Facile and Clean Release of Vertical Si Nanowires by Wet Chemical Etching Based on Alkali Hydroxides

A simple method to release Si nanowires (SiNWs) from a substrate, with their original length almost intact, is demonstrated. By exploiting the unique chemistry involved for the fabrication of vertical arrays of SiNWs in metal‐assisted chemical etching (MaCE) based either on HF/AgNO₃ or HF/H₂O₂ chemistries, wet etching with alkali hydroxides such as NaOH or KOH preferentially attacks the bottom part of the vertical SiNWs. A protective layer of Si oxide is found to exist on the outer wall of the SiNWs and to play the key role of etch mask during the release‐etching by alkali hydroxides. The clean release of SiNWs also enables the repeated use of the Si substrate for the fabrication of vertical SiNW arrays by MaCE. The released SiNWs are further used for the fabrication of field‐effect transistors on a flexible plastic substrate. The method developed here, when combined with a suitable assembling technique, can be very useful in implementing flexible electronics, or in the fabrication of SiNW composites with other functional materials.     

Platinum nanoparticle decorated silicon nanowire arrays for photoelectrochemical hydrogen production

Wafer-scale high density aligned p-type silicon nanowire (SiNW) arrays decorated with discrete platinum nanoparticles (PtNPs) have been fabricated by metal assisted electroless etching followed by an electroless platinum deposition process, and systematic investigations of photoelectrochemical behavior of Pt/SiNW were also reported in this study. Coating of PtNPs on SiNW sidewalls yielded a more positive onset potential (Vos), which enhances the photoelectrochemical hydrogen generation performance of the photoelectrodes, though excessive PtNPs deposition leads to a decreased photocurrent. Additionally, we have demonstrated that the photoelectrode consisting of longer SiNWs yielded a higher limiting current. However, when the length of SiNWs was increased further to >4 μm, the limiting current dramatically reduced, which is presumably because an increased interface recombination and scattering resulting from the increased surface area of SiNWs begin to play a dominant role. The results demonstrate Pt/SiNW to be a promising hybrid system for photoelectrochemical water splitting, and device performance may be further improved via optimal conditions of PtNPs deposition time and SiNWs length.     

Structures and field emission characteristics of ion irradiated silicon nanowire arrays

Silicon nanowire (SiNW) arrays irradiated by energetic Si ions were fabricated by metal vapor vacuum arc (MEVVA) ion implantation method. Hetero-structure of amorphous/crystalline nanowire was formed in which structure of the implanted region on the top of the nanowires was amorphous while the structure of unimplanted region on the bottom remained crystal. Field emission (FE) properties of the SiNW arrays could be improved and modulated by different implantation doses. A low turn-on field of 4.63 V/microm was observed in the SiNWs irradiated by 21 keV Si ion with a dose of 7.86 x 10(16)/cm2, and the applied field for the emission current density reaching 100 microA/cm2 is only 5.52 V/microm. The main reason for the efficient emission is attributed to the formation of amorphous SiNWs and structure defects after implantation. The ion irradiated SiNWs after post-annealing at high temperature had better FE property due to eliminating the restrain effect to electrons.     

Fabrication of large area high density, ultra-low reflection silicon nanowire arrays for efficient solar cell applications

High density vertically aligned and high aspect ratio silicon nanowire (SiNW) arrays have been fabricated on a Si substrate using a template and a catalytic etching process. The template was formed from polystyrene (PS) nanospheres with diameter 30–50 nm and density 10¹⁰/cm², produced by nanophase separation of PS-containing block-copolymers. The length of the SiNWs was controlled by varying the etching time with an etching rate of 12.5 nm/s. The SiNWs have a biomimetic structure with a high aspect ratio (∼100), high density, and exhibit ultra-low reflectance. An ultra-low reflectance of approximately 0.1% was achieved for SiNWs longer than 750 nm. Well-aligned SiNW/poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) heterojunction solar cells were fabricated. The n-type silicon nanowire surfaces adhered to PEDOT:PSS to form a core-sheath heterojunction structure through a simple and efficient solution process. The large surface area of the SiNWs ensured efficient collection of photogenerated carriers. Compared to planar cells without the nanowire structure, the SiNW/PEDOT:PSS heterojunction solar cell exhibited an increase in short-circuit current density from 2.35 mA/cm² to 21.1 mA/cm² and improvement in power conversion efficiency from 0.4% to 5.7%.      

