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In this study, the effects of variations in the height (h) and bottom radius (r) of black silicon microstructures on their absorptance and photoelectric response efficiency were analyzed. By using the relation cot⁡θ2=hr to combine the parameters, it was found that changes in morphology affected the absorptance of black silicon microstructures, with h being directly proportional to the absorptance, while r was inversely proportional. A positive correlation was observed between cot⁡θ2 and absorptance. However, the correlation between cot⁡θ2 and photoelectric response efficiency was not significant. Through Raman spectroscopy analysis of the samples, it was concluded that as the laser ablation energy density increased, more lattice defects were introduced, weakening the charge carrier transport efficiency. This study further elucidated the mechanism by which microstructural changes impacted the absorptance and energy density of black silicon, providing valuable insights for optimizing its energy density.

Black silicon was discovered by accident and considered an undesirable by-product of the silicon industry. A highly modified surface, consisting of pyramids, needles, holes, pillars, etc., provides high light absorption from the UV to the NIR range and gives black silicon its color—matte black. Although black silicon has already attracted some interest as a promising material for sensitive sensors, the potential of this material has not yet been fully exploited. Over the past three decades, black silicon has been actively introduced as a substrate for surface-enhanced Raman spectroscopy (SERS)—a molecule-specific vibrational spectroscopy technique—and successful proof-of-concept experiments have been conducted. This review focuses on the current progress in black silicon SERS biosensor fabrication, the recent advances in the design of the surface morphology and an analysis of the relation of surface micro-structuring and SERS efficiency and sensitivity. Much attention is paid to problems of non-invasiveness of the technique and biocompatibility of black silicon, its advantages over other SERS biosensors, cost-effectiveness and reproducibility, as well as the expansion of black silicon applications. The question of existing limitations and ways to overcome them is also addressed.

This article discusses a method for forming black silicon using plasma etching at a sample temperature range from −20 °C to +20 °C in a mixture of oxygen and sulfur hexafluoride. The surface morphology of the resulting structures, the autocorrelation function of surface features, and reflectivity were studied depending on the process parameters—the composition of the plasma mixture, temperature and other discharge parameters (radical concentrations). The relationship between these parameters and the concentrations of oxygen and fluorine radicals in plasma is shown. A novel approach has been studied to reduce the reflectance using conformal bilayer dielectric coatings deposited by atomic layer deposition. The reflectivity of the resulting black silicon was studied in a wide spectral range from 400 to 900 nm. As a result of the research, technologies for creating black silicon on silicon wafers with a diameter of 200 mm have been proposed, and the structure formation process takes no more than 5 min. The resulting structures are an example of the self-formation of nanostructures due to anisotropic etching in a gas discharge plasma. This material has high mechanical, chemical and thermal stability and can be used as an antireflective coating, in structures requiring a developed surface—photovoltaics, supercapacitors, catalysts, and antibacterial surfaces.

For uncooled infrared cameras based on microbolometers, silicon caps are often utilized to maintain a vacuum inside the packaged bolometer array. To reduce Fresnel reflection losses, anti-reflection coatings are typically applied on both sides of the silicon caps.This work investigates whether black silicon may be used as an alternative to conventional anti-reflective coatings. Reactive ion etching was used to etch the black silicon layer and deep cavities in silicon. The effects of the processed surfaces on optical transmission and image quality were investigated in detail by Fourier transform infrared spectroscopy and with modulated transfer function measurements. The results show that the etched surfaces enable similar transmission to the state-of-the-artanti-reflection coatings in the 8–12 µm range and possibly obtain wider bandwidth transmission up to 24 µm. No degradation in image quality was found when using the processed wafers as windows. These results show that black silicon can be used as an effective anti-reflection layer on silicon caps used in the vacuum packaging of microbolometer arrays.

