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Funding Information: German Research Foundation grant RA2832/1-1 (P.R., J.H.); Universität Osnabrück, Innovationspool (P.R., J.H.); World Premier International Research Center Initiative (WPI), MEXT, Japan (ASF); Academy of Finland project no. 314862 (Y.S.R., O.K., A.S.F.). Publisher Copyright: © 2023 American Chemical Society. Calcite, in the natural environment the most stable polymorph of calcium carbonate (CaCO3), not only is an abundant mineral in the Earth’s crust but also forms a central constituent in the biominerals of living organisms. Intensive studies of calcite(104), the surface supporting virtually all processes, have been performed, and the interaction with a plethora of adsorbed species has been studied. Surprisingly, there is still serious ambiguity regarding the properties of the calcite(104) surface: effects such as a row-pairing or a (2 × 1) reconstruction have been reported, yet so far without physicochemical explanation. Here, we unravel the microscopic geometry of calcite(104) using high-resolution atomic force microscopy (AFM) data acquired at 5 K combined with density functional theory (DFT) and AFM image calculations. A (2 × 1) reconstruction of a pg-symmetric surface is found to be the thermodynamically most stable form. Most importantly, a decisive impact of the (2 × 1) reconstruction on adsorbed species is revealed for carbon monoxide.

Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an H2O molecule isolated within an adsorbed buckminsterfullerene cage, and compare this to the intrafullerene position of HF. Using normal incidence X-ray standing wave (NIXSW) analysis, coupled with density functional theory and molecular dynamics simulations, we show that both H2O and HF are located at an off-centre position within the fullerene cage, caused by substantial intra-cage electrostatic fields generated by surface adsorption of the fullerene. The atomistic and electronic structure simulations also reveal significant internal rotational motion consistent with the NIXSW data. Despite this substantial intra-cage interaction, we find that neither HF or H2O contribute to the endofullerene frontier orbitals, confirming the chemical isolation of the encapsulated molecules. We also show that our experimental NIXSW measurements and theoretical data are best described by a mixed adsorption site model. The chemical nature of molecules encapsulated within fullerenes remain debated, with reports proposing a Faraday cage effect. Here, the authors show that H2O and HF molecules encapsulated inside a C60 cage experience a substantial intra-cage electrostatic interaction that results in off-center locations; despite this, the endofullerene’s frontier orbitals is unaffected, resulting in chemical shielding of the caged molecule.

Detailed information on structural, chemical, and physical properties of natural cleaved (10.4) calcite surfaces was obtained by a combined atomic force microscopy (AFM) and infrared (IR) study using CO as a probe molecule under ultrahigh vacuum (UHV) conditions. The structural quality of the surfaces was determined using non-contact AFM (NC-AFM), which also allowed assigning the adsorption site of CO molecules. Vibrational frequencies of adsorbed CO species were determined by polarization-resolved infrared reflection absorption spectroscopy (IRRAS). At low exposures, adsorption of CO on the freshly cleaved (10.4) calcite surface at a temperature of 62 K led to the occurrence of a single C-O vibrational band located at 2175.8 cm-1, blue-shifted with respect to the gas phase value. For larger exposures, a slight, coverage-induced redshift was observed, leading to a frequency of 2173.4 cm-1 for a full monolayer. The width of the vibrational bands is extremely small, providing strong evidence that the cleaved calcite surface is well-defined with only one CO adsorption site. A quantitative analysis of the IRRA spectra recorded at different surface temperatures revealed a CO binding energy of -0.31 eV. NC-AFM data acquired at 5 K for sub-monolayer CO coverage reveal single molecules imaged as depressions at the position of the protruding surface features, in agreement with the IRRAS results. Since there are no previous experimental data of this type, the interpretation of the results was aided by employing density functional theory calculations to determine adsorption geometries, binding energies, and vibrational frequencies of carbon monoxide on the (10.4) calcite surface. It was found that the preferred geometry of CO on this surface is adsorption on top of calcium in a slightly tilted orientation. With increased coverage, the binding energy shows a small decrease, revealing the presence of repulsive adsorbate-adsorbate interactions.

A distinct dumbbell shape is observed as the dominant contrast feature in the experimental data when imaging 1,1’-ferrocene dicarboxylic acid (FDCA) molecules on bulk and thin film CaF2(111) surfaces with non-contact atomic force microscopy (NC-AFM). We use NC-AFM image calculations with the probe particle model to interpret this distinct shape by repulsive interactions between the NC-AFM tip and the top hydrogen atoms of the cyclopentadienyl (Cp) rings. Simulated NC-AFM images show an excellent agreement with experimental constant-height NC-AFM data of FDCA molecules at several tip–sample distances. By measuring this distinct dumbbell shape together with the molecular orientation, a strategy is proposed to determine the conformation of the ferrocene moiety, herein on CaF2(111) surfaces, by using the protruding hydrogen atoms as markers.

