Superstructure of Fe5-xGeTe2 Determined by Te K-Edge Extended X-ray Absorption Fine Structure and Te Kα X-ray Fluorescence Holography.

The local structure of the two-dimensional van der Waals material, Fe5-xGeTe2, which exhibits unique structural/magnetic phase transitions, was investigated by Te K-edge extended X-ray absorption fine structure (EXAFS) and Te Kα X-ray fluorescence holography (XFH) over a wide temperature range. The formation of a trimer of Te atoms at low temperatures has been fully explored using these methods. An increase in the Te-Fe distance at approximately 150 K was suggested by EXAFS and presumably indicates the formation of a Te trimer. Moreover, XFH displayed clear atomic images of Te atoms. Additionally, the distance between the Te atoms shortened, as confirmed from the atomic images reconstructed from XFH, indicating the formation of a trimer of Te atoms, i.e., a charge-ordered superstructure. Furthermore, Te Kα XFH provided unambiguous atomic images of Fe atoms occupying the Fe1 site; the images were not clearly observed in the Ge Kα XFH that was previously reported because of the low occupancy of Fe and Ge atoms. In this study, EXAFS and XFH clearly showed the local structure around the Te atom; in particular, the formation of Te trimers caused by charge-ordered phase transitions was clearly confirmed. The charge-ordered phase transition is fully discussed based on the structural variation at low temperatures, as established from EXAFS and XFH.

Pressure Dependence of the Structural and Superconducting Properties of the Bi-Based Superconductor Bi2Pd3Se2.

The structural and superconducting properties of the Bi-based compound Bi2Pd3Se2 were investigated over a wide pressure range. The prepared Bi2Pd3Se2 sample was a superconductor with a superconducting transition temperature, Tc, of approximately 3.0 K, which differed from a previous report (Tc of less than 1.0 K). At ambient pressure, the powder X-ray diffraction (XRD) pattern of the Bi2Pd3Se2 sample was consistent with that previously reported for Bi2Pd3Se2. The Rietveld method was used to refine the crystal structure, which had a space group of C2/m (No. 12), as reported previously. This compound showed no clear anomaly due to the charge-density-wave (CDW) transition, as seen from the temperature dependence of magnetic susceptibility. However, the temperature dependence of electrical resistivity indicated a clear anomaly, presumably because of the CDW transition in the low-pressure range; the CDW transition temperature was approximately 230 K. The XRD patterns of the Bi2Pd3Se2 sample were measured at 0.160-22.7 GPa, and the patterns were well analyzed by both the Le Bail and Rietveld refinement methods, showing no structural phase transitions in the above pressure range. The pressure dependence of Tc of Bi2Pd3Se2 was recorded based on the temperature dependence of the electrical resistance, which showed an almost constant Tc at 0-13.7 GPa, and the Tc-pressure (p) behavior was fully discussed.

Direct Observation of Group-V Dopant Substitutional Defects in CdTe Single Crystals.

Point defect chemistry strongly affects the fundamental properties of materials and has a decisive impact on device performance. The Group-V dopant is prominent acceptor species with high hole concentration in CdTe; however, its local atomic structure is still not clear owing to difficulties in definitive measurements and discrepancies between experimental observations and theoretical models. Herein, we report on direct observation of the local structure for the As dopant in CdTe single crystals by the X-ray fluorescence holography (XFH) technique, which is a powerful tool to visualize three-dimensional atomic configurations around a specific element. The XFH result shows the As substituting on both Cd (AsCd) and Te (AsTe) sites. Although AsTe has been well known as a shallow acceptor, AsCd has not attracted much attention and been discussed so far. Our results provide new insights into point defects by expanding the experimental XFH study in combination with theoretical first-principles studies in II-VI semiconductors.

Emergence of a Pressure-Driven Superconducting Phase in Ba0.77Na0.23Ti2Sb2O.

