FeSe-based Superconductors Research Articles

Doping Mn into (LiOHFeSe superconducting crystals via ion-exchange and ion-release/introduction syntheses**Project supported by the National Natural Science Foundation of China (Grant Nos. 11574370 and 61501220), Frontier Program of the Chinese Academy of Sciences (Grant Nos. QYZDY-SSW-SLH001 and QYZDY-SSW-SLH008), the National Basic Research Program of China (Grant Nos. 2013CB921700 and 2016YFA0300301), and "Strategic Priority Research Program (B)" of the Chinese Academy

We report the success in introducing Mn into (LiOHFeSe superconducting crystals by applying two different hydrothermal routes, ion exchange (1-step) and ion release/introduction (2-step). The micro-region x-ray diffraction and energy dispersive x-ray spectroscopy analyses indicate that Mn has been doped into the lattice, and its content in the 1-step fabricated sample is higher than that in the 2-step one. Magnetic susceptibility and electric transport properties reveal that Mn doping influences little on the superconducting transition, regardless of 1-step or 2-step routes. By contrast, the characteristic temperature , at which the negative Hall coefficient reaches its minimum, is significantly reduced by Mn doping. This implies that the hole carriers contribution is obviously modified, and hence the hole band might have no direct relationship with the superconductivity in (LiOHFeSe superconductors. Our present hydrothermal methods of ion exchange and ion release/introduction provide an efficient way for elements substitution/doping into (LiOHFeSe superconductors, which will promote the in-depth investigations on the role of multiple electron and hole bands and their interplay with the high-temperature superconductivity in the FeSe-based superconductors.

Ubiquitous strong electron\u2013phonon coupling at the interface of FeSe/SrTiO3

The observation of replica bands in single-unit-cell FeSe on SrTiO3 (STO)(001) by angle-resolved photoemission spectroscopy (ARPES) has led to the conjecture that the coupling between FeSe electrons and the STO phonons are responsible for the enhancement of Tc over other FeSe-based superconductors. However the recent observation of a similar superconducting gap in single-unit-cell FeSe/STO(110) raised the question of whether a similar mechanism applies. Here we report the ARPES study of the electronic structure of FeSe/STO(110). Similar to the results in FeSe/STO(001), clear replica bands are observed. We also present a comparative study of STO(001) and STO(110) bare surfaces, and observe similar replica bands separated by approximately the same energy, indicating this coupling is a generic feature of the STO surfaces and interfaces. Our findings suggest that the large superconducting gaps observed in FeSe films grown on different STO surface terminations are likely enhanced by a common mechanism.

Metamorphoses of electronic structure of FeSe-based superconductors (Review Article)

The electronic structure of FeSe, the simplest iron-based superconductor (Fe-SC), conceals a potential of dramatic increase of Tc that realizes under pressure or in a single layer film. This is also the system where nematicity, the phenomenon of a keen current interest, is most easy to study since it is not accompanied by the antiferromagnetic transition like in all other Fe-SC's. Here we overview recent experimental data on electronic structure of FeSe-based superconductors: isovalently doped crystals, intercalates, and single layer films, trying to clarify its topology and possible relation of this topology to superconductivity. We argue that the marked differences between the experimental and calculated band structures for all FeSe compounds can be described by a hoping selective renormalization model for a spin/orbital correlated state that may naturally explain both the evolution of the band structure with temperature and nematicity.

New Alkali-Metal- and 2-Phenethylamine-Intercalated Superconductors Ax(C8H11N)yFe1−zSe (A = Li, Na) with the Largest Interlayer Spacings and Tc ∼ 40 K

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) {\AA}, 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 perpendicular to the FeSe layers. It appears that the relationship between $T_\mathrm{c}$ and $d$ in the FeSe-based intercalation superconductors is not domic but $T_\mathrm{c}$ is saturated at ~ 45 K, which is comparable to the $T_\mathrm{c}$ values of single-layer FeSe films, for $d$ $\geq$ 9 {\AA}.

