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      Perovskite–fullerene hybrid materials suppress hysteresis in planar diodes

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          Abstract

          Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite–PCBM hybrid solid with significantly reduced hysteresis and recombination loss achieved in a single step. This new material displays an efficient electrically coupled microstructure: PCBM is homogeneously distributed throughout the film at perovskite grain boundaries. The PCBM passivates the key PbI 3 antisite defects during the perovskite self-assembly, as revealed by theory and experiment. Photoluminescence transient spectroscopy proves that the PCBM phase promotes electron extraction. We showcase this mixed material in planar solar cells that feature low hysteresis and enhanced photovoltage. Using conductive AFM studies, we reveal the memristive properties of perovskite films. We close by positing that PCBM, by tying up both halide-rich antisites and unincorporated halides, reduces electric field-induced anion migration that may give rise to hysteresis and unstable diode behaviour.

          Abstract

          Metal halide perovskites are promising for solar energy harvesting, but currently prone to a large hysteresis and current instability. Here, Xu et al. show improvements in a hybrid material in which the fullerene is distributed at perovskite grain boundaries and thus passivates defects effectively.

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          Most cited references8

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          Enhanced photoluminescence and solar cell performance via Lewis base passivation of organic-inorganic lead halide perovskites.

          Organic-inorganic metal halide perovskites have recently emerged as a top contender to be used as an absorber material in highly efficient, low-cost photovoltaic devices. Solution-processed semiconductors tend to have a high density of defect states and exhibit a large degree of electronic disorder. Perovskites appear to go against this trend, and despite relatively little knowledge of the impact of electronic defects, certified solar-to-electrical power conversion efficiencies of up to 17.9% have been achieved. Here, through treatment of the crystal surfaces with the Lewis bases thiophene and pyridine, we demonstrate significantly reduced nonradiative electron-hole recombination within the CH(3)NH(3)PbI(3-x)Cl(x) perovskite, achieving photoluminescence lifetimes which are enhanced by nearly an order of magnitude, up to 2 μs. We propose that this is due to the electronic passivation of under-coordinated Pb atoms within the crystal. Through this method of Lewis base passivation, we achieve power conversion efficiencies for solution-processed planar heterojunction solar cells enhanced from 13% for the untreated solar cells to 15.3% and 16.5% for the thiophene and pyridine-treated solar cells, respectively.
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            Supramolecular halogen bond passivation of organic-inorganic halide perovskite solar cells.

            Organic-inorganic halide perovskites, such as CH3NH3PbX3 (X = I(-), Br(-), Cl(-)), are attracting growing interest to prepare low-cost solar cells that are capable of converting sunlight to electricity at the highest efficiencies. Despite negligible effort on enhancing materials' purity or passivation of surfaces, high efficiencies have already been achieved. Here, we show that trap states at the perovskite surface generate charge accumulation and consequent recombination losses in working solar cells. We identify that undercoordinated iodine ions within the perovskite structure are responsible and make use of supramolecular halogen bond complexation to successfully passivate these sites. Following this strategy, we demonstrate solar cells with maximum power conversion efficiency of 15.7% and stable power output over 15% under constant 0.81 V forward bias in simulated full sunlight. The surface passivation introduces an important direction for future progress in perovskite solar cells.
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              Materials processing routes to trap-free halide perovskites.

              Photovoltaic devices based on lead iodide perovskite films have seen rapid advancements, recently achieving an impressive 17.9% certified solar power conversion efficiency. Reports have consistently emphasized that the specific choice of growth conditions and chemical precursors is central to achieving superior performance from these materials; yet the roles and mechanisms underlying the selection of materials processing route is poorly understood. Here we show that films grown under iodine-rich conditions are prone to a high density of deep electronic traps (recombination centers), while the use of a chloride precursor avoids the formation of key defects (Pb atom substituted by I) responsible for short diffusion lengths and poor photovoltaic performance. Furthermore, the lowest-energy surfaces of perovskite crystals are found to be entirely trap-free, preserving both electron and hole delocalization to a remarkable degree, helping to account for explaining the success of polycrystalline perovskite films. We construct perovskite films from I-poor conditions using a lead acetate precursor, and our measurement of a long (600 ± 40 nm) diffusion length confirms this new picture of the importance of growth conditions.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Pub. Group
                2041-1723
                08 May 2015
                : 6
                : 7081
                Affiliations
                [1 ]Department of Electrical and Computer Engineering, University of Toronto , 10 King's College Road, Toronto, Ontario M5S 3G4, Canada
                [2 ]Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , 1 Bethel Valley Road, Oak Ridge, Tennessee 37831, USA
                [3 ]Department of Physics and Atmospheric Science, Dalhousie University , Room 319, Dunn Building, Halifax, Nova Scotia B3H 4R2, Canada
                [4 ]Department of Chemistry and Nano Science, Ewha Womans University , 52, Ewhayeodae-gil, Seodaemun-gu, Seoul 120-750, Korea
                Author notes
                Author information
                http://orcid.org/0000-0002-1069-9973
                http://orcid.org/0000-0003-0444-0479
                Article
                ncomms8081
                10.1038/ncomms8081
                4432582
                25953105
                9abe9a76-6ff7-41cd-a2fe-b0e201ace720
                Copyright © 2015, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 14 November 2014
                : 31 March 2015
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