Ion-flow-stimulated roughening transition is a phenomenon that may prove useful in the hierarchical structuring of nanostructures. In this work, we have investigated theoretically and experimentally the surface texturing of single-crystal and multi-crystalline silicon wafers irradiated using ion-beam flows. In contrast to previous studies, ions had relatively low energies, whereas flow densities were high enough to induce a quasi-liquid state in the upper silicon layers. The resulting surface modifications reduced the wafer light reflectance to values characteristic of black silicon, widely used in solar energetics. Features of nanostructures on different faces of silicon single crystals were studied numerically based on the mesoscopic Monte Carlo model. We established that the formation of nano-pyramids, ridges, and twisting dune-like structures is due to the stimulated roughening transition effect. The aforementioned variety of modified surface morphologies arises due to the fact that the effects of stimulated surface diffusion of atoms and re-deposition of free atoms on the wafer surface from the near-surface region are manifested to different degrees on different Si faces. It is these two factors that determine the selection of the allowable “trajectories” (evolution paths) of the thermodynamic system along which its Helmholtz free energy, F, decreases, concomitant with an increase in the surface area of the wafer and the corresponding changes in its internal energy, U (dU>0), and entropy, S (dS>0), so that dF=dU – TdS<0, where T is the absolute temperature. The basic theoretical concepts developed were confirmed in experimental studies, the results of which showed that our method could produce, abundantly, black silicon wafers in an environmentally friendly manner compared to traditional chemical etching.

Black silicon (b-Si)-assisted photovoltaic cells have textured b-Si surfaces, which have excellent light-trapping properties. There has been a limited amount of work performed on the theoretical modelling of b-Si photovoltaic cells, and hence, in this work, a coupled optical-electrical-thermal model has been proposed for the simulation of b-Si photovoltaic cells. In particular, the thermal aspects in b-Si photovoltaic cells have not been discussed in the literature. In the proposed model, the finite-difference time-domain (FDTD) method was used to study the optical response of the b-Si photovoltaic cell. Semiconductor equations were used for the electrical modelling of the cell. For the thermal model, the Energy Balance Transport Model was used. The developed model was used to simulate b-Si photovoltaic cells under thermophotovoltaic sources. The impacts of heat generation on the electrical performance of thermophotovoltaic cells are discussed. Simulation results from this study showed that black silicon layer improved efficiency and power output in thermophotovoltaic cells compared to thermophotovoltaic cells with no surface texture. In addition, heat generation due to Joule heating and electron thermalization in b-Si-assisted thermophotovoltaic cells reduced the open-circuit voltage and electrical performance.

Silicon microneedle (Si-MN) systems are a promising strategy for transdermal drug delivery due to their minimal invasiveness and ease of processing and application. Traditional Si-MN arrays are usually fabricated by using micro-electro-mechanical system (MEMS) processes, which are expensive and not suitable for large-scale manufacturing and applications. In addition, Si-MNs have a smooth surface, making it difficult for them to achieve high-dose drug delivery. Herein, we demonstrate a solid strategy to prepare a novel black silicon microneedle (BSi-MN) patch with ultra-hydrophilic surfaces for high drug loading. The proposed strategy consists of a simple fabrication of plain Si-MNs and a subsequent fabrication of black silicon nanowires. First, plain Si-MNs were prepared via a simple method consisting of laser patterning and alkaline etching. The nanowire structures were then prepared on the surfaces of the plain Si-MNs to form the BSi-MNs through Ag-catalyzed chemical etching. The effects of preparation parameters, including Ag+ and HF concentrations during Ag nanoparticle deposition and [HF/(HF + H2O2)] ratio during Ag-catalyzed chemical etching, on the morphology and properties of the BSi-MNs were investigated in detail. The results show that the final prepared BSi-MN patches exhibit an excellent drug loading capability, more than twice that of plain Si-MN patches with the same area, while maintaining comparable mechanical properties for practical skin piercing applications. Moreover, the BSi-MNs exhibit a certain antimicrobial activity that is expected to prevent bacterial growth and disinfect the affected area when applied to the skin.