The formation of insulator-supported functional molecular structures requires a firm anchoring of the molecular building blocks to the underlying surface. With a suitable anchoring mechanism, the f...

We present a theory for analyzing residence times of single molecules in a fixed detection area of a scanning tunneling microscope (STM). The approach is developed for one-dimensional molecule diffusion and can be extended to two dimensions by using the same methodology. Explicit results are derived for an harmonic attractive and repulsive tip-molecule interaction. Applications of the theory allows one to estimate the type and strength of interactions between the STM tip and the molecule. This includes the possibility of an estimation of molecule-molecule interaction when the tip is decorated by a molecule. Despite our focus on STM, this theory can analogously be applied to other experimental probes that monitor single molecules., Comment: 6 pages, 3 figures

A double sample holder supporting both a metal sample and an insulator crystal for high-resolution scanning probe microscopy experiments is described. The metal sample serves as a substrate for tip preparation and tip functionalization to efficiently and reliably enable high-resolution studies of the adjacent insulator surface. Imaging of Ag(111)/mica, Au(111)/mica, CaF2(111), and calcite(104) surfaces is demonstrated at 5 K, including images on calcite(104) produced with a CO terminated tip, which was prepared on the adjacent metal sample.

We introduce a procedure to determine accurate and precise force-distance curves in dynamic force measurements utilizing a sharp tip. While single force curves are prone to systematic, often unnoticed errors, we present their self-consistent retrieval by an alignment procedure using repetitive measurements with the force probe oscillating at varied amplitude. By processing model data, we show that the procedure provides the valid force curve, the actual oscillation amplitude, and fully compensates thermal drift. The benefit of the method is demonstrated by application to experimental data.

We investigate the ${\mathrm{CaF}}_{1}/\mathrm{Si}(111)$ interface using a combination of high-resolution scanning tunneling and noncontact atomic force microscopy operated at cryogenic temperature as well as x-ray photoelectron spectroscopy. Submonolayer ${\mathrm{CaF}}_{1}$ films grown at substrate temperatures between 550 and 600 ${}^{\ensuremath{\circ}}\mathrm{C}$ on $\mathrm{Si}(111)$ surfaces reveal the existence of two island types that are distinguished by their edge topology, nucleation position, measured height, and inner defect structure. Our data suggest a growth model where the two island types are the result of two reaction pathways during ${\mathrm{CaF}}_{1}$ interface formation. A key difference between these two pathways is identified to arise from the excess species during the growth process, which can be either fluorine or silicon. Structural details as a result of this difference are identified by means of high-resolution noncontact atomic force microscopy and add insights into the growth mode of this heteroepitaxial insulator-on-semiconductor system.

The KPFM signal for systems containing local charges can be expressed as a weighted sum over all local charges. The weight function for charges quantifies the contribution of each charge, depending on its position. In this chapter, we evaluate the KPFM weight function for charges by analyzing several application-relevant model systems. The intention of this chapter is to provide insights into the KPFM contrast formation in order to facilitate the KPFM data interpretation. For this, we concentrate on three model systems: (A) a conductive sample in ultra-high vacuum, (B) a dielectric sample in ultra-high vacuum, and (C) a dielectric sample in water. We calculate the weight function for charges for each of these systems using a conductive sphere as a tip model. While the analysis substantiates a number of known experimental observations, it reveals surprising effects in some environments. For example, the sign of the FM-KPFM signal reflects the sign of the charges measured in the systems A and B, but in system C the sign of the KPFM signal is found to be tip-sample distance dependent. Additionally, we deduce the lateral KPFM resolution limits and finally discuss the lateral decay of the weight function to assess how charges contribute to the signal. Our discussion is accompanied by an interactive visualization available at www.pc1.uni-bielefeld.de/kpfm.

