The band structure and the Fermi surface of the recently discovered superconductor (EMIM)$_x$FeSe are studied within the density functional theory in the generalized gradient approximation. We show that the bands near the Fermi level are formed primarily by Fe-$d$ orbitals. Although there is no direct contribution of EMIM orbitals to the near-Fermi level states, the presence of organic cations leads to a shift of the chemical potential. It results in the appearance of small electron pockets in the quasi-two-dimensional Fermi surface of (EMIM)$_x$FeSe.
Superconductivity with transition temperature Tc above 40 K was observed in protonated FeSe (Hy-FeSe) previously with the ionic liquid of EMIM-BF4 used in the electrochemical process. However, the real superconducting phase is not clear until now, and detailed structural, magnetization and electrical transport measurements are lacking. By using similar protonating technique on FeSe single crystals, we obtained superconducting samples with Tc above 40 K. We show that the obtained superconducting phase is not Hy-FeSe but actually an organic-ion (C6H11N2+ referred to as EMIM+)-intercalated phase …
The discovery of superconductivity in alkali-ammonia co-intercalated FeSe has generated intensive interest because of their highest Tc (~ 45 K) among iron-chalcogenide superconductors with bulk form. Here, we report the phase diagrams of two series of Li/Na-ammonia co-intercalated FeSe1-zTez. When superconductivity is suppressed by Te doping, the magnetic ordering states are emergent. Moreover, a novel phase Lix(NH3)yFe2-δTe2 with possible antiferromagnetism is discovered. This strongly indicates the intimate relation between superconductivity and magnetism in these materials, like in other ir…
We report here that a new superconducting phase with much higher Tc has been found in K intercalated FeSe compound with excess Fe. We successfully grew crystals by precisely controlling the starting amount of Fe. Besides the superconducting (SC) transition at ~30 K, we observed a sharp drop in resistivity and a kink in susceptibility at 44 K. By combining thermodynamic measurements with electron spin resonance (ESR), we demonstrate that this is a new SC transition. Structural analysis unambiguously reveals two phases coexisting in the crystals, which are responsible respectively for the SC tra…
Bulk FeSe becomes superconducting below 9\,K, but the critical temperature (T$_{c}$) is enhanced almost universally by a factor of $\sim$4-5 when it is intercalated with alkali elements. How intercalation modifies the structure is known from in-situ X-ray and neutron scattering techniques, but why T$_{c}$ changes so dramatically is not known. Here we show that there is one-to-one correspondence between the enhancement in magnetic instabilities at certain $\bf q$ vectors and superconducting pairing vertex, even while the nuclear spin relaxation rate ${1}/{(T_{1}T)}$ may not reflect this enhance…
Superconducting transition temperature (Tc) and critical current density (Jc) are two key factors that are not only crucial for probing high-temperature superconducting mechanisms, but also for practical applications. The simple crystal structure of FeSe is very favorable for the fabrication of thin films and wires, but its application is limited by the relatively low Tc and small Jc. A previous study has found that the Tc of FeSe can be significantly enhanced over 40 K by using the protonation method. Here, we present a systematic study of Jc and vortex properties of H+-intercalated FeSe (Hx-…
