Photorefractivity and photocurrent dynamics of triphenylamine-based polymer composites.

The photorefractive properties of triphenylamine polymer-based composites with various composition ratios were investigated via optical diffraction, response time, asymmetric energy transfer, and transient photocurrent. The composite consisted of a photoconductive polymer of poly((4-diphenylamino)benzyl acrylate), a photoconductive plasticizer of (4-diphenylamino)phenyl)methanol, a sensitizer of [6,6]-phenyl-C61-butyric acid methyl ester, and a nonlinear optical dye of (4-(azepan-1-yl)-benzylidene)malononitrile. The photorefractive properties and related quantities were dependent on the composition, which was related to the glass transition temperature of the photorefractive polymers. The quantum efficiency (QE) of photocarrier generation was evaluated from the initial slope of the transient photocurrent. Transient photocurrents were measured and showed two unique peaks: one in the range of 10-4 to 10-3 s and the other in the range of 10-1 to 1 s. The transient photocurrents was well simulated (or reproduced) by the expanded two-trapping site model with two kinds of photocarrier generation and recombination processes and two different trapping sites. The obtained photorefractive quantity of trap density was significantly related to the photoconductive parameters of QE.

In situ KPFM imaging of local photovoltaic characteristics of structured organic photovoltaic devices.

Here, we discuss the local photovoltaic characteristics of a structured bulk heterojunction, organic photovoltaic devices fabricated with a liquid carbazole, and a fullerene derivative based on analysis by scanning kelvin probe force microscopy (KPFM). Periodic photopolymerization induced by an interference pattern from two laser beams formed surface relief gratings (SRG) in the structured films. The surface potential distribution in the SRGs indicates the formation of donor and acceptor spatial distribution. Under illumination, the surface potential reversibly changed because of the generation of fullerene anions and hole transport from the films to substrates, which indicates that we successfully imaged the local photovoltaic characteristics of the structured photovoltaic devices. Using atomic force microscopy, we confirmed the formation of the SRG because of the material migration to the photopolymerized region of the films, which was induced by light exposure through photomasks. The structuring technique allows for the direct fabrication and the control of donor and acceptor spatial distribution in organic photonic and electronic devices with minimized material consumption. This in situ KPFM technique is indispensable to the fabrication of nanoscale electron donor and electron acceptor spatial distribution in the devices.

Efficient group delay averaging in graded-index plastic optical fiber with microscopic heterogeneous core.

Intrinsic mode coupling in a graded-index plastic optical fiber (GI POF) is investigated using the developed coupled power theory for a GI POF with a microscopic heterogeneous core. The results showed that the intrinsic material properties can induce random power transitions between all the guided modes, whereas the structural deformation of microbending results in nearest-neighbor coupling. It was numerically demonstrated that efficient group-delay averaging due to intrinsic mode coupling brings the pronounced bandwidth enhancement in fibers with much shorter length than the case of glass multimode fibers.

Thermally-induced phase transition of pseudorotaxane crystals: changes in conformation and interaction of the molecules and optical properties of the crystals.

This paper presents a pseudorotaxane that acts as a thermally driven molecular switch in the single-crystal state. Crystals of the cationic pseudorotaxane consisting of dibenzo[24]crown-8 (DB24C8) and N-(xylylammonium)-methylferrocene as the cyclic and axle component molecules, respectively, undergo crystalline-phase transition at 128 °C with heating and 116 °C with cooling, according to differential-scanning-calorimetry measurements. X-ray crystallographic analyses revealed that the phase transition was accompanied by rotation of the 4-methylphenyl group of the axle component molecule and a simultaneous shift in the position of the PF(6)(-) counteranion. Crystalline phase transition changes the conformation and position of the DB24C8 molecule relative to the ammonium cation partially; the interaction between the cyclic component and the PF(6)(-) anion in the crystal changes to a greater extent. Moreover, there are changes in the vibration angle (θ) and birefringence (Δn) on the (001) face of the crystal transitionally; θ is rotated by +12°, and Δn is decreased from 0.070 to 0.059 upon heating across the phase transition temperature. The phase transition and accompanying change in the optical properties of the crystal occur reversibly and repeatedly upon heating and cooling processes. The switching rotation of the aromatic plane of the molecule induces a change in the optical anisotropy of the crystal, which is regarded as a demonstration of a new type of optical crystal. Partial replacement of the PF(6)(-) anion with the bulkier AsF(6)(-) anion forms crystals with similar crystallographic parameters. An increase in the AsF(6)(-) content decreases the reversible-phase-transition temperature gradually down to 99 °C (T(end)) and 68 °C (T(exo)) ([AsF(6)(-)]:[PF(6)(-)] = 0.4:0.6).

