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

A special issue of Crystals (ISSN 2073-4352).

Deadline for manuscript submissions: closed (31 March 2018)

Special Issue Editor

Guest Editor
Dr. Wei Zhang

Advanced Technology Institute (ATI), University of Surrey, Guildford, Surrey, GU2 7XH, UK
Website | E-Mail
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

Manuscript Submission Information

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Keywords

  • Metal halide perovskites

  • Single crystals, nanocrystals, nanowires, nanorods

  • Semiconductors

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

Published Papers (9 papers)

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Research

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Open AccessArticle Effects of Iodine Doping on Carrier Behavior at the Interface of Perovskite Crystals: Efficiency and Stability
Crystals 2018, 8(5), 185; doi:10.3390/cryst8050185
Received: 22 March 2018 / Revised: 21 April 2018 / Accepted: 21 April 2018 / Published: 25 April 2018
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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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Open AccessArticle Enhancing Optically Pumped Organic-Inorganic Hybrid Perovskite Amplified Spontaneous Emission via Compound Surface Plasmon Resonance
Crystals 2018, 8(3), 124; doi:10.3390/cryst8030124
Received: 31 January 2018 / Revised: 23 February 2018 / Accepted: 1 March 2018 / Published: 7 March 2018
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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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Open AccessArticle A Feasible and Effective Post-Treatment Method for High-Quality CH3NH3PbI3 Films and High-Efficiency Perovskite Solar Cells
Crystals 2018, 8(1), 44; doi:10.3390/cryst8010044
Received: 14 December 2017 / Revised: 13 January 2018 / Accepted: 13 January 2018 / Published: 18 January 2018
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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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Open AccessArticle Improved Stability and Photoluminescence Yield of Mn2+-Doped CH3NH3PbCl3 Perovskite Nanocrystals
Crystals 2018, 8(1), 4; doi:10.3390/cryst8010004
Received: 21 November 2017 / Revised: 18 December 2017 / Accepted: 20 December 2017 / Published: 23 December 2017
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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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Open AccessArticle Atomic Characterization of Byproduct Nanoparticles on Cesium Lead Halide Nanocrystals Using High-Resolution Scanning Transmission Electron Microscopy
Crystals 2018, 8(1), 2; doi:10.3390/cryst8010002
Received: 23 November 2017 / Revised: 20 December 2017 / Accepted: 20 December 2017 / Published: 22 December 2017
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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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Open AccessArticle CH3NH3Cl Assisted Solvent Engineering for Highly Crystallized and Large Grain Size Mixed-Composition (FAPbI3)0.85(MAPbBr3)0.15 Perovskites
Crystals 2017, 7(9), 272; doi:10.3390/cryst7090272
Received: 17 July 2017 / Revised: 1 September 2017 / Accepted: 2 September 2017 / Published: 5 September 2017
Cited by 2 | PDF Full-text (3993 KB) | HTML Full-text | XML Full-text
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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Open AccessArticle Interfacial Kinetics of Efficient Perovskite Solar Cells
Crystals 2017, 7(8), 252; doi:10.3390/cryst7080252
Received: 9 June 2017 / Revised: 30 July 2017 / Accepted: 3 August 2017 / Published: 13 August 2017
Cited by 1 | PDF Full-text (2386 KB) | HTML Full-text | XML Full-text | Supplementary Files
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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Open AccessReview Growth of Metal Halide Perovskite, from Nanocrystal to Micron-Scale Crystal: A Review
Crystals 2018, 8(5), 182; doi:10.3390/cryst8050182
Received: 27 March 2018 / Revised: 17 April 2018 / Accepted: 17 April 2018 / Published: 24 April 2018
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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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Open AccessReview Anti-Solvent Crystallization Strategies for Highly Efficient Perovskite Solar Cells
Crystals 2017, 7(10), 291; doi:10.3390/cryst7100291
Received: 3 September 2017 / Revised: 25 September 2017 / Accepted: 26 September 2017 / Published: 28 September 2017
Cited by 3 | PDF Full-text (4760 KB) | HTML Full-text | XML Full-text
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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