Wolfgang M. Heckl

Self‐Assembled Two‐Dimensional Molecular Host‐Guest Architectures From Trimesic Acid

The adsorption of 1,3,5-Benzenetricarboxylic (Trimesic) Acid (TMA) to a single crystal graphite surface has been studied under Ultra High Vacuum conditions. This work focuses on inducing a particular self-assembly structure by OMBE (Organic Molecular Beam Epitaxy), characterized by periodic non-dense-packing of the molecules. Two coexisting phases could be imaged with sub-molecular resolution by STM. Induced by directed hydrogen bonding, the organic molecules built in both cases a two-dimensional grid architecture with molecular caves. This two-dimensional host structure can accept single trimesic acid guest molecules in different positions.

Reversible phase transitions in self-assembled monolayers at the liquid-solid interface: temperature-controlled opening and closing of nanopores.

We present a variable-temperature study of monolayer self-assembly at the liquid-solid interface. By means of in situ scanning tunneling microscopy (STM), reversible phase transitions from a nanoporous low-temperature phase to a more densely packed high-temperature phase are observed. The occurrence of the phase transition and the respective transition temperature were found to depend on the type of solvent and solute concentration. Estimates of the entropic cost and enthalpic gain upon monolayer self-assembly suggest that coadsorption of solvent molecules within the cavities of the nanoporous structure renders this polymorph thermodynamically stable at low temperatures. At elevated temperatures, however, desorption of these relatively weakly bound solvent molecules destabilizes the nanoporous polymorph, and the densely packed polymorph becomes thermodynamically favored. Interestingly, the structural phase transition provides external control over the monolayer morphology and, for the system under discussion, results in an effective opening and closing of supramolecular nanopores in a two-dimensional molecular monolayer.

Inverting dynamic force microscopy: From signals to time-resolved interaction forces

Transient forces between nanoscale objects on surfaces govern friction, viscous flow, and plastic deformation, occur during manipulation of matter, or mediate the local wetting behavior of thin films. To resolve transient forces on the (sub) microsecond time and nanometer length scale, dynamic atomic force microscopy (AFM) offers largely unexploited potential. Full spectral analysis of the AFM signal completes dynamic AFM. Inverting the signal formation process, we measure the time course of the force effective at the sensing tip. This approach yields rich insight into processes at the tip and dispenses with a priori assumptions about the interaction, as it relies solely on measured data. Force measurements on silicon under ambient conditions demonstrate the distinct signature of the interaction and reveal that peak forces exceeding 200 nN are applied to the sample in a typical imaging situation. These forces are 2 orders of magnitude higher than those in covalent bonds.

Thermodynamical equilibrium of binary supramolecular networks at the liquid-solid interface.

Coadsorption of two different carboxylic acids, benzenetribenzoic acid and trimesic acid, was studied at the liquid-solid interface in two different solvents (heptanoic and nonanoic acid). Independent alteration of both concentrations in binary solutions resulted in six nondensely packed monolayer phases with different structures and stoichiometries, as revealed by means of scanning tunneling microscopy (STM). All of these structures are stabilized by intermolecular hydrogen bonding between the carboxylic acid functional groups. Moreover, phase transitions of the monolayer structures, accompanied by an alteration of the size and shape of cavity voids in the 2D molecular assembly, could be achieved by in situ dilution. The emergence of the various phases could be described by a simple thermodynamic model.

Carboxylic Acids: Versatile Building Blocks and Mediators for Two-Dimensional Supramolecular Self-Assembly

Two-dimensional (2D) supramolecular self-assembly of various organic molecules at the liquid-solid interface is presented and discussed with a focus on compounds that are primarily functionalized by carboxylic groups. The main analytical tool utilized is scanning tunneling microscopy (STM), a high-resolution real-space technique capable of readily providing full crystallographic information (i.e., not only lattice parameters but also number, type, and orientation of molecules within the unit cell). Carboxylic groups are of particular interest because their combined donor and acceptor character with regard to hydrogen bonds provides reliable intermolecular cross-linking, thereby facilitating the self-assembly of well-ordered, stable monolayers. By means of various homomeric (monomolecular) and heteromeric (here, bimolecular) examples, this feature article illustrates the influence of both molecular structure and external conditions (type of solvent, concentration, etc.) on monolayer self-assembly at the liquid-solid interface. A very intriguing aspect of interfacial self-assembly is that many systems are thermodynamically controlled (i.e., adsorbed molecules at the surface are in equilibrium with molecules dissolved in the supernatant liquid phase). This offers the unique possibility not only to steer the system reliably by intensive thermodynamic parameters such as temperature and concentration but also to gain fundamental knowledge about decisive processes and steps in supramolecular self-assembly.

