BaCu4/3Si2/3P2 and BaCu2–(x+y)ZnxSiyP2: Expanding the Semiconducting Landscape in the ThCr2Si2-Type Family

Sarkar, Arka; Nepal, Niraj K.; Coban, Yagmur; Pike, Andrew; Harycki, Stasia; Viswanathan, Gayatri; Wang, Lin-Lin; Hautier, Geoffroy; Kovnir, Kirill

doi:10.1021/acs.inorgchem.5c01526

BaCu_4/3Si_2/3P₂ and BaCu_2–(x+y)Zn_xSi_yP₂: Expanding the Semiconducting Landscape in the ThCr₂Si₂-Type Family

Journal Article · Thu Jul 10 00:00:00 EDT 2025 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5c01526· OSTI ID:2998107

^[1]; Nepal, Niraj K. ^[2]; Coban, Yagmur ^[3]; ^[3]; Harycki, Stasia ^[4]; ^[1]; ^[5]; ^[3]; ^[1]

Iowa State Univ., Ames, IA (United States); Ames Laboratory (AMES), Ames, IA (United States)
Ames Laboratory (AMES), Ames, IA (United States)
Dartmouth College, Hanover, NH (United States)
Iowa State Univ., Ames, IA (United States)
Ames Laboratory (AMES), Ames, IA (United States); Iowa State Univ., Ames, IA (United States)

ThCr₂Si₂-type layered materials are a large family of compounds with applications ranging from thermoelectricity to magnetism, with the vast majority of the members exhibiting metallic behavior. Here, in this study, we synthesized a new group of materials with Cu-Si and Cu-Zn-Si square nets with the general formula BaCu_1.33Si_0.67P₂ and BaCu_2–(x+y)Zn_xSi_yP₂ (0 ≤ x ≤ 0.9; 0.3 ≤ y ≤ 0.7). Several synthesized compounds are charge-balanced semiconductors, which are rare in the ThCr₂Si₂ family. All the reported compounds crystallize in the ThCr₂Si₂-type tetragonal I4/mmm space group, with Cu/Zn/Si jointly occupying the same 4d crystallographic site. In the Zn-free composition, BaCu_1.33Si_0.67P₂, Ba, and P each occupy a single crystallographic site. The introduction of Zn results in the expansion of the unit cell and splitting the Ba atomic sites along the [001] direction. Such structural displacement of the Ba atoms was confirmed by the heat capacity measurements. Band structure and density-of-states calculations on ordered hypothetical structural models reveal either a small bandgap (∼0.2 eV) or semimetallic band structures. The compounds reported here exhibit high Seebeck coefficients and ultralow thermal conductivity, making them promising candidates for the development of thermoelectric materials.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

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

Grant/Contract Number:: AC02-07CH11358; SC0023509

OSTI ID:: 2998107

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 28 Vol. 64; ISSN 0020-1669; ISSN 1520-510X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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BaCu_4/3Si_2/3P₂ and BaCu_2–(x+y)Zn_xSi_yP₂: Expanding the Semiconducting Landscape in the ThCr₂Si₂-Type Family