Black silicon spacing effect on bactericidal efficacy against gram-positive bacteria.

The morphology of regular and uniform arrays of black silicon structures was evaluated for bactericidal efficacy against gram-positive, non-motileStaphylococcusepidermidis(S.epidermidis). In this study, uniform and regular arrays of black silicon structures were fabricated using nanosphere lithography and deep reactive ion etching. The effects of nanomorphology on bacterial killing were systematically evaluated using silicon nanostructures with pitches ranging from 300 to 1400 nm pitch on spherical cocci approximately 500 to 1000 nm in diameter. Our results show that nanostructure morphology factors such as height and roughness do not directly determine bactericidal efficacy. Instead, the spacing between nanostructures plays a crucial role in determining how bacteria are stretched and lysed. Nanostructures with smaller pitches are more effective at killing bacteria, and an 82 ± 3% enhancement in bactericidal efficacy was observed for 300 nm pitch nanoneedles surface compared to the flat control substrates.

Identification of Poly(ethylene terephthalate) Nanoplastics in Commercially Bottled Drinking Water Using Surface-Enhanced Raman Spectroscopy.

Micro/nanoplastics have emerged as global contaminants of serious concern to human and ecosystem health. However, identification and visualization of microplastics and particularly nanoplastics have remained elusive due to the lack of feasible and reliable analytical approaches, particularly for trace nanoplastics. Here, an efficient surface-enhanced Raman spectroscopy (SERS)-active substrate with triangular cavity arrays is reported. The fabricated substrate exhibited high SERS performance for standard polystyrene (PS) nanoplastic detection with size down to 50 nm and a detection limit of 0.001% (1.5 × 1011 particles/mL). Poly(ethylene terephthalate) (PET) nanoplastics collected from commercially bottled drinking water were detected with an average mean size of ∼88.2 nm. Furthermore, the concentration of the collected sample was estimated to be about 108 particles/mL by nanoparticle tracking analysis (NTA), and the annual nanoplastic consumption of human beings through bottled drinking water was also estimated to be about 1014 particles, assuming water consumption of 2 L/day for adults. The facile and highly sensitive SERS substrate provides more possibilities for detecting trace nanoplastics in an aquatic environment with high sensitivity and reliability.

Automated SEM Image Analysis of the Sphere Diameter, Sphere-Sphere Separation, and Opening Size Distributions of Nanosphere Lithography Masks.

Colloidal nanosphere monolayers­used as a lithography mask for site-controlled material deposition or removal­offer the possibility of cost-effective patterning of large surface areas. In the present study, an automated analysis of scanning electron microscopy (SEM) images is described, which enables the recognition of the individual nanospheres in densely packed monolayers in order to perform a statistical quantification of the sphere size, mask opening size, and sphere-sphere separation distributions. Search algorithms based on Fourier transformation, cross-correlation, multiple-angle intensity profiling, and sphere edge point detection techniques allow for a sphere detection efficiency of at least 99.8%, even in the case of considerable sphere size variations. While the sphere positions and diameters are determined by fitting circles to the spheres edge points, the openings between sphere triples are detected by intensity thresholding. For the analyzed polystyrene sphere monolayers with sphere sizes between 220 and 600 nm and a diameter spread of around 3% coefficients of variation of 6.8­8.1% for the opening size are found. By correlating the mentioned size distributions, it is shown that, in this case, the dominant contribution to the opening size variation stems from nanometer-scale positional variations of the spheres.

A Self-Ordered Nanostructured Transparent Electrode of High Structural Quality and Corresponding Functional Performance.

The preparation of a highly ordered nanostructured transparent electrode based on a combination of nanosphere lithography and anodization is presented. The size of perfectly ordered pore domains is improved by an order of magnitude with respect to the state of the art. The concomitantly reduced density of defect pores increases the fraction of pores that are in good electrical contact with the underlying transparent conductive substrate. This improvement in structural quality translates directly and linearly into an improved performance of energy conversion devices built from such electrodes in a linear manner.

Manipulation of hot electron flow on plasmonic nanodiodes fabricated by nanosphere lithography.

