Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis

P. Tim Prins; Federico Montanarella; Kim Dümbgen; Yolanda Justo; Johanna C. van der Bok; Stijn O.M. Hinterding; Jaco J. Geuchies; Jorick Maes; Kim De Nolf; Sander Deelen; Hans Meijer; Thomas Zinn; Andrei V. Petukhov; Freddy T. Rabouw; Celso De Mello Donega; Daniel Vanmaekelbergh; Zeger Hens

doi:10.1021/acs.nanolett.0c04813

Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis

P. Tim Prins
, Federico Montanarella
, Kim Dümbgen
, Yolanda Justo
, Johanna C. van der Bok
, Stijn O.M. Hinterding
, Jaco J. Geuchies
, Jorick Maes
, Kim De Nolf
, Sander Deelen
, Hans Meijer
, Thomas Zinn
, Andrei V. Petukhov
, Freddy T. Rabouw
, Celso De Mello Donega
, Daniel Vanmaekelbergh
, Zeger Hens (Corresponding author)

Research output: Contribution to journal › Article › Academic › peer-review

56 Citations (Scopus)

Abstract

Hot-injection synthesis is renowned for producing semiconductor nanocolloids with superb size dispersions. Burst nucleation and diffusion-controlled size focusing during growth have been invoked to rationalize this characteristic yet experimental evidence supporting the pertinence of these concepts is scant. By monitoring a CdSe synthesis in-situ with X-ray scattering, we find that nucleation is an extended event that coincides with growth during 15-20% of the reaction time. Moreover, we show that size focusing outpaces predictions of diffusion-limited growth. This observation indicates that nanocrystal growth is dictated by the surface reactivity, which drops sharply for larger nanocrystals. Kinetic reaction simulations confirm that this so-called superfocusing can lengthen the nucleation period and promote size focusing. The finding that narrow size dispersions can emerge from the counteracting effects of extended nucleation and reaction-limited size focusing ushers in an evidence-based perspective that turns hot injection into a rational scheme to produce monodisperse semiconductor nanocolloids.

Original language	English
Pages (from-to)	2487-2496
Number of pages	10
Journal	Nano Letters
Volume	21
Issue number	6
DOIs	https://doi.org/10.1021/acs.nanolett.0c04813
Publication status	Published - 24 Mar 2021

Bibliographical note

Funding Information:
Z.H. acknowledges support by FWO-Vlaanderen (research projects G0F0920N and G0B2921N) and Ghent University (BOF-GOA 01G01019). K.D. acknowledges FWO-Vlaanderen for a scholarship. Z.H., D.V.M., and F.M. acknowledge support by the European Commission via the Marie-Sklodowska Curie Action Phonsi (H2020-MSCA-ITN-642656). D.V., C.D.M.D., and F.T.R. acknowledge support by The Netherlands Organization for Scientific Research (NWO; grants 14614 “Q-Lumicon”, Veni 722.017.002) and The Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC). J.J.G. acknowledges financial support from the joint UU and ESRF Graduate Program. The authors thank the ESRF for providing beam time (experiment HC-3725), Jacques Gorini and Narayanan Theyencheri for assistance during beam time, and Liheng Wu and Matteo Cargnello for fruitful discussions.

Publisher Copyright:
©

Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.

Funding

Z.H. acknowledges support by FWO-Vlaanderen (research projects G0F0920N and G0B2921N) and Ghent University (BOF-GOA 01G01019). K.D. acknowledges FWO-Vlaanderen for a scholarship. Z.H., D.V.M., and F.M. acknowledge support by the European Commission via the Marie-Sklodowska Curie Action Phonsi (H2020-MSCA-ITN-642656). D.V., C.D.M.D., and F.T.R. acknowledge support by The Netherlands Organization for Scientific Research (NWO; grants 14614 “Q-Lumicon”, Veni 722.017.002) and The Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC). J.J.G. acknowledges financial support from the joint UU and ESRF Graduate Program. The authors thank the ESRF for providing beam time (experiment HC-3725), Jacques Gorini and Narayanan Theyencheri for assistance during beam time, and Liheng Wu and Matteo Cargnello for fruitful discussions.

