Mechanistic Insights into Oxidative Molecular Layer Deposition of Conjugated Polymers

Oxidative molecular layer deposition (oMLD) promises to enable molecular-level control of polymer structure through monomer-by-monomer growth via sequential, self-limiting, gas-phase surface reactions of monomer(s) and oxidant(s). However, only a few oMLD growth chemistries have been demonstrated to...

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Veröffentlicht in:Chemistry of materials 2023-01, Vol.35 (1), p.154-162
Hauptverfasser: Wyatt, Quinton K., Brathwaite, Katrina G., Ardiansyah, Muhammad, Paranamana, Nikhila C., Brorsen, Kurt R., Young, Matthias J.
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container_end_page 162
container_issue 1
container_start_page 154
container_title Chemistry of materials
container_volume 35
creator Wyatt, Quinton K.
Brathwaite, Katrina G.
Ardiansyah, Muhammad
Paranamana, Nikhila C.
Brorsen, Kurt R.
Young, Matthias J.
description Oxidative molecular layer deposition (oMLD) promises to enable molecular-level control of polymer structure through monomer-by-monomer growth via sequential, self-limiting, gas-phase surface reactions of monomer(s) and oxidant(s). However, only a few oMLD growth chemistries have been demonstrated to date, and limited mechanistic understanding is impairing progress in this field. Here, we examine oMLD growth using 3,4-ethylenedioxythiophene (EDOT), pyrrole (Py), p-phenylenediamine (PDA), thiophene (Thi), and furan (Fu) monomers. We establish key insights into the surface reaction mechanisms underlying oMLD growth. We specifically identify the importance of a two-electron chemical oxidant with sufficient oxidation strength to oxidize both a surface and a gas-phase monomer to enable oMLD growth. The mechanistic insights we report enable rational molecular assembly of copolymer structures to improve electrochemical capacity. This work is foundational to unlock molecular-level control of redox-active polymer structure and will enable the study of previously intractable questions regarding the molecular origins of polymer properties, allowing us to control and optimize polymer properties for energy storage, water desalination, and sensors.
doi_str_mv 10.1021/acs.chemmater.2c02923
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