Maskless Preparation of Spatially-Resolved Plasmonic Nanoparticles on Polydimethylsiloxane via In Situ Fluoride-Assisted Synthesis

Here, a fluoride-assisted route for the controlled in-situ synthesis of metal nanoparticles (NPs) (i.e., AgNPs, AuNPs) on polydimethylsiloxane (PDMS) is reported. The size and coverage of the NPs on the PDMS surface are modulated with time and over space during the synthetic process, leveraging the improved yield (10×) and faster kinetics (100×) of NP formation in the presence of F⁻ ions, compared to fluoride-free approaches. This enables the maskless preparation of both linear and step gradients and patterns of NPs in 1D and 2D on the PDMS surface. As an application in flexible plasmonics/photonics, continuous and step-wise spatial modulations of the plasmonic features of PDMS slabs with 1D and 2D AgNP gradients on the surface are demonstrated. An excellent spatially resolved tuning of key optical parameters, namely, optical density from zero to 5 and extinction ratio up to 100 dB, is achieved with AgNP gradients prepared in AgF solution for 12 minutes; the performance are comparable to those of commercial dielectric/interference filters. When used as a rejection filter in optical fluorescence microscopy, the AgNP-PDMS slabs are able to reject the excitation laser at 405 nm and retain the green fluorescence of microbeads (100 µm) used as test cases.     

Optical Characterization of High-Order 1-D Silicon Photonic Crystals

In this paper, we present numerical and experimental results on the spectral reflectivity of hybrid, high-order (up to 22nd) 1-D silicon photonic crystals (PCs) in the near-infrared region (wavelength range 1- 1.7 mum). Mechanically robust, vertical 1-D PCs with high aspect ratio and spatial period of 8 mum were fabricated by electrochemical micromachining of silicon, and tested in reflection with an improved optical setup, incorporating standard telecommunication single-mode optical fibers and a lensed fiber pigtail. A detailed theoretical, numerical analysis was performed to assess the effects of both non-idealities of the structures under test and constraints of the optical setup, on the spectral reflectivity. Experimental data were found in very good agreement with theoretical calculations, performed by using the characteristic matrix method, keeping into account an in-plane porosity variation for 1-D PCs, due to surface roughness of silicon walls, and the limited resolution bandwidth of the spectrum analyzer. Best optical performances, measured on the fabricated 1-D PC mirrors, consist of optical losses less than 0.8 dB in a bandgap around 1.5 mum and a -35 dB reflectivity minimum at a bandgap edge.     

Bandgap Tuning of Silicon Micromachined 1-D Photonic Crystals by Thermal Oxidation

Fabrication and optical testing of high-aspect-ratio 1D photonic crystals, obtained by electrochemical micromachining of silicon, are discussed in this paper. The devices consist of high-aspect-ratio periodic (P=4 mum) arrays of 1.22-mum-thick silicon walls separated by 2.78-mum-wide air gaps, with 100 mum etching depth. They were designed as hybrid quarter-wavelength reflectors with photonic bandgaps in the near-IR region, one in particular centered at lambda=1.55 mum. The fabrication process was improved to increase structure uniformity and strength. Thermal oxidation of the silicon structures was exploited to tune the wavelength position and width of the bandgaps. Fabricated devices, also with different silicon dioxide thicknesses, were optically tested by measuring their spectral reflectivity in the wavelength range of 1.0-1.7 mum. Experimental results were found in good agreement with the calculated spectra.     