Impurity scattering effects on the superconducting properties and the tetragonal-to-orthorhombic phase transition in FeSe

A comprehensive study of the doping dependence of the phase diagram of FeSe-based superconductors is still required due to the lack of a clean and systematic means of doping control. Here, we report on the magneto-optical imaging, thermodynamic and transport properties, as well as in situ angle-resolved photoemission spectroscopy (ARPES) studies of impurity scattering in stoichiometric FeSe single crystals. Co doping at the Fe site is found to decrease the superconducting transition temperature $({T}_{c})$. The upper critical field and specific heat all indicate a possible multiband superconductivity with strong coupling in the Co-doped system. A remarkable feature in FeSe is that its temperature dependent resistivity exhibits a wide hump at high temperatures, a signature of a crossover from a semiconductinglike behavior to metallic behavior. A structural tetragonal-to-orthorhombic phase transition $({T}_{s})$ (a consequence of the electronic nematicity) is suppressed by either physical or chemical pressures. Due to the reconstruction of the Fermi surface at ${T}_{s}$, specific heat anomalies at ${T}_{s}$ present $\mathrm{\ensuremath{\Delta}}{C}_{p}/{T}_{s}\ensuremath{\approx}{\ensuremath{\gamma}}_{n}$, being ${\ensuremath{\gamma}}_{n}$ the Sommerfield coefficient at low temperature. This reflect an additional electronic instability in the ${\mathrm{FeSe}}_{1\ensuremath{-}x}{\mathrm{S}}_{x}$ system. ARPES data between 180 and 282 K indicates the existence of a chemical potential shift with increasing thermal excitations, resulting in a change of the Fermi-surface topology and exhibiting a semimetal behavior. We found that the temperature-induced Lifshitz transition is much higher than the temperature for the nematic order.

Anomalous correlation effects and unique phase diagram of electron-doped FeSe revealed by photoemission spectroscopy.

FeSe layer-based superconductors exhibit exotic and distinctive properties. The undoped FeSe shows nematicity and superconductivity, while the heavily electron-doped KxFe2−ySe2 and single-layer FeSe/SrTiO3 possess high superconducting transition temperatures that pose theoretical challenges. However, a comprehensive study on the doping dependence of an FeSe layer-based superconductor is still lacking due to the lack of a clean means of doping control. Through angle-resolved photoemission spectroscopy studies on K-dosed thick FeSe films and FeSe0.93S0.07 bulk crystals, here we reveal the internal connections between these two types of FeSe-based superconductors, and obtain superconductivity below ∼46 K in an FeSe layer under electron doping without interfacial effects. Moreover, we discover an exotic phase diagram of FeSe with electron doping, including a nematic phase, a superconducting dome, a correlation-driven insulating phase and a metallic phase. Such an anomalous phase diagram unveils the remarkable complexity, and highlights the importance of correlations in FeSe layer-based superconductors.

From monolayer back to bulk FeSe-based high-temperature superconductors

From monolayer back to bulk FeSe-based high-temperature superconductors

Evolution of High-Temperature Superconductivity from a Low-T_{c} Phase Tuned by Carrier Concentration in FeSe Thin Flakes.

We report the evolution of superconductivity in an FeSe thin flake with systematically regulated carrier concentrations by the liquid-gating technique. With electron doping tuned by the gate voltage, high-temperature superconductivity with an onset at 48K can be achieved in an FeSe thin flake with T_{c} less than 10K. This is the first time such high temperature superconductivity in FeSe is achieved without either an epitaxial interface or external pressure, and it definitely proves that the simple electron-doping process is able to induce high-temperature superconductivity with T_{c}^{onset} as high as 48K in bulk FeSe. Intriguingly, our data also indicate that the superconductivity is suddenly changed from a low-T_{c} phase to a high-T_{c} phase with a Lifshitz transition at a certain carrier concentration. These results help to build a unified picture to understand the high-temperature superconductivity among all FeSe-derived superconductors and shed light on the further pursuit of a higher T_{c} in these materials.

