Inorganic Chemistry Frontiers
·
2023
·Vol. 10
·期 21
·6253-6261
·
IF 7
Hongshan Wang,Xueting Pan,Wang Zhao,Yu Chu,Junjie Li
Developing high-performance infrared (IR) nonlinear optical (NLO) materials is essential for modern laser technology, but challenging due to the competition of the NLO coefficient and band gap in the structure. Based on the “electronic structure engineering bucket effect” and systematic experimental investigations on the AIIBIICIVD4VI family, three new alkaline earth metal sulfides Mg0.6Cd1.4GeS4, CaCdGeS4, and BaZnGeS4 have been developed. The compounds show a structural change from the Pnma (CaCdGeS4) to the Fdd2 (BaZnGeS4) space group. Among them, BaZnGeS4 exhibits a phase-matching NLO response of ∼0.8× AGS, a wide band gap of 3.36 eV, and a high laser-induced damage threshold of ∼5.4× AGS, achieving a good balance between the NLO response and band gap, which makes it an excellent IR NLO material. Theoretical calculations show that the NLO effects of BaZnGeS4 originated from the [ZnS4] and [GeS4] NLO-active motifs. The results indicate that BaZnGeS4 is a promising anti-laser damage IR NLO material and enriches the chemical diversity of the AIIBIICIVD4VI family.
研究领域:
材料科学
·
光学工程
·
固体物理
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2016
·Vol. 45
·期 18
·7627-7633
·
IF 4.177
Molin Zhou,Chao Li,Xiaoshuang Li,Jiyong Yao,Yicheng Wu
Three new compounds (i.e., K2Sn2ZnSe6, Na2Ge2ZnSe6, and Na2In2GeSe6) with intriguing structural diversity and nonlinear optical properties were discovered for the first time. They crystallize in space groups P4/ncc, I4/mcm and Cc, respectively. In K2Sn2ZnSe6 and Na2Ge2ZnSe6, the [Sn(Ge)Se4] tetrahedra and [ZnSe4] tetrahedra are linked via edge-sharing to build up a 1D [Sn2ZnSe6] infinite chain separated by K+(Na+) cations along the c direction, while the structure of Na2In2GeSe6 is an interesting three-dimensional framework composed of [InSe4] and [GeSe4] tetrahedra via corner-sharing with Na+ cations in the cavities. The experimental optical band gaps of these compounds were determined as 1.71(2) eV, 2.36(4) eV and 2.47(2) eV, respectively, according to UV-vis-NIR diffuse reflectance spectroscopy. Interestingly, in addition to the large band gap (1.80 eV for AgGaSe2, as a comparison), Na2In2GeSe6 exhibits phase-matchable nonlinear optical (NLO) properties with a powder second harmonic generation signal about 0.8 times that of AgGaS2. Moreover, Na2In2GeSe6 melts congruently at a rather low temperature of 671 °C, which suggests that bulk crystals can be easily obtained by the Bridgman–Stockbarger method. Our preliminary results indicate that Na2In2GeSe6 has promising applications in IR nonlinear optics.
研究领域:
材料科学
·
晶体学
·
光学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2021
·
IF 3.498
Fang-Yu Yuan,Chen-Sheng Lin,Yi-Zhi Huang,Hao Zhang,An-Yi Zhou,Guo-Liang Chai,Wen-Dan Cheng
In this work, we chose to explore the infrared (IR) nonlinear optical (NLO) materials centering on Cd and Ge elements, and finally synthesized a new IR NLO quaternary selenide BaCdGeSe 4 . Compound BaCdGeSe 4 crystallizes in non-centrosymmetric (NCS) space group Fdd 2 (No. 43), and it is built by parallel two-dimensional (2D) anionic [CdGeSe 4 ] 2- layers with the cation Ba 2+ embedded between the layers. Under the 2050 nm laser excitation, compound BaCdGeSe 4 appears type-I phase-matchable behavior and its second-harmonic generation intensities is about 0.5 times of AgGaS 2 .
