Abstract Unlike single‐component 2D metal halide perovskites (MHPs) exhibiting sharp excitonic photoluminescence (PL), a broadband PL emerges in mixed Pb‐Sn 2D lattices. Two physical models –self‐trapped exciton and defect‐induced Stokes‐shift – are proposed to explain this unconventional phenomenon. However, the explanations provide limited rationalizations without consideration of the formidable compositional space, and thus, the fundamental origin of broadband PL remains elusive. Herein, the high‐throughput automated experimental workflow is established to systematically explore the broadband PL in mixed Pb‐Sn 2D MHPs, employing PEA (Phenethylammonium) as a model cation known to work as a rigid organic spacer. Spectrally, the broadband PL becomes further broadened with rapid PEA2PbI4phase segregation with increasing Pb concentrations during early‐stage crystallization. Counterintuitively, MHPs with high Pb concentrations exhibit prolonged PL lifetimes. Hyperspectral microscopy identifies substantial PEA2PbI4phase segregation in those films, hypothesizing that the establishment of charge transfer excitons by the phase segregation upon crystallization at high‐Pb compositions results in distinctive PL properties. These results indicate that two independent mechanisms—defect‐induced Stoke‐shifts and the establishment of charge transfer excitons by phase segregation—coexist which significantly correlates with the Pb:Sn ratio, thereby simultaneously contributing to the broadband PL emission in 2D mixed Pb‐Sn HPs.
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Light–ferroelectric interaction in two-dimensional lead iodide perovskites
The unique physical properties of two-dimensional (2D) metal halide perovskites (MHPs) such as nonlinear optics, anisotropic charge transport, and ferroelectricity have made these materials promising candidates for multifunctional applications. Recently, fluorine derivatives such as 4,4-difluoropiperidinium lead iodide perovskite or (4,4-DFPD, C 5 H 10 F 2 N) 2 PbI 4 have shown strong ferroelectricity as compared to other 2D MHPs. Although it was previously addressed that the ferroelectricity in MHPs can be affected by illumination, the underlying physical mechanisms of light–ferroelectricity interaction in 2D MHPs are still lacking. Here, we explore the electromechanical responses in 4,4-(DFPD) 2 PbI 4 thin films using advanced scanning probe microscopy techniques revealing ferroelectric domain structures. Hysteretic ferroelectric loops measured by contact-Kelvin probe force microscopy are dependent on domain structures under dark conditions, while ferroelectricity weakens under illumination. The X-ray diffraction patterns exhibit significant changes in preferential orientation of individual lattice planes under illumination. Particularly, the reduced intensity of the (1 1 1) lattice plane under illumination leads to transitioning from a ferroelectric to a paraelectric phase. The instability of positive ions, especially molecular organic cations, is observed under illumination by time-of-flight secondary ion mass spectrometry. The combination of crystallographic orientation and chemical changes under illumination clearly contributes to the origin of light–ferroelectricity interaction in 2D (4,4-DFPD, C 5 H 10 F 2 N) 2 PbI 4 .
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- Award ID(s):
- 2043205
- PAR ID:
- 10403476
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 10
- Issue:
- 18
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 10120 to 10131
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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