Metal Halide Perovskite Crystals: Growth Techniques, Properties and Emerging Applications

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Inorganic Crystalline Materials".

Deadline for manuscript submissions: closed (31 March 2018) | Viewed by 133681

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Guest Editor
Advanced Technology Institute (ATI), University of Surrey, Guildford, Surrey GU2 7XH, UK
Interests: photovoltaics; perovskites; semicondutors; optoelectronic devices

Special Issue Information

Dear Colleagues,

Metal halide perovskites have emerged as a rising star among various semiconductor materials in the past few years owing to their low cost, solution processability and fascinating combination of material properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion length, which enable a broad range of photovoltaic and optoelectronic applications. Accompanied by the success in photovoltaic community that has witnessed a certified power conversion efficiency of 22.1% through a few years’ efforts, the rapid advancement is also achieved in the areas of light-emitting diodes, lasers, photodetectors, and solar-to-fuel energy conversion devices. Beyond the dominant format of polycrystalline perovskite thin films for solar cell applications, recent progress in metal halide perovskite crystals, ranging from nanocrystals, nanowires to macroscopic single-crystals, has spurred paramount scientific and industrial interests. Great research efforts have endeavored to develop new techniques for crystal growth, investigate the physical and chemical properties of the materials and explore their emerging applications. The perovskite single crystals, for instance, provide an excellent platform to characterize a range of materials’ properties that could not be achieved by studying polycrystalline thin films. Understanding the mechanism of the crystal growth provides insights for the better control of polycrystalline thin film quality in terms of crystal orientation and defect density, the key facts that restrict the solar cell performance. Perovskite nanocrystals and nanowires exhibit superior luminescent performance than their thin film counterparts, enabling potential applications like large area display. These exciting achievements call for a rationalization of the different forms of perovskite semiconductors beyond the widely used polycrystalline thin films. In the current Special Issue: “Metal Halide Perovskite Crystals: Growth Techniques, Properties and Emerging Applications”, we aim to provide a forum for the discussion and presentation of recent advances in the fields of research related to metal halide perovskite crystals. The potential topics of interest could be, but are not limited to:

  • Growth techniques of metal halide perovskite single crystals, nanowire and nanocystals

  • Mechanism of crystal growth

  • Characterization of metal halide perovskite crystals

  • Emerging applications of metal halide perovskite crystals

Scientists working in this broad field, and many other aspects related to perovskite crystals but not summarized here, are invited to present their work in this Special Issue. Full papers, communications, and reviews are all welcome.

Dr. Wei Zhang
Guest Editor

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Keywords

  • Metal halide perovskites

  • Single crystals, nanocrystals, nanowires, nanorods

  • Semiconductors

  • Photovoltaics, light-emitting diodes, lasers, photodetectors, optical and optoelectronic devices

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Published Papers (13 papers)

