Synthesis, thermal processing, and thin film morphology of poly(3-hexylthiophene)-poly(styrenesulfonate) block copolymers

Harikrishna Erothu, Joanna Kolomanska, Priscilla Johnston, Stefan Schumann, Dargie Deribew, Daniel T.W. Toolan, Alberto Gregori, Christine Dagron-Lartigau, Giuseppe Portale, Wim Bras, Thomas Arnold, Andreas Distler, Roger C. Hiorns, Parvaneh Mokarian-Tabari, Timothy W. Collins, Jonathan R. Howse, Paul D. Topham*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


A series of novel block copolymers, processable from single organic solvents and subsequently rendered amphiphilic by thermolysis, have been synthesized using Grignard metathesis (GRIM) and reversible addition-fragmentation chain transfer (RAFT) polymerizations and azide-alkyne click chemistry. This chemistry is simple and allows the fabrication of well-defined block copolymers with controllable block lengths. The block copolymers, designed for use as interfacial adhesive layers in organic photovoltaics to enhance contact between the photoactive and hole transport layers, comprise printable poly(3-hexylthiophene)-block-poly(neopentyl p-styrenesulfonate), P3HT-b-PNSS. Subsequently, they are converted to P3HT-b-poly(p-styrenesulfonate), P3HT-b-PSS, following deposition and thermal treatment at 150 °C. Grazing incidence small- and wide-angle X-ray scattering (GISAXS/GIWAXS) revealed that thin films of the amphiphilic block copolymers comprise lamellar nanodomains of P3HT crystallites that can be pushed further apart by increasing the PSS block lengths. The approach of using a thermally modifiable block allows deposition of this copolymer from a single organic solvent and subsequent conversion to an amphiphilic layer by nonchemical means, particularly attractive to large scale roll-to-roll industrial printing processes.

Original languageEnglish
Pages (from-to)2107-2117
Number of pages11
Issue number7
Early online date25 Mar 2015
Publication statusPublished - 14 Apr 2015

Bibliographical note

Funding: European Union Seventh Framework Programme (FP7/2010 SYNABCO no. 273316 and FP7/2011 under grant agreement ESTABLIS no. 290022).


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