Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold. (17th February 2021)

• Record Type: Journal Article
• Authors: Lee, Shannon; Carnahan, Scott L.; Akopov, Georgiy; Yox, Philip; Wang, Lin‐Lin; Rossini, Aaron J.; Wu, Kui; Kovnir, Kirill
• Is Part Of: Advanced functional materials. Volume 31:Number 16(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-02-17
• Subjects: laser damage threshold -- noncentrosymmetric crystal structures -- second harmonic generation -- tetrel pnictides; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.202010293
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal‐rich silicon phosphides RuSi4 P4 and IrSi3 P3 are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X‐ray diffraction and 29 Si and 31 P magic angle spinning NMR. In agreement with previous report RuSi4 P4 crystallizes in NCS space group P 1, while IrSi3 P3 is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C 2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi4 P4 and IrSi3 P3 to be wide bandgap ( E g ) semiconductors, E g = 1.9 and 1.8 eV, respectively. RuSi4 P4 and IrSi3 P3 outperform the current state‐of‐the‐art infrared SHG material, AgGaS2, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi4 P4 and IrSi3 P3 are promising candidates for longer wavelength NLO materials. Abstract : RuSi4 P4 and IrSi3 P3 crystallizes in noncentrosymmetric structures composed of fac‐ octahedral M Si3 P3 units with strong directional covalent MSi and MP bonding. The developed novel synthetic method allows to produce bulk single‐phase samples, redetermine crystal structures, and characterize non‐linear optical properties. RuSi4 P4 and IrSi3 P3 show an outstanding combination of large second harmonic generation signal and laser damage threshold.