Pb₁₇O₈Cl₁₈: A Promising IR Nonlinear Optical Material with Large Laser Damage Threshold Synthesized in an Open System

Abstract

Mid-IR nonlinear optical (NLO) materials are of great importance in modern laser frequency conversion technology and optical parametric oscillator processes. However, the commercially available IR NLO crystals (e.g., AgGaQ2 (Q = S, Se) and ZnGeP2) suffer from two obstacles, low laser damage thresholds (LDTs) and the difficulty of obtaining high-quality crystals, both of which seriously hinder their applications. The introduction of Cl, an element with a large electronegativity, and Pb, a relatively heavy element to promote the optical properties, affords an oxide-based IR NLO material, Pb17O8Cl18 (POC). High-quality POC single crystals with sizes of up to 7 mm × 2 mm × 2 mm have been grown in an open system. Additionally, POC exhibits a large LDT of 408 MW/cm(2), 12.8 times that of AgGaS2. POC also exhibits an excellent second harmonic generation response: 2 times that of AgGaS2, the benchmark IR NLO crystal at 2090 nm, and 4 times that of KDP, the standard UV NLO crystal at 1064 nm. Thus, we believe that POC is a promising IR NLO material.

Coexistence of Strong Second Harmonic Generation Response and Wide Band Gap in AZn4Ga5S12 (A=K, Rb, Cs) with 3D Diamond‐like Frameworks

“…Significantly,s uch interesting structural modification not only maintains the 3D DLF structure of the parent structure (namely,a ll the MS 4 (M = Zn/Ga) tetrahedra aligning in the same direction), but also greatlyi ncreasest he E g .T he solidstate diffuse reflectance spectrao ft itle compounds and AGS (as the reference) are shown in Figure 3. [12] Surprisingly,s uch av alue is even greater than some notable IR halideso ro xides, for example, Cs 2 HgCl 2 I 2 (3.15 eV), [36] Pb 17 O 8 Cl 17 (3.44 eV), [37] Pb 2 B 5 O 9 I( 3.10 eV), [38] and Li 2 Ti(IO 3 ) 6 (3.00 eV). [12] Surprisingly,s uch av alue is even greater than some notable IR halideso ro xides, for example, Cs 2 HgCl 2 I 2 (3.15 eV), [36] Pb 17 O 8 Cl 17 (3.44 eV), [37] Pb 2 B 5 O 9 I( 3.10 eV), [38] and Li 2 Ti(IO 3 ) 6 (3.00 eV).…”

“…[29][30][31][32][33] The powder SHG properties were estimated on polycrystalline samples by using a2 050 nm Q-switch laser based on the Kurtz and Perry method. Moreover,t he relative LIDTsd ata of these polycrystallinec ompounds are about 36 AGS at the range of 150-210 mmp article size (Figure4b), which are larger than those of Na 2 Hg 3 Si 2 S 8 (4.5 AGS), [41] Na 2 ZnGe 2 S 6 (6.0 AGS), [22] Na 2 BaGeS 4 (8.0 AGS), [15] Pb 7 O 8 Cl 18 (12.8 AGS), [37] Ba 4 ZnGa 4 Se 10 Cl 2 (17.0 AGS), [42] and [Rb 3 Br][Ga 3 PS 8 ]( 29.0 AGS). Moreover,t he relative LIDTsd ata of these polycrystallinec ompounds are about 36 AGS at the range of 150-210 mmp article size (Figure4b), which are larger than those of Na 2 Hg 3 Si 2 S 8 (4.5 AGS), [41] Na 2 ZnGe 2 S 6 (6.0 AGS), [22] Na 2 BaGeS 4 (8.0 AGS), [15] Pb 7 O 8 Cl 18 (12.8 AGS), [37] Ba 4 ZnGa 4 Se 10 Cl 2 (17.0 AGS), [42] and [Rb 3 Br][Ga 3 PS 8 ]( 29.0 AGS).…”

Growth, Properties, and Theoretical Analysis of M2LiVO4 (M = Rb, Cs) Crystals: Two Potential Mid-Infrared Nonlinear Optical Materials

“…Remarkably, the reported materials show a relatively large E g among the known Mid-IR NLO crystals with high LDT i . e ., Pb 17 O 8 Cl 18 19 (3.44 eV and 12.8 × AgGaS 2 ), RbIO 3 (4.0 eV and about 20 × AgGaS 2 ) 21 , Na 2 BaSnS 4 (3.27 eV and about 5 × AgGaS 2 ) 17 and Na 2 ZnGe 2 S 6 (3.25 eV and 6 × AgGaS 2 ) 28 , which implies that the reported materials may be promising for application in high-energy laser systems. For comparison, although borate materials, such as β -BaB 2 O 4 (BBO) 4 , LiB 3 O 5 (LBO) 5 , possess a high LDT, they also show low optical transmittance in the Mid-IR (3–5 μm) range due to intrinsic vibration absorptions.

Figure 4Linear and nonlinear optical properties of RLVO and CLVO.

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“…The transmittance spectrum measurement indicates that CLVO has a wide transmission window range from 0.33 to 6.0 μm, which covers an important atmospheric transparent domain (3–5 μm). Remarkably, the reported materials show relatively large E g values (3.8 eV for RLVO and 3.7 eV for CLVO) and high LDT (about 28 × AgGaS 2 for RLVO and CLVO) among the known Mid-IR NLO crystals 17, 19, 21, 28 . The SHG measurements indicate that RLVO and CLVO have strong SHG efficiency of about 4 and 5 times that of KDP, respectively.…”

“…In recent research, many studies pay special attention to halides, iodates, molybdates, and vanadates since they normally exhibit large E g and diverse structural motifs so that it is possible to find materials with a subtle balance between large NLO efficiency and high LDT. A series of potential Mid-IR NLO crystals have been achieved, such as Pb 17 O 8 Cl 18 19 , α -AgI 3 O 8 and β -AgI 3 O 8 20 , RbIO 3 21 , Na 2 Te 3 Mo 3 O 16 22 , BaTeMo 2 O 9 23 , LiNa 5 Mo 9 O 30 24 , K 3 V 5 O 14 25, 26 and YCa 9 (VO 4 ) 7 27 . After a lot of screening and system performance evaluation, we think that Rb 2 LiVO 4 (RLVO) and Cs 2 LiVO 4 (CLVO) are good Mid-IR NLO materials.…”