ARTICLE pubs.acs.org/JPCC
Adsorption Structures and Electronic Properties of 1,4-Phenylene Diisocyanide on the Au(111) Surface J. Zhou,† D. Acharya,*,‡,|| N. Camillone III,§ P. Sutter,‡ and M. G. White*,†,§ †
Department of Chemistry, State University of New York (SUNY) at Stony Brook, Stony Brook, New York 11794, United States Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States § Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, United States ‡
ABSTRACT: The adsorption structures and electronic properties of 1,4-phenylene diisocyanide (PDI) on a Au(111) surface have been studied using temperature programmed desorption (TPD), two-photon photoemission (2PPE), and scanning tunneling microscopy (STM). As deposited at 95 K, PDI molecules form disordered islands and short one-dimensional chains on Au(111) terraces. The work function decreases with increasing PDI coverage, and an occupied electronic state appears at 0.88 eV below the Fermi level. Annealing to 300 K causes the PDI molecules to reorganize on the surface and form ordered, onedimensional molecular chains that extend for many tens of nanometers across the Au(111) terraces. The repeating structure of the molecular chains is consistent with a recently proposed [AuPDI]n structure in which PDI molecules lie parallel to the surface and are interconnected by Au adatoms released from the Au(111) surface. The formation of the molecular chains is accompanied by a large drop in the work function which we attribute to an increase in the number and magnitude of interfacial dipoles. The electronic structure of the molecular chains is also characterized by occupied and unoccupied states at 0.88 eV below and +3.32 eV above the Fermi level, respectively. The latter are most prominent after annealing a PDI/Au(111) surface to 300 K, indicating that they are associated with interfacial states of the one-dimensional molecular chains.
1. INTRODUCTION The electronic properties of organic molecules on metal substrates are of significant interest because of their central role in molecular electronics.14 Specifically, the energy level alignment of molecules bound to the metal surface determines the efficiency of charge transport between adsorbed molecules and the metal substrate.13 Of particular importance are the energy positions of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) relative to the Fermi edge (EF) of the metal contact, which are indicative of the junction bias required for hole and electron conduction, respectively. As a consequence, experimental characterization of the electronic structure of moleculemetal interfaces is essential to understanding and predicting the performance of molecular electronic devices. The thiolgold interaction is the most extensively studied contact in molecular electronics applications, largely because the strong chemical bond between the sulfur and gold atoms allows the formation of ordered overlayers, e.g., self-assembled monolayers (SAMs).57 However, susceptibility to oxidation79 and a high electron transfer barrier10 have motivated the search for new molecular junctions. More recently, isocyanides have attracted widespread interest for this application, as the NtC triple bond is expected to act as an effective bridge for connecting pπ orbitals of aromatic molecules with dπ orbitals of the metal contact. Indeed, recent conductance measurements using nanoparticlemolecule junctions showed that molecules containing isocyanide terminal r 2011 American Chemical Society
groups exhibit an order of magnitude increase in conductance over the same molecule with a thiol terminal group.11 Theoretical calculations also predicted a 6-fold increase in conductance of AuCN junctions compared to AuS interfaces.12 However, some groups have reported the opposite trend. For instance, conducting probe atomic force microscopy was used to investigate SAMs of several aromatic systems with isocyanide and thiol terminal groups on a Au surface and found that the AuCN junctions were more resistive.13 The apparent disagreement among experiments and theory means that no clear picture has emerged as to the effectiveness of the AuCN interface for charge transport. Moreover, meaningful comparisons with theory will require more direct experimental probes of the interfacial electronic structure on isocyanide-covered surfaces where the molecular coverage and morphology are known. In this work, we examined the morphology and electronic structure of 1,4-phenylene diisocyanide (PDI) molecules adsorbed on a Au(111) surface. The PDI/Au(111) system is an attractive model for studies of metalisocyanide interactions, as the PDI molecule represents the simplest aromatic isocyanide that can act as a π-conjugated molecular bridge between two metal electrodes. Previous experimental measurements of the conductance gap of PDI SAMs on a Au(111) surface placed the Received: June 7, 2011 Revised: September 1, 2011 Published: September 16, 2011 21151
dx.doi.org/10.1021/jp205349e | J. Phys. Chem. C 2011, 115, 21151–21160
