Design of high SERS sensitive substrates based on branched Ti nanorods.

This paper reports a rational design of branched titanium (Ti) nanorods formed by glancing angle physical vapor deposition and their applications as substrates for surface-enhanced Raman scattering (SERS). Ti nanorods with branches have larger surface areas than non-branched nanorods. However, Ti surface oxidizes easily resulting in very little SERS effect. The SERS sensitivity of the branched titanium nanorod is improved by annealing Ti nanorods in nitrogen in an effort to reduce oxidation. Additionally, the plasmonic resonance of the branched titanium nanorod is further improved by coating the top of the nanorods and branches with silver (Ag). The sensitivity of the SERS substrates is about 3700% that of as-deposited branched Ti nanorods with a native oxide layer. Our investigation provides a mechanism to fabricate sensitive SERS sensors of Ti nanorods that are known to be thermally and chemically stable and compatible with silicon-based electronics.

Catalyst-free synthesis of sub-5 nm silicon nanowire arrays with massive lattice contraction and wide bandgap.

The need for miniaturized and high-performance devices has attracted enormous attention to the development of quantum silicon nanowires. However, the preparation of abundant quantities of silicon nanowires with the effective quantum-confined dimension remains challenging. Here, we prepare highly dense and vertically aligned sub-5 nm silicon nanowires with length/diameter aspect ratios greater than 10,000 by developing a catalyst-free chemical vapor etching process. We observe an unusual lattice reduction of up to 20% within ultra-narrow silicon nanowires and good oxidation stability in air compared to conventional silicon. Moreover, the material exhibits a direct optical bandgap of 4.16 eV and quasi-particle bandgap of 4.75 eV with the large exciton binding energy of 0.59 eV, indicating the significant phonon and electronic confinement. The results may provide an opportunity to investigate the chemistry and physics of highly confined silicon quantum nanostructures and may explore their potential uses in nanoelectronics, optoelectronics, and energy systems.

Graphitic Nanocup Architectures for Advanced Nanotechnology Applications.

The synthesis of controllable hollow graphitic architectures can engender revolutionary changes in nanotechnology. Here, we present the synthesis, processing, and possible applications of low aspect ratio hollow graphitic nanoscale architectures that can be precisely engineered into morphologies of (1) continuous carbon nanocups, (2) branched carbon nanocups, and (3) carbon nanotubes-carbon nanocups hybrid films. These complex graphitic nanocup-architectures could be fabricated by using a highly designed short anodized alumina oxide nanochannels, followed by a thermal chemical vapor deposition of carbon. The highly porous film of nanocups is mechanically flexible, highly conductive, and optically transparent, making the film attractive for various applications such as multifunctional and high-performance electrodes for energy storage devices, nanoscale containers for nanogram quantities of materials, and nanometrology.

Ultrafast structural evolution and formation of linear carbon chains in single-walled carbon nanotube networks by femtosecond laser irradiation.

Inter-allotropic structural transformation of sp2 structured nanocarbon is a topic of fundamental and technological interest in scalable nanomanufacturing. Such modifications usually require extremely high temperature or high-energy irradiation, and are usually a destructive and time-consuming process. Here, we demonstrate a method for engineering a molecular structure of single-walled carbon nanotubes (SWNTs) and their network properties by femtosecond laser irradiation. This method allows effective coalescence between SWNTs, transforming them into other allotropic nanocarbon structures (double-walled, triple-walled and multi-walled nanotubes) with the formation of linear carbon chains. The nanocarbon network created by this laser-induced transformation process shows extraordinarily strong coalescence induced mode in Raman spectra and two-times enhanced electrical conductivity. This work suggests a powerful method for engineering sp2 carbon allotropes and their junctions, which provides possibilities for next generation materials with structural hybridization at the atomic scale.

Measuring Interfacial Adhesion of Carbon Nanotube Bundles and Electrospun Polymer Fibers.

Adhesion at the dissimilar interface of single wall carbon nanotube (SWCNT) bundles and electrospun polymer nanofibers (Espun) was directly measured using a nano cheese cutter. A sample fiber suspended at the tip of an atomic force microscope cantilever and another freestanding fiber on a mica substrate were arranged in a cross-cylinder configuration and allowed to adhere. External tensile load led to spontaneous detachment or "pull-off". Adhesion was shown to be dominated by van der Waals attraction, and the detachment process conforms to the classical Maugis parameter in the JKR-DMT transition.

Polypyrrole Films with Micro/Nanosphere Shapes for Electrodes of High-Performance Supercapacitors.

