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Keywords = organic–inorganic hybrid perovskite nanocrystals

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13 pages, 2644 KiB  
Article
Synergistic Halide- and Ligand-Exchanges of All-Inorganic Perovskite Nanocrystals for Near-Unity and Spectrally Stable Red Emission
by Kaiwang Chen, Dengliang Zhang, Qing Du, Wei Hong, Yue Liang, Xingxing Duan, Shangwei Feng, Linfeng Lan, Lei Wang, Jiangshan Chen and Dongge Ma
Nanomaterials 2023, 13(16), 2337; https://doi.org/10.3390/nano13162337 - 14 Aug 2023
Cited by 7 | Viewed by 2085
Abstract
All-inorganic perovskite nanocrystals (NCs) of CsPbX3 (X = Cl, Br, I) are promising for displays due to wide color gamut, narrow emission bandwidth, and high photoluminescence quantum yield (PLQY). However, pure red perovskite NCs prepared by mixing halide ions often result in [...] Read more.
All-inorganic perovskite nanocrystals (NCs) of CsPbX3 (X = Cl, Br, I) are promising for displays due to wide color gamut, narrow emission bandwidth, and high photoluminescence quantum yield (PLQY). However, pure red perovskite NCs prepared by mixing halide ions often result in defects and spectral instabilities. We demonstrate a method to prepare stable pure red emission and high-PLQY-mixed-halide perovskite NCs through simultaneous halide-exchange and ligand-exchange. CsPbBr3 NCs with surface organic ligands are first synthesized using the ligand-assisted reprecipitation (LARP) method, and then ZnI2 is introduced for anion exchange to transform CsPbBr3 to CsPbBrxI3−x NCs. ZnI2 not only provides iodine ions but also acts as an inorganic ligand to passivate surface defects and prevent ion migration, suppressing non-radiative losses and halide segregation. The luminescence properties of CsPbBrxI3−x NCs depend on the ZnI2 content. By regulating the ZnI2 exchange process, red CsPbBrxI3−x NCs with organic/inorganic hybrid ligands achieve near-unity PLQY with a stable emission peak at 640 nm. The CsPbBrxI3−x NCs can be combined with green CsPbBr3 NCs to construct white light-emitting diodes with high-color gamut. Our work presents a facile ion exchange strategy for preparing spectrally stable mixed-halide perovskite NCs with high PLQY, approaching the efficiency limit for display or lighting applications. Full article
(This article belongs to the Section Nanocomposite Materials)
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14 pages, 15273 KiB  
Article
Hybrid Organic–Inorganic Perovskite Superstructures for Ultrapure Green Emissions
by Wen Kiat Chan, Jiawei Chen, Donglei Zhou, Junzhi Ye, Ricardo Javier Vázquez, Cheng Zhou, Guillermo Carlos Bazan, Akshay Rao, Zhongzheng Yu and Timothy Thatt Yang Tan
Nanomaterials 2023, 13(5), 815; https://doi.org/10.3390/nano13050815 - 22 Feb 2023
Cited by 9 | Viewed by 2872
Abstract
All inorganic CsPbBr3 superstructures (SSs) have attracted much research interest due to their unique photophysical properties, such as their large emission red-shifts and super-radiant burst emissions. These properties are of particular interest in displays, lasers and photodetectors. Currently, the best-performing perovskite optoelectronic [...] Read more.
