Title:
High χ block copolymers for sub 20 nm pitch patterning: synthesis, solvent annealing, directed self assembly, and selective block removal

dc.contributor.advisor Henderson, Clifford L.
dc.contributor.advisor Tolbert, Laren M.
dc.contributor.author Jarnagin, Nathan D.
dc.contributor.committeeMember Collard, David
dc.contributor.committeeMember Reynolds, John
dc.contributor.committeeMember Bucknall, David
dc.contributor.department Chemistry and Biochemistry
dc.date.accessioned 2014-01-13T16:22:08Z
dc.date.available 2014-01-13T16:22:08Z
dc.date.created 2013-12
dc.date.issued 2013-09-03
dc.date.submitted December 2013
dc.date.updated 2014-01-13T16:22:08Z
dc.description.abstract Block copolymer (BCP) thin film patterns, generated using directed self-assembly (DSA) of diblock copolymers, have shown excellent promise as templates for semiconductor device manufacturing since they have the potential to produce feature pitches and sizes well below 20 nm and 10 nm, respectively, using current 193 nm optical lithography. The goal of this work is to explore block copolymers with sufficient thermodynamics driving force (as described by the Flory Huggins interaction parameter, χ) for phase separation at these smallest lengths scales. Here, poly(styrene)-b-poly(hydroxystyrene) is investigated since the PHOST domain is known to form extensive hydrogen bond networks resulting in increased χ due to this strong enthalpic interaction. In this work, nitroxide mediated polymerization (NMP) techniques were utilized to produce PS-b-PHOST diblock copolymers with a range of molecular weights (5000-30000) with low PDI approaching 1.2. The phase separation of low molecular weight PS-b-PHOST on neutral underlayer substrates via solvent annealing provided thin film vertical lamellae with 13 nm pitch. These results illustrate the improved resolution of PS-b-PHOST compared with the current industry standard of PS-b-PMMA (with 20 nm pitch). The directed self assembly of lamellar PS-b-PHOST patterns with 18 nm pitch via graphoepitaxy is demonstrated. Also, a highly selective atomic layer deposition (ALD) and etch technique was investigated which provided selective block removal of (PS-b-PHOST) block copolymer patterns which initially exhibited no inherent etch contrast. In this process, the PS domain is removed leaving a high fidelity etch relief pattern of the original block copolymer template. Finally, an alternative system is presented, namely Poly(trimethylsilylstyrene)-block-poly(hydroxystyrene) (PTMSS-b-PHOST), which utilizes silicon containing functionality in one of the blocks, providing high etch contrast. PTMSS-b-PHOST patterns were also exposed to oxygen plasma allowing selective block removal of the PS domain without the need for additional ALD processing steps.
dc.description.degree Ph.D.
dc.format.mimetype application/pdf
dc.identifier.uri http://hdl.handle.net/1853/50287
dc.language.iso en_US
dc.publisher Georgia Institute of Technology
dc.subject Block copolymer
dc.subject Phase separation
dc.subject Directed self-assembly
dc.subject Poly(styrene)-b-poly(hydroxystyrene)
dc.subject Atomic layer deposition
dc.subject Reactive ion etch
dc.subject Poly(trimethylsilylstyrene)-block-poly(hydroxystyrene)
dc.subject.lcsh Block copolymers
dc.subject.lcsh Diblock copolymers
dc.subject.lcsh Thin films
dc.subject.lcsh Self-assembly (Chemistry)
dc.title High χ block copolymers for sub 20 nm pitch patterning: synthesis, solvent annealing, directed self assembly, and selective block removal
dc.type Text
dc.type.genre Dissertation
dspace.entity.type Publication
local.contributor.advisor Tolbert, Laren M.
local.contributor.corporatename School of Chemistry and Biochemistry
local.contributor.corporatename College of Sciences
relation.isAdvisorOfPublication 4be1ea70-ac13-43da-9c67-0f32965bbac9
relation.isOrgUnitOfPublication f1725b93-3ab8-4c47-a4c3-3596c03d6f1e
relation.isOrgUnitOfPublication 85042be6-2d68-4e07-b384-e1f908fae48a
thesis.degree.level Doctoral
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