skip to main content


Title: Dual‐Protected Metal Halide Perovskite Nanosheets with an Enhanced Set of Stabilities
Abstract

Approaches to achieve stable perovskite nanocrystals (PNCs) of interest, in particular those with large structural anisotropy, through protective coating of the inorganic shell at a single‐nanocrystal (NC) level are comparatively few and limited in scope. Reported here is a robust amphiphilic‐diblock‐copolymer‐enabled strategy for crafting highly‐stableanisotropicCsPbBr3nanosheets (NSs) by in situ formation of a uniform inorganic shell (1st shielding) that is intimately ligated with hydrophobic polymers (2nd shielding). The dual‐protected NSs display an array of remarkable stabilities (i.e., thermal, photostability, moisture, polar solvent, aliphatic amine, etc.) and find application in white‐light‐emitting diodes. In principle, by anchoring other multidentate amphiphilic polymer ligands on the surface of PNCs, followed by templated‐growth of shell materials of interest, a rich variety of dual‐shelled, multifunctional PNCs with markedly improved stabilities can be created for use in optics, optoelectronics, and sensory devices.

 
more » « less
Award ID(s):
1914713 1903990
NSF-PAR ID:
10221818
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie International Edition
Volume:
60
Issue:
13
ISSN:
1433-7851
Page Range / eLocation ID:
p. 7259-7266
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Approaches to achieve stable perovskite nanocrystals (PNCs) of interest, in particular those with large structural anisotropy, through protective coating of the inorganic shell at a single‐nanocrystal (NC) level are comparatively few and limited in scope. Reported here is a robust amphiphilic‐diblock‐copolymer‐enabled strategy for crafting highly‐stableanisotropicCsPbBr3nanosheets (NSs) by in situ formation of a uniform inorganic shell (1st shielding) that is intimately ligated with hydrophobic polymers (2nd shielding). The dual‐protected NSs display an array of remarkable stabilities (i.e., thermal, photostability, moisture, polar solvent, aliphatic amine, etc.) and find application in white‐light‐emitting diodes. In principle, by anchoring other multidentate amphiphilic polymer ligands on the surface of PNCs, followed by templated‐growth of shell materials of interest, a rich variety of dual‐shelled, multifunctional PNCs with markedly improved stabilities can be created for use in optics, optoelectronics, and sensory devices.

     
    more » « less
  2. The past few years have witnessed rapid advances in the synthesis of high-quality perovskite nanocrystals (PNCs). However, despite the impressive developments, the stability of PNCs remains a substantial challenge. The ability to reliably improve stability of PNCs while retaining their individual nanometer size represents a critical step that underpins future advances in optoelectronic applications. Here, we report an unconventional strategy for crafting dual-shelled PNCs (i.e., polymer-ligated perovskite/SiO 2 core/shell NCs) with exquisite control over dimensions, surface chemistry, and stabilities. In stark contrast to conventional methods, our strategy relies on capitalizing on judiciously designed star-like copolymers as nanoreactors to render the growth of core/shell NCs with controlled yet tunable perovskite core diameter, SiO 2 shell thickness, and surface chemistry. Consequently, the resulting polymer-tethered perovskite/SiO 2 core/shell NCs display concurrently a stellar set of substantially improved stabilities (i.e., colloidal stability, chemical composition stability, photostability, water stability), while having appealing solution processability, which are unattainable by conventional methods. 
    more » « less
  3. Abstract

    Localized surface plasmon resonance (LSPR) is shown to be effective in trapping light for enhanced light absorption and hence performance in photonic and optoelectronic devices. Implementation of LSPR in all‐inorganic perovskite nanocrystals (PNCs) is particularly important considering their unique advantages in optoelectronics. Motivated by this, the first success in colloidal synthesis of AuCu/CsPbCl3core/shell PNCs and observation of enhanced light absorption by the perovskite CsPbCl3shell of thickness in the range of 2–4 nm, enabled by the LSPR AuCu core of an average diameter of 7.1 nm, is reported. This enhanced light absorption leads to a remarkably enhanced photoresponse in PNCs/graphene nanohybrid photodetectors using the AuCu/CsPbCl3core/shell PNCs, by more than 30 times as compared to the counterparts with CsPbCl3PNCs only (8–12 nm in dimension). This result illustrates the feasibility in implementation of LSPR light trapping directly in core/shell PNCs for high‐performance optoelectronics.

     
    more » « less
  4. Abstract

    Using deposition observations from precipitation samples collected by the National Atmospheric Deposition Program at 125 sites across the United States, we show that the mean wet deposition flux of non‐sea‐salt chloride (NSS Cl) has decreased by 83% throughout the eastern United States between 1998 and 2018. We find that 30% of the sites switch from having excess Cl− to being depleted in Cl. We attribute the observed decreases in NSS Cl− deposition to a 95% decrease in U.S. anthropogenic HCl emissions since 1998. We propose that industry emission controls that remove HCl as a cobenefit of NOxand SO2have caused significant decreases in NSS Cl− deposition throughout the eastern United States, in addition to shifts from coal to natural gas and to coal with lower Cl− content. Our analysis implies that the lower tropospheric reactive inorganic chlorine burden was larger over the United States in the past than it is today.

     
    more » « less
  5. Abstract

    A high‐throughput computational framework to identify novel multinary perovskite redox mediators is presented, and this framework is applied to discover the Gd‐containing perovskite oxide compositions Gd2BB′O6,GdA′B2O6, and GdA′BB′O6that split water. The computational scheme uses a sequence of empirical approaches to evaluate the stabilities, electronic properties, and oxygen vacancy thermodynamics of these materials, including contributions to the enthalpies and entropies of reduction, ΔHTRand ΔSTR. This scheme uses the machine‐learned descriptor τ to identify compositions that are likely stable as perovskites, the bond valence method to estimate the magnitude and phase of BO6octahedral tilting and provide accurate initial estimates of perovskite geometries, and density functional theory including magnetic‐ and defect‐sampling to predict STCH‐relevant properties. Eighty‐three promising STCH candidate perovskite oxides down‐selected from 4392 Gd‐containing compositions are reported, three of which are referred to experimental collaborators for characterization and exhibit STCH activity. The results demonstrate that the high‐throughput computational scheme described herein—which is used to evaluate Gd‐containing compositions but can be applied to any multinary perovskite oxide compositional space(s) of interest—accelerates the discovery of novel STCH active redox mediators with reasonable computational expense.

     
    more » « less