AAg₂PS₄(A = K, Na/K): the first-type of noncentrosymmetric alkali metal Ag-based thiophosphates exhibiting excellent second-order nonlinear optical performances

Abstract

The exploration of new infrared (IR) nonlinear optical (NLO) crystals with large second-harmonic generation (SHG) responses and high laser-induced damage thresholds (LIDTs) concurrently is urgent and challenging. Herein, the first-type...

Quaternary alkaline-earth metal thiophosphate SrAgPS4: syntheses, structures, and optical properties

“…22–25 Meanwhile, alkali metals are typically considered to be beneficial for enlarging the band gap due to their fully filled d or f orbitals, which prevent d–d or f–f electronic transitions. AHgPS 4 (A = Na, K), 26 KAg 2 PS 4 , 27 KREP 2 Se 6 (RE = Sm, Gd, Tb), 28 A 2 Zn 3 P 4 S 13 (A = Rb and Cs), 29 and other alkali metal thiophosphates were evaluated as outstanding IR NLO candidates. Alkaline-earth metals have similar characteristics to alkali metals and are often used in the design of wide-band gap NLO materials.…”

Revisiting two thiophosphate compounds constituting d0transition metal HfP2S6and d10transition metal α-Ag4P2S6as multifunctional materials for combining second harmonic generation response and photocurrent response

“…The only strong absorption at 550 cm −1 can be assigned to the ν (P–S) vibrations. 101 The IR spectrum of HfP 2 S 6 , α-Ag 4 P 2 S 6 , and β-Ag 4 P 2 S 6 is comparable to many thiophosphates such as AgCd 3 PS 6 , 42 KAg 2 PS 4 , 56 Sn 2 P 2 S 6 , 47 and AgHgPS 4 . 102…”

“…Thiophosphates, which combine both phosphorus and sulfur, are demonstrated to be good candidates for infrared nonlinear optical materials, where the promising properties originate from structure and chemical flexibility. The flexible [P x S y ] motifs interact with various cations generating many promising nonlinear optical materials including Rb 2 Ga 2 P 2 S 9 , 33 [K 3 Cl][Ga 3 PS 8 ], 34 [Rb 3 Cl][Ga 3 PS 8 ], 34 [K 3 Br][Ga 3 PS 8 ], 34 [Rb 3 Br][Ga 3 PS 8 ], 34 LiZnPS 4 , 35 CuZnPS 4 , 36 CuHgPS 4 , 37 AgZnPS 4 , 35 Ag 3 PS 4 , 38 LiGa 2 PS 6 , 39 AgGa 2 PS 6 , 40 LiCd 3 PS 6 , 39 CuCd 3 PS 6 , 41 AgCd 3 PS 6 , 42 Zn 3 P 2 S 8 , 43 Hg 3 P 2 S 8 , 44 Sn 2 P 2 S 6 , 45–47 KBiP 2 S 6 , 48 K 2 BaP 2 S 6 , 49 KSbP 2 S 6 , 49 Pb 2 P 2 S 6 , 50 α-Ba 2 P 2 S 6 , 50 Pb 3 P 2 S 8 , 51 RbBiP 2 S 6 , 52 Eu 2 P 2 S 6 , 53 Hg 2 P 2 S 6 , 54 ASrPS 4 (A = Li, Na, K, Rb, Cs), 55 AAg 2 PS 4 (A = K, Na/K), 56 etc. From the perspective of the constituting cations, the most explored cations for thiophosphate nonlinear optical materials are alkali metals and d 10 transition metals.…”

γ-P4S3I2: a new metal-free infrared second-order nonlinear optical crystal designed by polymorphism strategy

“…Exploring non-centrosymmetric (NCS) inorganic compounds is of great significance in the development of piezoelectric, pyroelectric, ferroelectric, and especially nonlinear optical (NLO) materials. [1][2][3][4][5][6] NLO materials are indispensable for applications in medical treatment, atmospheric detection and optical communication relying on frequency conversion. 7,8 To date, many well-known NLO crystals, such as β-BaB 2 O 4 , LiB 3 O 5 and CsLiB 6 O 10 as well as KTiOPO 4 and LiNbO 3 , have basically met the needs in the UV and visible (vis) regions.…”

“…Thiophosphates are a very promising system for mid-IR NLO applications because the existence of strong covalent P-S bonds not only improves the NLO response but can also drive the blue shift of the short-wave absorption edge; 29 for example, Hg 3 P 2 S 8 (2.72 eV, 4.2 × AgGaS 2 ), Eu 2 P 2 S 6 (2.54 eV, 0.9 × AgGaS 2 ), RbBiP 2 S 6 (2.10 eV, 11.9 × AgGaS 2 ) and CuHgPS 4 (2.03 eV, 6.5 × AgGaS 2 ) exhibit good IR-NLO performances. [30][31][32][33] In addition, positive valence P atoms have a flexible coordination environment (2)(3)(4), which is favorable in forming polymorphs. For example, the polymorphism of P 2 S 7 (α: P2 1 /c, β: P1 ˉ)34 exhibits two different crystal structures.…”