Scanning tunneling spectroscopy

Scanning tunneling spectroscopy (STS), an extension of scanning tunneling microscopy (STM), is used to provide information about the density of electrons in a sample as a function of their energy. In scanning tunneling microscopy, a metal tip is moved over a conducting sample without making physical contact. A bias voltage applied between the sample and tip allows a current to flow between the two. This is as a result of quantum tunneling across a barrier; in this instance, the physical distance between the tip and the sample The scanning tunneling microscope is used to obtain "topographs" - topographic maps - of surfaces. The tip is rastered across a surface and (in constant current mode), a constant current is maintained between the tip and the sample by adjusting the height of the tip. A plot of the tip height at all measurement positions provides the topograph. These topographic images can obtain atomically resolved information on metallic and semi-conducting surfaces However,

Carbon Nanotubes

Jaap Kroes

This thesis studies carbon nanotubes using state-of-the-art computational methods. Using large-scale quantum-mechanical calculations, based on density-functional-theory, we investigate several important aspects of the physics and chemistry of single-walled-nanotubes. The focus is on the effect of defects, namely adparticles and vacancies, on the structural, electronic and dynmical properties of the nanotubes. We also present preliminary results of simulations exploring a possible route for the formation of SWNTs from graphene nanoflakes. Adparticles include atomic hydrogen, oxygen, sulfur at different concentrations as well as nitrogen--oxides. Chemisorption of hydrogen as well as oxygen and isoelectronic species results in the formation of clusters on the sidewall, with characteristic structures corresponding to characteristic signatures in the electronic spectra. Especially in the case of oxygen, we find that relatively high energy barriers separate different structures: this shows that not only thermodynamically favored configurations are relevant for the understanding of oxygen chemisorption but the presence of traps cannot be neglected. The fingerpint of these traps is confirmed by scanning-tunneling spectroscopy. Trends with size and chirality of the nanotubes and oxygen coverage are studied in detail and also explained in terms of simple chemical descriptors. The importance of large-scale atomistic models is also emphasized to obtain convergent results and thus reliable predictions, and comparison is made of results we obtain using different gradient-corrected exchange-correlation functionals and in part with hybrid functionals. The study of nitrogen-oxides faces the difficulty to correctly represent physisorption, also with empirically corrected gradient-corrected exchange-correlation and hybrid functionals. Still our calculations of vibrational frequencies of different molecules on the sidewall, once compared with experiment, are able to distinguish the specific species observed in infrared spectra. Part of our work is centered on the comparison of widely used classical potentials (reactive force fields) with DFT results. Specifically we use them to study hydrogen and oxygen chemisorption, and especially examine the validity of several different force-fields for the description of the structure and energetics of single and double vacancies. In all cases, we find rather limited agreement with DFT results, showing the intrinsic difficulty to represent the subtle and intrinsic quantum effects governing the physico-chemical behavior of carbon nanotubes. Still, the wealth of results we have obtained might be useful for an improvement of these classical schemes for a specific application or other semi-classical models.

EPFL2014

Growth and characterization of specific self-assembled supramolecular architectures at crystal surfaces

Marta Canas Ventura

In the framework of this thesis self-assembled supramolecular architectures of several molecular species on crystal metal surfaces are characterized. These investigations combine results obtained by means of scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), X-Ray Photoelectron Spectroscopy (XPS), and Near-Edge X-Ray Absorption Fine Structure Spectroscopy (NEXAFS). The interest in controlling the formation of specific arrangements of supramolecular ensembles at surfaces is motivated to a great extent by the prospect to design molecular devices and nanomaterials with customized properties. The goal is a "spontaneous" creation of targeted, well-ordered molecular architectures, which shall be achieved by taking advantage of the molecule's propensity to self-assemble. Control means, in this context, predictability. This term address the accuracy of the prediction of the structures resulting from molecular self-assembly for systems exhibiting different characteristics. Here, system stands for a particular combination of a single-crystal surface and adsorbed molecular species. In a first part, the focus is given to the impact of a Pd(111) surface exhibiting high chemical activity. Due to surface induced deprotonation two resulting chemical states are found for the adsorbed terephthalic acid species. Deprotonation of the carboxyl moieties is observed to affect the topology of the molecular assemblies even though hydrogen bonds (H-bonds) are responsible for the stabilization of assemblies of both, intact and deprotonated molecular species. Therefore, the selective fabrication of a single specific molecular structure becomes a challenge when the surface is prone to induce chemical reactions. Secondly, a molecular species exhibiting conformational flexibility is studied on a largely inert Au(111) surface. It is observed that the characteristic conformational flexibility is also active on the surface, and the molecule is found to adopt different conformations depending on the locally most favorable bonding motif. In particular, phenyl groups may undergo a rotation such that one-dimensional chains can be stabilized by means of intermolecular H-bonds. This phenomenon is very interesting from an adsorbate-substrate interaction point of view, but it limits the predictability of supramolecular structures formed upon self-assembly. In a third step, a comparative study of the self-assembly of three closely related molecular species highlights the impact of concurrent competing intermolecular interactions. Molecules exhibiting an increasing number of possible interaction channels are found to assemble into an increasing number of distinct supramolecular architectures. The most flexible molecular species allowing for different hydrogen-bonding patterns as well as dipolar coupling self-assembles into various structurally complex architectures. Structural predictability, however, is low since the formation of one or the other assembly appears to depend on small variations in sample preparation conditions and on poorly controllable local surface properties. Finally, a system where the resulting structures fully agree with predictions evidences the possibility to control the formation of targeted specific supramolecular architectures. The formation of well ordered bimolecular ribbons and wires over extended length scales is accomplished by the rational choice of both, complementary building blocks for the selective formation of three-fold H-bonds and a nanostructured surface to guide the molecular self-assembly. Furthermore, the impact of H-bond formation on the electronic structure of self-assembled molecular building blocks is probed by STS measurements. The experimental data reveal shifts in the electronic levels depending on the H-bond configuration and on the local characteristics of the underlying surface. In order to improve the precision of such a study, single molecules, homo- and heteromolecular dimers as well as trimers are successfully isolated and assembled by molecular manipulation with the STM tip. Further STS studies on such artificially assembled structures are suggested.

