A hidden phase uncovered by ultrafast carrier dynamics in thin Bi2O2Se.

Bi2O2Se has attracted intensive attention due to its potential in electronics, optoelectronics, and ferroelectric applications. Despite that, there have only been a handful of experimental studies based on ultrafast spectroscopy to elucidate the carrier dynamics in Bi2O2Se thin films. Besides, different groups have reported various ultrafast timescales and associated mechanisms across films of different thicknesses. A comprehensive understanding in relation to thickness and fluence is still lacking. In this work, we have systematically explored the thickness-dependent Raman spectroscopy and ultrafast carrier dynamics in chemical vapor deposition (CVD)-grown Bi2O2Se thin films on a mica substrate with thicknesses varying from 22.44 nm down to 4.62 nm in both low and high pump fluence regions. Combining the thickness dependence and fluence dependence of the slow decay time, we demonstrate a hidden photoinduced ferroelectric transition in the thinner (<8 nm) Bi2O2Se films below the material damage thresholds, influenced by substrate-induced compressive strain and far-from-equilibrium excitation. Moreover, this transition can be manifested at high electronic excitation densities. Our results deepen the understanding of the interplay between the ferroelectric phase and semiconducting characteristics of Bi2O2Se thin films, offering potential applications in optoelectronic devices that benefit from the ferroelectric transition.

Efficient Carrier Transport in 2D Bi2O2Se/CsBi3I10 Perovskite Heterojunction Enables Highly-Sensitive Broadband Photodetection.

2D Bi2O2Se has recently garnered significant attention in the electronics and optoelectronics fields due to its remarkable photosensitivity, broad spectral absorption, and excellent long-term environmental stability. However, the development of integrated Bi2O2Se photodetector with high performance and low-power consumption is limited by material synthesis method and the inherent high carrier concentration of Bi2O2Se. Here, a type-I heterojunction is presented, comprising 2D Bi2O2Se and lead-free bismuth perovskite CsBi3I10, for fast response and broadband detection. Through effective charge transfer and strong coupling effect at the interfaces of Bi2O2Se and CsBi3I10, the response time is accelerated to 4.1 µs, and the detection range is expanded from ultraviolet to near-infrared spectral regions (365-1500 nm). The as-fabricated photodetector exhibits a responsivity of 48.63 AW-1 and a detectivity of 1.22×1012 Jones at 808 nm. Moreover, efficient modulation of the dominant photocurrent generation mechanism from photoconductive to photogating effect leads to sensitive response exceeding 103 AW-1 for heterojunction-based photo field effect transistor (photo-FETs). Utilizing the large-scale growth of both Bi2O2Se and CsBi3I10, the as-fabricated integrated photodetector array demonstrates outstanding homogeneity and stability of photo-response performance. The proposed 2D Bi2O2Se/CsBi3I10 perovskite heterojunction holds promising prospects for the future-generation photodetector arrays and integrated optoelectronic systems.

Asymmetric and Flexible Ag-MXene/ANFs Composite Papers for Electromagnetic Shielding and Thermal Management.

Lightweight, flexible, and electrically conductive thin films with high electromagnetic interference (EMI) shielding effectiveness and excellent thermal management capability are ideal for portable and flexible electronic devices. Herein, the asymmetric and multilayered structure Ag-MXene/ANFs composite papers (AMAGM) were fabricated based on Ag-MXene hybrids and aramid nanofibers (ANFs) via a self-reduction and alternating vacuum-assisted filtration process. The resultant AMAGM composite papers exhibit high electrical conductivity of 248,120 S m-1, excellent mechanical properties with tensile strength of 124.21 MPa and fracture strain of 4.98%, superior EMI shielding effectiveness (62 dB), ultra-high EMI SE/t (11,923 dB cm2 g-1) and outstanding EMI SE reliability as high as 96.1% even after 5000 cycles of bending deformation benefiting from the unique structure and the 3D network at a thickness of 34 µm. Asymmetric structures play an important role in regulating reflection and absorption of electromagnetic waves. In addition, the multifunctional nanocomposite papers reveal outstanding thermal management performances such as ultrafast thermal response, high heating temperatures at low operation voltage, and high heating stability. The results indicate that the AMAGM composite papers have excellent potential for high-integration electromagnetic shielding, wearable electronics, artificial intelligence, and high-performance heating devices.