All inorganic CsPbBr3 superstructures (SSs) have attracted much research interest due to their unique photophysical properties, such as their large emission red-shifts and super-radiant burst emissions. These properties are of particular interest in displays, lasers and photodetectors. Currently, the best-performing perovskite optoelectronic devices incorporate organic cations (methylammonium (MA), formamidinium (FA)), however, hybrid organic–inorganic perovskite SSs have not yet been investigated. This work is the first to report on the synthesis and photophysical characterization of APbBr3 (A = MA, FA, Cs) perovskite SSs using a facile ligand-assisted reprecipitation method. At higher concentrations, the hybrid organic–inorganic MA/FAPbBr3 nanocrystals self-assemble into SSs and produce red-shifted ultrapure green emissions, meeting the requirement of Rec. 2020 displays. We hope that this work will be seminal in advancing the exploration of perovskite SSs using mixed cation groups to further improve their optoelectronic applications. Full article
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17 pages, 4228 KiB  
Article
Lead-Free MDABCO-NH4I3 Perovskite Crystals Embedded in Electrospun Nanofibers
by Rosa M. F. Baptista, Gonçalo Moreira, Bruna Silva, João Oliveira, Bernardo Almeida, Cidália Castro, Pedro V. Rodrigues, Ana Machado, Michael Belsley and Etelvina de Matos Gomes
Materials 2022, 15(23), 8397; https://doi.org/10.3390/ma15238397 - 25 Nov 2022
Cited by 10 | Viewed by 2954
Abstract
In this work, we introduce lead-free organic ferroelectric perovskite N-methyl-N′-diazabicyclo[2.2.2]octonium)–ammonium triiodide (MDABCO-NH4I3) nanocrystals embedded in three different polymer fibers fabricated by the electrospinning technique, as mechanical energy harvesters. Molecular ferroelectrics offer the advantage of structural diversity and tunability, easy [...] Read more.
In this work, we introduce lead-free organic ferroelectric perovskite N-methyl-N′-diazabicyclo[2.2.2]octonium)–ammonium triiodide (MDABCO-NH4I3) nanocrystals embedded in three different polymer fibers fabricated by the electrospinning technique, as mechanical energy harvesters. Molecular ferroelectrics offer the advantage of structural diversity and tunability, easy fabrication, and mechanical flexibility. Organic–inorganic hybrid materials are new low-symmetry emerging materials that may be used as energy harvesters because of their piezoelectric or ferroelectric properties. Among these, ferroelectric metal-free perovskites are a class of recently discovered multifunctional materials. The doped nanofibers, which are very flexible and have a high Young modulus, behave as active piezoelectric energy harvesting sources that produce a piezoelectric voltage coefficient up to geff = 3.6 VmN−1 and show a blue intense luminescence band at 325 nm. In this work, the pyroelectric coefficient is reported for the MDABCO-NH4I3 perovskite inserted in electrospun fibers. At the ferroelectric–paraelectric phase transition, the embedded nanocrystals display a pyroelectric coefficient as high as 194 × 10−6 Cm−2k−1, within the same order of magnitude as that reported for the state-of-the-art bulk ferroelectric triglycine sulfate (TGS). The perovskite nanocrystals embedded into the polymer fibers remain stable in their piezoelectric output response, and no degradation is caused by oxidation, making the piezoelectric perovskite nanofibers suitable to be used as flexible energy harvesters. Full article
(This article belongs to the Special Issue Advanced Polymeric Materials: Synthesis, Properties, and Applications)
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14 pages, 2787 KiB  
Article
High Piezoelectric Output Voltage from Blue Fluorescent N,N-Dimethyl-4-nitroaniline Nano Crystals in Poly-L-Lactic Acid Electrospun Fibers
by Rosa M. F. Baptista, Bruna Silva, João Oliveira, Vahideh B. Isfahani, Bernardo Almeida, Mário R. Pereira, Nuno Cerca, Cidália Castro, Pedro V. Rodrigues, Ana Machado, Michael Belsley and Etelvina de Matos Gomes
Materials 2022, 15(22), 7958; https://doi.org/10.3390/ma15227958 - 10 Nov 2022
Cited by 4 | Viewed by 3010
Abstract
N,N-dimethyl-4-nitroaniline is a piezoelectric organic superplastic and superelastic charge transfer molecular crystal that crystallizes in an acentric structure. Organic mechanical flexible crystals are of great importance as they stand between soft matter and inorganic crystals. Highly aligned poly-l-lactic acid polymer [...] Read more.
