Modulating the density of silicon nanowire arrays for high-performance hydrovoltaic devices.

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.

Integration of silicon nanostructures for health and energy applications using MACE: a cost-effective process.

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.

Detection of water pollutants using super-hydrophobic porous silicon-based SERS substrates.

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.

Ultrafine Filteration of Metal Catalysts Enables Fabrication of Silicon Nanowires with Diameter Approaching a Unit Cell Size.

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.

Wafer-Scale Fabrication of Hierarchically Porous Silicon and Silica by Active Nanoparticle-Assisted Chemical Etching and Pseudomorphic Thermal Oxidation.

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.

Bi-Layer nanoimprinting lithography for metal-assisted chemical etching with application on silicon mold replication.

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.

Application of p and n-Type Silicon Nanowires as Human Respiratory Sensing Device.

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.

Inverse metal-assisted chemical etching of germanium with gold and hydrogen peroxide.

Metal-assisted chemical etching (MACE) is a flexible technique for texturing the surface of semiconductors. In this work, we study the spatial variation of the etch profile, the effect of angular orientation relative to the crystallographic planes, and the effect of doping type. We employ gold in direct contact with germanium as the metal catalyst, and dilute hydrogen peroxide solution as the chemical etchant. With this catalyst-etchant combination, we observe inverse-MACE, where the area directly under gold is not etched, but the neighboring, exposed germanium experiences enhanced etching. This enhancement in etching decays exponentially with the lateral distance from the gold structure. An empirical formula for the gold-enhanced etching depth as a function of lateral distance from the edge of the gold film is extracted from the experimentally measured etch profiles. The lateral range of enhanced etching is approximately 10-20µm and is independent of etchant concentration. At length scales beyond a few microns, the etching enhancement is independent of the orientation with respect to the germanium crystallographic planes. The etch rate as a function of etchant concentration follows a power law with exponent smaller than 1. The observed etch rates and profiles are independent of whether the germanium substrate is n-type, p-type, or nearly intrinsic.

Tailoring porous/filament silicon using the two-step Au-assisted chemical etching of p-type silicon for forming an ethanol electro-oxidation layer.

In this paper, we are reporting on the fabrication of a porous silicon/Au and silicon filament/Au using the two-step Au-assisted chemical etching of p-type Si with a specific resistivity of 0.01, 1, and 12 Ω·cm when varying the Au deposition times. The structure analysis results show that with an increasing Au deposition time of up to 7 min, the thickness of the porous Si layer increases for the same etching duration (60 min), and the morphology of the layer changes from porous to filamentary. This paper shows that the uniform macro-porous layers with a thickness of 125.5-171.2µm and a specific surface area of the mesopore sidewalls of 142.5-182 m2·g-1are formed on the Si with a specific resistivity of 0.01 Ω·cm. The gradient macro-porous layers with a thickness of 220-260µm and 210-290µm, the specific surface area of the mesopore sidewalls of 3.7-21.7 m2·g-1and 17-29 m2·g-1are formed on the silicon with a specific resistivity of 1 and 12 Ω·cm, respectively. The por-Si/Au has excellent low-temperature electro oxidation performance with ethanol, the activity of ethanol oxidation is mainly due to the synergistic effect of the Au nanoparticles and porous Si. The formation mechanism of the uniform and gradient macro-porous layers and ethanol electro-oxidation on the porous/filament silicon, decorated with Au nanoparticles, was established. The por-Si/Au structures with perpendicularly oriented pores, a high por-Si layer thickness, and a low mono-Si layer thickness (with a specific resistivity of 1 Ω·cm) are optimal for an effective ethanol electro-oxidation, which has been confirmed with chronoamperometry measurements.

Electrochemical nanoimprinting of silicon.

Scalable nanomanufacturing enables the commercialization of nanotechnology, particularly in applications such as nanophotonics, silicon photonics, photovoltaics, and biosensing. Nanoimprinting lithography (NIL) was the first scalable process to introduce 3D nanopatterning of polymeric films. Despite efforts to extend NIL's library of patternable media, imprinting of inorganic semiconductors has been plagued by concomitant generation of crystallography defects during imprinting. Here, we use an electrochemical nanoimprinting process-called Mac-Imprint-for directly patterning electronic-grade silicon with 3D microscale features. It is shown that stamps made of mesoporous metal catalysts allow for imprinting electronic-grade silicon without the concomitant generation of porous silicon damage while introducing mesoscale roughness. Unlike most NIL processes, Mac-Imprint does not rely on plastic deformation, and thus, it allows for replicating hard and brittle materials, such as silicon, from a reusable polymeric mold, which can be manufactured by almost any existing microfabrication technique.

Replacing Metals with Oxides in Metal-Assisted Chemical Etching Enables Direct Fabrication of Silicon Nanowires by Solution Processing.

