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.

High Transient-Thermal-Shock Resistant Nanochannel Tungsten Films.

Developing high-performance tungsten plasma-facing materials for fusion reactors is an urgent task. In this paper, novel nanochannel structural W films prepared by magnetron sputtering deposition were irradiated using a high-power pulsed electron beam or ion beam to study their edge-localized modes, such as transient thermal shock resistance. Under electron beam irradiation, a 1 µm thick nanochannel W film with 150 watt power showed a higher absorbed power density related cracking threshold (0.28-0.43 GW/m2) than the commercial bulk W (0.16-0.28 GW/m2) at room temperature. With ion beam irradiation with an energy density of 1 J/cm2 for different pulses, the bulk W displayed many large cracks with the increase of pulse number, while only micro-crack networks with a width of tens of nanometers were found in the nanochannel W film. For the mechanism of the high resistance of nanochannel W films to transient thermal shock, a residual stress analysis was made by Grazing-incidence X-ray diffraction (GIXRD), and the results showed that the irradiated nanochannel W films had a much lower stress than that of the irradiated bulk W, which indicates that the nanochannel structure can release more stress, due to its special nanochannel structure and ability for the annihilation of irradiation induced defects.

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.

Thermal Conductivity, Electrical Resistivity, and Microstructure of Cu/W Multilayered Nanofilms.

Metallic multilayered nanofilms have been extensively studied owing to their unique physical properties and applications. However, studies on the thermal conductivity and electrical resistivity of metallic multilayered nanofilms, as their important physical properties, are seldom reported. In this work, Cu/W multilayered nanofilms with periodic thickness varying from 6 to 150 nm were deposited by magnetron sputtering. The resistivities of the Cu/W multilayered nanofilms increase with the decrease of periodic thickness, especially when the periodic thickness is smaller than 37 nm. The resistivities of the multilayered nanofilms fit well with the Fuchs-Sondheimer and Mayadas-Shatzkes (FS-MS) model, which considers both interface scattering and grain boundary scattering. The thermal conductivities of the Cu/W multilayered nanofilms were measured by the three-omega (3ω) method, which decrease with a decrease of periodic thickness initially and increase at the smallest periodic thickness of 6 nm. The Boltzmann transport equation (BTE)-based model was used, to explain the periodic thickness-dependent thermal conductivity of metallic multilayered nanofilms by considering the contributions from both phonon and electron heat transport processes, where the calculated thermal conductivities agree well with the measured ones. The electrical resistivity and thermal conductivity strongly depend on the microstructures of the multilayered nanofilms.

Different Radiation Tolerances of Ultrafine-Grained Zirconia-Magnesia Composite Ceramics with Different Grain Sizes.

Developing high-radiation-tolerant inert matrix fuel (IMF) with a long lifetime is important for advanced fission nuclear systems. In this work, we combined zirconia (ZrO2) with magnesia (MgO) to form ultrafine-grained ZrO2-MgO composite ceramics. On the one hand, the formation of phase interfaces can stabilize the structure of ZrO2 as well as inhibiting excessive coarsening of grains. On the other hand, the grain refinement of the composite ceramics can increase the defect sinks. Two kinds of composite ceramics with different grain sizes were prepared by spark plasma sintering (SPS), and their radiation damage behaviors were evaluated by helium (He) and xenon (Xe) ion irradiation. It was found that these dual-phase composite ceramics had better radiation tolerance than the pure yttria-stabilized ZrO2 (YSZ) and MgO. Regarding He+ ion irradiation with low displacement damage, the ZrO2-MgO composite ceramic with smaller grain size had a better ability to manage He bubbles than the composite ceramic with larger grain size. However, the ZrO2-MgO composite ceramic with a larger grain size could withstand higher displacement damage in the phase transformation under heavy ion irradiation. Therefore, the balance in managing He bubbles and phase stability should be considered in choosing suitable grain sizes.

Fabrication of porous TiO2 nanorod array photoelectrodes with enhanced photoelectrochemical water splitting by helium ion implantation.

Porous photoelectrodes show high efficiency in hydrogen production by water splitting. However, fabrication of porous nanorods is usually difficult. Here, we report a simple approach to fabricate a kind of novel porous rutile titanium dioxide nanorod array by an advanced ion implantation method using multiple-energy helium ion implantation and subsequent annealing. The porous nanostructure enhances the photoelectrochemical performance of the titanium dioxide nanorod array photoelectrodes under Uv-visible light illumination, where the highest photocurrent density was relatively about 10 times higher than that of the pristine titanium dioxide nanorod array. The formation of nanocavities mainly contributes to the enhancement of the photocurrent density by trapping holes inside to separate the charge carriers. The study demonstrates that ion implantation could be an effective approach to develop novel porous nanostructural photoelectrodes for the application of hydrogen production.

