Jeff Kettle

Pd-Catalysed Direct Arylation Polymerisation for Synthesis of Low-Bandgap Conjugated Polymers and Photovoltaic Performance

Low-bandgap conjugated copolymers based on a donor-acceptor structure have been synthesised via palladium-complex catalysed direct arylation polymerisation. Initially, we report the optimisation of the synthesis of poly(cyclopentadithiophene-alt-benzothiadiazole) (PCPDTBT) formed between cyclopentadithiophene and dibromobenzothiadiazole units. The polymerisation condition has been optimised, which affords high-molecular-weight polymers of up to M(n) = 70 k using N-methylpyrrolidone as a solvent. The polymers are used to fabricate organic photovoltaic devices and the best performing PCPDTBT device exhibits a moderate improvement over devices fabricated using the related polymer via Suzuki coupling. Similar polymerisation conditions have also been applied for other monomer units.

Cyclopentadithiophene-benzothiadiazole oligomers and polymers; synthesis, characterisation, field-effect transistor and photovoltaic characteristics

Conjugated oligomers with various ratios of cyclopentadithiophene (CPDT) to benzothiadiazole (BT) repeating units are reported. These oligomers can be polymerised to high molecular weight polymers (Mn > 100k) by oxidative polymerisation using iron(III)chloride. The electronic properties of these materials were examined by cyclic voltammetry and UV-vis spectroscopy and the results compared to those calculated using density functional theory (DFT). Polymers with optimum ratios of CPDT : BT (2 : 1) units show hole mobilities in excess of 10−2 cm2 V−1 s−1 as the active layer in organic field effect transistors (OFETs). Bulk heterojunction organic photovoltaic (OPV) devices of these polymers with PCBM as the electron acceptor show a power conversion efficiency of 2.1% when processed in the absence of any additives. The reported OFET performance is significantly higher than the parent PCPDTBT alternating copolymer (CPDT : BT = 1 : 1) and also shows a moderate improvement in OPV performance.

Effect of hole transporting layers on the performance of PCPDTBT : PCBM organic solar cells

We study the performance of PCPDTBT : C71-PCBM organic photovoltaics (OPVs) for three hole transporting layers (HTL); PEDOT : PSS, nickel oxide (NiO) and molybdenum trioxide (MoO3). We show that devices fabricated with nickel oxide HTL demonstrate the highest power conversion efficiency and theoretical data using a transfer matrix model confirms that this is as a result of increased absorption in the active layer as well as a result of improved series resistance and improved matching of energy levels. Device degradation is studied and lifetime is highest for the NiO and MoO3 based devices, proving that OPVs with this material system are less sensitive to the environmental effects of water, oxygen and irradiance.

Efficient solar cells are more stable: the impact of polymer molecular weight on performance of organic photovoltaics

The principle remaining challenge in the research area of organic photovoltaic (OPV) materials is to develop solar cells that combine high efficiency, stability and reproducibility. Here, we demonstrate an experimental strategy which has successfully addressed this challenge. We produced a number of samples of the highly efficient PTB7 polymer with various molecular weights (Mn ∼ 40–220k). OPV cells fabricated with this polymer demonstrated significant improvement of the cell efficiency (by ∼90% relative) and lifetime (by ∼300% relative) with the Mn increase. We attribute these effects to the lower density of recombination centers (persistent radical defects revealed by EPR spectroscopy) and better photoactive layer morphology in the samples with higher Mn. Relevance of the observed correlation between the OPV efficiency and stability is discussed.

Outdoor performance of organic photovoltaics: Diurnal analysis, dependence on temperature, irradiance, and degradation

The outdoor dependence of temperature and diurnal irradiance on inverted organic photovoltaic (OPV) module performance has been analysed and benchmarked against monocrystalline-silicon (c-Si) photovoltaic technology. This is first such report and it is observed that OPVs exhibit poorer performance under low light conditions, such as overcast days, as a result of inflexion behaviour in the current-voltage curves, which limits the open-circuit voltage (VOC) and fill factor. These characteristics can be removed by photo-annealing at higher irradiance levels, which occur diurnally as irradiance increases after sunrise. We also report the first temperature coefficients for OPVs from outdoor data; the OPV modules showed a positive temperature coefficient, which compared to a negative coefficient from the c-Si modules. Overall, the cell degradation outdoors appears very severe for these modules and highlights the need for improved barrier.

Fabrication of planar organic nanotransistors using low temperature thermal nanoimprint lithography for chemical sensor applications

A new fabrication process for the patterning of organic semiconductors at the nanoscale has been developed using low temperature thermal nanoimprint lithography and the details of this process are discussed. Novel planar nanotransistors have been fabricated and characterized from poly(3-hexylthiophene) (P3HT) and we demonstrate the feasibility of using such devices as highly sensitive chemical sensors.

