Facile Synthesis of Mesoporous Nanohybrid Two-Dimensional Layered Ni-Cr-S and Reduced Graphene Oxide for High-Performance Hybrid Supercapacitors.

This study describes the single-step synthesis of a mesoporous layered nickel-chromium-sulfide (NCS) and its hybridization with single-layered graphene oxide (GO) using a facile, inexpensive chemical method. The conductive GO plays a critical role in improving the physicochemical and electrochemical properties of hybridized NCS/reduced GO (NCSG) materials. The optimized mesoporous nanohybrid NCSG is obtained when hybridized with 20% GO, and this material exhibits a very high specific surface area of 685.84 m2/g compared to 149.37 m2/g for bare NCS, and the pore diameters are 15.81 and 13.85 nm, respectively. The three-fold superior specific capacity of this optimal NCSG (1932 C/g) is demonstrated over NCS (676 C/g) at a current density of 2 A/g. A fabricated hybrid supercapacitor (HSC) reveals a maximum specific capacity of 224 C/g at a 5 A/g current density. The HSC reached an outstanding energy density of 105 Wh/kg with a maximum power density of 11,250 W/kg. A 4% decrement was observed during the cyclic stability study of the HSC over 5000 successive charge-discharge cycles at a 10 A/g current density. These results suggest that the prepared nanohybrid NCSG is an excellent cathode material for gaining a high energy density in an HSC.

High-Performance Washable PM2.5 Filter Fabricated with Laser-Induced Graphene.

This study demonstrates a novel application of laser-induced graphene (LIG) as a reusable conductive particulate matter (PM) filter. Four types of LIG-based filters were fabricated based on the laser-induced pyrolysis of thin polyimide (PI) sheets, each pyrolyzed on either a single side or both sides, with or without densification. The LIG filters exhibited a high removal efficiency while maintaining minimal pressure drop compared to a commercial fiberglass filter. The densified LIG (dLIG) filters displayed a higher PM2.5 removal efficiency (>99.86%) than regular LIG filters. The dLIG filters also exhibited excellent durability when tested for washability by ultrasonication in tap water. After being cleaned and left to dry, the structures of the dLIG filters were well-maintained; their filtration efficiencies were also well-maintained (less than a 7% change in PM2.5 removal efficiency), and their resistances only marginally increased (less than a 7% increase after five uses). These results demonstrate the robustness and reusability of the dLIG filters and the accessibility of their cleaning (not requiring aggressive cleaning agents). These promising features will enable the application of LIG in economical, scalable, and high-performance air cleaning.

Heat Scanning for the Fabrication of Conductive Fibers.

Conductive fibers are essential building blocks for implementing various functionalities in a textile platform that is highly conformable to mechanical deformation. In this study, two major techniques were developed to fabricate silver-deposited conductive fibers. First, a droplet-coating method was adopted to coat a nylon fiber with silver nanoparticles (AgNPs) and silver nanowires (AgNWs). While conventional dip coating uses a large ink pool and thus wastes coating materials, droplet-coating uses minimal quantities of silver ink by translating a small ink droplet along the nylon fiber. Secondly, the silver-deposited fiber was annealed by similarly translating a tubular heater along the fiber to induce sintering of the AgNPs and AgNWs. This heat-scanning motion avoids excessive heating and subsequent thermal damage to the nylon fiber. The effects of heat-scanning time and heater power on the fiber conductance were systematically investigated. A conductive fiber with a resistance as low as ~2.8 Ω/cm (0.25 Ω/sq) can be produced. Finally, it was demonstrated that the conductive fibers can be applied in force sensors and flexible interconnectors.

Simple fabrication of Co3O4 nanoparticles on N-doped laser-induced graphene for high-performance supercapacitors.

This study demonstrates a simple strategy to fabricate Co3O4 on N-doped laser-induced graphene (Co3O4-NLIG) based on duplicate laser pyrolysis, enabling the in situ generation of Co3O4 nanoparticles and heteroatom doping in laser-induced graphene (LIG). Morphological analyses reveal the uniform distribution of Co3O4 nanoparticles on the surface of the LIG structure. The modification of NLIG with Co3O4 nanoparticles results in impressive electrochemical performance due to the contributions from electric double-layer capacitance and pseudocapacitance. The optimal Co3O4-NLIG is produced at 20 wt% cobalt precursor loading (Co3O4-NLIG-20). In a three-electrode setup, this electrode exhibits a specific areal capacitance (C A) of 216.3 mF cm-2 at a current density of 0.5 mA cm-2 in a 1 M KOH electrolyte. When the optimal electrodes are assembled into a solid-state supercapacitor (Co3O4-NLIG-SC) using a poly(vinyl alcohol) phosphoric acid (PVA-H3PO4) gel electrolyte, a C A of 17.96 mF cm-2 is obtained with good cycling stability.

