Ion Irradiation Inducing Oxygen Vacancy-Rich NiO/NiFe2 O4 Heterostructure for Enhanced Electrocatalytic Water Splitting.

Oxygen evolution reaction (OER) is an obstacle to the electrocatalytic water splitting due to its unique four-proton-and-electron-transfer reaction process. Many methods, such as engineering heterostructure and introducing oxygen vacancy, have been used to improve the catalytic performance of electrocatalysts for OER. Herein, the above two kinds of regulation are simultaneously realized in a catalyst by using unique ion irradiation technology. A nanosheet structured NiO/NiFe2 O4 heterostructure with rich oxygen vacancies converted from nickel-iron layered double hydroxides by Ar+ ions irradiation shows significant enhancement in both OER and hydrogen evolution reaction performance. Density functional theory (DFT) calculations reveal that the construction of NiO/NiFe2 O4 can optimize the free energy of O* to OOH* process during OER reaction. The oxygen vacancy-rich NiO/NiFe2 O4 nanosheets have an overpotential of 279 mV at 10 mA cm-2 and a low Tafel slope of 42 mV dec-1 . Moreover, this NiO/NiFe2 O4 electrode shows an excellent long-term stability at 100 mA cm-2 for 450 h. The synergetic effects between NiO and NiFe2 O4 make NiO/NiFe2 O4 heterostructure have high conductivity and fast charge transfer, abundant active sites, and high catalytic reactivity, contributing to its excellent performance.

Springtail-Inspired Superamphiphobic Ordered Nanohoodoo Arrays with Quasi-Doubly Reentrant Structures.

The skin of springtails is well-known for being able to repel water and organic liquids using their hexagonally arranged protrusions with reentrant structures. Here, a method to prepare 100 nm-sized nanohoodoo arrays with quasi-doubly reentrant structures over square centimeters through combining the nanosphere lithography and the template-protected selective reactive ion etching technique is demonstrated. The top size of the nanohoodoos, the intra-nanohoodoo distance, and the height of the nanohoodoos can be readily controlled by the plasma-etching time of the polystyrene (PS) spheres, the size of the PS spheres used, and the reactive ion etching time of silicon. The strong structural control capability allows for the study of the relationship between the nanohoodoo structure and the wetting property. Superamphiphobic nanohoodoo arrays with outstanding water/organic liquid repellent properties are finally obtained. The superamphiphobic and liquid repellent properties endow the nanohoodoo arrays with remarkable self-cleaning performance even using hot water droplets, anti-fogging performance, and the surface-enhanced Raman scattering sensitivity improvement by enriching the analyte molecules on the nanohoodoo arrays. Overall, the simple and massive production of the superamphiphobic nanohoodoo structures will push their practical application processes in diverse fields where wettability and liquid repellency need to be carefully engineered.

Substantially Improving Device Performance of All-Inorganic Perovskite-Based Phototransistors via Indium Tin Oxide Nanowire Incorporation.

All-inorganic halide perovskites (IHPs) have attracted enormous attention due to their intrinsically high optical absorption coefficient and superior ambient stabilities. However, the photosensitivity of IHP-based photodetectors is still restricted by their poor conductivities. Here, a facile design of hybrid phototransistors based on the CsPbBr3 thin film and indium tin oxide (ITO) nanowires (NWs) integrated into a InGaZnO channel in order to achieve both high photoresponsivity and fast response is reported. The metallic ITO NWs are employed as electron pumps and expressways to efficiently extract photocarriers from CsPbBr3 and inject electrons into InGaZnO. The obtained device exhibits the outstanding responsivity of 4.9 × 106 A W-1 , which is about 100-fold better than the previous best results of CsPbBr3 -based photodetectors, together with the fast response (0.45/0.55 s), long-term stability (200 h in ambient), and excellent mechanical flexibility. By operating the phototransistor in the depletion regime, an ultrahigh specific detectivity up to 7.6 × 1013 Jones is achieved. More importantly, the optimized spin-coating manufacturing process is highly beneficial for achieving uniform InGaZnO-ITO/perovskite hybrid films for high-performance flexible detector arrays. All these results can not only indicate the potential of these hybrid phototransistors but also provide a valuable insight into the design of hybrid material systems for high-performance photodetection.

Modulating the filament rupture degree of threshold switching device for self-selective and low-current nonvolatile memory application.

