P. Dabrowski

Doping of graphene by a Au(111) substrate: Calculation strategy within the local density approximation and a semiempirical van der Waals approach

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 0.30-0.40 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.

Role of graphene defects in corrosion of graphene-coated Cu(111) surface

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 on gold: Electron density of states studies by scanning tunneling spectroscopy

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 Au/Cr/SiO2/Si substrate shows that gold substrate causes the Fermi level shift downwards which means that holes are donated by metal substrate to graphene which becomes p-type doped. These experimental results are in good accordance with recently published density function theory calculations.

Graphene growth on Ge(100)/Si(100) substrates by CVD method

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.

The role of water in resistive switching in graphene oxide

The resistive switching processes are investigated at the nano-scale in graphene oxide. The modification of the material resistivity is driven by the electrical stimulation with the tip of atomic force microscope. The presence of water in the atmosphere surrounding graphene oxide is found to be a necessary condition for the occurrence of the switching effect. In consequence, the switching is related to an electrochemical reduction. Presented results suggest that by changing the humidity level the in-plane resolution of data storage process can be controlled. These findings are essential when discussing the concept of graphene based resistive random access memories.

Doping domains in graphene on gold substrates: First-principles and scanning tunneling spectroscopy studies

We have studied the graphene/gold interface by means of density functional theory (DFT) and scanning tunneling spectroscopy (STS). Weak interaction between graphene and the underlying gold surface leaves unperturbed Dirac cones in the band-structure, but they can be shifted with respect to the Fermi level of the whole system, which results in effective doping of graphene. DFT calculations revealed that the interface is extremely sensitive to the adsorption distance and to the structure of metals surface, in particular strong variation in doping can be attributed to the specific rearrangements of substrates atoms, such as the change in the crystallographic orientation, relaxation or other modifications of the surface. On the other hand, STS experiments have shown the presence of energetic heterogeneity in terms of the changes in the local density of states (LDOS) measured at different places on the sample. Randomly repeated regions of zero-doping and p-type doping have been identified from parabolic shape characteristics and from well defined Dirac points, respectively. The doping domains of graphene on gold seem to be related to the presence of various types of the surface structure across the sample. DFT simulations for graphene interacting with Au have shown large differences in doping induced by considered structures of substrate, in agreement with experimental findings. All these results demonstrate the possibility of engineering the electronic properties of graphene, especially tuning the doping across one flake which can be useful for applications of graphene in electronic devices.

The study of the interactions between graphene and Ge(001)/Si(001)

The interaction between graphene and germanium surfaces was investigated using a combination of microscopic and macroscopic experimental techniques and complementary theoretical calculations. Density functional theory (DFT) calculations for different reconstructions of the Ge(001) surface showed that the interactions between graphene and the Ge(001) surface introduce additional peaks in the density of states, superimposed on the graphene valence and conduction energy bands. The growth of graphene induces nanofaceting of the Ge(001) surface, which exhibits well-organized hill and valley structures. The graphene regions covered by hills are of high quality and exhibit an almost linear dispersion relation, which indicates weak graphene–germanium interactions. On the other hand, the graphene component occupying valley regions is significantly perturbed by the interaction with germanium. It was also found that the stronger graphene–germanium interaction observed in the valley regions is connected with a lower local electrical conductivity. Annealing of graphene/Ge(001)/Si(001) was performed to obtain a more uniform surface. This process results in a surface characterized by negligible hill and valley structures; however, the graphene properties unexpectedly deteriorated with increasing uniformity of the Ge(001) surface. To sum up, it was shown that the mechanism responsible for the formation of local conductivity inhomogeneities in graphene covering the Ge(001) surface is related to the different strength of graphene–germanium interactions. The present results indicate that, in order to obtain high-quality graphene, the experimental efforts should focus on limiting the interactions between germanium and graphene, which can be achieved by adjusting the growth conditions.

Conductivity Contrast in SEM Images of Hydrogenated Graphene Grown on SiC

Graphene consists of a planar single sheet of sp-bonded carbon atoms arranged in a two-dimensional (2D) honeycomb lattice. One of methods of obtaining epitaxial graphene is growth on SiC(0001) by CVD (Chemical Vapour Deposition) [1]. In this growth mode the first carbon layer it is not a graphene one, it is attached to Si atoms of the substrate by sp bonds and it is called the buffer layer. The conversion of the buffer layer into graphene may be obtained by hydrogenation process. Hydrogen molecules introduced between the buffer layer and the SiC substrate, break most of the sp Si – C bonds and the buffer layer converts into graphene lattice [2].