Growth and Transfer of Seamless 3D Graphene-Nanotube Hybrids.

Seamlessly connected graphene and carbon nanotube hybrids (GCNTs) have great potential as carbon platform structures in electronics due to their high conductivity and high surface area. Here, we introduce a facile method for making patterned GCNTs and their intact transfer onto other substrates. The mechanism for selective growth of vertically aligned CNTs (VA-CNTs) on the patterned graphene is discussed. The complete transfer of the GCNT pattern onto other substrates is possible because of the mechanical strength of the GCNT hybrids. Electrical conductivity measurements of the transferred GCNT structures show Ohmic contact through the VA-CNTs to graphene--evidence of its integrity after the transfer process.

Graphene quantum dots as a highly efficient solution-processed charge trapping medium for organic nano-floating gate memory.

A highly efficient solution-processible charge trapping medium is a prerequisite to developing high-performance organic nano-floating gate memory (NFGM) devices. Although several candidates for the charge trapping layer have been proposed for organic memory, a method for significantly increasing the density of stored charges in nanoscale layers remains a considerable challenge. Here, solution-processible graphene quantum dots (GQDs) were prepared by a modified thermal plasma jet method; the GQDs were mostly composed of carbon without any serious oxidation, which was confirmed by x-ray photoelectron spectroscopy. These GQDs have multiple energy levels because of their size distribution, and they can be effectively utilized as charge trapping media for organic NFGM applications. The NFGM device exhibited excellent reversible switching characteristics, with an on/off current ratio greater than 10(6), a stable retention time of 10(4) s and reliable cycling endurance over 100 cycles. In particular, we estimated that the GQDs layer trapped ∼7.2 × 10(12) cm(-2) charges per unit area, which is a much higher density than those of other solution-processible nanomaterials, suggesting that the GQDs layer holds promise as a highly efficient nanoscale charge trapping material.

Three-Dimensional Networked Nanoporous Ta2O(5-x) Memory System for Ultrahigh Density Storage.

Oxide-based resistive memory systems have high near-term promise for use in nonvolatile memory. Here we introduce a memory system employing a three-dimensional (3D) networked nanoporous (NP) Ta2O5-x structure and graphene for ultrahigh density storage. The devices exhibit a self-embedded highly nonlinear I-V switching behavior with an extremely low leakage current (on the order of pA) and good endurance. Calculations indicated that this memory architecture could be scaled up to a ∼162 Gbit crossbar array without the need for selectors or diodes normally used in crossbar arrays. In addition, we demonstrate that the voltage point for a minimum current is systematically controlled by the applied set voltage, thereby offering a broad range of switching characteristics. The potential switching mechanism is suggested based upon the transformation from Schottky to Ohmic-like contacts, and vice versa, depending on the movement of oxygen vacancies at the interfaces induced by the voltage polarity, and the formation of oxygen ions in the pores by the electric field.

Organic nonvolatile memory devices with charge trapping multilayer graphene film.

We fabricated an array-type organic nonvolatile memory device with multilayer graphene (MLG) film embedded in polyimide (PI) layers. The memory devices showed a high ON/OFF ratio (over 10(6)) and a long retention time (over 10(4) s). The switching of the Al/PI/MLG/PI/Al memory devices was due to the presence of the MLG film inserted into the PI layers. The double-log current-voltage characteristics could be explained by the space-charge-limited current conduction based on a charge-trap model. A conductive atomic force microscopy found that the conduction paths in the low-resistance ON state were distributed in a highly localized area, which was associated with a carbon-rich filamentary switching mechanism.

Flexible organic solar cells composed of P3HT:PCBM using chemically doped graphene electrodes.

Flexible organic solar cells (OSCs) composed of blended films of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) were fabricated and investigated with chemically doped multilayer graphene films as transparent and conducting electrodes on plastic substrates. The sheet resistance of the chemically doped graphene film was reduced to half of its original value, resulting in a significant performance enhancement of OSCs featuring doped graphene electrodes. Moreover, there was no substantial variation observed in the fill factor and power conversion efficiency values of the flexible OSCs under bending conditions. A power conversion efficiency of ~2.5% for flexible OSCs with doped graphene electrodes was observed under bending conditions, even up to a 5.2 mm bending radius.

