Electronic and optical properties of supported C60 molecules studied by scanning tunneling microscopy

This thesis is primarily concerned with optical properties of adsorbed C60 molecules on metal and insulating substrates. These properties were studied on a single-molecule scale, using Scanning Tunneling Microscope-induced light emission spectroscopy (STM-LES). In the first part of the thesis (Chapter 2), we present the investigation of the structural and electronic properties of C60 islands on Au(111) and on ultrathin NaCl films. We further present a study of the structure of ultrathin sodium chloride films grown on Au(111), and the influence of the herringbone reconstruction on the interface state of a NaCl-covered Au(111) surface. In the second part of the thesis (Chapter 3 and 4), we show that applying a local technique such as STM induced optical spectroscopy enables the exploration of the optical characteristics of individual objects on the nanoscale. Contrary to conventional non-local techniques, the local character of this technique offers the unique possibility to select and probe individual atoms, molecules or clusters on surfaces. Here, we demonstrate the capability of STM-induced light emission spectroscopy (STM-LES) for the chemical recognition on a single-molecule scale. In Chapter 3, we present STM-induced light emission spectroscopy (STM-LES) of a clean Au(111) surface, Au(111) surface covered with islands of C60 molecules and of Au(111) covered with ultrathin NaCl films. We have performed an extensive investigation of the dependence of the gold plasmon spectra on tunneling current and voltage. We show the influence of nano-objects on the shape and intensity of the spectra. Furthermore, we investigated the influence of this experimental technique on morphological changes of surfaces and adsorbed layers. In Chapter 4, we present the first observation of energy resolved luminescence from selected C60 molecules excited by electrons tunnelling through a double barrier STM junction. A comparison with the luminescence spectra obtained by non-local spectroscopy from dispersed C60 molecules in rare gas matrices enables us to demonstrate the molecular origin of the detected light and to identify the observed spectral features. The present novel observation of both, fluorescence and phosphorescence constitutes a solid basis for the chemical identification of an individual C60 molecule.

Scanning Tunneling Luminescence of Pentacene Nanocrystals

Alexander Kabakchiev

Organic semiconductors are promising materials for future electronic and electroluminescence applications. A detailed understanding of organic layers and nano-sized crystals down to single molecules can address fundamental questions of contacting organic semiconductors at the nanometer limit and obtaining luminescence from them. In this thesis, electroluminescence spectra from pentacene, a policyclic hydrocarbon (acene), are discussed. The luminescence is induced by the current from the tip of a scanning tunneling microscope (STM). Pentacene is an organic semiconductor which gained a lot of attention in technology because of its electronic properties suitable for applications in thin film devices. Moreover, recent fundamental studies employed pentacene as a standard to demonstrate sub-molecular resolution by scanning probe techniques. This work reports the first observation of light emission from nanometer-sized pentacene crystals grown on an ultrathin insulating layer on noble metal surfaces. Different STM-techniques are combined to characterize the individual systems studied with respect to topography, crystal structure, electronic properties and work function changes. The initial step of the project was the implementation of an optical system for light collection from the tunnel-junction of a low-temperature STM. In the set-up, a novel approach based on the use of in situ adjustable lenses has been realized. Three lenses placed in the vicinity of the tip-apex allow light collection into three independent channels which can be used for versatile optical analysis. An important part in the characterization of the organic system was to clarify the interaction between adsorbed molecules and substrates. We investigated individual pentacene molecules on different ultrathin insulator-metal systems. With the STM tip in tunnel contact, the molecules are situated in a double barrier junction formed by the insulating layer on one side and the vacuum gap on the other side. The metal surface and the STM-tip form the electrodes. The electronic properties of pentacene in this configuration have been characterized. Insulator-metal-systems, which provide a good electronic decoupling for pentacene from the metal, have been chosen as substrates for the growth of pentacene nanocrystals. Using the sub-molecular resolution of the STM we resolved the structure of the top-layer of the pentacene nanocrystals and found that the crystal phase agrees with the pentacene bulk structure. Moreover, the comparison of charge injection barriers between individual molecules and nanocrystals of pentacene indicates a significant change of electronic properties after the formation of ordered structure from the individual building blocks. Optical spectroscopy of the emitted light reveals an excitonic emission from the nanocrystals, which is in very good agreement with photoemission spectra of macroscopic crystals. Although a highly localized current-injection by the STM tip is used for excitation, it can be concluded that the source of light emission is delocalized. In contrast to luminescence measurements reported for other organic materials in STM, the excitation is not localized on the individual molecule, into which a charge is injected by the STM-tip. Our study indicates the importance of inter-molecular coupling leading to a high mobility of the excited state which has to be considered in the framework of STM-induced luminescence. A further result is the observation of the Stark shift of pentacene luminescence, that has so far not been measured at large electric fields of the order of 1V/nm. The evaluation of the Stark shift provides information on dipole and polarizability change during the decay of an exciton. The measured large dipole change of the lowest singlet exciton in pentacene indicates a mixing of the Frenkel exciton (FE) with a small contribution of charge-transfer (CT). Finally, we developed a set-up for photon correlation measurements in the STM. The properties of photon statistics is a means which can unambiguously prove that the luminescence is due to a single-photon source, i.e. a light source which emits no more than one photon at a time. A typical example of such a source is the emission from a single molecule. We performed photon correlations measurements of the luminescence from pentacene and C60 nanocrystals. While the excitonic bulk emission of pentacene is not expected to represent a single photon emitter, we also did not observe anticorrelations in the case of C60 indicating the importance of the local environment in the STM-junction, e.g. the short distance to the metal electrodes.

