Trigonal Planar [HgSe<sub>3</sub>]<sup>4–</sup> Unit: A New Kind of Basic Functional Group in IR Nonlinear Optical Materials with Large Susceptibility and Physicochemical Stability

Li, Chao; Yin, Wenlong; Gong, Pifu; Li, Xiaoshuang; Zhou, Minqiang; Mar, Arthur; Lin, Zheshuai; Yao, Jiyong; Wu, Yicheng; Chen, Chuangtian

doi:10.1021/jacs.6b03107

Cited by 177 publications

(114 citation statements)

References 43 publications

(43 reference statements)

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“…During the past two decades,t he study of mid-IR NLO materials has been dominantly concentrated on non-oxide systems such as metal chalcogenides,p nictides,a nd halides mainly due to their superior IR transparency. [29,30] Tr aditionally,t oovercome the low LDTs of AgGaS 2 ,A gGaSe 2 ,a nd ZnGeP 2 ,t he investigations were mainly focused on metal chalcogenides revealing high LDTs with wide band gaps. [31,32] Since there is an inversely proportional relationship between NLO coefficients (d ij )a nd band gap (E g ), [33] multiple design and synthetic strategies such as various metal/anion group substitutions have been implemented in chalcogenides to achieve the so-called balanced condition (d ij !…”

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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Section: Introductionmentioning

confidence: 99%

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

2020

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“…Considering the structural asymmetry of K 2 ZnSn 3 Se 8 ,i ti s worth surveying its SHG properties ( Figure 5). [32][33][34][35][36][37][38][39][40][41][42][43] However, owing to the insufficiency of enough pure polycrystalline sample, only appropriate amount of single crystalso f K 2 ZnSn 3 Se 8 were manually selected and ground into fine powdert oinvestigate its SHG response. As displayed in Figure 3a,b yu sing aQ -switched Ho:Tm:Cr:YAG laser (2.09 mm, 3Hz, and 50 ns), the SHG intensity of K 2 ZnSn 3 Se 8 was determined as about 0.6 times that of AgGaS 2 at the particles ize of 20-41 mm.…”

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confidence: 99%

K₂ZnSn₃Se₈: A Non‐Centrosymmetric Zinc Selenidostannate(IV) Featuring Interesting Covalently Bonded [ZnSn₃Se₈]²⁻ Layer and Exhibiting Intriguing Second Harmonic Generation Activity

Zhou

Jiang

Yang

et al. 2017

Chemistry An Asian Journal

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Non-centrosymmetric zinc selenidostannate(IV) K ZnSn Se was synthesized. It features interesting covalently bonded [ZnSn Se ] layers with K cations filling in the interlayer voids. The phonon spectrum was calculated to clarify its structural stability. Based on the X-ray diffraction data along with the Raman spectrum, the major bonding features of the title compound were identified. According to the UV/vis-NIR spectroscopy, K ZnSn Se possesses a typical direct band gap of 2.10 eV, which is in good agreement with the band structure calculations. Moreover, our experimental measurements and detailed theoretical calculations reveal that K ZnSn Se is a new phase-matchable nonlinear optical material with a powder second harmonic generation (SHG) signal about 0.6 times of that of AgGaS .

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“…; Q = S, Se) . The flexible assembly of these units produces some IR‐NLO materials, such as 3‐D BaGa 4 S 7 , BaGa 4 Se 7 , Li 2 Ga 2 GeS 6 , A 2 Hg 3 M 2 S 8 (A = K, Rb; M = Ge, Sn), Ba 4 CuGa 5 Q 12 (Q = S, Se), Ba 2 Ga 8 MS 16 (M = Si, Ge), and Ba 6 Zn 7 Ga 2 S 16 , 2‐D Na 2 Ge 2 Se 5 , and [A 3 X][Ga 3 PS 8 ] (A = K, Rb; X = Cl, Br), 1‐D A 4 Ge 4 Se 12 (A = Rb, Cs), APSe 6 (A = K, Rb), and BaHg 2 Se 3 , and molecular ones, A 4 GeP 4 Se 12 (A = K, Rb, Cs), Cs 5 P 5 Se 12 , and Ba 23 Ga 8 Sb 2 S 38 . These discoveries highlight the guiding role of NLO functional motifs in the development of new IR‐NLO materials.…”

Section: Introductionmentioning

confidence: 99%

Strong SHG Response via High Orientation of Tetrahedral Functional Motifs in Polyselenide A₂Ge₄Se₁₀ (A = Rb, Cs)