In the last decade, impressive progress has been made, demonstrating covalent linkage of precursor molecules on various metal surfaces kept in ultrahigh vacuum. However, especially when having applications in mind, it is desirable to transfer the synthesis strategies from metal surfaces to other substrates. When aiming for using the created structures in future molecular electronic devices, bulk insulator surfaces are favored because of their potential to largely preserve the adsorbate’s electronic structure. On bulk insulator surfaces, however, on-surface synthesis is still in its infancy. This is partly due to the fact that insulators are difficult to access with standard surface science techniques such as scanning tunneling microscopy. More importantly, insulator surfaces pose fundamental challenges when aiming for on-surface reactions. A severe obstacle is the comparably weak interaction of precursor molecules with prototypical insulator surfaces. This weak interaction frequently leads to desorption of the precursor molecules before the reaction temperature is reached when initiating the desired reaction by heating the substrate. Moreover, many reactions—such as Ullmann coupling—are known to be catalyzed by the presence of metals. Despite these challenges, few examples exist that demonstrate covalent linking of precursor molecules on a bulk insulator surface. For these studies, calcite, being an insulator with a band gap of around 6 eV, has been proven to constitute a very suitable substrate. On this substrate, C–C coupling of halogen-substituted precursors has been presented even in the absence of a metal catalyst. Moreover, exploiting the different binding energies of chlorine, bromine, and iodine toward the phenyl group has enabled sequential and site-specific linkage as a promising approach toward hierarchical design. To avoid the above-mentioned obstacle of desorption upon thermal initiation, also photochemical initiation has been demonstrated by inducing a [2 + 2] cycloaddition of C 60 molecules. Current efforts are now directed toward exploring further classical reactions such as Glaser coupling or diacetylene polymerization for on-surface synthesis on bulk insulator substrates.

We analyze Kelvin probe force microscopy (KPFM) for tip-sample systems that contain static charges by presenting a rigorous derivation for the respective KPFM signal in all common KPFM modes, namely amplitude modulation, frequency modulation, or heterodyne detection in the static, open-loop or closed-loop variant. The electrostatic model employed in the derivation is based on a general electrostatic analysis of an arbitrary tip-sample geometry formed by two metals, and which can include a static charge distribution and dielectric material in-between. The effect of the electrostatic force on the oscillating tip is calculated from this model within the harmonic approximation, and the observables for each of the above KPFM modes are derived from the tip oscillation signal. Our calculation reveals that the KPFM signal can for all modes be written as a weighted sum over all charges, whereby each charge is multiplied with a position-dependent weighting factor depending on the tip-sample geometry, the KPFM mode, and the oscillation amplitude. Interestingly, as the weight function does not depend on the charges itself, the contribution of the void tip-sample system and the charge distribution can be well-separated in the KPFM signal. The weight function for charges allows for a detailed understanding of the KPFM contrast formation, and enables to trace the dependence of the KPFM signal on different parameters such as the tip-sample geometry or the oscillation amplitude.

The atomistic structure of the tip apex plays a crucial role in performing reliable atomic-scale surface and adsorbate manipulation using scanning probe techniques. We have developed an automated extraction routine for controlled removal of single hydrogen atoms from the H:Si(100) surface. The set of atomic extraction protocols detect a variety of desorption events during scanning tunneling microscope (STM)-induced modification of the hydrogen-passivated surface. The influence of the tip state on the probability for hydrogen removal was examined by comparing the desorption efficiency for various classifications of STM topographs (rows, dimers, atoms, etc). We find that dimer-row-resolving tip apices extract hydrogen atoms most readily and reliably (and with least spurious desorption), while tip states which provide atomic resolution counter-intuitively have a lower probability for single H atom removal.

The origin of so-called “subatomic” resolution in dynamic force microscopy has remained controversial since its first observation in 2000. A number of detailed experimental and theoretical studies have identified different possible physicochemical mechanisms potentially giving rise to subatomic contrast. In this study, for the first time we are able to assign the origin of a specific instance of subatomic contrast as being due to the back bonding of a surface atom in the tip−sample junction.

Wir zeigen die photochemisch induzierte Reaktion von C60 auf dem Nichtleiter Calcit, die mit Nichtkontakt-Rasterkraftmikroskopie untersucht wurde. Die Bildung kovalenter Bindungen wird durch die Verringerung intermolekularer Abstande offensichtlich. Diese Interpretation wird zusatzlich durch UV/Vis- und Massenspektren an dicken Filmen gestutzt. Die Bestrahlung von C60 fuhrt zu wohlgeordneten, kovalent verknupften Domanen. Daruber hinaus wird die Orientierung der Domanen durch die Gitterdimensionen des Calcitsubstrats vorgegeben. Die Gitterfehlanpassung gezielt zu nutzen, um bewusst die Richtung der Reaktion zu beeinflussen, ist ein neuer Ansatz, um Reaktionen auf Oberflachen maszuschneidern. Hier stellen wir eine Strategie vor, die es ermoglicht, orientierte, kovalente Netzwerke auf Nichtleitern zu generieren.

