Joachim Welker

Revealing the angular symmetry of chemical bonds by atomic force microscopy

Working the Angles on Chemical Bonding The forces exerted by chemical bonds depend not only on the distances between atoms but also upon the angles between them. Welker and Giessibl (p. 444; see the cover) probed the angular dependence of the CO molecule adsorbed on top of a copper atom on an atomically flat Cu(111) surface using both atomic force microscopy and scanning tunneling microscopy (STM). Probe tips with three different tip-atom-symmetry environments were used. All three tips delivered similar STM images, but force probes revealed the angular dependence of the CO bond to the surface and provided data for a model of the changes in bond energy. The angular dependence of chemical bonding forces was determined for carbon monoxide adsorbed on a copper surface atom. We have measured the angular dependence of chemical bonding forces between a carbon monoxide molecule that is adsorbed to a copper surface and the terminal atom of the metallic tip of a combined scanning tunneling microscope and atomic force microscope. We provide tomographic maps of force and current as a function of distance that revealed the emergence of strongly directional chemical bonds as tip and sample approach. The force maps show pronounced single, dual, or triple minima depending on the orientation of the tip atom, whereas tunneling current maps showed a single minimum for all three tip conditions. We introduce an angular dependent model for the bonding energy that maps the observed experimental data for all observed orientations and distances.

Near-field thermal imaging of nanostructured surfaces

We show that a near-field scanning thermal microscope, which essentially detects the local density of states of the thermally excited electromagnetic modes at nanometer distances from some material, can be employed for nanoscale imaging of structures on that materials surface. This finding is explained theoretically by an approach which treats the surface structure perturbatively.

Subatomic resolution force microscopy reveals internal structure and adsorption sites of small iron clusters

Metal clusters really close-up Atomic force microscopy (AFM) can be used to reveal subatomic structures. By this means, Emmrich et al. found that individual copper and iron atoms formed toroidal structures on a copper surface. These shapes arise from the electrostatic attractions in the center of the atoms and Pauli repulsions at their edges. Individual atoms within clusters have underlying surface symmetry and can bind to different surface sites as clusters form. Science, this issue p. 308 Torodial images of adsorbed metal atoms and clusters reflect their bonding symmetry. Clusters built from individual iron atoms adsorbed on surfaces (adatoms) were investigated by atomic force microscopy (AFM) with subatomic resolution. Single copper and iron adatoms appeared as toroidal structures and multiatom clusters as connected structures, showing each individual atom as a torus. For single adatoms, the toroidal shape of the AFM image depends on the bonding symmetry of the adatom to the underlying structure [twofold for copper on copper(110) and threefold for iron on copper(111)]. Density functional theory calculations support the experimental data. The findings correct our previous work, in which multiple minima in the AFM signal were interpreted as a reflection of the orientation of a single front atom, and suggest that dual and triple minima in the force signal are caused by dimer and trimer tips, respectively.

Phantom force induced by tunneling current: a characterization on Si(111).

Simultaneous measurements of tunneling current and atomic forces provide complementary atomic-scale data of the electronic and structural properties of surfaces and adsorbates. With these data, we characterize a strong impact of the tunneling current on the measured force on samples with limited conductivity. The effect is a lowering of the effective gap voltage through sample resistance which in turn lowers the electrostatic attraction, resulting in an apparently repulsive force. This effect is expected to occur on other low-conductance samples, such as adsorbed molecules, and to strongly affect Kelvin probe measurements when tunneling occurs.

The near-field scanning thermal microscope.

We report on the design, characterization, and performance of a near-field scanning thermal microscope capable to detect thermal heat currents mediated by evanescent thermal electromagnetic fields close to the surface of a sample. The instrument operates in ultrahigh vacuum and retains its scanning tunneling microscope functionality, so that its miniature, micropipette-based thermocouple sensor can be positioned with high accuracy. Heat currents on the order of 10(-7) W are registered in z spectroscopy at distances from the sample ranging from 1 to about 30 nm. In addition, the device provides detailed thermographic images of a samples surface.

The influence of chemical bonding configuration on atomic identification by force spectroscopy.

The force between two atoms depends not only on their chemical species and distance, but also on the configuration of their chemical bonds to other atoms. This strongly affects atomic force spectroscopy, in which the force between the tip of an atomic force microscope and a sample is measured as a function of distance. We show that the short-range forces between tip and sample atoms depend strongly on the configuration of the tip, to the point of preventing atom identification with a poorly defined tip. Our solution is to control the tip apex before using it for spectroscopy. We demonstrate a method by which a CO molecule on Cu can be used to characterize the tip. In combination with gentle pokes, this can be used to engineer a specific tip apex. This CO Front atom Identification (COFI) method allows us to use a well-defined tip to conduct force spectroscopy.

Analysis of force-deconvolution methods in frequency-modulation atomic force microscopy

Summary In frequency-modulation atomic force microscopy the direct observable is the frequency shift of an oscillating cantilever in a force field. This frequency shift is not a direct measure of the actual force, and thus, to obtain the force, deconvolution methods are necessary. Two prominent methods proposed by Sader and Jarvis (Sader–Jarvis method) and Giessibl (matrix method) are investigated with respect to the deconvolution quality. Both methods show a nontrivial dependence of the deconvolution quality on the oscillation amplitude. The matrix method exhibits spikelike features originating from a numerical artifact. By interpolation of the data, the spikelike features can be circumvented. The Sader–Jarvis method has a continuous amplitude dependence showing two minima and one maximum, which is an inherent property of the deconvolution algorithm. The optimal deconvolution depends on the ratio of the amplitude and the characteristic decay length of the force for the Sader–Jarvis method. However, the matrix method generally provides the higher deconvolution quality.

Application of the equipartition theorem to the thermal excitation of quartz tuning forks

The deflection signal of a thermally excited force sensor of an atomic force microscope can be analyzed to gain important information about the detector noise and about the validity of the equipartion theorem of thermodynamics. Here, we measured the temperature dependence of the thermal amplitude of a tuning fork and compared it to the expected values based on the equipartition theorem. In doing so, we prove the validity of these assumptions in the temperature range from 140 K to 300 K. Furthermore, the application of the equipartition theorem to quartz tuning forks at liquid helium temperatures is discussed.

Preparation of light-atom tips for scanning probe microscopy by explosive delamination

To obtain maximal resolution in scanning tunneling microscopy (STM) and atomic force microscopy, the size of the protruding tip orbital has to be minimized. Beryllium as tip material is a promising candidate for enhanced resolution because a beryllium atom has just four electrons, leading to a small covalent radius of only 96 pm. Besides that, beryllium is conductive and has a high elastic modulus, which is a necessity for a stable tip apex. However, beryllium tips that are prepared ex situ are covered with a robust oxide layer, which cannot be removed by just heating the tip. Here, the authors present a successful preparation method that combines the heating of the tip by field emission and a mild collision with a clean metal plate. That method yields a clean, oxide-free tip surface as proven by a work function of Φexpt=5.5 eV as deduced from a current-distance curve. Additionally, a STM image of the Si-(111)-(7×7) is presented to prove the single-atom termination of the beryllium tip.