Decoding the Structure of Benzodithiophene Polymers for High‐Efficiency Organic Solar Cells

Abstract The performance of organic electronic devices, such as solar cells, depends on understanding and controlling the solid‐state microstructure of semiconducting polymers. In this study, a detailed understanding of the aggregate states, solid‐state microstructure, and thermotropic behavior of the best‐performing family of polymers for solar cells, i.e., benzodithiophene‐based semiconducting polymers, is provided. Using D18, PBnDT‐FTAZ, and PBDB‐T‐Cl as model systems, this study reveals a unique solid mesophase, distinct from previously observed polymer mesophases, comprising stacked solid‐like and liquid‐like layers. This mesophase resembles sanidic structures while also sharing features with columnar mesophases like condis crystals and paracrystals. At a larger length scale, it organizes into nanoscale fibril‐like domains, with polymer backbones aligned along the fibril axis, coexisting with amorphous‐like glassy regions, reported here for the first time. Notably, high‐performance polymers such as D18, D18‐Cl, and PM6 contain minimal glassy regions. The thermotropic behavior of this biphasic nanomorphology is also examined, providing insights into how thermal annealing influences polymer structure. Understanding these solid‐aggregate states, the microstructure, and the thermal behavior enables a more precise framework for defining structure–function relationships in semiconducting polymers. This will have a significant impact on the entire field of organic electronics, from organic photovoltaics to bioelectronics to wearable electronics.

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Publication Details

Journal
Advanced Functional Materials
Published
2025-05-20
DOI
https://doi.org/10.1002/adfm.202503634
Citations
1
Primary Topic
Organic Electronics and Photovoltaics
Type
article
Field-Weighted Citation Impact
0.73

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article

Decoding the Structure of Benzodithiophene Polymers for High‐Efficiency Organic Solar Cells

Sara Marina, Daniele Cangialosi, Christian Müller, Matteo Sanviti et al.
1 citations
Advanced Functional Materials
Organic Electronics and Photovoltaics
0.73
article

Decoding the Structure of Benzodithiophene Polymers for High‐Efficiency Organic Solar Cells

Sara Marina, Daniele Cangialosi, Christian Müller, Matteo Sanviti, M. Eugenio Vázquez, Junkal Gutierrez, Eduardo Solano, Harald W. Ade, Valerio Di Lisio, Xabier Rodríguez‐Martínez, Agnieszka Tercjak, Jeromy James Rech, Sandra Hultmark, Jesika Asatryan, Wei You, Jaime Martín, Eugenio L. Solla
article en
1 citations

Abstract

Abstract The performance of organic electronic devices, such as solar cells, depends on understanding and controlling the solid‐state microstructure of semiconducting polymers. In this study, a detailed understanding of the aggregate states, solid‐state microstructure, and thermotropic behavior of the best‐performing family of polymers for solar cells, i.e., benzodithiophene‐based semiconducting polymers, is provided. Using D18, PBnDT‐FTAZ, and PBDB‐T‐Cl as model systems, this study reveals a unique solid mesophase, distinct from previously observed polymer mesophases, comprising stacked solid‐like and liquid‐like layers. This mesophase resembles sanidic structures while also sharing features with columnar mesophases like condis crystals and paracrystals. At a larger length scale, it organizes into nanoscale fibril‐like domains, with polymer backbones aligned along the fibril axis, coexisting with amorphous‐like glassy regions, reported here for the first time. Notably, high‐performance polymers such as D18, D18‐Cl, and PM6 contain minimal glassy regions. The thermotropic behavior of this biphasic nanomorphology is also examined, providing insights into how thermal annealing influences polymer structure. Understanding these solid‐aggregate states, the microstructure, and the thermal behavior enables a more precise framework for defining structure–function relationships in semiconducting polymers. This will have a significant impact on the entire field of organic electronics, from organic photovoltaics to bioelectronics to wearable electronics.

Advanced Functional MaterialsVol. 35(44)
Universidade da Coruña (ES), University of North Carolina at Chapel Hill (US), North Carolina State University (US), University of the Basque Country (ES), Universidade de Santiago de Compostela (ES), ALBA Synchrotron (Spain) (ES), Polymat (ES), Center for Research in Molecular Medicine and Chronic Diseases (ES), Material Physics Center (ES), Centro de Tecnologías Aeronauticas (Spain) (ES), Donostia International Physics Center (ES), Chalmers University of Technology (SE)
Vetenskapsrådet, Ministerio de Ciencia e Innovación, H2020 European Research Council
Openalex Percentile: Top 28%
Organic Electronics and Photovoltaics
0.73
DOIOpen Access PDFOpenAlex
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