N,N-dimethyl-4-nitroaniline is a piezoelectric organic superplastic and superelastic charge transfer molecular crystal that crystallizes in an acentric structure. Organic mechanical flexible crystals are of great importance as they stand between soft matter and inorganic crystals. Highly aligned poly-l-lactic acid polymer microfibers with embedded N,N-dimethyl-4-nitroaniline nanocrystals are fabricated using the electrospinning technique, and their piezoelectric and optical properties are explored as hybrid systems. The composite fibers display an extraordinarily high piezoelectric output response, where for a small stress of 5.0 × 103 Nm−2, an effective piezoelectric voltage coefficient of geff = 4.1 VmN−1 is obtained, which is one of the highest among piezoelectric polymers and organic lead perovskites. Mechanically, they exhibit an average increase of 67% in the Young modulus compared to polymer microfibers alone, reaching 55 MPa, while the tensile strength reaches 2.8 MPa. Furthermore, the fibers show solid-state blue fluorescence, important for emission applications, with a long lifetime decay (147 ns) lifetime decay. The present results show that nanocrystals from small organic molecules with luminescent, elastic and piezoelectric properties form a mechanically strong hybrid functional 2-dimensional array, promising for applications in energy harvesting through the piezoelectric effect and as solid-state blue emitters. Full article
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28 pages, 3584 KiB  
Review
Cesium Lead Iodide Perovskites: Optically Active Crystal Phase Stability to Surface Engineering
by Yixi Wang, Hairong Zhao, Marek Piotrowski, Xiao Han, Zhongsheng Ge, Lizhuang Dong, Chengjie Wang, Sowjanya Krishna Pinisetty, Praveen Kumar Balguri, Anil Kumar Bandela and Udayabhaskararao Thumu
Micromachines 2022, 13(8), 1318; https://doi.org/10.3390/mi13081318 - 15 Aug 2022
Cited by 17 | Viewed by 5582
Abstract
Among perovskites, the research on cesium lead iodides (CsPbI3) has attracted a large research community, owing to their all-inorganic nature and promising solar cell performance. Typically, the CsPbI3 solar cell devices are prepared at various heterojunctions, and working at fluctuating [...] Read more.
Among perovskites, the research on cesium lead iodides (CsPbI3) has attracted a large research community, owing to their all-inorganic nature and promising solar cell performance. Typically, the CsPbI3 solar cell devices are prepared at various heterojunctions, and working at fluctuating temperatures raises questions on the material stability-related performance of such devices. The fundamental studies reveal that their poor stability is due to a lower side deviation from Goldschmidt’s tolerance factor, causing weak chemical interactions within the crystal lattice. In the case of organic–inorganic hybrid perovskites, where their stability is related to the inherent chemical nature of the organic cations, which cannot be manipulated to improve the stability drastically whereas the stability of CsPbI3 is related to surface and lattice engineering. Thus, the challenges posed by CsPbI3 could be overcome by engineering the surface and inside the CsPbI3 crystal lattice. A few solutions have been proposed, including controlled crystal sizes, surface modifications, and lattice engineering. Various research groups have been working on these aspects and had accumulated a rich understanding of these materials. In this review, at first, we survey the fundamental aspects of CsPbI3 polymorphs structure, highlighting the superiority of CsPbI3 over other halide systems, stability, the factors (temperature, polarity, and size influence) leading to their phase transformations, and electronic band structure along with the important property of the defect tolerance nature. Fortunately, the factors stabilizing the most effective phases are achieved through a size reduction and the efficient surface passivation on the delicate CsPbI3 nanocrystal surfaces. In the following section, we have provided the up-to-date surface passivating methods to suppress the non-radiative process for near-unity photoluminescence quantum yield, while maintaining their optically active phases, especially through molecular links (ligands, polymers, zwitterions, polymers) and inorganic halides. We have also provided recent advances to the efficient synthetic protocols for optically active CsPbI3 NC phases to use readily for solar cell applications. The nanocrystal purification techniques are challenging and had a significant effect on the device performances. In part, we summarized the CsPbI3-related solar cell device performances with respect to the device fabrication methods. At the end, we provide a brief outlook on the view of surface and lattice engineering in CsPbI3 NCs for advancing the enhanced stability which is crucial for superior optical and light applications. Full article
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15 pages, 2506 KiB  
Article
Hybrid Perovskite/Polymer Materials: Preparation and Physicochemical Properties
by Martha Kafetzi, Stergios Pispas and George Mousdis
J. Compos. Sci. 2021, 5(11), 304; https://doi.org/10.3390/jcs5110304 - 19 Nov 2021
Cited by 4 | Viewed by 2918
Abstract
The aim of this work is to investigate the preparation, the optical properties, and the stability over time of a colloidal organic–inorganic hybrid perovskite (CH3NH3PbBr3)/random copolymer P(MMA-co-DMAEMA) system. Different ratios of perovskite to copolymer were used to [...] Read more.