The discovery of ThCr2Si2-type AxFe2-ySe2 (A = K, Rb, Cs and Tl) with Tc ~ 30K make much progress in iron-based superconducting field, but their multiple-phase separations are disadvantageous for understanding the origin. On the other hand, for small alkali metals, studies on (Li,Na)FeCu(S,Se)2 and NaFe2-δS2 shows that these compounds possess CaAl2Si2-type structure, implying that ThCr2Si2-type structure is unstable for small alkali-metal intercalated FeSe under high-temperature. Here we report a new intercalate Na0.65(1)Fe1.93(1)Se2 with Tc ~ 37 K, synthesized by low-temperature ammonothermal…
In the recently synthesized Li$_x$(NH$_2$)$_y$(NH$_3$)$_z$Fe$_2$Se$_2$ family of iron chalcogenides a molecular spacer consisting of lithium ions, lithium amide and ammonia separates layers of FeSe. It has been shown that upon variation of the chemical composition of the spacer layer, superconducting transition temperatures can reach $T_c\sim 44 \mathrm{K}$, but the relative importance of the layer separation and effective doping to the $T_c$ enhancement is currently unclear. Using state of the art band structure unfolding techniques, we construct eight-orbital models from ab-initio density fu…
Magnetic fluctuations in the molecular-intercalated FeSe superconductor Li{x}(ND2){y}(ND3){1-y}Fe2Se2 (Tc = 43K) have been measured by inelastic neutron scattering from a powder sample. The strongest magnetic scattering is observed at a wave vector Q ~ 1.4 A^{-1}, which is not consistent with the (pi,0) nesting wave vector that characterizes magnetic fluctuations in several other iron-based superconductors, but is close to the (pi, pi/2) position found for A{x}Fe{2-y}Se2 systems. At the energies probed (~ 5kB Tc), the magnetic scattering increases in intensity with decreasing temperature below…
The electronic structure and magnetism of a new magnetic intercalation compound (Li0.8Fe0.2)OHFeSe are investigated theoretically. The electronic structure calculations predict that the Fe in the (Li,Fe)OH intercalated layer is in +2 valence state, i.e. there is electron doping to the FeSe layer, resulting in the shrinking of the Fermi surface (FS) pocket around Gamma and a strong suppression of dynamical spin susceptibility at M in comparison with the bulk FeSe compound. The ground state of the FeSe layer is a striped antiferromagnetic (SAFM) metal, while the (Li,Fe)OH layer displays a very w…
New FeSe-based intercalation superconductors, $A_x$(C$_8$H$_{11}$N)$_y$Fe$_{1-z}$Se ($A$ = Li, Na), with $T_\mathrm{c}$ = 39-44 K have been successfully synthesized via the intercalation of alkali metals and 2-phenethylamine into FeSe. The interlayer spacings, namely, the distances between neighboring Fe layers, $d$, of $A_x$(C$_8$H$_{11}$N)$_y$Fe$_{1-z}$Se ($A$ = Li, Na) are 19.04(6) and 18.0(1) Å, respectively. These $d$ values are the largest among those of the FeSe-based intercalation compounds and are understood to be due to the intercalation of two molecules of 2-phenethylamine in series…
The superconductivity and intercalation statein the lithium-and hexamethylenediamine (HMDA)-intercalated superconductor Li$_x$(C$_6$H$_{16}$N$_2$)$_y$Fe$_{2-z}$Se$_2$ have been investigated from powder x-ray diffraction, thermogravimetric and magnetic susceptibility measurements, changing the intercalation temperature, $T_i$, and the Li content, $x$. Both Li and HMDA have been co-intercalated stably up to $x$ = 2 roughly in the molar ratio of $x : y = 2 : 1$. In the case of $T_i$ = 45$^\circ$C, it has been found that both Li and HMDA are co-intercalated locally at the edge of FeSe crystals, in…
New superconductors, Li$_x$(C$_n$H$_{2n+3}$N)$_y$Fe$_{1-z}$Se ($n$ = 6, 8, 18), have been synthesized via the co-intercalation of linear monoamines together with Li into FeSe. The distance between neighboring Fe layers expands up to 55.7 Å for n = 18, which is much larger than the previous record of 19 Å in the FeSe-based intercalation superconductors. Tc remains saturated at $\sim$42 K.
