Todd C. Schwendemann

Three-dimensional imaging of short-range chemical forces with picometre resolution

Chemical forces on surfaces have a central role in numerous scientific and technological fields, including catalysis, thin film growth and tribology. Many applications require knowledge of the strength of these forces as a function of position in three dimensions, but until now such information has only been available from theory. Here, we demonstrate an approach based on atomic force microscopy that can obtain this data, and we use this approach to image the three-dimensional surface force field of graphite. We show force maps with picometre and piconewton resolution that allow a detailed characterization of the interaction between the surface and the tip of the microscope in three dimensions. In these maps, the positions of all atoms are identified, and differences between atoms at inequivalent sites are quantified. The results suggest that the excellent lubrication properties of graphite may be due to a significant localization of the lateral forces.

Three-Dimensional Atomic Force Microscopy – Taking Surface Imaging to the Next Level

Materials properties are ultimately determined by the nature of the interactions between the atoms that form the material. On surfaces, the site-specific spatial distribution of force and energy fields governs the phenomena encountered. This article reviews recent progress in the development of a measurement mode called three-dimensional atomic force microscopy (3D-AFM) that allows the dense, three-dimensional mapping of these surface fields with atomic resolution. Based on noncontact atomic force microscopy, 3D-AFM is able to provide more detailed information on surface properties than ever before, thanks to the simultaneous multi-channel acquisition of complementary spatial data such as local energy dissipation and tunneling currents. By illustrating the results of experiments performed on graphite and pentacene, we explain how 3D-AFM data acquisition works, what challenges have to be addressed in its realization, and what type of data can be extracted from the experiments. Finally, a multitude of potential applications are discussed, with special emphasis on chemical imaging, heterogeneous catalysis, and nanotribology.

Combined low-temperature scanning tunneling/atomic force microscope for atomic resolution imaging and site-specific force spectroscopy.

We present the design and first results of a low-temperature, ultrahigh vacuum scanning probe microscope enabling atomic resolution imaging in both scanning tunneling microscopy (STM) and noncontact atomic force microscopy (NC-AFM) modes. A tuning-fork-based sensor provides flexibility in selecting probe tip materials, which can be either metallic or nonmetallic. When choosing a conducting tip and sample, simultaneous STM/NC-AFM data acquisition is possible. Noticeable characteristics that distinguish this setup from similar systems providing simultaneous STM/NC-AFM capabilities are its combination of relative compactness (on-top bath cryostat needs no pit), in situ exchange of tip and sample at low temperatures, short turnaround times, modest helium consumption, and unrestricted access from dedicated flanges. The latter permits not only the optical surveillance of the tip during approach but also the direct deposition of molecules or atoms on either tip or sample while they remain cold. Atomic corrugations as low as 1 pm could successfully be resolved. In addition, lateral drifts rates of below 15 pm/h allow long-term data acquisition series and the recording of site-specific spectroscopy maps. Results obtained on Cu(111) and graphite illustrate the microscopes performance.

Understanding scanning tunneling microscopy contrast mechanisms on metal oxides: a case study.

A comprehensive analysis of contrast formation mechanisms in scanning tunneling microscopy (STM) experiments on a metal oxide surface is presented with the oxygen-induced (2√2×√2)R45° missing row reconstruction of the Cu(100) surface as a model system. Density functional theory and electronic transport calculations were combined to simulate the STM imaging behavior of pure and oxygen-contaminated metal tips with structurally and chemically different apexes while systematically varying bias voltage and tip-sample distance. The resulting multiparameter database of computed images was used to conduct an extensive comparison with experimental data. Excellent agreement was attained for a large number of cases, suggesting that the assumed model tips reproduce most of the commonly encountered contrast-determining effects. Specifically, we find that depending on the bias voltage polarity, copper-terminated tips allow selective imaging of two structurally distinct surface Cu sites, while oxygen-terminated tips show complex contrasts with pronounced asymmetry and tip-sample distance dependence. Considering the structural and chemical stability of the tips reveals that the copper-terminated apexes tend to react with surface oxygen at small tip-sample distances. In contrast, oxygen-terminated tips are considerably more stable, allowing exclusive surface oxygen imaging at small tip-sample distances. Our results provide a conclusive understanding of fundamental STM imaging mechanisms, thereby providing guidelines for experimentalists to achieve chemically selective imaging by properly selecting imaging parameters.

