Dye-Sensitized Solar Cells Based on Organic Sensitizers with Different Conjugated Linkers: Furan, Bifuran, Thiophene, Bithiophene, Selenophene, and Biselenophene

Six organic dyes with different conjugated linkers such as furan, bifuran, thiophene, bithiophene, selenophene, and biselenophene have been prepared in combination with the dihexyloxy-substituted triphenylamine donor and the cyanoacrylic acid acceptor. In conjunction with an acetonitrile-based electrolyte and a solvent-free ionic liquid electrolyte, these dyes exhibit 6.88-7.77% and 6.39-7.00% efficiencies, respectively. We have demonstrated that furan and selenophene can be employed as building blocks of sensitizers in stable solar cells for the first time. We have also studied the influence of heteroatoms on photocurrents and photovoltages with the aid of quantum calculations and transient photoelectrical decay measurements. Temperature-dependent electrical impedance experiments have shown that a relatively low external quantum efficiency of the dye with biselenophene linker is not related to the charge collection yield in the case of an acetonitrile electrolyte.

An Extremely High Molar Extinction Coefficient Ruthenium Sensitizer in Dye-Sensitized Solar Cells: The Effects of pi-Conjugation Extension

We report a heteroleptic ruthenium complex (007) featuring the electron-rich 5-octyl-2,2'-bis(3,4-ethylenedioxythiophene) moiety conjugated with 2,2-bipyridine and exhibiting 10.7% power conversion efficiency measured at the AM1.5G conditions, thanks to the enhanced light-harvesting that is closely related to photocurrent. This C107 sensitizer has an extremely high molar extinction coefficient,of 27.4 x 10(3) M-1 cm(-1) at 559 nm in comparison to its analogue C103 (20.5 x 10(3) M-1 cm(-1) at 550 nm) or Z907 (12.2 x 10(3) M(-1)cm(-1) at 521 nm) with the corresponding 5-hexyl-3,4-ethylenedioxythiopliene- or nonyl-substituted bipyridyl unit. The augmentation of molar extinction coefficients and the bathochromic shift of low-energy absorption peaks along with the pi-conjugation extension are detailed by TD-DFT calculations. The absorptivity of mesoporous titania films grafted with Z907, C103, or C107 sublinearly increases with the molar extinction coefficient of sensitizers, which is consistent with the finding derived from the surface coverage measurements that the packing density of those sensitizers decreases with the geometric enlargement of ancillary ligands.

A Simple, Universal Colorimetric Assay for Endonuclease/Methyltransferase Activity and Inhibition Based on an Enzyme-Responsive Nanoparticle System

An enzyme responsive nanoparticle system that uses a DNA-gold nanoparticle (AuNP) assembly as the substrate has been developed for the simple, sensitive, and universal monitoring of restriction endonucleases in real time. This new assay takes advantage of the palindromic recognition sequence of the restriction nucleases and the unique optical properties of AuNPs and is simpler than the procedure previously described by by Xu et al. (Angew. Chem. Int. Ed. Engl. 2007, 46, 3468-3470). Because it involves only one type of ssDNA modified AuNPs, this assay can be directed toward most of the endonucleases by simply changing the recognition sequence found within the linker DNA. In addition, the endonuclease activity could be quantitatively analyzed by the value of the reciprocal of hydrolysis half time (t(1/2)(-1). Furthermore, our new design could also be applied to the assay of methyltransferase activity since the methylation of DNA inhibits its cleavage by the corresponding restriction endonuclease, and thus, this new methodology can be easily adapted to high-throughput screening of methyltransferase inhibitors.

A plasma sputtering decoration route to producing thickness-tunable ZnO/TiO2 core/shell nanorod arrays

We report a radio frequency magnetron sputtering method for producing TiO2 shell coatings directly on the surface of ZnO nanorod arrays. ZnO nanorod arrays were firstly fabricated on transparent conducting oxide substrates by a hydrothermal route, and subsequently decorated with TiO2 by a plasma sputtering deposition process. The core/shell nanorods have single-crystal ZnO cores and anatase TiO2 shells. The shells are homogeneously coated onto the whole ZnO nanorods without thickness change. This approach enables us to tailor the thickness of the TiO2 shell for desired photovoltaic applications on a one-nanometer scale. The function of the TiO2 shell as a blocking layer for increasing charge separation and suppression of the surface recombination was tested in dye-sensitized solar cells. The enhanced photocurrent and open-circuit voltage gave rise to increased photovoltaic efficiency and decreased dark current, indicating successful functioning of the TiO2 shell.