Resistive switching devices have tremendous potential for memory, logic, and neuromorphic computing applications. Cation-based resistive switching devices intrinsically show nonvolatile memory characteristics under high compliance current (I CC), while show volatile threshold switching (TS) selector characteristics under low I CC. However, separate researches about cation-based memory or selector are hard to evade the typical current-retention dilemma, which results in the hardship to obtain low-current memory and high-current selector. Here, we propose a novel strategy to realize nonvolatile storage characteristics in a volatile TS device by modulating the rupture degree of conductive filament (CF). Enlarging the rupture degree of the CF with a certain RESET process, as confirmed by transmission electron microscope and energy dispersive spectrometry results, the threshold voltage of the Ag/HfO2/Pt TS devices can be enlarged from 0.9 to 2.8 V. Generation of the voltage difference enables the volatile TS devices the ability of self-selective nonvolatile storage. Increasing the RESET magnitude and shrinking the device size have been proved effective ways to increase the read window of the TS memory (TSM) devices. Evading the limit of the current-retention dilemma, ultra-low energy dissipation can be obtained by decreasing I CC to nA level. With self-selective, low-energy, and potential high-density integration characteristics, the proposed TSM device can act as a potential supplement of novel storage class memories.

Active Electron Density Modulation of Co3 O4 -Based Catalysts Enhances their Oxygen Evolution Performance.

Despite the fact that many strategies have been developed to improve the efficiency of the oxygen evolution reaction (OER), the precise modulation of the surface electronic properties of catalysts to improve their catalytic activity is still challenging. Herein, we demonstrate that the surface active electron density of Co3 O4 can be effectively regulated by an argon-ion irradiation method. X-ray photoelectron and synchrotron x-ray absorption spectroscopy, UV photoelectron spectrometry, and DFT calculations show that the surface active electron density band center of Co3 O4 has been upshifted, leading to a significantly enhanced absorption capability of the oxo group. The optimized Co3 O4 -based catalysts exhibit an excellent overpotential of 260 mV at 10 mA cm-2 and Tafel slope of 54 mV dec-1 , superior to the capability of the benchmark RuO2 , representing one of the best Co-based OER catalysts. This approach could guide the future rational design and discovery of ideal electrocatalysts.

Volume-Enhanced Raman Scattering Detection of Viruses.

Virus detection and analysis are of critical importance in biological fields and medicine. Surface-enhanced Raman scattering (SERS) has shown great promise in small molecule and even single molecule detection, and can provide fingerprint signals of molecules. Despite the powerful detection capabilities of SERS, the size discrepancy between the SERS "hot spots" (generally, <10 nm) and viruses (usually, sub-100 nm) yields poor detection reliability of viruses. Inspired by the concept of molecular imprinting, a volume-enhanced Raman scattering (VERS) substrate composed of hollow nanocones at the bottom of microbowls (HNCMB) is developed. The hollow nanocones of the resulting VERS substrates serve a twofold purpose: 1) extending the region of Raman signal enhancement from the nanocone surface (e.g., surface "hot spots") to the hollow area within the cone (e.g., volume "hot spots")-a novel method of Raman signal enhancement, and 2) directing analyte such as viruses of a wide range of sizes to those VERS "hot spots" while simultaneously increasing the surface area contributing to SERS. Using HNCMB VERS substrates, greatly improved Raman signals of single viruses are demonstrated, an achievement with important implications in disease diagnostics and monitoring, biomedical fields, as well as in clinical treatment.

Anionic Dopant Delocalization through p-Band Modulation to Endow Metal Oxides with Enhanced Visible-Light Photoactivity.

An N-doped TiO2 model reveals a conceptually different mechanism for activating the N dopant based on delocalized orbital hybridization through O vacancy incorporation. Synchrotron-based X-ray absorption spectroscopy, time-resolved fluorescence, and DFT studies revealed that O vacancy incorporation can effectively stimulate the delocalization of N impurity states through p-band orbital modulation, which leads to a significant enhancement in photocarrier lifetime. Consequently, this effect also results in a remarkable increase in the incident photon-to-electron conversion efficiency in the range of 400-550 nm compared to that of conventional N-incorporated TiO2 (15 % versus 1 % at 450 nm). This work reveals the fundamental necessity of orbital modulation in the band engineering of metal oxides for driving solar water splitting and beyond.

Formation of tungsten oxide nanowires by ion irradiation and vacuum annealing.

Here we reported the fabrication of tungsten oxide (WO3-x ) nanowires by Ar+ ion irradiation of WO3 thin films followed by annealing in vacuum. The nanowire length increases with increasing irradiation fluence and with decreasing ion energy. We propose that the stress-driven diffusion of the irradiation-induced W interstitial atoms is responsible for the formation of the nanowires. Comparing to the pristine film, the fabricated nanowire film shows a 106-fold enhancement in electrical conductivity, resulting from the high-density irradiation-induced vacancies on the oxygen sublattice. The nanostructure exhibits largely enhanced surface-enhanced Raman scattering effect due to the oxygen vacancy. Thus, ion irradiation provides a powerful approach for fabricating and tailoring the surface nanostructures of semiconductors.

