High-pressure studies on Tc and crystal structure of iron chalcogenide superconductors

Abstract

The superconducting transition temperature, T_c, in iron-based solids can be enhanced by applied pressure: T_c increases from 8 to 37 K for the 11-type FeSe when the pressure is raised from 0 to 4 GPa. High-pressure studies can elucidate the mechanism of superconductivity in such novel materials. In this paper, we present a high-pressure study of Fe(Se_1?xTe_x) and Fe(Se_1?xS_x). In the case of Fe(Se_1?xTe_x), the maximum T_c under high pressure did not exceed the T_c of FeSe, which can be attributed to the structural transition to the monoclinic phase. For Fe(Se_1?xS_x) (0 < x < 0.3), T_c exhibited a significant increase with pressure; however, the maximum T_c under high pressure did not exceed the T_c of FeSe. This may be due to the disorder induced by substituting S for Se, which is similar to the pressure effect on T_c for the 1111-type superconductor Ca(Fe_1?xCo_x)AsF. The T_c of Fe(Se_1?xS_x) showed a complex behavior below 1 GPa, first decreasing and then increasing with increasing pressure. From high-pressure x-ray diffraction measurements, the T_c (P) curve was correlated with the local structural parameter.     

Te concentration dependent photoemission and inverse-photoemission study of FeSe1?xTex

We have characterized the electronic structure of FeSe_1−xTe_x for various x values using soft x-ray photoemission spectroscopy (SXPES), high-resolution photoemission spectroscopy (HRPES) and inverse photoemission spectroscopy (IPES). The SXPES valence band spectral shape shows that the 2 eV feature in FeSe, which was ascribed to the lower Hubbard band in previous theoretical studies, becomes less prominent with increasing x. HRPES exhibits systematic x dependence of the structure near the Fermi level (E_F): its splitting near E_F and filling of the pseudogap in FeSe. IPES shows two features, near E_F and approximately 6 eV above E_F; the former may be related to the Fe 3d states hybridized with chalcogenide p states, while the latter may consist of plane-wave-like and Se d components. In the incident electron energy dependence of IPES, the density of states near E_F for FeSe and FeTe has the Fano lineshape characteristic of resonant behavior. These compounds exhibit different resonance profiles, which may reflect the differences in their electronic structures. By combining the PES and IPES data the on-site Coulomb energy was estimated at 3.5 eV for FeSe.     

Magnetic excitations in iron chalcogenide superconductors

Nuclear magnetic resonance and neutron scattering experiments in iron chalcogenide superconductors are reviewed to make a survey of the magnetic excitations in FeSe, FeSe_1−xTe_x and alkali-metal-doped A_xFe_2−ySe₂ (A = K, Rb, Cs, etc). In FeSe, the intimate relationship between the spin fluctuations and superconductivity can be seen universally for the variations in the off-stoichiometry, the Co-substitution and applied pressure. The isovalent compound FeTe has a magnetic ordering with different wave vector from that of other Fe-based magnetic materials. The transition temperature T_c of FeSe increases with Te substitution in FeSe_1−xTe_x with small x, and decreases in the vicinity of the end member FeTe. The spin fluctuations are drastically modified by the Te substitution. In the vicinity of the end member FeTe, the low-energy part of the spin fluctuation is dominated by the wave vector of the ordered phase of FeTe; however, the reduction of T_c shows that it does not support superconductivity. The presence of same wave vector as that of other Fe-based superconductors in FeSe_1−xTe_x and the observation of the resonance mode demonstrate that FeSe_1−xTe_x belongs to the same group as most of other Fe-based superconductors in the entire range of x, where superconductivity is mediated by the spin fluctuations whose wave vector is the same as the nesting vector between the hole pockets and the electron pockets. On the other hand, the spin fluctuations differ for alkali-metal-doped A_xFe_2−ySe₂ and FeSe or other Fe-based superconductors in their wave vector and strength in the low-energy part, most likely because of the different Fermi surfaces. The resonance mode with different wave vector suggests that A_xFe_2−ySe₂ has an exceptional superconducting symmetry among Fe-based superconductors.     

