ACS Nano 4, 5773-5782 (2010) Coupling Epitaxy, Chemical Bonding, and Work Function at the Local Scale in Transition Metal-Supported Graphene Bo Wang, Marco Caffio, Catherine Bromley, Herbert Früchtl, and Renald Schaub* School of Chemistry, University of St. Andrews, St. Andrews, KY16 9ST, United Kingdom Corresponding Author (*): [email protected]. Resonance tunneling spectroscopy and density functional theory calculations are employed to explore local variations in the electronic surface potential of a single graphene layer grown on Rh(111). A work function modulation of 220 meV is experimentally measured, indicating that the chemical bonding strength varies significantly across the supercell of the Moiré pattern formed when graphene is bonded to Rh(111). In combination with high-resolution images, which provide precise knowledge of the local atomic registry at the carbonmetal interface, we identify experimentally, and confirm theoretically, the atomic configuration of maximum chemical bonding to the substrate. Our observations are at odds with reported trends for other transition metal substrates. We explain why this is the case by considering the various factors that contribute to the bonding at the graphene/metal interface. KEYWORDS Graphene, rhodium, chemical bonding, scanning tunnelling microscopy, density functional theory, work function dx.doi.org/10.1021/nn101520k Received: July 5, 2010 Accepted: September 24, 2010 Published: October 1, 2010 1 ACS Nano 4, 5773-5782 (2010) Graphene has attracted considerable interest since resonance tunnelling spectroscopy (RTS) researchers at the University of Manchester measurements to probe for the modulation of the extracted a single graphene sheet by electronic surface potential (or work function) across micromechanical cleavage.1 This sp2-bonded carbon the unit cell of the graphene superlattice. By network exhibits many unique properties related to combining microscopy and spectroscopy data, with the linear dispersion of its low-energy electronic the support of extended density functional theory excitations,2 and could lead to promising (DFT) calculations, the electronic coupling of the applications for unconventional graphene-based various local C-Rh registries is examined in detail, nanoelectronics. Recently, monolayer graphene whereby we identify experimentally and confirm (MG) was grown on transition metals (TM) by theoretically the atomic configurations of maximum chemical vapor deposition of small hydrocarbons at and minimum chemical bonding to the metal high temperatures.3-21 Hence, MG/TM constitutes an substrate. Our results are at odds with other MG/TM ideal model system for studies pertaining to studies and we will explain why this is the case, by heterogeneous catalysis. Coke formation (that is the providing a discussion of the electronic and blocking of the active sites of a working catalyst by a structural factors that contribute to the adsorption carbonaceous overlayer) is a severe problem for the of MG on TM surfaces. chemical industry.22 MG/TM also shows potential as a template (nanomesh) for nanotechnology; e.g., polarization-induced surface trapping of laterally organized atoms or molecules was recently demonstrated.11,23 The epitaxy of graphene on TMs has been studied by local and nonlocal surface sensitive techniques. Unlike free-standing graphene, MG/TM exhibits various Moiré superstructures, either 6,18,20 commensurate or incommensurate,12 depending on the magnitude of the lattice mismatch. In addition, recent scanning tunnelling microscopy4,6,13 and photoelectron spectroscopy3 studies have indicated that the morphology of graphene correlates with the strength of the orbital hybridization at the interface: graphene grows Figure 1: (a) Large-scale STM image of graphene/Rh(111), relatively flat on 5d TMs like Pt(111) and Ir(111) and 60×60 nm2. Inset: LEED pattern of graphene/Rh(111) is strongly corrugated on 4d TMs like Ru(0001) and acquired at 74 eV. (b) High-resolution STM image of Rh(111). Despite these efforts, very little is known on graphene/Rh(111). The dashed line highlights the unit cell the coupling between morphology (carbonmetal of the Moiré superstructure, with side lengths of approximately 2.9 nm. (c) Model of a 12C/11Rh registry) and orbital hybridization (chemical bonding) superstructure. The highlighted areas indicate local high- at the atomic scale. This knowledge is of crucial symmetry configurations: T = ring-top, B = ring-bridge, F = importance for the applications of graphene, not ring-fcc, and H = ring-hcp. Refer to text for a description of only in novel electronic devices where charge the registry labeling. (d) Typical STM line profile (in red) transfer is related to doping and electron emission acquired along the