A new layered iron-oxychalcogenide Na2Fe2OSe2 has been synthesized and structurally characterized by powder X-ray diffraction. The structure is formed by alternate stacking of the newly discovered [Fe2OSe2] blocks and double layers of Na. Conductivity study shows that Na2Fe2OSe2 is a semiconductor with activation energy of 0.26 eV. Magnetic susceptibility and heat capacity measurements reveal an antiferromagnetic phase transition occurs at TN=73 K. A broad maximum of magnetic susceptibility and a slow decay of the specific heat above TN, arises as a result of two-dimensional short-range spin correlation.
The ability to tune the iron chalcogenides BaFe2Q3 from Mott insulators, to metals and then superconductors with applied pressure has renewed interest in low-dimensional iron chalcogenides and oxychalcogenides. We report here a combined experimental and theoretical study on the iron oxychalcogenides BaFe2Q2O (Q=S, Se) and show that their magnetic behaviour results from nearest-neighbour magnetic exchange interactions via oxide and selenide anions of similar strength, with properties consistent with more localised electronic structures than those of BaFe2Q3 systems.
Using a combination of th local-density approximtion (LDA) and dynamicla mean-field theory (DMFT) calculations, we explore the correlated electronic structure of a member of the layered Iron oxychalcogenide Na_{2}Fe_{2}OSe_{2}. We find that the parent compund is a multi-orbital Mott insulator. Surprisingly, and somewhat reminiscent of the doped high-T_{c} cuprates, carrier localization is found to persist upon weak hole doping because the chemical potential lies in a gap structure wit almost vanishing density-of-states (DOS). On the other hand, in remarkable contrast, electron doping drives an…
An insulating ferromagnetic (FM) phase exists in the quasi-one-dimensional iron chalcogenide Ce$_2$O$_2$FeSe$_2$ but its origin is unknown. To understand the FM mechanism, here a systematic investigation of this material is provided, analyzing the competition between ferromagnetic and antiferromagnetic tendencies and the interplay of hoppings, Coulomb interactions, Hund's coupling, and crystal-field splittings. Our intuitive analysis based on second-order perturbation theory shows that large entanglements between doubly-occupied and half-filled orbitals play a key role in stabilizing the FM or…
We present the results of structural and magnetic phase comparisons of the iron oxychalcogenides La$_{2}$O$_{2}$Fe$_{2}$O$M$$_{2}$ ($M$ = S, Se). Elastic neutron scattering reveals that $M$ = S and Se have similar nuclear structures at room and low temperatures. We find that both materials obtain antiferromagnetic ordering at a Neel temperature $T_{N}$ 90.1 $\pm$ 0.16 K and 107.2 $\pm$ 0.06 K for $M$= Se and S, respectively. The magnetic arrangements of $M$ = S, Se are obtained through Rietveld refinement. We find the order parameter exponent $β$ to be 0.129 $\pm$ 0.006 for $M$ = Se and 0.133 …
We perform a combined experimental-theoretical study of the Fe-oxychalcogenides (FeO$\emph{Ch}$) series La$_{2}$O$_{2}$Fe$_{2}$O\emph{M}$_{2}$ (\emph{M}=S, Se), which is the latest among the Fe-based materials with the potential \ to show unconventional high-T$_{c}$ superconductivity (HTSC). A combination of incoherent Hubbard features in X-ray absorption (XAS) and resonant inelastic X-ray scattering (RIXS) spectra, as well as resitivity data, reveal that the parent FeO$\emph{Ch}$ are correlation-driven insulators. To uncover microscopics underlying these findings, we perform local density app…
Nematic fluctuations occur in a wide range of physical systems from liquid crystals to biological molecules to solids such as exotic magnets, cuprates and iron-based high-$T_c$ superconductors. Nematic fluctuations are thought to be closely linked to the formation of Cooper-pairs in iron-based superconductors. It is unclear whether the anisotropy inherent in this nematicity arises from electronic spin or orbital degrees of freedom. We have studied the iron-based Mott insulators La$_{2}$O$_{2}$Fe$_{2}$O$M$$_{2}$ $M$ = (S, Se) which are structurally similar to the iron pnictide superconductors. …
