Chlorinated Polymer Photovoltaic Materials

Chlorinated polymer photovoltaic materials represent a pivotal advancement in the design of organic solar cells, wherein chlorine atoms are strategically introduced into conjugated polymer backbones or acceptor end-groups to modulate electronic and morphological properties. The moderate electronegativity and vacant 3d orbitals of chlorine facilitate strong non-covalent interactions—such as Cl···S and Cl···π contacts—that tighten π–π stacking and deepen frontier molecular orbitals. These effects enhance exciton separation, charge mobility and open-circuit voltage while simultaneously improving morphological stability under operational stress. Research has explored global halogenation of donor–acceptor frameworks, as well as precise α- and β-position substitutions, to optimise intermolecular distances and electronic push–pull characteristics. When paired with complementary non-fullerene acceptors, chlorinated polymers have driven power conversion efficiencies beyond 15 % in the laboratory. Despite these successes, challenges remain in achieving large-area uniformity, long-term environmental resilience and scalable, eco-friendly chlorination protocols. Efforts are therefore directed towards green synthetic routes, the co-engineering of donor and acceptor energy levels, and the integration of novel materials for next-generation, commercially viable organic photovoltaic devices.

Research from Nature Portfolio

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Chlorinated Polymer Photovoltaic Materials publication trend

The graph below shows the total number of articles in chlorinated polymer photovoltaic materials across all publications each year (not limited to Nature Index journals).

Technical terms

Power conversion efficiency (PCE): The ratio of electrical power output to incident solar power input in a photovoltaic device.

Donor–acceptor (D–A) architecture: A molecular design combining electron-rich (donor) and electron-deficient (acceptor) segments to facilitate charge separation and transport.

π–π stacking: Non-covalent interactions between aromatic rings that govern molecular packing and charge mobility.

Non-fullerene acceptor (NFA): An organic semiconductor alternative to fullerene derivatives, used to accept electrons in bulk heterojunction solar cells.

Frontier molecular orbitals: The highest occupied and lowest unoccupied molecular orbitals that determine a material’s electronic energy levels and charge transfer characteristics.

References

1. Chlorination: An Effective Strategy for High‐Performance Organic Solar Cells. Advanced Science (2020).
2. Chlorinated Benzo[1,2‐b:4,5‐c′]dithiophene‐4,8‐dione Polymer Donor: A Small Atom Makes a Big Difference. Advanced Science (2021).
3. Enhancement of photovoltaic efficiency through fine adjustment of indacene‐based non‐fullerene acceptor by minimal chlorination for polymer solar cells. Nano Select (2020).