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Silicon nanowires (SiNWs) have demonstrated great potential for energy storage due to their exceptional electrical conductivity, large surface area, and wide compositional range. Metal-assisted chemical etching (MACE) is a widely used top-down technique for fabricating silicon micro/nanostructures. SiNWs fabricated by MACE exhibit significant surface areas and diverse surface chemistry. Since the material composition and surface chemistry have a significant impact on the electrochemical energy storage performance, integrating SiNWs with diverse materials like porous carbon, metal oxides/sulfides, and polymers, can establish composites with excellent properties. Hence, it is imperative to meticulously fabricate SiNW-based materials with customizable morphologies and enhanced electrochemical energy-storage performance. This review provides an in-depth study of recent advancements in SiNW-based materials with enhanced performance for energy storage systems, such as supercapacitors (SCs) and lithium-ion batteries (LIBs). It includes a concise overview of the history, MACE synthesis, and characteristics of SiNWs. Further, it also explores the key elements that influence the MACE process of SiNWs and delves into structural engineering. Additionally, we introduce recent advances in SiNW-based materials for the design of high-performance energy-storage devices, namely SCs and LIBs. Finally, we present the crucial future prospects of SiNW-based materials for energy-storage applications.

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We report the synthesis of vertically aligned silicon nanowire (VA-SiNW) oligomer arrays coated with Au nanoparticle (NP) monolayers via a combination of colloidal lithography, metal-assisted chemical etching, and directed NP assembly. Arrays of SiNW monomers (i.e., isolated NWs), dimers, and tetramers are synthesized, decorated with AuNPs, and tested for their performance in surface-enhanced Raman spectroscopy. The ∼20 nm AuNPs easily enter within the ca. 40 nm gaps of the SiNW oligomers, thus reaching the hot spot region. At 785 nm excitation, the AuNPs@SiNW dimer arrays provide the highest Raman signal, in agreement with electromagnetic simulations showing a high electric field enhancement at the Au/Si interface within the dimer gap region.

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Silicon-based material is regarded as one of the most promising anodes for next-generation high-performance lithium-ion batteries (LIBs) due to its high theoretical capacity and low cost. Harnessing silicon carbide's robustness, we designed a novel porous silicon with a sandwich structure of carbon/silicon carbide/Ag-modified porous silicon (Ag-PSi@SiC@C). Different from the conventional SiC interface characterized by a frail connection, a robust dual covalent bond configuration, dependent on SiC and SiOC, has been successfully established. Moreover, the innovative sandwich structure effectively reduces detrimental side reactions on the surface, eases volume expansion, and bolsters the structural integrity of the silicon anode. The incorporation of silver nanoparticles contributes to an improvement in overall electron transport capacity and enhances the kinetics of the overall reaction. Consequently, the Ag-PSi@SiC@C electrode, benefiting from the aforementioned advantages, demonstrates a notably elevated lithium-ion mobility (2.4 * 10-9 cm2·s-1), surpassing that of silicon (5.1 * 10-12 cm2·s-1). The half-cell featuring Ag-PSi@SiC@C as the anode demonstrated robust rate cycling stability at 2.0 A/g, maintaining a capacity of 1321.7 mAh/g, and after 200 cycles, it retained 962.6 mAh/g. Additionally, the full-cell, featuring an Ag-PSi@SiC@C anode and a LiFePO4 (LFP) cathode, exhibits outstanding longevity. Hence, the proposed approach has the potential to unearth novel avenues for the extended exploration of high-performance silicon-carbon anodes for LIBs.

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Silicon in its nanoscale range offers a versatile scope in biomedical, photovoltaic, and solar cell applications. Due to its compatibility in integration with complex molecules owing to changes in charge density of as-fabricated Silicon Nanostructures (SiNSs) to realize label-free and real-time detection of certain biological and chemical species with certain biomolecules, it can be exploited as an indicator for ultra-sensitive and cost-effective biosensing applications in disease diagnosis. The morphological changes of SiNSs modified receptors (PNA, DNA, etc) have huge future scope in optimized sensitivity (due to conductance variations of SiNSs) of target biomolecules in health care applications. Further, due to the unique optical and electrical properties of SiNSs realized using the chemical etching technique, they can be used as an indicator for photovoltaic and solar cell applications. In this work, emphasis is given on different critical parameters that control the fabrication morphologies of SiNSs using metal-assisted chemical etching technique (MACE) and its corresponding fabrication mechanisms focusing on numerous applications in energy storage and health care domains. The evolution of MACE as a low-cost, easy process control, reproducibility, and convenient fabrication mechanism makes it a highly reliable-process friendly technique employed in photovoltaic, energy storage, and biomedical fields. Analysis of the experimental fabrication to obtain high aspect ratio SiNSs was carried out using iMAGEJ software to understand the role of surface-to-volume ratio in effective bacterial interfacing. Also, the role of silicon nanomaterials has been discussed as effective anti-bacterial surfaces due to the presence of silver investigated in the post-fabrication energy dispersive x-ray spectroscopy analysis using MACE.

