All-Polymer Microcavities for the Fluorescence Radiative Rate Modification of a Diketopyrrolopyrrole Derivative

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dc.contributor.authorMegahd, Heba
dc.contributor.authorLova, Paola
dc.contributor.authorSardar, Samim
dc.contributor.authorD'Andrea, Cosimo
dc.contributor.authorLanfranchi, Andrea
dc.contributor.authorKoszarna, Beata
dc.contributor.authorPatrini, Maddalena
dc.contributor.authorGryko, Daniel T.
dc.contributor.authorComoretto, Davide
dc.contributor.organizationDipartimento di Chimica e Chimica Industriale, Università degli Studi di Genovaen
dc.contributor.organizationCenter for Nano Science and Technology at PoliMi, Istituto Italiano di Tecnologiaen
dc.contributor.organizationInstitute of Organic Chemistry, Polish Academy of Sciencesen
dc.contributor.organizationDipartimento di Fisica, Università degli Studi di Paviaen
dc.date.accessioned2022-09-13T12:49:47Z
dc.date.available2022-09-13T12:49:47Z
dc.date.issued2022
dc.description.abstractControlling the radiative rate of emitters with macromolecular photonic structures promises flexible devices with enhanced performances that are easy to scale up. For instance, radiative rate enhancement empowers low-threshold lasers, while rate suppression affects recombination in photovoltaic and photochemical processes. However, claims of the Purcell effect with polymer structures are controversial, as the low dielectric contrast typical of suitable polymers is commonly not enough to provide the necessary confinement. Here we show all-polymer planar microcavities with photonic band gaps tuned to the photoluminescence of a diketopyrrolopyrrole derivative, which allows a change in the fluorescence lifetime. Radiative and nonradiative rates were disentangled systematically by measuring the external quantum efficiencies and comparing the planar microcavities with a series of references designed to exclude any extrinsic effects. For the first time, this analysis shows unambiguously the dye radiative emission rate variations obtained with macromolecular dielectric mirrors. When different waveguides, chemical environments, and effective refractive index effects in the structure were accounted for, the change in the radiative lifetime was assigned to the Purcell effect. This was possible through the exploitation of photonic structures made of polyvinylcarbazole as a high-index material and the perfluorinated Aquivion as a low-index one, which produced the largest dielectric contrast ever obtained in planar polymer cavities. This characteristic induces the high confinement of the radiation electric field within the cavity layer, causing a record intensity enhancement and steering the radiative rate. Current limits and requirements to achieve the full control of radiative rates with polymer planar microcavities are also addressed.en
dc.description.sponsorshipUniversity of Genova (FRA 2019–2020) Ministry of the Instruction, University and Research, PRIN2020 (2020TS9LXS) Foundation for Polish Science (TEAM POIR.04.04.00-00-3CF4/16-00)
dc.identifier.citationACS Omega 2022, 7, 15499−15506 ; https://doi.org/10.1021/acsomega.2c00167en
dc.identifier.doi10.1021/acsomega.2c00167
dc.identifier.issn2470-1343
dc.identifier.urihttps://open.icm.edu.pl/handle/123456789/21624
dc.language.isoen
dc.publisherAmerican Chemical Societyen
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Międzynarodowe*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subjectcavitiesen
dc.subjectlayersen
dc.subjectmicrocavityen
dc.subjectoptical propertiesen
dc.subjectpolymersen
dc.titleAll-Polymer Microcavities for the Fluorescence Radiative Rate Modification of a Diketopyrrolopyrrole Derivativeen
dc.typearticleen
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