David S. Germack

Substrate-dependent interface composition and charge transport in films for organic photovoltaics

The buried interface composition of polymer-fullerene blends is found by near-edge x-ray absorption fine structure spectroscopy to depend on the surface energy of the substrate upon which they are cast. The interface composition determines the type of charge transport measured with thin film transistors. These results have implications for organic photovoltaics device design and the use of transistors to evaluate bulk mobility in blends.

High performance airbrushed organic thin film transistors

Spray-deposited poly-3-hexylthiophene (P3HT) transistors were characterized using electrical and structural methods. Thin-film transistors with octyltrichlorosilane treated gate dielectrics and spray-deposited P3HT active layers exhibited a saturation regime mobility as high as 0.1 cm2 V−1 s−1, which is comparable to the best mobilities observed in high molecular mass P3HT transistors prepared using other methods. Optical and atomic force microscopy showed the presence of individual droplets with an average diameter of 20 μm and appreciable large-scale film inhomogeneities. Despite these inhomogeneities, near-edge x-ray absorption fine structure spectroscopy of the device-relevant channel interface indicated excellent orientation of the P3HT.

Chemically enhancing block copolymers for block-selective synthesis of self-assembled metal oxide nanostructures.

We report chemical modification of self-assembled block copolymer thin films by ultraviolet light that enhances the block-selective affinity of organometallic precursors otherwise lacking preference for either copolymer block. Sequential precursor loading and reaction facilitate formation of zinc oxide, titanium dioxide, and aluminum oxide nanostructures within the polystyrene domains of both lamellar- and cylindrical-phase modified polystyrene-block-poly(methyl methacrylate) thin film templates. Near-edge X-ray absorption fine structure measurements and Fourier transform infrared spectroscopy show that photo-oxidation by ultraviolet light creates Lewis basic groups within polystyrene, resulting in an increased Lewis base-acid interaction with the organometallic precursors. The approach provides a method for generating both aluminum oxide patterns and their corresponding inverses using the same block copolymer template.

Directed assembly of P3HT:PCBM blend films using a chemical template with sub-300 nm features.

Surface energy has been demonstrated as a means to direct interfacial-layer composition in polymer:fullerene blends utilized as active layers in organic photovoltaic devices. Combined with recent materials advances in the preparation of nanoscale chemical patterns, surface energy control of nanophase separation presents an opportunity to employ patterned surface energy templates to control the 3D blend morphology of polymer:fullerene blends. This report details the directed assembly of poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) blends atop linear grating patterns with domains of alternating high and low surface energy of 50 to 600 nm in width prepared by nanoscale oxidative lithography of alkyl-terminated self-assembled monolayers on SiO2 and SiH surfaces. Tapping-, contact-, and current-sensing AFM studies demonstrated that chemical patterns were effective at directing the 3D morphology of P3HT:PCBM blends at dimensions of >200 nm. As the dimensionality of domains approached 100 nm, the chemical patterns were no longer able to direct phase segregation, evidence that a directed spinodal decomposition mechanism was responsible for the observed morphology. Surprisingly, the low surface energy component (P3HT) was found to be atop the high surface energy domains of the template, in conflict with current understanding of the role of surface energy directed assembly in polymer blends. These results suggest that the directed spinodal decomposition mechanism applies to conjugated polymer:fullerene blends, but that additional parameters unique to these types of systems will require refinement of the theory to adequately describe and predict the behavior of these scientifically and industrially interesting materials.

Confinement-Induced Reduction in Phase Segregation and Interchain Disorder in Bulk Heterojunction Films

The effects of thin-film confinement on the material properties of ultrathin polymer (electron donor):fullerene (electron acceptor) bulk heterojunction films can be important for both fundamental understanding and device applications such as thin-film photovoltaics. We use variable angle spectroscopic ellipsometry and near edge X-ray absorption fine structure spectroscopy to measure the optical constants, donor-acceptor volume fraction profile, and the degree of interchain order as a function of the thickness of a poly(3-hexythiophene-2,5-diyl) and phenyl-C61-butyric acid methyl ester bulk heterojunction film. We find that as the thickness of the bulk heterojunction film is decreased from 200 nm to the thickness confinement regime (less than 20 nm), the vertical phase segregation gradient of the donor and acceptor phases becomes less pronounced. In addition, observing the change in exciton bandwidth and the shift of absorption resonances (0-0 and 0-1) relative to neat donor and acceptor films, we find that the conjugation length and disorder in ultrathin films (20 nm) are less affected than thicker (200 nm) films by the addition of fullerene into the polymer. We believe that these findings could be important for discovering methods of precisely controlling the properties of bulk heterojunction films with crucial implications for designing more efficient organic-based photovoltaics.

Spray deposited poly-3-hexylthiophene thin film transistors

Organic thin film transistors (OTFTs) are attractive for large-area and low-cost applications such as display backplanes, environmental sensors, and radio-frequency identification circuits. However, these size and cost advantages cannot be leveraged by the most common techniques used in OTFT fabrication, i.e., spin coating or inkjet printing, because both methods are inherently slow. Spray deposition of organic thin films provides an alternative high throughput processing scheme in which large areas can be coated quickly. Although spray painted organic solar cells have been previously demonstrated, there is currently almost no work that discusses spray deposited OTFTs. In this work, fabrication of poly-3-hexylthiophene (P3HT) transistors via a spray deposition technique is investigated, and their resulting properties are compared to that of spin coated OTFTs.