The iron chalcogenides FeSe and FeS are superconductors composed of two-dimensional sheets held together by van der Waals interactions, which makes them prime candidates for the intercalation of various guest species. We review the intercalation chemistry of FeSe and FeS superconductors and discuss their synthesis, structure, and physical properties. Before we review the latest work in this area, we provide a brief background on the intercalation chemistry of other inorganic materials that exhibit enhanced superconducting properties upon intercalation, which include the transition metal dichal…
We report on the synthesis of large single crystals of a new FeSe-layer superconductor Cs0.8(FeSe0.98)2. X-ray powder diffraction, neutron powder-diffraction and magnetization measurements have been used to compare the crystal structure and the magnetic properties of Cs0.8(FeSe0.98)2 with those of the recently discovered potassium intercalated system KxFe2Se2. The new compound Cs0.8(FeSe0.98)2 shows a slightly lower superconducting transition temperature (Tc=27.4 K) in comparison to 29.5 in K0.8(FeSe0.98)2). The volume of the crystal unit cell increases by replacing K by Cs - the c-parameter g…
Intercalation of organic cations in superconducting iron selenide can significantly increase the critical temperature (Tc). We present an electrochemical method using beta-FeSe crystals (Tc ~ 8 K) floating on a mercury cathode to intercalate tetramethylammonium ions (TMA+) quantitatively to obtain bulk samples of (TMA)0.5Fe2Se2 with Tc = 43 K. The layered crystal structure is closely related to the ThCr2Si2-type with disordered TMA+ ions between the FeSe layers. Although the organic ions are not detectable by X-ray diffraction, packing requirements as well as first principle DFT calculations c…
Post-annealing effects on the crystal structure and superconductivity of the lithium- and hexamethylenediamine (HMDA)-intercalated superconductor Lix(C6H16N2)yFe2-zSe2 have been investigated. Through the post-annealing, a two-step reduction of the interlayer spacing between neighboring Fe layers, d, has been observed. It has been found that a new phase of Lix(C6H16N2)yFe2-zSe2 with d= 10.30(2) Å and Tc = 41 K different from the as-intercalated phase is stabilized owing to the possible stable inclination of HMDA intercalated between FeSe layers. This result supports the domic relation between T…
Superconducting properties were studied on high quality superconductors $Ba_{x}(NH_{3})Fe_{2}Se_{2}$ ($T_{c}$ = 39 K) and $Sr_{x}(NH_{3})Fe_{2}Se_{2}$ ($T_{c}$ = 44 K) prepared by intercalating Ba/Sr atoms into tetragonal $β$-FeSe by liquid ammonia. The elongated c-axis and almost unchanged a-axis of $Ba_{x}(NH_{3})Fe_{2}Se_{2}$, comparing with $β$-FeSe, suggested an unchanged intra-$Fe_{2}Se_{2}$-layer structure and the $T_{c}$ enhancement is due to a 3D to 2D-like Fermi surface transformation. The superconducting coherent lengths $ξ$(0), Ginzburg-Landau parameters $κ$ and penetration depths …
Iron-based superconductors are well known for their complex interplay between structure, magnetism and superconductivity. FeSe offers a particularly fascinating example. This material has been intensely discussed because of its extended nematic phase, whose relationship with magnetism is not obvious. Superconductivity in FeSe is highly tunable, with the superconducting transition temperature, $T_\mathrm{c}$, ranging from 8 K in bulk single crystals at ambient pressure to almost 40 K under pressure or in intercalated systems, and to even higher temperatures in thin films. In this topical review…
The missing hole packets near the Brillouin zone center render unique electronic structures to the heavily electron doped FeSe-based superconductors with Tc above 40 K. It challenges the existing scenario accounting for the nature of superconductivity in the iron-based family. Yet, one hurdle that has to be overcome is the materials complexity in the rather limited number of compounds. Here we report the growth of heavily electron doped Li-NH3 intercalated FeSe single crystals that are free of such complexities and allow access to the intrinsic superconducting properties. Our results show extr…
