000003669 001__ 3669
000003669 005__ 20240523045646.0
000003669 0247_ $$2doi$$a10.6082/uchicago.3669
000003669 041__ $$aen
000003669 245__ $$aOrganic Self-Assembled Monolayers: Chemical and Structural Responses to Temperature, Light, and Reactive Gas Species
000003669 260__ $$bThe University of Chicago
000003669 269__ $$a2022-03
000003669 300__ $$a104
000003669 336__ $$aDissertation
000003669 502__ $$bPh.D.
000003669 520__ $$aCharacterising the structural dynamics of materials is crucial to their implementation in real-world applications. Knowing how a system will respond to a particular stimulus, and understanding that response from a fundamental chemistry standpoint, is key to success in nanoscience. Accordingly, this thesis describes the use of kinetics and dynamics experiments to relate the structural behaviour of organic self-assembled monolayers to their environmentalconditions.
The work herein examines three different self-assembled monolayers perturbed by three different external stresses. First, we present the classic self-assembly system of alkanethiols on Au(111) and show how their ability to effectively passivate metal surfaces when bombarded with reactive gas species is strongly dependent on both film thickness and substrate temperature. The use of localised imaging techniques such as scanning tunnelling microscopy (STM) allows us to relate these observations to the monolayer restructuring and surface rearrangement that occurs throughout the reaction.
Second, we study how the topographical and crystalline nature of novel wafer-scale two-dimensional (2D) porphyrin polymers (specifically, metal-organic frameworks (MOFs)) are impacted by sample annealing and post-anneal cooling rates. Understanding these temperature-dependent structural phases is important for knowing the application limitations of such films – and for recognising previously unknown application potential.
Finally, we explore the cooperative dynamics of azobenzene-functionalised liquid crystal (LC) thin films in response to irradiation with ultraviolet (UV) light. Although much work has already been done on the production of azo-functionalised thin films, it remains challenging to induce simultaneous and coherent isomerisation of an entire film. Understanding the dynamic interaction between molecules within the film is therefore crucial to making uniformly switchable films a molecular engineering reality.
000003669 542__ $$fUniversity of Chicago dissertations are covered by copyright.
000003669 650__ $$aPhysical chemistry
000003669 650__ $$aMaterials Science
000003669 653__ $$achemical dynamics
000003669 653__ $$amaterials science
000003669 653__ $$areaction kinetics
000003669 653__ $$ascanning tunnelling microscopy
000003669 653__ $$aself-assembled monolayers
000003669 653__ $$asurface science
000003669 690__ $$aPhysical Sciences Division
000003669 691__ $$aChemistry
000003669 7001_ $$aBrown, Sarah$$uUniversity of Chicago
000003669 72012 $$aSteven J. Sibener
000003669 72014 $$aAndrei Tokmakoff
000003669 72014 $$aDavid A. Mazziotti
000003669 8564_ $$9ba4487d1-6655-4225-8bda-a652469e5ebc$$s80168296$$uhttps://knowledge.uchicago.edu/record/3669/files/Brown_uchicago_0330D_16193.pdf$$ePublic
000003669 909CO $$ooai:uchicago.tind.io:3669$$pDissertations$$pGLOBAL_SET
000003669 983__ $$aDissertation