Synthesis and Transport Properties of the Family of Zintl Phases Ca3RESb3 (RE = La–Nd, Sm, Gd–Tm, Lu): Exploring the Roles of Crystallographic Disorder and Core 4f Electrons for Enhancing Thermoelectric Performance

Ogunbunmi, Michael O.; Baranets, Sviatoslav; Bobev, Svilen

doi:10.1021/acs.chemmater.1c03300

Title: Synthesis and Transport Properties of the Family of Zintl Phases Ca₃RESb₃ (RE = La–Nd, Sm, Gd–Tm, Lu): Exploring the Roles of Crystallographic Disorder and Core 4f Electrons for Enhancing Thermoelectric Performance

Journal Article · Fri Dec 03 00:00:00 EST 2021 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c03300· OSTI ID:1876202

Ogunbunmi, Michael O. ^[1];

^[1];

^[1]

Univ. of Delaware, Newark, DE (United States)

Zintl phases with complex crystal structures have been studied as promising candidate-materials for thermoelectric (TE) applications. Here, we report the syntheses of the family of rare-earth metal Zintl phases with the general formula Ca_4–xRE_xSb₃ (x ≈ 1; RE = La–Nd, Sm, Gd–Tm, Lu). The structural elucidation is based on refinements of single-crystal X-ray diffraction data for 12 unique chemical compositions. The cubic structure is confirmed as belonging to the anti-Th₃P₄ structure type (space group I4¯3d, no. 220, Z = 4), where the Ca and RE atoms share the same atomic site with ca. 75% and 25% occupancies, respectively. Such crystallographic disordering of divalent Ca and trivalent RE atoms in the structure provides a pathway to intricate bonding. The latter, together with the presence of heavy elements such as Sb and the lanthanides, are expected to enhance the scattering probability of phonons, thereby leading to as low thermal conductivity κ as that of the ordered RE₄Sb₃. The drive of the hypothetical parent compound Ca₄Sb₃ to be stabilized by alloying with rare-earth metals can be understood following the Zintl-Klemm concept, as the resultant formula may be rationalized as (Ca²⁺)₃RE³⁺(Sb^3–)₃, indicating the realization of closed-shell electronic configurations for all elements. This notion is confirmed by electronic structure calculations, which reveal narrow bandgaps E_g = 0.77 and 0.53 eV for Ca₃LaSb₃ and Ca₃LuSb₃, respectively. Additionally, the incorporation of RE atoms into the structure drives the phase into a state of a degenerate semiconductor with dominant hole charge carriers.

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Research Organization:: Univ. of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008885

OSTI ID:: 1876202

Journal Information:: Chemistry of Materials, Vol. 33, Issue 23; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CSD 2111094: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vrtq The current record is supplemented by this dataset	dataset	January 2021
CSD 2111095: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vrvr The current record is supplemented by this dataset	dataset	January 2021
CSD 2111096: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vrws The current record is supplemented by this dataset	dataset	January 2021
CSD 2111097: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vrxt The current record is supplemented by this dataset	dataset	January 2021
CSD 2111098: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vryv The current record is supplemented by this dataset	dataset	January 2021
CSD 2111099: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vrzw The current record is supplemented by this dataset	dataset	January 2021
CSD 2111100: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vs0y The current record is supplemented by this dataset	dataset	January 2021
CSD 2111101: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vs1z The current record is supplemented by this dataset	dataset	January 2021
CSD 2111102: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vs20 The current record is supplemented by this dataset	dataset	January 2021
CSD 2111103: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vs31 The current record is supplemented by this dataset	dataset	January 2021
CSD 2111104: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vs42 The current record is supplemented by this dataset	dataset	January 2021
CSD 2111105: Experimental Crystal Structure Determination O., Ogunbunmi, Michael; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc28vs53 The current record is supplemented by this dataset	dataset	January 2021

Title: Synthesis and Transport Properties of the Family of Zintl Phases Ca3RESb3 (RE = La–Nd, Sm, Gd–Tm, Lu): Exploring the Roles of Crystallographic Disorder and Core 4f Electrons for Enhancing Thermoelectric Performance

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Title: Synthesis and Transport Properties of the Family of Zintl Phases Ca₃RESb₃ (RE = La–Nd, Sm, Gd–Tm, Lu): Exploring the Roles of Crystallographic Disorder and Core 4f Electrons for Enhancing Thermoelectric Performance