Black silicon (bSi) is a highly absorptive material in the UV-vis and NIR spectral range. Photon trapping ability makes noble metal plated bSi attractive for fabrication of surface enhanced Raman spectroscopy (SERS) substrates. By using a cost-effective room temperature reactive ion etching method, we designed and fabricated the bSi surface profile, which provides the maximum Raman signal enhancement under NIR excitation when a nanometrically-thin gold layer is deposited. The proposed bSi substrates are reliable, uniform, low cost and effective for SERS-based detection of analytes, making these materials essential for medicine, forensics and environmental monitoring. Numerical simulation revealed that painting bSi with a defected gold layer resulted in an increase in the plasmonic hot spots, and a substantial increase in the absorption cross-section in the NIR range.

This article discusses a method for forming black silicon using plasma etching at a sample temperature range from -20 °C to +20 °C in a mixture of oxygen and sulfur hexafluoride. The surface morphology of the resulting structures, the autocorrelation function of surface features, and reflectivity were studied depending on the process parameters-the composition of the plasma mixture, temperature and other discharge parameters (radical concentrations). The relationship between these parameters and the concentrations of oxygen and fluorine radicals in plasma is shown. A novel approach has been studied to reduce the reflectance using conformal bilayer dielectric coatings deposited by atomic layer deposition. The reflectivity of the resulting black silicon was studied in a wide spectral range from 400 to 900 nm. As a result of the research, technologies for creating black silicon on silicon wafers with a diameter of 200 mm have been proposed, and the structure formation process takes no more than 5 min. The resulting structures are an example of the self-formation of nanostructures due to anisotropic etching in a gas discharge plasma. This material has high mechanical, chemical and thermal stability and can be used as an antireflective coating, in structures requiring a developed surface-photovoltaics, supercapacitors, catalysts, and antibacterial surfaces.

Reactive multilayer systems represent an innovative approach for potential usage in chip joining applications. As there are several factors governing the energy release rate and the stored chemical energy, the impact of the morphology and the microstructure on the reaction behavior is of great interest. In the current work, 3D reactive microstructures with nanoscale Al/Ni multilayers were produced by alternating deposition of pure Ni and Al films onto nanostructured Si substrates by magnetron sputtering. In order to elucidate the influence of this 3D morphology on the phase transformation process, the microstructure and the morphology of this system were characterized and compared with a flat reactive multilayer system on a flat Si wafer. The characterization of both systems was carried out before and after a rapid thermal annealing treatment by using scanning and transmission electron microscopy of the cross sections, selected area diffraction analysis, and differential scanning calorimetry. The bent shape of multilayers caused by the complex topography of silicon needles of the nanostructured substrate was found to favor the atomic diffusion at the early stage of phase transformation and the formation of two intermetallic phases Al0.42Ni0.58 and AlNi3, unlike the flat multilayers that formed a single phase AlNi after reaction.

For uncooled infrared cameras based on microbolometers, silicon caps are often utilized to maintain a vacuum inside the packaged bolometer array. To reduce Fresnel reflection losses, anti-reflection coatings are typically applied on both sides of the silicon caps.This work investigates whether black silicon may be used as an alternative to conventional anti-reflective coatings. Reactive ion etching was used to etch the black silicon layer and deep cavities in silicon. The effects of the processed surfaces on optical transmission and image quality were investigated in detail by Fourier transform infrared spectroscopy and with modulated transfer function measurements. The results show that the etched surfaces enable similar transmission to the state-of-the-artanti-reflection coatings in the 8-12 µm range and possibly obtain wider bandwidth transmission up to 24 µm. No degradation in image quality was found when using the processed wafers as windows. These results show that black silicon can be used as an effective anti-reflection layer on silicon caps used in the vacuum packaging of microbolometer arrays.

Since black silicon was discovered by coincidence, the special material was explored for many amazing material characteristics in optical, surface topography, and so on. Because of the material property, black silicon is applied in many spheres of a photodetector, photovoltaic cell, photo-electrocatalysis, antibacterial surfaces, and sensors. With the development of fabrication technology, black silicon has expanded in more and more applications and has become a research hotspot. Herein, this review systematically summarizes the fabricating method of black silicon, including nanosecond or femtosecond laser irradiation, metal-assisted chemical etching (MACE), reactive ion etching (RIE), wet chemical etching, electrochemical method, and plasma immersion ion implantation (PIII) methods. In addition, this review focuses on the progress in multiple black silicon applications in the past 10 years. Finally, the prospect of black silicon fabricating and various applications are outlined.

