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.

Array density effect on the optical and photoelectric properties of silicon nanowire arrays via Ag-assisted chemical etching.

Ag-assisted chemical etching (AgACE) is a low-cost method to produce silicon nanowires (SiNWs) for photoelectric applications. Structure parameters of SiNWs have great impact on their optical and photoelectric properties, which are worth studying for fabricating high-performance devices. However, array density of SiNWs via AgACE, as an important structural parameter, has not been sufficiently investigated. Here, array density effect on the optical and photoelectric properties of SiNWs is experimentally investigated. SiNW arrays with different densities (silicon occupation ratio of 7%-34.5%) were prepared through controlling the reaction time of silicon wafers in the seed solution (tseed). The SiNW array with atseedof 90 s shows optimum light absorption over 98% in the wavelength range of 300-1000 nm, though all the samples have light absorption over 95% due to the light trapping effect of nanowire array structure. In addition, the SiNW array with atseedof 90 s exhibits the best photoelectric property. SiNW arrays with shortertseedand higher density suffer more surface recombination, harming the photoelectric property. In SiNW arrays with longertseedthan 90 s and lower density, some SiNWs topple down and break, which has an adverse effect on transport and collection of carriers. These results indicate that the array density of SiNWs via AgACE has obvious effect on their photoelectric property. SiNW arrays via AgACE with atseedof 90 s are ideal for photoelectric devices. This work is potential to guide SiNW fabrication for photoelectric applications.

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.

Constant Electricity Generation in Nanostructured Silicon by Evaporation-Driven Water Flow.

Recently, hydrovoltaic technology emerged as a novel renewable energy harvesting method, which dramatically extends the capability to harvest water energy. However, the urgent issue restricting its device performance is poor carrier transport properties of the solid surface if large charged interface is considered simultaneously. Herein, a hydrovoltaic device based on silicon nanowire arrays (SiNWs), which provide large charged surface/volume ratio and excellent carrier transport properties, yields sustained electricity by a carrier concentration gradient induced by evaporation-induced water flow inside nanochannels. The device can yield direct current with a short-circuit current density of over 55 µA cm-2 , which is three orders larger than a previously reported analogous device (approximately 40 nA cm-2 ). Moreover, it exhibits a constant output power density of over 6 µW cm-2 and an open-circuit voltage of up to 400 mV. Our finding may pave a way for developing energy-harvesting devices from ubiquitous evaporation-driven internal water flow in nature with semiconductor material of silicon.

Electrochemical Deposition of Conformal and Functional Layers on High Aspect Ratio Silicon Micro/Nanowires.

Development of new synthetic methods for the modification of nanostructures has accelerated materials design advances to furnish complex architectures. Structures based on one-dimensional (1D) silicon (Si) structures synthesized using top-down and bottom-up methods are especially prominent for diverse applications in chemistry, physics, and medicine. Yet further elaboration of these structures with distinct metal-based and polymeric materials, which could open up new opportunities, has been difficult. We present a general electrochemical method for the deposition of conformal layers of various materials onto high aspect ratio Si micro- and nanowire arrays. The electrochemical deposition of a library of coaxial layers comprising metals, metal oxides, and organic/inorganic semiconductors demonstrate the materials generality of the synthesis technique. Depositions may be performed on wire arrays with varying diameter (70 nm to 4 µm), pitch (5 µ to 15 µ), aspect ratio (4:1 to 75:1), shape (cylindrical, conical, hourglass), resistivity (0.001-0.01 to 1-10 ohm/cm2), and substrate orientation. Anisotropic physical etching of wires with one or more coaxial shells yields 1D structures with exposed tips that can be further site-specifically modified by an electrochemical deposition approach. The electrochemical deposition methodology described herein features a wafer-scale synthesis platform for the preparation of multifunctional nanoscale devices based on a 1D Si substrate.

S-Scheme Porphyrin Covalent Organic Framework Heterojunction for Boosted Photoelectrochemical Immunoassays in Myocardial Infarction Diagnosis.