Metal-assisted chemical etching (MACE) has emerged as an effective method to fabricate high aspect ratio nanostructures. This method requires a catalytic mask that is generally composed of a metal. Here, we challenge the general view that the catalyst needs to be a metal by introducing oxide-assisted chemical etching (OACE). We perform etching with metal oxides such as RuO2 and IrO2 by transposing materials used in electrocatalysis to nanofabrication. These oxides can be solution-processed as polymers exhibiting similar capabilities of metals for MACE. Nanopatterned oxides can be obtained by direct nanoimprint lithography or block-copolymer lithography from chemical solution on a large scale. High aspect ratio silicon nanostructures were obtained at the sub-20 nm scale exclusively by cost-effective solution processing by halving the number of fabrication steps compared to MACE. In general, OACE is expected to stimulate new fundamental research on chemical etching assisted by other materials, providing new possibilities for device fabrication.

Mass Fabrication of 3D Silicon Nano-/Microstructures by Fab-Free Process Using Tip-Based Lithography.

Methods for the mass fabrication of 3D silicon (Si) microstructures with a 100 nm resolution are developed using scanning probe lithography (SPL) combined with metal-assisted chemical etching (MACE). Protruding Si structures, including Si nanowires of over 10 µm in length and atypical shaped Si nano- and micropillars, are obtained via the MACE of a patterned gold film (negative tone) on Si substrates by dip-pen nanolithography (DPN) with polymer or by nanoshaving alkanethiol self-assembled monolayers (SAMs). Furthermore, recessed Si structures with arbitrary patterning and channels less than 160 nm wide and hundreds of nanometers in depth are obtained via the MACE of a patterned gold film (positive tone) on Si substrates by alkanethiol DPN. As an example of applications using protruded Si structures, nanoimprinting in an area of up to a centimeter is demonstrated through 1D and 2D SPL combined with MACE. Similarly, submicrometer polydimethylsiloxane (PDMS) stamps are employed over millimeter-scale areas for applications using recessed Si structures. In particular, the mass production of arbitrarily shaped Si microparticles at submicrometer resolution is developed using silicon-on-insulator substrates, as demonstrated using optical microresonators, surface-enhanced Raman scattering templates, and smart microparticles for fluorescence signal coding.

Kinked Silicon Nanowires: Superstructures by Metal-Assisted Chemical Etching.

We report on metal-assisted chemical etching of Si for the synthesis of mechanically stable, hybrid crystallographic orientation Si superstructures with high aspect ratio, above 200. This method sustains high etching rates and facilitates reproducible results. The protocol enables the control of the number, angle, and location of the kinks via successive etch-quench sequences. We analyzed relevant Au mask catalyst features to systematically assess their impact on a wide spectrum of etched morphologies that can be easily attained and customized by fine-tuning of the critical etching parameters. For instance, the designed kinked Si nanowires can be incorporated in biological cells without affecting their viability. An accessible numerical model is provided to explain the etch profiles and the physicochemical events at the Si/Au-electrolyte interface and offers guidelines for the development of finite-element modeling of metal-assisted Si chemical etching.

Hybrid Anodic and Metal-Assisted Chemical Etching Method Enabling Fabrication of Silicon Carbide Nanowires.

Silicon carbide (SiC) is one of the most important third-generation semiconductor materials. However, the chemical robustness of SiC makes it very difficult to process, and only very limited methods are available to fabricate nanostructures on SiC. In this work, a hybrid anodic and metal-assisted chemical etching (MACE) method is proposed to fabricate SiC nanowires based on wet etching approaches at room temperature and under atmospheric pressure. Through investigations of the etching mechanism and optimal etching conditions, it is found that the metal component plays at least two key roles in the process, i.e., acting as a catalyst to produce hole carriers and introducing band bending in SiC to accumulate sufficient holes for etching. Through the combined anodic and MACE process the required electrical bias is greatly lowered (3.5 V for etching SiC and 7.5 V for creating SiC nanowires) while enhancing the etching efficiency. Furthermore, it is demonstrated that by tuning the etching electrical bias and time, various nanostructures can be obtained and the diameters of the obtained pores and nanowires can range from tens to hundreds of nanometers. This facile method may provide a feasible and economical way to fabricate SiC nanowires and nanostructures for broad applications.

Metal Nanoparticle-Decorated Silicon Nanowire Arrays on Silicon Substrate and their Applications.

