Journal ArticleDOI

# Hyper-expanded interlayer separations in superconducting barium intercalates of FeSe.

09 Apr 2015-Chemical Communications (The Royal Society of Chemistry)-Vol. 51, Iss: 33, pp 7112-7115

TL;DR: The values of Tc are primarily dependent on Ba content, and are further modulated by the interlayer spacing through facile intercalation and deintercalation of ammonia.

AbstractIntercalation of Ba in β-FeSe by ammonothermal synthesis results in the formation of different superconducting phases with interlayer distance ranging between 8.4 and 13.1 A. The values of Tc are primarily dependent on Ba content, and are further modulated by the interlayer spacing through facile intercalation and deintercalation of ammonia.

Topics: , Barium (50%)

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Abstract: 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 dichalcogenides, fullerenes, and layered cobalt oxides. From past studies of these intercalated superconductors, we discuss the role of the intercalates in terms of charge doping, structural distortions, and Fermi surface reconstruction. We also briefly review the physical and chemical properties of the host materials—mackinawite-type FeS and β-FeSe. The three types of intercalates for the iron chalcogenides can be placed in three categories: 1.) alkali and alkaline earth cations intercalated through the liquid ammonia technique; 2.) cations intercalated with organic amines such as ethylenediamine; and 3.) layered hydroxides intercalated during hydrothermal conditions. A recurring theme in these studies is the role of the intercalated guest in electron doping the chalcogenide host and in enhancing the two-dimensionality of the electronic structure by spacing the FeSe layers apart. We end this review discussing possible new avenues in the intercalation chemistry of transition metal monochalcogenides, and the promise of these materials as a unique set of new inorganic two-dimensional systems.

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### Cites background from "Hyper-expanded interlayer separatio..."

• ...ing the intercalation of cations via liquid ammonia.[133] Initially, a fast intercalation occurs at 200 K with a char-...

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TL;DR: The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations, and assumes the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, to be an intrinsic property of the system.
Abstract: Alkali metal intercalated iron selenide superconductors A x Fe2-y Se2 (where A = K, Rb, Cs, Tl/K, and Tl/Rb) are characterized by several unique properties, which were not revealed in other superconducting materials. The compounds crystallize in overall simple layered structure with FeSe layers intercalated with alkali metal. The structure turned out to be pretty complex as the existing Fe-vacancies order below ~550 K, which further leads to an antiferromagnetic ordering with Neel temperature fairly above room temperature. At even lower temperatures a phase separation is observed. While one of these phases stays magnetic down to the lowest temperatures the second is becoming superconducting below ~30 K. All these effects give rise to complex relationships between the structure, magnetism and superconductivity. In particular the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, is assumed to be an intrinsic property of the system. Since the discovery of superconductivity in those compounds in 2010 they were investigated very extensively. Results of the studies conducted using a variety of experimental techniques and performed during the last five years were published in hundreds of reports. The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations.

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##### References
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Journal ArticleDOI
, Lu Wei1, Yang Jie1, Yi Wei1
Abstract: We report the superconductivity in iron-based oxyarsenide Sm[O1-xFx]FeAs, with the onset resistivity transition temperature at 55.0K 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 up to now.

1,418 citations

Journal ArticleDOI
, Tao Wu1, Gang Wu1
25 May 2008-Nature
Abstract: The recently discovered layered rare-earth metal oxypnictides have reinvigorated research into high-temperature superconductivity. The first of these, found only a few months ago, had a transition temperature of 26 K. A recent paper in Nature reported an iron–arsenic-based material superconducting at 43 K with the application of pressure. Previously only copper oxides superconductors had beaten the 40 K barrier. Now Chen et al. report bulk superconductivity in the samarium–arsenide oxide SmFeAsO1−xFx with a transition temperature of 43 K without this pressure. A report on the discovery of bulk superconductivity in samarium-arsenide oxides SmFeAsO1−xFx with a transition temperature as high as 43 K. Since the discovery of high-transition-temperature (high-Tc) superconductivity in layered copper oxides, extensive effort has been devoted to exploring the origins of this phenomenon. A Tc higher than 40 K (about the theoretical maximum predicted from Bardeen–Cooper–Schrieffer theory1), however, has been obtained only in the copper oxide superconductors. The highest reported value for non-copper-oxide bulk superconductivity is Tc = 39 K in MgB2 (ref. 2). The layered rare-earth metal oxypnictides LnOFeAs (where Ln is La–Nd, Sm and Gd) are now attracting attention following the discovery of superconductivity at 26 K in the iron-based LaO1-xF x FeAs (ref. 3). Here we report the discovery of bulk superconductivity in the related compound SmFeAsO1-xF x , which has a ZrCuSiAs-type structure. Resistivity and magnetization measurements reveal a transition temperature as high as 43 K. This provides a new material base for studying the origin of high-temperature superconductivity.

