Highly efficient spin-conversion effect leading to energy up-converted electroluminescence in singlet fission photovoltaics

Free charge generation in donor-acceptor (D-A) based organic photovoltaic diodes (OPV) progresses through formation of charge-transfer (CT) and charge-separated (CS) states and excitation decay to the triplet level is considered as a terminal loss. On the other hand a direct excitation decay to the triplet state is beneficial for multiexciton harvesting in singlet fission photovoltaics (SF-PV) and the formation of CT-state is considered as a limiting factor for multiple triplet harvesting. These two extremes when present in a D-A system are expected to provide important insights into the mechanism of free charge generation and spin-character of bimolecular recombination in OPVs. Herein, we present the complete cycle of events linked to spin conversion in the model OPV system of rubrene/C60. By tracking the spectral evolution of photocurrent generation at short-circuit and close to open-circuit conditions we are able to capture spectral changes to photocurrent that reveal the triplet character of CT-state. Furthermore, we unveil an energy up-conversion effect that sets in as a consequence of triplet population build-up where triplet-triplet annihilation (TTA) process effectively regenerates the singlet excitation. This detailed balance is shown to enable a rare event of photon emission just above the open-circuit voltage (VOC) in OPVs.

3D hierarchical rutile TiO2 and metal-free organic sensitizer producing dye-sensitized solar cells 8.6% conversion efficiency

Three-dimensional (3D) hierarchical nanoscale architectures comprised of building blocks, with specifically engineered morphologies, are expected to play important roles in the fabrication of 'next generation' microelectronic and optoelectronic devices due to their high surface-to-volume ratio as well as opto-electronic properties. Herein, a series of well-defined 3D hierarchical rutile TiO2 architectures (HRT) were successfully prepared using a facile hydrothermal method without any surfactant or template, simply by changing the concentration of hydrochloric acid used in the synthesis. The production of these materials provides, to the best of our knowledge, the first identified example of a ledgewise growth mechanism in a rutile TiO2 structure. Also for the first time, a Dye-sensitized Solar Cell (DSC) combining a HRT is reported in conjunction with a high-extinction-coefficient metal-free organic sensitizer (D149), achieving a conversion efficiency of 5.5%, which is superior to ones employing P25 (4.5%), comparable to state-of-the-art commercial transparent titania anatase paste (5.8%). Further to this, an overall conversion efficiency 8.6% was achieved when HRT was used as the light scattering layer, a considerable improvement over the commercial transparent/reflector titania anatase paste (7.6%), a significantly smaller gap in performance than has been seen previously.

Improved photovoltaic performance of dye-sensitized solar cells with modified self-assembling highly ordered mesoporous TiO 2 photoanodes

Strategies for improving the photovoltaic performance of dye-sensitized solar cells (DSSCs) are proposed by modifying highly transparent and highly ordered multilayer mesoporous TiO 2 photoanodes through nitrogen-doping and top-coating with a light-scattering layer. The mesoporous TiO 2 photoanodes were fabricated by an evaporation-induced self-assembly method. In regard to the modification methods, the light-scattering layer as a top-coating was proved to be superior to nitrogen-doping in enhancing not only the power conversion efficiency but also the fill factor of DSSCs. The optimized bifunctional photoanode consisted of a 30-layer mesoporous TiO 2 thin film (4.15 μm) and a Degussa P25 light-scattering top-layer (4 μm), which gives rise to a ∼200% higher cell efficiency than for unmodified cells and a fill factor of 0.72. These advantages are attributed to its higher dye adsorption, better light scattering, and faster photon-electron transport. Such a photoanode configuration provides an efficient way to enhance the energy conversion efficiency of DSSCs.

Vacuum ultraviolet/atomic oxygen erosion resistance of amorphous Si0.26C0.43N0.31 coating

An amorphous silicon carbonitride (Si1-x-yCxN y, x = 0:43, y = 0:31) coating was deposited on polyimide substrate using the magnetron-sputtering method. Exposure tests of the coated polyimide in atomic oxygen beam and vacuum ultraviolet radiation were performed in a ground-based simulator. Erosion kinetics measurements indicated that the erosion yield of the Si0.26C0.43N0.31 coating was about 1.5x and 1.8 × 10-26 cm3 /atom during exposure in single atomic oxygen beam, simultaneous atomic oxygen beam, and vacuum ultraviolet radiation, respectively. These values were 2 orders of magnitude lower than that of bare polyimide substrate. Scanning electron and atomic force microscopy, X-ray photoelectron spectrometer, and Fourier transformed infrared spectroscopy investigation indicated that during exposures, an oxide-rich layer composed of SiO2 and minor Si-C-O formed on the surface of the Si 0.26C0.43N0.31 coating, which was the main reason for the excellent resistance to the attacks of atomic oxygen. Moreover, vacuum ultraviolet radiation could promote the breakage of chemical bonds with low binding energy, such as C-N, C = N, and C-C, and enhance atomic oxygen erosion rate slightly.

