Donal D. C. Bradley

Simultaneous optimization of charge-carrier mobility and optical gain in semiconducting polymer films.

The combination of efficient light emission and high charge-carrier mobility has thus far proved elusive for polymer semiconductors, with high mobility typically achieved by cofacial pi-electron system to pi-electron system interactions that quench exciton luminescence. We report a new strategy, comprising the introduction of a limited number of more effective hopping sites between otherwise relatively isolated, and thus highly luminescent, polyfluorene chains. Our approach results in polymer films with large mobility (mu approximately 3-6 x 10(-2) cm2 V-1 s-1) and simultaneously excellent light-emission characteristics. These materials are expected to be of interest for light-emitting transistors, light-emitting diode sources for optical communications and may offer renewed hope for electrically pumped laser action. In the last context, optically pumped distributed feedback lasers comprising one-dimensional etched silica grating structures coated with polymer have state-of-the-art excitation thresholds (as low as 30 W cm(-2) (0.1 nJ per pulse or 0.3 microJ cm-2) for 10 Hz, 12 ns, 390 nm excitation) and slope efficiencies (up to 11%).

Monolithically integrated dye-doped PDMS long-pass filters for disposable on-chip fluorescence detection

We report the fabrication of high quality monolithically integrated optical long-pass filters, for use in disposable diagnostic microchips. The filters were prepared by incorporating dye molecules directly into the microfluidic chip substrate, thereby providing a fully integrated solution that removes the usual need for discrete optical filters. In brief, lysochrome dyes were added to a poly(dimethylsiloxane) (PDMS) monomer prior to moulding of the microchip from a structured SU-8 master. Optimum results were obtained using 1 mm layers of PDMS doped with 1200 microg mL(-1) Sudan II, which resulted in less than 0.01% transmittance below 500 nm (OD 4), >80% above 570 nm, and negligible autofluorescence. These spectral characteristics compare favourably with commercially available Schott-glass long-pass filters, indicating that high quality optical filters can be straightforwardly integrated into the form of PDMS microfluidic chips. The filters were found to be robust in use, showing only slight degradation after extended illumination and negligible dye leaching after prolonged exposure to aqueous solutions. The provision of low cost high quality integrated filters represents a key step towards the development of high-sensitivity disposable microfluidic devices for point-of-care diagnostics.

Low-voltage organic transistors based on solution processed semiconductors and self-assembled monolayer gate dielectrics

Reduction in the operating voltage of organic transistors is of high importance for successful implementation in low-power electronic applications. Here we report on low-voltage n-channel transistors fabricated employing a combination of soluble organic semiconductors and a self-assembled gate dielectric. The high geometric capacitance of the nanodielectric allows transistor operation below 2V. Solution processing is enabled by analysis of the surface energy compatibility of the dielectric and semiconductor solutions. Electron mobilities in the range of 0.01–0.04cm2∕Vs and threshold voltages ⩽0.35V are demonstrated. The present work paves the way toward solution processable low-voltage/power, organic complementary circuits.

Integrated thin-film polymer/fullerene photodetectors for on-chip microfluidic chemiluminescence detection

We report the use of solution-processed thin-film organic photodiodes for microscale chemiluminescence. The active layer of the photodiodes comprised a 1 : 1 blend by weight of the conjugated polymer poly(3-hexylthiophene) [P3HT] and [6,6]-phenyl-C(61)-butyric acid-methylester [PCBM]--a soluble derivative of C(60). The devices had an active area of 1 mm x 1 mm, and a broad-band response from 350 to 700 nm, with an external quantum efficiency of more than 50% between 450 and 550 nm. The photodiodes have a simple layered structure that permits facile integration with planar chip-based systems. To evaluate the suitability of the organic devices as integrated detectors for microscale chemiluminescence, a peroxyoxalate based chemiluminescence reaction (PO-CL) was monitored within a poly(dimethyl-siloxane) (PDMS) microfluidic device. Quantitation of hydrogen peroxide indicated excellent linearity and yielded a detection limit of 10 microM, comparable with previously reported results using micromachined silicon microfluidic chips with integrated silicon photodiodes. The combination of organic photodiodes with PDMS microfluidic chips offers a means of creating compact, sensitive and potentially low-cost microscale CL devices with wide-ranging applications in chemical and biological analysis and clinical diagnostics.

High-performance organic integrated circuits based on solution processable polymer-small molecule blends

The prospect of realizing high-performance organic circuits via large-area fabrication is attractive for many applications of organic microelectronics. Here we report solution processed organic field-effect transistors and circuits based on polymer-small molecule blends comprising of polytriarylamine and 5,11-bis(triethylsilylethynyl) anthradithiophene. By optimizing blend composition and deposition conditions we are able to demonstrate short channel, bottom-gate, bottom-contact transistors with high mobility and excellent reproducibility. Using these transistors we have built unipolar voltage inverters and ring oscillators with a single stage delay of 712 ns. These are among the fastest organic circuits reported to date and could satisfy the performance requirements of low-end electronic applications.

