Rb₁₀Zn₄Sn₄S₁₇: A Chalcogenide with Large Laser Damage Threshold Improved from the Mn-Based Analogue

Abstract

In the military and civilian fields, with the development of new technologies, high-powered nonlinear optical (NLO) crystals demonstrate broad application prospects. In this work, for purposes of designing a better NLO material, a new chalcogenide Rb 10 Zn 4 Sn 4 S 17 was successfully designed with a high temperature solid-state method on the basis of previously reported compound Sr 3 MnSn 2 S 8 . The experimental results indicate that Rb 10 Zn 4 Sn 4 S 17 possesses a prominent band gap of 3.59 eV, compared with the laser damage threshold (LDT) of Sr 3 MnSn 2 S 8 (3 times that of AgGaS 2 ); Rb 10 Zn 4 Sn 4 S 17 shows an outstanding LDT about 5 times that of AgGaS 2 . Meanwhile, it has an ideal second harmonic generation (SHG) response approximately 0.7 times that of AgGaS 2 .

Solvothermal Syntheses of Three-Dimensional Open-Framework Thioantimonates Displaying Nonlinear Optical Responses

“…One effective method for the designed synthesis of new SHG crystals is to introduce asymmetric moieties into one crystalline material. , These asymmetric moieties include metal cations with lone-pair electrons (e.g., Pb 2+ , Bi 3+ , Sb 3+ , Sn 2+ ), − second-order Jahn–Teller cation-centered polyhedra (e.g., Mo 6+ , W 6+ , Nb 5+ , Ti 4+ ), − and asymmetric tetrahedra [MQ 4 ] (M = Ga 3+ , In 3+ , Ge 4+ , etc. ; Q = S, Se, etc.…”

LiBa4Ga5Q12 (Q = S, Se): Noncentrosymmetric Metal Chalcogenides with a Cesium Chloride Topological Structure Displaying a Remarkable Laser Damage Threshold

“…Recently, numerous experiments have shown that metal chalcogenides are abundant research resources for developing novel IR NLO materials due to their broad optical transparency and strong SHG responses derived from favorable covalent bonding characters. − Specifically, the main-group-metal elements (e.g., Ga, In, Si, Ge, Sn) are often four-coordinated with chalcogen atoms to adopt asymmetric tetrahedral configurations, which are regarded as the typical “NLO active units” and play a very important role in achieving both noncentrosymmetric structures and strong SHG responses. − In addition, enlarging the band gap is known as an effective strategy to overcome the most demanding problems of TPA and low LDT in IR NLO materials. Hence, the alkali or alkaline-earth metals without d–d or f–f electronic transitions have been taken into consideration in the tetrahedra-containing chalcogen system to improve the LDTs of NLO materials. − The strategy has been confirmed by recently reported metal chalcogenides with large LDT, such as LiGaS 2 (11× that of AGS), BaGa 4 S 7 (3× that of AGS), Li 2 ZnSiS 4 (10× that of AGS), Li 2 BaGeS 4 (11× that of AGS), Ba 6 Zn 7 Ga 2 S 16 (28× that of AGS), Rb 10 Zn 4 Sn 4 S 17 (5× that of AGS), (K 0.38 Ba 0.81 )­Ga 2 Se 4 (13× that of AGS), Na 4 MgSi 2 Se 6 (9× that of AGS), Na 2 BaGeS 4 (8× that of AGS), Li 2 MnGeS 4 (40× that of AGS), and Na 2 Hg 3 Si 2 S 8 (4.5× that of AGS). − …”

Infrared nonlinear optical sulfide CsCd4In5S12 exhibiting large second harmonic generation response

“…The promising IR-NLO materials for applications should satisfy the following conditions: a high SHG coefficient, a large LIDT, a wide IR transmission range, phase matching behavior and high thermal stability. [19][20][21][22][23][24][25][26] However, it is difficult to maintain the balance among the above properties, which encourages the development of new structural design strategies for highperformance IR-NLO materials. Fundamental building units (FBUs), such as d 10 cationcentred tetrahedral anionic groups ([CdS 4 ] 6À , [HgS 4 ] 6À , [InS 4 ] 5À , [GaS 4 ] 5À , [GeS 4 ] 4À , etc.…”

“…The promising IR-NLO materials for applications should satisfy the following conditions: a high SHG coefficient, a large LIDT, a wide IR transmission range, phase matching behavior and high thermal stability. 19–26 However, it is difficult to maintain the balance among the above properties, which encourages the development of new structural design strategies for high-performance IR-NLO materials.…”