Since the first report of thiol-based self-assembled monolayers (SAMs) 30 years ago, these structures have been examined in a huge variety of applications. The oxidative and thermal instabilities of these systems are widely known, however, and are an impediment to their widespread commercial use. Here, we describe the generation of N-heterocyclic carbene (NHC)-based SAMs on gold that demonstrate considerably greater resistance to heat and chemical reagents than the thiol-based counterparts. This increased stability is related to the increased strength of the gold-carbon bond relative to that of a gold-sulfur bond, and to a different mode of bonding in the case of the carbene ligand. Once bound to gold, NHCs are not displaced by thiols or thioethers, and are stable to high temperatures, boiling water, organic solvents, pH extremes, electrochemical cycling above 0 V and 1% hydrogen peroxide. In particular, benzimidazole-derived carbenes provide films with the highest stabilities and evidence of short-range molecular ordering. Chemical derivatization can be employed to adjust the surface properties of NHC-based SAMs.

The formation of organic films on gold employing N-heterocyclic carbenes (NHCs) has been previously shown to be a useful strategy for generating stable organic films. However, NHCs or NHC precursors typically require inert atmosphere and harsh conditions for their generation and use. Herein we describe the use of benzimidazolium hydrogen carbonates as bench stable solid precursors for the preparation of NHC films in solution or by vapour-phase deposition from the solid state. The ability to prepare these films by vapour-phase deposition permitted the analysis of the films by a variety of surface science techniques, resulting in the first measurement of NHC desorption energy (158±10 kJ mol−1) and confirmation that the NHC sits upright on the surface. The use of these films in surface plasmon resonance-type biosensing is described, where they provide specific advantages versus traditional thiol-based films.

Although the self-assembly of organic ligands on gold has been dominated by sulfur-based ligands for decades, a new ligand class, N-heterocyclic carbenes (NHCs), has appeared as an interesting alternative. However, fundamental questions surrounding self-assembly of this new ligand remain unanswered. Herein, we describe the effect of NHC structure, surface coverage, and substrate temperature on mobility, thermal stability, NHC surface geometry, and self-assembly. Analysis of NHC adsorption and self-assembly by scanning tunneling microscopy and density functional theory have revealed the importance of NHC-surface interactions and attractive NHC-NHC interactions on NHC monolayer structures. A remarkable way these interactions manifest is the need for a threshold NHC surface coverage to produce upright, adatom-mediated adsorption motifs with low surface diffusion. NHC wingtip structure is also critical, with primary substituents leading to the formation of flat-lying NHC2Au complexes, which have high mobility when isolated, but self-assemble into stable ordered lattices at higher surface concentrations. These and other studies of NHC surface chemistry will be crucial for the success of these next-generation monolayers.

The electronic structure of the Si͑111͒-In͑4ϫ1͒ system, between the Fermi level and the vacuum level, has been studied using inverse photoemission. Single domain 4ϫ1 overlayers were grown on vicinal Si͑111͒ surfaces that were offcut by 3°towards ͓ 1 12͔. In contrast to an earlier inverse photoemission study of this system, which was performed on a multidomain sample, but in agreement with recent photoemission and STM studies, the overlayer system was found to be metallic. A clear Fermi level crossing was detected near the Brillouin zone boundary at X. We suggest a possible reinterpretation of the inverse photoemission study that naturally resolves the controversy about the surface metallicity. ͓S0163-1829͑97͒00948-X͔ PHYSICAL REVIEW B

No abstract

It is found that an ordered and air-stable GaAs͑111͒A-͑1ϫ1͒-Cl surface can be produced by chemical etching/passivation with dilute HCl solution. The synchrotron polarization-dependent Cl K-edge x-ray absorption near-edge structure and x-ray photoelectron spectroscopy studies showed that the surface is terminated with Ga-Cl bonds oriented along the surface normal. Low-energy electron diffraction studies showed a bulklike ͑1ϫ1͒ structure on the Cl-terminated GaAs͑111͒A surface. The Cl termination eliminates surface band-gap states caused by surface oxides. Photoluminescence measurements showed a dramatic increase in the near-band radiative emission rate corresponding to reduction in the occupied surface band-gap states. A reduction of surface gap states by Cl termination was confirmed by surface photovoltage measurements.

We report the first atomic resolution scanning tunneling microscopy images of the InP͑100͒-͑2 3 4͒ surface. High resolution images were obtained for both occupied and unoccupied states. The 34 periodicity is due to missing rows, and the 32 periodicity to the repetition of what appear to be trimer units. It is demonstrated that the images are inconsistent with dimer-based models proposed for related semiconductor surfaces such as GaAs. [S0031-9007(96)

The equilibrium geometry, electronic structure and energetic stability of Bi nanolines on clean and hydrogenated Si(001) surfaces have been examined by means of ab initio total energy calculations and scanning tunnelling microscopy. For the Bi nanolines on a clean Si surface the two most plausible structural models, the Miki or M model (Miki et al 1999 Phys. Rev. B 59 14868) and the Haiku or H model (Owen et al 2002 Phys. Rev. Lett. 88 226104), have been examined in detail. The results of the total energy calculations support the stability of the H model over the M model, in agreement with previous theoretical results. For Bi nanolines on the hydrogenated Si(001) surface, we find that an atomic configuration derived from the H model is also more stable than an atomic configuration derived from the M model. However, the energetically less stable (M) model exhibits better agreement with experimental measurements for equilibrium geometry. The electronic structures of the H and M models are very similar. Both models exhibit a semiconducting character, with the highest occupied Bi-derived bands lying at approximately 0.5 eV below the valence band maximum. Simulated and experimental STM images confirm that at a low negative bias the Bi lines exhibit an 'antiwire' property for both structural models.