Surface Nanofabrication in Photosensitive Polymers at the diffraction limit of light and down to 47 nm by Metal Tip-Enhanced Near Field light : Light Induced Nanomovement of Polymers

This paper discusses surface nanofabrication in azo-polymers. Nanoscale polymer movement is induced by a tightly focused laser beam in an azo-polymer film just at the diffraction limit of light. The deformation pattern which is produced by photoisomerization of the azo dye is strongly dependent on the incident laser polarization and the longitudinal focus position of the laser beam along the optical axis. The anisotropic nanofluidity of the polymer film and the optical gradient force played important roles in the light induced polymer movement. We also explored the limits of the size of the photo-induced deformation, and we found that the deformation depends on the laser intensity and the exposure time. The smallest deformation size achieved was 200 nm in full width of half maximum; a value which is nearly equal to the size of the diffraction limited laser spot. Beyond the limit of light diffraction, a nano protrusion was optically induced on the surface of the films by metal tip enhanced near-filed illumination. A silver coated tip was located inside the diffraction limited spot of a focused laser beam (460 nm), and an enhanced near-field, with 30 nm light spot, was generated in the vicinity of the tip due to localized surface plasmons. The incident light intensity was carefully regulated to induce surface nanodeformation by such a near-field spot. A nano protrusion with 47 nm full width of half maximum and 7 nm height was induced with a resolution beyond the diffraction limit of the light. The protrusion occurs because the film is attracted towards the tip end during irradiation. At the top of the protrusion, an anisotropic nanomovement of the polymer occurs in a direction nearly parallel to the polarization of the incident light, and suggests the existence at the tip end of not only a longitudinal, i.e., along the tip long axis, but also a lateral component of the electric field of light. The azo-polymer film helps map the electric field in the close vicinity of the tip.This paper discusses surface nanofabrication in azo-polymers. Nanoscale polymer movement is induced by a tightly focused laser beam in an azo-polymer film just at the diffraction limit of light. The deformation pattern which is produced by photoisomerization of the azo dye is strongly dependent on the incident laser polarization and the longitudinal focus position of the laser beam along the optical axis. The anisotropic nanofluidity of the polymer film and the optical gradient force played important roles in the light induced polymer movement. We also explored the limits of the size of the photo-induced deformation, and we found that the deformation depends on the laser intensity and the exposure time. The smallest deformation size achieved was 200 nm in full width of half maximum; a value which is nearly equal to the size of the diffraction limited laser spot. Beyond the limit of light diffraction, a nano protrusion was optically induced on the surface of the films by metal tip enhanced near-filed illumination. A silver coated tip was located inside the diffraction limited spot of a focused laser beam (460 nm), and an enhanced near-field, with 30 nm light spot, was generated in the vicinity of the tip due to localized surface plasmons. The incident light intensity was carefully regulated to induce surface nanodeformation by such a near-field spot. A nano protrusion with 47 nm full width of half maximum and 7 nm height was induced with a resolution beyond the diffraction limit of the light. The protrusion occurs because the film is attracted towards the tip end during irradiation. At the top of the protrusion, an anisotropic nanomovement of the polymer occurs in a direction nearly parallel to the polarization of the incident light, and suggests the existence at the tip end of not only a longitudinal, i.e., along the tip long axis, but also a lateral component of the electric field of light. The azo-polymer film helps map the electric field in the close vicinity of the tip

In-situ real-time observation of photo-induced nanoscale azo-polymer motions using high-speed atomic force microscopy combined with an inverted optical microscope

High-speed atomic force microscopy (HS-AFM) is an indispensable technique in the biological field owing to its excellent imaging capability for the real-time observation of biomolecules with high spatial resolution. Furthermore, recent developments have established a tip-scan stand-alone HS-AFM that can be combined with an optical microscope, drastically improving its versatility for studying various complex phenomena. Although HS-AFM has mainly been used in biology, it has considerable potential to contribute to various research fields. One of the great candidates is a photoactive material, such as an azo-polymer, which plays a vital role in multiple optical applications because of its unique nanoscale motion under light irradiation. In this study, we demonstrate the in-situ real-time observation of nanoscale azo-polymer motion by combining tip-scan HS-AFM with an optical system, allowing HS-AFM observations precisely aligned with a tightly focused laser position. We successfully observed the dynamic evolution of unique morphologies in azo-polymer films, attributed to photoinduced nano-movements. Moreover, real-time topographic line profile analyses facilitated precise and quantitative investigations of morphological changes, which provided novel insights into the deformation mechanism. This significant demonstration would pave the way for the application of HS-AFM in wide research fields, from biology to material science and physical chemistry

Optical Characterization of Ultra-Thin Films of Azo-Dye-Doped Polymers Using Ellipsometry and Surface Plasmon Resonance Spectroscopy