Moldless Printing of Silicone Lenses with Embedded Nanostructured Optical Filters

In this work, both light‐shaping and image magnification features are integrated into a single lens element using a moldless procedure that takes advantage of the physical and optical properties of mesoporous silicon (PSi) photonic crystal nanostructures. Casting of a liquid poly(dimethylsiloxane) pre‐polymer solution onto a PSi film generates a droplet with a contact angle that is readily controlled by the silicon nanostructure, and adhesion of the cured polymer to the PSi photonic crystal allows preparation of lightweight (10 mg) freestanding lenses (4.7 mm focal length) with an embedded optical component (e.g., optical rugate filter, resonant cavity, and distributed Bragg reflector). The fabrication process shows excellent reliability (yield 95%) and low cost and the lens is expected to have implications in a wide range of applications. As a proof‐of‐concept, using a single monolithic lens/filter element it is demonstrated: fluorescence imaging of isolated human cancer cells with rejection of the blue excitation light, through a lens that is self‐adhered to a commercial smartphone; shaping of the emission spectrum of a white light emitting diode to tune the color from red through blue; and selection of a narrow wavelength band (bandwidth 5 nm) from a fluorescent molecular probe.     

4D Printing of a Bioinspired Microneedle Array with Backward‐Facing Barbs for Enhanced Tissue Adhesion

Microneedle (MN), a miniaturized needle with a length‐scale of hundreds of micrometers, has received a great deal of attention because of its minimally invasive, pain‐free, and easy‐to‐use nature. However, a major challenge for controlled long‐term drug delivery or biosensing using MN is its low tissue adhesion. Although microscopic structures with high tissue adhesion are found from living creatures in nature (e.g., microhooks of parasites, barbed stingers of honeybees, quills of porcupines), creating MNs with such complex microscopic features is still challenging with traditional fabrication methods. Here, a MN with bioinspired backward‐facing curved barbs for enhanced tissue adhesion, manufactured by a digital light processing 3D printing technique, is presented. Backward‐facing barbs on a MN are created by desolvation‐induced deformation utilizing cross‐linking density gradient in a photocurable polymer. Barb thickness and bending curvature are controlled by printing parameters and material composition. It is demonstrated that tissue adhesion of a backward‐facing barbed MN is 18 times stronger than that of barbless MN. Also demonstrated is sustained drug release with barbed MNs in tissue. Improved tissue adhesion of the bioinspired MN allows for more stable and robust performance for drug delivery, biofluid collection, and biosensing.     

1D and 2D Field Effect Transistors in Gas Sensing: A Comprehensive Review

Rapid progress in the synthesis and fundamental understanding of 1D and 2D materials have solicited the incorporation of these nanomaterials into sensor architectures, especially field effect transistors (FETs), for the monitoring of gas and vapor in environmental, food quality, and healthcare applications. Yet, several challenges have remained unaddressed toward the fabrication of 1D and 2D FET gas sensors for real-field applications, which are related to properties, synthesis, and integration of 1D and 2D materials into the transistor architecture. This review paper encompasses the whole assortment of 1D—i.e., metal oxide semiconductors (MOXs), silicon nanowires (SiNWs), carbon nanotubes (CNTs)—and 2D—i.e., graphene, transition metal dichalcogenides (TMD), phosphorene—materials used in FET gas sensors, critically dissecting how the material synthesis, surface functionalization, and transistor fabrication impact on electrical versus sensing properties of these devices. Eventually, pros and cons of 1D and 2D FETs for gas and vapor sensing applications are discussed, pointing out weakness and highlighting future directions.     

Low-concentration NO/sub 2/ detection with an adsorption porous silicon FET

Adsorption porous silicon FET (APSFET) is a porous silicon (PS)-based device constituted of a FET structure with a porous adsorbing layer between drain and source. Adsorbed gas molecules in the porous layer induce an inverted channel in the crystalline silicon under the PS itself. The mobile charge per unit area in the channel depends on the molecular gas concentrations in the sensing layer so that adsorbed gas molecules play a role similar to the charge on the gate of a FET. In this work, NO/sub 2/ detection by using the APSFET is demonstrated for the first time. NO/sub 2/ concentration as low as 100 ppb was detected. Devices with both as-grown and oxidized PS layers were fabricated and compared in order to investigate the effect of a low-temperature thermal oxidation on the electrical performances of the sensor. Nonoxidized sensors show a high sensitivity only for fresh devices, which reduces with the aging of the sample. Oxidation of the PS layer improves the electrical performance of sensors, in terms of stability, recovery time, and interference with the relative humidity level, keeping the high sensitivity to nitrogen dioxide.     