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Super hydrophobic porous silicon surface is prepared using a wet chemical synthesis route. Scanning electron microscopic investigation confirms a correlation between pore size and reaction time. SERS substrates are prepared by silver nanoparticle deposition on porous silicon surface. They exhibit excellent characteristics in terms of sensitivity, reproducibility, stability, and uniformity. They could detect rhodamine 6G in femtomolar range with SERS enhancement factor of ~ 6.1 × 1012, which is best ever reported for these substrates. Molecule-specific sensing of water pollutants such as methylene blue, glyphosate, and chlorpyrifos, is demonstrated for concentrations well below their permissible limits along with excellent enhancement factors. Porous silicon substrate functionalized with Ag nanoparticles demonstrates to be a promising candidate for low-cost, long-life, reliable sensors for environmental conservation applications.

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The application of nanotechnology in developing novel thermoelectric materials has yielded remarkable advancements in material efficiency. In many instances, dimensional constraints have resulted in a beneficial decoupling of thermal conductivity and power factor, leading to large increases in the achievable thermoelectric figure of merit (ZT). For instance, the ZT of silicon increases by nearly two orders of magnitude when transitioning from bulk single crystals to nanowires. Metal-assisted chemical etching offers a viable, low-cost route for preparing silicon nanopillars for use in thermoelectric devices. The aim of this paper is to review strategies for obtaining high-density forests of Si nanopillars and achieving high-quality contacts on them. We will discuss how electroplating can be used for this aim. As an alternative, nanopillars can be embedded into appropriate electrical and thermal insulators, with contacts made by metal evaporation on uncapped nanopillar tips. In both cases, it will be shown how achieving control over surface termination and defectivity is of paramount importance, demonstrating how a judicious control of defectivity enhances contact quality.

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Hydrovoltaic devices (HDs) based on silicon nanowire (SiNW) arrays have received intensive attention due to their simple preparation, mature processing technology, and high output power. Investigating the impact of structure parameters of SiNWs on the performance of HDs can guide the optimization of the devices, but related research is still not sufficient. This work studies the effect of the SiNW density on the performance of HDs. SiNW arrays with different densities were prepared by controlling the react time of Si wafers in the seed solution (tseed) in metal-assisted chemical etching. Density of SiNW array gradually decreases with the increase oftseed. HDs were fabricated based on SiNW arrays with different densities. The research results indicate that the open-circuit voltage gradually decreases with increasingtseed, while the short-circuit current first increases and then decreases with increasingtseed. Overall, SiNW devices withtseedof 20 s and 60 s have the best output performance. The difference in output performance of HDs based on SiNWs with different densities is attributed to the difference in the gap sizes between SiNWs, specific surface area of SiNWs, and the number of SiNWs in parallel. This work gives the corresponding relationship between the preparation conditions of SiNWs, array density, and output performance of hydrovoltaic devices. Density parameters of SiNW arrays with optimized output performance and corresponding preparation conditions are revealed. The relevant results have important reference value for understanding the mechanism of HDs and designing structural parameters of SiNWs for high-performance hydrovoltaic devices.

