Andrew J. Parnell

Depletion of PCBM at the Cathode Interface in P3HT/PCBM Thin Films as Quantified via Neutron Reflectivity Measurements

[*] Dr. A. J. Parnell, A. J. Pearson, Dr. P. A. Staniec, A. J. C. Dennison, Dr. H. Hamamatsu, Prof. D. G. Lidzey, Prof. R. A. L. Jones Department of Physics and Astronomy, The University of Sheffield Hicks Building, Hounsfield Road, Sheffield, S3 7RH (UK) E-mail: a.j.parnell@sheffield.ac.uk; d.g.lidzey@sheffield.ac.uk Dr. A. D. F. Dunbar Department of Chemical and Process Engineering, The University of Sheffield Sir Robert Hadfield Building, Mappin St, Sheffield S1 3JD (UK)

In situ imaging and height reconstruction of phase separation processes in polymer blends during spin coating

Spin coating polymer blend thin films provides a method to produce multiphase functional layers of high uniformity covering large surface areas. Applications for such layers include photovoltaics and light-emitting diodes where performance relies upon the nanoscale phase separation morphology of the spun film. Furthermore, at micrometer scales, phase separation provides a route to produce self-organized structures for templating applications. Understanding the factors that determine the final phase-separated morphology in these systems is consequently an important goal. However, it has to date proved problematic to fully test theoretical models for phase separation during spin coating, due to the high spin speeds, which has limited the spatial resolution of experimental data obtained during the coating process. Without this fundamental understanding, production of optimized micro- and nanoscale structures is hampered. Here, we have employed synchronized stroboscopic illumination together with the high light gathering sensitivity of an electron-multiplying charge-coupled device camera to optically observe structure evolution in such blends during spin coating. Furthermore the use of monochromatic illumination has allowed interference reconstruction of three-dimensional topographies of the spin-coated film as it dries and phase separates with nanometer precision. We have used this new method to directly observe the phase separation process during spinning for a polymer blend (PS-PI) for the first time, providing new insights into the spin-coating process and opening up a route to understand and control phase separation structures.

Direct visualization of the real time swelling and collapse of a poly(methacrylic acid) brush using atomic force microscopy

The reversible height change dynamics of a poly(methacrylic acid) brush, a weak polyelectrolyte in response to pH changes, were observed using atomic force microscopy. The brush thickness could be repeatably and reversibly switched between 40 nm at pH 3 and 120 nm at pH 10.5. The swelling and collapse transitions took 6 s in the AFM measurements, but high resolution force spectroscopy measurements showed that the collapse can be made to happen in less than a second. We conclude that the response time of these switches is limited in practise by the physical time taken to exchange solvents and by the intrinsic slow dynamics in the brush.

Molecular weight dependent vertical composition profiles of PCDTBT:PC71BM blends for organic photovoltaics

We have used Soxhlet solvent purification to fractionate a broad molecular weight distribution of the polycarbazole polymer PCDTBT into three lower polydispersity molecular weight fractions. Organic photovoltaic devices were made using a blend of the fullerene acceptor PC71BM with the molecular weight fractions. An average power conversion efficiency of 5.89% (peak efficiency of 6.15%) was measured for PCDTBT blend devices with a number average molecular weight of Mn = 25.5 kDa. There was significant variation between the molecular weight fractions with low (Mn = 15.0 kDa) and high (Mn = 34.9 kDa) fractions producing devices with average efficiencies of 5.02% and 3.70% respectively. Neutron reflectivity measurements on these polymer:PC71BM blend layers showed that larger molecular weights leads to an increase in the polymer enrichment layer thickness at the anode interface, this improves efficiency up to a limiting point where the polymer solubility causes a reduction of the PCDTBT concentration in the active layer.

Mechanical actuation by responsive polyelectrolyte brushes and triblock gels

Progress in the development of actuating molecular devices based on responsive polymers is reviewed. The synthesis and characterization of “grafted from” brushes and triblock copolymers is reported. The responsive nature of polyelectrolyte brushes, grown by surface initiated atomic transfer radical polymerization (ATRP), has been characterized by scanning force microscopy, neutron reflectometry, and single molecule force measurements. The molecular response is measured directly for the brushes in terms of both the brush height and composition and the force generated by a single molecule. Triblock copolymers, based on hydrophobic end blocks and polyacid mid‐block, have been used to produce polymer gels where the deformation of the molecules can be followed directly by small angle X‐ray scattering (SAXS), and a correlation between molecular shape change and macroscopic deformation has been established. A Landolt pH‐oscillator, based on bromate/sulfite/ferrocyanide, with a room temperature period of 20 min and a range of 3.1<pH<7.0, was used to drive periodic oscillations in volume in this pH responsive hydrogel. The triblock copolymers demonstrate that the individual response of the polyelectrolyte molecules scale affinely to produce the macroscopic response of the system in an oscillating chemical reaction. Dedicated to Professor John L. Stanford on the occasion of his 60th birthday.

