Unconventional excitonic states with phonon sidebands in layered silicon diphosphide.

Complex correlated states emerging from many-body interactions between quasiparticles (electrons, excitons and phonons) are at the core of condensed matter physics and material science. In low-dimensional materials, quantum confinement affects the electronic, and subsequently, optical properties for these correlated states. Here, by combining photoluminescence, optical reflection measurements and ab initio theoretical calculations, we demonstrate an unconventional excitonic state and its bound phonon sideband in layered silicon diphosphide (SiP2), where the bound electron-hole pair is composed of electrons confined within one-dimensional phosphorus-phosphorus chains and holes extended in two-dimensional SiP2 layers. The excitonic state and emergent phonon sideband show linear dichroism and large energy redshifts with increasing temperature. Our ab initio many-body calculations confirm that the observed phonon sideband results from the correlated interaction between excitons and optical phonons. With these results, we propose layered SiP2 as a platform for the study of excitonic physics and many-particle effects.

Symmetric Ambipolar Thin-Film Transistors and High-Gain CMOS-like Inverters Using Environmentally Friendly Copper Nitride.

Oxide semiconductor thin-film transistors (TFTs) are currently used as the fundamental building blocks in commercial flat-panel displays because of the excellent performance of n-channel TFTs. However, except for a few materials, their p-channel performances have not been acceptable. Although some p-type oxide semiconductors exhibit superior hole transport properties, their TFT performances are greatly deteriorated, which is a major obstacle in the development of complementary metal-oxide-semiconductor (CMOS) circuits. Herein, an ionic nitride semiconductor, copper nitride (Cu3N), composed of environmentally benign elements is shown to exhibit highly symmetric hole and electron transport, indicating its suitability for application in CMOS circuits. We performed a two-step investigation. The first step was to examine the ultimate potential of Cu3N using an electric-double-layer transistor structure with epitaxial Cu3N channels measured at 220 K, which exhibited ambipolar operation with hole and electron mobilities of ∼5 and ∼10 cm2 V-1 s-1, respectively, and a high on/off ratio of ∼105. The second step is to demonstrate the feasibility of TFT circuits with a polycrystalline channel on non-single-crystal (SiO2/Si) substrates. CMOS-like inverters composed of two polycrystalline Cu3N ambipolar TFTs on a SiO2/Si substrate exhibited a high voltage gain of ∼100.

Material Design of p-Type Transparent Amorphous Semiconductor, Cu-Sn-I.

Transparent amorphous semiconductors (TAS) that can be fabricated at low temperature are key materials in the practical application of transparent flexible electronics. Although various n-type TAS materials with excellent performance, such as amorphous In-Ga-Zn-O (a-IGZO), are already known, no complementary p-type TAS has been realized to date. Here, a material design concept for p-type TAS materials is proposed utilizing the pseudo s-orbital nature of spatially spreading iodine 5p orbitals and amorphous Sn-containing CuI (a-CuSnI) thin film is reported as an example. The resulting a-CuSnI thin films fabricated by spin coating at low temperature (140 °C) have a smooth surface. The Hall mobility increases with the hole concentration and the largest mobility of ≈9 cm2 V-1 s-1 is obtained, which is comparable with that of conventional n-type TAS.

Large-moment antiferromagnetic order in overdoped high-Tc superconductor 154SmFeAsO1-x D x.

In iron-based superconductors, high critical temperature (Tc) superconductivity over 50 K has only been accomplished in electron-doped hREFeAsO (hRE is heavy rare earth (RE) element). Although hREFeAsO has the highest bulk Tc (58 K), progress in understanding its physical properties has been relatively slow due to difficulties in achieving high-concentration electron doping and carrying out neutron experiments. Here, we present a systematic neutron powder diffraction study of 154SmFeAsO1-x D x , and the discovery of a long-range antiferromagnetic ordering with x ≥ 0.56 (AFM2) accompanying a structural transition from tetragonal to orthorhombic. Surprisingly, the Fe magnetic moment in AFM2 reaches a magnitude of 2.73 µB/Fe, which is the largest in all nondoped iron pnictides and chalcogenides. Theoretical calculations suggest that the AFM2 phase originates in kinetic frustration of the Fe-3dxy orbital, in which the nearest-neighbor hopping parameter becomes zero. The unique phase diagram, i.e., highest-Tc superconducting phase adjacent to the strongly correlated phase in electron-overdoped regime, yields important clues to the unconventional origins of superconductivity.