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Research

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22 pages, 2790 KiB  
Article
Metal Halide Perovskite Single Crystals: From Growth Process to Application
by Shuigen Li, Chen Zhang, Jiao-Jiao Song, Xiaohu Xie, Jian-Qiao Meng and Shunjian Xu
Crystals 2018, 8(5), 220; https://doi.org/10.3390/cryst8050220 - 17 May 2018
Cited by 33 | Viewed by 14239
Abstract
As a strong competitor in the field of optoelectronic applications, organic-inorganic metal hybrid perovskites have been paid much attention because of their superior characteristics, which include broad absorption from visible to near-infrared region, tunable optical and electronic properties, high charge mobility, long exciton [...] Read more.
As a strong competitor in the field of optoelectronic applications, organic-inorganic metal hybrid perovskites have been paid much attention because of their superior characteristics, which include broad absorption from visible to near-infrared region, tunable optical and electronic properties, high charge mobility, long exciton diffusion length and carrier recombination lifetime, etc. It is noted that perovskite single crystals show remarkably low trap-state densities and long carrier diffusion lengths, which are even comparable with the best photovoltaic-quality silicon, and thus are expected to provide better optoelectronic performance. This paper reviews the recent development of crystal growth in single-, mixed-organic-cation and fully inorganic halide perovskite single crystals, in particular the solution approach. Furthermore, the application of metal hybrid perovskite single crystals and future perspectives are also highlighted. Full article
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9 pages, 1092 KiB  
Article
Effects of Iodine Doping on Carrier Behavior at the Interface of Perovskite Crystals: Efficiency and Stability
by Guilin Liu, Lang Liu, Xiuxiu Niu, Huanping Zhou and Qi Chen
Crystals 2018, 8(5), 185; https://doi.org/10.3390/cryst8050185 - 25 Apr 2018
Cited by 11 | Viewed by 4974
Abstract
The interface related to the polycrystalline hybrid perovskite thin film plays an essential role in the resulting device performance. Iodine was employed as an additive to modify the interface between perovskite and spiro-OMeTAD hole transport layer. The oxidation ability of iodine significantly improved [...] Read more.
The interface related to the polycrystalline hybrid perovskite thin film plays an essential role in the resulting device performance. Iodine was employed as an additive to modify the interface between perovskite and spiro-OMeTAD hole transport layer. The oxidation ability of iodine significantly improved the efficiency of charge extraction for perovskite solar cells. It reveals that the Open Circuit Voltage (Voc) and Fill Factor (FF) of perovskite solar cells were improved substantially due to the dopant, which is mainly attributed to the interfacial improvement. It was found that the best efficiency of the devices was achieved when the dopant of iodine was in equivalent mole concentration with that of spiro-OMeTAD. Moreover, the long-term stability of the corresponding device was investigated. Full article
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9 pages, 3668 KiB  
Article
Enhancing Optically Pumped Organic-Inorganic Hybrid Perovskite Amplified Spontaneous Emission via Compound Surface Plasmon Resonance
by Xiaoyan Wu, Yanglong Li, Wei Li, Lingyuan Wu, Bo Fu, Weiping Wang, Guodong Liu, Dayong Zhang, Jianheng Zhao and Ping Chen
Crystals 2018, 8(3), 124; https://doi.org/10.3390/cryst8030124 - 7 Mar 2018
Cited by 9 | Viewed by 4940
Abstract
Organic-inorganic hybrid perovskite has attracted intensive attention from researchers as the gain medium in lasing devices. However, achieving electrically driven lasing remains a significant challenge. Modifying the devices’ structure to enhance the optically pumped amplified spontaneous emission (ASE) is the key issue. In [...] Read more.
