Dirac Nodal Line in Hourglass Semimetal Nb3SiTe6.

Glide-mirror symmetry in nonsymmorphic crystals can foster the emergence of novel hourglass nodal loop states. Here, we present spectroscopic signatures from angle-resolved photoemission of a predicted topological hourglass semimetal phase in Nb3SiTe6. Linear band crossings are observed at the zone boundary of Nb3SiTe6, which could be the origin of the nontrivial Berry phase and are consistent with a predicted glide quantum spin Hall effect; such linear band crossings connect to form a nodal loop. Furthermore, the saddle-like Fermi surface of Nb3SiTe6 observed in our results helps unveil linear band crossings that could be missed. In situ alkali-metal doping of Nb3SiTe6 also facilitated the observation of other band crossings and parabolic bands at the zone center correlated with accidental nodal loop states. Overall, our results complete the system's band structure, help explain prior Hall measurements, and suggest the existence of a nodal loop at the zone center of Nb3SiTe6.

Integrated optical chip for a high-resolution, single-resonance-mode x-ray monochromator system.

An integrated optical chip that minimizes the size of the energy-tuning single-resonance-mode x-ray monochromator system into a 3cm×5cm silicon wafer is proposed. A Fabry-Perot x-ray resonator and two back-reflecting Si mirrors are employed on the wafer as the optical components, where Si(12 4 0) back reflection is used for both Fabry-Perot resonance and re-diffraction of the x-ray beams from the resonator in the incident direction. We can achieve an energy bandwidth of 3.4 meV in single-mode x rays and tune the energy by temperature variation. Such Si chips can be readily employed at the synchrotron beamlines and conventional x-ray laboratories for high-resolution investigations.

Os Doping Suppressed Cu-Fe Charge Transfer and Induced Structural and Magnetic Phase Transitions in LaCu3Fe4-xOsxO12 (x = 1 and 2).

B-site Os-doped quadruple perovskite oxides LaCu3Fe4-xOsxO12 (x = 1 and 2) were prepared under high-pressure and high-temperature conditions. Although parent compound LaCu3Fe4O12 experiences Cu-Fe intermetallic charge transfer that changes the Cu3+/Fe3+ charge combination to Cu2+/Fe3.75+ at 393 K, in the Os-doped samples, the Cu and Fe charge states are found to be constant 2+ and 3+, respectively, indicating the complete suppression of charge transfer. Correspondingly, Os6+ and mixed Os4.5+ valence states are determined by X-ray absorption spectroscopy for x = 1 and x = 2 compositions, respectively. The x = 1 sample crystallizes in an Fe/Os disordered structure with the Im3̅ space group. It experiences a spin-glass transition around 480 K. With further Os substitution up to x = 2, the crystal symmetry changes to Pn3̅, where Fe and Os are orderly distributed in a rocksalt-type fashion at the B site. Moreover, this composition shows a long-range Cu2+(↑)Fe3+(↑)Os4.5+(↓) ferrimagnetic ordering near 520 K. This work provides a rare example for 5d substitution-suppressed intermetallic charge transfer as well as induced structural and magnetic phase transitions with high spin ordering temperature.

Time-resolved X-ray reflection phases of the nearly forbidden Si(222) reflection under laser excitation.

The covalent electron density, which makes Si(222) measurable, is subject to laser excitation. The three-wave Si(222)/(13 {\overline 1}) diffraction at 7.82 keV is used for phase measurements. It is found that laser excitation causes a relative phase change of around 4° in Si(222) in the first 100 ps of excitation and this is gradually recovered over several nanoseconds. This phase change is due to laser excitation of covalent electrons around the silicon atoms in the unit cell and makes the electron density deviate further from the centrosymmetric distribution.

Near-Room-Temperature Ferrimagnetic Ordering in a B-Site-Disordered 3d-5d-Hybridized Quadruple Perovskite Oxide, CaCu3Mn2Os2O12.

