Rb2CdBr2I2: A New IR Nonlinear Optical Material with a Large Laser Damage Threshold

Wu, Qi; Meng, Xiang‐Gao; Zhong, Cheng; Chen, Xingguo; Qin, Jingui

doi:10.1021/ja412405u

Cited by 140 publications

(85 citation statements)

References 22 publications

(20 reference statements)

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“…To further appraise its potential device application, laser‐induced damage experiments of 1 were performed under intense laser irradiation (Figure c). Its single‐shot surface damage threshold is measured up to ∼8.9 GW/cm 2 , which is almost order of magnitude larger than other NLO switching materials . Hence, it allows us to overcome the stability problems arising in the polymers and enables efficient control over the bulk SHG responses, which is usually proportional to the power density of the fundmental beam.…”

Section: Resultsmentioning

confidence: 99%

Second‐Order Nonlinear Optical Switch of a New Hydrogen‐Bonded Supramolecular Crystal with a High Laser‐Induced Damage Threshold

Sun

Zhang

et al. 2014

Advanced Optical Materials

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advantages, such as large NLO effects, ultrafast responses, and high laser-induced damage thresholds. Several organic molecules and metal-organic compounds have displayed NLO switching in solution, by utilizing the chemical procedures of protonation, two-photon absorption, or oxidation/reduction. [ 2 ] However, the search for highly effi cient solid-state switches remains a challenge, particularly for second-harmonic generation (SHG) activities, because the macroscopic noncentrosymmetric (NCS) arrangement of NLO moieties must be reversibly controlled in a collective manner. [ 3 ] As far as we are aware, only a few solid-state SHG switches have been reported, including organometallic thin fi lms for redox switching, photochromic anil crystals and polymer fi lms, etc. [ 4 ] The switching-induced irreversible changes of the initial chromophore alignment severely limits the number of "on"/"off" cycles in these cases. Moreover, their inferior resistance to laser-induced damage also suppresses the NLO switching effi ciency, [ 5 ] since materials should suffer from high-power laser radiation and thus high laser-induced damage thresholds are essential.Crystalline materials with phase transitions (PTs) have attracted great interest, [ 6 ] since they display outstanding performances around the transition point ( T c ) and their bulk physical properties can be modulated. [ 7 ] In this context, thermally driven structural deformations during PTs afford a great possibility for high-performance SHG switches. Using this conceptually new scheme, simple organic salts and organic-inorganic hybrids have been reported to be potential NLO switches. [ 8 ] During our investigation of novel SHG modulators, H-bonded materials with long-range order of their dipolar arrangement provide us with promising SHG switch candidates. One of our strategies is to discover the hidden pseudo-symmetry induced by hydrogen bonds, [ 9 ] which may be destroyed during PTs and arouse macroscopic dipole moments, corresponding to the generation of SHG signals. [ 10 ] In the present work, a new supramolecular crystal, bis-(imidazolium hydrochlorate) dihydrate 18-crown-6 ( 1 ), is fi rstly reported as a solid-state SHG modulator with a superior switching contrast (∼12) and remarkable switching reversibility. Strikingly, its laser-induced damage threshold (up to ∼8.9 GW/cm 2 ) is much higher than other materials, which guarantees its conversion effi ciency under the high-power laser. As far as we Organic nonlinear optical (NLO) materials are anticipated as the competitive successors to inorganic compounds in the highly controllable photonic devices. Here, a new supramolecular crystal, bis(imidazolium hydrochlorate) dihydrate 18-crown-6 ( 1 ), behaves as a potential modulator of quadratic NLO responses. It is found that ( 1) possesses a superior NLO switchingcontrast of up to ∼12, a remarkable switching reversibility, and a quite high laser-induced damage threshold (up to ∼8.9 GW/cm 2 ), which may guarantee its device application. In addition, mechanism stu...

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Section: Resultsmentioning

confidence: 99%

Second‐Order Nonlinear Optical Switch of a New Hydrogen‐Bonded Supramolecular Crystal with a High Laser‐Induced Damage Threshold

Sun

Zhang

et al. 2014

Advanced Optical Materials

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“…[40] However,i ti su sually difficult to grow large single crystals with high quality for chalcogenides because of the harsh conditions and laborintensive processes.M eanwhile,h alides were proposed as another promising mid-IR NLO materials. [41] Af ew representative metal halides with wide IR transparent range and considerable LDT include Rb 2 CdBr 2 I 2 , [42] Cs 2 HgI 2 Cl 2 , [43] (Hg 6 P 3 )(In 2 Cl 9 ), [44] Hg 2 BrI 3 , [45] NaSb 3 F 10 , [46] HgBr 2 , [47] and K 2 SbF 2 Cl 3 . [48] Notably,s ome of the crystals can be grown in mild conditions via hydrothermal or solution methods.…”