Achieving A‐Site Termination on La0.18Sr0.82Al0.59Ta0.41O3 Substrates

Smooth substrate surfaces terminated with a single atomic plane are essential for perfecting the epitaxial growth of transition metal oxide fi lms. SrTiO 3 (STO), which is closely lattice matched to many transition metal oxides, is extensively used in part because TiO 2 -terminated surfaces exhibiting singleunit-cell steps can be achieved through etching and annealing techniques. [ 1–5 ] In addition to improving the epitaxial growth of fi lms, substrates terminated by a single atomic plane enable interfaces between transition metal oxides to be studied. For example, TiO 2 -terminated substrates have enabled the interface between LaAlO 3 and STO to be probed where metallicity and superconductivity have been unexpectedly observed. [ 6 , 7 ]

Interface and electronic characterization of thin epitaxial Co3O4 films

The interface and electronic structure of thin (∼20–74 nm) Co3O4(1 1 0) epitaxial films grown by oxygen-assisted molecular beam epitaxy on MgAl2O4(1 1 0) single crystal substrates have been investigated by means of real and reciprocal space techniques. As-grown film surfaces are found to be relatively disordered and exhibit an oblique low energy electron diffraction (LEED) pattern associated with the O-rich CoO2 bulk termination of the (1 1 0) surface. Interface and bulk film structure are found to improve significantly with post-growth annealing at 820 K in air and display sharp rectangular LEED patterns, suggesting a surface stoichiometry of the alternative Co2O2 bulk termination of the (1 1 0) surface. Non-contact atomic force microscopy demonstrates the presence of wide terraces separated by atomic steps in the annealed films that are not present in the as-grown structures; the step height of ≈2.7 A corresponds to two atomic layers and confirms a single termination for the annealed films, consistent with the LEED results. A model of the (1×1) surfaces that allows for compensation of the polar surfaces is presented.

Data acquisition and analysis procedures for high-resolution atomic force microscopy in three dimensions

Data acquisition and analysis procedures for noncontact atomic force microscopy that allow the recording of dense three-dimensional (3D) surface force and energy fields with atomic resolution are presented. The main obstacles for producing high-quality 3D force maps are long acquisition times that lead to data sets being distorted by drift, and tip changes. Both problems are reduced but not eliminated by low-temperature operation. The procedures presented here employ an image-by-image data acquisition scheme that cuts measurement times by avoiding repeated recording of redundant information, while allowing post-acquisition drift correction. All steps are detailed with the example of measurements performed on highly oriented pyrolytic graphite in ultrahigh vacuum at a temperature of 6 K. The area covered spans several unit cells laterally and vertically from the attractive region to where no force could be measured. The resulting fine data mesh maps piconewton forces with <7 pm lateral and<2 pm vertical resolution. From this 3D data set, two-dimensional cuts along any plane can be plotted. Cuts in a plane parallel to the sample surface show atomic resolution, while cuts along the surface normal visualize how the attractive atomic force fields extend into vacuum. At the same time, maps of the tip-sample potential energy, the lateral tip-sample forces, and the energy dissipated during cantilever oscillation can be produced with identical resolution.

Probing three-dimensional surface force fields with atomic resolution: Measurement strategies, limitations, and artifact reduction

Summary Noncontact atomic force microscopy (NC-AFM) is being increasingly used to measure the interaction force between an atomically sharp probe tip and surfaces of interest, as a function of the three spatial dimensions, with picometer and piconewton accuracy. Since the results of such measurements may be affected by piezo nonlinearities, thermal and electronic drift, tip asymmetries, and elastic deformation of the tip apex, these effects need to be considered during image interpretation. In this paper, we analyze their impact on the acquired data, compare different methods to record atomic-resolution surface force fields, and determine the approaches that suffer the least from the associated artifacts. The related discussion underscores the idea that since force fields recorded by using NC-AFM always reflect the properties of both the sample and the probe tip, efforts to reduce unwanted effects of the tip on recorded data are indispensable for the extraction of detailed information about the atomic-scale properties of the surface.

Exploring atomic-scale lateral forces in the attractive regime: a case study on graphite (0001)

A non-contact atomic force microscopy-based method has been used to map the static lateral forces exerted on an atomically sharp Pt/Ir probe tip by a graphite surface. With measurements carried out at low temperatures and in the attractive regime, where the atomic sharpness of the tip can be maintained over extended time periods, the method allows the quantification and directional analysis of lateral forces with piconewton and picometer resolution as a function of both the in-plane tip position and the vertical tip-sample distance, without limitations due to a finite contact area or to stick-slip-related sudden jumps of tip apex atoms. After reviewing the measurement principle, the data obtained in this case study are utilized to illustrate the unique insight that the method offers. In particular, the local lateral forces that are expected to determine frictional resistance in the attractive regime are found to depend linearly on the normal force for small tip-sample distances.

Three-dimensional interaction force and tunneling current spectroscopy of point defects on rutile TiO2(110)

The extent to which point defects affect the local chemical reactivity and electronic properties of an oxide surface was evaluated with picometer resolution in all three spatial dimensions using simultaneous atomic force/scanning tunneling microscopy measurements performed on the (110) face of rutile TiO2. Oxygen atoms were imaged as protrusions in both data channels, corresponding to a rarely observed imaging mode for this prototypical metal oxide surface. Three-dimensional spectroscopy of interaction forces and tunneling currents was performed on individual surface and subsurface defects as a function of tip-sample distance. An interstitial defect assigned to a subsurface hydrogen atom is found to have a distinct effect on the local density of electronic states on the surface, but no detectable influence on the tip-sample interaction force. Meanwhile, spectroscopic data acquired on an oxygen vacancy highlight the role of the probe tip in chemical reactivity measurements.