Significantly enhanced visible light response in single TiO2 nanowire by nitrogen ion implantation.

The metal-oxide semiconductor TiO2 shows enormous potential in the field of photoelectric detection; however, UV-light absorption only restricts its widespread application. It is considered that nitrogen doping can improve the visible light absorption of TiO2, but the effect of traditional chemical doping is far from being used for visible light detection. Herein, we dramatically broadened the absorption spectrum of the TiO2 nanowire (NW) by nitrogen ion implantation and apply the N-doped single TiO2 NW to visible light detection for the first time. Moreover, this novel strategy effectively modifies the surface states and thus regulates the height of Schottky barriers at the metal/semiconductor interface, which is crucial to realizing high responsivity and a fast response rate. Under the illumination of a laser with a wavelength of 457 nm, our fabricated photodetector exhibits favorable responsivity (8 A W-1) and a short response time (0.5 s). These results indicate that ion implantation is a promising method in exploring the visible light detection of TiO2.

Significantly Enhanced Visible Light Photoelectrochemical Activity in TiO2 Nanowire Arrays by Nitrogen Implantation.

Titanium oxide (TiO2) represents one of most widely studied materials for photoelectrochemical (PEC) water splitting but is severely limited by its poor efficiency in the visible light range. Here, we report a significant enhancement of visible light photoactivity in nitrogen-implanted TiO2 (N-TiO2) nanowire arrays. Our systematic studies show that a post-implantation thermal annealing treatment can selectively enrich the substitutional nitrogen dopants, which is essential for activating the nitrogen implanted TiO2 to achieve greatly enhanced visible light photoactivity. An incident photon to electron conversion efficiency (IPCE) of ∼10% is achieved at 450 nm in N-TiO2 without any other cocatalyst, far exceeding that in pristine TiO2 nanowires (∼0.2%). The integration of oxygen evolution reaction (OER) cocatalyst with N-TiO2 can further increase the IPCE at 450 nm to ∼17% and deliver an unprecedented overall photocurrent density of 1.9 mA/cm(2), by integrating the IPCE spectrum with standard AM 1.5G solar spectrum. Systematic photoelectrochemical and electrochemical studies demonstrated that the enhanced PEC performance can be attributed to the significantly improved visible light absorption and more efficient charge separation. Our studies demonstrate the implantation approach can be used to reliably dope TiO2 to achieve the best performed N-TiO2 photoelectrodes to date and may be extended to fundamentally modify other semiconductor materials for PEC water splitting.

Integration of High-k Oxide on MoS2 by Using Ozone Pretreatment for High-Performance MoS2 Top-Gated Transistor with Thickness-Dependent Carrier Scattering Investigation.

A top-gated MoS2 transistor with 6 nm thick HfO2 is fabricated using an ozone pretreatment. The influence to the top-gated mobility brought about by the deposition of HfO2 is studied statistically, for the first time. The top-gated mobility is suppressed by the deposition of HfO2 , and multilayered samples are less susceptible than monolayer ones.

Floating gate memory-based monolayer MoS2 transistor with metal nanocrystals embedded in the gate dielectrics.

Charge trapping layers are formed from different metallic nanocrystals in MoS2 -based nanocrystal floating gate memory cells in a process compatible with existing fabrication technologies. The memory cells with Au nanocrystals exhibit impressive performance with a large memory window of 10 V, a high program/erase ratio of approximately 10(5) and a long retention time of 10 years.

Monolayer graphene on nanostructured Ag for enhancement of surface-enhanced Raman scattering stable platform.

We have reported that the Ag nanostructure-based substrate is particularly suitable for surface-enhanced Raman scattering when it is coated with monolayer graphene, an optically transparent and chemistry-inertness material in the visible range. Ag bowtie nanoantenna arrays and Ag nanogrids were fabricated using plasma-assisted nanosphere lithography. Our measurements show that atmospheric sulfur containing compounds are powerless to break in the monolayer graphene to vulcanize the surfaces of the Ag bowtie nanoantenna arrays and Ag nanogrids by various means, including scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS). Furthermore, the Ag nanostructure substrate coated with the monolayer graphene film shows a larger enhancement of Raman activity and the electromagnetic field than the uncoated substrate. Compared with those of bare Ag nanostructures, the averaged EFs of graphene-film-coated Ag nanostructures were estimated to be about 21 and 5 for Ag bowtie nanoantenna arrays and nanogrids after one month later in air, respectively. These observations are further supported by theoretical calculations.

