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The electrical double layer (EDL), consisting of two parallel layers of opposite charges, is foundational to many interfacial phenomena and unique in atomically thin materials. An important but unanswered question is how the "transparency" of atomically thin materials to their substrates influences the formation of the EDL. Here, we report that the EDL of graphene is directly affected by the surface energy of the underlying substrates. Cyclic voltammetry and electrochemical impedance spectroscopy measurements demonstrate that graphene on hydrophobic substrates exhibits an anomalously low EDL capacitance, much lower than what was previously measured for highly oriented pyrolytic graphite, suggesting disturbance of the EDL ("disordered EDL") formation due to the substrate-induced hydrophobicity to graphene. Similarly, electrostatic gating using EDL of graphene field-effect transistors shows much lower transconductance levels or even no gating for graphene on hydrophobic substrates, further supporting our hypothesis. Molecular dynamics simulations show that the EDL structure of graphene on a hydrophobic substrate is disordered, caused by the disruption of water dipole assemblies. Our study advances understanding of EDL in atomically thin limit.

Graphene has attracted great attention as an alternative to conventional metallic or transparent conducting electrodes. Despite its similarities with conventional electrodes, recent studies have shown that a single-atom layer of graphene possesses unique characteristics, such as a tunable work function and transparencies for electric potential, reactivity, and wetting. Nevertheless, a systematic analysis of graphene and semiconductor junction characteristics has not yet been carried out. Here, we report the photoresponse characteristics of graphene-on-GaN Schottky junction photodiodes (Gr-GaN SJPDs), showing a typical rectifying behavior and distinct photovoltaic and photoelectric responses. Following the initial abrupt response to UV illumination, the Gr-GaN SJPDs exhibited a distinct difference in photocarrier dynamics depending on the applied bias voltage, which is characterized by either a negative or positive change in photocurrent with time. We propose underlying mechanisms for the anomalous photocarrier dynamics based on the interplay between electrostatic molecular interactions over the one-atom-thick graphene and GaN junction and trapped photocarriers at the defect states in the GaN thin film.

Large area growth of single- and few-layer graphene has been established, yet its prerequisite of metallic catalysts has impeded direct graphene growth on three-dimensional (3D) dielectric substrates. Here, we report a new strategy for direct chemical-vapor-deposition (CVD) growth of graphene films on 3D patterned sapphire substrates by placing the target surfaces in contact with or close to a Cu catalyst. This approach can yield uniform coatings of few-layer graphene films on complex structures on the centimeter scale, as confirmed by detailed scanning electron microscopy and Raman spectroscopy studies. In addition, we showed that 3D graphene can possess ambipolar field-effect transistor (FET) characteristics by applying the gate voltage through an ion-gel dielectric sheet. The 3D graphene FET device was further employed as a pressure and touch sensing device, where the sensitivity was effectively enhanced by the 3D topology.

We report the synthesis, fabrication, and characterization of a nanotube-on-graphene (NT-on-Gr) field-effect sensor array for electrical detection of the biological activity of living cells. In order to form vertical nanotubes on a graphene surface, Ge/Si core-shell nanowires were vertically grown on graphene, followed by cap opening and Ge core-etching processes. Source-drain current versus water-gate potential measurements in electrolyte solutions with various pH values showed typical gate-dependent ambipolar characteristics with a decrease in pH sensitivity versus that of a flat graphene field-effect sensor. This is associated with limited solution gating of Si nanotubes that form nanoscale fluidic channels and thus interconnect the solution with the graphene field-effect sensor. The Si nanotubes also bridged interconnections between cells and the graphene field effect sensors, which were then able to record electrical spike peaks caused by cell networks.

We report the improvement in the sensing performance of electrolyte-gated graphene field-effect transistor (FET) sensors capable of detecting tau protein through a simplified, linker-free, anti-tau antibody immobilization process. For most of the graphene-based immunosensor, linkers, such as pyrenebutanoic acid, succinimidyl ester (PSE) must be used to the graphene surface, while the other side of linkers serves to capture the antibodies that can specifically interact with the target biomarker. In this study, graphene was patterned into eight different types and linker-free patterned graphene FET sensors were fabricated to verify their detection performance. The linker-free antibody immobilization to patterned graphene exhibited that the antibody was immobilized to the edge defect and had a doping-like behaviors on graphene. As the tau protein concentration in the electrolyte increased from 10 fg/ml to 1 ng/ml, the performances, charge neutral point shift and current change rate of the patterned graphene sensors without linkers were enhanced 2–3 times compared to a pristine graphene sensor with the PSE linker. Moreover, tau protein in the plasma of five Alzheimer's disease patients was measured using a linker-free patterned graphene sensor. It shows a 3–4 times higher current change rate than that of pristine graphene sensor with the PSE linker. Since the antibody is immobilized directly without a linker, a patterned graphene sensor without a linker can operate more sensitively in higher ionic concentration electrolyte.

We report the role of defects in enzymatic graphene field-effect transistor sensors by introducing engineered defects in graphene channels. Compared with conventional graphene sensors (Gr sensors), graphene mesh sensors (GM sensors), with an array of circular holes, initially exhibited a higher irreversible response to glucose, involving strong chemisorption to edge defects. However, after immobilization of glucose oxidase, the irreversibility of the responses was substantially diminished, without any reduction in the sensitivity of the GM sensors (i.e., -0.53 mV/mM for the GM sensor vs -0.37 mV/mM for Gr sensor). Furthermore, multiple cycle operation led to rapid sensing and improved the reversibility of GM sensors. In addition, control tests with sensors containing a linker showed that sensitivity was increased in Gr sensors but decreased in GM sensors. Our findings indicate that edge defects can be used to replace linkers for immobilization of glucose oxidase and improve charge transfer across glucose oxidase-graphene interfaces.

We propose a novel wallpapering-inspired strategy to create wrinkles in a desired location and direction of single-layer graphene (Gr). The key to controlling the wrinkles is to regulate the permeation and release of solution through a regular array of holes between the substrate surface and Gr-based thin membrane (Gr/Cu in the first stage and Gr in the second stage). Microscopic analysis showed that neighboring holes were interconnected by straightened wrinkles with a width of 300–500 nm and height of 10–20 nm, while surface corrugations (e.g., ripples and wrinkles) were suppressed on the planar regions surrounded by wrinkles. Wrinkling mechanism was further verified by in-situ optical microscopy and comparative analysis of Gr/Cu ripples and Gr wrinkles. Our approach is simple yet universally applicable to diverse types of thin membranes, thereby offering a robust and versatile route to engineering properties of atomically thin materials.

Chemically synthesized semiconductor nanowires (NWs) have demonstrated substantial promise for nanoelectronics, nanoenergy, and nanobiotechnology, but the lack of an effective and controllable assembly process has limited the wide adoption of NWs in these areas. Here we demonstrate a facile, robust, and controllable approach to assembling and densifying a parallel array of NWs using shrinkable shape memory polymers. Using thermal-induced shrinkage of polystyrene, we were able to successfully assemble and densify NW arrays up to close-packing and, furthermore, achieve tunable density (up to ∼300% amplification of density) by controlling the shrinkage process. We also demonstrate scalable assembly and densification of NWs on a 2.5 × 6 inch scale to explore the manufacturability of the shrink-induced assembly process. Finally, we demonstrate the successful transfer of the shrink-assembled NW arrays onto various 2-dimensional and 3-dimensional substrates without compromising the integrity of NW assembly and density.

Zn-polar (0001) surfaces are more chemically reactive than other surfaces of ZnO crystals and drive preferential anisotropic and asymmetric growth along the [0001] direction, which facilitates growth of c-axis oriented, one-dimensional ZnO nanostructures. Accordingly, capping the top (0001) surface of ZnO crystals can impede c-axis growth and thus serve to modulate growth habits. In this study, we generated vertically aligned ZnO hexagonal nanotube-rod (h-NTR) hybrids by modulating growth habits during a second-stage process. Electron microscopy studies revealed the formation of very thin (10–20 nm) single-crystalline nanotube walls along the edges of underlying hexagonal rod tops capped with Si. In addition, spatially resolved investigation of ZnO h-NTR indicated an abrupt increase in the measured bandgap across rod-tube junctions, which was ascribed to a quantum confinement effect and Burstein–Moss effect of carriers within the very thin nanotube walls.

Graphene has been intensively studied for applications to high-performance sensors, but the sensing characteristics of graphene devices have varied from case to case, and the sensing mechanism has not been satisfactorily determined thus far. In this review, we describe recent progress in engineering of the defects in graphene grown by a silica-assisted chemical vapor deposition technique and elucidate the effect of the defects upon the electrical response of graphene sensors. This review provides guidelines for engineering and/or passivating defects to improve sensor performance and reliability.

