The effect of an atomically deposited layer of alumina on NiO in P-type dye-sensitized solar cells

We present a systematic investigation of the fundamental effects of an atomically deposited alumina (AlO(x)H(y)) onto the NiO films in p-type dye-sensitized solar cells (p-DSCs). With P1 as the sensitizing dye and 0.1 M I(2) and 1.0 M LiI in 3-methoxypropionitrile as the electrolyte, one atomic layer deposition (ALD) cycle of alumina was used to achieve a 74% increase in the overall conversion efficiency of a NiO-based DSC. The open circuit voltage of the cells increased from 0.11 to 0.15 V, and the short circuit current density increased from 0.83 to 0.95 mA/cm(2). Adsorption isotherm studies were performed to show that the amount of dye adsorbed on the NiO-alumina film is slightly lower than the amount adsorbed on the nontreated NiO film. The increased J(sc) was therefore assigned to the increased efficiency of carrier collection at the semiconductor-FTO interface. Our study of the photocurrent onset potentials of NiO and NiO-alumina films with the chopped light measurement technique showed no definitive difference in the onset potential values. However, the DSCs based on NiO-alumina showed a higher recombination resistance value from the electrochemical impedance studies and a higher diode ideality factor from the V(oc) versus ln(light intensity) plots as compared to the DSCs based on untreated NiO. It has thus been established that the increase in V(oc) upon alumina treatment arises due to a higher resistance for electron-hole recombination across NiO surface locally.     

Lyotropic self-assembly of high-aspect-ratio semiconductor nanowires of single-crystal ZnO

Lyotropic nanowire dispersions are attractive precursors for semiconductor device fabrication because they permit the alignment control of active nanomaterials. The reliable production of nanowire-based mesophases, however, is very challenging in practice. We show that appropriately functionalized high-aspect-ratio nanowires of single-crystal ZnO spontaneously form nematic phases in organic and aqueous media. These systems show isotropic, biphasic, and nematic phases on increasing concentration, in reasonable agreement with Onsager's theory for rigid rods interacting via excluded volume. Suspensions were readily processed to produce films with large-area monodomains of aligned nanowires. Imprints of the director field in quiescently dried films display a propensity for bend deformation in the organic mesophase versus splay deformation in the aqueous case, suggesting that system elasticity may be tuned via surface functionalization. These results provide critical insight for the utilization of semiconductor nanowires as novel mesogens and further enable the use of solution-based routes for fabricating optoelectronic devices.     

Syntheses and optoelectronic properties of quinoxaline polymers: The effect of donor unit

Tuning the bandgap of electrochromic polymers is one of the important research topics in electrochromism. To understand clearly the effect of donor unit in donor–acceptor–donor‐type polymers, 2,3‐bis(4‐tert‐butylphenyl)‐5,8‐di(thiophen‐2‐yl)quinoxaline and 2,3‐bis(4‐tert‐butylphenyl)‐5‐(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐ 5‐yl)‐8‐(thiophen‐2‐yl)quinoxaline were synthesized and polymerized potentiodynamically. Their electrochemical and spectroelectrochemical studies were performed, and the results were compared with those of poly(2,3‐bis(4‐tert‐butylphenyl)‐5,8‐bis(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl)quinoxaline) (Gunbas et al., Adv Mater 2008, 20, 691–695). A blue shift in the polymer π–π* transitions revealed that the bandgap of such polymers with the same acceptor unit is related to the electron density of donor units. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Benzotriazole derivatives as long wavelength photosensitizers for diaryliodonium salt initiators

Two benzotriazole derivative dyes 4,7‐bis(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl)‐2‐dodecyl‐2H‐benzo[1,2,3]triazole, and 2‐dodecyl‐4,7‐bis(4‐hexylthiophen‐2‐yl)‐2H‐benzo[d][1,2,3]triazole are shown to work as efficient photosensitizers for a diphenyliodonium salt initiator in cationic photopolymerization of epoxide and vinyl monomers. Substituted thienyl groups are attached to benzotriazole backbone to extend conjugation and enhance electron density of the molecules. Thereby, it was possible to initiate polymerizations at room temperature using long wavelength UV and visible light. The progress of photopolymerizations was monitored using optical pyrometry. The photopolymerization of an epoxide monomer using solar irradiation was also demonstrated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A highly regioselective synthesis of 1‐n‐methyl‐spiro‐[2,3′“]‐oxindole‐spiro‐[3,2”]indane‐1“, 3”‐dione‐4‐arylpyrrolidines through 1,3‐dipolar cycloaddition protocol