EPFL2008

An Experimental Setup for Heterogeneous Catalysis on Atomically Defined Metal Nanostructures

Jean-Guillaume De Groot

The main objective of this PhD thesis is to link the atomic scale structure to the catalytic properties of self-assembled nanostructures. The growth and characterization of these nanostructures was carried out in an ultra-high vacuum (UHV) chamber initially designed for the study of the kinetics of epitaxial growth of thin films and nanostructures by variable temperature scanning tunneling microscopy. During this PhD thesis, we built a very sensitive and selective gas detector based on a quadrupole mass spectrometer and adapted to the geometry of this UHV system. The proper functioning of the gas detector is confirmed by temperature programmed desorptions of Xe on Ag(100) which demonstrate the very high sensitivity of the device of about

10^{-6}

~monolayer (ML). The zero-order desorption parameters obtained for the first monolayer of Xe adsorbed on Ag(100) are

E_d=0.22-0.23

~eV with a prefactor

\nu_0

between

4\times10^{12}

^{-1}

and

1 \times10^{13}

^{-1}

. An exchange process between Fe adatoms and Ag atoms from the Ag(100) surface is identified by means of temperature programmed desorption of N

_2

. Desorption spectra suggest that the exchange is complete from an annealing temperature of 140~K. Our study of the catalytic activity of metal nanostructures focuses on the ability of passivated Fe clusters to adsorb N

_2

molecules without dissociating them, which is a fundamental step in the bio-inspired heterogeneous catalysis of ammonia. The first system investigated for the growth of Fe clusters is MgO/Ag(100). Diffusion of Fe adatoms deposited on a MgO monolayer is observed from an annealing temperature of 280~K onwards. Fe clusters with an average size of

12.1\pm 0.5

~atoms are obtained on a MgO monolayer by thermal ripening of 0.072~ML of Fe deposited at 40~K. No sign of N

_2

adsorption was observed on these clusters by thermal programmed desorption investigation. The second system chosen for the growth of Fe clusters is graphene/Ir(111) obtained by chemical vapor deposition. The deposition of 0.3 and 0.4 ML of Fe on a graphene/Ir(111) sample at 50~K, followed by annealing at 300~K, generates a superlattice of Fe clusters which matches the periodicity of the moiré formed by graphene/Ir(111). The theoretically expected mean cluster size is 26 atoms for 0.3~ML of Fe, and 35 atoms for 0.4~ML of Fe. The temperature stability of the clusters obtained with 0.4~ML Fe is investigated from 300~K to 600~K. It is established that Smoluchowski ripening takes place as the annealing temperature increases and the superlattice structure has completely disappeared after annealing at 600~K. Temperature programmed desorption of molecularly adsorbed N

_2

at 50~K on a sample with 0.4~ML of Fe deposited on graphene/Ir(111) reveals 3 desorption peaks at 120~K, 92~K, and 60~K. In addition, slow dissociation of nitrogen molecules at 50~K adsorbed on the higher energy adsorption sites is demonstrated.

EPFL2021

An Experimental Setup for Heterogeneous Catalysis on Atomically Defined Metal Nanostructures

Jean-Guillaume De Groot