We report superconductivity in the novel 112-type iron-based compound Ca 1Àx La x FeAs 2 . Single-crystal X-ray diffraction analysis revealed that the compound crystallizes in a monoclinic structure (space group P2 1 ), in which Fe 2 As 2 layers alternate with Ca 2 As 2 spacer layers such that monovalent arsenic forms zigzag chains. Superconductivity with a transition temperature (T c ) of 34 K was observed for the x ¼ 0:1 sample, while the x ¼ 0:21 sample exhibited trace superconductivity at 45 K. First-principles band calculations demonstrated the presence of almost cylindrical Fermi surfaces, favorable for the high T c in La-doped CaFeAs 2 .KEYWORDS: iron-based superconductors, Ca-La-Fe-As, 112-type, CaFeAs 2Since the discovery of superconductivity with a transition temperature (T c ) of 26 K in LaFeAsO 1Àx F x , 1) there has been tremendous effort towards synthesizing novel iron pnictide superconductors. [2][3][4][5][6][7][8][9][10][11][12][13][14] All of the iron pnictide superconductors identified so far consist of a common structural motif, i.e., Fe 2 As 2 layers that are alternately stacked with various kinds of spacer layers. Therefore, the central goal for realizing a higher T c has been finding a novel spacer layer that can suitably tune the electronic states of Fe 2 As 2 layers.Recently, superconductivity has been discovered in Ca 10 (Pt n As 8 )(Fe 2Àx Pt x As 2 ) 5 , which consists of As-As dimers with a formal electron count of As 2À in the spacer layer. [15][16][17][18] Because of the 4p 3 electron configuration of elemental arsenic, arsenic can form various bonding structures: (i) Isolated arsenic with a formal electron count of As 3À . Examples include A 3 As (A ¼ Li, Na, and K) and iron-based superconductors. (ii) Dimerized As-As with a single bond. Its formal electron count is As 2À . Sr 2 As 2 and Ca 10 (Pt n As 8 )(Fe 2Àx Pt x As 2 ) 5 with As-As dimer bonds in the spacer layer can be categorized here. (iii) A one-dimensional chain connected by arsenic single bonds with a formal electron count of As À . This category includes KAs as an example. Realizing novel iron-based superconductors with spacer layers composed of complex bonding networks of arsenic such as (iii) has been a longstanding challenge: Shim et al. have theoretically proposed the hypothetical compound BaFeAs 2 (112-type) with spacer layers of the arsenic square network, and suggested that such compounds can be used to examine the role of charge and polarization fluctuations as well as the importance of two-dimensionality in the mechanism of superconductivity. 19) Although the 112-type iron pnictides AEFeAs 2 (AE ¼ Ca, Sr, Ba) have not yet been synthesized, the isostructural compounds RET As 2 (RE = rare-earth elements; T ¼ Cu, Ag, Au) have been studied intensively. 20,21) In this letter, we present a report on the novel 112-type iron-based superconductor Ca 1Àx La x FeAs 2 . Although pure CaFeAs 2 was not obtained, we found that the substitution of a small amount of La for Ca stabilizes the 112 phase. Thus, Ca 1Àx La x FeAs 2 ...

We report the unprecedented square-planar coordination of iridium in the iron iridium arsenide Ca 10 (Ir 4 As 8 )(Fe 2 As 2 ) 5 . This material experiences superconductivity at 16 K. X-ray photoemission spectroscopy and first-principles band calculation suggest Ir(II) oxidation state, which yields electrically conductive Ir 4 As 8 layers. Such metallic spacer layers are thought to enhance the interlayer coupling of Fe 2 As 2 , in which superconductivity emerges, thus offering a way to control the superconducting transition temperature.

The crystal structure of the excitonic insulator Ta 2 NiSe 5 has been investigated under a range of pressures, as determined by the complementary analysis of both single-crystal and powder synchrotron X-ray diffraction measurements. The monoclinic ambient-pressure excitonic insulator phase II transforms upon warming or under a modest pressure to give the semiconducting C-centred orthorhombic phase I. At higher pressures (i.e. >3 GPa), transformation to the primitive orthorhombic semimetal phase III occurs. This transformation from phase I to phase III is a pressure-induced first-order phase transition, which takes place through coherent sliding between weakly coupled layers. This structural phase transition is significantly influenced by Coulombic interactions in the geometric arrangement between interlayer Se ions. Furthermore, upon cooling, phase III transforms into the monoclinic phase IV, which is analogous to the excitonic insulator phase II. Finally, the excitonic interactions appear to be retained despite the observed layer sliding transition.

1T-TiSe 2 has a semimetallic band structure at room temperature and undergoes phase transition to a triple-q charge density wave (CDW) state with a commensurate superlattice structure (2a × 2a × 2c) below T c ≈ 200 K at ambient pressure. This phase transition is caused by cooperative phenomena involving electron-phonon and electron-hole (excitonic) interactions, and cannot be described by a standard CDW framework. By Cu intercalation or the application of pressure, this phase transition temperature is suppressed and superconductivity (SC) appears. However, it is not clear what kind of order parameters are affected by these two procedures. We investigated the crystal structure of Cu x TiSe 2 and pressurized 1T-TiSe 2 around the SC state by synchrotron x-ray diffraction on single crystals. In the high-temperature phase, the variation of structural parameters for the case of Cu intercalation and application of pressure are considerably different. Moreover, the relationship between the critical points of the CDW phase transition and the SC dome are also different for the two cases. The excitonic interaction appears to play an important role in the P−T phase diagram of 1T-TiSe 2 , but not in the x−T phase diagram.

We report the development of an apparatus for Bragg coherent X-ray diffraction imaging (Bragg-CDI) at BL22XU of SPring-8, and show some typical results of the three dimensional imaging of BaTiO3 fine particles obtained using the apparatus. We studied two types of sample—particles with cubic-like shapes, and particles rich in curved surfaces. The shapes and sizes of the particles were successfully reconstructed, and are approximately consistent with results from scanning electron microscope (SEM) measurements. Further, details of the internal structure and reverse surface of the particles was obtained, information which is not available from SEM measurements. Our technique can currently be used to study particles as small as around 100 nm in size. Bragg-CDI is a powerful technique for investigating nanosized crystalline particles, and will open the door to studying particles located within devices such as multi-layered ceramic capacitors, inaccessible by electron beam techniques.