Common electronic origin of superconductivity in (Li,Fe)OHFeSe bulk superconductor and single-layer FeSe/SrTiO3 films

The mechanism of high-temperature superconductivity in the iron-based superconductors remains an outstanding issue in condensed matter physics. The electronic structure plays an essential role in dictating superconductivity. Recent revelation of distinct electronic structure and high-temperature superconductivity in the single-layer FeSe/SrTiO3 films provides key information on the role of Fermi surface topology and interface in inducing or enhancing superconductivity. Here we report high-resolution angle-resolved photoemission measurements on the electronic structure and superconducting gap of an FeSe-based superconductor, (Li0.84Fe0.16)OHFe0.98Se, with a Tc at 41 K. We find that this single-phase bulk superconductor shows remarkably similar electronic behaviours to that of the superconducting single-layer FeSe/SrTiO3 films in terms of Fermi surface topology, band structure and the gap symmetry. These observations provide new insights in understanding high-temperature superconductivity in the single-layer FeSe/SrTiO3 films and the mechanism of superconductivity in the bulk iron-based superconductors.

Robust superconductivity and transport properties in (Li1-x Fe x )OHFeSe single crystals

The recently discovered (Li${_{1-x}}$Fe${_x}$)OHFeSe superconductor with $T_c$ about 40K provides a good platform for investigating the magnetization and electrical transport properties of FeSe-based superconductors. By using a hydrothermal ion-exchange method, we have successfully grown crystals of (Li${_{1-x}}$Fe${_x}$)OHFeSe. X-ray diffraction on the sample shows the single crystalline PbO-type structure with the c-axis preferential orientation. Magnetic susceptibility and resistive measurements show an onset superconducting transition at around ${T_c}$=38.3K. Using the magnetization hysteresis loops and Bean critical state model, a large critical current ${J_s}$ is observed in low temperature region. The critical current density is suppressed exponentially with increasing magnetic field. Temperature dependencies of resistivity under various currents and fields are measured, revealing a robust superconducting current density and bulk superconductivity.

New Superconducting Phase of Lix(C6H16N2)yFe2−zSe2 with Tc = 41 K Obtained through the Post-Annealing

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 Tc and d in the FeSe-based intercalation superconductors. The reason why Tc increases with a decrease in d through the post-annealing is discussed.

Electrochemical synthesis of alkali-intercalated iron selenide superconductors**Project supported by the National Natural Science Foundation of China (Grant Nos. 51322211and 91422303), the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (Grant No. XDB07020100), Beijing Nova Program of China (Grant No. 2011096), and K. C. Wong Education Foundation, Hong Kong, China.

Electrochemical method has been used to insert K/Na into FeSe lattice to prepare alkali-intercalated iron selenides at room temperature. Magnetization measurement reveals that KxFe2Se2 and NaxFe2Se2 are superconductive at 31 K and 46 K, respectively. This is the first successful report of obtaining metal-intercalated FeSe-based high-temperature superconductors using electrochemical method. It provides an effective route to synthesize metal-intercalated layered compounds for new superconductor exploration.

Phase diagram of (Li(1-x)Fe(x))OHFeSe: a bridge between iron selenide and arsenide superconductors.

Previous experimental results have shown important differences between iron selenide and arsenide superconductors which seem to suggest that the high-temperature superconductivity in these two subgroups of iron-based families may arise from different electronic ground states. Here we report the complete phase diagram of a newly synthesized superconducting (SC) system, (Li1-xFex)OHFeSe, with a structure similar to that of FeAs-based superconductors. In the non-SC samples, an antiferromagnetic (AFM) spin-density-wave (SDW) transition occurs at ∼127 K. This is the first example to demonstrate such an SDW phase in an FeSe-based superconductor system. Transmission electron microscopy shows that a well-known √5×√5 iron vacancy ordered state, resulting in an AFM order at ∼500 K in AyFe2-xSe2 (A = metal ions) superconductor systems, is absent in both non-SC and SC samples, but a unique superstructure with a modulation wave vector q = (1)/2(1,1,0), identical to that seen in the SC phase of KyFe2-xSe2, is dominant in the optimal SC sample (with an SC transition temperature Tc = 40 K). Hence, we conclude that the high-Tc superconductivity in (Li1-xFex)OHFeSe stems from the similarly weak AFM fluctuations as FeAs-based superconductors, suggesting a universal physical picture for both iron selenide and arsenide superconductors.

