Thilo Glatzel

Kelvin Probe Force Microscopy

Introduction.- I. Technical Aspects.- Experimental technique and working modes.- Phase Modulation Kelvin Probe Microscopy.- Data interpretation, spatial resolution and deconvolution.- Contribution of the numerical approach to Kelvin probe force microscopies.- Quantum mechanical simulations of electrostatic tip-sample interactions.- II. Selected Applications.- Surface properties of III-V semiconductors.- Electronic surface properties of semiconductors devices.- Optoelectronic studies of solar cells.- Electrical characterization of low dimensional systems (quantum/nano-structures).- Electronic structure of molecular assemblies.- KPFM for biochemical analysis.- Local work function analysis of photo catalysts.- Kelvin probe force microscopy with atomic resolution.- Summary.

Analytical approach to the local contact potential difference on (001) ionic surfaces: Implications for Kelvin probe force microscopy

An analytical model of the electrostatic force between the tip of a non-contact Atomic Force Microscope (nc-AFM) and the (001) surface of an ionic crystal is reported. The model is able to account for the atomic contrast of the local contact potential difference (CPD) observed while nc-AFM-based Kelvin Probe Force Microscopy (KPFM) experiments. With the goal in mind to put in evidence this short-range electrostatic force, the Madelung potential arising at the surface of the ionic crystal is primarily derived. The expression of the force which is deduced can be split into two major contributions: the first stands for the coupling between the microscopic structure of the tip apex and the capacitor formed between the tip, the ionic crystal and the counter-electrode; the second term depicts the influence of the Madelung surface potential on the mesoscopic part of the tip, independently from its microscopic structure. These short-range electrostatic forces are in the range of ten pico-Newtons. When explicitly considering the crystal polarization, an analytical expression of the bias voltage to be applied on the tip to compensate for the local CPD, i.e. to cancel the short-range electrostatic force, is derived. The compensated CPD has the lateral periodicity of the Madelung surface potential. However, the strong dependence on the tip geometry, the applied modulation voltage as well as the tip-sample distance, which can even lead to an overestimation of the real surface potential, makes quantitative KPFM measurements of the local CPD extremely difficult.

Probing atomic structure and Majorana wavefunctions in mono-atomic Fe chains on superconducting Pb surface

Motivated by the striking promise of quantum computation, Majorana bound states (MBSs) in solid-state systems have attracted wide attention in recent years. In particular, the wavefunction localization of MBSs is a key feature and crucial for their future implementation as qubits. Here, we investigate the spatial and electronic characteristics of topological superconducting chains of iron atoms on the surface of Pb(110) by combining scanning tunneling microscopy (STM) and atomic force microscopy (AFM). We demonstrate that the Fe chains are mono-atomic, structured in a linear fashion, and exhibit zero-bias conductance peaks at their ends which we interprete as signature for a Majorana bound state. Spatially resolved conductance maps of the atomic chains reveal that the MBSs are well localized at the chain ends (below 25 nm), with two localization lengths as predicted by theory. Our observation lends strong support to use MBSs in Fe chains as qubits for quantum computing devices.

The role of the cantilever in Kelvin probe force microscopy measurements

Summary The role of the cantilever in quantitative Kelvin probe force microscopy (KPFM) is rigorously analyzed. We use the boundary element method to calculate the point spread function of the measuring probe: Tip and cantilever. The calculations show that the cantilever has a very strong effect on the absolute value of the measured contact potential difference even under ultra-high vacuum conditions, and we demonstrate a good agreement between our model and KPFM measurements in ultra-high vacuum of NaCl monolayers grown on Cu(111). The effect of the oscillating cantilever shape on the KPFM resolution and sensitivity has been calculated and found to be relatively small.

Functionalized Truxenes: Adsorption and Diffusion of Single Molecules on the KBr(001) Surface

In this work, we have studied the adsorption and diffusion of large functionalized organic molecules on an insulating ionic surface at room temperature using a noncontact atomic force microscope (NC-AFM) and theoretical modeling. Custom designed syn-5,10,15-tris(4-cyanophenylmethyl)truxene molecules are adsorbed onto the nanoscale structured KBr(001) surface at low coverages and imaged with atomic and molecular resolution with the NC-AFM. The molecules are observed rapidly diffusing along the perfect monolayer step edges and immobilized at monolayer kink sites. Extensive atomistic simulations elucidate the mechanisms of adsorption and diffusion of the molecule on the different surface features. The results of this study suggest methods of controlling the diffusion of adsorbates on insulating and nanostructured surfaces.

Atomic-Scale Mechanical Properties of Orientated C60 Molecules Revealed by Noncontact Atomic Force Microscopy

In this work, the mechanical properties of C(60) molecules adsorbed on Cu(111) are measured by tuning-fork-based noncontact atomic force microscopy (nc-AFM) and spectroscopy at cryogenic conditions. Site-specific tip-sample force variations are detected above the buckyball structure. Moreover, high-resolution images obtained by nc-AFM show the chemical structure of this molecule and describes unambiguously its orientations on the surface.

