Clathrates Ba8{Zn, Cd}xSi46-x, x .apprx. 7: synthesis, crystal structure and thermoelectric properties

Autor(en)
Andrij Grytsiv, Nataliya Melnychenko-Koblyuk, Peter Franz Rogl, Ernst Bauer, Roman Lackner, Esmaeil Royanian, Gerald Giester, Adriana Saccone
Abstrakt

Novel ternary type-I clathrate compds. Ba8{Zn, Cd}xSi46-x, x .apprx. 7 have been synthesized from the elements by melting and reacting in quartz ampoules. Structural investigations for both compds., i.e. x-ray single-crystal data at 300, 200 and 100 K for Ba8Zn7Si39 and Rietveld data for Ba8Cd7Si39, confirm cubic primitive symmetry consistent with the space group type Pm.hivin.3n (aBa8Zn7Si39 = 1.043 72(1) nm; aBa8Cd7Si39 = 1.058 66(3) nm). Whereas for Ba8Zn7Si39 site 16i is completely occupied by Si atoms, a random atom distribution with different Zn/Si ratio exists for the two sites, 6d (0.77Zn + 0.23Si) and 24k (0.91Si + 0.09Zn). No vacancies are encountered and all atom sites are fully occupied. This atom distribution is independent of temp. Rietveld refinements for Ba8Cd7Si39 show that the 6d site is fully occupied by Cd atoms, leaving only the 24k site for a random occupation (0.96Si + 0.04Cd) consistent with the chem. formula Ba8Cd7Si39. The temp.-dependent x-ray spectra for Ba8Zn7Si39 define an Einstein mode, E,U33 = 80 K. Studies of transport properties show electrons as the majority charge carriers in the system. Although the Cd- and Zn-based samples are isoelectronic, a significantly different electronic transport points towards substantial differences in the electronic d. of states in both cases.

Organisation(en)
Institut für Physikalische Chemie, Institut für Mineralogie und Kristallographie
Externe Organisation(en)
Technische Universität Wien, Università degli Studi di Genova
Journal
Journal of Physics: Condensed Matter
Band
21
Seiten
1-8
Anzahl der Seiten
8
ISSN
0953-8984
Publikationsdatum
2009
Peer-reviewed
Ja
ÖFOS 2012
105113 Kristallographie, 1040 Chemie
Link zum Portal
https://ucrisportal.univie.ac.at/de/publications/61d99894-c1e3-43a7-bb27-65a63f6d7605