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Low-energy Electron Induced Chemistry in Supported Molecular Films

Abstract : High-energy irradiation of condensed matter leads to the production of copious amounts of low-energy (0-20 eV) secondary electrons. These electrons are known to trigger various dissociative processes leading to observed damages including erosion and chemical modifications. The resulting reactive species within the condensed media can also lead to the synthesis of new molecules. This has implications in several applications most especially in the design of lithographic methods, focused beam-assisted deposition, as well as in astrochemistry. In all these applications, it is important to identify the processes induced by low-energy electrons, study the reactive fragments and stable molecules produced to determine possibilities of controlling them, and generate quantitative data to gauge the efficiencies of these processes. The approach developed for this PhD work consists of directly irradiating surfaces and interfaces using low-energy electrons and studying the processes that arise. The responses of different model molecular films (of varying thickness) were studied as a function of incident electron energy and dose. In favorable cases, methodologies proposed herein can be used to estimate effective cross sections of observed processes. Three complementary surface-sensitive techniques were utilized for this purpose. To characterize the deposited films and formed residues, the High Resolution Electron-Energy Loss Spectroscopy (HREELS) and Temperature Programmed Desorption (TPD) were used. Neutral fragments (as opposed to their often-detected ionic counterparts) desorbing under electron irradiation were monitored using a mass spectrometer in a technique called Electron Stimulated Desorption (ESD).Within the context of surface functionalization, the grafting of sp2-hybridized carbon centers on a polycrystalline hydrogenated diamond substrate was realized through electron irradiation of a thin layer of benzylamine precursor deposited on its surface. At 11 eV, the dominant mechanism is proposed to be neutral dissociation of the precursor molecules. The effective cross section of the grafting process was estimated in only a single measurement from the HREELS map of the sample surface, taking advantage of the electron beam profile. Within the context of astrochemistry, on the other hand, the responses of crystalline and amorphous NH3 ices were studied under electron impact. The desorption of intact NH3 was observed which resulted in the direct erosion of the film proceeding through a mechanism consistent with desorption induced by electronic transitions (DIET). Different fragmentation and recombination processes were also observed as evidenced by detected neutral species like NHx (x=1,2), N2, and H2. Aside from desorption, a wealth of chemical processes was also observed at 13 eV. Temporal ESD at this energy allowed for the estimation of the effective cross section of NH3 desorption and observing the delayed desorption of N2 and H2. TPD analysis of the residues also provided evidence of N2H2 and N2H4 synthesis in the film. These results can help explain the observed discrepancies in abundances of NH3 and N2 in dense regions in space. Lastly, this PhD work will present prospects for these electron-induced processes to be constrained spatially in microscopic dimensions for lithographic applications. The feasibility of the procedure utilizing Low-Energy Electron Microscope (LEEM) was demonstrated on a terphenylthiol self-assembled monolayer (TPT SAM) specimen. Spots of 5 μm in diameter with different work functions were imprinted on the surface using energies from 10-50 eV. Electron-induced reactions in thin-film resists (PMMA, poly(methyl methacrylate)) were also studied at low-energy identifying opportunities for energy- and spatially-resolved surface modification.
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Submitted on : Wednesday, March 20, 2019 - 9:45:40 AM
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Leo Albert Sala. Low-energy Electron Induced Chemistry in Supported Molecular Films. Materials. Université Paris-Saclay, 2018. English. ⟨NNT : 2018SACLS438⟩. ⟨tel-02073621⟩

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