A solution concentration dependent transition from self-stratification to lateral phase separation in spin-cast PS:d-PMMA thin films

Thin films with a rich variety of different nano-scale morphologies have been produced by spin casting solutions of various concentrations of PS:d-PMMA blends from toluene solutions. During the spin casting process specular reflectivity and off-specular scattering data were recorded and ex situ optical and atomic force microscopy, neutron reflectivity and ellipsometry have all been used to characterise the film morphologies. We show that it is possible to selectively control the film morphology by altering the solution concentration used. Low polymer concentration solutions favour the formation of flat in-plane phase-separated bi-layers, with a d-PMMA-rich layer underneath a PS-rich layer. At intermediate concentrations the films formed consist of an in-plane phase-separated bi-layer with an undulating interface and also have some secondary phase-separated pockets rich in d-PMMA in the PS-rich layer and vice versa. Using high concentration solutions results in laterally phase-separated regions with sharp interfaces. As with the intermediate concentrations, secondary phase separation was also observed, especially at the top surface.

Directed phase separation of PFO:PS blends during spin-coating using feedback controlled in situ stroboscopic fluorescence microscopy

Uniform thin-films of polymer blends can be produced through spin-coating, which is used on an industrial scale for the production of light emitting diodes, and more recently organic photovoltaic devices. Here, we present the results of the direct observation, and control, over the phase separation of polystyrene and poly(9,9′-dioctylfluorene) during spin-coating using high speed stroboscopic fluorescence microscopy. This new approach, imaging the fluorescence, from a blend of fluorescent + non-fluorescent polymers allows for intensity to be directly mapped to composition, providing a direct determination of composition fluctuations during the spin-coating process. We have studied the compositional development and corresponding structural development for a range of compositions, which produce a range of different phase separated morphologies. We initially observe domains formed by spinodal decomposition, coarsening via Ostwald Ripening until an interfacial instability causes break-up of the bicontinuous morphology. Ostwald ripening continues, and depending upon composition a bicontinuous morphology is re-established. By observing compositional and morphological development in real-time, we are able to direct and control morphological structure development through control of the spin coating parameters via in situ feedback.

Coassembled nanostructured bioscaffold reduces the expression of proinflammatory cytokines to induce apoptosis in epithelial cancer cells

The local inflammatory environment of the cell promotes the growth of epithelial cancers. Therefore, controlling inflammation locally using a material in a sustained, non-steroidal fashion can effectively kill malignant cells without significant damage to surrounding healthy cells. A promising class of materials for such applications is the nanostructured scaffolds formed by epitope presenting minimalist self-assembled peptides; these are bioactive on a cellular length scale, while presenting as an easily handled hydrogel. Here, we show that the assembly process can distribute an anti-inflammatory polysaccharide, fucoidan, localized to the nanofibers within the scaffold to create a biomaterial for cancer therapy. We show that it supports healthy cells, while inducing apoptosis in cancerous epithelial cells, as demonstrated by the significant down-regulation of gene and protein expression pathways associated with epithelial cancer progression. Our findings highlight an innovative material approach with potential applications in local epithelial cancer immunotherapy and drug delivery.

Continuously tuneable optical filters from self-assembled block copolymer blends

We demonstrate that two symmetric high molecular weight diblock copolymers, of differing molecular weights, can be blended together and subsequently shear aligned to form one photonic structure without macrophase separation. The lameller period depends on the composition of the blend and gives a photonic structure that is easily tuneable in the wavelength range (λpeak = 400–850 nm).

Understanding and controlling morphology evolution via DIO plasticization in PffBT4T-2OD/PC71BM devices.

We demonstrate that the inclusion of a small amount of the co-solvent 1,8-diiodooctane in the preparation of a bulk-heterojunction photovoltaic device increases its power conversion efficiency by 20%, through a mechanism of transient plasticisation. We follow the removal of 1,8-diiodooctane directly after spin-coating using ellipsometry and ion beam analysis, while using small angle neutron scattering to characterise the morphological nanostructure evolution of the film. In PffBT4T-2OD/PC71BM devices, the power conversion efficiency increases from 7.2% to above 8.7% as a result of the coarsening of the phase domains. This coarsening process is assisted by thermal annealing and the slow evaporation of 1,8-diiodooctane, which we suggest, acts as a plasticiser to promote molecular mobility. Our results show that 1,8-diiodooctane can be completely removed from the film by a thermal annealing process at temperatures ≤100 °C and that there is an interplay between the evaporation rate of 1,8-diiodooctane and the rate of domain coarsening in the plasticized film which helps elucidate the mechanism by which additives improve device efficiency.