Influence of Se on the electron mobility in thermal evaporated Bi2(Te1−xSex)3 thin films

Thermoelectric solid solutions of Bi₂ (Te_1−xSe_x)₃ with x = 0, 0.2, 0.4, 0.6, 0.8 and 1 were grown using the Bridgman technique. Thin films of these materials of different compositions were prepared by conventional thermal evaporation of the prepared bulk materials. The temperature dependence of the electrical conductivity σ, free carriers concentration n, mobility μ_H, and seebeck coefficient S, of the as-deposited and films annealed at different temperatures, have been studied at temperature ranging from 300 to 500 K. The temperature dependence of σ revealed an intrinsic conduction mechanism above 400 K, while for temperatures less than 400 K an extrinsic conduction is dominant.The activation energy, ΔE, and the energy gap, E_g, were found to increase with increasing Se content. The variation of S with temperature revealed that the samples with different compositions x are degenerate semiconductors with n-type conduction. Both, the annealing and composition effects on Hall constant, R_H, density of electron carriers, n, Hall mobility, μ_H, and the effective mass, m^∗/m₀ are studied in the above temperature range.     

Luminescence properties of Sn2P2Se6 crystals

A large family of Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) semiconductor-ferroelectric crystals were obtained by the Bridgman technique. The photoluminescence properties of the Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) family crystals strongly depend on their chemical composition, excitation energy and temperature. The influence of the Pb → Sn and S → Se isovalent substitutions on the luminescence properties of a crystal with the Sn₂P₂Se₆ basic composition was investigated. A broad emission band observed in the Sn₂P₂Se₆ crystal with a maximum roughly at 600 nm (at T = 8.6 K) was assigned to a band-to-band electron-hole recombination, whereas broad emission bands, peaked near 785 nm (at T = 8.6 K) and 1025 nm (at T = 44 K) were assigned to an electron-hole recombination from defect levels localised within the bandgap. Possible types of recombination defect centres and specific mechanisms of luminescence in the Sn₂P₂Se₆ semiconductor-ferroelectric crystals were considered and discussed on the basis of the obtained results and the referenced data.     

High-Pressure Studies on Superconductivity in LaFeAsO1−x F x and SmFeAsO1−x F x

The pressure dependence on the superconducting transition temperature (T _c ) was investigated for the iron-based superconductors LaFeAsO_1−x F _x and SmFeAsO_1−x F _x . The T _c ’s increase largely for LaFeAsO_1−x F _x with a small increase of pressure, while a sharp decrease of T _c was observed for SmFeAsO_1−x F _x . The electrical resistivity measurements reveal pressure-induced superconductivity for undoped LaFeAsO and SmFeAsO. These pressure effects seem to be related to an anisotropic decrease of the lattice constants under high pressure from the x-ray diffraction measurements up to 10 GPa for the LaFeAsO_1−x F _x system.     

XPS study of CZTSSe monograin powders

The surface and bulk composition of Cu₂ZnSn(Se_xS_1-x)₄ (CZTSSe) monograin powders were investigated by X-ray photoelectron spectroscopy (XPS). The concentration depth profiling of CZTSSe monograin powders was obtained by Ar⁺ ion etching.According to the XPS spectra of CZTSSe monograin powder, the binding energies of Zn 2p_3/2, Cu 2p_3/2, Sn 3d_5/2, S 2p_3/2 and Se 3d_5/2 core levels after surface cleaning are located at 1021.6 eV, 932.4 eV, 486.1 eV, 161.5 eV, 53.9 eV, respectively. From XPS depth profile analysis, Cu deficiency and the excess of chalcogenides on the powder crystals surface were observed.     

Structural Studies of the Superconducting La2.5Y0.5CaBa3(Cu1?xFex)7Oz (0 ≤ x ≤ 0.1) Perovskite System by Neutron Diffraction

