Chemical doping has recently become a very important strategy to induce superconductivity especially in complex compounds. Distinguished examples include Ba-doped La$_2$CuO$_4$ (the first high temperature superconductor), K-doped BaBiO$_3$, K-doped C$_{60}$ and Na$_{x}$CoO$_{2}\cdot y$H$_{2}$O. The most recent example is F-doped LaFeAsO, which leads to a new class of high temperature superconductors. One notes that all the above dopants are non-magnetic, because magnetic atoms generally break superconducting Cooper pairs. In addition, the doping site was out of the (super)conducting structural unit (layer or framework). Here we report that superconductivity was realized by doping magnetic element cobalt into the (super)conducting-active Fe$_2$As$_2$ layers in LaFe$_{1-x}$Co$_{x}$AsO. At surprisingly small Co-doping level of $x$=0.025, the antiferromagnetic spin-density-wave transition in the parent compound is completely suppressed, and superconductivity with $T_c\sim $ 10 K emerges. With increasing Co content, $T_c$ shows a maximum of 13 K at $x\sim 0.075$, and then drops to below 2 K at $x$=0.15. This result suggests essential differences between previous cuprate superconductor and the present iron-based arsenide one.
The iron oxyarsenide TbFeAsO0.85 was synthesized by a high-pressure method. A high-quality polycrystalline sample was obtained and characterized by measurements of magnetic susceptibility and electrical resistivity. Bulk superconductivity with Tc of 42 K was clearly established without an F doping usually conducted to tune on superconductivity in the iron oxypnictide.
Hole-doping of NdFeAsO via partial replacement of Nd3+ by Sr2+ is a successful route to obtain superconducting phases (Tc = 13.5 K for a Sr2+ content of 20%); however, the structural and electronic response with doping is different from and non-symmetric to that in the electron-doped side of the phase diagram.
Epitaxial thin films of LaFeAsO were fabricated on MgO (001) and mixed-perovskite (La, Sr)(Al, Ta)O3 (001) single-crystal substrates by pulsed laser deposition using a Nd:YAG second harmonic source and a 10 at.% F-doped LaFeAsO disk target. Temperature dependences of the electrical resistivities showed no superconducting transition in the temperature range of 2-300 K, and were similar to those of undoped polycrystalline bulk samples. The transmittance spectrum exhibited a clear peak at ~0.2 eV, which is explained by ab-initio calculations.
Iron-based oxypnictides substituted with yttrium have been prepared via a conventional solid state reaction. The product after first 50 hours of reaction showed diamagnetic-like transition at around 10 K but was not superconducting, while additional 72 hours of high temperature heat treatment was required to yield superconducting sample which was doped with fluoride. Temperature dependence of the susceptibility shows both screening and Meissner effect at around 10 K, while resistance as a function of temperature displayed a drop at around the same temperature.
A wide-range doping was achieved by a high-pressure method for TbFeAsO1-x from "under doped" to "over doped" superconducting compositions throughout the optimized superconductivity (Tc of 44 K). Tc vs. lattice constant shows a dome-shaped feature, while Tc vs. the lattice constant likely follows a unique empirical curve over the doping range. The relatively large amount of oxygen vacancies up to 0.3 per the formula unit was introduced possibly because of the smaller replacement Tb than the other Ln (rare-earth element) in the LnFeAsO1-x system.
Pure phases of a new oxyarsenide superconductor of the nominal composition CeOFe0.9Co0.1As was successfully synthesized by solid state reaction in sealed silica ampoules at 1180 C. It crystallizes in the layered tetragonal ZrCuSiAs type structure (sp gp P4/nmm) with lattice parameter of a = 3.9918(5) angstrom and c = 8.603(1) angstrom. A sharp superconducting transition is observed at 11.31 K with an upper critical field of 45.22 T at ambient pressure. The superconducting transition temperature is drastically lowered (~ 4.5, 4.9 K) on increasing the concentration (x = 0.15, 0.2) of cobalt.
