Publication date: 15th December 2025
High throughput discovery in organic and hybrid photovoltaics increasingly relies on photoluminescence as a fast proxy for optoelectronic quality. Yet, once charge selective contacts are introduced, photoluminescence can become a trap rather than a guide. In our work we show that strong photoluminescence quenching can occur under open circuit conditions even for highly efficient photovoltaic heterojunctions, creating a false negative problem that can systematically eliminate the most promising interfaces during screening. We address this bottleneck by combining steady state and transient photoluminescence with contactless transient surface photovoltage on representative half device stacks. The key idea is to separate what photoluminescence cannot disambiguate on its own, namely whether quenching originates from beneficial charge extraction or from harmful nonradiative recombination. The joint readout provides a direct window into extraction dynamics and interfacial loss channels, enabling a physically grounded classification of heterojunction behavior that is compatible with rapid screening workflows. To move beyond phenomenology, we introduce a digital replica of the interface that explains why photoluminescence can remain strongly quenched after extraction. The model identifies Coulomb attraction together with interfacial recombination as the fundamental mechanisms that drive this behavior, clarifying why photoluminescence based metrics can become non predictive once selective contacts are present. Building on these insights, we present a practical decision tree for interpreting photoluminescence in the presence of selective contacts and for triaging heterojunctions toward device integration. This provides a route to unify accelerated materials discovery with accelerated device discovery, and it enables measurement protocols that are immediately relevant for data rich optimization and future self driving laboratories. The methodology is broadly transferable across photovoltaics, photodetectors, and LEDs. (https://arxiv.org/abs/2510.11548)
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