Bad metal properties have motivated a description of the parent iron pnictides as correlated metals on the verge of Mott localization. What has been unclear is whether interactions can push these and related compounds to the Mott insulating side of the phase diagram. Here we consider the iron oxychalcogenides La2O2Fe2O(Se,S)2, which contain an Fe square lattice with an expanded unit cell. We show theoretically that they contain enhanced correlation effects through band narrowing compared to LaOFeAs, and we provide experimental evidence that they are Mott insulators with moderate charge gaps. W…
The Mott-insulating iron oxychalcogenides exhibit complex magnetic behaviour and we report here a neutron diffraction investigation into the magnetic ordering in La2O2Fe2OS2. This quaternary oxysulfide adopts the anti-Sr2MnO2Sb2-type structure and orders antiferromagnetically below TN = 105 K. We consider both its long-range magnetic structure and its magnetic microstructure, and the onset of magnetic order. It adopts the multi-k vector "2k" magnetic structure (k = (0.5 0 0.5) and k = (0 0.5 0.5) and has similarities with related iron oxychalcogenides, illustrating the robust nature of the "2k…
We describe the local structural properties of the iron oxychalcogenides, La$_2$O$_2$Fe$_2$O$M_2$ ($M$ = S, Se), by using pair distribution function (PDF) analysis applied to total scattering data. Our results of neutron powder diffraction show that $M$ = S and Se possess similar nuclear structure at low and room temperatures. The local crystal structures were studied by investigating deviations in atomic positions and the extent of the formation of orthorhombicity. Analysis of the total scattering data suggests that buckling of the Fe$_2$O plane occurs below 100 K. The buckling may occur conc…
We suggest that Cobalt-Oxychalcogenide layers constructed by vertex sharing CoA$_2$O$_2$ (A=S,Se,Te) tetrahedra, such as BaCoAO, are strongly correlated multi-orbital electron systems that can provide important clues on the cause of unconventional superconductivity. Differing from cuprates and iron-based superconductors, these systems lack of the C$_4$ rotational symmetry. However, their parental compounds possess antiferromagnetic(AFM) Mott insulating states through pure superexchange interactions and the low energy physics near Fermi surfaces upon doping is also attributed mainly to the thre…
The new layered manganese oxychalcogenides (LaO)$_2$Mn$_2$Se$_2$O and (BaF)$_2$Mn$_2$Se$_2$O, isostructural to (LaO)$_2$Fe$_2$Se$_2$O, were synthesized by using solid state reaction. The single crystals of former compound were also successfully grown by using high temperature fusion method. The polycrytalline samples showed the insulating behavior, with the activation energy gaps of about 278 meV and 416 meV for (LaO)$_2$Mn$_2$Se$_2$O and (BaF)$_2$Mn$_2$Se$_2$O, respectively. The magnetic susceptibility indicated an antiferromagnetic (AFM) transition at around 160K and strong anisotropic magne…
We have successfully synthesized a new layered iron oxychalcogenide BaFe2OSe2 single crystal. This compound is built up of Ba and Fe-Se(O) layers alternatively stacked along the c-axis. The Fe-Se(O) layers contain double chains of edge-shared Fe-Se(O) tetrahedra that propagate along the b-axis and are bridged by oxygen along the a-axis. Physical property measurements indicate that BaFe2OSe2 is a semiconductor without the Curie-Weiss behavior up to 350 K. There is a possible long range antiferromagnetic (AFM) transition at 240 K, corresponding to the peak in specific heat measurement and two gl…
A layered iron oxide \rfeo ($R$: rare-earth elements) is an exotic dielectric material with charge-order (CO) driven electric polarization and magnetoelectric effect caused by spin-charge coupling. In this paper, a theory of electronic structure and dielectric property in \rfeo is presented. Charge frustration in paired-triangular lattices allows a charge imbalance without inversion symmetry. Spin frustration induces reinforcement of this polar CO by a magnetic ordering. We also analyze an orbital model for the Fe ion which does not show a conventional long-range order.