We demonstrate a simple and efficient one-step procedure for synthesizing a solid state polypyrrole (PPy) thin film for supercapacitor applications using alternating current impedance spectroscopy. By controlling the frequency and amplitude we were able to create unique PPy nano/microstructures with a particular morphology of the loop. Our PPy micro/nanosphere shows extremely high capacitance of 568 F/g, which is close to the theoretical value of 620 F/g and 20-100% higher than that of other reported PPy electrodes. Most of all, this material presents high capacitance and significantly improved electrochemical stability without pulverization of its structure, demonstrating 77% retention of the capacitance value even after 10 000 charge/discharge cycles. These results are a consequence of the larger surface area and adequate porosity generated due to the balance between the nano/micro PPy loops. This created porous structure also allows the favored penetration of electrolyte and high ion mobility within the polymer and prevents the mechanical failure of the physical structure during volume variation associated with the insertion/deinsertion of ions upon cycling.

Vapor-Phase-Gating-Induced Ultrasensitive Ion Detection in Graphene and Single-Walled Carbon Nanotube Networks.

Designing ultrasensitive detectors often requires complex architectures, high-voltage operations, and sophisticated low-noise measurements. In this work, it is shown that simple low-bias two-terminal DC-conductance values of graphene and single-walled carbon nanotubes are extremely sensitive to ionized gas molecules. Incident ions form an electrode-free, dielectric- or electrolyte-free, bias-free vapor-phase top-gate that can efficiently modulate carrier densities up to ≈0.6 × 1013 cm-2 . Surprisingly, the resulting current changes are several orders of magnitude larger than that expected from conventional electrostatic gating, suggesting the possible role of a current-gain inducing mechanism similar to those seen in photodetectors. These miniature detectors demonstrate charge-current amplification factor values exceeding 108 A C-1 in vacuum with undiminished responses in open air, and clearly distinguish between positive and negative ions sources. At extremely low rates of ion incidence, detector currents show stepwise changes with time, and calculations suggest that these stepwise changes can result from arrival of individual ions. These sensitive ion detectors are used to demonstrate a proof-of-concept low-cost, amplifier-free, light-emitting-diode-based low-power ion-indicator.

Inter-allotropic transformations in the heterogeneous carbon nanotube networks.

The allotropic transformations of carbon provide an immense technological interest for tailoring the desired molecular structures in the scalable nanoelectronic devices. Herein, we explore the effects of morphology and geometric alignment of the nanotubes for the re-engineering of carbon bonds in the heterogeneous carbon nanotube (CNT) networks. By applying alternating voltage pulses and electrical forces, the single-walled CNTs in networks were predominantly transformed into other predetermined sp2 carbon structures (multi-walled CNTs and multi-layered graphitic nanoribbons), showing a larger intensity in a coalescence-induced mode of Raman spectra with the increasing channel width. Moreover, the transformed networks have a newly discovered sp2-sp3 hybrid nanostructures in accordance with the alignment. The sp3 carbon structures at the small channel are controlled, such that they contain up to about 29.4% networks. This study provides a controllable method for specific types of inter-allotropic transformations/hybridizations, which opens up the further possibility for the engineering of nanocarbon allotropes in the robust large-scale network-based devices.

Highly Anisotropic Adhesive Film Made from Upside-Down, Flat, and Uniform Vertically Aligned CNTs.

We have created a multifunctional dry adhesive film with transferred vertically aligned carbon nanotubes (VA-CNTs). This unique VA-CNT film was fabricated by a multistep transfer process, converting the flat and uniform bottom of VA-CNTs grown on atomically flat silicon wafer substrates into the top surface of an adhesive layer. Unlike as-grown VA-CNTs, which have a nonuniform surface, randomly entangled CNT arrays, and a weak interface between the CNTs and substrates, this transferred VA-CNT film shows an extremely high coefficient of static friction (COF) of up to 60 and a shear adhesion force 30 times higher (12 N/cm2) than that of the as-grown VA-CNTs under a very small preloading of 0.2 N/cm2. Moreover, a near-zero normal adhesion force was observed with 20 mN/cm2 preloading and a maximum 100-µm displacement in a piezo scanner, demonstrating ideal properties for an artificial gecko foot. Using this unique structural feature and anisotropic adhesion properties, we also demonstrate effective removal and assembly of nanoparticles into organized micrometer-scale circular and line patterns by a single brushing of this flat and uniform VA-CNT film.

Printing Highly Controlled Suspended Carbon Nanotube Network on Micro-patterned Superhydrophobic Flexible Surface.

