Growth kinetics determine the polydispersity and size of PbS and PbSe nanocrystals

Campos, Michael P. and De Roo, Jonathan and Greenberg, Matthew W. and McMurtry, Brandon M. and Hendricks, Mark P. and Bennett, Ellie and Saenz, Natalie and Sfeir, Matthew Y. and Abécassis, Benjamin and Ghose, Sanjit K. and Owen, Jonathan S.. (2022) Growth kinetics determine the polydispersity and size of PbS and PbSe nanocrystals. Chemical Science, 13 (16). pp. 4555-4565.

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Official URL: https://edoc.unibas.ch/91287/

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A library of thio- and selenourea derivatives is used to adjust the kinetics of PbE (E = S, Se) nanocrystal formation across a 1000-fold range (k(r) = 10(-1) to 10(-4) s(-1)), at several temperatures (80-120 degrees C), under a standard set of conditions (Pb : E = 1.2 : 1, [Pb(oleate)(2)] = 10.8 mM, [chalcogenourea] = 9.0 mM). An induction delay (t(ind)) is observed prior to the onset of nanocrystal absorption during which PbE solute is observed using in situ X-ray total scattering. Density functional theory models fit to the X-ray pair distribution function (PDF) support a Pb-2(mu(2)-S)(2)(Pb(O2CR)(2))(2) structure. Absorption spectra of aliquots reveal a continuous increase in the number of nanocrystals over more than half of the total reaction time at low temperatures. A strong correlation between the width of the nucleation phase and reaction temperature is observed that does not correlate with the polydispersity. These findings are antithetical to the critical concentration dependence of nucleation that underpins the La Mer hypothesis and demonstrates that the duration of the nucleation period has a minor influence on the size distribution. The results can be explained by growth kinetics that are size dependent, more rapid at high temperature, and self limiting at low temperatures.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Nanomaterials (De Roo)
UniBasel Contributors:De Roo, Jonathan
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:15 Dec 2022 10:06
Deposited On:15 Dec 2022 08:47

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