Hideo Hosono

LnNiSi (Ln = La–Nd) comprising a three-dimensional NiSi framework has electrons in the crystallographic cavity space. In the temperature region 473–773 K, it accepts the insertion/de-insertion of hydrogen topotactically without a change in unitcell volume. The insertion of hydrogens into the cavity space is accompanied by a redox reaction with the orbitals of atoms constituting the cavity wall. Having small work functions, such intermetallic electrides exhibit metallic electrical and magnetic properties. Owing to a high electron-donating power and reversible exchange between hydrogen and the electrons, Ru5wt%-loaded LaNiSi powder worked as an efficient catalyst for ammonia synthesis under ambient pressure.

A cubic variant of CaH₂ adopting a fluorite-type crystal structure was synthesized by cationic substitution with La or Y, yielding the first alkaline earth hydride-based with fluorite-type framework. The material has a bandgap of ∼2.5 eV (greenish yellow in color), which is much smaller than that of orthorhombic PbCl₂-type CaH₂ (4.4 eV) and is, in fact, the smallest among alkaline or alkaline earth metal hydrides reported to date. Analysis of the density functional theory band structure of cubic-CaH₂ indicates that its conduction band minimum is formed mainly by the interaction between the Ca 3d e_g orbitals around the crystallographic cavity defined by cubes of H^– ions. The use of such cavities in the creation of low-lying conduction band minima by semiconductors is extremely rare, and has similarities to inorganic electrides.

The electronic structures of the antifluorite‐type compound Mg₂Si is described in which a sublattice of short cation–cation contacts creates a very low conduction band minimum. Since Mg₂Si shows n‐type conductivity without intentional carrier doping, the present result indicates that the cage defined by the cations plays critical roles in carrier transport similar to those of inorganic electrides, such as 12 CaO⋅7 Al₂O₃:e⁻ and Ca₂N. A distinct difference in the location of conduction band minimum between Mg₂Si and the isostructural phase Na₂S is explained in terms of factors such as the differing interaction strengths of the Si/S 3s orbitals with the cation levels, with the more core‐like character of the S 3s leading to a relatively low conduction band energy at the Γ point. Based on these results and previous research on electrides, approaches can be devised to control the energy levels of cation sublattices in semiconductors.

In view of the strong electron-donating nature of H^– and extensive vacancy formation in metals by hydrogen insertion, a series of LnH_2+x (Ln = La, Ce, or Y) compounds with fluorite-type structures were verified to be the first hydride-based electride, where itinerant electrons populating the cage are surrounded by H^– anions. The electron transfer into the cage probably originates from Ln–cage covalent interaction. To the best of our knowledge, anion-rich electrides are extremely rare, and a key requirement for their formation is that the cage site is not occupied by lone pair electrons of the adjacent ions. In the case of LnH₂, the cage site is surrounded by eight H^– anions with isotopic electronic character caused by the lack of mixing of H p-orbital character. Notably, Ru-loaded LnH_2+x electride powders synthesized by hydrogen embrittlement (Ln = La or Ce) were found to work as efficient catalysts for ammonia synthesis at ambient pressure, without showing serious signs of hydrogen poisoning. There are several possible origins of the observed high catalytic activity in the hydride promotors: the small work function of LnH_2+x derived from the covalent interaction between Ln cation and the H^– σ donor, and the formation of Ln nitride during catalytic reaction.

The 1111-type iron arsenide hydride CaFe1-xCoxAsH was synthesized by high-pressure solid-state reaction, and its electronic structure and superconducting properties were investigated. Bulk superconductivity was observed at x = 0.07-0.26. A maximum superconducting critical temperature Tcmax of 23 K was observed at x = 0.07. These values are in agreement with those of CaFe1-xCoxAsF. The calculated Fermi surface of CaFeAsH has a small three-dimensional 3D hole pocket around the Gamma point. This is a result of weak covalent bonding between the As 4p and H 1s orbitals. No such covalency exists in CaFeAsF, because the energy level of the F 2p orbital is sufficiently deep to inhibit overlap with the As 4p orbital. The similar superconducting properties of CaFe1-xCoxAsH and CaFe1-xCoxAsF are explained on the nesting scenario. The small 3D hole pocket of CaFe1-xCoxAsH does not significantly contribute to electron excitation. These findings encourage exploration of hydrogen-containing 1111-type iron-based materials with lower anisotropies and higher Tc applicable to superconducting wires and tapes.

La-substituted CaFeAsH,(Ca1-xLax)FeAsH, were synthesized by the solid state reaction at 1173 K under high pressure of 2.5 GPa. The r-T anomaly corresponding to tetragonal to orthorhombic structural transition was suppressed by La-substitution and then the superconductivity was observed at an electron doping content of Ne > 0.05. The maximum onset Tc of 47.4 K was reached for Ne = 0.18, which is significant increase compared to 23 K achieved by direct electron doping to the FeAs-layer via Co-substitution to the Fe-site. This value of Tc value fits well to the phenomenological relation between Tc and the bond angle of As-Fe-As in indirectly electron doped LnFeAsO (Ln = Lanthanide). These results indicate that the electron was doped via the indirect mode through the aliovalent ion substitution to CaH-layer (Ca2+ La3+ + e-).

Iron arsenide superconductors based on the material LaFeAsO1-xFx 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 O2- with F- suppresses these transitions and gives rise to superconductivity with a maximum Tc = 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 LaFeAsO1-xHx (x < 0.53) and, in addition to the conventional superconducting dome seen in LaFeAsO1-xFx, we find a second dome in the range 0.21 < x < 0.53, with a maximum Tc of 36 K at x = 0.3. Density functional theory calculations reveal that the three Fe 3d bands (xy, yz, 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 Tc.

Stimulated by the discovery of the iron oxypnictide superconductor with ZrCuSiAs-type structure in 2008, extensive exploration of its isostructural and isoelectronic compounds has started. These compounds, including oxides, fluorides, and hydrides, can all be simply recognized as valence compounds for which the octet rule is valid. We report herein the first example of a ZrCuSiAs-type hydride, CaNiGeH, which violates the octet rule. This hydride was synthesized by hydrogenation of the CeFeSi-type compound CaNiGe under pressurized hydrogen. Powder diffraction and theoretical simulation confirm that H enters into the interstitial position of the Ca₄ tetrahedron, leading to notable anisotropic expansion of the unit cell along the c axis. Density functional theory calculations indicate the modification of the chemical bonding and formation of ionic Ca–H bond as a result of hydrogen insertion. Furthermore, CaNiGeH shows Pauli paramagnetism and metallic conduction similar to that of CaNiGe, but its carrier type changes to hole and the carrier density is drastically reduced as compared to CaNiGe. Mn-doping at the Ni site introduces magnetism to both the parent compound and the hydride. The measurement demonstrates that hydrogenation of CaNi_1–xMn_xGe reduces ferromagnetic ordering of Mn ions and induces huge magnetic hysteresis, whereas the spin glass state observed for the parent compound is preserved in the hydride. The hydrogenation-induced changes in the electric and magnetic properties are interpreted in terms of development of two-dimensionality in crystal structure as well as electronic state.