2‐Arylidene‐1,3‐indanediones undergo a regioselective 1,3‐dipolar cycloaddition reaction with the azomethine ylide derived from isatin and sarcosine by decarboxylative route affording a series of 1‐N‐methyl — spiro[2.3′“]oxindole‐spiro[3.2”]indane‐1“,3”‐diones‐4‐aryl pyrrolidines. The structures were established by spectroscopic techniques as well as single crystal X‐ray analysis. Density functional theory at B3L YP/6‐31G^* and the semi empirical AM₁ calculations were employed to rationalize the observed results. The experimental regioselectivity of 1,3‐dipolar cycloadditions could be corroborated nicely with the computed Fukui frontier orbital energies and reaction energies.     

Electrochemical Behaviour and Rapid Determination of L‐Dopa at Electrochemically Pretreated Screen Printed Carbon Electrode

A simple and rapid voltammetric method based on a disposable electrochemically pretreated screen‐printed carbon electrode is proposed for the determination of L ‐dopa. Under optimum differential pulse voltammetry conditions a limit of detection of 3.6×10^?7 M for L ‐dopa was obtained. The method was successfully applied to the determination of L ‐dopa in a commercial pharmaceutical formulation.     

Preparation of thin stable erbium target sandwiched between carbon layers

Targets of isotopically enriched ¹⁷⁰Er (erbium) were prepared on 45 μg/cm² carbon backing using the method of vacuum evaporation. Another layer of carbon with thickness 23 μg/cm² was deposited on it as a protective cap with the help of an electron gun. Carbon backing, Er and the capping carbon layer were deposited using resistive heating and electron gun deposition without disturbing the vacuum. The thickness of ¹⁷⁰Er was measured by X-ray fluorescence analysis as well as with Rutherford backscattering spectrometry and it was found to be 150 μg/cm². Successful preparation of sandwiched targets was very sensitive to substrate temperature, deposition rate, duration of in situ annealing, cooling rate etc.     

A Novel siloxane-containing dicarboxylic acid, 1,3-bis(p-carboxyphenylene-ester-methylene)tetramethyldisiloxane,and its derivatives: ester macrocycle and supramolecular structure with a copper complex

The new dicarboxylic acid, 1,3-bis(p-carboxyphenylene-ester-methylene)tetramethyldisiloxane (H₂L, 1) was obtained by treating 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane with a mixture of terephthalic acid and terephthalic acid sodium salt in a 1:1 ratio. In this approach, besides the desired compound 1 (33 wt % yield), the condensation cyclic dimer 2 (7 wt % yield) and an oligomer 3 (10 wt % yield) resulted. The reaction between dicarboxylic acid H₂L, where L is the carboxylate ligand, along with imidazole as co-ligand, and copper hydroxide resulted in the formation of a coordination compound [Cu(HIm)₄(H₂O)₂]L·4.5H₂O (4). Single-crystal X-ray crystallography has revealed that the crystal structure of 4 is a self-assembled H-bonded three-dimensional supramolecular structure. FTIR and NMR spectral techniques were also used to characterize the formed structures. Optical and thermal properties of all compounds were studied. The stability of the supramolecular structure in solution (methanol) and with temperature was studied using ATR-FTIR. The ability of the macrocycle 2 to bind potassium cations in solution was investigated by UV–vis spectrophotometry.     

A palladium-catalyzed three-component cross-coupling of conjugated dienes or terminal alkenes with vinyl triflates and boronic acids

A three-component coupling of vinyl triflates and boronic acids to alkenes catalyzed by palladium is reported. Using 1,3-dienes, selective 1,2-alkene difunction-alization is observed, whereas the use of terminal alkenes results in 1,1-alkene difunctionalization. The reaction outcome is attributed to the formation of stabilized, cationic Pd-π-allyl intermediates to regulate β-hydride elimination.