Ultrathin Boundary-Less SnO2 Films with Surface-Activated Two-Dimensional Nanograins Enable Fast and Sensitive Hydrogen Gas Sensing.

Fast and reliable semiconductor hydrogen sensors are crucially important for the large-scale utilization of hydrogen energy. One major challenge that hinders their practical application is the elevated temperature required, arising from undesirable surface passivation and grain-boundary-dominated electron transportation in the conventional nanocrystalline sensing layers. To address this long-standing issue, in the present work, we report a class of highly reactive and boundary-less ultrathin SnO2 films, which are fabricated by the topochemical transformation of 2D SnO transferred from liquid Sn-Bi droplets. The ultrathin SnO2 films are purposely made to consist of well-crystallized quasi-2D nanograins with in-plane grain sizes going beyond 30 nm, whereby the hydroxyl adsorption and grain boundary side-effects are effectively suppressed, giving rise to an activated (101)-dominating dangling-bond surface and a surface-controlled electrical transportation with an exceptional electron mobility of 209 cm2 V-1 s-1. Our work provides a new cost-effective strategy to disruptively improve the gas reception and transduction of SnO2. The proposed chemiresistive sensors exhibit fast, sensitive, and selective hydrogen sensing performance at a much-reduced working temperature of 60 °C. The remarkable sensing performance as well as the simple and scalable fabrication process of the ultrathin SnO2 films render the thus-developed sensors attractive for long awaited practical applications in hydrogen-related industries.

Structural Engineering of Anode Materials for Low-Temperature Lithium-Ion Batteries: Mechanisms, Strategies, and Prospects.

The severe degradation of electrochemical performance for lithium-ion batteries (LIBs) at low temperatures poses a significant challenge to their practical applications. Consequently, extensive efforts have been contributed to explore novel anode materials with high electronic conductivity and rapid Li+ diffusion kinetics for achieving favorable low-temperature performance of LIBs. Herein, we try to review the recent reports on the synthesis and characterizations of low-temperature anode materials. First, we summarize the underlying mechanisms responsible for the performance degradation of anode materials at subzero temperatures. Second, detailed discussions concerning the key pathways (boosting electronic conductivity, enhancing Li+ diffusion kinetics, and inhibiting lithium dendrite) for improving the low-temperature performance of anode materials are presented. Third, several commonly used low-temperature anode materials are briefly introduced. Fourth, recent progress in the engineering of these low-temperature anode materials is summarized in terms of structural design, morphology control, surface & interface modifications, and multiphase materials. Finally, the challenges that remain to be solved in the field of low-temperature anode materials are discussed. This review was organized to offer valuable insights and guidance for next-generation LIBs with excellent low-temperature electrochemical performance.

Significant hydrogen generation via photo-mechanical coupling in flexible methylammonium lead iodide nanowires.

The flexoelectric effect, which refers to the mechanical-electric coupling between strain gradient and charge polarization, should be considered for use in charge production for catalytically driving chemical reactions. We have previously revealed that halide perovskites can generate orders of higher magnitude flexoelectricity under the illumination of light than in the dark. In this study, we report the catalytic hydrogen production by photo-mechanical coupling involving the photoflexoelectric effect of flexible methylammonium lead iodide (MAPbI3) nanowires (NWs) in hydrogen iodide solution. Upon concurrent light illumination and mechanical vibration, large strain gradients were introduced in flexible MAPbI3 NWs, which subsequently induced significant hydrogen generation (at a rate of 756.5 µmol g-1 h-1, surpassing those values from either photo- or piezocatalysis of MAPbI3 nanoparticles). This photo-mechanical coupling strategy of mechanocatalysis, which enables the simultaneous utilization of multiple energy sources, provides a potentially new mechanism in mechanochemistry for highly efficient hydrogen production.

Laser irradiation induced structural transformation in layered transition metal trichalcogenide nanoflakes.

