Formation of Interstitial Hot-Spots Using the Reduced Gap-Size between Plasmonic Microbeads Pattern for Surface-Enhanced Raman Scattering Analysis.

To achieve an effective surface-enhanced Raman scattering (SERS) sensor with periodically distributed "hot spots" on wafer-scale substrates, we propose a hybrid approach combining physical nano-imprint lithography and a chemical deposition method to form a silver microbead array. Nano-imprint lithography (NIL) can lead to mass-production and high throughput, but is not appropriate for generating strong "hot-spots." However, when we apply electrochemical deposition to an NIL substrate and the reaction time was increased to 45 s, periodical "hot-spots" between the microbeads were generated on the substrates. It contributed to increasing the enhancement factor (EF) and lowering the detection limit of the substrates to 4.40 × 106 and 1.0 × 10-11 M, respectively. In addition, this synthetic method exhibited good substrate-to-substrate reproducibility (RSD < 9.4%). Our research suggests a new opportunity for expanding the SERS application.

An Ultrasensitive Laser-Induced Graphene Electrode-Based Triboelectric Sensor Utilizing Trapped Air as Effective Dielectric Layer.

Air, a widely recognized dielectric material, is employed as a dielectric layer in this study. We present a triboelectric sensor with a laser-induced graphene (LIG) electrode and an air-trapped pad using silicone rubber (SR). A very thin device with a thickness of 1 mm and an effective gap for contact-separation between the films of silicone rubber and polyimide (PI) of 0.6 mm makes the device extremely highly sensitive for very low amplitudes of pressure. The fabrication of LIG as an electrode material on the surface of PI is the key reason for the fabrication of the thin sensor. In this study, we showed that the fabricated air-trapped padded sensor (ATPS) has the capability to generate an output voltage of ~32 V, a short-circuit current of 1.2 µA, and attain a maximum power density of 139.8 mW m-2. The performance of the ATPS was compared with a replicated device having a hole on the pad, allowing air to pass through during contact-separation. The observed degradation in the electrical output suggests that the trapped air in the pad plays a crucial role in enhancing the output voltage. Therefore, the ATPS emerges as an ultra-sensitive sensor for healthcare sensing applications.

Multimodal E-Textile Enabled by One-Step Maskless Patterning of Femtosecond-Laser-Induced Graphene on Nonwoven, Knit, and Woven Textiles.

Personal wearable devices are considered important in advanced healthcare, military, and sports applications. Among them, e-textiles are the best candidates because of their intrinsic conformability without any additional device installation. However, e-textile manufacturing to date has a high process complexity and low design flexibility. Here, we report the direct laser writing of e-textiles by converting raw Kevlar textiles to electrically conductive laser-induced graphene (LIG) via femtosecond laser pulses in ambient air. The resulting LIG has high electrical conductivity and chemical reliability with a low sheet resistance of 2.86 Ω/□. Wearable multimodal e-textile sensors and supercapacitors are realized on different types of Kevlar textiles, including nonwoven, knit, and woven structures, by considering their structural textile characteristics. The nonwoven textile exhibits high mechanical stability, making it suitable for applications in temperature sensors and micro-supercapacitors. On the other hand, the knit textile possesses inherent spring-like stretchability, enabling its use in the fabrication of strain sensors for human motion detection. Additionally, the woven textile offers special sensitive pressure-sensing networks between the warp and weft parts, making it suitable for the fabrication of bending sensors used in detecting human voices. This direct laser synthesis of arbitrarily patterned LIGs from various textile structures could result in the facile realization of wearable electronic sensors and energy storage.

Highly Sensitive and Reliable microRNA Detection with a Recyclable Microfluidic Device and an Easily Assembled SERS Substrate.

