We have synthesized a Ba-doped FeSe superconductor using liquid ammonia, and investigated in detail the structure and composition of the Ba-FeSe phase. In the superconducting phase, both the Tc and the shielding fraction are almost unchanged even if the nominal composition of Ba is varied in the region from 0.3 to 0.7. The optimized Tc is 38.8 K. We have determined the structure of the superconducting phase with X-ray powder diffraction (using synchrotron radiation) and here describe the co-intercalation of Ba and NH3 molecules between the FeSe layers.
Solvothermal intercalation of ethylenediamine molecules into FeSe separates the layers by 1078 pm and creates a different stacking. FeSe(en)0.3 is not superconducting although each layer exhibits the stripe-type crystal structure and the Fermi surface topology of superconducting FeSe. FeSe(en)0.3 requires electron-doping for high-Tc similar to monolayers of FeSe@SrTiO3, whose much higher Tc may arise from the proximity of the oxide surface.
57Fe-Mossbauer spectra of superconducting beta-FeSe, the Li/NH3 intercalate product and a subsequent sample of this intercalate treated with moist He gas have been measured in temperature range 4.7 - 290 K. A correlation is established between hyperfine parameters and critical temperature Tc in these phases. A strong increase of isomer shift upon intercalation is explained by a charge transfer from the Li/NH3 intercalate to the FeSe layers resulting in an increase of Tc up to 42 K. A significant decrease of the quadrupole splitting above 240 K has been attributed to diffusive motion of Li+ ion…
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 dicstance between neighboring Fe layers, d, is 16.225(5) $\mathring{\text{A}}$, 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 appea…
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 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 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…
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…
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…
The recent discovery of high temperature superconductivity in a layered iron arsenide has led to an intensive search to optimize the superconducting properties of iron-based superconductors by changing the chemical composition of the spacer layer that is inserted between adjacent anionic iron arsenide layers. Until now, superconductivity has only been found in compounds with a cationic spacer layer consisting of metal ions: Li+, Na+, K+, Ba2+ or a PbO-type or perovskite-type oxide layer. Electronic doping is usually necessary to control the fine balance between antiferromagnetism and supercond…
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…
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.
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…
The superconducting critical temperature, $T_{\rm c}$, of FeSe can be dramatically enhanced by intercalation of a molecular spacer layer. Here we report on a $^{77}$Se, $^7$Li and $^1$H nuclear magnetic resonance (NMR) study of the powdered hyper-interlayer-expanded Li$_{x}($C$_2$H$_8$N$_2$)$_y$Fe$_{2-z}$Se$_2$ with a nearly optimal $T_{\rm c}=45$~K. The absence of any shift in the $^7$Li and $^1$H NMR spectra indicates a complete decoupling of interlayer units from the conduction electrons in FeSe layers, whereas nearly temperature-independent $^7$Li and $^1$H spin-lattice relaxation rates ar…
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 …
Using a field-effect transistor (FET) configuration with solid Li-ion conductor (SIC) as gate dielectric, we have successfully tuned carrier density in FeSe$_{0.5}$Te$_{0.5}$ thin flakes, and the electronic phase diagram has been mapped out. It is found that electron doping controlled by SIC-FET leads to a suppression of the superconducting phase, and eventually gives rise to an insulating state in FeSe$_{0.5}$Te$_{0.5}$. During the gating process, the (001) peak in XRD patterns stays at the same position and no new diffraction peak emerges, indicating no evident Li$^+$ ions intercalation into…
A general feature of unconventional superconductors is the existence of a superconducting dome in the phase diagram as a function of carrier concentration. For the simplest iron-based superconductor FeSe (with transition temperature Tc ~ 8 K), its Tc can be greatly enhanced by doping electrons via many routes, even up to 65 K in monolayer FeSe/SiTiO3. However, a clear phase diagram with carrier concentration for FeSe-derived superconductors is still lacking. Here, we report the observation of a series of discrete superconducting phases in FeSe thin flakes by continuously tuning carrier concent…
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…
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 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 FeSe superconductor and its related systems have attracted much attention in the iron-based superconductors owing to their simple crystal structure and peculiar electronic and physical properties. The bulk FeSe superconductor has a superconducting transition temperature (Tc) of ~8 K; it can be dramatically enhanced to 37 K at high pressure. On the other hand, its cousin system, FeTe, possesses a unique antiferromagnetic ground state but is non-superconducting. Substitution of Se by Te in the FeSe superconductor results in an enhancement of Tc up to 14.5 K and superconductivity can persist …
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…
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…
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 …
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.
We have performed transverse- and zero-field muon spin rotation/relaxation experiments, as well as magnetometry measurements, on samples of Fe1-xVxSe and their Li+NH3 intercalates Li0.6(NH2)0.2(NH3)0.8 Fe1-x Vx Se. We examine the low vanadium substitution regime: x = 0.005, 0.01, and 0.02. The intercalation reaction significantly increases the critical temperature (Tc) and the superfluid stiffness for all x. The nonintercalated samples all exhibit Tc = 8.5 K while the intercalated samples all show an enhanced Tc > 40 K. Vanadium substitution has a negligible effect on Tc, but seems to suppress…
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 …
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…
Following a recent proposal by Burrard-Lucas et al. [unpublished, arXiv: 1203.5046] we intercalated FeSe by Li in liquid ammonia. We report on the synthesis of new LixFe2Se2(NH3)y phases as well as on their magnetic and superconducting properties. We suggest that the superconducting properties of these new hybride materials appear not to be influenced by the presence of electronically-innocent Li(NH2) salt moieties. Indeed, high onset temperatures of 44 K and shielding fractions of almost 80% were only obtained in samples containing exclusively Lix(NH3)y moieties acting simultaneously as elect…
It has long been a challenging task to find compounds with similar crystal and electronic structures as cuprate superconductors with low dimensionality and strong antiferromagnetic fluctuations. The parent compounds of cuprate superconductors are Mott insulators with strong in-plane antiferromagnetic exchange interactions between Cu moments. Here we show, based on first-principles density functional calculations, that AFeSe2 (A=Tl, K, Rb, or Cs) exhibit many of the physical properties common to the cuprate parent compounds: (1) the FeSe2 layer in AFeSe2 is similar in crystalline and electronic…
Recently discovered A-Fe-Se (A - alkali metal) materials have questioned the most popular theories of iron-based superconductors because of their unusual electronic structure [1]. Controversial photoemission data taken in the superconducting state [2-7] are in conflict with highly magnetic state seen by neutron-, muSR-spectroscopies and transport/thermodynamic probes [8-10]. These results lead to suggestions to consider all iron-based materials as originating from Mott-insulators or semiconductors, thus once again raising the question of close relation between the cuprates and Fe-based superco…
