Since the discovery of highly conducting polyacetylene by Shirakawa, MacDiarmid, and Heeger in 1977, π-conjugated systems have attracted much attention as futuristic materials for the development and production of the next generation of electronics, that is, organic electronics. Conceptually, organic electronics are quite different from conventional inorganic solid state electronics because the structural versatility of organic semiconductors allows for the incorporation of functionality by molecular design. This versatility leads to a new era in the design of electronic devices. To date, the great number of π-conjugated semiconducting materials that have either been discovered or synthesized generate an exciting library of π-conjugated systems for use in organic electronics. 11 However, some key challenges for further advancement remain: the low mobility and stability of organic semiconductors, the lack of knowledge regarding structure property relationships for understanding the fundamental chemical aspects behind the structural design, and realization of desired properties. Organic field-effect transistors (OFETs) are a kind of device consisting of an organic semiconducting layer, a gate insulator layer, and three terminals (drain, source, and gate electrodes). OFETs are not only essential building blocks for the next generation of cheap and flexible organic circuits, but they also provide an important insight into the charge transport of πconjugated systems. Therefore, they act as strong tools for the exploration of the structure property relationships of πconjugated systems, such as parameters of field-effect mobility (μ, the drift velocity of carriers under unit electric field), current on/off ratio (the ratio of the maximum on-state current to the minimum off-state current), and threshold voltage (the minimum gate voltage that is required to turn on the transistor). 17 Since the discovery of OFETs in the 1980s, they have attracted much attention. Research onOFETs includes the discovery, design, and synthesis of π-conjugated systems for OFETs, device optimization, development of applications in radio frequency identification (RFID) tags, flexible displays, electronic papers, sensors, and so forth. It is beyond the scope of this review to cover all aspects of π-conjugated systems; hence, our focus will be on the performance analysis of π-conjugated systems in OFETs. This should make it possible to extract information regarding the fundamental merit of semiconducting π-conjugated materials and capture what is needed for newmaterials and what is the synthesis orientation of newπ-conjugated systems. In fact, for a new science with many practical applications, the field of organic electronics is progressing extremely rapidly. For example, using “organic field effect transistor” or “organic field effect transistors” as the query keywords to search the Web of Science citation database, it is possible to show the distribution of papers over recent years as shown in Figure 1A. It is very clear

Semiconducting π-conjugated systems in field-effect transistors: a material odyssey of organic electronics.

The increasing energy demand in the near future will force us to seek environmentally clean alternative energy resources. The emergence of nanomaterials as the new building blocks to construct light energy harvesting assemblies has opened up new ways to utilize renewable energy sources. This article discusses three major ways to utilize nanostructures for the design of solar energy conversion devices:  (i) Mimicking photosynthesis with donor−acceptor molecular assemblies or clusters, (ii) semiconductor assisted photocatalysis to produce fuels such as hydrogen, and (iii) nanostructure semiconductor based solar cells. This account further highlights some of the recent developments in these areas and points out the factors that limit the efficiency optimization. Strategies to employ ordered assemblies of semiconductor and metal nanoparticles, inorganic-organic hybrid assemblies, and carbon nanostructures in the energy conversion schemes are also discussed. Directing the future research efforts toward utiliza...

Meeting the Clean Energy Demand: Nanostructure Architectures for Solar Energy Conversion

