Adsorption of multifunctional molecules on the Ge(100)-2x1 surface
- The technological revolution that started with digital electronics more than 50 years ago has pushed the limits of scalability in device fabrication. Device features are currently at the nanometer scale, which requires structures to be built with atomic level accuracy. Advances in nanotechnology have opened up an exciting area of research that allows for molecular level control of device surfaces. Organic molecules can provide the tailorability required to continue the progress of semiconductor technologies. Organic functionalization provides a pathway to control the surface at the molecular level. Fundamental understanding of the adsorption phenomena between organic molecules and the surface is critical to achieve a stable inorganic/organic interface for the creation of hybrid nanostructures. This thesis aims to expand our current toolkit on functionalization to molecules that have multiple functionalities that can react with the surface. The reaction mechanism of these molecules is complex as there are several driving forces that can play a role during adsorption and influence the final reaction products. This thesis covers the adsorption of multifunctional molecules on the Ge(100)-2×1 surface using a combination of experimental and theoretical techniques: Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We explored the adsorption of four different molecules: 1,2,3-benzenetriol (C6H6O3); 1,3,5-benzenetriol (C6H6O3); 2-hydroxymethyl-1,3-propanediol (C4H10O3); pyrazine (C4H6N2). These are the first reported studies of these molecules on the Ge(100) surface. In order to understand the extent to which molecular geometry affects surface coverage, a detailed comparison of the adsorption of two triol molecules was carried out: 1,3,5-benzenetriol which has a rigid phenyl backbone and 2-hydroxymethyl-1,3-propanediol with a flexible alkyl backbone. DFT results showed that the rigid backbone exhibits a higher degree of strain, which translates to a loss of exothermicity in the reaction coordinate. Experiments showed that the flexibility of the alkyl backbone provides higher rotational degrees of freedom and an enhancement in surface coverage. In order to understand the effect of intermolecular interactions, the adsorption of 1,2,3-benzenetriol was explored. Interestingly, we found that at high coverage, intramolecular hydrogen bonding in singly and dually adsorbate products breaks to form intermolecular hydrogen bonding with a nearby adsorbate, which provides enhanced stabilization of the surface adduct. This additional stabilization may lower the reactivity of unreacted functional groups even if an empty nearby Ge site is available for reaction. The distribution of products resulted in primarily bidentate adsorbates, leaving an unreacted moiety at the surface. We also found evidence of coverage and temperature effects on adsorbed pyrazine molecules on the Ge surface. It was observed that this molecule adsorbs on Ge through both carbon and nitrogen moieties and the product distribution changes as a function of coverage and temperature. At low coverage, incoming molecules react primarily through C-cycloaddition reactions and N dative bonds. However, as the density of adsorbates increases, new incoming molecules adsorbed primarily through the nitrogen moiety. Furthermore, as the temperature increases, the product distribution changed from primarily non-activated dative bond to activated cycloaddition products. Overall, the studies in this thesis provide new insight into competition and selectivity in adsorption of multifunctional molecules on the Ge(100)-2×1 surface.
|Type of resource
|electronic; electronic resource; remote
|1 online resource.
|Sandoval, Tania E
|Stanford University, Department of Chemical Engineering.
|Jaramillo, Thomas Francisco
|Jaramillo, Thomas Francisco
|Statement of responsibility
|Tania E. Sandoval.
|Submitted to the Department of Chemical Engineering.
|Thesis (Ph.D.)--Stanford University, 2018.
- © 2018 by Tania Elizabeth Sandoval Salas
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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