showing 32 related works from this author
The weight function for charges - A rigorous theoretical concept for Kelvin probe force microscopy
2016
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. Dependin…
Substrate templating upon self-assembly of hydrogen-bonded molecular networks on an insulating surface.
2012
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 struct…
Atomic-resolution imaging of clean and hydrogen-terminated C(100)-(2×1)diamond surfaces using noncontact AFM
2010
Received 22 April 2010; published 14 May 2010High-purity, type IIa diamond is investigated by noncontact atomic force microscopy NC-AFM .Wepresent atomic-resolution images of both the electrically conducting hydrogen-terminated C 100 - 2 1 :Hsurface and the insulating C 100 - 2 1 surface. For the hydrogen-terminated surface, a nearly square unitcell is imaged. In contrast to previous scanning tunneling microscopy experiments, NC-AFM imaging allowsboth hydrogen atoms within the unit cell to be resolved individually, indicating a symmetric dimer alignment.Upon removing the surface hydrogen, the diamond sample becomes insulating. We present atomic-resolutionimages, revealing individual C-C dim…
Frequency-modulated atomic force microscopy operation by imaging at the frequency shift minimum: the dip-df mode.
2014
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 pre…
On-surface covalent linking of organic building blocks on a bulk insulator.
2011
On-surface synthesis in ultrahigh vacuum provides a promising strategy for creating thermally and chemically stable molecular structures at surfaces. The two-dimensional confinement of the educts, the possibility of working at higher (or lower) temperatures in the absence of solvent, and the templating effect of the surface bear the potential of preparing compounds that cannot be obtained in solution. Moreover, covalently linked conjugated molecules allow for efficient electron transport and are, thus, particularly interesting for future molecular electronics applications. When having these applications in mind, electrically insulating substrates are mandatory to provide sufficient decoupli…
Substrate templating guides the photoinduced reaction of C60on calcite
2014
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 c…
Racemic and Optically Pure Heptahelicene-2-carboxylic Acid: Its Synthesis and Self-Assembly into Nanowire-Like Aggregates
2010
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 spectr…
Insights into Kelvin probe force microscopy data of insulator-supported molecules
2015
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…
Racemic and Optically Pure Heptahelicene-2-carboxylic Acid: Its Synthesis and Self-Assembly into Nanowire-Like Aggregates (Eur. J. Org. Chem. 5/2011)
2011
The cover picture shows heptahelicene-2-carboxylic acid, whose synthesis and self-assembly are central to the article. The background features Prague's riverbank, which is intermixed with the nanowire-like aggregates of heptahelicene-2-carboxylic acid. The alignment of the swans makes the link between self-assembly and the Prague view. Details are discussed in the article by I. G. Stara, I. Starý, A. Kuhnle et al. on p. 853 ff. Background photo by M. Bělohradský.
Vertical and lateral drift corrections of scanning probe microscopy images
2010
A procedure is presented for image correction of scanning probe microscopy data that is distorted by linear thermal drift. The procedure is based on common ideas for drift correction, which the authors combine to a comprehensive step-by-step description of how to measure drift velocities in all three dimensions and how to correct the images using these velocities. The presented method does not require any knowledge about size or shape of the imaged structures. Thus, it is applicable to any type of scanning probe microscopy image, including images lacking periodic structures. Besides providing a simple, ready-to-use description of lateral and vertical drift correction, they derive all formul…
Flexible drift-compensation system for precise 3D force mapping in severe drift environments
2011
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 …
Templating: Substrate Templating upon Self-Assembly of Hydrogen-Bonded Molecular Networks on an Insulating Surface (Small 19/2012)
2012
Molecular Self-Assembly of Enantiopure Heptahelicene-2-Carboxylic Acid on Calcite (1014)
2012
Chirality can have a decisive influence on the molecular structure formation upon self-assembly on surfaces. In this paper, we study the structures formed by enantiopure (M)-heptahelicene-2-carboxylic acid ((M)-[7]HCA) on the calcite (10 (1) over bar4) cleavage plane under ultrahigh vacuum conditions. Previous noncontact atomic force microscopy studies have revealed that the racemic mixture of (M)-[7]HCA and (P)-[7]FICA (1:1) self-assembles into well-defined molecular double rows that are oriented along the calcite [01 (1) over bar0] direction. Here, we investigate the enantiopure (M)[7]HCA compound, resulting in distinctly different molecular structures upon deposition onto calcite (10 (1)…
Direct Visualization of Molecule Deprotonation on an Insulating Surface
2012
Elucidating molecular-scale details of basic reaction steps on surfaces is decisive for a fundamental understanding of molecular reactivity within many fields, including catalysis and on-surface synthesis. Here, the deprotonation of 2,5-dihydroxybenzoic acid (DHBA) deposited onto calcite (101;4) held at room temperature is followed in situ by noncontact atomic force microscopy. After deposition, the molecules form two coexisting phases, a transient striped phase and a stable dense phase. A detailed analysis of high-resolution noncontact atomic force microscopy images indicates the transient striped phase being a bulk-like phase, which requires hydrogen bonds between the carboxylic acid moie…
Growth kinetics of racemic heptahelicene-2-carboxylic acid nanowires on calcite (104).