Molecular self-assembly on surfaces is dictated by the delicate balance between intermolecular and molecule-surface interactions. For many insulating surfaces, however, the molecule-surface interactions are weak and rather unspecific. Enhancing these interactions, on the other hand, often puts a severe limit on the achievable structural variety. To grasp the full potential of molecular self-assembly on these application-relevant substrates, therefore, requires strategies for anchoring the molecular building blocks toward the surface in a way that maintains flexibility in terms of intermolecular interaction and relative molecule orientation. Here, we report the design of a site-specific anchor functionality that provides strong anchoring toward the surface, resulting in a well-defined adsorption position. At the same time, the anchor does not significantly interfere with the intermolecular interaction, ensuring structural flexibility. We demonstrate the success of this approach with three molecules from the class of shape-persistent oligo(p-benzamide)s adsorbed onto the calcite(10.4) surface. These molecules have the same aromatic backbone with iodine substituents, providing the same basic adsorption mechanism to the surface calcium cations. The backbone is equipped with different functional groups. These have a negligible influence on the molecular adsorption on the surface but significantly change the Intermolecular interaction. We show that distinctly different molecular structures are obtained that wet the surface due to the strong linker while maintaining variability in the relative molecular orientation. With this study, we thus provide a versatile strategy for increasing the structural richness in molecular self-assembly on Insulating substrates.

Molecular self-assembly of racemic heptahelicene-2-carboxylic acid on a dielectric substrate at room temperature can be used to generate wire-like organic nanostructures consisting of single and double molecular rows. By means of non-contact atomic force microscopy, we investigate the growth of the wire-like pattern after deposition by experimental and theoretical means. From analyzing the time dependence of the mean row length, two distinct regimes were found. At the early post-deposition stage, the mean length grows in time. Subsequently, a crossover to a second regime is observed, where the mean row length remains nearly constant. We explain these findings by a mean-field rate equation approach providing a comprehensive picture of the growth kinetics. As a result, we demonstrate that the crossover between the two distinct regimes is accomplished by vanishing of the homochiral single rows. At later stages only heterochiral double row structures remain. Published by AIP Publishing.

It is generally accepted that the exposed surfaces of silicon crystals are highly reactive due to the dangling bonds which protrude into the vacuum. However, surface reconstruction not only modifies the reactivity of bulk silicon crystals, but also plays a key role in determining the properties of silicon nanocrystals. In this study we probe the reactivity of silicon clusters at the end of a scanning probe tip by examining their interaction with closed-shell fullerene molecules. Counter to intuitive expectations, many silicon clusters do not react strongly with the fullerene cage, and we find that only specific highly oriented clusters have sufficient reactivity to break open the existing carbon-carbon bonds.

One-dimensional polymer chains consisting of π-conjugated porphyrin units are formed via Glaser coupling on a Ag(111) surface. Scanning probe microscopy reveals the covalent structure of the products and their ordering. The conformational flexibility within the chains is investigated via a comparision of room temperature and cryogenic measurements.

A comprehensive discussion of the physical origins of Kelvin probe force microscopy (KPFM) signals for charged systems is given. We extend the existing descriptions by including the openloop operation mode, which is relevant when performing KPFM in electrolyte solutions. We define the contribution of charges to the KPFM signal by a weight function, which depends on the electric potential and on the capacitance of the tip-sample system. We analyze the sign as well as the lateral decay of this weight function for different sample types, namely, conductive samples as well as dielectric samples with permittivities both larger and smaller than the permittivity of the surrounding medium. Depending on the surrounding medium the sign of the weight function can be positive or negative, which can lead to a contrast inversion for single charges. We furthermore demonstrate that the KPFM signal on thick dielectric samples can scale with the sample size-rendering quantitative statements regarding the charge density challenging. Thus, knowledge on the weight function for charges is crucial for qualitative as well as quantitative statements regarding charges beneath the tip. (C) 2016 AIP Publishing LLC.

Nuclear spins of phosphorus [P] donor atoms in crystalline silicon are among the most coherent qubits found in nature. For their utilization in scalable quantum computers, distinct donor electron wavefunctions must be controlled and probed through electrical coupling by application of either highly localized electric fields or spin-selective currents. Due to the strong modulation of the P-donor wavefunction by the silicon lattice, such electrical coupling requires atomic spatial accuracy. Here, the spatially controlled application of electrical current through individual pairs of phosphorus donor electron states in crystalline silicon and silicon dangling bond states at the crystalline silicon (100) surface is demonstrated using a high‐resolution scanning probe microscope operated under ultra‐high vacuum and at a temperature of 4.3K. The observed pairs of electron states display qualitatively reproducible current-voltage characteristics with a monotonous increase and intermediate current plateaus.