Energy conversion to generate hot electrons through the excitation of localized surface plasmon resonance (LSPR) in metallic nanostructures is an emerging strategy in photovoltaics and photocatalytic devices. Important factors for surface plasmon and hot electron generation are the size, shape, and materials of plasmonic metal nanostructures, which affect LSPR excitation, absorbance, and hot electron collection. Here, we fabricated the ordered structure of metal-semiconductor plasmonic nanodiodes using nanosphere lithography and reactive ion etching. Two types of hole-shaped plasmonic nanostructures with the hole diameter of 280 and 115 nm were fabricated on Au/TiO2Schottky diodes. We show that hot electron flow can be manipulated by changing the size of plasmonic nanostructures on the Schottky diode. We show that the short-circuit photocurrent changes and the incident photon-to-electron conversion efficiency results exhibit the peak shift depending on the structures. These phenomena are explicitly observed with finite difference time domain simulations. The capability of tuning the morphology of plasmonic nanostructure on the Schottky diode can give rise to new possibilities in controlling hot electron generation and developing novel hot-electron-based energy conversion devices.

Zeta Potential Dependent Self-Assembly for Very Large Area Nanosphere Lithography.

Nanosphere lithography offers a rapid, low-cost approach for patterning of large-area two-dimensional periodic nanostructures. However, a complete understanding of the nanosphere self-assembly process is necessary to enable further development and scaling of this technology. The self-assembly of nanospheres into two-dimensional periodic arrays has previously been attributed solely to the Marangoni force; however, we demonstrate that the ζ potential of the nanosphere solution is critically important for successful self-assembly to occur. We discuss and demonstrate how this insight can be used to greatly increase self-assembled 2D periodic array areas while decreasing patterning time and cost. As a representative application, we fabricate antireflection nanostructures on a transparent flexible polymer substrate suitable for use as a large-area (270 cm2), broadband, omnidirectional antireflection film.

A gold coated polystyrene ring microarray formed by two-step patterning: construction of an advanced microelectrode for voltammetric sensing.

A two-step patterning process was developed based on nanosphere lithography and plasma etching to fabricate an array of electrodes with two different gold ring structures: the arrays of Au micro-ring electrode (Au-MRE) and Au covered with polystyrene micro-ring electrode (Au-PS-MRE). The Au-MRE structure was fabricated by etching a monolayer of polystyrene (PS) spheres on indium tin oxide (ITO) surface to generate PS rings on ITO glass. PS rings served as a mask in secondary etching for blocking an interaction of oxygen plasma and ITO surface to create a ring-patterned ITO surface. Then, the PS residue was removed and gold was deposited. The site-selective electrodeposition of gold was carried out and an array of a gold ring structure was formed on the ITO glass. The Au-PS-MRE structure was fabricated by keeping the PS residue from second etching before deposition of gold. The Au-PS-MRE microelectrode was studied by using hexacyanoferrate as an electrochemical probe where it displayed steady state current in cyclic voltammetry. The respective calibration plots were acquired at a working potential of 0.31 V and 0.12 V (vs. Ag/AgCl) for oxidation and reduction reaction, respectively. The sensitivity is as high as 163.4-220.7 µA·mM-1·mm-2 which is larger by a factor of 95-132 compared to a conventional gold film macroelectrode. The detection limit (at a signal-to-noise ratio of 3) is 2.2 µM. This approach thus yields relatively effective and low-cost fabrication without resorting to high resolution instruments. Conceivably, the technique may be used to produce microelectrode arrays on a large scale. Graphical abstract Schematic presentation of a novel fabrication process of micro-ring electrode arrays. Two-step patterning based on nanosphere lithography leads to electrodes with great electrochemical performance. Direct deposition metal in the presence of polystyrene (PS) mask induces the formation of a new structure with arrays of gold covered with PS microring on the indium tin oxide (ITO) coated glass. The microelectrode-like behavior has been achieved using this fabrication process.

Palladium-Decorated Silicon Nanomesh Fabricated by Nanosphere Lithography for High Performance, Room Temperature Hydrogen Sensing.

A hydrogen (H2 ) gas sensor based on a silicon (Si) nanomesh structure decorated with palladium (Pd) nanoparticles is fabricated via polystyrene nanosphere lithography and top-down fabrication processes. The gas sensor shows dramatically improved H2 gas sensitivity compared with an Si thin film sensor without nanopatterns. Furthermore, a buffered oxide etchant treatment of the Si nanomesh structure results in an additional performance improvement. The final sensor device shows fast H2 response and high selectivity to H2 gas among other gases. The sensing performance is stable and shows repeatable responses in both dry and high humidity ambient environments. The sensor also shows high stability without noticeable performance degradation after one month. This approach allows the facile fabrication of high performance H2 sensors via a cost-effective, complementary metal-oxide-semiconductor (CMOS) compatible, and scalable nanopatterning method.

