Peter A Sloan

Two-electron dissociation of single molecules by atomic manipulation at room temperature

Using the tip of a scanning tunnelling microscope (STM) to mechanically manipulate individual atoms and molecules on a surface is now a well established procedure. Similarly, selective vibrational excitation of adsorbed molecules with an STM tip to induce motion or dissociation has been widely demonstrated. Such experiments are usually performed on weakly bound atoms that need to be stabilized by operating at cryogenic temperatures. Analogous experiments at room temperature are more difficult, because they require relatively strongly bound species that are not perturbed by random thermal fluctuations. But manipulation can still be achieved through electronic excitation of the atom or molecule by the electron current tunnelling between STM tip and surface at relatively high bias voltages, typically 1–5 V. Here we use this approach to selectively dissociate chlorine atoms from individual oriented chlorobenzene molecules adsorbed on a Si(111)-7 × 7 surface. We map out the final destination of the chlorine daughter atoms, finding that their radial and angular distributions depend on the tunnelling current and hence excitation rate. In our system, one tunnelling electron has nominally sufficient energy to induce dissociation, yet the process requires two electrons. We explain these observations by a two-electron mechanism that couples vibrational excitation and dissociative electron attachment steps.

A new mechanism of atomic manipulation: bond-selective molecular dissociation via thermally activated electron attachment

We report a new mechanism of (bond-selective) atomic manipulation in the scanning tunneling microscope (STM). We demonstrate a channel for one-electron-induced C-Cl bond dissociation in chlorobenzene molecules chemisorbed on the Si(111)-7 × 7 surface, at room temperature and above, which is thermally activated. We find an Arrhenius thermal energy barrier to one-electron dissociation of 0.8 ± 0.2 eV, which we correlate explicitly with the barrier between chemisorbed and physisorbed precursor states of the molecule. Thermal excitation promotes the target molecule from a state where one-electron dissociation is suppressed to a transient state where efficient one-electron dissociation, analogous to the gas-phase negative-ion resonance process, occurs. We expect the mechanism will be obtained in many surface systems, and not just in STM manipulation, but in photon and electron beam stimulated (selective) chemistry.

Atomically resolved real-space imaging of hot electron dynamics

The dynamics of hot electrons are central to understanding the properties of many electronic devices. But their ultra-short lifetime, typically 100 fs or less, and correspondingly short transport length-scale in the nanometre range constrain real-space investigations. Here we report variable temperature and voltage measurements of the nonlocal manipulation of adsorbed molecules on the Si(111)-7 × 7 surface in the scanning tunnelling microscope. The range of the nonlocal effect increases with temperature and, at constant temperature, is invariant over a wide range of electron energies. The measurements probe, in real space, the underlying hot electron dynamics on the 10 nm scale and are well described by a two-dimensional diffusive model with a single decay channel, consistent with 2-photon photo-emission (2PPE) measurements of the real time dynamics.

Time-resolved scanning tunnelling microscopy for molecular science

Time-resolved scanning tunnelling microscopy (STM) and its application in molecular science are reviewed. STM can image individual atoms and molecules and thus is able to observe the results of molecular processes such as diffusion, desorption, configuration switching, bond-breaking and chemistry, on the atomic scale. This review will introduce time-resolved STM, its experimental limitations and implementations with particular emphasis on thermally activated and tunnelling current induced molecular processes. It will briefly examine the push towards ultrafast imaging. In general, results achieved by time-resolved STM demonstrate the necessity of both space and time resolution for fully characterizing molecular processes on the atomic scale.

Manipulation of polyatomic molecules with the scanning tunnelling microscope at room temperature : chlorobenzene adsorption and desorption from Si(111)-(7 × 7)

We report the imaging of chlorobenzene molecules chemisorbed on the Si(111)-(7 ? 7) surface at room temperature with the scanning tunnelling microscope, and the desorption of the molecules by the tunnelling current. Detailed voltage-dependent imaging (at positive bias) allows the elucidation of the number and orientation of all the adsorbate configurations in the 7 ? 7 unit cell. At negative bias the adsorbate was observed to affect the imaging properties of neighbouring half unit cells. The threshold voltage required for desorption of the chlorobenzene molecules was invariant to small changes in the tip-state, the adsorption site (corner adatom, middle adatom, faulted or unfaulted half of the unit cell) and the kind of doping of the substrate (n?or p?type).

