Abstract
Quantum dotsĀ (QD) have been gaining popularity within the field of biomedical diagnostics research because of their unique electrochemiluminescence (ECL) properties. During the past two decades, great efforts have been devoted to the development of ECL luminophores and coreactants. However, the current understanding of ECL generation upon QDs is largely inherited from the theories developed by Bard and coworkers. Two types of charge-transfer mechanisms have been postulated for ECL generation: (i) intraparticle charge-transfer between coreactant radical and QD radical, (ii) interparticle charge-transfer between opposite-charged QD radicals. The manipulation and effective probing of these routes remain a fundamental challenge due to the extremely short lifetime of radicals and their stochastic collisions. In this chapter, we designed QD aerogels as luminophores to elucidate the charge-transfer mechanisms for ECL generation. The CdSe QD aerogel prepared via a versatile water-induced gelation strategy was used for designing novel ECL luminophores. The efficient charge transport and greatly improved ECL efficiency based on the strong electronic coupling between adjacent QDs within the aerogel networks were explored. The selectively enhanced interparticle charge-transfer route for coreactant-based ECL systems was proposed. In addition, the charge-transport-promoted ECL mechanism was further verified by designing CdSe-CdTe mixed QD aerogels, where the interparticle charge-transfer route could be clearly decoupled from the intraparticle charge-transfer route. Finally, we presented an evaluation of energy level alignments and Fermi level of QDs to further verify the interparticle charge-transfer route within the CdSe-CdTe mixed QD aerogels. The study conducted on a fundamental understanding of ECL further supports the utilization of next-generation QD-based devices.
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Acknowledgments
This study was supported by the National Natural Science Foundation of China (22174087, 52201262), Guangdong Basic and Applied Basic Research Foundation (2021A1515110920), Natural Science Foundation of Shandong Province (ZR2022QE001), Taishan Scholars Program of Shandong Province (tsqn202211042), Fundamental Research Funds of Shandong University (ZY202006), and Jinan Bureau of Science and Technology (2021GXRC127). The author (DNT) wishes to thank Prof. Guizheng Zou, School of Chemistry and Chemical Engineering at Shandong University for UV-Vis, PL, electrochemistry, ECL analysis, and DFT calculation. DNT acknowledges Drs. Guocan Jiang and Anatol Prudnikau, Physical Chemistry at Technische UniversitƤt Dresden, for the synthesis of samples and corresponding characterizations used in this study. DNT acknowledges RenĆ© HĆ¼bner, Institute of Ion Beam Physics and Materials Research at Helmholtz-Zentrum Dresden-Rossendorf, for TEM analysis. The author thanks Prof. Alexander EychmĆ¼ller for fruitful discussion in this work.
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Gao, X., Cai, B. (2024). Interparticle Charge Transport Enhances Electrochemiluminescence of Quantum Dots. In: Krishnamoorthy, S., Iniewski, K.(. (eds) Advances in Fabrication and Investigation of Nanomaterials for Industrial Applications . Springer, Cham. https://doi.org/10.1007/978-3-031-42700-8_8
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