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Defects in metal triiodide perovskite materials towards high-performance solar cells: Origin, impact, characterization, and engineering

The rapid development of solar cells (SCs) based on organic-inorganic hybrid metal triiodide perovskite (MTP) materials holds great promise for next-generation photovoltaic devices. The demonstrated power conversion efficiency of the SCs based on MTP (PSCs for short) has reached over 20%. An MTP material is a kind of soft ionic solid semiconductor. The intrinsic optoelectronic properties of MTP are greatly determined by several factors, such as the crystalline phase, doping type, impurities, elemental composition, and defects in its crystal structure. In the development of PSCs, a good understanding and smart engineering of the defects in MTP have been demonstrated to be a key factor for the fabrication of high-efficiency PSCs. In this review, we start with a brief introduction to the types of defects and the mechanisms for their formation in MTP. Then, the positive and negative impacts of defects on the important optoelectronic features of MTP are presented. The optoelectronic properties mainly include charge recombination, charge transport, ion migration, and structural stability. Moreover, commonly used techniques for the characterization of the defects in MTP are systematically summarized. Recent progress on the state-of-the-art defect engineering approaches for the optimization of PSC devices is also summarized, and we also provide some perspectives on the development of high-efficiency PSCs with long-term stability through the optimization of the defects in MTP.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Thermal studies of new Cu(I) and Ag(I) complexes with bipyridine isomers

The complexes of the general formula MLSCN (M=Cu(I), Ag(I), L=2,2′-bipyridine=2-bipy, 4,4′-bipyridine=4-bipy or 2,4′-bipyridine=2,4’bipy) have been prepared and their IR spectra examined. The nature of metal-ligand coordination is discussed. Thermal decomposition in air of these complexes occurred in several successive endothermic and exothermic processes and the residue was Cu2O and Ag, respectively.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Aromatic Thiocyanation using Supported Copper(I) Thiocyanate

Charcoal Supported copper(I) thiocyanate can be used to convert bromo- and iodo-benzenes into phenyl thiocyanates with no contamination from phenyl isothiocyanates.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Effect of metal oxidation state on FRET: A Cu(i) silent but selectively Cu(ii) responsive fluorescent reporter and its bioimaging applications

Copper(ii) and copper(i) complexes of a newly designed and crystallographically characterized Schiff base (HL) derived from rhodamine hydrazide and cinnamaldehyde were isolated in pure form formulated as [Cu(L)(NO3)] (L-Cu) (1) and [Cu(HL)(CH3CN)(H2O)]ClO4 (HL-Cu) (2), and characterized by physicochemical and spectroscopic tools. Interestingly, complex 1 but not 2 offers red fluorescence in solution state, and eventually HL behaves as a Cu(ii) ions selective FRET based fluorosensor in HEPES buffer (1 mM, acetonitrile-water: 1/5, v/v) at 25 C at biological pH with almost no interference of other competitive ions. The dependency of the FRET process on the +2 oxidation state of copper has been nicely supported by exhaustive experimental studies comprising electronic, fluorimetric, NMR titration, and theoretical calculations. The sensing ability of HL has been evaluated by the LOD value towards Cu(ii) ions (83.7 nM) and short responsive time (5-10 s). Even the discrimination of copper(i) and copper(ii) has also been done using only UV-Vis spectroscopic study. The efficacy of this bio-friendly probe has been determined by employing HL to detect the intercellular distribution of Cu(ii) ions in HeLa cells by developing image under fluorescence microscope. This journal is

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Final Thoughts on Chemistry for Cuprous thiocyanate

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Surface properties of lead-free halide double perovskites: Possible visible-light photo-catalysts for water splitting

Halide double perovskites based on combinations of monovalent and trivalent cations have been proposed as promising lead-free alternatives to lead halide perovskites. Among the newly synthesized compounds Cs2BiAgCl6, Cs2BiAgBr6, Cs2SbAgCl6, and Cs2InAgCl6, some exhibit bandgaps in the visible range and all have low carrier effective masses; therefore, these materials constitute potential candidates for various opto-electronic applications. Here, we use first-principles calculations to investigate the electronic properties of the surfaces of these four compounds and determine, for the first time, their ionization potential and electron affinity. We find that the double perovskites Cs2BiAgCl6 and Cs2BiAgBr6 are potentially promising materials for photo-catalytic water splitting, while Cs2InAgCl6 and Cs2SbAgCl6 would require controlling their surface termination to obtain energy levels appropriate for water splitting. The energy of the halogen p orbitals is found to control the conduction band level; therefore, we propose that mixed halides could be used to fine-tune the electronic affinity.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Top Picks: new discover of Cuprous thiocyanate

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Planar perovskite solar cells employing copper(I) thiocyanate/N,N?-di(1-naphthyl)-N,N?-diphenyl-(1,1?-biphenyl)-4,4?-diamine bilayer structure as hole transport layers