Synthesis of Visible Light Excitable Carbon Dot Phosphor-Al2 O3 Hybrids for Anti-Counterfeiting and Information Encryption.

The preparation of room temperature phosphorescent carbon dots still faces great challenges, especially in the case of carbon dots endowed of visible-light excitable room temperature phosphorescence (RTP). To date, a limited number of substrates have been exploited to synthesize room temperature phosphorescent carbon dots, and most of them can emit RTP only in solid state. Here, the synthesis of a composite obtained from the calcination of green carbon dots (g-CDs) blended with aluminum hydroxide (Al(OH)3 ) is reported. The resultant hybrid material g-CDs@Al2 O3 exhibits blue fluorescence and green RTP emissions in an on/off switch process at 365 nm. Notably, this composite manifests strong resistance to extreme acid and basic conditions up to 30 days of treatment. The dense structure of Al2 O3 formed by calcination contributes to the phosphorescent emission of g-CDs. Surprisingly, g-CDs@Al2 O3 can also emit yellow RTP under irradiation with white light. The multicolor emissions can be employed for anti-counterfeiting and information encryption. This work provides a straightforward approach to produce room temperature phosphorescent carbon dots for a wide range of applications.

Waste to treasure: Superwetting foam enhanced by bamboo powder for sustainable on-demand oil-water separation.

Low-cost and sustainable superwetting materials are urgently required for oily wastewater treatment. Many poly(vinylidene fluoride) (PVDF)-based materials have been designed for oil-water separation. However, their fabrication processes frequently require toxic organic solvents and high-cost materials (e.g., carbon tubes and graphene). In this study, a highly porous and superhydrophobic bamboo powders (BP)-enhanced PVDF foam (SBPF) was fabricated via an organic solvent-free process. The SBPF exhibits efficient adsorption and recovery for various oils and organic solvents. Moreover, the SBPF shows high adsorption and separation performance under ultraviolet exposure and turbulent environments. It can also be used for water-in-oil emulsions separation, with a high separation efficiency more than 99.3 % under gravity. Interestingly, the amphiphilic PVDF-BP foam (ABPF) shows underwater superoleophobicity and underoil superhydrophobicity after delignification of SBPF. Owing to the conversion of wettability, it presents a high performance in treatment of both surfactant-stabilied water-in-oil and oil-in-water emulsions with the high separation efficiency achieving more than 99.6 % and 99.5 % respectively under gravity. In addition, the ABPF shows a high separation performance even after ten cycles. Hence, this fabricated organic solvent-free foams are promising candidates for sustainable on-demand separation of oils or organic solvents and water in complex environments.

Robust Hydrogel Adhesion by Harnessing Bioinspired Interfacial Mineralization.

Hydrogels have gained intensive interest in biomedical and flexible electronics, and adhesion of hydrogels to substrates or devices is indispensable in these application scenarios. Although numerous hydrogel adhesion strategies have been developed, it is still challenging to achieve a hydrogel with robust adhesion interface through a universal yet simple method. Here, a strategy for establishing strong interfacial adhesion between various hydrogels and a wide variety of substrates (i.e., soft hydrogels and rigid solids, including glass, aluminum, PET, nylon and PDMS) even under wet conditions, is reported. This strong interfacial adhesion is realized by constructing a bioinspired mineralized transition layer through ion diffusion and subsequent mineral deposition. This strategy is not only generally applicable to a broad range of substrates and ionic pairs, but also compatible with various fabrication approaches without compromising their interfacial robustnesses. This strategy is further demonstrated in the application of single-electrode triboelectric nanogenerators (TENG), where a robust interface between the hydrogel and elastomer layers is enabled to ensure a reliable signal generation and output.

Interfacial electronic structure engineering on molybdenum sulfide for robust dual-pH hydrogen evolution.