A new 3d-5d hybridization oxide, CaCu3Mn2Os2O12 (CCMOO), was prepared by high-pressure and high-temperature synthesis methods. The compound crystallizes to an A-site-ordered but B-site-disordered quadruple perovskite structure with a space group of Im3̅ (No. 204). The charge states of the transition metals are determined to be Cu2+/Mn3.5+/Os4.5+ by X-ray absorption spectroscopy. Although most B-site-disordered perovskites possess lower spin-ordering temperatures or even nonmagnetic transitions, the current CCMOO displays a long-range ferrimagnetic phase transition with a critical temperature as high as ∼280 K. Moreover, a large saturated magnetic moment is found to occur [7.8 µB/formula units (f.u.) at 2 K]. X-ray magnetic circular dichroism shows a Cu2+(↑)Mn3.5+(↑)Os4.5+(↓) ferrimagnetic coupling. The corner-sharing Mn/OsO6 octahedra with mixed Mn and Os charge states make the compound metallic in electrical transport, in agreement with a specific heat fitting at low temperature. This work provides a rare example with high spin-ordering temperature and a large magnetic moment in B-site-disordered 3d-5d hybridization perovskite oxides.

Directed Vertical Diffusion of Photovoltaic Active Layer Components into Porous ZnO-Based Cathode Buffer Layers.

Cathode buffer layers (CBLs) can effectively further the efficiency of polymer solar cells (PSCs), after optimization of the active layer. Hidden between the active layer and cathode of the inverted PSC device configuration is the critical yet often unattended vertical diffusion of the active layer components across CBL. Here, a novel methodology of contrast variation with neutron and anomalous X-ray reflectivity to map the multicomponent depth compositions of inverted PSCs, covering from the active layer surface down to the bottom of the ZnO-based CBL, is developed. Uniquely revealed for a high-performance model PSC are the often overlooked porosity distributions of the ZnO-based CBL and the differential diffusions of the polymer PTB7-Th and fullerene derivative PC71 BM of the active layer into the CBL. Interface modification of the ZnO-based CBL with fullerene derivative PCBEOH for size-selective nanochannels can selectively improve the diffusion of PC71 BM more than that of the polymer. The deeper penetration of PC71 BM establishes a gradient distribution of fullerene derivatives over the ZnO/PCBE-OH CBL, resulting in markedly improved electron mobility and device efficiency of the inverted PSC. The result suggests a new CBL design concept of progressive matching of the conduction bands.

Defect engineering by synchrotron radiation X-rays in CeO2 nanocrystals.

This work reports an unconventional defect engineering approach using synchrotron-radiation-based X-rays on ceria nanocrystal catalysts of particle sizes 4.4-10.6 nm. The generation of a large number of oxygen-vacancy defects (OVDs), and therefore an effective reduction of cations, has been found in CeO2 catalytic materials bombarded by high-intensity synchrotron X-ray beams of beam size 1.5 mm × 0.5 mm, photon energies of 5.5-7.8 keV and photon fluxes up to 1.53 × 1012 photons s-1. The experimentally observed cation reduction was theoretically explained by a first-principles formation-energy calculation for oxygen vacancy defects. The results clearly indicate that OVD formation is mainly a result of X-ray-excited core holes that give rise to valence holes through electron down conversion in the material. Thermal annealing and subvalent Y-doping were also employed to modulate the efficiency of oxygen escape, providing extra control on the X-ray-induced OVD generating process. Both the core-hole-dominated bond breaking and oxygen escape mechanisms play pivotal roles for efficient OVD formation. This X-ray irradiation approach, as an alternative defect engineering method, can be applied to a wide variety of nanostructured materials for physical-property modification.

Three-dimensional ultrafast charge-density-wave dynamics in CuTe.

Charge density waves (CDWs) involved with electronic and phononic subsystems simultaneously are a common quantum state in solid-state physics, especially in low-dimensional materials. However, CDW phase dynamics in various dimensions are yet to be studied, and their phase transition mechanism is currently moot. Here we show that using the distinct temperature evolution of orientation-dependent ultrafast electron and phonon dynamics, different dimensional CDW phases are verified in CuTe. When the temperature decreases, the shrinking of c-axis length accompanied with the appearance of interchain and interlayer interactions causes the quantum fluctuations (QF) of the CDW phase until 220 K. At T < 220 K, the CDWs on the different ab-planes are finally locked with each other in anti-phase to form a CDW phase along the c-axis. This study shows the dimension evolution of CDW phases in one CDW system and their stabilized mechanisms in different temperature regimes.