The determination of optical constants (i.e., real and imaginary parts of the complex refractive index (nc) and thickness (d)) of ultrathin films is often required in photonics. It may be done by using, for example, surface plasmon resonance (SPR) spectroscopy combined with either profilometry or atomic force microscopy (AFM). SPR yields the optical thickness (i.e., the product of nc and d) of the film, while profilometry and AFM yield its thickness, thereby allowing for the separate determination of nc and d. In this paper, we use SPR and profilometry to determine the complex refractive index of very thin (i.e., 58 nm) films of dye-doped polymers at different dye/polymer concentrations (a feature which constitutes the originality of this work), and we compare the SPR results with those obtained by using spectroscopic ellipsometry measurements performed on the same samples. To determine the optical properties of our film samples by ellipsometry, we used, for the theoretical fits to experimental data, Bruggeman’s effective medium model for the dye/polymer, assumed as a composite material, and the Lorentz model for dye absorption. We found an excellent agreement between the results obtained by SPR and ellipsometry, confirming that SPR is appropriate for measuring the optical properties of very thin coatings at a single light frequency, given that it is simpler in operation and data analysis than spectroscopic ellipsometry

Deuterated Glutamate-Mediated Neuronal Activity on Micro-Electrode Arrays

The excitatory synaptic transmission is mediated by glutamate (GLU) in neuronal networks of the mammalian brain. In addition to the synaptic GLU, extra-synaptic GLU is known to modulate the neuronal activity. In neuronal networks, GLU uptake is an important role of neurons and glial cells for lowering the concentration of extracellular GLU and to avoid the excitotoxicity. Monitoring the spatial distribution of intracellular GLU is important to study the uptake of GLU, but the approach has been hampered by the absence of appropriate GLU analogs that report the localization of GLU. Deuterium-labeled glutamate (GLU-D) is a promising tracer for monitoring the intracellular concentration of glutamate, but physiological properties of GLU-D have not been studied. Here we study the effects of extracellular GLU-D for the neuronal activity by using primary cultured rat hippocampal neurons that form neuronal networks on microelectrode array. The frequency of firing in the spontaneous activity of neurons increased with the increasing concentration of extracellular GLU-D. The frequency of synchronized burst activity in neurons increased similarly as we observed in the spontaneous activity. These changes of the neuronal activity with extracellular GLU-D were suppressed by antagonists of glutamate receptors. These results suggest that GLU-D can be used as an analog of GLU with equivalent effects for facilitating the neuronal activity. We anticipate GLU-D developing as a promising analog of GLU for studying the dynamics of glutamate during neuronal activity

Mapping the “Forbidden” Transverse-Optical Phonon in Single Strained Silicon (100) Nanowire

The accurate manipulation of strain in silicon nanowires can unveil new fundamental properties and enable novel or enhanced functionalities. To exploit these potentialities, it is essential to overcome major challenges at the fabrication and characterization levels. With this perspective, we have investigated the strain behavior in nanowires fabricated by patterning and etching of 15 nm thick tensile strained silicon (100) membranes. To this end, we have developed a method to excite the “forbidden” transverse-optical (TO) phonons in single tensile strained silicon nanowires using high-resolution polarized Raman spectroscopy. Detecting this phonon is critical for precise analysis of strain in nanoscale systems. The intensity of the measured Raman spectra is analyzed based on three-dimensional field distribution of radial, azimuthal, and linear polarizations focused by a high numerical aperture lens. The effects of sample geometry on the sensitivity of TO measurement are addressed. A significantly higher sensitivity is demonstrated for nanowires as compared to thin layers. In-plane and out-of-plane strain profiles in single nanowires are obtained through the simultaneous probe of local TO and longitudinal-optical (LO) phonons. New insights into strained nanowires mechanical properties are inferred from the measured strain profiles

Nano-Analysis of DNA Conformation Changes Induced by Transcription Factor Complex Binding Using Plasmonic Nanodimers

The plasmon resonant wavelength for a pair of gold nanoparticles, or gold nanodimer, increases inversely with the gap distance between the two nanoparticles. Taking advantage of this property, we performed nanoscale measurements of DNA conformation changes induced by transcription factor binding. Gold nanoparticles were bridged by double-stranded DC5 DNA that included binding sequences for the transcription factors SOX2 and PAX6, which interact on the DC5 enhancer sequence and activate transcription. The gold nanodimers bound by SOX2 shifted the plasmon resonant wavelength from 586.8 to 604.1 nm, indicating that SOX2 binding induces DNA bending. When the SOX2 formed a ternary complex with PAX6 on DC5, the plasmon resonant wavelength showed a further shift to 611.6 nm, indicating additional bending in the DC5 sequence. Furthermore, we investigated DNA conformation changes induced by SOX2 and PAX6 on the DC5-con sequence, which is a consensus sequence of DC5 for the PAX6 binding region that strengthens the PAX6 binding but at the same time disrupts SOX2–PAX6-dependent transcriptional activation. When the PAX6 binding sequence in DC5 was altered to DC5-con, the plasmon resonant wavelength shifted much less to 606.5 nm, which is more comparable to the 603.9 nm by SOX2 alone. These results demonstrate that SOX2–PAX6 cobinding induces a large conformation change in DC5 DNA