Suspended single-walled carbon nanotubes (SWCNTs) offer unique functionalities for electronic and electromechanical systems. Due to their outstanding flexible nature, suspended SWCNT architectures have great potential for integration into flexible electronic systems. However, current techniques for integrating SWCNT architectures with flexible substrates are largely absent, especially in a manner that is both scalable and well controlled. Here, we present a new nanostructured transfer paradigm to print scalable and well-defined suspended nano/microscale SWCNT networks on 3D patterned flexible substrates with micro- to nanoscale precision. The underlying printing/transfer mechanism, as well as the mechanical, electromechanical, and mechanical resonance properties of the suspended SWCNTs are characterized, including identifying metrics relevant for reliable and sensitive device structures. Our approach represents a fast, scalable and general method for building suspended nano/micro SWCNT architectures suitable for flexible sensing and actuation systems.

Scalable Transfer of Suspended Two-Dimensional Single Crystals.

Large-scale suspended architectures of various two-dimensional (2D) materials (MoS2, MoSe2, WS2, and graphene) are demonstrated on nanoscale patterned substrates with different physical and chemical surface properties, such as flexible polymer substrates (polydimethylsiloxane), rigid Si substrates, and rigid metal substrates (Au/Ag). This transfer method represents a generic, fast, clean, and scalable technique to suspend 2D atomic layers. The underlying principle behind this approach, which employs a capillary-force-free wet-contact printing method, was studied by characterizing the nanoscale solid-liquid-vapor interface of 2D layers with respect to different substrates. As a proof-of-concept, a photodetector of suspended MoS2 has been demonstrated with significantly improved photosensitivity. This strategy could be extended to several other 2D material systems and open the pathway toward better optoelectronic and nanoelectromechnical systems.

Sculpting carbon bonds for allotropic transformation through solid-state re-engineering of -sp2 carbon.

Carbon forms one of nature's strongest chemical bonds; its allotropes having provided some of the most exciting scientific discoveries in recent times. The possibility of inter-allotropic transformations/hybridization of carbon is hence a topic of immense fundamental and technological interest. Such modifications usually require extreme conditions (high temperature, pressure and/or high-energy irradiations), and are usually not well controlled. Here we demonstrate inter-allotropic transformations/hybridizations of specific types that appear uniformly across large-area carbon networks, using moderate alternating voltage pulses. By controlling the pulse magnitude, small-diameter single-walled carbon nanotubes can be transformed predominantly into larger-diameter single-walled carbon nanotubes, multi-walled carbon nanotubes of different morphologies, multi-layered graphene nanoribbons or structures with sp(3) bonds. This re-engineering of carbon bonds evolves via a coalescence-induced reconfiguration of sp(2) hybridization, terminates with negligible introduction of defects and demonstrates remarkable reproducibility. This reflects a potential step forward for large-scale engineering of nanocarbon allotropes and their junctions.

Carbon nanotube core graphitic shell hybrid fibers.

A carbon nanotube yarn core graphitic shell hybrid fiber was fabricated via facile heat treatment of epoxy-based negative photoresist (SU-8) on carbon nanotube yarn. The effective encapsulation of carbon nanotube yarn in carbon fiber and a glassy carbon outer shell determines their physical properties. The higher electrical conductivity (than carbon fiber) of the carbon nanotube yarn overcomes the drawbacks of carbon fiber/glassy carbon, and the better properties (than carbon nanotubes) of the carbon fiber/glassy carbon make up for the lower thermal and mechanical properties of the carbon nanotube yarn via synergistic hybridization without any chemical doping and additional processes.

High-performance H(2)S detection by redox reactions in semiconducting carbon nanotube-based devices.

Here we report the highly effective detection of hydrogen sulfide (H2S) gas by redox reactions based on single-walled carbon nanotubes (SWCNTs) functionalized with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a catalyst and we also discuss the important role of water vapor in the electrical conductivity of SWCNTs during the sensing of H2S molecules. To explore the H2S sensing mechanism, we investigate the adsorption properties of H2S on carbon nanotubes (CNTs) and the effects of the TEMPO functionalization using first-principles density functional theory (DFT) and we summarize current changes of devices resulting from the redox reactions in the presence of H2S. The semiconducting-SWCNT (s-SWCNT) device functionalized with TEMPO shows a very high sensitivity of 420% at 60% humidity, which is 17 times higher than a bare s-SWCNT device under dry conditions. Our results offer promising prospects for personal safety and real-time monitoring of H2S gases with the highest sensitivity and low power consumption and potentially at a low cost.

Liquid metal nanodroplet dynamics inside nanocontainers.