In this paper, we study the plasma-less etching of crystalline silicon (c-Si) by F2/N2 gas mixture at moderately elevated temperatures. The etching is performed in an inline etching tool, which is specifically developed to lower costs for products needing a high volume manufacturing etching platform such as silicon photovoltaics. Specifically, the current study focuses on developing an effective front-side texturing process on Si(100) wafers. Statistical variation of the tool parameters is performed to achieve high etching rates and low surface reflection of the textured silicon surface. It is observed that the rate and anisotropy of the etching process are strongly defined by the interaction effects between process parameters such as substrate temperature, F2 concentration, and process duration. The etching forms features of sub-micron dimensions on c-Si surface. By maintaining the anisotropic nature of etching, weighted surface reflection (Rw) as low as Rw < 2% in Si(100) is achievable. The lowering of Rw is mainly due to the formation of deep, density grade nanostructures, so-called black silicon, with lateral dimensions that are smaller to the major wavelength ranges of interest in silicon photovoltaics.

Integration of living cells with nonbiological surfaces (substrates) of sensors, scaffolds, and implants implies severe restrictions on the interface quality and properties, which broadly cover all elements of the interaction between the living and artificial systems (materials, surface modifications, drug-eluting coatings, etc.). Substrate materials must support cellular viability, preserve sterility, and at the same time allow real-time analysis and control of cellular activity. We have compared new substrates based on graphene and pyrolytic carbon (PyC) for the cultivation of living cells. These are PyC films of nanometer thickness deposited on SiO2 and black silicon and graphene nanowall films composed of graphene flakes oriented perpendicular to the Si substrate. The structure, morphology, and interface properties of these substrates are analyzed in terms of their biocompatibility. The PyC demonstrates interface biocompatibility, promising for controlling cell proliferation and directional intercellular contact formation while as-grown graphene walls possess high hydrophobicity and poor biocompatibility. By performing experiments with C6 glioma cells we discovered that PyC is a cell-friendly coating that can be used without poly-l-lysine or other biopolymers for controlling cell adhesion. Thus, the opportunity to easily control the physical/chemical properties and nanotopography makes the PyC films a perfect candidate for the development of biosensors and 3D bioscaffolds.

This paper mainly studied the electrical performance improvement of black silicon photovoltaic (PV) cells and modules. The electrical performance of the cells and modules matched with black silicon was optimized through three different experiments. Firstly, in the pre-cleaning step, the effect of lotion selection on the cell performance was studied. Compared with alkaline lotion, using acidic lotion on black silicon wafer can achieve an efficiency improvement of the black silicon cell by nearly 0.154%. Secondly, the influence of oxygen flux control of the thermal oxidation step on the improvement of cell efficiency was studied. The addition of the thermal oxidation step and its oxygen flux control resulted in an efficiency increase of the black silicon cell of nearly 0.11%. The most optimized volume control of the oxygen flux is at 2200 standard cubic centimeter per minute (SCCM). Finally, in the module packaging process, the selection of components will also greatly affect the performance of the black silicon PV module. The most reasonable selection of components can increase the output power of the black silicon PV module by 6.13 W. In a word, the technical indication of the electrical performance improvement suggested in this study plays an important guiding role in the actual production process.

Successful direct route production of silicon nanostructures from diatomaceous earth (DE) on a single crystalline silicon wafer via the magnesiothermic reduction reaction is reported. The formed porous coating of 6 µm overall thickness contains silicon as the majority phase along with minor traces of Mg, as evident from SEM-EDS and the Focused Ion Beam (FIB) analysis. Raman peaks of silicon at 519 cm−1 and 925 cm−1 were found in both the film and wafer substrate, and significant intensity variation was observed, consistent with the SEM observation of the directly formed silicon nanoflake layer. Microstructural analysis of the flakes reveals the presence of pores and cavities partially retained from the precursor diatomite powder. A considerable reduction in surface reflectivity was observed for the silicon nanoflakes, from 45% for silicon wafer to below 15%. The results open possibilities for producing nanostructured silicon with a vast range of functionalities.