Direct observation of charge ordering in magnetite using resonant multiwave x-ray diffraction.

Charge disproportion at octahedral Fe sites in magnetite was observed at low temperature using two inversion-symmetry related three-wave resonant x-ray diffraction, 022-311 and 002-̅3̅1, near the iron K edge. Both of the three-wave cases involve the (002) forbidden-weak reflection. The self-normalized three-wave to two-wave (002) diffraction intensity ratio automatically cancels the self-absorption effect and leads to direct determination of charge disproportion for magnetite below 120 K. This approach provides a more direct and effective way for extracting charge-ordering information.

Formation of Co-O bonds and reversal of thermal annealing effects induced by X-ray irradiation in (Y, Co)-codoped CeO2 nanocrystals.

We report an unconventional effect of synchrotron X-ray irradiation in which Co-O bonds in thermally annealed (Y, Co)-codoped CeO2 nanocrystal samples were formed due to, instead of broken by, X-ray irradiation. Our experimental data indicate that escaping oxygen atoms from X-ray-broken Ce-O bonds may be captured by Co dopant atoms to form additional Co-O bonds. Consequently, the Co dopant atoms were pumped by X-rays from the energetically-favored thermally-stable Co-O4 square-planar structure to the metastable octahedral Co-O6 environment, practically a reversal of thermal annealing effects in (Y, Co)-codoped CeO2 nanocrystals. The band gap of doped CeO2 with Co dopant in the Co-O6 structure was previously found to be 1.61 eV higher than that with Co in the Co-O4 environment. Therefore, X-ray irradiation can work with thermal annealing in opposing directions to fine tune and optimize the band gap of the material for specific technological applications.

Hydrogen spillover in complex oxide multifunctional sites improves acidic hydrogen evolution electrocatalysis.

Improving the catalytic efficiency of platinum for the hydrogen evolution reaction is valuable for water splitting technologies. Hydrogen spillover has emerged as a new strategy in designing binary-component Pt/support electrocatalysts. However, such binary catalysts often suffer from a long reaction pathway, undesirable interfacial barrier, and complicated synthetic processes. Here we report a single-phase complex oxide La2Sr2PtO7+δ as a high-performance hydrogen evolution electrocatalyst in acidic media utilizing an atomic-scale hydrogen spillover effect between multifunctional catalytic sites. With insights from comprehensive experiments and theoretical calculations, the overall hydrogen evolution pathway proceeds along three steps: fast proton adsorption on O site, facile hydrogen migration from O site to Pt site via thermoneutral La-Pt bridge site serving as the mediator, and favorable H2 desorption on Pt site. Benefiting from this catalytic process, the resulting La2Sr2PtO7+δ exhibits a low overpotential of 13 mV at 10 mA cm-2, a small Tafel slope of 22 mV dec-1, an enhanced intrinsic activity, and a greater durability than commercial Pt black catalyst.

Reduction of dopant ions and enhancement of magnetic properties by UV irradiation in Ce-doped TiO2.

We report the experimental observation of and theoretical explanation for the reduction of dopant ions and enhancement of magnetic properties in Ce-doped TiO2 diluted magnetic semiconductors from UV-light irradiation. Substantial increase in Ce3+ concentration and creation of oxygen vacancy defects in the sample due to UV-light irradiation was observed by X-ray and optical methods. Magnetic measurements demonstrate a combination of paramagnetism and ferromagnetism up to room temperatures in all samples. The magnetization of both paramagnetic and ferromagnetic components was observed to be dramatically enhanced in the irradiated sample. First-principle theoretical calculations show that valence holes created by UV irradiation can substantially lower the formation energy of oxygen vacancies. While the electron spin densities for defect states near oxygen vacancies in pure TiO2 are in antiferromagnetic orientation, they are in ferromagnetic orientations in Ce-doped TiO2. Therefore, the ferromagnetically-oriented spin densities near oxygen vacancies created by UV irradiation are the most probable cause for the experimentally observed enhancement of magnetism in the irradiated Ce-doped TiO2.

The Observation of Interchain Motion in Self-Assembled Crystalline Platinum(II) Complexes: An Exquisite Case but By No Means the Only One in Molecular Solids.