main diagonal of a supercell, and height properties,24,25 but also in catalysis where activation profile (in blue) of the carbon atoms along the main is key to chemical reactivity. diagonal of the DFT computed 12C/11Rh supercell. In this work, we investigate the registry of a single Figure 1a presents a typical STM image of monolayer layer of graphene with respect to the underlying graphene on a Rh(111) surface. The expected Rh(111) substrate at the atomic scale by low- hexagonal Moiré superstructure induced by the temperature scanning tunneling microscopy (STM). lattice mismatch of graphene (2.46 Å) on Rh(111) Our high resolution images show that the variation (2.69 Å) is easily identifiable. The superstructure of the tunneling contrast of graphene on Rh(111) is exhibits a remarkable coherence length, in excess of much richer than that on other TMs. Notably, we 100 nm, and is essentially limited by structural identify a specific local C-Rh registry that exhibits a defects inherently present on the substrate beneath strong contrast minimum in the STM signal unseen (such as step edges and other crystalline for other systems, suggesting that the chemical imperfections). An atomically resolved image of the bonding of graphene with a Rh substrate is different. overlayer is shown in Figure 1b. The analysis of many To investigate this, we performed site-specific similar images shows that the periodicity of the 2 ACS Nano 4, 5773-5782 (2010) superlattice is approximately 29 Å. This value hollow hcp and fcc substrates sites. This can be corresponds to the expected periodicity of 29.6 Å easily achieved by imaging the Rh(111) single-crystal resulting from a 12C/11Rh coincidence lattice across a step edge with atomic resolution. Note that (where X/Y denotes the size relationship with the once this assignment is firmly established, further underlying substrate: X graphene unit cells distinction between the ring-fcc and -hcp registries accommodated on Y unit cells of the support). In of graphene becomes trivial: it can be seen from agreement with our topographic observations, LEED Figure 1b that the three ring-bridge sites define patterns (Figure 1a, inset) show hexagonally within each supercell a single triangle with darker arranged satellites around the (111) substrate spots, edges, the center of which corresponds to the ring- indicative of a superstructure with a periodicity of 12 hcp configuration. As will become apparent later, the graphene lattice constants and aligned with the high unambiguous assignment of the STM topographic symmetry directions of the substrate. features with the local high-symmetry configurations is central to the interpretation and understanding of Our observations are similar in many aspects to our spectroscopic measurements and theoretical reports of MG on Ru(0001),4,5 Pd(111),15 and calculations. Ir(111)13 (these substrates and Rh(111) share a comparable lattice mismatch of approximately 10% Why is the STM topographic appearance of MG with graphene), with the exception of one striking adsorbed on Rh(111) so different when compared to difference: a comparison of our high-resolution STM that of other TM substrates, and in particular to the images of MG/Rh(111) (as in Figure 1b) with similar fairly similar Ru(0001) substrate? This question is of images reported for graphene adsorbed on crucial importance for two reasons. First, a variation Ru(0001),4,5 Ir(111),13 and Pd(111)15 reveals that the in the tunnelling contrast necessarily reflects tunneling contrast over graphene is significantly (besides geometrical considerations) a change in richer in the case of our Rh substrate (see also the local density of electronic states at the Fermi level STM line profile shown in Figure 1d). Of particular that depends on the degree of C-Rh interaction interest, three regions of pronounced contrast strength induced by hybridization between the d minima are easily distinguished per supercell (their band of the metal and the states of graphene. appearance as minima is independent of the STM tip Second, the ring-bridge configurations, seen as STM state and the tunneling parameters). These graphitic contrast minima on Rh substrates, have so far largely regions do not show a particularly outstanding been ignored in previous experimental and characteristic on other TM surfaces. We note that a theoretical studies. This is unsurprising due to their broad region of maximum contrast stands as the lack of distinctiveness on other TM substrates. In common feature in the STM images of graphene what follows, we will show that this particular adsorbed on all four substrates. registry corresponds to the local atomic arrangement of strongest chemical bonding between To discuss the atomic registry within a supercell, we