Enhancement in the photodetection of ZnO nanowires by introducing surface-roughness-induced traps.

We investigated the enhanced photoresponse of ZnO nanowire transistors that was introduced with surface-roughness-induced traps by a simple chemical treatment with isopropyl alcohol (IPA). The enhanced photoresponse of IPA-treated ZnO nanowire devices is attributed to an increase in adsorbed oxygen on IPA-induced surface traps. The results of this study revealed that IPA-treated ZnO nanowire devices displayed higher photocurrent gains and faster photoswitching speed than transistors containing unmodified ZnO nanowires. Thus, chemical treatment with IPA can be a useful method for improving the photoresponse of ZnO nanowire devices.

Nonvolatile write-once-read-many times memory devices based on the composites of poly(4-vinylphenol)/Vulcan XC-72.

We fabricated write-once-read-many times (WORM) type organic memory devices in 8 x 8 cross-bar structure. The active material for organic based WORM memory devices is mixture of both poly(4-vinyphenol) (PVP) and Vulcan XC-72s. From the electrical characteristics of the WORM memory devices, we observed two different resistance states, low resistance state and high resistance state, with six orders of ON/OFF ratio (I(ON)/I(OFF) - 10(6)). In addition, the WORM memory devices were maintained for longer than 50000 seconds without any serious degradation.

Unipolar bistable switching of organic non-volatile memory devices with poly(styrene-co-styrenesulfonic acid Na).

We demonstrated unipolar organic bistable memory devices with 8 x 8 cross-bar array type structure. The active material for the organic non-volatile memory devices is poly(styrene-co-styrenesulfonic acid Na) (PSSANa). From the electrical measurements of the PSSANa organic memory devices, we observed rewritable unipolar switching behaviors with a stable endurance and narrow cumulative probability. Also the PSSANa memory devices exhibited a uniform cell-to-cell switching with a high ON/OFF ratio of approximately 10(5) and good retention time of approximately 10(4) seconds without significant degradation.

Structurally Engineered Nanoporous Ta2O5-x Selector-Less Memristor for High Uniformity and Low Power Consumption.

A memristor architecture based on metal-oxide materials would have great promise in achieving exceptional energy efficiency and higher scalability in next-generation electronic memory systems. Here, we propose a facile method for fabricating selector-less memristor arrays using an engineered nanoporous Ta2O5-x architecture. The device was fabricated in the form of crossbar arrays, and it functions as a switchable rectifier with a self-embedded nonlinear switching behavior and ultralow power consumption (∼2.7 × 10-6 W), which results in effective suppression of crosstalk interference. In addition, we determined that the essential switching elements, such as the programming power, the sneak current, the nonlinearity value, and the device-to-device uniformity, could be enhanced by in-depth structural engineering of the pores in the Ta2O5-x layer. Our results, on the basis of the structural engineering of metal-oxide materials, could provide an attractive approach for fabricating simple and cost-efficient memristor arrays with acceptable device uniformity and low power consumption without the need for additional addressing selectors.

Laser-Induced Graphene in Controlled Atmospheres: From Superhydrophilic to Superhydrophobic Surfaces.

The modification of graphene-based materials is an important topic in the field of materials research. This study aims to expand the range of properties for laser-induced graphene (LIG), specifically to tune the hydrophobicity and hydrophilicity of the LIG surfaces. While LIG is normally prepared in the air, here, using selected gas atmospheres, a large change in the water contact angle on the as-prepared LIG surfaces has been observed, from 0° (superhydrophilic) when using O2 or air, to >150° (superhydrophobic) when using Ar or H2 . Characterization of the newly derived surfaces shows that the different wetting properties are due to the surface morphology and chemical composition of the LIG. Applications of the superhydrophobic LIG are shown in oil/water separation as well as anti-icing surfaces, while the versatility of the controlled atmosphere chamber fabrication method is demonstrated through the improved microsupercapacitor performance generated from LIG films prepared in an O2 atmosphere.

Three-Dimensional Rebar Graphene.