We consider the role played by the 4f states in the rare-earth oxyarsenides REOFeAs (RE=Ce,Pr,Nd) and the oxyphosphate CeOFeP, using a first-principles technique that combines the local density approximation and dynamical mean-field theory (LDA+DMFT). In the Pr and Nd compounds, the 4f states are located well below and above the Fermi level E_F, and essentially do not interact with the iron 3d bands located near E_F, resulting in local moment behavior. In the Ce compounds, our results reveal a qualitatively different picture, with the 3d-4f hybridization being sufficiently strong to give rise …
Point contact spectroscopy (PCS) is a technique which can reveal the size and symmetry of a superconducting gap ($Δ$) and is especially useful for new materials such as the iron-based superconductors. PCS is usually employed in conjunction with the extended Blonder-Tinkham-Klapwijk (BTK) model which is used to extract information such as the existence of nodes in $Δ$ from PCS data obtained on unconventional superconductors. The BTK model uses a dimensionless parameter $Z$ to quantify the barrier strength across a normal metal - superconductor junction. We have used a unique feature of PCS whic…
Here we report the superconductivity in the iron-based oxyarsenide Sm[O1-xFx]FeAs, with the onset resistivity transition temperature at 55.0 K and Meissner transition at 54.6 K. This compound has the same crystal structure as LaOFeAs with shrunk crystal lattices, and becomes the superconductor with the highest critical temperature among all materials besides copper oxides.
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…
Epitaxial growth of Fe-based superconductors such as Co-doped SrFe$_2$As$_2$ (SrFe$_2$As$_2$:Co) was reported recently, but has still insufficient properties for device application because they have rough surfaces and are decomposed by reactions with water vapor in an ambient atmosphere. This letter reports that epitaxial films of Co-doped BaFe$_2$As$_2$ grown at 700 oC show the onset superconducting transition tempearture of 20 K. The transition is sharper than those observed on the SrFe$_2$As$_2$:Co films, which would originate from their improved crystallinity. These films also have atomica…
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…
We have discovered new layered oxyarsenides (Fe2As2)(Sr4M2O6) (M = Sc, Cr: M-22426). These materials are isostructural with (Fe2P2)(Sr4Sc2O6), which was found in our previous study. The new compounds are tetragonal with a space group of P4/nmm and consist of the anti-fluorite type FeAs layer and perovskite-type blocking layer. The lattice constants are a = 4.050 A, c = 15.809 A for M = Sc and a = 3.918 A, c = 15.683 A for M = Cr. These compounds have long interlayer Fe-Fe distances corresponding to the c-axis length, the 15.8 A in Sc-22426 is the longest in the iron-based oxypnictide systems. …
While the impurity-induced nanoscale electronic disorder has been extensively reported in the underdoped iron pnictides, its microscopic origins remain elusive. Recent scanning tunneling microscopy (STM) measurements reveal a dimer-type resonant structure induced by cobalt doping. These dimers are randomly distributed but uniformly aligned with the antiferromagnetic a axis. A theory of the impurity-induced quasiparticle interference patterns is presented that shows the local density of states developing an oscillatory pattern characterized by both geometry and orbital content of the {\em recon…
We report the results of a study of magnetic field features of electron transport in heterojunctions with NS boundary inside iron-based superconductors, represented by a binary phase of $α$ - FeSe and oxyarsenide pnictide LaO(F)FeAs. We used the ability of self magnetic field of the transport current to partially destroy superconductivity, no matter how low the field may be, in the NS interface area, where, due to the proximity effect, the superconducting order parameter, $Δ$, disperses from 1 to 0 within the scale of the Ginzburg-Landau coherence length. The following features of transport we…
In a conventional superconductor, the spin-lattice relaxation rate on all nuclei should have the same temperature dependence below Tc. We performed $^{23}$Na, $^{75}$As, and $^{59}$Co NMR studies on single crystals of NaFe0.95Co0.05As, and found that spin-lattice relaxation rates show very different temperature dependent power-law behavior on three sites. We propose that such site-dependent behavior is due to the facts that the superconductor has two gaps of very different sizes. The power-law exponent of each nucleus is affected by the strength of the hyperfine coupling to the small gap. We a…
