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

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

doi:10.1039/d1ce00877c

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

CrystEngComm, v.23 no.40, 2021년, pp.7097 - 7107

Sa, Hayeon (Department of Chemistry and BK21Four Research Team, Chungbuk National University) , Lee, Junsu (Department of Chemistry and BK21Four Research Team, Chungbuk National University) , Hong, Yeongjin (Department of Chemistry and BK21Four Research Team, Chungbuk National University) , Han, Mi-Kyung (Department of Chemistry and Nanoscience, Ewha Womans University) , Jo, Hongil (Department of Chemistry, Sogang University) , Moon, Dohyun (Beamline Department, Pohang Accelerator Laboratory) , Ok, Kang Min (Department of Chemistry, Sogang University) , Kim, Sung-Jin (Department of Chemistry and Nanoscience, Ewha Womans University) , You, Tae-Soo (Department of Chemistry and BK21Four Research Team, Chungbuk National University)

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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 tetragonal I4/mmm (Z = 4, Pearson code tI84) 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 Sb4 tetramers caused ca. 2.6-3.7% (fractional percentage) of Sb deficiencies and eventually resulted in keeping the p-type character of the Ca11−xGdxSb10−y system 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.Graphic AbstractThree novel Zintl phases in the Ca11−xGdxSb10−y system were synthesized, and the early stage of the single-crystal growth process and the “tipping point” of the cationic site preference for the size-factor criterion were thoroughly investigated.

참고문헌 (33)

Encyclopedia of Inorganic and Bioinorganic Chemistry Owens-Baird 2017 1 B.Owens-Baird , S.Heinrich and K.Kovnir , Thermoelectric materials, in: Encyclopedia of Inorganic and Bioinorganic Chemistry , Wiley , New York, USA , 2017 , pp. 1-35
Renewable Sustainable Energy Rev. Elsheikh 30 2014 10.1016/j.rser.2013.10.027 337

상세보기
Science DiSalvo 285 1999 10.1126/science.285.5428.703 703

상세보기
Nature Pei 473 2011 10.1038/nature09996 66

상세보기
Angew. Chem., Int. Ed. Zeier 55 2016 10.1002/anie.201508381 6826

상세보기
Adv. Mater. Pei 24 2012 10.1002/adma.201202919 6125

상세보기
Nat. Rev. Mater. Zeier 1 2016 10.1038/natrevmats.2016.32 16032

상세보기
Chem. Mater. Toberer 22 2010 10.1021/cm901956r 624

상세보기
Inorg. Chem. Nam 56 2017 10.1021/acs.inorgchem.7b00617 7099

상세보기
Dalton Trans. Choi 46 2017 10.1039/C7DT02410J 11840

상세보기
Inorg. Chem. Sa 60 2021 10.1021/acs.inorgchem.0c03705 10124

상세보기
Cryst. Growth Des. Lee 19 2019 10.1021/acs.cgd.9b00368 3498

상세보기
Cryst. Growth Des. Lee 20 2020 10.1021/acs.cgd.0c00311 4503

상세보기
APEX2 2007 APEX2 , Bruker AXS Inc. , Madison, WI, USA , 2007
SAINT 2002 SAINT , Bruker AXS Inc. , Madison, WI, USA , 2002
SADABS Sheldrick 2003 G. M.Sheldrick , SADABS , University of Göttingen , Göttingen, Germany , 2003
J. Synchrotron Radiat. Shin 23 2016 10.1107/S1600577515021633 369

상세보기
Methods in Enzymology, in: Macromolecular Crystallography, Part A Otwinowski 276 1997 10.1016/S0076-6879(97)76066-X 307 Z.Otwinowski and W.Minor , in Methods in Enzymology, in: Macromolecular Crystallography, Part A , ed. C. W. Carter Jr and R. M. Sweet , Academic Press , San Diego, CA, USA , 1997 , vol. 276 , pp. 307-326
Acta Crystallogr., Sect. C: Struct. Chem. Ovchinnikov 74 2018 10.1107/S2053229618001596 269

상세보기
Phys. Rev. B Sturza 89 2018 054012
J. Appl. Crystallogr. Gelato 20 1987 10.1107/S0021889887086965 139

상세보기
Phys. Rev. B: Solid State Andersen 12 1975 10.1103/PhysRevB.12.3060 3060

상세보기
Phys. Rev. Lett. Andersen 53 1984 10.1103/PhysRevLett.53.2571 2571

상세보기
Phys. Rev. B: Condens. Matter Mater. Phys. Lambrecht 34 1986 10.1103/PhysRevB.34.2439 2439

상세보기
The TB-LMTO-ASA Program (ver. 4.7) Jepsen 1999 O.Jepsen , A.Burkhardt and O. K.Andersen , The TB-LMTO-ASA Program (ver. 4.7) , Max-Plank-Institut für Festkörperforschung , Stuttgart, Germany , 1999
Z. Phys. B: Condens. Matter Jepsen 97 1995 10.1007/BF01317585 35

상세보기
Phys. Rev. B: Condens. Matter Mater. Phys. Blöchl 49 1994 10.1103/PhysRevB.49.16223 16223

상세보기
Phys. Rev. B: Condens. Matter Mater. Phys. May 80 2009 10.1103/PhysRevB.80.125205 125205

상세보기
The Elements Emsley 1989 J.Emsley , The Elements , Oxford University Press , New York, USA , 1989
Acta Crystallogr., Sect. A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr. Shannon 32 1976 10.1107/S0567739476001551 751

상세보기
Acta Mater. Ren 143 2018 10.1016/j.actamat.2017.10.015 265

상세보기
Chem. Mater. Zhou 32 2020 10.1021/acs.chemmater.9b04131 776

상세보기
Adv. Funct. Mater. Toberer 18 2008 10.1002/adfm.200800298 2795

상세보기

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

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

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