Ion-flow-stimulated roughening transition is a phenomenon that may prove useful in the hierarchical structuring of nanostructures. In this work, we have investigated theoretically and experimentally the surface texturing of single-crystal and multi-crystalline silicon wafers irradiated using ion-beam flows. In contrast to previous studies, ions had relatively low energies, whereas flow densities were high enough to induce a quasi-liquid state in the upper silicon layers. The resulting surface modifications reduced the wafer light reflectance to values characteristic of black silicon, widely used in solar energetics. Features of nanostructures on different faces of silicon single crystals were studied numerically based on the mesoscopic Monte Carlo model. We established that the formation of nano-pyramids, ridges, and twisting dune-like structures is due to the stimulated roughening transition effect. The aforementioned variety of modified surface morphologies arises due to the fact that the effects of stimulated surface diffusion of atoms and re-deposition of free atoms on the wafer surface from the near-surface region are manifested to different degrees on different Si faces. It is these two factors that determine the selection of the allowable "trajectories" (evolution paths) of the thermodynamic system along which its Helmholtz free energy, F , decreases, concomitant with an increase in the surface area of the wafer and the corresponding changes in its internal energy, U (dU>0), and entropy, S (dS>0), so that dF=dU - TdS<0, where T is the absolute temperature. The basic theoretical concepts developed were confirmed in experimental studies, the results of which showed that our method could produce, abundantly, black silicon wafers in an environmentally friendly manner compared to traditional chemical etching.

We present two simple methods, with parallel and serial gas flows, for the stacking of microfabricated silicon fuel cells with integrated current collectors, flow fields and gas diffusion layers. The gas diffusion layer is implemented using black silicon. In the two stacking methods proposed in this work, the fluidic apertures and gas flow topology are rotationally symmetric and enable us to stack fuel cells without an increase in the number of electrical or fluidic ports or interconnects. Thanks to this simplicity and the structural compactness of each cell, the obtained stacks are very thin (~1.6 mm for a two-cell stack). We have fabricated two-cell stacks with two different gas flow topologies and obtained an open-circuit voltage (OCV) of 1.6 V and a power density of 63 mW·cm−2, proving the viability of the design.

In this study, needle-like and pyramidal hybrid black silicon structures were prepared by performing metal-assisted chemical etching (MACE) on alkaline-etched silicon wafers. Effects of the MACE time on properties of the black silicon wafers were investigated. The experimental results showed that a minimal reflectance of 4.6% can be achieved at the MACE time of 9 min. The height of the nanostructures is below 500 nm, unlike the height of micrometers needed to reach the same level of reflectance for the black silicon on planar wafers. A stacked layer of silicon nitride (SiNx) grown by inductively-coupled plasma chemical vapor deposition (ICPCVD) and aluminum oxide (Al2O3) by spatial atomic layer deposition was deposited on the black silicon wafers for passivation and antireflection. The 3 min MACE etched black silicon wafer with a nanostructure height of less than 300 nm passivated by the SiNx/Al2O3 layer showed a low surface recombination rate of 43.6 cm/s. Further optimizing the thickness of ICPCVD-SiNx layer led to a reflectance of 1.4%. The hybrid black silicon with a small nanostructure size, low reflectance, and low surface recombination rate demonstrates great potential for applications in optoelectronic devices.

Pattern formation of pyrolyzed carbon (PyC) and tetrahedral amorphous carbon (ta-C) thin films were investigated at micro- and nanoscale. Micro- and nanopillars were fabricated from both materials, and their biocompatibility was studied with cell viability tests. Carbon materials are known to be very challenging to pattern. Here we demonstrate two approaches to create biocompatible carbon features. The microtopographies were 2 μ m or 20 μ m pillars (1:1 aspect ratio) with three different pillar layouts (square-grid, hexa-grid, or random-grid orientation). The nanoscale topography consisted of random nanopillars fabricated by maskless anisotropic etching. The PyC structures were fabricated with photolithography and embossing techniques in SU-8 photopolymer which was pyrolyzed in an inert atmosphere. The ta-C is a thin film coating, and the structures for it were fabricated on silicon substrates. Despite different fabrication methods, both materials were formed into comparable micro- and nanostructures. Mouse neural stem cells were cultured on the samples (without any coatings) and their viability was evaluated with colorimetric viability assay. All samples expressed good biocompatibility, but the topography has only a minor effect on viability. Two μ m pillars in ta-C shows increased cell count and aggregation compared to planar ta-C reference sample. The presented materials and fabrication techniques are well suited for applications that require carbon chemistry and benefit from large surface area and topography, such as electrophysiological and -chemical sensors for in vivo and in vitro measurements.