We have investigated the effect of Fe substitution on the structural and superconducting properties of La_2.5Y_0.5CaBa₃(Cu_1–x Fe _x )₇O _z system by Rietveld refinement of the neutron diffraction patterns of three samples with x = 0.02 (labelled B₁), x = 0.06 (B₂), and x = 0.10 (B₃) along with X-ray diffraction, resistivity, AC susceptibility, and oxygen-content measurements. Samples B₁, B₂, and B₃ are superconducting with T _c ^R=0 values of 73, 62, and 41 K, respectively. Neutron diffraction studies confirm (i) the formation of a single phase tetragonal structure (space group P4/mmm) for all three samples, (ii) Ca and Y ions substitution at the La site concomitantly displaces La onto Ba sites, and (iii) increasing x from 0.02 to 0.10 increases oxygen content (the amount of oxygen per unit cell), as well as Cu(1)— O(4) and Cu(1)— O(1) bond lengths whereas Cu(2)— O(4) bond length decreases with corresponding decrease in T _c to 41 K due to increasing occupancy of Fe ions at Cu(2) site. The change in bond lengths with oxygen content are essentially the same as those of Fe content (x). Present studies establish a correlation between the bond lengths (Cu(1)— O(1), Cu(1)— O(4), and Cu(2)— O(4)) and the measured T _c values of three samples.     

Study of electrical properties of CIGS thin films prepared by multistage processes

In this work, the dispersion mechanisms affecting the electric transport in CuIn_1−xGa_xSe₂ (CIGS) thin films grown by a chemical reaction of the precursor species, which are evaporated sequentially in two and three-stage processes are analyzed. It was found, through conductivity and Hall coefficient measurements carried out as functions of temperature, that the electrical conductivity of the CuIn_1−xGa_xSe₂ films is affected by the transport of free carriers in extended states of the conduction band as well as for variable range hopping transport mechanisms, each one predominating in a different temperature range.     

Nanoscale structure and atomic disorder in the iron-based chalcogenides

The multiband iron-based superconductors have layered structure with a phase diagram characterized by a complex interplay of charge, spin and lattice excitations, with nanoscale atomic structure playing a key role in their fundamental electronic properties. In this paper, we briefly review nanoscale structure and atomic disorder in iron-based chalcogenide superconductors. We focus on the Fe(Se,S)_1−xTe_x (11-type) and K_0.8Fe_1.6Se₂ (122-type) systems, discussing their local structure obtained by extended x-ray absorption fine structure. Local structure studies on the Fe(Se,S)_1−xTe_x system reveal clear nanoscale phase separation characterized by coexisting components of different atomic configurations, similar to the case of random alloys. In fact, the Fe–Se/S and Fe–Te distances in the ternary Fe(Se,S)_1−xTe_x are found to be closer to the respective distances in the binary FeSe/FeS and FeTe systems, showing significant divergence of the local structure from the average one. The observed features are characteristic of ternary random alloys, indicating breaking of the local symmetry in these materials. On the other hand, K_0.8Fe_1.6Se₂ is known for phase separation in an iron-vacancy ordered phase and an in-plane compressed lattice phase. The local structure of these 122-type chalcogenides shows that this system is characterized by a large local disorder. Indeed, the experiments suggest a nanoscale glassy phase in K_0.8Fe_1.6Se₂, with the superconductivity being similar to the granular materials. While the 11-type structure has no spacer layer, the 122-type structure contains intercalated atoms unlike the 1111-type REFeAsO (RE = rare earth) oxypnictides, having well-defined REO spacer layers. It is clear that the interlayer atomic correlations in these iron-based superconducting structures play an important role in structural stability as well as superconductivity and magnetism.     

Superconductivity of Ba1 ? xKxBiO3 (0.35 < x < 1) Synthesized by the High Pressure and High Temperature Technique

Ba_{1 – x} K _x BiO₃ (BKBO) samples with 0.35 < x < 1 were synthesized by the high pressure and high temperature technique. XRD analysis showed that the BKBO samples were single phase for the whole range of the potassium doping concentration. The change of superconducting transition temperature, T _c, as well as lattice parameters have been investigated upon doping concentration. As the K doping concentration (x) increases from x = 0.37, T _c decreases from 30.4 K to almost zero at x = 0.74. However, in some BKBO samples without including any barium in the starting composition (x = 1), which is denoted as KBO samples, superconductivity is observed with T _c as high as 9 K with partial substitutions of Bi at the K site. Depending on the synthesis condition of the KBO samples, T _c and lattice parameters were different from sample to sample. Compared with other superconducting bismuthates, the evolution of T _c by potassium doping in the cubic BKBO system is discussed in terms of its electronic band structure.     

