Rattling of Oxygen Ions in a Sub-Nanometer-Sized Cage Converts Terahertz Radiation to Visible Light.

A simple and robust approach to visualization of continuous wave terahertz (CW-THz) light would open up opportunities to couple physical phenomena that occur at fundamentally different energy scales. Here we demonstrate how nanoscale cages of Ca12Al14O33 crystal enable conversion of CW-THz radiation to visible light. These crystallographic cages are partially occupied with weakly bonded oxygen ions and give rise to a narrow conduction band that can be populated with localized, yet mobile electrons. CW-THz light excites a nearly stand-alone rattling motion of the encaged oxygen species, which promotes electron transfer from them to the neighboring vacant cages. When the power of CW-THz light reaches tens of watts, the coupling between forced rattling in the confined space, electronic excitation and ionization of oxygen species, and corresponding recombination processes result in emission of bright visible light.

Chemical Design and Example of Transparent Bipolar Semiconductors.

Transparent bipolar semiconductors (TBSCs) are in demand for transparent electronics to serve as the basis for next generation optoelectronic devices. However, the poor carrier controllability in wide-bandgap materials makes the realization of a bipolar nature difficult. Only two materials, CuInO2 and SnO, have been reported as TBSCs. To satisfy demand for the coexistence of transparency and bipolarity, we propose a design concept with three strategies; choice of early transition metals (eTM) such as Y3+ and Zr4+ for improving controllability of carrier doping, design of chemical bonds to obtain an appropriate band structure for bipolar doping, and use of a forbidden band-edge transition to retain transparency. This approach is verified through a practical examination of a candidate material, tetragonal ZrOS, which is chosen by following the criteria. ZrOS exhibits an excellent controllability of the electrical conductivity (10-7-10-2 S cm-1), p- or n-type nature with ∼10-2 S cm-1 by Y or F doping, respectively, and optically wide gap (below 10-4 cm-1 up to ∼2.5 eV). This concept provides a new kind of TBSC based on eTM ionic compounds.

Transparent amorphous oxide semiconductors for organic electronics: Application to inverted OLEDs.

Efficient electron transfer between a cathode and an active organic layer is one key to realizing high-performance organic devices, which require electron injection/transport materials with very low work functions. We developed two wide-bandgap amorphous (a-) oxide semiconductors, a-calcium aluminate electride (a-C12A7:e) and a-zinc silicate (a-ZSO). A-ZSO exhibits a low work function of 3.5 eV and high electron mobility of 1 cm2/(V · s); furthermore, it also forms an ohmic contact with not only conventional cathode materials but also anode materials. A-C12A7:e has an exceptionally low work function of 3.0 eV and is used to enhance the electron injection property from a-ZSO to an emission layer. The inverted electron-only and organic light-emitting diode (OLED) devices fabricated with these two materials exhibit excellent performance compared with the normal type with LiF/Al. This approach provides a solution to the problem of fabricating oxide thin-film transistor-driven OLEDs with both large size and high stability.

Water Durable Electride Y5Si3: Electronic Structure and Catalytic Activity for Ammonia Synthesis.

We report an air and water stable electride Y5Si3 and its catalytic activity for direct ammonia synthesis. It crystallizes in the Mn5Si3-type structure and confines 0.79/f.u. anionic electrons in the quasi-one-dimensional holes. These anionic electrons strongly hybridize with yttrium 4d electrons, giving rise to improved chemical stability. The ammonia synthesis rate using Ru(7.8 wt %)-loaded Y5Si3 was as high as 1.9 mmol/g/h under 0.1 MPa and at 400 °C with activation energy of ∼50 kJ/mol. Its strong electron-donating ability to Ru metal of Y5Si3 is considered to enhance nitrogen dissociation and reduce the activation energy of ammonia synthesis reaction. Catalytic activity was not suppressed even after Y5Si3, once dipped into water, was used as the catalyst promoter. These findings provide novel insights into the design of simple catalysts for ammonia synthesis.

n-type conversion of SnS by isovalent ion substitution: Geometrical doping as a new doping route.

Tin monosulfide (SnS) is a naturally p-type semiconductor with a layered crystal structure, but no reliable n-type SnS has been obtained by conventional aliovalent ion substitution. In this work, carrier polarity conversion to n-type was achieved by isovalent ion substitution for polycrystalline SnS thin films on glass substrates. Substituting Pb(2+) for Sn(2+) converted the majority carrier from hole to electron, and the free electron density ranged from 10(12) to 10(15) cm(-3) with the largest electron mobility of 7.0 cm(2)/(Vs). The n-type conduction was confirmed further by the position of the Fermi level (EF) based on photoemission spectroscopy and electrical characteristics of pn heterojunctions. Density functional theory calculations reveal that the Pb substitution invokes a geometrical size effect that enlarges the interlayer distance and subsequently reduces the formation energies of Sn and Pb interstitials, which results in the electron doping.

