Two-dimensional organic-inorganic hybrid halide perovskites possess diverse structural polymorphs with versatile physical properties, which can be controlled by order-disorder transition of the spacer cation, making them attractive for constructing semiconductor homojunctions. Here, we demonstrate a space-cation-dopant-induced phase stabilization approach to creating a lateral homojunction composed of ordered and disordered phases within a two-dimensional perovskite. By doping a small quantity of pentylammonium into (butylammonium)PbI or vice versa, we effectively suppress the ordering transition of the spacer cation and the associated out-of-plane octahedral tilting in the inorganic framework, resulting in phase pining of the disordered phase when decreasing temperature or increasing pressure. This enables epitaxial growth of a two-dimensional perovskite homojunction with tunable optical properties under temperature and pressure stimuli, as well as directional exciton diffusion across the interface. Our results demonstrate a previously unexplored strategy for constructing two-dimensional perovskite heterostructures by thermodynamic tuning and spacer cation doping.
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http://dx.doi.org/10.1038/s41467-024-47406-1 | DOI Listing |
ACS Appl Mater Interfaces
January 2025
Key Laboratory of Luminescence and Optical Information, Beijing Jiaotong University, Ministry of Education, Beijing 100044, China.
Quasi-two-dimensional (quasi-2D) mixed-halide perovskites are a requisite for their applications in highly efficient blue perovskite light-emitting diodes (PeLEDs) owing to their strong quantum confinement effect and high exciton binding energy. The pace of quasi-2D blue PeLEDs is hindered primarily by two factors: challenges in precisely managing the phase distribution and defect-mediated nonradiative recombination losses. Herein, we utilize 2,2-diphenylethylamine (DPEA) with bulky steric hindrance to disturb the assembly process of a slender spacer host cation, 4-fluorophenylethylammonium (-F-PEA), enhancing phase distribution management in quasi-2D PeLEDs.
View Article and Find Full Text PDFNanoscale
January 2025
Joint Key Laboratory of the Ministry of Education, Institute of Applied Physics and Materials Engineering, University of Macau, Macau SAR 999078, China.
Two-dimensional organic-inorganic perovskites have garnered extensive interest owing to their unique structure and optoelectronic performance. However, their loose structures complicate the elucidation of mechanisms and tend to cause uncertainty and variations in experimental and calculated results. This can generally be rooted in dynamically swinging spacer molecules through two mechanisms: one is the intrinsic geometric steric effect, and the other is related to the electronic effect orbital overlapping and electronic screening.
View Article and Find Full Text PDFACS Mater Au
January 2025
Beijing National Laboratory for Molecular Science, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Two-dimensional lead iodide perovskites have attracted significant attention for their potential applications in optoelectronic and photonic devices due to their tunable excitonic properties. The choice of organic spacer cations significantly influences the light emission and exciton transport properties of these materials, which are vital for their device performance. In this Perspective, we discuss the impact of spacer cations on lattice dynamics and exciton-phonon coupling, focusing on three representative 2D lead iodide perovskites that exhibit distinct types of structural distortions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
University of Fribourg Faculty of Science: Universite de Fribourg Faculte de sciences et de medecine, Adolphe Merkle Institue, Chemin des Verdiers 4, 1700, Fribourg, SWITZERLAND.
Metal halide perovskites have shown exceptional potential in converting solar energy to electric power in photovoltaics, yet their application is hampered by limited operational stability. This stimulated the development of hybrid layered (two-dimensional, 2D) halide perovskites based on hydrophobic organic spacers, templating perovskite slabs, as a more stable alternative. However, conventional organic spacer cations are electronically insulating, resulting in charge confinement within the inorganic slabs, thus limiting their functionality.
View Article and Find Full Text PDFNanomaterials (Basel)
December 2024
Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, 01069 Dresden, Germany.
Understanding the interplay between the molecular structure of the ionic liquid (IL) subunit, the resulting nanostructure and ion transport in polymerized ionic liquids (PILs) is necessary for the realization of high-performance solid-state electrolytes required in various advanced applications. Herein, we present a detailed structural characterization of a recently synthesized series of acrylate-based PIL homopolymers and networks with imidazolium cations and chloride anions with varying alkyl spacer and terminal group lengths designed for organic solid-state batteries based on X-ray scattering. The impact of the concentrations of both the crosslinker and added tetrabutylammonium chloride (TBACl) conducting salt on the structural characteristics is also investigated.
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