Synthesis of New Lithium- and Monoamine-Intercalated Superconductors Li$_x$(C$_n$H$_{2n+3}$N)$_y$Fe$_{1-z}$Se ($n$ = 6, 8, 18) with the Dramatically Expanded Interlayer Spacing
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.
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…
Behavior consistent with Coulomb-mediated high-T$_C$ superconductivity is shown to be present in the intercalated group-4-metal nitride halides A$_x$(S)$_y$MNX, where the MNX host (M = Ti, Zr, Hf; X = Cl, Br) is partially intercalated with cations A$_x$ and optionally molecular species (S)$_y$ in the van der Waals gap between the halide X layers, expanding the basal-plane spacing d. The optimal transition temperature is modeled by T$_{C0}$ ${\propto}$ ζ$^{-1}$(σ/$A$)$^{1/2}$, where the participating fractional charge per area per formula unit σ/$A$ and the distance ζ, given by the transverse A…
We have succeeded in synthesizing new intercalation superconductors Lix(C2H8N2)yMoSe2 and Lix(C6H16N2)yMoSe2 with Tc = 4.2 and 3.8-6.0 K, respectively, via the co-intercalation of lithium and ethylenediamine or hexamethylenediamine into semiconducting 2H-MoSe2. It has been found that the Tc values are related not to the interlayer spacing between MoSe2 layers so much but to the electronic density of states (EDOS) at the Fermi level. Moreover, only Li-intercalated LixMoSe2 with a small interlayer spacing has been found to be non-superconducting. Accordingly, it has been concluded that not only …
The weak van der Waals interlayer interactions in the transition metal dichalcogenide (TMD) materials have created a rich platform to study their exotic electronic properties through chemical doping or physical gating techniques. We reported bulk superconductivity up to 7.6 K through careful manipulation of the charge carrier density and interlayer spacing d in the chemically intercalated two dimensional 1T-SnSe2 phase. We found, for the first time in the two dimensional SnSe2, that polar organic molecules cointercalated with the alkali metal Li into the basal layers, thus significantly enhanc…
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…
Extracting intrinsic superconducting properties in intercalated layered superconductors using an extended 2D Tinkham model
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所凝聚态物理国家实验室）；School of Physical Sciences, University of Chinese Academy of Sciences（中国科学院大学物理科学学院）；RIKEN Center for Emergent Matter Science (CEMS)（理化学研究所新兴物质科学中心）；Key Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement, Ministry of Education, School of Physics, Beijing Institute of Technology（北京理工大学物理学院教育部先进光电子量子架构与测量重点实验室）；Songshan Lake Materials Laboratory（松山湖材料实验室）
In their article, Zhang et al. [Phys. Rev. B 86, 024516 (2012)] present a remarkable result for A$_x$(S)$_y$TiNCl compounds ($α$-phase TiNCl partially intercalated with alkali A and optionally co-intercalated molecular species S), finding the superconducting transition temperature T$_C$ scales with $d$$^{-1}$, where the spacing $d$ between TiNCl layered structures depends on intercalant thickness. Recognizing that this behavior indicates interlayer coupling, Zhang et al. cite, among other papers, the interlayer Coulombic pairing mechanism picture [Harshman et al., J. Phys.: Condens. Matter 23,…
New intercalation superconductors of Li$_x$(C$_2$H$_8$N$_2$)$_y$TiSe$_2$ and Li$_x$(C$_6$H$_{16}$N$_2$)$_y$TiSe$_2$ with $T_{\rm c}$ = 4.2 K have successfully been synthesized via the co-intercalation of lithium and ethylenediamine or hexamethylenediamine into 1T-TiSe$_2$. Moreover, it has been found that both intercalation compounds of Li$_x$TiSe$_2$ and (C$_2$H$_8$N$_2$)$_y$TiSe$_2$ also show superconductivity with $T_{\rm c}$ = 2.4 K and 2.8 K, respectively. These results indicate that both the electron doping due to the intercalation of lithium and the expansion of the interlayer spacing b…
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…
Superconductivity with zero resistance transition temperature (Tc) up to 8.4 K and 8.3 K can be obtained by doping cobalt and sodium in alfa-FeSe with the nominal composition of Fe0.92Co0.08Se and Na0.1FeSe, respectively. The electrical resistivity and AC magnetic susceptibility of the prepared samples, measured with physical property measurement system (PPMS), unambiguously consistent with each other to indicate that the samples are superconductive. The respective doping mechanisms for cobalt and sodium into the parent alfa-FeSe are the Fe-site substitution and the interlayer insertion. It is…
