2(C3H7N6)+·2Cl−·H2O: an ultraviolet nonlinear optical crystal with large birefrigence and strong second-harmonic generation

Liu, Lehui; Hu, Chun‐Li; Bai, Zhiyong; Yuan, Feifei; Huang, Yu Ping; Zhang, Lizhen; Lin, Zhoubin

doi:10.1039/d0cc06558g

“…[2a] Figure 3b shows that the SHG intensity of I is about 11.4 times that of KDP at the same particle size ranging from 109-150 μm. This powder SHG response is much larger than those of reported SHG materials with isolated benzene-like rings, such as (C 3 H 7 N 6 ) 2 Cl 2 •H 2 O (4.3 × KDP) [20] and (C 5 H 6 ON)(H 2 PO 4 ) (3.0 × KDP), [1f, 21] as well as the commercial SHG crystal β-BaB 2 O 4 (6.0 × KDP). [22] Recently, a variety of oxides were reported with both large SHG responses and birefringence, such as CeF 2 (SO 4 ) (SHG = 8.0 × KDP and Δn = 0.361@546 nm), [23] Sc(IO 3 ) 2 -(NO 3 ) (SHG = 4.0 × KDP and Δn = 0.348@546 nm), [24] K 2 Sb-(P 2 O 7 )F (SHG = 4.0 × KDP and Δn = 0.157@546 nm), [25] SbB 3 O 6 (SHG = 3.5 × KDP and Δn = 0.290@546 nm), [26] and Be 2 (BO 3 )(IO 3 ) (SHG = 7.2 × KDP and Δn cal = 0.172@1064 nm).…”

Section: Methodsmentioning

confidence: 72%

A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses

Li

¹

,

Zhang

²

,

Xiong

³

et al. 2022

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Antiperovskites have been studied since the 1980s because of their rich physical and chemical properties, but their linear and second-order nonlinear optical responses remain largely unknown. Here we report a new polar crystal, Cs 3 Cl(HC 3 N 3 S 3 ) (I), which features a quasi-one-dimensional antiperovskite structure composed of ClCs 6 polyhedra and A-site [HC 3 N 3 S 3 ] 2À rings. To our best knowledge, this kind of antiperovskite structure is reported for the first time. Remarkably, I exhibits a very strong nonlinear optical response up to 11.4 times that of the benchmark KH 2 PO 4 and exceptionally large birefringence of 0.52. The first-principles calculations and structural analyses reveal that [HC 3 N 3 S 3 ] 2À is the "material gene" while the antiperovskite structural feature making it in a favorable arrangement. This work provides a new structural platform for the rational design of integrated optoelectronic materials with linear and second-order nonlinear optical responses.

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“…Moreover, 6‐membered B 3 O 6 [10] and C 3 N 3 O 3 [11] anionic rings can help to produce large birefringence, for instance, the commercial α‐BaB 2 O 4 with B 3 O 6 anionic rings [12] . Recently reported studies on 2(C 3 H 7 N 6 ) + ⋅2 Cl − ⋅H 2 O suggest that melamine (MLA) cation can also act as a superior birefringent functional unit, [13] as melamine possesses planar π‐conjugated electrons and has similar structure geometry with that of (C 3 N 3 O 3 ) 3− anions.…”

