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      Fabrication of Semiconducting Methylammonium Lead Halide Perovskite Particles by Spray Technology

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          Abstract

          In this “nano idea” paper, three concepts for the preparation of methylammonium lead halide perovskite particles are proposed, discussed, and tested. The first idea is based on the wet chemistry preparation of the perovskite particles, through the addition of the perovskite precursor solution to an anti-solvent to facilitate the precipitation of the perovskite particles in the solution. The second idea is based on the milling of a blend of the perovskite precursors in the dry form, in order to allow for the conversion of the precursors to the perovskite particles. The third idea is based on the atomization of the perovskite solution by a spray nozzle, introducing the spray droplets into a hot wall reactor, so as to prepare perovskite particles, using the droplet-to-particle spray approach (spray pyrolysis). Preliminary results show that the spray technology is the most successful method for the preparation of impurity-free perovskite particles and perovskite paste to deposit perovskite thin films. As a proof of concept, a perovskite solar cell with the paste prepared by the sprayed perovskite powder was successfully fabricated.

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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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            Ligand-Mediated Synthesis of Shape-Controlled Cesium Lead Halide Perovskite Nanocrystals via Reprecipitation Process at Room Temperature.

            Colloidal nanocrystals of fully inorganic cesium lead halide (CsPbX3, X = Cl, Br, I, or combinations thereof) perovskites have attracted much attention for photonic and optoelectronic applications. Herein, we demonstrate a facile room-temperature (e.g., 25 °C), ligand-mediated reprecipitation strategy for systematically manipulating the shape of CsPbX3 colloidal nanocrystals, such as spherical quantum dots, nanocubes, nanorods, and nanoplatelets. The colloidal spherical quantum dots of CsPbX3 were synthesized with photoluminescence (PL) quantum yield values up to >80%, and the corresponding PL emission peaks covering the visible range from 380 to 693 nm. Besides spherical quantum dots, the shape of CsPbX3 nanocrystals could be engineered into nanocubes, one-dimensional nanorods, and two-dimensional few-unit-cell-thick nanoplatelets with well-defined morphology by choosing different organic acid and amine ligands via the reprecipitation process. The shape-dependent PL decay lifetimes have been determined to be several to tens to hundreds of nanoseconds. Our method provides a facile and versatile route to rationally control the shape of the CsPbX3 perovskites nanocrystals, which will create opportunities for applications such as displays, lasing, light-emitting diodes, solar concentrators, and photon detection.
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              Synthesis and Optical Properties of Lead-Free Cesium Tin Halide Perovskite Nanocrystals.

              Metal halide perovskite crystal structures have emerged as a class of optoelectronic materials, which combine the ease of solution processability with excellent optical absorption and emission qualities. Restricting the physical dimensions of the perovskite crystallites to a few nanometers can also unlock spatial confinement effects, which allow large spectral tunability and high luminescence quantum yields at low excitation densities. However, the most promising perovskite structures rely on lead as a cationic species, thereby hindering commercial application. The replacement of lead with nontoxic alternatives such as tin has been demonstrated in bulk films, but not in spatially confined nanocrystals. Here, we synthesize CsSnX3 (X = Cl, Cl0.5Br0.5, Br, Br0.5I0.5, I) perovskite nanocrystals and provide evidence of their spectral tunability through both quantum confinement effects and control of the anionic composition. We show that luminescence from Sn-based perovskite nanocrystals occurs on pico- to nanosecond time scales via two spectrally distinct radiative decay processes, which we assign to band-to-band emission and radiative recombination at shallow intrinsic defect sites.
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                Author and article information

                Contributors
                1143709026@sjtu.edu.cn
                morteza.eslamian@sjtu.edu.cn , morteza.eslamian@gmail.com
                Journal
                Nanoscale Res Lett
                Nanoscale Res Lett
                Nanoscale Research Letters
                Springer US (New York )
                1931-7573
                1556-276X
                10 January 2018
                10 January 2018
                2018
                : 13
                : 6
                Affiliations
                University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai, 200240 China
                Author information
                http://orcid.org/0000-0002-8096-1447
                Article
                2430
                10.1186/s11671-017-2430-0
                5760486
                29318465
                fdf5d7a6-e270-4f87-97ef-25cb8bbde293
                © The Author(s) 2018

                Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License ( http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided 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.

                History
                : 10 October 2017
                : 28 December 2017
                Funding
                Funded by: FundRef http://dx.doi.org/10.13039/501100001809, National Natural Science Foundation of China;
                Funded by: FundRef http://dx.doi.org/10.13039/501100003395, Shanghai Municipal Education Commission;
                Categories
                Nano Idea
                Custom metadata
                © The Author(s) 2018

                Nanomaterials
                perovskite solar cells,perovskite particles,perovskite nanocrystals,droplet-to-particle,spray pyrolysis

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