Computer-generated holograms have wide applications in different fields of optics, ranging from imaging, data storage, to security.Herein, we report a new method for the fabrication of large-scale computer-generated holograms from an inexpensive material, such as Silicon. Our approach exploits dry etching to create a series of broadband nanoantennas, which can tune the reflectivity of Si from an average of 0.35 to 0.1 in the entire visible range. We demonstrated the realisation of different images at wavelengths of 450 nm, 532 nm, and 632 nm with an efficiency of 10%, 14%, and 12%, respectively, thus opening up the application of large-scale broadband computer-generated holographic surfaces.

For more than 15 years FerroAtlantica (now Ferroglobe) has been developing a method of silicon purification to obtain Upgraded Metallurgical Grade Silicon (UMG-Si) for PV solar application without blending. After many improvements and optimizations, the final process has clearly demonstrated its validity in terms of quality and costs. In this paper the authors present new results stemming from a first mass-production campaign and a detailed description of the purification process that results in the tested UMG-Si. The subsequent steps in the value chain for the wafer, cell and module manufacturing are also described. Two independent companies, among the Tier-1 solar cells producers, were selected for the industrial test, each using a different solar cell technology: Al-BSF and black silicon + PERC. Cells and modules were manufactured in conventional production lines and their performances compared to those obtained with standard polysilicon wafers produced in the same lines and periods. Thus, for Al-BSF technology, the average efficiency of solar cells obtained with UMG-Si was (18.4 ± 0.4)% compared to 18.49% obtained with polysilicon-made wafers. In the case of black silicon + PERC, the average efficiency obtained with UMG-Si was (20.1 ± 0.6)%, compared to 20.41% for polysilicon multicrystalline wafers.

Industrial Czochralski silicon (Cz-Si) photovoltaic (PV) efficiencies have routinely reached >20% with the passivated emitter rear cell (PERC) design. Nanostructuring silicon (black-Si) by dry-etching decreases surface reflectance, allows diamond saw wafering, enhances metal gettering, and may prevent power conversion efficiency degradation under light exposure. Black-Si allows a potential for >20% PERC cells using cheaper multicrystalline silicon (mc-Si) materials, although dry-etching is widely considered too expensive for industrial application. This study analyzes this economic potential by comparing costs of standard texturized Cz-Si and black mc-Si PERC cells. Manufacturing sequences are divided into steps, and costs per unit power are individually calculated for all different steps. Baseline costs for each step are calculated and a sensitivity analysis run for a theoretical 1 GW/year manufacturing plant, combining data from literature and industry. The results show an increase in the overall cell processing costs between 15.8% and 25.1% due to the combination of black-Si etching and passivation by double-sided atomic layer deposition. Despite this increase, the cost per unit power of the overall PERC cell drops by 10.8%. This is a significant cost saving and thus energy policies are reviewed to overcome challenges to accelerating deployment of black mc-Si PERC across the PV industry.

