Effect of double doping on crystal structure and electrical conductivity of CaO and WO₃-doped Bi₂O₃

The atomic arrangement of WO₃-doped Bi₂O₃ was found similar to that of the fluorite structure. However, the electrical conductivity of WO₃-doped Bi₂O₃ is significantly lower than that of commonly used Y₂O₃-doped Bi₂O₃. The structure and electrical conductivity of samples formulated as (Ca_xW_0.15Bi_0.85-x)₂O_3.45-x (x=0, 0.1, 0.2 and 0.3) were investigated. The as-sintered (W_0.15Bi_0.85)₂O_3.45 and (Ca_0.1W_0.15Bi_0.75)₂O_3.35 exhibit similar single tetragonal structure that is isostructural with 7Bi₂O₃·2WO₃. Therefore, (W_0.15Bi_0.85)₂O_3.45 and (Ca_0.1W_0.15Bi_0.75)₂O_3.35 formed a superstructure consisting of 10 enlarged cubic fluorite subcells. However, the as-sintered samples consist of a tetragonal structure and tetragonal CaWO₄ for x=0.2 and 0.3 because the oxygen vacancy concentration increases. The conductivities of (Ca_xW_0.15Bi_0.85-x)₂O_3.45-x (x=0, 0.1, 0.2 and 0.3) did not exhibit linear dependence with x value. The best conductivity is 2.35×10^-2Scm^-1 at 700°C for x=0.1 that is higher than that of Ca-free (W_0.15Bi_0.85)₂O_3.45. The higher conductivity of (Ca_0.1W_0.15Bi_0.75)₂O_3.35 than (W_0.15Bi_0.85)₂O_3.45 may result from the higher anion vacancy concentration and more symmetrical structure.