Nakamura Takashi, Yashiro Keiji, Sato Kazuhisa, Mizusaki Junichiro
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1, Katahira, Aoba-Ku, Sendai, 980-8577, Japan.
Phys Chem Chem Phys. 2009 May 7;11(17):3055-62. doi: 10.1039/b823364k. Epub 2009 Mar 18.
In order to elucidate the electronic state and the conduction mechanism of La(2-x)Sr(x)NiO(4+delta) at high temperatures, electrical conductivity, Seebeck coefficient, and nonstoichiometric oxygen content of La(2-x)Sr(x)NiO(4+delta) (x = 0, 0.2, 0.4) were measured as a function of Sr content, temperature, and oxygen partial pressure. The hole mobility is estimated from the electrical conductivity and oxygen content. The mobility decreases slightly as temperature increases, like metals at high temperatures. The relationships between Seebeck coefficient and electrical conductivity, and Seebeck coefficient and hole concentration can be explained by the metallic conduction model. Semi-quantitative analyses strongly indicate that electrons (holes) are itinerant in La(2-x)Sr(x)NiO(4+delta) and the conduction mechanism of La(2-x)Sr(x)NiO(4+delta) is metal-like band conduction at high temperatures. Based on the experimental results and discussions, a schematic of the energy levels and band structure is proposed. At high temperatures, metallic conduction is induced by a free hole in the sigma(x2-y2) band composed of a d(x2-y2) orbital.
为了阐明高温下La(2 - x)Sr(x)NiO(4 + δ)的电子态和传导机制,测量了La(2 - x)Sr(x)NiO(4 + δ)(x = 0、0.2、0.4)的电导率、塞贝克系数和非化学计量氧含量随Sr含量、温度和氧分压的变化关系。通过电导率和氧含量估算空穴迁移率。迁移率随温度升高略有下降,类似于高温下的金属。塞贝克系数与电导率以及塞贝克系数与空穴浓度之间的关系可以用金属传导模型来解释。半定量分析有力地表明,电子(空穴)在La(2 - x)Sr(x)NiO(4 + δ)中是巡游的,并且La(2 - x)Sr(x)NiO(4 + δ)在高温下的传导机制是类金属带传导。基于实验结果和讨论,提出了能级和能带结构的示意图。在高温下,金属传导是由由d(x2 - y2)轨道组成的σ(x2 - y2)带中的自由空穴引起的。