Heteroanionic Control of Exemplary Second-Harmonic Generation and Phase Matchability in 1D LiAsS2- xSex

Benjamin M. Oxley, Jeong Bin Cho, Abishek K. Iyer, Michael J. Waters, Jingyang He, Nathan C. Smith, Chris Wolverton, Venkatraman Gopalan, James M. Rondinelli, Joon I. Jang*, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

The isostructural heteroanionic compounds β-LiAsS2-xSex(x = 0, 0.25, 1, 1.75, 2) show a positive correlation between selenium content and second-harmonic response and greatly outperform the industry standard AgGaSe2. These materials crystallize in the noncentrosymmetric space group Cc as one-dimensional 1/[AsQ2]-(Q = S, Se, S/Se) chains consisting of corner-sharing AsQ3trigonal pyramids with charge-balancing Li+atoms interspersed between the chains. LiAsS2-xSexmelts congruently for 0 ≤ x ≤ 1.75, but when the Se content exceeds x = 1.75, crystallization is complicated by a phase transition. This behavior is attributed to the β- to α-phase transition present in LiAsSe2, which is observed in the Se-rich compositions. The band gap decreases with increasing Se content, starting at 1.63 eV (LiAsS2) and reaching 1.06 eV (β-LiAsSe2). Second-harmonic generation measurements as a function of wavelength on powder samples of β-LiAsS2-xSexshow that these materials exhibit significantly higher nonlinearity than AgGaSe2(d36= 33 pm/V), reaching a maximum of 61.2 pm/V for LiAsS2. In comparison, single-crystal measurements for LiAsSSe yielded a deff= 410 pm/V. LiAsSSe, LiAsS0.25Se1.75, and β-LiAsSe2show phase-matching behavior for incident wavelengths exceeding 3 μm. The laser-induced damage thresholds from two-photon absorption processes are on the same order of magnitude as AgGaSe2, with S-rich materials slightly outperforming AgGaSe2and Se-rich materials slightly underperforming AgGaSe2.

Original languageEnglish (US)
Pages (from-to)13903-13912
Number of pages10
JournalJournal of the American Chemical Society
Volume144
Issue number30
DOIs
StatePublished - Aug 3 2022

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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