Recent progress on magnetic iron oxide nanoparticles: synthesis, surface functional strategies and biomedical applications.

This review focuses on the recent development and various strategies in the preparation, microstructure, and magnetic properties of bare and surface functionalized iron oxide nanoparticles (IONPs); their corresponding biological application was also discussed. In order to implement the practical in vivo or in vitro applications, the IONPs must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of IONPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The new functionalized strategies, problems and major challenges, along with the current directions for the synthesis, surface functionalization and bioapplication of IONPs, are considered. Finally, some future trends and the prospects in these research areas are also discussed.

Rational design of sub-parts per million specific gas sensors array based on metal nanoparticles decorated nanowire enhancement-mode transistors.

"One key to one lock" hybrid sensor configuration is rationally designed and demonstrated as a direct effective route for the target-gas-specific, highly sensitive, and promptly responsive chemical gas sensing for room temperature operation in a complex ambient background. The design concept is based on three criteria: (i) quasi-one-dimensional metal oxide nanostructures as the sensing platform which exhibits good electron mobility and chemical and thermal stability; (ii) deep enhancement-mode field-effect transistors (E-mode FETs) with appropriate threshold voltages to suppress the nonspecific sensitivity to all gases (decouple the selectivity and sensitivity away from nanowires); (iii) metal nanoparticle decoration onto the nanostructure surface to introduce the gas specific selectivity and sensitivity to the sensing platform. In this work, using Mg-doped In2O3 nanowire E-mode FET sensor arrays decorated with various discrete metal nanoparticles (i.e., Au, Ag, and Pt) as illustrative prototypes here further confirms the feasibility of this design. Particularly, the Au decorated sensor arrays exhibit more than 3 orders of magnitude response to the exposure of 100 ppm CO among a mixture of gases at room temperature. The corresponding response time and detection limit are as low as ∼4 s and ∼500 ppb, respectively. All of these could have important implications for this "one key to one lock" hybrid sensor configuration which potentially open up a rational avenue to the design of advanced-generation chemical sensors with unprecedented selectivity and sensitivity.

Tuning Surface Potential Polarization to Enhance N2 Affinity for Ammonia Electrosynthesis.

Electrocatalytic N2 reduction reaction (NRR) to synthesize ammonia is a sustainable reaction that is expected to replace Haber Bosch process. Laminated Bi2WO6 has great potential as an NRR electrocatalyst, however, the effective activity requires that the inert substrate is fully activated. Here, for the first time, success is achieved in activating the Bi2WO6 basal planes with NRR activity through Ti doping. The introduction of Ti successfully tunes the surface potential distribution and enhances the N2 adsorption. The subsequently strong hybrid coupling of d(Ti)-p(N) orbitals fills the electronic state of N2 antibonding molecular orbital, which greatly weakens the bonding strength of N≡N bonds. Further, in situ synchrotron radiation-based Fourier transform infrared (SR-FTIR) spectrum and theoretical calculations show that surface potential polarization enhances the adsorption of HNN* by Bi-Ti dual-metal sites, which is beneficial for the subsequent activation hydrogenation process. The Ti-Bi2WO6 nanosheets achieve 11.44% Faradaic efficiency (-0.2 V vs. RHE), a NH3 yield rate of 23.14 µg mg-1 h-1 (15N calibration), and satisfactory stability in 0.1 M HCl environment. The mutual assistance of theory and experiment can help understand and develop of excellent two-dimensional (2D) materials for the NRR.

Recent Progress in the Application of Ion Beam Technology in the Modification and Fabrication of Nanostructured Energy Materials.

The development of green, renewable energy conversion and storage systems is an urgent task to address the energy crisis and environmental issues in the future. To achieve high performance, stable, and safe operation of energy conversion and storage systems, energy materials need to be modified and fabricated through rationalization. Among various modification and fabrication strategies, ion beam technology has been widely used to introduce various defects/dopants into energy materials and fabricate various nanostructures, where the structure, composition, and property of prefabricated materials can be further accurately tailored to achieve better performance. In this paper, we review the recent progress in the application of ion beam technology in material modification and fabrication, focusing on nanostructured energy materials for energy conversion and storage including photo- (electro-) water splitting, batteries (solar cells, fuel cells, and metal-ion batteries), supercapacitors, thermoelectrics, and hydrogen storage. This review first provides a brief basic overview of ion beam technology and describes the classification and technological advantages of ion beam technology in the modification and fabrication of materials. Then, modification of energy materials by ion beams is reviewed mainly concerning doping and defect introduction. Fabrication of energy materials is also discussed mainly in terms of heterojunctions, nanoparticles, nanocavities, and other nanostructures. In particular, we emphasize the advantages of ion beam technology in improving the performance of energy materials. Finally, we point out our understanding of challenges and future perspectives in applying ion beam technology for the modification and fabrication of energy materials.