Green apatites: hydride ions, electrons and their interconversion in the crystallographic channel.

Hydride (H(-)) ions and electrons in channel sites of the lattice of calcium phosphate apatites are characterized. Solid-state chemical reduction using TiH2 is effective for doping of H(-) ions into apatites. Irradiation of the H(-) ion-doped apatite with ultraviolet (UV) light induces green coloration. Electron paramagnetic resonance (EPR) reveals that this colour centre is attributed to electrons captured at a vacant anion site in the crystallographic channel, forming F(+) centres. Transient H(0) atoms are detected at low temperatures by EPR. The concentration of UV-induced electrons in the apatite at room temperature decays according to second-order kinetics because of the chemical reactions involving two electrons; overall, electron generation and thermal decay can be described as: H(-) + O(2-) ↔ 2e(-) + OH(-). (1)H magic angle spinning nuclear magnetic resonance spectroscopy is used to identify H(-) ions in the apatite, which are characterized by a chemical shift of +3.4 ppm. Various types of O-H groups including OH(-) ions in the channel and protons bound to phosphate groups are concurrently formed, and are identified by considering the relationship between the O-H stretching frequency and the (1)H chemical shift. The complementary results obtained by EPR and NMR reveal that the H(-) ions and transient H(0) atoms are located at the centre of Ca3 triangles in the apatite, while the electrons are located in the centre of Ca6 octahedra. These findings provide an effective approach for identifying new classes of mixed-oxide-hydride or -electride crystals.

Electric double-layer transistor using layered iron selenide Mott insulator TlFe1.6Se2.

A(1-x)Fe(2-y)Se2 (A = K, Cs, Rb, Tl) are recently discovered iron-based superconductors with critical temperatures (Tc) ranging up to 32 K. Their parent phases have unique properties compared with other iron-based superconductors; e.g., their crystal structures include ordered Fe vacancies, their normal states are antiferromagnetic (AFM) insulating phases, and they have extremely high Néel transition temperatures. However, control of carrier doping into the parent AFM insulators has been difficult due to their intrinsic phase separation. Here, we fabricated an Fe-vacancy-ordered TlFe1.6Se2 insulating epitaxial film with an atomically flat surface and examined its electrostatic carrier doping using an electric double-layer transistor (EDLT) structure with an ionic liquid gate. The positive gate voltage gave a conductance modulation of three orders of magnitude at 25 K, and further induced and manipulated a phase transition; i.e., delocalized carrier generation by electrostatic doping is the origin of the phase transition. This is the first demonstration, to the authors' knowledge, of an EDLT using a Mott insulator iron selenide channel and opens a way to explore high Tc superconductivity in iron-based layered materials, where carrier doping by conventional chemical means is difficult.

Hydride ion as photoelectron donor in microporous crystal.

Atomic hydrogen (H0) and trapped electrons generated by UV illumination (lambda approximately 330 nm) at 4 K were observed using electron paramagnetic resonance (EPR) in a 12CaO.7Al2O3 (C12A7) crystal heated in a hydrogen atmosphere. The concentration ratio of generated H0 to the electrons encaged in the subnanometer-sized cages of C12A7 (F+ centers) is almost 1:1, providing direct evidence that a hydride ion, H-, accommodated in the cage by the heat treatment was dissociated to a pair of an H0 and an electron by a UV photon: H- --> H0 + e- (F+). After annealing at 300 K, H0 was completely annihilated, while approximately 60% of the trapped electrons survived. The remaining electrons can hop between neighboring cages and give electrical conductivity to C12A7. The hyperfine splitting of the EPR spectrum of H0 in C12A7 (48.6 mT) is 4% smaller than that of the neutral hydrogen atom (50.6 mT), implying that H0 is trapped at the interstitial sites among the cages.

Microporous crystal 12CaO x 7Al(2)O(3) encaging abundant O(-) radicals.

Extremely high concentrations (>1020 cm-3) of active oxygenic radicals, O- and O2-, have been created in the zeolitic crystal, 12CaO.7Al2O3 (C12A7), which can accommodate anions in its cavities. An increase in oxygen pressure and a decrease in water vapor pressure at high temperature enhance the formation of the radicals. The oxidation of Pt is observed on the surface of the material as a result of reaction with the active oxygens.