The ferromagnetic behaviour of conducting polymers revisited

The magnetic properties of doped pellets of poly(3-methylthiophene) showing room temperature ferromagnetic behaviour have been discussed in a previous article. The magnetic behaviour was attributed to a weak ferromagnetic phase, due to the superexchange interaction of polarons via the dopant anions. The Dzialoshinsky-Morya interaction among canted spins was proposed to explain the ferromagnetism. In this article the main conclusions of that work concerning the magnetic behaviour are revised. The basic assumption now is that the magnetic moments are spin 1/2 polarons that can interact antiferromagnetically and/or ferromagnetically. In the small crystalline regions of the polymer, which are identified with the polymer portion that remains ferromagnetic at room temperature, the interaction gives rise to S = 0 and 1 bipolarons and the S = 1 triplet state is lower in energy. In the disordered region, disorder will prevent the complete S = 1 and 0 coupling and bands of polarons ferromagnetically and antiferromagnetically coupled will appear. Using this approach, all the magnetization data can be qualitatively explained, as well as the electron spin resonance data.

Polarons, bipolarons, and crystallization in conducting polymers: An ESR study

Electron spin resonance (ESR) experiments give extremely important information concerning spin arrangements in conducting polymers. This is evidenced by the behavior of the ESR lines as a function of temperature and microwave power. Our ESR data of pressed pellets of ClO- 4 doped poly(3-methylthiophene) (P3MT) synthesized at 25 °C show the predominance of polarons. Instead, the sample prepared at 5 °C shows the predominance of bipolarons. Besides, for both types of samples, crystallization, observed from the ESR data, has shown a rearrangement of spin species.

Polaronic ferromagnetism in conducting polymers

Ferromagnetic behavior at room temperature is reported in metal-free-conducting polymer samples of poly(3-methylthiophene) doped with ClO 4 -. Magnetic moments associated with spin 1/2 positive polarons are possibly interacting through a Dzialoshinski-Moriya anisotropic superexchange via the dopant anions, giving rise to weak ferromagnetism. © 2001 Elsevier Science B.V. All rights reserved.

DLTS investigation of acceptor states in P3MeT Schottky barrier diodes

Deep Level Transient Spectroscopy (DLTS) has been used to investigate hole traps in the depletion region of Schottky barrier diodes formed from electropolymerised poly(3-methylthiophene). The capacitance transients appear to be composed of a fast and a slow component. Analysis of the slower component using the ''rate window'' technique yields isochronal differential capacitance curves that depend on temperature in the manner predicted by theory.

Influence of fabrication conditions on the electrical behaviour of polymer Schottky diodes

Evidence is presented which shows that anomalies in the I-V characteristics of Schottky diodes formed from electrodeposited poly(3-methylthiophene) are related to the time films are held under vacuum prior to deposition of the rectifying aluminium electrode. For short times (similar to 15 mins) a plateau appears in the forward bias characteristic which disappears leading to a significant voltage offset as the device ages or is driven into high forward bias.

Determination of deep and shallow levels in conjugated polymers by electrical methods

Conjugated organic semiconductors have been submitted to various electrical measurement techniques in order to reveal information about shallow levels and deep traps in the forbidden gap. The materials consisted of poly[2-methoxy, 5 ethyl (2' hexyloxy) paraphenylenevinylene] (MEH-PPV), poly(3-methylthiophene) (PMeT), and alpha-sexithienyl (alpha T6) and the employed techniques were IV, CV, admittance spectroscopy, TSC, capacitance and current transients. (C) 1999 Elsevier Science B.V. All rights reserved.

Photocurrents in P3MeT Schottky barrier diodes

The photocurrent action spectrum of a Schottky diode formed from electrodeposited poly(3-methylthiophene) is shown to follow closely the UV-visible absorption spectrum. At low forward bias, the peak photocurrent asymptotes to the expected square-root dependence on total potential, V-t, across the depletion region. At high reverse bias the superlinear dependence of the photocurrent on V-t suggests that internal photoemission from the rectifying aluminium electrode may be the dominant process.

Schottky barrier diodes from semiconducting polymers

Schottky barrier diodes based on Al/poly(3-methylthiophene)/Au have been fabricated and their electrical behaviour investigated. I-V characteristics revealed a dependence on the fabrication conditions, specifically on the time under vacuum prior to evaporation of the rectifying contact and post-metal annealing at elevated temperature. The available evidence is consistent with the formation of a thin insulating layer between the metal and the polymer following these procedures. Long periods under vacuum prior to deposition of the aluminium electrode reduced the likelihood of such a layer forming. Capacitance-voltage plots of the devices were stable to voltage cycling, so long as the forward voltage did not exceed similar to 1 V. Above this a small degree of hysteresis was observed, which is attributed to the filling/emptying of interface states or traps in the polymer.

DLTS investigation of acceptor states in P3MeT Schottky barrier diodes

Deep Level Transient Spectroscopy (DLTS) has been used to investigate hole traps in the depletion region of Schottky barrier diodes formed from electropolymerised poly(3-methylthiophene). The capacitance transients appear to be composed of a fast and a slow component. Analysis of the slower component using the ''rate window'' technique yields isochronal differential capacitance curves that depend on temperature in the manner predicted by theory.

