DOI: https://doi.org/10.29363/nanoge.emlem.2022.023
Publication date: 15th July 2022
The integration of triplet-triplet annihilation (TTA) components as electrically and optically active elements in vertically-structured photoactive device architectures is a challenging task to achieve. Herein we present a simple methodology for incorporating a photon absorbing layer of the (2,3,7,8,12,13,17,18-octaethyl-porphyrinato) platinumII (PtOEP) metallorganic complex, as a self-TTA annihilator medium in a vertically stacked photodiode device structure. At low-power illumination, the PtOEP photodiode exhibits photocurrent generation via the fusion of optically-induced PtOEP excited states and it develops an open-circuit voltage as high as 1.15 V. The structural and spectroscopic characterization of the nanostructured PtOEP photoactive layer in combination with electronic structure calculations identify emissive PtOEP dimer species as the annihilating excited state responsible for the formation of charges. The participation of the fusion process in the mechanism of charge photogeneration manifests in the supralinear dependence of the short-circuit current density on the incoming photoexcitation intensity, both when incoherent and coherent light is used for illuminating the PtOEP photodiode. The photoresponse of the PtOEP device allows for the highly selective and sensitive photodetection within the 500 - 560 nm narrow spectral range. At short-circuit conditions a power-law is observed in the dependence of the device responsivity on fluence. Based on a scrutinized device engineering methodology the PtOEP annihilator is further utilized for stimulating the response of UV-only organic photodetector with visible light. In overall, these findings propose that triplet-excited annihilator species with appropriately selected frontier orbital energetics are valuable photoactive components, capable to extend the photosensitivity spectral window of electronic devices with a vertically-configured device structure.
This work was co-funded by the European Regional Development Fund and the Republic of Cyprus through project EXCELLENCE/1216/0010 ‘Low Photon-Energy Up-Conversion induced Sensitized Photocurrent Generation in Organic Photodiodes’ of the Research and Innovation Foundation.
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