Free-standing robust three-dimensional (3D) rebar graphene foams (GFs) were developed by a powder metallurgy template method with multiwalled carbon nanotubes (MWCNTs) as a reinforcing bar, sintered Ni skeletons as a template and catalyst, and sucrose as a solid carbon source. As a reinforcement and bridge between different graphene sheets and carbon shells, MWCNTs improved the thermostability, storage modulus (290.1 kPa) and conductivity (21.82 S cm-1) of 3D GF resulting in a high porosity and structurally stable 3D rebar GF. The 3D rebar GF can support >3150× the foam's weight with no irreversible height change, and shows only a ∼25% irreversible height change after loading >8500× the foam's weight. The 3D rebar GF also shows stable performance as a highly porous electrode in lithium ion capacitors (LICs) with an energy density of 32 Wh kg-1. After 500 cycles of testing at a high current density of 6.50 mA cm-2, the LIC shows 78% energy density retention. These properties indicate promising applications with 3D rebar GFs in devices requiring stable mechanical and electrochemical properties.

Three-Dimensional Printed Graphene Foams.

An automated metal powder three-dimensional (3D) printing method for in situ synthesis of free-standing 3D graphene foams (GFs) was successfully modeled by manually placing a mixture of Ni and sucrose onto a platform and then using a commercial CO2 laser to convert the Ni/sucrose mixture into 3D GFs. The sucrose acted as the solid carbon source for graphene, and the sintered Ni metal acted as the catalyst and template for graphene growth. This simple and efficient method combines powder metallurgy templating with 3D printing techniques and enables direct in situ 3D printing of GFs with no high-temperature furnace or lengthy growth process required. The 3D printed GFs show high-porosity (∼99.3%), low-density (∼0.015g cm-3), high-quality, and multilayered graphene features. The GFs have an electrical conductivity of ∼8.7 S cm-1, a remarkable storage modulus of ∼11 kPa, and a high damping capacity of ∼0.06. These excellent physical properties of 3D printed GFs indicate potential applications in fields requiring rapid design and manufacturing of 3D carbon materials, for example, energy storage devices, damping materials, and sound absorption.

Rivet Graphene.

Large-area graphene has emerged as a promising material for use in flexible and transparent electronics due to its flexibility and optical and electronic properties. The anchoring of transition metal nanoparticles on large-area single-layer graphene is still a challenge. Here, we report an in situ preparation of carbon nano-onion-encapsulated Fe nanoparticles on rebar graphene, which we term rivet graphene. The hybrid film, which allows for polymer-free transfer and is strong enough to float on water with no added supports, exhibits high optical transparency, excellent electric conductivity, and good hole/electron mobility under certain tensile/compressive strains. The results of contact resistance and transfer length indicate that the current in the rivet graphene transistor does not just flow at the contact edge. Carbon nano-onions encapsulating Fe nanoparticles on the surface enhance the injection of charge between rivet graphene and the metal electrode. The anchoring of Fe nanoparticles encapsulated by carbon nano-onions on rebar graphene will provide additional avenues for applications of nanocarbon-based films in transparent and flexible electronics.

Flexible Nanoporous WO3-x Nonvolatile Memory Device.

Flexible resistive random access memory (RRAM) devices have attracted great interest for future nonvolatile memories. However, making active layer films at high temperature can be a hindrance to RRAM device fabrication on flexible substrates. Here, we introduced a flexible nanoporous (NP) WO3-x RRAM device using anodic treatment in a room-temperature process. The flexible NP WO3-x RRAM device showed bipolar switching characteristics and a high ION/IOFF ratio of ∼10(5). The device also showed stable retention time over 5 × 10(5) s, outstanding cell-to-cell uniformity, and bending endurance over 10(3) cycles when measured in both the flat and the maximum bending conditions.

Composites of Graphene Nanoribbon Stacks and Epoxy for Joule Heating and Deicing of Surfaces.

A conductive composite of graphene nanoribbon (GNR) stacks and epoxy is fabricated. The epoxy is filled with the GNR stacks, which serve as a conductive additive. The GNR stacks are on average 30 nm thick, 250 nm wide, and 30 µm long. The GNR-filled epoxy composite exhibits a conductivity >100 S/m at 5 wt % GNR content. This permits application of the GNR-epoxy composite for deicing of surfaces through Joule (voltage-induced) heating generated by the voltage across the composite. A power density of 0.5 W/cm(2) was delivered to remove ∼1 cm-thick (14 g) monolith of ice from a static helicopter rotor blade surface in a -20 °C environment.

High-Performance Pseudocapacitive Microsupercapacitors from Laser-Induced Graphene.

