Szymon Godlewski

Adsorption and Self-Assembly of Large Polycyclic Molecules on the Surfaces of TiO2 Single Crystals

Titanium dioxide is one of the most frequently studied metal oxides, and its (110) rutile surface serves as a prototypical model for the surface science of such materials. Recent studies have also shown that the (011) surface is relatively easy for preparation in ultra-high vacuum (UHV) and that both the (110) and (011) surfaces could be precisely characterized using scanning tunneling microscopy (STM). The supramolecular self-assembly of organic molecules on the surfaces of titanium dioxide plays an important role in nanofabrication, and it can control the formation and properties of nanostructures, leading to wide range of applications covering the fields of catalysis, coatings and fabrication of sensors and extends to the optoelectronic industry and medical usage. Although the majority of experiments and theoretical calculations are focused on the adsorption of relatively small organic species, in recent years, there has been increasing interest in the properties of larger molecules that have several aromatic rings in which functional units could also be observed. The purpose of this review is to summarize the achievements in the study of single polycyclic molecules and thin layers adsorbed onto the surfaces of single crystalline titanium dioxide over the past decade.

Supramolecular ordering of PTCDA molecules: the key role of dispersion forces in an unusual transition from physisorbed into chemisorbed state.

Adsorption and self-assembly of large π-conjugated 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) molecules on rutile TiO(2)(110) surface have been investigated using a combination of high-resolution scanning tunneling microscopy (STM), low-energy electron diffraction, and density functional theory calculations with inclusion of Grimme treatment of the dispersion forces (DFT-D). Evolution of the STM images as a function of PTCDA coverage is caused by transition of the adsorption mode from physisorbed single adspecies and meandering stripes into spontaneously ordered chemisorbed molecular assemblies. This change in the adsorption fashion is accompanied by significant bending of the intrinsically flat, yet elastic, PTCDA molecule, which allows for strong electronic coupling of the dye adspecies with the TiO(2) substrate. Extensive DFT-D modeling has revealed that adsorption is controlled by interfacial and intermolecular dispersion forces playing a dominant role in the adsorption of single PTCDA species, their self-organization into the meandering stripes, and at the monolayer coverage acting collectively to surmount the chemisorption energy barrier associated with the molecule bending. Analysis of the resulting density of states has revealed that alignment of the energy levels and strong electronic coupling at the PTCDA/TiO(2) interface are beneficial for dye sensitization purposes.

Adsorption of organic molecules on the TiO2(011) surface: STM study

High resolution scanning tunneling microscopy has been applied to investigate adsorption and self-assembly of large organic molecules on the TiO(2)(011) surface. The (011) face of the rutile titania has been rarely examined in this context. With respect to possible industrial applications of rutile, quite often in a powder form, knowledge on behavior of organic molecules on that face is required. In the presented study we fill in the gap and report on experiments focused on the self-assembly of organic nanostructures on the TiO(2)(011) surface. We use three different kinds of organic molecules of potential interest in various applications, namely, PTCDA and CuPc representing flat, planar stacking species, and Violet Landers specially designed for new applications in molecular electronics. In order to reach a complete picture of molecular behavior, extended studies with different surface coverage ranging from single molecule up to 2 monolayer (ML) thick films are performed. Our results show that the adsorption behavior is significantly different from previously observed for widely used metallic templates. Creation of highly ordered molecular lines, quasi-ordered wetting layers, controlled geometrical reorientation upon thermal treatment, existence of specific adsorption geometries, and prospects for tip-induced molecule ordering and manipulation provide better understanding and add new phenomena to the knowledge on the (011) face of rutile titania.

Contacting a conjugated molecule with a surface dangling bond dimer on a hydrogenated Ge(001) surface allows imaging of the hidden ground electronic state.

Fabrication of single-molecule logic devices requires controlled manipulation of molecular states with atomic-scale precision. Tuning molecule-substrate coupling is achieved here by the reversible attachment of a prototypical planar conjugated organic molecule to dangling bonds on the surface of a hydrogenated semiconductor. We show that the ground electronic state resonance of a Y-shaped polyaromatic molecule physisorbed on a defect-free area of a fully hydrogenated surface cannot be observed by scanning tunneling microscopy (STM) measurements because it is decoupled from the Ge bulk states by the hydrogen-passivated surface. The state can be accessed by STM only if the molecule is contacted with the substrate by a dangling bond dimer. The reversibility of the attachment processes will be advantageous in the construction of surface atomic-scale circuits composed of single-molecule devices interconnected by the surface dangling bond wires.

Nanofabrication of PTCDA molecular chains on rutile TiO2(011)-(2 × 1) surfaces

The adsorption of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on a rutile TiO(2)(011)-(2 × 1) surface is studied using ultra-high vacuum scanning tunneling microscopy. The self-assembly process is dominated by the fine interplay between the lateral intermolecular interactions and the binding to the substrate. By means of temperature-induced change in the adsorption configuration and the activation of diffusion, the molecules are assembled into one-dimensional chains oriented along the [Formula: see text] crystallographic direction.

