0000000000122247
AUTHOR
Markus Kittelmann
On-Surfaces Synthesis on Insulating Substrates
On-surface synthesis has attracted great attention in recent years due to its promising potential for creating functional structures on surfaces. An important aspect of on-surface synthesis is the capability to arrive at covalently linked thermally stable structures that offer the possibility for application even in harsh environments outside ultra-high vacuum conditions. Additionally, covalent linking allows for fabricating conjugated structures with superior electron transport properties. Especially, the latter is of tremendous interest when considering future applications in the field of molecular electronics. Having molecular electronics applications in mind explains the need for decoup…
Atomic-resolution imaging of clean and hydrogen-terminated C(100)-(2×1)diamond surfaces using noncontact AFM
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…
On-surface covalent linking of organic building blocks on a bulk insulator.
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
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…
How deprotonation changes molecular self-assembly – an AFM study in liquid environment
We study the influence of Alizarin Red S deprotonation on molecular self-assembly at the solid-liquid interface of the natural cleavage plane of calcite immersed in aqueous solution. To elucidate the adsorption details, we perform pH dependent high-resolution atomic force microscopy measurements. When Alizarin Red S is deposited onto calcite(10.4) in a liquid environment at an acidic pH of 5, weakly bound, ordered islands with a (3 x 3) superstructure are observed. A sharp structural transition is revealed when increasing the pH above 8. Above this pH, stable needle-like structures oriented along the [01.0] direction form on the surface. Comparing these results with potentiometric titration…
Adsorption Structures of Amino Acids on Calcite(104)
Elucidating the interaction details of proteins with the most stable cleavage plane of calcite , namely calcite(104), is of great importance for understanding the physicochemical mechanisms behind biomineralisation. In this context, amino acids are generally believed to serve as suitable model molecules, as they constitute the basic building blocks of proteins. In this work, we present a non-contact atomic force microscopy (NC-AFM) investigation of the adsorption of five proteinogenic amino acids on calcite(104) under ultra-high vacuum (UHV) conditions. For studying the structures formed from comparatively large amino acids, enantiopure tryptophan, tyrosine and aspartic acid molecules are d…
Increasing the Templating Effect on a Bulk Insulator Surface: From a Kinetically Trapped to a Thermodynamically More Stable Structure
Molecular self-assembly, governed by the subtle balance between intermolecular and molecule- surface interactions, is generally associated with the thermodynamic ground state, while the competition between kinetics and thermodynamics during its formation is often neglected. Here, we present a simple model system of a benzoic acid derivative on a bulk insulator surface. Combining high-resolution non-contact atomic force microscopy experiments and density functional theory, we characterize the structure and the thermodynamic stability of a set of temperature-dependent molecular phases formed by 2,5-dihydroxybenzoic acid molecules, self- assembled on the insulating calcite (10.4) surface. We d…
Molecular Self-Assembly of Enantiopure Heptahelicene-2-Carboxylic Acid on Calcite (1014)
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
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…
From dewetting to wetting molecular layers: C60 on CaCO3(10 ̅14) as a case study.
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…
Controlled Activation of Substrate Templating in Molecular Self-Assembly by Deprotonation
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 Flexibility
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…
Decisive influence of substitution positions in molecular self-assembly
Molecular self-assembly provides a versatile tool for creating functional molecular structures at surfaces. A rational design of molecular structure formation requires not only an in-depth understanding of the subtle balance between intermolecular and molecule-surface interactions, but might also involve considering chemical changes of the molecules, such as deprotonation. Here, we present a systematic investigation of a comparatively simple class of molecules, namely dihydroxybenzoic acid, which, nevertheless, enables creating a rich variety of structures when deposited onto calcite (10.4) held at room temperature. Based on non-contact atomic force microscopy measurements in ultra-high vac…
Molecular self-assembly on an insulating surface: interplay between substrate templating and intermolecular interactions
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
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…
Mechanisms of covalent dimerization on a bulk insulating surface
Combining density functional theory and high resolution NC-AFM experiments, we have studied the on surface reaction mechanisms' responsible for the covalent dimerization of 4-iodobenzoic acid (IBA) organic molecules on the calcite (10.4), insulating surface. When annealed at 580 K, the Molecules assemble in one-dimensional chains of covalently bound dimers: The chains have a unique orientation and result from a complex set of processes, including a nominally rather. costly double dehalogenation reaction followed by dimerization. First, focusing on the latter two processes and using the nudged elastic band method, we analyze a number of possible mechanisms involving one and two molecules, an…
Sequential and site-specific on-surface synthesis on a bulk insulator
cited By 15; International audience; The bottom-up construction of functional devices from molecular building blocks offers great potential in tailoring materials properties and functionality with utmost control. An important step toward exploiting bottom-up construction for real-life applications is the creation of covalently bonded structures that provide sufficient stability as well as superior charge transport properties over reversibly linked self-assembled structures. On-surface synthesis has emerged as a promising strategy for fabricating stable, covalently bound molecular structure on surfaces. So far, a majority of the structures created by this method have been obtained from a rat…
Tuning molecular self-assembly on bulk insulator surfaces by anchoring of the organic building blocks.
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…
Influence of charge transfer doping on the morphologies of C60islands on hydrogenated diamond C(100)-(2×1)
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…