Postgrowth tuning of the bandgap of single-layer molybdenum disulfide films by sulfur/selenium exchange.

We demonstrate bandgap tuning of a single-layer MoS2 film on SiO2/Si via substitution of its sulfur atoms by selenium through a process of gentle sputtering, exposure to a selenium precursor, and annealing. We characterize the substitution process both for S/S and S/Se replacement. Photoluminescence and, in the latter case, X-ray photoelectron spectroscopy provide direct evidence of optical band gap shift and selenium incorporation, respectively.

Amplification of conformational effects via tert-butyl groups: hexa-tert-butyl decacyclene on Cu(100) at room temperature.

The design of molecular systems as functional elements for use in next-generation electronic sensors and devices often relies on the addition of functional groups acting as spacers to modify adsorbate-substrate interactions. Although advantageous in many regards, these spacer groups have the secondary effect of amplifying internal conformational effects of the parent molecule. Here we investigate one such molecule-2,5,8,11,14,17-hexa-tert-butyl-decacyclene (HBDC, C60H66)-deposited on Cu(100) at monolayer and submonolayer coverages using an ultra-high vacuum (UHV) scanning tunneling microscope (STM).

Steric blocking as a tool to control molecular film geometry at a metal surface.

The application of steric blocking in surface science is exemplified by the control of surface patterns through the selective methylation of pentacenetetrone. Pentacenetetrones interact (with one another) on Cu(111) via intermolecular hydrogen bonding involving the carbonyl oxygen and the adjacent hydrogen atoms. Steric blocking of the intermolecular interaction by the successive insertion of inert methyl groups at terminal locations transforms a dense molecular pattern first into isolated double rows and eventually into single rows in a highly predictable fashion.

Tunability in polyatomic molecule diffusion through tunneling versus pacing.

The diffusion temperature of molecular 'walkers', molecules that are capable of moving unidirectionally across a substrate violating its symmetry, can be tuned over a wide range utilizing extension of their aromatic backbone, insertion of a second set of substrate linkers (converting bipedal into quadrupedal species), and substitution on the ring. Density functional theory simulation of the molecular dynamics identifies the motion of the quadrupedal species as pacing (as opposed to trotting or gliding). Knowledge about the diffusion mode allows us to draw conclusions on the relevance of tunneling to the surface diffusion of polyatomic organic molecules.

H-atom position as pattern-determining factor in arenethiol films.

The evolution of a low coverage of benzenethiol molecules on Cu(111) during annealing shows the prevalence of S...

Surface diffusive motion in a periodic and asymmetric potential.

9,10-Dithioanthracene adsorbed on Cu(111) diffuses exclusively along the high-symmetry axis of the molecule-substrate system. Further reduction of the symmetry of the system by asymmetric methylation does not reduce the symmetry of the motion although it has a substantial effect on the diffusion rate (100-fold reduction) and renders the diffusion barrier asymmetric. This is in contrast to the behavior expected of a classical particle, and it provides a direct single-molecule-scale vista on the validity of The Principle of Microscopic Reversibility first formulated by Tolman in 1924, which despite its fundamental role has attracted little visualization.

A homomolecular porous network at a Cu(111) surface.

Anthraquinone molecules self-assemble on a Cu(111) surface into a large two-dimensional honeycomb network (square root of 304 x square root of 304)R23 degrees with pore diameters of approximately 50 A. The spontaneous formation of a pattern containing pores roughly five times larger than the size of the constituent molecules is unprecedented. The network originates from a delicate balance between substrate-mediated repulsion and intermolecular attraction involving an unusual chemical motif: hydrogen bonding between a carbonyl oxygen and an aromatic hydrogen atom.

Oxadiazole-metal interface: from isolated molecules to pi-stacking.

Derivatives of 2,5-diaryl-1,3,4-oxadiazole are used widely for electron transport in organic light emitting diodes (OLED). This study addresses the structure of 2,5-diphenyl-1,3,4-oxadiazole (PPD) molecules on Cu(111) using scanning tunneling microscopy (STM) and density function theory (DFT): at incomplete coverage, PPD molecules are found horizontally on the surface; once the surface area is insufficient to accommodate all adsorbates in this fashion, a pi-stacked film of vertically arranged molecules is formed. In contrast to bulk PPD, in this film, the molecules are arranged face-to-face at a separation of square root(3a0) = 4.

Coverage and nearest-neighbor dependence of adsorbate diffusion.

We present data on the coverage and nearest-neighbor dependences of the diffusion of CO on Cu(111) by time-lapsed scanning tunneling microscope (STM) imaging. Most notable is a maximum in diffusivity of CO at a local coverage of one molecule per 20 substrate atoms and a repulsion between CO molecules upon approach closer than three adsites, which in combination with a less pronounced increase in potential energy at the diffusion transition state, leads to rapid diffusion of CO molecules around one another. We propose a new method of evaluating STM-based diffusion data that provides all parameters necessary for the modeling of the dynamics of an adsorbate population.

Unidirectional adsorbate motion on a high-symmetry surface: "walking" molecules can stay the course.

Step edges and low-symmetry faces of metal crystals can restrict the diffusive motion of adsorbates, yet they offer little flexibility with regards to the location and/or direction of the guided motion. We show inherently unidirectional motion of an organic molecule on a high-symmetry thermodynamic-equilibrium metal surface [Cu(111)]. Sequential placement of the substrate linkers of 9,10-dithioanthracene prevents it from rotating or veering off course.