研究领域:
材料科学
·
晶体学
·
光学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2021
·
IF 5.165
Wenfeng Zhou,Qing Zhang,Wen-Dong Yao,Huaiguo Xue,Sheng-Ping Guo
One of the key scientific issues for exploration of novel infrared nonlinear optical (NLO) crystals is to obtain ones with good hybrid NLO behaviors. Herein, we report four diamond-like Ag-based sulfides via stepwise Li substitution of Ag in Ag2ZnSnS4, including Ag2ZnSnS4 (1), (Li1.22Ag0.78)ZnSnS4 (2), (Li1.58Ag0.42)ZnSnS4 (3), and Li2ZnSnS4 (4). With the increase of Li content, the sulfide’s noncentrosymmetric crystal structure changes from tetragonal I42m for 1, to orthorhombic Pmn21 for 2 and 3, and to monoclinic Pn for 4. Accordingly, their NLO responses are improved along with the increase of Li content, viz. from non-NLO-active for 1, to non-phase-matchable for 2 and 3, and to phase-matchable for 4. Their optical band gaps also increase regularly. The relationship between their chemical compositions, crystal structures, and NLO activities is investigated by means of chemical structural analysis and theoretical calculation. This work offers a new systematic case for designing promising NLO-active compounds via rarely adopted cation’s stepwise partial substitution and understanding the chemical composition–structure–NLO property relationship.
研究领域:
材料科学
·
化学
✓ 已验证
DOI
PubMed
高影响因子
CRYSTAL GROWTH & DESIGN
·
2018
·
IF 3.972
Yan-Yan Li,Hui Wang,Bo-Wen Sun,Qin-Qin Ruan,Yan-Ling Geng,Peng-Fei Liu,Lei Wang,Li-Ming Wu
Two new mid-infrared (MIR) nonlinear optical (NLO) chalcogenide crystals, Ba10Zn7In6S26 (1) and Ba10Zn7Ga6Se26 (2) were discovered by traditional solid state reactions. Compounds 1 and 2 are isostructural, and they represent a novel three-dimensional (3D) framework made by apex-sharing T2 supertetrahedron 2D layers that are stacked alternately by another kind of T2 supertetrahedra though sharing apexes along the c direction, with T1 tetrahedra inserting in the tunnels and Ba2+ cations locating both in the voids and in the tunnels. Among them, 1 shows attractive MIR NLO properties with a wide band gap of 3.0 eV, a strong second harmonic generation (SHG) signal about 4.1 times that of the commercial AgGaS2 at particle sizes of 30–46 μm under a 2.05 μm laser radiation, and a high laser damage threshold (LDT) of 37.2 times that of benchmark AgGaS2 at particle sizes of 150–210 μm under a 1.064 μm laser radiation. This distinguishes 1 as a new promising MIR NLO material. In addition, the density functional theory (DFT) analyses suggest that the SHG response of 1 comes mainly from the electronic transitions from S 3p to Ba 5d, Zn 4s, Zn 3d, In 5s, and In 5p states.
研究领域:
材料科学
·
晶体学
✓ 已验证
DOI
高影响因子
CHEMISTRY OF MATERIALS
·
2021
·
IF 9.811
Yilei Hu,Xingxing Jiang,Chao Wu,Zhipeng Huang,Zheshuai Lin,Mark G. Humphrey,Chi Zhang
Tailored structural modulation to combine a broad optical band gap, large nonlinear optical (NLO) effect, and moderate birefringence in a single molecule is a crucial challenge for functional NLO material design. In this study, two first fluorinated molybdate fluoroiodates A2MoO2F3(IO2F2) [A = Rb (RMOFI), Cs (CMOFI)] were successfully accomplished by combining fluorinated d0-transition metal (TM) octahedra [MoO3F3] with fluoroiodate group [IO2F2]. These two compounds crystallize in noncentrosymmetric space group Cmc21 while featuring a zero-dimensional (0D) [MoO2F3(IO2F2)]2– functional motif, and their respective alkali–metal cations act as linkers in polyanions. Both RMOFI and CMOFI possess large second-harmonic generation (SHG) effects (5.0 × KH2PO4 (RMOFI) and 4.5 × KH2PO4 (CMOFI) at 1064 nm), wide band gaps (3.77 eV (RMOFI) and 3.43 eV (CMOFI)), sufficient birefringences (0.217 (RMOFI) and 0.204 (CMOFI) at 1064 nm) to achieve phase-matchable (PM) and broad infrared (IR) transparency region, suggesting that RMOFI and CMOFI can be promising NLO materials in the IR field. Theoretical calculations elucidate that the strong SHG responses and enlarged birefringences of the title compounds originate from the 0D [MoO2F3(IO2F2)]2– functional unit. This is in sharp contrast to the previous work that most fluoroiodates adopt centrosymmetric structures. Our study illustrates that introducing fluorinated d0-TM octahedra into fluoroiodate systems can be a facile method for developing high-performance nonlinear optical materials.
