Toshihiko Nagamura

Ultrafast wide range all-optical switch using complex refractive-index changes in a composite film of silver and polymer containing photochromic dye

An all-optical ultrafast switch which operates at a wide wavelength range has been demonstrated based on photoinduced changes of real and/or imaginary parts of complex refractive index in a composite thin film of silver and polymer containing photochromic spiropyran dye. Very fast switching ON and OFF of a reading beam within 20 ns in a 400–800 nm range was achieved at the incident angle of guided-wave mode using a photochromic spiropyran-doped polystyrene thin film and a ns pulsed UV or visible laser as a writing beam. These responses were caused by the changes of complex refractive index due to photochromism. No applied power was required to hold the switched state. An image was also written to the probe beam by irradiation through a pattern.

Ultrafast all-optical switch using complex refractive index changes of thin films containing photochromic dye

An all-optical switch has been proposed based on photoinduced changes of an imaginary part of complex refractive index in a composite thin film made by silver and polymer thin films containing photochromic dye. Very fast switching on and switching off of a reading beam was demonstrated at the incident angle of guided wave mode using a photochromic spiropyran-doped polystyrene thin film and a ns pulsed laser as a writing beam. These responses were caused by the changes of an extinction coefficient due to photochromism. No applied power was required to hold the switched state.

Interfacial Mobility of Polymers on Inorganic Solids

The segmental mobility of a typical amorphous polymer, polystyrene, at the interfaces with solid substrates was noninvasively examined by fluorescence lifetime measurements using evanescent wave excitation in conjunction with coarse-grained molecular dynamics simulation. The glass transition temperature (T(g)) was discernibly higher at the interface than in the internal bulk region. Measurements at different incident angles of excitation pulses revealed that T(g) became higher closer to the interface. The gradient became more marked with an increasing difference in the free energy at the interface between the polymer and solid substrate. The T(g) value at the interface decreased with decreasing molecular weight. However, the decrement for the interfacial T(g) was not as much as that for the bulk T(g), due to the restriction of chain end portions by the substrate. Finally, it was observed that when a film became thinner than 50 nm, the depressed mobility at the interface coupled with the enhanced mobility induced by the presence of the surface. The experimental and simulation results were in good accord with each other.

Polymer thin films containing Eu(III) complex as lanthanide lasing medium

Direct evidence of lanthanide(III) lasing using Eu(III) complex in polymer thin films (threshold level <0.05 mJ) is reported. The thin film consists of polystyrene containing Eu(III) complexes based on two criteria: (1) Higher emission quantum yield of Eu(III) complexes, which increases the rs (energy density), and (2) faster radiation rate at large B (Einstein coefficient). The microcavity was constructed by coating a glass substrate with a film having a high refractive index. The film thickness was found to be 1.71 mm. The threshold level for laser transmission was found to be <0.05 mJ.

Local conformation of poly(methyl methacrylate) at nitrogen and water interfaces

The local conformation of poly(methyl methacrylate) (PMMA) chains at the nitrogen (N2) and water interfaces was studied by infrared-visible sum-frequency generation (SFG) spectroscopy. Although SFG spectra in the C–H region for PMMA at the N2 interface have been hitherto reported, the peak assignments are not in accord with one another. Thus, we first made accurate assignments of SFG peaks using films, which had been well annealed at a temperature above the glass transition temperature for a long time, of three different deuterated PMMAs as well as normal protonated PMMA. At the N2 interface, hydrophobic functional groups such as α methyl, ester methyl and methylene groups were present. While the α methyl group was oriented along the direction parallel to the interface, ester methyl and methylene groups were oriented normal to the interface. Quantitative discussion concerning the orientation of the functional groups of PMMA at the N2 interface was aided by a model calculation. Once the PMMA film contacted water, the carbonyl groups of the PMMA side chains were oriented to the water phase to form hydrogen bonds with water molecules, resulting in the migration of ester methyl into the internal region of the film. Concurrently, the methylene groups became randomly oriented at the water interface and/or in part migrated into the internal region. Interestingly, the α methyl groups still existed at the water interface oriented along the parallel direction. The outermost region of PMMA in water can consist of hydrophilic and hydrophobic domains with sub-nanometre scale. Water molecules H-bond to themselves near the hydrophobic domains, leading to the formation of an ice-like structure of water molecules. However, water molecules adjacent to the hydrophilic domains H-bond with carbonyl groups.

Determination of performance on tunnel conduction through molecular wire using a conductive atomic force microscope

Performance of nonresonant tunnel conduction through a self-assembled monolayer of conjugated molecules fabricated on gold (111) was determined by virtue of nanometer-scale electrical probe measurement using a conductive atomic force microscope. Electrical measurements with nanometer spatial resolution enabled mapping of tunnel current as well as efficiency of tunnel conduction through molecular wire by analyzing length dependence on current. A series of conjugated molecules with different numbers of oligothiophene rings proved to possess a high tunnel-conduction efficiency.

Novel all optical light modulation based on complex refractive index changes of organic dye‐doped polymer film upon photoexcitation

A novel all‐optical light modulation has been proposed based on photoinduced changes of an imaginary part of complex refractive index in guided wave geometry. Very fast and repeated modulation of a reading beam (reflected intensity) was demonstrated at the incident angle corresponding to a sharp guided wave resonance using phthalocyanine‐doped poly(vinyl alcohol) film as a photoresponsive layer and a nanosecond pulsed laser as a writing beam. Such responses were mainly due to the formation and decay of excited triplet phthalocyanine. The rise and fall time was markedly improved as compared with previous systems based on photothermal changes of the refractive index.

Ultrafast optical switching by photoinduced electrochromism in cast films of polymeric 4,4′-bipyridinium salts with di-iodides

Femtosecond dynamics of color changes due to photoinduced electron transfer and reverse reactions in polymeric 4,4′-bipyridinium di-iodides salts were studied with a fs laser pump–probe technique. The characteristic color change was shown to take place in less than 1 ps by fs-laser excitation of an ion-pair charge-transfer band, which may be applied to ultrafast THz all-optical switching devices using visible light.

Luminescent charge-transfer complexes of 4,4′-bipyridinium ion with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion

Abstract 4,4′-bipyridinium ions form ion-pair charge-transfer (CT) complexes with tetrakis[3,5-bis(trifluoromethyl)phenyl] borate anion with a discrete absorption maximum at 420 nm in methanol and at 475 nm in 1,2-dimethoxyethane. These CT complexes in 1,2-dimethoxyethane at 20°C show broad structureless luminescence with a maximum at 553 nm, almost a mirror image of the CT absorption spectrum. The luminescence could not be observed for CT complexes in methanol. This is the first observation of luminescence from excited ion-pair CT complexes in solutions at room temperature.

Variable-temperature independently driven four-tip scanning tunneling microscope

The authors have developed an ultrahigh vacuum (UHV) variable-temperature four-tip scanning tunneling microscope (STM), operating from room temperature down to 7 K, combined with a scanning electron microscope (SEM). Four STM tips are mechanically and electrically independent and capable of positioning in arbitrary configurations in nanometer precision. An integrated controller system for both of the multitip STM and SEM with a single computer has also been developed, which enables the four tips to operate either for STM imaging independently and for four-point probe (4PP) conductivity measurements cooperatively. Atomic-resolution STM images of graphite were obtained simultaneously by the four tips. Conductivity measurements by 4PP method were also performed at various temperatures with the four tips in square arrangement with direct contact to the sample surface.