Unravelling the photodegradation mechanisms of a low bandgap polymer by combining experimental and modeling approaches

Large-scale introduction of Organic Solar Cells (OSCs) onto the market is currently limited by their poor stability in light and air, factors present in normal working conditions for these devices. Thus, great efforts have to be undertaken to understand the photodegradation mechanisms of their organic materials in order to find solutions that mitigate these effects. This study reports on the elucidation of the photodegradation mechanisms occurring in a low bandgap polymer, namely, Si-PCPDTBT (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]). Complementary analytical techniques (AFM, HS-SPME-GC-MS, UV-vis and IR spectroscopy) have been employed to monitor the modification of the chemical structure of the polymer upon photooxidative aging and the subsequent consequences on its architecture and nanomechanical properties. Furthermore, these different characterization techniques have been combined with a theoretical approach based on quantum chemistry to elucidate the evolution of the polymer alkyl side chains and backbone throughout exposure. Si-PCPDTBT is shown to be more stable against photooxidation than the commonly studied p-type polymers P3HT and PCDTBT, while modeling demonstrated the benefits of using silicon as a bridging atom in terms of photostability. (Figure Presented).

Cobalt promoted TiO2/GO for the photocatalytic degradation of oxytetracycline and Congo Red

A family of titania derived nanocomposites synthesized via sol-gel and hydrothermal routes exhibit excellent performance for the photocatalytic degradation of two important exemplar water pollutants, oxytetracycline and Congo Red. Low loadings of Co3O4 nanoparticles dispersed over the surfaces of anatase TiO2 confer visible light photoactivity for the aqueous phase decomposition of organics through the resulting heterojunction and reduced band gap. Subsequent modification of these Co3O4/TiO2 composites by trace amounts of graphene oxide nanosheets in the presence of a diamine linker further promotes both oxytetracycline and Congo Red photodegradation under simulated solar and visible irradiation, through a combination of enhanced photoresponse and consequent radical generation. Radical quenching and fluorescence experiments implicate holes and hydroxyl radicals as the respective primary and secondary active species responsible for oxidative photodegradation of pollutants.

Photosensitivity mechanism of undoped poly(methyl methacrylate) under UV radiation at 325 nm and its spatial resolution limit

In this Letter, we provide evidence suggesting that the main photosensitive mechanism of an undoped poly(methyl methacrylate)-based microstructured optical fiber under UV radiation at 325 nm is a competitive process of both photodegradation and polymerization. We found experimentally that increasing strain during photo-inscription leads to an increased photosensitivity, which is evidence of photodegradation. Likewise, refractive index change in the fiber was measured to be positive, which provides evidence for further polymerization of the material. Finally, we relate the data obtained to the spatial recording resolution of the samples. © 2014 Optical Society of America.

Synthesis of CuS and CuS/ZnS core/shell nanocrystals for photocatalytic degradation of dyes under visible light

High quality CuS and CuS/ZnS core/shell nanocrystals (NCs) were synthesized in a large quantity using a facile hydrothermal method at low temperatures of 60 C and evaluated in the photodegradation of Rhodamine B (RhB) under visible light irradiation. Synthesis time plays an important role in controlling the morphology, size and photocatalytic activity of both CuS and CuS/ZnS core/shell NCs which evolve from spherical shaped particles to form rods with increasing reaction time, and after 5 h resemble "flower" shaped morphologies in which each "flower" is composed of many NCs. Photocatalytic activity originates from photo-generated holes in the narrow bandgap CuS, with encapsulation by large bandgap ZnS layers used to form the core/shell structure that improves the resistance of CuS towards photocorrosion. Such CuS/ZnS core/shell structures exhibit much higher photocatalytic activity than CuS or ZnS NCs alone under visible light illumination, and is attributed to higher charge separation rates for the photo-generated carriers in the core/shell structure. © 2013 Elsevier B.V.

Characterization of polymer fiber Bragg grating with ultrafast laser micromachining

We report that the main photosensitive mechanism of poly(methyl methacrylate)-based optical fiber Bragg grating (POFBG) under ultraviolet laser micromachining is a complex process of both photodegradation and negative thermo-optic effect. We found experimentally the unique characteristics of Bragg resonance splitting and reunion during the laser micromachining process providing the evidence of photodegradation, while the mean refractive index change of POFBG was measured to be negative confirming further photodegradation of polymer fiber. The thermal-induced refractive index change of POFBG was also observed by recording the Bragg wavelength shift. Furthermore, the dynamic thermal response of the micromachined-POFBG was demonstrated under constant humidity, showing a linear and negative response of around -47.1 pm/°C.

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.

Effects in ultrafast laser micromachining PMMA-based optical fibre grating

Ultrafast laser owns extreme small beam size and high pulse intensity which enable spatial localised modification either on the surface or in the bulk of materials. Therefore, ultrafast laser has been widely used to micromachine optical fibres to alter optical structures. In order to do the precise control of the micromachining process to achieve the desired structure and modification, investigations on laser parameters control should be carried out to make better understanding of the effects in the laser micromachining process. These responses are important to laser machining, most of which are usually unknown during the process. In this work, we report the real time monitored results of the reflection of PMMA based optical fibre Bragg gratings (POFBGs) during excimer ultraviolet laser micromachining process. Photochemical and thermal effects have been observed during the process. The UV radiation was absorbed by the PMMA material, which consequently induced the modifications in both spatial structure and material properties of the POFBG. The POFBG showed a significant wavelength blue shift during laser micromachining. Part of it attributed to UV absorption converted thermal energy whilst the other did not disappear after POFBG cooling off, which attributed to UV induced photodegradation in POF.