Molybdenum disulfide, as an electronic highly-adjustable catalysts material, tuning its electronic structure is crucial to enhance its intrinsic hydrogen evolution reaction (HER) activity. Nevertheless, there are yet huge challenges to the understanding and regulation of the surface electronic structure of molybdenum disulfide-based catalysts. Here we address these challenges by tuning its electronic structure of phase modulation synergistic with interfacial chemistry and defects from phosphorus or sulfur implantation, and we then successfully design and synthesize electrocatalysts with the multi-heterojunction interfaces (e.g., 1T0.81-MoS2@Ni2P), demonstrating superior HER activities and good stabilities with a small overpotentials of 38.9 and 95 mV at 10 mA/cm2, a low Tafel slopes of 41 and 42 mV/dec in acidic as well as alkaline surroundings, outperforming commercial Pt/C catalyst and other reported Mo-based catalysts. Theoretical calculation verified that the incorporation of metallic-phase and intrinsic HER-active Ni-based materials into molybdenum disulfide could effectively regulate its electronic structure for making the bandgap narrower. Additionally, X-ray absorption spectroscopy indicate that reduced nickel possesses empty orbitals, which is helpful for additional H binding ability. All these factors can decrease Mo-H bond strength, greatly improving the HER catalytic activity of these materials.

Solvent-free processing of eco-friendly magnetic and superhydrophobic absorbent from all-plant-based materials for efficient oil and organic solvent sorption.

The unique features of bioresources such as cellulose and bio-wax include renewability, biodegradability, low cost, and abundance on Earth. Therefore, their efficient use is essential for a sustainable economy. Herein, we report a facile method for the surface modification of pretreated cotton with a bio-wax emulsion in water and Fe3O4 nanoparticles to fabricate a green, durable, magnetic, and superhydrophobic/superoleophilic absorbent for the sorption of oil and organic solvents. Magnetic superhydrophobic cotton (MSC) was successfully prepared via a simple two-step dip-coating method without using any toxic organic reagents. The as-prepared MSC was used to selectively absorb various types of oils and organic solvents up to approximately 20-50 times its own weight. Furthermore, it exhibited a stable magnetic responsivity and high reusability in oil/water separation cycles. In addition, the removal and collection of the absorbed oil/organic solvents were easily achieved with distillation and a vacuum air pump. Moreover, the as-prepared MSC was used in a heavy oil/water gravity-separation filter system and in the continuous collection of a light oil from water surfaces using a pump. The proposed concept may provide a green and sustainable strategy for fabricating superhydrophobic/superoleophilic materials for efficient sorption of oils and organic solvents.

Controlled Growth of Large-Sized and Phase-Selectivity 2D GaTe Crystals.

GaTe has recently attracted significant interest due to its direct bandgap and unique phase structure, which makes it a good candidate for optoelectronics. However, the controllable growth of large-sized monolayer and few-layer GaTe with tunable phase structures remains a great challenge. Here the controlled growth of large-sized GaTe with high quality, chemical uniformity, and good reproducibility is achieved through liquid-metal-assisted chemical vapor deposition method. By using liquid Ga, the rapid growth of 2D GaTe flakes with high phase-selectivity can be obtained due to its reduced reaction temperature. In addition, the method is used to synthesize many Ga-based 2D materials and their alloys, showing good universality. Raman spectra suggest that the as-grown GaTe own a relatively weak van der Waals interaction, where monoclinic GaTe displays highly-anisotropic optical properties. Furthermore, a p-n junction photodetector is fabricated using GaTe as a p-type semiconductor and 2D MoSe2 as a typical n-type semiconductor. The GaTe/MoSe2 heterostructure photodetector exhibits large photoresponsivity of 671.52 A W-1 and high photo-detectivity of 1.48 × 1010 Jones under illumination, owing to the enhanced light absorption and good quality of as-grown GaTe. These results indicate that 2D GaTe is a promising candidate for electronic and photoelectronic devices.

Self-templated formation of (NiCo)9S8 yolk-shelled spheres for high-performance hybrid supercapacitors.

Rational materials design for the synthesis of desirable hollow micro- and nanostructures has recently revealed the remarkable potential for high-performance energy storage and conversion devices. Owing to their unique "core-void-shell" structural configurations, yolk-shell-structured electrode materials can achieve intimate contact with the electrolyte and alleviate the volume expansion issue during electrochemical cycling, which is therefore poised to further boost the electrochemical properties of hybrid supercapacitors. Herein, a facile self-templated strategy, consisting of a hydrothermal step and a high-temperature sulfurization process, has been developed for the construction of yolk-shell (NiCo)9S8 spheres in situ coated by graphite carbon ((NiCo)9S8/GC) due to the non-equilibrium thermal treatment of alkali metal alkoxides. The as-synthesized yolk-shelled sphere exhibits a high specific capacitance of 1434.4 F g-1 (179.3 mA h g-1) at a current density of 1 A g-1, and good rate capability and cycling stability with 83.1% capacitance retention at 8 A g-1 over 5000 cycles. To further demonstrate its practical application, a hybrid supercapacitor device was assembled using (NiCo)9S8/GC as the battery-type positive electrode and activated carbon (AC) as the capacitive-type electrode. The as-fabricated device can reach a wide voltage window of up to 1.6 V, deliver a high energy density of 55.6 W h kg-1 at a power density of 800.3 W kg-1 and maintain 90.2% of specific capacitance after 3000 cycles.