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…
The electronic structure of electron doped iron-arsenide superconductors Ba(Fe1- xCox)2As2 has been measured with Angle Resolved Photoemission Spectroscopy. The data reveal a marked photon energy dependence of points in momentum space where the bands cross the Fermi energy, a distinctive and direct signature of three-dimensionality in the Fermi surface topology. By providing a unique example of high temperature superconductivity hosted in layered compounds with three-dimensional electronic structure, these findings suggest that the iron-arsenides are unique materials, quite different from the …
Electronic structure and dielectric property in an electronic ferroelectricty, where electric polarization is driven by an electronic charge order without inversion symmetry, are studied. Motivated from layered iron oxides, roles of quantum fluctuation on ferroelectricity in a paired-triangular lattice are focused on. Three types of the extended V-t model are examined by the variational Monte-Carlo method with the Gutzwiller-type correlation factor. It is shown that electron transfer between the triangular layers corresponding to the inter-layer polarization fluctuation promotes the three-fold…
We report high-resolution photoemission spectroscopy of newly-discovered iron-based layered superconductor La(O$_{0.93}$F$_{0.07}$)FeAs (Tc = 24 K). We found that the superconducting gap shows a marked deviation from the isotropic s-wave symmetry. The estimated gap size at 5 K is 3.6 meV in the s- or axial p-wave case, while it is 4.1 meV in the polar p- or d-wave case. We also found a pseudogap of 15-20 meV above Tc, which is gradually filled-in with increasing temperature and closes at temperature far above Tc similarly to copper-oxide high-temperature superconductors.
We study a doubly-degenerate orbital model on a honeycomb attice. This is a model for orbital states in multiferroic layered iron oxides. The classical and quantum models are analyzed by spin-wave approximation, Monte-Carlo simulation and Lanczos method. A macroscopic number of degeneracy exists in the classical ground state. In the classical model, a peak in the specific heat appears at a temperature which is much lower than the mean-field ordering one. Below this temperature, angle of orbital pseudo-spin is fixed, but conventional orbital orders are not suggested. The degeneracy in the groun…
Dielectric and magnetic phenomena in spin and charge frustrated system RFe2O4 (R is a rare-earth metal ion) are studied. An electronic model for charge, spin and orbital degrees in a pair of triangular-lattice planes is derived. We analyze this model by utilizing the mean-field approximation and the Monte-Carlo simulation in a finite size cluster. A three fold-type charge ordered structure with charge imbalance between the planes is stabilized in finite temperatures. This polar charge order is reinforced by spin ordering of Fe ions. This novel magneto-dielectric phenomenon is caused by spin fr…
We investigate interplay between magnetic fluctuations and superconductivity in the effective five-band Hubbard model for iron-oxypnictide superconductors on the basis of the fluctuation-exchange approximation. As for the normal-state properties, we find the pseudogap behavior in the NMR relaxation rate and the spectral weight in the electron-doped region, while we cannot find such behavior in the hole-doped region. The pseudogap behavior originates from the band structure effect, that is, existence of high density of states just below the Fermi level. Solving the superconducting Eliashberg eq…
A1-xFe2-ySe2 (A = K, Cs, Rb, Tl) are recently discovered iron-based superconductors with critical temperatures (Tc) ranging up to 32 K. Their parent phases have unique properties when compared with other iron-based superconductors; e.g., their crystal structures include ordered Fe vacancies, their normal states are antiferromagnetic (AFM) insulating phases, and they have extremely high Néel transition temperatures. However, control of carrier doping into the parent AFM insulators has been difficult due to their intrinsic phase separation. Here, we fabricated an Fe-vacancy-ordered TlFe1.6Se2 in…
