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DOE OSTI · 3374563

Solid-State Side-Chain Functionalization of Conjugated Polymers for Expanded Chemical and Functional Versatility

Li, Nan [University of Chicago, IL (United States)] (ORCID:000000016818035X)·Liu, Zhichang [University of Chicago, IL (United States)]·Mysona, Joshua [University of Chicago, IL (United States)]·Shan, Naisong [University of Chicago, IL (United States)] (ORCID:0000000214766539)·Strzalka, Joseph [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000346198932)·de Pablo, Juan J. [University of Chicago, IL (United States)]·Wang, Sihong [University of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); CZ Biohub Chicago, LLC, Chicago, IL (United States)] (ORCID:0000000236110004)
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Abstract

Conjugated polymers that integrate diverse chemical functionalities with high electronic performance are essential for advanced organic electronic, optoelectronic, and biointerfaced technologies. Achieving such multifunctionality typically requires grafting functional units onto polymer side chains. However, conventional solution-phase approaches remain constrained by solubility limitations, side-chain-induced packing disruptions, and challenges in preserving charge transport. Here, we introduce a solid-state side-chain functionalization strategy that exploits a swellable polar side-chain architecture and azide–alkyne click chemistry to enable efficient molecular diffusion and reaction throughout predeposited polymer thin films. This approach substantially broadens the chemical compatibility of graftable units and mitigates the adverse effects on the electrical property. Moreover, the method supports spatially selective functionalization within a continuous film, enabling the patterned incorporation of chemically distinct groups to produce spatially defined optical properties. Here, this solid-state strategy thus provides a versatile platform for constructing conjugated polymers with expanded chemical versatility, preserved electronic performance, and programmable spatial functionality.

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Conjugated polymersFunctionalizationPolymer filmsPolymersTransistors

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Li, Nan [University of Chicago, IL (United States)] (ORCID:000000016818035X), Liu, Zhichang [University of Chicago, IL (United States)], Mysona, Joshua [University of Chicago, IL (United States)], Shan, Naisong [University of Chicago, IL (United States)] (ORCID:0000000214766539), Strzalka, Joseph [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000346198932), de Pablo, Juan J. [University of Chicago, IL (United States)], Wang, Sihong [University of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); CZ Biohub Chicago, LLC, Chicago, IL (United States)] (ORCID:0000000236110004). 2026-03-02. Solid-State Side-Chain Functionalization of Conjugated Polymers for Expanded Chemical and Functional Versatility. https://doi.org/10.1021/jacs.5c21851

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DOE OSTI2026

Tuning Thermal Stability through Dopant Size in Chemically Doped DPP–Thiophene Polymers

Molecular doping of conjugated polymers (CPs) is a key strategy for improving the performance of organic electronics devices, particularly thermoelectrics. Doped donor–acceptor (D–A) conjugated polymers, characterized by a tunable energy gap between the Fermi level and the transport band, show great promise in achieving high electrical conductivity (σ) while preserving a favorable Seebeck coefficient (S). Despite the promising performance enhancement of chemically doped D–A polymers, their thermal stability remains largely underexplored, a crucial consideration for the long-term operation of organic thermoelectric devices. In this study, we investigated the dopant size-dependent thermal stability of a diketopyrrolopyrrole-thiophene (DPP-T) D–A copolymer, utilizing two p-dopants: 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ) and Mo(tfd-CO 2 Me) 3 . Temperature-dependent UV–vis–NIR spectroscopy revealed that DPP-T/F 4 TCNQ is more prone to dedoping under a high temperature thermal stress than DPP-T/Mo(tfd-CO 2 Me) 3 . Although the F 4 TCNQ doped polymer shows higher initial in-plane conductivity than its Mo(tfd-CO 2 Me) 3 counterpart, it undergoes a conductivity loss of more than an order of magnitude after annealing at 120 °C for 30 min. In contrast, the in-plane conductivity of DPP-T/Mo(tfd-CO 2 Me) 3 remains stable under the same thermal conditions. Thermogravimetric analysis ruled out dopant sublimation as a primary contributor to dedoping, leading us to attribute the conductivity loss in F 4 TCNQ-doped DPP-T to dopant phase separation and migration. This observation was further confirmed by X-ray scattering studies and nanoscale infrared microscopy and spectroscopy studies. This work could provide further insights into the thermal stability of doped conjugated polymers and suggests that incorporating bulkier dopants is an effective strategy to enhance the thermal robustness of doped DPP-type systems.

Conjugated polymers↗