Efficient Energy Transfer Process in 2D (C6H5CH2NH3)2(Pb,Mn)Br4 Layered Metal Halide
Marta Campolucci a b, Emanuela Sartori a, Stefano Toso b c, Zeger Hens d, Liberato Manna b, Federico Locardi a b
a Department of Chemistry and Industrial Chemistry, Università degli Studi di Genova, Via Dodecaneso 31, 16146 Genova, Italy
b Nanochemistry Department, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
c International Doctoral Program in Science, Università Cattolica del Sacro Cuore, 25121 Brescia, Italy
d Physics and Chemistry of Nanostructures group (PCN), Ghent University, Krijgslaan 281, Gent 9000, Belgium
Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS23 & Sustainable Technology Forum València (STECH23) (MATSUS23)
#2DPERO - 2D Perovskites: Synthesis, Properties, and Applications
València, Spain, 2023 March 6th - 10th
Organizers: Simon Kahmann and Loreta A. Muscarella
Poster, Marta Campolucci, 331
Publication date: 22nd December 2022

Starting from the well-studied ABX3 (A = CH3NH3+, Cs+; B = bivalent metal cation, X = Cl-, Br-, I-) perovskite, new derivates can be obtained with the partial or full substitution of the A and B cations with different metal ions [1]. Besides a change in the elemental composition, the dimension of the ion in the A site enlarges the formation of polymorphs of a lower dimensionality (2D or 0D). Indeed, the use of an organic cation, usually bigger than the inorganic metal ion, is one of the most promising strategies to tune and confer new optoelectronic properties in metal halide compounds [2]. For example, the 2D layered lead halides have excellent emission comparable with the 3D counterpart but with better electronic conductivity and quantum confinement effect observable even in the bulk materials [3].

Here, we present our recent results on the preparation of emissive 2D (Pb,Mn)-based hybrid metal halide as single crystals. Starting from the reported synthesis of Bz2PbBr4 (Bz+ = (C6H5CH2NH3)+), the Pb2+ was progressively replaced by Mn2+, even if the percentage of Pb substitution strongly depends on the metal ratio in the starting materials. The presence of Bz cation in the structure is confirmed by FTIR analyses. The emission varies from the light blue of Bz2PbBr4 to the typical orange one of the Mn. The PL spectrum exhibits a weak emission for the excitonic peak at 410 nm and a strong Mn emission, centered at 610 nm, ascribable to the spin-forbidden Mn2+ d−d transition (4T16A1). The ABS spectra demonstrate that even at low Pb concentrations it is observable an energy-transfer process from the Pb2+ to Mn2+ emitter. Interestingly, the emission intensity reaches the maximum for the experimental Mn composition of 8.0% (PLQY » 47.9%), even if a notable value is measurable also for the Mn-rich composition (PLQY » 37.2% for Mn = 66.5%).

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