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The effect of Al2O3 barrier layers in TiO 2/Dye/CuSCN photovoltage cells explored by recombination and DOS characterization using transient photovoltage measurements

Solid-state dye-sensitized solar cells of the type TiO2/dye/ CuSCN have been made with thin Al2O3 barriers between the TiO2 and the dye. The Al2O3-treated cells show improved voltages and fill factors but lower short-circuit currents. Transient photovoltage and photocurrent measurements have been used to find the pseudo-first-order recombination rate constant (kpfo) and capacitance as a function of potential. Results show that kpfo is dependent on Va?? with the same form as in TiO2/dye/electrolyte cells. The added Al2O3 layer acts as a “tunnel barrier”, reducing the kpfo and thus increasing V a??. The decrease in KpfO also results in an increased fill factor. Capacitance vs voltage plots show the same curvature (a??150 mV/decade) as found in Tio2dye/ electrolyte cells. The application of one AL2O3 layer does not cause a significant shift in the shape or position of the capacitance curve, indicating that changes in band offset play a lesser role in the observed Va?? increase. Cells made with P25 TiO2 have, on average, 2.5 times slower recombination rate constants (longer lifetimes) than those made with colloidal TiO 2. The cells with P25 also show 2.3 times higher trap density (DOS), which results in little change in the Va?? between the two types of TiO2. It is further noted that the recombination current in these cells cannot be calculated from the total charge times the first order rate constant. A 2005 American Chemical Society.

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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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Extended supramolecular structures derived from metal pseudohalides and 4,4?-bipyridinium derivative: Synthesis, structures and optical properties

Four novel extended supramolecular structures based on pseudohalides (SCN) and the flexible cationic ligand 1,4-bis(4,4?-bipyridinium)butane ditetrafluoroborate (bbpyb), namely [bbpyb][Hg(SCN)4] (1), [Cu2(bbpyb)(SCN)4]n (2), [Ag2(bbpyb)(SCN)4]n (3) and [Cu6(bbpyb)(SCN)8]n (4) have been solvothermally synthesized and characterized by IR spectroscopy, thermal gravimetric analysis(TGA), PXRD, UV-Vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. Compound 1 is a 0D supramolecular structure consisted of one linear cationic ligand bbpyb2+ and inorganic mononuclear anion [Hg(SCN)4]2-. Compounds 2 and 3 exhibit infinite two-dimensional anionic architecture, which represent the same (6,3) topology. In compound 4, the cationic ligand bbpyb2+ bridge [Cu6(SCN)8] cluster unit to generate a 3D coordination framework. The structural diversities show that the pseudohalides (SCN) and cationic ligand should very likely be excellent candidates to construct higher dimensional extend supramolecular architectures. In addition, the optical band gap and photocatalytic properties of compounds 1-4 were also investigated.

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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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Stepwise addition of CuNCS onto [Et4N][Tp*WS3]: Design, syntheses, structures and third-order nonlinear optical properties

Stepwise reactions of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 1-4 equiv. of CuNCS (and Et4NBr in the case of three equiv. of CuNCS) afforded the [1 + 1] to [1 + 4] addition products [Et4N][Tp*WS(mu-S) 2(CuNCS)]¡¤0.5CH2Cl2 (2¡¤0.5CH 2Cl2), [Et4N][Tp*W(mu3-S) (mu-S)2(CuNCS)2]¡¤ClCH2CH 2Cl (3¡¤ClCH2CH2Cl), [Et 4N]2[Tp*W(mu3-S)3(CuNCS) 3(mu3-Br)]¡¤1.5aniline (4¡¤1.5aniline), and {[Et4N][Tp*W(mu3-S)3(Cu-mu-SCN) 3(Cu-mu3-NCS)]}n (5). Compounds 2-5 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and single-crystal X-ray crystallography. The cluster anion of 2 contains a [WS2Cu] core formed by addition of one CuNCS group onto the [Tp*WS3] species. The cluster anion of 3 has a butterfly-shaped [WS3Cu2] core constructed by addition of two CuNCS groups onto the [Tp*WS3] species. The cluster dianion of 4 consists of a cubane-like [Tp*WS3Cu3(mu3-Br)] core assembled by addition of three CuNCS groups onto the [Tp*WS 3] species followed by filling a mu3-Br into the void of the incomplete cubane-like [Tp*WS3(CuNCS)3] fragment. 5 has a 2D cluster-supported layer network in which each [Tp*WS3Cu3] core acting as a pyramidal 3-connecting node interconnects with the [Cu(NCS)4] units through thiocyanate bridges. In addition, the third-order nonlinear optical (NLO) performances of 2-5 in DMF were also investigated by Z-scan techniques.

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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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THERAPEUTIC COMPOUNDS AND COMPOSITIONS

Compounds of general formula (I) and compositions comprising compounds of general formula I that modulate pyruvate kinase are described herein. Also described herein are methods of using the compounds that modulate pyruvate kinase in the treatment of diseases.