We investigated the pressure dependence of electric transport in a superconducting sample, Ba0.77Na0.23Ti2Sb2O, to complete the phase diagram of superconducting transition temperature (Tc) against pressure (p). This superconducting sample exhibits a Tc value of 5.8 K at ambient pressure. Here, the superconductivity of the recently reported sample was investigated over a wide pressure range. The Tc value monotonously decreased with pressure below 8 GPa. Interestingly, the Tc value rapidly increased above 8 GPa and slowly declined with pressure above 11 GPa. Thus, a new superconducting phase was discovered above ∼9 GPa. The crystal structure of Ba0.77Na0.23Ti2Sb2O was also elucidated at 0-22.0 GPa with synchrotron X-ray powder diffraction. Consequently, an evident relation between the crystal structure and the superconductivity was revealed, namely, a clear structural phase transition was observed at 8-11 GPa, where the Tc value rapidly increased against pressure. This study provides detailed information on the superconductivity of Ba0.77Na0.23Ti2Sb2O under pressure, which will lead to a comprehensive understanding of pressure-driven superconductivity.

Synthesis of the extended phenacene molecules, [10]phenacene and [11]phenacene, and their performance in a field-effect transistor.

The [10]phenacene and [11]phenacene molecules have been synthesized using a simple repetition of Wittig reactions followed by photocyclization. Sufficient amounts of [10]phenacene and [11]phenacene were obtained, and thin-film FETs using these molecules have been fabricated with SiO2 and ionic liquid gate dielectrics. These FETs operated in p-channel. The averaged measurements of field-effect mobility, <µ>, were 3.1(7) × 10-2 and 1.11(4) × 10-1 cm2 V-1 s-1, respectively, for [10]phenacene and [11]phenacene thin-film FETs with SiO2 gate dielectrics. Furthermore, [10]phenacene and [11]phenacene thin-film electric-double-layer (EDL) FETs with ionic liquid showed low-voltage p-channel FET properties, with <µ> values of 3(1) and 1(1) cm2 V-1 s-1, respectively. This study also discusses the future utility of the extremely extended π-network molecules [10]phenacene and [11]phenacene as the active layer of FET devices, based on the experimental results obtained.

π-electron S = ½ quantum spin-liquid state in an ionic polyaromatic hydrocarbon.

Molecular solids with cooperative electronic properties based purely on π electrons from carbon atoms offer a fertile ground in the search for exotic states of matter, including unconventional superconductivity and quantum magnetism. The field was ignited by reports of high-temperature superconductivity in materials obtained by the reaction of alkali metals with polyaromatic hydrocarbons, such as phenanthrene and picene, but the composition and structure of any compound in this family remained unknown. Here we isolate the binary caesium salts of phenanthrene, Cs(C14H10) and Cs2(C14H10), to show that they are multiorbital strongly correlated Mott insulators. Whereas Cs2(C14H10) is diamagnetic because of orbital polarization, Cs(C14H10) is a Heisenberg antiferromagnet with a gapped spin-liquid state that emerges from the coupled highly frustrated Δ-chain magnetic topology of the alternating-exchange spiral tubes of S = ½ (C14H10)•- radical anions. The absence of long-range magnetic order down to 1.8 K (T/J ≈ 0.02; J is the dominant exchange constant) renders the compound an excellent candidate for a spin-½ quantum-spin liquid (QSL) that arises purely from carbon π electrons.

Unconventional high-Tc superconductivity in fullerides.

A3C60 molecular superconductors share a common electronic phase diagram with unconventional high-temperature superconductors such as the cuprates: superconductivity emerges from an antiferromagnetic strongly correlated Mott-insulating state upon tuning a parameter such as pressure (bandwidth control) accompanied by a dome-shaped dependence of the critical temperature, Tc However, unlike atom-based superconductors, the parent state from which superconductivity emerges solely by changing an electronic parameter-the overlap between the outer wave functions of the constituent molecules-is controlled by the C60 (3-) molecular electronic structure via the on-molecule Jahn-Teller effect influence of molecular geometry and spin state. Destruction of the parent Mott-Jahn-Teller state through chemical or physical pressurization yields an unconventional Jahn-Teller metal, where quasi-localized and itinerant electron behaviours coexist. Localized features gradually disappear with lattice contraction and conventional Fermi liquid behaviour is recovered. The nature of the underlying (correlated versus weak-coupling Bardeen-Cooper-Schrieffer theory) s-wave superconducting states mirrors the unconventional/conventional metal dichotomy: the highest superconducting critical temperature occurs at the crossover between Jahn-Teller and Fermi liquid metal when the Jahn-Teller distortion melts.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'.

