Stable holographic gratings with small-molecular trisazobenzene derivatives.

We present a series of small-molecular trisazobenzene chromophores, including, for instance, 1,3,5-tris{[4-[4-[(4-cyanophenyl)azo]phenoxy]butyryl]amino}benzene that feature a remarkably stable light-induced orientation in initially amorphous thin-film architectures. It is demonstrated that for optimal performance it is critical to design chemical structures that allow formation of both an amorphous and a liquid-crystalline phase. In the present approach, the liquid-crystalline feature was introduced by inserting decoupling spacers between a trisfunctionalized benzene core and the three azobenzene moieties, as well as adding polar end groups to the latter. To compensate for the deleterious reduction of the glass transition temperature associated with the spacers in the compounds, polar units were incorporated between the benzene core and the side groups. Intriguingly, the molecular glasses that feature a latent liquid-crystalline phase display a remarkable "postdevelopment", i.e., an increase of the amplitude of refractive index modulation in holographic experiments after writing of optical gratings is arrested, exceeding 20% for the previously mentioned derivative. Thus, these nonpolymeric, azobenzene-containing compounds presented in this work appear to be attractive candidates for fabrication of stable holographic volume gratings.

Multicomponent semiconducting polymer systems with low crystallization-induced percolation threshold.

Blends and other multicomponent systems are used in various polymer applications to meet multiple requirements that cannot be fulfilled by a single material. In polymer optoelectronic devices it is often desirable to combine the semiconducting properties of the conjugated species with the excellent mechanical properties of certain commodity polymers. Here we investigate bicomponent blends comprising semicrystalline regioregular poly(3-hexylthiophene) and selected semicrystalline commodity polymers, and show that, owing to a highly favourable, crystallization-induced phase segregation of the two components, during which the semiconductor is predominantly expelled to the surfaces of cast films, we can obtain vertically stratified structures in a one-step process. Incorporating these as active layers in polymer field-effect transistors, we find that the concentration of the semiconductor can be reduced to values as low as 3 wt% without any degradation in device performance. This is in stark contrast to blends containing an amorphous insulating polymer, for which significant reduction in electrical performance was reported. Crystalline-crystalline/semiconducting-insulating multicomponent systems offer expanded flexibility for realizing high-performance semiconducting architectures at drastically reduced materials cost with improved mechanical properties and environmental stability, without the need to design all performance requirements into the active semiconducting polymer itself.

Crystalline-crystalline block copolymers of regioregular poly(3-hexylthiophene) and polyethylene by ring-opening metathesis polymerization.

Block copolymers of regioregular poly(3-hexylthiophene) (P3HT) and polyethylene (PE) were synthesized through the chain transfer of olefin-terminated P3HT in the presence of cyclooctene via ring-opening metathesis polymerization (ROMP). Subsequent hydrogenation of the poly(cyclooctene) block yielded high molecular weight, crystalline-crystalline P3HT-PE block copolymers, which are thermally stable and resistant to solvents under ambient conditions. These copolymers were characterized by 1H NMR, DSC, and WAXS and represent the first materials of a class of crystalline-crystalline semiconducting-insulating block copolymers.

Organic thin-film electronics from vitreous solution-processed rubrene hypereutectics.

Electronic devices based on single crystals of organic semiconductors provide powerful means for studying intrinsic charge-transport phenomena and their fundamental electronic limits. However, for technological exploitation, it is imperative not to be confined to the tedious growth and cumbersome manipulation of molecular crystals-which generally show notoriously poor mechanical properties-but to be able to process such materials into robust architectures by simple and efficient means. Here, we advance a general route for facile fabrication of thin-film devices from solution. The key beneficial feature of our process-and the principal difference from existing vapour deposition and solution-processing schemes-is the incorporation of a glass-inducing diluent that enables controlled crystallization from an initial vitreous state of the organic semiconductor, formed in a selected area of the phase diagram of the two constituents. We find that the vitrifying diluent does not adversely affect device performance. Indeed, our environmentally stable, discrete rubrene-based transistors rival amorphous silicon devices, reaching saturated mobilities of up to 0.7 cm2 V-1 s-1, ON-OFF ratios of >or=10(6) and subthreshold slopes as steep as 0.5 V per decade. A nearly temperature-independent device mobility, indicative of a high crystalline quality of our solution-processed, rubrene-based films, corroborates these findings. Inverter and ring-oscillator structures are also demonstrated.