Reproducible dry and wet transfer techniques were developed to improve the transfer of large-area monolayer graphene grown on copper foils by chemical vapor deposition (CVD). The techniques reported ...here allow transfer onto three different classes of substrates: substrates covered with shallow depressions, perforated substrates, and flat substrates. A novel dry transfer technique was used to make graphene-sealed microchambers without trapping liquid inside. The dry transfer technique utilizes a polydimethylsiloxane frame that attaches to the poly(methyl methacrylate) spun over the graphene film, and the monolayer graphene was transferred onto shallow depressions with 300 nm depth. The improved wet transfer onto perforated substrates with 2.7 μm diameter holes yields 98% coverage of holes covered with continuous films, allowing the ready use of Raman spectroscopy and transmission electron microscopy to study the intrinsic properties of CVD-grown monolayer graphene. Additionally, monolayer graphene transferred onto flat substrates has fewer cracks and tears, as well as lower sheet resistance than previous transfer techniques. Monolayer graphene films transferred onto glass had a sheet resistance of ∼980 Ω/sq and a transmittance of 97.6%. These transfer techniques open up possibilities for the fabrication of various graphene devices with unique configurations and enhanced performance.
Graphene single crystals with dimensions of up to 0.5 mm on a side were grown by low-pressure chemical vapor deposition in copper-foil enclosures using methane as a precursor. Low-energy electron ...microscopy analysis showed that the large graphene domains had a single crystallographic orientation, with an occasional domain having two orientations. Raman spectroscopy revealed the graphene single crystals to be uniform monolayers with a low D-band intensity. The electron mobility of graphene films extracted from field-effect transistor measurements was found to be higher than 4000 cm2 V−1 s−1 at room temperature.
The ability to protect refined metals from reactive environments is vital to many industrial and academic applications. Current solutions, however, typically introduce several negative effects, ...including increased thickness and changes in the metal physical properties. In this paper, we demonstrate for the first time the ability of graphene films grown by chemical vapor deposition to protect the surface of the metallic growth substrates of Cu and Cu/Ni alloy from air oxidation. In particular, graphene prevents the formation of any oxide on the protected metal surfaces, thus allowing pure metal surfaces only one atom away from reactive environments. SEM, Raman spectroscopy, and XPS studies show that the metal surface is well protected from oxidation even after heating at 200 °C in air for up to 4 h. Our work further shows that graphene provides effective resistance against hydrogen peroxide. This protection method offers significant advantages and can be used on any metal that catalyzes graphene growth.
The growth of high-quality single crystals of graphene by chemical vapor deposition on copper (Cu) has not always achieved control over domain size and morphology, and the results vary from lab to ...lab under presumably similar growth conditions. We discovered that oxygen (O) on the Cu surface substantially decreased the graphene nucleation density by passivating Cu surface active sites. Control of surface O enabled repeatable growth of centimeter-scale single-crystal graphene domains. Oxygen also accelerated graphene domain growth and shifted the growth kinetics from edge-attachment-limited to diffusion-limited. Correspondingly, the compact graphene domain shapes became dendritic. The electrical quality of the graphene films was equivalent to that of mechanically exfoliated graphene, in spite of being grown in the presence of O.
Using micro-Raman spectroscopy, the thermal conductivity of a graphene monolayer grown by chemical vapor deposition and suspended over holes with different diameters ranging from 2.9 to 9.7 μm was ...measured in vacuum, thereby eliminating errors caused by heat loss to the surrounding gas. The obtained thermal conductivity values of the suspended graphene range from (2.6 ± 0.9) to (3.1 ± 1.0) × 103 Wm−1K−1 near 350 K without showing the sample size dependence predicted for suspended, clean, and flat graphene crystal. The lack of sample size dependence is attributed to the relatively large measurement uncertainty as well as grain boundaries, wrinkles, defects, or polymeric residue that are possibly present in the measured samples. Moreover, from Raman measurements performed in air and CO2 gas environments near atmospheric pressure, the heat transfer coefficient for air and CO2 was determined and found to be (2.9 +5.1/−2.9) and (1.5 +4.2/−1.5) × 104 Wm−2K−1, respectively, when the graphene temperature was heated by the Raman laser to about 510 K.
