用电子密度泛函理论（DFT）研究了萤石型ThO $_{2}$与三价阳离子（Sc，In，Y，Nd，La）氧化物固溶体中的混合和缺陷有序的热力学.通过DFT计算的晶格代数技术枚举的结构，我们确定了最低能量的模式，为四个单独的掺杂剂浓度的缺陷集群。最稳定的结构的特征在于氧亚晶格上最近邻空位之间的排斥相互作用。相对于组成氧化物的形成的结晶度对于所考虑的所有掺杂剂都是正的，并且显示出随着三价掺杂剂的尺寸和电负性的减小而在量值上减小的趋势。由于La掺杂剂的小的正形成势和低的氧空位结合能，预测La $_{2}$ O $_{3}$ -ThO $_{2}$固溶体相对于所考虑的其它异价掺杂剂具有相对高的离子电导率。我们的研究结果进行了比较，为更广泛的研究ZrO $_{2}$和CeO $_{2}$萤石结构的三价阳离子的固溶体。
英文摘要：
The energetics of mixing and defect ordering in solid solutions of fluorite-structured ThO$_{2}$ with oxides of trivalent cations (Sc, In, Y, Nd, La) are investigated by electronic density-functional-theory (DFT). Through DFT calculations of structures enumerated by lattice-algebra techniques, we identify the lowest-energy patterns for defect clustering for four separate dopant concentrations. The most stable structures are characterized by a repulsive interaction between nearest-neighbor vacancies on the oxygen sublattice. The enthalpies of formation with respect to constituent oxides are positive for all dopants considered, and show a tendency to decrease in magnitude as the size and electronegativity of the trivalent dopant decrease. Due to the small positive formation enthalpies and low oxygen-vacancy binding energy with La dopants, La$_{2}$O$_{3}$-ThO$_{2}$ solid solutions are predicted to have relatively high ionic conductivities relative to those for the other aliovalent dopants considered. Our results are compared with those for the more widely studied ZrO$_{2}$ and CeO$_{2}$ fluorite-structured solid solutions with trivalent cations.
Hopping versus bulk conductivity in transparent oxides: 12CaO.7Al2O3
对钙铝石基氧化物[Ca 12 Al 14 O 32]{2+}（2 e-）的第一性原理计算揭示了其高导电性的机理。这种材料的电子和光学性质的详细比较与最近发现的新的透明导电氧化物，H掺杂的UV激活的Ca 12 Al 14 O 33，使我们得出结论，在[Ca 12 Al 14 O 32]{2+}（2 e-）的增强的导电性是通过消除的库仑阻塞的载流子。这导致从掺杂H的UV辐照的Ca 12 Al 14 O33中的库仑能隙的变程跳跃行为转变为[Ca 12 Al 14 O32]{2+}（2 e-）中的体电导。此外，在[Ca_（12）Al_（14）O_（32）]{2+}（2 e-）中获得的导电电子的高度离域性表明，它不能被归类为最初建议的钙钛矿。
