Synthesis of Rhenium-Doped Copper Twin Boundary for High-Turnover-Frequency Electrochemical Nitrogen Reduction.

The precise design and synthesis of active sites to improve catalyst's performance has emerged as a promising tactic for electrochemistry. However, it is challenging to combine different types of active sites and manipulate them simultaneously at atomic resolution. Here, we present a strategy to synthesize Re atom-doped Cu twin boundaries (TBs), through pulsed electrodeposition and boundary segregation. The Re-doped Cu TBs demonstrate a highly efficient nitrogen reduction reaction (NRR) performance. Re-doped Cu TBs showed a turnover frequency of ∼5889 s-1, ∼800 times higher than the pure Cu TB active centers (∼7 s-1). In addition to the "acceptance-donation" activation of N2 molecules, theoretical calculations also reveal that the Re-Re dimer on TB can boost the NRR and impede the hydrogen evolution reaction synchronously, rendering Re-doped Cu TB catalysts with high NRR activity and selectivity.

Robust Tunability and Newly Emerged Q Resonance of Ba0.8Sr0.2TiO3-Based Microwave Capacitors under Gamma Irradiations.

The complex resonance of dielectric quality factor Q, combined with a capacitance tunability n higher than 3:1 without any dispersion, was achieved in the voltage-tunable interdigital capacitors (IDCs) based on epitaxial Ba0.8Sr0.2TiO3 ferroelectric thin films across the microwave L (1-2 GHz), S (2-4 GHz), and C (4-8 GHz) bands at room temperature. The resonant Q and n features were driven by the microwave responses of the ferroelectric nanodomains engineered in the films. To promote their application in space radiation environments, the evolutions of Q and n both as functions of frequency f (1-8 GHz) and applied electric field E (0-240 kV/cm) were systematically investigated under a series of gamma-ray irradiations up to 100 kGy. The robust capacitance tunability was accompanied by the emergence of an additional Q resonance at 2.3 GHz in most post-irradiated devices, which is ascribed to extra polar nanoregions of expanded surface lattices associated with oxygen vacancies induced by irradiations.

Micelle-directed self-assembly of single-crystal-like mesoporous stoichiometric oxides for high-performance lithium storage.

Due to their uncontrollable assembly and crystallization process, the synthesis of mesoporous metal oxide single crystals remains a formidable challenge. Herein, we report the synthesis of single-crystal-like mesoporous Li2TiSiO5 by using soft micelles as templates. The key lies in the atomic-scale self-assembly and step-crystallization processes, which ensure the formation of single-crystal-like mesoporous Li2TiSiO5 microparticles via an oriented attachment growth mechanism under the confinement of an in-situ formed carbon matrix. The mesoporous Li2TiSiO5 anode achieves a superior rate capability (148 mAh g-1 at 5.0 A g-1) and outstanding long-term cycling stability (138 mAh g-1 after 3000 cycles at 2.0 A g-1) for lithium storage as a result of the ultrafast Li+ diffusion caused by penetrating mesochannels and nanosized crystal frameworks (5-10 nm). In comparison, bulk Li2TiSiO5 exhibits poor rate capability and cycle performance due to micron-scale diffusion lengths. This method is very simple and reproducible, heralding a new way of designing and synthesizing mesoporous single crystals with controllable frameworks and chemical functionalities.

Seeded growth of single-crystal black phosphorus nanoribbons.

Two-dimensional materials have emerged as an important research frontier for overcoming the challenges in nanoelectronics and for exploring new physics. Among them, black phosphorus, with a combination of a tunable bandgap and high mobility, is one of the most promising systems. In particular, black phosphorus nanoribbons show excellent electrostatic gate control, which can mitigate short-channel effects in nanoscale transistors. Controlled synthesis of black phosphorus nanoribbons, however, has remained an outstanding problem. Here we report large-area growth of black phosphorus nanoribbons directly on insulating substrates. We seed the chemical vapour transport growth with black phosphorus nanoparticles and obtain uniform, single-crystal nanoribbons oriented exclusively along the [100] crystal direction. With comprehensive structural calculations, we discover that self-passivation at the zigzag edges holds the key to the preferential one-dimensional growth. Field-effect transistors based on individual nanoribbons exhibit on/off ratios up to ~104, confirming the good semiconducting behaviour of the nanoribbons. These results demonstrate the potential of black phosphorus nanoribbons for nanoelectronic devices and also provide a platform for investigating the exotic physics in black phosphorus.