Preparation of reticulated MAX-phase support with morphology-controllable nanostructured ceria coating for gas exhaust catalyst devices

Reticulated porous Ti3AlC2 ceramic, a member of the MAX-phase family (Mn+1AXn phases, where M is an early transition metal, A is an A-group element, and X is carbon and/or nitrogen), was prepared from the highly dispersed aqueous suspension by a replica template method. Through a cathodic electrogeneration method, nanocrystalline catalytic CeO2 coatings were deposited on the conductive porous Ti 3AlC2 supports. By adjusting the pH value and cathodic deposition current, coatings exhibiting nanocellar, nanosheets-like, or bubble-free morphologies can be obtained. This work expects to introduce a novel practically feasible material system and a catalytic coating preparation technique for gas exhaust catalyst devices.

Hydrocarbon oxidation and three-way catalytic activity on a single step directly coated cordierite monolith: High catalytic activity of Ce0.98Pd0.02O2−δ

Catalytic activity of cordierite honeycomb by a completely new coating method for the oxidation of major hydrocarbons in exhaust gas is reported here. The new coating process consists of (a) dipping and growing γ-Al2O3 on cordierite by combustion of monolith dipped in the aqueous solution of Al(NO3)3 and oxalyldihydrazide (ODH) (or glycine) at 600 °C and active catalyst phase Ce0.98Pd0.02O2−δ on γ-Al2O3-coated cordierite again by combustion of monolith dipped in the aqueous solution of ceric ammonium nitrate, ODH and 1.2 × 10−3 M PdCl2 solution at 500 °C. Weight of active catalyst can be varied from 0.02 wt% to 2 wt% which is sufficient but can be loaded even up to 12 wt% by repeating dip dry combustion. Adhesion of catalyst to cordierite surface is via oxide growth, which is very strong. ‘HC’ oxidation over the monolith catalyst is carried out with a mixture having the composition, 470 ppm of both propene and propane and 870 ppm of both ethylene and acetylene with the varying amount of O2. Three-way catalytic test is done by putting hydrocarbon mixture along with CO (10 000 ppm), NO (2000 ppm) and O2 (15 000 ppm). Below 350 °C full conversion is achieved. In this method, handling of nano-material powder is avoided.

Anthranilic acid oxidase system of Tecomastans—III.: Studies on the conversion of o-aminophenol to catechol

The terminal step in the oxidation of anthranilic acid to catechol by anthranilic acid oxidase system from Tecoma stans, which converts o-aminophenol to catechol has been studied in detail. The reaction catalyses the conversion of one molecule of o-aminophenol to one molecule each of ammonia and catechol. The partially purified enzyme has a pH optimum of 6·2 in citrate-phosphate buffer and a temperature optimum of 45°. The metal ions, Mg2+, Co2+ and Fe3+ were inhibitory to the reaction. Metal chelating agents like 8-hydroxyquinoline, o-phenanthroline, and diethyldithiocarbamate, caused a high degree of inhibition. A sulfhydryl requirement for the reaction was inferred from the inhibition of the reaction by p-chloromercuribenzoate and its reversal with GSH. Atebrin inhibition was reversed by addition of FAD to the reaction mixture.

Conversion of isophenoxazine to catechol in Tecoma stans

Isophenoxazine, formed by the condensation of two molecules of o-aminophenol, is reduced by an enzyme system from Tecoma stans leaves to two molecules of catechol. The reaction proceeds well under anaerobic conditions; a 1–2 mole stoichiometry between the substrate disappeared and the product formed was maintained. The enzyme showed maximum activity at pH 5. The substrate at high concentrations caused a diminution in the activity and the optimum concentration of substrate was at 6 × 10−4 Image . The enzyme preparation was able to convert cinnabarinic acid and diphenylene dioxide 2,3-quinone into the corresponding catechol substances. The diphenylene dioxide 2,3-quinone at the same concentration was three times more susceptible to enzymic cleavage than isophenoxazine. Cinnabarinic acid inhibited the enzymic cleavage of isophenoxazine competitively. None of the known electron donors was found to activate the reaction. Inhibition studies suggested that intact sulfhydryl groups are necessary for enzyme activity. Heavy metal ions like Hg++, Ag+, Co++, Fe++, Ni++, and Fe3++ inhibited the reaction. Metal chelating agents did not have any effect on the enzyme.

The conversion of 3-hydroxyanthranilic acid to cinnabarinic acid by the nuclear fraction of rat liver

Although several authors have implicated 3-hydroxyanthranilic acid (3-OHA) as an intermediate in tryptophaniacin pathway in animals (Kaplan, 1961), alternative pathways of metabolism of this compound have not been fully explored. Madhusudanan Nair obtained an enzyme from spinach leaves which could convert 3-OHA to cinnabarinic acid (private communication). Viollier and Süllmann (1950) reported the conversion of 3-OHA to an unidentified red compound by rat liver homogenates. The present investigation describes the identification of this product as cinnabarinic acid (2-amino-3-H-isophenoxazine-3-one-1,9-dicarboxylic acid). Cinnabarinic acid is known to occur in nature along with cinnabarin is olated from the fungus Polystictus sanguineus (Gripenberg et al., 1957; Gripenberg, 1958).