Decoration of surfaces with size-selected clusters and molecular manipulation at room temperature: precision and uncertainty in organizing atoms

The deposition onto surfaces of clusters of atoms, prepared and size–selected in the gas phase, is, like atomic or molecular manipulation with the scanning tunnelling microscope, an appealing (but parallel) route to the creation of nanoscale surface features. Both of these seemingly orthogonal approaches allow, in principle, a selected number of atoms to be organized, and both are strongly affected by the lateral thermal diffusion of the constituent atoms, molecules or clusters over the surface. In this sense, the room–temperature (as opposed to cryogenic–temperature) regime can be regarded as a hostile environment for organizing atoms. In this paper we review recent achievements in size–selected cluster deposition and molecular manipulation at room temperature and thus address the fundamental question: with what precision can we organize atoms at room temperature?

Molecular and atomic manipulation mediated by electronic excitation of the underlying Si(111)-7x7 surface

We report the local atomic manipulation properties of chemisorbed toluene molecules on the Si(111)-7x7 surface and of the silicon adatoms of the surface. Charge injected directly into the molecule, or into its underlying bonding silicon adatom, can induce the molecule to change bonding site. The voltage dependence of the rates of these processes match closely with scanning tunnelling spectroscopy of the toluene and adatom species. The branching ratio between toluene molecules which are moved to a neighbouring site, or those that travel further is invariant to voltage, suggesting a common final manipulation step for both injection into the molecule and into the bonding adatom site. At low temperatures the rate of silicon adatom manipulation matches that of toluene manipulation, further suggesting that all these manipulation processes are driven by electronic excitation of the underlying silicon surface. Our results therefore suggest that a common non-adiabatic process mediates atomic and molecular manipulation induced by the STM on the Si(111)-7x7 surface and may also mediate similar manipulation induced by the laser irradiation of the Si(111)-7x7 surface.

Concerted Thermal-Plus-Electronic Nonlocal Desorption of Chlorobenzene from Si(111)-7 × 7 in the STM

The rate of desorption of chemisorbed chlorobenzene molecules from the Si(111)-7 × 7 surface, induced by nonlocal charge injection from an STM tip, depends on the surface temperature. Between 260 and 313 K, we find an Arrhenius thermal activation energy of 450 ± 170 meV, consistent with the binding energy of physisorbed chlorobenzene on the same surface. Injected electrons excite the chlorobenzene molecule from the chemisorption state to an intermediate physisorption state, followed by thermal desorption. We find a second thermal activation energy of 21 ± 4 meV in the lower temperature region between 77 and 260 K, assigned to surface phonon excitation.

Mapping the plasmon response of Ag nanoislands on graphite at 100 nm resolution with scanning probe energy loss spectroscopy

We demonstrate plasmon mapping of Ag nanostructures on graphite using scanning probe energy loss spectroscopy (SPELS) with a spatial resolution of 100 nm. In SPELS, an STM tip is used as a localized source of field-emitted electrons to probe the sample surface. The energy loss spectrum of the backscattered electrons is measured to provide a chemical signature of the surface under the tip. We acquire three images simultaneously with SPELS: i) constant-current field-emission images, which provide topographical information; ii) backscattered electron images, which display material contrast; and iii) SPELS images, where material-dependent features such as plasmons are mapped.

Preparing and regulating a bi-stable molecular switch by atomic manipulation

We present a scanning tunneling microscopy (STM) investigation into the influence of the STM tip on the adsorption site switching of polychlorinatedbiphenyl (PCB) molecules on the Si(111)-7 × 7 surface at room temperature. From an initially stable adsorption configuration, atomic manipulation by charge injection from the STM tip prepared a new bi-stable configuration that switched between two bonding arrangements. No switching rate bias dependence was found for +1.0 to +2.2 V. Assuming a thermally driven switching process we find that the measured energy barriers to switching are influenced by the exact location of the STM tip by more than 10%. We propose that this energy difference is due the dispersion interaction between the tip and the molecule.