Section: Introductionmentioning

confidence: 99%

Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials

2020

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To design high-performance mid-infrared (mid-IR) nonlinear optical (NLO) materials,w eh ave focused on the combination of aheavy metal lone pair cation, Pb 2+ and mixed oxyhalides.Asystematic investigation in PbO-PbCl 2 -PbBr 2 system led us to discover the first examples of NLO lead mixed oxyhalides,n amely,P b 13 O 6 Cl 4 Br 10 ,P b 13 O 6 Cl 7 Br 7 ,a nd Pb 13 O 6 Cl 9 Br 5 .A ll the reported materials have remarkably comprehensive properties including broad IR transparency (up to 14.0 mm), qualified second harmonic generation (SHG) responses (0.6-0.9 AgGaS 2 ), wide band gaps (3.05-3.21 eV), and ease of crystal growth. Interestingly,acentimeter-sized single crystal (2.9 1.3 0.5 cm 3 )o fP b 13 O 6 Cl 9 Br 5 revealing aw ide transparent range (0.384-14.0 mm) and high laser damage threshold (LDT) (14.6 AgGaS 2 )h as been successfully grown in an open system. The study suggests that all the reported mixed oxyhalides are outstanding candidates for mid-IR NLO materials.

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“…A crystallographic non‐centrosymmetric (NCS) structure is the prerequisite condition of an NLO material. Over the past decades, numerous strategies have been introduced to design new NCS materials, and many MFIR NLO compounds with strong powder SHG responses have been discovered and prepared . Among them, construction of diamond‐like frameworks (DLFs) has been considered as one of the most effective methods to obtain new MFIR NLO materials with excellent properties; typical examples include BaGa 4 Q 7 (Q=S, Se), Ba 3 AGa 5 Se 10 Cl 2 (A=K‐Cs), PbGa 4 S 7 , Li 2 CdGeS 4 , and BaGa 2 MQ 6 (M=Si, Ge, Sn; Q=S, Se) …”

Section: Introductionmentioning

confidence: 99%

Non‐centrosymmetric Selenides AZn₄In₅Se₁₂ (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties

Lin

Zheng

et al. 2016

Chemistry An Asian Journal

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Two new non-centrosymmetric polar quaternary selenides, namely, RbZn In Se and CsZn In Se , have been synthesized and structurally characterized. They exhibit a 3D diamond-like framework (DLF) consisting of corner-shared MSe (M=Zn/In) tetrahedra, in which the A ions are located. Both compounds are thermally stable up to 1300 K and exhibit large transmittance in the infrared region (0.65-25 μm) with measured optical band gaps of 2.06 eV for RbZn In Se and 2.11 eV for CsZn In Se . Inspiringly, they exhibit a good balance between strong second harmonic generation (SHG) efficiency (3.9 and 3.5×AgGaS ) and high laser-induced damage thresholds (13.0×AgGaS ). Theoretical calculations based on density functional theory (DFT) methods confirm that such strong SHG responses originate from the 3D DLF structure.

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Rb₂CdBr₂I₂: A New IR Nonlinear Optical Material with a Large Laser Damage Threshold

Cited by 140 publications

References 22 publications

Second‐Order Nonlinear Optical Switch of a New Hydrogen‐Bonded Supramolecular Crystal with a High Laser‐Induced Damage Threshold

Second‐Order Nonlinear Optical Switch of a New Hydrogen‐Bonded Supramolecular Crystal with a High Laser‐Induced Damage Threshold

Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials

Non‐centrosymmetric Selenides AZn₄In₅Se₁₂ (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties

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Rb2CdBr2I2: A New IR Nonlinear Optical Material with a Large Laser Damage Threshold

Cited by 140 publications

References 22 publications

Second‐Order Nonlinear Optical Switch of a New Hydrogen‐Bonded Supramolecular Crystal with a High Laser‐Induced Damage Threshold

Second‐Order Nonlinear Optical Switch of a New Hydrogen‐Bonded Supramolecular Crystal with a High Laser‐Induced Damage Threshold

Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials

Non‐centrosymmetric Selenides AZn4In5Se12 (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties

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Rb₂CdBr₂I₂: A New IR Nonlinear Optical Material with a Large Laser Damage Threshold

Non‐centrosymmetric Selenides AZn₄In₅Se₁₂ (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties