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      Formation Mechanisms and Phase Stability of Solid-State Grown CsPbI 3 Perovskites

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          Abstract

          CsPbI 3 inorganic perovskite is synthesized by a solvent-free, solid-state reaction, and its structural and optical properties can be deeply investigated using a multi-technique approach. X-ray Diffraction (XRD) and Raman measurements, optical absorption, steady-time and time-resolved luminescence, as well as High-Resolution Transmission Electron Microscopy (HRTEM) imaging, were exploited to understand phase evolution as a function of synthesis time length. Nanoparticles with multiple, well-defined crystalline domains of different crystalline phases were observed, usually surrounded by a thin, amorphous/out-of-axis shell. By increasing the synthesis time length, in addition to the pure α phase, which was rapidly converted into the δ phase at room temperature, a secondary phase, Cs 4PbI 6, was observed, together with the 715 nm-emitting γ phase.

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          Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber.

          Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI(3-x)Cl(x)) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of ~100 nanometers. These results justify the high efficiency of planar heterojunction perovskite solar cells and identify a critical parameter to optimize for future perovskite absorber development.
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            Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut

            Metal halides perovskites, such as hybrid organic–inorganic CH3NH3PbI3, are newcomer optoelectronic materials that have attracted enormous attention as solution-deposited absorbing layers in solar cells with power conversion efficiencies reaching 20%. Herein we demonstrate a new avenue for halide perovskites by designing highly luminescent perovskite-based colloidal quantum dot materials. We have synthesized monodisperse colloidal nanocubes (4–15 nm edge lengths) of fully inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I or mixed halide systems Cl/Br and Br/I) using inexpensive commercial precursors. Through compositional modulations and quantum size-effects, the bandgap energies and emission spectra are readily tunable over the entire visible spectral region of 410–700 nm. The photoluminescence of CsPbX3 nanocrystals is characterized by narrow emission line-widths of 12–42 nm, wide color gamut covering up to 140% of the NTSC color standard, high quantum yields of up to 90%, and radiative lifetimes in the range of 1–29 ns. The compelling combination of enhanced optical properties and chemical robustness makes CsPbX3 nanocrystals appealing for optoelectronic applications, particularly for blue and green spectral regions (410–530 nm), where typical metal chalcogenide-based quantum dots suffer from photodegradation.
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              Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%

              We report on solid-state mesoscopic heterojunction solar cells employing nanoparticles (NPs) of methyl ammonium lead iodide (CH3NH3)PbI3 as light harvesters. The perovskite NPs were produced by reaction of methylammonium iodide with PbI2 and deposited onto a submicron-thick mesoscopic TiO2 film, whose pores were infiltrated with the hole-conductor spiro-MeOTAD. Illumination with standard AM-1.5 sunlight generated large photocurrents (JSC) exceeding 17 mA/cm2, an open circuit photovoltage (VOC) of 0.888 V and a fill factor (FF) of 0.62 yielding a power conversion efficiency (PCE) of 9.7%, the highest reported to date for such cells. Femto second laser studies combined with photo-induced absorption measurements showed charge separation to proceed via hole injection from the excited (CH3NH3)PbI3 NPs into the spiro-MeOTAD followed by electron transfer to the mesoscopic TiO2 film. The use of a solid hole conductor dramatically improved the device stability compared to (CH3NH3)PbI3 -sensitized liquid junction cells.
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                Author and article information

                Contributors
                Role: Academic Editor
                Journal
                Nanomaterials (Basel)
                Nanomaterials (Basel)
                nanomaterials
                Nanomaterials
                MDPI
                2079-4991
                14 July 2021
                July 2021
                : 11
                : 7
                : 1823
                Affiliations
                [1 ]Department of Physics, Campus of Monserrato, University of Cagliari, 09042 Monserrato, Italy; jessica.satta@ 123456dsf.unica.it (J.S.); daniele.chiriu@ 123456dsf.unica.it (D.C.); cm.carbonaro@ 123456dsf.unica.it (C.M.C.)
                [2 ]Nabla Lab, Biological and Environmental Sciences and Engineering (BESE) Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia; alberto.casu@ 123456kaust.edu.sa
                [3 ]Laboratory of Materials Science and Nanotechnology, CR-INSTM, Department of Chemistry and Pharmacy, University of Sassari, Via Vienna 2, 07100 Sassari, Italy; lstagi@ 123456uniss.it
                Author notes
                Author information
                https://orcid.org/0000-0002-9591-0095
                https://orcid.org/0000-0002-5056-2170
                https://orcid.org/0000-0003-2097-1229
                https://orcid.org/0000-0001-6353-6409
                https://orcid.org/0000-0002-7238-8425
                https://orcid.org/0000-0001-6191-4613
                Article
                nanomaterials-11-01823
                10.3390/nano11071823
                8308418
                b7ff7cef-0743-4abf-b6fa-a3ba12ad06b1
                © 2021 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 10 June 2021
                : 08 July 2021
                Categories
                Article

                cspbi3,inorganic lead halide perovskites,solid-state synthesis,phase stability

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