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      Smoothing the energy transfer pathway in quasi-2D perovskite films using methanesulfonate leads to highly efficient light-emitting devices

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          Abstract

          Quasi-two-dimensional (quasi-2D) Ruddlesden–Popper (RP) perovskites such as BA 2Cs n–1 Pb n Br 3 n+1 (BA = butylammonium, n > 1) are promising emitters, but their electroluminescence performance is limited by a severe non-radiative recombination during the energy transfer process. Here, we make use of methanesulfonate (MeS) that can interact with the spacer BA cations via strong hydrogen bonding interaction to reconstruct the quasi-2D perovskite structure, which increases the energy acceptor-to-donor ratio and enhances the energy transfer in perovskite films, thus improving the light emission efficiency. MeS additives also lower the defect density in RP perovskites, which is due to the elimination of uncoordinated Pb 2+ by the electron-rich Lewis base MeS and the weakened adsorbate blocking effect. As a result, green light-emitting diodes fabricated using these quasi-2D RP perovskite films reach current efficiency of 63 cd A −1 and 20.5% external quantum efficiency, which are the best reported performance for devices based on quasi-2D perovskites so far.

          Abstract

          Owing to large exciton binding energy, quasi-2D perovskite is promising for light-emitting application, yet inhomogeneous phases distribution limits the potential. Here, the authors improve the performance by using MeS additive to regulate the phase distribution and to reduce defect density in the films.

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          Most cited references65

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          Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent

          Metal halide perovskite materials are an emerging class of solution-processable semiconductors with considerable potential for use in optoelectronic devices1-3. For example, light-emitting diodes (LEDs) based on these materials could see application in flat-panel displays and solid-state lighting, owing to their potential to be made at low cost via facile solution processing, and could provide tunable colours and narrow emission line widths at high photoluminescence quantum yields4-8. However, the highest reported external quantum efficiencies of green- and red-light-emitting perovskite LEDs are around 14 per cent7,9 and 12 per cent8, respectively-still well behind the performance of organic LEDs10-12 and inorganic quantum dot LEDs13. Here we describe visible-light-emitting perovskite LEDs that surpass the quantum efficiency milestone of 20 per cent. This achievement stems from a new strategy for managing the compositional distribution in the device-an approach that simultaneously provides high luminescence and balanced charge injection. Specifically, we mixed a presynthesized CsPbBr3 perovskite with a MABr additive (where MA is CH3NH3), the differing solubilities of which yield sequential crystallization into a CsPbBr3/MABr quasi-core/shell structure. The MABr shell passivates the nonradiative defects that would otherwise be present in CsPbBr3 crystals, boosting the photoluminescence quantum efficiency, while the MABr capping layer enables balanced charge injection. The resulting 20.3 per cent external quantum efficiency represents a substantial step towards the practical application of perovskite LEDs in lighting and display.
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            Bright light-emitting diodes based on organometal halide perovskite.

            Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI(3-x)Cl(x) perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9'-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr(-1) m(-2) at a current density of 363 mA cm(-2), with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m(-2) at a current density of 123 mA cm(-2), giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications.
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              Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes.

              Organic-inorganic hybrid perovskites are emerging low-cost emitters with very high color purity, but their low luminescent efficiency is a critical drawback. We boosted the current efficiency (CE) of perovskite light-emitting diodes with a simple bilayer structure to 42.9 candela per ampere, similar to the CE of phosphorescent organic light-emitting diodes, with two modifications: We prevented the formation of metallic lead (Pb) atoms that cause strong exciton quenching through a small increase in methylammonium bromide (MABr) molar proportion, and we spatially confined the exciton in uniform MAPbBr3 nanograins (average diameter = 99.7 nanometers) formed by a nanocrystal pinning process and concomitant reduction of exciton diffusion length to 67 nanometers. These changes caused substantial increases in steady-state photoluminescence intensity and efficiency of MAPbBr3 nanograin layers.
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                Author and article information

                Contributors
                andrey.rogach@cityu.edu.hk
                yangxy@shu.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                23 February 2021
                23 February 2021
                2021
                : 12
                : 1246
                Affiliations
                [1 ]GRID grid.39436.3b, ISNI 0000 0001 2323 5732, Key Laboratory of Advanced Display and System Applications of Ministry of Education, , Shanghai University, ; Shanghai, 200072 People’s Republic of China
                [2 ]GRID grid.64924.3d, ISNI 0000 0004 1760 5735, College of Materials Science and Engineering, , Jilin University, ; Changchun, 130012 People’s Republic of China
                [3 ]GRID grid.59053.3a, ISNI 0000000121679639, CAS Key Laboratory of Crust-Mantle Materials and Environments, School of Earth and Space Sciences, , University of Science and Technology of China, ; Hefei, 230026 People’s Republic of China
                [4 ]GRID grid.216938.7, ISNI 0000 0000 9878 7032, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, , Nankai University, ; Tianjin, 300071 People’s Republic of China
                [5 ]GRID grid.35030.35, ISNI 0000 0004 1792 6846, Department of Materials Science and Engineering, and Centre for Functional Photonics (CFP), , City University of Hong Kong, Kowloon, ; Hong Kong SAR, People’s Republic of China
                [6 ]GRID grid.458506.a, ISNI 0000 0004 0497 0637, Shanghai Synchrotron Radiation Facility (SSRF), Zhangjiang Lab, , Shanghai Advanced Research Institute, Chinese Academy of Sciences, ; Shanghai, 201204 People’s Republic of China
                [7 ]GRID grid.49470.3e, ISNI 0000 0001 2331 6153, Key Lab of Artificial Micro- and Nano-Structures of Ministry of Education of China, School of Physics and Technology, , Wuhan University, ; Wuhan, 430072 People’s Republic of China
                Author information
                http://orcid.org/0000-0002-2514-4700
                http://orcid.org/0000-0001-7528-4405
                http://orcid.org/0000-0002-6221-7585
                http://orcid.org/0000-0001-6580-9255
                http://orcid.org/0000-0003-1103-804X
                http://orcid.org/0000-0002-1749-2799
                http://orcid.org/0000-0002-6144-1761
                http://orcid.org/0000-0002-8263-8141
                http://orcid.org/0000-0003-3597-1491
                Article
                21522
                10.1038/s41467-021-21522-8
                7902836
                33623029
                d436c61f-2a3c-4e07-860a-39fed2d39b42
                © The Author(s) 2021

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 4 September 2020
                : 28 January 2021
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100001809, National Natural Science Foundation of China (National Science Foundation of China);
                Award ID: 51675322
                Award ID: 61735004
                Award Recipient :
                Funded by: National Key Research and Development Program of China, 2016YFB0401702
                Categories
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                Custom metadata
                © The Author(s) 2021

                Uncategorized
                materials for devices,nanoscale devices,lasers, leds and light sources
                Uncategorized
                materials for devices, nanoscale devices, lasers, leds and light sources

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