Hierarchical CdS Nanorod@SnO2 Nanobowl Arrays for Efficient and Stable Photoelectrochemical Hydrogen Generation.

An efficient photoanode based on CdS nanorod@SnO2 nanobowl (CdS NR@SnO2 NB) arrays is designed and fabricated by the preparation of SnO2 nanobowl arrays via nanosphere lithography followed by hydrothermal growth of CdS nanorods on the inner surface of the SnO2 nanobowls. A photoelectrochemical (PEC) device constructed by using this hierarchical CdS NR@SnO2 NB photoanode presents significantly enhanced performance with a photocurrent density of 3.8 mA cm-2 at 1.23 V versus a reversible hydrogen electrode (RHE) under AM1.5G solar light irradiation, which is about 2.5 times higher than that of CdS nanorod arrays. After coating with a thin layer of SiO2 , the photostability of the CdS NR@SnO2 NB arrays is greatly enhanced, resulting in a stable photoanode with a photocurrent density of 3.0 mA cm-2 retained at 1.23 V versus the RHE. The much improved performance of the CdS NR@SnO2 NB arrays toward PEC hydrogen generation can be ascribed to enlarged surface area arising from the hierarchical nanostructures, improved light harvesting owing to the NR@NB architecture containing multiple scattering centers, and enhanced charge separation/collection efficiency due to the favorable CdS-SnO2 heterojunction.

Nanosphere Lithography on Fiber: Towards Engineered Lab-On-Fiber SERS Optrodes.

In this paper we report on the engineering of repeatable surface enhanced Raman scattering (SERS) optical fiber sensor devices (optrodes), as realized through nanosphere lithography. The Lab-on-Fiber SERS optrode consists of polystyrene nanospheres in a close-packed arrays configuration covered by a thin film of gold on the optical fiber tip. The SERS surfaces were fabricated by using a nanosphere lithography approach that is already demonstrated as able to produce highly repeatable patterns on the fiber tip. In order to engineer and optimize the SERS probes, we first evaluated and compared the SERS performances in terms of Enhancement Factor (EF) pertaining to different patterns with different nanosphere diameters and gold thicknesses. To this aim, the EF of SERS surfaces with a pitch of 500, 750 and 1000 nm, and gold films of 20, 30 and 40 nm have been retrieved, adopting the SERS signal of a monolayer of biphenyl-4-thiol (BPT) as a reliable benchmark. The analysis allowed us to identify of the most promising SERS platform: for the samples with nanospheres diameter of 500 nm and gold thickness of 30 nm, we measured values of EF of 4 × 105, which is comparable with state-of-the-art SERS EF achievable with highly performing colloidal gold nanoparticles. The reproducibility of the SERS enhancement was thoroughly evaluated. In particular, the SERS intensity revealed intra-sample (i.e., between different spatial regions of a selected substrate) and inter-sample (i.e., between regions of different substrates) repeatability, with a relative standard deviation lower than 9 and 15%, respectively. Finally, in order to determine the most suitable optical fiber probe, in terms of excitation/collection efficiency and Raman background, we selected several commercially available optical fibers and tested them with a BPT solution used as benchmark. A fiber probe with a pure silica core of 200 µm diameter and high numerical aperture (i.e., 0.5) was found to be the most promising fiber platform, providing the best trade-off between high excitation/collection efficiency and low background. This work, thus, poses the basis for realizing reproducible and engineered Lab-on-Fiber SERS optrodes for in-situ trace detection directed toward highly advanced in vivo sensing.

Double Fano resonances in individual metallic nanostructure for high sensing sensitivity.

In this paper, we report the design and observation of double Fano resonances (DFRs) in an individual symmetry reduced nanostructure and the induced high sensing sensitivity. Such a plasmonic nanostructure consists of a partially overlapped double metallic nanotriangles with unequal sizes fabricated by using the fast and low-cost angle-resolved nanosphere lithography. Symmetry breaking generates two narrow quadrupolar dark modes, which further enhance the coupling with fundamental bright dipole modes within the same structure, manifesting the effect of DFRs. The resonance wavelength and line shape of DFRs can be tailored by changing the degree of asymmetry as well as the size of the designed nanostructure. Based on DFRs, a high sensitivity to dielectric environment with a maximum figure of merit of 35 is measured. Due to fast manufacturing process with high reproducibility and high structural tunability, the fabricated individual metallic nanostructure provides an opportunity to significant potential applications in localized surface plasmon resonance (LSPR) based single or double-wavelength sensors in the near-infrared region.

