Isoindigo dye incorporated copolymers with naphthalene and anthracene: promising materials for stable organic field effect transistors

In this paper, we report the design and synthesis of isoindigo based low band gap polymer semiconductors, poly{N,N′-(2-octyldodecyl)-isoindigo-alt- naphthalene} (PISD-NAP) and poly{N,N′-(2-octyldodecyl)-isoindigo-alt- anthracene} (PISD-ANT). A series of donor-acceptor (D-A) copolymers can be prepared where donor and acceptor conjugated blocks can be attached alternately using organometallic coupling. In these polymers, an isoindigo dye acceptor moiety has been attached alternately with naphthalene and anthracene donor comonomer blocks by Suzuki coupling. PISD-NAP and PISD-ANT exhibit excellent solution processibility and good film-forming properties. Gel permeation chromatography exhibits a higher molecular mass with lower polydispersity. UV-vis-NIR absorption of these polymers exhibits a wide absorption band ranging from 300 nm to 800 nm, indicating the low band gap nature of the polymers. Optical band gaps calculated from the solid state absorption cutoff value for PISD-NAP and PISD-ANT are around 1.80 eV and 1.75 eV, respectively. Highest occupied molecular orbital (HOMO) values calculated respectively for PISD-NAP and PISD-ANT thin films on glass substrate by photoelectron spectroscopy in air (PESA) are 5.66 eV and 5.53 eV, indicative of the good stability of these materials in organic electronic device applications. These polymers exhibit p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices in ambient conditions. The highest hole mobility of 0.013 cm2 V-1 s-1 is achieved in top contact and bottom-gate OTFT devices for PISD-ANT, whereas polymer PISD-NAP exhibited a hole mobility of 0.004 cm2 V -1 s-1. When these polymer semiconductors were used as a donor and PC71BM as an acceptor in OPV devices, the highest power conversion efficiency (PCE) of 1.13% is obtained for the PISD-ANT polymer.

Stable organic photovoltaics using Ag thin film anodes

The interaction at the interface between a metal electrode and photoactive polymer is crucial for overall performance and stability of organic photovoltaics (OPVs). In this article, we report a comparative study of the stability of thin film Ag and indium tin oxide (ITO) as electrodes when used in conjunction with an interfacial PEDOT:PSS layer for P3HT:PCBM blend OPV devices. XPS measurements were taken for Ag and ITO/PEDOT:PSS layered samples with different exposure times to ambient conditions (∼25 °C, ∼50% relative humidity) to investigate the migration of Ag and In into the PEDOT:PSS layer. The change in efficiency of OPVs with a longer exposure time and degree of migration is explained by the analysis of XPS results. We propose the mechanism behind the interactions occurring at the interfaces. The efficiency of the ITO electrode OPVs continuously decreased to below 10% of the initial efficiency. However, the Ag devices displayed a slower degradation and maintained 50% of the initial efficiency for the same period of time.

Structural identification of hindered amine light stabilisers in coil coatings using electrospray ionisation tandem mass spectrometry

Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post-production, in-service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI-MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6-tetramethylpiperidine-based HALS. Fragmentation mechanisms for the \[M + H](+) ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS(3) mass spectra of N-H, N-CH(3), N-C(O)CH(3) and N-OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N-H, N-CH3 or N-C(0)CH3 functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester-based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright (C) 2010 John Wiley & Sons, Ltd.

A study of diphenylfumaronitrile and furan-substituted diketopyrrolopyrrole alternating copolymer and its thin-film transistors

A fused aromatic furan-substituted diketopyrrolopyrrole and novel diphenylfumaronitrile conjugated building blocks are used for the synthesis of an alternating copolymer (DPFN-DPPF) via Suzuki polycondensation. In this paper, the first attempt to use the diphenylfumaronitrile building block for the synthesis of conjugated polymer is described. The number-average and weight-average molecular weights calculated for DPFN-DPPF are 20?661 and 66?346 g mol-1, respectively. The optical bandgap calculated for DPFN-DPPF is 1.53 eV whereas the highest occupied molecular orbital (HOMO) value calculated by photoelectron spectroscopy in air (PESA) is 5.50 eV. The calculated HOMO value is lower, which is suitable for stable organic electronic devices. DPFN-DPPF polymer is used as an active layer in bottom-contact bottom-gate organic thin-film transistor devices and the thin film exhibits a hole mobility of 0.20 cm2 V-1 s-1 in air.

A fluorenone based low band gap solution processable copolymer for air stable and high mobility organic field effect transistors

A fluorenone based alternating copolymer (PFN-DPPF) with a furan based fused aromatic moiety has been designed and synthesized. PFN-DPPF exhibits a small band gap with a lower HOMO value. Testing this polymer semiconductor as the active layer in organic thin-film transistors results in hole mobilities as high as 0.15 cm2 V-1 s-1 in air.