The aim of this work is to investigate the preparation, the optical properties, and the stability over time of a colloidal organic–inorganic hybrid perovskite (CH3NH3PbBr3)/random copolymer P(MMA-co-DMAEMA) system. Different ratios of perovskite to copolymer were used to study its effect on stability and properties. The optical properties were investigated by UV-Vis and fluorescence spectroscopy. Dynamic light scattering was used to determine the size, and the size polydispersity of the colloidal hybrid particles; while morphology was investigated by transmission electron microscopy. Photoluminescence decay studies revealed the interaction of the random copolymer with the perovskite. Finally, thin-films were prepared, to investigate the optical properties of the samples in the absence of the solvent. High temporal stability of the optical properties of thin hybrid films was observed under certain conditions. Full article
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19 pages, 2331 KiB  
Review
The Contribution of NMR Spectroscopy in Understanding Perovskite Stabilization Phenomena
by Federica Aiello and Sofia Masi
Nanomaterials 2021, 11(8), 2024; https://doi.org/10.3390/nano11082024 - 8 Aug 2021
Cited by 15 | Viewed by 8472
Abstract
Although it has been exploited since the late 1900s to study hybrid perovskite materials, nuclear magnetic resonance (NMR) spectroscopy has only recently received extraordinary research attention in this field. This very powerful technique allows the study of the physico-chemical and structural properties of [...] Read more.
Although it has been exploited since the late 1900s to study hybrid perovskite materials, nuclear magnetic resonance (NMR) spectroscopy has only recently received extraordinary research attention in this field. This very powerful technique allows the study of the physico-chemical and structural properties of molecules by observing the quantum mechanical magnetic properties of an atomic nucleus, in solution as well as in solid state. Its versatility makes it a promising technique either for the atomic and molecular characterization of perovskite precursors in colloidal solution or for the study of the geometry and phase transitions of the obtained perovskite crystals, commonly used as a reference material compared with thin films prepared for applications in optoelectronic devices. This review will explore beyond the current focus on the stability of perovskites (3D in bulk and nanocrystals) investigated via NMR spectroscopy, in order to highlight the chemical flexibility of perovskites and the role of interactions for thermodynamic and moisture stabilization. The exceptional potential of the vast NMR tool set in perovskite structural characterization will be discussed, aimed at choosing the most stable material for optoelectronic applications. The concept of a double-sided characterization in solution and in solid state, in which the organic and inorganic structural components provide unique interactions with each other and with the external components (solvents, additives, etc.), for material solutions processed in thin films, denotes a significant contemporary target. Full article
(This article belongs to the Special Issue Stable Perovskite Materials: From Synthesis to Optoelectronic Devices)
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11 pages, 2069 KiB  
Article
Facile Synthesis of Methylammonium Lead Iodide Perovskite with Controllable Morphologies with Enhanced Luminescence Performance
by Tao Wang, Huafang Zhang, Sumin Hou, Yan Zhang, Quanjun Li, Zhenlong Zhang, Huiping Gao and Yanli Mao
Nanomaterials 2019, 9(12), 1660; https://doi.org/10.3390/nano9121660 - 21 Nov 2019
Cited by 16 | Viewed by 6162
Abstract
Organic–inorganic hybrid perovskites with well-defined morphology have attracted much attention due to their unique photophysical properties. However, controlling the morphology of nanocrystalline perovskite to improve its photoelectric application remains a challenge. In this article, using a modified solution deposition method, we successfully synthesized [...] Read more.