2016
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 a…
From dewetting to wetting molecular layers: C60 on CaCO3(10 ̅14) as a case study.
2012
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…
Discriminating short-range from van der Waals forces using total force data in noncontact atomic force microscopy
2014
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 fitti…
Controlled Activation of Substrate Templating in Molecular Self-Assembly by Deprotonation
2013
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 …
Controlling Molecular Self-Assembly on an Insulating Surface by Rationally Designing an Efficient Anchor Functionality That Maintains Structural Flex…
2013
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 anch…
Molecular self-assembly on an insulating surface: interplay between substrate templating and intermolecular interactions
2012
We report on molecular self-assembly of biphenyl-4,4'-dicarboxylic acid (BPDCA) on CaCO3(10 (1) over bar4) under ultra-high vacuum conditions. Two-dimensional, ordered islands are obtained upon deposition at room temperature, coexisting with a streaky structure that is ascribed to individual, mobile molecules forming a two-dimensional gas-like phase. High-resolution non-contact atomic force microscopy (NC-AFM) images of the molecular islands reveal an ordered inner structure that is dominated by rows of molecules aligned side by side running along the [(42) over bar 61] crystallographic direction. A detailed analysis of these rows exhibits inter-row distances that are multiples of the calci…
Templatgesteuerte Photoreaktion von C60auf Calcit
2014
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…
Clear signature of the (2 x 1) reconstruction of calcite (1014).
2010
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 (10 (1) over bar4) 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…
Single-molecule switching with non-contact atomic force microscopy
2011
We report upon controlled switching of a single 3,4,9,10-perylene tetracarboxylic diimide derivative molecule on a rutile TiO(2)(110) surface using a non-contact atomic force microscope at room temperature. After submonolayer deposition, the molecules adsorb tilted on the bridging oxygen row. Individual molecules can be manipulated by the atomic force microscope tip in a well-controlled manner. The molecules are switched from one side of the row to the other using a simple approach, taking benefit of the sample tilt and the topography of the titania substrate. From density functional theory investigations we obtain the adsorption energies of different positions of the molecule. These adsorp…
Thermal noise limit for ultra-high vacuum noncontact atomic force microscopy
2013
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 displacemen…
Interpretation of KPFM Data with the Weight Function for Charges
2018
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 charge…
Tuning molecular self-assembly on bulk insulator surfaces by anchoring of the organic building blocks.
2013
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-ass…
Imaging Static Charge Distributions: A Comprehensive KPFM Theory
2018
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 observab…
Combined NC-AFM and DFT study of the adsorption geometry of trimesic acid on rutile TiO2(110)
2010
The adsorption behavior of trimesic acid (TMA) on rutile TiO(2)(110) is studied by means of non-contact atomic force microscopy (NC-AFM) and density-functional theory (DFT). Upon low-coverage adsorption at room temperature, NC-AFM imaging reveals individual molecules, centered above the surface titanium rows. Based on the NC-AFM results alone it is difficult to deduce whether the molecules are lying flat or standing upright on the surface. To elucidate the detailed adsorption geometry, we perform DFT calculations, considering a large number of different adsorption positions. Our DFT calculations suggest that single TMA molecules adsorb with the benzene ring parallel to the surface plane. In…
NC-AFM contrast formation on the calcite ($10\bar {1}4$) surface
2012
Calcite, the most stable polymorph of calcium carbonate, is one of the most abundant simple salts in the geological environment. Consequently, its natural 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 calcite s…
Determining cantilever stiffness from thermal noise
2013
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 frequ…
Influence of charge transfer doping on the morphologies of C60islands on hydrogenated diamond C(100)-(2×1)
2012
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…
Self-assembly of Organic Molecules on Insulating Surfaces
2015
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 i…