Excited-state dynamics in diketopyrrolopyrrole-based copolymer for organic photovoltaics investigated by transient optical spectroscopy

We investigate the photoexcited state dynamics in a donor-acceptor copolymer, poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]- pyrrole-1,4-dione-alt-naphthalene} (pDPP-TNT), by picosecond fluorescence and femtosecond transient absorption spectroscopies. Timeresolved fluorescence lifetime measurements of pDPP-TNT thin films reveal that the lifetime of the singlet excited state is 185 ± 5 ps and that singlet-singlet annihilation occurs at excitation photon densities above 6 × 1017 photons/cm3. From the results of singlet-singlet annihilation analysis, we estimate that the single-singlet annihilation rate constant is (6.0 ± 0.2) × 109cm3 s-1 and the singlet diffusion length is -7 nm. From the comparison of femtosecond transient absorption measurements and picosecond fluorescence measurements, it is found that the time profile of the photobleaching signal in the charge-transfer (CT) absorption band coincides with that of the fluorescence intensity and there is no indication of long-lived species, which clearly suggests that charged species, such as polaron pairs and triplet excitons, are not effectively photogenerated in the neat pDPP-TNT polymer.

Electrical characteristics of lateral heterostructure organic field-effect bipolar transistors

We describe and discuss the unique electrical characteristics of an organic field-effect transistor in which the active layer consists of a type II lateral heterojunction located approximately midway between the source and drain. The two active semiconductors on either side of the junction transport only one carrier type each, with the other becoming trapped, which leads to devices that operate in only the steady state when there is balanced electron and hole injections from the drain and source. We describe the unique transfer characteristics of such devices in two material systems.

Organic non-fullerene acceptors for organic photovoltaics

Heterojunction organic photovoltaics have been the subject of intensive academic interest over the past two decades, and significant commercial efforts have been directed towards this area with the vision of developing the next generation of low-cost solar cells. Materials development has played a vital role in the dramatic improvement of organic solar cell performance in recent years, and this is driven primarily by the advancement of p-type semiconductors as donor materials. With the highest performing solar cells today dominated by acceptors based on members of the fullerene family, much less attention has been devoted to other classes of n-type acceptors. In this review, we will provide an overview of the progress in the synthesis, characterization and implementation of the various classes of non-fullerenebased n-type organic acceptors for photovoltaic applications.

Pyridine-incorporated dihexylquaterthiophene : a novel blue emitter for organic light emitting diodes (OLEDs)

The synthesis and characterisation of 2,5-bis(5′-hexyl-[2,2′- bithiophen]-5-yl)pyridine (Th4PY) and its use as a blue emitter in organic light emitting diodes (OLEDs) is reported. Th4PY was synthesised in high yield using a straightforward Suzuki coupling route with commercially available starting materials. As Th4PY is both soluble and has low molecular weight, blue OLEDs were fabricated using both spin-coating and vacuum deposition thin film processing techniques to study the effect of processing on device performance. OLED devices using a spin-coated layer consisting of 4′,4′′- tris(N-carbazolyl)triphenylamine (TCTA) and 2-(4-biphenylyl)-5-(4-tert- butylphenyl)-1,3,4-oxadiazole (PBD) as a host matrix together with Th4PY as emitter exhibited highly efficient sky-blue emission with a low turn-on voltage of 3V, a maximum brightness close to 15000cdm-2 at 8V, and a maximum luminous efficiency of 7.4cdA -1 (6.3lmW -1) with CIE coordinates of x≤0.212, y≤0.320. The device performance characteristics are compared using various matrices and processing techniques. The promising sky-blue OLED performance, solution processability, and ambient stability make Th4PY a promising blue emitter for application in OLEDs.

High-mobility organic thin film transistors based on benzothiadiazole- sandwiched dihexylquaterthiophenes

We report here the synthesis, characterization, and organic thin-film transistor (OTFT) mobilities of 4,7-bis(5-(5-hexylthiophen-2-yl)thiophen-2-yl) benzo[1,2,5]thiadiazole (DH-BTZ-4T). DH-BTZ-4T was prepared in one high-yield step from commercially available materials using Suzuki chemistry and purified by column chromatography. OTFTs with hole mobilities of 0.17 cm2/(Vs) and on/off current ratios of 1 × 105 were prepared from DH-BTZ-4T active layers deposited by vacuum deposition. As DH-BTZ-4T is soluble in common solvents, solution processed devices were also prepared by spin coating yielding preliminary mobilities of 6.0 × 10-3 cm 2/(Vs). The promising mobilities and low band gap (1.90 eV) coupled with solution processability and ambient stability makes this material an excellent candidate for application in organic electronics.

