Electrochemical reduction is used to synthesize indium-gallium-hydroxide-nitrate nanoclusters which are shown to be promising precursors for thin-film transistors.
Alkyl-substituted quaterthiophenes on Au(111) form dimers linked by their alkyl substituents and, instead of adopting the trans conformation found in bulk oligothiophene crystals, assume cis conformations. Surprisingly, the impact of the conformation is not decisive in determining the lowest unoccupied molecular orbital energy. Scanning tunneling microscopy and spectroscopy of the adsorption geometries and electronic structures of alkyl-substituted quaterthiophenes show that the orbital energies vary substantially because of local variations in the Au(111) surface reactivity. These results demonstrate that interfacial oligothiophene conformations and electronic structures may differ substantially from those expected based on the band structures of bulk oligothiophene crystals.
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.
Charge
transport in electronic applications involving molecular
semiconductor materials strongly depends on the electronic properties
of molecular-scale layers interfacing with external electrodes. In
particular, local variations in molecular environments can have a
significant impact on the interfacial electronic properties. In this
study, we use scanning tunneling microscopy and spectroscopy to investigate
the self-assembly regimes and resulting electronic structures of alkyl-substituted
quaterthiophenes adsorbed on the Au(111) surface. We find that at
dilute molecular concentrations, dimerized cis conformers were formed,
while at higher concentrations corresponding to small fractions of
a submonolayer, the molecular conformation converted to trans, with
the molecules self-assembled into ordered islands. At approximately
half-monolayer concentrations, the structure of the self-assembled
islands transformed again showing a different type of the trans conformation
and qualitatively different registry with the Au(111) lattice structure.
Molecular distributions are observed to vary significantly due to
variations in local molecular environments, as well as due to variations
in the Au(111) surface reactivity. While the observed conformational
diversity suggests the existence of local variations in the molecular
electronic structure, significant electronic differences are found
even with molecules of identical apparent adsorption configurations.
Our results show that a significant degree of electronic disorder
may be expected even in a relatively simple system composed of conformationally
flexible molecules adsorbed on a metal surface, even in structurally
well-defined self-assembled molecular layers.
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