Twisted π-system chromophores for all-optical switching.

Molecular chromophores with twisted π-electron systems have been shown to possess unprecedented values of the quadratic hyperpolarizability, ß, with very large real parts and much smaller imaginary parts. We report here an experimental and theoretical study which shows that these twisted chromophores also possess very large values of the real part of the cubic hyperpolarizability, γ, which is responsible for nonlinear refraction. Thus, for the two-ring twisted chromophore TMC-2 at 775 nm, relatively close to one-photon resonance, n(2) extrapolated to neat substance is large and positive (1.87 × 10(-13) cm(2)/W), leading to self-focusing. Furthermore, the third-order response includes a remarkably low two-photon absorption coefficient, which means minimal nonlinear optical losses: the T factor, α(2)λ/n(2), is 0.308. These characteristics are attributed to closely spaced singlet biradical and zwitterionic states and offer promise for applications in all-optical switching.

Structure-performance correlations in vapor phase deposited self-assembled nanodielectrics for organic field-effect transistors.

Organic field-effect transistor (OFETs) are fabricated using thin, vapor-deposited films of both the gate dielectric (vapor-deposited self-assembled nanodielectric, v-SAND) and the organic semiconductor. The nanoscopic self-assembled gate dielectrics are structurally organized via molecular precursor hydrogen-bonding interactions, followed by planarization with a vapor-deposited inorganic SiO(x) film. It is shown here that the metal-insulator-semiconductor (MIS) and OFET device electrical properties are sensitive to the v-SAND molecular dipolar orientation. In addition, alternating (organic/inorganic/organic/...) and nonalternating (1 organic layer + 1 inorganic layer) v-SAND microstructural arrangements are investigated, and the microstructures are correlated with MIS and OFET device characteristics. Films with alternating microstructures have larger capacitances than nonalternating films of the same thickness. However, they also have larger leakage currents, associated with the enhanced polarization of well-ordered dipolar films. For pentacene OFETs, the largest mobilities (approximately 3 cm(2)/(V s)) are associated with the high-capacitance nonalternating microstructure, and the lowest mobilities (approximately 0.5 cm(2)/(V s)) are associated with the alternating microstructure. v-SAND gated ambient-stable, n-type organic semiconductors show the opposite trends, where slightly greater OFET performance is observed with the lower-capacitance gate dielectric. For the p-type and one of the n-type v-SAND-based OFETs, the performance (under vacuum and ambient) is comparable to, or surpasses, that of previously reported devices using conventional SiO(2) as the gate dielectric. More importantly, the devices fabricated here operate at far lower voltages. These results indicate that v-SAND dielectrics are promising for future flexible organic electronics requiring low-temperature, solvent-free deposition conditions.