To improve lipase activity and make the particulate carrier for practical application, lipase was conjugated to chitosan(Mwavg=80,000) by immine reaction. The lipase activity of conjugate was 93% of its initial activity at room temperature for 7 months, whereas the intact lipase activity decreased to 40%. And then, lipase-chitosan conjugate was intercalated within porous silica. The composite was characterized by X-ray diffraction, scanning electron microscopy, thermo gravimetric analysis. The Pore size was regulated in the range of 5~15nm. The maximum enzyme activity of lipase-chitosan conjugate needs the structure with 15nm pore of mesoporous silica. The resultant composite was found to have the free flowing property and keep up inner lipase activity.

We have studied the role of defects in electrolyte-gated graphene mesh (GM) field-effect transistors (FETs) by introducing engineered edge defects in graphene (Gr) channels. Compared with Gr-FETs, GM-FETs were characterized as having large increments of Dirac point shift (∼30-100 mV/pH) that even sometimes exceeded the Nernst limit (59 mV/pH) by means of electrostatic gating of H(+) ions. This feature was attributed to the defect-mediated chemisorptions of H(+) ions to the graphene edge, as supported by Raman measurements and observed cycling characteristics of the GM FETs. Although the H(+) ion binding to the defects increased the device response to pH change, this binding was found to be irreversible. However, the irreversible component showed relatively fast decay, almost disappearing after 5 cycles of exposure to solutions of decreasing pH value from 8.25 to 6.55. Similar behavior could be found in the Gr-FET, but the irreversible component of the response was much smaller. Finally, after complete passivation of the defects, both Gr-FETs and GM-FETs exhibited only reversible response to pH change, with similar magnitude in the range of 6-8 mV/pH.

A microfluidization and solvent evaporation method was employed to prepare poly(methyl methacrylate) (PMMA) nanoparticles containing coenzyme Q10. Dynamic light scattering and transmission electron microscopy showed that the mean diameter of the nanoparticles was highly influenced by the kind of surfactants used and the recycling number of the microfluidization process. Particles with sizes from 40 to 260 nm and low polydispersities were produced with good reproducibility. Despite a very high target drug loading yield, 38.7% (w/w), the actual loading efficiency reached above 95%, as demonstrated by 1H NMR analysis. Coenzyme Q10 formed a crystal structure within the polymer matrix with a melting temperature of 48 °C, as demonstrated by differential scanning calorimetry. No free drug crystals were found in the aqueous suspension of nanoparticles. A comparative study on structural stability of coenzyme Q10 showed that both UV and high temperature-induced drug inactivation were effectively hindered when the drug was encapsulated within the polymer nanoparticles.

We fabricated flexible and transparent hydrogen gas sensors based on a palladium-decorated graphene mesh. Electron microscopy analysis confirmed that ~2–3 nm diameter Pd nanoparticles were uniformly dispersed on the graphene mesh surfaces. The sensors were highly transparent with an average optical transmission of >90% to visible light and they exhibited good electrical stability with a resistance change of 1.5% under a tensile strain of 1.1% in a cyclic bending-unbending test. Compared with graphene-based sensors, the graphene mesh sensors exhibited a faster response to hydrogen gas with sensitivity as high as ~5% at a low concentration of 10 ppm H2/air, even at room temperature. The enhanced H2 detection characteristic of the graphene mesh sensors is attributed to the existence of edges.

An easy method of measurement of the zeta potentials of sub-50-nm polymeric nanoparticles is suggested. Although zeta potential measurements of nanoparticles or emulsions above 50 nm have been successfully carried out, zeta potentials of emulsions or nanoparticles below 50 nm could not be precisely measured in the region of extremely low conductivity by conventional electrophoresis with a He-Ne laser. However, zeta potentials of sub-50-nm nanoparticles were measured in the region of thin electrical double layers by addition of sodium chloride and zeta potentials in the condition without sodium chloride could be predicted by extrapolation of the measured potentials. The electrophoretic mobility of 150-nm nanoparticles stabilized with sodium dodecylsulfate was the same as that calculated from extrapolation of the measured ones. The zeta potentials of sub-50-nm nanoparticles stabilized with sodium dodecylsulfate could be calculated by the same procedure.