Soshi Iimura

Two-dome structure in electron-doped iron arsenide superconductors

Iron arsenide superconductors based on the material LaFeAsO(1-x)F(x) are characterized by a two-dimensional Fermi surface (FS) consisting of hole and electron pockets yielding structural and antiferromagnetic transitions at x=0. Electron doping by substituting O(2-) with F(-) suppresses these transitions and gives rise to superconductivity with a maximum T(c) of 26 K at x=0.1. However, the over-doped region cannot be accessed due to the poor solubility of F(-) above x=0.2. Here we overcome this problem by doping LaFeAsO with hydrogen. We report the phase diagram of LaFeAsO(1-x)H(x) (x<0.53) and, in addition to the conventional superconducting dome seen in LaFeAsO(1-x)F(x), we find a second dome in the range 0.21<x<0.53, with a maximum T(c) of 36 K at x=0.3. Density functional theory calculations reveal that the three Fe 3d bands (xy, yz and zx) become degenerate at x=0.36, whereas the FS nesting is weakened monotonically with x. These results imply that the band degeneracy has an important role to induce high T(c).

Discovery of earth-abundant nitride semiconductors by computational screening and high-pressure synthesis.

Nitride semiconductors are attractive because they can be environmentally benign, comprised of abundant elements and possess favourable electronic properties. However, those currently commercialized are mostly limited to gallium nitride and its alloys, despite the rich composition space of nitrides. Here we report the screening of ternary zinc nitride semiconductors using first-principles calculations of electronic structure, stability and dopability. This approach identifies as-yet-unreported CaZn2N2 that has earth-abundant components, smaller carrier effective masses than gallium nitride and a tunable direct bandgap suited for light emission and harvesting. High-pressure synthesis realizes this phase, verifying the predicted crystal structure and band-edge red photoluminescence. In total, we propose 21 promising systems, including Ca2ZnN2, Ba2ZnN2 and Zn2PN3, which have not been reported as semiconductors previously. Given the variety in bandgaps of the identified compounds, the present study expands the potential suitability of nitride semiconductors for a broader range of electronic, optoelectronic and photovoltaic applications.

Identical effects of indirect and direct electron doping of superconducting BaFe2As2thin films

Electron doping of a 122-type iron pnictide BaFe2As2 by substituting the Ba site with an aliovalent ion (indirect doping), which had been unsuccessful by conventional solid-state synthesis methods, was achieved by a non-equilibrium film growth process. The substitution with La was substantiated by a systematic shrinkage of the c-axis lattice parameter due to the smaller ionic radius of La3+ than that of Ba2+. A negative Hall coefficient indicated that the majority carriers were electrons, as is consistent with this aliovalent ion doping. The La substitution suppressed an antiferromagnetic transition and induced bulk superconductivity at a maximum onset critical temperature (Tc) of 22.4 K. The electronic phase diagram for (Ba1-xLax)Fe2As2 was built, which revealed that the indirect electron doping at the Ba site with La [(Ba1-xLax)Fe2As2] exhibits almost the same Tc - doping level relation as that of the direct electron-doping at the Fe site with Co [Ba(Fe1-xCox)2As2]. This finding clarified that Tc in 122-type compounds is not affected by a crystallographic doping site, which is in sharp contrast to the 1111-type compounds, REFeAsO (RE = rare earth). It is tentatively attributed to the differences in their dimensionality of electronic structures and electron pairing symmetries.

Detection of Antiferromagnetic Ordering in Heavily Doped LaFeAsO_{1-x}H_{x} Pnictide Superconductors Using Nuclear-Magnetic-Resonance Techniques

We studied double superconducting (SC) domes in LaFeAsO(1-x)H(x) by using 75As and 1H nuclear-magnetic-resonance techniques and unexpectedly discovered that a new antiferromagnetic (AF) phase follows the double SC domes on further H doping, forming a symmetric alignment of AF and SC phases in the electronic phase diagram. We demonstrated that the new AF ordering originates from the nesting between electron pockets, unlike the nesting between electron and hole pockets, as seen in the majority of undoped pnictides. The new AF ordering is derived from the features common to high-Tc pnictides; however, it has not been reported so far for other high-Tc pnictides because of their poor electron doping capability.

Superconductivity at 52 K in hydrogen-substituted LaFeAsO1-xHx under high pressure

The 1111-type iron-based superconductor LnFeAsO1-xFx (Ln stands for lanthanide) is the first material with a Tc above 50 K, other than cuprate superconductors. Electron doping into LaFeAsO by H, rather than F, revealed a double-dome-shaped Tc-x diagram, with a first dome (SC1, 0.05<x<0.20) and a second dome (SC2, 0.2<x<0.5). Here, we report the Tc for the whole hydrogen-doping range in LaFeAsO1-xHx under pressures of up to 19 GPa. Tc rises to 52 K at 6 GPa for the Tc-valley composition between the two Tc domes. This is the first instance of the Tc exceeding 50 K in La-1111-type iron-based superconductors. On the other hand, the Tc of SmFeAsO1-xHx decreased continually, keeping its single-dome structure up to 15 GPa. The present findings strongly suggest that the main reason for realization of the Tc >50 K observed in RE-1111 compounds (RE: Pr, Sm, and Gd) at ambient pressure is the merging of SC1 and SC2.

