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Real-Time X-ray Scattering Discovers Rich Phase Behavior in PbS Nanocrystal Superlattices during In Situ Assembly

  • Irina Lokteva*
    Irina Lokteva
    Deutsches Elektronen-Synchrotron DESY, Notkestraße 85, 22607 Hamburg, Germany
    The Hamburg Centre for Ultrafast Imaging (CUI), Luruper Chaussee 149, 22761 Hamburg, Germany
    *Email: [email protected]
  • Michael Dartsch
    Michael Dartsch
    Deutsches Elektronen-Synchrotron DESY, Notkestraße 85, 22607 Hamburg, Germany
    The Hamburg Centre for Ultrafast Imaging (CUI), Luruper Chaussee 149, 22761 Hamburg, Germany
  • Francesco Dallari
    Francesco Dallari
    Deutsches Elektronen-Synchrotron DESY, Notkestraße 85, 22607 Hamburg, Germany
  • Fabian Westermeier
    Fabian Westermeier
    Deutsches Elektronen-Synchrotron DESY, Notkestraße 85, 22607 Hamburg, Germany
  • Michael Walther
    Michael Walther
    Deutsches Elektronen-Synchrotron DESY, Notkestraße 85, 22607 Hamburg, Germany
  • Gerhard Grübel
    Gerhard Grübel
    Deutsches Elektronen-Synchrotron DESY, Notkestraße 85, 22607 Hamburg, Germany
    The Hamburg Centre for Ultrafast Imaging (CUI), Luruper Chaussee 149, 22761 Hamburg, Germany
  • , and 
  • Felix Lehmkühler
    Felix Lehmkühler
    Deutsches Elektronen-Synchrotron DESY, Notkestraße 85, 22607 Hamburg, Germany
    The Hamburg Centre for Ultrafast Imaging (CUI), Luruper Chaussee 149, 22761 Hamburg, Germany
Cite this: Chem. Mater. 2021, 33, 16, 6553–6563
Publication Date (Web):August 4, 2021
https://doi.org/10.1021/acs.chemmater.1c02159
Copyright © 2021 The Authors. Published by American Chemical Society

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    Abstract

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    During the self-organization of colloidal semiconductor nanoparticles by solvent evaporation, nanoparticle interactions are substantially determined by the organic ligands covering the inorganic core. However, the influence of the ligand grafting density on the assembly pathway is often not considered in experiments. Here, we carry out an in situ synchrotron small-angle X-ray scattering and X-ray cross-correlation analysis study of the real-time assembly of oleic acid-capped PbS nanocrystals at a low ligand coverage of 2.7 molecules/nm2. With high temporal and spatial resolution, we monitor the transitions from the colloidal suspension through the solvated superlattice states into the final dried superstructure. In a single in situ experiment, we observe a two-dimensional hexagonal, hexagonal close-packed, body-centered cubic, body-centered tetragonal (with different degrees of tetragonal distortion), and face-centered cubic superlattice phases. Our results are compared to the self-organization of PbS nanocrystals with a higher ligand coverage up to 4.5 molecules/nm2, revealing different assembly pathways. This highlights the importance of determining the ligand coverage in assembly experiments to approach a complete understanding of the assembly mechanism as well as to be able to predict and produce the targeted superstructures.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.1c02159.

    • Calculation of the evaporation rate during the in situ self-assembly; determination of the ligand grafting density using the thermogravimetric analysis; optical microscopy images of the dry self-assembled superlattice film; SAXS curves from 29.15 min until 37.43 min after the start of evaporation; X-ray cross-correlation analysis of the two-dimensional SAXS patterns; detailed analysis of the superlattice at 99.65 min; and calculation of the packing efficiency of ligated nanocrystals (PDF)

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    Cited By

    This article is cited by 7 publications.

    1. Christian P. N. Tanner, James K. Utterback, Joshua Portner, Igor Coropceanu, Avishek Das, Christopher J. Tassone, Samuel W. Teitelbaum, David T. Limmer, Dmitri V. Talapin, Naomi S. Ginsberg. In Situ X-ray Scattering Reveals Coarsening Rates of Superlattices Self-Assembled from Electrostatically Stabilized Metal Nanocrystals Depend Nonmonotonically on Driving Force. ACS Nano 2024, 18 (7) , 5778-5789. https://doi.org/10.1021/acsnano.3c12186
    2. Nele N. Striker, Irina Lokteva, Michael Dartsch, Francesco Dallari, Claudia Goy, Fabian Westermeier, Verena Markmann, Svenja C. Hövelmann, Gerhard Grübel, Felix Lehmkühler. Dynamics and Time Scales of Higher-Order Correlations in Supercooled Colloidal Systems. The Journal of Physical Chemistry Letters 2023, 14 (20) , 4719-4725. https://doi.org/10.1021/acs.jpclett.3c00631
    3. Emanuele Marino, Daniel J. Rosen, Shengsong Yang, Esther H.R. Tsai, Christopher B. Murray. Temperature-Controlled Reversible Formation and Phase Transformation of 3D Nanocrystal Superlattices Through In Situ Small-Angle X-ray Scattering. Nano Letters 2023, 23 (10) , 4250-4257. https://doi.org/10.1021/acs.nanolett.3c00299
    4. Daniel E. Clark, Victoria A. Lumsargis, Daria D. Blach, Kuixin Zhu, Alexander J. Shumski, Lehan Yao, Qian Chen, Libai Huang, Christina W. Li. Quantifying Structural Heterogeneity in Individual CsPbBr3 Quantum Dot Superlattices. Chemistry of Materials 2022, 34 (22) , 10200-10207. https://doi.org/10.1021/acs.chemmater.2c03153
    5. Mathias Micheel, Raktim Baruah, Krishan Kumar, Maria Wächtler. Assembly, Properties, and Application of Ordered Group II–VI and IV–VI Colloidal Semiconductor Nanoparticle Films. Advanced Materials Interfaces 2022, 9 (28) , 2201039. https://doi.org/10.1002/admi.202201039
    6. Zhong‐Peng Lv, Martin Kapuscinski, Gábor Járvás, Shun Yu, Lennart Bergström. Time‐Resolved SAXS Study of Polarity‐ and Surfactant‐Controlled Superlattice Transformations of Oleate‐Capped Nanocubes During Solvent Removal. Small 2022, 18 (22) , 2106768. https://doi.org/10.1002/smll.202106768
    7. Yutong Gao, Youshuang Zhou, Xiangyun Xu, Chungui Chen, Bijin Xiong, Jintao Zhu. Fabrication of Oriented Colloidal Crystals from Capillary Assembly of Polymer‐Tethered Gold Nanoparticles. Small 2022, 18 (13) , 2106880. https://doi.org/10.1002/smll.202106880

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