研究领域:
材料科学
·
晶体化学
✓ 已验证
DOI
高影响因子
Small
·
2023
·Vol. 20
·期 3
·2306459
·
IF 13.3
Shuoxing Yang,Hongping Wu,Zhanggui Hu,Jiyang Wang,Yicheng Wu,Hongwei Yu
Nonlinear optical (NLO) crystals are indispensable for the solid-state lasers for their ability to expand wavelength spectral to the regions where the directing lasing is difficult or even impossible, yet the rational design of a high-performance NLO crystal remains a great challenge owing to the severe structural and properties’ requirements. Herein, a new noncentrosymmetric (NCS) and polar gallium iodate, LiGa(IO 3 ) 4 , with a novel 2D anionic layer, is successfully designed and synthesized by the aliovalent substitution strategy based on classic α-LiIO 3 . The 2D [Ga(IO 3 ) 4 ] ∞ − layer in LiGa(IO 3 ) 4 is built from the GaO 6 octahedra and highly polarizable units IO 3 . Compared with its parent compound, the partial replacement of A-site Li + cation with main group Ga 3+ cation facilitates LiGa(IO 3 ) 4 to possess excellent NLO properties, including the large second-harmonic generation (SHG) response (14 × KH 2 PO 4 (KDP) @ 1064 nm), wide bandgap (4.25 eV), large birefringence (0.23 @ 1064 nm), and wide optical transparency from UV to mid-IR. These reveal that LiGa(IO 3 ) 4 will be a promising NLO crystal.
研究领域:
材料科学
·
晶体工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2021
·Vol. 27
·期 21
·6538-6544
·
IF 5.236
Yi Huang,Le Gao,HaoHai Yu,Zhihua Yang,Junjie Li,Shilie Pan
Graphical Laser damage limitation : Promising ternary infrared nonlinear optical (NLO) materials, Na 6 MQ 4 (M=Zn, Cd; Q=S, Se), with unique [NaQ 4 ] NLO-active groups, are successfully prepared. Theoretical calculations and statistical analyses indicate that the second-harmonic generation effect and band gap in the compounds originate mainly from the distorted NaQ 4 NLO-active units with a short Na−S bond length. Four sodium-based ternary IR nonlinear optical (NLO) materials, Na 6 MQ 4 (M=Zn, Cd; Q=S, Se), were prepared through a high-temperature flux method. The crystal structure of the compounds is built up of isolated [MQ 4 ] tetrahedra and a 3D framework formed by the NaQ n ( n =4, 5) units. The two selenides, Na 6 MSe 4 (M=Zn, Cd), as promising IR NLO materials, show moderate second-harmonic generation (SHG) responses (0.9 and 0.5×AgGaS 2 ) with good phase-matching behavior, as well as high laser damage thresholds (2 and 1.9×AgGaS 2 ). The two sulfides, Na 6 MS 4 (M=Zn, Cd), exhibit higher laser damage thresholds (13 and 4×AgGaS 2 ), but smaller SHG responses (0.3 and 0.2×AgGaS 2 ). Theoretical calculations and statistical analyses indicate that the SHG effect and band gap in the compounds originate mainly from the distorted NaQ 4 NLO-active units with a short Na−S bond length, which provides a new insight into the design of novel IR NLO materials.
研究领域:
材料科学
·
光学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMISTRY OF MATERIALS
·
2017
·
IF 9.466
Bin-Wen Liu,Min-Yi Zhang,Xiao-Ming Jiang,Shu-Fang Li,Hui-Yi Zeng,Guo-Qiang Wang,Yu-Hang Fan,Yong-Fei Su,Chunsen Li,Guo-Cong Guo,Jin-Shun Huang
Two new polar polyselenides Rb4Ge4Se12 (1) and Cs4Ge4Se12 (2) with rarely reported dimeric [Ge2Se4(μ-Se2)]4– units were synthesized. They present large second-harmonic generation (SHG) intensities of 7.5 and 6.5 times that of the benchmark AgGaS2 with type I phase-matching behavior, high laser-induced damaged thresholds, a wide transmission region and congruently melting behavior, making them excellent candidates for IR nonlinear optical (NLO) applications. The SHG functional motifs of both compounds are determined to be [Ge2Se4(μ-Se2)]4– unit by time-dependent density functional theory calculation, which further reveals that charge transfers from the lone pairs of terminal Se atoms to the five σ* orbitals of five-membered ring Ge2Se3 have a predominant contribution to the total SHG effect.
