Structural, electronic properties and Fermi surface of ThCr2Si2-type tetragonal KFe2S2, KFe2Se2, and KFe2Te2 phases as parent systems of new ternary iron-chalcogenide superconductors
First principles FLAPW-GGA method was used for the comparative study of the structural and electronic properties of three related tetragonal ThCr2Si2-type phases KFe2Ch2, where Ch are S, Se, and Te. The main trends in electronic bands, densities of states and Fermi surfaces for AFe2Ch2 are analyzed in relation to their structural parameters. We found that at the anion replacements (S<->Se<->Te) any critical changes in electronic structure of KFe2Ch2 phases are absent. On the other hand, our analysis of structural and electronic parameters for hypothetical KFe2Te2 allows to assume that this system may be proposed as perspective parent phase for search of new iron-chalcogenide superconducting materials.
The 11-type Fe-chalcogenides belong to the family of Fe-based superconductors. In these compounds, the interstitial Fe is known to strongly influence the magnetic and superconducting properties. Here we present the chemical homogeneity range of ternary compounds Fe$_{1+y}$Te$_{1-x}$Se$_x$ based on powder x-ray diffraction, energy dispersive x-ray analysis and magnetization measurements. Our investigations show that the maximum amount of excess Fe in homogeneous Fe$_{1+y}$Te$_{1-x}$Se$_x$ decreases with increase in Se substitution for Te. Using our synthesis procedure, single-phase Fe$_{1+y}$Te…
Here we report the first observation of superconductivity in the AB2X4-type ternary telluride CuIr2Te4, which is synthesized by a solid-state method in an evacuated quartz jacket. It adopts a disordered trigonal structure with space group P3m1 (No. 164), which embodies a two-dimensional IrTe2 layers and intercalated by Cu between the layers. We use a combination of experimental and first principles calculation analysis to look insight into the structural and physical properties. CuIr2Te4 consistently exhibited a bulk superconductivity transition at 2.5 K in electrical resistivity, magnetic sus…
We predict a new class of three dimensional topological insulators in thallium-based III-V-VI$_2$ ternary chalcogenides, including TlBiQ$_2$ and TlSbQ$_2$ (Q = Te, Se and S). These topological insulators have robust and simple surface states consisting of a single Dirac cone at the $Γ$ point. The mechanism for topological insulating behavior is elucidated using both first principle calculations and effective field theory models. Remarkably, one topological insulator in this class, TlBiTe$_2$ is also a superconductor when doped with $p$-type carriers. We discuss the possibility that this materi…
Here we establish a combined electronic phase diagram of isoelectronic FeSe1-xSx (0.19 > x > 0.0) and FeSe1-yTey (0.04 < y < 1.0) single crystals. The FeSe1-yTey crystals with y = 0.04 - 0.30 are grown by a hydrothermal ion-deintercalation (HID) method. Based on combined experiments of the specific heat, electrical transport, and angle-resolved photoemission spectroscopy, no signature of the tetragonal-symmetry-broken transition to orthorhombic (nematic) phase is observed in the HID FeSe1-yTey samples, as compared with the FeSe1-xSx samples showing this transition at Ts. A ubiquitous dip-like …
Impurity scattering is found to lead to quasi-one dimensional nanoscale modulation of the local density of states in the iron pnictides and chalcogenides. This `quasiparticle interference' feature is remarkably similar across a wide variety of pnictide and chalcogenide phases, suggesting a common origin. We show that a unified understanding of the experiments can be obtained by simply invoking a four-fold symmetry breaking $d_{xz}-d_{yz}$ orbital splitting, of a magnitude already suggested by the experiments. This can explain the one-dimensional characteristics in the local density of states o…
Iron-chalcogenide superconductor Fe$_{1.03}$Se$_{0.5}$Te$_{0.5}$ has been investigated under high pressure using synchrotron based x-ray diffraction and mid-infrared reflectance measurements at room temperature. Pressure dependence of the superconducting transition temperature (T$_c$) of the same sample has been determined by temperature-dependent resistance measurements up to 10 GPa. Although the high pressure orthorhombic phase ($\textit{Pbnm}$) starts emerging at 4 GPa, structural transition becomes clearly observable above 10 GPa. A strong correlation is observed between the Fe(Se,Te)$_{4}…
We have used scanning micro x-ray diffraction to characterize different phases in superconducting K$_{x}$Fe$_{2-y}$Se$_2$ as a function of temperature, unveiling the thermal evolution across the superconducting transition temperature (T$_c\sim$32 K), phase separation temperature (T$_{ps}\sim$520 K) and iron-vacancy order temperature (T$_{vo}\sim$580 K). In addition to the iron-vacancy ordered tetragonal magnetic phase and orthorhombic metallic minority filamentary phase, we have found a clear evidence of the interface phase with tetragonal symmetry. The metallic phase is surrounded by this int…
