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
Journal of Materials Chemistry C
·
2022
·Vol. 10
·期 23
·9146-9151
·
IF 8.067
Ming-Ze Li,Lin-Tao Jiang,Shao-Min Pei,Bin-Wen Liu,Xiao-Ming Jiang,Guo-Cong Guo
Two new IR NLO compounds, namely Rb2Zn3P4S13 (1) and Cs2Zn3P4S13 (2), have been obtained by introducing d10 closed-shell cations in an alkali-metal containing thiophosphate system. Compounds 1 and 2 are isostructural and feature a 3D [Zn3P4S13] anionic framework. Both compounds exhibit moderate phase-matching SHG intensities at 1910 nm (0.1 × AGS for 1 and 2) and high LIDTs (6.1 × AGS for 1 and 5.2 × AGS for 2). They have wide transparent regions of 2.5–17.7 μm and 2.5–17.0 μm for 1 and 2, respectively, which cover the important far-IR atmospheric window of 3–5 and 8–14 μm for practical applications. Both compounds simultaneously contain two types of NLO-active thiophosphate units (PS4 and P2S6) in their structures, which to the best of our knowledge, is unprecedented in known IR NLO thiophosphates. The NLO efficiencies of 1 and 2 are mainly due to the covalent [Zn2P2S7]2− framework, in which the contribution of P2S6 units is remarkably larger than that of the PS4 units. This work sheds light on the design of promising IR NLO materials by mixing different thiophosphate functional motifs.
研究领域:
材料科学
·
晶体化学
✓ 已验证
DOI
高影响因子
Advanced Optical Materials
·
2023
·Vol. 11
·期 16
·2300736
·
IF 9
Jiazheng Zhou,Linan Wang,Yu Chu,Hongshan Wang,Shilie Pan,Junjie Li
The exploration of antilaser damage wide bandgap infrared (IR) nonlinear optical (NLO) materials is urgent but challenging. Herein, by introducing the idea of fluorination into chalcogenides, a wide bandgap IR NLO material Na 3 SiS 3 F with unprecedented [SiS 3 F] tetrahedra is designed and synthesized. Na 3 SiS 3 F shows a wide bandgap of 4.75 eV (the largest one in the reported quaternary metal chalcogenides), resulting in a high laser damage induced threshold of ≈5 × AgGaS 2 (AGS). Meanwhile, the compound has a moderate NLO response (≈0.3 ×AGS) with phase-matching behavior, large birefringence (0.15@1064 nm), and wide IR transparent region. The introduction of fluorine breaks the structural symmetry and broadens the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap, polarizability anisotropy, and hyperpolarizability of the Si–S tetrahedral unit. The results indicate that Na 3 SiS 3 F is a promising IR NLO material for the high-power laser application and open an avenue for the design of new wide bandgap IR NLO materials based on NLO-active [SiS x F 4− x ] ( x = 1, 2, 3) mixed anionic tetrahedral group.
研究领域:
材料科学
·
光学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Physics
·
2023
·
IF 11.5
Ya-Xiang Han,Chun-Li Hu,Bing-Xuan Li,Jiang-Gao Mao
Aliovalent substitution is an effective route to design new nonlinear optical (NLO) crystals. Using SrCdSiS 4 as a parent compound, two new infrared NLO lanthanide thiosilicates, namely LnLiSiS 4 (Ln = La and Ce), have been successfully obtained through aliovalent substitution. Interestingly, these compounds exhibit [LiSiS 4 ] 3- layers composed of vertex- and edge-shared LiS 4 and SiS 4 tetrahedra that significantly different from the [LnSiS 4 ] 3- layers composed of edge-shared LnS 6 trigonal prisms (or LnS 7 monocapped trigonal prisms) and SiS 4 tetrahedra in other ALnSiS 4 (A = K, Rb, Cs, Ln = lanthanide) compounds with larger sized alkali cations. LnLiSiS 4 (Ln = La and Ce) also achieve balanced properties for good infrared NLO materials: largest SHG response among all known thiosilicates (2.0 and 2.1 × AgGaS 2 @ 2 μm for LaLiSiS 4 and CeLiSiS 4 respectively) with phase matching ability, high laser induced damage threshold (14 and 9 times of AgGaS 2 ), wide bandgap (3.71 and 2.92 eV), wide infrared transmission range (0.35–18 μm) and good thermal stability above 700 °C. This work not only enriches the structure chemistry of lanthanide thiosilicates, but also provides an efficient route to design new high performance IR NLO materials.