Towards microalbuminuria determination on a disposable diagnostic microchip with integrated fluorescence detection based on thin-film organic light emitting diodes.

As a first step towards a fully disposable stand-alone diagnostic microchip for determination of urinary human serum albumin (HSA), we report the use of a thin-film organic light emitting diode (OLED) as an excitation source for microscale fluorescence detection. The OLED has a peak emission wavelength of 540 nm, is simple to fabricate on flexible or rigid substrates, and operates at drive voltages below 10 V. In a fluorescence assay, HSA is reacted with Albumin Blue 580, generating a strong emission at 620 nm when excited with the OLED. Filter-less discrimination between excitation light and generated fluorescence is achieved through an orthogonal detection geometry. When the assay is performed in 800 microm deep and 800 microm wide microchannels on a poly(dimethylsiloxane)(PDMS) microchip at flow rates of 20 microL min(-1), HSA concentrations down to 10 mg L(-1) can be detected with a linear range from 10 to 100 mg L(-1). This sensitivity is sufficient for the determination of microalbuminuria (MAU), an increased urinary albumin excretion indicative of renal disease (clinical cut-off levels: 15-40 mg L(-1)).

Electronic properties of ZnO field-effect transistors fabricated by spray pyrolysis in ambient air

We report the application of spray pyrolysis (SP) for the deposition of high quality zinc oxide (ZnO) films and the fabrication of thin-film transistors. The chemical, structural, optical, and electronic properties of as-deposited ZnO films are studied using infrared spectroscopy, atomic force microscopy, UV-visible spectroscopic ellipsometry, and field-effect measurements. SP ZnO films are found to be uniform and polycrystalline with a band gap of 3.32 eV. ZnO transistors exhibit n-channel characteristics with electron mobility in the range 10–22u2002cm2/Vs. Device performance is found to depend on the work function of source/drain metal electrodes and on the device architecture employed.

Patterning of organic devices by interlayer lithography

We report a new lithographic procedure that enables the patterning of as-received semiconducting polymers and small molecules at the near micron level without causing discernible degradation of the patterned material. The method involves a minimum of processing steps, requires no modification of the active layer, and is compatible with both rigid and flexible substrates. The technique makes use of an intermediate resist layer between the substrate and the active layer, i.e.underneath the active layer, and involves the simultaneous patterning of the resist and active layers in a single expose/develop step. The technique has been successfully applied to the fabrication of flexible ITO-free light-emitting diodes and photodiodes, yielding peak quantum efficiencies of 8.8 cd A−1 and 57% respectively comparable to similar devices fabricated on ITO-coated glass. It is also readily extendible to the patterning on a single substrate of multiple devices incorporating different component materials, e.g. the red, green and blue pixels of a colour display.

Planar heterojunction organic photovoltaic diodes via a novel stamp transfer process

Solution-processed, planar heterojunction organic photovoltaic diodes offer several potential advantages over bulk heterojunction structures in relation to electrode selectivity, reduced dark currents and suitability for fundamental studies. They have, however, received less interest in recent years, in large part due to fabrication difficulties encountered for sequential solution deposition steps. In this study, a novel stamp transfer technique that allows ready fabrication of planar heterojunctions from a variety of solution-processed organic materials is applied to construct bilayer heterojunctions from poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM). We show that whilst as made planar heterojunctions yield relatively poor photocurrent generation (compared to equivalent bulk heterojunction devices), thermal annealing improves their performance via creation of a diffuse mixed P3HT:PCBM interface layer. Good device performance with the anticipated low dark current is then achieved. Spectroscopic ellipsometry allows us to monitor the changes in the interface layer that result from annealing. We also model the external quantum efficiency spectra and show that they are consistent with the ellipsometry data. Furthermore, it is shown that good device performance is strongly dependent on the P3HT and PCBM layer ordering with respect to the electrodes, confirming the important role of electrode selectivity. Melting of incorrectly ordered planar heterojunction devices (with donor next to the high work function and acceptor next to the low work function electrode) leads to the formation of bulk heterojunction devices, thereby recovering much of the desired performance.

New light from hybrid inorganic-organic emitters

We present the highlights of a research programme on hybrid inorganic?organic light emitters. These devices combine recent developments in III?V nitride technology (including UV emitting micro-arrays and specifically tailored quantum wells) with conjugated polymers to access the entire visible spectrum. Two types of devices are studied, those based on down conversion of the quantum well emission by radiative transfer and those based on non-radiative resonant energy transfer. The spectral and operating characteristics of the devices are described in detail. Selectable colour micro-arrays and bar emitters are demonstrated. The nature of the non-radiative energy transfer process has also been studied and we find transfer efficiencies of up to 43% at 15?K, with a 1/R2 dependence on the distance between quantum well and polymer layer, suggesting a plane?plane interaction. The relative importance of the non-radiative resonant energy transfer process increases with temperature to be up to 20 times more efficient, at 300?K, than the radiative transfer process.