Key Role of d(0) and d(10) Cations for the Design of Semiconducting Colusites: Large Thermoelectric ZT in Cu26Ti2Sb6S32 Compounds

Takashi Hagiwara (1) , Koichiro Suekuni (1) , Pierric Lemoine (2) , Andrew R. Supka (3) , Raju Chetty (4) , Emmanuel Guilmeau (5) , Bernard Raveau (5) , Marco Fornari (3) , Michihiro Ohta (4) , Rabih Al Rahal Al Orabi (3) , Hikaru Saito (1) , Katsuaki Hashikuni (1) , Michitaka Ohtaki (1)

1 Kyushu University
2 ISCR - Institut des Sciences Chimiques de Rennes
3 CMU - Central Michigan University
4 AIST - National Institute of Advanced Industrial Science and Technology
5 CRISMAT - Laboratoire de cristallographie et sciences des matériaux

Cu-S-based materials with sphalerite-derivative structures are of interest for their complex cationic distribution, rich crystal structure chemistry, and potential in energy conversion and optoelectronic applications. In this study, a new member of colusite, Cu26Ti2Sb6S32, was designed by exploiting the key role of d(0) (T) and d(10) (M) cations in the sphalerite-derivative structure of Cu26T2M6S32 colusites. We succeeded to incorporate d(0) Ti4+ and d(10) Sb5+ into T and M sites, respectively, with a tetrahedral coordination rarely found for these two cations in solid-state chemistry. The synthesis produced the first semiconducting compound with the colusite structure. In addition, Cu26Ti2Sb6S32 exhibits a low lattice thermal conductivity. Partial substitution of Ge for Sb increased the hole carrier concentration, leading to an enhanced thermoelectric power factor and dimensionless figure of merit (ZT of 0.9 at 673 K). The electronic and phonon structures, responsible for the high thermoelectric performance, were elucidated by first-principles calculations.

Mots clés: Phonons; Scanning transmission electron microscopy; Chemical structure; Diffraction; Cations

Domaines: Chimie; Matériaux

Takashi Hagiwara, Koichiro Suekuni, Pierric Lemoine, Andrew R. Supka, Raju Chetty, et al.. Key Role of d(0) and d(10) Cations for the Design of Semiconducting Colusites: Large Thermoelectric ZT in Cu26Ti2Sb6S32 Compounds. Chemistry of Materials, 2021, 33 (9), pp.3449-3456. ⟨10.1021/acs.chemmater.1c00872⟩. ⟨hal-03267856⟩