研究领域:
材料科学
·
晶体化学
✓ 已验证
DOI
高影响因子
INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Guili Wang,Pifu Gong,Jiyong Yao
A new quaternary Hg-based selenide K2HgGe3Se8 was successfully synthesized and characterized as an engaging infrared (IR) nonlinear optical (NLO) material, which crystallizes in the P21 space group of the noncentrosymmetric monoclinic crystal system. The crystal structure of K2HgGe3Se8 is characterized by the stacking of countless [HgGe3Se8]2−2∞ layers with K+ cations filling the interlayers. The UV–vis–NIR diffuse reflectance spectrum shows that K2HgGe3Se8 possesses an indirect band gap of 2.13 eV. The second harmonic generation (SHG) response of K2HgGe3Se8 is approximately 1.1 times that of AgGaS2 (AGS) within the particle size of 20–50 μm along with a nonphase-matching (NPM) behavior at 2090 nm, as indicated by the SHG test. K2HgGe3Se8 also has a large powder laser-induced damage threshold (∼ 2.3 × AGS). As revealed by theoretical calculations, the optical properties of K2HgGe3Se8 are predominantly determined by [HgSe4] and [GeSe4] tetrahedra, and K2HgGe3Se8 possesses a calculated optical band gap of 1.44 eV together with a maximum SHG coefficient d22 of −7.70 pm V–1.
研究领域:
材料科学
·
光学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
DALTON TRANSACTIONS
·
2017
·Vol. 46
·期 43
·14771-14778
·
IF 4.029
Rui-Huan Duan,Peng-Fei Liu,Hua Lin,Shang-Xiong Huangfu,Li-Ming Wu
The desirable development of infrared nonlinear optical (IR NLO) materials is to design new compounds which exhibit wide band gaps and strong second harmonic generation (SHG) responses. Herein, we report three new sulfides, Ba4Ga4SnS12 (1), Ba12Sn4S23 (2) and Ba7Sn3S13 (3), with wide band gaps of 2.90, 2.98 and 3.0 eV, respectively, which have been successfully synthesized for the first time. Significantly, compound 1 exhibited a large SHG coefficient (34 × KDP), illustrating a good balance between the band gap and the SHG response. Single crystal X-ray diffraction determined that compound 1 crystallizes in the non-centrosymmetric space group P21c and it was characterized as an interesting kite-shaped linkage motif of ∞[Ga4SnS12]. Compounds 2 and 3 crystallize in the space groups of P21c and Pnma, respectively. In addition, compounds 2 and 3 were characterized as zero-dimensional (0D) structures comprising isolated SnS4 tetrahedra with Ba2+ cations and S2− anions located between them. However, compound 2 contains extra disulfide S22− anions in its isolated structure. Moreover, the theoretical calculations demonstrated that SHG responses for compound 1 could be ascribed to the transitions from S-3p and Ga-4p states to Ba-5d, Ga-4p and Sn-5p states. By analysing the relationship between the structures and properties for Pb4Ga4GeS12-type compounds, it was concluded that site disorder could be an effective way to improve optical properties.
