- Nano Express
- Open Access
Copper-Assisted Direct Growth of Vertical Graphene Nanosheets on Glass Substrates by Low-Temperature Plasma-Enhanced Chemical Vapour Deposition Process
© Ma et al. 2015
- Received: 28 April 2015
- Accepted: 24 July 2015
- Published: 4 August 2015
Vertical graphene (VG) nanosheets are directly grown below 500 °C on glass substrates by a one-step copper-assisted plasma-enhanced chemical vapour deposition (PECVD) process. A piece of copper foil is located around a glass substrate as a catalyst in the process. The effect of the copper catalyst on the vertical graphene is evaluated in terms of film morphology, growth rate, carbon density in the plasma and film resistance. The growth rate of the vertical graphene is enhanced by a factor of 5.6 with the copper catalyst with denser vertical graphene. The analysis of optical emission spectra suggests that the carbon radical density is increased with the copper catalyst. Highly conductive VG films having 800 Ω/□ are grown on glass substrates with Cu catalyst at a relatively low temperature.
- Low temperature
- Vertical graphene nanosheets
- Glass substrate
- Copper-assisted growth
Various carbon nanostructures have received enormous attention recently due to their excellent physical properties. For example, graphene, an sp 2 -hybridized two-dimensional carbon material, shows excellent physical properties in intrinsic mobility [1, 2], mechanical strength , optical transmittance  and electric conductivity . These properties make graphene a promising material in a wide range of applications of electronics [6, 7], optoelectronics [8, 9], sensors [10, 11], batteries  and supercapacitors [13–17]. Enormous processes have been developed for the synthesis of graphene including exfoliation from highly oriented pyrolytic graphite (HOPG), reduction of chemically exfoliated graphene oxide (RGO), thermal decomposition of SiC and chemical vapour deposition (CVD). In general, these processes generate in-plane-oriented monolayer or multi-layer graphene films.
Recently, three-dimensional (3D) graphene attracts attention due to its high surface-area-to-volume ratio . Vertical graphene (VG) nanosheet is one of the popular 3D carbon structure materials , which has been applied to various applications of field emitters [7, 18], supercapacitors [19–22] and batteries [23, 24]. In practice, VG films have been typically grown on metal substrates at a relatively high temperature [10, 16], close to 1000 °C, which limits the use of various low-melting-temperature substrates. Yang et al. reported the growth of VG films on dielectric substrates (SiO2)  at the temperature of 900 °C. However, the growth rate drops significantly at the temperature below 900 °C. Liu et al. reported the synthesis of carbon nanosheets on a metal-coated glass at a low temperature. In fact, it is a kind of process to grow carbon-based material directly on metal . Recently, the catalytic effect of copper on graphene growth has been reported in high-temperature CVD processes [27, 28], whereas it has not been studied in a plasma-enhanced chemical vapour deposition (PECVD) process. Furthermore, low operation temperature is necessary for an economic and facile process, which can be more feasible for industrial application. Especially, it can pave the way for more applicable substrate materials . For instance, glass is a widely used commercial material with a cheap price but low melting temperature, which should be adopted in a low-temperature process.
In this work, VG films were grown on glass substrates in plasma-enhanced CVD with copper foils at a relatively low temperature, and the properties of vertical graphene films were investigated with the catalytic effect of copper foil in the PECVD process.
Optical emission spectra (OES) were taken during the growth process by a high-resolution spectrometer (HR4000CG-UV-NIR, Ocean Optics). The VG film structure was analysed with field emission SEM (JEOL, JSM7401F). High-resolution transmission electron microscopy (HRTEM, JEM-2100F JEOL) was taken to confirm successful growth of graphene in nanoscale. Chemical elements of as-prepared films were determined by an energy-dispersive spectrometer (EDS, JEOL, JSM 6700F). Carbon bonding structure was analysed by Raman spectroscopy (Renishaw, RM-1000 Invia) with a wavelength of 532 nm (Ar+ ion laser). The optical transmittance of VG films was determined by a UV-vis spectrophotometer (UV-650, JASCO) in the visible and infrared ranges.
Energy-dispersive spectrometer analysis results of VG on glass grown with assistance of a copper catalyst
In this work, vertically oriented conductive graphene film is synthesized directly on glass substrates with a copper catalyst in a low-temperature PECVD process. The catalytic mechanism of copper in the VG growth process is investigated in this work. The transparency and sheet resistance of the VG films were characterized with different growth times. The direct growth of the VG on glass substrates with copper in the PECVD process presented in this work does not require any additional substrate etching or transfer processes. This VG growth process is expected to facilitate the scaleup and makes VG production more economic for potential industrial production. The large surface area of VG films provides a big advantage in the application of electrical devices and energy storage devices.
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2011-0006268). This research was also supported by the MKE (The Ministry of Knowledge Economy), Korea, under the ITRC (Information Technology Research Center)) support program (NIPA-2012-H0301-12-4013) supervised by the NIPA (National IT Industry Promotion Agency).
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