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Through-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone
Monali N Basutkar1, Saumil Samant1, Joseph Strzalka2
1Department of Polymer Engineering, University of Akron , Akron, Ohio 44325, United States.
Nano Letters
|November 15, 2017
Summary
Template-free self-assembly creates vertically aligned nanodomains in ultrathin block copolymer films. This breakthrough, using cold zone annealing, enables advanced nanoelectronics and nanomembranes without surface modification.
Area of Science:
- Materials Science
- Polymer Science
- Nanotechnology
Background:
- Ultrathin lamellar block copolymer (l-BCP) films are crucial for advanced devices.
- Achieving vertically oriented nanodomains is technologically significant for enhanced interconnectivity and interfacial area.
- Existing methods often require complex surface modifications or additives.
Purpose of the Study:
- To report the first template-free formation of full through-thickness vertically oriented lamellar domains in ultrathin polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films.
- To investigate the mechanism coupling molecular relaxation with macroscopic strain under thermal gradients.
- To establish the parametric window for vertical ordering using a coupling constant.
Main Methods:
- Utilized sharp thermal gradient cold zone annealing (CZA-S) to impose a transient vertical strain field.
- Employed in situ grazing incidence small-angle X-ray scattering (GISAXS) to track morphology evolution in real-time.
- Quantified the parametric window for vertical ordering via a coupling constant C (= v∇T).
Main Results:
- Achieved full through-thickness vertical lamellar ordering in 100 nm PS-b-PMMA films without any surface modification or additives.
- Demonstrated that vertical ordering is driven by molecular relaxation coupled with macroscopic vertical strain from CZA-S.
- Identified the critical role of thermal gradient (∇T) and sample sweep rate (v) in achieving vertical alignment.
Conclusions:
- Developed a novel, template-free method for producing vertically ordered l-BCP films.
- The CZA-S process is a scalable, roll-to-roll compatible technique, making it industrially relevant.
- This advancement facilitates the fabrication of next-generation nanoelectronic and nanomembrane devices.