Field-effect transistors fabricated on graphene grown by chemical vapor deposition (CVD) often exhibit large hysteresis accompanied by low mobility, high positive backgate voltage corresponding to ...the minimum conductivity point (V min), and high intrinsic carrier concentration (n 0). In this report, we show that the mobility reported to date for CVD graphene devices on SiO2 is limited by trapped water between the graphene and SiO2 substrate, impurities introduced during the transfer process and adsorbates acquired from the ambient. We systematically study the origin of the scattering impurities and report on a process which achieves the highest mobility (μ) reported to date on large-area devices for CVD graphene on SiO2: maximum mobility (μmax) of 7800 cm2/(V·s) measured at room temperature and 12 700 cm2/(V·s) at 77 K. These mobility values are close to those reported for exfoliated graphene on SiO2 and can be obtained through the careful control of device fabrication steps including minimizing resist residue and non-aqueous transfer combined with annealing. It is also observed that CVD graphene is prone to adsorption of atmospheric species, and annealing at elevated temperature in vacuum helps remove these species.
By combining a graphene layer and aligned multiwalled carbon nanotube (MWNT) sheets in two different configurations, i) graphene on the top of MWNTs and ii) MWNTs on the top of the graphene, it is ...demonstrated that optical, electrical, and electromechanical properties of the resulting hybrid films depend on configurations.
The fundamental properties of graphene are making it an attractive material for a wide variety of applications. Various techniques have been developed to produce graphene and recently we discovered ...the synthesis of large area graphene by chemical vapor deposition (CVD) of methane on Cu foils. We also showed that graphene growth on Cu is a surface-mediated process and the films were polycrystalline with domains having an area of tens of square micrometers. In this paper, we report on the effect of growth parameters such as temperature, and methane flow rate and partial pressure on the growth rate, domain size, and surface coverage of graphene as determined by Raman spectroscopy, and transmission and scanning electron microscopy. On the basis of the results, we developed a two-step CVD process to synthesize graphene films with domains having an area of hundreds of square micrometers. Scanning electron microscopy and Raman spectroscopy clearly show an increase in domain size by changing the growth parameters. Transmission electron microscopy further shows that the domains are crystallographically rotated with respect to each other with a range of angles from about 13 to nearly 30°. Electrical transport measurements performed on back-gated FETs show that overall films with larger domains tend to have higher carrier mobility up to about 16 000 cm2 V−1 s−1 at room temperature.
Understanding and engineering the domain boundaries in chemically vapor deposited monolayer graphene will be critical for improving its properties. In this study, a combination of transmission ...electron microscopy (TEM) techniques including selected area electron diffraction, high resolution transmission electron microscopy (HR-TEM), and dark field (DF) TEM was used to study the boundary orientation angle distribution and the nature of the carbon bonds at the domain boundaries. This report provides an important first step toward a fundamental understanding of these domain boundaries. The results show that, for the graphene grown in this study, the 46 measured misorientation angles are all between 11° and 30° (with the exception of one at 7°). HR-TEM images show the presence of adsorbates in almost all of the boundary areas. When a boundary was imaged, defects were seen (dangling bonds) at the boundaries that likely contribute to adsorbates binding at these boundaries. DF-TEM images also showed the presence of a “twinlike” boundary.
The interfacial capacitance of large area, single layer graphene was directly measured with electrolyte accessing both sides of the graphene sheet. PMMA and photoresist patterns were used as supports ...to suspend the CVD grown graphene in electrolyte during electrochemical testing. Both one and two sides of single layer graphene films were measured and compared. The results show that the area normalized charge that can be stored simultaneously on both sides is significantly lower than could be stored on just one side of single layer graphene, consistent with charge storage having a quantum capacitance component. These measurements are also consistent with the specific capacitance of graphene materials as previously measured in supercapacitor cells and provide a basis for the further understanding and development of graphene based materials for electrical energy storage.
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