Phase Stability, Band Gap Tuning, and Rashba Splitting in Selenium-Alloyed Bournonite: CuPbSb(S1–xSex)3

Chang, Eric T.; Koknat, Gabrielle; Wessler, Garrett McKeown; Yao, Yi; Blum, Volker; Mitzi, David B.

doi:10.1021/acs.chemmater.2c03109

Title: Phase Stability, Band Gap Tuning, and Rashba Splitting in Selenium-Alloyed Bournonite: CuPbSb(S_1–xSe_x)₃

Journal Article · 10 January 2023 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.2c03109 · OSTI ID:1971071

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^[1]; Wessler, Garrett McKeown ^[1]; Yao, Yi ^[1];

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Duke Univ., Durham, NC (United States)

Recently, bournonite (CuPbSbS₃) has been identified as a potential ferroelectric photovoltaic (PV) material with a 1.3 eV band gap, which falls in an appropriate range for single junction PV devices. Progress in applying bournonite has yielded several studies reporting successful thin-film processing, the most recent of which demonstrated a 2.65% power conversion efficiency for a bournonite-based PV device. In an effort to explore bournonite band gap engineering for PV and other prospective applications (e.g., thermoelectric, spintronic), we here consider the solid-state synthesis of selenium-alloyed bournonite, CuPbSb(S_1-xSe_x)₃, across the full range of x (0.0 ≤ x ≤ 1.0), and report phase purity for 0.0 ≤ x ≤ 0.5. We characterize the crystal structure and band gap of the samples using X-ray diffraction and diffuse reflectance spectroscopy, determining a band gap decrease for single-phase samples from 1.25 eV at x = 0.0 to 1.06 eV at x = 0.5. Formation energies determined using dispersion corrected hybrid density functional theory (DFT) support experimental findings and are consistent with the stability (instability) of the x = 0.5 (x = 1.0) structure relative to starting materials. The computed band structures show a decreasing trend in the band gap with increasing x, again consistent with experiment, with the states at the conduction (valence) band minima (maxima) being principally derived from Pb (S/Se) states. Spin texture analysis and detailed comparison of spin splitting parameters show that Se-alloying modifies the band gap while maintaining Rashba spin splitting character within the electronic structure. Rashba splitting is most pronounced for the conduction band minimum along the Γ-X path in the Brillouin zone. Energy separation between spin states is maintained at ΔE~0.2 eV for the various Se contents, with σz as the spin direction. Furthermore, a smaller spin splitting occurs along Γ-Z (decreasing value with increasing x), with σ_x as the spin direction.

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Research Organization:: Duke Univ., Durham, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: SC0020061; AC02-05CH11231; ACI-1548562

OSTI ID:: 1971071

Journal Information:: Chemistry of Materials, Vol. 35; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Phase Stability, Band Gap Tuning, and Rashba Splitting in Selenium-Alloyed Bournonite: CuPbSb(S1–xSex)3

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Title: Phase Stability, Band Gap Tuning, and Rashba Splitting in Selenium-Alloyed Bournonite: CuPbSb(S_1–xSe_x)₃