Vibrational Excitation in Electron Transport through Carbon Nanotube Quantum Dots

Electron transport in single-walled carbon nanotubes (SWCNTs) is extremely sensitive to environmental effects. SWCNTs experiencing an inhomogeneous environment are effectively subjected to a disorder potential, which can lead to localized electronic states. An important element of the physical picture of such states localized on the nanometer-scale is the existence of a local vibronic mainfold resulting from the localization-enhanced electron-vibrational coupling. In this Letter, scanning tunneling spectroscopy (STS) is used to study the quantum-confined electronic states in SWCNTs deposited on the Au(111) surface. STS spectra show the vibrational overtones identified as D-band Kekulé vibrational modes and K-point transverse out-of plane phonons. The presence of these vibrational modes in the STS spectra suggests rippling distortion and dimerization of carbon atoms on the SWCNT surface. The present study thus, for the first time, experimentally connects the properties of well-defined localized electronic states to the properties of their associated vibronic states

Self-Trapping of Charge Carriers in Semiconducting Carbon Nanotubes: Structural Analysis

The spatial extent of charged electronic states in semiconducting carbon nanotubes with indices (6,5) and (7,6) was evaluated using density functional theory. It was observed that electrons and holes self-trap along the nanotube axis on length scales of about 4 and 8 nm, respectively, which localize cations and anions on comparable length scales. Self-trapping is accompanied by local structural distortions showing periodic bond-length alternation. The average lengthening (shortening) of the bonds for anions (cations) is expected to shift the G-mode frequency to lower (higher) values. The smaller-diameter nanotube has reduced structural relaxation due to higher carbon–carbon bond strain. The reorganization energy due to charge-induced deformations in both nanotubes is found to be in the 30–60 meV range. Our results represent the first theoretical simulation of self-trapping of charge carriers in semiconducting nanotubes, and agree with available experimental data

Collaboration and Near-Peer Mentoring as a Platform for Sustainable Science Education Outreach

Decreased funding for middle and high school education has resulted in reduced classroom time, which, when coupled with an increased focus on standardized testing, has decreased the exposure of many middle school students to hands-on science education. To help address these challenges, we developed an integrated outreach program, spanning grades 6–12, designed to engage students by bringing students to the University of Oregon to perform hands-on laboratory experiments. Initially developed to supplement science education lost to state-mandated furlough days, the programmatic design can be applied readily in other contexts including afterschool, weekend, or summer programs. The outreach activities and scaffolding rely heavily on near-peer mentoring, which provides a visible pathway for younger students to envision themselves as future scientists while also providing mentoring and leadership opportunities for high school, undergraduate, and graduate students. The use of near-peer mentoring is also critically important for the program’s sustainability because it enables a more efficient allocation of graduate student and faculty time. In the first 2.5 years, over 450 middle school students have participated in the program and student feedback shows that students are engaged and excited about the outreach activities

Spatial Mapping of Sub-Bandgap States Induced by Local Nonstoichiometry in Individual Lead Sulfide Nanocrystals

The properties of photovoltaic devices based on colloidal nanocrystals are strongly affected by localized sub-bandgap states associated with surface imperfections. A correlation between their properties and the atomic-scale structure of chemical imperfections responsible for their appearance must be established to understand the nature of such surface states. Scanning tunneling spectroscopy is used to visualize the manifold of electronic states in annealed ligand-free lead sulfide nanocrystals supported on the Au(111) surface. Delocalized quantum-confined states and localized sub-bandgap states are identified, for the first time, via spatial mapping. Maps of the sub-bandgap states show localization on nonstoichiometric adatoms self-assembled on the nanocrystal surfaces. The present model study sheds light onto the mechanisms of surface state formation that, in a modified form, may be relevant to the more general case of ligand-passivated nanocrystals, where under-coordinated surface atoms exist due to the steric hindrance between passivating ligands attached to the nanocrystal surface

Adsorption-Induced Conformational Isomerization of Alkyl-Substituted Thiophene Oligomers on Au(111): Impact on the Interfacial Electronic Structure

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

Coverage-Dependent Self-Assembly Regimes of Alkyl-Substituted Thiophene Oligomers on Au(111): Scanning Tunneling Microscopy and Spectroscopy

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

Creation and Annihilation of Charge Traps in Silicon Nanocrystals: Experimental Visualization and Spectroscopy

Recent studies have shown the presence of an amorphous surface layer in nominally crystalline silicon nanocrystals (SiNCs) produced by some of the most common synthetic techniques. The amorphous surface layer can serve as a source of deep charge traps, which can dramatically affect the electronic and photophysical properties of SiNCs. We present results of a scanning tunneling microscopy/scanning tunneling spectroscopy (STM/STS) study of individual intragap states observed on the surfaces of hydrogen-passivated SiNCs deposited on the Au(111) surface. STS measurements show that intragap states can be formed reversibly when appropriate voltage–current pulses are applied to individual SiNCs. Analysis of STS spectra suggests that the observed intragap states are formed via self-trapping of charge carriers injected into SiNCs from the STM tip. Our results provide a direct visualization of the charge trap formation in individual SiNCs, a level of detail which until now had been achieved only in theoretical studies

Quantum Confinement of Surface Electrons by Molecular Nanohoop Corrals

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 <i>within</i> 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