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Accurate and fast breath monitoring is of great importance for various healthcare applications, for example, medical diagnoses, studying sleep apnea, and early detection of physiological disorders. Devices meant for such applications tend to be uncomfortable for the subject (patient) and pricey. Therefore, there is a need for a cost-effective, lightweight, small-dimensional, and non-invasive device whose presence does not interfere with the observed signals. This paper reports on the fabrication of a highly sensitive human respiratory sensor based on silicon nanowires (SiNWs) fabricated by a top-down method of metal-assisted chemical-etching (MACE). Besides other important factors, reducing the final cost of the sensor is of paramount importance. One of the factors that increases the final price of the sensors is using gold (Au) electrodes. Herein, we investigate the sensor's response using aluminum (Al) electrodes as a cost-effective alternative, considering the fact that the electrode's work function is crucial in electronic device design, impacting device electronic properties and electron transport efficiency at the electrode-semiconductor interface. Therefore a comparison is made between SiNWs breath sensors made from both p-type and n-type silicon to investigate the effect of the dopant and electrode type on the SiNWs respiratory sensing functionality. A distinct directional variation was observed in the sample's response with Au and Al electrodes. Finally, performing a qualitative study revealed that the electrical resistance across the SiNWs renders greater sensitivity to breath than to dry air pressure. No definitive research demonstrating the mechanism behind these effects exists, thus prompting our study to investigate the underlying process.

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We report the use of thermal dewetting to structure gold-based catalytic etching masks for metal-assisted chemical etching (MACE). The approach involves low-temperature dewetting of metal films to generate metal holey meshes with tunable morphologies. Combined with MACE, dewetting-assisted patterning is a simple, benchtop route to synthesize Si nanotubes, Si nanowalls, and Si nanowires with defined dimensions and optical properties. The approach is compatible with the synthesis of both black and colored nanostructured silicon substrates. In particular, we report the lithography-free fabrication of silicon nanowires with diameters down to 40 nm that support leaky wave-guiding modes, giving rise to vibrant colors. Additionally, micrometer-sized areas with tunable film composition and thickness were patterned via shadow masking. After dewetting and MACE, such patterned metal films produced regions with distinct nanostructured silicon morphologies and colors. To-date, the fabrication of colored silicon has relied on complicated nanoscale patterning processes. Dewetting-assisted patterning provides a simpler alternative that eliminates this requirement. Finally, the simple transfer of resonant SiNWs into ethanolic solutions with well-defined light absorption properties is reported. Such solution-dispersible SiNWs could open new avenues for the fabrication of ultrathin optoelectronic devices with enhanced and tunable light absorption.

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This paper reports a new type of nanoimprinting method called Bi-layer nanoimprinting lithography (BL-NIL), which can work along with metal-assisted chemical etching (MaCE) for fabricating nanostructures on silicon. In contrast to conventional nanoimprinting techniques, BL-NIL adds an interposing layer between the imprinting resist layer and silicon substrate. After the standard imprinting process, dry etching was used to etch away the residual imprinting layer and part of the interposing layer. Finally, the remaining interposing layer was wet-etched using its remover. This innovative approach can ensure cleanliness at the metal/silicon interface after metal lift-off processes, and therefore guarantees the success of MaCE. By combining BL-NIL and MaCE, expensive silicon molds with sub-micrometer/nanometer-scale feature sizes can be easily replicated and preserved. This is important for the application of nanoimprinting technologies in industrial manufacturing.

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In this study, we investigated the use of porous silicon (PSi) fabricated using metal-assisted chemical etching (MACE) as a substrate for the deposition of Au nanoparticles (NPs) for the reduction of nitroaromatic compounds. PSi provides a high surface area for the deposition of Au NPs, and MACE allows for the fabrication of a well-defined porous structure in a single step. We used the reduction of p-nitroaniline as a model reaction to evaluate the catalytic activity of Au NPs on PSi. The results indicate that the Au NPs on the PSi exhibited excellent catalytic activity, which was affected by the etching time. Overall, our results highlighted the potential of PSi fabricated using MACE as a substrate for the deposition of metal NPs for catalytic applications.

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Antimicrobial resistance (AMR) is a major health threat worldwide and the culture-based bacterial detection methods are slow. Surface-enhanced Raman spectroscopy (SERS) can be used to identify target analytes in real time with sensitivity down to the single-molecule level, providing a promising solution for the culture-free bacterial detection. We report the fabrication of SERS substrates having tightly packed silver (Ag) nanoparticles loaded onto long silicon nanowires (Si NWs) grown by the metal-assisted chemical etching (MACE) method for the detection of bacteria. The optimized SERS chips exhibited sensitivity down to 10-12 M concentration of R6G molecules and detected reproducible Raman spectra of bacteria down to a concentration of 100 colony forming units (CFU)/mL, which is a thousand times lower than the clinical threshold of bacterial infections like UTI (105 CFU/mL). A Siamese neural network model was used to classify SERS spectra from bacteria specimens. The trained model identified 12 different bacterial species, including those which are causative agents for tuberculosis and urinary tract infection (UTI). Next, the SERS chips and another Siamese neural network model were used to differentiate AMR strains from susceptible strains of Escherichia coli (E. coli). The enhancement offered by SERS chip-enabled acquisitions of Raman spectra of bacteria directly in the synthetic urine by spiking the sample with only 103 CFU/mL E. coli. Thus, the present study lays the ground for the identification and quantification of bacteria on SERS chips, thereby offering a potential future use for rapid, reproducible, label-free, and low limit detection of clinical pathogens.