We report density functional calculations of electronic structure and magnetic properties of ternary iron chalcogenide TlFe$_{2}$Se$_{2}$, which occurs in the ThCr$_{2}$Si$_{2}$ structure and discuss the results in relation to the iron-based superconductors. The ground state is antiferromagnetic with checkerboard order and Fe moment $\sim$ 1.90 $μ$B. There is strong magnetoelastic coupling similar to the Fe-based superconductors, reflected in a sensitivity of the Se position to magnetism. Tl is monovalent in this compound, providing heavy electron-doping of 0.5 additional carriers per Fe relat…
We have synthesized tetragonal iron selenide and telluride superconductors through solid state reaction at 450deg.C and 550deg.C respectively. These synthesis temperatures have been established by optimization. Electrical resistivity and magnetic susceptibility measurements (4.2-300 K) confirm superconductivity with Tc of around 8.5 K in all selenide samples of nominal composition Fe1+deltaSe (delta=0.02-0.22). However, Scanning Electron Microscopy/ Energy Dispersive Spectroscopy studies clearly indicate that the actual stoichiometric ratio of Fe : Se for all the samples synthesized is around …
This article reviews recent experimental investigations on two binary Fe-chalcogenides: FeSe and Fe$_{1+y}$Te. The main focus is on synthesis, single crystal growth, chemical composition, as well as on the effect of excess iron on structural, magnetic, and transport properties of these materials. The structurally simplest Fe-based superconductor Fe$_{1+x}$Se with a critical temperature $T_c \approx$ 8.5 K undergoes a tetragonal to orthorhombic phase transition at a temperature $T_s \approx$ 87 K. No long-range magnetic order is observed down to the lowest measured temperature in Fe$_{1+x}$Se. …
The ternary iron arsenide BaFe2As2 with the tetragonal ThCr2Si2-type structure exhibits a spin density wave (SDW) anomaly at 140 K, very similar to LaFeAsO, the parent compound of the iron arsenide superconductors. BaFe2As2 is a poor Pauli-paramagnetic metal and undergoes a structural and magnetic phase transition at 140 K, accompanied by strong anomalies in the specific heat, electrical resistance and magnetic susceptibility. In the course of this transition, the space group symmetry changes from tetragonal (I4/mmm) to orthorhombic (Fmmm). 57Fe Moessbauer spectroscopy experiments show a singl…
The structural and electronic properties of hypothetical Ru$_x$Fe$_{1-x}$Se and Ru$_x$Fe$_{1-x}$Te systems have been investigated from first principles within the density functional theory (DFT). Reasonable values of lattice parameters and chalcogen atomic positions in the tetragonal unit cell of iron chalcogenides have been obtained with the use of norm-conserving pseudopotentials. The well known discrepancies between experimental data and DFT-calculated results for structural parameters of iron chalcogenides are related to the semicore atomic states which were frozen in the used here approac…
Recently synthesized metastable tetragonal CoSe, isostructural to the FeSe superconductor, offers a new avenue for investigating systems in close proximity to the iron-based superconductors. We present magnetic and transport property measurements on powders and single crystals of CoSe. High field magnetic susceptibility measurements indicate a suppression of the previously reported 10 K ferromagnetic transition with the magnetic susceptibility exhibiting time-dependence below the proposed transition. Dynamic scaling analysis of the time-dependence yields a critical relaxation time of $τ^{*} = …
Here we report the synthesis and discovery of superconductivity in a novel ternary iridium-arsenide compound BaIr2As2. The polycrystalline BaIr2As2 sample was synthesized by a high temperature and high pressure method. Crystal structural analysis indicates that BaIr2As2 crystallizes in the ThCr2Si2-type layered tetragonal structure with space group I4/mmm (No. 139), and the lattice parameters were refined to be a = 4.052(9) Å and c = 12.787(8) Å. By the electrical resistivity and magnetic susceptibility measurements we found type-II superconductivity in the new BaIr2As2 compound with a Tc (cri…
We use inelastic neutron scattering to study the low energy spin excitations in moderately doped non-superconducting Fe$_{1.01}$Te$_{0.72}$Se$_{0.28}$. The spin excitations in this system contain components near (0.5,0,0) and (0.5,0.5,0) in a-b plane reciprocal lattice units using tetragonal unit cell notation (a=b=3.772 Åand c=6.061 Å). At low energies the scattering is centered around (0.5,0,0). With increasing energy, the spectral weight of low energy spin excitations centered around (0.5,0,0) abruptly shifts around 3 meV to the incommensurate spin excitations centered around (0.5,0.5,0). H…
Deviations of low-energy electronic structure of iron-based superconductors from density functional theory predictions have been parametrized in terms of band- and orbital-dependent mass renormalizations and energy shifts. The former have typically been described in terms of a local self-energy within the framework of dynamical mean field theory, while the latter appears to require non-local effects due to interband scattering. By calculating the renormalized bandstructure in both random phase approximation (RPA) and the two-particle self-consistent approximation (TPSC), we show that correlati…