High-performance mesoporous γ-Fe2O3 sphere/graphene aerogel composites towards enhanced lithium storage.

Transition metal oxides have recently been demonstrated as highly attractive anodes for high-capacity lithium ion batteries, whose electrochemical properties could be further improved through rational architecture design and incorporating reliable conductive network. Herein, mesoporous γ-Fe2O3 spheres/graphene aerogel composites were synthesized via a solvothermal pathway followed by suitable annealing. Experimental results reveal the uniform mesoporous structure and well-dispersed γ-Fe2O3 spheres with the size of 300-400 nm embedded in the mesopores of the graphene aerogel network. Compared with α-Fe2O3/graphene aerogel and pure γ-Fe2O3, the as-synthesized composite delivers, at the first cycle, a high discharging capacity of 1080 mAh g-1 at current density of 200 mA g-1. Even at much higher current density of 8000 mA g-1, satisfactory discharging capacities of 421.5 mAh g-1 can still be achieved. Upon 100 charging-discharging cycles, the specific capacity of as high as 890.5 mAh g-1 at 200 mA g-1 is maintained. The enhanced electrochemical properties could be attributed to their favorable three-dimensional graphene aerogel network, which accounts for the improved structural stability and electronic conductivity of γ-Fe2O3 during the lithiation/delithiation process.

Selenium-rich nickel cobalt bimetallic selenides with core-shell architecture enable superior hybrid energy storage devices.

The continuous exploration of advanced electrode materials is of remarkable significance to revolutionize next-generation high-performance energy storage devices towards a green future. Benefiting from their electrochemically active sites and abundant redox centers, bimetallic selenides with desirable nanostructures recently have emerged as promising electrode alternatives for battery-supercapacitor hybrid (BSH) devices which demonstrate enormous potential in bridging the gap between electrochemical properties with high power densities (supercapacitors) and energy densities (batteries). Herein, employing the hydrothermal approach with solid Ni-Co spheres as precursors followed by the selenization process, selenide-rich bimetallic selenide spheres with a core-shell nanostructure were rationally designed and synthesized for use as the cathode electrode in superior BSH devices. The as-obtained (NiCo)9Se8/(NiCo)0.85Se (Ni-Co-Se) exhibits a high specific capacity of 164.44 mA h g-1 at a current density of 1 A g-1 with 85.72% capacity retention even after 5000 cycles at a current density of as high as 8 A g-1, suggesting its great promise in practical applications for BSH devices. By integrating activated carbon as the anode with the as-obtained bimetallic selenides as the cathode, an alkaline aqueous BSH device is fabricated and delivers a high energy density of 37.54 W h kg-1 at a high power density of 842.7 W kg-1. It is found that the excellent electrochemical performances can be ascribed to facile ion and electron transport pathways, high electrical conductivity and reliable structural robustness of the prepared selenides. Moreover, the synthetic strategy presented in this paper opens up an avenue to guide the synthesis of various anion doped bimetallic compounds towards high-performance energy conversion and storage devices.

Achieving Ultrahigh Capacity with Self-Assembled Ni(OH)2 Nanosheet-Decorated Hierarchical Flower-like MnCo2O4.5 Nanoneedles as Advanced Electrodes of Battery-Supercapacitor Hybrid Devices.

