Design and morphological investigation of high-χ catechol-containing styrenic block copolymers

Guillaume Pino (1) , Cian Cummins (1) , Daniele Mantione (1) , Nils Demazy (2, 1) , Alberto Alvarez- Fernandez (1) , Stefan Guldin (3) , Guillaume Fleury (1) , Georges Hadziioannou (1) , Eric Cloutet (1) , Cyril Brochon (1)

1 Team 4 LCPO : Polymer Materials for Electronic, Energy, Information and Communication Technologies
2 LCPO - Laboratoire de Chimie des Polymères Organiques
3 UCL - University College of London [London]

We report the synthesis of multifunctional block copolymers (BCPs) showing a high Flory-Huggins interaction parameter (χ) which enable sub-10 nm line space structures for a low degree of polymerization (N). The high χ BCPs are based on a poly(3,4-dihydroxystyrene)block-poly(4-trimethylsilylstyrene) (PDHS-b-PTMSS) architecture. The controlled synthesis of the PDHS-b-PTMSS precursors was performed using user-friendly sequential nitroxide mediated polymerization (NMP) polymerization of 3,4-diacetoxysytrene and 4trimethylsilylstyrene (PDAS-b-PTMSS). Thereafter, acid-catalyzed deprotection of the acetoxy moieties produced a library of PDHS-b-PTMSS BCPs with molecular weights ranging from 2.1 to 44.5 kg/mol. Bulk lamellar and cylindrical structures with periodicities as small as 8 nm were revealed by small-angle X-ray scattering. Moreover, PDHS-b-PTMSS thin films were assembled using solvent vapor annealing to define 10 nm line-space patterns in favorable conditions, i.e. at 20°C for 20 minutes. In summary, our work brings further knowledge to the BCP toolbox for next-generation nano-manufacturing needs.

Mots clés: Block copolymer; Self-assembly; NMP

Domaines: Polymères

Guillaume Pino, Cian Cummins, Daniele Mantione, Nils Demazy, Alberto Alvarez- Fernandez, et al.. Design and morphological investigation of high-χ catechol-containing styrenic block copolymers. Macromolecules, In press, ⟨10.1021/acs.macromol.2c00476⟩. ⟨hal-03728252⟩