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Copper (I) Selenocyanate (CuSeCN) as a Novel Hole-Transport Layer for Transistors, Organic Solar Cells, and Light-Emitting Diodes

The synthesis and characterization of copper (I) selenocyanate (CuSeCN) and its application as a solution-processable hole-transport layer (HTL) material in transistors, organic light-emitting diodes, and solar cells are reported. Density-functional theory calculations combined with X-ray photoelectron spectroscopy are used to elucidate the electronic band structure, density of states, and microstructure of CuSeCN. Solution-processed layers are found to be nanocrystalline and optically transparent (>94%), due to the large bandgap of ?3.1 eV, with a valence band maximum located at ?5.1 eV. Hole-transport analysis performed using field-effect measurements confirms the p-type character of CuSeCN yielding a hole mobility of 0.002 cm2 V?1 s?1. When CuSeCN is incorporated as the HTL material in organic light-emitting diodes and organic solar cells, the resulting devices exhibit comparable or improved performance to control devices based on commercially available poly(3,4-ethylenedioxythiophene):polystyrene sulfonate as the HTL. This is the first report on the semiconducting character of CuSeCN and it highlights the tremendous potential for further developments in the area of metal pseudohalides.

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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”

 

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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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Composition-controlled catalysis of reduced graphene oxide supported CuPd alloy nanoparticles in the hydrolytic dehydrogenation of ammonia borane

Addressed herein is the composition-controlled catalysis of CuPd alloy nanoparticles (NPs) supported on reduced graphene oxide (RGO) in the hydrolytic dehydrogenation of ammonia borane (AB). Nearly monodisperse CuPd alloy NPs were synthesized by using a surfactant-assisted organic solution phase protocol comprising the co-reduction of acetylacetonate complexes of Pd and Cu by morpholine borane complex in oleylamine and 1-octadecene at 80 C. The presented recipe allowed us to make a composition control over the CuPd alloy NPs. Three different compositions of CuPd alloy NPs (2.7 nm Cu30Pd70, 2.9 nm Cu48Pd52, 3.0 nm Cu75Pd25) could be prepared among which the Cu75Pd25 NPs showed the best catalytic performance in hydrogen generation from the hydrolysis of AB. Among the various support materials tested for as-prepared Cu75Pd25 alloy NPs, the RGO-Cu75Pd25 catalysts showed the highest performance in the hydrolysis of AB. Moreover, the activity of the RGO-Cu75Pd25 catalysts were dramatically enhanced by annealing them at 400 C for 1 h under Ar-H2 (5% H2) gas flow and an unprecedented TOF value of 29.9 min-1 was obtained in the hydrolysis of AB at room temperature. The reported TOF value here is much higher than RGO-Cu (TOF = 3.61 min-1) and even higher than RGO-Pd catalysts (TOF = 26.6 min-1). The detailed kinetics of RGO-Cu75Pd25 catalyzed AB hydrolysis was also studied depending on catalyst concentration, substrate concentration and temperature. The apparent activation energy of the catalytic hydrolysis of AB was calculated to be 45 ¡À 3 kJ mol-1.

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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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Oxidation of metallic copper with complexones in organic media

Direct oxidation of copper in organic media with complexones (sterically hindered o-quinones; acetylacetone and pyridine as stabilizing ligands) was studied. From the complexes obtained, the initial components can be regenerated.

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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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Transition metal complexes containing the S(NtBu)42- tetraimidosulfate dianion

Three novel metal complexes [(acac)2Cu2(NtBu)4S] (3), [Li(thf)4]2[I4Cd2(NtBu)4S] (4) and [(thf)2Li{(SiMe3)2N}Zn(NtBu)4S] (5) are prepared from the intended transmetalation of the dilithium complex of N,N?,N??,N???-tetrakis(tert-butyl)tetraimidosulfate [(thf)4Li2(NtBu)4S] (1). The two lithium cations are replaced by either the cationic (acac)Cu(ii) moiety, the neutral I2Cd(ii) residue or only a single lithium cation is substituted by the cationic (Me3Si)2NZn(ii) fragment. The complexes show two main results: first the S(NtBu)42- tetrahedron can serve as a ligand to transition metals from the soft Cu(ii) to the harder Zn(ii) at opposite sides and second the S-N bond distances vary only marginally in response to the various metals and the four distances constantly sum up to 6.38(2) A. Hence the electropositive sulfur atom responds by internal shift to the metal-polarized negative charge at the outside of the S(NR)42- tetrahedron. This journal is

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

 

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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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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”