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Several 14-membered thia crown ether ionophores having a bulky block subunit were synthesized, and their chemical structures and ion selectivities were examined in detail when these compounds were used as an ion-sensing component of an ion-selective electrode. The ionophores of both cyclic and noncyclic thia ethers exhibited a high selectivity for silver ion (Ag(+)), in which the sulfur atom in the ionophore molecule plays a role as the effective coordination donor site for the silver ion. The best Ag(+)-selective electrode was prepared with the 14-membered thia crown ether having one sulfur atom, three oxygen atoms, and a bulky pinan subunit. The ion selectivity of this electrode for Ag(+) was over 10(4) times that for other metal cations. In the case where the sulfide in the thia ether ionophore was changed to sulfoxide by oxidation, ion selectivity for mercury ion became higher; therefore, the sulfoxide was found to be an effective coordination site for the mercury ion. The ion selectivity features of noncyclic sulfide, sulfoxide, and sulfone were also examined and compared with the results of the cyclic and noncyclic thia ethers.

An investigation was made of the reasons why ferroelectric PbTiO3 films are hard to grow on single-crystal Si substrates. PbTiO3 films were formed on Si(100) and MgO(100) single-crystal substrates, and X-ray photoelectron spectroscopy (XPS) was used to analyze the composition, chemical structure and oxidation state at the interface between the substrate and the film. It was found that lead, oxygen and silicon diffused markedly at the interface and that the PbTiO3 film experienced both a lead deficiency and Si diffusion. These phenomena are thought to be the reasons why it is difficult to form good PbTiO3 films on silicon substrates by chemical vapor deposition (CVD). It was observed that the addition of TiO2 and ZrO2 films at the interface with the silicon substrate reduced the diffusion of Si to the PbTiO3 film.

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