Cardiac troponin I (cTnI) is an extremely sensitive biomarker for early indication of acute myocardial infarction (AMI). However, it still remains a tough challenge for many newly developed cTnI biosensors to achieve superior sensing performance including high sensitivity, rapid detection, and resistance to interference in clinical serum samples. Herein, a novel photocathodic immunosensor toward cTnI sensing has been successfully developed by designing a unique S-scheme heterojunction based on the porphyrin-based covalent organic frameworks (p-COFs) and p-type silicon nanowire arrays (p-SiNWs). In the novel heterojunction, the p-SiNWs are employed as the photocathode platform to acquire a strong photocurrent response. The in situ-grown p-COFs can accelerate the spatial migration rate of charge carriers by forming proper band alignment with the p-SiNWs. The crystalline π-conjugated network of p-COFs with abundant amino groups also promotes the electron transfer and anti-cTnI immobilizing process. The developed photocathodic immunosensor demonstrates a broad detection range of 5 pg/mL-10 ng/mL and a low limit of detection (LOD) of 1.36 pg/mL in clinical serum samples. Besides, the PEC sensor owns several advantages including good stability and superior anti-interference ability. By comparing our results with that of the commercial ELISA method, the relative deviations range from 0.06 to 0.18% (n = 3), and the recovery rates range from 95.4 to 109.5%. This work displays a novel strategy to design efficient and stable PEC sensing platforms for cTnI detection in real-life serums and provides guidance in future clinical diagnosis.

A Hygroscopic Janus Heterojunction for Continuous Moisture-Triggered Electricity Generators.

Moisture-triggered electricity generator (MEG) harvesting energy from the ubiquity of atmospheric moisture is one of the promising potential candidates for renewable power demand. However, MEG device performance is strongly dependent on the moisture concentration, which results in its large fluctuation of the electrical output. Here, a Janus heterojunction MEG device consisting of nanostructured silicon and hygroscopic polyelectrolyte incorporating hydrophilic carbon nanotube mesh is proposed to enable ambient moisture harvesting and continuous stable electrical output delivery. The nanostructured silicon with a large surface/volume ratio provides strong coupling interaction with water molecules for charge generation. A polyelectrolyte of polydiallyl dimethylammonium chloride (PDDA) can facilitate charge selective transporting and enhance the effectiveness of moisture-absorbing in an arid environment simultaneously. The conductive, porous, and hydrophilic carbon nanotube mesh allows water to be ripped through as well as the generated charges being collected timely. As such, any generated charge carriers in the Janus heterojunction can be efficiently swept toward their respective electrodes, because of the device asymmetric contact. A MEG device continuously delivers an open-circuit voltage of 1.0 V, short-circuit current density of 8.2 µA/cm2, and output power density of 2.2 µW/cm2 under an ambient environment (60% relative humidity, 25 °C), which is a record value over the previously reported values. Furthermore, the infrared thermal measurements also reveal that the moisture-triggered electricity generation power is likely ascribed to surrounding thermal energy collected by the MEG device. Our results provide an insightful rationale for the design of device structure and understanding of the working mechanism of MEG, which is of great importance to promote the efficient electricity conversion induced by moisture in the atmosphere.

Effect of Local Topography on Cell Division of Staphylococcus spp.

Surface engineering is a promising strategy to limit or prevent the formation of biofilms. The use of topographic cues to influence early stages of biofilm formationn has been explored, yet many fundamental questions remain unanswered. In this work, we develop a topological model supported by direct experimental evidence, which is able to explain the effect of local topography on the fate of bacterial micro-colonies of Staphylococcus spp. We demonstrate how topological memory at the single-cell level, characteristic of this genus of Gram-positive bacteria, can be exploited to influence the architecture of micro-colonies and the average number of surface anchoring points over nano-patterned surfaces, formed by vertically aligned silicon nanowire arrays that can be reliably produced on a commercial scale, providing an excellent platform to investigate the effect of topography on the early stages of Staphylococcus spp. colonisation. The surfaces are not intrinsically antimicrobial, yet they delivered a topography-based bacteriostatic effect and a significant disruption of the local morphology of micro-colonies at the surface. The insights from this work could open new avenues towards designed technologies for biofilm engineering and prevention, based on surface topography.

