Non-contact atomic force microscopy (NC-AFM) at true atomic resolution is used to investigate the (110) surface of rutile TiO 2. We are able to simultaneously resolve both bridging oxygen and titanium atoms of this prototypical oxide surface. Furthermore, the characteristic defect species, i.e. bridging oxygen vacancies, single and double hydroxyls as well as subsurface defects, are identified in the very same frame. We employ density functional theory (DFT) calculations to obtain a comprehensive understanding of the relation between the tip apex structure and the observed image contrast. Our results provide insight into the physical mechanisms behind atomic-scale contrast, indicating that electrostatic interaction can lead to a far more complex contrast than commonly assumed.
Molecular self-assembly is employed for creating unidirectional molecular nanostructures on a truly insulating substrate, namely the (101 j 4) cleavage plane of calcite. The molecule used is racemic heptahelicene-2-carboxylic acid, which forms structures, well-aligned along the [010] crystallographic direction and stable at room temperature. Precise control of both molecule-substrate and molecule-molecule interaction is required, leading to the formation of such wire-like structures of well-defined width and lengths exceeding 100 nm. This subtle balance is governed by the heptahelicene-2-carboxylic acid used in this study, allowing for both hydrogen bond formation as well as π-π stacking.
Non-contact atomic force microscopy is used to study C(60) molecules deposited on the rutile TiO(2)(110) surface in situ at room temperature. At submonolayer coverages, molecules adsorb preferentially at substrate step edges. Upon increasing coverage, ordered islands grow from the decorated step edges onto the lower terraces. Simultaneous imaging of bridging oxygen rows of the substrate and the C(60) island structure reveals that the C(60) molecules arrange themselves in a centered rectangular superstructure, with the molecules lying centered in the troughs formed by the bridging oxygen rows. Although the TiO(2)(110) surface exhibits a high density of surface defects, the observed C(60) islands are of high order. This indicates that the C(60) intermolecular interaction dominates over the molecule-substrate interactions that may cause structural perturbations on a defective surface. Slightly protruding C(60) strands on the islands are attributed to anti-phase boundaries due to stacking faults resulting from two islands growing together.
The adsorption of 3,4,9,10-perylene tetracarboxylic diimide derivative molecules on the rutile TiO 2 ͑110͒ surface was investigated by noncontact atomic force microscopy and density-functional theory ͑DFT͒ calculations. After submonolayer deposition, individual molecules are observed to adsorb with their main axis aligned along the ͓001͔ direction and centered on top of the bridging oxygen rows. Depending on the tip termination, two distinctly different molecular contrasts are achieved. In the first mode, the molecules are imaged as bright elongated features, while in another mode the molecules appear with a bright rim and a dark bow-shaped center. Comparison with the defect density on the bare TiO 2 ͑110͒ surface suggests that the molecules preferentially anchor to surface defects. Our DFT calculations reveal details of the molecular adsorption position, confirming the experimentally observed adsorption on top of the bridging oxygen rows. The DFT results indicate that diffusion along the rows should be quite easily possible, while diffusion perpendicular to the rows seems to be hindered by a significant energy barrier.
Calcite, the most stable polymorph of calcium carbonate, is one of the most abundant simple salts in the geological environment. Consequently, its natural (1014) cleavage plane has been studied extensively by a wide range of surface-sensitive techniques, giving indications for two reconstructions, namely a (2 × 1) and a so-called 'row-pairing' reconstruction. The existence of the (2 × 1) reconstruction has been discussed controversially in the literature, but is now confirmed as a true surface property. In contrast, a comprehensive discussion on the existence of the row-pairing reconstruction is lacking so far.Here, we present a non-contact atomic force microscopy (NC-AFM) study of the (1014) calcite surface performed in an ultra-high vacuum. We discuss a broad variety of different NC-AFM contrasts and present a comprehensive classification scheme. This scheme encompasses a total of 12 different contrast modes. Atomically resolved NC-AFM images are shown, giving experimental evidence for 10 of these contrast modes. In particular, some of these modes allow for identification of the two surface reconstructions while others do not. This variety in appearances provides an explanation for the seemingly contradicting observations in the literature. Based on a detailed investigation of the influence of tip termination and interaction regime, we further analyse the existence of the row-pairing reconstruction.
Calcite is a mineral of fundamental importance that plays a crucial role in many fields of research such as biomineralization, biomolecule adsorption, and reactivity as well as industrial and daily life applications. Consequently, the most stable cleavage plane of calcite has been studied extensively using both direct imaging techniques such as atomic force microscopy as well as spectroscopic and diffraction techniques. Several surface structures have been reported for the (1014) cleavage plane of calcite differing from the simple bulk-truncated structure and an ongoing controversy exists in literature whether the cleavage plane exhibits a (2 x 1) reconstruction or not. We study the (1014) cleavage plane using high-resolution noncontact atomic force microscopy (NC-AFM) under ultrahigh vacuum conditions and obtain a clear signature of the (2 x 1) reconstruction. This reconstruction is observed in very narrow tip-surface distance ranges only, explaining why in some experiments the reconstruction has been observed and in others not. Moreover, as all sample preparation is performed in ultrahigh vacuum, the possibility of the (2 x 1) reconstruction being adsorbate-induced appears rather unlikely. Additionally, tip-induced surface changes are ruled out as origin for the observed reconstruction either. In conclusion, our study suggests that the (2 x 1) reconstruction is a true surface property of the (1014) cleavage plane of calcite.
The acquisition of dense 3D data sets is of great importance, but also a challenge for scanning probe microscopy (SPM). Thermal drift often induces severe distortions in the data, which usually constrains the acquisition of dense data sets to experiments under ultra-high vacuum and low-temperature conditions. Atom tracking is an elegant approach to compensate for thermal drift and to position the microscope tip with highest precision. Here, we present a flexible drift compensation system which can easily be connected to existing SPM hardware. Furthermore, we describe a 3D data acquisition and position correction protocol, which is capable of handling large and non-linear drift as typically present in room temperature measurements. This protocol is based on atom-tracking for precise positioning of the tip and we are able to acquire dense 3D data sets over several hours at room temperature. The performance of the protocol is demonstrated by presenting 3D data taken on a CaCO(3)(10 ̅14) surface with the data density being as large as 85×85×500 pixel.
A key issue for high-resolution frequency-modulation atomic force microscopy imaging in liquids is minimizing the frequency noise, which requires a detailed analysis of the corresponding noise contributions. In this paper, we present a detailed description for modifying a commercial atomic force microscope (Bruker MultiMode V with Nanoscope V controller), aiming at atomic-resolution frequency-modulation imaging in ambient and in liquid environment. Care was taken to maintain the AFMs original stability and ease of operation. The new system builds upon an optimized light source, a new photodiode and an entirely new amplifier. Moreover, we introduce a home-built liquid cell and sample holder as well as a temperature-stabilized isolation chamber dedicated to low-noise imaging in liquids. The success of these modifications is measured by the reduction in the deflection sensor noise density from initially 100 fm/√Hz to around 10 fm/√Hz after modification. The performance of our instrument is demonstrated by atomically resolved images of calcite taken under liquid conditions.
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