Stabilization of the Polar Structure and Giant Second‐Order Nonlinear Response of Single Crystal γ‐NaAs0.95Sb0.05Se2. (19th December 2022)

• Record Type: Journal Article
• Authors: Iyer, Abishek K.; He, Jingyang; Xie, Hongyao; Goodling, Devin; Chung, Duck‐Young; Gopalan, Venkatraman; Kanatzidis, Mercouri G.
• Is Part Of: Advanced functional materials. Volume 33:Number 9(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-12-19
• Subjects: chalcogenides -- crystals -- Infrared laser -- polymorphic transitions -- Second Harmonic Generation; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.202211969
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: The dearth of suitable materials significantly restricts the practical development of infrared (IR) laser systems with highly efficient and broadband tuning. Recently, γ‐NaAsSe2 is reported, and it exhibits a large nonlinear second‐harmonic generation (SHG) coefficient of 590 pm V −1 at 2 µm. However, the crystal growth of γ‐NaAsSe2 is challenging because it undergoes a phase transition to centrosymmetric δ‐NaAsSe2 . Herein, the stabilization of non‐centrosymmetric γ‐NaAsSe2 by doping the As site with Sb, which results in γ‐NaAs0.95 Sb0.05 Se2 is reported. The congruent melting behavior is confirmed by differential thermal analysis with a melting temperature of 450 °C and crystallization temperature of 415 °C. Single crystals with dimensions of 3 mm × 2 mm are successfully obtained via zone refining and the Bridgman method. The purification of the material plays a significant role in crystal growth and results in a bandgap of 1.78 eV and thermal conductivity of 0.79 Wm −1 K −1 . The single‐crystal SHG coefficient of γ‐NaAs0.95 Sb0.05 Se2 exhibits an enormous value of | d 11 | = 648 ± 74 pm V −1, which is comparable to that of γ‐NaAsSe2 and ≈20× larger than that of AgGaSe2 . The bandgap of γ‐NaAs0.95 Sb0.05 Se2 (1.78 eV) is similar to that of AgGaSe2, thus rendering it highly attractive as a high‐performing nonlinear optical material. Abstract : High performing non‐centrosymmetric γ‐NaAsSe2 is stabilized by doping the As site with Sb, resulting in γ‐NaAs0.95 Sb0.05 Se2. Large single crystals are successfully obtained via zone refining and the Bridgman method. A giant second harmonic generation (SHG) coefficient of | d 11 | = 648 ± 74 pm V −1 is observed at 2 µm. These properties make it a promising candidate for infrared laser applications.