We report ^{31}P and ^{139}La NMR studies of (La_{0.87}Ca_{0.13})FePO, which is a family member of the recently discovered superconductor LaFeAs(O_{1-x}F_x). In the normal state, Knight shift and $1/T_1T$ show that a Fermi-liquid state with moderate ferromagnetic fluctuations emerges below 30K. From 1/T_1T of ^{31}P and ^{139}La, quasi-two dimensional electronic structure is suggested, in which the FeP layer is more conductive than the LaO layer. In the superconducting (SC) state, although a clear Meissner signal was observed, 1/T_1T increases below T_c, in contrast to a decrease of 1/T_1T due…
Based on the effective four-band model we analyze the spin response in the normal and superconducting states of the Fe-pnictide superconductors. While the normal state spin excitations are dominated by the continuum of the interorbital antiferromagnetic fluctuations and the intraband spin density wave fluctuations, the unconventional superconductivity yields different feedback. The resonance peak in form of the well-defined spin exciton occurs {\it only} for the interband scattering at the antiferromagnetic momentum ${\bf Q}_{AFM}$ for the $s_\pm$ (extended s-wave) superconducting order parame…
$^{75}$As and $^{139}$La field-swept NMR spectra were obtained for the novel weakly itinerant ferromagnet LaCoAsO with 2D layered structure above the Curie temperature of 55 K. By analyzing NMR spectra, temperature dependences of Knight shift $K$ and nuclear quadrupole resonance frequency $ν_Q$ were obtained successfully for each nucleus. We confirmed from the so-called $K$-$χ$ plots that the macroscopic magnetization of our {LaCoAsO} powder sample is intrinsic and does not contain the contribution from impurity phases. We estimated hyperfine coupling constants from the slope of $K$-$χ$ plots …
57Fe Mössbauer spectroscopy was applied to an iron-based layered compound CeFePO. At temperatures from 9.4 to 293 K, no magnetic splitting was observed in the Mössbauer spectra of CeFePO indicating a paramagnetic phase of the Fe magnetic sublattice. All the spectra were fitted with a small quadrupole splitting, and the Debye temperature of CeFePO was found to be \sim448 K. The isomer shift at room temperature, 0.32 mm/s, was almost equal to those of LnFeAsO (Ln = La, Ce, Sm). Comparing s-electron density using the isomer shifts and unit cell volumes, it was found that the Fe of CeFePO has a si…
We report transport and thermodynamic properties of stoichiometric single crystals of the hexagonal iron-pnictide FeCrAs. The in-plane resistivity shows an unusual "non-metallic" dependence on temperature T, rising continuously with decreasing T from ~ 800 K to below 100 mK. The c-axis resistivity is similar, except for a sharp drop upon entry into an antiferromagnetic state at T_N 125 K. Below 10 K the resistivity follows a non-Fermi-liquid power law, rho(T) = rho_0 - AT^x with x<1, while the specific heat shows Fermi liquid behaviour with a large Sommerfeld coefficient, gamma ~ 30 mJ/mol K^2…
The response of the worldwide scientific community to the discovery in 2008 of superconductivity at Tc = 26 K in the Fe-based compound LaFeAsO_{1-x}F_x has been very enthusiastic. In short order, other Fe-based superconductors with the same or related crystal structures were discovered with Tc up to 56 K. Many experiments were carried out and theories formulated to try to understand the basic properties of these new materials and the mechanism for Tc. In this selective critical review of the experimental literature, we distill some of this extensive body of work, and discuss relationships betw…
It is demonstrated that SC mechanism of doped Fe-based compounds is characteristic for itinerant electron systems with coexistence of both (e-e)- and (e-h)-pairing arising due to electron-phonon and Coulomb interactions, respectively. The higher Tc of the SC transition here (as compared with conventional (LTSC) BCS-systems without (e-h)-pairing) is a natural consequence of (e-e)-pairing at the background of high density of states which arises in the narrow energy range near dielectric-(SDW)-gap (pseudogap) edges due to removing of electronic states from the energy region of dielectric (SDW) ga…
