Quantum confinement of two-dimensional surface electronic states has been explored as a way for controllably modifying the electronic structures of a variety of coinage metal surfaces. In this Letter, we use scanning tunneling microscopy and spectroscopy (STM/STS) to study the electron confinement within individual ring-shaped cycloparaphenylene (CPP) molecules forming self-assembled films on Ag(111) and Au(111) surfaces. STM imaging and STS mapping show the presence of electronic states localized in the interiors of CPP rings, inconsistent with the expected localization of molecular electronic orbitals. Electronic energies of these states show considerable variations correlated with the molecular shape. These observations are explained by the presence of localized states formed due to confinement of surface electrons by the CPP skeletal framework, which thus acts as a molecular electronic "corral". Our experiments suggest an approach to robust large-area modification of the surface electronic structure via quantum confinement within molecules forming self-assembled layers.

We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

The photophysical properties of silicon semiconductor nanocrystals (SiNCs) are extremely sensitive to the presence of surface chemical defects, many of which are easily produced by oxidation under ambient conditions. The diversity of chemical structures of such defects and the lack of tools capable of probing individual defects continue to impede understanding of the roles of these defects in SiNC photophysics. We use scanning tunneling spectroscopy to study the impact of surface defects on the electronic structures of hydrogen-passivated SiNCs supported on the Au(111) surface. Spatial maps of the local electronic density of states (LDOS) produced by our measurements allowed us to identify locally enhanced defect-induced states as well as quantum-confined states delocalized throughout the SiNC volume. We use theoretical calculations to show that the LDOS spectra associated with the observed defects are attributable to Si-O-Si bridged oxygen or Si-OH surface defects.

Alkali halides are well-known for their tendency to form rock-salt-like crystal structures. Here we present a scanning tunneling microscopy study of a previously unreported alternative structure of one such alkali halide, RbI. When deposited on Ag(111) at a low submonolayer surface coverage, RbI forms islands with hexagonally coordinated atomic structures, in contrast to the expected rock-salt structures typically observed for such alkali halide films on metal surfaces. At a near-monolayer RbI surface coverage, we observe the coexistence of the hexagonally coordinated phase and a square-coordinated rock-salt-like RbI phase that is analogous to that observed for other alkali halides. Our density functional theory calculations for this system highlight the role of RbI−Ag interfacial charge transfer in defining the RbI structure and the impact of local atomic coordination on the RbI−Ag charge-transfer interaction.

We present scanning tunneling microscopy and spectroscopy (STM/STS) investigations of the electronic structures of different alkyl-substituted oligothiophenes on the Au(111) surface. STM imaging showed that on Au(111), oligothiophenes adopted distinct straight and bent conformations. By combining STS maps with STM images, we visualize, in real space, particle-in-a-box-like oligothiophene molecular orbitals. We demonstrate that different planar conformers with significant geometrical distortions of oligothiophene backbones surprisingly exhibit very similar electronic structures, indicating a low degree of conformation-induced electronic disorder. The agreement of these results with gas-phase density functional theory calculations implies that the oligothiophene interaction with the Au(111) surface is generally insensitive to molecular conformation.