Here we report direct observations of spatial movements of nanodroplets of Pb metal trapped inside sealed carbon nanocontainers. We find drastic changes in the mobility of the liquid droplets as the particle size increases from a few to a few ten nanometers. In open containers the droplet becomes immobile and readily evaporates to the vacuum environment. The particle mobility strongly depends on confinement, particle size, and wetting on the enclosed surface. The collisions between droplets increase mobility but the tendency is reversed if collisions lead to droplet coalescence. The dynamics of confined nanodroplets could provide new insights into the activity of nanostructures in spatially constrained geometries.

Tunable graphene-silicon heterojunctions for ultrasensitive photodetection.

We present the photodetection properties of graphene/Si heterojunctions both in the photocurrent and photovoltage modes. Monolayer graphene/Si junctions were found to be excellent weak-signal detectors with photovoltage responsivity exceeding 10(7) V/W and with noise-equivalent-power reaching ∼1 pW/Hz(1/2), potentially capable of distinguishing materials with transmittance, T = 0.9995 in a 0.5 s integration time. In the photocurrent mode, the response was found to remain linear over at least six decades of incident power (P), with tunable responsivity up to 435 mA/W (corresponding to incident photon conversion efficiency (IPCE) > 65%) obtained by layer thickening and doping. With millisecond-scale responses and ON/OFF ratios exceeding 10(4), these photodiodes are highly suitable for tunable and scalable broadband (400 < λ < 900 nm) photodetectors, photometers, and millisecond-response switching, spectroscopic and imaging devices, and further, and are architecturally compatible with on-chip low-power optoelectronics.

A facile route for 3D aerogels from nanostructured 1D and 2D materials.

Aerogels have numerous applications due to their high surface area and low densities. However, creating aerogels from a large variety of materials has remained an outstanding challenge. Here, we report a new methodology to enable aerogel production with a wide range of materials. The method is based on the assembly of anisotropic nano-objects (one-dimensional (1D) nanotubes, nanowires, or two-dimensional (2D) nanosheets) into a cross-linking network from their colloidal suspensions at the transition from the semi-dilute to the isotropic concentrated regime. The resultant aerogels have highly porous and ultrafine three-dimensional (3D) networks consisting of 1D (Ag, Si, MnO(2), single-walled carbon nanotubes (SWNTs)) and 2D materials (MoS(2), graphene, h-BN) with high surface areas, low densities, and high electrical conductivities. This method opens up a facile route for aerogel production with a wide variety of materials and tremendous opportunities for bio-scaffold, energy storage, thermoelectric, catalysis, and hydrogen storage applications.

Carbon nanotube-nanocup hybrid structures for high power supercapacitor applications.

Here, we design and develop high-power electric double-layer capacitors (EDLCs) using carbon-based three dimensional (3-D) hybrid nanostructured electrodes. 3-D hybrid nanostructured electrodes consisting of vertically aligned carbon nanotubes (CNTs) on highly porous carbon nanocups (CNCs) were synthesized by a combination of anodization and chemical vapor deposition techniques. A 3-D electrode-based supercapacitor showed enhanced areal capacitance by accommodating more charges in a given footprint area than that of a conventional CNC-based device.

Transparent, flexible supercapacitors from nano-engineered carbon films.

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications.

Bundling dynamics regulates the active mechanics and transport in carbon nanotube networks and their nanocomposites.

High-density carbon nanotube networks (CNNs) continue to attract interest as active elements in nanoelectronic devices, nanoelectromechanical systems (NEMS) and multifunctional nanocomposites. The interplay between the network nanostructure and its properties is crucial, yet current understanding remains limited to the passive response. Here, we employ a novel superstructure consisting of millimeter-long vertically aligned single walled carbon nanotubes (SWCNTs) sandwiched between polydimethylsiloxane (PDMS) layers to quantify the effect of two classes of mechanical stimuli, film densification and stretching, on the electronic and thermal transport across the network. The network deforms easily with an increase in the electrical and thermal conductivities, suggestive of a floppy yet highly reconfigurable network. Insight from atomistically informed coarse-grained simulations uncover an interplay between the extent of lateral assembly of the bundles, modulated by surface zipping/unzipping, and the elastic energy associated with the bent conformations of the nanotubes/bundles. During densification, the network becomes highly interconnected yet we observe a modest increase in bundling primarily due to the reduced spacing between the SWCNTs. The stretching, on the other hand, is characterized by an initial debundling regime as the strain accommodation occurs via unzipping of the branched interconnects, followed by rapid rebundling as the strain transfers to the increasingly aligned bundles. In both cases, the increase in the electrical and thermal conductivity is primarily due to the increase in bundle size; the changes in network connectivity have a minor effect on the transport. Our results have broad implications for filamentous networks of inorganic nanoassemblies composed of interacting tubes, wires and ribbons/belts.