Intrinsic transmission bandwidths of graded-index plastic optical fibers.

We theoretically demonstrate that microscopic heterogeneous properties can enhance the transmission bandwidths of graded-index plastic optical fibers (POFs) for short-haul communication networks. The heterogeneities of the POF cores are quantitatively correlated with mode couplings by modifying the coupled power equation with consideration of the spatial correlation characteristics of the heterogeneities. Using the modified theory, we clarify that the larger fluctuation size and/or amplitude results in higher bandwidth because of greater forward scattering and/or higher scattering efficiency, respectively. This suggests that the multimode fiber bandwidths can depend on the macroscopically observed index profiles as well as on the microscopic material properties.

Electron donor and acceptor spatial distribution in structured bulk heterojunction photovoltaic devices induced by periodic photopolymerization.

Donor and acceptor spatial distributions were directly formed in a surface relief grating of structured bulk heterojunction (BHJ) photovoltaic devices by simple periodic photopolymerization. Enhanced photocurrents were observed in the structured BHJ photovoltaic devices and formation of the D/A spatial distribution was confirmed by Kelvin probe force microscopy. This technique enables the fabrication of structured BHJ photovoltaic devices with solution-processable organic semiconductors, and has tremendous potential for controlling D/A spatial distribution in organic optoelectronics devices.

Photoinduced control over the self-organized orientation of amorphous molecular materials using polarized light.

Novel chiral amorphous molecular materials containing photoresponsive azobenzene moieties were designed and synthesized. These materials led to the formation of smooth and uniform thin films without grain boundaries. Photoirradiation of the thin film with linearly and elliptically polarized light caused trans-cis photoisomerization of the azobenzene moieties and resulted in an anisotropic orientation of the materials. Maximum change in a value of birefringence, Deltan, after irradiation of the linearly polarized light is about 0.08 with a response time of 10 s. However, when irradiation was ceased after photoinduced orientation, the value of Deltan decreased due to relaxation of the azobenzene moieties. Furthermore, these materials exhibited a high efficiency of a photoinduced polarization rotation over 30 deg mum(-1) after irradiation with the elliptically polarized light for 60 s. We also found that the efficiency depends on ellipticity of the incident light and on the thickness of the sample. The origin of the large change in the molecular orientation is the anisotropic arrangement of the azobenzenes in the terminal groups upon irradiation with the linearly and elliptically polarized light.

Surface waves in photorefractive polymer films.

We observed the temporal development of surface waves and investigated their power propagation loss in typical photorefractive polymer films sandwiched between ITO glass substrates. We found that amplified scattered waves generated in a pumped region started to develop into surface waves from a point where they reached the substrate through the self-bending effect. The surface waves propagated over a distance of 1.7 mm, thereby confining the power to a region at a distance of 30 microns from the substrate. Considerable propagation power loss of the surface waves was observed at a low pumping power of the beam; however, the power loss decreased considerably when the beam had high power.

Metal-organic thin-film transistor (MOTFT) based on a bis(o-diiminobenzosemiquinonate) nickel(II) complex.

The semiconducting film based on bis(o-diiminobenzosemiquinonate) nickel(II) complex showed uniaxial orientation structure along the normal to the substrate and good p-type metal-organic thin-film transistor (MOTFT) character.