Structure Tuning, Strong Second Harmonic Generation Response, and High Optical Stability of the Polar Semiconductors Na1-xKxAsQ2

Iyer, Abishek K.; Cho, Jeong Bin; Byun, Hye Ryung; Waters, Michael J.; Hao, Shiqiang; Oxley, Benjamin M.; Gopalan, Venkat; Wolverton, Christopher; Rondinelli, James M.; Jang, Joon I.; Kanatzidis, Mercouri G.

doi:10.1021/jacs.1c07993

Title: Structure Tuning, Strong Second Harmonic Generation Response, and High Optical Stability of the Polar Semiconductors Na_1-xK_xAsQ₂

Journal Article · Tue Oct 19 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c07993· OSTI ID:1846300

^[1]; Cho, Jeong Bin ^[2]; Byun, Hye Ryung ^[2]; Waters, Michael J. ^[1];

^[1]; Oxley, Benjamin M. ^[1]; Gopalan, Venkat ^[3];

^[1];

^[2];

^[4]

Northwestern University, Evanston, IL (United States)
Sogang University, Seoul (Korea, Republic of)
Pennsylvania State University, State College, PA (United States)
Northwestern University, Evanston, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

We report the mixed cation compounds Na_1-xK_xAsSe₂ (x = 0.8, 0.65, 0.5) and Na_0.1K_0.9AsS₂ crystallize in the polar noncentrosymmetric space group Cc. The AAsQ(2) (A = alkali metals, Q = S, Se) family features one-dimensional (1D) ¹/_∞[AQ₂^-] chains comprising corner-sharing pyramidal AQ₃ units in which the packing of these chains is dependent on the alkali metals. The parallel ¹/_∞[AQ(2)^-] chains interact via short As ∙∙∙Se contacts, which increase in length when the fraction of K atoms is increased. The increase in the As ∙∙∙Se interchain distance increases the band gap from 1.75 eV in γ-NaAsSe₂ to 2.01 eV in Na_0.35K_0.65AsSe₂, 2.07 eV in Na_0.2K_0.8AsSe₂, and 2.18 eV in Na_0.1K_0.9AsS₂. The Na_1-xK_xAsSe₂ (x = 0.8, 0.65) compounds melt congruently at approximately 316 °C. Wavelength-dependent second harmonic generation (SHG) measurements on powder samples of Na_1-xK_xAsSe₂ (x = 0.8, 0.65, 0.5) and Na_0.1K_0.9AsS₂ suggest that Na_0.2K_0.8AsSe₂ and Na_0.1K_0.9AsS₂ have the highest SHG response and exhibit significantly higher laser-induced damage thresholds (LIDTs). Theoretical SHG calculations on Na_0.5K_0.5AsSe₂ confirm its SHG response with the highest value of d₃₃ = 22.5 pm/V χ₃₃₃⁽²⁾ = 45.0 pm/V). The effective nonlinearity for a randomly oriented powder is calculated to be d_eff = 18.9 pm/V χ_eff⁽²⁾ = 37.8 pm/V), which is consistent with the experimentally obtained value of d_eff = 16.5 pm/V χ_eff⁽²⁾ = 33.0 pm/V). Three-photon absorption is the dominant mechanism for the optical breakdown of the compounds under intense excitation at 1580 nm, with Na_0.2K_0.8AsSe₂ exhibiting the highest stability.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation of Korea (NRF); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; FA9550-18-S-0003; ECCS-2025633; DMR-2011208; SC0014520; 2020R1F1A1069646; 2021R1A2C2013625

OSTI ID:: 1846300

Journal Information:: Journal of the American Chemical Society, Vol. 143, Issue 43; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Structure Tuning, Strong Second Harmonic Generation Response, and High Optical Stability of the Polar Semiconductors Na1-xKxAsQ2

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Title: Structure Tuning, Strong Second Harmonic Generation Response, and High Optical Stability of the Polar Semiconductors Na_1-xK_xAsQ₂