Influence of fabrication conditions on the electrical behaviour of polymer Schottky diodes

Evidence is presented which shows that anomalies in the I-V characteristics of Schottky diodes formed from electrodeposited poly(3-methylthiophene) are related to the time films are held under vacuum prior to deposition of the rectifying aluminium electrode. For short times (similar to 15 mins) a plateau appears in the forward bias characteristic which disappears leading to a significant voltage offset as the device ages or is driven into high forward bias.

Determination of deep and shallow levels in conjugated polymers by electrical methods

Conjugated organic semiconductors have been submitted to various electrical measurement techniques in order to reveal information about shallow levels and deep traps in the forbidden gap. The materials consisted of poly[2-methoxy, 5 ethyl (2' hexyloxy) paraphenylenevinylene] (MEH-PPV), poly(3-methylthiophene) (PMeT), and alpha-sexithienyl (alpha T6) and the employed techniques were IV, CV, admittance spectroscopy, TSC, capacitance and current transients. (C) 1999 Elsevier Science B.V. All rights reserved.

Photocurrents in P3MeT Schottky barrier diodes

The photocurrent action spectrum of a Schottky diode formed from electrodeposited poly(3-methylthiophene) is shown to follow closely the UV-visible absorption spectrum. At low forward bias, the peak photocurrent asymptotes to the expected square-root dependence on total potential, V-t, across the depletion region. At high reverse bias the superlinear dependence of the photocurrent on V-t suggests that internal photoemission from the rectifying aluminium electrode may be the dominant process.

Schottky barrier diodes from semiconducting polymers

Schottky barrier diodes based on Al/poly(3-methylthiophene)/Au have been fabricated and their electrical behaviour investigated. I-V characteristics revealed a dependence on the fabrication conditions, specifically on the time under vacuum prior to evaporation of the rectifying contact and post-metal annealing at elevated temperature. The available evidence is consistent with the formation of a thin insulating layer between the metal and the polymer following these procedures. Long periods under vacuum prior to deposition of the aluminium electrode reduced the likelihood of such a layer forming. Capacitance-voltage plots of the devices were stable to voltage cycling, so long as the forward voltage did not exceed similar to 1 V. Above this a small degree of hysteresis was observed, which is attributed to the filling/emptying of interface states or traps in the polymer.