Optimized unconventional superconductivity in a molecular Jahn-Teller metal.

Understanding the relationship between the superconducting, the neighboring insulating, and the normal metallic state above T c is a major challenge for all unconventional superconductors. The molecular A3C60 fulleride superconductors have a parent antiferromagnetic insulator in common with the atom-based cuprates, but here, the C60 (3-) electronic structure controls the geometry and spin state of the structural building unit via the on-molecule Jahn-Teller effect. We identify the Jahn-Teller metal as a fluctuating microscopically heterogeneous coexistence of both localized Jahn-Teller-active and itinerant electrons that connects the insulating and superconducting states of fullerides. The balance between these molecular and extended lattice features of the electrons at the Fermi level gives a dome-shaped variation of T c with interfulleride separation, demonstrating molecular electronic structure control of superconductivity.

Synthesis of face-centred cubic Cs3C60 in THF.

A solution chemistry synthetic route yields Cs(3)C(60) with a face-centred cubic structure. The described method uses well-established Schlenk techniques and THF as a solvent. The controlled addition of an organo-metallic salt reducing agent prevents the formation of C(60)(4-) salts. The final product can be precipitated from the solution using hexane as an anti-solvent.

Size and symmetry of the superconducting gap in the f.c.c. Cs3C60 polymorph close to the metal-Mott insulator boundary.

The alkali fullerides, A(3)C(60) (A = alkali metal) are molecular superconductors that undergo a transition to a magnetic Mott-insulating state at large lattice parameters. However, although the size and the symmetry of the superconducting gap, Δ, are both crucial for the understanding of the pairing mechanism, they are currently unknown for superconducting fullerides close to the correlation-driven magnetic insulator. Here we report a comprehensive nuclear magnetic resonance (NMR) study of face-centred-cubic (f.c.c.) Cs(3)C(60) polymorph, which can be tuned continuously through the bandwidth-controlled Mott insulator-metal/superconductor transition by pressure. When superconductivity emerges from the insulating state at large interfullerene separations upon compression, we observe an isotropic (s-wave) Δ with a large gap-to-superconducting transition temperature ratio, 2Δ0/k(B)T(c) = 5.3(2) [Δ0 = Δ(0 K)]. 2Δ0/k(B)T(c) decreases continuously upon pressurization until it approaches a value of ~3.5, characteristic of weak-coupling BCS theory of superconductivity despite the dome-shaped dependence of Tc on interfullerene separation. The results indicate the importance of the electronic correlations for the pairing interaction as the metal/superconductor-insulator boundary is approached.

Dynamic Jahn-Teller effect in the parent insulating state of the molecular superconductor Cs3C60.

The 'expanded fulleride' Cs(3)C(60) is an antiferromagnetic insulator in its normal state and becomes a molecular superconductor with T(c) as high as 38 K under pressure. There is mounting evidence that superconductivity is not of the conventional BCS type and electron-electron interactions are essential for its explanation. Here we present evidence for the dynamic Jahn-Teller effect as the source of the dramatic change in electronic structure occurring during the transition from the metallic to the localized state. We apply infrared spectroscopy, which can detect subtle changes in the shape of the C(60)3- ion due to the Jahn-Teller distortion. The temperature dependence of the spectra in the insulating phase can be explained by the gradual transformation from two temperature-dependent solid-state conformers to a single one, typical and unique for Jahn-Teller systems. These results unequivocally establish the relevance of the dynamic Jahn-Teller effect to overcoming Hund's rule and forming a low-spin state, leading to a magnetic Mott-Jahn-Teller insulator.

Nanoscale effects on the stability of the λ-Ti3O5 polymorph.