Herein, we report an efficient method to produce silver (Ag) nanoparticle-decorated silicon (Si) nanowire (NW) arrays on a pyramidal Si (P-Si) substrate by using a pure chemical method and rapid thermal annealing in different atmospheres. A metal-assisted chemical etching technique was used to produce vertical Si NW arrays on pyramidal Si. The etching was observed to be heavily dependent on the substrate type. On planar Si (100), the etching was observed to occur in a uniform manner. However, the etching rate was observed to increase from the top to the base of the Si pyramid. The Si NWs produced from P-Si have zig-zag sidewalls as observed from high-resolution transmission electron microscopy images. However, for the same oxidant concentration, Si NWs produced from planar Si (100) consist of straight and amorphous sidewalls. Local variation of oxidant concentration is responsible for the formation of different sidewalls. The substrates are both surface-enhanced Raman scattering (SERS) active and hydrophobic. The hydrophobicity is due to the dual scale of roughness contributed to by both pyramidal and NW structures. Finite-difference time-domain simulation shows that the gap between two Ag spheres and also the gap between Si NWs and Ag spheres contributed to SERS enhancement.

Texturing Silicon Nanowires for Highly Localized Optical Modulation of Cellular Dynamics.

Engineered silicon-based materials can display photoelectric and photothermal responses under light illumination, which may lead to further innovations at the silicon-biology interfaces. Silicon nanowires have small radial dimensions, promising as highly localized cellular modulators, however the single crystalline form typically has limited photothermal efficacy due to the poor light absorption and fast heat dissipation. In this work, we report strategies to improve the photothermal response from silicon nanowires by introducing nanoscale textures on the surface and in the bulk. We next demonstrate high-resolution extracellular modulation of calcium dynamics in a number of mammalian cells including glial cells, neurons, and cancer cells. The new materials may be broadly used in probing and modulating electrical and chemical signals at the subcellular length scale, which is currently a challenge in the field of electrophysiology or cellular engineering.

Lithiation Behavior of Silicon Nanowire Anodes for Lithium-Ion Batteries: Impact of Functionalization and Porosity.

Metal-assisted chemical etching (MACE) provides a versatile way to synthesize silicon nanowires (SiNW) of different morphologies. MACE was used to synthesize oxide-free porous and nonporous SiNW for use as anodes for lithium-ion batteries. To improve their processing behavior, the SiNW were functionalized using acrylic acid. Differential capacity plots were used as a way to identify the degradation processes during cycling through tracking the formation of Li15 Si4 and changes in polarization. The cycling performance between porous and nonporous SiNW differed regarding Coulombic efficiency and cycling stability. The differences were attributed to the porous hull and its ability to reduce the volume expansion, although not through its porous nature but the reduced uptake of Li ions.

Fabricating and Controlling Silicon Zigzag Nanowires by Diffusion-Controlled Metal-Assisted Chemical Etching Method.

Silicon (Si) zigzag nanowires (NWs) have a great potential in many applications because of its high surface/volume ratio. However, fabricating Si zigzag NWs has been challenging. In this work, a diffusion-controlled metal-assisted chemical etching method is developed to fabricate Si zigzag NWs. By tailoring the composition of etchant to change its diffusivity, etching direction, and etching time, various zigzag NWs can be easily fabricated. In addition, it is also found that a critical length of NW (>1 µm) is needed to form zigzag nanowires. Also, the amplitude of zigzag increases as the location approaches the center of the substrate and the length of zigzag nanowire increases. It is also demonstrated that such zigzag NWs can help the silicon substrate for self-cleaning and antireflection. This method may provide a feasible and economical way to fabricate zigzag NWs and novel structures for broad applications.

Reliable Fabrication of Metal Contacts on Silicon Nanowire Forests.

We present a technique for the fabrication of an electrical (and thermal) contact on the top ends of a large number of vertical silicon nanowires, which are fabricated perpendicularly to a silicon wafer (silicon nanowire forest). The technique is based on electrochemical deposition of copper and has been developed on silicon nanowire forests, fabricated by metal assisted chemical etching. We demonstrate that copper grows selectively only on the top end of the silicon nanowires, forming a layer onto the top of the forest. The presence of a predeposited metal seed is fundamental for the selective growth, meanwhile the process is very strong with respect to other parameters, such as concentration of the electrolytic solution and current density, used during the metal deposition. Typical I-V characteristics of top-to-bottom conduction through silicon nanowire forests with different n-doping are shown and discussed.

Inverse metal-assisted chemical etching produces smooth high aspect ratio InP nanostructures.

Creating high aspect ratio (AR) nanostructures by top-down fabrication without surface damage remains challenging for III-V semiconductors. Here, we demonstrate uniform, array-based InP nanostructures with lateral dimensions as small as sub-20 nm and AR > 35 using inverse metal-assisted chemical etching (I-MacEtch) in hydrogen peroxide (H2O2) and sulfuric acid (H2SO4), a purely solution-based yet anisotropic etching method. The mechanism of I-MacEtch, in contrast to regular MacEtch, is explored through surface characterization. Unique to I-MacEtch, the sidewall etching profile is remarkably smooth, independent of metal pattern edge roughness. The capability of this simple method to create various InP nanostructures, including high AR fins, can potentially enable the aggressive scaling of InP based transistors and optoelectronic devices with better performance and at lower cost than conventional etching methods.