Furan containing diketopyrrolopyrrole copolymers : synthesis, characterization, organic field effect transistor performance and photovoltaic properties

In this work, we report design, synthesis and characterization of solution processable low band gap polymer semiconductors, poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-phenylene} (PDPP-FPF), poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene} (PDPP-FNF) and poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-anthracene} (PDPP-FAF) using the furan-containing 3,6-di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBF) building block. As DBF acts as an acceptor moiety, a series of donor-acceptor (D-A) copolymers can be generated when it is attached alternatively with phenylene, naphthalene or anthracene donor comonomer blocks. Optical and electrochemical characterization of thin films of these polymers reveals band gaps in the range of 1.55-1.64 eV. These polymers exhibit excellent hole mobility when used as the active layer in organic thin-film transistor (OTFT) devices. Among the series, the highest hole mobility of 0.11 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices using PDPP-FNF. When these polymers are used as a donor and [70]PCBM as the acceptor in organic photovoltaic (OPV) devices, power conversion efficiencies (PCE) of 2.5 and 2.6% are obtained for PDPP-FAF and PDPP-FNF polymers, respectively. Such mobility values in OTFTs and performance in OPV make furan-containing DBF a very promising block for designing new polymer semiconductors for a wide range of organic electronic applications.

A benzothiadiazole end capped donor–acceptor based small molecule for organic electronics

A benzothiadiazole end-capped small molecule 3,6-bis(5-(benzo[c][1,2,5] thiadiazol-4-yl)thiophen-2-yl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-1, 4(2H,5H)-dione (BO-DPP-BTZ) using a fused aromatic moiety DPP (at the centre) is designed and synthesized. BO-DPP-BTZ is a donor-acceptor-donor (D-A-D) structure which possesses a band gap of 1.6 eV and exhibits a strong solid state ordering inferred from ∼120 nm red shift of the absorption maxima from solution to thin film. Field-effect transistors utilizing a spin coated thin film of BO-DPP-BTZ as an active layer exhibited a hole mobility of 0.06 cm 2 V-1 s-1. Solution-processed bulk heterojunction organic photovoltaics employing a blend of BO-DPP-BTZ and [70]PCBM demonstrated a power conversion efficiency of 0.9%.

Relation between charge carrier mobility and lifetime in organic photovoltaics

The relationship between charge carrier lifetime and mobility in a bulk heterojunction based organic solar cell, utilizing diketopyrrolopyrole- naphthalene co-polymer and PC71BM in the photoactive blend layer, is investigated using the photoinduced charge extraction by linearly increasing voltage technique. Light intensity, delay time, and temperature dependent experiments are used to quantify the charge carrier mobility and density as well as the temperature dependence of both. From the saturation of photoinduced current at high laser intensities, it is shown that Langevin-type bimolecular recombination is present in the studied system. The charge carrier lifetime, especially in Langevin systems, is discussed to be an ambiguous and unreliable parameter to determine the performance of organic solar cells, because of the dependence of charge carrier lifetime on charge carrier density, mobility, and type of recombination. It is revealed that the relation between charge mobility (μ) and lifetime (τ) is inversely proportional, where the μτ product is independent of temperature. The results indicate that in photovoltaic systems with Langevin type bimolecular recombination, the strategies to increase the charge lifetime might not be beneficial because of an accompanying reduction in charge carrier mobility. Instead, the focus on non-Langevin mechanisms of recombination is crucial, because this allows an increase in the charge extraction rate by improving the carrier lifetime, density, and mobility simultaneously. © 2013 AIP Publishing LLC.

Nanoscale phase domain structure and associated device performance of organic solar cells based on a diketopyrrolopyrrole polymer

We investigate the blend morphology and performance of bulk heterojunction organic photovoltaic devices comprising the donor polymer, pDPP-TNT (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) and the fullerene acceptor, [70]PCBM ([6,6]-phenyl C71-butyric acid methyl ester). The blend morphology is heavily dependent upon the solvent system used in the fabrication of thin films. Thin films spin-coated from chloroform possess a cobblestone-like morphology, consisting of thick, round-shaped [70]PCBM-rich mounds separated by thin polymer-rich valleys. The size of the [70]PCBM domains is found to depend on the overall film thickness. Thin films spin-coated from a chloroform:dichlorobenzene mixed solvent system are smooth and consist of a network of pDPP-TNT nanofibers embedded in a [70]PCBM-rich matrix. Rinsing the films in hexane selectively removes [70]PCBM and allows for analysis of domain size and purity. It also provides a means for investigating exciton dissociation efficiency through relative photoluminescence yield measurements. Devices fabricated from chloroform solutions show much poorer performance than the devices fabricated from the mixed solvent system; this disparity in performance is seen to be more pronounced with increasing film thickness. The primary cause for the improved performance of devices fabricated from mixed solvents is attributed to the greater donor-acceptor interfacial area and resulting greater capacity for charge carrier generation.