All-solid-state, flexible, symmetric, and asymmetric microsupercapacitors are fabricated by a simple method in a scalable fashion from laser-induced graphene on commercial polyimide films, followed by electrodeposition of pseudocapacitive materials on the interdigitated in-plane architectures. These microsupercapacitors demonstrate comparable energy density to commercial lithium thin-film batteries, yet exhibit more than two orders of magnitude higher power density with good mechanical flexibility.

Isoindigo-Based Donor-Acceptor Conjugated Polymers for Air-Stable Nonvolatile Memory Devices.

Nonvolatile resistive memory devices based on a new low bandgap donor-acceptor (D-A) conjugated polymer, poly((E)-6,6'-bis(2,3-dihydrothieno[3,4-b][1,4]dioxine-5-yl)-1,1'-bis(2-octyldodecyl)-[3,3'-biindolinyi-dene]-2,2'-dione) (PIDED), which are fabricated and operated in ambient air, are reported. The D-A conjugated polymer is synthesized from 2,3-dihydrothieno[3,4-b][1,4]dioxine and isoindigo as an electron donor and an electron acceptor, respectively, using CH-arylation polymerization. The devices show nonvolatile, unipolar resistive switching behaviors with a high on/off current ratio (∼104), excellent endurance cycles (>200 cycles), and a long retention time (>104 s) in ambient air. These properties remain stable in ambient air over one year, demonstrating that the device performance is significantly unaffected by exposure to air as the isoindigo has strong electron-withdrawing character and the PIDED exhibits a high degree of crystallinity. This study may pave the way for use of practical nonvolatile organic memory devices operating in ambient air.

Flexible and twistable non-volatile memory cell array with all-organic one diode-one resistor architecture.

Flexible organic memory devices are one of the integral components for future flexible organic electronics. However, high-density all-organic memory cell arrays on malleable substrates without cross-talk have not been demonstrated because of difficulties in their fabrication and relatively poor performances to date. Here we demonstrate the first flexible all-organic 64-bit memory cell array possessing one diode-one resistor architectures. Our all-organic one diode-one resistor cell exhibits excellent rewritable switching characteristics, even during and after harsh physical stresses. The write-read-erase-read output sequence of the cells perfectly correspond to the external pulse signal regardless of substrate deformation. The one diode-one resistor cell array is clearly addressed at the specified cells and encoded letters based on the standard ASCII character code. Our study on integrated organic memory cell arrays suggests that the all-organic one diode-one resistor cell architecture is suitable for high-density flexible organic memory applications in the future.

Flexible molecular-scale electronic devices.

Flexible materials and devices could be exploited in light-emitting diodes, electronic circuits, memory devices, sensors, displays, solar cells and bioelectronic devices. Nanoscale elements such as thin films, nanowires, nanotubes and nanoparticles can also be incorporated into the active films of mechanically flexible devices. Large-area devices containing extremely thin films of molecular materials represent the ultimate scaling of flexible devices based on organic materials, but the influence of bending and twisting on the electrical and mechanical stability of such devices has never been examined. Here, we report the fabrication and characterization of two-terminal electronic devices based on self-assembled monolayers of alkyl or aromatic thiol molecules on flexible substrates. We find that the charge transport characteristics of the devices remain stable under severe bending conditions (radius ≤ 1 mm) and a large number of repetitive bending cycles (≥1,000). The devices also remain reliable in various bending configurations, including twisted and helical structures.

Flexible organic memory devices with multilayer graphene electrodes.

We fabricated 8 × 8 cross-bar array-type flexible organic resistive memory devices with transparent multilayer graphene (MLG) electrodes on a poly(ethylene terephthalate) substrate. The active layer of the memory devices is a composite of polyimide and 6-phenyl-C61 butyric acid methyl ester. The sheet resistance of the MLG film on memory device was found to be ∼270 Ω/◻, and the transmittance of separated MLG film from memory device was ∼92%. The memory devices showed typical write-once-read-many (WORM) characteristics and an ON/OFF ratio of over ∼10(6). The memory devices also exhibited outstanding cell-to-cell uniformity with flexibility. There was no substantial variation observed in the current levels of the WORM memory devices upon bending and bending cycling up to 10 000 times. A retention time of over 10(4) s was observed without fluctuation under bending.