This study develops a terahertz (THz) chemical microscope (TCM) that visualizes the distribution of chemical reaction on a silicon-based sensing chip. This chip, called the sensing plate, was fabricated by depositing Si thin films on a sapphire substrate and thermally oxidizing the Si film surface. The Si thin film of the sensing plate was irradiated from the substrate side by a femtosecond laser, generating THz pulses that were radiated into free space through the surface field effect of the Si thin film. The surface field responds to chemical reactions on the surface of the sensing plate, changing the amplitude of the THz pulses. This paper first demonstrates the principle and experimental setup of the TCM and performs the imaging and measurement of chemical reactions, including the reactions of bio-related materials.

Terahertz chemical microscopy has been developed for measuring the pH of a solution using only a small volume. The microsolution wells were fabricated on the surface of the sensing plate using a conventional photolithograph technique. Because the pH value can be calculated from the amplitude of a terahertz wave directly radiated from a sensing plate by a femtosecond laser irradiation, this method does not require any reference electrode in the solution. Thus, pH measurement can be achieved with a volume as small as 16 nL.

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Suppression of protein adsorption is a necessary property for materials used in the living body. In this study, thermoresponsive and degradable hydrogels were prepared by the radical polymerization of 2-methylene-1,3-dioxepane, 2-hydroxyethyl acrylate (HEA), and poly(ethylene glycol) monomethacrylate (PEGMA). The prepared hydrogels re-exposed PEG-grafted chains to the interface through surface degradation, which was confirmed by the maintenance of the chemical composition of the hydrogel surfaces after hydrolysis. Notably, adsorbed proteins can be removed from the hydrogel surfaces through hydrogel surface degradation at least thrice.

We have developed various types of terahertz sensing systems for evaluation of bio-related materials. Here, we describe a terahertz chemical microscopy that we have invented and demonstrate a label-free immune assay and evaluation of penetration speed of cosmetic liquid, each of which was realized using different way of use of the terahertz chemical microscopy.