Phase relations in the pseudo ternary system In2O3-TiO2-BO (B: Zn, Co and Ni) at 1200 °C in air

Francisco Brown, Ivan Edmundo Jacobo-Herrera, Victor Emmanuel Alvarez-Montaño, Noboru Kimizuka, Tomonosuke Hirano, Ryotaro Sekine, Saleem J. Denholme, Nobuaki Miyakawa, Akihiko Kudo, Akihide Iwase, Yuichi Michiue

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© 2017 Elsevier Inc. Phase relations in the pseudo ternary systems In2O3-TiO2-ZnO, In2O3-TiO2-CoO and In2O3-TiO2-NiO at 1200 °C in air were determined by means of a classic quenching method. In6Ti6BO22(B: Zn, Co and Ni) which has the monoclinic In(Fe1/4Ti3/4)O27/8-type of structure with a 4-dimensional super space group exists in a stable form. There exist homologous phases In1+x(Ti1/2Zn1/2)1−xO3(ZnO)m(m: natural number, 0<x ≤ 1) having the InGaO3(ZnO)m-type of the layered crystal structures such as In1+x(Ti1/2Zn1/2)1−xO3(ZnO) (0.12 ≤ x ≤ 0.29), In1+x(Ti1/2Zn1/2)1−x(ZnO)2(0.12 ≤ x ≤ 0.50), In1+x(Ti1/2Zn1/2)1−xO3(ZnO)3(0.15 ≤ x ≤ 0.84), In1+x(Ti1/2Zn1/2)1−x(ZnO)4(0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1−xO3(ZnO)5(0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1−x(ZnO)6(0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1−xO3(ZnO)7(0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1−x(ZnO)8(?<x ≤ 1), In1+x(Ti1/2Zn1/2)1−xO3(ZnO)9(0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1−x(ZnO)10(?<x ≤ 1), and In1+x(Ti1/2Zn1/2)1−xO3(ZnO)11(0.15 ≤ x ≤ 1)… without an upper limit of m in the pseudo ternary system In2O3-TiO2-ZnO. All the ions are on the trigonal lattice points, the In(III) is in the octahedral coordination with the oxygen and the {Inx(Ti1/2Zn1/2)1−xZnm} is in the trigonalbipyramidal coordination with oxygen in the crystal structures of each homologous compound. They have R3¯m (No. 166) for m = odd or P63/mmc (No. 194) for m = even in space group. Lattice constants for each of the homologous compounds as a hexagonal setting and In6Ti6BO22as the monoclinic system were determined by means of the powder X-ray diffraction method at room temperature. The temperature dependence of resistivity for In1+x(Ti1/2Zn1/2)1−x(ZnO)4(0.15 ≤ x ≤ 1) showed semiconducting-like behavior for all samples examined at T(K) = 2–300. The resistivity increased systematically with decreasing x (0.7 ≤ x ≤ 1), and it was found that samples where x ≤ 0.7 became insulators. The optical band gap Eg(eV) of In1+x(Ti1/2Zn1/2)1−x(ZnO)4has been estimated from the diffuse reflection spectra for the whole range of x (0.15 ≤ x ≤ 1). A minimum value of 2.0717 eV for x = 1 and a maximum one of 3.066 eV for x = 0.15 were observed. Dependence of the crystal structures of the InAO3(BO), In(Ti1/2B1/2)O3(B′O) and stability of In6Ti6BO22upon the constituent cations in the pseudo quaternary system In2O3-TiO2-A2O3-BO (A: Fe, Ga and Cr; B, B′: Mg, Zn, Co, Ni, Ca and Sr) were discussed in terms of their ionic radii and site preference effects.
Idioma originalInglés estadounidense
Páginas (desde-hasta)865-875
Número de páginas11
PublicaciónJournal of Solid State Chemistry
EstadoPublicada - 1 feb 2018


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