Wafer-Scale Synthesis of Graphene on Sapphire: Toward Fab-Compatible Graphene.

The adoption of graphene in electronics, optoelectronics, and photonics is hindered by the difficulty in obtaining high-quality material on technologically relevant substrates, over wafer-scale sizes, and with metal contamination levels compatible with industrial requirements. To date, the direct growth of graphene on insulating substrates has proved to be challenging, usually requiring metal-catalysts or yielding defective graphene. In this work, a metal-free approach implemented in commercially available reactors to obtain high-quality monolayer graphene on c-plane sapphire substrates via chemical vapor deposition is demonstrated. Low energy electron diffraction, low energy electron microscopy, and scanning tunneling microscopy measurements identify the Al-rich reconstruction 31 × 31 R ± 9 ° of sapphire to be crucial for obtaining epitaxial graphene. Raman spectroscopy and electrical transport measurements reveal high-quality graphene with mobilities consistently above 2000 cm2 V-1 s-1 . The process is scaled up to 4 and 6 in. wafers sizes and metal contamination levels are retrieved to be within the limits for back-end-of-line integration. The growth process introduced here establishes a method for the synthesis of wafer-scale graphene films on a technologically viable basis.

Evolutionary kinetics of graphene formation on copper.

It has been claimed that graphene growth on copper by chemical vapor deposition is dominated by crystallization from the surface initially supersaturated with carbon adatoms, which implies that the growth is independent of hydrocarbon addition after the nucleation phase. Here, we present an alternative growth model based on our observations that oppose this claim. Our Gompertzian sigmoidal growth kinetics and secondary nucleation behavior support the postulate that the growth can be controlled by adsorption-desorption dynamics and the dispersive kinetic processes of catalytic dissociation and dehydrogenation of carbon precursors on copper.

Industrial Graphene Coating of Low-Voltage Copper Wires for Power Distribution.

Copper (Cu) is the electrical conductor of choice in many categories of electrical wiring, with household and building installation being the major market of this metal. This work demonstrates the coating of Cu wires-with diameters relevant for low-voltage (LV) applications-with graphene. The chemical vapor deposition (CVD) coating process is rapid, safe, scalable, and industrially compatible. Graphene-coated Cu wires display good oxidation resistance and increased electrical conductivity (up to 1% immediately after coating and up to 3% after 24 months), allowing for wire diameter reduction and thus significant savings in wire production costs. Combined spectroscopic and diffraction analysis indicates that the conductivity increase is due to a change in Cu crystallinity induced by the coating process conditions, while electrical testing of aged wires shows that graphene plays a major role in maintaining improved electrical performances over long periods of time. Finally, graphene coating of Cu wires using an ambient-pressure roll-to-roll (R2R) CVD reactor is demonstrated. This enables the in-line production of graphene-coated metallic wires as required for industrial scale-up.

Microwave devices: carbon nanotubes as cold cathodes.

To communicate, spacecraft and satellites rely on microwave devices, which at present are based on relatively inefficient thermionic electron sources that require heating and cannot be switched on instantaneously. Here we describe a microwave diode that uses a cold-cathode electron source consisting of carbon nanotubes and that operates at high frequency and at high current densities. Because it weighs little, responds instantaneously and has no need of heating, this miniaturized electron source should prove valuable for microwave devices used in telecommunications.

Deterministic cold cathode electron emission from carbon nanofibre arrays.

The ability to accurately design carbon nanofibre (CN) field emitters with predictable electron emission characteristics will enable their use as electron sources in various applications such as microwave amplifiers, electron microscopy, parallel beam electron lithography and advanced Xray sources. Here, highly uniform CN arrays of controlled diameter, pitch and length were fabricated using plasma enhanced chemical vapour deposition and their individual emission characteristics and field enhancement factors were probed using scanning anode field emission mapping. For a pitch of 10 µm and a CN length of 5 µm, the directly measured enhancement factors of individual CNs was 242, which was in excellent agreement with conventional geometry estimates (240). We show here direct empirical evidence that in regular arrays of vertically aligned CNs the overall enhancement factor is reduced when the pitch between emitters is less than half the emitter height, in accordance to our electrostatic simulations. Individual emitters showed narrow Gaussian-like field enhancement distributions, in excellent agreement with electric field simulations.

Carbon nanotube based photocathodes.

This paper describes a novel photocathode which is an array of vertically aligned multi-walled carbon nanotubes (MWCNTs), each MWCNT being associated with one p-i-n photodiode. Unlike conventional photocathodes, the functions of photon-electron conversion and subsequent electron emission are physically separated. Photon-electron conversion is achieved with p-i-n photodiodes and the electron emission occurs from the MWCNTs. The current modulation is highly efficient as it uses an optically controlled reconfiguration of the electric field at the MWCNT locations. Such devices are compatible with high frequency and very large bandwidth operation and could lead to their application in compact, light and efficient microwave amplifiers for satellite telecommunication. To demonstrate this new photocathode concept, we have fabricated the first carbon nanotube based photocathode using silicon p-i-n photodiodes and MWCNT bunches. Using a green laser, this photocathode delivers 0.5 mA with an internal quantum efficiency of 10% and an I(ON)/I(OFF) ratio of 30.

Optical performance of carbon-nanotube electron sources.

The figure of merit for the electron optical performance of carbon-nanotube (CNT) electron sources is presented. This figure is given by the relation between the reduced brightness and the energy spread in the region of stable emission. It is shown experimentally that a CNT electron source exhibits a highly stable emission process that follows the Fowler-Nordheim theory for field emission, fixing the relationship among the energy spread, the current, and the radius. The performance of the CNT emitter under realistic operating conditions is compared with state-of-the-art electron point sources. It is demonstrated that the reduced brightness is a function of the tunneling parameter, a measure of the energy spread at low temperatures, only, independent of the geometry of the emitter.

Achieving high-current carbon nanotube emitters.

When a carbon nanotube emitter is operated at high currents (typically above 1 microA per emitter), a small voltage drop ( approximately few volts) along its length or at its contact generates a reverse/canceling electric field that causes a saturation-like deviation from the classical Fowler-Nordheim behavior with respect to the applied electric field. We present a correction to the Fowler-Nordheim equation to account for this effect, which is experimentally verified using field emission and contact electrical measurements on individual carbon nanotube emitters. By using rapid thermal annealing to improve both the crystallinity of the carbon nanotubes and their electrical contact to the substrate, it is possible to reduce this voltage drop, allowing very high currents of up to 100 microA to be achieved per emitter with no significant deviation from the classical Fowler-Nordheim behavior.