In organic and organometallic solids, upon electronic excitation, most intermolecular structural relaxations follow a pathway along the π-π stacking direction or metal-metal bond with significant coupling strength. Differently, we discovered that the self-assembled platinum(II) complexes, Pt(fppz)2, exhibit an unusual interchain contraction. The ground-state and excited-state multiple local minima were distinguished by temperature-dependent excitation/emission spectra, indicating the existence of multiple local minima. The time-resolved emission decay revealed the excited-state structural relaxation lifetime with τobs = 41 ns at 298 K. Temperature-dependent X-ray diffraction analysis showed that the packing geometries contract 0.6 Å along the interchain direction (a-axis) at 50 K compared to the geometries at 298 K. Such structural displacements render the slow internal conversion rate in the excited states. We thus demonstrate the correlation between the packing geometries and the excited-state dynamics of the self-assembled Pt(II) complexes, shedding light on the unique direction of interchain structural deformation of the molecular aggregates.

Topological Proximity-Induced Dirac Fermion in Two-Dimensional Antimonene.

Antimonene is a promising two-dimensional (2D) material that is calculated to have a significant fundamental bandgap usable for advanced applications such as field-effect transistors, photoelectric devices, and the quantum-spin Hall (QSH) state. Herein, we demonstrate a phenomenon termed topological proximity effect, which occurs between a 2D material and a three-dimensional (3D) topological insulator (TI). We provide strong evidence derived from hydrogen etching on Sb2Te3 that large-area and well-ordered antimonene presents a 2D topological state. Delicate analysis with a scanning tunneling microscope of the evolutionary intermediates reveals that hydrogen etching on Sb2Te3 resulted in the formation of a large area of antimonene with a buckled structure. A topological state formed in the antimonene/Sb2Te3 heterostructure was confirmed with angle-resolved photoemission spectra and density-functional theory calculations; in particular, the Dirac point was located almost at the Fermi level. The results reveal that Dirac fermions are indeed realized at the interface of a 2D normal insulator (NI) and a 3D TI as a result of strong hybridization between antimonene and Sb2Te3. Our work demonstrates that the position of the Dirac point and the shape of the Dirac surface state can be tuned by varying the energy position of the NI valence band, which modifies the direction of the spin texture of Sb-BL/Sb2Te3 via varying the Fermi level. This topological phase in 2D-material engineering has generated a paradigm in that the topological proximity effect at the NI/TI interface has been realized, which demonstrates a way to create QSH systems in 2D-material TI heterostructures.

A combinatory ferroelectric compound bridging simple ABO3 and A-site-ordered quadruple perovskite.

The simple ABO3 and A-site-ordered AA'3B4O12 perovskites represent two types of classical perovskite functional materials. There are well-known simple perovskites with ferroelectric properties, while there is still no report of ferroelectricity due to symmetry breaking transition in A-site-ordered quadruple perovskites. Here we report the high pressure synthesis of an A-site-ordered perovskite PbHg3Ti4O12, the only known quadruple perovskite that transforms from high-temperature centrosymmetric paraelectric phase to low-temperature non-centrosymmetric ferroelectric phase. The coordination chemistry of Hg2+ is changed from square planar as in typical A-site-ordered quadruple perovskite to a rare stereo type with 8 ligands in PbHg3Ti4O12. Thus PbHg3Ti4O12 appears to be a combinatory link from simple ABO3 perovskites to A-site-ordered AA'3Ti4O12 perovskites, sharing both displacive ferroelectricity with former and structure coordination with latter. This is the only example so far showing ferroelectricity due to symmetry breaking phase transition in AA'3B4O12-type A-site-ordered perovskites, and opens a direction to search for ferroelectric materials.

High-pressure synthesis and spin glass behavior of a Mn/Ir disordered quadruple perovskite CaCu3Mn2Ir2O12.

A new 3d-5d hybridized quadruple perovskite oxide, CaCu3Mn2Ir2O12, was synthesized by high-pressure and high-temperature methods. The Rietveld structure analysis reveals that the compound crystallizes in an [Formula: see text]-type perovskite structure with space group Im-3, where the Ca and Cu are 1:3 ordered at fixed atomic positions. At the B site the 3d Mn and the 5d Ir ions are disorderly distributed due to the rare equal +4 charge states for both of them as determined by x-ray absorption spectroscopy. The competing antiferromagnetic and ferromagnetic interactions among Cu2+, Mn4+, and Ir4+ ions give rise to spin glass behavior, which follows a conventional dynamical slowing down model.