The superconducting transition temperature, $T_{\rm{c}}$, of FeSe can be significantly enhanced several-fold by applying pressure, electron doping, intercalating spacing layer, and reducing dimensionality. Various ordered electronic phases, such as nematicity and spin density waves, have also been observed accompanying high-$T_{\rm{c}}$ superconductivity. Investigation on the evolution of the electronic structure with $T_{\rm{c}}$ is essential to understanding electronic behavior and high-$T_{\rm{c}}$ superconductivity in FeSe and its derived superconductors. In this report, we have found a se…
New iron-based intercalation superconductors Ax(C2H8N2)yFe2-zSe2 (A = Li, Na) with Tc = 45 K have successfully been synthesized via intercalation of dissolved alkaline metal in ethylenediamine. The c-axis lengths of Ax(C2H8N2)yFe2-zSe2 (A = Li, Na) are 20.74(7) Å and 21.9(1) Å, respectively, and are about 50 % larger than that of KxFe2Se2, indicating that not only alkaline metal but also ethylenediamine is intercalated between the Se-Se layers of FeSe. It seems that the high-Tc of Ax(C2H8N2)yFe2-zSe2 (A = Li, Na) is caused by the possible two-dimensional electronic structure due to the large c…
The parent compound of an unconventional superconductor must contain unusual correlated electronic and magnetic properties of its own. In the high-Tc potassium intercalated FeSe, there has been significant debate regarding what the exact parent compound is. Our studies unambiguously show that the Fe-vacancy ordered K2Fe4Se5 is the magnetic, Mott insulating parent compound of the superconducting state. Non-superconducting K2Fe4Se5 becomes a superconductor after high temperature annealing, and the overall picture indicates that superconductivity in K2-xFe4+ySe5 originates from the Fe-vacancy ord…
A new iron-based superconductor Li$_x$(C$_2$H$_8$N$_2$)$_y$Fe$_{2-z}$Se$_2$ with $T_c$ = 45 K has successfully been synthesized via intercalation of dissolved lithium metal in ethylenediamine. The distance between neighboring Fe layers is 10.37 Å and much larger than those of FeSe with $T_c$ = 8 K and K$_x$Fe$_2$Se$_2$ with $T_c$ ~ 30 K. It seems that the high-$T_c$ of Li$_x$(C$_2$H$_8$N$_2$)$_y$Fe$_{2-z}$Se$_2$ is caused by the possible two-dimensional electronic structure due to the large $c$-axis length.
The superconducting properties of a recently discovered high $T_{\rm c}$ superconductor, Sr/ammonia-intercalated FeSe, have been measured using pulsed magnetic fields down to $4.\,\rm {K}$ and muon spin spectroscopy down to $1.5\,\rm K$. This compound exhibits intrinsic disorder resulting from random stacking of the FeSe layers along the $c$-axis that is not present in other intercalates of the same family. This arises because the coordination requirements of the intercalated Sr and ammonia moieties imply that the interlayer stacking (along $c$) involves a translation of either ${\bf a}/2$ or …
The van-der-Waals gap of iron chalcogenide superconductors can be intercalated with a variety of inorganic and organic compounds that modify the electron doping level of the iron layers. In Lix(C3N2H10)0.37FeSe, a dome in the superconducting transition temperature Tc has been reported to occur in the doping range of x=0.06 to x=0.68. We use a combination of density functional theory and spin fluctuation theory to capture the evolution of superconducting transition temperatures theoretically. We clearly demonstrate how the changing electronic structure supports an increasing superconducting Tc.…
We report the low-temperature electronic and magnetic properties of the alkali metal-organic solvent intercalated iron selenide superconductor Lix(C5H5N)yFe2-zSe using muon-spin-spectroscopy measurements. The zero-field \muSR results indicate that nearly half of the sample is magnetically ordered and there is a spatial phase separation between the superconducting and the magnetic fraction. The transverse-field \muSR results show that the temperature dependence of the penetration depth λ(T) in the mixed state of Lix(C5H5N)yFe2-zSe can be explained using a two-gap s+s-wave model with gap values …
We report on a new iron selenide superconductor with a TC onset of 45K and the nominal composition Lix(C5H5N)yFe2-zSe2, synthesized via intercalation of dissolved alkaline metal in anhydrous pyridine at room temperature. This superconductor exhibits a broad transition, reaching zero resistance at 10K. Magnetization measurements reveal a superconducting shielding fraction of approximately 30%. Analogous phases intercalated with Na, K and Rb were also synthesized and characterized. The superconducting transition temperature of Lix(C5H5N)yFe2-zSe2 is clearly enhanced in comparison to the known su…
