CHEMISTRY OF MATERIALS
·
2021
·
IF 9.811
Dequan Jiang,Zimin Jiang,Huimin Song,Pei Wang,Hui Luo,Chen Li,Ke Liu,Ting Wen,Wenge Yang,Yusheng Zhao,Yonggang Wang
Materials with excellent nonlinear optical properties, especially the second-harmonic-generation (SHG) ability that can double the frequency of a laser ω to 2ω, are greatly important to modern optical technology. Recently, a temperature-induced SHG “on–off” phenomenon has been reported in dozens of metal–organic complexes, which have emerged as candidates in advanced optoelectronic applications. As a counterpart to temperature, pressure is also expected to trigger a SHG “on–off” phenomenon; nevertheless, such material is relatively limited. Herein, we report the observation of a pressure-induced SHG “on–off” phenomenon accompanied by a structural phase transition and piezochromism in CdTeMoO6. Under ∼10 GPa compression, the material exhibits a sharp transition from the “SHG-on” state to the “SHG-off” state. Coupled with the SHG “on–off” phenomenon, a structural transition occurs from two-dimensional to three-dimensional due to the dramatic change in the coordination environments of Te4+ and Mo6+ from [TeO4] and [MoO4] tetrahedra to [TeO6] and [MoO6] octahedra, respectively. The suppression of stereoactive lone-pair electrons on Te4+ is considered to be responsible for the SHG-off state under high pressure. Piezochromism from colorless to black is also observed coupled with the SHG “on–off” phenomenon, which can be attributed to the hybridization between Mo 4d and O 2p orbitals. Moreover, we demonstrate that the “three-in-one” transition (structural transition, SHG on–off, and piezochromism) is irreversible at room temperature but reversible upon annealing at increased temperatures (230–350 °C) with SHG, lattice dimension and color returning to those of the initial state. All of these behaviors make CdTeMoO6 a maneuverable pressure- and temperature-regulated SHG switching material with pragmatic multifunctionality.
研究领域:
材料科学
·
光电技术
·
固体物理
·
非线性光学
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2024
·Vol. 53
·期 29
·12331-12337
·
IF 3.5
Sujuan Yu,Jiangtao Fan,Zhanggui Hu,Yicheng Wu
The exploration of nonlinear optical crystals with ultraviolet (UV) transparent ranges and easy-to-grow large-size crystals is one of the current research interests. Herein, by combining borate and phosphate groups, a novel congruently melting alkali-mixed metal borophosphate, Li3Na7B4P6O26 (LNBPO) with UV transparency was successfully designed and synthesized using a high-temperature flux method. LNBPO crystallizes in the non-centrosymmetric (NCS) and polar orthorhombic space group Pca21 (no. 29), showcasing interesting (B2P3O13)∞ chains along the c axis. Notably, LNBPO has a moderate second harmonic generation (SHG) response (∼0.38 × KDP) and displays a wide transmission ranging from 0.22 to 3.68 μm, as measured by a [001]-oriented crystal wafer. Furthermore, a high-quality single crystal of LNBPO with sizes up to 14 × 14 × 12 mm3 was grown using the top-seeded solution growth method. The refractive indices of LNBPO were determined by applying the minimum deviation angle method. These results show that LNBPO possesses a phase-matching wavelength as short as 483 nm, indicating its potential as a new UV NLO crystal.
研究领域:
材料科学
·
晶体学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Gen Li,Wei Zeng,Gangji Yi,Xuan Zou,Xize Zhan,Hongmei Zeng,Zhien Lin,Guohong Zou
Oxyhalides are promising candidates for nonlinear optical (NLO) applications due to their unique structural and optical properties. In this study, we report the synthesis of two tellurium-based oxyhalides, Te8O15Cl2 and Te6O11Cl2, which exhibit distinct structural features and exceptional optical performance. Te8O15Cl2 crystallizes in a noncentrosymmetric 2D layered structure, while Te6O11Cl2 adopts a centrosymmetric 1D chain arrangement. Both compounds display wide optical transmission windows (0.30/0.31–25 μm), with Te8O15Cl2 achieving a large second-harmonic generation (SHG) efficiency surpassing conventional materials and a significant birefringence (Δn = 0.185 at 546 nm). The SHG response of Te8O15Cl2 is attributed to the alignment of nonlinear-active units driven by the [TeO3Cl] disphenoid and the stereochemically active lone pairs (SCALPs), facilitated by halogen-mediated structural distortion. These results highlight the potential of halogen modification for the design of advanced NLO materials with enhanced performance.