Crystal growth and structural analysis of zirconium sulphoselenide single crystals

A series of zirconium sulphoselenide (ZrS _x Se_3−x , where x = 0, 0·5, 1, 1·5, 2, 2·5, 3) single crystals have been grown by chemical vapour transport technique using iodine as a transporting agent. The optimum condition for the growth of these crystals is given. The stoichiometry of the grown crystals were confirmed on the basis of energy dispersive analysis by X-ray (EDAX) and the structural characterization was accomplished by X-ray diffraction (XRD) studies. The crystals are found to possess monoclinic structure. The lattice parameters, volume, particle size and X-ray density have been carried out for these crystals. The effect of sulphur proportion on the lattice parameter, unit cell volume and X-ray density in the series of ZrS _x Se_3−x single crystals have been studied and found to decrease in all these parameters with rise in sulphur proportion. The grown crystals were examined under optical zoom microscope for their surface topography study. Hall effect measurements were carried out on grown crystals at room temperature. The negative value of Hall coefficient implies that these crystals are n-type in nature. The conductivity is found to decrease with increase of sulphur content in the ZrS _x Se_3−x series. The electrical resistivity parallel to c-axis as well as perpendicular to c-axis have been carried out in the temperature range 303–423 K. The results obtained are discussed in detail.     

Structure and cation distribution in perovskites with small cations at the A site: the case of ScCoO3

We synthesize ScCoO₃ perovskite and its solid solutions, ScCo_1−xFe_xO₃ and ScCo_1−xCr_xO₃, under high pressure (6 GPa) and high temperature (1570 K) conditions. We find noticeable shifts from the stoichiometric compositions, expressed as (Sc_1−xM_x)MO₃ with x = 0.05–0.11 and M = Co, (Co, Fe) and (Co, Cr). The crystal structure of (Sc_0.95Co_0.05)CoO₃ is refined using synchrotron x-ray powder diffraction data: space group Pnma (No. 62), Z = 4 and lattice parameters a = 5.26766(1) Å, b = 7.14027(2) Å and c = 4.92231(1) Å. (Sc_0.95Co_0.05)CoO₃ crystallizes in the GdFeO₃-type structure similar to other members of the perovskite cobaltite family, ACoO₃ (A³⁺ = Y and Pr-Lu). There is evidence that (Sc_0.95Co_0.05)CoO₃ has non-magnetic low-spin Co³⁺ ions at the B site and paramagnetic high-spin Co³⁺ ions at the A site. In the iron-doped samples (Sc_1−xM_x)MO₃ with M = (Co, Fe), Fe³⁺ ions have a strong preference to occupy the A site of such perovskites at small doping levels.     

Microstructures and thermoelectric properties of p-type pseudo-binary AgxBi0.5Sb1.5−xTe3 (x = 0.05–0.4) alloys prepared by cold pressing

The p-type pseudo-binary Ag_xBi_0.5Sb_1.5−xTe₃ (x = 0.05–0.4) alloys were prepared by cold pressing. The thermal conductivities (κ) were calculated from the values of heat capacities, densities and thermal diffusivities measured, and range approximately from 0.66 to 0.56 (W K^− 1 m^− 1) for the Ag_xBi_0.5Sb_1.5−xTe₃ alloy with molar fraction x being 0.4. Combining with the electrical properties obtained in the previous study, the maximum dimensionless figure of merit ZT of 1.1 was obtained at the temperature of 558 K.     

Influence of transition metals substitution on the superconductor Bi4Ca3Sr3Cu4O y

The results of our investigation on the specimens Bi₄Ca₃Sr₃Cu_4−x T _xO _y (T=Fe, Co, Ni,x⩽0.5) synthesized in air are presented. Fe and Co substituents result in the formation of Bi₂Sr₂CuO _y -type of phase, with considerable depression ofT _c of the main phase. However, Ni is completely soluble with Cu in this concentration range without significant depression of superconducting transition temperature (T _c). This difference in the solubility behaviour of Fe and Co on the one hand and Ni on the other is explained taking into account ionic charge and coordination number mismatches.     

