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DALTON TRANSACTIONS · 2024 ·Vol. 53 ·期 29 ·12331-12337 · IF 3.5

Li3Na7B4P6O26: a new ultraviolet transparent congruently melting non-linear optical crystal

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.

CAS / MDL: 10043-35-3
研究领域: 材料科学 · 晶体学
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INORGANIC CHEMISTRY · 2021 · IF 5.165

Two Lead Halides with Strong SHG Response Obtained by the Isovalent Substitutions of Alkali Metal Cation and Halogen Anion

Qirui Shui,Ruibiao Fu,Hongxin Tang,Yuanbin Fang,Zuju Ma,Xintao Wu

The substitution of alkali metal cation or halogen anion based on nonlinear crystals is an effective strategy to exploit new optical materials. The strategy has been successfully expanded to discover two new lead halides, Rb3Pb2(CH3COO)2X5 (X = Br, Cl). The substitution of the Cs+ cation with a Rb+ cation can not only increase the local dipole moment of the distorted [PbBr4O2] polyhedron but also reduce the cell unit, resulting in a large net macroscopic polarization. Therefore, Rb3Pb2(CH3COO)2Br5 possesses a strong second-harmonic generation (SHG) response (6 × KDP) and a large birefringence (0.18@1064 nm). Furthermore, by the substitution of the Br– anion with a Cl– anion, Rb3Pb2(CH3COO)2Cl5 exhibits a high laser damage threshold (LDT, 84 × AgGaS2) and a short UV cutoff edge of 287 nm, as well as moderate SHG response (3 × KDP) and birefringence (0.11@1064 nm). Detailed theory calculations elucidate the origin of the linear and nonlinear optical properties of these compounds.

研究领域: 材料科学 · 光学
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Advanced Optical Materials · 2024 · IF 8

Achieving the Birefringence Optimization by Methyl Modulation in Organic Nonlinear Optical Crystals

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
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DALTON TRANSACTIONS · 2023 · IF 4

NaMoO3(IO3)(H2O): water molecule introduction induces strong second harmonic generation response, widened band gap and large anisotropy

Yi Shui,Zhengli Liang,Zhenhua Li,Jiahao Wan,Lehui Liu,Xingxing Jiang,Zheshuai Lin,Hongming Liu

Exploring feasible tactics to induce the formation of non-centrosymmetric (NCS) structures, especially from centrosymmetric (CS) structures, is essential for the development of nonlinear optical crystals with more potential. An NCS alkali metal-containing molybdenum iodate hydrate, namely, NaMoO3(IO3)(H2O), was designed based on the CS matrix NaMoO3(IO3) via introducing a water molecule into the structure. The introduction of one crystalline water molecule results in the rearrangement of Λ-shaped cis-[MoO4(IO3)2] units, and the proper array of the cis-[MoO4(IO3)2] units in NaMoO3(IO3)(H2O) results in its strong SHG response of 4.6 × KH2PO4. In addition, NaMoO3(IO3)(H2O) exhibits a wider optical bandgap of 3.44 eV and a larger birefringence of 0.231 than its matrix. Furthermore, the framework of NaMoO3(IO3)(H2O) is highly similar to that of α-KMoO3(IO3), with water molecules assisting Na+ cations in occupying the position of K+. However, due to the extra hydrogen bond of water molecules, the [MoO3(IO3)]∞ layers in NaMoO3(IO3)(H2O) retain a parallel-stacking arrangement, different from the antiparallel arrangement of layers in α-KMoO3(IO3) with a centric structure. This study confirms the feasibility of applying a water molecule to adjust the orientation of basic building block units to assemble an NCS structure based on CS crystals.

CAS / MDL: 1313-27-5
研究领域: 材料科学 · 光学 · 晶体学
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