Intercalation route to nano-hybrids: inorganic/organic-high T_c cuprate hybrid materials

Abstract

A systematic application of intercalation techniques to layered superconducting oxides enables us to open a new chapter in the development of nano-hybrids with various functions. Recently we were successful in preparing a new series of inorganic-inorganic nano-hybrids, M-X-Bi₂Sr₂Ca_m–1Cu_mO_y (M=Hg, Ag, Au; X=Br, I; m=1-3) and organic-inorganic ones, R₂HgI₄-Bi₂Sr₂Ca_m–1Cu_mO_y (R=organic cation). Our synthetic strategies are based on (1) HSAB (hard-soft acid-base) interactions and (2) interlayer complexation concepts. Since the iodine species in IBi₂Sr₂Ca_m–1Cu_mO_y are stabilized as I3– (soft base) with a charge transfer between host and guest, soft Lewis acids like Ag⁺, Au⁺, and Hg²⁺ can be further intercalated into the iodine layers inbetween the (Bi-O) double layers. On the other hand, new organic-inorganic nano-hybrids (R₂HgI₄-Bi₂Sr₂Ca_m–1Cu_mO_y) have also been achieved through the intercalative complex-salt formation reaction between preintercalated HgI₂ molecules and R⁺I^– salts in the interlayer space of Bi₂Sr₂Ca_m–1Cu_mO_y. Compared to the pure compounds the superconducting transition temperatures of the organic-salt intercalates are little changed even with a large basal increment upon intercalation, indicating a two-dimensional nature of the high-T _c superconductivity. From the viewpoint of application, the intercalation of large organic molecules provides a new synthetic route to high-T _c superconducting thin-film and nano-particles by separating superconducting blocks into isolated single sheets.

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