Antoni Tekiel

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.

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.

Room-Temperature Single-Electron Charging Detected by Electrostatic Force Microscopy

We use atomic force microscopy to measure electron addition spectra of individual Au nanoparticles that exhibit Coulomb blockade at room temperature. The cantilever tip charges individual nanoparticles supported on an ultra-thin NaCl film via single-electron tunneling from the metal back electrode. The tunneling is detected by measuring frequency shift and damping of the oscillating cantilever. Finite element electrostatic calculations indicate that the total nanoparticle capacitance is dominated by mutual capacitance to the back electrode.

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.

Layer-by-layer growth of sodium chloride overlayers on an Fe(001)-p(1 × 1)O surface

Ultra-thin NaCl films epitaxially grown on an Fe(001)-p(1 × 1)O surface have been investigated in ultra-high vacuum by non-contact atomic force microscopy and low energy electron diffraction. It has been found that at temperatures below 145 °C NaCl initially grows as monoatomic thick islands on substrate terraces, while at temperatures above 175 °C biatomic thick islands are also formed at substrate step edges. Both types of islands have the same Fe(001)-O[100] [parallel] NaCl(001)[110] orientation, leading to a (4 × 4) superstructure, where the NaCl unit cell is oriented at 45° with respect to the substrate. Interestingly, no c(2 × 2) superstructure with the NaCl unit cell oriented at 0° has been observed. The oxygen on the iron surface promotes layer-by-layer growth, resulting in atomically flat films with 40-60 nm wide terraces at coverages ranging from 0.75 to 12 ML. Such NaCl films are of much higher quality than MgO films grown on Fe(001) and Fe(001)-p(1 × 1)O surfaces and represent a unique epitaxial system of an alkali halide on a pure metallic substrate. The reduced number of defects and the layer-by-layer mode of growth make this system very attractive for applications where an atomically defined tunnel barrier is required to control the properties of a device.

Field deposition from metallic tips onto insulating substrates

The deposition of gold ions from atomic force microscope cantilever tips onto bulk insulating substrates with nearby surface electrodes is discussed. Numerical models of the potential distribution are used to estimate potential barriers for the desorption process. These models indicate deposition height thresholds of 7-10 nm with the tip 20-25 nm from the metallic electrode edge over a KBr surface but greater than 20 nm high for InP/GaAs/InP substrates with a two-dimensional electron gas (2DEG) as the back electrode. Experimental results for the deposition of gold clusters over KBr surfaces near metal electrodes in ultra-high vacuum (UHV) are presented and show promising agreement with calculations of the deposition threshold heights. Deposition of clusters over InP is discussed for comparison and indicates similar trends.

Photovoltaics at the nanoscale

Nanoscale thin film morphology has been identified as an important factor in organic solar cell device func- tionality and efficiency. To better understand the limiting factors, it is important to work at the length scale of these processes. A study of thin films of organic molecules with Kelvin probe force microscopy (KPFM) to observe charge distribution and non-contact atomic force microscopy (NC-AFM) to simultaneously obtain structural information is presented. This allows investigation of the structure-function relationships in molecu- lar photovoltaics at the nanometer scale. PTCDI (3,4,9,10-perylenetetracarboxylic diimide) and CuPc (copper phthalocyanine) are used as organic molecules and are precisely grown on alkali halide substrates.