-x)Mn(x)As electrodes and II-VI ZnSe tunnel barriers. The high tunnel magnetoresistance (TMR) ratio up to 100% we observed indicates high spin polarization at the barrier/electrodes interfaces. We found anisotropic tunneling conductance having a magnitude of 10% with respect to the direction of magnetization to linearly depend on the magnetic anisotropy energy of Ga(1-x)Mn(x)As. This proves that the spin-orbit interactions in the valence band of Ga(1-x)M(x)As are responsible for the tunnel anisotropic magnetoresistance (TAMR) effect.     

First-principles calculation of alloy scattering in Ge(x)Si(1-x)

First-principles electronic structure methods are used to find the rates of intravalley and intervalley n-type carrier scattering due to alloy disorder in Si(1-x)Ge(x) alloys. The required alloy scattering matrix elements are calculated from the energy splitting of nearly degenerate Bloch states which arises when one average host atom is replaced by a Ge or Si atom in supercells containing up to 128 atoms. Scattering parameters for all relevant Delta and L intravalley and intervalley alloy scattering are calculated. Atomic relaxation is found to have a substantial effect on the scattering parameters. f-type intervalley scattering between Delta valleys is found to be comparable to other scattering channels. The n-type carrier mobility, calculated from the scattering rate using the Boltzmann transport equation in the relaxation time approximation, is in excellent agreement with experiments on bulk, unstrained alloys.     

Mn distribution and spin polarization in Ga(1-x)Mn x As

Using the density functional full-potential linearized augmented plane wave approach, the x-ray absorption and magnetic circular dichroism (XMCD) spectra of Ga(1-x)Mn x As are calculated. Significantly, XMCD of Mn is highly sensitive to the change in environment, and thus can be utilized to characterize impurity distribution. The nature of Mn-induced spin polarization on Ga and As sites, vital for the carrier mediated magnetic ordering, is discussed in light of computational and experimental results.     

Influence of Se atoms on the properties of amorphous Ge

Electron spin resonance (ESR), electrical and optical measurements have been made for Ge_1?xSe_x (0?x?0.35) films in order to elucidate relations between tetrahedrally bonded amorphous semiconductors and chalcogenide amorphous semiconductors. The ESR signal due to dangling bonds in amorphous Ge decreases by increasing Se content. For more than about 20 at. % Se, the electrical conductivity is the activation type and the optical gap increases with the increase of Se content. The model of charged dangling bonds by Street and Mott seems to explain the experimental results.     

77Se solid-state NMR investigations on As(x)Se(1-x) glasses using CPMG acquisition under MAS

⁷⁷Se (I=1/2) solid-state NMR is a very sensitive probe of the local structure of selenide glasses, which themselves are promising for optical applications. In this work, we show that although ⁷⁷Se has a low natural abundance (7.58%) and a wide spectral range, the sensitivity can be dramatically increased using Carr–Purcell–Meiboom–Gill (CPMG) trains of rotor-synchronized π pulses during the detection of ⁷⁷Se magnetization but may be affected by chemical shift anisotropy when the Magic Angle Spinning rate is not fast enough and by offset effects. The indirect dimension of the T₂^CPMG-resolved spectrum shows a strong influence of the J-couplings between naturally occurring ⁷⁷Se pairs. The resulting spectra show that the structural model known as “chains crossing model” is not entirely suitable to describe the glassy network of the Se-rich compositions.     

Microscopic coexistence of superconductivity and magnetism in Ba(1-x)K(x)Fe2As2

It is widely believed that, in contrast to its electron-doped counterparts, the hole-doped compound Ba(1-x)K(x)Fe(2)As(2) exhibits a mesoscopic phase separation of magnetism and superconductivity in the underdoped region of the phase diagram. Here, we report a combined high-resolution x-ray powder diffraction and volume-sensitive muon spin rotation study of Ba(1-x)K(x)Fe(2)As(2) showing that this paradigm does not hold true in the underdoped region of the phase diagram (0≤x≤0.25). Instead we find a microscopic coexistence of the two forms of order. A competition of magnetism and superconductivity is evident from a significant reduction of the magnetic moment and a concomitant decrease of the magnetoelastically coupled orthorhombic lattice distortion below the superconducting phase transition.     