Laser Pyrolysis of Imprinted Furan Pattern for the Precise Fabrication of Microsupercapacitor Electrodes.

The design or dimension of micro-supercapacitor electrodes is an important factor that determines their performance. In this study, a microsupercapacitor was precisely fabricated on a silicon substrate by irradiating an imprinted furan micropattern with a CO2 laser beam under ambient conditions. Since furan is a carbon-abundant polymer, electrically conductive and porous carbon structures were produced by laser-induced pyrolysis. While the pyrolysis of a furan film in a general electric furnace resulted in severe cracks and delamination, the laser pyrolysis method proposed herein yielded porous carbon films without cracks or delamination. Moreover, as the imprinting process already designated the furan area for laser pyrolysis, high-precision patterning was achieved in the subsequent laser pyrolysis step. This two-step process exploited the superior resolution of imprinting for the fabrication of a laser-pyrolyzed carbon micropattern. As a result, the technical limitations of conventional laser direct writing could be overcome. The laser-pyrolyzed carbon structure was employed for microsupercapacitor electrodes. The microsupercapacitor showed a specific capacitance of 0.92 mF/cm2 at 1 mA/cm2 with a PVA-H2SO4 gel electrolyte, and retained an up to 88% capacitance after 10,000 charging/discharging cycles.

Hierarchically Structured Laser-Induced Graphene for Enhanced Boiling on Flexible Substrates.

Thermal management problems in high-power flexible electronics are exacerbated by the design complexity and requirement of stringent temperature control to prevent skin burns. Thus, effective heat dissipation methods applicable to flexible electronics on polymer substrates are an essential device design component. Accordingly, this study investigates the pool boiling heat transfer characteristics and potential enhancements, enabled by laser-induced graphene (LIG), which is both highly porous and bendable. Patterned LIG with a mesh spacing of 200 µm was formed on flexible polyimide substrates by laser direct writing, and the resulting surfaces exhibited enhanced heat transfer characteristics. Pool boiling experiments were conducted with an FC-72 working fluid to investigate the heat removal capability of LIG, and its performance was further improved by separating the liquid supply passages from the vapor escape routes. Overall, the inclusion of LIG resulted in a 2- to 3-fold increase in both the critical heat flux (33.6 W/cm2) and heat transfer coefficient (7.6 kW/(m2·K)), compared to pristine polyimide films.

Development of a Protein Microarray Chip with Enhanced Fluorescence for Identification of Semen and Vaginal Fluid.

The detection of body fluids has been used to identify a suspect and build a criminal case. As the amount of evidence collected at a crime site is limited, a multiplex identification system for body fluids using a small amount of sample is required. In this study, we proposed a multiplex detection platform using an Ag vertical nanorod metal enhanced fluorescence (MEF) substrate for semen and vaginal fluid (VF), which are important evidence in cases of sexual crime. The Ag nanorod MEF substrate with a length of 500 nm was fabricated by glancing angle deposition, and amino functionalization was conducted to improve binding ability. The effect of incubation time was analyzed, and an incubation time of 60 min was selected, at which the fluorescence signal was saturated. To assess the performance of the developed identification chip, the identification of semen and VF was carried out. The developed sensor could selectively identify semen and VF without any cross-reactivity. The limit of detection of the fabricated microarray chip was 10 times better than the commercially available rapid stain identification (RSID) Semen kit.

Laser-Induced Reduction of Graphene Oxide by Intensity-Modulated Line Beam for Supercapacitor Applications.

Supercapacitors are irreplaceable energy-storage devices for high power output and rapid charge/discharge of electrical energy. In this study, the laser-based fabrication of reduced graphene oxide (rGO) electrodes for supercapacitors is demonstrated with several new features of laser irradiation. A conventional CO2 laser irradiation system is equipped with (1) a nitrogen blower to avoid combustion of the GO paper, (2) a cylindrical lens for producing a wide line beam, and (3) an optical chopper system for generating an intensity-modulated laser beam. Scanning of the intensity-modulated line beam transforms an extended area of GO into chemically reduced and physically porous graphene. The effects of the laser beam modifications and scanning parameters on the electrochemical performance of the rGO electrode are investigated. The rGO electrode exhibits a high specific capacitance (up to ∼130 F/g) at a current density of 1 A/g. This work can serve as a reference for the process optimization of laser-induced GO reduction.