A simple coordinate transformation method for quickly locating the features of interest in TEM samples.

We developed a simple coordinate transformation method for quickly locating features of interest (FOIs) of samples in transmission electron microscope (TEM). The method is well suited for conducting sample searches in aberration-corrected scanning/transmission electron microscopes (S/TEM), where the survey can be very time-consuming because of the limited field of view imposed by the highly excited objective lens after fine-tuning the aberration correctors. For implementation, a digital image of the sample and the TEM holder was captured using a simple stereo-optical microscope. Naturally presented geometric patterns on the holder were referenced to construct a projective transformation between the electron and optical coordinate systems. The test results demonstrated that the method was accurate and required no electron microscope or specimen holder modifications. Additionally, it eliminated the need to mount the sample onto specific patterned TEM grids or deposit markers, resulting in universal applications for most TEM samples, holders and electron microscopes for fast FOI identification. Furthermore, we implemented the method into a Gatan script for graphical-user-interface-based step-by-step instructions. Through online communication, the script enabled real-time navigation and tracking of the motion of samples in TEM on enlarged optical images with a panoramic view.

Hexagonal-Ge Nanostructures with Direct-Bandgap Emissions in a Si-Based Light-Emitting Metasurface.

Si-based emitters have been of great interest as an ideal light source for monolithic optical-electronic integrated circuits (MOEICs) on Si substrates. However, the general Si-based material is a diamond structure of cubic lattice with an indirect band gap, which cannot emit light efficiently. Here, hexagonal-Ge (H-Ge) nanostructures within a light-emitting metasurface consisting of a cubic-SiGe nanodisk array are reported. The H-Ge nanostructure is naturally formed within the cubic-Ge epitaxially grown on Si (001) substrates due to the strain-induced nanoscale crystal structure transformation assisted by far-from-equilibrium growth conditions. The direct-bandgap features of H-Ge nanostructures are observed and discussed, including a rather strong and linearly power-dependent photoluminescence (PL) peak around 1562 nm at room temperature and temperature-insensitive PL spectrum near room temperature. Given the direct-bandgap nature, the heterostructure of H-Ge/C-Ge, and the compatibility with the sophisticated Si technology, the H-Ge nanostructure has great potential for innovative light sources and other functional devices, particularly in Si-based MOEICs.

Spontaneous rotational symmetry breaking in KTaO3 heterointerface superconductors.

Broken symmetries play a fundamental role in superconductivity and influence many of its properties in a profound way. Understanding these symmetry breaking states is essential to elucidate the various exotic quantum behaviors in non-trivial superconductors. Here, we report an experimental observation of spontaneous rotational symmetry breaking of superconductivity at the heterointerface of amorphous (a)-YAlO3/KTaO3(111) with a superconducting transition temperature of 1.86 K. Both the magnetoresistance and superconducting critical field in an in-plane field manifest striking twofold symmetric oscillations deep inside the superconducting state, whereas the anisotropy vanishes in the normal state, demonstrating that it is an intrinsic property of the superconducting phase. We attribute this behavior to the mixed-parity superconducting state, which is an admixture of s-wave and p-wave pairing components induced by strong spin-orbit coupling inherent to inversion symmetry breaking at the heterointerface of a-YAlO3/KTaO3. Our work suggests an unconventional nature of the underlying pairing interaction in the KTaO3 heterointerface superconductors, and brings a new broad of perspective on understanding non-trivial superconducting properties at the artificial heterointerfaces.

Self-rolling of vanadium dioxide nanomembranes for enhanced multi-level solar modulation.