Heptahelicene-2-carboxylic acid was effectively synthesised from suitably functionalised naphthalene building blocks. Methoxy-substituted 1,1'-ethyne-1,2-diylbis(2-but-3-yn-1-ylnaphthalene) was cyclised in the presence of CpCo(CO)(2)/PPh(3) to 2-methoxy-7,8,11,12-tetrahydroheptahelicene, which was converted into heptahelicen-2-yl trifluoromethanesulfonate. This reactive intermediate underwent Pd(OAc)(2)/dppp-catalysed methoxycarbonylation reaction to provide, after hydrolysis, heptahelicene-2-carboxylic acid. The racemate was resolved into enantiomers by semipreparative HPLC on a chiral column. The helicity of (+)-(P)-heptahelicene-2-carboxylic acid was assigned by correlating its CD spectrum to that of the known (+)-(P)-heptahelicene. Racemic heptahelicene-2-carboxylic acid was deposited on calcite (10-14) to undergo self-assembly into nanowire-like aggregates as demonstrated by noncontact atomic force microscopy (NC-AFM).

The coverage-dependent mode of adsorption of terephthalic acid [C6H4(COOH)(2), TPA] on rutile TiO2(110) was investigated by means of noncontact atomic force microscopy (NC-AFM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy under ultrahigh vacuum conditions at room temperature. Individual molecules are observed to adsorb in an disordered, flat-lying geometry at low coverages up to similar to 0.3 monolayer (ML). The molecules are immobile at room temperature. implying a diffusion barrier larger than 0.8 eV. This rather high value might be explained by anchoring to surface defect sites. A transition from flat-lying to upright-oriented molecules is revealed by NEXAFS when saturation coverage is achieved. High-resolution NC-AFM images reveal two different Structures at coverages between similar to 0.8 and 1 ML: (i) a well-ordered (2 x 1) structure and (ii) a structure of single and paired rows oriented along the [001] crystallographic direction. The latter structure might originate from a pairwise interaction of two neighboring molecules through the top carboxyl groups. Further increase in the exposure results in it saturation of the corresponding signal in the NEXAFS spectra, revealing that the growth of TPA oil TiO2(110) at room temperature is self-limiting.

We present the local charge state modification at room temperature of small insulator-supported molecular ensembles formed by 1,1'-ferrocenedicarboxylic acid on calcite. Single electron tunnelling between the conducting tip of a noncontact atomic force microscope (NC-AFM) and the molecular islands is observed. By joining NC-AFM with Kelvin probe force microscopy, successive charge build-up in the sample is observed from consecutive experiments. Charge transfer within the islands and structural relaxation of the adsorbate/surface system is suggested by the experimental data.

We present a detailed analysis and understanding of Kelvin probe force microscopy (KPFM) data for a system of point charges in a vacuum-dielectric tip-sample system. Explicit formulae describing the KPFM signal $\ensuremath{\Delta}V$ are derived for the two KPFM operation modes, namely amplitude modulation and frequency modulation (FM). The formulae allow for a physical interpretation of the resulting KPFM signal, reveal contributing parameters, and especially disclose an additive behavior. We numerically evaluate these equations and show exemplary KPFM slice data for a single point charge. The theoretical analysis is complemented by two-dimensional FM-KPFM maps obtained experimentally on 2,5-dihydrobenzoic acid on calcite $(1\phantom{\rule{0.59998pt}{0ex}}0\phantom{\rule{0.59998pt}{0ex}}.\phantom{\rule{0.59998pt}{0ex}}4)$. The molecules assemble in two coexisting phases understood as protonated and deprotonated molecules. The two-dimensional maps reveal a convex shape of the KPFM signal $\ensuremath{\Delta}V$ across the islands and a clear difference between the two phases is revealed. Furthermore, we apply the theoretically suggested difference strategy to extract the molecular component from the measured total KPFM signal.

Molecular self-assembly is known to provide a powerful tool for creating functional structures, with the ultimate structure and functionality encoded in the molecular building blocks. Upon molecule deposition onto surfaces, functional structures have been created ranging from defect-free, highly symmetric two-dimensional layers to complex assemblies with dedicated functionality. Especially organic molecules play a key role for molecular self-assembly due to their impressive structural flexibility and the high degree of control by chemical synthesis. Furthermore, the surface itself provides another exciting dimension: adjusting the subtle balance between intermolecular and molecule-surface interactions allows creating a broad variety of structures and explains the great success when confining molecular self-assembly to surfaces. While most of the structures realized so far have been fabricated on metallic substrates, comparatively little is known about molecular self-assembly on insulating surfaces. However, extending the materials basis to insulating substrates is of increasing interest to benefit from self-assembly strategies for emerging technologies such as molecular (opto)electronics. For the latter and further related applications, decoupling of the electronic structure from the underlying substrate is mandatory for the device functionality. Moreover, future applications will require the molecular structure to be stable at room temperature rather than at low temperatures. On insulating support surfaces, however, most attempts to create self-assembled molecular structures at room temperature have been hampered by the weak molecule-surface interactions. Thus, considerable effort has been made to establish means for increasing the molecule-surface interaction and to provide strategies for tailoring the anchoring of the molecules towards the surface. Non-contact atomic force microscopy has been proven to provide an indispensable tool for direct imaging of molecular structures on electronically insulating surfaces with molecular resolution. Besides imaging, this technique also offers the potential to obtain complementary information, for example when performing Kelvin probe force microscopy or three-dimensional force mapping. In this chapter, we report the current status of molecular self-assembly on insulating surfaces in ultra-high vacuum with a special emphasis on structures stable at room temperature. Basic molecular self-assembly principles are reviewed and applied to the specific situation of prototypical insulating surfaces. Strategies for anchoring organic molecules towards insulating surfaces are discussed in the view of macroscopic as well as microscopic parameters such as the surface energy and detailed molecule-surface binding motifs. Based on structure optimization at the molecular level, the molecule-surface interaction can be tuned to adjust the final assembly, ranging from largely unperturbed molecular bulk crystals to strongly substrate-templated overlayers. Finally, current research topics are outlined, focusing on efforts directed towards steadily increasing the control of the resulting structures.