Preparation and characterization of CuIn1 − xGaxSe2 − ySy thin film solar cells by rapid thermal processing

This paper describes the synthesis and characterization of CuIn_1 − xGa_xSe_2 − yS_y (CIGSeS) thin-film solar cells prepared by rapid thermal processing (RTP). An efficiency of 12.78% has been achieved on ~ 2 µm thick absorber. Materials characterization of these films was done by SEM, EDS, XRD, and AES. J-V curves were obtained at different temperatures. It was found that the open circuit voltage increases as temperature decreases while the short circuit current stays constant. Dependence of the open circuit voltage and fill factor on temperature has been estimated. Bandgap value calculated from the intercept of the linear extrapolation was 1.1-1.2 eV. Capacitance-voltage analysis gave a carrier density of 4.0 × 10¹⁵ cm^− 3.     

Instantaneous preparation of CuIn(S1 − x, Sex)2 films by means of sparks using microwave irradiation

CuIn(S_1 − x,Se_x)₂ (CISSe) films aimed at flexible solar cells were directly prepared on Ti foils from elemental In, Cu, S, and Se particle precursor using microwave irradiation. The formation of the CISSe phase was deduced from X-ray diffraction (XRD) patterns. The (112) peaks of CISSe were well defined and the lattice constants increased in direct proportion to the S/(S + Se) ratio almost satisfying Vegard's law. In particular, CuInSe₂ was formed in the desired chalcopyrite lattice as indicated by the presence of (101), (103) and (211) peaks in the XRD pattern. Porous surfaces and formation of by-products were avoided by employing an evaporated In and Cu films instead of In and Cu particles.     

Te concentration dependent photoemission and inverse-photoemission study of FeSe1−xTex

Abstract

We have characterized the electronic structure of FeSe_1?xTe_x for various x values using soft x-ray photoemission spectroscopy (SXPES), high-resolution photoemission spectroscopy (HRPES) and inverse photoemission spectroscopy (IPES). The SXPES valence band spectral shape shows that the 2 eV feature in FeSe, which was ascribed to the lower Hubbard band in previous theoretical studies, becomes less prominent with increasing x. HRPES exhibits systematic x dependence of the structure near the Fermi level (E_F): its splitting near E_F and filling of the pseudogap in FeSe. IPES shows two features, near E_F and approximately 6 eV above E_F; the former may be related to the Fe 3d states hybridized with chalcogenide p states, while the latter may consist of plane-wave-like and Se d components. In the incident electron energy dependence of IPES, the density of states near E_F for FeSe and FeTe has the Fano lineshape characteristic of resonant behavior. These compounds exhibit different resonance profiles, which may reflect the differences in their electronic structures. By combining the PES and IPES data the on-site Coulomb energy was estimated at 3.5 eV for FeSe.     

Tuning the optical properties of alloyed CdSexS1 − x nanoparticles by changing the constituent stoichiometry

The spherical particles CdSe_xS_1 − x with 30-80 nm in radius have been successfully prepared by the hydrothermal reaction at 200 °C. The structure characterization which has been carried out using X-ray diffraction (XRD) shows hexagonal crystal structure. Novel properties have been observed via UV-visual absorption spectra and photoluminescence (PL) spectra. The absorption shoulder and the luminescence emission peaks have been tuned by changing the mole ratio of Se in the CdSe_xS_1 − x samples.     

CIGS thin-film solar cells on steel substrates

Steel foil is an attractive candidate for use as a flexible substrate material for Cu(In_x,Ga_1 − x)Se₂ solar cells (CIGS). It is stable at the high temperatures involved during CIGS processing and is also commercially available. Stainless chromium (Cr) steel is more expensive than Cr-free steel sheets, but the latter are not stable against corrosion. We processed CIGS solar cells on both types of substrates. The main problem arising here is the diffusion of detrimental elements from the substrate into the CIGS absorber layer. The diffusion of iron (Fe) and other substrate elements into the CIGS layer was investigated by Secondary Ion Mass Spectrometry (SIMS). The influence of the impurities on the solar cell parameters was determined by current voltage (JV) and external quantum efficiency (EQE) measurements. A direct correlation between the Fe content in the CIGS layer and the solar cell efficiency was found. The diffusion of Fe could be strongly reduced by a diffusion barrier layer. Thus we could process CIGS solar cells with a conversion efficiency of 12.8% even on Cr-free steel substrate.