Surface-enhanced Raman spectroscopy (SERS) detection in microfluidics is an interesting topic because of its high sensitivity, miniaturization, and ability to perform online detection. However, the difficulties in generating SERS-based microfluidic devices with uniform signal reproducibility and high sensitivity have hindered their widespread application. In addition, the recyclability of the SERS-based microfluidic devices can contribute to their broad commercialization, but the possible contamination in the detection area and cumbersome cleaning procedures remain a challenge. In this study, we describe a repeatable SERS-based microfluidic device comprising a disposable SERS substrate and a reusable microfluidic channel. The microfluidic channel was prepared via mechanical processing, and the SERS substrate was fabricated by nanoimprint lithography and electrodeposition. The SERS substrate and microfluidic channel can be attached easily because they were assembled using screws. The SERS substrate achieved an excellent SERS enhancement factor greater than 108 over a large sample area, signal uniformity, and substrate-to-substrate reproducibility. This guaranteed reliable and sensitive signals in every experiment. Furthermore, the disposable SERS substrate contributed exact detection of target molecules. Finally, their practical application was demonstrated with the repeated use of the microfluidic device by detecting a specific micro-RNA, (miR-34a) at a concentration as low as 5 fM.

Hierarchically Porous, Laser-Pyrolyzed Carbon Electrode from Black Photoresist for On-Chip Microsupercapacitors.

We report a laser-pyrolyzed carbon (LPC) electrode prepared from a black photoresist for an on-chip microsupercapacitor (MSC). An interdigitated LPC electrode was fabricated by direct laser writing using a high-power carbon dioxide (CO2) laser to simultaneously carbonize and pattern a spin-coated black SU-8 film. Due to the high absorption of carbon blacks in black SU-8, the laser-irradiated SU-8 surface was directly exfoliated and carbonized by a fast photo-thermal reaction. Facile laser pyrolysis of black SU-8 provides a hierarchically macroporous, graphitic carbon structure with fewer defects (ID/IG = 0.19). The experimental conditions of CO2 direct laser writing were optimized to fabricate high-quality LPCs for MSC electrodes with low sheet resistance and good porosity. A typical MSC based on an LPC electrode showed a large areal capacitance of 1.26 mF cm-2 at a scan rate of 5 mV/s, outperforming most MSCs based on thermally pyrolyzed carbon. In addition, the results revealed that the high-resolution electrode pattern in the same footprint as that of the LPC-MSCs significantly affected the rate performance of the MSCs. Consequently, the proposed laser pyrolysis technique using black SU-8 provided simple and facile fabrication of porous, graphitic carbon electrodes for high-performance on-chip MSCs without high-temperature thermal pyrolysis.

System for Fabrication of Large-Area Roll Molds by Step-and-Repeat Liquid Transfer Imprint Lithography.

The effective production of nanopatterned films generally requires a nanopatterned roll mold with a large area. We report on a novel system to fabricate large-area roll molds by recombination of smaller patterned areas in a step-and-repeat imprint lithography process. The process is accomplished in a method similar to liquid transfer imprint lithography (LTIL). The stamp roll with a smaller area takes up the liquid resist by splitting from a donor substrate or a donor roll. The resist is then transferred from a stamp roll to an acceptor roll and stitched together in a longitudinal and, if necessary, in a circumferential direction. During transfer, the nanostructured resist is UV-exposed and crosslinked directly on the acceptor roll. The acceptor roll with the stitched and recombined stamp patterns is ready to be used as a large-area roll mold for roll-based imprinting. A system for this purpose was designed, and its operation was demonstrated taking the example of an acceptor roll of 1 m length and 250 mm diameter, which was covered by 56 patterned areas. Such a system represents an elegant and efficient tool to recombine small patterned areas directly on a large roll mold and opens the way for large-area roll-based processing.

Vertical alignments of graphene sheets spatially and densely piled for fast ion diffusion in compact supercapacitors.

Supercapacitors with porous carbon structures have high energy storage capacity. However, the porous nature of the carbon electrode, composed mainly of carbon nanotubes (CNTs) and graphene oxide (GO) derivatives, negatively impacts the volumetric electrochemical characteristics of the supercapacitors because of poor packing density (<0.5 g cm(-3)). Herein, we report a simple method to fabricate highly dense and vertically aligned reduced graphene oxide (VArGO) electrodes involving simple hand-rolling and cutting processes. Because of their vertically aligned and opened-edge graphene structure, VArGO electrodes displayed high packing density and highly efficient volumetric and areal electrochemical characteristics, very fast electrolyte ion diffusion with rectangular CV curves even at a high scan rate (20 V/s), and the highest volumetric capacitance among known rGO electrodes. Surprisingly, even when the film thickness of the VArGO electrode was increased, its volumetric and areal capacitances were maintained.