Quantifying the atomic-level mechanics of single long physisorbed molecular chains

Significance Mechanical properties of biopolymers such as DNA and proteins have been studied to understand the details of complex processes in living systems via systematic statistical analyses of repeated measurements. However, the mechanical behavior of a single molecular chain pulled off a surface has never been investigated with atomic-scale resolution. Herein, we present such a study on in situ polymerized fluorene chains by pulling individual chains with the tip of an atomic force microscope at 4.8 K. The measured variations of the force gradient provide detailed insights into the detachment process of fluorene units and the role of near-incommensurability with the substrate structure. Individual in situ polymerized fluorene chains 10–100 nm long linked by C–C bonds are pulled vertically from an Au(111) substrate by the tip of a low-temperature atomic force microscope. The conformation of the selected chains is imaged before and after manipulation using scanning tunneling microscopy. The measured force gradient shows strong and periodic variations that correspond to the step-by-step detachment of individual fluorene repeat units. These variations persist at constant intensity until the entire polymer is completely removed from the surface. Calculations based on an extended Frenkel–Kontorova model reproduce the periodicity and magnitude of these features and allow us to relate them to the detachment force and desorption energy of the repeat units. The adsorbed part of the polymer slides easily along the surface during the pulling process, leading to only small oscillations as a result of the high stiffness of the fluorenes and of their length mismatch with respect to the substrate surface structure. A significant lateral force also is caused by the sequential detachment of individual units. The gained insight into the molecule–surface interactions during sliding and pulling should aid the design of mechanoresponsive nanosystems and devices.

Obtaining Detailed Structural Information about Supramolecular Systems on Surfaces by Combining High-Resolution Force Microscopy with ab Initio Calculations

State-of-the art experimental techniques such as scanning tunneling microscopy have great difficulties in extracting detailed structural information about molecules adsorbed on surfaces. By combining atomic force microscopy and Kelvin probe force microscopy with ab initio calculations, we demonstrate that we can obtain a wealth of detailed structural information about the molecule itself and its environment. Studying an FFPB molecule on a gold surface, we are able to determine its exact location on the surface, the nature of its bonding properties with neighboring molecules that lead to the growth of one-dimensional strips, and the internal torsions and bendings of the molecule.

Directed rotations of single porphyrin molecules controlled by localized force spectroscopy.

Directed molecular repositioning is a key step toward the build up of molecular machines. To artificially generate and control the motion of molecules on a surface, excitations by light, chemical, or electrical energy have been demonstrated. Here, the application of local mechanical forces is implemented to achieve directed rotations of molecules. Three-dimensional force spectroscopy with sub-Ångström precision is used to characterize porphyrin derivatives with peripheral carbonitrile groups. Extremely small areas on these molecules (≈ 100 × 100 pm(2)) are revealed which can be used to control rotations. In response to the local mechanical forces, the molecular structure elastically deforms and then changes its conformation, which leads to its rotation. Depending on the selection of one of four submolecular areas, the molecule is either rotated clockwise or counterclockwise.

Multiscale approach for simulations of Kelvin Probe force microscopy with atomic resolution

The distance dependence and atomic-scale contrast recently observed in nominal contact potential difference (CPD) signals simultaneously recorded by the Kelvin probe force microscopy (KPFM) using non-contact atomic force microscopy is addressed theoretically. In particular, we consider probing an insulating surface where the applied bias voltage affects electrostatic forces acting on the atomic scale. Our approach is a multiscale one. First, the electrostatics of the macroscopic tip-cantilever-sample system is treated, both analytically and numerically. Then the resulting electric field under the tip apex is inserted into a series of density functional theory calculations for a realistic neutral but reactive silicon nano-scale tip interacting with a NaCl(001) sample. Theoretical expressions for amplitude modulation (AM) and frequency modulation (FM) KPFM signals and for the corresponding local contact potential differences (LCPD) are obtained and evaluated for several tip oscillation amplitudes A up to 10 nm. For A = 0.01 nm, the computed LCPD contrast is proportional to the slope of the atomistic force versus bias in the AM mode and to its derivative with respect to the tip-sample separation in the FM mode. Being essentially constant over a few Volts, this slope is the basic quantity which determines variations of the atomic-scale LCPD contrast. Already above A = 0.1 nm, the LCPD contrasts in both modes exhibit almost the same spatial dependence as the slope. As the most basic quantity, the slope is shown to be approximately expressed in terms of intrinsic charge distribution and dipole moment and their variation due to the chemical interactions. The slope is also influenced by the macroscopic bodies. As a second part, we introduce a method to measure the distances between atomic configurations which is useful when seeking the tip-apex structures. The broad application of this method includes conformational search and machine-learning based interatomic potentials.