A portable microevaporator for low temperature single atom studies by scanning tunneling and dynamic force microscopy.

Here, we present a microevaporator setup for single adatom deposition at low temperature, which is a prerequisite for most single atom studies with scanning probe techniques. The construction of the microevaporator is based on the tungsten filament of a modified halogen lamp, covered with the required adsorbate. Very stable evaporation conditions were obtained, which were controlled by the filament current. The installation of this microevaporator on a manipulator enabled its transportation directly to the sample at the microscope kept at 5 K. In this way, the controlled deposition of Li onto Ag(100), Li, Pd, and Au onto MgO/Ag(001) as well as Au onto alumina/NiAl(110) at low temperature has been performed. The obtained images recorded after the deposition show the presence of single Li/Au atoms on the sample surfaces as a prove for successful dispersion of single atoms onto the sample surface using this technique.

Measuring the charge state of point defects on MgO/Ag(001).

A detailed understanding of surface defects is highly desirable, e.g. to clarify their role as active sites in catalysis. Here localized defects on the surface of MgO films deposited on Ag(001) are investigated. Since the electronic structure of color centers depends on their local position, spectroscopic signals are highly convoluted and often difficult to disentangle. In this study we aimed to obtain morphological and spectroscopic information on single color centers at a microscopic level with frequency modulated dynamic force microscopy (FM-DFM) and scanning tunneling microscopy (STM) in an ultrahigh vacuum and at low temperature. Four of the major and in literature mostly discussed defect types on MgO have been characterized by their charge state and finally identified by the complementary application of FM-DFM and STM in combination with density functional theory results.

Au dimers on thin MgO(001) films: flat and charged or upright and neutral?

A combination of low temperature scanning tunneling microscopy (STM) and theoretical calculations is used to investigate Au dimers, supported on thin MgO(001) films, whose thickness was chosen such that charge transfer from the Ag substrate to the deposited Au is possible. Au dimers exist not only in an upright geometry--as theoretically predicted to be the most stable configuration--but also as flat lying dimers which populate a manifold of different azimuthal orientations. Apart from the difference in adsorption configurations, these two isomers exhibit rather different electronic structures: while upright dimers are neutral, flat ones are charged.

Oxygen-deficient line defects in an ultrathin aluminum oxide film.

A model for the straight antiphase domain boundary of the ultrathin aluminum oxide film on the NiAl(110) substrate is derived from scanning tunneling microscopy measurements and density-functional theory calculations. Although the local bonding environment of the perfect film is maintained, the structure is oxygen deficient and possesses a favorable adsorption site. The domain boundary exhibits a downwards band bending and three characteristic unoccupied electronic states, in excellent agreement with scanning tunneling spectroscopy measurements.

Bulk electronic structure of metals resolved with scanning tunneling microscopy.

We demonstrate that bulk band structure can have a strong influence in scanning tunneling microscopy measurements by resolving electronic interference patterns associated with scattering phenomena of bulk states at a metal surface and reconstructing the bulk band topology. Our data reveal that bulk information can be detected because states at the edge of the surface-projected bulk band have a predominant role on the scattering patterns. With the aid of density functional calculations, we associate this effect with an intrinsic increase in the projected density of states of edge states. This enhancement is characteristic of the three-dimensional bulk band curvature, a phenomenon analog to a van Hove singularity.

Frequency modulated atomic force microscopy on MgO(001) thin films: interpretation of atomic image resolution and distance dependence of tip-sample interaction.

Atomically resolved images on a MgO(001) thin film deposited on Ag(001) obtained in ultrahigh vacuum by frequency modulated atomic force microscopy at low temperature are presented and analysed. Images obtained in the attractive regime show a different type of contrast formation from those acquired in the repulsive regime. For the interpretation of the image contrast we have investigated the tip-sample interaction. Force and energy were recovered from frequency shift versus distance curves. The derived force curves have been compared to the force laws of long-range, short-range and contact forces. In the attractive regime close to the minimum of the force-distance curve elastic deformations have been confirmed. The recovered energy curve has been scaled to the universal Rydberg model, yielding a decay length of l = 0.3 nm and ΔE = 4.2 aJ (26 eV) for the maximum adhesion energy. A universal binding-energy-distance relation is confirmed for the MgO(001) thin film.

Role of spin in quasiparticle interference.

Quasiparticle interference patterns measured by scanning tunneling microscopy can be used to study the local electronic structure of metal surfaces and high-temperature superconductors. Here, we show that even in nonmagnetic systems the spin of the quasiparticles can have a profound effect on the interference patterns. On Bi(110), where the surface state bands are not spin degenerate, the patterns are not related to the dispersion of the electronic states in a simple way. In fact, the features which are expected for the spin-independent situation are absent and the observed interference patterns can be interpreted only by taking spin-conserving scattering events into account.

