Silica Particle-Mediated Growth of Single Crystal Graphene Ribbons on Cu(111) Foil.

The authors report the growth of micrometer-long single-crystal graphene ribbons (GRs) (tapered when grown above 900 °C, but uniform width when grown in the range 850 °C to 900 °C) using silica particle seeds on single crystal Cu(111) foil. Tapered graphene ribbons grow strictly along the Cu<101> direction on Cu(111) and polycrystalline copper (Cu) foils. Silica particles on both Cu foils form (semi-)molten Cu-Si-O droplets at growth temperatures, then catalyze nucleation and drive the longitudinal growth of graphene ribbons. Longitudinal growth is likely by a vapor-liquid-solid (VLS) mechanism but edge growth (above 900 °C) is due to catalytic activation of ethylene (C2 H4 ) and attachment of C atoms or species ("vapor solid" or VS growth) at the edges. It is found, based on the taper angle of the graphene ribbon, that the taper angle is determined by the growth temperature and the growth rates are independent of the particle size. The activation enthalpy (1.73 ± 0.03 eV) for longitudinal ribbon growth on Cu(111) from ethylene is lower than that for VS growth at the edges of the GRs (2.78 ± 0.15 eV) and for graphene island growth (2.85 ± 0.07 eV) that occurs concurrently.

The effects of sub-bandgap transitions and the defect density of states on the photocurrent response of a single ZnO-coated silica nanospring.

The electrical and optoelectronic properties of nanometer-sized ZnO structures are highly influenced by its native point defects. Understanding and controlling these defects are essential for the development of high-performance ZnO-based devices. Here, an electrical device consisting of a polycrystalline ZnO-coated silica nanospring was fabricated and used to characterize the electrical and photoconductive properties of the ZnO layer using near-UV (405 nm) and sub-bandgap (532 and 633 nm) excitation sources. We observe a photocurrent response with all three wavelengths and notably with 532 nm green illumination, which is the energy associated with deep oxygen vacancies. The polycrystalline ZnO-coated silica nanospring exhibits a high responsivity of 1740 A W-1 with the 405 nm excitation source. Physical models are presented to describe the photocurrent rise and decay behavior of each excitation source where we suggest that the rise and decay characteristics are highly dependent on the energy of the excitation source and the trapping of electrons and holes in intermediate defect levels in the bandgap. The energy levels of the trap depths were determined from the photoconductive decay data and are matched to the reported energy levels of singly and doubly ionized oxygen vacancies. A phenomenological model to describe the dependence of the saturation photocurrent on excitation intensity is presented in order to understand the characteristics of the observed breaks in the slopes of the saturation photocurrent versus excitation intensity profile.

Large-area single-crystal AB-bilayer and ABA-trilayer graphene grown on a Cu/Ni(111) foil.

High-quality AB-stacked bilayer or multilayer graphene larger than a centimetre has not been reported. Here, we report the fabrication and use of single-crystal Cu/Ni(111) alloy foils with controllable concentrations of Ni for the growth of large-area, high-quality AB-stacked bilayer and ABA-stacked trilayer graphene films by chemical vapour deposition. The stacking order, coverage and uniformity of the graphene films were evaluated by Raman spectroscopy and transmission electron microscopy including selected area electron diffraction and atomic resolution imaging. Electrical transport (carrier mobility and band-gap tunability) and thermal conductivity (the bilayer graphene has a thermal conductivity value of about 2,300 W m-1 K-1) measurements indicated the superior quality of the films. The tensile loading response of centimetre-scale bilayer graphene films supported by a 260-nm thick polycarbonate film was measured and the average values of the Young's modulus (478 GPa) and fracture strength (3.31 GPa) were obtained.

Chemically induced transformation of chemical vapour deposition grown bilayer graphene into fluorinated single-layer diamond.

Notwithstanding the numerous density functional studies on the chemically induced transformation of multilayer graphene into a diamond-like film carried out to date, a comprehensive convincing experimental proof of such a conversion is still lacking. We show that the fluorination of graphene sheets in Bernal (AB)-stacked bilayer graphene grown by chemical vapour deposition on a single-crystal CuNi(111) surface triggers the formation of interlayer carbon-carbon bonds, resulting in a fluorinated diamond monolayer ('F-diamane'). Induced by fluorine chemisorption, the phase transition from (AB)-stacked bilayer graphene to single-layer diamond was studied and verified by X-ray photoelectron, UV photoelectron, Raman, UV-Vis and electron energy loss spectroscopies, transmission electron microscopy and density functional theory calculations.

Colossal grain growth yields single-crystal metal foils by contact-free annealing.

Single-crystal metals have distinctive properties owing to the absence of grain boundaries and strong anisotropy. Commercial single-crystal metals are usually synthesized by bulk crystal growth or by deposition of thin films onto substrates, and they are expensive and small. We prepared extremely large single-crystal metal foils by "contact-free annealing" from commercial polycrystalline foils. The colossal grain growth (up to 32 square centimeters) is achieved by minimizing contact stresses, resulting in a preferred in-plane and out-of-plane crystal orientation, and is driven by surface energy minimization during the rotation of the crystal lattice followed by "consumption" of neighboring grains. Industrial-scale production of single-crystal metal foils is possible as a result of this discovery.

Signal-to-Noise Enhancement of a Nanospring Redox-Based Sensor by Lock-in Amplification.

A significant improvement of the response characteristics of a redox chemical gas sensor (chemiresistor) constructed with a single ZnO coated silica nanospring has been achieved with the technique of lock-in signal amplification. The comparison of DC and analog lock-in amplifier (LIA) AC measurements of the electrical sensor response to toluene vapor, at the ppm level, has been conducted. When operated in the DC detection mode, the sensor exhibits a relatively high sensitivity to the analyte vapor, as well as a low detection limit at the 10 ppm level. However, at 10 ppm the signal-to-noise ratio is 5 dB, which is less than desirable. When operated in the analog LIA mode, the signal-to-noise ratio at 10 ppm increases by 30 dB and extends the detection limit to the ppb range.

The effect of the periodic boundary conditions of a ZnO-coated nanospring on its surface redox-induced electrical response.

A redox chemical sensor (chemiresistor) was constructed with a single ZnO coated silica nanospring. The chemiresistor response to toluene vapor as a function of the sensor temperature (T(NS)) and vapor temperature (T(V)) was measured and analyzed. The maximum sensitivity of the single ZnO coated nanospring device occurred at the sensor temperature (T(NS)) of 310 °C and at the vapor temperature (T(V)) of 250 °C. The characteristics of the electrical response of a single ZnO coated nanospring device were compared to those of a ZnO thin film. The single ZnO nanospring sensor was less responsive to small changes in toluene concentration relative to the ZnO thin film, but has a lower ultimate detection level. A computational model to simulate an electrical response of the single nanospring sensor and the thin film indicated that the differences between their response characteristics is due to the geometry of the nanospring and corresponding periodic boundary conditions imposed by the nanospring geometry, which is absent in a thin film.