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.
Poly(3,4-ethylene dioxythiophene) (PEDOT) has a high theoretical charge storage capacity, making it of interest for electrochemical applications including energy storage and water desalination. Nanoscale thin films of PEDOT are particularly...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.