We present atomic-scale force interaction data acquired on an insulating low-symmetry substrate, namely the calcite(10.4) surface. A pronounced asymmetry of the imaged species is apparent along the vertical axis, which will be identified as a tilted band of purely attractive short-range interaction forces. An independent determination of the absolute surface orientation by an optical method suggests that the observed asymmetry is related to the tilt of the carbonate groups within the surface, which, in turn, is linked to the surface orientation. Thus our noncontact atomic force microscopy based work presents the determination of the absolute orientation for a low-symmetry surface.

Noncontact atomic force microscopy (NC-AFM) is now routinely capable of obtaining submolecular resolution, readily resolving the carbon backbone structure of planar organic molecules adsorbed on metal substrates. Here we show that the same resolution may also be obtained for molecules adsorbed on a reactive semiconducting substrate. Surprisingly, this resolution is routinely obtained without the need for deliberate tip functionalization. Intriguingly, we observe two chemically distinct apex types capable of submolecular imaging. We characterize our tip apices by “inverse imaging” of the silicon adatoms of the Si(111)−7×7 surface and support our findings with detailed density functional theory (DFT) calculations. We also show that intramolecular resolution on individual molecules may be readily obtained at 78 K, rather than solely at 5 K as previously demonstrated. Our results suggest a wide range of tips may be capable of producing intramolecular contrast for molecules adsorbed on semiconductor surfaces, leading to a much broader applicability for submolecular imaging protocols.

Noncontact atomic force microscopy (NC-AFM) features the measurement of forces with highest spatial resolution and sensitivity, resolving forces of the order of pico-Newtons with submolecular resolution. However, the measured total force is a mixture composed of various interactions. While some interactions such as electrostatic or magnetic forces can be excluded by a careful design of the experiment, the subtraction of van der Waals forces, which mainly originate from London dispersion interactions between the macroscopic tip shank and the bulk sample, remains a challenge. We present the determination of the inherently present van der Waals forces in total interaction force data from fitting a suitable model, allowing for extraction of the short-range force component. We compare the applicability of several van der Waals models based on experimental interaction data from the calcite(1014) surface. The feasibility to fit these models to experimental data is critically discussed. We furthermore introduce criteria to assess the transition point from pure long-range interaction to mixed shortand long-range forces based on the variance of lateral and vertical force data. This determination allows us to extract the short-range interaction forces, which remained a challenge so far in NC-AFM experiments.

Hydrogen bonding underpins the properties of a vast array of systems spanning a wide variety of scientific fields. From the elegance of base pair interactions in DNA to the symmetry of extended supramolecular assemblies, hydrogen bonds play an essential role in directing intermolecular forces. Yet fundamental aspects of the hydrogen bond continue to be vigorously debated. Here we use dynamic force microscopy (DFM) to quantitatively map the tip-sample force field for naphthalene tetracarboxylic diimide molecules hydrogen-bonded in two-dimensional assemblies. A comparison of experimental images and force spectra with their simulated counterparts shows that intermolecular contrast arises from repulsive tip-sample interactions whose interpretation can be aided via an examination of charge density depletion across the molecular system. Interpreting DFM images of hydrogen-bonded systems therefore necessitates detailed consideration of the coupled tip-molecule system: analyses based on intermolecular charge density in the absence of the tip fail to capture the essential physical chemistry underpinning the imaging mechanism., Hydrogen bonding is an important force in nature, directing and controlling the assembly of numerous natural and synthetic structures. Here the authors show that the interpretation of intermolecular contrast in atomic force microscope images of hydrogen-bonded assemblies necessitates detailed consideration of the coupled tip-molecule system.