Glutathione-Sensitive Silicon Nanowire Arrays for Gene Transfection.

Ingenious surface modification strategies and special topological morphologies endow the biomaterial interface with excellent ability to regulate the cell fate. In this work, a gene delivery platform based on glutathione-sensitive silicon nanowire arrays (SiNWAs) is developed, exhibiting good transfection efficiency of several cell types. Briefly, the surface of SiNWAs is grafted of PEICBA, a branched cationic polymer cross-linked by disulfide bonds (SN-PEICBA). When the cells adhere to the platform surface, silicon nanowires penetrate into the cells and the high concentration of reduced glutathione (GSH) in cytoplasm breaks the disulfide bonds (S-S) in PEICBA. The plasmid DNA preloaded on the cationic polymers is successfully delivered to the nuclei through the nonlysosomal pathway. Cells harvested from the SN-PEICBA show high retention of viability and the platform surface can be reused though S-S replacement for at least three times. In general, our platform is a creative combination of intracellular responsive strategy and surface morphology, which has great potential for auxiliary use in ex vivo cell-based therapies and various biomedical applications.

A Smart Antibacterial Surface for the On-Demand Killing and Releasing of Bacteria.

For various human healthcare and industrial applications, endowing surfaces with the capability to not only efficiently kill bacteria but also release dead bacteria in a rapid and repeatable fashion is a promising but challenging effort. In this work, the synergistic effects of combining stimuli-responsive polymers and nanomaterials with unique topographies to achieve smart antibacterial surfaces with on-demand switchable functionalities are explored. Silicon nanowire arrays are modified with a pH-responsive polymer, poly(methacrylic acid), which serves as both a dynamic reservoir for the controllable loading and release of a natural antimicrobial lysozyme and a self-cleaning platform for the release of dead bacteria and the reloading of new lysozyme for repeatable applications. The functionality of the surface can be simply switched via step-wise modification of the environmental pH and can be effectively maintained after several kill-release cycles. These results offer a new methodology for the engineering of surfaces with switchable functionalities for a variety of practical applications in the biomedical and biotechnology fields.

Processing-Induced Electrically Active Defects in Black Silicon Nanowire Devices.

Silicon nanowires (Si NWs) are widely investigated nowadays for implementation in advanced energy conversion and storage devices, as well as many other possible applications. Black silicon (BSi)-NWs are dry etched NWs that merge the advantages related to low-dimensionality with the special industrial appeal connected to deep reactive ion etching (RIE). In fact, RIE is a well established technique in microelectronics manufacturing. However, RIE processing could affect the electrical properties of BSi-NWs by introducing deep states into their forbidden gap. This work applies deep level transient spectroscopy (DLTS) to identify electrically active deep levels and the associated defects in dry etched Si NW arrays. Besides, the successful fitting of DLTS spectra of BSi-NWs-based Schottky barrier diodes is an experimental confirmation that the same theoretical framework of dynamic electronic behavior of deep levels applies in bulk as well as in low dimensional structures like NWs, when quantum confinement conditions do not occur. This has been validated for deep levels associated with simple pointlike defects as well as for deep levels associated with defects with richer structures, whose dynamic electronic behavior implies a more complex picture.

Gold Nanowire Bundles Grown Radially Outward from Silicon Micropillars.

One-dimensional (1D) micro- and nanostructures have become increasingly popular because of their tremendous prospect in various applications. While the design and fabrication of these structures from a single component in two-dimensional (2D) arrays is common, the attainment of hierarchical three-dimensional (3D) architectures made up of multicomponent one-dimensional structures is rare. Herein we report, for the first time, the lateral growth of gold nanowires from the sidewalls of substrate grown silicon micropillars to form a unique "wire-on-pillar" architecture. Unlike zero-dimensional (0D) point-like, 1D linear, and 2D planar Au structures, the obtained 3D "wire-on-pillar" Au architecture provides abundant hotspots between adjacent Au wires, which led to remarkably high surface-enhanced Raman scattering (SERS) signals.