Integrate silver colloids with silicon nanowire arrays for surface-enhanced Raman scattering

A facile method to prepare uniform and reproducible surface-enhanced Raman scattering (SERS) substrates is presented. Quasi-spherical silver colloids prepared by microwave heating and wafer-scale uniform silicon nanowire (SiNW) arrays fabricated via wet chemical etching were united together as SERS substrates. The novel SERS substrates displayed stronger Raman enhancement than conventional silver colloids as well as outstanding uniformity and reproducibility in our experiments. In addition, it was found that the cross section of SiNW arrays possessed stronger enhancement activity than the front side. The enhancement effects of two adjacent SiNWs (as a simplification of SiNW arrays) were evaluated by the finite difference time domain (FDTD) method.     

Porous Silicon Nanoneedles Modulate Endocytosis to Deliver Biological Payloads

Owing to their ability to efficiently deliver biological cargo and sense the intracellular milieu, vertical arrays of high aspect ratio nanostructures, known as nanoneedles, are being developed as minimally invasive tools for cell manipulation. However, little is known of the mechanisms of cargo transfer across the cell membrane‐nanoneedle interface. In particular, the contributions of membrane piercing, modulation of membrane permeability and endocytosis to cargo transfer remain largely unexplored. Here, combining state‐of‐the‐art electron and scanning ion conductance microscopy with molecular biology techniques, it is shown that porous silicon nanoneedle arrays concurrently stimulate independent endocytic pathways which contribute to enhanced biomolecule delivery into human mesenchymal stem cells. Electron microscopy of the cell membrane at nanoneedle sites shows an intact lipid bilayer, accompanied by an accumulation of clathrin‐coated pits and caveolae. Nanoneedles enhance the internalization of biomolecular markers of endocytosis, highlighting the concurrent activation of caveolae‐ and clathrin‐mediated endocytosis, alongside macropinocytosis. These events contribute to the nanoneedle‐mediated delivery (nanoinjection) of nucleic acids into human stem cells, which distribute across the cytosol and the endolysosomal system. This data extends the understanding of how nanoneedles modulate biological processes to mediate interaction with the intracellular space, providing indications for the rational design of improved cell‐manipulation technologies.     

Observation of room-temperature negative differential resistance in Gd-doped Si nanowires on Si(110) surface

The massively parallel arrays of highly periodic Gd-doped Si nanowires (SiNWs) self-organized on Si(110)-16?×?2 surface were investigated by scanning tunneling microscopy and spectroscopy. These periodic Gd-doped SiNWs are atomically precise and show equal size, periodic positions, and high-integration densities. Surprisingly, the scanning tunneling spectroscopy results show that each metallic-like, Gd-doped SiNW exhibits room-temperature negative differential resistance (RT-NDR) behavior, which can be reproducible with various Gd dopings and is independent of the tips. Such massively parallel arrays of highly ordered and atomically identical Gd-doped SiNWs with one-dimensional laterally confined RT-NDR can be exploited in Si-based RT-NDR nanodevices.     

Lipoplex‐Mediated Single‐Cell Transfection via Droplet Microfluidics

While lipoplex (cationic lipid‐nucleic acid complex)‐mediated intracellular delivery is widely adopted in mammalian cell transfection, its transfection efficiency for suspension cells, e.g., lymphatic and hematopoietic cells, is reported at only ≈5% or even lower. Here, efficient and consistent lipoplex‐mediated transfection is demonstrated for hard‐to‐transfect suspension cells via a single‐cell, droplet‐microfluidics approach. In these microdroplets, monodisperse lipoplexes for effective gene delivery are generated via chaotic mixing induced by the serpentine microchannel and co‐confined with single cells. Moreover, the cell membrane permeability increases due to the shear stress exerted on the single cells when they pass through the droplet pinch‐off junction. The transfection efficiency, examined by the delivery of the pcDNA3‐EGFP plasmid, improves from ≈5% to ≈50% for all three tested suspension cell lines, i.e., K562, THP‐1, Jurkat, and with significantly reduced cell‐to‐cell variation, compared to the bulk method. Efficient targeted knockout of the TP53BP1 gene for K562 cells via the CRISPR (clustered regularly interspaced short palindromic repeats)–CAS9 (CRISPR‐associated nuclease 9) mechanism is also achieved using this platform. Lipoplex‐mediated single‐cell transfection via droplet microfluidics is expected to have broad applications in gene therapy and regenerative medicine by providing high transfection efficiency and low cell‐to‐cell variation for hard‐to‐transfect suspension cells.     