We report a de Haas-van Alphen effect study of the Fermi surface of CaFe2P2 using low temperature torque magnetometry up to 45 T. This system is a close structural analogue of the collapsed tetragonal non-magnetic phase of CaFe2As2. We find the Fermi surface of CaFe2P2 to differ from other related ternary phosphides in that its topology is highly dispersive in the c-axis, being three-dimensional in character and with identical mass enhancement on both electron and hole pockets (~1.5). The dramatic change in topology of the Fermi surface suggests that in a state with reduced (c/a) ratio, when b…
The structural and magnetic phase transitions of the ternary iron arsenides SrFe2As2 and EuFe2As2 were studied by temperature-dependent x-ray powder diffraction and 57-Fe Moessbauer spectroscopy. Both compounds crystallize in the tetragonal ThCr2Si2-type structure at room temperature and exhibit displacive structural transitions at 203 K (SrFe2As2) or 190 K (EuFe2As2) to orthorhombic lattice symmetry in agreement with the group-subgroup relationship between I4/mmm and Fmmm. 57-Fe Moessbauer spectroscopy experiments with SrFe2 As2 show full hyperfine field splitting below the phase transition t…
In this paper, we address a number of outstanding issues concerning the nature and the role of magnetic inhomogenities in the iron chalcogenide system FeTe1-xSex and their correlation with superconductivity in this system. We report morphology of superconducting single crystals of FeTe0.65Se0.35 studied with transmission electron microscopy, high angle annular dark field scanning transmission electron microscopy and their magnetic and superconducting properties characterized with magnetization, specific heat and magnetic resonance spectroscopy. Our data demonstrate a presence of nanometre scal…
An SDW antiferromagnetic (SDW-AF) low temperature phase transition is generally observe and the AF spin fluctuations are considered to play an important role for the superconductivity paring mechanism in FeAs superconductors. However, a similar magnetic phase transition is not observed in FeSe superconductors, which has caused considerable discussion. We report on the intrinsic electronic states of FeSe as elucidated by transport measurements under magnetic fields using a high quality single crystal. A mobility spectrum analysis, an ab initio method that does not make assumptions on the transp…
It is well established that the occurrence of superconductivity in iron pnictides is closely related to the tetragonal to orthorhombic structural and antiferromagnetic (AFM) phase transitions. It, however, has not been clear whether the same scenario is appropriate for iron chalcogenide counterparts due to the absence of parent compounds for the latter family of superconductors. Here, we report the synthesis and structure determination of two novel phases in ethylenediamine intercalated FeSe, one is tetragonal and the other orthorhombic in room temperature, which can be stabilized with neutral…
A complete phase diagram and its corresponding physical properties are essential prerequisites to understand the underlying mechanism of iron based superconductivity. For the structurally simplest 11 (FeSeTe) system, earlier attempts using bulk samples have not been able to do so due to the fabrication difficulties. Here, thin FeSexTe1-x films with the Se content covering the full range were fabricated by using pulsed laser deposition method. Crystal structure analysis shows that all films retain the tetragonal structure in room temperature. Significantly, the highest superconducting transitio…
Neutron and x-ray total scattering measurements have been performed on powder samples of the iron chalcogenide superconductor FeSe. Using pair distribution function (PDF) analysis of the total scattering data to investigate short-range atomic correlations, we establish the existence of an instantaneous, local orthorhombic structural distortion attributable to nematic fluctuations that persists well into the high-temperature tetragonal phase, at least up to 300 K and likely to significantly higher temperatures. This short-range orthorhombic distortion is correlated over a length scale of about …
Superconducting iron chalcogenide FeSe has the simplest crystal structure among all the Fe-based superconductors. Unlike other iron pnictides, FeSe exhibits no long range magnetic order accompanying the tetragonal-to-orthorhombic structural distortion, which raises the fundamental question about the role of magnetism and its associated spin fluctuations in mediating both nematicity and superconductivity. The extreme sensitivity of FeSe to external pressure suggests that chemical pressure, induced by substitution of Se by the smaller ion S, could also a be good tuning parameter to further study…