In recent years, organic solar cells utilizing π-conjugated polymers have attracted widespread interest in both the academic and, increasingly, the commercial communities. These polymers are promising in terms of their electronic properties, low cost, versatility of functionalization, thin film flexibility, and ease of processing. These factors indicate that organic solar cells, although currently producing relatively low power conversion efficiencies (∼5-7%),1–3 compared to inorganic solar cells, have the potential to compete effectively with alternative solar cell technologies. However, in order for this to be feasible, the efficiencies of organic solar cells need further improvement. This is the focus of extensive studies worldwide. The backbone of a π-conjugated polymer is comprised of a linear series of overlapping pz orbitals that have formed via sp2 hybridization, thereby creating a conjugated chain of delocalized electron density. It is the interaction of these π electrons that dictates the electronic characteristics of the polymer. The energy levels become closely spaced as the delocalization length increases, resulting in a ‘band’ structure somewhat similar to that observed in inorganic solid-state semiconductors. In contrast to the latter, however, the primary photoexcitations in conjugated polymers are bound electron-hole pairs (excitons) rather than free charge carriers; this is largely due to their low dielectric constant and the presence of significant electron-lattice interactions and electron correlation effects.4 In the absence of a mechanism to dissociate the excitons into free charge carriers, the exciton will undergo radiative and nonradiative decay, with a typical exciton lifetime in the range from 100 ps to 1 ns. Achieving efficient charge photogeneration has long been recognized as a vital challenge for molecular-based solar cells. For example, the first organic solar cells were simple single-layer devices based on the pristine polymer and two electrodes of different work function. These devices, based on a Schottky diode structure, resulted in poor photocurrent efficiency.5–7 Relatively efficient photocurrent generation in an organic device was first reported by Tang in 1986,8 employing a vacuum-deposited CuPc/ perylene derivative donor/acceptor bilayer device. The differing electron affinities (and/or ionization potentials) between these two materials created an energy offset at their interface, thereby driving exciton dissociation. However, the efficiency of such bilayer devices is limited by the requirement of exciton diffusion to the donor/acceptor interface, typically requiring film thicknesses less than the optical absorption depth. Organic materials usually exhibit exciton diffusion lengths of ∼10 nm and optical absorption depths of 100 nm, although we note significant progress is now being made with organic materials with exciton diffusion lengths comparable to or exceeding their optical absorption depth.9–12 The observation of ultrafast photoinduced electron transfer13,14 from a conjugated polymer to C60 and the * To whom correspondence should be addressed. E-mail: j.durrant@ imperial.ac.uk. Chem. Rev. 2010, 110, 6736–6767 6736

Charge Photogeneration in Organic Solar Cells

Electron and ambipolar transport in organic field-effect transistors.

Unique electronic and chemical properties of metal nanoparticles have drawn the attention of chemists, physicists, biologists, and engineers who wish to use them for the development of new generation nanodevices. Metal nanoparticles such as gold and silver show noticeable photoactivity under UV−visible irradiation as is evident from the photoinduced fusion and fragmentation processes. Binding a photoactive molecule (e.g., pyrene) to metal nanoparticle enhances the photochemical activity and renders the organic−inorganic hybrid nanoassemblies suitable for light-harvesting and optoelectronic applications. The nature of charge-transfer interaction of fluorophore with gold surface dictates the pathways with which the excited-state deactivates. Obtaining insight into energy and electron-transfer processes is important to improve the charge separation efficiencies in metal−fluorophore nanoassemblies and photocatalytic activity of metal−semiconductor composites.

https://pubs.acs.org/doi/pdf/10.1021/jp0209289

Photophysical, photochemical and photocatalytic aspects of metal nanoparticles

We report the performance of solution-processed n-type organic thin-film transistors (OTFTs) based on C60 derivatives. Long-chain alkyl-substituted C60, C60-fused N-methylpyrrolidine-meta-C12 phenyl (C60MC12), was used as a semiconducting layer. The C60MC12-thin-film transistor shows high electron mobility of 0.067cm2∕Vs in saturation regime. From the result of x-ray diffraction analysis, the C60MC12 active layer forms highly ordered crystalline film. We found that self-assemble ability of long alkyl chains plays an important role for fabrication of highly ordered crystalline film, leading to achievement of high electron mobility in solution-processed n-type OTFTs.

Solution-processed n-type organic thin-film transistors with high field-effect mobility

Simulation of Fractal Immittance by Analog Circuits: An Approach to the Optimized Circuits

An extended model of flow orientation has been developed for analyzing the inplane anisotropy in Langmuir-Blodgett (LB) films by taking into account the viscoelastic nature of a condensed monolayer at the air-water interface as a Bingham plasticity. The model is based on a two-dimensional fluid and a line-sink as representing the monolayer and the substrate, respectively. The predictions from the present model with respect to the dichroic behavior have been experimentally verified employing a mixed LB system of a merocyanine dye and a fatty acid. The model is also consistent with the remarks from ESR line-shape analysis reported previously and those from analysis of the optical absorption spectra using the extended dipole theory. These results show that the inner stress due to the velocity gradient in the monolayer during the deposition is the origin of the in-plane anisotropy.

Kazuhiro Saito

Papers

Solution-processed n-type organic thin-film transistors with high field-effect mobility

Simulation of Fractal Immittance by Analog Circuits: An Approach to the Optimized Circuits

Origin of the In-Plane Anisotropy in Langmuir-Blodgett Films

Origin of the open-circuit voltage of organic thin-film solar cells based on conjugated polymers

Efficient oligothiophene:fullerene bulk heterojunction organic photovoltaic cells