Nanowire arrays in multicrystalline silicon thin films on glass: a promising material for research and applications in nanotechnology

Silicon nanowires (SiNW) were formed on large grained, electron-beam crystallized silicon (Si) thin films of only ～6 μm thickness on glass using nanosphere lithography (NSL) in combination with reactive ion etching (RIE). Electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM) studies revealed outstanding structural properties of this nanomaterial. It could be shown that SiNWs with entirely predetermined shapes including lengths, diameters and spacings and straight side walls form independently of their crystalline orientation and arrange in ordered arrays on glass. Furthermore, for the first time grain boundaries could be observed in individual, straightly etched SiNWs. After heat treatment an electronic grade surface quality of the SiNWs could be shown by X-ray photoelectron spectroscopy (XPS). Integrating sphere measurements show that SiNW patterning of the multicrystalline Si (mc-Si) starting thin film on glass substantially increases absorption and reduces reflection, as being desired for an application in thin film photovoltaics (PV). The multicrystalline SiNWs directly mark a starting point for research not only in PV but also in other areas like nanoelectronics, surface functionalization, and nanomechanics.     

Extended arrays of vertically aligned sub-10 nm diameter [100] Si nanowires by metal-assisted chemical etching

Large-area high density silicon nanowire (SiNW) arrays were fabricated by metal-assisted chemical etching of silicon, utilizing anodic aluminum oxide (AAO) as a patterning mask of a thin metallic film on a Si (100) substrate. Both the diameter of the pores in the AAO mask and the thickness of the metal film affected the diameter of SiNWs. The diameter of the SiNWs decreased with an increase of thickness of the metal film. Large-area SiNWs with average diameters of 20 nm down to 8 nm and wire densities as high as 10 (10) wires/cm (2) were accomplished. These SiNWs were single crystalline and vertically aligned to the (100) substrate. It was revealed by transmission electron microscopy that the SiNWs were of high crystalline quality and showed a smooth surface.     

Radial junction amorphous silicon solar cells on PECVD-grown silicon nanowires

Constructing radial junction hydrogenated amorphous silicon (a-Si:H) solar cells on top of silicon nanowires (SiNWs) represents a promising approach towards high performance and cost-effective thin film photovoltaics. We here develop an all-in?situ strategy to grow SiNWs, via a vapour-liquid-solid (VLS) mechanism on top of ZnO-coated glass substrate, in a plasma-enhanced chemical vapour deposition (PECVD) reactor. Controlling the distribution of indium catalyst drops allows us to tailor the as-grown SiNW arrays into suitable size and density, which in turn results in both a sufficient light trapping effect and a suitable arrangement allowing for conformal coverage of SiNWs by subsequent a-Si:H layers. We then demonstrate the fabrication of radial junction solar cells and carry on a parametric study designed to shed light on the absorption and quantum efficiency response, as functions of the intrinsic a-Si:H layer thickness and the density of SiNWs. These results lay a solid foundation for future structural optimization and performance ramp-up of the radial junction thin film a-Si:H photovoltaics.     

High-efficiency si/polymer hybrid solar cells based on synergistic surface texturing of Si nanowires on pyramids

An efficient Si/PEDOT:PSS hybrid solar cell using synergistic surface texturing of Si nanowires (SiNWs) on pyramids is demonstrated. A power conversion efficiency (PCE) of 9.9% is achieved from the cells using the SiNW/pyramid binary structure, which is much higher than similar cells based on planar Si, pyramid-textured Si, and SiNWs. The PCE is the highest reported to-date for hybrid cells based on Si nanostructures and PEDOT.     

Vertical transfer of uniform silicon nanowire arrays via crack formation

Vertical transfer of silicon nanowire (SiNW) arrays with uniform length onto adhesive substrates was realized by the assistance of creating a horizontal crack throughout SiNWs. The crack is formed by adding a water soaking step between consecutive Ag-assisted electroless etching processes of Si. The crack formation is related to the delamination, redistribution, and reattachment of the Ag film during the water soaking and subsequent wet etching steps. Moreover, the crack facilitates embedding SiNWs inside polymers.     

Synthetically encoded ultrashort-channel nanowire transistors for fast, pointlike cellular signal detection

Nanostructures, which have sizes comparable to biological functional units involved in cellular communication, offer the potential for enhanced sensitivity and spatial resolution compared to planar metal and semiconductor structures. Silicon nanowire (SiNW) field-effect transistors (FETs) have been used as a platform for biomolecular sensors, which maintain excellent signal-to-noise ratios while operating on lengths scales that enable efficient extra- and intracellular integration with living cells. Although the NWs are tens of nanometers in diameter, the active region of the NW FET devices typically spans micrometers, limiting both the length and time scales of detection achievable with these nanodevices. Here, we report a new synthetic method that combines gold-nanocluster-catalyzed vapor-liquid-solid (VLS) and vapor-solid-solid (VSS) NW growth modes to produce synthetically encoded NW devices with ultrasharp (<5 nm) n-type highly doped (n(++)) to lightly doped (n) transitions along the NW growth direction, where n(++) regions serve as source/drain (S/D) electrodes and the n-region functions as an active FET channel. Using this method, we synthesized short-channel n(++)/n/n(++) SiNW FET devices with independently controllable diameters and channel lengths. SiNW devices with channel lengths of 50, 80, and 150 nm interfaced with spontaneously beating cardiomyocytes exhibited well-defined extracellular field potential signals with signal-to-noise values of ca. 4 independent of device size. Significantly, these "pointlike" devices yield peak widths of ～500 μs, which is comparable to the reported time constant for individual sodium ion channels. Multiple FET devices with device separations smaller than 2 μm were also encoded on single SiNWs, thus enabling multiplexed recording from single cells and cell networks with device-to-device time resolution on the order of a few microseconds. These short-channel SiNW FET devices provide a new opportunity to create nanoscale biomolecular sensors that operate on the length and time scales previously inaccessible by other techniques but necessary to investigate fundamental, subcellular biological processes.     

Cellular binding and internalization of functionalized silicon nanowires

Nanostructures with precise control of sizes and shapes, intrinsic read-out signals for tracking, and flexible surface chemistry for bioconjugation can offer an excellent system to study interaction between nanomaterials and cells. In this paper, a new nanobio system based on functionalized silicon nanowires (SiNWs) was developed. Using the intensive and intrinsic nonlinear optical signal of SiNWs, we visualized the interaction between the folate and amine group functionalized SiNWs and cells by monitoring the cellular binding and uptake of SiNWs in real time. We demonstrated that the strong specific ligand-receptor interaction between folate on NWs and folate receptors on CHO-β cell membranes expedited agglomeration of folate modified SiNWs on cells and internalization of NWs. Such specific targeting was further confirmed through control experiments done with normal CHO cell without folate receptors. Weaker nonspecific charge-charge attraction led to longer time required for amino group modified SiNWs to be bound on cell membrane. No effective accumulation was noticed for unmodified SiNW with native oxidized surface layer. In addition, we also observed the binding was independent of length for NWs ranging between 2.5 and 8.0 μm. Uptake of NWs highly depended on length and NWs longer than 5 μm were difficult to be internalized. Our results provided an insight of cellular interaction with 1-dimensional nanomaterials.     

Interfacing Inorganic Nanowire Arrays and Living Cells for Cellular Function Analysis

Inorganic nanowires are among the most attractive functional materials, which have emerged in the past two decades. They have demonstrated applications in information technology and energy conversion, but their utility in biological or biomedical research remains relatively under‐explored. Although nanowire‐based sensors have been frequently reported for biomolecular detection, interfacing nanowire arrays and living mammalian cells for the direct analysis of cellular functions is a very recent endeavor. Cell‐penetrating nanowires enabled effective delivery of biomolecules, electrical and optical stimulation and recording of intracellular signals over a long period of time. Non‐penetrating, high‐density nanowire arrays display rich interactions between the nanostructured substrate and the micro/nanoscale features of cell surfaces. Such interactions enable efficient capture of rare cells including circulating tumor cells and trafficking leukocytes from complex biospecimens. It also serves as a platform for probing cell traction force and neuronal guidance. The most recent advances in the field that exploits nanowire arrays (both penetrating and non‐penetrating) to perform rapid analysis of cellular functions potentially for disease diagnosis and monitoring are reviewed.     

