Atomically Resolved Defects on Thin Molybdenum Carbide (α-Mo2C) Crystals.

Thin transition metal carbides (TMCs) garnered significant attention in recent years due to their attractive combination of mechanical and electrical properties with chemical and thermal stability. On the other hand, a complete picture of how defects affect the physical properties and application potential of this emerging class of materials is lacking. Here, we present an atomic-resolution study of defects on thin crystals of molybdenum carbide (α-Mo2C) grown via chemical vapor deposition (CVD) by way of conductive atomic force microscopy (C-AFM) measurements under ambient conditions. Defects are characterized based on the type (enhancement/attenuation) and spatial extent (compact/extended) of the effect they have on the conductivity landscape of the crystal surfaces. Ab initio calculations performed by way of density functional theory (DFT) are employed to gather clues about the identity of the defects.

True Atomic-Resolution Surface Imaging and Manipulation under Ambient Conditions via Conductive Atomic Force Microscopy.

A great number of chemical and mechanical phenomena, ranging from catalysis to friction, are dictated by the atomic-scale structure and properties of material surfaces. Yet, the principal tools utilized to characterize surfaces at the atomic level rely on strict environmental conditions such as ultrahigh vacuum and low temperature. Results obtained under such well-controlled, pristine conditions bear little relevance to the great majority of processes and applications that often occur under ambient conditions. Here, we report true atomic-resolution surface imaging via conductive atomic force microscopy (C-AFM) under ambient conditions, performed at high scanning speeds. Our approach delivers atomic-resolution maps on a variety of material surfaces that comprise defects including single atomic vacancies. We hypothesize that atomic resolution can be enabled by either a confined, electrically conductive pathway or an individual, atomically sharp asperity at the tip-sample contact. Using our method, we report the capability of in situ charge state manipulation of defects on MoS2 and the observation of an exotic electronic effect: room-temperature charge ordering in a thin transition metal carbide (TMC) crystal (i.e., an MXene), α-Mo2C. Our findings demonstrate that C-AFM can be utilized as a powerful tool for atomic-resolution imaging and manipulation of surface structure and electronics under ambient conditions, with wide-ranging applicability.

Intercalation leads to inverse layer dependence of friction on chemically doped MoS2.

We present results of atomic-force-microscopy-based friction measurements on Re-doped molybdenum disulfide (MoS2). In stark contrast to the widespread observation of decreasing friction with increasing number of layers on two-dimensional (2D) materials, friction on Re-doped MoS2exhibits an anomalous, i.e. inverse, dependence on the number of layers. Raman spectroscopy measurements combined withab initiocalculations reveal signatures of Re intercalation. Calculations suggest an increase in out-of-plane stiffness that inversely correlates with the number of layers as the physical mechanism behind this remarkable observation, revealing a distinctive regime of puckering for 2D materials.

In Situ Imaging of Candida albicans Hyphal Growth via Atomic Force Microscopy.

Candida albicans is an opportunistic fungal pathogen of humans known for its ability to cause a wide range of infections. One major virulence factor of C. albicans is its ability to form hyphae that can invade host tissues and cause disseminated infections. Here, we introduce a method based on atomic force microscopy to investigate C. albicans hyphae in situ on silicone elastomer substrates, focusing on the effects of temperature and antifungal drugs. Hyphal growth rates differ significantly for measurements performed at different physiologically relevant temperatures. Furthermore, it is found that fluconazole is more effective than caspofungin in suppressing hyphal growth. We also investigate the effects of antifungal drugs on the mechanical properties of hyphal cells. An increase in Young's modulus and a decrease in adhesion force are observed in hyphal cells subjected to caspofungin treatment. Young's moduli are not significantly affected following treatment with fluconazole; the adhesion force, however, increases. Overall, our results provide a direct means of observing the effects of environmental factors and antifungal drugs on C. albicans hyphal growth and mechanics with high spatial resolution.IMPORTANCECandida albicans is one of the most common pathogens of humans. One important virulence factor of C. albicans is its ability to form elongated hyphae that can invade host tissues and cause disseminated infections. Here, we show the effect of different physiologically relevant temperatures and common antifungal drugs on the growth and mechanical properties of C. albicans hyphae using atomic force microscopy. We demonstrate that minor temperature fluctuations within the normal range can have profound effects on hyphal cell growth and that different antifungal drugs impact hyphal cell stiffness and adhesion in different ways.

Genetically-Tunable Mechanical Properties of Bacterial Functional Amyloid Nanofibers.

Bacterial biofilms are highly ordered, complex, dynamic material systems including cells, carbohydrates, and proteins. They are known to be resistant against chemical, physical, and biological disturbances. These superior properties make them promising candidates for next generation biomaterials. Here we investigated the morphological and mechanical properties (in terms of Young's modulus) of genetically-engineered bacterial amyloid nanofibers of Escherichia coli (E. coli) by imaging and force spectroscopy conducted via atomic force microscopy (AFM). In particular, we tuned the expression and biochemical properties of the major and minor biofilm proteins of E. coli (CsgA and CsgB, respectively). Using appropriate mutants, amyloid nanofibers constituting biofilm backbones are formed with different combinations of CsgA and CsgB, as well as the optional addition of tagging sequences. AFM imaging and force spectroscopy are used to probe the morphology and measure the Young's moduli of biofilm protein nanofibers as a function of protein composition. The obtained results reveal that genetically-controlled secretion of biofilm protein components may lead to the rational tuning of Young's moduli of biofilms as promising candidates at the bionano interface.

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 nm(2)) 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.

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.

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.

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

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 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.

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.

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.

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 microscope's performance.