Organic–inorganic hybrid perovskites with well-defined morphology have attracted much attention due to their unique photophysical properties. However, controlling the morphology of nanocrystalline perovskite to improve its photoelectric application remains a challenge. In this article, using a modified solution deposition method, we successfully synthesized uniform methylammonium lead iodide (MAPbI3) nanoplates, nanocubes, and nanorods and investigated the effect of morphology on the photoelectric properties of these materials. We found that the morphology can be controlled by regulating the amounts of reactant methylammonium iodide (MAI) and the rate at which MAPbI3 precursor is added into toluene solution, and that the corresponding size distributions can be optimized by tuning the final vacuum-drying temperature. The morphology has an obvious effect on the bandgap optimization and fluorescence enhancement of MAPbI3, and the nanoplates exhibit stronger photoluminescence intensity and have a longer carrier lifetime than nanocubes and nanorods. The results show that the morphologies of MAPbI3 perovskite nanocrystals can be controlled by tuning the synthesizing conditions, and the MAPbI3 perovskite nanocrystals with special morphology can be used in special nanosize optoelectronic devices. Full article
(This article belongs to the Special Issue Synthesis and Applications of Nanomaterials Based on Perovskites)
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28 pages, 7971 KiB  
Review
Nanostructured Perovskite Solar Cells
by Calum McDonald, Chengsheng Ni, Paul Maguire, Paul Connor, John T. S. Irvine, Davide Mariotti and Vladimir Svrcek
Nanomaterials 2019, 9(10), 1481; https://doi.org/10.3390/nano9101481 - 18 Oct 2019
Cited by 24 | Viewed by 12678
Abstract
Over the past decade, lead halide perovskites have emerged as one of the leading photovoltaic materials due to their long carrier lifetimes, high absorption coefficients, high tolerance to defects, and facile processing methods. With a bandgap of ~1.6 eV, lead halide perovskite solar [...] Read more.
Over the past decade, lead halide perovskites have emerged as one of the leading photovoltaic materials due to their long carrier lifetimes, high absorption coefficients, high tolerance to defects, and facile processing methods. With a bandgap of ~1.6 eV, lead halide perovskite solar cells have achieved power conversion efficiencies in excess of 25%. Despite this, poor material stability along with lead contamination remains a significant barrier to commercialization. Recently, low-dimensional perovskites, where at least one of the structural dimensions is measured on the nanoscale, have demonstrated significantly higher stabilities, and although their power conversion efficiencies are slightly lower, these materials also open up the possibility of quantum-confinement effects such as carrier multiplication. Furthermore, both bulk perovskites and low-dimensional perovskites have been demonstrated to form hybrids with silicon nanocrystals, where numerous device architectures can be exploited to improve efficiency. In this review, we provide an overview of perovskite solar cells, and report the current progress in nanoscale perovskites, such as low-dimensional perovskites, perovskite quantum dots, and perovskite-nanocrystal hybrid solar cells. Full article
(This article belongs to the Special Issue Advances in Emerging Solar Cells)
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12 pages, 2383 KiB  
Article
Stability of Hybrid Organic-Inorganic Perovskite CH3NH3PbBr3 Nanocrystals under Co-Stresses of UV Light Illumination and Temperature
by Weijie Guo, Nan Chen, Binbin Xu, Yijun Lu, Bin Li, Tingzhu Wu, Qijin Cheng, Yang Li, Jin Chen, Yue Lin and Zhong Chen
Nanomaterials 2019, 9(8), 1158; https://doi.org/10.3390/nano9081158 - 13 Aug 2019
Cited by 10 | Viewed by 5166
Abstract
Hybrid organic–inorganic metal halide perovskite nanocrystals (NCs) are among the candidates for color conversion materials in displays, especially in NC-based micro-light-emitting diode (micro-LED) displays. However, these NCs are still lacking long-term stability, which has hindered their large-scale applications. We mimic the working conditions, [...] Read more.
Hybrid organic–inorganic metal halide perovskite nanocrystals (NCs) are among the candidates for color conversion materials in displays, especially in NC-based micro-light-emitting diode (micro-LED) displays. However, these NCs are still lacking long-term stability, which has hindered their large-scale applications. We mimic the working conditions, which include ultraviolet light illumination at 323 K and three different types of atmosphere (N2, vacuum, and air), respectively, to investigate the stability of CH3NH3PbBr3 NCs embedded in the polyvinylidene fluoride matrix. X-ray diffraction results indicate the generation of NH4Pb2Br5, which is produced from the encapsulated CH3NH3PbBr3 NCs in all three atmospheres, and the decomposition generates a large amount of accompanying interface defects at the surface area of NCs, resulting in the significant decrease of the photoluminescence (PL) intensity. This work highlights the stability-related mechanism of CH3NH3PbBr3 NCs under combined external stresses that mimic operating conditions. In addition, this work also suggests a new method for conducting aging tests and contributes to developing effective routes towards higher stability of perovskite NCs. 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 26 | Viewed by 17204
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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