1,285 citations

Journal ArticleDOI

15 May 2008-Nature
TL;DR: It is reported that increasing the pressure causes a steep increase in the onset Tc of F-doped LaOFeAs, to a maximum of ∼43 K at ∼4 GPa, which is the highest Tc reported to date.
Abstract: The hunt for new materials exhibiting high-temperature superconductivity is on again. A complex iron-based oxide, containing lanthanum and arsenic, was recently found to exhibit a transition temperature (Tc) of about 26 K when doped with fluoride ions. That's respectable, but far from the heights achieved in copper oxide superconductors. Now Takahashi et al. show that the application of around 40,000 atmospheres of pressure can raise the Tc of this material substantially, to about 43 K. This is the highest tc yet reported for a non-copper-based material. What is more, this record is unlikely to last for long: the complexity of 'iron oxypnictides' of this type offers considerable flexibility for chemical modification, and we can expect to hear of yet higher transition temperatures. This paper — and the prospect of a new wave of superconductor fever — is the subject of an Editorial in the 24 April issue of Nature (452, 914; 2008). The application of pressure can raise the superconducting transition temperature of oxypnictide (a pnicogen being a group V element) substantially, to a maximum value of about 43 K. This is the highest transition temperature yet reported for a non-copper-based material, but this record is unlikely to last for long: the material system offers considerable flexibility for chemical modification, and we can reasonably anticipate that this record will soon be superseded. The iron- and nickel-based layered compounds LaOFeP (refs 1, 2) and LaONiP (ref. 3) have recently been reported to exhibit low-temperature superconducting phases with transition temperatures Tc of 3 and 5 K, respectively. Furthermore, a large increase in the midpoint Tc of up to ∼26 K has been realized4 in the isocrystalline compound LaOFeAs on doping of fluoride ions at the O2- sites (LaO1-xFxFeAs). Experimental observations5,6 and theoretical studies7,8,9 suggest that these transitions are related to a magnetic instability, as is the case for most superconductors based on transition metals. In the copper-based high-temperature superconductors, as well as in LaOFeAs, an increase in Tc is often observed as a result of carrier doping in the two-dimensional electronic structure through ion substitution in the surrounding insulating layers, suggesting that the application of external pressure should further increase Tc by enhancing charge transfer between the insulating and conducting layers. The effects of pressure on these iron oxypnictide superconductors may be more prominent than those in the copper-based systems, because the As ion has a greater electronic polarizability, owing to the covalency of the Fe–As chemical bond, and, thus, is more compressible than the divalent O2- ion. Here we report that increasing the pressure causes a steep increase in the onset Tc of F-doped LaOFeAs, to a maximum of ∼43 K at ∼4 GPa. With the exception of the copper-based high-Tc superconductors, this is the highest Tc reported to date. The present result, together with the great freedom available in selecting the constituents of isocrystalline materials with the general formula LnOTMPn (Ln, Y or rare-earth metal; TM, transition metal; Pn, group-V, ‘pnicogen’, element), indicates that the layered iron oxypnictides are promising as a new material platform for further exploration of high-temperature superconductivity.

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TL;DR: The synthesis of Li(x)( NH(2))(y)(NH(3))(1-y)Fe(2)Se(2), with lithium ions, lithium amide and ammonia acting as the spacer layer between FeSe layers, which exhibits superconductivity at 43(1) K, higher than in any FeSe-derived compound reported so far.
Abstract: 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 superconductivity. Superconductivity has also been reported in FeSe, which contains neutral layers similar in structure to those found in the iron arsenides but without the spacer layer. Here we demonstrate the synthesis of Lix(NH2)y(NH3)1-yFe2Se2 (x ~0.6 ; y ~ 0.2), with lithium ions, lithium amide and ammonia acting as the spacer layer, which exhibits superconductivity at 43(1) K, higher than in any FeSe-derived compound reported so far and four times higher at ambient pressure than the transition temperature, Tc, of the parent Fe1.01Se. We have determined the crystal structure using neutron powder diffraction and used magnetometry and muon-spin rotation data to determine the superconducting properties. This new synthetic route opens up the possibility of further exploitation of related molecular intercalations in this and other systems in order to greatly optimize the superconducting properties in this family.

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