Early stage of the single-crystal growth and tipping point of the cationic site preference in Gd-doped Zintl phase thermoelectric materials

Hayeon Sa, Junsu Lee, Yeongjin Hong, Mi Kyung Han, Hongil Jo, Dohyun Moon, Kang Min Ok, Sung Jin Kim, Tae Soo You

Research output: Contribution to journalArticlepeer-review

2 Scopus citations


Three novel Zintl phase solid solutions in the Ca11−xGdxSb10−y(0.36(2) ≤x≤ 0.58(4), 0.26(1) ≤y≤ 0.37(1)) system have been successfully synthesized by arc melting, and their crystal structures were carefully characterized by powder and single-crystal X-ray diffraction analyses. During the synthesis, as we changed the reaction time, we were able to observe the early stages of the crystal growth process for a cubic-shaped single crystal with hummocky-type patterns on it. All three title compounds adopted the tetragonalI4/mmm(Z= 4, Pearson codetI84) space group and crystallized in the Ho11Ge10-type phase. The overall complex crystal structure contained three Ca/Gd mixed sites with particular site preferences and one Sb site with some occupational deficiencies. A series of DFT calculations and detailed structure analyses proved that the observed cationic site preference should be attributed to the size-factor criterion rather than the electronic-factor criterion, and the Gd-containing title compounds became a tipping point for the size factor criterion in the overall Ca11−xRExSb10−y(RE = rare-earth metals) series. Theoretical investigations indicated that the energetically unfavorable antibonding character of the Sb-Sb interaction on the Sb4tetramers causedca.2.6-3.7% (fractional percentage) of Sb deficiencies and eventually resulted in keeping the p-type character of the Ca11−xGdxSb10−ysystem despite the successful n-type Gd doping. According to the temperature-dependent thermoelectric property measurements, the relatively “heavier” Gd dopants successfully improved the electrical conductivity, Seebeck coefficient, and thermal conductivity of Ca10.63(4)Gd0.37Sb9.74(1)compared to those of two previously reported Ca10.75(3)Nd0.26Sb9.82(1)and Ca10.82(4)Sm0.18Sb9.86(1), which contained the relatively “lighter” Nd and Sm dopants.

Original languageEnglish
Pages (from-to)7097-7107
Number of pages11
Issue number40
StatePublished - 28 Oct 2021

Bibliographical note

Funding Information:
The research grants are provided by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (NRF-2021R1A2C1003661 and 2019R1A2C3005530).

Publisher Copyright:
© The Royal Society of Chemistry 2021.


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