The Journal of Physical Chemistry C HOMO level 0.38 ( 0.1 eV below EF.14 To our knowledge, no experimental information on the relative energy of the LUMO level of PDIAu contacts has been reported. Inverse photoemission studies of 4,40 -biphenyl diisocyanide (BPDI), with two phenyl rings between the NC end groups, on Au(111) revealed a broad feature at 4 eV above EF. After deconvolution, a peak at 5.3 eV above EF was assigned to the LUMO level of BPDI.15 Since PDI has a somewhat smaller HOMOLUMO gap (8.6 eV16) than BPDI (10.0 eV15) in the gas phase, the LUMOEF energy gap for PDI/Au(111) would be expected to be somewhat lower than 5 eV. The latter would still represent a substantial barrier to electron transmission across a PDIAu interface.10,15 The electron transport properties of PDImetal junctions have been the subject of a number of theoretical studies. Xue and Ratner, using a Green’s function method and a single PDI molecule bridging two Au electrodes, predicted the LUMO level to be in near resonance with EF of the Au contact.17 Calculations of electron transmission across the AuPDIAu bridge showed a large zero-bias conductance which was attributed to near resonant tunneling through the LUMO. More recently, Li et al. explored the electronic structure of PDI on Au(111) at low coverage under the assumption that the molecules are bound with their molecular axes perpendicular to the surface via one AuCN linkage.16 The LUMOEF gap for the AuCN contact was calculated to be 0.7 eV, suggesting a substantially smaller barrier for electron transmission compared to that expected on the basis of the inverse photoemission measurements of BPDI/ Au(111).15 However, DFT calculations generally underestimate HOMOLUMO gaps compared to experiments.18 To address this deficiency, Li et al. performed additional calculations including self-energy corrections and surface polarization effects. With these corrections, the LUMO state of PDI on Au(111) shifted further from the EF level by about 1.52 eV,19 a value still significantly smaller than that for BPDI/Au(111).15 The general discrepancy among theoretical studies makes it important to obtain direct experimental determinations of the energy level alignment of the AuPDI interface for understanding and interpreting the macroscopic transport measurements. In addition to direct determination of the LUMO level energy, it is important to understand the relationship between the electronic structure and the moleculemetal chemical interactions and molecular binding geometry. In both the experimental and theoretical studies discussed above, it has been assumed the PDI molecules bind end-on to the Au surface through a single Au—C bond. This bonding geometry is consistent with infrared spectroscopy measurements which indicate the presence of two CtN frequencies corresponding to a free —NtC group and one shifted to higher frequency which was assigned to —NtC —Au.2023 However, very recent STM imaging experiments show that PDI deposited on Au(111) at low coverage (0.004 ML) forms one-dimensional (1-D) structures whose repeat distance is consistent with chains of alternating PDI molecules and Au adatoms.24,25 In this model, the PDI molecules lie parallel to the surface and are bonded at each end to Au adatoms which are pulled from the surface (or step edge) by the strong Auisocyanide interaction. Support for the proposed [AuPDI]n structure was provided by infrared reflectance absorption spectroscopy (IRAS) measurements for PDI dosed on Au(111) at 300 K, showing only one CtN band whose frequency (2137 cm1) is consistent with Au—CtN binding.25 Only at the highest PDI exposures was a shoulder at lower frequency detected (2123 cm1), which was attributed to PDI molecules bounded vertically on top
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of the Au-adatoms. The results of DFT calculations were also reported which show that the binding energy for [AuPDI]n chains on a (4 4) Au(111) slab is nearly 4 times greater than the vertical bonding geometry calculated by Li et al., using similar methods.16,25 These recent studies suggest that the PDI adsorption structure on Au(111) produced by physical vapor deposition may be quite different from that for PDI SAMs prepared from solution. A surface morphology involving extended molecular chains with interspersed Au contacts offers interesting possibilities for charge transfer, but little is known about the electronic properties of the PDIAu interface and its dependence on coverage or growth conditions. In this work, we have studied the adsorption structures and electronic properties of PDI on Au(111) with temperature programmed desorption (TPD), two-photon photoemission (2PPE) spectroscopy, scanning tunneling microscopy (STM), and spectroscopy (STS). STM images show that molecules deposited at 95 K adsorb in small disordered patches and at step edges. 2PPE measurements of such surfaces indicate that the work function decreases with increasing coverage and reveal the presence of an occupied electronic state at 0.88 eV below the Fermi level. The occupied state is also observed by STS. Annealing to 300 K results in a marked change in the adsorption structure and the electronic structure of the PDIAu interface. STM images show that the disordered structures observed at 95 K give way to long, 1-D molecular chains that cover the surfaces of the Au(111) terraces when the surface is annealed to 300 K. At high coverage, the 1-D chains dominate the surface topography with essentially all of the molecules bound in chain structures. The periodicity of the corrugation along the chains is the same as that observed by Boscoboinik et al.,24,25 and consistent with the formation of parallel molecular chains with a [AuPDI]n repeating unit. This structural rearrangement is accompanied by a large decrease in the work function indicative of the formation of interface dipoles and the appearance of an unoccupied state with an energy of 3.32 eV above the Fermi level. The 2PPE peaks corresponding to the occupied and unoccupied states are most prominent after annealing to 300 K, indicating that they are associated with electronic states of the 1-D molecular chains.
2. EXPERIMENTAL METHODS The experiments were performed in an ultrahigh vacuum (UHV) chamber (base pressure