研究领域:
材料科学
·
光学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
DALTON TRANSACTIONS
·
2013
·Vol. 42
·期 19
·7051-7058
·
IF 3.806
Chao Huang,Chun-Li Hu,Xiang Xu,Bing-Ping Yang,Jiang-Gao Mao
The synthesis, crystal and band structures and optical characterizations of a new polar thallium(I) vanadyl iodate, namely Tl(VO)2O2(IO3)3, are reported. Tl(VO)2O2(IO3)3 crystallizes in the orthorhombic polar space group Ima2 (No. 46) with a = 14.1143(17), b = 10.2116(12), c = 8.0319(9) Å, V = 1157.6(2) Å3 and Z = 4. The structure of Tl(VO)2O2(IO3)3 exhibits a 1D [(VO)2O2(IO3)3]− chain in which neighboring distorted VO6 octahedra are interconnected by both bridging oxo and iodate anions. The SHG measurements on Tl(VO)2O2(IO3)3, using a 2050 nm laser radiation, showed a moderate strong SHG response of 1.2 × KTP(KTiOPO4). Furthermore, the material is phase-matchable. Theoretical calculations based on DFT methods were performed by using the total-energy code CASTEP.
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DOI
高影响因子
Advanced Optical Materials
·
2025
·
IF 7.2
Meng-Na Jing,Si-Fan Lu,Ming-Xin Li,Xiao-Ming Jiang,Bin-Wen Liu,Guo-Cong Guo
Nonlinear optical (NLO) crystals demonstrate notable NLO effects, which are predominantly attributed to their anionic groups. However, the role of cations has long been overlooked. For the first time, S 2− , Cl − , and O 2− are successfully incorporated into two new salt-inclusion oxychalcogenides, namely, [La 4 Cl 3 S][GaGeS 6 O] ( 1 ) and [La 4 Cl 2 S 2 ][Ge 2 S 6 O] ( 2 ), which are characterized by highly distorted and polarizable polycations and anionic groups. Notably, they exhibit substantial second-harmonic generation (SHG) intensities of 2.7 and 3.8 × AgGaS 2 @1700 nm, respectively. To the best of knowledge, the latter represents the highest value recorded for all oxychalcogenides constructed from tetrahedral structural units. Crystal structure analysis and theoretical calculations reveal that the distorted tetrahedral units in the host lattice and the polyhedral units in the guest lattice considerably contributed to the SHG coefficients. Furthermore, compounds 1 and 2 display favorable laser-induced damage thresholds (4.4 and 7.2 × AgGaS 2 @1064 nm) along with expanded transparency windows. This finding underscores the potential of host–guest architectures with multiple anions for markedly enhancing SHG coefficients, which paves the way for the development of new NLO materials.
研究领域:
材料科学
·
光学
✓ 已验证
产品关联
DOI
高影响因子
OPTIK
·
2021
·
IF 2.443
Siyuan Hu,Tongpeng Zhao,Kai Xu,Shaohua Ji,Lifeng Cao,Bing Teng
1-(4-methoxyphenyl)-3-(3,4-dimethoxyphenyl)-2-propen-1-one(DMMC), a chalcone derivative was synthesized by Claisen-Schmidt condensation reaction method. The growth of DMMC in methanol was used the slow evaporation technique. Single crystal X-ray diffraction revealed that the space group of DMMC is P2 1 . The intermolecular interaction of crystal was analyzed by Hirshfeld surface. The second harmonic generation efficiency of DMMC was measured by Kurtz-Perry powder method. When the particle size was between 250 and 300 μm, the SHG efficiency of DMMC was the largest, which was about 60 times that of the KDP with the same particle size. All functional groups of the crystal were identified by FT-IR and 1 H NMR spectral. This crystal had a wide transmission range in the region of 350−2000 nm with the cut off wavelength is 400 nm. The thermal properties of the sample were tested, and the melting point was at 95.59 °C. The dielectric constant of the compounds was found to be 17 below 45 °C.