Organic-inorganic hybrid perovskite has attracted intensive attention from researchers as the gain medium in lasing devices. However, achieving electrically driven lasing remains a significant challenge. Modifying the devices’ structure to enhance the optically pumped amplified spontaneous emission (ASE) is the key issue. In this work, gold nanoparticles (Au NPs) are first doped into PEDOT: PSS buffer layer in a slab waveguide device structure: Quartz/PEDOT: PSS (with or w/o Au NPs)/CH3NH3PbBr3. As a result, the facile device shows a significantly enhanced ASE intensity and a narrowed full width at half maximum. Based on experiments and theoretical simulation data, the improvement is mainly a result of the compound surface plasmon resonance, including simultaneous near- and far-field effects, both of which could increase the density of excitons excited state and accelerate the radiative decay process. This method is highly significant for the design and development and fabrication of high-performance organic-inorganic hybrid perovskite lasing diodes. Full article
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12 pages, 23022 KiB  
Article
A Feasible and Effective Post-Treatment Method for High-Quality CH3NH3PbI3 Films and High-Efficiency Perovskite Solar Cells
by Yaxiao Jiang, Limin Tu, Haitao Li, Shaohua Li, Shi-E Yang and Yongsheng Chen
Crystals 2018, 8(1), 44; https://doi.org/10.3390/cryst8010044 - 18 Jan 2018
Cited by 16 | Viewed by 6306
Abstract
The morphology control of CH3NH3PbI3 (MAPbI3) thin-film is crucial for the high-efficiency perovskite solar cells, especially for their planar structure devices. Here, a feasible and effective post-treatment method is presented to improve the quality of MAPbI [...] Read more.
The morphology control of CH3NH3PbI3 (MAPbI3) thin-film is crucial for the high-efficiency perovskite solar cells, especially for their planar structure devices. Here, a feasible and effective post-treatment method is presented to improve the quality of MAPbI3 films by using methylamine (CH3NH2) vapor. This post-treatment process is studied thoroughly, and the perovskite films with smooth surface, high preferential growth orientation and large crystals are obtained after 10 s treatment in MA atmosphere. It enhances the light absorption, and increases the recombination lifetime. Ultimately, the power conversion efficiency (PCE) of 15.3% for the FTO/TiO2/MAPbI3/spiro-OMeTAD/Ag planar architecture solar cells is achieved in combination with this post-treatment method. It represents a 40% improvement in PCE compared to the best control cell. Moreover, the whole post-treatment process is simple and cheap, which only requires some CH3NH2 solution in absolute ethanol. It is beneficial to control the reaction rate by changing the volume of the solution. Therefore, we are convinced that the post-treatment method is a valid and essential approach for the fabrication of high-efficiency perovskite solar cells. Full article
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2721 KiB  
Article
Improved Stability and Photoluminescence Yield of Mn2+-Doped CH3NH3PbCl3 Perovskite Nanocrystals
by Xianli Li, Yan Guo and Binbin Luo
Crystals 2018, 8(1), 4; https://doi.org/10.3390/cryst8010004 - 23 Dec 2017
Cited by 30 | Viewed by 6845
Abstract
Organic–inorganic CH3NH3PbCl3 perovskite nanocrystals (PNCs) doped with Mn2+, CH3NH3PbxMn1−xCl3, have been successfully prepared using a reprecipitation method at room temperature. Structural and morphological characterizations reveal that the CH3NH3PbxMn1−xCl3 PNCs with cubic phase transforms from particles to cubes and increases in size from 16.2 [...] Read more.
Organic–inorganic CH3NH3PbCl3 perovskite nanocrystals (PNCs) doped with Mn2+, CH3NH3PbxMn1−xCl3, have been successfully prepared using a reprecipitation method at room temperature. Structural and morphological characterizations reveal that the CH3NH3PbxMn1−xCl3 PNCs with cubic phase transforms from particles to cubes and increases in size from 16.2 ± 4.4 nm in average diameter to 25.3 ± 7.2 nm in cubic length after the addition of Mn2+ precursor. The CH3NH3PbxMn1−xCl3 PNCs exhibit a weak exciton emission at ~405 nm with a low absolute quantum yield (QY) of around 0.4%, but a strong Mn2+ dopant emission at ~610 nm with a high QY of around 15.2%, resulting from efficient energy transfer from the PNC host to the Mn2+ dopant via the 4T1→6A1 transition. In addition, the thermal and air stability of CH3NH3PbxMn1−xCl3 PNCs are improved due to the passivation with (3-aminopropyl) triethoxysilane (APTES), which is important for applications such as light emitting diodes (LEDs). Full article
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5197 KiB  
