Metal‐assisted etching is used in conjunction with block‐copolymer lithography to create ordered and densely‐packed arrays of high‐aspect‐ratio single‐crystal silicon nanowires with uniform crystallographic orientations. Nanowires with diameters and spacings down to 19 nm and 10 nm, respectively, are created as either continuous carpets or as carpets within trenches. Wires with aspect ratios up to 220 are fabricated, and capillary‐induced clustering of wires is eliminated through post‐etching critical point drying. The wires are single crystals with 〈100〉 axis directions. The distribution of wire diameters is narrow and closely follows the size distribution of the block copolymer, with a standard deviation of 3.12 nm for wires of mean diameters 22.06 nm. Wire arrays formed in carpets and in channels have hexagonal order with good fidelity to the block copolymer pattern. Fabrication of wires in topographic features demonstrates the ability to accurately control wire placement. Wire arrays made using this new process will have applications in the creation of arrays of photonic and sensing devices.
Monitoring the dynamic chemical and thermal state of a cell during operation is crucial to making meaningful advancements in battery technology as safety and reliability cannot be compromised. Here we demonstrate the feasibility of incorporating optical fiber Bragg grating sensors inside commercial 18650 cells. By adjusting fiber morphologies, wavelength changes associated with both temperature and pressure are decoupled with high accuracy, and this allows for tracking of chemical events such as solid electrolyte interphase formation and structural evolution. Additionally, we demonstrate how multiple sensors can function as a microcalorimeter to monitor the heat generated by the cell. Resolving this heat in detail is not possible with conventional isothermal calorimetry and the importance of assessing the cell's heat capacity contribution is presented. Collectively, these findings offer a scalable solution for screening electrolyte additives, rapidly identifying the best formation processes of commercial batteries, and designing thermal battery management systems with enhanced safety.
We report the extraordinary result of rapid fibre Bragg grating inscription in doped polymer optical fibres based on polymethyl methacrylate in only 7 ms, which is two orders of magnitude faster than the inscription times previously reported. This was achieved using a new dopant material, diphenyl disulphide, which was found to enable a fast, positive refractive index change using a low ultraviolet dose. These changes were investigated and found to arise from photodissociation of the diphenyl disulphide molecule and subsequent molecular reorganization. We demonstrate that gratings inscribed in these fibres can exhibit at least a 15 times higher sensitivity than silica glass fibre, despite their quick inscription times. As a demonstration of the sensitivity, we selected a highly stringent situation, namely, the monitoring of a human heartbeat and respiratory functions. These findings could permit the inscription of fibre Bragg gratings during the fibre drawing process for mass production, allowing cost-effective, single-use, in vivo sensors among other potential uses.
A systematic study of metal‐catalyzed etching of (100), (110), and (111) silicon substrates using gold catalysts with three varying geometrical characteristics: isolated nanoparticles, metal meshes with small hole spacings, and metal meshes with large hole spacings is carried out. It is shown that for both isolated metal catalyst nanoparticles and meshes with small hole spacings, etching proceeds in the crystallographically preferred <100> direction. However, the etching is confined to the single direction normal to the substrate surface when a catalyst meshes with large hole spacings is used. We have also demonstrated that the metal catalyzed etching method when used with metal mesh with large hole spacings can be extended to create arrays of polycrystalline and amorphous vertically aligned silicon nanowire by confining the etching to proceed in the normal direction to the substrate surface. The ability to pattern wires from polycrystalline and amorphous silicon thin films opens the possibility of making silicon nanowire array‐based devices on a much wider range of substrates.
Attempts to use aluminum-based anodes in lithium-ion batteries often fail due to fast capacity fading. Generally, this has been attributed to pulverization of the electrode and the large volume changes associated with the phase transformation between the crystalline α and β phases of Li-Al alloys. In this study, these transformations were investigated in aluminum films that were lithiated either electrochemically or via direct reaction with lithium metal. Scanning electron microscopy was used to image the samples at different stages of (de)lithiation. By imaging the same locations before and after each step, it can be seen that alloying between Li and Al proceeds from distinct nucleation sites. In situ and ex situ observations reveal that the α-to-β phase transformation is highly anisotropic and causes strong distortions of the film morphology, but only a relatively small amount of mechanical damage such as cracks and delamination. Comparisons between films that were lithiated to 70% and 100% of the theoretical capacity of LiAl indicate that the critical, irreversible damage is more dependent on depth of discharge than on the volume contraction caused by delithiation. Our observations challenge the pessimistic view that pulverization is unavoidable during the phase transformations of the Li-Al system.
Aluminum is an attractive anode material for lithium‐ion batteries (LIBs) owing to its low cost, light weight, and high specific capacity. However, utilization of Al‐based anodes is significantly limited by drastic capacity fading during cycling. Herein, a systematic study is performed to investigate the kinetics of electrochemical lithiation of Al thin films to understand the mechanisms governing the phase transformation, by using an operando light microscopy platform. Operando videos reveal that nuclei appear at random positions and expand to form quasi‐circular patches that grow and merge until the phase transformation is complete. Based on this direct evidence, models of the lithiation processes in Al anodes are discussed and reaction‐controlled kinetics are suggested. The growth rate of LiAl depends on the potential and increases considerably as higher overpotentials are approached. Lastly, improved cycling performance of Al‐based anodes can be realized by two approaches: 1) by controlling the lithiation extent, the cycling life of Al thin film is extended from 5 cycles to 25 cycles; 2) the performance can be optimized by adjusting the kinetics. Together, this work offers a renewed promise for the commercialization of Al‐based anodes in LIBs where the performance requirements are compatible with the proposed cycle life‐extending strategies.
We report the fabrication of silicon nanopillar-based nanocapacitor arrays using metal-assisted etching in conjunction with electrodeposition. The high aspect ratio made possible by the catalyzed etching provides for an increased effective electrode area and hence a significant improvement in the capacitance density. Electroplated Ni electrode forms a conformal layer over the silicon nanopillars. Capacitance measurements show the expected trend as a function of pillar height and array period. The fabrication approach is simple, compatible with integration into standard silicon technology, and easily scalable.
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