Synthesis of chemically bonded graphene/carbon nanotube composites and their application in large volumetric capacitance supercapacitors.

Chemically bonded graphene/carbon nanotube composites as flexible supercapacitor electrode materials are synthesized by amide bonding. Carbon nanotubes attached along the edges and onto the surface of graphene act as spacers to increase the electrolyte-accessible surface area. Our lamellar structure electrodes demonstrate the largest volumetric capacitance (165 F cm(-3) ) ever shown by carbon-based electrodes.

Selective gas transport through few-layered graphene and graphene oxide membranes.

Graphene is a distinct two-dimensional material that offers a wide range of opportunities for membrane applications because of ultimate thinness, flexibility, chemical stability, and mechanical strength. We demonstrate that few- and several-layered graphene and graphene oxide (GO) sheets can be engineered to exhibit the desired gas separation characteristics. Selective gas diffusion can be achieved by controlling gas flow channels and pores via different stacking methods. For layered (3- to 10-nanometer) GO membranes, tunable gas transport behavior was strongly dependent on the degree of interlocking within the GO stacking structure. High carbon dioxide/nitrogen selectivity was achieved by well-interlocked GO membranes in high relative humidity, which is most suitable for postcombustion carbon dioxide capture processes, including a humidified feed stream.

Efficient fabrication of wafer scale thin film of individualized single-walled carbon nanotubes by dual-nozzle spin casting.

In this paper, a dual-nozzle spin casting method was proposed to form a thin film of individualized single-walled carbon nanotubes (SWNTs) at the wafer scale. Each nozzle simultaneously ejected the SWNT solution and methanol, respectively. During the ejection process, two solutions were mixed at the contacting end of the nozzles and then dropped onto the substrate. Functionalization of the wafer substrate with the amine group improved the uniformity of the SWNT thin film as well as the adhesion between the individualized SWNTs and the substrate. The best condition of the spin casting involved the substrate functionalization using 3-aminopropyltriethosilane aqueous solution with a concentration of approximately 10 mM and a deposition velocity of approximately 5000 rpm. The root-mean-square roughness of the fabricated SWNT layer over the wafer substrate was found to be 1.4-1.8 nm, which indicated that the resultant thin film was one or two layers of SWNTs. The wafer scale SWNT thin film formed by dual-nozzle spin casting can be further used for the mass production and high integration of the SWNT nanoelectronic devices.

Quantitative displacement measurement of a nanotube cantilever with nanometer accuracy using epifluorescence microscopy.

A method to measure the deflection of a nanotube cantilever with nanometer accuracy in an air or liquid environment is presented. We attached fluorescent dyes at the end of a nanotube to detect its deflection. The nanotube cantilever was fabricated with a multiwalled carbon nanotube that is attached to the end of an electrochemically etched tungsten tip, and it was imaged in an epifluorescence microscope system. The fluorescence intensity distribution of the fluorescent particles at the end of the nanotube was approximated with a Gaussian and fitted by least-squares method. Finally, we were able to measure the displacement of the nanotube cantilever during electrostatic actuation with positional accuracy of a few nanometers. This technique can be applied to a manipulator or a force transducer on related a few piconewton forces.

Deterministic fabrication of carbon nanotube probes using the dielectrophoretic assembly and electrical detection.

We report the controlled dielectrophoretic assembly for the deterministic fabrication of carbon nanotube (CNT) probes. Electrical detection was applied to the dielectrophoretic assembly of CNT probes. Dielectrophoretic manipulation with an ac electric field of 5 MHz was used to form the CNT bridge across oppositely aligned tungsten tips (W-tips). A dc electric field was simultaneously applied to monitor the direct current flowing through the gap. The detected nanocurrent reveals that the CNT bridge is formed between W-tips in real time. We compared current data with bundle diameter of CNT probes in field emission scanning electron microscopy (FE-SEM) images. As the number of assembled CNTs increased, current was increased. With the obtained linear relationship, the number of the attached CNTs can be estimated without confirmation of the FE-SEM image. This combined use of the current detection method with dielectrophoretic manipulation will provide a reliable process for the fabrication of CNT probes.