Laser irradiation is a powerful tool in inducing changes in lattice structures and properties of two-dimensional (2D) materials through processes such as heating, bleaching, catalysis, etc. However, the underlying mechanisms of such transformations vary dramatically in different 2D materials. Here, we report the structural transformation of layered titanium trisulfide (TiS3) to titanium disulfide (TiS2) after irradiation. We systematically characterized the dependence of the transformation on laser power, flake thickness, irradiation time, and vacuum conditions using microscopic and spectroscopic methods. The underlying mechanism is confirmed as the heat-induced materials decomposition, a process that also occurs in many other transition metal trichalcogenide materials. Furthermore, we demonstrate that this spatial-resolved method also enables the creation of in-plane TiS3-TiS2 heterostructures. Our study identifies a new family of 2D materials that undergo a structural transformation after laser irradiation and enriches the methods available for developing new prototypes of low-dimensional devices in the future.

Dynamic Observations on Formation of Coffee-Ring Structures from the Degradation of Cesium Lead Halide Perovskite Nanocrystals.

Nanomaterials of halide perovskites have attracted increasing attention for their remarkable potential in optoelectronic devices, but their instability to environmental factors is the core issue impeding their applications. In this context, the microscopic understanding of their structural degradation mechanisms upon external stimuli remains incomplete. Herein, we took an emerging member of this material family, Cs4PbBr6 nanocrystals (NCs), as an example and investigated the degradation pathways as well as underlying mechanisms under an electron beam by using in situ transmission electron microscopy. Our atomic-scale study identified the distinct degradation stages for the NCs toward interesting coffee-ring PbBr2 structures, which are caused by the organic surface capping agents as well as surface energy of NCs. Our findings present a fundamental insight for the degradation of halide perovskite NCs and may provide indispensable guidance for their structural design and stability improvement.

Quasi-One-Dimensional ZrS3 Nanoflakes for Broadband and Polarized Photodetection with High Tuning Flexibility.

Two-dimensional (2D) layered materials with low crystal symmetries have exhibited unique anisotropic physical properties. Here, we report systematic studies on the photoresponse of field effect transistors (FETs) fabricated using quasi-one-dimensional ZrS3 nanoflakes. The as-fabricated phototransistors exhibit a broadband photocurrent response from ultraviolet to visible regions, where the responsivity and detectivity can be enhanced via additional gate voltages. Furthermore, benefiting from the strong in-plane anisotropy of ZrS3, we observe a gate-voltage and illumination wavelength-dependent polarized photocurrent response, while its sub-millisecond-time response speed is also polarization-dependent. Our results demonstrate the flexible tunability of photodetectors based on anisotropic layered semiconductors, which substantially broadens the application of low symmetry layered materials in polarization-sensitive optoelectronic devices.

Coexistence of logarithmic and SdH quantum oscillations in ferromagnetic Cr-doped tellurium single crystals.

We report the synthesis of transition-metal-doped ferromagnetic elemental single-crystal semiconductors with quantum oscillations using the physical vapor transport method. The 7.7 atom% Cr-doped Te crystals (Cr:Te) show ferromagnetism, butterfly-like negative magnetoresistance in the low temperature (<3.8 K) and low field (<0.15 T) region, and high Hall mobility, e.g. 1320 cm2V-1s-1at 30 K and 350 cm2V-1s-1at 300 K, implying that Cr:Te crystals are ferromagnetic elemental semiconductors. WhenB// [001] // I, the maximum negative MR is ∼-27% atT= 20 K andB= 8 T. In the low temperature semiconducting region, Cr:Te crystals show strong discrete scale invariance dominated logarithmic quantum oscillations when the direction of the magnetic fieldBis parallel to the [100] crystallographic direction (B// [100]) and show Landau quantization dominated Shubnikov-de Haas oscillations forB// [210] direction, which suggests the broken rotation symmetry of the Fermi pockets in the Cr:Te crystals. The findings of coexistence of multiple quantum oscillations and ferromagnetism in such an elemental quantum material may inspire more study of narrow bandgap semiconductors with ferromagnetism and quantum phenomena.

Growth of single-crystal black phosphorus and its alloy films through sustained feedstock release.