High critical current densities (Jc) > 1 MA/cm2 were realized in cobalt-doped BaFe2As2 (BaFe2As2:Co) films on flexible metal substrates with biaxially-textured MgO base-layers fabricated by an ion-beam assisted deposition technique. The BaFe2As2:Co films showed small in-plane crystalline misorientations (delta fai BaFe2As2:Co) of ~3o regardless of doubly larger misorientaions of the MgO base-layers (delta fai MgO = 7.3o), and exhibited high self-field Jc up to 3.5 MA/cm2 at 2 K. These values are comparable to that on MgO single crystals and the highest Jc among iron pnictide superconducting ta…
The remarkably high superconducting transition temperature and upper critical field of iron(Fe)-based layered superconductors, despite ferromagnetic material base, open the prospect for superconducting electronics. However, success in superconducting electronics has been limited because of difficulties in fabricating high-quality thin films. We report the growth of high-quality c-axis-oriented cobalt(Co)-doped SrFe2As2 thin films with bulk superconductivity by using an in-situ pulsed laser deposition technique with a 248-nm-wavelength KrF excimer laser and an arsenic(As)-rich phase target. The…
In high-superconducting transition temperature ($T_{\rm c}$) iron-based superconductors, interband sign reversal ($s_{\rm \pm}$) and sign preserving ($s_{\rm ++}$) $s$-wave superconducting states have been primarily discussed as the plausible superconducting mechanism. We study Co impurity scattering effects on the superconductivity in order to achieve an important clue on the pairing mechanism using single crystal Fe$_{1-x}$Co$_x$Se and depict a phase diagram of a FeSe system. Both superconductivity and structural transition / orbital order are suppressed by the Co replacement on the Fe sites…
We report Raman scattering spectra of iron-pnictide superconductor Ba(Fe$_{1-x}$Co$_x$)$_2$As$_2$ single crystals with varying cobalt $x$ content. Upon cooling through the tetragonal-to-orthorhombic transition, we observe a large splitting of the E$_g$ in-plane phonon modes involving Fe and As displacements. The splitting of the in-plane phonons at the transition is strongly reduced upon doping and disappears for $x=0.06$ qualitatively following the trend displayed by the Fe magnetic moment. The origin of the splitting is discussed in terms of magnetic frustration inherent to iron-pnictide sys…
The 1144 iron arsenide (e.g. CaKFe4As4) has recently been discovered and inspired a tide of search for superconductors. Such far, the discovered compounds are confined to iron arsenides (ABFe4As4), where A and B are either alkali metals or alkaline earth elements. In this work, we propose two directions in searching 1144 structures: (i) using tri-valence cations for A; (ii) substituting the transition metal, e.g. replacing Fe by Co. Following the two directions, we employ density functional theory to study stability and electronic structures of 1144 pnictides of various tri-valence cations (La…
Additional charge carriers were introduced to the iron oxyarsenide Sr4Sc2Fe2As2O6 under a high-pressure condition, followed by measurements of electrical resistivity, Hall coefficient, and magnetic susceptibility. The host compound Sr4Sc2Fe2As2O6 shows metallic conductivity down to ~200 K and turns to show a semiconducting-like conductivity accompanied by a positive magneto-resistance (22% at 70 kOe). Although the carrier density is comparable at 300 K (5.9x1021 cm-3) with that of the other Fe-based superconductors, no superconductivity appears down to 2 K. This is primarily because the net ca…
We report synthesis, crystal structure and physical properties of a novel quinary compound RbGd$_2$Fe$_4$As$_4$O$_2$. The new iron oxyarsenide is isostructural to the fluo-arsenide KCa$_2$Fe$_4$As$_4$F$_2$, both of which contain separate double Fe$_2$As$_2$ layers that are self hole-doped in the stoichiometric composition. Bulk superconductivity at $T_\mathrm{c}$ = 35 K is demonstrated by the measurements of electrical resistivity, dc magnetic susceptibility and heat capacity. An exceptionally high value of the initial slope of the upper critical field ($μ_0$d$H_{\mathrm{c2}}$/d$T|_{T_\mathrm{…
The compound EuFe(2-x)Co(x)As2 was investigated by means of the 57Fe and 151Eu Moessbauer spectroscopy versus temperature (4.2 - 300 K) for x=0 (parent), x=0.34 - 0.39 (superconductor) and x=0.58 (overdoped). It was found that spin density wave (SDW) is suppressed by Co-substitution, however it survives in the region of superconductivity, but iron spectra exhibit some non-magnetic component in the superconducting region. Europium orders anti-ferromagnetically regardless of the Co concentration with the spin re-orientation from the a-axis in the parent compound toward c-axis with the increasing…