Article
Atomic Characterization of Byproduct Nanoparticles on Cesium Lead Halide Nanocrystals Using High-Resolution Scanning Transmission Electron Microscopy
by Mian Zhang, Hongbo Li, Qiang Jing, Zhenda Lu and Peng Wang
Crystals 2018, 8(1), 2; https://doi.org/10.3390/cryst8010002 - 22 Dec 2017
Cited by 25 | Viewed by 7053
Abstract
Recent microstructural studies on lead halide perovskite nanocrystals have consistently reported the coexistence of byproduct nanoparticles (NPs). However, the nature of these NPs and their formation mechanism are still a matter of debate. Herein, we have investigated the structure and compositions of the [...] Read more.
Recent microstructural studies on lead halide perovskite nanocrystals have consistently reported the coexistence of byproduct nanoparticles (NPs). However, the nature of these NPs and their formation mechanism are still a matter of debate. Herein, we have investigated the structure and compositions of the NPs located on colloidal cesium lead bromide nanocrystals (CsPbBr3 NCs), mainly through aberration-corrected transmission electron microscopy and spectroscopy. Our results show that these NPs can be assigned to PbBr2 and CsPb2Br5. The new CsPb2Br5 species are formed by reacting CsPbBr3 NCs with the remaining PbBr2 during the drying process. In addition, observation of the metallic Pb NPs are ascribed to the electron damage effect on CsPbBr3 NCs during transmission electron microscopy imaging. Full article
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3993 KiB  
Article
CH3NH3Cl Assisted Solvent Engineering for Highly Crystallized and Large Grain Size Mixed-Composition (FAPbI3)0.85(MAPbBr3)0.15 Perovskites
by Yihui Li, Taiyang Zhang, Feng Xu, Yong Wang, Ge Li, Yang Yang and Yixin Zhao
Crystals 2017, 7(9), 272; https://doi.org/10.3390/cryst7090272 - 5 Sep 2017
Cited by 28 | Viewed by 10237
Abstract
High-quality mixed-cation lead mixed-halide (FAPbI3)0.85(MAPbBr3)0.15 perovskite films have been prepared using CH3NH3Cl additives via the solvent engineering method. The UV/Vis result shows that the addition of additives leads to enhanced absorptions. XRD [...] Read more.
High-quality mixed-cation lead mixed-halide (FAPbI3)0.85(MAPbBr3)0.15 perovskite films have been prepared using CH3NH3Cl additives via the solvent engineering method. The UV/Vis result shows that the addition of additives leads to enhanced absorptions. XRD and SEM characterizations suggest that compact, pinhole-free and uniform films can be obtained. This is attributable to the crystallization improvement caused by the CH3NH3Cl additives. The power conversion efficiency (PCE) of the F-doped SnO2 (FTO)/compact-TiO2/perovskite/Spiro-OMeTAD/Ag device increases from 15.3% to 16.8% with the help of CH3NH3Cl additive. Full article
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2386 KiB  
Article
Interfacial Kinetics of Efficient Perovskite Solar Cells
by Pankaj Yadav, Daniel Prochowicz, Michael Saliba, Pablo P. Boix, Shaik M. Zakeeruddin and Michael Grätzel
Crystals 2017, 7(8), 252; https://doi.org/10.3390/cryst7080252 - 13 Aug 2017
Cited by 26 | Viewed by 8405
Abstract
Perovskite solar cells (PSCs) have immense potential for high power conversion efficiency with an ease of fabrication procedure. The fundamental understanding of interfacial kinetics in PSCs is crucial for further improving of their photovoltaic performance. Herein we use the current-voltage (J-V) [...] Read more.
Perovskite solar cells (PSCs) have immense potential for high power conversion efficiency with an ease of fabrication procedure. The fundamental understanding of interfacial kinetics in PSCs is crucial for further improving of their photovoltaic performance. Herein we use the current-voltage (J-V) characteristics and impedance spectroscopy (IS) measurements to probe the interfacial kinetics on efficient MAPbI3 solar cells. We show that series resistance (RS) of PSCs exhibits an ohmic and non-ohmic behavior that causes a significant voltage drop across it. The Nyquist spectra as a function of applied bias reveal the characteristic features of ion motion and accumulation that is mainly associated with the MA cations in MAPbI3. With these findings, we provide an efficient way to understand the working mechanism of perovskite solar cells. Full article
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Review

