Mehmet Z. Baykara

Noncontact atomic force microscopy

No other method has opened the door to progress in nanoscience and nanotechnology as much as the introduction of scanning probe methods did in the 1980s, since they offer a way to visualize the nanoworld. For maximum impact, however, the ability to image and manipulate individual atoms is the key. Initially, scanning tunneling microscopy was the only scanning-probe-based method that was able to achieve this resolution. Atomic force microscopy (AFM), on the other hand, was quickly developed into a versatile tool with applications ranging from materials characterization in ultrahigh vacuum and nanofabrication under ambient conditions, to biological studies in liquids, but its resolution was limited to the nanometer scale. The reason for this restriction resulted from the fact that the resolution in probe microscopy scales with the sharpness of the tip. In conventional AFM operational modes, a tip that is located at the end of a leaf spring (the so-called cantilever) is either dragged over the surface in permanent contact or gently taps the surface while vibrating, and, whichever mode is used, tips quickly blunt through either permanent or intermittent contact. Maintaining the atomic sharpness of an initially atomically sharp tip requires that the tip never touches the surface. But how can the tip know that the surface is there if it is not allowed to touch? This problem was solved in the 1990s through the realization that the attractive forces acting on the tip when it is in close proximity to the sample affect the resonance frequency of the cantilever even though it is not in actual contact with the surface. Noncontact atomic force microscopy (NC-AFM) makes use of this effect by tracking the shift of the cantilever resonance frequency due to the force field of the surface without ever establishing physical contact between the tip and sample. Much to the astonishment of many, changes induced by individual atoms turned out to induce frequency shifts that are large enough to be detected, and thus atomic-scale imaging with AFM became a reality. Since the beginnings, almost two decades ago, NC-AFM has evolved into a powerful method that is able not just to image surfaces, but also to quantify tip–sample forces and interaction potentials as well as to manipulate individual atoms on conductors, semiconductors, and insulators alike. For the community to keep track of the rapid development in the field, a series of annual international conferences, starting in Osaka, Japan in 1998, has been established. The most recent conference from this series was held in Lindau, Germany, from September 18–22, 2011. Once again, substantial progress was presented; NC-AFM is now able to quantitatively map three-dimensional force fields of surfaces with atomic resolution in ultrahigh vacuum as well as in liquids, and methodological developments add more information to the measurements, for example, through the driving of higher cantilever harmonics or the recording of tunneling currents. For this Thematic Series of the Beilstein Journal of Nanotechnology, many of the presenters from the Lindau conference agreed to submit contributions in order to assemble a series that showcases the present state of the art in the field. I would like to thank all authors who have contributed their excellent original work to this series, all referees whose promptly provided reports have provided valuable suggestions for further improvements while keeping the publication times short, and the entire NC-AFM community for supporting the open access policy of the Beilstein Journal of Nanotechnology. Udo D. Schwarz New Haven, February 2012

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.

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.

Structural lubricity under ambient conditions.

Despite its fundamental importance, physical mechanisms that govern friction are poorly understood. While a state of ultra-low friction, termed structural lubricity, is expected for any clean, atomically flat interface consisting of two different materials with incommensurate structures, some associated predictions could only be quantitatively confirmed under ultra-high vacuum (UHV) conditions so far. Here, we report structurally lubric sliding under ambient conditions at mesoscopic (∼4,000–130,000 nm2) interfaces formed by gold islands on graphite. Ab initio calculations reveal that the gold–graphite interface is expected to remain largely free from contaminant molecules, leading to structurally lubric sliding. The experiments reported here demonstrate the potential for practical lubrication schemes for micro- and nano-electromechanical systems, which would mainly rely on an atomic-scale structural mismatch between the slider and substrate components, via the utilization of material systems featuring clean, atomically flat interfaces under ambient conditions.

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.

Noncontact Atomic Force Microscopy: An Emerging Tool for Fundamental Catalysis Research

Although atomic force microscopy (AFM) was rapidly adopted as a routine surface imaging apparatus after its introduction in 1986, it has not been widely used in catalysis research. The reason is that common AFM operating modes do not provide the atomic resolution required to follow catalytic processes; rather the more complex noncontact (NC) mode is needed. Thus, scanning tunneling microscopy has been the principal tool for atomic scale catalysis research. In this Account, recent developments in NC-AFM will be presented that offer significant advantages for gaining a complete atomic level view of catalysis. The main advantage of NC-AFM is that the image contrast is due to the very short-range chemical forces that are of interest in catalysis. This motivated our development of 3D-AFM, a method that yields quantitative atomic resolution images of the potential energy surfaces that govern how molecules approach, stick, diffuse, and rebound from surfaces. A variation of 3D-AFM allows the determination of forces required to push atoms and molecules on surfaces, from which diffusion barriers and variations in adsorption strength may be obtained. Pushing molecules towards each other provides access to intermolecular interaction between reaction partners. Following reaction, NC-AFM with CO-terminated tips yields textbook images of intramolecular structure that can be used to identify reaction intermediates and products. Because NC-AFM and STM contrast mechanisms are distinct, combining the two methods can produce unique insight. It is demonstrated for surface-oxidized Cu(100) that simultaneous 3D-AFM/STM yields resolution of both the Cu and O atoms. Moreover, atomic defects in the Cu sublattice lead to variations in the reactivity of the neighboring O atoms. It is shown that NC-AFM also allows a straightforward imaging of work function variations which has been used to identify defect charge states on catalytic surfaces and to map charge transfer within an individual molecule. These advances highlight the potential for NC-AFM-based methods to become the cornerstone upon which a quantitative atomic scale view of each step of a catalytic process may be gained. Realizing this potential will rely on two breakthroughs: (1) development of robust methods for tip functionalization and (2) simplification of NC-AFM instrumentation and control schemes. Quartz force sensors may offer paths forward in both cases. They allow any material with an atomic asperity to be used as a tip, opening the door to a wide range of surface functionalization chemistry. In addition, they do not suffer from the instabilities that motivated the initial adoption of complex control strategies that are still used today.