Persistent nucleation and size dependent attachment kinetics produce monodisperse PbS nanocrystals

Abécassis, Benjamin; Greenberg, Matthew W.; Bal, Vivekananda; McMurtry, Brandon M.; Campos, Michael P.; Guillemeney, Lilian; Mahler, Benoît; Prévost, Sylvain; Sharpnack, Lewis; Hendricks, Mark P.; Derosha, Daniel; Bennett, Ellie; Saenz, Natalie; Peters, Baron; Owen, Jonathan S.

doi:10.1039/d1sc06134h

Cited by 16 publications

(23 citation statements)

References 39 publications

(64 reference statements)

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“…We have observed similarly prolonged nucleation under identical conditions using in situ X-ray scattering measurements that will be reported elsewhere. 44 The increasing nanocrystal concentrations observed here provide a direct measure of the nucleation kinetics because the final nanocrystals do not significantly ripen or agglomerate under these conditions. 26,30 Hence, the steadily increasing [NC] shows that crystal nucleation continues throughout a significant fraction of the total reaction time rather than occurring in a burst.…”

Section: Resultsmentioning

confidence: 80%

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

et al. 2022

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Section: Resultsmentioning

confidence: 80%

“…A similar conclusion is reached in a related study on PbS to be published elsewhere. 44 More detailed understanding of the factors controlling the growth rate would, therefore, enable the rational optimization of size distributions.…”

Section: Discussionmentioning

confidence: 99%

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

et al. 2022

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“…Overall, this ligand-based approach allows us to fine-tune particle size over a wide range and is applicable to both monosulfide and monoselenide compositions, with little to no variation in other synthetic conditions. This mixed precursor approach to fine-tune particle size is a versatile addition to the synthetic nanochemistry toolbox, which nicely complements other available methods for controlling particle size of colloidal nanocrystals. ,, …”

Section: Resultsmentioning

confidence: 99%

“…This mixed precursor approach to fine-tune particle size is a versatile addition to the synthetic nanochemistry toolbox, which nicely complements other available methods for controlling particle size of colloidal nanocrystals. 26,47,48 Spectroscopic Analysis of Surface Ligand Coordination. The infrared spectra of all the binary alkaline-earth chalcogenides show vibrations consistent with the presence of carboxylate ligands (Figure 7).…”

Section: Resultsmentioning

confidence: 99%

Alkaline-Earth Chalcogenide Nanocrystals: Solution-Phase Synthesis, Surface Chemistry, and Stability

et al. 2022

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Increasing demand for effective energy conversion materials and devices has renewed interest in semiconductors comprised of earth-abundant and biocompatible elements. Alkaline-earth sulfides doped with rare earth ions are versatile optical materials. However, relatively little is known about controlling the dimensionality, surface chemistry, and inherent optical properties of the undoped versions of alkaline-earth mono- and polychalcogenides. We describe the colloidal synthesis of alkaline-earth chalcogenide nanocrystals through the reaction of metal carboxylates with carbon disulfide or selenourea. Systematic exploration of the synthetic phase space allows us to tune particle sizes over a wide range using a mixture of commercially available carboxylate precursors. Solid-state NMR spectroscopy confirms the phase purity of the selenide compositions. Surface characterization reveals that bridging carboxylates and amines preferentially terminate the surface of the nanocrystals. While these materials are colloidally stable in the mother solution, the selenides are susceptible to oxidation over time, eventually degrading to selenium metal through polyselenide intermediates. As part of these investigations, we have developed the colloidal syntheses of barium di- and triselenides, two among few reported nanocrystalline alkaline-earth polychalcogenides. Electronic structure calculations reveal that both materials are indirect band gap semiconductors. The colloidal chemistry presented here may enable the synthesis of more complex, multinary chalcogenide materials containing alkaline-earth elements.

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“…146 These mechanisms link the narrow polydispersity to a brief period of nucleation that precedes growth and a growth process that is limited by diffusion of monomers to the nanocrystals surface, and a homogeneous ripening process that broadens the polydispersity while increases the average size. However, recent kinetics investigations of InP, 150 CdSe, 151 PbS and PbSe 129,152 QD syntheses have observed long nucleation periods that in some cases continue throughout the synthesis and are concurrent with growth, as well as attachment limited growth kinetics that support size distribution focusing. Indeed, a recent comprehensive review of semiconductor, metal, and oxide nanoparticle formation concluded that, "compelling evidence for burst nucleation and diffusion-controlled growth in semiconductor nanoparticle formation is missing" and "a primary working hypothesis going forward to test and to try to disprove, is that nucleation may well more often be continuous".…”

Section: -Growth Mechanisms That Support Narrow Polydispersitiesmentioning

confidence: 99%

Design rules for obtaining narrow luminescence from semiconductors made in solution

Nguyen

Dixon

Dou

et al. 2023

Preprint

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Solution processed semiconductors are in demand for present and next-generation optoelectronic technologies ranging from displays to quantum light sources because of their scalability and ease of integration into devices with diverse form factors. One of the central requirements of semiconductors used in all these applications is a narrow photoluminescence (PL) linewidth. Narrow emission linewidths are needed to ensure both color and single-photon purity, raising the question of what design rules are needed to obtain narrow emission from semiconductors made in solution. In this review we first examine the requirements for colloidal emitters for a variety of applications including light-emitting diodes, photodetectors, lasers, and quantum information science. Next, we will delve into the sources of spectral broadening, including homogeneous broadening from dynamical broadening mechanisms in single-particle spectra, heterogeneous broadening from static structural differences in ensemble spectra, and spectral diffusion. Then, we compare the current state of the art in terms of emission linewidth for a variety of colloidal materials including II-VI quantum dots (QDs) and nanoplatelets, III-V QDs, alloyed QDs, metal-halide perovskites including nanocrystals and 2D structures, doped nanocrystals, and, finally, as a point of comparison, organic molecules. We end with some conclusions and connections, with an outline of promising paths forward.

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Persistent nucleation and size dependent attachment kinetics produce monodisperse PbS nanocrystals

Abstract: Modern syntheses of colloidal nanocrystals yield extraordinarily narrow size distributions that are believed to result from a rapid “burst of nucleation” (La Mer, JACS, 1950, 72(11), 4847–4854) followed by diffusion...

Cited by 16 publications

References 39 publications

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

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

Alkaline-Earth Chalcogenide Nanocrystals: Solution-Phase Synthesis, Surface Chemistry, and Stability

Design rules for obtaining narrow luminescence from semiconductors made in solution

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