The synthesis and photoluminescence properties of selenium-treated porous silicon nanowire arrays

Here we prepared vertical and single crystalline porous silicon nanowire (SiNW) arrays using the silver-assisted electroless etching method. The selenization was carried out by annealing the samples in vacuum with selenium atmosphere. The selenization treatment at 700?°C is useful for investigating the photoluminescence (PL) properties of porous SiNWs, with an enhancement of 30 times observed. The observed PL peaks blue-shift to 650 nm and the decomposition of the spectrum reveals that three PL bands with different origins are obtained. It is proved that selenization treatment could remove the Si-H bonds on the surface and form Si-Se bonds, which could increase the absorbance of the SiNWs and also enhance the stability of the PL intensity. These Se-treated porous SiNWs may be useful as nanoscale optoelectronic devices.     

Impurity Doping in Silicon Nanowires

Silicon nanowires (SiNWs) have considerable potential to assist the realization of next‐generation metal‐oxide semiconductor field‐effect transistors (MOSFETs) with vertical structures. Impurity doping and its control is a key technique in the creation of SiNW devices, which renders it necessary to develop characterization methods for dopant atoms in SiNWs. In this Research News, we described how the states of the dopant atoms boron and phosphorus can be detected.     

Functionalization of silicon nanowire surfaces with metal-organic frameworks

Metal-organic frameworks (MOFs) and silicon nanowires (SiNWs) have been extensively studied due to their unique properties; MOFs have high porosity and specific surface area with well-defined nanoporous structure, while SiNWs have valuable one-dimensional electronic properties. Integration of the two materials into one composite could synergistically combine the advantages of both materials and lead to new applications. We report the first example of a MOF synthesized on surface-modified SiNWs. The synthesis of polycrystalline MOF-199 (also known as HKUST-1) on SiNWs was performed at room temperature using a step-by-step (SBS) approach, and X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy dispersive spectroscopy elemental mapping were used to characterize the material. Matching of the SiNW surface functional groups with the MOF organic linker coordinating groups was found to be critical for the growth. Additionally, the MOF morphology can by tuned by changing the soaking time, synthesis temperature and precursor solution concentration. This SiNW/MOF hybrid structure opens new avenues for rational design of materials with novel functionalities.      

Silicon-Nanotube-Mediated Intracellular Delivery Enables Ex Vivo Gene Editing

Engineered nano–bio cellular interfaces driven by vertical nanostructured materials are set to spur transformative progress in modulating cellular processes and interrogations. In particular, the intracellular delivery—a core concept in fundamental and translational biomedical research—holds great promise for developing novel cell therapies based on gene modification. This study demonstrates the development of a mechanotransfection platform comprising vertically aligned silicon nanotube (VA-SiNT) arrays for ex vivo gene editing. The internal hollow structure of SiNTs allows effective loading of various biomolecule cargoes; and SiNTs mediate delivery of those cargoes into GPE86 mouse embryonic fibroblasts without compromising their viability. Focused ion beam scanning electron microscopy (FIB-SEM) and confocal microscopy results demonstrate localized membrane invaginations and accumulation of caveolin-1 at the cell–NT interface, suggesting the presence of endocytic pits. Small-molecule inhibition of endocytosis suggests that active endocytic process plays a role in the intracellular delivery of cargo from SiNTs. SiNT-mediated siRNA intracellular delivery shows the capacity to reduce expression levels of F-actin binding protein (Triobp) and alter the cellular morphology of GPE86. Finally, the successful delivery of Cas9 ribonucleoprotein (RNP) to specifically target mouse Hprt gene is achieved. This NT-enhanced molecular delivery platform has strong potential to support gene editing technologies.