Proceedings of MATSUS Spring 2024 Conference (MATSUS24)
DOI: https://doi.org/10.29363/nanoge.matsus.2024.097
Publication date: 18th December 2023
Organic photovoltaic (OPV) devices require active layers comprised of molecular heterojunctions to split excitons into free charges. These molecular heterojunctions are comprised of a binary blend of electron donor and electron acceptor material, where the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) offsets are sufficient for exciton dissociation. While optimising the morphology of organic photovoltaic active layers is increasingly important, measuring the morphology accurately has for some time been a challenge for researchers in the discipline. Here we report, for the first time, sub-4 nm mapping of donor : acceptor nanoparticle composition in eco-friendly colloidal dispersions for organic photovoltaics.1 Low energy scanning transmission electron microscopy (STEM) energy dispersive X-ray spectroscopy (EDX) mapping has revealed the internal morphology of organic semiconductor donor : acceptor blend nanoparticles at the sub-4 nm level. A unique element was available for utilisation as a fingerprint element to differentiate donor from acceptor material in each blend system. Si was used to map the location of donor polymer PTzBI-Si in PTzBI-Si:N2200 nanoparticles, and S (in addition to N) was used to map donor polymer TQ1 in TQ1:PC71BM nanoparticles. For select material blends, synchrotron-based scanning transmission X-ray microscopy (STXM), was demonstrated to remain as the superior chemical contrast technique for mapping organic donor : acceptor morphology, including for material combinations lacking a unique fingerprint element, or systems where the unique element is in a terminal functional group and hence can be easily damaged under the electron beam, e.g. F on PTQ10 donor polymer in the PTQ10:IDIC donor : acceptor blend. We provide both qualitative and quantitative compositional mapping of organic semiconductor nanoparticles with STEM EDX, with sub-domains resolved in nanoparticles as small as 30 nm in diameter. The sub-4 nm mapping technology presented shows great promise for the optimisation of organic semiconductor blends for applications in organic electronics (solar cells and bioelectronics) and photocatalysis, and has further applications in organic core–shell nanomedicines.
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