Black phosphorus (BP), a fascinating semiconductor with high mobility and a tunable direct bandgap, has emerged as a candidate beyond traditional silicon-based devices for next-generation electronics and optoelectronics. The ability to grow large-scale, high-quality BP films is a prerequisite for scalable integrated applications but has thus far remained a challenge due to unmanageable nucleation events. Here we develop a sustained feedstock release strategy to achieve subcentimetre-size single-crystal BP films by facilitating the lateral growth mode under a low nucleation rate. The as-grown single-crystal BP films exhibit high crystal quality, which brings excellent field-effect electrical properties and observation of pronounced Shubnikov-de Haas oscillations, with high mobilities up to ~6,500 cm2 V-1 s-1 at low temperatures. We further extend this approach to the growth of single-crystal BP alloy films, which broaden the infrared emission regime of BP from 3.7 µm to 6.9 µm at room temperature. This work will greatly facilitate the development of high-performance electronics and optoelectronics based on BP family materials.

Aluminum Impurity from Current Collectors Reactivates Degraded NCM Cathode Materials toward Superior Electrochemical Performance.

The huge amount of degraded NCM (LiNi0.5Co0.2Mn0.3O2) cathode materials from spent lithium-ion batteries is arising as a serious environmental issue as well as a severe waste of metal resources, and therefore, direct recycling of them toward usable electrode materials again is environmentally and economically more attractive in contrast to present metallurgical treatments. In this work, we design a robust two-step method for direct recycling of degraded NCM materials, which uses the aluminum impurity from the attached current collector to supplement the transition metal vacancies for simultaneous elemental compensation and structural restoration. This single-element compensation strategy leads to the regeneration of high-quality NCM material with depressed cation disordering and stabilized layered structure. Moreover, the regenerated NCM material with controllable Al doping delivered an outstanding electrochemical performance; specifically, the capacity (158.6 mAh g-1), rate capability (91.6 mAh g-1 at 5 C), and cycling stability (89.6% capacity retention after 200 cycles) of the regenerated NCM material are even comparable with those of fresh materials. The as-established regeneration protocol has its chance in simplifying the industrial recycling process of degraded NCM materials.

A Two-Stage Network for Zero-Shot Low-Illumination Image Restoration.

Due to the influence of poor lighting conditions and the limitations of existing imaging equipment, captured low-illumination images produce noise, artifacts, darkening, and other unpleasant visual problems. Such problems will have an adverse impact on the following high-level image understanding tasks. To overcome this, a two-stage network is proposed in this paper for better restoring low-illumination images. Specifically, instead of manipulating the raw input directly, our network first decomposes the low-illumination image into three different maps (i.e., reflectance, illumination, and feature) via a Decom-Net. During the decomposition process, only reflectance and illumination are further denoised to suppress the effect of noise, while the feature is preserved to reduce the loss of image details. Subsequently, the illumination is deeply adjusted via another well-designed subnetwork called Enhance-Net. Finally, the three restored maps are fused together to generate the final enhanced output. The entire proposed network is optimized in a zero-shot fashion using a newly introduced loss function. Experimental results demonstrate that the proposed network achieves better performance in terms of both objective evaluation and visual quality.

Spray-Coated Superhydrophobic Overlayer with Photothermal and Electrothermal Functionalities for All-Weather De/anti-icing Applications.

High-performance de/anti-icing overlayers which can be deposited on diverse surfaces offer great potential in many industrial settings and daily life, yet a versatile overlayer applicable to all-weather conditions (high humidity, low temperature, raining, snowing, etc.) is in high demand for practical applications. This study presents the fabrication and application of a superhydrophobic overlayer with a bioinspired hierarchical surface which additionally possesses photothermal and electrothermal functionalities, so it can operate as a de/anti-icing layer in extreme environments. The overlayer, with a papilla-like microstructure similar to that of a lotus leaf, features polydopamine-decorated layered basic zinc acetate microparticles distributed in the framework of multiwalled carbon nanotubes. Specifically, the overlayer is superhydrophobic, and its capability of suppressing the condensation of water droplets and growth of ice crystals is verified by both in situ environmental scanning electron microscopy observations and freezing experiments. Moreover, the overlayer can be warmed up to 74 and 105 °C under the excitation of sunlight and direct current bias, respectively, which is sufficiently high for deicing in severe weather. It is worth mentioning that the overlayer is produced by a spray-coating technique; therefore, it is suitable for large-scale deployment on arbitrary substrate materials. The findings provide insights into a new strategy for engineering multifunctional overlayers and can lead to expanding applications of composite coatings.