Funders	Funder number
Research Foundation Flanders	G0B2921N, G0F0920N
Marie Skłodowska‐Curie	H2020-MSCA-ITN-642656
Netherlands Center for Multiscale Catalytic Energy Conversion
European Union's Horizon 2020 - Research and Innovation Framework Programme	642656
European Commission
Ulster University
European Synchrotron Radiation Facility
Nederlandse Organisatie voor Wetenschappelijk Onderzoek	722.017.002, 14614
Ghent University	BOF-GOA 01G01019

Keywords

in-situ analysis
monodisperse
nanocolloids
nucleation and growth
photoluminescence
quantum dots

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10.1021/acs.nanolett.0c04813

Cite this

Prins, P. T., Montanarella, F., Dümbgen, K., Justo, Y., van der Bok, J. C., Hinterding, S. O. M., Geuchies, J. J., Maes, J., De Nolf, K., Deelen, S., Meijer, H., Zinn, T., Petukhov, A. V., Rabouw, F. T., De Mello Donega, C., Vanmaekelbergh, D., & Hens, Z. (2021). Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis. Nano Letters, 21(6), 2487-2496. https://doi.org/10.1021/acs.nanolett.0c04813

@article{ff9c8e16f19b43f6b0c669c65d9b7a3e,

title = "Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis",

abstract = "Hot-injection synthesis is renowned for producing semiconductor nanocolloids with superb size dispersions. Burst nucleation and diffusion-controlled size focusing during growth have been invoked to rationalize this characteristic yet experimental evidence supporting the pertinence of these concepts is scant. By monitoring a CdSe synthesis in-situ with X-ray scattering, we find that nucleation is an extended event that coincides with growth during 15-20\% of the reaction time. Moreover, we show that size focusing outpaces predictions of diffusion-limited growth. This observation indicates that nanocrystal growth is dictated by the surface reactivity, which drops sharply for larger nanocrystals. Kinetic reaction simulations confirm that this so-called superfocusing can lengthen the nucleation period and promote size focusing. The finding that narrow size dispersions can emerge from the counteracting effects of extended nucleation and reaction-limited size focusing ushers in an evidence-based perspective that turns hot injection into a rational scheme to produce monodisperse semiconductor nanocolloids. ",

keywords = "in-situ analysis, monodisperse, nanocolloids, nucleation and growth, photoluminescence, quantum dots",

author = "Prins, \{P. Tim\} and Federico Montanarella and Kim D{\"u}mbgen and Yolanda Justo and \{van der Bok\}, \{Johanna C.\} and Hinterding, \{Stijn O.M.\} and Geuchies, \{Jaco J.\} and Jorick Maes and \{De Nolf\}, Kim and Sander Deelen and Hans Meijer and Thomas Zinn and Petukhov, \{Andrei V.\} and Rabouw, \{Freddy T.\} and \{De Mello Donega\}, Celso and Daniel Vanmaekelbergh and Zeger Hens",

note = "Funding Information: Z.H. acknowledges support by FWO-Vlaanderen (research projects G0F0920N and G0B2921N) and Ghent University (BOF-GOA 01G01019). K.D. acknowledges FWO-Vlaanderen for a scholarship. Z.H., D.V.M., and F.M. acknowledge support by the European Commission via the Marie-Sklodowska Curie Action Phonsi (H2020-MSCA-ITN-642656). D.V., C.D.M.D., and F.T.R. acknowledge support by The Netherlands Organization for Scientific Research (NWO; grants 14614 “Q-Lumicon”, Veni 722.017.002) and The Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC). J.J.G. acknowledges financial support from the joint UU and ESRF Graduate Program. The authors thank the ESRF for providing beam time (experiment HC-3725), Jacques Gorini and Narayanan Theyencheri for assistance during beam time, and Liheng Wu and Matteo Cargnello for fruitful discussions. Publisher Copyright: {\textcopyright} Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2021",

month = mar,

day = "24",

doi = "10.1021/acs.nanolett.0c04813",

language = "English",

volume = "21",

pages = "2487--2496",

journal = "Nano Letters",

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Prins, PT, Montanarella, F, Dümbgen, K, Justo, Y, van der Bok, JC, Hinterding, SOM, Geuchies, JJ, Maes, J, De Nolf, K, Deelen, S, Meijer, H, Zinn, T, Petukhov, AV, Rabouw, FT, De Mello Donega, C, Vanmaekelbergh, D & Hens, Z 2021, 'Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis', Nano Letters, vol. 21, no. 6, pp. 2487-2496. https://doi.org/10.1021/acs.nanolett.0c04813

TY - JOUR

T1 - Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis

AU - Prins, P. Tim

AU - Montanarella, Federico

AU - Dümbgen, Kim

AU - Justo, Yolanda

AU - van der Bok, Johanna C.