We report anisotropy of the upper critical field (Bc2) of an intercalated graphite superconductor YbC6 (Tc = 6.5 K) determined from angular dependent magnetoresistance measurements. Though the perpendicular coherence length is much longer than interlayer spacing, measured angular dependences of Bc2 are well fitted by the Lawrence-Doniach model or the Tinkham model, which are known to be applicable to quasi two-dimensional materials or thin films, rather than the effective mass model. This observation is similar to the measurements for the other intercalated graphite superconductor, CaC6, by Jo…
We study superconductivity in multilayer copper oxides, in the frame of a realistic microscopic formulation. Solving the full temperature dependent BCS gap equations, we obtain a maximum in the transition temperature Tc for M=3 or 4 CuO2 layers in the unit cell for appropriate values of the interlayer tunneling (negative pair tunneling), and via the consideration of the doping imbalance between the inner and outer layers. This is the ubiquitous experimental result for Ca intercalated copper oxides, as opposed to other intercalating elements. Further, using a restricted set of parameters, we ob…
Raman spectroscopy measurements have been performed on alpha-, beta-, gamma-NaxCoO2 phases differing in their stacking of CoO6 octahedra along the c-axis direction. The results demonstrate that, in general, there are five active phonons for gamma-Na0.75CoO2, two Raman active phonons for alpha-NaCoO2, and four Raman active phonons for beta-NaCoO2. We have also performed Raman scattering measurements on several gamma-(Ca,Sr)xCoO2 (0.15 <= x <= 0.35) samples which show well-defined intercalated Ca/Sr-ordering. The experimental data show that the intercalated cation ordering could result in visibl…
Transition metal dichalcogenides (TMDs) are quasi-two-dimensional layered compounds exhibiting strongly competing charge-density wave (CDW) and superconducting (SC) order parameters (OPs). The weak van der Waals interlayer bonding between hexagonal layers of octahedral or trigonal prismatic TMD building blocks allows for many polytypes. The non-superconducting $1T$ polytypes can have one or more CDWs. The $2H$ polytypes have two or more Fermi surfaces and saddle bands, allowing for dual orderings, which can be coexisting CDW and SC orderings, two SC gaps as in MgB$_2$, or two CDW gaps. The CDW…
Motivated by the recent discovery of superconductivity in Ca- and Yb-intercalated graphite (CaC$_{6}$ and YbC$_{6}$) and from the ongoing debate on the nature and role of the interlayer state in this class of compounds, in this work we critically study the electron-phonon properties of a simple model based on primitive graphite. We show that this model captures an essential feature of the electron-phonon properties of the Graphite Intercalation Compounds (GICs), namely, the existence of a strong dormant electron-phonon interaction between interlayer and $π^{\ast}$ electrons, for which we provi…
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 …
We report muon spin relaxation ($μ$SR) and magnetization measurements, together with synthesis and characterization, of the Li-intercalated layered superconductors Li$_{x}$HfNCl and Li$_{x}$ZrNCl with/without co-intercalation of THF (tetrahydrofuran) or PC (propylene carbonate). The 3-dimensional (3-d) superfluid density $n_{s}/m^{*}$ (superconducting carrier density / effective mass), as well as the two dimensional superfluid density $n_{s2d}/m^{*}_{ab}$ (2-dimensional (2-d) area density of superconducting carriers / ab-plane effective mass), have been derived from the $μ$SR results of the ma…
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…
Two-dimensional iron-chalcogenide intercalates display a remarkable correlation of the interlayer spacing with the enhancement of the superconducting critical temperature ($T_c$). In this work, synchrotron x-ray absorption ($XAS$, at Fe and Se K edges) and emission ($XES$) spectroscopies, allow to discuss how the important rise of $T_c$ (44 K) in the molecule intercalated $\rm Li_x(C_5H_5N)_yFe_{2-z}Se_2$ relates to the electronic and local structure changes felt by the inorganic host upon doping ($x$). $XES$ shows that widely-separated layers of edge-sharing $\rm FeSe_4$ tetrahedra, carry low…