Thermochromic window develops as a competitive solution for carbon emissions due to comprehensive advantages of its passivity and effective utilization of energy. How to further enhance the solar modulation ([Formula: see text]) of thermochromic windows while ensuring high luminous transmittance ([Formula: see text]) becomes the latest challenge to touch the limit of energy efficiency. Here, we show a smart window combining mechanochromism with thermochromism by self-rolling of vanadium dioxide (VO2) nanomembranes to enhance multi-level solar modulation. The mechanochromism is introduced by the temperature-controlled regulation of curvature of rolled-up smart window, which benefits from effective strain adjustment in VO2 nanomembranes upon the phase transition. Under geometry design and optimization, the rolled-up smart window with high [Formula: see text] and [Formula: see text] is achieved for the modulation of indoor temperature self-adapted to seasons and climate. Furthermore, such rolled-up smart window enables high infrared reflectance after triggered phase transition and acts as a smart lens protective cover for strong radiation. This work supports the feasibility of self-rolling technology in smart windows and lens protection, which promises broad interest and practical applications of self-adapting devices and systems for smart building, intelligent sensors and actuators with the perspective of energy efficiency.

Electronically phase separated nano-network in antiferromagnetic insulating LaMnO3/PrMnO3/CaMnO3 tricolor superlattice.

Strongly correlated materials often exhibit an electronic phase separation (EPS) phenomena whose domain pattern is random in nature. The ability to control the spatial arrangement of the electronic phases at microscopic scales is highly desirable for tailoring their macroscopic properties and/or designing novel electronic devices. Here we report the formation of EPS nanoscale network in a mono-atomically stacked LaMnO3/CaMnO3/PrMnO3 superlattice grown on SrTiO3 (STO) (001) substrate, which is known to have an antiferromagnetic (AFM) insulating ground state. The EPS nano-network is a consequence of an internal strain relaxation triggered by the structural domain formation of the underlying STO substrate at low temperatures. The same nanoscale network pattern can be reproduced upon temperature cycling allowing us to employ different local imaging techniques to directly compare the magnetic and transport state of a single EPS domain. Our results confirm the one-to-one correspondence between ferromagnetic (AFM) to metallic (insulating) state in manganite. It also represents a significant step in a paradigm shift from passively characterizing EPS in strongly correlated systems to actively engaging in its manipulation.

Two-Dimensional Superconductivity at the Titanium Sesquioxide Heterointerface.

The study of exotic superconductivity in two dimensions has been a central theme in the solid state and materials research communities. Experimentally exploring and identifying exotic, fascinating interface superconductors with a high transition temperature (Tc) are challenging. Here, we report an experimental observation of intriguing two-dimensional superconductivity with a Tc of up to 3.8 K at the interface between a Mott insulator Ti2O3 and polar semiconductor GaN. At the verge of superconductivity, we also observe a striking quantum metallic-like state, demonstrating that it is a precursor to the two-dimensional superconductivity as the temperature is decreased. Our work shows an exciting opportunity to exploit the underlying, emergent quantum phenomena at the heterointerfaces via heterostructure engineering.

Extensive Broadband Near-Infrared Emissions from GexSi1-x Alloys on Micro-Hole Patterned Si(001) Substrates.

Broadband near-infrared (NIR) luminescent materials have been continuously pursued as promising candidates for optoelectronic devices crucial for wide applications in night vision, environment monitoring, biological imaging, etc. Here, graded GexSi1-x (x = 0.1-0.3) alloys are grown on micro-hole patterned Si(001) substrates. Barn-like islands and branch-like nanostructures appear at regions in-between micro-holes and the sidewalls of micro-holes, respectively. The former is driven by the efficient strain relation. The latter is induced by the dislocations originating from defects at sidewalls after etching. An extensive broadband photoluminescence (PL) spectrum is observed in the NIR wavelength range of 1200-2200 nm. Moreover, the integrated intensity of the PL can be enhanced by over six times in comparison with that from the reference sample on a flat substrate. Such an extensively broad and strong PL spectrum is attributed to the coupling between the emissions of GeSi alloys and the guided resonant modes in ordered micro-holes and the strain-enhanced decomposition of alloys during growth on the micro-hole patterned substrate. These results demonstrate that the graded GexSi1-x alloys on micro-hole pattered Si substrates may have great potential for the development of innovative broadband NIR optoelectronic devices, particularly to realize entire systems on a Si chip.

Cathodoluminescence visualisation of local thickness variations of GaAs/AlGaAs quantum-well tubes on nanowires.