Owing to its extremely low light absorption, black silicon has been widely investigated and reported in recent years, and simultaneously applied to various disciplines. Black silicon is, in general, fabricated on flat surfaces based on the silicon substrate. However, with three normal fabrication methods—plasma dry etching, metal-assisted wet etching, and femtosecond laser pulse etching—black silicon cannot perform easily due to its lowest absorption and thus some studies remained in the laboratory stage. This paper puts forward a novel secondary nanostructured black silicon, which uses the dry-wet hybrid fabrication method to achieve secondary nanostructures. In consideration of the influence of the structure’s size, this paper fabricated different sizes of secondary nanostructured black silicon and compared their absorptions with each other. A total of 0.5% reflectance and 98% absorption efficiency of the pit sample were achieved with a diameter of 117.1 μm and a depth of 72.6 μm. In addition, the variation tendency of the absorption efficiency is not solely monotone increasing or monotone decreasing, but firstly increasing and then decreasing. By using a statistical image processing method, nanostructures with diameters between 20 and 30 nm are the majority and nanostructures with a diameter between 10 and 40 nm account for 81% of the diameters.

Sputtered reactive multilayers applied as a heat source in electronic joining processes are an emerging technology. Their use promises low-stress assembly of components while improving thermal contact and reducing thermal resistance. Nanostructured surface modifications can significantly enhance adhesion and reliability of joints between different materials. This work examines reactive multilayer of nickel and aluminum, directly sputtered on nanostructured black silicon surfaces and compares their phase transformation with reference samples deposited on pristine silicon surface. The investigation of the quenched self-propagating reaction reveals a clear influence of the nanostructured surface on the prolongation of the phase transition. Rapid thermal annealing tests result in the formation of Al1.1Ni0.9 phase. The nanostructured interface seems to hinder the full transformation of the parent material. The surface modification improves the adhesion of the formed alloy on silicon surfaces and can possibly increase the reliability of joints based on reactive aluminum/nickel multilayer. The use of black silicon, a nanostructured surface modification, is thus a promising approach to realize reliable multi-material joints in complex systems.

Structural anti-reflective coating and bactericidal surfaces, as well as many other effects, rely on high-aspect-ratio (HAR) micro- and nanostructures, and thus, are of great interest for a wide range of applications. To date, there is no widespread fabrication of dense or isolated HAR nanopillars based on UV nanoimprint lithography (UV-NIL). In addition, little research on fabricating isolated HAR nanopillars via UV-NIL exists. In this work, we investigated the mastering and replication of HAR nanopillars with the smallest possible diameters for dense and isolated arrangements. For this purpose, a UV-based nanoimprint lithography process was developed. Stability investigations with capillary forces were performed and compared with simulations. Finally, strategies were developed in order to increase the stability of imprinted nanopillars or to convert them into nanoelectrodes. We present UV-NIL replication of pillars with aspect ratios reaching up to 15 with tip diameters down to 35 nm for the first time. We show that the stability could be increased by a factor of 58 when coating them with a 20 nm gold layer and by a factor of 164 when adding an additional 20 nm thick layer of SiN. The coating of the imprints significantly improved the stability of the nanopillars, thus making them interesting for a wide range of applications.

Silicon microneedle (Si-MN) systems are a promising strategy for transdermal drug delivery due to their minimal invasiveness and ease of processing and application. Traditional Si-MN arrays are usually fabricated by using micro-electro-mechanical system (MEMS) processes, which are expensive and not suitable for large-scale manufacturing and applications. In addition, Si-MNs have a smooth surface, making it difficult for them to achieve high-dose drug delivery. Herein, we demonstrate a solid strategy to prepare a novel black silicon microneedle (BSi-MN) patch with ultra-hydrophilic surfaces for high drug loading. The proposed strategy consists of a simple fabrication of plain Si-MNs and a subsequent fabrication of black silicon nanowires. First, plain Si-MNs were prepared via a simple method consisting of laser patterning and alkaline etching. The nanowire structures were then prepared on the surfaces of the plain Si-MNs to form the BSi-MNs through Ag-catalyzed chemical etching. The effects of preparation parameters, including Ag + and HF concentrations during Ag nanoparticle deposition and [HF/(HF + H 2 O 2 )] ratio during Ag-catalyzed chemical etching, on the morphology and properties of the BSi-MNs were investigated in detail. The results show that the final prepared BSi-MN patches exhibit an excellent drug loading capability, more than twice that of plain Si-MN patches with the same area, while maintaining comparable mechanical properties for practical skin piercing applications. Moreover, the BSi-MNs exhibit a certain antimicrobial activity that is expected to prevent bacterial growth and disinfect the affected area when applied to the skin.