Microengineered Bioartificial Liver Chip for Drug Toxicity Screening

Microfluidic 3D cell culture is a promising technology for the screening of drug toxicity profiles. In this study, a bioartificial liver consisting of a surface‐engineered microfluidic silicon chip with microtrenches mimicking hepatic sinusoids is shown to extend 3D primary hepatocyte culture and improve in vitro drug screening for hepatotoxicity, with respect to the state‐of‐the‐art literature on this subject. Primary hepatocytes hosted in the 3D heparin‐coated microtrenches (the bioartificial liver) secrete high levels of albumin and urea over 4 weeks. The cytotoxicity of common drugs, namely, acetaminophen, chlorpromazine, and tacrine, was assessed on primary hepatocytes both at day 1 and day 7. The results suggest that mimicking hepatic sinusoids using a microtrench format allows the maintenance of difficult‐to‐culture primary hepatocytes to be extended to 4 weeks and provides an alternative model to animal studies for the screening of the cytotoxicity of new drugs.     

Controlled Microfabrication of High‐Aspect‐Ratio Structures in Silicon at the Highest Etching Rates: The Role of H2O2 in the Anodic Dissolution of Silicon in Acidic Electrolytes

In this work the authors report on the controlled electrochemical etching of high‐aspect‐ratio (from 5 to 100) structures in silicon at the highest etching rates (from 3 to 10 µm min^?1) at room temperature. This allows silicon microfabrication entering a previously unattainable region where etching of high‐aspect‐ratio structures (beyond 10) at high etching rate (over 3 µm min^?1) was prohibited for both commercial and research technologies. Addition of an oxidant, namely H₂O₂, to a standard aqueous hydrofluoric (HF) acid electrolyte is used to dramatically change the stoichiometry of the silicon dissolution process under anodic biasing without loss of etching control accuracy at the higher depths (up to 200 µm). The authors show that the presence of H₂O₂ reduces the valence of the dissolution process to 1, thus rendering the electrochemical etching more effective, and catalyzes the etching rate by opening a more efficient path for silicon dissolution with respect to the well‐known Gerischer mechanism, thus increasing the etching speed at both shorter and higher depths.     

Solution-Processable Carbon Nanotube Nanohybrids for Multiplexed Photoresponsive Devices

Here, the formation of carbon nanotube (CNT)-based nanohybrids in aqueous solution is reported, where DNA-wrapped CNTs (DNA-CNTs) act as templates for the growth of PbS and CdS nanocrystals, toward the formation of PbS-DNA-CNT and CdS-DNA-CNT heterostructures. Solution-processed multiplexed photoresponsive devices are fabricated from these nanohybrids, displaying a sensitivity to a broad range of illumination wavelengths (405, 532, and 650 nm). The DNA-CNT and CdS-DNA-CNT devices show a drop in the current while PbS-DNA-CNT's current increases upon light illumination, indicating a difference in the operational mechanisms between the hybrids. Furthermore, the ON/OFF photoresponse of PbS-DNA-CNT is only 1 s as compared to 200 s for the other two nanohybrid devices. The mechanisms of the different photoresponses are investigated by comparing the performance under an inert and air atmosphere, and gate dependence device analysis and transient absorption spectroscopy measurements are also conducted. The results reveal that photoinduced oxygen desorption is responsible for the slower photoresponse by DNA-CNT and CdS-DNA-CNT, while photoinduced charge transfer dominates the much faster response of PbS-DNA-CNT devices. The strategy developed is of general applicability for the bottom-up assembly of CNT-based nanohybrid optoelectronic systems and the fabrication of solution-processable multiplexed devices.