New Intercalation Superconductor Lix(C6H16N2)yFe2−zSe2 with a Very Large Interlayer-Spacing and Tc = 38 K

A new iron-based superconductor, Lix(C6H16N2)yFe2−zSe2, with Tc = 38 K has successfully been synthesized via the intercalation of lithium and hexamethylenediamine into FeSe. The superconducting transition has been confirmed not only by magnetic susceptibility measurements but also by electrical resistivity ones. The interlayer spacing, namely, the distance between neighboring Fe layers, d, is 16.225(5) Å, which is the largest among those of FeSe-based intercalation compounds. It has been found that the dependence of Tc on d in FeSe-based intercalation superconductors appears domic.

Single nonmagnetic impurity resonance in FeSe-based 122-type superconductors as a probe for pairing symmetry

We study the effect of a single nonmagnetic impurity in AyFe2−xSe2 (A = K, Rb, or Cs) superconductors by considering various pairing states based on a three-orbital model consistent with the photoemission experiments. The local density of states on and near the impurity site has been calculated by solving the Bogoliubov-de Gennes equations self-consistently. The impurity-induced in-gap bound states are found only for attractive impurity scattering potential, as in the cases of doping of Co or Ni, which is characterized by the strong particle-hole asymmetry, in the nodeless dx2−y2 wave pairing state. This property may be used to probe the pairing symmetry of FeSe-based 122-type superconductors.

A few points on iron-based superconductors

We highlight a few points on iron-based superconductors in this paper. Experimental evidence for intrinsic inhomogeneity and phase separation in Fe-based superconductors is reviewed first. The non-BCS feature and other similarities between the Fe-based superconductors and the cuprates are also presented. The pressure effect on the FeSe-based superconductors observed recently is then discussed in terms of the interplay between superconducting transition temperature and structural characters. It is suggested that there is room for exploring new superconductors with higher transition temperature and that the improvement on the sample quality is necessary for further investigation on the superconducting mechanism.

FeSe-based superconductors (11, 122-type): phase diagram, crystal growth and characterization

FeSe-based superconductors (11, 122-type): phase diagram, crystal growth and characterization

Se77NMR investigation of theKxFe2−ySe2high-Tcsuperconductor (Tc=33K)

We report a comprehensive 77Se NMR study of the structural, magnetic, and superconducting properties of a single crystalline sample of the newly discovered FeSe-based high temperature superconductor K(x)Fe(2-y)Se(2) (Tc=33K) in a broad temperature range up to 290 K. We will compare our results with those reported for FeSe (Tc=9K) and FeAs-based high Tc systems.

The development of the superconducting PbO-type β-FeSe and related compounds

An overview of the recent development of the superconducting FeSe 1− x and related compounds is presented. Methods to synthesize high purity polycrystalline samples, single crystals and thin films with preferred orientation are described. In addition to the synthesis of FeSe and FeSeTe, the effects of various partial chemical substitutions on Fe and Se/Te site are described. It was found that the effects of chemical doping to the Se-site or Fe-site are rather different. Ionic size of the dopant is found to play a critical role on the occurrence of superconductivity. We also review the physical properties, including transport, magnetic, and thermal properties. There exist interesting transport anomalies in the resistivity at low temperature, and it was found that a structural distortion at low temperature is critical to the occurrence of superconductivity in these materials. However, the exact origin of these observed anomalies is not clear, and the exact pairing symmetry in FeSe-based superconductors is also still in question.