Propriétés optiques de monocouches moléculaires auto-assemblées sur surfaces métalliques

Abstract : One of the most widely studied type of photochromic molecules are azo-dye molecules whose photo-isomerization reaction entails important mass transport processes in polymer matrices.The aim of this PhD Thesis was to get a better understanding of the key parameters controling such photomechanical properties. For this purpose, we have driven some studies on Self-Assembled Monolayers (SAMs) formed by azobenzene derivatives grafted to alkanethiol linkers on atomically flat gold surfaces. Self-assembling offers the possibility to perform both scanning tunnelling microscopy (STM) experiments at the molecular scale and contact angle measurement at the macroscopic scale.A derivative alkanethiol system has been chosen to take benefit from the alkanethiol ability to form dense and regular self-assembled monolayers. Another interest of the alkanethiol linker is to easily adjust distance between the azo moiety and the gold surface through the length of the alkane chain. Then, this type of SAMs seems to be the good candidate to study the influence of (1) charges coupling effects between the neighbouring azo moieties and between the molecules and the metallic surface and (2) steric hindrance problems. Both a short (3 carbon atoms – “azoC3”) and a long (12 carbon atoms – “azo-C12”) alkane linker have more specifically been investigated. Although STM characterization have shown that azoC3 was organizing into a dense and regular packing showing a network quite similar to the one observed in the case of alkanethiols self-assembly, no modification could be evidenced upon illumination. Polarity modification between the trans and cis photoisomers, probed by wetting measurements, confirm the lack of photo-reactivity of these molecules grafted through a short linker to the metallic substrate. However, photo-isomerization effects have been observed at the macroscopic scale on polycristallines substrates for the long linker (“azo-C12”). The reasons for such behavior come from the intrinsic properties of alkanethiol SAMs: a dense network involves a restricted free volume and significant intermolecular interactions that add additional de-excitation channels thus leading to a quenching of the photoinduced conformational changes, except at surface defects areas. These findings have been supported by complementary characterizations of fluorescence of similar thiolates SAMs. We have demonstrated that an alkane spacer corresponding to 11 C was allowing electronic decoupling thus leading to fluorescent emission in the case of non-dense thiolated SAMs of fluorescein derivatives. However, these studies have also confirmed the difficulty to control the dilution of photosensitive molecules (photochromic or fluorescent) inserted within thiolated SAMs.In order to overcome this problem, we have demonstrated the interest of another original molecular system whose extended head group permits the formation of a network less densely-packed than those formed by alkanethiol derivatives. These molecular systems self-assemble by physisorption onto graphite (HOPG) substrates, their organization properties being also maintained for graphene sheets deposited onto copper substrates. Advantageously, these sheets can easily be transferred to transparent substrates. These studies open thus new perspectives for the realization of simultaneous in-situ experiments coupling molecular scale topography informations using local probe microscopy (AFM or STM) and larger scale optical measurents (inverted optical microscopy) towards more accurate characterizations.
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Maud Jaouen. Propriétés optiques de monocouches moléculaires auto-assemblées sur surfaces métalliques. Science des matériaux [cond-mat.mtrl-sci]. Université Paris Sud - Paris XI, 2014. Français. ⟨NNT : 2014PA112307⟩. ⟨tel-01127060⟩

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