Based on first-principles FLAPW-GGA calculation, we have investigated electronic structure of newly discovered oxygen-free 38K superconductor Ba1-xKxFe2As2 in comparison with parent phase - tetragonal ternary iron arsenide BaFe2As2. The density of states, magnetic properties, near-Fermi bands compositions, together with Sommerfeld coefficients and molar Pauli paramagnetic susceptibility are evaluated. The results allow us to classify these systems as quasi-two-dimensional ionic metals, where the conduction is strongly anisotropic, only happening on the (Fe-As) layers. According to our calculat…
We investigated the evolution of the temperature-composition phase diagram of Fe$_{1+y}$Te upon Se substitution. In particular, the effect of Se substitution on the two-step, coupled magneto-structural transition in Fe$_{1+y}$Te single crystals is investigated. To this end, the nominal Fe excess was kept at $y$ = 0.12. For low Se concentrations, the two magneto-structural transitions displayed a tendency to merge. In spite of the high Fe-content, superconductivity emerges for Se concentrations, $x \geq$ 0.1. We present a temperature-composition phase diagram to demonstrate the interplay of str…
Among iron chalcogenide superconductors, FeS can be viewed as a simple, highly compressed relative of FeSe without nematic phase and with weaker electronic correlations. Under pressure, however, the superconductivity of stoichiometric FeS disappears and reappears, forming two domes. We perform electronic structure and spin fluctuation theory calculations for tetragonal FeS in order to analyze the nature of the superconducting order parameter. In the random phase approximation we find a gap function with d-wave symmetry at ambient pressure, in agreement with several reports of a nodal supercond…
In several families of iron-based superconducting materials, a d-wave pairing instability may compete with the leading s-wave instability. Here we show that when both states have comparable free energies, superconducting and nematic degrees of freedom are strongly coupled. While nematic order causes a sharp non-analytic increase in $T_{c}$, nematic fluctuations can change the character of the s-wave to d-wave transition, favoring an intermediate state that does not break time-reversal symmetry but does break tetragonal symmetry. The coupling between superconductivity and nematicity is also man…
The interest in Fe-chalcogenide unconventional superconductors is intense after the critical temperature of FeSe was reported enhanced by more than one order of magnitude in the monolayer limit at the interface to an insulating oxide substrate. In heterostructures comprising interfaces of FeSe with topological insulators, additional interesting physical phenomena is predicted to arise e.g. in form of {\it topological superconductivity}. So far superconductive properties of Fe-chalcogenide monolayers were mostly studied by local scanning tunneling spectroscopy experiments, which can detect pseu…
In iron-based superconductors, high critical temperature (Tc) superconductivity over 50 K has only been accomplished in electron-doped hREFeAsO (hRE = heavy rare earth (RE) element). While hREFeAsO has the highest bulk Tc (58 K), progress in understanding its physical properties has been relatively slow due to difficulties in achieving high concentration electron-doping and carrying out neutron-experiments. Here, we present a systematic neutron powder diffraction (NPD) study of 154SmFeAsO1-xDx, and the discovery of a new long-range antiferromagnetic ordering with x >= 0.56 (AFM2) accompanying …
In the iron pnictides and chalcogenides, multiple orbitals participate in the superconducting state, enabling different gap structures to be realized in distinct materials. Here we argue that the spectral weights of these orbitals can in principle be controlled by a tetragonal symmetry-breaking uniaxial strain, due to the enhanced nematic susceptibility of many iron-based superconductors. By investigating multi-orbital microscopic models in the presence of orbital order, we show that not only $T_{c}$ can be enhanced, but pairs of accidental gap nodes can be annihilated and created in the Fermi…
Iron-based chalcogenides are complex superconducting systems in which orbitally-dependent electronic correlations play an important role. Here, using high-resolution angle-resolved photoemission spectroscopy, we investigate the effect of these electronic correlations outside the nematic phase in the tetragonal phase of superconducting FeSe1-xSx (x = 0; 0:18; 1). With increasing sulfur substitution, the Fermi velocities increase significantly and the band renormalizations are suppressed towards a factor of 1.5-2 for FeS. Furthermore, the chemical pressure leads to an increase in the size of the…
In the present paper, DFT (Density Functional Theory) based first-principles methods are applied to investigate the mechanical and bonding properties of newly synthesized T2 phase superconductor Ta5GeB2 for the first time. The calculated lattice constants are in reasonable agreement with the experiment. The elastic constants (Cij), bulk modulus (B), shear modulus (G), Young's modulus (Y), Poisson ratio (nu), Pugh ratio (G/B), and elastic anisotropy factor, A, of Ta5GeB2 are calculated to explore the mechanical behavior of the compound.To give an explanation of the bonding nature of this new te…