Spatially selective p-type doping for constructing lateral WS2 p-n homojunction via low-energy nitrogen ion implantation.

The construction of lateral p-n junctions is very important and challenging in two-dimensional (2D) semiconductor manufacturing process. Previous researches have demonstrated that vertical p-n junction can be prepared simply by vertical stacking of 2D materials. However, interface pollution and large area scalability are challenges that are difficult to overcome with vertical stacking technology. Constructing 2D lateral p-n homojunction is an effective strategy to address these issues. Spatially selective p-type doping of 2D semiconductors is expected to construct lateral p-n homojunction. In this work, we have developed a low-energy ion implantation system that reduces the implanted energy to 300 eV. Low-energy implantation can form a shallow implantation depth, which is more suitable for modulating the electrical and optical properties of 2D materials. Hence, we utilize low-energy ion implantation to directly dope nitrogen ions into few-layer WS2 and successfully realize a precise regulation for WS2 with its conductivity type transforming from n-type to bipolar or even p-type conduction. Furthermore, the universality of this method is demonstrated by extending it to other 2D semiconductors, including WSe2, SnS2 and MoS2. Based on this method, a lateral WS2 p-n homojunction is fabricated, which exhibits significant rectification characteristics. A photodetector based on p-n junction with photovoltaic effect is also prepared, and the open circuit voltage can reach to 0.39 V. This work provides an effective way for controllable doping of 2D semiconductors.

Fabrication and properties of TiO2 nanofilms on different substrates by a novel and universal method of Ti-ion implantation and subsequent annealing.

We report a new, novel and universal method to fabricate high-quality titanium dioxide (TiO2) nanofilms on different substrates by a solid phase growth process of ion implantation and subsequent annealing in oxygen atmosphere. Ti ions were implanted into fused silica, soda lime glass, Z-cut quartz, or (0001) α-sapphire by a metal vapor vacuum arc (MEVVA) ion source implanter to fluences of 0.75, 1.5 and 3 × 10(17) ions cm(-2) with a nominal accelerating voltage of 20 kV. To understand the influence of the annealing temperature, time, and substrate on the formation and phase transformation of the TiO2 nanofilms, the Ti-ion-implanted substrates were annealed in oxygen atmosphere from 500 to 1000 °C for 1-6 h. The formation of TiO2 nanofilms resulted from the slow out-diffusion of implanted Ti ions from the substrates which were then oxidized at the surfaces. The thickness and phase of the nanofilms can be tailored by controlling the implantation and annealing parameters. Since the TiO2 nanofilms are formed under high temperature and low growth rate, they show good crystallinity and antibacterial properties, with good film adhesion and stability, suggesting that the TiO2 nanofilms formed by this method have great potential in applications such as antibacterial and self-cleaning transparent glass.

Controllable synthesis of recyclable core-shell γ-Fe2O3@SnO2 hollow nanoparticles with enhanced photocatalytic and gas sensing properties.

Composite materials containing different components with well-defined structures may cooperatively enhance their performance and extend their applications. In this work, core-shell γ-Fe2O3@SnO2 hollow nanoparticles (NPs) were synthesized by a low-cost and environmentally friendly seed-mediated hydrothermal method. Firstly, the γ-Fe2O3 hollow NPs were synthesized by a template-free method. Then they were used as the cores for the growth of SnO2 shells. The thickness of the shell can be simply tailored by controlling the reaction time. Various techniques, including SEM, XRD, TEM and HRTEM, were employed to investigate the morphology, structure and formation process of the special core-shell hollow structures. The combination of magnetic semiconductor (γ-Fe2O3) and wide band-gap semiconductor (SnO2) endowed them with great potential to be used as recyclable photocatalysts. Experiments on photo-degradation of Rhodamin B (RhB) dye in the presence of the samples showed that the hybrid structures possessed higher photocatalytic activities than the monomer structures of SnO2 and γ-Fe2O3 materials indicating a strong coupling enhancement effect between the wide and narrow band-gap semiconductors. Moreover, the gas sensing tests of the γ-Fe2O3@SnO2 hollow NPs revealed that the samples exhibited fast response and recovery rates, which enable them to be promising materials for gas sensors.