Fabrication of Ordered SnO2 Nanostructures with Enhanced Humidity Sensing Performance.

Ordered SnO2 nanostructures were prepared as humidity sensors by nanosphere lithography with the magnetron sputtering technique. The X-ray diffraction patterns of SnO2 nanostructures show that all intense diffraction peaks correspond to the crystallographic planes of SnO2. The Atomic Force Microscope (AFM) mage shows that these SnO2 nanostructures exhibited a classic honeycomb structure. The resistance of this sensor was measured to show that the resistance of the sensor decreases with an increase from lower relative humidity (RH) to higher RH. Additionally, the longest response/recovery time was 32 s/42 s for 11-96% RH. The hysteresis for the SnO2 nanostructure sensor was <5%.

Heterostructured TiO2 Nanorod@Nanobowl Arrays for Efficient Photoelectrochemical Water Splitting.

Heterostructured TiO2 nanorod@nanobowl (NR@NB) arrays consisting of rutile TiO2 nanorods grown on the inner surface of arrayed anatase TiO2 nanobowls are designed and fabricated as a new type of photoanodes for photoelectrochemical (PEC) water splitting. The unique heterostructures with a hierarchical architecture are readily fabricated by interfacial nanosphere lithography followed by hydrothermal growth. Owing to the two-dimensionally arrayed structure of anatase nanobowls and the nearly radial alignment of rutile nanorods, the TiO2 NR@NB arrays provide multiple scattering centers and hence exhibit an enhanced light harvesting ability. Meanwhile, the large surface area of the NR@NB arrays enhances the contact with the electrolyte while the nanorods offer direct pathways for fast electron transfer. Moreover, the rutile/anatase phase junction in the NR@NB heterostructure improves charge separation because of the facilitated electron transfer. Accordingly, the PEC measurements of the TiO2 NR@NB arrays on the fluoride-doped tin oxide (FTO) substrate show significantly enhanced photocatalytic properties for water splitting. Under AM1.5G solar light irradiation, the unmodified TiO2 NR@NB array photoelectrode yields a photocurrent density of 1.24 mA cm(-2) at 1.23 V with respect to the reversible hydrogen electrode, which is almost two times higher than that of the TiO2 nanorods grown directly on the FTO substrate.

Size-Tunable Organic Nanodot Arrays: A Versatile Platform for Manipulating and Imaging Cells.

Arrays of protein nanodots with dot-size tuned independently of spacing (e.g., ∼100 to 600 nm diameter for 900 nm spacing) are fabricated. The mechanism of size control is demonstrated, by numerical simulations, to arise from shadow effects during deposition of a sacrificial metal mask. We functionalize the nanodots with antibodies and embed them in a polymer-cushion or in lipid-bilayers or transfer them to soft elastomers. Their ability to influence cell architecture and local membrane organization is demonstrated in T-lymphocytes, using reflection interference contrast and total internal reflection fluorescence microscopy.

Nanoscale Interfacial Engineering for Flexible Barrier Films.

Alternating layers of organic and oxide thin films used as diffusion barriers in emerging flexible device technologies are vulnerable to degradation under the influence of mechanical stresses, temperature cycling, photodegradation, and chemically active environmental species. Delamination of the internal organic to oxide interfaces often limits the operational lifetime of the barrier system. We demonstrate a method for increasing the adhesion of organic and oxide thin films by generating nanostructures at the interface. We show that the adhesion of an acrylate to silicon oxide model system can be increased by up to an order of magnitude (from ∼2 J/m(2) to 24 J/m(2)). By altering the diameter and depth of the patterns in the model systems, the adhesion energy can be changed, and the delamination pathway can be controlled. In addition, we show that a patterned interface maintains a higher adhesion than its planar counterpart for all durations of UV-A and UV-B exposure.

Interfacial nanosphere lithography toward Ag2S-Ag heterostructured nanobowl arrays with effective resistance switching and enhanced photoresponses.