Iron-chalcogenide single crystals with the nominal composition FeSe$_{0.5}$Te$_{0.5}$ and a transition temperature of $T_{c}\simeq14.6$ K were synthesized by the Bridgman method. The structural and anisotropic superconducting properties of those crystals were investigated by means of single crystal X-ray and neutron powder diffraction, SQUID and torque magnetometry, and muon-spin rotation. Room temperature neutron powder diffraction reveals that 95% of the crystal volume is of the same tetragonal structure as PbO. The structure refinement yields a stoichiometry of Fe_1.045Se_0.406Te_0.594. Add…
Since the discovery of superconductivity in LaFePO in 2006, numerous iron-based superconductors have been identified within diverse structure families, all of which combine iron with a group-V (pnictogen) or group-VI (chalco- gen) element. Unconventional superconductivity is extremely rare among transition metal compounds outside these layered iron systems and the cuprates, and it is almost universally associated with highly anisotropic electronic properties and nearly 2D Fermi surface geometries. The iron-based intermetallic YFe$_2$Ge$_2$ features a 3D Fermi surface and a strongly enhanced lo…
We report synthesis of non superconducting parent compound of iron chalcogenide, i.e., FeTe single crystal by self flux method. The FeTe single crystal is crystallized in tetragonal structure with the P4/nmm space group. The detailed SEM (scanning electron microscopy) results showed that the crystals are formed in slab like morphology and are near (slight deficiency of Te) stoichiometric with homogenous distribution of Fe and Te. The coupled structural and magnetic phase transition is seen at around 70K in both electrical resistivity and magnetization measurements, which is hysteric (deltaT = …
We study the crystalline and electronic properties of the $\textrm{Fe}_{1-x}\textrm{Co}_x\textrm{Se}$ system ($x=0$, 0.25, 0.5, 0.75, and 1.0) using X-ray diffraction, X-ray spectroscopy and density functional theory. We show that the introduction of Co $3d$ states in FeSe relaxes the bond strengths and induces a structural transition from tetragonal to hexagonal whose crossover takes place at $x\approx0.38$. This structural transition in turn modifies the magnetic order which can be related to the spin state. Using resonant inelastic X-ray spectroscopy we estimate the spin state of the system…
The crystal and magnetic structures of the superconducting iron based chalcogenides RbyFe2-xSe2 have been studied by means of single crystal synchrotron x-ray and high resolution neutron powder diffraction in the temperature range 2-570 K. The ground state of the crystal is an intrinsically phase separated state with two distinct by symmetry phases. The main phase has the iron vacancy ordered \surd5x\surd5 superstructure (I4/m space group) with AFM ordered Fe spins. The minority phase does not have \surd5x\surd5-type of ordering and has smaller in plane lattice constant a and larger tetragonal…
Structure and composition of iron chalcogenides have a delicate relationship with magnetism and superconductivity. In this report we investigate the iron sulfide layered tetragonal phase (t-FeS), and compare with three-dimensional hexagonal phase (h-FeS). X-ray diffraction reveals the absence of structural transitions for both t- and h-FeS below room temperature, and gives phase compositions of Fe0.93(1)S and Fe0.84(1)S, respectively, for the samples studied here. The a lattice parameter of bigger than 3.68 A is significant for causing bulk superconductivity in iron sulfide, which is controlle…
This paper explains the multi-orbital band structures and itinerant magnetism of the iron-pnictide and chalcogenides. We first describe the generic band structure of an isolated FeAs layer. Use of its Abelian glide-mirror group allows us to reduce the primitive cell to one FeAs unit. From density-functional theory, we generate the set of eight Fe $d$ and As $p$ localized Wannier functions for LaOFeAs and their tight-binding (TB) Hamiltonian, $h(k)$. We discuss the topology of the bands, i.e. allowed and avoided crossings, the origin of the d6 pseudogap, as well as the role of the As $p$ orbita…
A time-resolved synchrotron X-ray total scattering study sheds light on the evolution of the different structural length scales involved during the intercalation of the layered iron-selenide host by organic molecular donors, aiming at the formation of the expanded lattice $Li_x(C_5H_5N)_yFe_{2-z}Se_2$ hybrid superconductor. The intercalates are found to crystallize in the tetragonal $ThCr_2Si_2$-type structure at the average level, however, with an enhanced interlayer iron-selenide spacing (d= 16.2 Å) that accommodates the heterocyclic molecular spacers. Quantitative atomic pair distribution f…
