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      Hollow metal halide perovskite nanocrystals with efficient blue emissions

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          Abstract

          A hollow nanostructure enables color tuning of metal halide perovskites with efficient blue emissions from cesium lead bromide.

          Abstract

          Metal halide perovskite nanocrystals (NCs) have emerged as new-generation light-emitting materials with narrow emissions and high photoluminescence quantum efficiencies (PLQEs). Various types of perovskite NCs, e.g., platelets, wires, and cubes, have been discovered to exhibit tunable emissions across the whole visible spectrum. Despite remarkable advances in the field of perovskite NCs, many nanostructures in inorganic NCs have not yet been realized in metal halide perovskites, and producing highly efficient blue-emitting perovskite NCs remains challenging and of great interest. Here, we report the discovery of highly efficient blue-emitting cesium lead bromide (CsPbBr 3) perovskite hollow NCs. By facile solution processing of CsPbBr 3 precursor solution containing ethylenediammonium bromide and sodium bromide, in situ formation of hollow CsPbBr 3 NCs with controlled particle and pore sizes is realized. Synthetic control of hollow nanostructures with quantum confinement effect results in color tuning of CsPbBr 3 NCs from green to blue, with high PLQEs of up to 81%.

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          Maximizing and stabilizing luminescence from halide perovskites with potassium passivation

          Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield-a quantity that must be maximized to obtain high efficiency-remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can approach the efficiency limits in tandem solar cells, coloured-light-emitting diodes and other optoelectronic applications.
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            Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions

            We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.
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              Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications, and Their Optical Properties

              Metal halide perovskites represent a flourishing area of research, which is driven by both their potential application in photovoltaics and optoelectronics and by the fundamental science behind their unique optoelectronic properties. The emergence of new colloidal methods for the synthesis of halide perovskite nanocrystals, as well as the interesting characteristics of this new type of material, has attracted the attention of many researchers. This review aims to provide an up-to-date survey of this fast-moving field and will mainly focus on the different colloidal synthesis approaches that have been developed. We will examine the chemistry and the capability of different colloidal synthetic routes with regard to controlling the shape, size, and optical properties of the resulting nanocrystals. We will also provide an up-to-date overview of their postsynthesis transformations, and summarize the various solution processes that are aimed at fabricating halide perovskite-based nanocomposites. Furthermore, we will review the fundamental optical properties of halide perovskite nanocrystals by focusing on their linear optical properties, on the effects of quantum confinement, and on the current knowledge of their exciton binding energies. We will also discuss the emergence of nonlinear phenomena such as multiphoton absorption, biexcitons, and carrier multiplication. Finally, we will discuss open questions and possible future directions.
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                Author and article information

                Journal
                Sci Adv
                Sci Adv
                SciAdv
                advances
                Science Advances
                American Association for the Advancement of Science
                2375-2548
                April 2020
                24 April 2020
                : 6
                : 17
                : eaaz5961
                Affiliations
                [1 ]Materials Science and Engineering Program, Florida State University, Tallahassee, FL 32306, USA.
                [2 ]Chemical and Biomedical Engineering, FAMU-FSU College of Engineering, Florida State University, Tallahassee, FL 32310, USA.
                [3 ]Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA.
                [4 ]National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310, USA.
                Author notes
                [*]

                Present address: Global Solar Energy, Tucson, AZ 85747, USA.

                []Corresponding author. Email: bma@ 123456fsu.edu
                Author information
                http://orcid.org/0000-0002-0671-8588
                http://orcid.org/0000-0001-9388-7517
                http://orcid.org/0000-0003-0625-8881
                http://orcid.org/0000-0001-9955-1598
                http://orcid.org/0000-0001-9605-1803
                http://orcid.org/0000-0002-7290-1401
                http://orcid.org/0000-0001-9291-5061
                http://orcid.org/0000-0003-1573-8019
                Article
                aaz5961
                10.1126/sciadv.aaz5961
                7182421
                32426465
                98547bbc-8360-430c-bdad-1f016c9e053b
                Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

                This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

                History
                : 22 September 2019
                : 27 January 2020
                Funding
                Funded by: doi http://dx.doi.org/10.13039/100000001, National Science Foundation;
                Award ID: 1709116; 1912911; 1644779
                Funded by: doi http://dx.doi.org/10.13039/100000181, Air Force Office of Scientific Research;
                Award ID: 17RT0906
                Categories
                Research Article
                Research Articles
                SciAdv r-articles
                Chemistry
                Materials Science
                Materials Science
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