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      Lead‐Free Hybrid Perovskite Absorbers for Viable Application: Can We Eat the Cake and Have It too?

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          Abstract

          Many years since the booming of research on perovskite solar cells (PSCs), the hybrid perovskite materials developed for photovoltaic application form three main categories since 2009: (i) high‐performance unstable lead‐containing perovskites, (ii) low‐performance lead‐free perovskites, and (iii) moderate performance and stable lead‐containing perovskites. The search for alternative materials to replace lead leads to the second group of perovskite materials. To date, a number of these compounds have been synthesized and applied in photovoltaic devices. Here, lead‐free hybrid light absorbers used in PV devices are focused and their recent developments in related solar cell applications are reviewed comprehensively. In the first part, group 14 metals (Sn and Ge)‐based perovskites are introduced with more emphasis on the optimization of Sn‐based PSCs. Then concerns on halide hybrids of group 15 metals (Bi and Sb) are raised, which are mainly perovskite derivatives. At the same time, transition metal Cu‐based perovskites are also referred. In the end, an outlook is given on the design strategy of lead‐free halide hybrid absorbers for photovoltaic applications. It is believed that this timely review can represent our unique view of the field and shed some light on the direction of development of such promising materials.

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          Inorganic caesium lead iodide perovskite solar cells

          The vast majority of perovskite solar cell research has focused on organic–inorganic lead trihalide perovskites; herein, we present working inorganic CsPbI 3 perovskite solar cells for the first time. The vast majority of perovskite solar cell research has focused on organic–inorganic lead trihalide perovskites. Herein, we present working inorganic CsPbI 3 perovskite solar cells for the first time. CsPbI 3 normally resides in a yellow non-perovskite phase at room temperature, but by careful processing control and development of a low-temperature phase transition route we have stabilised the material in the black perovskite phase at room temperature. As such, we have fabricated solar cell devices in a variety of architectures, with current–voltage curve measured efficiency up to 2.9% for a planar heterojunction architecture, and stabilised power conversion efficiency of 1.7%. The well-functioning planar junction devices demonstrate long-range electron and hole transport in this material. Importantly, this work identifies that the organic cation is not essential, but simply a convenience for forming lead triiodide perovskites with good photovoltaic properties. We additionally observe significant rate-dependent current–voltage hysteresis in CsPbI 3 devices, despite the absence of the organic polar molecule previously thought to be a candidate for inducing hysteresis via ferroelectric polarisation. Due to its space group, CsPbI 3 cannot be a ferroelectric material, and thus we can conclude that ferroelectricity is not required to explain current–voltage hysteresis in perovskite solar cells. Our report of working inorganic perovskite solar cells paves the way for further developments likely to lead to much more thermally stable perovskite solar cells and other optoelectronic devices.
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            Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications

            Hybrid AMX3 perovskites (A = Cs, CH3NH3; M = Sn, Pb; X = halide) have revolutionized the scenario of emerging photovoltaic technologies, with very recent results demonstrating 15% efficient solar cells. The CH3NH3PbI3/MAPb(I1−xClx)3 perovskites have dominated the field, while the similar CH3NH3SnI3 has not been exploited for photovoltaic applications. Replacement of Pb by Sn would facilitate the large uptake of perovskite-based photovoltaics. Despite the extremely fast progress, the materials electronic properties which are key to the photovoltaic performance are relatively little understood. Density Functional Theory electronic structure methods have so far delivered an unbalanced description of Pb- and Sn-based perovskites. Here we develop an effective GW method incorporating spin-orbit coupling which allows us to accurately model the electronic, optical and transport properties of CH3NH3SnI3 and CH3NH3PbI3, opening the way to new materials design. The different CH3NH3SnI3 and CH3NH3PbI3 electronic properties are discussed in light of their exploitation for solar cells, and found to be dominantly due to relativistic effects. These effects stabilize the CH3NH3PbI3 material towards oxidation, by inducing a deeper valence band edge. Relativistic effects, however, also increase the material band-gap compared to CH3NH3SnI3, due to the valence band energy downshift (~0.7 eV) being only partly compensated by the conduction band downshift (~0.2 eV).
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              Tabulated values of the Shockley–Queisser limit for single junction solar cells

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                Author and article information

                Contributors
                peng.gao@fjirsm.ac.cn
                Journal
                Adv Sci (Weinh)
                Adv Sci (Weinh)
                10.1002/(ISSN)2198-3844
                ADVS
                Advanced Science
                John Wiley and Sons Inc. (Hoboken )
                2198-3844
                20 November 2017
                February 2018
                : 5
                : 2 ( doiID: 10.1002/advs.v5.2 )
                : 1700331
                Affiliations
                [ 1 ] CAS Key Laboratory of Design and Assembly of Functional Nanostructures and Fujian Provincial Key Laboratory of Nanomaterials Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou 350002 China
                [ 2 ] Laboratory of Advanced Functional Materials Xiamen Institute of Rare Earth Materials Haixi Institute Chinese Academy of Sciences Xiamen 361021 China
                Author notes
                Author information
                http://orcid.org/0000-0002-6016-3229
                Article
                ADVS448
                10.1002/advs.201700331
                5827473
                660498c5-95d8-4ec6-9205-8c99e0fe367f
                © 2017 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim

                This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

                History
                : 02 July 2017
                : 24 August 2017
                Page count
                Figures: 26, Tables: 2, Pages: 33, Words: 21138
                Funding
                Funded by: Haixi Institute Chinese Academy of Sciences
                Award ID: 1017001
                Categories
                Review
                Reviews
                Custom metadata
                2.0
                advs448
                February 2018
                Converter:WILEY_ML3GV2_TO_NLMPMC version:version=5.3.3 mode:remove_FC converted:21.03.2018

                bismuth halide perovskite,lead‐free absorbers,low dimensional materials,perovskite solar cell,tin halide perovskite

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