Rapid solvo-microwave annealing for optimizing ordered nanostructures and crystallization of regioregular polythiophene-based block copolymers
- Authors
- Han, Junghun; Kim, Jin-Seong; Shin, Jae Man; Yun, Hongseok; Kim, Youngkwon; Park, Hyeonjung; Kim, Bumjoon J.
- Issue Date
- Sep-2019
- Publisher
- ROYAL SOC CHEMISTRY
- Citation
- POLYMER CHEMISTRY, v.10, no.36, pp.4962 - 4972
- Journal Title
- POLYMER CHEMISTRY
- Volume
- 10
- Number
- 36
- Start Page
- 4962
- End Page
- 4972
- URI
- http://scholarworks.bwise.kr/ssu/handle/2018.sw.ssu/40511
- DOI
- 10.1039/c9py00871c
- ISSN
- 1759-9954
- Abstract
- Manipulation of crystalline structures of conjugated polymers (CPs) within nanostructured block copolymer (BCP) domains is crucial to enhance their electrical properties. However, this has been a challenge due to the intrinsic incompatibility between crystallization and phase-separation process of CP-based BCPs, which often causes break-out crystallization and results in disordered nanostructures and poor electrical properties. Herein, we demonstrate solvo-microwave annealing as an effective method for producing thin film structures of CP-based BCPs with well-ordered nanostructures and high crystallinity in a very short processing time (similar to 3 min). This approach is applied for poly(3-dodecylthiophene)-block-poly(lactic acid) (P3DDT-b-PLA) copolymers as a model system, where the PLA block offers the additional benefit of selective etchability to provide an on-chip etch mask for pattern transfer. The conventional thermal annealing process, even with a long annealing time (similar to 24 h), resulted in incompatibility between ordered nanostructures and the crystallization of the conjugated polymer. In contrast, the solvo-microwave annealing with a combination of heat and solvent vapor treatment was employed to grant enhanced chain mobility and solvent interaction with the pi-pi structure of the conjugated polymer. As a result, this process rapidly generated nanostructures with very few defects within 3 min and, at the same time, the highly crystalline intermolecular ordering of the P3DDT blocks occurred. Furthermore, we demonstrate the successful transfer of highly-ordered P3DDT structures after the removal of the PLA domain, which is important for potential applications in nanolithography and electronics.
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