Identification of the degradation mechanisms of organic solar cells:active layer and interfacial layers

Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.

Design and characterization of zeolite membranes for fluid separation

Experimental and theoretical methods have been used to study zeolite structures, properties and applications as membranes for separation purposes. Thin layers of silicalite-1 and Na-LTA zeolites have been synthesised onto carbon-graphite supports using a hydrothermal synthesis procedure. The separation behaviour of the composite membranes was characterized by gas permeation studies of pure, binary and ternary mixtures of methane, ethane and propane. The influence of temperature and feed gas mixture composition on the separation and selectivity performance of the membranes was also investigated. It was found that the silicalite-1 composite membranes synthesised onto the 4 hour oxidized carbon-graphite supports showed the most promising separation behaviour of all the composite membranes investigated. Molecular simulation methods were used to gain an understanding of how hydrocarbon molecules behave both within the pores and on the surfaces of silicalite-1, mordenite and LTA zeolites. Molecular dynamic simulations were used to investigate the influence of temperature and molecular loadings on the diffusional behaviour of hydrocarbons in zeolites. Both hydroxylated (surface termination with hydroxyl groups) and non-hydroxylated silicalite-1 and Na-mordenite surfaces were generated. For both zeolites the most stable surfaces correspond to the {010} surface. For the silicalite-1 {010} surface the adsorption of hydrocarbons and molecular water onto the hydroxylated surface showed a favourable exothermic adsorption process compared to adsorption on the non-hydroxylated surface. With the Na-mordenite {010} surface the adsorption of hydrocarbons onto both the hydroxylated and non-hydroxylated surfaces had a combination of favourable and non-favourable adsorption energies, while the adsorption of molecular water onto both types of surface was found to be a favourable adsorption process.

Dielectric and electro-optical properties of some cyanobiphenyl liquid-crystals

A variety of methods have been reviewed for obtaining parallel or perpendicular alignment in liquid-crystal cells. Some of these methods have been selected and developed and were used in polarised spectroscopy, dielectric and electro-optic studies. Also, novel dielectric and electro-optic cells were constructed for use over a range of temperature. Dielectric response of thin layers of E7 and E8 (eutectic mixture liquid-crystals) have been measured in the frequency range (12 Hz-100 kHz) and over a range of temperature (183-337K). Dielectric spectra were also obtained for supercooled E7 and E8 in the Hz and kHz range. When the measuring electric field was parallel to the nematic director, one loss peak (low-frequency relaxation process) was observed for E7 and for E8, that exhibits a Debye-type behaviour in the supercooled systems. When the measuring electric field was perpendicular to the nematic director, two resolved dielectric processes have been observed. The phase transitions, effective molecular polarisabilities, anisotropy of polarisabilities and order parameters of three liquid crystal homologs (5CB, 6CB, and 7CB), 60CB and three eutectic nematic mixtures E7, E8, and E607 were calculated using optical and density data measured at several temperatures. The order parameters calculated using the different methods of Vuks, Neugebauer, Saupe-Maier, and Palffy-Muhoray are nearly the same for the liquid crystals considered in the present study. Also, the interrelationship between density and refractive index and the molecular structure of these liquid crystals were established. Accurate dielectric and dipole results of a range of liquid-crystal forming molecules at several temperatures have reported. The role of the cyano-end group, biphenyl core, and flexible tail in molecular association, were investigated using the dielectric method for some molecules which have a structural relationship to the nematogens. Analysis of the dielectric data for solution of the liquid-crystals indicated a high molecular association, comparable to that observed in the nematic or isotropic phases. Electro-optic Kerr effect were investigated for some alkyl cyanobiphenyls, their nematic mixtures and the eutectic mixture liquid-crystals E7 and E8 in the isotropic phase and solution. The Kerr constant of these liquid crystals found to be very high at the nematic-isotropic transition temperatures as the molecules are expected to be highly ordered close to phase transition temperatures. Dynamic Kerr effect behaviour and transient molecular reorientation were also observed in thin layers of some alkyl cyanobiphenyls. Dichroic ratio R and order parameters of solutions containing some azo and anthraquinone dyes in the nematic solvent (E7 and E8), were investigated by the measurement of the intensity of the absorption bands in the visible region of parallel aligned samples. The effective factors on the dichroic ratio of the dyes dissolved in the nematic solvents were determined and discussed.

A study of the formation of amorphous calcium phosphate and hydroxyapatite on melt quenched Bioglass(A (R)) using surface sensitive shallow angle X-ray diffraction

Melt quenched silicate glasses containing calcium, phosphorous and alkali metals have the ability to promote bone regeneration and to fuse to living bone. These glasses, including 45S5 Bioglass(A (R)) [(CaO)(26.9)(Na2O)(24.4)(SiO2)(46.1)(P2O5)(2.6)], are routinely used as clinical implants. Consequently there have been numerous studies on the structure of these glasses using conventional diffraction techniques. These studies have provided important information on the atomic structure of Bioglass(A (R)) but are of course intrinsically limited in the sense that they probe the bulk material and cannot be as sensitive to thin layers of near-surface dissolution/growth. The present study therefore uses surface sensitive shallow angle X-ray diffraction to study the formation of amorphous calcium phosphate and hydroxyapatite on Bioglass(A (R)) samples, pre-reacted in simulated body fluid (SBF). Unreacted Bioglass(A (R)) is dominated by a broad amorphous feature around 2.2 A...(-1) which is characteristic of sodium calcium silicate glass. After reacting Bioglass(A (R)) in SBF a second broad amorphous feature evolves similar to 1.6 A...(-1) which is attributed to amorphous calcium phosphate. This feature is evident for samples after only 4 h reacting in SBF and by 8 h the amorphous feature becomes comparable in magnitude to the background signal of the bulk Bioglass(A (R)). Bragg peaks characteristic of hydroxyapatite form after 1-3 days of reacting in SBF.