Since black silicon was discovered by coincidence, the special material was explored for many amazing material characteristics in optical, surface topography, and so on. Because of the material property, black silicon is applied in many spheres of a photodetector, photovoltaic cell, photo-electrocatalysis, antibacterial surfaces, and sensors. With the development of fabrication technology, black silicon has expanded in more and more applications and has become a research hotspot. Herein, this review systematically summarizes the fabricating method of black silicon, including nanosecond or femtosecond laser irradiation, metal-assisted chemical etching (MACE), reactive ion etching (RIE), wet chemical etching, electrochemical method, and plasma immersion ion implantation (PIII) methods. In addition, this review focuses on the progress in multiple black silicon applications in the past 10 years. Finally, the prospect of black silicon fabricating and various applications are outlined.

In this paper, we study the plasma-less etching of crystalline silicon (c-Si) by F 2 /N 2 gas mixture at moderately elevated temperatures. The etching is performed in an inline etching tool, which is specifically developed to lower costs for products needing a high volume manufacturing etching platform such as silicon photovoltaics. Specifically, the current study focuses on developing an effective front-side texturing process on Si(100) wafers. Statistical variation of the tool parameters is performed to achieve high etching rates and low surface reflection of the textured silicon surface. It is observed that the rate and anisotropy of the etching process are strongly defined by the interaction effects between process parameters such as substrate temperature, F 2 concentration, and process duration. The etching forms features of sub-micron dimensions on c-Si surface. By maintaining the anisotropic nature of etching, weighted surface reflection ( R w ) as low as R is mainly due to the formation of deep, density grade nanostructures, so-called black silicon, with lateral dimensions that are smaller to the major wavelength ranges of interest in silicon photovoltaics.w < 2% in Si(100) is achievable. The lowering of R w is mainly due to the formation of deep, density grade nanostructures, so-called black silicon, with lateral dimensions that are smaller to the major wavelength ranges of interest in silicon photovoltaics.

Successful direct route production of silicon nanostructures from diatomaceous earth (DE) on a single crystalline silicon wafer via the magnesiothermic reduction reaction is reported. The formed porous coating of 6 µm overall thickness contains silicon as the majority phase along with minor traces of Mg, as evident from SEM-EDS and the Focused Ion Beam (FIB) analysis. Raman peaks of silicon at 519 cm - 1 and 925 cm - 1 were found in both the film and wafer substrate, and significant intensity variation was observed, consistent with the SEM observation of the directly formed silicon nanoflake layer. Microstructural analysis of the flakes reveals the presence of pores and cavities partially retained from the precursor diatomite powder. A considerable reduction in surface reflectivity was observed for the silicon nanoflakes, from 45% for silicon wafer to below 15%. The results open possibilities for producing nanostructured silicon with a vast range of functionalities., Competing Interests: The authors declare no conflict of interest.

In this study, needle-like and pyramidal hybrid black silicon structures were prepared by performing metal-assisted chemical etching (MACE) on alkaline-etched silicon wafers. Effects of the MACE time on properties of the black silicon wafers were investigated. The experimental results showed that a minimal reflectance of 4.6% can be achieved at the MACE time of 9 min. The height of the nanostructures is below 500 nm, unlike the height of micrometers needed to reach the same level of reflectance for the black silicon on planar wafers. A stacked layer of silicon nitride (SiN x ) grown by inductively-coupled plasma chemical vapor deposition (ICPCVD) and aluminum oxide (Al 2 O 3 ) by spatial atomic layer deposition was deposited on the black silicon wafers for passivation and antireflection. The 3 min MACE etched black silicon wafer with a nanostructure height of less than 300 nm passivated by the SiN x /Al 2 O 3 layer showed a low surface recombination rate of 43.6 cm/s. Further optimizing the thickness of ICPCVD-SiN x layer led to a reflectance of 1.4%. The hybrid black silicon with a small nanostructure size, low reflectance, and low surface recombination rate demonstrates great potential for applications in optoelectronic devices.