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Advanced functionalities of silicon nanowires are size-dependent and downscaling of the nanostructure often leads to higher device performances. Single-crystal silicon nanowires with diameters approaching a single unit cell are fabricated using membrane-filtrated catalyst assisted chemical etching. Atomically filtrated gold is used as uniform pattern to direct anisotropic etching of dense silicon nanowire arrays. The size of the nanowires can be controlled by engineering the molecular weight of Poly(methyl methacrylate) used to fabricate the polymer globule membranes. The smallest silicon nanowires with 0.9 nm diameters exhibit direct, and wide band gap of 3.55 eV and establishes a new record. The experimentally obtained silicon nanowires in this size fill the valuable gap below the few-nanometer regime where to date only theoretical predictions have been available. This fabrication approach could provide facile access to atomic-scale silicon, which can bring further advancement to next generation nanodevices.

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Antireflective (AR) surface texturing is a feasible way to boost the light absorption of photosensitive materials and devices. As a plasma-free etching method, metal-assisted chemical etching (MacEtch) has been employed for fabricating GaN AR surface texturing. However, the poor etching efficiency of typical MacEtch hinders the demonstration of highly responsive photodetectors on an undoped GaN wafer. In addition, GaN MacEtch requires metal mask patterning by lithography, which leads to a huge processing complexity when the dimension of GaN AR nanostructure scales down to the submicron range. In this work, we have developed a facile texturing method of forming a GaN nanoridge surface on an undoped GaN thin film by a lithography-free submicron mask-patterning process via thermal dewetting of platinum. The nanoridge surface texturing effectively reduces the surface reflection in the ultraviolet (UV) regime, which can be translated to a 6-fold enhancement in responsivity (i.e., 115 A/W) of the photodiode at 365 nm. The results demonstrated in this work show that MacEtch can offer a viable route for enhanced UV light-matter interaction and surface engineering in GaN UV optoelectronic devices.

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In this study, we developed active substrates consisting of Ag-decorated silicon nanowires on a Si substrate using a single-step Metal Assisted Chemical Etching (MACE) process, and evaluated their performance in the identification of low concentrations of Rhodamine 6G using surface-enhanced photoluminescence spectroscopy. Different structures with Ag-aggregates as well as Ag-dendrites were fabricated and studied depending on the etching parameters. Moreover, the addition of Au nanoparticles by simple drop-casting on the MACE-treated surfaces can enhance the photoluminescence significantly, and the structures have shown a Limit of Detection of Rhodamine 6G down to 10-12 M for the case of the Ag-dendrites enriched with Au nanoparticles.

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Many biological materials exhibit a multiscale porosity with small, mostly nanoscale pores as well as large, macroscopic capillaries to simultaneously achieve optimized mass transport capabilities and lightweight structures with large inner surfaces. Realizing such a hierarchical porosity in artificial materials necessitates often sophisticated and expensive top-down processing that limits scalability. Here, an approach that combines self-organized porosity based on metal-assisted chemical etching (MACE) with photolithographically induced macroporosity for the synthesis of single-crystalline silicon with a bimodal pore-size distribution is presented, i.e., hexagonally arranged cylindrical macropores with 1 µm diameter separated by walls that are traversed by pores 60 nm across. The MACE process is mainly guided by a metal-catalyzed reduction-oxidation reaction, where silver nanoparticles (AgNPs) serve as the catalyst. In this process, the AgNPs act as self-propelled particles that are constantly removing silicon along their trajectories. High-resolution X-ray imaging and electron tomography reveal a resulting large open porosity and inner surface for potential applications in high-performance energy storage, harvesting and conversion or for on-chip sensorics and actuorics. Finally, the hierarchically porous silicon membranes can be transformed structure-conserving by thermal oxidation into hierarchically porous amorphous silica, a material that could be of particular interest for opto-fluidic and (bio-)photonic applications due to its multiscale artificial vascularization.

