The successful integration of graphene into microelectronic devices is strongly dependent on the availability of direct deposition processes, which can provide uniform, large area and high quality graphene on nonmetallic substrates. As of today the dominant technology is based on Si and obtaining graphene with Si is treated as the most advantageous solution. However, the formation of carbide during the growth process makes manufacturing graphene on Si wafers extremely challenging. To overcome these difficulties and reach the set goals, we proposed growth of high quality graphene layers by the CVD method on Ge(100)/Si(100) wafers. In addition, a stochastic model was applied in order to describe the graphene growth process on the Ge(100)/Si(100) substrate and to determine the direction of further processes. As a result, high quality graphene was grown, which was proved by Raman spectroscopy results, showing uniform monolayer films with FWHM of the 2D band of 32 cm−1.
We have performed a density functional study of graphene adsorbed on Au(111) surface using both a local density approximation and a semiempirical van der Waals approach proposed by Grimme, known as the DFT-D2 method. Graphene physisorbed on metal has the linear dispersion preserved in the band structure, but the Fermi level of the system is shifted with respect to the conical points, which results in a doping effect. We show that the type and amount of doping depends not only on the choice of the exchange-correlation functional used in the calculations, but also on the supercell geometry that models the physical system. We analyzed how the factors such as the in-plane cell parameter and interlayer spacing in gold influence the Fermi-level shift, and we found that even a small variation in these parameters may cause a transition from p-type to n-type doping. We have selected a reasonable set of model parameters and obtained that graphene is either undoped or at most slightly p-type doped on the clean Au(111) surface, which seems to be in line with experimental findings. On the other hand, modifications of the substrate lattice may induce larger doping, up to 0.30\char21{}0.40 eV, depending on the graphene-metal adsorption distance. The sensitivity of the graphene-gold interface to the structural parameters may allow to tune doping across the samples, which could lead to possible applications in graphene-based electronic devices. We believe that the present remarks can be also useful for other studies based on the periodic DFT.
Protection of Cu(111) surface by chemical vapor deposition graphene coating is investigated. The X-ray photoemission spectroscopy results do not reveal any signs of corrosion on graphene-coated Cu(111), and suggest perfect protection of copper surface against interaction with atmospheric gases. However, the scanning tunneling spectroscopy results show that cracks in the graphene sheet open up windows for nanoscale corrosion. We have shown also that such local corrosions are not only limited to the discontinuities but may also progresses underneath the graphene cover.
Graphene devices require electric contacts with metals, particularly with gold. Scanning tunneling spectroscopy studies of electron local density of states performed on mono-, bi-, and trigraphene layer deposited on metallic substrate shows that gold substrate causes the Fermi level shift downwards which means that holes are donated by metal substrate to graphene which becomes -type doped. These experimental results are in good accordance with recently published density function theory calculations.
Various experimental data revealing large-area high-quality graphene films grown by the CVD method on Ge(001)/Si(001) substrates are presented. SEM images have shown that the structure of nano-facets is formed on the entire surface of Ge(001), which is covered by a graphene layer over the whole macroscopic sample surface of 1 cm2. The hill-and-valley structures are positioned 90° to each other and run along the direction. The hill height in relation to the valley measured by STM is about 10 nm. Raman measurements have shown that a uniform graphene monolayer covers the nano-facet structures on the Ge(001) surface. Raman spectroscopy has also proved that the grown graphene monolayer is characterized by small strain variations and minimal charge fluctuations. Atomically resolved STM images on the hills of the nanostructures on the Ge(001) surface have confirmed the presence of a graphene monolayer. In addition, the STS/CITS maps show that high-quality graphene has been obtained on such terraces. The subsequent coalescence of graphene domains has led to a relatively well-oriented large-area layer. This is confirmed by LEED measurements, which have indicated that two orientations are preferable in the grown large-area graphene monolayer. The presence of large-area coverage by graphene has been also confirmed by low temperature Hall measurements of a macroscopic sample, showing an n-type concentration of 9.3 × 1012 cm−2 and a mobility of 2500 cm2 V−1 s−1. These important characteristic features of graphene indicate a high homogeneity of the layer grown on the large area Ge(001)/Si(001) substrates.