Effects of Side-Chain Length and Functionality on Polar Poly(dioxythiophene)s for Saline-Based Organic Electrochemical Transistors.

DiTullio, Brandon T; Savagian, Lisa R; Bardagot, Olivier; De Keersmaecker, Michel; Österholm, Anna M; Banerji, Natalie; Reynolds, John R (2023). Effects of Side-Chain Length and Functionality on Polar Poly(dioxythiophene)s for Saline-Based Organic Electrochemical Transistors. Journal of the American Chemical Society, 145(1), pp. 122-134. American Chemical Society 10.1021/jacs.2c08850

[img] Text
jacs.2c08850.pdf - Published Version
Restricted to registered users only
Available under License Publisher holds Copyright.

Download (3MB) | Request a copy
[img]
Preview
Text
Accepted_version_Ditullio__J._Am._Chem._Soc._2023__145_122_134.pdf - Accepted Version
Available under License Publisher holds Copyright.

Download (902kB) | Preview
[img]
Preview
Text
ja2c08850_si_001.pdf - Supplemental Material
Available under License Publisher holds Copyright.

Download (6MB) | Preview

Understanding the impact of side chains on the aqueous redox properties of conjugated polymers is crucial to unlocking their potential in bioelectrochemical devices, such as organic electrochemical transistors (OECTs). Here, we report a series of polar propylenedioxythiophene-based copolymers functionalized with glyme side chains of varying lengths as well as an analogue with short hydroxyl side chains. We show that long polar side chains are not required for achieving high volumetric capacitance (C*), as short hydroxy substituents can afford facile doping and high C* in saline-based electrolytes. Furthermore, we demonstrate that varying the length of the polar glyme chains leads to subtle changes in material properties. Increasing the length of glyme side chain is generally associated with an enhancement in OECT performance, doping kinetics, and stability, with the polymer bearing the longest side chains exhibiting the highest performance ([μC*]OECT = 200 ± 8 F cm-1 V-1 s-1). The origin of this performance enhancement is investigated in different device configurations using in situ techniques (e.g., time-resolved spectroelectrochemistry and chronoamperometry). These studies suggest that the performance improvement is not due to significant changes in C* but rather due to variations in the inferred mobility. Through a thorough comparison of two different architectures, we demonstrate that device geometry can obfuscate the benchmarking of OECT active channel materials, likely due to contact resistance effects. By complementing all electrochemical and spectroscopic experiments with in situ measurements performed within a planar OECT device configuration, this work seeks to unambiguously assign material design principles to fine-tune the properties of poly(dioxythiophene)s relevant for application in OECTs.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Bardagot, Olivier Nicolas Ludovic, Banerji, Natalie

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

0002-7863

Publisher:

American Chemical Society

Language:

English

Submitter:

Pubmed Import

Date Deposited:

10 Jan 2023 13:01

Last Modified:

13 Jan 2024 00:25

Publisher DOI:

10.1021/jacs.2c08850

PubMed ID:

36563183

BORIS DOI:

10.48350/176486

URI:

https://boris.unibe.ch/id/eprint/176486

Actions (login required)

Edit item Edit item
Provide Feedback