研究领域:
材料科学
·
化学
✓ 已验证
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2024
·
IF 6.1
Luli Wang,Han Luo,Siyu Chen,Ling Huang,Liling Cao,Xuehua Dong,Guohong Zou
In this study, we successfully synthesized two novel non-centrosymmetric (NCS) antimony halide compounds, RbSbF3Cl and Rb3Sb4F14Cl. These compounds were formed by combining Sb3+ cations, which possess stereochemically active lone pairs (SCALP), with halogen atoms (fluorine and chlorine). The introduction of mixed halogen atoms enables Sb atoms to adopt multiple coordination modes, which in turn promotes the development of both compounds towards NCS structures. Notably, Rb3Sb4F14Cl demonstrated a large second harmonic generation (SHG) response, approximately three times greater than that of KH2PO4 (KDP), along with a wide transparency range from 0.27 to 13.3 μm and a high laser damage threshold (LDT) of 223 MW cm−2. These exceptional properties indicate that Rb3Sb4F14Cl is a highly promising nonlinear optical (NLO) crystal with excellent overall performance, making it suitable for potential applications spanning the short-wave ultraviolet (UV) to mid-infrared (IR) spectral regions. In contrast, RbSbF3Cl exhibits a large birefringence of 0.31 at 546 nm as a uniaxial crystal, suggesting its practicability as a birefringent material.
研究领域:
材料科学
·
光学
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY OF MATERIALS
·
2019
·
IF 10.159
Tongtong Yu,Shanpeng Wang,Xiang Zhang,Chenning Li,Jie Qiao,Ning Jia,Bing Han,Sheng-Qing Xia,Xutang Tao
Mid-infrared (MIR) nonlinear optical (NLO) crystals are crucial in generating MIR lasers, which are important in civilian and military applications. Compared to the extensively investigated ternary and quaternary chalcogenide NLO crystals, ternary phosphide crystals have a large nonlinearity coefficient and a wide transparency range. For instance, the well-known ternary chalcopyrite phosphide NLO crystal, ZnGeP2, possesses a large nonlinearity coefficient (deff = 75 pm/V) and a broad transmittance range of 0.75–12 μm. However, its applications in the far-infrared laser range were hindered by its strong absorption near 9 and 10–12 μm. Here, considering that Mn2+ not only makes contributions to large second-harmonic generation (SHG) response but also extends the transparency wavelength range, a new ternary chalcopyrite phosphide crystal, MnSiP2 (MSP), was rationally designed by substituting a II-site metal (Zn or Cd) for Mn in the II-Si-P2 family. In this work, the synthesis and single-crystal growth of MSP were systematically investigated. The theoretical and experimental characterizations demonstrated that MSP exhibits a good balance between strong SHG behavior (6 × AgGaS2) and large laser damage threshold (about 70 MW/cm2). Specifically, the long-wavelength MIR cutoff edge of MSP is 18.2 μm, and the outstanding terahertz (THz) transmittance covers the range of 0.4–2.0 THz, indicating the ultrabroad transparency range. This work may provide a feasible strategy and impel one to search for promising outstanding MIR NLO crystals in the ternary phosphide family.
研究领域:
材料科学
·
光学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTAL GROWTH & DESIGN
·
2026
·
IF 3.6
Lv Sheng,Song Liangcheng,Xu Yanling,Zhou Jiahao,Zhu Chongqiang,Yang Chunhui
Cs 2 HgI 4 is demonstrated to be a
promising
infrared nonlinear optical (IR NLO) crystal through a combined experimental
and theoretical investigation. Phase-pure Cs 2 HgI 4 was synthesized via solution evaporation in acetone, where the formation
of [HgI 4 ] 2– complexes served as a critical
switch to solubilize CsI through a positive-feedback coupling mechanism,
representing a fundamental advancement from aqueous heterogeneous
precipitation to organic-phase homogeneous reaction. Guided by precisely
determined solubility and metastable zone width in methanol, a bulk
single crystal with dimensions of 5 × 5 × 2 mm 3 was grown via the slow cooling method. PXRD, high-resolution X-ray
rocking curve, XPS, TGA/DSC, and long-term air-exposure tests confirmed
high phase purity, crystalline perfection, chemical stability, and
thermal robustness. Optical measurements revealed a direct bandgap
of 2.82 eV and an ultrabroad transmission window spanning from 0.43
to 79.1 μm. Powder SHG measurements demonstrated phase-matching
behavior with an effective nonlinear coefficient d eff of 13.49 pm/V (∼1.36 × AgGaS 2 ) and a high LIDT of 6.01 MW cm –2 (1.9 × AgGaS 2 ). DFT calculations further showed that the superior performance
originates from the dual-orbital hybridization mechanism of Hg–I
bonds within [HgI 4 ] tetrahedra, while the incorporation
of Cs + widens the bandgap through enhanced ionic character.
This synergistic interplay between covalent and ionic motifs establishes
Cs 2 HgI 4 as a competitive candidate for IR NLO
applications, and the synthetic strategy developed herein provides
a new reaction engineering paradigm for solution-based growth of metal
halide NLO crystals.
