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

13 Scopus citations


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
Issue number30
StatePublished - Aug 3 2022

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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