Ferroelectric-like behaviour of melanin:humidity effect on current-voltage characteristics

The influence of low vacuum on quasistatic current-voltage (I–V) dependences and the impact of wet air pulse on dynamic bipolar I-V-loops and unipolar I-V-curves of fungal melanin thin layers have been studied for the first time. The threshold hysteresis voltages of I–V dependences are near to the standard electrode potentials of anodic water decomposition. Short wet air pulse impact leads to sharp increase of the current and appearance of “hump”-like and “knee”-like features of I-V-loops and I-V-curves, respectively. By treatment of I-V-loop allowing for I-V-curve shape the maxima of displacement current are revealed. The peculiarities of I-V-characteristics were modelled by series-parallel RC-circuit with Zener diodes as nonlinear elements. As a reason of appearance of temporal polar media with reversible ferroelectric-like polarization and ionic space charge transfer is considered the water-assisted dissociation of some ionic groups of melanin monomers that significantly influences electrophysical parameters of melanin nanostructures.

Thin film bearings with phase change of lubricant

The possible evaporation of lubricant in fluid film bearings has been investigated theoretically and by experiment using a radial flow hydrostatic bearing supplied with liquid refrigerant R114. Good correlation between measured and theoretical values was obtained using a bespoke computational fluid dynamic model in which the flow was assumed to be laminar and adiabatic. The effects of viscous dissipation and vapour generation within the fluid film are fully accounted for by applying a fourth order Runge-Kutta routine to satisfy the radial and filmwise transverse constraints of momentum, energy and mass conservation. The results indicate that the radial velocity profile remains parabolic while the flow remains in the liquid phase and that the radial rate of enthalpy generation is then constant across the film at a given radius. The results also show that evaporation will commence at a radial location determined by geometry and flow conditions and in fluid layers adjacent to the solid boundaries. Evaporation is shown to progress in the radial direction and the load carrying capacity of such a bearing is reduced significantly. Expressions for the viscosity of the liquid/vapour mixture found in the literature survey have not been tested against experimental data. A new formulation is proposed in which the suitable choice of a characteristic constant yields close representation to any of these expressions. Operating constraints imposed by the design of the experimental apparatus limited the extent of the surface over which evaporation could be obtained, and prevented clear identification of the most suitable relationship for the viscosity of the liquid/vapour mixture. The theoretical model was extended to examine the development of two phase flow in a rotating shaft face seal of uniform thickness. Previous theoretical analyses have been based on the assumption that the radial velocity profile of the flow is always parabolic, and that the tangential component of velocity varies linearly from the value at the rotating surface, to zero at the stationary surface. The computational fluid dynamic analysis shows that viscous shear and dissipation in the fluid adjacent to the rotating surface leads to developing evaporation with a consequent reduction in tangential shear forces. The tangential velocity profile is predicted to decay rapidly through the film, exhibiting a profile entirely different to that assumed by previous investigators. Progressive evaporation takes place close to the moving wall and does not occur completely at a single radial location, as has been claimed in earlier work.

Synthesis, thermal processing, and thin film morphology of poly(3-hexylthiophene)-poly(styrenesulfonate) block copolymers

A series of novel block copolymers, processable from single organic solvents and subsequently rendered amphiphilic by thermolysis, have been synthesized using Grignard metathesis (GRIM) and reversible addition-fragmentation chain transfer (RAFT) polymerizations and azide-alkyne click chemistry. This chemistry is simple and allows the fabrication of well-defined block copolymers with controllable block lengths. The block copolymers, designed for use as interfacial adhesive layers in organic photovoltaics to enhance contact between the photoactive and hole transport layers, comprise printable poly(3-hexylthiophene)-block-poly(neopentyl p-styrenesulfonate), P3HT-b-PNSS. Subsequently, they are converted to P3HT-b-poly(p-styrenesulfonate), P3HT-b-PSS, following deposition and thermal treatment at 150 °C. Grazing incidence small- and wide-angle X-ray scattering (GISAXS/GIWAXS) revealed that thin films of the amphiphilic block copolymers comprise lamellar nanodomains of P3HT crystallites that can be pushed further apart by increasing the PSS block lengths. The approach of using a thermally modifiable block allows deposition of this copolymer from a single organic solvent and subsequent conversion to an amphiphilic layer by nonchemical means, particularly attractive to large scale roll-to-roll industrial printing processes.

Generation and performance of localised surface plasmons utilising nano-scale structured multi-layered thin films deposited upon D-shaped optical fiber

A new generation of surface plasmonic optical fibre sensors is fabricated using multiple coatings deposited on a lapped section of a single mode fibre. Post-deposition UV laser irradiation using a phase mask produces a nano-scaled surface relief grating structure, resembling nano-wires. The overall length of the individual corrugations is approximately 14 μm with an average full width half maximum of 100 nm. Evidence is presented to show that these surface structures result from material compaction created by the silicon dioxide and germanium layers in the multi-layered coating and the surface topology is capable of supporting localised surface plasmons. The coating compaction induces a strain gradient into the D-shaped optical fibre that generates an asymmetric periodic refractive index profile which enhances the coupling of the light from the core of the fibre to plasmons on the surface of the coating. Experimental data are presented that show changes in spectral characteristics after UV processing and that the performance of the sensors increases from that of their pre-UV irradiation state. The enhanced performance is illustrated with regards to change in external refractive index and demonstrates high spectral sensitivities in gaseous and aqueous index regimes ranging up to 4000 nm/RIU for wavelength and 800 dB/RIU for intensity. The devices generate surface plasmons over a very large wavelength range, (visible to 2 μm) depending on the polarization state of the illuminating light. © 2013 SPIE.