Controlling factors of T c dome structure in 1111-type iron arsenide superconductors

We investigated the effects of phosphorus substitution on the shape of the Tc(x) dome in 1111-type SmFeAs1-yPyO1-xHx (0 H-) exerts a chemical pressure effect, i.e., a structural reduction of the Pn-Fe-Pn angle {\alpha} (Pn = P, As) and also dopes electrons into the FePn layer to induce superconductivity. Isovalent phosphorus substitution (P3- -> As3-) can induce only a chemical pressure effect, i.e., an increase of {\alpha} for La-substitution of Sm-sites. As y increases from 0.0 to 0.5, the single Tc dome gradually splits into two domes, similar to those of LaFeAsO1-xHx with a Tc valley at x ~ 0.16. We found that the Tc valley is located around (x, {\alpha}) ~ (0.16, 113{\deg}) for both SmFeAs1-yPyO1-xHx and LaFeAsO1-xHx series, irrespective of changes in the Pn anion and Ln cation species. This result suggests that suppression of Tc leads to the emergence of a Tc valley when both the shape of FePn4 tetrahedra represented by {\alpha} and electron doping level of x meet the above criterion in 1111 type iron oxypnictide superconductors.

Formation and Characterization of Hydrogen Boride Sheets Derived from MgB2 by Cation Exchange

Two-dimensional (2D) materials are promising for applications in a wide range of fields because of their unique properties. Hydrogen boride sheets, a new 2D material recently predicted from theory, exhibit intriguing electronic and mechanical properties as well as hydrogen storage capacity. Here, we report the experimental realization of 2D hydrogen boride sheets with an empirical formula of H1B1, produced by exfoliation and complete ion-exchange between protons and magnesium cations in magnesium diboride (MgB2) with an average yield of 42.3% at room temperature. The sheets feature an sp2-bonded boron planar structure without any long-range order. A hexagonal boron network with bridge hydrogens is suggested as the possible local structure, where the absence of long-range order was ascribed to the presence of three different anisotropic domains originating from the 2-fold symmetry of the hydrogen positions against the 6-fold symmetry of the boron networks, based on X-ray diffraction, X-ray atomic pair distribution functions, electron diffraction, transmission electron microscopy, photo absorption, core-level binding energy data, infrared absorption, electron energy loss spectroscopy, and density functional theory calculations. The established cation-exchange method for metal diboride opens new avenues for the mass production of several types of boron-based 2D materials by countercation selection and functionalization.

Hydrogen-Substituted Superconductors SmFeAsO1–xHx Misidentified As Oxygen-Deficient SmFeAsO1–x

We investigated the preferred electron dopants at the oxygen sites of 1111-type SmFeAsO by changing the atmospheres around the precursor with the composition of Sm:Fe:As:O = 1:1:1:1 - x in high-pressure synthesis. Under H2O and H2 atmospheres, hydrogens derived from H2O or H2 molecules were introduced into the oxygen sites as a hydride ion, and SmFeAsO(1-x)Hx was obtained. However, when the H2O and H2 sources were removed from the synthetic process, nearly stoichiometric SmFeAsO was obtained and the maximum amount of oxygen vacancies introduced remained x = 0.05(4). Density functional theory calculations indicated that substitution of hydrogen in the form of H(-) is more stable than the formation of an oxygen vacancy at the oxygen site of SmFeAsO. These results strongly imply that oxygen-deficient SmFeAsO(1-x) reported previously is SmFeAsO(1-x)Hx with hydride ion incorporated unintentionally during high-pressure synthesis.

Switching of intra-orbital spin excitations in electron-doped iron pnictide superconductors

We investigate the doping dependence of the magnetic excitations in two-superconducting-dome-system LaFeAsO1-xDx. Using inelastic neutron scattering, spin fluctuations at different wavenumbers were observed under both superconducting domes around x = 0.1 and 0.4, but vanished at x = 0.2 corresponding to the Tc valley. Theoretical calculations indicate that the characteristic doping dependence of spin fluctuations is rationally explained as a consequence of the switching of the two intra-orbital nestings within Fe-3dYZ, ZX and 3dX2-Y2 by electron doping. The present results imply that the multi-orbital nature plays an important role in the doping and / or material dependence of the Tc of the iron pnictide superconductors.

Robust Spin Fluctuations and s± Pairing in the Heavily Electron Doped Iron-Based Superconductors

We theoretically study the spin fluctuation and superconductivity in La1111 and Sm1111 iron-based superconductors for a wide range of electron doping. When we take into account the band structure variation by electron doping, the hole Fermi surface originating from the \(d_{X^{2}-Y^{2}}\) orbital turns out to be robust against electron doping, and this gives rise to large spin fluctuations and consequently \(s\pm\) pairing even in the heavily doped regime. The stable hole Fermi surface is larger for Sm1111 than for La1111, which can be considered as the origin of the apparent difference in the phase diagram.