Grafted fluoropolymers as supports for solid-phase organic chemistry : preparation and characterization

Solid-phase organic chemistry has rapidly expanded in the last decade, and, as a consequence, so has the need for the development of supports that can withstand the extreme conditions required to facilitate some reactions. The authors here prepare a thermally stable, grafted fluoropolymer support (see Figure for an example) in three solvents, and found that the penetration of the graft was greatest in dichloromethane.

Determination of coastal ground and surface water processes and character by use of hydrochemistry and stable isotopes, Fraser Coast, Queensland

This study was part of an integrated project developed in response to concerns regarding current and future land practices affecting water quality within coastal catchments and adjacent marine environments. Two forested coastal catchments on the Fraser Coast, Australia, were chosen as examples of low-modification areas with similar geomorphological and land-use characteristics to many other coastal zones in southeast Queensland. For this component of the overall project, organic , physico-chemical (Eh, pH and DO), ionic (Fe2+, Fe3+), and isotopic (ä13CDIC, ä15NDIN ä34SSO4) data were used to characterise waters and identify sources and processes contributing to concentrations and form of dissolved Fe, C, N and S within the ground and surface waters of these coastal catchments. Three sites with elevated Fe concentrations are discussed in detail. These included a shallow pool with intermittent interaction with the surface water drainage system, a monitoring well within a semi-confined alluvial aquifer, and a monitoring well within the fresh/saline water mixing zone adjacent to an estuary. Conceptual models of processes occurring in these environments are presented. The primary factors influencing Fe transport were; microbial reduction of Fe3+ oxyhydroxides in groundwaters and in the hyporheic zone of surface drainage systems, organic input available for microbial reduction and Fe3+ complexation, bacterial activity for reduction and oxidation, iron curtain effects where saline/fresh water mixing occurs, and variation in redox conditions with depth in ground and surface water columns. Data indicated that groundwater seepage appears a more likely source of Fe to coastal waters (during periods of low rainfall) via tidal flux. The drainage system is ephemeral and contributes little discharge to marine waters. However, data collected during a high rainfall event indicated considerable Fe loads can be transported to the estuary mouth from the catchment.

Influence of organic matter in road deposited particulates in heavy metal accumulation and transport

The research study discussed in the paper investigated the influence of organic matter on heavy metal adsorption for different particle size ranges of build-up solids. Samples collected from road surfaces were assessed for organic matter content, mineral composition, particle size distribution and effective cation exchange capacity. It was found that the organic matter plays a key role in >75µm particles in the adsorption of Zinc, Lead, Nickel and Copper, which are generated by traffic activities. Clay forming minerals and metal oxides of Iron, Aluminium and Manganese was found to be important for heavy metal adsorption to <75µm particles. It was also found that heavy metals adsorbed to organic matter are strongly bound to particles and these metal ions will not be bio-available if the chemical quality of the media remains stable.

Fabrication and characterization of plasma polymer thin films from monoterpene alcohols for applications in organic electronics and biotechnology