Liu

Zeng

et al. 2018

Advanced Optical Materials

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and strong nonlinearity. However, these materials suffer from intrinsic drawbacks, such as low laser damage threshold and two-photon absorptions, which seriously limit their high-power applications. Therefore, new promising IR-NLO materials need to be discovered.Motivated by Chen's anionic group theory, [6] which states that NLO efficiency mainly originates from anionic groups, many NLO-active structure building units (NLO functional motifs) [7] have been developed over the past few decades, such as those with d 0 transition-metal centers (e.g., Ti 4+ , Zr 4+ , Nb 5+ , Ta 5+ , Mo 6+ , etc.) [8] or maingroup cations with stereoactive lone pairs (e.g., Pb 2+ , Sb 3+ , Te 4+ , I 5+ , etc.), [9] and distorted tetrahedral MQ 4 (M = Zn, Ga, Ge, In, Sn, etc.; Q = S, Se). [10] The flexible assembly of these units produces some IR-NLO materials, such as 3These discoveries highlight the guiding role of NLO functional motifs in the development of new IR-NLO materials.SHG may originate from static and induced dipole moments. Some well-known IR-NLO functional motifs, including the distorted tetrahedral MQ 4 that usually exists in many IR-NLO metal chalcogenides, [10] possess a static dipole moment. However, their overall contributions to the total SHG responses of some compounds are negligible because the tetrahedral units are not properly aligned, thereby canceling out to a large extent the static contributions along different directions and leaving only the laser-induced contributions. For instance, in AgGaS 2 , AgGaSe 2 , and ZnGeP 2 , the static SHG contributions from GaS 4 , GaSe 4, and GeP 4 tetrahedra are exactly zero because of their nonpolar symmetry. Therefore, to maximize the static NLO contributions to the SHG response, structures with NLO-active units which are aligned in an almost parallel manner must be designed.The induced contribution of an NLO material to the SHG response is dominated by charge transfers which are close to the Fermi level. The terminal chalcogen atoms and those atoms which form QQ bonds in metal chalcogenides usually have a much larger contribution than the bridged chalcogen atoms which are connected to two neighboring metal Nonlinear optical (NLO) materials with strong second harmonic generation (SHG) responses are technologically and scientifically important for tunable lasers. This work puts forward a new strategy for designing promising infrared nonlinear optical (IR-NLO) materials with strong SHG responses by strengthening both the static and induced contributions via the high orientation of NLO functional motifs. Two new polyselenides Rb 2 Ge 4 Se 10 and Cs 2 Ge 4 Se 10 are studied to verify the strategy, they have 2D infinite 2 ∞ ∞ [Ge 4 Se 10 ] 2− layers comprising highly oriented distorted GeSe 4 tetrahedra. Their large SHG signals (8.0 and 8.5 times that of commercial AgGaS 2 ) can be ascribed to both the static contribution enhancement from the high orientation of the local dipole moment of GeSe 4 tetrahedra and the induced contribution enhancement from terminal and SeSe bon...

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Trigonal Planar [HgSe₃]^4– Unit: A New Kind of Basic Functional Group in IR Nonlinear Optical Materials with Large Susceptibility and Physicochemical Stability

Cited by 177 publications

References 43 publications

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

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

K₂ZnSn₃Se₈: A Non‐Centrosymmetric Zinc Selenidostannate(IV) Featuring Interesting Covalently Bonded [ZnSn₃Se₈]²⁻ Layer and Exhibiting Intriguing Second Harmonic Generation Activity

Strong SHG Response via High Orientation of Tetrahedral Functional Motifs in Polyselenide A₂Ge₄Se₁₀ (A = Rb, Cs)

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Trigonal Planar [HgSe3]4– Unit: A New Kind of Basic Functional Group in IR Nonlinear Optical Materials with Large Susceptibility and Physicochemical Stability

Cited by 177 publications

References 43 publications

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

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

K2ZnSn3Se8: A Non‐Centrosymmetric Zinc Selenidostannate(IV) Featuring Interesting Covalently Bonded [ZnSn3Se8]2− Layer and Exhibiting Intriguing Second Harmonic Generation Activity

Strong SHG Response via High Orientation of Tetrahedral Functional Motifs in Polyselenide A2Ge4Se10 (A = Rb, Cs)

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Trigonal Planar [HgSe₃]^4– Unit: A New Kind of Basic Functional Group in IR Nonlinear Optical Materials with Large Susceptibility and Physicochemical Stability

K₂ZnSn₃Se₈: A Non‐Centrosymmetric Zinc Selenidostannate(IV) Featuring Interesting Covalently Bonded [ZnSn₃Se₈]²⁻ Layer and Exhibiting Intriguing Second Harmonic Generation Activity

Strong SHG Response via High Orientation of Tetrahedral Functional Motifs in Polyselenide A₂Ge₄Se₁₀ (A = Rb, Cs)