Role and determining factor of substitutional defects on thermal conductivity: A study of La2(Zr1−xBx)2O7 (B = Hf, Ce, 0 ⩽ x ⩽ 0.5) pyrochlore solid solutions

The effects and determining factors of substitutional defects on thermal conductivity (k) have been studied by introducing Hf4+ (96% heavier than, but a similar size to, Zr4+) and Ce4+ (21% larger and 50% heavier), to replace Zr4+ on the B site of La2Zr2O7 pyrochlores. La2(Zr1−xCex)2O7, exhibits a flatter k-T curve and a dramatically reduced high-temperature plateau kmin. This is because the size rather than the mass difference between guest and host ions determines the flatness of k-T curves, whereas the absolute mass and size values of a dopant - particularly the latter - determine the plateau kmin, as kmin is proportional to the square root of the ratio of the elastic modulus E to the average atomic mass. Further, larger guest ion tends to effectively weaken a bond that shows ionic character and thus reduces E. The insights gained into the high-temperature plateau regime provide guidelines for the design and selection of a low-k material at high temperatures.