AU - Hinterding, Stijn O.M.

AU - Geuchies, Jaco J.

AU - Maes, Jorick

AU - De Nolf, Kim

AU - Deelen, Sander

AU - Meijer, Hans

AU - Zinn, Thomas

AU - Petukhov, Andrei V.

AU - Rabouw, Freddy T.

AU - De Mello Donega, Celso

AU - Vanmaekelbergh, Daniel

AU - Hens, Zeger

N1 - Funding Information: Z.H. acknowledges support by FWO-Vlaanderen (research projects G0F0920N and G0B2921N) and Ghent University (BOF-GOA 01G01019). K.D. acknowledges FWO-Vlaanderen for a scholarship. Z.H., D.V.M., and F.M. acknowledge support by the European Commission via the Marie-Sklodowska Curie Action Phonsi (H2020-MSCA-ITN-642656). D.V., C.D.M.D., and F.T.R. acknowledge support by The Netherlands Organization for Scientific Research (NWO; grants 14614 “Q-Lumicon”, Veni 722.017.002) and The Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC). J.J.G. acknowledges financial support from the joint UU and ESRF Graduate Program. The authors thank the ESRF for providing beam time (experiment HC-3725), Jacques Gorini and Narayanan Theyencheri for assistance during beam time, and Liheng Wu and Matteo Cargnello for fruitful discussions. Publisher Copyright: © Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/3/24

Y1 - 2021/3/24

N2 - Hot-injection synthesis is renowned for producing semiconductor nanocolloids with superb size dispersions. Burst nucleation and diffusion-controlled size focusing during growth have been invoked to rationalize this characteristic yet experimental evidence supporting the pertinence of these concepts is scant. By monitoring a CdSe synthesis in-situ with X-ray scattering, we find that nucleation is an extended event that coincides with growth during 15-20% of the reaction time. Moreover, we show that size focusing outpaces predictions of diffusion-limited growth. This observation indicates that nanocrystal growth is dictated by the surface reactivity, which drops sharply for larger nanocrystals. Kinetic reaction simulations confirm that this so-called superfocusing can lengthen the nucleation period and promote size focusing. The finding that narrow size dispersions can emerge from the counteracting effects of extended nucleation and reaction-limited size focusing ushers in an evidence-based perspective that turns hot injection into a rational scheme to produce monodisperse semiconductor nanocolloids.

AB - Hot-injection synthesis is renowned for producing semiconductor nanocolloids with superb size dispersions. Burst nucleation and diffusion-controlled size focusing during growth have been invoked to rationalize this characteristic yet experimental evidence supporting the pertinence of these concepts is scant. By monitoring a CdSe synthesis in-situ with X-ray scattering, we find that nucleation is an extended event that coincides with growth during 15-20% of the reaction time. Moreover, we show that size focusing outpaces predictions of diffusion-limited growth. This observation indicates that nanocrystal growth is dictated by the surface reactivity, which drops sharply for larger nanocrystals. Kinetic reaction simulations confirm that this so-called superfocusing can lengthen the nucleation period and promote size focusing. The finding that narrow size dispersions can emerge from the counteracting effects of extended nucleation and reaction-limited size focusing ushers in an evidence-based perspective that turns hot injection into a rational scheme to produce monodisperse semiconductor nanocolloids.

KW - in-situ analysis

KW - monodisperse

KW - nanocolloids

KW - nucleation and growth

KW - photoluminescence

KW - quantum dots

UR - https://www.scopus.com/pages/publications/85103392036

U2 - 10.1021/acs.nanolett.0c04813

DO - 10.1021/acs.nanolett.0c04813

M3 - Article

C2 - 33661650

AN - SCOPUS:85103392036

SN - 1530-6984

VL - 21

SP - 2487

EP - 2496

JO - Nano Letters

JF - Nano Letters

IS - 6

ER -

Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis

Abstract

Bibliographical note

Funding

Keywords

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