Narrow bandgap in ß-BaZn2As2 and its chemical origins.

ß-BaZn2As2 is known to be a p-type semiconductor with the layered crystal structure similar to that of LaZnAsO, leading to the expectation that ß-BaZn2As2 and LaZnAsO have similar bandgaps; however, the bandgap of ß-BaZn2As2 (previously reported value ~0.2 eV) is 1 order of magnitude smaller than that of LaZnAsO (1.5 eV). In this paper, the reliable bandgap value of ß-BaZn2As2 is determined to be 0.23 eV from the intrinsic region of the temperature dependence of electrical conductivity. The origins of this narrow bandgap are discussed based on the chemical bonding nature probed by 6 keV hard X-ray photoemission spectroscopy, hybrid density functional calculations, and the ligand theory. One origin is the direct As-As hybridization between adjacent [ZnAs] layers, which leads to a secondary splitting of As 4p levels and raises the valence band maximum. The other is that the nonbonding Ba 5d(x(2)-y(2)) orbitals form an unexpectedly deep conduction band minimum (CBM) in ß-BaZn2As2 although the CBM of LaZnAsO is formed mainly of Zn 4s. These two origins provide a quantitative explanation for the bandgap difference between ß-BaZn2As2 and LaZnAsO.

NH(2-) dianion entrapped in a nanoporous 12CaO·7Al2O3 crystal by ammonothermal treatment: reaction pathways, dynamics, and chemical stability.

Inorganic imides are useful for hydrogen storage and base-catalyzed reactions but are extremely unstable under ambient conditions, which hinders their practical use as functional materials. Here, we demonstrate that NH2(-) and H(-), as well as NH(2-), can be incorporated into the nanocages of the mayenite crystals, [Ca24Al28O64](4+)(e(-))4 and [Ca24Al28O64](4+)(O(2-))2, by ammonothermal treatment. We evaluated the reaction conditions and found that the anion exchange reaction proceeded at higher than 500 °C. Raman spectroscopy showed that the N-H band position of encaged NH(2-) was close to that of CaNH and MgNH crystals. We also studied the reaction pathways that yield NH2(-) and NH(2-) anions and their dynamic motions by (1)H NMR spectroscopy. Successive reactions of encaged e(-) and O(2-) ions with NH3 yielded NH2(-), NH(2-), and H(-) or OH(-), in which the O(2-) ion reacted more efficiently with NH3. The maximum NH(2-) concentration and content were ∼2.7 × 10(20) cm(-3) and ∼0.25 (wt %)NH, respectively. The short spin-lattice relaxation time found in (1)H NMR suggests that the incorporated NH2(-) and NH(2-) rotate or librate in the cage near room temperature. Stability tests showed that the encaged NH(2-) ions are chemically stable under ambient conditions and in organic solvents. These results are attributed to the encapsulation of active anions within subnanometer-sized cages composed of Ca-O-Al oxide frameworks. The encaged NH(2-) desorbed as NH3 at higher than 500 °C under vacuum (Ea = 172 kJ mol(-1)). It is thus expected that C12A7:NH(2-) will function as a reactive nitrogen source for nitrogen transfer reactions by in situ cage degradation.

Layered compounds BaM2Ge4Ch6 (M = Rh, Ir and Ch = S, Se) with pyrite-type building blocks and Ge-Ch heteromolecule-like anions.

The structures and chemical features of layered compounds BaM2Ge4Ch6 (M = Rh, Ir; Ch = S, Se) synthesized by high-pressure and high-temperature methods have been systematically studied. These compounds crystallize in an orthorhombic phase with space group Pbca (No. 61). These compounds have the remarkable structural feature of M-Ge-Ch pyrite-type building units, stacking with Ba-Ch layers alternatively along the c axis. It is very rare and novel that pyrite-type subunits are the building blocks in layered compounds. Theoretical calculations and experimental results indicate that there are strongly polarized covalent bonds between Ge and Ch atoms, forming heteromolecule-like anions in these compounds. Moreover, Ge atoms in this structure exhibit an unusual valence state (∼+1) due to the tetrahedral coordination environment of Ge atoms along with M and Ch atoms simultaneously.

Indium-based ultraviolet-transparent electroconductive oxyfluoride InOF: ambient-pressure synthesis and unique electronic properties in comparison with In2O3.

A method for the synthesis of single-phase powdered InOF under ambient pressure has been developed. The method involves pyrolysis of a hydrate of InF3 in an O2 atmosphere of controlled humidity. Various intermediate phases were formed during the pyrolysis, and their structures and interconversions were analyzed. Combined results of optical absorption measurements and density functional calculations indicate that InOF is a direct band gap material with a band gap energy of ∼3.7 eV. Unlike In2O3, the electrical conductivity of polycrystalline InOF pellets can be controlled over ∼8 orders of magnitude from ∼10(-8) S cm(-1) to ∼2 S cm(-1) by thermal annealing, and the sample with the highest conductivity was a nearly degenerate n-type semiconductor with a relatively small carrier concentration of ∼10(18) cm(-3). The work function of InOF measured by ultraviolet photoelectron spectroscopy is ∼3.5 eV and is smaller by ∼1.5 eV than that of In2O3. This difference comes from a decrease in the electron affinity.

