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Title: The Role of Dimer Formation in the Nucleation of Superlattice Transformations and Its Impact on Disorder

Abstract

The formation of defect-free two-dimensional nanocrystal (NC) superstructures remains a challenge as persistent defects hinder charge delocalization and related device performance. Understanding defect formation is an important step toward developing strategies to mitigate their formation. However, specific mechanisms of defect formation are difficult to determine, as superlattice phase transformations that occur during fabrication are quite complex and there are a variety of factors influencing the disorder in the final structure. Here, we use Molecular Dynamics (MD) and electron microscopy in concert to investigate the nucleation of the epitaxial attachment of lead chalcogenide (PbX, where X = S, Se) NC assemblies. We use an updated implementation of an existing reactive force field in an MD framework to investigate how initial orientational (mis)alignment of the constituent building blocks impacts the final structure of the epitaxially connected superlattice. This Simple Molecular Reactive Force Field (SMRFF) captures both short-range covalent forces and long-range electrostatic forces and allows us to follow orientational and translational changes of NCs during superlattice transformation. Our simulations reveal how robust the oriented attachment is with regard to the initial configuration of the NCs, measuring its sensitivity to both in-plane and out-of-plane misorientation. We show that oriented attachment nucleates through themore » initial formation of dimers, which corroborate experimentally observed structures. We present high-resolution structural analysis of dimers at early stages of the superlattice transformation and rationalize their contribution to the formation of defects in the final superlattice. Collectively, the simulations and experiments presented in this paper provide insights into the nucleation of NC oriented attachment, the impact of the initial configuration of NCs on the structural fidelity of the final epitaxially connected superlattice, and the propensity to form commonly observed defects, such as missing bridges and atomic misalignment in the superlattice due to the formation of dimers. Here, we present potential strategies to mitigate the formation of superlattice defects.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Johns Hopkins University, Baltimore, MD (United States)
  2. Cornell University, Ithaca, NY (United States)
Publication Date:
Research Org.:
Johns Hopkins University, Baltimore, MD (United States); Cornell Univ., Ithaca, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
Cornell Center for Materials Research; Weill Institute for Cell and Molecular Biology at Cornell University; Kavli Institute for Nanoscale Science at Cornell University; Maryland Advanced Research Computing Center (MARCC)
OSTI Identifier:
1651184
Alternate Identifier(s):
OSTI ID: 1833367
Grant/Contract Number:  
SC0018026
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 14; Journal Issue: 9; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 74 ATOMIC AND MOLECULAR PHYSICS; 72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; 36 MATERIALS SCIENCE; 42 ENGINEERING; Molecular simulation; reactive force field; atomistic mechanism; nanocrystals; oriented attachment; superlattice; disorder

Citation Formats

Chen, Isaiah Y., Cimada daSilva, Jessica, Balazs, Daniel M., Smeaton, Michelle A., Kourkoutis, Lena F., Hanrath, Tobias, and Clancy, Paulette. The Role of Dimer Formation in the Nucleation of Superlattice Transformations and Its Impact on Disorder. United States: N. p., 2020. Web. doi:10.1021/acsnano.0c03800.
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Chen, Isaiah Y., Cimada daSilva, Jessica, Balazs, Daniel M., Smeaton, Michelle A., Kourkoutis, Lena F., Hanrath, Tobias, & Clancy, Paulette. The Role of Dimer Formation in the Nucleation of Superlattice Transformations and Its Impact on Disorder. United States. https://doi.org/10.1021/acsnano.0c03800
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Chen, Isaiah Y., Cimada daSilva, Jessica, Balazs, Daniel M., Smeaton, Michelle A., Kourkoutis, Lena F., Hanrath, Tobias, and Clancy, Paulette. Mon . "The Role of Dimer Formation in the Nucleation of Superlattice Transformations and Its Impact on Disorder". United States. https://doi.org/10.1021/acsnano.0c03800. https://www.osti.gov/servlets/purl/1651184.
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@article{osti_1651184,
title = {The Role of Dimer Formation in the Nucleation of Superlattice Transformations and Its Impact on Disorder},
author = {Chen, Isaiah Y. and Cimada daSilva, Jessica and Balazs, Daniel M. and Smeaton, Michelle A. and Kourkoutis, Lena F. and Hanrath, Tobias and Clancy, Paulette},
abstractNote = {The formation of defect-free two-dimensional nanocrystal (NC) superstructures remains a challenge as persistent defects hinder charge delocalization and related device performance. Understanding defect formation is an important step toward developing strategies to mitigate their formation. However, specific mechanisms of defect formation are difficult to determine, as superlattice phase transformations that occur during fabrication are quite complex and there are a variety of factors influencing the disorder in the final structure. Here, we use Molecular Dynamics (MD) and electron microscopy in concert to investigate the nucleation of the epitaxial attachment of lead chalcogenide (PbX, where X = S, Se) NC assemblies. We use an updated implementation of an existing reactive force field in an MD framework to investigate how initial orientational (mis)alignment of the constituent building blocks impacts the final structure of the epitaxially connected superlattice. This Simple Molecular Reactive Force Field (SMRFF) captures both short-range covalent forces and long-range electrostatic forces and allows us to follow orientational and translational changes of NCs during superlattice transformation. Our simulations reveal how robust the oriented attachment is with regard to the initial configuration of the NCs, measuring its sensitivity to both in-plane and out-of-plane misorientation. We show that oriented attachment nucleates through the initial formation of dimers, which corroborate experimentally observed structures. We present high-resolution structural analysis of dimers at early stages of the superlattice transformation and rationalize their contribution to the formation of defects in the final superlattice. Collectively, the simulations and experiments presented in this paper provide insights into the nucleation of NC oriented attachment, the impact of the initial configuration of NCs on the structural fidelity of the final epitaxially connected superlattice, and the propensity to form commonly observed defects, such as missing bridges and atomic misalignment in the superlattice due to the formation of dimers. Here, we present potential strategies to mitigate the formation of superlattice defects.},
doi = {10.1021/acsnano.0c03800},
journal = {ACS Nano},
number = 9,
volume = 14,
place = {United States},
year = {Mon Aug 17 00:00:00 EDT 2020},
month = {Mon Aug 17 00:00:00 EDT 2020}
}
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