The effects of shell characteristics on the current-voltage behaviors of dye-sensitized solar cells based on ZnO/TiO2 core/shell arrays

The ZnO/TiO2 core/shell structure was formed through deposition of a TiO2 coating layer on the hydrothermally fabricated ZnO nanorod arrays through radio frequency magnetron sputtering. The effects of the TiO2 shell's characteristics on the current-voltage behaviors of the core/shell-based dye-sensitized solar cells (CS-DSSC) were investigated. As the rates of injection, transfer, and recombination of electrons of such CS-DSSC were affected significantly by the crystallization, morphology, and continuity of the TiO2 shells, the photovoltaic efficiency was accordingly varied remarkably. In addition, the efficiency was further improved by enhancing the surface area in the core/shell electrode.

Efficient multilayer white polymer light-emitting diodes with aluminum cathodes

Efficient multilayer white polymer light-emitting diodes (WPLEDs) with aluminum cathodes are fabricated. The multilayer structure is composed of a water soluble hole-injection layer, a toluene-soluble emissive layer, and an alcohol-soluble emissive layer. The polarity difference of the solvents used for spin coating these polymers allows for realization of the multilayer polymer structure. The recombination zone confined at the interface of the two emissive polymers avoids exciton quenching by electrodes, and white emission is realized by harvesting photons emitted from the two emissive polymers. A maximum luminous efficiency of 16.9 cd/A and a power efficiency of 11.1 lm/W are achieved for this WPLED.

Modeling of organic light-emitting diodes with graded concentration in the emissive multilayer

We model the electrical behavior of organic light-emitting diodes whose emissive multilayer is formed by blends of an electron transporting material, tris-(8-hydroxyquinoline) aluminum (Alq(3)) and a hole transporting material, N,N-'-diphenyl-N,N-'-bis(1,1(')-biphenyl)-4,4-diamine. The multilayer is composed of layers of different concentration. The Alq(3) concentration gradually decreases from the cathode to the anode. We demonstrate that these graded devices have higher efficiency and operate at lower applied voltages than devices whose emissive layer is made of nominally homogeneous blends. Our results show an important advantage of graded devices, namely, the low values of the recombination rate distribution near the cathode and the anode, so that electrode quenching is expected to be significantly suppressed in these devices.

A dinuclear aluminum 8-hydroxyquinoline complex with high electron mobility for organic light-emitting diodes

A dinuclear aluminum 8-hydroxyquinoline complex (DAlq(3)) with improved electron mobility was designed for organic light-emitting diodes. The electron mobility in DAlq(3) was determined via transient electroluminescence (EL) from bilayer devices with structure of indium tin oxide (ITO)/N,N-'-di(naphthalene-1-yl)-N,N-'-diphenyl-benzidine (NPB)/DAlq(3)/Mg:Ag. It was found that the electron mobility in DAlq(3) is between 3.7-8.4x10(-6) cm(2)/Vs at electric fields ranging between 1.2x10(6) and 4.0x10(6) V/cm, which is a factor of two higher than that in Alq(3). The DAlq(3) also shows a higher EL efficiency of 2.2 cd/A (1.2 Lm/W), as compared to Alq(3) with an EL efficiency of 2.0 cd/A (1.0 Lm/W), which is attributed to more balanced electron and hole recombination due to the improved electron mobility of DAlq(3).

Multi-color long-lasting phosphorescence in Mn2+-doped ZnO-B2O3-SiO2 glass-ceramics

Multi-color LLP phenomenon was observed in Mn2+-doped ZnO-B2O3-SiO2 glassceramics after the irradiation of a UV lamp at room temperature. Transparent ZnO-B2O3-SiO2 glass emitted reddish LLP while opaque glass-ceramics prepared by the glass sample after heat treatment emitted yellowish or greenish LLP. The change of the phosphorescence is due to the alteration of co-ordination state of Mn2+. The phosphorescence of the samples was seen in the dark with naked eyes even 12 h after the irradiation with a UV lamp (lambda(max) = 254 nm) for 30 min. Based on the approximative t(-1) decay law of the phosphorescence, we suggest that the LLP is attributed to the thermally assisted electron-hole recombination.