Effect of Enhanced Thermal Stability of Alumina Support Layer on Growth of Vertically Aligned Single-Walled Carbon Nanotubes and Their Application in Nanofiltration Membranes.

We investigate the thermal stability of alumina supporting layers sputtered at different conditions and its effect on the growth of aligned single-walled carbon nanotube arrays. Radio frequency magnetron sputtering of alumina under oxygen-argon atmosphere produces a Si-rich alumina alloy film on a silicon substrate. Atomic force microscopy on the annealed catalysts reveals that Si-rich alumina films are more stable than alumina layers with low Si content at the elevated temperatures at which the growth of single-walled carbon nanotubes is initiated. The enhanced thermal stability of the Si-rich alumina layer results in a narrower (< 2.2 nm) diameter distribution of the single-walled carbon nanotubes. Thanks to the smaller diameters of their nanotube pores, membranes fabricated with vertically aligned nanotubes grown on the stable layers display improved ion selectivity.

Directed dewetting of amorphous silicon film by a donut-shaped laser pulse.

Irradiation of a thin film with a beam-shaped laser is proposed to achieve site-selectively controlled dewetting of the film into nanoscale structures. As a proof of concept, the laser-directed dewetting of an amorphous silicon thin film on a glass substrate is demonstrated using a donut-shaped laser beam. Upon irradiation of a single laser pulse, the silicon film melts and dewets on the substrate surface. The irradiation with the donut beam induces an unconventional lateral temperature profile in the film, leading to thermocapillary-induced transport of the molten silicon to the center of the beam spot. Upon solidification, the ultrathin amorphous silicon film is transformed to a crystalline silicon nanodome of increased height. This morphological change enables further dimensional reduction of the nanodome as well as removal of the surrounding film material by isotropic silicon etching. These results suggest that laser-based dewetting of thin films can be an effective way for scalable manufacturing of patterned nanostructures.

Highly flexible, all solid-state micro-supercapacitors from vertically aligned carbon nanotubes.

We report a highly flexible planar micro-supercapacitor with interdigitated finger electrodes of vertically aligned carbon nanotubes (VACNTs). The planar electrode structures are patterned on a thin polycarbonate substrate with a facile, maskless laser-assisted dry transfer method. Sputtered Ni is used to reduce the in-plane resistance of the VACNT electrodes. An ionogel, an ionic liquid in a semi-solid matrix, is used as an electrolyte to form a fully solid-state device. We measure a specific capacitance of 430 µF cm(-2) for a scan rate of 0.1 V s(-1) and achieve rectangular cyclic voltammograms at high scan rates of up to 100 V s(-1). Minimal change in capacitance is observed under bending. Mechanical fatigue tests with more than 1000 cycles confirm the high flexibility and durability of the novel material combination chosen for this device. Our results indicate that this scalable and facile fabrication technique shows promise for application in integrated energy storage for all solid-state flexible microdevices.

In situ monitoring of laser-assisted hydrothermal growth of ZnO nanowires: thermally deactivating growth kinetics.

The laser-assisted hydrothermal growth kinetics of a cluster of ZnO nanowires are studied based on optical in situ growth monitoring. The growth yields are orders of magnitude higher than those of conventional hydrothermal methods that use bulk heating. This remarkable improvement is attributed to suppression of precursor depletion occurring by homogeneous growth reactions, as well as to enhanced mass transport. The obtained in situ data show gradually decaying growth kinetics even with negligible precursor consumption. It is revealed that the growth deceleration is caused by thermal deactivation resulting from heat dissipation through the growing nanowires. Finally, it is demonstrated that the tailored temporal modulation of the input power enables sustained growth to extended dimensions. These results provide a key to highly efficient use of growth precursors that has been pursued for industrial use of this functional metal oxide semiconductor.

Laser-assisted simultaneous transfer and patterning of vertically aligned carbon nanotube arrays on polymer substrates for flexible devices.

We demonstrate a laser-assisted dry transfer technique for assembling patterns of vertically aligned carbon nanotube arrays on a flexible polymeric substrate. A laser beam is applied to the interface of a nanotube array and a polycarbonate sheet in contact with one another. The absorbed laser heat promotes nanotube adhesion to the polymer in the irradiated regions and enables selective pattern transfer. A combination of the thermal transfer mechanism with rapid direct writing capability of focused laser beam irradiation allows us to achieve simultaneous material transfer and direct micropatterning in a single processing step. Furthermore, we demonstrate that malleability of the nanotube arrays transferred onto a flexible substrate enables post-transfer tailoring of electric conductance by collapsing the aligned nanotubes in different directions. This work suggests that the laser-assisted transfer technique provides an efficient route to using vertically aligned nanotubes as conductive elements in flexible device applications.