Atomic-scale mechanisms on the stepwise growth of MoxW1-xS2 into hexagonal flakes.

The systematic in situ transmission electron microscopy (TEM) analysis suggests three stepwise formation stages during the growth of MoxW1-xS2 hexagonal flakes, which are the initial assembly of precursors into vertical structures, subsequent transition into horizontal structures, and final surface relaxing and faceting into hexagonal flakes.

Few-Layered MnAl2S4 Dielectrics for High-Performance van der Waals Stacked Transistors.

The gate dielectric layer is an important component in building a field-effect transistor. Here, we report the synthesis of a layered rhombohedral-structured MnAl2S4 crystal, which can be mechanically exfoliated down to the monolayer limit. The dielectric properties of few-layered MnAl2S4 flakes are systematically investigated, whereby they exhibit a relative dielectric constant of over 6 and an electric breakdown field of around 3.9 MV/cm. The atomically smooth thin MnAl2S4 flakes are then applied as a dielectric top gate layer to realize a two-dimensional van der Waals stacked field-effect transistor, which uses MoS2 as a channel material. The fabricated transistor can be operated at a small drain-source voltage of 0.1 V and gate voltages within ranges of ±2 V, which exhibit a large on-off ratio over 107 at 0.5 V and a low subthreshold swing value of 80 mV/dec. Our work demonstrates that the few-layered MnAl2S4 can work as a dielectric layer to realize high-performance two-dimensional transistors, and thus broadens the research on high-κ 2D materials and may provide new opportunities in developing low-dimensional electronic devices with a low power consumption in the future.

Multistep nucleation visualized during solid-state crystallization.

Mechanisms of nucleation have been debated for more than a century, despite successes of classical nucleation theory. The nucleation process has been recently argued as involving a nonclassical mechanism (the "two-step" mechanism) in which an intermediate step occurs before the formation of a nascent ordered phase. However, a thorough understanding of this mechanism, in terms of both microscopic kinetics and thermodynamics, remains experimentally challenging. Here, in situ observations using transmission electron microscopy on a solid-state nucleation case indicate that early-stage crystallization can follow the non-classical pathway, yet proceed via a more complex manner in which multiple metastable states precede the emergence of a stable nucleus. The intermediate steps were sequentially isolated as spinodal decomposition of amorphous precursor, mass transport and structural oscillations between crystalline and amorphous states. Our experimental and theoretical analyses support the idea that the energetic favorability is the driving force for the observed sequence of events. Due to the broad applicability of solid-state crystallization, the findings of this study offer new insights into modern nucleation theory and a potential avenue for materials design.

Plasmon-induced trap filling at grain boundaries in perovskite solar cells.

The deep-level traps induced by charged defects at the grain boundaries (GBs) of polycrystalline organic-inorganic halide perovskite (OIHP) films serve as major recombination centres, which limit the device performance. Herein, we incorporate specially designed poly(3-aminothiophenol)-coated gold (Au@PAT) nanoparticles into the perovskite absorber, in order to examine the influence of plasmonic resonance on carrier dynamics in perovskite solar cells. Local changes in the photophysical properties of the OIHP films reveal that plasmon excitation could fill trap sites at the GB region through photo-brightening, whereas transient absorption spectroscopy and density functional theory calculations correlate this photo-brightening of trap states with plasmon-induced interfacial processes. As a result, the device achieved the best efficiency of 22.0% with robust operational stability. Our work provides unambiguous evidence for plasmon-induced trap occupation in OIHP and reveals that plasmonic nanostructures may be one type of efficient additives to overcome the recombination losses in perovskite solar cells and thin-film solar cells in general.

Visualization of Bubble Nucleation and Growth Confined in 2D Flakes.