Organic hole transport materials, such as N 2,N 2,N 2?,N 2?,N 7,N 7,N 7?,N 7?-octakis(4-methoxyphenyl)-9,9?-spirobi[9H-fluorene]-2,2?,7,7?-tetramine (Spiro-OMeTAD), are commonly used as the hole transport materials in efficient perovskite solar cells, but the chemical synthetic procedure may increase the cost of the photovoltaic devices. On the other hand, inorganic hole transport materials, such as copper(I) thiocyanate (CuSCN) or copper(I) iodide (CuI), have potential for the manufacture of efficient and low-cost perovskite solar cells, but the performance of these devices is still imperfect. In this study, we demonstrate the use of an inorganic CuSCN and organic N,N?-di(1-naphthyl)-N,N?-diphenyl-(1,1?-biphenyl)-4,4?-diamine (NPB) hybrid bilayer as an alternative hole transport layer for planar CH3NH3PbI3 perovskite solar cells. The electronic behavior of the bilayer and the performance of the corresponding devices were discussed. As a result, the power conversion efficiency (PCE) for the best cells at AM1.5G illumination with a shadow mask was 12.3%.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Formation of a disorderd hetero-junction by diffusion of CuI from CuSCN into In2S3 layers: A surface photovoltage study

Charge-selective disordered hetero-junctions were formed in evaporated In2S3 layers by diffusing at 200 C CuI from a CuSCN source. The thicknesses of In2S3 layers and diffusion times were varied between 5 and 80 nm and between 2 and 19 min, respectively. In some cases CuSCN layers were etched back with pyridine. Spectral and time-dependent surface photovoltage measurements were carried out in the capacitor arrangement. It was observed that a competing process of charge separation and relaxation was initiated together with the formation of the charge-selective In2S3/In2S3:Cu hetero-junction. Modulated SPV amplitude for different annealing times and thicknesses of the evaporated In2S3 layers. Copyright

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Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Understanding of perovskite crystal growth and film formation in scalable deposition processes

Hybrid organic-inorganic perovskite photovoltaics (PSCs) have attracted significant attention during the past decade. Despite the stellar rise of laboratory-scale PSC devices, which have reached a certified efficiency over 25% to date, there is still a large efficiency gap when transiting from small-area devices to large-area solar modules. Efficiency losses would inevitably arise from the great challenges of homogeneous coating of large-area high quality perovskite films. To address this problem, we provide an in-depth understanding of the perovskite nucleation and crystal growth kinetics, including the LaMer and Ostwald ripening models, which advises us that fast nucleation and slow crystallization are essential factors in forming high-quality perovskite films. Based on these cognitions, a variety of thin film engineering approaches will be introduced, including the anti-solvent, gas-assisted and solvent annealing treatments, Lewis acid-base adduct incorporation, etc., which are able to regulate the nucleation and crystallization steps. Upscaling the photovoltaic devices is the following step. We summarize the currently developed scalable deposition technologies, including spray coating, slot-die coating, doctor blading, inkjet printing and vapour-assisted deposition. These are more appealing approaches for scalable fabrication of perovskite films than the spin coating method, in terms of lower material/solution waste, more homogeneous thin film coating over a large area, and better morphological control of the film. The working principles of these techniques will be provided, which direct us that the physical properties of the precursor solutions and surface characteristics/temperature of the substrate are both dominating factors influencing the film morphology. Optimization of the perovskite crystallization and film formation process will be subsequently summarized from these aspects. Additionally, we also highlight the significance of perovskite stability, as it is the last puzzle to realize the practical applications of PSCs. Recent efforts towards improving the stability of PSC devices to environmental factors are discussed in this part. In general, this review, comprising the mechanistic analysis of perovskite film formation, thin film engineering, scalable deposition technologies and device stability, provides a comprehensive overview of the current challenges and opportunities in the field of PSCs, aiming to promote the future development of cost-effective up-scale fabrication of highly efficient and ultra-stable PSCs for practical applications.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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CYCLIC CARBOXYLIC ACID COMPOUND AND USE THEREOF

[Means to solve problem] A novel cyclic carboxylic acid formed by the addition reaction of an unsaturated carboxylic acid with a conjugated diene compound and a metal salt thereof are disclosed. A compounding agent (A) for an antifouling paint comprising one or more substances selected from the novel cyclic carboxylic acid, a derivative of the cyclic carboxylic acid (except a metal salt), a metal salt of the cyclic carboxylic acid and a metal salt of a derivative of the cyclic carboxylic acid, and an antifouling paint composition comprising the compounding agent (A) and a copolymer (B) for a self-polishing type antifouling paint are also disclosed. [Effect] The antifouling paint composition can form an antifouling coating film which is a small burden to the environment, is uniformly eroded at a given rate, is capable of maintaining excellent antifouling performance for a long period of time and is applicable to ships or the like used in the highly fouling sea area.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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High-Performance Inverted Perovskite Solar Cells Using Doped Poly(triarylamine) as the Hole Transport Layer

Organolead trihalide perovskite materials have attracted considerable interest because of their successful application in fabricating high-efficiency photovoltaic cells. Charge transport layers play a significant role in improving the efficiency and stability of perovskite solar cells (PSCs). In this work, we investigated the p-type doping effect of the poly(triarylamine) (PTAA) layer on the performance of PSCs by using three dopants. We observe that doping copper(I) thiocyanate (CuSCN) into PTAA led to a higher performance improvement for the PSCs than the use of copper(I) iodide (CuI) or lithium salt (Li-TFSI) as the dopant. The power conversion efficiency (PCE) of the PSCs significantly improved from 14.22% to 18.16% upon doping 2.0 wt % CuSCN with simultaneously enhanced open-circuit voltage, short-circuit current density, and fill factor. The long-term stability of the PSCs was also improved with significantly reduced PCE degradation (from 79% to 25%) after 200 h. Our results provide a simple method to improve the performance of planar PSCs by adding dopants into PTAA.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”