Activation and splitting of carbon dioxide on the surface of an inorganic electride material.

Activation of carbon dioxide is the most important step in its conversion into valuable chemicals. Surfaces of stable oxide with a low work function may be promising for this purpose. Here we report that the surfaces of the inorganic electride [Ca24Al28O64](4+)(e(-))4 activate and split carbon dioxide at room temperature. This behaviour is attributed to a high concentration of localized electrons in the near-surface region and a corrugation of the surface that can trap oxygen atoms and strained carbon monoxide and carbon dioxide molecules. The [Ca24Al28O64](4+)(e(-))4 surface exposed to carbon dioxide is studied using temperature-programmed desorption, and spectroscopic methods. The results of these measurements, corroborated with ab initio simulations, show that both carbon monoxide and carbon dioxide adsorb on the [Ca24Al28O64](4+)(e(-))4 surface at RT and above and adopt unusual configurations that result in desorption of molecular carbon monoxide and atomic oxygen upon heating.

Dicalcium nitride as a two-dimensional electride with an anionic electron layer.

Recent studies suggest that electrides--ionic crystals in which electrons serve as anions--are not exceptional materials but rather a generalized form, particularly under high pressure. The topology of the cavities confining anionic electrons determines their physical properties. At present, reported confining sites consist only of zero-dimensional cavities or weakly linked channels. Here we report a layered-structure electride of dicalcium nitride, Ca(2)N, which possesses two-dimensionally confined anionic electrons whose concentration agrees well with that for the chemical formula of [Ca(2)N](+)·e(-). Two-dimensional transport characteristics are demonstrated by a high electron mobility (520 cm(2) V(-1) s(-1)) and long mean scattering time (0.6 picoseconds) with a mean free path of 0.12 micrometres. The quadratic temperature dependence of the resistivity up to 120 Kelvin indicates the presence of an electron-electron interaction. A striking anisotropic magnetoresistance behaviour with respect to the direction of magnetic field (negative for the field perpendicular to the conducting plane and positive for the field parallel to it) is observed, confirming diffusive two-dimensional transport in dense electron layers. Additionally, band calculations support confinement of anionic electrons within the interlayer space, and photoemission measurements confirm anisotropic low work functions of 3.5 and 2.6 electronvolts, revealing the loosely bound nature of the anionic electrons. We conclude that Ca(2)N is a two-dimensional electride in terms of [Ca(2)N](+)·e(-).

Surface of room-temperature-stable electride [Ca24Al28O64]4+(e-)4: preparation and its characterization by atomic-resolution scanning tunneling microscopy.

The nanocage compound crystal [Ca24Al28O64]4+(e-)4 (C12A7:e-) is a room-temperature-stable electride. Although bulk C12A7:e- exhibits metallic conduction, the surface of an as-prepared sample or one prepared by mechanical fracture in ultrahigh vacuum is almost insulating and exhibits distinct non-ohmic contact. We studied whether the intrinsic surface of this electride exhibits metallic conduction or not by examining various conditions for preparing the intrinsic surface. A combination of sputtering with thermal annealing led to the emergence of metallic conductivity in a specific condition. Suitably prepared surfaces revealed ohmic contact even in an ambient atmosphere. Atomic-resolution scanning tunneling microscopy (STM) images of the surfaces were consistent with a structural model in which the cage structure in the bulk C12A7:e- electride is conserved at the surface.

Room temperature-stable electride as a synthetic organic reagent: application to pinacol coupling reaction in aqueous media.

Room temperature-stable inorganic electride [Ca(24)Al(28)O(68)](4+)4e(-) was employed for a pinacol coupling reaction in aqueous media. Ca-Al-O gel formed by the destruction of the crystal structure of an electride by water media played a key role in transferring the electron to electrophilic aldehydes. Aromatic aldehydes reacted smoothly with moderate to high yields.

High-density electron anions in a nanoporous single crystal: [Ca24Al28O64]4+(4e-).

We removed approximately 100% of clathrated oxygen ions from the crystallographic cages in a single crystal of 12CaO.7Al2O3, leading to the formation of high-density (approximately 2 x 10(21) cm-3) electrons highly localized in the cages. The resulting electron forms a structure that we interpret as an F+ center and migrates throughout the crystal by hopping to a neighboring cage with conductivity approximately 100 siemens per centimeter, demonstrating that the encaged electron behaves as an anion. The electron anions couple antiferromagnetically with each other, forming a diamagnetic pair or singlet bipolaron. The resulting [Ca24Al28O64]4+(4e-) may be regarded as a thermally and chemically stable single crystalline "electride."