Enhancement of catalytic activity by UV-light irradiation in CeO2 nanocrystals.

Ultraviolet (UV) light irradiation on CeO2 nanocrystals catalysts has been observed to largely increase the material's catalytic activity and reactive surface area. As revealed by x-ray absorption near edge structure (XANES) analysis, the concentration of subvalent Ce3+ ions in the irradiated ceria samples progressively increases with the UV-light exposure time. The increase of Ce3+ concentration as a result of UV irradiation was also confirmed by the UV-vis diffuse reflectance and photoluminescence spectra that indicate substantially increased concentration of oxygen vacancy defects in irradiated samples. First-principle formation-energy calculation for oxygen vacancy defects revealed a valence-hole-dominated mechanism for the irradiation-induced reduction of CeO2 consistent with the experimental results. Based on a Mars-van Krevelen mechanism for ceria catalyzed oxidation processes, as the Ce3+ concentration is increased by UV-light irradiation, an increased number of reactive oxygen atoms will be captured from gas-phase O2 by the surface Ce3+ ions, and therefore leads to the observed catalytic activity enhancement. The unique annealing-free defect engineering method using UV-light irradiation provides an ultraconvenient approach for activity improvement in nanocrystal ceria for a wide variety of catalytic applications.

Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite.

We have identified an often observed yet unresolved intermediate structure in a popular processing with dimethylformamide solutions of lead chloride and methylammonium iodide for perovskite solar cells. With subsecond time-resolved grazing-incidence X-ray scattering and X-ray photoemission spectroscopy, supplemental with ab initio calculation, the resolved intermediate structure (CH3NH3)2PbI2Cl2·CH3NH3I features two-dimensional (2D) perovskite bilayers of zigzagged lead-halide octahedra and sandwiched CH3NH3I layers. Such intermediate structure reveals a hidden correlation between the intermediate phase and the composition of the processing solution. Most importantly, the 2D perovskite lattice of the intermediate phase is largely crystallographically aligned with the [110] planes of the three-dimensional perovskite cubic phase; consequently, with sublimation of Cl ions from the organo-lead octahedral terminal corners in prolonged annealing, the zigzagged octahedral layers of the intermediate phase can merge with the intercalated methylammonium iodide layers for templated growth of perovskite crystals. Regulated by annealing temperature and the activation energies of the intermediate and perovskite, deduced from analysis of temperature-dependent structural kinetics, the intermediate phase is found to selectively mature first and then melt along the layering direction for epitaxial conversion into perovskite crystals. The unveiled epitaxial conversion under growth kinetics controls might be general for solution-processed and intermediate-templated perovskite formation.

Robustness of a Topologically Protected Surface State in a Sb2Te2Se Single Crystal.

A topological insulator (TI) is a quantum material in a new class with attractive properties for physical and technological applications. Here we derive the electronic structure of highly crystalline Sb2Te2Se single crystals studied with angle-resolved photoemission spectra. The result of band mapping reveals that the Sb2Te2Se compound behaves as a p-type semiconductor and has an isolated Dirac cone of a topological surface state, which is highly favored for spintronic and thermoelectric devices because of the dissipation-less surface state and the decreased scattering from bulk bands. More importantly, the topological surface state and doping level in Sb2Te2Se are difficult to alter for a cleaved surface exposed to air; the robustness of the topological surface state defined in our data indicates that this Sb2Te2Se compound has a great potential for future atmospheric applications.

Multiple wave diffraction anomalous fine structure.

A new method, multiple-wave diffraction anomalous fine structure, combining the x-ray multiple-wave diffraction and diffraction anomalous fine structure techniques, is proposed. The real part of dispersion correction Deltaf' and fine structure chi function can be obtained directly by multiple diffraction analysis without using Kramers-Krönig relations and kinematical fitting of diffracted intensity. Better wave vector sensitivity of the fine structure is expected. The multiple-wave diffraction anomalous fine structure experiment for a GaAs single crystal is reported as an example.