Forbes Scott, Tseng Yu-Chih, Mozharivskyj Yurij
Department of Chemistry and Chemical Biology, McMaster University , 1280 Main Street West, Hamilton, Ontario L8S 4M1, Canada.
Inorg Chem. 2015 Feb 2;54(3):815-20. doi: 10.1021/ic501808y. Epub 2014 Sep 25.
Syntheses of europium metal, selenium powder, and the Sb(2)Se(3)/Bi(2)Se(3) binaries were observed to produce crystal clusters of the EuSbSe(3) and EuBiSe(3) phases. These phases crystallize with the P2(1)2(1)2(1) space group and can be easily identified based on their growth habits, forming large clusters of needles. Previous literature suggested that their structure is charge-balanced with all europium atoms in the divalent state and one-quarter of the selenium atoms forming trimers. Physical property measurements on a pure sample of EuSbSe(3) revealed typical Arrhenius-type electrical resistivity, being approximately 3 orders of magnitude too large for thermoelectric applications. Electronic structure calculations indicated that both EuSbSe(3) and EuBiSe(3) are narrow-band-gap semiconductors, in good agreement with the electrical resistivity data. The valence and conduction band states near the Fermi level are dominated by the Sb/Bi and Se p states, as expected given their small difference in electronegativity.
观察到铕金属、硒粉以及Sb(2)Se(3)/Bi(2)Se(3)二元化合物的合成产生了EuSbSe(3)和EuBiSe(3)相的晶体簇。这些相以P2(1)2(1)2(1)空间群结晶,并且基于它们的生长习性很容易识别,形成大的针状簇。先前的文献表明,它们的结构是电荷平衡的,所有铕原子处于二价状态,四分之一的硒原子形成三聚体。对EuSbSe(3)纯样品的物理性质测量显示出典型的阿仑尼乌斯型电阻率,对于热电应用来说大约大3个数量级。电子结构计算表明,EuSbSe(3)和EuBiSe(3)都是窄带隙半导体,这与电阻率数据非常吻合。正如预期的那样,鉴于它们在电负性上的微小差异,费米能级附近的价带和导带态由Sb/Bi和Se p态主导。