Density functional theory calculations on graphene/α-SiO2(0001) interface
© Ao et al; licensee Springer. 2012
Received: 23 November 2011
Accepted: 28 February 2012
Published: 28 February 2012
In this work, the graphene/α-SiO2(0001) interface is calculated using density functional theory. On the oxygen-terminated SiO2 surface, atomic structure reconstruction occurs at the graphene/SiO2 interface to eliminate the dangling bonds. The interface interaction is 77 meV/C atom, which indicates that van der Waals force dominates the interaction, but it is stronger than the force between the graphene layers in graphite. The distance between graphene and the SiO2 surface is 2.805 Å, which is smaller than the 3.4 Å interlayer distance of graphite. In addition, the SiO2 substrate induces p-type doping in graphene and opens a small gap of 0.13 eV at the Dirac point of graphene, which is desirable for electronic device applications.
Graphene, a single two-dimensional layer of graphite in hexagonal structure, is the starting point for many nanographite devices with promising electrical properties . After the theoretical prediction of the peculiar electronic properties of graphene in 1947 by Wallace  and the subsequent studies on its magnetic spectrum [3, 4], it took half a century until the graphene could be first experimentally fabricated , and its anomalous quantum Hall effect has been measured [5–7], which encourages numerous works on it now [8–11].
However, the instability of a freestanding graphene (it has an intrinsic three-dimensional structure or ripples)  leads graphene to be used on devices by laying it on a substrate. For example, the insulating substrates made from silicon dioxide [SiO2] are widely used as a dielectric medium in electronic devices. The electrical properties of graphene can be modified using electrical gates, substrates, and chemical species such as atoms and molecules [13, 14]. It has been reported that graphene grown on a SiC surface was n-type and was exhibiting a gap of about 0.26 eV . A theoretical study on bilayer graphene grown on a SiC surface showed that the first carbon layer formed covalent bonds with SiC and acted as a buffer layer, and the graphene nature properties were recovered by the second carbon layer [16, 17]. For graphene supported by SiO2, previous works studied the electrical properties of graphene and the doping effect of the SiO2 substrate [18–23]. They found that graphene was p doped when the graphene was weakly bonded to an O-terminated surface with hydrogen passivation. However, graphene would exhibit a finite bandgap if there is a strong interaction with an O-terminated surface while n doping took place on a Si-terminated surface with the active dangling bonds [20, 21]. In these works, they considered that graphene would form C-O or C-Si bonds on the interface due to the dangling bonds associated with the absence of hydrogen passivation. However, when graphene is used in an electronic device, the graphene layer is usually deposited on a surface of the SiO2 substrate where the atomic structure of the surface is usually considered to reconstruct to eliminate the dangling bonds . In addition, the atomic force microscopy [AFM] image indicated that the height of a single graphene layer on the SiO2 substrate is around 4 Å, which is a bit larger than the 3.4 Å of the graphite interlayer distance . Therefore, the interaction between graphene and the SiO2 surface should be a weak van der Waals interaction without the formation of strong covalent bonds.
In this work, we investigate the graphene/α-SiO2(0001) interface through density functional theory [DFT] calculations with considerations on surface reconstruction of SiO2. The interfacial atomic structure and the effects of the substrate on corresponding electronic structure of graphene will also be studied.
There are two fundamental types of surfaces: the surface with the termination of the Si atoms or the surface with the termination of the O atoms. Based on the atomic structure study of α-SiO2(0001) surface using the first principles , the O-terminated surface was more stable where covalent bonds between two O atoms on a particular Si atom were formed. Therefore, the O-terminated surface is selected for study in this work.
The graphene/α-SiO2(0001) interface is constructed based on the bulk structures. A vacuum thickness of 12 Å is added above the graphene layer to ensure the interaction between the repeated slabs in the normal direction of the surface to be small enough. The simulation cell parameters of the graphene and the SiO2 substrate are a = b = 4.920 Å, α = β = 90°, and γ = 120° and a = b = 4.910 Å, α = β = 90°, and γ = 120°, respectively, where a small lattice mismatch is within a range of 0.3%, as shown in Figure 1a. Based on the AFM result, it is known that the height of the single graphene layer on the SiO2 substrate is around 4 Å . Thus, in the initial structure of graphene/α-SiO2 interface, as shown in Figure 1a, the distance between graphene and SiO2 [d0] is set as 4.0 Å. In the simulation process, a structural relaxation process is allowed for C atoms in the graphene and all Si and O atoms in the substrate, except that the atoms of the lowest O-Si-O monolayer are fixed.