The nanocrystalline valency-delocalized λ-phase of the binary oxide Ti(3)O(5) has recently emerged as a promising phase-change material that exhibits rapid photo-reversible optical and resistance changes at ambient temperature. Nanoscaling caused the monoclinic-λ to monoclinic charge-ordered ß-phase structural instability to shift to considerably lower temperatures compared to the bulk material, and led to a broad thermal hysteresis. The structural transformation was accompanied by a large change in volume and large lattice relaxations, which imply the presence of strong electron-phonon coupling. We attribute the suppression of the phase transition to the enhanced surface energy on the nanoscale.

Polymorphism control of superconductivity and magnetism in Cs(3)C(60) close to the Mott transition.

The crystal structure of a solid controls the interactions between the electronically active units and thus its electronic properties. In the high-temperature superconducting copper oxides, only one spatial arrangement of the electronically active Cu(2+) units-a two-dimensional square lattice-is available to study the competition between the cooperative electronic states of magnetic order and superconductivity. Crystals of the spherical molecular C(60)(3-) anion support both superconductivity and magnetism but can consist of fundamentally distinct three-dimensional arrangements of the anions. Superconductivity in the A(3)C(60) (A = alkali metal) fullerides has been exclusively associated with face-centred cubic (f.c.c.) packing of C(60)(3-) (refs 2, 3), but recently the most expanded (and thus having the highest superconducting transition temperature, T(c); ref. 4) composition Cs(3)C(60) has been isolated as a body-centred cubic (b.c.c.) packing, which supports both superconductivity and magnetic order. Here we isolate the f.c.c. polymorph of Cs(3)C(60) to show how the spatial arrangement of the electronically active units controls the competing superconducting and magnetic electronic ground states. Unlike all the other f.c.c. A(3)C(60) fullerides, f.c.c. Cs(3)C(60) is not a superconductor but a magnetic insulator at ambient pressure, and becomes superconducting under pressure. The magnetic ordering occurs at an order of magnitude lower temperature in the geometrically frustrated f.c.c. polymorph (Néel temperature T(N) = 2.2 K) than in the b.c.c.-based packing (T(N) = 46 K). The different lattice packings of C(60)(3-) change T(c) from 38 K in b.c.c. Cs(3)C(60) to 35 K in f.c.c. Cs(3)C(60) (the highest found in the f.c.c. A(3)C(60) family). The existence of two superconducting packings of the same electronically active unit reveals that T(c) scales universally in a structure-independent dome-like relationship with proximity to the Mott metal-insulator transition, which is governed by the role of electron correlations characteristic of high-temperature superconducting materials other than fullerides.

Structural phase transitions and superconductivity in Fe(1+delta)Se0.57Te0.43 at ambient and elevated pressures.

The ternary iron chalcogenide, Fe(1.03)Se(0.57)Te(0.43) is a member of the recently discovered family of Fe-based superconductors with an ambient pressure T(c) of 13.9 K and a simple structure comprising layers of edge-sharing distorted Fe(Se/Te)(4) tetrahedra separated by a van der Waals gap. Here we study the relationship between its structural and electronic responses to the application of pressure. T(c) depends sensitively on applied pressure attaining a broad maximum of 23.3 K at approximately 3 GPa. Further compression to 12 GPa leads to a metallic but nonsuperconducting ground state. High-resolution synchrotron X-ray diffraction shows that the superconducting phase is metrically orthorhombic at ambient pressure but pressurization to approximately 3 GPa leads to a structural transformation to a more distorted structure with monoclinic symmetry. The exact coincidence of the crystal symmetry crossover pressure with that at which T(c) is maximum reveals an intimate link between crystal and electronic structures of the iron chalcogenide superconductors.

The disorder-free non-BCS superconductor Cs3C60 emerges from an antiferromagnetic insulator parent state.