Fourier transformed atomic force microscopy: tapping mode atomic force microscopy beyond the Hookian approximation

The periodic impact force induced by the tip‐sample contact in tapping mode atomic force microscopy (TM-AFM ) gives rise to anharmonic oscillations of the sensing cantilever. These anharmonic signals can be understood with a model which goes beyond the common Hookian approximation: the cantilever is described as a multiple degree of freedom system. A theoretical analysis of the anharmonic signals in the light of the extended model shows that these signals contain information on the elastic properties of the specimen surface. In Fourier transformed operation mode of TM-AFM the anharmonic oscillations are analyzed in the frequency domain. This allows for the reconstruction of characteristics of the tip‐sample force, like contact time and maximum contact force.

Thermomechanical noise of a free v-shaped cantilever for atomic-force microscopy

We have calculated the thermal noise of a v-shaped AFM cantilever (Microlever, Type E, Thermomicroscopes) by means of a finite element analysis. The modal shapes of the first 10 eigenmodes are displayed as well as the numerical constants, which are needed for the calibration using the thermal noise method. In the first eigenmode, values for the thermomechanical noise of the z-displacement at 22 degrees C temperature of square root of u2(1) = A/square root of c(cant) and the photodiode signal (normal-force) of S2(1) = A/square root of c(cant) were obtained. The results also indicate a systematic deviation ofthe spectral density of the thermomechanical noise of v-shaped cantilevers as compared to rectangular beam-shaped cantilevers.

Isoreticular Two-Dimensional Covalent Organic Frameworks Synthesized by On-Surface Condensation of Diboronic Acids

On-surface self-condensation of 1,4-benzenediboronic acid was previously shown to yield extended surface-supported, long-range-ordered two-dimensional covalent organic frameworks (2D COFs). The most important prerequisite for obtaining high structural quality is that the polycondensation (dehydration) reaction is carried out under slightly reversible reaction conditions, i.e., in the presence of water. Only then can the subtle balance between kinetic and thermodynamic control of the polycondensation be favorably influenced, and defects that are unavoidable during growth can be corrected. In the present study we extend the previously developed straightforward preparation protocol to a variety of para-diboronic acid building blocks with the aim to tune lattice parameters and pore sizes of 2D COFs. Scanning tunneling microscopy is employed for structural characterization of the covalent networks and of noncovalently self-assembled structures that form on the surface prior to the thermally activated polycondensation reaction.

Synthesis of Well-Ordered COF Monolayers: Surface Growth of Nanocrystalline Precursors versus Direct On-Surface Polycondensation

Two different straightforward synthetic approaches are presented to fabricate long-range-ordered monolayers of a covalent organic framework (COF) on an inert, catalytically inactive graphite surface. Boronic acid condensation (dehydration) is employed as the polymerization reaction. In the first approach, the monomer is prepolymerized by a mere thermal treatment into nanocrystalline precursor COFs. The precursors are then deposited by drop-casting onto a graphite substrate and characterized by scanning tunneling microscopy (STM). While in the precursors monomers are already covalently interlinked into the final COF structure, the resulting domain size is still rather small. We show that a thermal treatment under reversible reaction conditions facilitates on-surface ripening associated with a striking increase of the domain size. Although this first approach allows studying different stages of the polymerization, the direct polymerization, that is, without the necessity of preceding reaction steps, is desirable. We demonstrate that even for a comparatively small diboronic acid monomer a direct thermally activated polymerization into extended COF monolayers is achievable.

Higher harmonics imaging in tapping-mode atomic-force microscopy

In tapping-mode atomic-force microscopy usually amplitude and phase of the cantilever motion are acquired. These signals are related to the fundamental oscillation frequency neglecting information at higher frequencies. However, the nonlinear contact between tip and sample induces higher frequency vibrations that are harmonics of the fundamental. In order to recover the available information the full tip motion has to be analyzed. The higher harmonics can be employed for image formation. A setup that consists of two independently operated lock-in amplifiers is used to detect higher harmonics in the dynamic atomic-force microscopy signal. Higher harmonic imaging proves to be useful to monitor the imaging conditions in tapping mode and can be applied for nanoscale imaging with a material contrast.