Nonacene Generated by On-Surface Dehydrogenation

The on-surface synthesis of nonacene has been accomplished by dehydrogenation of an air-stable partially saturated precursor, which could be aromatized by using a combined scanning tunneling and atomic force microscope as well as by on-surface annealing. This transformation allowed the in-detail analysis of the electronic properties of nonacene molecules physisorbed on Au(111) by scanning tunneling spectroscopy measurements. The spatial mapping of molecular orbitals was corroborated by density functional theory calculations. Furthermore, the thermally induced dehydrogenation uncovered the isomerization of intermediate dihydrononacene species, which allowed for their in-depth structural and electronic characterization.

Single-Molecule Rotational Switch on a Dangling Bond Dimer Bearing

One of the key challenges in the construction of atomic-scale circuits and molecular machines is to design molecular rotors and switches by controlling the linear or rotational movement of a molecule while preserving its intrinsic electronic properties. Here, we demonstrate both the continuous rotational switching and the controlled step-by-step single switching of a trinaphthylene molecule adsorbed on a dangling bond dimer created on a hydrogen-passivated Ge(001):H surface. The molecular switch is on-surface assembled when the covalent bonds between the molecule and the dangling bond dimer are controllably broken, and the molecule is attached to the dimer by long-range van der Waals interactions. In this configuration, the molecule retains its intrinsic electronic properties, as confirmed by combined scanning tunneling microscopy/spectroscopy (STM/STS) measurements, density functional theory calculations, and advanced STM image calculations. Continuous switching of the molecule is initiated by vibronic excitations when the electrons are tunneling through the lowest unoccupied molecular orbital state of the molecule. The switching path is a combination of a sliding and rotation motion over the dangling bond dimer pivot. By carefully selecting the STM conditions, control over discrete single switching events is also achieved. Combined with the ability to create dangling bond dimers with atomic precision, the controlled rotational molecular switch is expected to be a crucial building block for more complex surface atomic-scale devices.

Adsorption of Large Organic Molecules on Clean and Hydroxylated Rutile TiO2(110) Surfaces

Behavior of large organic molecules equipped with spacer groups (Violet Landers, VL) on the TiO(2)(110)-(1x1) surfaces is investigated by means of high-resolution scanning tunneling microscopy (STM). Two distinct adsorption geometries are observed. We demonstrate that the molecule adsorption morphology can be alternated by well-controlled STM tip-induced manipulation. It is used to probe the mobility of molecules and reveals locking in one of the analyzed adsorption sites, thus allow to enhance or reduce the mobility along the [001] direction. Field induced hydrogen desorption is used to perform lateral STM manipulation on a hydroxyl-free surface, which provides insight into the influence of surface hydroxyl groups on the molecule behavior. The ability to image with submolecular resolution both the central board and the spacer groups of the VL molecule is demonstrated.

[11]Anthrahelicene on InSb(001) c(8×2): A Low‐Temperature Scanning Probe Microscopy Study

The adsorption of individual [11]anthrahelicene molecules and their self-assembly into monolayer islands on an InSb(001) c(8×2) reconstructed surface is studied with low-temperature scanning probe microscopy. A racemic mixture is deposited on atomically flat terraces of InSb at room temperature. At lower coverage, the molecules tend to decorate atomic step edges of the substrate. At higher coverage, [11]anthrahelicene molecules form 2D islands. A quasi-hexagonal ordering of molecules within the layer is identified. Furthermore, it is shown that molecules adsorb with the helical axis almost perpendicular to the substrate. Interference between tunneling through the molecular layer and directly through space is reported. Finally, experimental results are compared to those of theoretical calculations.

Tunneling spectroscopy of close-spaced dangling-bond pairs in Si(001):H

We present a combined experimental and theoretical study of the electronic properties of close-spaced dangling-bond (DB) pairs in a hydrogen-passivated Si(001):H p-doped surface. Two types of DB pairs are considered, called “cross” and “line” structures. Our scanning tunneling spectroscopy (STS) data show that, although the spectra taken over different DBs in each pair exhibit a remarkable resemblance, they appear shifted by a constant energy that depends on the DB-pair type. This spontaneous asymmetry persists after repeated STS measurements. By comparison with density functional theory (DFT) calculations, we demonstrate that the magnitude of this shift and the relative position of the STS peaks can be explained by distinct charge states for each DB in the pair. We also explain how the charge state is modified by the presence of the scanning tunneling microscopy (STM) tip and the applied bias. Our results indicate that, using the STM tip, it is possible to control the charge state of individual DBs in complex structures, even if they are in close proximity. This observation might have important consequences for the design of electronic circuits and logic gates based on DBs in passivated silicon surfaces.