Unique Ag2 S-Ag heterostructured nanobowl arrays consisting of Ag2 S nanonets lying on Ag nanobowl arrays are fabricated by two-step nanosphere lithography at the gas-liquid interface. These Ag2 S-Ag heterostructured nanobowl arrays exhibit effective resistance switching behaviors and enhanced photoresponses, showing potential application in both electric devices and photocatalysis.

Au@MnO2 core-shell nanomesh electrodes for transparent flexible supercapacitors.

A novel Au@MnO2 supercapacitor is presented. The sophisticated core-shell architecture combining an Au nanomesh core with a MnO2 shell on a flexible polymeric substrate is demonstrated as an electrode for high performance transparent flexible supercapacitors (TFSCs). Due to their unique structure, high areal/gravimetric capacitance and rate capability for TFSCs are achieved.

Physiochemical Coupled Dynamic Nanosphere Lithography Enabling Multiple Metastructures from Single Mask.

Metastructures are widely used in photonic devices, energy conversion, and biomedical applications. However, to fabricate multiple patterns continuously in single etching protocol with highly tunable photonic properties is challenging. Here, a simple and robust dynamic nanosphere lithography is proposed by inserting a spacer between the nanosphere assembly and the wafer. The nanosphere diameter decrease and uneven penetration of the spacer during etching lead to a dynamic masking process. Coupled anisotropic physical ion sputtering and ricocheting with isotropic chemical radical etching achieve highly tunable structures with various 3D patterns continuously forming through a single etching process. Specifically, the nanosphere diameters define the periodicity, the etched spacer forms the upper parts, and the wafer forms the lower parts. Each part of the structure is highly tunable through changing nanosphere diameter, spacer thickness, and etch conditions. Using this protocol, numerous structures of varying sizes including nanomushrooms, nanocones, nanopencils, and nanoneedles with diverse shapes are realized as proof of concepts. The broadband antireflection ability of the nanostructures and their use in surface-enhanced Raman spectroscopy are also demonstrated for practical application. This method substantially simplifies the fabrication procedure of various metastructures, paving the way for its application in multiple disciplines especially in photonic devices.

Multi-Level Pyramidal Microstructure-Based Pressure Sensors with High Sensitivity and Wide Linear Range for Healthcare Monitoring.

Flexible pressure sensors have garnered significant attention in the field of wearable healthcare due to their scalability and shape variability. However, a crucial challenge in their practical application for various healthcare scenarios is striking a balance between the sensitivity and sensing range. This limitation arises from the reduced compressibility of the microstructures on the surface of pressure-sensitive materials under high pressure, resulting in progressive saturation of the sensor's response and leading to a restricted and nonlinear pressure sensing range. In this study, we present a novel approach utilizing multi-level pyramidal microstructures in flexible pressure sensors to achieve both high sensitivity (8775 kPa-1) and linear response (R2 = 0.997) over a wide pressure range (up to 1000 kPa). The effectiveness of the proposed design stems from the compensatory behavior of the lower pyramidal microstructures, which counteracts the declining sensitivity associated with the gradual hardening of the higher pyramidal microstructures. Furthermore, the sensor demonstrates a fast response time of 11.6 ms and a fast relaxation time of 3.8 ms and can reliably detect pressures as low as 30.2 Pa. Our findings highlight the applicability of this flexible pressure sensor in diverse human body health detection tasks, ranging from weak pulses to finger flexion and plantar pressure distribution. Notably, the proposed sensor design eliminates the need for replacing flexible pressure sensors with varying ranges, thereby enhancing their practical utility.

Parallel fabrication of plasmonic nanocone sensing arrays.

A fully parallel approach for the fabrication of arrays of metallic nanocones and triangular nanopyramids is presented. Different processes utilizing nanosphere lithography for the creation of etch masks are developed. Monolayers of spheres are reduced in size and directly used as masks, or mono- and double layers are employed as templates for the deposition of aluminum oxide masks. The masks are transferred into an underlying gold or silver layer by argon ion milling, which leads to nanocones or nanopyramids with very sharp tips. Near the tips the enhancement of an external electromagnetic field is particularly strong. This fact is confirmed by numerical simulations and by luminescence imaging in a confocal microscope. Such localized strong fields can amongst others be utilized for high-resolution, high-sensitivity spectroscopy and sensing of molecules near the tip. Arrays of such plasmonic nanostructures thus constitute controllable platforms for surface-enhanced Raman spectroscopy. A thin film of pentacene molecules is evaporated onto both nanocone and nanopyramid substrates, and the observed Raman enhancement is evaluated.