Recently, metal-halide perovskites have rapidly emerged as efficient light emitters with near-unity quantum yield and size-dependent optical and electronic properties, which have attracted considerable attention from researchers. However, the ultrafast nucleation rate of ionic perovskite counterparts severely limits the in-depth exploration of the growth mechanism of colloidal nanocrystals (NCs). Herein, we used an inorganic ligand nitrosonium tetrafluoroborate (NOBF) to trigger a slow post-synthesis transformation process, converting non-luminescent CsPbBr NCs into bright green luminescent CsPbBr NCs to elucidate the concrete transformation mechanism four stages: (i) the dissociation of pristine NCs, (ii) the formation of Pb-Br intermediates, (iii) low-dimensional nanoplatelets (NPLs) and (iv) cubic CsPbBr NCs, corresponding to the blue-to-green emission process. The desorption and reorganization of organic ligands induced by NO and the involvement of BF in the ligand exchange process played pivotal roles in this dissolution-recrystallization of NCs. Moreover, controlled shape evolution from anisotropic NPLs to NCs was investigated through variations in the amount of NOBF. This further validates that additives exert a decisive role in the symmetry and growth of nanostructured perovskite crystals during phase transition based on the ligand-exchange mechanism. This finding serves as a source of inspiration for the synthesis of highly luminescent CsPbBr NCs, providing valuable insights into the chemical mechanism in post-synthesis transformation.
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http://dx.doi.org/10.1039/d3nr05215j | DOI Listing |
J Am Chem Soc
December 2024
Department of Materials Science and Engineering, City University of Hong Kong, Kowloon 999077, Hong Kong SAR, P. R. China.
The desorption of conventional ligands from the surface of halide perovskite nanocrystals (NCs) often causes their structural instability and deterioration of the optoelectronic properties. To address this challenge, we present an approach of using a bidentate Lewis base ligand, namely, 1,4-bis(diphenylphosphino)butane (DBPP), for the synthesis of CsPbBr NCs. The phosphine group of DBPP has a strong interaction with the PbBr precursor, forming a highly crystalline intermediate complex during the reaction.
View Article and Find Full Text PDFChem Sci
November 2024
Department of Chemistry, Indian Institute of Technology Kanpur Kanpur - 208 016 UP India +91 512 259 6806 +91 512 259 6312.
Quantum-confined, two-dimensional (2D) CsPbBr (CPB) nanoplates (NPLs) have emerged as exceptional candidates for next-generation blue LEDs and display technology applications. However, their large surface-to-volume ratio and detrimental bromide vacancies adversely affect their photoluminescence quantum yield (PLQY). Additionally, external perturbations such as heat, light exposure, moisture, oxygen, and solvent polarity accelerate their transformation into three-dimensional (3D), green-emitting CPB nanocrystals (NCs), thereby resulting in the loss of their quantum confinement.
View Article and Find Full Text PDFACS Appl Mater Interfaces
December 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India.
Excited-state interactions at the interfaces of nanocrystals play a crucial role in determining photocatalytic efficiency. CsPbBr nanocrystals (CPB NCs), celebrated for their exceptional photophysical properties, have been explored for organic photocatalysis. However, their intrinsic limitations, such as charge carrier recombination and stability issues, hinder their full potential.
View Article and Find Full Text PDFJ Phys Chem Lett
December 2024
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
Lead halide perovskite nanocrystals (NCs) have attracted much attention as materials for light-emitting diodes and quantum light sources. A deep understanding of exciton-phonon couplings is essential for obtaining a narrow emission line, weak phonon-sideband photoluminescence (PL), and a long exciton coherence time, which are especially useful for high-color-purity quantum-light-source applications. Here, we report the PL spectra of single CsPbBr NCs at 5.
View Article and Find Full Text PDFAll-inorganic lead halide perovskite nanocrystals (NCs) have excellent optoelectronic properties and promising applications. Improving the stability of inorganic halide NCs and optimizing their photoluminescence quantum yields (PLQY) has become an urgent task. Constructing core-shell structures is an effective method to improve the environmental stability and PLQY, however, realizing core-shell structured perovskite NCs with good dispersion and multiple perovskites encapsulated within the shell material remains challenging.
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