We studied the formation of zinc selenide (ZnSe) from zinc chloride (ZnCl2) and trioctylphosphine selenide (TOP=Se) in oleylamine, a chemistry originally proposed to grow ZnSe shells around InP core quantum dots. By monitoring the formation of ZnSe in reactions with and without InP seeds by quantitative absorbance and nuclear magnetic resonance (NMR) spectroscopy, we observe that the ZnSe formation rate is independent of the presence of InP cores. Similar to the seeded growth of CdSe and CdS, this observation supports a ZnSe growth mechanism through the inclusion of reactive ZnSe monomers that form homogeneously in the solution. Furthermore, by combining NMR and mass spectrometry, we identified the dominant reaction products of the ZnSe formation reaction as oleylammonium chloride and amino-substitutions of TOP, i.e., iminophosphoranes (TOP=NR), aminophosphonium chloride salts [TOP(NHR)Cl], and bis(amino)phosphoranes [TOP(NHR)2]. Based on the acquired results, we outline a reaction scheme that involves the complexation of TOP=Se by ZnCl2, followed by the nucleophilic addition of oleylamine onto the Lewis acid activated P–Se bond, thereby eliminating ZnSe monomers and forming amino-substitutions of TOP. Our work highlights the central role of oleylamine, acting as both the nucleophile and Brønsted base, in the transformation of metal halides and alkylphosphine chalcogenides into metal chalcogenides.
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14 June 2023
Research Article|
June 08 2023
Mechanistic study of ZnSe nanocrystal formation from zinc halides
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40 Years of Colloidal Nanocrystals in JCP
Leila Mingabudinova
;
Leila Mingabudinova
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Validation, Visualization, Writing – original draft, Writing – review & editing)
Physics and Chemistry of Nanostructures, Department of Chemistry, Ghent University
, B-9000 Gent, Belgium
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Luca Giordano
;
Luca Giordano
(Data curation, Investigation)
Physics and Chemistry of Nanostructures, Department of Chemistry, Ghent University
, B-9000 Gent, Belgium
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Mickael D. Tessier
;
Mickael D. Tessier
(Writing – review & editing)
Physics and Chemistry of Nanostructures, Department of Chemistry, Ghent University
, B-9000 Gent, Belgium
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Zeger Hens
;
Zeger Hens
a)
(Funding acquisition, Methodology, Project administration, Resources, Supervision, Validation, Writing – review & editing)
Physics and Chemistry of Nanostructures, Department of Chemistry, Ghent University
, B-9000 Gent, Belgium
a)Authors to whom correspondence should be addressed: zeger.hens@ugent.be and pjschiet.schiettecatte@ugent.be
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Pieter Schiettecatte
Pieter Schiettecatte
a)
(Conceptualization, Formal analysis, Methodology, Validation, Visualization, Writing – original draft, Writing – review & editing)
Physics and Chemistry of Nanostructures, Department of Chemistry, Ghent University
, B-9000 Gent, Belgium
a)Authors to whom correspondence should be addressed: zeger.hens@ugent.be and pjschiet.schiettecatte@ugent.be
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a)Authors to whom correspondence should be addressed: zeger.hens@ugent.be and pjschiet.schiettecatte@ugent.be
J. Chem. Phys. 158, 224701 (2023)
Article history
Received:
January 31 2023
Accepted:
May 12 2023
Citation
Leila Mingabudinova, Luca Giordano, Mickael D. Tessier, Zeger Hens, Pieter Schiettecatte; Mechanistic study of ZnSe nanocrystal formation from zinc halides. J. Chem. Phys. 14 June 2023; 158 (22): 224701. https://doi.org/10.1063/5.0144683
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