Measurement of contact voltage drop and resistance in organic solar cells

Bulk heterojunction organic solar cells based on poly[4,7-bis(3- dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] and [6,6]-phenyl C71-butyric acid methyl ester are investigated. A prominent kink is observed in the fourth quadrant of the current density-voltage (J-V) response. Annealing the active layer prior to cathode deposition eliminates the kink. The kink is attributed to an extraction barrier. The J-V response in these devices is well described by a power law. This behavior is attributed to an imbalance in charge carrier mobility. An expected photocurrent for the device displaying a kink in the J-V response is determined by fitting to a power law. The difference between the expected and measured photocurrent allows for the determination of a voltage drop within the device. Under simulated 1 sun irradiance, the peak voltage drop and contact resistance at short circuit are 0.14 V and 90 Ω, respectively. © 2012 American Institute of Physics.

Valuing the influence of underlying attitudes and the demand for organic milk in Japan

Subjective perceptions about a product affect consumer choice. Accordingly, acquiring the underlying demand characteristics that consumers find desirable is vital for firms planning future marketing strategies. However, the extent to which product-specific perceptions affect consumer choice is poorly understood. New agricultural standards for organic livestock were introduced in Japan in November 2005 and are expected to influence the market significantly. Choice modeling (CM) is used to explore how consumers evaluate the latent demands and conventional attributes (or tangible values) of organic milk. The results suggest that latent demands, along with socioeconomic characteristics and conventional attributes, provide strong incentives for consumers to move from the purchase of conventional milk to organic milk. The analysis indicates that latent demands reflecting the safeness of organic milk, the better taste of organic milk, the image of environmental friendliness in the production process, and the image of the health and comfort of the cows are important factors that influence consumers' purchasing decisions. However, each specific factor has a corresponding conventional tangible attribute that needs to be targeted in marketing strategy.

Engineering thin film semiconductor gas sensors to increase sensitivity and decrease operation temperature

Thin film nanostructured gas sensors typically operate at temperatures above 400°C, but lower temperature operation is highly desirable, especially for remote area field sensing as this reduces significantly power consumption. We have investigated a range of sensor materials based on both pure and doped tungsten oxide (mainly focusing on Fe-doping), deposited using both thermal evaporation and electron-beam evaporation, and using a variety of post-deposition annealing. The films show excellent sensitivity at operating temperatures as low as 150°C for detection of NO2. There is a definite relationship between the sensitivity and the crystallinity and nanostructure obtained through the deposition and heat treatment processes, as well as variations in the conductivity caused both by doping and heat treatmetn. The ultimate goal of this work is to control the sensing properties, including selectivity to specific gases through the engineering of the electronic properties and the nanostructure of the films.

Three-dimensional off-design numerical analysis of an organic Rankine cycle radial-inflow turbine

Optimisation of organic Rankine cycles(ORCs for binary cycle applications could play a major role in determining the competitiveness of low to moderate renewable sources. An important aspect of the optimisation is to maximise the turbine output power for a given resource. This requires careful attention to the turbine design notably through numerical simulations. Challenges in the numerical modelling of radial-inflow turbines using high-density working fluids still need to be addressed in order to improve the turbine design and better optimise ORCs. Thispaper presents preliminary 3D numerical simulations of a high-density radial-inflow ORC turbine in sensible geothermal conditions. Following extensive investigation of the operating conditions and thermodynamic cycle analysis, therefrigerant R143a is chosen as the high-density working fluid. The 1D design of the candidate radial-inflow turbine is presented in details. Furthermore, commercially-available software Ansys-CFX is used to perform preliminary steady-state 3D CFD simulations of the candidate R143a radial-inflow turbine for a number of operating conditions including off-design conditions. The real-gas properties are obtained using the Peng–Robinson equations of state.The thermodynamic ORC cycle is presented. The preliminary design created using dedicated radial-inflow turbine software Concepts-Rital is discussed and the 3D CFD results are presented and compared against the meanline analysis.

Greenhouse gas emissions from sub-tropical agricultural soils after addition of organic by-products

As the cost of mineral fertilisers increases globally, organic soil amendments (OAs) from agricultural sources are increasingly being used as substitutes for nitrogen. However, the impact of OAs on the production of greenhouse gases (CO2 and N2O) is not well understood. A 60-day laboratory incubation experiment was conducted to investigate the impacts of applying OAs (equivalent to 296 kg N ha−1 on average) on N2O and CO2 emissions and soil properties of clay and sandy loam soils from sugar cane production. The experiment included 6 treatments, one being an un-amended (UN) control with addition of five OAs being raw mill mud (MM), composted mill mud (CM), high N compost (HC), rice husk biochar (RB), and raw mill mud plus rice husk biochar (MB). These OAs were incubated at 60, 75 and 90% water-filled pore space (WFPS) at 25°C with urea (equivalent to 200 kg N ha−1) added to the soils thirty days after the incubation commenced. Results showed WFPS did not influence CO2 emissions over the 60 days but the magnitude of emissions as a proportion of C applied was RB < CM < MB < HC