We present spatially and spectrally resolved emission from nanowires with a thin radial layer of GaAs embedded in AlGaAs barriers, grown radially around taper-free GaAs cores. The GaAs layers are thin enough to show quantization, and are quantum wells. Due to their shape, they are referred to as quantum well tubes (QWTs). We have investigated three different nominal QWT thicknesses: 1.5, 2.0, and 6.0 nm. They all show average emission spectra from the QWT with an energy spread corresponding to a thickness variation of ±30%. We observe no thickness gradient along the length of the nanowires. Individual NWs show a number of peaks, corresponding to different QW thicknesses. Apart from the thinnest QWT, the integrated emission from the QWTs shows homogeneous emission intensity along the NW. The thinnest QWTs show patchy emission patterns due to the incomplete coverage of the QWT. We observe a few NWs with larger diameters. The QWTs in these NWs show spatially resolved variations across the NW. An increase in the local thickness of the QWT at the corners blocks the diffusion of carriers from facet to facet, thereby enabling us to visualise the thickness variations of the radial quantum wells.

Direct experimental evidence of physical origin of electronic phase separation in manganites.

Electronic phase separation in complex oxides is the inhomogeneous spatial distribution of electronic phases, involving length scales much larger than those of structural defects or nonuniform distribution of chemical dopants. While experimental efforts focused on phase separation and established its correlation with nonlinear responses under external stimuli, it remains controversial whether phase separation requires quenched disorder for its realization. Early theory predicted that if perfectly "clean" samples could be grown, both phase separation and nonlinearities would be replaced by a bicritical-like phase diagram. Here, using a layer-by-layer superlattice growth technique we fabricate a fully chemically ordered "tricolor" manganite superlattice, and compare its properties with those of isovalent alloyed manganite films. Remarkably, the fully ordered manganite does not exhibit phase separation, while its presence is pronounced in the alloy. This suggests that chemical-doping-induced disorder is crucial to stabilize the potentially useful nonlinear responses of manganites, as theory predicted.

Imaging Beam-Sensitive Materials by Electron Microscopy.

Electron microscopy allows the extraction of multidimensional spatiotemporally correlated structural information of diverse materials down to atomic resolution, which is essential for figuring out their structure-property relationships. Unfortunately, the high-energy electrons that carry this important information can cause damage by modulating the structures of the materials. This has become a significant problem concerning the recent boost in materials science applications of a wide range of beam-sensitive materials, including metal-organic frameworks, covalent-organic frameworks, organic-inorganic hybrid materials, 2D materials, and zeolites. To this end, developing electron microscopy techniques that minimize the electron beam damage for the extraction of intrinsic structural information turns out to be a compelling but challenging need. This article provides a comprehensive review on the revolutionary strategies toward the electron microscopic imaging of beam-sensitive materials and associated materials science discoveries, based on the principles of electron-matter interaction and mechanisms of electron beam damage. Finally, perspectives and future trends in this field are put forward.

Radial Growth Evolution of InGaAs/InP Multi-Quantum-Well Nanowires Grown by Selective-Area Metal Organic Vapor-Phase Epitaxy.

III-V semiconductor multi-quantum-well nanowires (MQW NWs) via selective-area epitaxy (SAE) is of great importance for the development of nanoscale light-emitting devices for applications such as optical communication, silicon photonics, and quantum computing. To achieve highly efficient light-emitting devices, not only the high-quality materials but also a deep understanding of their growth mechanisms and material properties (structural, optical, and electrical) are extremely critical. In particular, the three-dimensional growth mechanism of MQWs embedded in a NW structure by SAE is expected to be different from that of those grown in a planar structure or with a catalyst and has not yet been thoroughly investigated. In this work, we reveal a distinctive radial growth evolution of InGaAs/InP MQW NWs grown by the SAE metal organic vapor-phase epitaxy (MOVPE) technique. We observe the formation of zinc blende (ZB) QW discs induced by the axial InGaAs QW growth on the wurtzite (WZ) base-InP NW and propose it as the key factor driving the overall structure of radial growth. The role of the ZB-to-WZ change in the driving of the overall growth evolution is supported by a growth formalism, taking into account the formation-energy difference between different facets. Despite a polytypic crystal structure with mixed ZB and WZ phases across the MQW region, the NWs exhibit high uniformity and desirable QW spatial layout with bright room-temperature photoluminescence at an optical communication wavelength of ∼1.3 µm, which is promising for the future development of high-efficiency light-emitting devices.