In frequency modulated non-contact atomic force microscopy, the change of the cantilever frequency (Delta f) is used as the input signal for the topography feedback loop. Around the Delta f(z) minimum, however, stable feedback operation is challenging using a standard proportional-integral-derivative (PID) feedback design due to the change of sign in the slope. When operated under liquid conditions, it is furthermore difficult to address the attractive interaction regime due to its often moderate peakedness. Additionally, the Delta f signal level changes severely with time in this environment due to drift of the cantilever frequency f(0) and, thus, requires constant adjustment. Here, we present an approach overcoming these obstacles by using the derivative of Delta f with respect to z as the input signal for the topography feedback loop. Rather than regulating the absolute value to a preset setpoint, the slope of the Delta f with respect to z is regulated to zero. This new measurement mode not only makes the minimum of the Delta f(z) curve directly accessible, but it also benefits from greatly increased operation stability due to its immunity against f(0) drift. We present isosurfaces of the Delta f minimum acquired on the calcite CaCO3(1014) surface in liquid environment, demonstrating the capability of our method to image in the attractive tip-sample interaction regime. (C) 2014 AIP Publishing LLC.

cited By 7; International audience; A substrate-guided photochemical reaction of C60 fullerenes on calcite, a bulk insulator, investigated by non-contact atomic force microscopy is presented. The success of the covalent linkage is evident from a shortening of the intermolecular distances, which is clearly expressed by the disappearance of the moiré pattern. Furthermore, UV/Vis spectroscopy and mass spectrometry measurements carried out on thick films demonstrate the ability of our setup for initiating the photoinduced reaction. The irradiation of C60 results in well-oriented covalently linked domains. The orientation of these domains is dictated by the lattice dimensions of the underlying calcite substrate. Using the lattice mismatch to deliberately steer the direction of the chemical reaction is expected to constitute a general design principle for on-surface synthesis. This work thus provides a strategy for controlled fabrication of oriented, covalent networks on bulk insulators.

Molecular self-assembly constitutes a versatile strategy for creating functional structures on surfaces. Tuning the subtle balance between intermolecular and molecule-surface interactions allows structure formation to be tailored at the single-molecule level. While metal surfaces usually exhibit interaction strengths in an energy range that favors molecular self-assembly, dielectric surfaces having low surface energies often lack sufficient interactions with adsorbed molecules. As a consequence, application-relevant, bulk insulating materials pose significant challenges when considering them as supporting substrates for molecular self-assembly. Here, the current status of molecular self-assembly on surfaces of wide-bandgap dielectric crystals, investigated under ultrahigh vacuum conditions at room temperature, is reviewed. To address the major issues currently limiting the applicability of molecular self-assembly principles in the case of dielectric surfaces, a systematic discussion of general strategies is provided for anchoring organic molecules to bulk insulating materials.

cited By 7; International audience; Templated assembly of organic molecules constitutes a promising approach for fabricating functional nanostructures at surfaces with molecular-scale control. Using the substrate template for steering the adsorbate growth enables creating a rich variety of molecular structures by tuning the subtle balance of intermolecular and molecule–surface interactions. On insulating surfaces, however, surface templating is largely absent due to the comparatively weak molecule–surface interactions compared to metallic substrates. Here, we demonstrate the activation of substrate templating in molecular self-assembly on a bulk insulator by controlled deprotonation of the adsorbed molecules upon annealing. Upon deposition of 4-iodobenzoic acid onto the natural cleavage plane of calcite held at room temperature, high molecular mobility is observed, indicating a small diffusion barrier. Molecular islands only nucleate at step edges. These islands show no commensurability with the underlying substrate, clearly indicating the absence of surface templating. Upon annealing the substrate, the molecules undergo a transition from the protonated to the deprotonated state. In the deprotonated state, the molecules adopt a well-defined adsorption position, resulting in a distinctly different, substrate-templated molecular structure that is stable at room temperature. Our work, thus, demonstrates the controlled activation of substrate templating by changing the molecule–surface interaction upon annealing.

The noise of the frequency-shift signal Δf in noncontact atomic force microscopy (NC-AFM) consists of cantilever thermal noise, tip–surface-interaction noise and instrumental noise from the detection and signal processing systems. We investigate how the displacement-noise spectral density dz at the input of the frequency demodulator propagates to the frequency-shift-noise spectral density dΔf at the demodulator output in dependence of cantilever properties and settings of the signal processing electronics in the limit of a negligible tip–surface interaction and a measurement under ultrahigh-vacuum conditions. For a quantification of the noise figures, we calibrate the cantilever displacement signal and determine the transfer function of the signal-processing electronics. From the transfer function and the measured dz, we predict dΔf for specific filter settings, a given level of detection-system noise spectral density dzds and the cantilever-thermal-noise spectral density dzth. We find an excellent agreement between the calculated and measured values for dΔf. Furthermore, we demonstrate that thermal noise in dΔf, defining the ultimate limit in NC-AFM signal detection, can be kept low by a proper choice of the cantilever whereby its Q-factor should be given most attention. A system with a low-noise signal detection and a suitable cantilever, operated with appropriate filter and feedback-loop settings allows room temperature NC-AFM measurements at a low thermal-noise limit with a significant bandwidth.