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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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p-Doping of Copper(I) Thiocyanate (CuSCN) Hole-Transport Layers for High-Performance Transistors and Organic Solar Cells

The ability to tune the electronic properties of soluble wide bandgap semiconductors is crucial for their successful implementation as carrier-selective interlayers in large area opto/electronics. Herein the simple, economical, and effective p-doping of one of the most promising transparent semiconductors, copper(I) thiocyanate (CuSCN), using C60F48 is reported. Theoretical calculations combined with experimental measurements are used to elucidate the electronic band structure and density of states of the constituent materials and their blends. Obtained results reveal that although the bandgap (3.85 eV) and valence band maximum (?5.4 eV) of CuSCN remain unaffected, its Fermi energy shifts toward the valence band edge upon C60F48 addition?an observation consistent with p-type doping. Transistor measurements confirm the p-doping effect while revealing a tenfold increase in the channel’s hole mobility (up to 0.18 cm2 V?1 s?1), accompanied by a dramatic improvement in the transistor’s bias-stress stability. Application of CuSCN:C60F48 as the hole-transport layer (HTL) in organic photovoltaics yields devices with higher power conversion efficiency, improved fill factor, higher shunt resistance, and lower series resistance and dark current, as compared to control devices based on pristine CuSCN or commercially available HTLs.

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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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All-solution-processed high-performance quantum dot light emitting devices employing an inorganic thiocyanate as hole injection layer

We report here the all-solution-processed, high-efficiency quantum dot light emitting diode (QLED) employing inorganic copper (I) thiocyanate (CuSCN) as hole injection layer. In comparison with the widely used injection material of poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS), the hole injection into the QD layer is significantly improved, allowing low turn-on voltage, high luminance and efficiency. By optimizing the multilayer structure and synergistically balancing the carrier injection, the resulting QLEDs exhibit high performance with the maximum current efficiency of 52.4 cd/A and external quantum efficiency of 12.0% for green device, 17.0 cd/A and 16.2% for red device. These results indicate that CuSCN is a reliable hole transport materials for low-cost, high-efficiency QLED devices.

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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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Chemical synthesis of Cd-free wide band gap materials for solar cells

Chemical methods are nowadays very attractive, since they are relatively simple, low cost and convenient for larger area deposition of thin films. In this paper, we outline our work related to the synthesis and characterization of some wide band gap semiconducting material thin films prepared by using solution methods, namely, chemical bath deposition and successive ionic layer adsorption and reaction (SILAR). The optimum preparative parameters are given and respective structural, surface morphological, compositional, optical, and electrical properties are described. Some materials we used in solar cells as buffer layers and achieved remarkable results, which are summarized.

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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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Metals doped cesium based all inorganic perovskite solar cells: Investigations on Structural, morphological and optical properties

Organic containing methylammonium and formamidinium lead halide perovskite has emerged as photovoltaic materials for the past few years, but instability of the organic compounds in perovskite has been a major issue with regard to commercial applications. Herein, we present an ?all solid state? planar perovskite solar cells (PSCs) based ?organic-free? CsPbI3 and both ?organic and iodine free? CsPbBr3 perovskite. We have used solid state based copper (I) thiocyanate (CuSCN) as a hole transport material (HTM) in PSCs. Selected metal ions such as ‘sn, In, Cu and Ag? were used as dopant in both CsPbI3 and CsPbBr3 perovskite for reduce toxic lead content. Further, for the first time, by the use of highly stable black phase CsPbI3 film prepared by doping Sn ions with different concentrations, the efficiency of the device increased from 0.75% to 5.12%. Moreover, pure and metal doped CsPbBr3 based PSCs were fabricated and analyzed their structural and photovoltaic performance under the same measurement condition. This research work highlights a process of fabricating solid state PSCs and particularly addresses the effect of metal ion incorporation on the performance of cesium based PSCs.

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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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Synthesis and Properties of Copper(II) Thiocyanato Complexes with Imino Oximes

Reaction of copper(I) thiocyanate with imino oximes 3-<<2-(alkylamino)ethyl>imino>-2-butanone oximes or 3-<<2-(dialkylamino)ethyl>imino>-2-butanone oximes, (abbreviated as Hdox-enRR’), gave a series of copper(II) complexes which consist of binuclear complexes with a thiocyanate anion coordinated to the copper (II)ion.The magnetic susceptibilities over the temperature range 77-320 K show a strong antiferromagnetic spin coupling through the N-O bridge for these complexes.The magnetic behavior can be explained by using the Bleaney-Bowers equation.

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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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Syntheses, topological analyses and photoelectric properties of Ag(I)/Cu(I) metal-organic frameworks based on a tetradentate imidazolate ligand

A new tetradentate imidazolate ligand 1,1?,1?,1???-(2,2?,4,4?,6,6?-hexamethylbiphenyl-3,3?,5,5?-tetrayl)tetrakis(methylene)(1H-imidazole) (L) and four Ag(I)/Cu(I) coordination polymers, namely [(MCN)3L]n (1: M=Ag; 2: M=Cu), and [(MSCN)2L]n (3: M=Ag; 4: M=Cu) are described. All four new coordination polymers were fully characterized by infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction. Compound 1 features a 3D supramolecular framework constructed by 1D chains through inter-chain Ag-N(CN) and inter-layer Ag-N(L) weak interactions with an uninodal 66 topology. Complex 2 presents a 3D framework characterized by a tetranodal (3,4)-connected (3¡¤4¡¤5¡¤102¡¤11)(3¡¤4¡¤5¡¤6¡¤7¡¤9)(3¡¤6¡¤7)(6¡¤102) topology. Complexes 3 and 4 are isostructural, and both have a 3D network of trinodal 4-connected (4¡¤85)2(42¡¤82¡¤102)(42¡¤84)2 topology. The luminescent properties for these compounds in the solid state as well as the possible ferroelectric behavior of 1 are discussed.

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