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DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2025
·
IF 4.7
Chunxiang Wu,Yuze Li,Zhengli Liang,Xiao Jiang,Hui Fang,Lixiang Qin,Xingyuan Bai,Lehui Liu,Xingxing Jiang,Zheshuai Lin,Hongming Liu
Second harmonic generation (SHG) response, birefringence, and optical band gap are several critical parameters of nonlinear optical (NLO) crystals. However, due to the mutual influence and constraints among the fundamental properties of NLO crystals, simultaneously optimizing these performance parameters poses a significant challenge. Herein, lanthanide iodates crystallizing in centrosymmetric (CS) space group were selected as parents, by introducing [SO 4 ] group and water molecule to induce symmetry breaking, a series of mixed-anion lanthanide iodate-sulfate hydrates, RE(IO 3 )(SO 4 )(H 2 O) 2 ∙H 2 O (RE = Eu, Gd, Tb, Yb, Y), were obtained. Their structures changed from the CS space group of the parents to non-centrosymmetric (NCS) one ( P 2 1 2 1 2 1 ). These crystals exhibit strong SHG responses (0.79−1.21 × KH 2 PO 4 ), moderate birefringence (0.061−0.109), short UV transmission cutoff edges (∼240 nm), and wide optical bandgaps (4.24−4.32 eV), demonstrating their potential as NLO crystalline materials with excellent comprehensive properties. This work highlights a feasible strategy of introducing [SO 4 ] group and water molecule into CS iodates to construct NCS structures, thereby developing potential high-performance NLO crystal materials.
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产品关联
DOI
高影响因子
Science China-Chemistry
·
2026
·
IF 9.7
Huang Chunmei,Pang Xuan,Li Fuming,Cao Shumei,Pan Shilie,Mutailipu Miriding
Nonlinear optical (NLO) and birefringent crystals are pivotal for advancing photonic technologies, enabling critical functions from laser frequency conversion to quantum information processing. To address the pressing need for miniaturized devices with enhanced optical anisotropy, we strategically select 5-hydroxy-2-pyridinecarboxylic acid (C 6 H 5 NO 3 ), a low-toxicity, cost-effective organic molecule featuring a pyridine-derived π -conjugated system marginally expanded beyond benzene, as NLO functional motif. This molecular design incorporates dual-functional OH/COOH groups that synergistically extend π -delocalization within the planar six-membered ring and provide two anionic states ([C 6 H 4 NO 3 ] − and [C 6 H 3 NO 3 ] 2− ), facilitating diverse supramolecular assemblies with alkali/alkalineearth metal ions. Through confined assembly optimization, we discovered a crystal Na 2 (C 6 H 3 NO 3 )·H 2 O, which achieves an excellent ultraviolet (UV) NLO performance: phase-matched second harmonic generation (SHG) intensity (14.0 × KH 2 PO 4 (KDP) at 1064 nm, the highest among planar mono-six-membered-ring systems), giant birefringence (0.487 at 546 nm), and a UV cutoff edge (321 nm). Multimodal analyses confirm the planar organic anion [C 6 H 3 NO 3 ] 2− as the origin of these exceptional optical responses, where ionic bonding and N–O/N layer confinement enforce optimal alignment.
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产品关联
DOI
高影响因子
Advanced Optical Materials
·
2024
·
IF 8
Dongling Yang,Hongyuan Sha,Zujian Wang,Rongbing Su,Chao He,Bin Su,Xiaoming Yang,Xifa Long
Non-centrosymmetric organics are promising nonlinear optical (NLO) candidates, which always exhibit a short UV absorption cutoff edge, and a strong second harmonic generation (SHG) response, but an overlarge birefringence. Here, in order to optimize the birefringence, the methyl modulation of π-conjugated organic planar units is proposed and implemented with the urea structure as a template. Thus, N -methylurea and N,N' -dimethylurea crystals are obtained by partially replacing hydrogen atoms with methyl groups. This replacement reduces hydrogen donors and weakens interchain hydrogen bonds, which facilitates the decreasing density and the parallel arrangement of π-conjugated planar units. Hence, both N -methylurea and N,N' -dimethylurea crystals exhibit not only an optimized birefringence ( N -methylurea ≈0.099 and N,N' -dimethylurea ≈0.072 at 546 nm) but also an enhanced SHG response ( N -methylurea ≈1.2 × β -BaB 2 O 4 and N,N' -dimethylurea ≈1.9 × β -BaB 2 O 4 ), while maintaining a short UV absorption cutoff edge. Therefore, this work provides a novel strategy for the structural design and performance modulation of organic NLO crystals.
研究领域:
材料科学
·
光学
✓ 已验证
DOI
高影响因子
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