Insights into the Crystal Structure and Thermoelectric Properties of the Zintl Phase Ca9Cd3+x–yMx+ySb9 (M = Cu, Zn) System

IF 7.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2024-12-16 DOI:10.1021/acs.chemmater.4c02740

Junsu Lee, Minkyoung Kim, Ji Hee Pi, Myung-Ho Choi, Kang Min Ok, Kyu Hyoung Lee, Tae-Soo You

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Abstract

Four quaternary Zintl phase solid-solutions in the Ca₉Cd_3+x–yM_x+ySb₉ (M = Cu, Zn) system were successfully synthesized, and their crystal structures were characterized by using both powder X-ray and single-crystal X-ray diffractions. All title compounds adopted the Ca₉Zn_3.1In_0.9Sb₉-type phase, featuring three-dimensional anionic frameworks composed of tetrahedral [MSb₄] and tricoordinated [MSb₃] moieties interconnected via vertex-sharing. Detailed structural analyses revealed that various types of partial and mixed occupations existed at the M sites, and the Zn2 site in Ca₉Cd_2.65(1)Zn_1.84(2)Sb₉ exhibited a trigonal pyramid geometry, distinct from the simple planar geometry observed in parental Ca₉Zn_3.1In_0.9Sb₉. The density of states (DOS) analyses revealed successful p-type doping in the Cu-containing compound, indicated by a shift in the Fermi level and an increase in the hole carrier concentration. Crystal orbital Hamilton population curves displayed optimized interatomic interactions between neighboring anionic elements, maintaining structural stability despite a slight increase in the DOS level. Thermoelectric property measurements were conducted for the first time on the Ca₉Zn_3.1In_0.9Sb₉-type phase. The results demonstrated that the Zn-containing compounds exhibited higher Seebeck coefficients and lower thermal conductivities, resulting in larger ZT values compared to the Cu-containing compounds. The highest ZT value of 0.70 at 775 K was observed for Ca₉Cd_4.05Zn_0.45Sb₉.

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对锌相 Ca9Cd3+x-yMx+ySb9 (M = 铜、锌) 体系晶体结构和热电特性的见解

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.