In situ TEM near-field optical probing of nanoscale silicon crystallization.

Laser-based processing enables a wide variety of device configurations comprising thin films and nanostructures on sensitive, flexible substrates that are not possible with more traditional thermal annealing schemes. In near-field optical probing, only small regions of a sample are illuminated by the laser beam at any given time. Here we report a new technique that couples the optical near-field of the laser illumination into a transmission electron microscope (TEM) for real-time observations of the laser-materials interactions. We apply this technique to observe the transformation of an amorphous confined Si volume to a single crystal of Si using laser melting. By confinement of the material volume to nanometric dimensions, the entire amorphous precursor is within the laser spot size and transformed into a single crystal. This observation provides a path for laser processing of single-crystal seeds from amorphous precursors, a potentially transformative technique for the fabrication of solar cells and other nanoelectronic devices.

Growth kinetics of vertically aligned carbon nanotube arrays in clean oxygen-free conditions.

Vertically aligned carbon nanotubes (CNTs) are an important technological system, as well as a fascinating system for studying basic principles of nanomaterials synthesis; yet despite continuing efforts for the past decade many important questions about this process remain largely unexplained. We present a series of parametric ethylene chemical vapor deposition growth studies in a "hot-wall" reactor using ultrapure process gases that reveal the fundamental kinetics of the CNT growth. Our data show that the growth rate is proportional to the concentration of the carbon feedstock and monotonically decreases with the concentration of hydrogen gas and that the most important parameter determining the rate of the CNT growth is the production rate of active carbon precursor in the gas phase reaction. The growth termination times obtained with the purified gas mixtures were strikingly insensitive to variations in both hydrogen and ethylene pressures ruling out the carbon encapsulation of the catalyst as the main process termination cause.

pH-tunable ion selectivity in carbon nanotube pores.

The selectivity of ion transport in nanochannels is of primary importance for a number of physical, chemical, and biological processes ranging from fluid separation to ion-channel-regulated cellular processes. Fundamental understanding of these phenomena requires model nanochannels with well-defined and controllable structural properties. Carbon nanotubes provide an ideal choice for nanofluidic studies because of their simple chemistry and structure, the atomic scale smoothness and chemical inertness of the graphitic walls, and the tunability of their diameter and length. Here, we investigate the selectivity of single and, for the first time, binary salt mixtures transport through narrow carbon nanotubes that act as the only pores in a silicon nitride membrane. We demonstrate that negatively charged carboxylic groups are responsible for the ion rejection performance of carbon nanotube pores and that ion permeation of small salts can be tuned by varying solution pH. Investigation of the effect of solution composition and ion valences for binary electrolytes with common cation in a pressure-driven flow reveals that the addition of slower diffusing multivalent anions to a solution of faster diffusing monovalent anions favors permeation of the monovalent anion. Larger fractions and valences of the added multivalent anions lower the rejection of the monovalent anion. In some cases, we observe negative rejection at low monovalent ion content.

Mechanism and kinetics of growth termination in controlled chemical vapor deposition growth of multiwall carbon nanotube arrays.

We have investigated growth kinetics of multiwall carbon nanotube (MWCNT) arrays produced by catalytic thermal decomposition of ethylene gas in hydrogen, water, and argon mixture. The MWCNT growth rate exhibits a nonmonotonic dependence on total pressure and reaches a maximum at approximately 750 Torr of total pressure. Water concentrations in excess of 3000 ppm lead to the decrease in the observed growth rate. Optimal pressure and water concentration combination results in a reliable growth of well-aligned MWCNT arrays at a maximum growth rate of approximately 30 microm/min. These MWCNT arrays can reach heights of up to 1 mm with typical standard deviations for the array height of less than 8% over a large number of process runs spread over the time of 8 months. Nanotube growth rate in this optimal growth region remains essentially constant until growth reaches an abrupt and irreversible termination. We present a quantitative model that shows how accumulation of the amorphous carbon patches at the catalyst particle surface and the carbon diffusion to the growing nanotube perimeter causes this abrupt growth cessation. The influence of the partial pressures of ethylene and hydrogen on the ethylene decomposition driving force explains the nonlinear behavior of the growth rate as a function of total process pressure.