Ln10S14O (Ln = La, Pr, Nd, Sm) Oxysulfides: A Series of Direct n-Type Semiconductors

Wuille Bille, Brian A.; Kundmann, Anna C.; Osterloh, Frank E.; Velázquez, Jesús M.

doi:10.1021/acs.chemmater.2c01244

Ln₁₀S₁₄O (Ln = La, Pr, Nd, Sm) Oxysulfides: A Series of Direct n-Type Semiconductors

Journal Article · Thu Aug 04 00:00:00 EDT 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c01244· OSTI ID:1903349

^[1]; Kundmann, Anna C. ^[2]; ^[2]; ^[2]

Univ. of California, Davis, CA (United States); UC Davis
Univ. of California, Davis, CA (United States)

Lanthanoid oxysulfides are promising materials for technological applications owing to their magnetic, photoluminescent, catalytic, and optoelectronic properties. In this work, we report the solid-state synthesis and structural characterization of Ln₁₀S₁₄O (Ln = La, Ce, Pr, Nd, Sm) oxysulfides. Then, we present a thorough discussion on their electronic and photophysical properties. Through Tauc plot analysis and the derivation of the absorption spectrum fitting method (DASF), we determine that all oxysulfides have direct band gaps with energies of 2.84 eV (La), 2.02 eV (Ce), 2.56 eV (Pr), 2.64 eV (Nd), and 2.41 eV (Sm). Furthermore, surface photovoltage spectroscopy (SPS) shows photovoltage (ΔCPD) values of –0.4 to –1.1 V for La-, Pr-, Nd-, and Sm-containing compounds when illuminated near the optical band gap, indicating that these oxysulfides are n-type semiconductors, which is consistent with Mott–Schottky analysis. Photovoltages under sub-band gap illumination energy and photovoltage decay data suggest mid-band gap states possibly arising from the lanthanoid 4f orbitals and/or defects within the crystal structure or at the particle surfaces. These photophysical properties suggest possible applications of the oxysulfides in photoelectrochemical and photovoltaic energy conversion.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Davis, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); Research Corporation for Science Advancement (RCSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; SC0015329

OSTI ID:: 1903349

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 16 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Ln10S14O (Ln = La, Pr, Nd, Sm) Oxysulfides: A Series of Direct n-Type Semiconductors

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Ln₁₀S₁₄O (Ln = La, Pr, Nd, Sm) Oxysulfides: A Series of Direct n-Type Semiconductors