Emergent electronic phenomena in iron-based superconductors have been at the forefront of condensed matter physics for more than a decade. Much has been learned about the origin and intertwined roles of ordered phases, including nematicity, magnetism, and superconductivity, in this fascinating class of materials. In recent years, focus has been centered on the peculiar and highly unusual properties of FeSe and its close cousins. This family of materials has attracted considerable attention due to the discovery of unexpected superconducting gap structures, a wide range of superconducting critic…
We report on synthesis of single crystals of BaFe2Se3 and study of their crystal and magnetic structures by means of synchrotron single crystal X-ray and neutron powder diffraction. The crystal structure has orthorhombic symmetry and consists of double chains of FeSe4 edge connected tetrahedra intercalated by barium. Below 240 K long range block-spin checkerboard antiferromagnetic (AFM) order is developed. The magnetic structure is similar to one observed in A0.8Fe1.6Se2 (A=K, Rb or Cs) superconductors. The crystals exhibit a transition to the diamagnetic state with an onset transition tempera…
The FeSe-based superconductors exhibit a wide range of critical temperature Tc under a variety of material and physical conditions, but extensive studies to date have yet to produce a consensus view on the underlying mechanism. Here we report on a systematic Raman scattering work on intercalated FeSe superconductors Lix(NH3)yFe2Se2 and (Li,Fe)OHFeSe compared to pristine FeSe. All three crystals show an anomalous power-law temperature dependence of phonon linewidths, deviating from the standard anharmonic behavior. This intriguing phenomenon is attributed to electron-phonon coupling effects enh…
We review a variety of theoretical and experimental results concerning electronic band structure of superconducting materials based on FeSe monolayers. Three type of systems are analyzed: intercalated FeSe systems A_xFe_2Se_{2-x}S_x and [Li_{1-x}Fe_xOH]FeSe as well as the single FeSe layer films on SrTiO_3 substrate. We present the results of detailed first principle electronic band structure calculations for these systems together with comparison with some experimental ARPES data. The electronic structure of these systems is rather different from that of typical FeAs superconductors, which is…
Using the constraints imposed by the crystalline symmetry of FeSe and the experimentally observed phenomenology, we analyze the possible pairing symmetry of the superconducting order parameter focusing on intercalated and monolayer FeSe compounds. Such analysis leads to three possible pairing symmetry states -- s-wave, d-wave, and helical p-wave. Despite the differences in the pairing symmetry, each of these states is fully gapped with gap minimum centered above the normal state Fermi surface, in agreement with photoemission data of Y. Zhang et al. The analysis provides additional insights int…
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…
Distinctive superconducting behaviors between bulk and monolayer FeSe make it challenging to obtain a unified picture of all FeSe-based superconductors. We investigate the ultrafast quasiparticle (QP) dynamics of an intercalated superconductor (Li1-xFex)OHFe1-ySe, which is a bulk crystal but shares a similar electronic structure with single-layer FeSe on SrTiO3. We obtain the electron-phonon coupling (EPC) constant λA1g (0.22 +/- 0.04), which well bridges that of bulk FeSe crystal and single-layer FeSe on SrTiO3. Moreover, we find that such a positive correlation between λA1g and superconducti…
The latest discovery of high temperature superconductivity signature in single-layer FeSe is significant because it is possible to break the superconducting critical temperature ceiling (maximum Tc~55 K) that has been stagnant since the discovery of Fe-based superconductivity in 2008. It also blows the superconductivity community by surprise because such a high Tc is unexpected in FeSe system with the bulk FeSe exhibiting a Tc at only 8 K at ambient pressure which can be enhanced to 38 K under high pressure. The Tc is still unusually high even considering the newly-discovered intercalated FeSe…