We have successfully prepared the new layered oxypnictides $Sr_4Sc_2O_6M_2As_2$ (M=Fe and Co). They adopt the tetragonal structure, being the same as that of $Sr_4Sc_2O_6Fe_2P_2$. The lattice constants are a=0.4045 nm and c= 0.5802 nm for M=Fe, and a=0.4045 nm and c=1.5695 nm for M=Co, respectively. Their transport and magnetic properties have been systematically studied. The temperature dependence of Hall coefficient and thermoelectric powder for $Sr_4Sc_2O_6Fe_2As_2$ compound show complicated behavior, similar to that of iron-based parent compounds LnOFeAs and $BaFe_2As_2$. It suggests that …
The recent discovery of superconductivity in the iron-based layered pnictides with T_c ranging between 26 and 56K generated enormous interest in the physics of these materials. Here, we review some of the peculiarities of the antiferromagnetic order in the iron pnictides, including the selection of the stripe magnetic order and the formation of the Ising-nematic state in the unfolded BZ within an itinerant description. In addition we analyze the properties of the quasiparticle interference spectrum in the parent antiferromagnetic phase.
The recent discovery of superconductivity under high pressure in the two-leg ladder compound BaFe$_2$S$_3$ [H. Takahashi et al., Nature Materials 14, 1008 (2015)] opens a broad avenue of research, because it represents the first report of pairing tendencies in a quasi one-dimensional iron-based high critical temperature superconductor. Similarly as in the case of the cuprates, ladders and chains can be far more accurately studied using many-body techniques and model Hamiltonians than their layered counterparts, particularly if several orbitals are active. In this publication, we derive a two-o…
Study of superconductivity in layered iron-based materials was initiated in 2006 by Hosono's group, and boosted in 2008 by the superconducting transition temperature, Tc, of 26 K in LaFeAsO1-xFx. Since then, enormous researches have been done on the materials, with Tc reaching as high as 55 K. Here, we review briefly experimental and theoretical results on atomic and electronic structures and magnetic and superconducting properties of FeAs-based superconductors and related compounds. We seek for clues for unconventional superconductivity in the materials.
A Ginzburg-Landau approach to fluctuations of a layered superconductor in a magnetic field is used to show that the interlayer coupling can be incorporated within an interacting self-consistent theory of a single layer, in the limit of a large number of neighboring layers. The theory exhibits two phase transitions -- a vortex liquid-to-solid transition is followed by a Bose-Einstein condensation into the Abrikosov lattice -- illustrating the essential role of interlayer coupling. Using this theory, explicit expressions for magnetization, specific heat, and fluctuation conductivity are derived.…
We report a combined experimental and theoretical investigation of the layered antimonide PrMnSbO which is isostructural to the parent phase of the iron pnictide superconductors. We find linear resistivity near room temperature and Fermi liquid-like T^{2} behaviour below 150 K. Neutron powder diffraction shows that unfrustrated C-type Mn magnetic order develops below \sim 230 K, followed by a spin-flop coupled to induced Pr order. At T \sim 35 K, we find a tetragonal to orthorhombic (T-O) transition. First principles calculations show that the large magnetic moments observed in this metallic c…
Coexistence of phases, characterized by different electronic degrees of freedom, commonly occurs in layered superconductors. Among them, alkaline intercalated chalcogenides are model systems showing microscale coexistence of paramagnetic (PAR) and antiferromagnetic (AFM) phases, however, temporal behavior of different phases is still unknown. Here, we report the first visualization of the atomic motion in the granular phase of K$_{x}$Fe$_{2-y}$Se$_2$ using X-ray photon correlation spectroscopy. Unlike the PAR phase, the AFM texture reveals an intermittent dynamics with avalanches as in martens…
Employing a combination of \emph{ab initio} band structure theory and dynamical mean-field theory we explain the experimentally observed linear temperature increase of the magnetic susceptibility of the iron pnictide material BaFe$_{2}$As$_{2}$. The microscopic origin of this anomalous behaviour is traced to a sharp peak in the spectral function located approximately 100 meV below the Fermi level. This peak is due to the weak dispersion of two-dimensional bands associated with the layered crystal structure of pnictides.