We critically discuss the extraction of intrinsic cantilever properties, namely eigenfrequency fn, quality factor Qn and specifically the stiffness kn of the nth cantilever oscillation mode from thermal noise by an analysis of the power spectral density of displacement fluctuations of the cantilever in contact with a thermal bath. The practical applicability of this approach is demonstrated for several cantilevers with eigenfrequencies ranging from 50 kHz to 2 MHz. As such an analysis requires a sophisticated spectral analysis, we introduce a new method to determine kn from a spectral analysis of the demodulated oscillation signal of the excited cantilever that can be performed in the frequency range of 10 Hz to 1 kHz regardless of the eigenfrequency of the cantilever. We demonstrate that the latter method is in particular useful for noncontact atomic force microscopy (NC-AFM) where the required simple instrumentation for spectral analysis is available in most experimental systems.

We report the formation of extended molecular layers of C-60 molecules on a dielectric surface at room temperature. In sharp contrast to previous C-60 adsorption studies on prototypical ionic crystal surfaces, a wetting layer is obtained when choosing the calcite (CaCO3)(10 (1) over bar4) surface as a substrate. Non-contact atomic force microscopy data reveal an excellent match of the hexagonal lattice of the molecular layer with the unit cell dimension of CaCO3(10 (1) over bar4) in the [01 (1) over bar0] direction, while a lattice mismatch along the [(4) over bar(2) over bar 61] direction results in a large-scale moire modulation. Overall, a (2 x 15) wetting layer is obtained. The distinct difference observed microscopically upon C-60 adsorption on CaCO3(10 (1) over bar4) compared to other dielectric surfaces is explained by a macroscopic picture based on surface energies. Our example demonstrates that this simple surface-energy based approach can provide a valuable estimate for choosing molecule-insulator systems suitable for molecular self-assembly at room temperature.

M olecular self-assembly on insulating surfaces, despite being highly relvant to many applications, generally suffers from the weak molecule–surface interactions present on dielectric surfaces, especially when benchmarked against metallic substrates. Therefore, to fully exploit the potential of molecular self-assembly, increasing the infl uence of the substrate constitutes an essential prerequisite. Upon deposition of terephthalic acid and trimesic acid onto the natural cleavage plane of calcite, extended hydrogen-bonded networks are formed, which wet the substrate. The observed structural complexity matches the variety realized on metal surfaces. A detailed analysis of the molecular structures observed on calcite reveals a signifi cant infl uence of the underlying substrate, clearly indicating a substantial templating effect of the surface on the resulting molecular networks. This work demonstrates that choosing suitable molecule/substrate systems allows for tuning the balance between intermolecular and molecule–surface interactions even in the case of typically weakly interacting insulating surfaces. This study, thus, provides a strategy for deliberately exploiting substrate templating to increase the structural variety in molecular selfassembly on a bulk insulator at room temperature. Templating

The adsorption and island formation of C${}_{60}$ fullerenes on the hydrogenated C(100)-($2\ifmmode\times\else\texttimes\fi{}1$):H diamond surface is studied using high-resolution noncontact atomic force microscopy in ultrahigh vacuum. At room temperature, C${}_{60}$ fullerene molecules assemble into monolayer islands, exhibiting a hexagonally close-packed internal structure. Dewetting is observed when raising the substrate temperature above approximately 505 K, resulting in two-layer high islands. In contrast to the monolayer islands, these double-layer islands form extended wetting layers. This peculiar behavior is explained by an increased molecule-substrate binding energy in the case of double-layer islands, which originates from charge transfer doping. Only upon further increasing the substrate temperature to approximately 615 K, the wetting layer desorbs, corresponding to a binding energy of the charge transfer-stabilized film of 1.7 eV.

Calcite, the most stable polymorph of calcium carbonate, is one of the most abundant simple salts in the geological environment. Consequently, its natural (10 (1) over bar4) cleavage plane has been studied extensively by a wide range of surface-sensitive techniques, giving indications for two reconstructions, namely a (2 x 1) and a so-called 'row-pairing' reconstruction. The existence of the (2 x 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 (10 (1) over bar4) 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.