Improved efficiency by a graded emissive region in organic light-emitting diodes

Electrical and optical properties of organic light-emitting diodes (OLEDs) with a stepwise graded bipolar transport emissive layer for a better control of charge transport and recombination are presented. The graded bipolar transport layer was formed by co-evaporating a hole-transporting material N,N-'-diphenyl-N,N-'-bis(1,1(')-biphenyl)-4,4(')-diamine (NPB) and an electron-transporting/emissive material tris-(8-hydroxyquinoline) aluminum (Alq(3)) in steps, where each step has a different concentration ratio of NPB to Alq(3). Compared to a conventional heterojunction OLED, electroluminescence efficiency was enhanced by a factor of more than 1.5, whereas the turn-on voltage remained unchanged in the graded structure.

Long lasting phosphorescence, thermoluminescence and electron spin resonance property of Mn2+ activated ZnO-Al2O3SiO2 ceramic

The long lasting phosphorescence (LLP) phenomenon in Mn2+-doped ceramic based on ZnO-Al2O3-SiO2 (ZASM) is observed. After irradiation by a UVP standard mercury lamp peaking at 254 nm with a power of 0.6 mW/cm(2) for 15 min, the ceramic sample emits a bright green light peaking at 519 nm, which can be seen in the dark even 15 h after the removal of UVP standard mercury lamp by the naked eyes whose limit of light perception is 0.32 mcd/m(2). The initial afterglow intensity reaches about 1900 mcd/m(2), and the color coordinate (X, Y) is (0.2280, 0.5767) at about 10 s after stopping irradiation. The thermoluminescence (TL) spectra show that there are at least three kinds of trap centers with different trap levels while electron spin resonance (ESR) spectra indicate that there are electron- and hole-trapping centers induced after irradiation by a UVP standard mercury lamp. Based on these measurements, the LLP is considered to be due to the recombination of electrons and holes at trapping centers with different levels, which are firstly thermally released back to Mn2+ and then give rise to the bright green LLP at room temperature.

Effect on the property of the photoinduced carrier transport of CdS as sensitizer for TiO2 nanoparticulate thin films

The TiO2 nanoparticle thin films have been sensitized in situ with CdS nanoparticles. The SPS measurement showed that large surface state density was present on the TiO2 nanoparticles and the surface state can be efficiently decreased by sensitization as well as selecting suitable heat treatment, Both the photocurrent response and the charge recombination kinetics in TiO2 thin films were strongly influenced by trapping/detrapping of surface states. The slow photocurrent response of TiO2 nanoparticulate thin films upon the illumination was attributed to the trap saturation effects, The semiconductor sensitization made the slow photoresponse disappeared and the steady-state photocurrent value increased drastically, which suggested that the sensitization of TiO2 thin films with CdS could get a better charge separation and provide a simple alternative to minimize the effect of surface state on the photocurrent response.

Photoluminescence of aggregated C-60 in nano-size at room temperature

When the aggregation of C-60 is arranged in mono-dispersed state on the ITO substrate, the photoluminescence (PL) spectra are observed clearly. These emission peaks are attributed to recombination of self - trapped excitons, the zero-phonon exciton (R-0) and its phonon replicas.

The effect of chain flexibility and chain mobility on radiation crosslinking of polymers

Radiation crosslinking of polymers mainly depends on the structure of polymer chain. The flexibility and mobility of chain directly influence the possibility of the reactive radicals recombination. Flexible chain is easier to crosslink than rigid-chain polymer. The latter must be crosslinked at high temperature, as most polymers can only crosslink above their melting point. Structural effect also influences the mechanism of radiation crosslinking of polymers. We find from the results in literature and in our laboratory that, the flexibility chain polymer mainly crosslinked with H type, but the rigid chain polymer mainly crosslinked with Y type. (C) 2001 Published by Elsevier Science Ltd.

CHEMICAL-IONIZATION MASS-SPECTROMETRY OF BENZOYL PEROXIDE - A RADICAL AROMATIC-SUBSTITUTION RESULTING IN BIPHENYLCARBOXYLIC ACID IN THE GAS-PHASE

A radical aromatic substitution resulting in biphenylcarboxylic acid is inferred for the decomposition of benzoyl peroxide from the chemical ionization and collision-induced dissociation mass spectra. The thermolysis of benzoyl peroxide gives rise to a benzoyloxy radical, which undergoes rapid decarboxylation and hydrogen abstraction leading to phenyl radical and benzoic acid, respectively. Attack of the resulting phenyl radical on the benzoic acid results in bipbenylcarboxylic acid. On the other hand, the phenyl radical abstracts a hydrogen atom to yield benzene, which is then subjected to the attack of a benzoyloxy radical, affording phenyl benzoate. This substitution reaction rather than the recombination of benzoyloxy and phenyl radicals is found to be responsible for the formation of phenyl benzoate under the present conditions.