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In this paper, we exploit the perspective of luminescent Si nanowires (NWs) in the growing field of commercial biosensing nanodevices for the selective recognition of proteins and pathogen genomes. We fabricated quantum confined fractal arrays of Si NWs with room temperature emission at 700 nm obtained by thin-film, metal-assisted, chemical etching with high production output at low cost. The fascinating optical features arising from multiple scattering and weak localization of light promote the use of Si NWs as optical biosensing platforms with high sensitivity and selectivity. In this work, label-free Si NW optical sensors are surface modified for the selective detection of C-reactive protein through antigen-gene interaction. In this case, we report the lowest limit of detection (LOD) of 1.6 fM, fostering the flexibility of different dynamic ranges for detection either in saliva or for serum analyses. By varying the NW surface functionalization with the specific antigen, the luminescence quenching of NW biosensors is used to measure the hepatitis B-virus pathogen genome without PCR-amplification, with an LOD of about 20 copies in real samples or blood matrix. The promising results show that NW optical biosensors can detect and isolate extracellular vesicles (EV) marked with CD81 protein with unprecedented sensitivity (LOD 2 × 105 sEV/mL), thus enabling their measurement even in a small amount of blastocoel fluid.

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The fabrication of nanostructures usually involves chemical processes that have in certain steps. Especially, it is necessary to use the chemical etching method to release the as-patterned structures from the substrate in most of the transfer techniques. Here, a novel scheme of template transfer as developed for the fabrication of freestanding Au nanomembranes and nanowires by using a soluble PVP adhesive. The nanomembranes feature the periodic nanohole arrays with high uniformity. Without the substrates, these plasmonic nanohole arrays show symmetric and antisymmetric resonance modes with bright and dark spectral features, respectively, in transmission. Through the spectral analysis for reflection, we have disclosed that the usual dark mode in transmission is not really dark, but it reveals a distinct feature in reflection. Two coupling modes present distinct spectral features in transmission and reflection due to their different loss channels. To show their versatility, the freestanding nanomembranes were also employed as secondary templates to form Si nanowire arrays by the metal-assisted chemical etching method.

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Despite its high theoretical capacity, silicon anode has limited intrinsic conductivity and experiences significant volume changes during charge-discharge. To overcome these issues, facile metal-assisted chemical etching and in-situ polymerization of aniline are employed to produce a dense 1D polyaniline/silicon nanowire forest without noticeable agglomeration as a free-standing anode for lithium-ion batteries. This hybrid electrode possesses high cycling performance, delivering a stable capacity capped at 2 mAh cm-2 for 346 cycles of charge-discharge. Maximum capacity of 2 mAh cm-2 is also achievable at high-rate cell testing of 2 mA cm-2 , which cannot be obtained by the anode with plain silicon wafer and silicon nanowire only. The introduction of polyaniline on the silicon nanowire is shown to reduce the solid electrolyte interface (SEI) resistance, stabilize the SEI layer, further alleviate the effect of volume changes, and boost the conductivity of the hybrid anode, resulting in the high electrochemical performance of the anode.

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Metal-assisted electrochemical nanoimprinting (Mac-Imprint) scales the fabrication of micro- and nanoscale 3D freeform geometries in silicon and holds the promise to enable novel chip-scale optics operating at the near-infrared spectrum. However, Mac-Imprint of silicon concomitantly generates mesoscale roughness (e.g., protrusion size ≈45 nm) creating prohibitive levels of light scattering. This arises from the requirement to coat stamps with nanoporous gold catalyst that, while sustaining etchant diffusion, imprints its pores (e.g., average diameter ≈42 nm) onto silicon. In this work, roughness is reduced to sub-10 nm levels, which is in par with plasma etching, by decreasing pore size of the catalyst via dealloying in far-from equilibrium conditions. At this level, single-digit nanometric details such as grain-boundary grooves of the catalyst are imprinted and attributed to the resolution limit of Mac-Imprint, which is argued to be twice the Debye length (i.e., 1.7 nm)-a finding that broadly applies to metal-assisted chemical etching. Last, Mac-Imprint is employed to produce single-mode rib-waveguides on pre-patterned silicon-on-insulator wafers with root-mean-square line-edge roughness less than 10 nm while providing depth uniformity (i.e., 42.9 ± 5.5 nm), and limited levels of silicon defect formation (e.g., Raman peak shift < 0.1 cm-1 ) and sidewall scattering.