Meguya Ryu

Silk fibroin as a water-soluble bio-resist and its thermal properties

Thermal diffusivity of silk fibroin films, α = (1.6 ± 0.24) × 10−7 m2 s−1, was measured by a direct contact method. It was shown to be reduced down to ∼1 × 10−7 m2 s−1 in the crystallized phase, consistent with the multi-domain composition of β-sheet assemblies. Crystalline silk with β-sheets was made by dipping into alcohol and was used as a positive electron beam lithography (EBL) resist. It is shown by direct IR imaging of the 1619 cm−1 amide-I CO spectral signature and 3290 cm−1 amide-A N–H stretching band that an e-beam is responsible for unzipping β-sheets, which subsequently results in exposed areas returning to a water soluble state. This makes it possible to develop a water-based biocompatible silk resist and use it in lithography applications. The general principles of protein crystallization, traceable to spectral changes in IR amide bands of silk, can be used as a guide for the creation of new protein EBL resists and to quantify the electron dose required for solubility. Foam formation and laser treatments of silk can provide new approaches in surface functionalization and fabrication of 3D bio-scaffolds.

Nanostructured Antireflective and Thermoisolative Cicada Wings

Inter-related mechanical, thermal, and optical macroscopic properties of biomaterials are defined at the nanoscale by their constituent structures and patterns, which underpin complex functions of an entire bio-object. Here, the temperature diffusivity of a cicada (Cyclochila australasiae) wing with nanotextured surfaces was measured using two complementary techniques: a direct contact method and IR imaging. The 4-6-μm-thick wing section was shown to have a thermal diffusivity of α⊥ = (0.71 ± 0.15) × 10(-7) m(2)/s, as measured by the contact temperature wave method along the thickness of the wing; it corresponds to the inherent thermal property of the cuticle. The in-plane thermal diffusivity value of the wing was determined by IR imaging and was considerably larger at α∥ = (3.6 ± 0.2) × 10(-7) m(2)/s as a result of heat transport via air. Optical properties of wings covered with nanospikes were numerically simulated using an accurate 3D model of the wing pattern and showed that light is concentrated between spikes where intensity is enhanced by up to 3- to 4-fold. The closely packed pattern of nanospikes reduces the reflectivity of the wing throughout the visible light spectrum and over a wide range of incident angles, hence acting as an antireflection coating.

Silk: Optical Properties over 12.6 Octaves THz-IR-Visible-UV Range

Domestic (Bombyx mori) and wild (Antheraea pernyi) silk fibers were characterised over a wide spectral range from THz 8 cm−1 (λ= 1.25 mm, f= 0.24 THz) to deep-UV 50×103 cm−1 (λ= 200 nm, f= 1500 THz) wavelengths or over a 12.6 octave frequency range. Spectral features at β-sheet, α-coil and amorphous fibroin were analysed at different spectral ranges. Single fiber cross sections at mid-IR were used to determine spatial distribution of different silk constituents and revealed an α-coil rich core and more broadly spread β-sheets in natural silk fibers obtained from wild Antheraea pernyi moths. Low energy T-ray bands at 243 and 229 cm−1 were observed in crystalline fibers of domestic and wild silk fibers, respectively, and showed no spectral shift down to 78 K temperature. A distinct 20±4 cm−1 band was observed in the crystalline Antheraea pernyi silk fibers. Systematic analysis and assignment of the observed spectral bands is presented. Water solubility and biodegradability of silk, required for bio-medical and sensor applications, are directly inferred from specific spectral bands.

Thermal conductivity of silicon nanocrystals and polystyrene nanocomposite thin films

Silicon nanocrystals (SiNCs) are well known for their size-dependent optical and electronic properties; they also have the potential for low yet controllable thermal properties. As a silicon-based low-thermal conductivity material is required in microdevice applications, SiNCs can be utilized for thermal insulation. In this paper, SiNCs and polymer nanocomposites were produced, and their thermal conductivity, including the density and specific heat, was measured. Measurement results were compared with thermal conductivity models for composite materials, and the comparison shows a decreasing value of the thermal conductivity, indicating the effect of the size and presence of the nanostructure on the thermal conductivity. Moreover, employing silicon inks at room temperature during the fabrication process enables a low cost of fabrication and preserves the unique properties of SiNCs.

Black-CuO: surface-enhanced Raman scattering and infrared properties.

Large surface area samples of nanotextured black CuO were prepared by chemical etching of Cu for use in surface-enhanced Raman scattering (SERS). The SERS intensity of a self-assembled monolayer (SAM) of thiophenol was proportional to the thickness of a nanoscale-conformal Au film deposited by magnetron sputtering over the black CuO. A very high SERS yield of ∼10(4) counts per s per mW was observed for the thiophenol SAM on the thickest Au films studied here. Synchrotron X-ray photoelectron spectroscopy was used to confirm that the surface of the chemically etched Cu was covered by high purity CuO. IR spectral characterization of the black CuO showed a close to linear increase in reflectivity from 25 to 100% over the range of 4000-500 cm(-1) wavenumbers (or 2.5-20 μm in wavelength). Sensing applications and thermal effects in SERS are discussed.

