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Title: Programmable Colloidal Approach to Hierarchical Structures of Methylammonium Lead Bromide Perovskite Nanocrystals with Bright Photoluminescent Properties

Abstract

Here, systematic tailoring of nanocrystal architecture could provide unprecedented control over their electronic, photophysical, and charge transport properties for a variety of applications. However, at present, manipulation of the shape of perovskite nanocrystals is done mostly by trial-and-error-based experimental approaches. Here, we report systematic colloidal synthetic strategies to prepare methylammonium lead bromide quantum platelets and quantum cubes. In order to control the nucleation and growth processes of these nano crystals, we appropriately manipulate the solvent system, surface ligand chemistry, and reaction temperature causing syntheses into anisotropic shapes. We demonstrate that both the presence of chlorinated solvent and a long chain aliphatic amine in the reaction mixture are crucial for the formation of ultrathin quantum platelets (similar to 1.5 nm in thickness), which is driven by mesoscale-assisted growth of spherical seed nanocrystals (similar to 1.6 nm in diameter) through attachment of monomers onto selective crystal facets. A combined surface and structural characterization, along with small-angle X-ray scattering analysis, confirm that the long hydrocarbon of the aliphatic amine is responsible for the well ordered hierarchical stacking of the quantum platelets of 3.5 nm separation. In contrast, the formation of similar to 12 nm edge-length quantum cubes is a kinetically driven process inmore » which a high flux of monomers is achieved by supplying thermal energy. The photoluminescence quantum yield of our quantum platelets (similar to 52%) is nearly 2-fold higher than quantum cubes. Moreover, the quantum platelets display a lower nonradiative rate constant than that found with quantum cubes, which suggests less surface trap states. Together, our research has the potential both to improve the design of synthetic methods for programmable control of shape and assembly and to provide insight into optoelectronic properties of these materials for solid-state device fabrication, e.g., light-emitting diodes, solar cells, and lasing materials.« less

Authors:
 [1];  [2];  [1];  [3]; ORCiD logo [1]
  1. Indiana Univ.-Purdue Univ. Indianapolis, Indianapolis, IN (United States)
  2. Indiana Univ.-Purdue Univ. Fort Wayne, Fort Wayne, IN (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division
OSTI Identifier:
1377608
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 8; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Teunis, Meghan B., Johnson, Merrell A., Muhoberac, Barry B., Seifert, Soenke, and Sardar, Rajesh. Programmable Colloidal Approach to Hierarchical Structures of Methylammonium Lead Bromide Perovskite Nanocrystals with Bright Photoluminescent Properties. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.6b05393.
Teunis, Meghan B., Johnson, Merrell A., Muhoberac, Barry B., Seifert, Soenke, & Sardar, Rajesh. Programmable Colloidal Approach to Hierarchical Structures of Methylammonium Lead Bromide Perovskite Nanocrystals with Bright Photoluminescent Properties. United States. https://doi.org/10.1021/acs.chemmater.6b05393
Teunis, Meghan B., Johnson, Merrell A., Muhoberac, Barry B., Seifert, Soenke, and Sardar, Rajesh. 2017. "Programmable Colloidal Approach to Hierarchical Structures of Methylammonium Lead Bromide Perovskite Nanocrystals with Bright Photoluminescent Properties". United States. https://doi.org/10.1021/acs.chemmater.6b05393. https://www.osti.gov/servlets/purl/1377608.
@article{osti_1377608,
title = {Programmable Colloidal Approach to Hierarchical Structures of Methylammonium Lead Bromide Perovskite Nanocrystals with Bright Photoluminescent Properties},
author = {Teunis, Meghan B. and Johnson, Merrell A. and Muhoberac, Barry B. and Seifert, Soenke and Sardar, Rajesh},
abstractNote = {Here, systematic tailoring of nanocrystal architecture could provide unprecedented control over their electronic, photophysical, and charge transport properties for a variety of applications. However, at present, manipulation of the shape of perovskite nanocrystals is done mostly by trial-and-error-based experimental approaches. Here, we report systematic colloidal synthetic strategies to prepare methylammonium lead bromide quantum platelets and quantum cubes. In order to control the nucleation and growth processes of these nano crystals, we appropriately manipulate the solvent system, surface ligand chemistry, and reaction temperature causing syntheses into anisotropic shapes. We demonstrate that both the presence of chlorinated solvent and a long chain aliphatic amine in the reaction mixture are crucial for the formation of ultrathin quantum platelets (similar to 1.5 nm in thickness), which is driven by mesoscale-assisted growth of spherical seed nanocrystals (similar to 1.6 nm in diameter) through attachment of monomers onto selective crystal facets. A combined surface and structural characterization, along with small-angle X-ray scattering analysis, confirm that the long hydrocarbon of the aliphatic amine is responsible for the well ordered hierarchical stacking of the quantum platelets of 3.5 nm separation. In contrast, the formation of similar to 12 nm edge-length quantum cubes is a kinetically driven process in which a high flux of monomers is achieved by supplying thermal energy. The photoluminescence quantum yield of our quantum platelets (similar to 52%) is nearly 2-fold higher than quantum cubes. Moreover, the quantum platelets display a lower nonradiative rate constant than that found with quantum cubes, which suggests less surface trap states. Together, our research has the potential both to improve the design of synthetic methods for programmable control of shape and assembly and to provide insight into optoelectronic properties of these materials for solid-state device fabrication, e.g., light-emitting diodes, solar cells, and lasing materials.},
doi = {10.1021/acs.chemmater.6b05393},
url = {https://www.osti.gov/biblio/1377608}, journal = {Chemistry of Materials},
issn = {0897-4756},
number = 8,
volume = 29,
place = {United States},
year = {2017},
month = {4}
}

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Works referencing / citing this record:

In situ tetrafluoroborate-modified MAPbBr 3 nanocrystals showing high photoluminescence, stability and self-assembly behavior
journal, January 2020


Continuous low temperature synthesis of MAPbX 3 perovskite nanocrystals in a flow reactor
journal, January 2018


Perovskite-Based Nanocrystals: Synthesis and Applications beyond Solar Cells
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Insights into the role of the lead/surfactant ratio in the formation and passivation of cesium lead bromide perovskite nanocrystals
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