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37 pages, 22091 KiB  
Review
Analysing the Prospects of Perovskite Solar Cells within the Purview of Recent Scientific Advancements
by Aakash Bhat, Bhanu Pratap Dhamaniya, Priyanka Chhillar, Tulja Bhavani Korukonda, Gaurav Rawat and Sandeep K. Pathak
Crystals 2018, 8(6), 242; https://doi.org/10.3390/cryst8060242 - 6 Jun 2018
Cited by 14 | Viewed by 6651
Abstract
For any given technology to be successful, its ability to compete with the other existing technologies is the key. Over the last five years, perovskite solar cells have entered the research spectrum with tremendous market prospects. These cells provide easy and low cost [...] Read more.
For any given technology to be successful, its ability to compete with the other existing technologies is the key. Over the last five years, perovskite solar cells have entered the research spectrum with tremendous market prospects. These cells provide easy and low cost processability and are an efficient alternative to the existing solar cell technologies in the market. In this review article, we first go over the innovation and the scientific findings that have been going on in the field of perovskite solar cells (PSCs) and then present a short case study of perovskite solar cells based on their energy payback time. Our review aims to be comprehensive, considering the cost, the efficiency, and the stability of the PSCs. Later, we suggest areas for improvement in the field, and how the future might be shaped. Full article
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14 pages, 4748 KiB  
Review
Emerging Characterizing Techniques in the Fine Structure Observation of Metal Halide Perovskite Crystal
by Kongchao Shen, Jinping Hu, Zhaofeng Liang, Jinbang Hu, Haoliang Sun, Zheng Jiang and Fei Song
Crystals 2018, 8(6), 232; https://doi.org/10.3390/cryst8060232 - 23 May 2018
Cited by 8 | Viewed by 7661
Abstract
Driven by its appealing application in the energy harvesting industry, metal halide perovskite solar cells are attracting increasing attention from various fields, such as chemistry, materials, physics, and energy-related industries. While the energy conversion efficiency of the perovskite solar cell is being investigated [...] Read more.
Driven by its appealing application in the energy harvesting industry, metal halide perovskite solar cells are attracting increasing attention from various fields, such as chemistry, materials, physics, and energy-related industries. While the energy conversion efficiency of the perovskite solar cell is being investigated often by various research groups, the relationship between the surface structure and the property is still ambiguous and, therefore, becomes an urgent topic due to its wide application in the real environment. Recently, the fine structure characterization of perovskite crystals has been analysed by varying techniques, such as XRD, synchrotron-based grazing incidence XRD, XAFS, and STM, in addition to others. In this review article, we will summarize recent progresses in the monitoring of fine nanostructures of the surface and crystal structures of perovskite films, mainly by XAFS, XRD, and STM, focusing on the discussion of the relationship between the properties and the stability of perovskite solar cells. Furthermore, a prospective is given for the development of experimental approaches towards fine structure characterization. Full article
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18 pages, 7064 KiB  
Review
Twin Domains in Organometallic Halide Perovskite Thin-Films
by Wei Liu, Yang Liu, Ju Wang, Cuncun Wu, Congyue Liu, Lixin Xiao, Zhijian Chen, Shufeng Wang and Qihuang Gong
Crystals 2018, 8(5), 216; https://doi.org/10.3390/cryst8050216 - 16 May 2018
Cited by 18 | Viewed by 8110
Abstract
The perovskite is a class of material with crystalline structure similar to CaTiO3. In recent years, the organic-inorganic hybrid metallic halide perovskite has been widely investigated as a promising material for a new generation photovoltaic device, whose power conversion efficiency (PCE) [...] Read more.
The perovskite is a class of material with crystalline structure similar to CaTiO3. In recent years, the organic-inorganic hybrid metallic halide perovskite has been widely investigated as a promising material for a new generation photovoltaic device, whose power conversion efficiency (PCE) record reaches 22.7%. One of its underlying morphological characteristics is the twin domain within those sub-micron sized crystal grains in perovskite thin films. This is important for discussion since it could be the key for understanding the fundamental mechanism of the device’s high performance, such as long diffusion distance and low recombination rate. This review aims to summarize studies on twin domains in perovskite thin films, in order to figure out its importance, guide the current studies on mechanism, and design new devices. Firstly, we introduce the research history and characteristics of widely known twin domains in inorganic perovskite BaTiO3. We then focus on the impact of the domain structure emerging in hybrid metallic halide perovskite thin films, including the observation and discussion on ferroelectricity/ferroelasity. The theoretical analysis is also presented in this review. Finally, we present a spectroscopic method, which can reveal the generality of twin domains within perovskite thin films. We anticipate that this summary on the structural and physical properties of organometallic halide perovskite will help to understand and improve the high-performance of photovoltaic devices. Full article