Data preparation for focused ion beam machining of complex three-dimensional structures

The realization of complex three-dimensional structures at micro- and nanometre scale in various materials is of great importance for a number of micromechanical, microoptical, and microelectronic applications. Focused ion beam (FIB) patterning is one of the promising technologies for producing such three-dimensional structures utilizing layer-by-layer fabrication methods. A novel and efficient data preparation approach is proposed in this paper for layer-based FIB processing. By applying it, complex surfaces can be designed easily in any three-dimensional computer-aided design (CAD) package and then converted into GDSII streams for FIB sputtering or deposition. To validate the proposed CAD/CAM approach an experimental study was conducted. The factors that can affect the accuracy of the structures produced by layer-based FIB processing are also discussed. By assessing all stages of the proposed approach and the results of its experimental validation, conclusions are drawn about its applicability.

Organic photovoltaics based on a crosslinkable PCPDTBT analogue; synthesis, morphological studies, solar cell performance and enhanced lifetime†

A thermally crosslinkable poly(cyclopentadithiophene-alt-benzothiadiazole) (PCPDTBT) analogue copolymer with 2-ethylhexyl group and 5-hexenyl group on 4,4-positions of cyclopentadithiophene has been synthesised by palladium catalyzed Suzuki coupling reaction. Space-Charge Limited Current (SCLC) devices show hole mobility of up to 3 × 10−4 cm2 V−1 s−1. In addition, organic photovoltaics (OPVs) were fabricated using fullerene derivatives as acceptor materials. The best performing device exhibited Power Conversion Efficiency (PCE) at 2.0%, which could be improved to 3.7% after inclusion of dithiol additives. Most significantly, the lifetime of the OPV was enhanced by the crosslinking; when light soaked at 1 sun of irradiance, a half-life, t1/2 = 419 hours was measured, which is 51% improvement over an OPV using standard PCPDTBT. This higher stability is accounted for the crosslinkable structure of the polymer after annealing. The crosslinking reaction was confirmed by solubility tests, Fourier transform infrared spectroscopy and morphological analysis conducted by Atomic Force Microscopy and simultaneous synchrotron grazing-incidence small-/wide-angle X-ray scattering.

Overcoming material challenges for replication of “motheye lenses” using step and flash imprint lithography for optoelectronic applications

In this article, the fabrication and characterization of two-dimensional (2D) and three-dimensional (3D) structures using focused ion beam milling onto templates for step and flash imprint lithography (S-FIL) is discussed. It has been discovered that the 2D linewidth and height are closely related to the ion dose. At low doses (∼1pC∕μm2), the surface of the quartz template swells, thus, affecting the shape of the subsequent imprint. Furthermore, it has been shown that during UV curing of the S-FIL resist, the polymeric resist layer contracts as it solidifies, resulting in a dimensionally reduced replication of the original structure. The authors introduce a method to overcome the problem for 3D patterns, using a “multilayer” imprinting technique and apply this technique to the fabrication of “motheye” lenses. With respect to the imprinted replica, they show that the feature profile using this approach has a high fidelity in comparison to the template structure, and thus motheye lenses can be consistently ...

Cyclopentadithiophene–benzothiadiazole copolymers with permutations of repeating unit length and ratios; synthesis, optical and electrochemical properties and photovoltaic characteristics

Conjugated copolymers with varying ratios and lengths of cyclopentadithiophene (CPDT) to benzothiadiazole (BT) repeating units, –[(CPDT)x–(BT)y]n–, have been synthesized by palladium complex catalysed Suzuki coupling polymerisation, direct arylation polymerisation or oxidative polymerisation using iron(III) chloride. The different permutations of the co-polymers allow for tuning of the optical and electrical properties. To our knowledge, this is one of the first studies of its kind for conjugated polymers for use in OPVs. The optical band gaps were measured between 1.7 and 2.0 eV in film, in which the polymer with ratios of CPDT : BT (x : y = 1 : 1) units showed the lowest bandgap followed by x : y = 1 : 2, 2 : 1, 2 : 2 and 3 : 3. Hole mobility and solar cell performance of these polymers with PC61BM as the electron acceptor were measured. A relatively small variation in hole mobility was observed between polymers. However, the best reported power conversion efficiency (PCE) was measured at 2.5% when processed in the absence of any additives using the polymer with ratios of CPDT : BT (x : y = 2 : 2), which was followed by the ratios of x : y = 2 : 1, 1 : 1, 1 : 2 and 3 : 3, indicating that variation of the ratios and length of donor and acceptor units affect OPV performance and better performance is achievable by careful consideration of the donor-to-acceptor ratio.