Dual interfacial modifications of hierarchically structured iodine-doped ZnO photoanodes for high-efficiency dye-sensitized solar cells

A nanocomposite porous electrode structure consisting of hierarchical iodine-doped zinc oxide (I-ZnO) aggregates combined with the two simple solution-processed interfacial modifications i.e. a ZnO compact layer (CL) and a TiO2 protective layer (PL) has been developed in order to understand electron transport and recombination in the photoanode matrix, together with boosting the conversion efficiency of I-ZnO based dye-sensitized solar cells (DSCs). Electrochemical impedance spectra demonstrate that ZnO CL pre-treatment and TiO2 PL post-treatment synergistically reduce charge-transfer resistance and suppress electron recombination. Furthermore, the electron lifetime in two combined modifications of IZnO + CL + PL photoelectrode is the longest in comparison with the other three photoelectrodes. As a consequence, the overall conversion efficiency of I-ZnO + CL + PL DSC is significantly enhanced to 6.79%, with a 36% enhancement compared with unmodified I-ZnO DSC. Moreover, the stability of I-ZnO + CL + PL cell is improved as compared to I-ZnO one. The mechanism of electron transfer and recombination upon the introduction of ZnO CL and TiO2 PL is also proposed in this work.

Ionic liquid as plasticizer for europium(III)-doped luminescent poly(methyl methacrylate) films

Flexible luminescent polymer films were obtained by doping europium(III) complexes in blends of poly(methyl methacrylate) (PMMA) and the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(6)mim][Tf2N]. Different europium(III) complexes have been incorporated in the polymer/ionic liquid matrix: [C(6)mim][Eu(nta)(4)], [C(6)mim][Eu(tta)(4)], [Eu(tta)(3)(phen)] and [choline](3)[Eu(dpa)(3)], where nta is 2-naphthoyltrifluoroacetonate, tta is 2-thenoyltrifluoroacetonate, phen is 1,10-phenanthroline, dpa is 2,6-pyridinedicarboxylate ( dipicolinate) and choline is the 2-hydroxyethyltrimethyl ammonium cation. Bright red photoluminescence was observed for all the films upon irradiation with ultraviolet radiation. The luminescent films have been investigated by high-resolution steady-state luminescence spectroscopy and by time-resolved measurements. The polymer films doped with beta-diketonate complexes are characterized by a very intense D-5(0) -> F-7(2) transition ( up to 15 times more intense than the D-5(0) -> F-7(1)) transition, whereas a marked feature of the PMMA films doped with [choline](3)[Eu(dpa)(3)] is the long lifetime of the D-5(0) excited state (1.8 ms).

Poly(epsilon-caprolactone) and poly(epsilon-caprolactone)-polyvinylpyrrolidone-iodine blends as ureteral biomaterials: characterisation of mechanical and surface properties, degradation and resistance to encrustation in vitro.

This study describes the physicochemical properties and in vitro resistance to encrustation of solvent cast films composed of either poly(epsilon-caprolactone) (PCL), prepared using different ratios of high (50,000) to low (4000) (molecular weight) m.wt., or blends of PCL and the polymeric antimicrobial complex, poly(vinylpyrrolidone)-iodine (PVP-I). The incorporation of PVP-I offered antimicrobial activity to the biomaterials. Films were characterised in terms of mechanical (tensile analysis, dynamic mechanical thermal analysis) and surface properties (dynamic contact angle analysis, scanning electron microscopy), whereas degradation (at 37degreesC in PBS at pH 7.4) was determined gravimetrically. The resistance of the films to encrustation was evaluated using an in vitro encrustation model. Reductions in the ratio of high:low-m.wt. PCL significantly reduced the ultimate tensile strength, % elongation at break and the advancing contact angle of the films. These effects were attributed to alterations in the amorphous content and the more hydrophilic nature of the films. Conversely, there were no alterations in Young's modulus, the viscoelastic properties and glass-transition temperature. Incorporation of PVP-I did not affect the mechanical or rheological properties of the films, indicative of a limited interaction between the two polymers in the solid state. Manipulation of the high:low m.wt. ratio of PCL significantly altered the degradation of the films, most notably following longer immersion periods, and resistance to encrustation. Accordingly, maximum degradation and resistance to encrustation was observed with the biomaterial composed of 40:60 high:low m.wt. ratios of PCL; however, the mechanical properties of this system were considered inappropriate for clinical application. Films composed of either 50:50 or 60:40 ratio of high:low m.wt. PCL offered an appropriate compromise between physicochemical properties and resistance to encrustation. This study has highlighted the important usefulness of degradable polymer systems as ureteral biomaterials

Near infrared electroluminescence from neodymium complex-doped polymer light emitting diodes

Organic light emitting diode devices employing organometallic Nd(9-hydroxyphenalen-1-one)(3) complexes as near infrared emissive dopants dispersed within poly(N-vinylcarbazole) (PVK) host matrices have been fabricated by spin-casting layers of the doped polymer onto glass/indium tin oxide (ITO)/3,4-polyethylene-dioxythiophene-polystyrene sulfonate (PEDOT) substrates. Room temperature electroluminescence, centered at similar to 1065 nm. was observed from devices top contacted by evaporated aluminum or calcium metal cathodes and was assigned to transitions between the F-4(3/2) -> I-4(11/2) levels of the Nd3+ ions. In particular, a near infrared irradiance of 8.5 nW/mm(2) and an external quantum efficiency of 0.007% was achieved using glass/ITO/PEDOT/PVK:Nd(9-hydroxyphenalen-1-one)(3)/Ca/Al devices. (c) 2005 Elsevier B.V. All rights reserved.

