4.8 Article

Formation and Near-Infrared Emission of CsPbI3 Nanoparticles Embedded in Cs4PbI6 Crystals

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 13, Issue 29, Pages 34742-34751

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c08920

Keywords

Cs4PbI6; perovskite; crystals; near-infrared; CsPbI3; electron microscopy; embedded nanoparticles

Funding

  1. Advanced Research Center of Green Materials Science and Technology from The Featured Area Research Center Program within Ministry of Education [107L9006]
  2. Ministry of Science and Technology in Taiwan [MOST 109-2113-M-002-020-MY3, MOST 107-2113-M-002-008-MY3, MOST 110-2923-M-002017-MY3, MOST 107-2923-M-002-004-MY3, MOST 107-3017-F-002-001]
  3. National Science Center Poland Grant Opus [2016/23/B/ST3/03911, 2019/33/B/ST3/00406]
  4. National Center for Research and Development Poland Grant [PL-TW/VIII/1/2021]

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Cs4PbI6, a rarely investigated member of the Cs4PbX6 family, has been successfully synthesized and optimized with the addition of ZnI2 as an effective supplier of iodide ions. The material exhibits strong red to near-infrared emission properties, attributed to numerous embedded CsPbI3 nanocrystallites. High-resolution transmission electron microscopy confirmed a raisin bread-like structure of the Cs4PbI6 crystals, which were successfully used to fabricate a NIR mini-LED for biological applications.
Cs4PbI6, as a rarely investigated member of the Cs4PbX6 (X is a halogen element) family, has been successfully synthesized at low temperatures, and the synthetic conditions have been optimized. Metal iodides such as LiI, KI, NiI2, CoI2, and ZnI2, as additives, play an important role in enhancing the formation of the Cs4PbI6 microcrystals. ZnI2 with the lowest dissociation energy is the most efficient additive to supply iodide ions, and its amount of addition has also been optimized. Strong red to near-infrared (NIR) emission properties have been detected, and its optical emission centers have been identified to be numerous embedded perovskite-type alpha-CsPbI3 nanocrystallites (similar to 5 nm in diameter) based on investigations of temperature- and pressure-dependent photoluminescent properties. High-resolution transmission electron microscopy was used to detect these hidden nanoparticles, although the material was highly beam-sensitive and confirmed a raisin bread-like structure of the Cs4PbI6 crystals. A NIR mini-LED for the biological application has been successfully fabricated using as-synthesized Cs4PbI6 crystals. This work provides information for the future development of infrared fluorescent nanoscale perovskite materials.

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