Results and discussion
Atomic structure parameters of bulk SiO2, clean SiO2(0001) surface, and graphene/SiO2(0001) interface
Clean SiO2 slab
Graphene/SiO2 (structure A)
In addition, Table 1 also shows the distance between the first and second Si layers [d1] and the Si-O-Si bond angle [α1] in different structures; d1bulk > d1clean > d1A and α1bulk > α1clean > α1A are found. In light of Figure 1, d1 is affected by both l0 and α1. The former brings out d1bulk < d1clean, and the latter leads to d1bulk > d1clean. Therefore, the effect of α1 on d1 is stronger than that of l0. Comparing structure A with the clean SiO2 surface slab, both l0 and α1 lead to the decrease of d1, where d1 and l0 of structure A shrink to about 4%.
Quantitative experimental data for the interaction strength of graphene/substrate interface is very limited. The first principle calculations showed that the binding energy of graphene on a Si-terminated SiO2 surface is around 20 meV/C atom with interface distance d0 = 3.29 Å and that on a hydrogen passivation O-terminated SiO2 surface is 0.13 eV/C atom with d0 = 2.58 Å . In addition, the interlayer binding energy in graphite was reported to be 50 to 60 meV . In the system of structure A, the binding energy calculated between graphene and the SiO2 substrate is about 77 meV/C atom, which is larger than that in graphite and also in the graphene on Si-terminated SiO2 surface, but it is smaller than that on the hydrogen-passivated O-terminated SiO2 surface. Note that d0 in structure A is 2.820 Å, which is smaller than 3.14 Å in graphite and graphene laid on the Si-terminated SiO2 surface, but it is larger than that on hydrogen-passivated O-terminated SiO2 surface. It is known that the binding energy is inversely proportional to d0. The system of graphene on hydrogen-passivated O-terminated SiO2 surface has the smallest d0 and the strongest binding energy. A previous study implied that the C-C bond is weakened through the strengthening of bonds to the substrate . A similar phenomenon is found in structure A where the C-C bond length of graphene is 1.430 Å, which is longer than the 1.420 Å in graphite. Thus, the adsorption of graphene on SiO2 with structure A is stronger than that between the bulk graphite layers as shown previously.
Charge transfer and atomic charge obtained by Mulliken analysis
In bulk SiO2 and graphite (e)
In clean SiO2 slab and graphene (e)
In structure A (e)
In addition, the electron charges of O4 and O8 atoms at the SiO2 surface are -0.448 and -0.424 e, respectively, for structure A. Those in the clean SiO2(0001) slab are -0.396 and -0.293 e, and in bulk SiO2 are both -0.781 e. On the other hand, the charges of Si15, which binds with O4 and O8, are 1.681, 1.510, and 1.562 e in structure A, clean SiO2 slab, and bulk SiO2, respectively. It is known that the bond strength is in proportion with the multiplication absolute value of changes of the O and Si atoms. Therefore, the interaction between O4 and Si15, and O8 and Si15 are the strongest in bulk SiO2, followed by that in structure A, and the weakest was that in the SiO2 slab. These also agree with the results in Table 1 where the Si-O l0 at the surface or interface is l0bulk < l0A < l0clean.
In conclusion, DFT calculations were employed to study the graphene/α-SiO2(0001) interface with an oxygen-terminated SiO2 surface. After geometry relaxation, a stable structure with a distance between graphene and the SiO2 surface, d0 = 2.805 Å, was observed. In addition, the structure reconstruction of the SiO2 surface took place where the two O atoms binding on a particular Si atom form a covalent bond on the surface to eliminate the surface dangling bonds. Simulation results indicate that the interface interaction is 77 meV/C atom, which indicates that the van der Waals force dominates the interaction. Furthermore, the SiO2 substrate induces p-type doping in graphene and open a small gap of 0.13 eV at the Dirac point of graphene.
The financial supports from the Vice-Chancellor's Postdoctoral Research Fellowship Program of the University of New South Wales (SIR50/PS19184), the ECR grant of the University of New South Wales (SIR30/PS24201), the Faculty Grant of the University of New South Wales (IR001/PS27218), ARC Discovery project of DP1096769 of Australia, and the National Key Basic Research and Development Program (grant no. 2010CB631001) of China are acknowledged.
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