Holy Water: Photo-Brightening in Quasi-2D Perovskite Films under Ambient Enables Highly Performing Light-Emitting Diodes

Quasi-2D perovskites provide new opportunities for lighting and display applications due to their high radiative recombination and excellent stability. However, seldom attention has been placed on their self-stability/working operation under ambient storage. Herein, quasi-2D perovskites/Polyethylene oxide (PEO) films are studied, showing an unforeseen photo-brightening effect under ambient storage (i.e., an increase of the photoluminescence quantum yield from 55% to 74% after 100 days). In stark contrast, those stored under a dark/inert atmosphere show a significant decrease down to 38%. This counterintuitive phenomenon responds to the increasing radiative recombination rate caused by the passivation of the surface Br vacancies in the presence of physically adsorbed water molecules, as corroborated by in situ/ex situ X-ray photoelectron spectroscopy and density functional theory calculations. Capitalizing on this surprising effect, stable light-emitting diodes (LEDs) using quasi-2D perovskites/PEO color filters are fabricated, realizing high stabilities of ≈400 h@10 mA under operating ambient conditions, representing a 20-fold enhancement compared to LEDs with 3D counter partners. Hence, this study reveals a unique insight into the impact of water passivation on the optical/structural properties of quasi-2D perovskite films, broadening their applications under operating ambient conditions.Y.D. thanks the financial support from the China Scholarship Council (CSC, no. 201808440326). Financial support has been received from AEI-MINECO/FEDER, UE through the Nympha Project (PID2019-106315RB-I00), the regional government of "Comunidad de Madrid" and the European Structural Funds through FotoArt-CM Project (S2018/NMT-4367). F.O. acknowledges funding from the Marie Skłodowska-Curie grant agreement no 754382. M.U.K. and G.N. thank ELI-ALPS, which is supported by the European Union and co-financed by the European Regional Development Fund (GI-NOP-2.3.6-15-2015-00001). This publication has also received funding from PANOSC, the European Union's Horizon 2020 research and innovation programme under grant agreement no 823852. M.U.K. and G.N. also acknowledge Project no. 2019-2.1.13-TÉT-IN-2020-00059 which has been implemented with the support provided from the National Research, Development and Innovation Fund of Hungary, financed under the 2019-2.1.13-TÉT-IN funding scheme. O.A.R. has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 899987. R.D.C. and L.M.C. acknowledge the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 956923

Expanding the carbo ‐Benzene Chemical Space for Electron‐Accepting Ability: Trifluorotolyl/Tertiobutyl Substitution Balance

International audienceWith the view to altering the lipophilicity and electron accepting ability of the tetraphenyl-carbo-benzene scaffold, peripheral fluorination of the C18 ring through aromatic linkers was envisaged from the C18Ph6 and o-tBu2C18Ph4 references, by replacement of two Ph substituents with two p-CF3-C6H4 counterparts (FTol). The synthesis relied on a [8+10] macrocyclization involving a common bis(trifluorotolyl)-tetraynedione, followed by reductive aromatization of the resulting [6]pericyclynediols. While p-FTol2C18Ph4 proved to be hardly tractable due to an extremely low solubility, p-FTol2-o-tBu2C18Ph2 could be extensively studied by X-ray crystallography, NMR and UV/Vis spectroscopy, voltammetry, STM imaging of monolayers, and AFM imaging of binary films with P3HT or PC71BM fabricated by spin-coating for organic photovoltaic cells and J−V curve measurement thereof. The electronic and polarity properties are correlated with moderate but consistent electron-withdrawing effects of the CF3 groups, in agreement with the DFT-calculated frontier orbitals and multipole moments. The results provide guidelines for optimization of fluorinated carbo-benzene targets