Potassium doping effect on the lattice softening and electronic structure of Ba(1-x)K(x)Fe(2)As(2) probed by X-ray absorption spectroscopy

Ba(1-x)K(x)Fe(2)As(2) superconducting samples (x = 0, 0.2, 0.4, 0.5) were synthesized by the solid-state reaction method. In this contribution the doping effect of potassium on the lattice dynamics in this newly discovered Ba(1-x)K(x)Fe(2)As(2) superconductor has been investigated by extended X-ray absorption fine-structure spectroscopy. The analysis shows that with potassium doping an increased disorder in the iron layers is mainly related to the softening of the Fe-Fe bond. Information about the electronic structure of these materials has also been obtained by looking at the X-ray absorption near-edge structure spectra that point out the presence of holes in the Fe-3d/As-4p hybridized orbital of the BaFe(2)As(2)-based system.     

First-order transition from a Kondo insulator to a ferromagnetic metal in single crystalline FeSi(1-x)Ge(x)

The phase diagram of FeSi(1-x)Ge(x), obtained from magnetic, thermal, and transport measurements on single crystals, shows a discontinuous transition from Kondo insulator to ferromagnetic metal with x at a critical concentration, x(c) approximately 0.25. The gap of the insulating phase strongly decreases with x. The specific heat gamma coefficient appears to track the density of states of a Kondo insulator. The phase diagram is consistent with an insulator-metal transition induced by a reduction of the hybridization with x in conjunction with disorder on the Si/Ge ligand site.     

Ag–Ge–Se glasses: a vibrational spectroscopy study

Ag_x(Ge_0.25Se_0.75)_100−x glasses with x varying from 0 to 25 have been shown to exhibit a conductivity threshold around x ~8–10. In this work, the structural changes induced by introduction of Ag in Ge₂₅Se₇₅ glass have been investigated using Raman and infra‐red spectroscopies. In ambient conditions, changes are observed in position, width and intensity for vibrations assigned to Ge–Se bonds, showing that the tetrahedral network is relaxed and gains flexibility as Ag is introduced. High pressure experiments on two glasses containing 5 and 25 at.% Ag confirm that Ag‐rich (25%) glasses clearly exhibit higher compressibility than Ag‐poor (5%) glasses. Copyright © 2013 John Wiley & Sons, Ltd.     

The superconducting transition temperatures of Fe(1+x)Se(1-y), Fe(1+x)Se(1-y)Te(y) and (K/Rb/Cs)(z)Fe(2-x)Se2

In a recent contribution to this journal, it was shown that the transition temperatures of optimal high-T(C) compounds obey the algebraic relation T(C0) = k(-1)(B)/?ζ, where ? is related to the mean spacing between interacting charges in the layers, ζ is the distance between interacting electronic layers, β is a universal constant and k(B) is Boltzmann's constant. The equation was derived assuming pairing based on interlayer Coulomb interactions between physically separated charges. This theory was initially validated for 31 compounds from five different high-T(C) families (within an accuracy of ±1.37 K). Herein we report the addition of Fe(1+x)Se(1-y) and Fe(1+x)Se(1-y)Te(y) (both optimized under pressure) and A(z)Fe(2-x)Se(2) (for A = K, Rb or Cs) to the growing list of Coulomb-mediated superconducting compounds in which T(C0) is determined by the above equation. Doping in these materials is accomplished through the introduction of excess Fe and/or Se deficiency, or a combination of alkali metal and Fe vacancies. Consequently, a very small number of vacancies or interstitials can induce a superconducting state with a substantial transition temperature. The confirmation of the above equation for these Se-based Fe chalcogenides increases to six the number of superconducting families for which the transition temperature can be accurately predicted.     

Ge self-diffusion in epitaxial Si(1)-(x)Ge(x) layers

Diffusion coefficients and activation energies have been determined for Ge diffusion in strain-relaxed Si(1)-(x)Ge(x) with x = 0.00, 0.10, 0.20, 0.30, 0.40, and 0.50. The activation energy drops from 4.7 eV in Si and Si(0.90)Ge(0.10) to 3.2 eV at x = 0.50. This value compares with the literature value for Ge self-diffusion in Ge, suggesting Ge-like diffusion already at x approximately equal to 0.5. The effect of strain on the diffusion was also studied showing a decrease in diffusion coefficient and an increase in activation energy upon going from compressive over relaxed to tensile strain.     

