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Controlled Transfer Of Macroscopically Organized Nanoscopically Patterned Sub–10 nm Features onto 2D Crystalline and Amorphous Materials
thesisposted on 05.08.2020, 19:10 by Tyson C DavisTyson C Davis
Surface level molecules act as an interface that mediates between the surface and the environment. In this way, interfacial molecules are responsible for conferring characteristics of relevance to many modern material science problems, such as electrical conductivity and wettability. For many applications, such as organic photovoltaics and nanoelectronics, macroscopic placement of chemical patterns at the sub-10 nm must be achieved to advance next generation device applications.
In the work presented here, we show that sub-10 nm orthogonal features can be prepared by translating the building principles of the lipid bilayer into striped phase lipids on 2D materials (e.g. highly ordered pyrolytic graphite (HOPG), MoS2). Macroscopic patterning of these nanoscopic elements is achieved via Langmuir Schafer deposition of polymerizable diyne amphiphiles. On the Langmuir trough, amphiphiles at the air water interface are ordered into features that can be observed on the macroscale using Brewster angle microscopy. Upon contact of the 2D material with the air-water interface the macroscopic pattern on the trough is transferred to the 2D material creating a macroscopic pattern consisting of sub-10 nm orthogonal chemistries. We also show here how hierarchical ordering can be accomplished via noncovalent microcontact printing of amphiphiles onto 2D materials. Microcontact printing allows a greater measure of control over the placement and clustering of interfacial molecules.
The alkyl chain/surface enthalpy has a great deal of influence over the ordering of amphiphiles at the sub-nm scale. Here, we examine this influence by depositing diyne amphiphiles onto MoS2 which has a weaker alkyl adsorption enthalpy compared to HOPG. We found that dual-chain amphiphiles deposited on MoS2 adopt a geometry that maximized the molecule-molecule interaction compared to the geometry adopted on HOPG.
Finally, we show how the hierarchical pattern of diyne amphiphiles can be transferred off of the 2D material onto an amorphous material. This is done by reacting the amorphous material with the conjugated backbone of the diyne moiety through a hydrosilylation reaction to exfoliate the film from the 2D crystalline material. The resulting polymer ‘skin’ has many applications were controlling interfacial properties of an amorphous material is important.