Tailoring Interlayer Charge Transfer Dynamics in 2D Perovskites with Electroactive Spacer Molecules.

Autor: Boeije Y; Department of Chemical Engineering and Biotechnology, University of Cambridge, Philippa Fawcett Drive, Cambridge CB3 0AS, U.K.; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K., Van Gompel WTM; Institute for Materials Research (IMO-IMOMEC), Hybrid Materials Design (HyMaD), Hasselt University, Martelarenlaan 42, B-3500 Hasselt, Belgium., Zhang Y; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K.; Cambridge Graphene Centre, Department of Engineering, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0FA, U.K., Ghosh P; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K., Zelewski SJ; Department of Chemical Engineering and Biotechnology, University of Cambridge, Philippa Fawcett Drive, Cambridge CB3 0AS, U.K.; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K.; Department of Semiconductor Materials Engineering, Faculty of Fundamental Problems of Technology, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland., Maufort A; Institute for Materials Research (IMO-IMOMEC), Hybrid Materials Design (HyMaD), Hasselt University, Martelarenlaan 42, B-3500 Hasselt, Belgium., Roose B; Department of Chemical Engineering and Biotechnology, University of Cambridge, Philippa Fawcett Drive, Cambridge CB3 0AS, U.K., Ooi ZY; Department of Chemical Engineering and Biotechnology, University of Cambridge, Philippa Fawcett Drive, Cambridge CB3 0AS, U.K., Chowdhury R; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K., Devroey I; Institute for Materials Research (IMO-IMOMEC), Hybrid Materials Design (HyMaD), Hasselt University, Martelarenlaan 42, B-3500 Hasselt, Belgium., Lenaers S; Institute for Materials Research (IMO-IMOMEC), Hybrid Materials Design (HyMaD), Hasselt University, Martelarenlaan 42, B-3500 Hasselt, Belgium., Tew A; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K., Dai L; Department of Chemical Engineering and Biotechnology, University of Cambridge, Philippa Fawcett Drive, Cambridge CB3 0AS, U.K.; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K., Dey K; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K., Salway H; Department of Chemical Engineering and Biotechnology, University of Cambridge, Philippa Fawcett Drive, Cambridge CB3 0AS, U.K., Friend RH; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K., Sirringhaus H; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K., Lutsen L; Institute for Materials Research (IMO-IMOMEC), Hybrid Materials Design (HyMaD), Hasselt University, Martelarenlaan 42, B-3500 Hasselt, Belgium., Vanderzande D; Institute for Materials Research (IMO-IMOMEC), Hybrid Materials Design (HyMaD), Hasselt University, Martelarenlaan 42, B-3500 Hasselt, Belgium., Rao A; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K., Stranks SD; Department of Chemical Engineering and Biotechnology, University of Cambridge, Philippa Fawcett Drive, Cambridge CB3 0AS, U.K.; Department of Physics, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2023 Oct 04; Vol. 145 (39), pp. 21330-21343. Date of Electronic Publication: 2023 Sep 22.
DOI: 10.1021/jacs.3c05974
Abstrakt: The family of hybrid organic-inorganic lead-halide perovskites are the subject of intense interest for optoelectronic applications, from light-emitting diodes to photovoltaics to X-ray detectors. Due to the inert nature of most organic molecules, the inorganic sublattice generally dominates the electronic structure and therefore the optoelectronic properties of perovskites. Here, we use optically and electronically active carbazole-based Cz-C i molecules, where C i indicates an alkylammonium chain and i indicates the number of CH 2 units in the chain, varying from 3 to 5, as cations in the two-dimensional (2D) perovskite structure. By investigating the photophysics and charge transport characteristics of (Cz-C i ) 2 PbI 4 , we demonstrate a tunable electronic coupling between the inorganic lead-halide and organic layers. The strongest interlayer electronic coupling was found for (Cz-C 3 ) 2 PbI 4 , where photothermal deflection spectroscopy results remarkably reveal an organic-inorganic charge transfer state. Ultrafast transient absorption spectroscopy measurements demonstrate ultrafast hole transfer from the photoexcited lead-halide layer to the Cz-C i molecules, the efficiency of which increases by varying the chain length from i = 5 to i = 3. The charge transfer results in long-lived carriers (10-100 ns) and quenched emission, in stark contrast to the fast (sub-ns) and efficient radiative decay of bound excitons in the more conventional 2D perovskite (PEA) 2 PbI 4 , in which phenylethylammonium (PEA) acts as an inert spacer. Electrical charge transport measurements further support enhanced interlayer coupling, showing increased out-of-plane carrier mobility from i = 5 to i = 3. This study paves the way for the rational design of 2D perovskites with combined inorganic-organic electronic properties through the wide range of functionalities available in the world of organics.
Databáze: MEDLINE