High critical temperature superconductors have zero power consumption and could be used to produce ideal electric power lines. The principal obstacle in fabricating superconducting wires and tapes is grain boundaries-the misalignment of crystalline orientations at grain boundaries, which is unavoidable for polycrystals, largely deteriorates critical current density. Here, we report that High critical temperature iron pnictide superconductors have advantages over cuprates with respect to these grain boundary issues. The transport properties through well-defined bicrystal grain boundary junction…
Raman spectroscopy of a cobalt-doped iron-pnictide superconductor reveals the complex electronic structure of the superconducting state in this material. [Viewpoint on Phys. Rev. B 80, 180510 (2009), arXiv:0910.0898]
We report the first ^{75}As-NMR study on a single crystal of the hole-doped iron-pnictide superconductor Ba_{0.7}K_{0.3}Fe_2As_{2} (T_c = 31.5 K). We find that the Fe antiferromagnetic spin fluctuations are anisotropic and are weaker compared to underdoped copper-oxides or cobalt-oxide superconductors. The spin lattice relaxation rate 1/T_1 decreases below T_c with no coherence peak and shows a step-wise variation at low temperatures, which is indicative of multiple superconducting gaps, as in the electron-doped Pr(La)FeAsO$_{1-x}$F$_{x}$. Furthermore, no evidence was obtained for a microscopi…
We have synthesized 10 new iron oxyarsenides, K$Ln_2$Fe$_4$As$_4$O$_2$ ($Ln$ = Gd, Tb, Dy, and Ho) and Cs$Ln_2$Fe$_4$As$_4$O$_2$ ($Ln$ = Nd, Sm, Gd, Tb, Dy, and Ho), with the aid of lattice-match [between $A$Fe$_2$As$_2$ ($A$ = K and Cs) and $Ln$FeAsO] approach. The resultant compounds possess hole-doped conducting double FeAs layers, [$A$Fe$_4$As$_4$]$^{2-}$, that are separated by the insulating [$Ln_2$O$_2$]$^{2+}$ slabs. Measurements of electrical resistivity and dc magnetic susceptibility demonstrate bulk superconductivity at $T_\mathrm{c}$ = 33 - 37 K. We find that $T_\mathrm{c}$ correlat…
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…
Thin films of the iron-based superconductor BaFe2(As1-xPx)2 (Ba122:P) were fabricated on polycrystalline metal-tape substrates with two kinds of in-plane grain boundary alignments (well aligned (4 deg.) and poorly aligned (8 deg.)) by pulsed laser deposition. The poorly aligned substrate is not applicable to cuprate-coated conductors because the in-plane alignment >4 deg. results in exponential decay of the critical current density (Jc). The Ba122:P film exhibited higher Jc at 4 K when grown on the poorly aligned substrate than on the well-aligned substrate even though the crystallinity was po…
The fluorine-doped rare-earth iron oxyarsenides, REFeAsO1-xFx (RE =rare earth) have recently emerged as a new family of high-temperature superconductors with transition temperatures (Tc) as high as 55 K (refs 1-4). Early work has provided compelling evidence that the undoped parent materials exhibit spin-density-wave (SDW) antiferromagnetic order and undergo a structural phase transition from tetragonal to orthorhombic crystal symmetry upon cooling.5 Both the magnetic and structural instabilities are suppressed upon doping with fluoride ions before the appearance of superconductivity.6,7 Here …
We report the successful substitution of cobalt, nickel, and copper for iron in the 1038 phase parent compound Ca$_{10}$(FeAs)$_{10}$(Pt$_3$As$_8$) yielding Ca$_{10}$(Fe$_{1-x}$Co$_x$As)$_{10}$(Pt$_3$As$_8$), Ca$_{10}$(Fe$_{1-x}$Ni$_x$As)$_{10}$(Pt$_3$As$_8$), and Ca$_{10}$(Fe$_{1-x}$Cu$_x$As)$_{10}$(Pt$_3$As$_8$), respectively. Superconductivity is induced in Co and Ni doped compounds reaching critical temperatures up to 15 K, similar to known Pt substituted Ca$_{10}$(Fe$_{1-x}$Pt$_x$As)$_{10}$(Pt$_3$As$_8$), whereas no superconductivity was detected in Ca$_{10}$(Fe$_{1-x}$Cu$_x$As)$_{10}$(Pt…
The interplay of orbital and spin degrees of freedom is the fundamental characteristic in numerous condensed matter phenomena, including high temperature superconductivity, quantum spin liquids, and topological semimetals. In iron-based superconductors (FeSCs), this causes superconductivity to emerge in the vicinity of two other instabilities: nematic and magnetic. Unveiling the mutual relationship among nematic order, spin fluctuations, and superconductivity has been a major challenge for research in FeSCs, but it is still controversial. Here, by carrying out 77Se nuclear magnetic resonance (…