The nucleation and growth of bubbles within a solid matrix is a ubiquitous phenomenon that affects many natural and synthetic processes. However, such a bubbling process is almost "invisible" to common characterization methods because it has an intrinsically multiphased nature and occurs on very short time/length scales. Using in situ transmission electron microscopy to explore the decomposition of a solid precursor that emits gaseous byproducts, the direct observation of a complete nanoscale bubbling process confined in ultrathin 2D flakes is presented here. This result suggests a three-step pathway for bubble formation in the confined environment: void formation via spinodal decomposition, bubble nucleation from the spherization of voids, and bubble growth by coalescence. Furthermore, the systematic kinetics analysis based on COMSOL simulations shows that bubble growth is actually achieved by developing metastable or unstable necks between neighboring bubbles before coalescing into one. This thorough understanding of the bubbling mechanism in a confined geometry has implications for refining modern nucleation theories and controlling bubble-related processes in the fabrication of advanced materials (i.e., topological porous materials).

Rational Design and in-situ Synthesis of Ultra-Thin ß-Ni(OH)2 Nanoplates for High Performance All-Solid-State Flexible Supercapacitors.

The all-solid-state flexible supercapacitor (AFSC), one of the most flourishing energy storage devices for portable and wearable electronics, attracts substantial attentions due to their high flexibility, compact size, improved safety, and environmental friendliness. Nevertheless, the current AFSCs usually show low energy density, which extremely hinders their practical applications. Herein, ultra-thin ß-Ni(OH)2 nanoplates with thickness of 2.4 ± 0.2 nm are in-situ grown uniformly on Ni foam by one step hydrothermal treatment. Thanks to the ultra-thin nanostructure, ß-Ni(OH)2 nanoplates shows a specific capacitance of 1,452 F g-1 at the scan rate of 3 mV s-1. In addition, the assembled asymmetric AFSC [Ni(OH)2//Activated carbon] shows a specific capacitance of 198 F g-1. It is worth noting that the energy density of the AFSC can reach 62 Wh kg-1 while keeping a high power density of 1.5 kW kg-1. Furthermore, the fabricated AFSCs exhibit satisfied fatigue behavior and excellent flexibility, and about 82 and 86% of the capacities were retained after 5,000 cycles and folding over 1,500 times, respectively. Two AFSC in series connection can drive the electronic watch and to run stably for 10 min under the bending conditions, showing a great potential for powering portable and wearable electronic devices.

Atomic Steps Induce the Aligned Growth of Ice Crystals on Graphite Surfaces.

Heterogeneous ice nucleation on atmospheric aerosols strongly affects the earth's climate, and at the microscopic level, surface-irregularity-induced ice crystallization behaviors are common but crucial. Because of the lack of visual evidence and effective experimental methods, the mechanism of atomic-structure-dependent ice formation on aerosol surfaces is poorly understood. Here we chose highly oriented pyrolytic graphite (HOPG) to represent soot (a primary aerosol), and environmental scanning electron microscopy (ESEM) was performed for in situ observations of ice formation. We found that hexagonal ice crystals show an aligned growth pattern via a two-stage pathway with one a axis coinciding with the direction of atomic step edges on the HOPG surface. Additionally, the ice crystals grow at a noticeably higher speed along this direction. This study reveals the role of atomic surface defects in heterogeneous ice nucleation and may pave the way to control icing-related processes in practical applications.

Magnetotransport and magnetic properties of the layered noncollinear antiferromagnetic Cr2Se3 single crystals.

We report on the growth of high-quality stoichiometric layered Cr2Se3 single crystals with metallic and noncollinear antiferromagnetic ground state using the chemical vapor transport (CVT) method. The crystals show weak ferromagnetism in the in-plane and out-of-plane directions below the Neél temperature (T N), however, the field-cooled out-of-plane magnetization at 500 Oe and 10 K (∼0.24 µ B/f.u.) is approximately 15 times larger than that of the in-plane one, indicating strong c-axis easy uniaxial magnetic anisotropy, which is further supported by the in-plane and out-of-plane isothermal anisotropic magnetic hysteresis loops and the angular dependent magnetoresistance (MR). The latter also reveals a decrease of the coercive field of the crystal upon the tilting of the weak ferromagnetic easy axis away from the direction of the magnetic field. Further, the out-of-plane isothermal MR are negative below T N and show butterfly shapes for T < 10 K and couple with the magnetic hysteresis M(H) loop. These results may help researchers better understand the interplay between the weak ferromagnetism and the magnetotransport properties of 2D itinerant noncollinear antiferromagnetic systems.