Mechanistic Study of the Formation of Bright White Light-Emitting Ultrasmall CdSe Nanocrystals: Role of Phosphine Free Selenium Precursors

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• 作者：Sukanta Dolai ; Poulami Dutta ; Barry B. Muhoberac ; Charles D. Irving ; Rajesh Sardar
• 刊名：Chemistry of Materials
• 出版年：2015
• 出版时间：February 10, 2015
• 年：2015
• 卷：27
• 期：3
• 页码：1057-1070
• 全文大小：716K
• ISSN：1520-5002

文摘

We have designed a new nonphosphinated reaction pathway, which includes synthesis of a new, highly reactive Se-bridged organic species (chalcogenide precursor), to produce bright white light-emitting ultrasmall CdSe nanocrystals of high quality under mild reaction conditions. The detailed characterization of structural properties of the selenium precursor through combined ⁷⁷Se NMR and laser desorption ionization鈥搈ass spectrometry (LDI-MS) provided valuable insights into Se release and delineated the nanocrystal formation mechanism at the molecular level. The ¹H NMR study showed that the rate of disappearance of Se precursor maintained a single-exponential decay with a rate constant of 2.3 脳 10^鈥? s^鈥? at room temperature. Furthermore, the combination of LDI-MS and optical spectroscopy was used for the first time to deconvolute the formation mechanism of our bright white light-emitting nanocrystals, which demonstrated initial formation of a smaller key nanocrystal intermediate (CdSe)₁₉. Application of thermal driving force for destabilization resulted in (CdSe)_n nanocrystal generation with n = 29鈥?6 through continuous dissolution and addition of monomer onto existing nanocrystals while maintaining a living-polymerization type growth mode. Importantly, our ultrasmall CdSe nanocrystals displayed an unprecedentedly large fluorescence quantum yield of 鈭?7% for this size regime (<2.0 nm diameter). These mixed oleylamine and cadmium benzoate ligand-coated CdSe nanocrystals showed a fluorescence lifetime of 鈭?0 ns, a significantly large value for such small nanocrystals, which was due to delocalization of the exciton wave function into the ligand monolayer. We believe our findings will be relevant to formation of other metal chalcogenide nanocrystals through expansion of the understanding and manipulation of surface ligand chemistry, which together will allow the preparation of 鈥?i>artificial solids鈥?with high charge conductivity and mobility for advanced solid-state device applications.