Self-assembled Ni(OH)2 nanosheet-decorated hierarchical flower-like MnCo2O4.5 nanoneedles were synthesized via a cost-effective and facile hydrothermal strategy, aiming to realize a high-capacity advanced electrode of a battery-supercapacitor hybrid (BSH) device. It is demonstrated that the as-synthesized hierarchical flower-like MnCo2O4.5@Ni(OH)2-nanosheet electrode exhibits a high specific capacity of 318 mAh g-1 at a current density of 3 A g-1 and still maintains a capacity of 263.5 mAh g-1 at a higher current density of 20 A g-1, with an extremely long cycle lifespan of 87.7% capacity retention after 5000 cycles. Moreover, using the unique core-shell structure as the cathode and hollow Fe2O3 nanoparticles/reduced graphene oxide as the anode, the BSH device delivers a high energy density of 56.53 Wh kg-1 when the power density reaches 1.9 kW kg-1, and there is an extraordinarily good cycling stability with the capacity retention rate of 90.4% after 3000 cycles. It is believed that the superior properties originate from desirable core-shell structures alleviating the impact of volume changes as well as the existence of two-dimensional Ni(OH)2 nanosheets with more active sites, thereby improving the cycle stability and achieving ultrahigh capacity. These results will provide more access to the rational material design of diverse nanostructures toward high-performance energy storage devices.

Enhanced Transmission and Self-Cleaning of Patterned Sapphire Substrates Prepared by Wet Chemical Etching Using Silica Masks.

Highly transparent and superhydrophilic sapphire with surface antireflective subwavelength structures were prepared by wet etching using colloidal monolayer silica masks. The film thicknesses of the silica masks were adjusted by the volume concentrations of polystyrene spheres. The evolution of etching morphologies of sapphire was studied, and antireflective concave pyramid nanoarrays on sapphire substrates were designed by calculation and were then prepared. The transmission and wettability of as-obtained patterned sapphire substrates were also investigated. As for sapphire with optimum surface concave micropyramid arrays, average visible transmittance can reach 91.7%, which is apparently higher than that of flat sapphire (85.5%). Moreover, the concave pyramid arrays can significantly increase the surface hydrophilicity of sapphire, exhibiting a water contact angle of 12.6° compared with 62.7° of flat sapphire. The proposed method can be an excellent strategy for preparing antireflective and self-cleaning concave micropyramid subwavelength structures on sapphire without complicated equipment and expensive raw materials.

Broad-band anti-reflective pore-like sub-wavelength surface nanostructures on sapphire for optical windows.

Compared with conventional anti-reflective film, an anti-reflective sub-wavelength surface structure provides an ideal choice for a sapphire optical window especially in harsh environments. However, it is still a challenge to obtain a sapphire anti-reflective surface microstructure because of its high hardness and chemical inertness. In this paper, combined with optical simulation, we proposed a facile method based on the anodic oxidation of aluminum film and following epitaxial annealing. Al thin film was deposited on a sapphire substrate by magnetron sputtering, and anodic oxidation was then performed to prepare surface pore-like structures on the Al film. Followed by two-step annealing, both the anodic oxidized coating and underlying unoxidized Al film were transformed totally into alumina. The parameters of anodic oxidation were analyzed to obtain the optimal pore-like structures for the antireflection in the mid-infrared and visible spectrum regions, respectively. Finally, the optimized surface sub-wavelength nanostructure on sapphire can increase the transmittance by 7% in the wavelength range of 3000-5000 nm and can increase 13.2% significantly for visible spectrum region, respectively. Meanwhile, the surface wettability can be also manipulated effectively. The preparation of surface pore-like sub-wavelength structure by the annealing of anodic oxidized aluminum film on sapphire is a feasible, economical and convenient approach and can find the applications for various optoelectronic fields.

Large-scale fabrication of nanopatterned sapphire substrates by annealing of patterned Al thin films by soft UV-nanoimprint lithography.

Large-scale nanopatterned sapphire substrates were fabricated by annealing of patterned Al thin films. Patterned Al thin films were obtained by soft UV-nanoimprint lithography and reactive ion etching. The soft mold with 550-nm-wide lines separated by 250-nm space was composed of the toluene-diluted polydimethylsiloxane (PDMS) layer supported by the soft PDMS. Patterned Al thin films were subsequently subjected to dual-stage annealing due to the melting temperature of Al thin films (660°C). The first comprised a low-temperature oxidation anneal at 450°C for 24 h. This was followed by a high-temperature annealing in the range of 1,000°C and 1,200°C for 1 h to induce growth of the underlying sapphire single crystal to consume the oxide layer. The SEM results indicate that the patterns were retained on sapphire substrates after high-temperature annealing at less than 1,200°C. Finally, large-scale nanopatterned sapphire substrates were successfully fabricated by annealing of patterned Al thin films for 24 h at 450°C and 1 h at 1,000°C by soft UV-nanoimprint lithography.