We have performed 31P-NMR measurements of the c-axis-aligned poly-crystal Ce(Ru1-xFex)PO with a two-dimensional layered structure in order to understand the origin of TCurie suppression by Fe substitution. The variation in the magnetic-fluctuation character with respect to x is investigated from the in-plane and out-of plane fluctuations and the relationship between the static spin susceptibility and the in-plane fluctuation. It was found that three-dimensional ferromagnetic (FM) correlations are dominant and give rise to the FM ordering in CeRuPO. The out-of-plane fluctuations are significant…
In the layered iron-based superconductor YFe2Ge2, a high Sommerfeld ratio of ~100 mJ/molK^2 and a T^(3/2) temperature dependence of the electrical resistivity at low temperature T indicate strong electronic correlations and point towards an unconventional pairing state. We have investigated the role of composition and annealing conditions in optimizing the growth of high-quality YFe2Ge2. Our findings confirm that bulk superconductivity is observed in samples with disorder scattering rates less than 2 k_B T_c/hbar. Fe deficiency on the Fe site is identified as the dominant source of disorder, w…
The insulating iron compounds Eu$_2$SrFe$_2$O$_6$ and Sr$_3$Fe$_2$O$_4$Cl$_2$ have high-temperature antiferromagnetic (AF) order despite their different layered structures. Here we carry out density functional calculations and Monte Carlo simulations to study their electronic structures and magnetic properties aided with analyses of the crystal field, magnetic anisotropy, and superexchange. We find that both compounds are Mott insulators and in the high-spin (HS) Fe$^{2+}$ state ($S$ = 2) accompanied by the weakened crystal field. Although they have different local coordination and crystal fie…
We study the layered $J_1$-$J_2$ classical Heisenberg model on the square lattice using a self-consistent bond theory. We derive the phase diagram for fixed $J_1$ as a function of temperature $T$, $J_2$ and interplane coupling $J_z$. Broad regions of (anti)ferromagnetic and stripe order are found, and are separated by a first-order transition near $J_2\approx 0.5$ (in units of $|J_1|$). Within the stripe phase the magnetic and vestigial nematic transitions occur simultaneously in first-order fashion for strong $J_z$. For weaker $J_z$ there is in addition, for $J_2^*<J_2 < J_2^{**}$, an interme…
The recent discovery of superconductivity with relatively high transition temperature Tc in the layered iron-based quaternary oxypnictides La[ O1-xFx] FeAs was a real surprise. The excitement generated can be seen by the number of subsequent works published within a very short period of time. Although there exists superconductivity in alloy that contains Fe element, LaOMPn (with M= Fe, Ni; and Pn=P and As) is the first system where Fe-element plays the key role to the occurrence of superconductivity. LaOMPn has a layered crystal structure with an Fe-based plane. It is quite natural to ask whet…
The recent discovery of superconductivity in BaFe$_2$S$_3$ [Takahashi {\it et al.}, Nat. Mater. {\bf 14}, 1008 (2015)] has stimulated considerable interest in 123-type iron chalcogenides. This material is the first reported iron-based two-leg ladder superconductor, as opposed to the prevailing two-dimensional layered structures of the iron superconductors family. Once the hydrostatic pressure exceeds $11$ GPa, BaFe$_2$S$_3$ changes from a semiconductor to a superconductor below $24$~K. Although previous calculations correctly explained its ground state magnetic state and electronic structure, …
