A new growth process for crystalline ultra-thin layers of conjugated oligomers used in field-effect transistor applications

Most organic semiconductor materials dewet on silicon wafers with thermal oxide layers. While Si-wafers represent convenient substrates for building a field effect transistor (FET), dewetting largely destroys the possibility for obtaining a compact and continuous crystalline thin organic semiconductor film and thus limits the mobility in these systems. Using oligothiophenes, we present an approach where the initial dewetting process can be turned into an advantage for generating very thin but large crystalline domains of a size up to the millimetres with all molecules sharing a single orientation. Our approach can be easily extended to other molecules, which have strongly differing growth velocities in the various directions of the crystal, for example due to directional π-stacking interactions. FETs devices based on such large crystalline domains showed charge carrier mobilities that were two orders of magnitude higher compared to non-crystallized films

Potentiostatic controlled nucleation and growth modes of electrodeposited cobalt thin films on n-Si(1 1 1)

The nucleation and growth of Co electrodeposits on n-Si(1 1 1) substrate have been investigated as a function of the applied potential in a large potential range using electrochemical techniques (voltammetry and chrono-amperometry) and surface imaging by atomic force microscopy (AFM). The surface preparation of the sample is crucial and we achieve a controlled n-Si(1 1 1) surface with mono-atomic steps and flat terraces. Using Scharifker-Hills models for fitting the current-time transients, we show that a transition from an instantaneous nucleation process to a progressive one occurs when the overpotential increases. A good agreement between the nucleation and growth parameters extracted from the models and the AFM data’s is observed. The growth is of the Volmer-Weber type with a roughness and a spatial extension in the substrate plane of the deposited islands that increase with thickness

Nanoparticle Assembling through Click Chemistry Directed by Mixed SAMs for Magnetic Applications

International audience"Click" chemistry, used to promote nanoparticle assemblies, is a powerful strategy which has emerged very recently to control the spatial arrangement of nanoparticles onto surfaces. Such a strategy may be of high interest for applications such as magnetic recording media or magnetic sensors which are based on the fine control of the collective properties of nanoparticles. Nevertheless, self-assembly driven by clickable functional groups still remains to be understood. Mixed self-assembled monolayers (SAMs) of alkane−thiol molecules were used to control the spatial arrangement of nanoparticles onto gold substrates. This approach was combined with click chemistry in order to control the immobilization of nanoparticles on selective areas through specific copper catalyzed alkyne−azide cycloaddition (CuAAC) reaction. Mixed SAMs consist of co-adsorbed 11-(undec-1-ynyl)thiol (S-CC) and 12-(dodecane)thiol (S-CH 3) molecules. The variation of the molar ratio between both molecules resulted in significant modulation of the structure of nanoparticle assemblies. The spatial arrangement of nanoparticles revealed the very complex structure of alkyne/methylene terminated mixed SAMs. Alkyne terminal groups could not be only studied by the usual characterization surface techniques such as PM-IRRAS and XPS. Therefore, azido-terminated nanoparticles acted as probing agents to determine the spatial distribution of alkyne groups at the surface of mixed SAMs. This approach was combined with scanning tunneling microscopy (STM) and DFT calculations to get a deeper insight into the structure of mixed SAMs of S-CC and S-CH 3 molecules. Gold substrate topography, chemical affinity of molecules, intermolecular interactions and length of alkyl chains were found to be critical parameters that rule the SAM structure

A new growth process for crystalline ultra-thin layers of conjugated oligomers used in field-effect transistor applications

Most organic semiconductor materials dewet on silicon wafers with thermal oxide layers. While Si-wafers represent convenient substrates for building a field effect transistor (FET), dewetting largely destroys the possibility for obtaining a compact and continuous crystalline thin organic semiconductor film and thus limits the mobility in these systems. Using oligothiophenes, we present an approach where the initial dewetting process can be turned into an advantage for generating very thin but large crystalline domains of a size up to the millimetres with all molecules sharing a single orientation. Our approach can be easily extended to other molecules, which have strongly differing growth velocities in the various directions of the crystal, for example due to directional π-stacking interactions. FETs devices based on such large crystalline domains showed charge carrier mobilities that were two orders of magnitude higher compared to non-crystallized films

Thermal exfoliation of fluorinated graphite

International audienceThe thermal exfoliation of graphite fluoride was investigated using two starting materials: fluorinated HOPG and powdered room temperature graphite fluoride (RTGF) post-treated in pure F2 gas in order to adjust the relative contents of intercalated species, the carbon hybridization and the C–F bonding. Firstly, the thermal exfoliation of HOPG sample (of composition CF0.57) at the nanoscale is highlighted using scanning tunneling microscopy (STM). Such process involves a defluorination, which is accelerated by disruption of the graphene sheets. Similar breaking occurs during the exfoliation of post-treated RTGF and evolves CF4 and C2F6 gases. Moreover, the exfoliation using a thermal shock is assisted by the fast deintercalation of the catalyst species in the region where the covalence of the C–F bonds is weakened. In such way, exfoliation occurs with the quasi-total defluorination

Highly n-doped graphene generated through intercalated terbium atoms

We obtained highly n-type doped graphene by intercalating terbium atoms between graphene and SiC(0001) through appropriate annealing in ultrahigh vacuum. After terbium intercalation angle-resolved-photoelectron spectroscopy (ARPES) showed a drastic change in the band structure around the K points of the Brillouin zone: the well-known conical dispersion band of a graphene monolayer was superposed by a second conical dispersion band of a graphene monolayer with an electron density reaching 10(15) cm(-2). In addition, we demonstrate that atom intercalation proceeds either below the buffer layer or between the buffer layer and the monolayer graphene. The intercalation of terbium below a pure buffer layer led to the formation of a highly n-doped graphene monolayer decoupled from the SiC substrate, as evidenced by ARPES and x-ray photoelectron spectroscopy measurements. The band structure of this highly n-doped monolayer graphene showed a kink (a deviation from the linear dispersion of the Dirac cone), which has been associated with an electron-phonon coupling constant one order of magnitude larger than those usually obtained for graphene with intercalated alkali metals

STM Studies of Self-Assembled Tetrathiafulvalene (TTF) Derivatives on Graphene: Influence of the Mode of Deposition

The conformations and the self-assembly process of tetrathiafulvalene (TTF) derivatives functionalized by lateral alkylthio chains deposited on graphene/SiC(0001) in ultrahigh vacuum (UHV) and at the solid–liquid interface are studied by scanning tunneling microscopy (STM). The study in UHV evidences a “molecular fastener” effect induced by the increase of van der Waals interactions between the alkylthio side chains which forces the major part of the molecules to self-organize in π–π stacked edge-on conformation. The study at the solid–liquid interface reveals a drastically different behavior with molecules lying flat on the surface as the solvent is involved in the stabilization of the molecular layer. This work raises a burning issue concerning the choice of the deposition method for graphene functionalization with such molecules

Morphology and composition of Au catalysts on Ge(111) obtained by thermal dewetting

International audienceWe investigate the chemical and morphological structure of the Au nanodots on Ge(111) which serve as catalysts for the formation of epitaxial Ge nanowires. The spatial localization of Au is investigated by X-ray spectromicroscopy and transmission electron microscopy. We show that dewetting of an Au film on Ge(111) gives rise to a thin Au-Ge wetting layer and Au-Ge dots. These dots are crystallized but not with a single crystallographic orientation. Thanks to the spatially resolved X-ray and transmission electron microscopy measurements, a chemical characterization of both binary Au-Ge catalysts and wetting layer is obtained at the nanoscale. We show that Ge vertical growth is achieved even without external Ge supply