Direct large-area growth of graphene on silicon for potential ultra-low-friction applications and silicon-based technologies.

Deposition of layers of graphene on silicon has the potential for a wide range of optoelectronic and mechanical applications. However, direct growth of graphene on silicon has been difficult due to the inert, oxidized silicon surfaces. Transferring graphene from metallic growth substrates to silicon is not a good solution either, because most transfer methods involve multiple steps that often lead to polymer residues or degradation of sample quality. Here we report a single-step method for large-area direct growth of continuous horizontal graphene sheets and vertical graphene nano-walls on silicon substrates by plasma-enhanced chemical vapor deposition (PECVD) without active heating. Comprehensive studies utilizing Raman spectroscopy, x-ray/ultraviolet photoelectron spectroscopy (XPS/UPS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and optical transmission are carried out to characterize the quality and properties of these samples. Data gathered by the residual gas analyzer (RGA) during the growth process further provide information about the synthesis mechanism. Additionally, ultra-low friction (with a frictional coefficient ∼0.015) on multilayer graphene-covered silicon surface is achieved, which is approaching the superlubricity limit (for frictional coefficients <0.01). Our growth method therefore opens up a new pathway towards scalable and direct integration of graphene into silicon technology for potential applications ranging from structural superlubricity to nanoelectronics, optoelectronics, and even the next-generation lithium-ion batteries.

Single-step growth of graphene and graphene-based nanostructures by plasma-enhanced chemical vapor deposition.

The realization of many promising technological applications of graphene and graphene-based nanostructures depends on the availability of reliable, scalable, high-yield and low-cost synthesis methods. Plasma enhanced chemical vapor deposition (PECVD) has been a versatile technique for synthesizing many carbon-based materials, because PECVD provides a rich chemical environment, including a mixture of radicals, molecules and ions from hydrocarbon precursors, which enables graphene growth on a variety of material surfaces at lower temperatures and faster growth than typical thermal chemical vapor deposition. Here we review recent advances in the PECVD techniques for synthesis of various graphene and graphene-based nanostructures, including horizontal growth of monolayer and multilayer graphene sheets, vertical growth of graphene nanostructures such as graphene nanostripes with large aspect ratios, direct and selective deposition of monolayer and multi-layer graphene on nanostructured substrates, and growth of multi-wall carbon nanotubes. By properly controlling the gas environment of the plasma, it is found that no active heating is necessary for the PECVD growth processes, and that high-yield growth can take place in a single step on a variety of surfaces, including metallic, semiconducting and insulating materials. Phenomenological understanding of the growth mechanisms are described. Finally, challenges and promising outlook for further development in the PECVD techniques for graphene-based applications are discussed.

Vertically-aligned graphene nanowalls grown via plasma-enhanced chemical vapor deposition as a binder-free cathode in Li-O2 batteries.

In the present report, vertically-aligned graphene nanowalls are grown on Ni foam (VA-G/NF) using plasma-enhanced chemical vapor deposition method at room temperature. Optimization of the growth conditions provides graphene sheets with controlled defect sites. The unique architecture of the vertically-aligned graphene sheets allows sufficient space for the ionic movement within the sheets and hence enhancing the catalytic activity. Further modification with ruthenium nanoparticles (Ru NPs) drop-casted on VA-G/NF improves the charge overpotential for lithium-oxygen (Li-O2) battery cycles. Such reduction we believe is due to the easier passage of ions between the perpendicularly standing graphene sheets thereby providing ionic channels.

Stabilization of hybrid perovskite CH3NH3PbI3 thin films by graphene passivation.

We report the long-term stability of water-sensitive hybrid perovskites CH3NH3PbI3 that were protected with monolayer graphene. This successful passivation was enabled by our development of a new water-free and polymer-free graphene transfer method. Monolayer graphene samples grown by plasma-enhanced chemical vapor deposition and transferred onto different substrates with the water/polymer-free method were found to preserve their high-quality characteristics after the transfer, as manifested by the studies of Raman, X-ray and ultraviolet photoemission spectroscopy (XPS and UPS), optical absorption, and sheet resistance. Additionally, XPS, UPS and optical absorption studies of fully graphene-covered CH3NH3PbI3 thin films showed spectral invariance even after 3 months, which was in sharp contrast to the drastic spectral changes after merely one week in control CH3NH3PbI3 samples without graphene protection. This successful demonstration of the graphene-enabled passivation and long-term stability of CH3NH3PbI3 thin films therefore opens up a new pathway towards realistic photovoltaic applications of hybrid perovskites.

Two-dimensional dopant profiling by electrostatic force microscopy using carbon nanotube modified cantilevers.

A two-dimensional (2D) dopant profiling technique is demonstrated in this work. We apply a unique cantilever probe in electrostatic force microscopy (EFM) modified by the attachment of a multiwalled carbon nanotube (MWNT). Furthermore, the tip apex of the MWNT was trimmed to the sharpness of a single-walled carbon nanotube (SWNT). This ultra-sharp MWNT tip helps us to resolve dopant features to within 10 nm in air, which approaches the resolution achieved by ultra-high vacuum scanning tunnelling microscopy (UHV STM). In this study, the CNT-probed EFM is used to profile 2D buried dopant distribution under a nano-scale device structure and shows the feasibility of device characterization for sub-45 nm complementary metal-oxide-semiconductor (CMOS) field-effect transistors.