The body-centered cubic A15-structured cesium fulleride Cs3C60 is not superconducting at ambient pressure and is free from disorder, unlike the well-studied face-centered cubic A3C60 alkali metal fulleride superconductors. We found that in Cs3C60, where the molecular valences are precisely assigned, the superconducting state at 38 kelvin emerges directly from a localized electron antiferromagnetic insulating state with the application of pressure. This transition maintains the threefold degeneracy of the active orbitals in both competing electronic states; it is thus a purely electronic transition to a superconducting state, with a dependence of the transition temperature on pressure-induced changes of anion packing density that is not explicable by Bardeen-Cooper-Schrieffer (BCS) theory.

Crystal structure of the new FeSe(1-x) superconductor.

The newly discovered superconductor FeSe(1-x) (x approximately 0.08, T(c)(onset) approximately 13.5 K at ambient pressure rising to 27 K at 1.48 GPa) exhibits a structural phase transition from tetragonal to orthorhombic below 70 K at ambient pressure-the crystal structure in the superconducting state shows remarkable similarities to that of the REFeAsO(1-x)F(x) (RE = rare earth) superconductors.

Doping dependence of the pressure response of Tc in the SmO(1-x)F(x)FeAs superconductors.

The superconducting transition temperature of the high-Tc SmO1-xFxFeAs superconductors increases monotonically as the F-doping level x increases to 0.20. High-pressure magnetization experiments reveal a strong sensitivity of Tc to interatomic distances in the underdoped regime (x

Bulk superconductivity at 38 K in a molecular system.

C(60)-based solids are archetypal molecular superconductors with transition temperatures (Tc) as high as 33 K (refs 2-4). Tc of face-centred-cubic (f.c.c.) A(3)C(60) (A=alkali metal) increases monotonically with inter C(60) separation, which is controlled by the A(+) cation size. As Cs(+) is the largest such ion, Cs(3)C(60) is a key material in this family. Previous studies revealing trace superconductivity in Cs(x)C(60) materials have not identified the structure or composition of the superconducting phase owing to extremely small shielding fractions and low crystallinity. Here, we show that superconducting Cs(3)C(60) can be reproducibly isolated by solvent-controlled synthesis and has the highest Tc of any molecular material at 38 K. In contrast to other A(3)C(60) materials, two distinct cubic Cs(3)C(60) structures are accessible. Although f.c.c. Cs(3)C(60) can be synthesized, the superconducting phase has the A15 structure based uniquely among fullerides on body-centred-cubic packing. Application of hydrostatic pressure controllably tunes A15 Cs(3)C(60) from insulating at ambient pressure to superconducting without crystal structure change and reveals a broad maximum in Tc at approximately 7 kbar. We attribute the observed Tc maximum as a function of inter C(60)separation--unprecedented in fullerides but reminiscent of the atom-based cuprate superconductors--to the role of strong electronic correlations near the metal-insulator transition onset.

Mixed valency in rare-earth fullerides.

Mixed-valence phenomena associated with the highly correlated narrow-band behaviour of the 4f electrons in rare earths are well documented for a variety of rare-earth chalcogenides, borides and intermetallics (Kondo insulators and heavy fermions). The family of rare-earth fullerides with stoichiometry RE2.75C60 (RE=Sm, Yb, Eu) also displays an analogous phenomenology and a remarkable sensitivity of the rare-earth valency to external stimuli (temperature and pressure) making them the first known molecular-based members of this fascinating class of materials. Using powerful crystallographic and spectroscopic techniques which provide direct indications of what is happening in these materials at the microscopic level, we find a rich variety of temperature- and pressure-driven abrupt or continuous valence transitions-the electronically active fulleride sublattice acts as an electron reservoir that can accept electrons from or donate electrons to the rare-earth 4f/5d bands, thereby sensitively modulating the valence of the rare-earth sublattice.

Direct observation of magnetic ordering in the (CH3NH2)K3C60 fulleride.

The zero-field muon-spin-relaxation (ZF-micro(+)SR) technique provides direct observation of the development of antiferromagnetic long range order in the hyperexpanded methylaminated fulleride salt, (CH(3)NH(2))K(3)C(60) below T(N) approximately 10 K-coherent ordering of the electronic magnetic moments leads to a local field of approximately 25 G at the muon site at 1.2 K.