Axicon Lens for Electrons Using a Magnetic Vortex: The Efficient Generation of a Bessel Beam.

We demonstrate experimentally an efficient electron axicon lens using a magnetic vortex. We show that naturally occurring magnetic vortices with circular magnetic moment distributions in a soft-magnetic thin film create conical phase shifts for fast electrons. Such radially symmetric linear phase ramps are equivalent to ideal light optical axicons. We apply this lens to generate efficient nondiffracting electron Bessel beams, which we observe experimentally in through-focus Lorentz images as well as in propagated off-axis electron holograms. This highlights the potential for using magnetic nanostructures as highly efficient and flexible phase plates for crafting desired electron beam shapes.

Bimetallic Ions Codoped Nanocrystals: Doping Mechanism, Defect Formation, and Associated Structural Transition.

Ionic codoping offers a powerful approach for modifying material properties by extending the selection of potential dopant ions. However, it has been a major challenge to introduce certain ions that have hitherto proved difficult to use as dopants (called "difficult-dopants") into crystal structures at high concentrations, especially through wet chemical synthesis. Furthermore, the lack of a fundamental understanding of how codopants are incorporated into host materials, which types of defect structures they form in the equilibrium state, and what roles they play in material performance, has seriously hindered the rational design and development of promising codoped materials. Here we take In3+ (difficult-dopants) and Nb5+ (easy-dopants) codoped anatase TiO2 nanocrystals as an example and investigate the doping mechanism of these two different types of metal ions, the defect formation, and their associated impacts on high-pressure induced structural transition behaviors. It is experimentally demonstrated that the dual mechanisms of nucleation and diffusion doping are responsible for the synergic incorporation of these two dopants and theoretically evidenced that the defect structures created by the introduced In3+, Nb5+ codopants, their resultant Ti3+, and oxygen vacancies are locally composed of both defect clusters and equivalent defect pairs. These formed local defect structures then act as nucleation centers of baddeleyite- and α-PbO2-like metastable polymorphic phases and induce the abnormal trans-regime structural transition of codoped anatase TiO2 nanocrystals under high pressure. This work thus suggests an effective strategy to design and synthesize codoped nanocrystals with highly concentrated difficult-dopants. It also unveils the significance of local defect structures on material properties.

Quantum Confined Stark Effect in a GaAs/AlGaAs Nanowire Quantum Well Tube Device: Probing Exciton Localization.

In this Letter, we explore the nature of exciton localization in single GaAs/AlGaAs nanowire quantum well tube (QWT) devices using photocurrent (PC) spectroscopy combined with simultaneous photoluminescence (PL) and photoluminescence excitation (PLE) measurements. Excitons confined to GaAs quantum well tubes of 8 and 4 nm widths embedded into an AlGaAs barrier are seen to ionize at high bias levels. Spectroscopic signatures of the ground and excited states confined to the QWT seen in PL, PLE, and PC data are consistent with simple numerical calculations. The demonstration of good electrical contact with the QWTs enables the study of Stark effect shifts in the sharp emission lines of excitons localized to quantum dot-like states within the QWT. Atomic resolution cross-sectional TEM measurements and an analysis of the quantum confined Stark effect of these dots provide insights into the nature of the exciton localization in these nanostructures.

Emergence of localized states in narrow GaAs/AlGaAs nanowire quantum well tubes.

We use low-temperature photoluminescence, photoluminescence excitation, and photoluminescence imaging spectroscopy to explore the optical and electronic properties of GaAs/AlGaAs quantum well tube (QWT) heterostructured nanowires (NWs). We find that GaAs QWTs with widths >5 nm have electronic states which are delocalized and continuous along the length of the NW. As the NW QWT width decreases from 5 to 1.5 nm, only a single electron state is bound to the well, and no optical excitations to a confined excited state are present. Simultaneously, narrow emission lines (fwhm < 600 µeV) appear which are localized to single spatial points along the length of the NW. We find that these quantum-dot-like states broaden at higher temperatures and quench at temperatures above 80 K. The lifetimes of these localized states are observed to vary from dot to dot from 160 to 400 ps. The presence of delocalized states and then localized states as the QWTs become more confined suggests both opportunities and challenges for possible incorporation into quantum-confined device structures.