Photo-controllable thermal diffusivity and thermal conductivity driven by the orientation change of nematic liquid crystal with azo-dendrimers

We measured the temperature dependences of anisotropic thermal properties, i.e., thermal diffusivity, thermal effusivity, thermal conductivity, and heat capacity per unit volume, of a nematogen 4′-n-pentyloxybiphenyl-4-carbonitrile (5OCB) containing a small amount (0.02 wt. %) of dendritic azobenzene derivatives (azo-dendrimer), using a temperature wave method. The azo-dendrimers spontaneously adsorb on cell surfaces and act as a command surface, i.e., photo-induced planar/homeotropic alignment by ultraviolet/visible light illumination. By using this effect, we demonstrated thermal property changes except for the heat capacity by almost two times within a few tens of seconds. The phenomenon can be applied to a sheet with photo-controllable thermal diffusivity or thermal conductivity.

Si-based infrared optical filters

Abstract. Pyramidal silicon nanospikes, termed black-Si (b-Si), with controlled height of 0.2 to 1  μm, were fabricated by plasma etching over 3-in wafers and were shown to act as variable density filters in a wide range of the IR spectrum 2.5 to 20  μm, with transmission and its spectral gradient dependent on the height of the spikes. Such variable density IR filters can be utilized for imaging and monitoring applications. Narrow IR notch filters were realized with gold mesh arrays on Si wafers prospective for applications in surface-enhanced IR absorption sensing and “cold materials” for heat radiation into atmospheric IR transmission window. Both types of filters for IR: spectrally variable and notch are made by simple fabrication methods.

Micro-thermocouple on nano-membrane: thermometer for nanoscale measurements

A thermocouple of Au-Ni with only 2.5-μm-wide electrodes on a 30-nm-thick Si3N4 membrane was fabricated by a simple low-resolution electron beam lithography and lift off procedure. The thermocouple is shown to be sensitive to heat generated by laser as well as an electron beam. Nano-thin membrane was used to reach a high spatial resolution of energy deposition and to realise a heat source of sub-1 μm diameter. This was achieved due to a limited generation of secondary electrons, which increase a lateral energy deposition. A low thermal capacitance of the fabricated devices is useful for the real time monitoring of small and fast temperature changes, e.g., due to convection, and can be detected through an optical and mechanical barrier of the nano-thin membrane. Temperature changes up to ~2 × 105 K/s can be measured at 10 kHz rate. A simultaneous down-sizing of both, the heat detector and heat source strongly required for creation of thermal microscopy is demonstrated. Peculiarities of Seebeck constant (thermopower) dependence on electron injection into thermocouple are discussed. Modeling of thermal flows on a nano-membrane with presence of a micro-thermocouple was carried out to compare with experimentally measured temporal response.

Orientational Mapping Augmented Sub-Wavelength Hyper-Spectral Imaging of Silk

Molecular alignment underpins optical, mechanical, and thermal properties of materials, however, its direct measurement from volumes with micrometer dimensions is not accessible, especially, for structurally complex bio-materials. How the molecular alignment is linked to extraordinary properties of silk and its amorphous-crystalline composition has to be accessed by a direct measurement from a single silk fiber. Here, we show orientation mapping of the internal silk fiber structure via polarisation-dependent IR absorbance at high spatial resolution of 4.2 μm and 1.9 μm in a hyper-spectral IR imaging by attenuated total reflection using synchrotron radiation in the spectral fingerprint region around 6 μm wavelength. Free-standing longitudinal micro-slices of silk fibers, thinner than the fiber cross section, were prepared by microtome for the four polarization method to directly measure the orientational sensitivity of absorbance in the molecular fingerprint spectral window of the amide bands of β-sheet polypeptides of silk. Microtomed lateral slices of silk fibers, which may avoid possible artefacts that affect spectroscopic measurements with fibers of an elliptical cross sections were used in the study. Amorphisation of silk by ultra-short laser single-pulse exposure is demonstrated.

Non-contact temperature field measurement of solids by infrared multispectral thermotransmittance

This work aims to achieve contactless absolute-temperature measurements of infrared-semi-transparent solids using an infrared thermal and spectroscopic imaging technique. The multispectral thermo-transmittance coefficient fields in the 3–5 μm wavelength range for Sapphire, KBr, and Silicon are determined to be 6 × 10−4 K−1, 4 × 10−4 K−1, and −3 × 10−3 K−1, respectively. The most interesting result is the high temperature-dependent transmittance coefficient in the middle wave infrared region. With these coefficients, the absolute temperature fields in a range from room temperature to 140 °C are shown.