EPFL2010

Plasmon enhanced luminescence from fullerene molecules excited by local electron tunneling

Frédéric Rossel

This thesis reports on the optical properties of fullerene molecules forming nanoscale crystals grown on ultrathin NaCl films on Au(111) investigated by Scanning Tunneling Microscope (STM)-induced light emission spectroscopy. In this regard, an existing optical setup has been improved. The new instrument facilitates the alignment of the detection lens with the tunnel junction. STM images of the investigated samples show that, upon adsorption on a NaCl covered Au(111) surface, C60 and C70 crystallize into multilayer islands with a hexagonally arranged close-packed top layer in which electron-poor regions on one molecule face electron-rich regions on the adjacent molecule. Luminescence spectra from these nanocrystals induced by electrons tunneling through a double barrier STM junction are presented. Their bias dependence as well as their similarity with laser-induced photoluminescence spectra indicate a hot electron injection mechanism followed by a radiative decay associated with the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO–LUMO) gap of the molecules. Local fluorescence and phosphorescence of C70 molecules are identified, leading to unambiguous chemical recognition on the nanoscale. Moreover, the molecular luminescence is demonstrated to be selectively enhanced by localized surface plasmons in the STM tip-sample gap, the tunnel junction acting as an optical antenna. Finally, the results of a scanning tunneling microscopy and scanning tunneling spectroscopy investigations of self-assembled islands of Azure A molecules on a Au(111) substrate are presented. Although no final conclusion can be drawn on the molecular arrangement owing to the impossibility to recognize specific parts of the molecule, the presence of these structures is found to modify the Au(111) herringbone reconstruction.

EPFL2009

Biological samples studied by optical nanospectroscopy

Johanna Generosi

The different parts of the electromagnetic spectrum result in diverse effects upon interaction with matter: according to the wavelength, the radiation has energy appropriate for the excitation of a specific physical process. X-rays can be used as a tool to analyze the structure of matter since their wavelength is comparable with the interatomic distances. Infrared light is in the spectral region that excites molecular vibrations and is employed to investigate the chemical composition of a material. Visible radiation can study the optical properties of a sample, such as the fluorescence and the absorbance, and provide a chemical fingerprint when the inelastically scattered light is detected. In this thesis work these light sources are used in diverse experimental approaches to study structured biological specimens, resulting in a detailed chemical and physical characterization at the atomic and molecular scale. Conventional spectroscopy is often not enough sensitive and spatially resolved to detect specific elements or domains in a sample. The need of imaging objects on increasingly finer scales and spatially localize specific molecules, brought to combine infrared, visible and Raman spectroscopy with scanning near-field microscopy giving rise to a powerful nanospectroscopic tool used to perform simultaneous topographical measurements and optical/chemical characterizations with subwavelength resolution, overcoming the diffraction limit of light. Our study combines X-ray diffraction and reflectivity with optical nanospectroscopy to investigate the order and clustering of lipid bilayers, the interaction between solid-supported membranes and embedded alamethicin peptides, the optical and chemical properties of hippocampal neuron cells and the trafficking mechanism of specific neuron receptors.

EPFL2009

Scanning Tunneling Luminescence of Pentacene Nanocrystals

Alexander Kabakchiev

EPFL2010