Narrow bandwidth red electroluminescence from solution-processed lanthanide-doped polymer thin films

Narrow bandwidth red electroluminescence from OLED devices fabricated using a simple solution-based approach is demonstrated. A spin-casting method is employed to fabricate organic light emitting diode (OLED) devices comprising a poly(N-vinylcarbazole) (PVK) host matrix doped with a europium beta-diketonate complex, Eu(dbM)(3)(Phen) (dibenzoylmethanate, dbm; 1,10-phenanthroline, Phen) on glass/ indium tin oxide (ITO)/3,4-polyethylene-dioxythiophene-polystyrene sulfonate (PEDOT) substrates. Saturated red europium ion emission, based on the (5)Do ->F-7(2) transition, is centered at a wavelength of 612 nm with a full width at half maximum of 3.5 rim. A maximum external quantum efficiency of 6.3 x 10(-2) cd/A (3.1 X 10(-2)%) and a maximum luminance of 130 cd/M-2 at 400 mA/cm(2) and 25 V is measured for ITO/PEDOT/PVK:Eu(dbM)3(Phen)/Ca/Al devices. This measured output luminance is comparable to that of devices fabricated using more sophisticated small molecule evaporation techniques. (c) 2005 Elsevier B.V All rights reserved.

UV VIS AND RESONANCE RAMAN SPECTROELECTROCHEMICAL PROPERTIES OF TRANSITION-METAL CENTERS IMMOBILIZED WITHIN A POLY(AMINO ACID) MATRIX - ILLUSTRATED WITH AN IRON PORPHYRIN

An iron prophyrin complex has been immobilized on the surfaces of platinum, silver, and indium doped-tin oxide coated glass by using the poly(gamma-ethyl L-glutamate)-N-(3-aminopropyl)imidazole derivative 1 as a linking agent, thus allowing-the surface-enhanced resonance Raman and UV-VIS absorption spectra and electrochemical properties of the porphyrin to be studied in solvents in which it is not normally soluble.

Luminescence temperature sensing using poly(vinyl alcohol)-encapsulated Ru(bpy)(3)(2+) films

The ruthenium(II) diimine complexes, such as ruthenium(II) tris( bipyridyl), Ru(bpy)(3)(2+), possess highly luminescent excited states that are not only readily quenched by oxygen but also by an increase in temperature. The former effect can be rendered insignificant by encapsulating the complex in an oxygen impermeable polymer, although encapsulation often leads also to a loss of temperature sensitivity. The luminescence properties of Ru(bpy)(3)(2+) encapsulated in PVA were studied as a function of oxygen concentration and temperature and found to be independent of the former, but still very sensitive towards the latter. The results were fitted to an established Arrhenius-type equation, based on thermal quenching of the emitting state by a slightly higher (Delta E = 3100 cm(-1)) (3)d-d state that deactivates very rapidly (10(-13) s) via a non-radiative process.

Effects of storage on thermomechanical properties of poly(epsilon-caprolactone) blends containing poly(vinyl pyrrolidone/iodine)

This study reports the effects of: the molecular weight ratio of poly(epsilon -caprolactone) (PCL) in blends containing polymer of high (50 000 g mol(-1)) and low (4000 g mol(-1)) molecular weight; the concentration (0, 1, and 5 wt-%) of poly(vinyl pyrrolidone/iodine) (PVP/I); and storage at 30 degreesC and 75% relative humidity; on the thermomechanical properties of films prepared by solvent evaporation from solutions containing both PCL and PVP/I. The tensile properties were found to be statistically dependent on the molecular weight ratio of PCL but not on the concentration of PVP/I. The reductions in tensile strength and elongation at break associated with increasing amounts of low molecular weight PCL were attributed to a reduction in the concentration of chain entanglements. No changes were observed in viscoelastic properties or the glass transition temperature. Following storage there were no changes in the tensile strength, glass transition temperature, or viscoelastic properties of the films; however, significant reductions in elongation at break were observed. It is suggested that this is due to hydrolytic chain scission of amorphous PCL. Inclusion of 5 wt-% PVP/I increased this process in films containing 100:0 and 80:20 high/low molecular weight PCL (but not 60.40), but the extent of this was small. This study highlighted significant aging properties of PCL in a moist atmosphere. Consequently, it is recommended that suitable packaging materials should be employed to control the exposure of PCL films to water during storage.