{"title":"CsPbBr3 纳米晶体的化学不稳定性以及合成前体驱动的 CsPbBr3 和 Cs4PbBr6 纳米晶体之间的可逆转变","authors":"Huan Tian, Yi Liu and Feng-Lei Jiang*, ","doi":"10.1021/acs.chemmater.4c0201810.1021/acs.chemmater.4c02018","DOIUrl":null,"url":null,"abstract":"<p >Perovskite nanocrystals attract growing interest owing to their unique optoelectronic properties. However, their chemical stability is relatively poor due to their ionic nature. In this work, we found that inorganic cations (e.g., Cs<sup>+</sup>) and ligands (e.g., didodecyldimethylammonium bromide, DDAB), used in the synthesis of CsPbBr<sub>3</sub> nanocrystals (NCs) at ambient temperature, quickly converted CsPbBr<sub>3</sub> NCs to Cs<sub>4</sub>PbBr<sub>6</sub> NCs during the synthesis or postsynthetic treatment. These cations (Cs<sup>+</sup>, DDA<sup>+</sup>) were involved in both the chemical composition and dissociation of CsPbBr<sub>3</sub> NCs. Nevertheless, DDA<sup>+</sup> induced the generation of an impurity in addition to Cs<sub>4</sub>PbBr<sub>6</sub> NCs due to its different nature from that of Cs<sup>+</sup>. The transformation process was observed by optical spectroscopy and transmission electron microscopy. The reverse transformation of Cs<sub>4</sub>PbBr<sub>6</sub> NCs to CsPbBr<sub>3</sub> NCs can be carried out completely by adding sufficient PbBr<sub>2</sub> into Cs<sub>4</sub>PbBr<sub>6</sub> NCs. Therefore, the forward and backward reactions were driven by Cs<sup>+</sup> and Pb<sup>2+</sup>. With additional DDAB for passivation during the reverse transformation, the resulting product possessed a better photoluminescence quantum yield (PLQY, ∼90%) compared with that without the involvement of DDAB (∼69%). By considering the Cs<sub>4</sub>PbBr<sub>6</sub> NCs as the Cs source, the reverse transformation can be analogized to the synthesis of CsPbBr<sub>3</sub> NCs, providing a possible strategy for synthesizing luminescent perovskite NCs at room temperature with theoretical stoichiometry.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Chemical Instability of CsPbBr3 Nanocrystals and the Reversible Transformation between CsPbBr3 and Cs4PbBr6 Nanocrystals as Driven by Synthetic Precursors\",\"authors\":\"Huan Tian, Yi Liu and Feng-Lei Jiang*, \",\"doi\":\"10.1021/acs.chemmater.4c0201810.1021/acs.chemmater.4c02018\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Perovskite nanocrystals attract growing interest owing to their unique optoelectronic properties. However, their chemical stability is relatively poor due to their ionic nature. In this work, we found that inorganic cations (e.g., Cs<sup>+</sup>) and ligands (e.g., didodecyldimethylammonium bromide, DDAB), used in the synthesis of CsPbBr<sub>3</sub> nanocrystals (NCs) at ambient temperature, quickly converted CsPbBr<sub>3</sub> NCs to Cs<sub>4</sub>PbBr<sub>6</sub> NCs during the synthesis or postsynthetic treatment. These cations (Cs<sup>+</sup>, DDA<sup>+</sup>) were involved in both the chemical composition and dissociation of CsPbBr<sub>3</sub> NCs. Nevertheless, DDA<sup>+</sup> induced the generation of an impurity in addition to Cs<sub>4</sub>PbBr<sub>6</sub> NCs due to its different nature from that of Cs<sup>+</sup>. The transformation process was observed by optical spectroscopy and transmission electron microscopy. The reverse transformation of Cs<sub>4</sub>PbBr<sub>6</sub> NCs to CsPbBr<sub>3</sub> NCs can be carried out completely by adding sufficient PbBr<sub>2</sub> into Cs<sub>4</sub>PbBr<sub>6</sub> NCs. Therefore, the forward and backward reactions were driven by Cs<sup>+</sup> and Pb<sup>2+</sup>. With additional DDAB for passivation during the reverse transformation, the resulting product possessed a better photoluminescence quantum yield (PLQY, ∼90%) compared with that without the involvement of DDAB (∼69%). By considering the Cs<sub>4</sub>PbBr<sub>6</sub> NCs as the Cs source, the reverse transformation can be analogized to the synthesis of CsPbBr<sub>3</sub> NCs, providing a possible strategy for synthesizing luminescent perovskite NCs at room temperature with theoretical stoichiometry.</p>\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-09-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.chemmater.4c02018\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.chemmater.4c02018","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Chemical Instability of CsPbBr3 Nanocrystals and the Reversible Transformation between CsPbBr3 and Cs4PbBr6 Nanocrystals as Driven by Synthetic Precursors
Perovskite nanocrystals attract growing interest owing to their unique optoelectronic properties. However, their chemical stability is relatively poor due to their ionic nature. In this work, we found that inorganic cations (e.g., Cs+) and ligands (e.g., didodecyldimethylammonium bromide, DDAB), used in the synthesis of CsPbBr3 nanocrystals (NCs) at ambient temperature, quickly converted CsPbBr3 NCs to Cs4PbBr6 NCs during the synthesis or postsynthetic treatment. These cations (Cs+, DDA+) were involved in both the chemical composition and dissociation of CsPbBr3 NCs. Nevertheless, DDA+ induced the generation of an impurity in addition to Cs4PbBr6 NCs due to its different nature from that of Cs+. The transformation process was observed by optical spectroscopy and transmission electron microscopy. The reverse transformation of Cs4PbBr6 NCs to CsPbBr3 NCs can be carried out completely by adding sufficient PbBr2 into Cs4PbBr6 NCs. Therefore, the forward and backward reactions were driven by Cs+ and Pb2+. With additional DDAB for passivation during the reverse transformation, the resulting product possessed a better photoluminescence quantum yield (PLQY, ∼90%) compared with that without the involvement of DDAB (∼69%). By considering the Cs4PbBr6 NCs as the Cs source, the reverse transformation can be analogized to the synthesis of CsPbBr3 NCs, providing a possible strategy for synthesizing luminescent perovskite NCs at room temperature with theoretical stoichiometry.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.