After more than twenty years of basic and applied research, the use of nanotechnology in the design and manufacture of nanoscale materials is rapidly increasing, particularly in commercial applications that span from electronics across renewable energy areas, and biomedical devices. Novel polymers are attracting significant attention for they promise to provide a low−cost high−performance alternative to existing materials. Furthermore, these polymers have the potential to overcome limitations imposed by currently available materials thus enabling the development of new technologies and applications that are currently beyond our reach. This work focuses on the development of a range of new low−cost environmentally−friendly polymer materials for applications in areas of organic (flexible) electronics, optics, and biomaterials. The choice of the monomer reflects the environmentally−conscious focus of this project. Terpinen−4−ol is a major constituent of Australian grown Melaleuca alternifolia (tea tree) oil, attributed with the oil's antimicrobial and anti−inflammatory properties. Plasma polymerisation was chosen as a deposition technique for it requires minimal use of harmful chemicals and produces no hazardous by−products. Polymer thin films were fabricated under varied process conditions to attain materials with distinct physico−chemical, optoelectrical, biological and degradation characteristics. The resultant materials, named polyterpenol, were extensively characterised using a number of well−accepted and novel techniques, and their fundamental properties were defined. Polyterpenol films were demonstrated to be hydrocarbon rich, with variable content of oxygen moieties, primarily in the form of hydroxyl and carboxyl functionalities. The level of preservation of original monomer functionality was shown to be strongly dependent on the deposition energy, with higher applied power increasing the molecular fragmentation and substrate temperature. Polyterpenol water contact angle contact angle increased from 62.7° for the 10 W samples to 76.3° for the films deposited at 100 W. Polymers were determined to resist solubilisation by water, due to the extensive intermolecular and intramolecular hydrogen bonds present, and other solvents commonly employed in electronics and biomedical processing. Independent of deposition power, the surface topography of the polymers was shown to be smooth (Rq <0.5 nm), uniform and defect free. Hardness of polyterpenol coatings increased from 0.33 GPa for 10 W to 0.51 GPa for 100 W (at 500 μN load). Coatings deposited at higher input RF powers showed less mechanical deformation during nanoscratch testing, with no considerable damage, cracking or delamination observed. Independent of the substrate, the quality of film adhesion improved with RF power, suggesting these coatings are likely to be more stable and less susceptible to wear. Independent of fabrication conditions, polyterpenol thin films were optically transparent, with refractive index approximating that of glass. Refractive index increased slightly with deposition power, from 1.54 (10 W) to 1.56 (100 W) at 500 nm. The optical band gap values declined with increasing power, from 2.95 eV to 2.64 eV, placing the material within the range for semiconductors. Introduction of iodine impurity reduced the band gap of polyterpenol, from 2.8 eV to 1.64 eV, by extending the density of states more into the visible region of the electromagnetic spectrum. Doping decreased the transparency and increased the refractive index from 1.54 to 1.70 (at 500 nm). At optical frequencies, the real part of permittivity (k) was determined to be between 2.34 and 2.65, indicating a potential low-k material. These permittivity values were confirmed at microwave frequencies, where permittivity increased with input RF energy – from 2.32 to 2.53 (at 10 GHz ) and from 2.65 to 2.83 (at 20 GHz). At low frequencies, the dielectric constant was determined from current−voltage characteristics of Al−polyterpenol−Al devices. At frequencies below 100 kHz, the dielectric constant varied with RF power, from 3.86 to 4.42 at 1 kHz. For all samples, the resistivity was in order of 10⁸−10⁹ _m (at 6 V), confirming the insulating nature of polyterpenol material. In situ iodine doping was demonstrated to increase the conductivity of polyterpenol, from 5.05 × 10⁻⁸ S/cm to 1.20 × 10⁻⁶ S/cm (at 20 V). Exposed to ambient conditions over extended period of time, polyterpenol thin films were demonstrated to be optically, physically and chemically stable. The bulk of ageing occurred within first 150 h after deposition and was attributed to oxidation and volumetric relaxation. Thermal ageing studies indicated thermal stability increased for the films manufactured at higher RF powers, with degradation onset temperature associated with weight loss shifting from 150 ºC to 205 ºC for 10 W and 100 W polyterpenol, respectively. Annealing the films to 405 °C resulted in full dissociation of the polymer, with minimal residue. Given the outcomes of the fundamental characterisation, a number of potential applications for polyterpenol have been identified. Flexibility, tunable permittivity and loss tangent properties of polyterpenol suggest the material can be used as an insulating layer in plastic electronics. Implementation of polyterpenol as a surface modification of the gate insulator in pentacene-based Field Effect Transistor resulted in significant improvements, shifting the threshold voltage from + 20 V to –3 V, enhancing the effective mobility from 0.012 to 0.021 cm²/Vs, and improving the switching property of the device from 10⁷ to 10⁴. Polyterpenol was demonstrated to have a hole transport electron blocking property, with potential applications in many organic devices, such as organic light emitting diodes. Encapsulation of biomedical devices is also proposed, given that under favourable conditions, the original chemical and biological functionality of terpinen−4−ol molecule can be preserved. Films deposited at low RF power were shown to successfully prevent adhesion and retention of several important human pathogens, including P. aeruginosa, S. aureus, and S. epidermidis, whereas films deposited at higher RF power promoted bacterial cell adhesion and biofilm formation. Preliminary investigations into in vitro biocompatibility of polyterpenol demonstrated the coating to be non−toxic for several types of eukaryotic cells, including Balb/c mice macrophage and human monocyte type (HTP−1 non-adherent) cells. Applied to magnesium substrates, polyterpenol encapsulating layer significantly slowed down in vitro biodegradation of the metal, thus increasing the viability and growth of HTP−1 cells. Recently, applied to varied nanostructured titanium surfaces, polyterpenol thin films successfully reduced attachment, growth, and viability of P. aeruginosa and S. aureus.

Organic–inorganic bismuth (III)-based material: A lead-free, air-stable and solution-processable light-absorber beyond organolead perovskites

Methylammonium bismuth (III) iodide single crystals and films have been developed and investigated. We have further presented the first demonstration of using this organic–inorganic bismuth-based material to replace lead/tin-based perovskite materials in solution-processable solar cells. The organic–inorganic bismuth-based material has advantages of non-toxicity, ambient stability, and low-temperature solution-processability, which provides a promising solution to address the toxicity and stability challenges in organolead- and organotin-based perovskite solar cells. We also demonstrated that trivalent metal cation-based organic–inorganic hybrid materials can exhibit photovoltaic effect, which may inspire more research work on developing and applying organic-inorganic hybrid materials beyond divalent metal cations (Pb (II) and Sn (II)) for solar energy applications.