Thick-Layer Lead Iodide Perovskites with Bifunctional Organic Spacers Allylammonium and Iodopropylammonium Exhibiting Trap-State Emission.
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The nature of the organic cation in two-dimensional (2D) hybrid lead iodide perovskites tailors the structural and technological features of the resultant material. Herein, we present three new homologous series of (100) lead iodide perovskites with the organic cations allylammonium (AA) containing an unsaturated CC group and iodopropylammonium (IdPA) containing iodine on the organic chain: (AA)2MAn-1PbnI3n+1 (n = 3-4), [(AA)x(IdPA)1-x]2MAn-1PbnI3n+1 (n = 1-4), and (IdPA)2MAn-1PbnI3n+1 (n = 1-4), as well as their perovskite-related substructures. We report the in situ transformation of AA organic layers into IdPA and the incorporation of these cations simultaneously into the 2D perovskite structure. Single-crystal X-ray diffraction shows that (AA)2MA2Pb3I10 crystallizes in the space group P21/c with a unique inorganic layer offset (0, <1/2), comprising the first example of n = 3 halide perovskite with a monoammonium cation that deviates from the Ruddlesden-Popper (RP) halide structure type. (IdPA)2MA2Pb3I10 and the alloyed [(AA)x(IdPA)1-x]2MA2Pb3I10 crystallize in the RP structure, both in space group P21/c. The adjacent II interlayer distance in (AA)2MA2Pb3I10 is 5.6 , drawing the [Pb3I10]4- layers closer together among all reported n = 3 RP lead iodides. (AA)2MA2Pb3I10 presents band-edge absorption and photoluminescence (PL) emission at around 2.0 eV that is slightly red-shifted in comparison to (IdPA)2MA2Pb3I10. The band structure calculations suggest that both (AA)2MA2Pb3I10 and (IdPA)2MA2Pb3I10 have in-plane effective masses around 0.04m0 and 0.08m0, respectively. IdPA cations have a greater dielectric contribution than AA. The excited-state dynamics investigated by transient absorption (TA) spectroscopy reveal a long-lived (100 ps) trap state ensemble with broad-band emission; our evidence suggests that these states appear due to lattice distortions induced by the incorporation of IdPA cations.
