Kyoko Masui

Direct Laser Writing of 3D Architectures of Aligned Carbon Nanotubes

Direct laser writing through two-photon polymerization lithography is used to fabricate 3D nanostructures containing aligned single-wall carbon nanotubes (SWCNTs). SWCNTs are aligned in the laser scanning directions while they are embedded in the structure. The alignment is induced by spatial confinement, volume shrinkage, and the optical gradient force. This method is expected to lead to new applications based on aligned SWCNTs.

Laser fabrication of Au nanorod aggregates microstructures assisted by two-photon polymerization.

We demonstrate fabrication of Au nanorod aggregates microstructures by means of a femtosecond near-infrared laser. The laser light was tightly focused into colloidal Au nanorods dispersed in photopolymerizable metyl-methacrylate (MMA) compound to induce two-photon polymerization (TPP). TPP of MMA glued the nanorods together to form solid microstrucures of aggregates. The laser light excited a local surface plasmon, resulting in confinement of TPP in the vicinity of nanorods. Concurrenly occurring optical accumulation of nanorods created a unique mechanism for the formation of nanorod aggregates into desired microstructures. This technique would be a clue for a novel micro/nanofabrication method for plasmonic materials and devices.

Size dependent nanomechanics of coil spring shaped polymer nanowires.

Direct laser writing (DLW) via two-photon polymerization (TPP) has been established as a powerful technique for fabrication and integration of nanoscale components, as it enables the production of three dimensional (3D) micro/nano objects. This technique has indeed led to numerous applications, including micro- and nanoelectromechanical systems (MEMS/NEMS), metamaterials, mechanical metamaterials, and photonic crystals. However, as the feature sizes decrease, an urgent demand has emerged to uncover the mechanics of nanosized polymer materials. Here, we fabricate coil spring shaped polymer nanowires using DLW via two-photon polymerization. We find that even the nanocoil springs follow a linear-response against applied forces, following Hooke’s law, as revealed by compression tests using an atomic force microscope. Further, the elasticity of the polymer material is found to become significantly greater as the wire radius is decreased from 550 to 350 nm. Polarized Raman spectroscopy measurements show that polymer chains are aligned in nanowires along the axis, which may be responsible for the size dependence. Our findings provide insight into the nanomechanics of polymer materials fabricated by DLW, which leads to further applications based on nanosized polymer materials.

Macroscopic ensembles of aligned carbon nanotubes in bubble imprints studied by polarized raman microscopy

We study the alignment of single-wall carbon nanotubes (SWCNTs) in bubble imprints through polarized Raman microscopy. A hemispherical bubble containing SWCNTs is pressed against a glass substrate, resulting in an imprint of the bubble membrane with a coffee ring on the substrate. We find that macroscopic ensembles of aligned SWCNTs are obtained in the imprints, in which there are three patterns of orientations: (i) azimuthal alignment on the coffee ring, (ii) radial alignment at the edge of the membrane, and (iii) random orientation at the center of the membrane. We also find that the alignment of SWCNTs in the imprints can be manipulated by spinning bubbles. The orientation of SWCNTs on the coffee ring is directed radially, which is orthogonal to the case of unspun bubbles. This approach enables one to align SWCNTs in large quantities and in a short time, potentially opening up a wide range of CNT-based electronic and optical applications.

Two photon polymerization lithography for 3D microfabrication of single wall carbon nanotube/polymer composites

Two photon polymerization (TPP) lithography has been established as a powerful tool to develop 3D fine structures of polymer materials, opening up a wide range applications such as micro-electromechanical systems (MEMS). TPP lithography is also promising for 3D micro fabrication of nanocomposites embedded with nanomaterials such as metal nanoparticles. Here, we make use of TPP lithography to fabricate 3D micro structural single wall carbon nanotube (SWCNT)/polymer composites. SWCNTs exhibit remarkable mechanical, electrical, thermal and optical properties, which leads to enhance performances of polymers by loading SWCNTs. SWCNTs were uniformly dispersed in an acrylate UV-curable monomer including a few amounts of photo-initiator and photo-sensitizer. A femtosecond pulsed laser emitting at 780 nm was focused onto the resin, resulting in the photo-polymerization of a nanometric volume of the resin through TPP. By scanning the focus spot three dimensionally, arbitrary 3D structures were created. The spatial resolution of the fabrication was sub-micrometer, and SWCNTs were embedded in the sub-micro sized structures. The fabrication technique enables one to fabricate 3D micro structural SWCNT/polymer composites into desired shapes, and thus the technique should open up the further applications of SWCNT/polymer composites such as micro sized photomechanical actuators.

Femtosecond laser fabrication of gold nanorod/polymer composite microstructures

We present a fabrication method of gold nanorod/ polymer composite microstructures by means of a femtosecond near-infrared laser light. The mechanism of this method is based on a cooperation of two optical reactions; two-photon polymerization (TPP) reaction only at the surface of gold nanorods, and optical accumulation of gold nanorods in photo-polymerizable resin. Gold nanorods were mass-produced by seed mediated growth method, and were mono-dispersed in photo-resin. The wavelength of the laser light was tuned resonant to two-photon absorption of the photo-resin, and also close to a longitudinal local surface plasmon resonance (LSPR) mode of the gold nanorods. The laser light excited LSPR onto gold nanorods, resulting in the formation of thin polymer layer only at their surface through TPP. Concurrently occurring optical accumulation of gold nanorods by continuous irradiation of laser light, gold nanorods got together into focus spot. The TPP layer at the surface of gold nanorods worked as a glue to stick one another for forming their aggregated structure in micro/nano scale. By controlling the intensity and the exposure time of laser light, an optimal condition was found to induce dominant polymerization without any thermal damages. The scanning of the focus spot makes it possible to create arbitrary micro/nano structures. This method has a potential to create plasmonic optical materials by controlling the alignment of gold nanorods.

Residual pesticide detection on food with particle-enhanced Raman scattering

Modern farming relies highly on pesticides to protect agricultural food items from insects for high yield and better quality. Increasing use of pesticide has raised concern about its harmful effects on human health and hence it has become very important to detect even small amount of pesticide residues. Raman spectroscopy is a suitable nondestructive method for pesticide detection, however, it is not very effective for low concentration of pesticide molecules. Here, we report an approach based on plasmonic enhancement, namely, particle enhanced Raman spectroscopy (PERS), which is rapid, nondestructive and sensitive. In this technique, Raman signals are enhanced via the resonance excitation of localized plasmons in metallic nanoparticles. Gold nanostructures are promising materials that have ability to tune surface plasmon resonance frequency in visible to near-IR, which depends on shape and size of nanostructures. We synthesized gold nanorods (GNRs) with desired shape and size by seed mediated growth method, and successfully detected very tiny amount of pesticide present on food items. We also conformed that the detection of pesticide was not possible by usual Raman spectroscopy.