An exact particle-hole transformation is discovered in a local-moment model for a single layer of heavily electron-doped FeSe. The model harbors hidden magnetic order between the iron d_xz and d_yz orbitals at the wavenumber (pi,pi). It potentially is tied to the magnetic resonances about the very same Neel ordering vector that have been recently discovered in intercalated FeSe. Upon electron doping, the local-moment model successfully accounts for the electron-pocket Fermi surfaces observed experimentally at the corner of the two-iron Brillouin zone in electron-doped FeSe, as well as for isot…
Potassium intercalated FeSe has been reported as a superconductor with superconducting transition temperatures ($T_{\rm c}$'s) of 30-48 K. However, there is no clear answer to identify the relationship between the surface morphology, compositional ratio and its crystal structure. This report directly reveals the correspondence among these three characteristics in single crystals with a $T_{\rm c}$ onset of around 44 K using a micro-sampling technique. Island-like parts on the surface of the crystals clearly have the K$_x$Fe$_2$Se$_2$ structure with perfect FeSe layers, which is formed in conju…
The superconducting critical temperature $T_{\mathrm{c}}$ of intercalated iron-selenide superconductor (Li,Fe)OHFeSe (FeSe11111) can be increased to 42 K from 8 K of bulk FeSe. It shows remarkably similar electronic properties as the high-$T_{\mathrm{c}}$ monolayer FeSe and provides a bulk counterpart to investigate the origin of enhanced superconductivity. Unraveling the nature of excitations is crucial for understanding the pairing mechanism in high-$T_{\mathrm{c}}$ iron selenides. Here we use resonant inelastic x-ray scattering (RIXS) to investigate the excitations in FeSe11111. Our high-qu…
FeSe-derived superconductors show some unique behaviors relative to iron-pnictide superconductors, which are very helpful to understand the mechanism of superconductivity in high-Tc iron-based superconductors. The low-energy electronic structure of the heavily electron-doped AxFe2Se2 (A=K, Rb, Cs) demonstrates that interband scattering or Fermi surface nesting is not a necessary ingredient for the unconventional superconductivity in iron-based superconductors. The superconducting transition temperature (Tc) in the one-unit-cell FeSe on SrTiO3 substrate can reach as high as ~65 K, largely trans…
We studied the correlation among structure and transport properties and superconductivity in the different $A_x$Fe$_2$Se$_2$ single crystals ($A$ = K, Rb, and Cs). Two sets of (00$l$) reflections are observed in the X-ray single crystal diffraction patterns, and arise from the intrinsic inhomogeneous distribution of the intercalated alkali atoms. The occurrence of superconductivity is closely related to the {\sl c}-axis lattice constant, and the $A$ content is crucial to superconductivity. The hump observed in resistivity seems to be irrelevant to superconductivity. There exist many deficienci…
Using angle-resolved photoemission spectroscopy (ARPES), we revealed the surface electronic structure and superconducting gap of (Li$_{0.8}$Fe$_{0.2}$)OHFeSe, an intercalated FeSe-derived superconductor without antiferromagnetic phase or Fe-vacancy order in the FeSe layers, and with a superconducting transition temperature ($T_c$) $\sim$ 40 K. We found that (Li$_{0.8}$Fe$_{0.2}$)OH layers dope electrons into FeSe layers. The electronic structure of surface FeSe layers in (Li$_{0.8}$Fe$_{0.2}$)OHFeSe resembles that of Rb$_x$Fe$_{2-y}$Se$_2$ except that it only contains half of the carriers due …
(Li0.8Fe0.2)OHFeSe is a newly-discovered intercalated iron-selenide superconductor with a Tc above 40 K, which is much higher than the Tc of bulk FeSe (8 K). Here we report a systematic study of (Li0.8Fe0.2)OHFeSe by low temperature scanning tunneling microscopy (STM). We observed two kinds of surface terminations, namely FeSe and (Li0.8Fe0.2)OH surfaces. On the FeSe surface, the superconducting state is fully gapped with double coherence peaks, and a vortex core state with split peaks near EF is observed. Through quasi-particle interference (QPI) measurements, we clearly observed intra- and i…