GexSb20Se80-x玻璃的拉曼光谱和X射线光电子能谱

用拉曼散射光谱和X射线光电子能谱研究了Ge_xSb₂₀Se_80-x(x=5 mol%, 10 mol%, 15 mol%, 17.5 mol%, 20 mol%和25 mol%)玻璃的结构. 通过对拉曼光谱和X射线光电子能谱(Ge 3d, Sb 4d 和Se 3d谱)进行分解, 发现当硫系玻璃处于富Se状态下时, 玻璃结构中会出现Se–Se–Se结构单元, 其数量随着Ge含量的增加而迅速减少, 并最终在Ge₁₅Sb₂₀Se₆₅玻璃结构中消失; Ge和Sb原子分别以GeSe_4/2 四面体和SbSe_3/2三角锥结构单元在玻璃结构中出现, GeSe_4/2四面体结构单元的数量会随着Ge浓度的增加而增加, 而SbSe_3/2三角锥结构单元的数量基本保持稳定. 另一方面, 在缺Se的硫系玻璃中, 玻璃会有Ge–Ge和Sb–Sb同极键产生, 随着Ge含量的增大, 这种同极键的数量会越来越多; 而GeSe_4/2四面体和SbSe_3/2三角锥结构的数量则相应减少. 在所有玻璃样品的结构中均有同极键Se–Se的存在. 当玻璃组分越接近完全化学计量配比时, 异质键Ge–Se和Sb–Se将占据玻璃结构中的主导地位, 同极键Ge–Ge, Sb–Sb和Se–Se 的比例降为最小.     

Room temperature oxidation of Cu(3)Ge films grown on Si and Si(1-x)Ge(x) substrates

Room temperature oxidation of Cu3Ge films grown on Si, Si(0.85)Ge(0.15) and Si(0.52)Ge(0.48) substrates, respectively, at a temperature of 200-300 degrees C was studied using transmission electron microscopy (TEM) in conjunction with energy dispersive spectrometry (EDS) and scanning electron microscopy (SEM). For Cu(3)Ge films grown at 200 degrees C and subsequently exposed in air for 1 week oxide protrusions and oxide networks appeared in the film surface and grain boundaries of Cu(3)Ge, respectively. At room temperature O from air and Si from the substrate, diffused along the grain boundaries of Cu(3)Ge to react with Cu(3)Ge grains, initiating the Cu(3)Si-catalyzed oxidation. Cu(3)Ge films are superior to Cu(3)(Si(1-x)Gex) films in retarding Cu(3)Si-catalyzed oxidation. Annealing at 300 degrees C allowed Si diffusion from the substrate into the Cu(3)Ge overlayer to form Cu(3)(Si(1-x)Gex), enhancing the Cu(3)Si-catalyzed oxidation rate. In the present study, Cu(3)Ge films grown on Si(0.52)Ge(0.48) at 200 degrees C show the best resistance to room temperature oxidation because higher Ge concentration in the substrate and lower temperature annealing can more effectively retard Si diffusion from the substrate into the Cu(3)Ge overlayer, and hence reduce the Cu(3)Si-catalyzed oxidation rate.     

Single-Ion Kondo scaling of the coherent Fermi liquid regime in Ce(1-x)La(x)Ni2Ge2

Thermodynamic and transport properties of the La-diluted Kondo lattice CeNi(2)Ge(2) were studied in a wide temperature range. The Ce-rich alloys Ce(1-x)La(x)Ni(2)Ge(2) were found to exhibit distinct features of the coherent heavy Fermi liquid. At intermediate compositions (0.7≤x≤0.9), non-Fermi liquid properties have been observed, followed by the local Fermi liquid behavior in the dilute limit. The 4f-electron contribution to the specific heat was found to follow the predictions of the Kondo-impurity model in both the local as well as the coherent regimes, with the characteristic Kondo temperature decreasing rapidly from about 30 K for the parent compound CeNi(2)Ge(2) to about 1 K in the most dilute samples. The specific heat does not show any evidence for the emergence of a new characteristic energy scale related to the formation of the coherent Kondo lattice.