Properties of lignin and poly(hydroxybutyrate) blends

The Queensland University of Technology (QUT) allows the presentation of a thesis for the Degree of Doctor of Philosophy in the format of published or submitted papers, where such papers have been published, accepted or submitted during the period of candidature. This thesis is composed of Seven published/submitted papers and one poster presentation, of which five have been published and the other two are under review. This project is financially supported by the QUTPRA Grant. The twenty-first century started with the resurrection of lignocellulosic biomass as a potential substitute for petrochemicals. Petrochemicals, which enjoyed the sustainable economic growth during the past century, have begun to reach or have reached their peak. The world energy situation is complicated by political uncertainty and by the environmental impact associated with petrochemical import and usage. In particular, greenhouse gasses and toxic emissions produced by petrochemicals have been implicated as a significant cause of climate changes. Lignocellulosic biomass (e.g. sugarcane biomass and bagasse), which potentially enjoys a more abundant, widely distributed, and cost-effective resource base, can play an indispensible role in the paradigm transition from fossil-based to carbohydrate-based economy. Poly(3-hydroxybutyrate), PHB has attracted much commercial interest as a plastic and biodegradable material because some its physical properties are similar to those of polypropylene (PP), even though the two polymers have quite different chemical structures. PHB exhibits a high degree of crystallinity, has a high melting point of approximately 180°C, and most importantly, unlike PP, PHB is rapidly biodegradable. Two major factors which currently inhibit the widespread use of PHB are its high cost and poor mechanical properties. The production costs of PHB are significantly higher than for plastics produced from petrochemical resources (e.g. PP costs $US1 kg-1, whereas PHB costs $US8 kg-1), and its stiff and brittle nature makes processing difficult and impedes its ability to handle high impact. Lignin, together with cellulose and hemicellulose, are the three main components of every lignocellulosic biomass. It is a natural polymer occurring in the plant cell wall. Lignin, after cellulose, is the most abundant polymer in nature. It is extracted mainly as a by-product in the pulp and paper industry. Although, traditionally lignin is burnt in industry for energy, it has a lot of value-add properties. Lignin, which to date has not been exploited, is an amorphous polymer with hydrophobic behaviour. These make it a good candidate for blending with PHB and technically, blending can be a viable solution for price and reduction and enhance production properties. Theoretically, lignin and PHB affect the physiochemical properties of each other when they become miscible in a composite. A comprehensive study on structural, thermal, rheological and environmental properties of lignin/PHB blends together with neat lignin and PHB is the targeted scope of this thesis. An introduction to this research, including a description of the research problem, a literature review and an account of the research progress linking the research papers is presented in Chapter 1. In this research, lignin was obtained from bagasse through extraction with sodium hydroxide. A novel two-step pH precipitation procedure was used to recover soda lignin with the purity of 96.3 wt% from the black liquor (i.e. the spent sodium hydroxide solution). The precipitation process is presented in Chapter 2. A sequential solvent extraction process was used to fractionate the soda lignin into three fractions. These fractions, together with the soda lignin, were characterised to determine elemental composition, purity, carbohydrate content, molecular weight, and functional group content. The thermal properties of the lignins were also determined. The results are presented and discussed in Chapter 2. On the basis of the type and quantity of functional groups, attempts were made to identify potential applications for each of the individual lignins. As an addendum to the general section on the development of composite materials of lignin, which includes Chapters 1 and 2, studies on the kinetics of bagasse thermal degradation are presented in Appendix 1. The work showed that distinct stages of mass losses depend on residual sucrose. As the development of value-added products from lignin will improve the economics of cellulosic ethanol, a review on lignin applications, which included lignin/PHB composites, is presented in Appendix 2. Chapters 3, 4 and 5 are dedicated to investigations of the properties of soda lignin/PHB composites. Chapter 3 reports on the thermal stability and miscibility of the blends. Although the addition of soda lignin shifts the onset of PHB decomposition to lower temperatures, the lignin/PHB blends are thermally more stable over a wider temperature range. The results from the thermal study also indicated that blends containing up to 40 wt% soda lignin were miscible. The Tg data for these blends fitted nicely to the Gordon-Taylor and Kwei models. Fourier transform infrared spectroscopy (FT-IR) evaluation showed that the miscibility of the blends was because of specific hydrogen bonding (and similar interactions) between reactive phenolic hydroxyl groups of lignin and the carbonyl group of PHB. The thermophysical and rheological properties of soda lignin/PHB blends are presented in Chapter 4. In this chapter, the kinetics of thermal degradation of the blends is studied using thermogravimetric analysis (TGA). This preliminary investigation is limited to the processing temperature of blend manufacturing. Of significance in the study, is the drop in the apparent energy of activation, Ea from 112 kJmol-1 for pure PHB to half that value for blends. This means that the addition of lignin to PHB reduces the thermal stability of PHB, and that the comparative reduced weight loss observed in the TGA data is associated with the slower rate of lignin degradation in the composite. The Tg of PHB, as well as its melting temperature, melting enthalpy, crystallinity and melting point decrease with increase in lignin content. Results from the rheological investigation showed that at low lignin content (.30 wt%), lignin acts as a plasticiser for PHB, while at high lignin content it acts as a filler. Chapter 5 is dedicated to the environmental study of soda lignin/PHB blends. The biodegradability of lignin/PHB blends is compared to that of PHB using the standard soil burial test. To obtain acceptable biodegradation data, samples were buried for 12 months under controlled conditions. Gravimetric analysis, TGA, optical microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), FT-IR, and X-ray photoelectron spectroscopy (XPS) were used in the study. The results clearly demonstrated that lignin retards the biodegradation of PHB, and that the miscible blends were more resistant to degradation compared to the immiscible blends. To obtain an understanding between the structure of lignin and the properties of the blends, a methanol-soluble lignin, which contains 3× less phenolic hydroxyl group that its parent soda lignin used in preparing blends for the work reported in Chapters 3 and 4, was blended with PHB and the properties of the blends investigated. The results are reported in Chapter 6. At up to 40 wt% methanolsoluble lignin, the experimental data fitted the Gordon-Taylor and Kwei models, similar to the results obtained soda lignin-based blends. However, the values obtained for the interactive parameters for the methanol-soluble lignin blends were slightly lower than the blends obtained with soda lignin indicating weaker association between methanol-soluble lignin and PHB. FT-IR data confirmed that hydrogen bonding is the main interactive force between the reactive functional groups of lignin and the carbonyl group of PHB. In summary, the structural differences existing between the two lignins did not manifest itself in the properties of their blends.

Conjoint use of Dibenzosilole and Indan-1,3-dione Functionalities to Prepare an Efficient Non-Fullerene Acceptor for Solution-Processable Bulk-Heterojunction Solar Cells

A solution-processable, non-fullerene electron acceptor, 2,2′-(((5,5-dioctyl-5 H-dibenzo[b,d]silole-3,7-diyl)bis(thiophene-5,2-diyl))bis(methanylylidene))bis(1 H-indene-1,3(2 H)-dione) (called N5) comprised of dibenzosilole and 1,3-indanedione building blocks was designed, synthesized, and fully characterized. N5 is highly soluble in various organic solvents, has high thermal stability, and has energy levels matching those of archetypal donor poly(3-hexylthiophene). Solution-processable, bulk-heterojunction solar cells afforded promising power conversion efficiency of 2.76 % when N5 was used as a non-fullerene electron acceptor along with the conventional donor polymer poly(3-hexylthiophene). As per our knowledge, the material reported herein is the first example in the literature where synchronous use of such building blocks is demonstrated in the design an efficient, non-fullerene acceptor.