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Research Article

Size matters: Steric hindrance of precursor molecules controlling the evolution of CdSe magic-size clusters and quantum dots

Juan Shen1, Chaoran Luan2( ), Nelson Rowell3, Yang Li4, Meng Zhang1, Xiaoqin Chen4, Kui Yu1,2,4( )
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, China
Laboratory of Ethnopharmacology, Tissue-orientated Property of Chinese Medicine Key Laboratory of Sichuan Province, West China School of Medicine, West China Hospital, Sichuan University, Chengdu 610065, China
Metrology Research Centre, National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada
Engineering Research Center in Biomaterials, Sichuan University, Chengdu 610065, China
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Graphical Abstract

The size of Cd precursor determined by the steric hindrance of the acid additive plays a decisive role in the selective synthesis of magic-size clusters (MSCs) or quantum dots (QDs). When the ligand of Cd precursor has relatively small (R = CH3–) or large (R = C6H5–) steric hindrance, the pathway of the self-assembly of Cd and Se precursors is promoted or suppressed, respectively.

Abstract

Little is known about how to precisely promote the selective production of either colloidal semiconductor metal chalcogenide (ME), magic-size clusters (MSCs), or quantum dots (QDs). Recently, a two-pathway model has been proposed to comprehend their evolution; here, we reveal for the first time that the size of precursors plays a decisive role in the selected evolution pathway of MSCs and QDs. With the reaction of cadmium myristate (Cd(MA)2) and tri-n-octylphosphine selenide (SeTOP) in 1-octadecene (ODE) as a model system, the size of Cd precursors was manipulated by the steric hindrance of carboxylic acid (RCOOH) additive. Without RCOOH, the reaction produced both CdSe MSCs and QDs (from 100 to 240 °C). With RCOOH, the reaction produced MSCs or QDs when R was small (such as CH3−) or large (such as C6H5−), respectively. According to the two-pathway model, the selective evolution is attributed to the promotion and suppression of the self-assembly of Cd and Se precursors, respectively. We propose that the addition of carboxylic acid may occur ligand exchange with Cd(MA)2, causing the different sizes of Cd precursor. The results suggest that the size of Cd precursors regulates the self-assemble behavior of the precursors, which dictates the directed evolution of either MSCs or QDs. The present findings bring insights into the two-pathway model, as the size of M and E precursors determine the evolution pathways of MSCs or QDs, the understanding of which is of great fundamental significance toward mechanism-enabled design and predictive synthesis of functional nanomaterials.

Keywords

cadmium selenide (CdSe)magic-size clusters (MSCs)quantum dots (QDs)self-assemblysteric hindrance

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Nano Research
Volume 15 Issue 9,
September 2022
Pages 8564-8572
DOI: 10.1007/s12274-022-4421-4
Cite this article:
Shen J, Luan C, Rowell N, et al. Size matters: Steric hindrance of precursor molecules controlling the evolution of CdSe magic-size clusters and quantum dots. Nano Research, 2022, 15(9): 8564-8572. https://doi.org/10.1007/s12274-022-4421-4
Topics:
Semiconductor quantum dots

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Received: 14 February 2022
Revised: 27 March 2022
Accepted: 12 April 2022
Published: 31 May 2022
© Tsinghua University Press 2022
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