A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

• Published in: Angewandte Chemie International Edition Vol. 58; no. 7; pp. 2098 - 2102
• Main Authors: Chen, Jin, Hu, Chun‐Li, Mao, Fei‐Fei, Feng, Jiang‐He, Mao, Jiang‐Gao
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 11.02.2019
• Edition: International ed. in English
• Subjects: aliovalent substitution; Anions; Cations; Energy gap; Fluorides; Gallium; Harmonic generations; hydrothermal synthesis; Laser damage; nonlinear optical materials; Nonlinear optics; Optical materials; Optics; Potassium phosphate; Potassium phosphates; Silver gallium sulfide; Substitutes; theoretical studies; aliovalent substitution; theoretical studies; hydrothermal synthesis; nonlinear optical materials
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201813968

Two mixed‐metal gallium iodate fluorides, namely, α‐ and β‐Ba2[GaF4(IO3)2](IO3) (1 and 2), have been designed by the aliovalent substitutions of α‐ and β‐Ba2[VO2F2(IO3)2](IO3) (3 and 4) involving one cationic and two anionic sites. Both 1 and 2 display large second‐harmonic generation responses (≈6×KH2PO4 (KDP)), large energy band gaps (4.61 and 4.35 eV), wide transmittance ranges (≈0.27–12.5 μm), and high relevant laser‐induced damage thresholds (29.7× and 28.3×AgGaS2, respectively), which indicates that 1 and 2 are potential second‐order nonlinear optical materials in the ultraviolet to mid‐infrared. Our studies propose that three‐site aliovalent substitution is a facile route for the discovery of good NLO materials. Trading places: Two new nonlinear optical materials, α‐ and β‐Ba2[GaF4(IO3)2](IO3) (1 and 2), were designed via three‐site aliovalent substitution of VO4F2 in α‐ and β‐Ba2[VO2F2(IO3)2](IO3) by GaO2F4. The new materials display large second‐harmonic generation responses (≈6×KH2PO4 (KDP)), wide energy band gaps (4.61 and 4.35 eV), and high laser damage thresholds (29.7× and 28.3× relative to that of AgGaS2).