研究领域:
材料科学
·
化学
·
光学
✓ 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
Materials
·
2021
·Vol. 14
·期 20
·6166
·
IF 3.623
Hongbo Gao,Kewang Zhang,Ailijiang Abudurusuli,Chen Bai,Zhihua Yang,Kangrong Lai,Junjie Li,Shilie Pan
Two new diamond-like (DL) chalcogenides, Li2MgGeSe4and Li2MgSnSe4, have been successfully synthesized using a conventional high-temperature solid-state method. The two compounds crystallize in the non-centrosymmetric space groupPmn21witha= 8.402 (14) Å,b= 7.181 (12) Å,c= 6.728 (11) Å,Z= 2 for Li2MgSnSe4, anda= 8.2961 (7) Å,b= 7.0069 (5) Å,c= 6.6116 (6) Å,Z= 2 for Li2MgGeSe4. The calculated results show that the second harmonic generation (SHG) coefficients of Li2MgSnSe4(d33= 12.19 pm/v) and Li2MgGeSe4(d33= −14.77 pm/v), mainly deriving from the [MSe4] (M = Ge, Sn) tetrahedral units, are close to the one in the benchmark AgGaS2(d14= 13.7 pm/V). The calculated band gaps for Li2MgSnSe4and Li2MgGeSe4are 2.42 and 2.44 eV, respectively. Moreover, the two compounds are the first series of alkali and alkaline-earth metal DL compounds in the I2-II-IV-VI4family, enriching the structural diversity of DL compounds.Keywords:diamond-like structure;chalcogenides;infrared nonlinear optical materials;second harmonic generation
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Advanced Optical Materials
·
2022
·Vol. 10
·期 6
·2102673
·
IF 10.05
Jiankang Wang,Hongping Wu,Hongwei Yu,Zhanggui Hu,Jiyang Wang,Yicheng Wu
Developing mid-infrared (MIR) nonlinear optical (NLO) crystals is of current research interest, but their rational design is still faced by a great challenge because of the inherent conflict between large second harmonic generation (SHG) response and wide bandgap. To reconcile these conflicting properties, the best way is to combine multiple anions together. Up to now, various MIR NLO crystals with multiple anions are reported, such as oxychalcogenides, oxyhalides, and salt-inclusion chalcogenide-halides. However remarkably, the nonsalt-inclusion chalcohalides with chalcogenide Q 2– (Q = S, Se) and halide X – (X = F, Cl, Br) anions combined with the same central cations are still rarely reported. Herein, a lead chalcohalide Pb 4 SeBr 6 is reported, which belongs to the nonsalt-inclusion chalcohalide and is synthesized by the rational aliovalent substitution of Se 2– for Br – anions with PbBr 2 as the template. Importantly, this compound can exhibit excellent NLO properties, including large SHG response (1.3 × AgGaS 2 (AGS)), wide IR transparent region (0.5–25 µm), and high laser damage thresholds (10 × AGS) as well as the congruently melting performance. These indicate that Pb 4 SeBr 6 is a promising MIR NLO crystal and it will also provide some insights for exploring new MIR NLO crystals based on the rational partial anion substitution.
研究领域:
材料科学
·
光学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Guili Wang,Chunxiao Li,Ming-Hsien Lee,Jiyong Yao
Currently, oxychalcogenides with mixed-anion groups that integrate the property advantages of oxides (wide optical band gap) and chalcogenides [strong second harmonic generation (SHG) response] through chemical substitution engineering have attracted widespread interest and are considered to be important candidates for infrared (IR) nonlinear optical (NLO) materials. Herein, the first Hg-based oxychalcogenide Sr2HgGe2OS6 with mixed anion [GeOS3] units has been successfully synthesized through a spontaneous crystallization method, which exhibits a favorable balance between the strong SHG response (0.7 × AgGaS2) and large optical band gap (2.9 eV). In addition, Sr2HgGe2OS6 shows high laser-induced damage threshold (LIDT, 2.1 × AgGaS2) as well as phase-matching (PM) performance. Theoretical calculations indicate that the Sr2HgGe2OS6 encompasses large birefringence of 0.128@2090 nm (3.3 × AgGaS2) and its SHG density mainly comes from [HgS4] tetrahedra and [GeOS3] units. This work not only demonstrates that Sr2HgGe2OS6 is a promising IR NLO material but also provides new ideas for the exploration of Hg-based oxychalcogenide 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
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
危险品化学品经营许可证（带存储）