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25 pages, 9371 KiB  
Review
Growth of Metal Halide Perovskite, from Nanocrystal to Micron-Scale Crystal: A Review
by Haijiao Harsan Ma, Muhammad Imran, Zhiya Dang and Zhaosheng Hu
Crystals 2018, 8(5), 182; https://doi.org/10.3390/cryst8050182 - 24 Apr 2018
Cited by 25 | Viewed by 16049
Abstract
Metal halide perovskite both in the form of nanocrystal and thin films recently emerged as the most promising semiconductor material covering a huge range of potential applications from display technologies to photovoltaics. Colloidal inorganic and organic–inorganic hybrid metal halide perovskite nanocrystals (NCs) have [...] Read more.
Metal halide perovskite both in the form of nanocrystal and thin films recently emerged as the most promising semiconductor material covering a huge range of potential applications from display technologies to photovoltaics. Colloidal inorganic and organic–inorganic hybrid metal halide perovskite nanocrystals (NCs) have received tremendous attention due to their high photoluminescence quantum yields, while large grain perovskite films possess fewer defects, and a long diffusion length providing high-power conversion efficiency in planar devices. In this review, we summarize the different synthesis routes of metal halide perovskite nanocrystals and the recent methodologies to fabricate high-quality micron scale crystals in the form of films for planar photovoltaics. For the colloidal synthesis of halide perovskite NCs, two methods including ligand-assisted reprecipitation and hot injection are mainly applied, and the doping of metal ions in NCs as well as anion exchange reactions are widely used to tune their optical properties. In addition, recent growth methods and underlying mechanism for high-quality micron size crystals are also investigated, which are summarized as solution-process methods (including the anti-solvent method, solvent vapor annealing technology, Ostwald ripening, additive engineering and geometrically-confined lateral crystal growth) and the physical method (vapor-assisted crystal growth). Full article
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4760 KiB  
Review
Anti-Solvent Crystallization Strategies for Highly Efficient Perovskite Solar Cells
by Maria Konstantakou, Dorothea Perganti, Polycarpos Falaras and Thomas Stergiopoulos
Crystals 2017, 7(10), 291; https://doi.org/10.3390/cryst7100291 - 28 Sep 2017
Cited by 156 | Viewed by 29982
Abstract
Solution-processed organic-inorganic halide perovskites are currently established as the hottest area of interest in the world of photovoltaics, ensuring low manufacturing cost and high conversion efficiencies. Even though various fabrication/deposition approaches and device architectures have been tested, researchers quickly realized that the key [...] Read more.
Solution-processed organic-inorganic halide perovskites are currently established as the hottest area of interest in the world of photovoltaics, ensuring low manufacturing cost and high conversion efficiencies. Even though various fabrication/deposition approaches and device architectures have been tested, researchers quickly realized that the key for the excellent solar cell operation was the quality of the crystallization of the perovskite film, employed to assure efficient photogeneration of carriers, charge separation and transport of the separated carriers at the contacts. One of the most typical methods in chemistry to crystallize a material is anti-solvent precipitation. Indeed, this classical precipitation method worked really well for the growth of single crystals of perovskite. Fortunately, the method was also effective for the preparation of perovskite films by adopting an anti-solvent dripping technique during spin-coating the perovskite precursor solution on the substrate. With this, polycrystalline perovskite films with pure and stable crystal phases accompanied with excellent surface coverage were prepared, leading to highly reproducible efficiencies close to 22%. In this review, we discuss recent results on highly efficient solar cells, obtained by the anti-solvent dripping method, always in the presence of Lewis base adducts of lead(II) iodide. We present all the anti-solvents that can be used and what is the impact of them on device efficiencies. Finally, we analyze the critical challenges that currently limit the efficacy/reproducibility of this crystallization method and propose prospects for future directions. Full article
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