Section: Figurementioning

confidence: 99%

A Hybrid Halide Perovskite Birefringent Crystal

Zhao

¹

,

Huang

²

,

Zhang

³

et al. 2022

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Birefringent crystals that can modulate the polarization of light play a significant role in modern optical devices including polarizing microscopes, optical isolators, and achromatic quarter-wave plates. To date, commercial birefringent crystals are exclusively limited to purely inorganic compounds. Here we report a new organic-inorganic hybrid halide, MLAPbBr 4 (MLA = melamine), which features a (110)-oriented layered perovskite structure. Although the 6s 2 lone-pair electrons of Pb 2 + cations are stereochemically inert, MLAPbBr 4 exhibits a birefringence of 0.322@550 nm, which exceeds those of all commercial birefringent crystals. The first-principles calculations reveal that this birefringence should be ascribed to the highly dislocated π-conjugation of MLA cations and high distortion of PbBr 6 octahedra. This work highlights the persistently neglected great potential of hybrid halide perovskites as birefringent crystals.Birefringent crystals play a significant role in optical devices, e.g. polarizing microscopes, optical isolators, achromatic quarter-wave plates, and phase compensators, etc. [1] At present, commercial birefringent crystals mainly include YVO 4 (birefringence Δn = 0.204@532 nm), [2] LiNbO 3 (Δn = 0.074@546 nm), [3] TiO 2 (Δn = 0.256@546 nm), [4] CaCO 3 (Δn = 0.172@532 nm), [5] and α-BaB 2 O 4 (Δn = 0.122@546 nm). [6] Among them, the applications of natural birefringent crystals (e.g., CaCO 3 and TiO 2 ) are limited by their inadequate crystal quality such as defects and impurities. Artificial birefringent crystals (e.g., YVO 4 , LiNbO 3 , and α-BaB 2 O 4 ), on the other hand, are relatively expensive and the growth of single crystals is energy-consuming. Hence, it is still of great scientific and technological significance to design and synthesize new birefringent crystals.

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“…[2a] Figure 3b shows that the SHG intensity of I is about 11.4 times that of KDP at the same particle size ranging from 109-150 μm. This powder SHG response is much larger than those of reported SHG materials with isolated benzene-like rings, such as (C 3 H 7 N 6 ) 2 Cl 2 •H 2 O (4.3 × KDP) [20] and (C 5 H 6 ON)(H 2 PO 4 ) (3.0 × KDP), [1f, 21] as well as the commercial SHG crystal β-BaB 2 O 4 (6.0 × KDP). [22] Recently, a variety of oxides were reported with both large SHG responses and birefringence, such as CeF 2 (SO 4 ) (SHG = 8.0 × KDP and Δn = 0.361@546 nm), [23] Sc(IO 3 ) 2 -(NO 3 ) (SHG = 4.0 × KDP and Δn = 0.348@546 nm), [24] K 2 Sb-(P 2 O 7 )F (SHG = 4.0 × KDP and Δn = 0.157@546 nm), [25] SbB 3 O 6 (SHG = 3.5 × KDP and Δn = 0.290@546 nm), [26] and Be 2 (BO 3 )(IO 3 ) (SHG = 7.2 × KDP and Δn cal = 0.172@1064 nm).…”

Section: Second-harmonic Generation (Shg) Crystals Belong Tomentioning

confidence: 72%

A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses

Li

¹

,

Zhang

²

,

Xiong

³

et al. 2022

Angewandte Chemie

0

View full text Add to dashboard Cite

Antiperovskites have been studied since the 1980s because of their rich physical and chemical properties, but their linear and second-order nonlinear optical responses remain largely unknown. Here we report a new polar crystal, Cs 3 Cl(HC 3 N 3 S 3 ) (I), which features a quasi-one-dimensional antiperovskite structure composed of ClCs 6 polyhedra and A-site [HC 3 N 3 S 3 ] 2À rings. To our best knowledge, this kind of antiperovskite structure is reported for the first time. Remarkably, I exhibits a very strong nonlinear optical response up to 11.4 times that of the benchmark KH 2 PO 4 and exceptionally large birefringence of 0.52. The first-principles calculations and structural analyses reveal that [HC 3 N 3 S 3 ] 2À is the "material gene" while the antiperovskite structural feature making it in a favorable arrangement. This work provides a new structural platform for the rational design of integrated optoelectronic materials with linear and second-order nonlinear optical responses.

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2(C₃H₇N₆)⁺·2Cl⁻·H₂O: an ultraviolet nonlinear optical crystal with large birefrigence and strong second-harmonic generation

Abstract: Large birefringence (∆n = 0.277 at 546 nm) and strong second-harmonic generation (SHG) intensity (4.3 × KDP) achieve remarkable balance among a potential ultraviolet nonlinear optical crystal, 2(C3H7N6)+·2Cl-·H2O. Results of...

Cited by 55 publications

References 45 publications

A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses

A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses

A Hybrid Halide Perovskite Birefringent Crystal

A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses

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