Abstract
Translating the ultrahigh intrinsic conductivity of conjugated polymers into bulk 3D architectures remains a formidable challenge due to the fundamental dichotomy between rheological printability and electronic purity. Existing strategies necessitate a compromise: solution-processing requires insulating binders that degrade charge transport, while binder-free vapor-phase polymerization (VPP) is kinetically confined to surface-limited thin films by diffusion constraints. Here, we introduce atomized oxidative polymerization (AOP), a manufacturing paradigm that overcomes these kinetic barriers via active, layer-by-layer monomer atomization. This approach ensures stoichiometric reaction conditions throughout the printed volume, driving a structural transition toward highly conductive quinoid-dominant chains with enhanced π-π stacking. The resulting binder-free poly(3,4-ethylenedioxythiophene) (PEDOT) structures achieve bulk conductivities exceeding 950 S/cm and superior mechanical stiffness, while uniquely exhibiting suppressed thermal transport characteristic of a phonon glass, effectively decoupling electrical and thermal transport. AOP establishes a generalizable platform for fabricating dense, insoluble conjugated polymer architectures for advanced applications, including high-efficiency organic thermoelectrics, thermally stable biointerfaces, and energy storage devices, without the limitations of traditional solution or vapor-phase processing.
Recommended Citation
T. P. Plateau et al., "Atomized Oxidative Polymerization as a 3D Printing Platform for Binder-Free, Bulk Conductive Polymer Architectures," Advanced Functional Materials, Wiley; Wiley-VCH Verlag, Jan 2026.
The definitive version is available at https://doi.org/10.1002/adfm.76488
Department(s)
Mechanical and Aerospace Engineering
Publication Status
Open Access
Keywords and Phrases
3D printing; additive fabrication; bulk structures; conductive polymers; PEDOT
International Standard Serial Number (ISSN)
1616-3028; 1616-301X
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2026 Wiley; Wiley-VCH Verlag, All rights reserved.
Creative Commons Licensing
This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License.
Publication Date
01 Jan 2026
