Through-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing [Thru-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing]

Basutkar, Monali N.; Samant, Saumil; Strzalka, Joseph; Yager, Kevin G.; Singh, Gurpreet; Karim, Alamgir

doi:10.1021/acs.nanolett.7b04028

Title: Through-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing [Thru-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing]

Journal Article · Tue Nov 14 00:00:00 EST 2017 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.7b04028· OSTI ID:1415487

^[1];

^[1]; Strzalka, Joseph ^[2];

^[3]; Singh, Gurpreet ^[1];

^[1]

Univ. of Akron, Akron, OH (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Here, template-free directed self-assembly of ultrathin (~10’s nm) lamellar block copolymer (l-BCP) films of high-interfacial area into vertically oriented nanodomains holds much technological relevance for fabrication of next-generation devices from nanoelectronics to nanomembranes due to domain interconnectivity and high interfacial area. We report for the first time, the formation of full thru-thickness vertically oriented lamellar domains in 100 nm thin polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films on quartz substrate, achieved without any PMMA-block wetting layer formation, quartz surface modification (templating chemical, topographical) or system modifications (added surfactant, top-layer coat). Vertical ordering of l-BCPs results from the coupling between a molecular and a macroscopic phenomenon. A molecular relaxation induced vertical l-BCP ordering occurs under a transient macroscopic vertical strain field, imposed by a high film thermal expansion rate under sharp thermal gradient cold zone annealing (CZA-S). The parametric window for vertical ordering is quantified via a coupling constant, C (= v∇T), whose range is established in terms of a thermal gradient (∇T) above a threshold value, and an optimal dynamic sample sweep rate (v ~ d/τ), where τ is the l-BCP’s longest molecular relaxation time and d is the T_g,heat-T_g,cool distance. Real-time CZA-S morphology evolution of vertically oriented l-BCP tracked along ∇T using in-situ Grazing Incidence Small Angle X-ray Scattering exhibited an initial formation phase of vertical lamellae, a polygrain structure formation stage, and a grain coarsening phase to fully vertically ordered l-BCP morphology development. CZA-S is a roll-to-roll manufacturing method, rendering this template-free thru-thickness vertical ordering of l-BCP films highly attractive and industrially relevant.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1415487

Journal Information:: Nano Letters, Vol. 17, Issue 12; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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Title: Through-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing [Thru-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing]

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