Mesoscopic chiral reshaping of the Ag(110) surface induced by the organic molecule PVBA.

We report scanning tunneling microscopy observations on the restructuring of a Ag(110) surface induced by the molecule 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA). Our data reveal that the surface undergoes a mesoscopic step faceting following exposure to submonolayer coverages and thermal activation. A sawtooth arrangement evolves implying long-range mass transport of substrate atoms and forming a regular arrangement of kink sites. Its formation is associated with the molecules' functional headgroups forming carboxylates with [100] Ag microfacets at step edges, and eventually operating to reshape the surface morphology. Interestingly, the resulting microfacets act as chiral templates for the growth of supramolecular PVBA structures. Theoretical modeling based on ab initio results indicates that chiral recognition processes discriminating between the two enantiomers of adsorbed PVBA molecules occur in this process.

Selectivity in vibrationally mediated single-molecule chemistry.

The selective excitation of molecular vibrations provides a means to directly influence the speed and outcome of chemical reactions. Such mode-selective chemistry has traditionally used laser pulses to prepare reactants in specific vibrational states to enhance reactivity or modify the distribution of product species. Inelastic tunnelling electrons may also excite molecular vibrations and have been used to that effect on adsorbed molecules, to cleave individual chemical bonds and induce molecular motion or dissociation. Here we demonstrate that inelastic tunnelling electrons can be tuned to induce selectively either the translation or desorption of individual ammonia molecules on a Cu(100) surface. We are able to select a particular reaction pathway by adjusting the electronic tunnelling current and energy during the reaction induction such that we activate either the stretching vibration of ammonia or the inversion of its pyramidal structure. Our results illustrate the ability of the scanning tunnelling microscope to probe single-molecule events in the limit of very low yield and very low power irradiation, which should allow the investigation of reaction pathways not readily amenable to study by more conventional approaches.

Atomic structure of antiphase domain boundaries of a thin Al2O3 film on NiAl(110).

Line defects of a thin alumina film on NiAl(110) have been studied on the atomic level with scanning tunneling microscopy at 4 K. While boundaries between two reflection domains do not expose a characteristic structure, antiphase domain boundaries are well ordered. The latter boundaries result from the insertion of a row of O atoms, as atomically resolved images of the topmost oxygen layer show. The insertion occurs only in two of the three characteristic directions of the quasihexagonal O lattice. Depending on the direction, either straight or zigzagged boundaries form. An atomic characterization of line defects on the oxide surface is a first step to correlate their topographic structure and chemical activity.

Adsorbate-substrate vibrational modes of benzene on Ag(110) resolved with scanning tunneling spectroscopy.

Using a low temperature scanning tunneling microscope, we have detected low energy adsorbate-substrate (external or frustrated) vibrational modes of benzene molecules adsorbed on a Ag(110) surface. We demonstrate that such vibrations represent a fingerprint of the molecules' chemical state and environment; two different vibrational spectra are measured on molecules populating two different adsorption states. We also find that the distortion of the adsorption geometry of the molecules may give rise to the excitation of additional (initially hidden) modes. Important differences in the spatial distribution of the inelastic signal are also observed for these external modes.

Radiation exposure and recognition of electron microscopic images of protamine at high resolution.

The effect of radiation exposure on visual recognition of individual macromolecules of the protein protamine was examined using high resolution electron microscopy in scanning transmission, fixed beam transmission, dark field and bright field, and recording of images on plates or via video imaging systems including image intensifiers and digital image storage. Loss of recognition of protamine, including its 5 A substructure, followed approximately three-hit kinetics with a Do on the exponential portion of the curve of about 470 e/A2. In spite of the inevitable chemical damage at high doses, virtually all molecules in orientations that exhibited the characteristic protamine structure could still be recognized in dark field scanning transmission or fixed beam bright field at 100-200 e/A2. Recognition fell from 30 to 6% when doses were increased from 1000 to 2000 e/A2 in fixed beam dark field. Exposure rates, varied over seven orders of magnitude from 0.15 e/A2-s to 3 X 10(6) e/A2-s, had no effect at all on the recognition of structures.

A TV system for image recording and processing in conventional transmission electron microscopy.

An image processing system for a CTEM is described which is particularly suited for the imaging of radiation-sensitive objects. It consists of an image intensifier device for single electron counting, a digital storage unit and a video recorder for intermediate storage of low-dose image series. During on-line operation the information can be transferred to a computer for further processing. The output can be transferred onto a second digital storage unit and observed on a monitor. The influence on the DQE of the pulse height distribution of the single electron video signals and of a multiple counting are eliminated by means of special electronic components. Various modes of operation and application possibilities of the image processing system are discussed.