研究领域:
材料科学
·
光学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Qianzhen Zhang,Ran An,Abudukadi Tudi,Jiongquan Chen,Xiaoqin Ma,Xifa Long,Zhihua Yang,Shilie Pan,Yun Yang
Developing new short-wavelength nonlinear optical (NLO) crystals has always been a significant and challenging area of research. Herein, guided by the cooperative optimization strategy, three new rare-earth metal borate fluorides, K 2 GdB 3 O 6 F 2 , Rb 2 LuB 3 O 6 F 2 , and Cs 2 LuB 3 O 6 F 2 , are rationally designed and fabricated by synergically assembling advantageous functional groups. Among them, a structural evolution from centrosymmetric K 2 GdB 3 O 6 F 2 to non-centrosymmetric Rb 2 LuB 3 O 6 F 2 and Cs 2 LuB 3 O 6 F 2 reveals that the [B 3 O 6 ] group contributes to the control of structural symmetry, owing to its sensitivity to the coordination of rare earth metal polyhedra. Notably, all the three title compounds exhibit short cutoff edges less than 200 nm, with Cs 2 LuB 3 O 6 F 2 displaying a large experimental frequency doubling effect of 1.5 × KH 2 PO 4 . The type-I shortest phase-matching wavelengths for Rb 2 LuB 3 O 6 F 2 and Cs 2 LuB 3 O 6 F 2 are evaluated to be 210 and 202 nm, respectively, indicating their potential for direct output of 213 coherent lights through a fifth harmonic generation process of Nd: YAG laser. This study provides new insights into the rational design and development of short-wavelength NLO materials by exploring the sensitivity of the [B 3 O 6 ] groups to the surrounding coordination environment, thereby fostering innovation in the field of NLO materials.
研究领域:
材料科学
·
无机化学
·
光学材料
·
非线性光学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Science
·
2022
·Vol. 9
·期 14
·2105787
·
IF 17.521
Jindong Chen,Qingchen Wu,Haotian Tian,Xiaotian Jiang,Feng Xu,Xin Zhao,Zheshuai Lin,Min Luo,Ning Ye
Pnictides are superior infrared (IR) nonlinear optical (NLO) material candidates, but the exploration of NLO pnictides is still tardy due to lack of rational material design strategies. An in-depth understanding structure–performance relationship is urgent for designing novel and eminent pnictide NLO materials. Herein, this work unravels a vital band gap mechanism of pnictides, namely P atom with low coordination numbers (2 CN) will cause the decrease of band gap due to the delocalization of non-bonding electron pairs. Accordingly, a general design paradigm for NLO pnictides, ionicity–covalency–metallicity regulation is proposed for designing wide-band gap NLO pnictides with maintained SHG effect. Driven by this idea, millimeter-level crystals of MgSiP2 are synthesized with a wide band gap (2.34 eV), a strong NLO performance (3.5 x AgGaS 2 ), and a wide IR transparency range (0.53–10.3 µm). This work provides an essential guidance for the future design and synthesis of NLO pnictides, and also opens a new perspective at Zintl chemistry important for other material fields.
研究领域:
材料科学
·
非线性光学
·
固态化学
·
津特尔化学
·
红外材料
✓ 已验证
DOI
高影响因子
CRYSTENGCOMM
·
2011
·Vol. 14
·期 3
·1031-1037
·
IF 4.006
Liang Li,Huijuan Cui,Zhou Yang,Xutang Tao,Xinsong Lin,Ning Ye,Huai Yang
The synthesis of a series of thienyl-substituted pyridinium salts with different counter-anions and their second-order nonlinear optical (NLO) properties are described. Kurtz powder tests revealed that, out of the twelve new pyridinium salts, four possess noncentrosymmetric structures and the maximum powder second harmonic generation (SHG) efficiency is 0.6 times of DAST. Single crystals of three new salts were successfully obtained from methanol by slow evaporation method. X-Ray studies exhibited that they crystallized in the monoclinic space groupP21/c, P21, and P21/n, respectively. (E)-4-(2-(5-(dimethylamino)thiophen-2-yl)vinyl)-1-methylpyridinium 4-hydroxybenzenesulfonate (3c) forms a hydrated noncentrosymmetric phase with a large macroscopic optical nonlinearity 0.5 times of that of DAST at the non-resonant wavelength of λ = 2109 nm, while both (E)-4-(2-(5-(dimethylamino)thiophen-2-yl)vinyl)-1-methylpyridinium 2-amino-3,5-dimethylbenzenesulfonate (3i) and (E)-4-(2-(5-(dimethylamino)thiophen-2-yl)vinyl)-1-methylpyridinium iodide (3a) crystallize in centrosymmetric structures.
研究领域:
有机化学
·
材料科学
·
非线性光学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）