Formation of Carbonized Polystyrene Sphere/hemisphere Shell Arrays by Ion Beam Irradiation and Subsequent Annealing or Chloroform Treatment.

Heat-resistant two-dimensional (2D) sphere/hemisphere shell array is significant for the fabrication of novel nanostructures. Here large-area, well-ordered arrays of carbonized polystyrene (PS) hollow sphere/hemisphere with controlled size and morphology are prepared by combining the nanosphere self-assembly, kV Ag ion beam modification, and subsequent annealing or chloroform treatment. Potential mechanisms for the formation and evolution of the heat-resistant carbonized PS spherical shell with increasing ion fluence and energy are discussed. Combined with noble metal or semiconductor, these modified PS sphere arrays should open up new possibilities for high-performance nanoscale optical sensors or photoelectric devices.

N Doping to ZnO Nanorods for Photoelectrochemical Water Splitting under Visible Light: Engineered Impurity Distribution and Terraced Band Structure.

Solution-based ZnO nanorod arrays (NRAs) were modified with controlled N doping by an advanced ion implantation method, and were subsequently utilized as photoanodes for photoelectrochemical (PEC) water splitting under visible light irradiation. A gradient distribution of N dopants along the vertical direction of ZnO nanorods was realized. N doped ZnO NRAs displayed a markedly enhanced visible-light-driven PEC photocurrent density of ~160 µA/cm(2) at 1.1 V vs. saturated calomel electrode (SCE), which was about 2 orders of magnitude higher than pristine ZnO NRAs. The gradiently distributed N dopants not only extended the optical absorption edges to visible light region, but also introduced terraced band structure. As a consequence, N gradient-doped ZnO NRAs can not only utilize the visible light irradiation but also efficiently drive photo-induced electron and hole transfer via the terraced band structure. The superior potential of ion implantation technique for creating gradient dopants distribution in host semiconductors will provide novel insights into doped photoelectrode materials for solar water splitting.

Spindle-like alpha-Fe2O3 embedded with TiO2 nanocrystalline: ion implantation preparation and enhanced magnetic properties.

Mastery of the structure of nanomaterials enables control of their properties to enhance their performance for a given application. A scalable method for synthesis of alpha-Fe2O3/TiO2 bi-component nanoparticles (NPs) with novel structure (TiO2 NPs filled into the a-Fe,203) by combining with wet-chemical route and ion implantation-based physical route has been proposed. Different implanted energy and the magnetic properties of bi-component a-Fe203/TiO2 NPs were investigated. The results illustrate alpha-Fe2O3/TiO2 composite NPs can be obtained by Ti ions implantation with different energy, and the saturation magnetization (M(s)) of the samples after ion implantation are significantly enhanced. The results also reveal that conversion phase from hematite to magnetite have been occurred under the thermal effects during ion implantation.

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.

Efficiency enhancements in Ag nanoparticles-SiO2-TiO2 sandwiched structure via plasmonic effect-enhanced light capturing.

TiO2-SiO2-Ag composites are fabricated by depositing TiO2 films on silica substrates embedded with Ag nanoparticles. Enhancement of light absorption of the nanostructural composites is observed. The light absorption enhancement of the synthesized structure in comparison to TiO2 originated from the near-field enhancement caused by the plasmonic effect of Ag nanoparticles, which can be demonstrated by the optical absorption spectra, Raman scattering investigation, and the increase of the photocatalytic activity. The embedded Ag nanoparticles are formed by ion implantation, which effectively prevents Ag to be oxidized through direct contact with TiO2. The suggested incorporation of plasmonic nanostructures shows a great potential application in a highly efficient photocatalyst and ultra-thin solar cell.

Enhanced photocatalysis by coupling of anatase TiO2 film to triangular Ag nanoparticle island.

In order to overcome the low utilization ratio of solar light and high electron-hole pair recombination rate of TiO2, the triangular Ag nanoparticle island is covered on the surface of the TiO2 thin film. Enhancement of the photocatalytic activity of the Ag/TiO2 nanocomposite system is observed. The increase of electron-hole pair generation is caused by the enhanced near-field amplitudes of localized surface plasmon of the Ag nanoparticles. The efficiently suppressed recombination of electron-hole pair caused by the metal-semiconductor contact can also enhance the photocatalytic activity of the TiO2 film.