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A large optical anisotropy is the most important parameter of birefringent crystals. Integrating π-conjugated groups with large polarizable anisotropy into target compounds is a common strategy for constructing brilliant birefringent crystals. However, the key problem is to enhance the density of the birefringence-active units and further arrange them parallelly. In this study, three novel birefringent crystals, C9H7NBrX (X = Cl, Br, NO3), are successfully synthesized by introducing a new birefringence-active [C9H7NBr]+ unit. Interestingly, these compounds feature similar layered structures but exhibit different optical anisotropies at 550 nm (0.277 for C9H7NBrCl, 0.328 for C9H7NBrBr, and 0.401 for C9H7NBrNO3) owing to the different anions in them. Particularly, the small trigonal planar NO3 anions perfectly fill the interstices of the π-conjugated [C9H7NBr]+ groups with large optical anisotropy, with the resulting compound C9H7NBrNO3 showing superior optical properties compared to the others. The above findings provide strategies for designing new optical materials with large birefringence by matching birefringence-active groups of different sizes. Additionally, a new theory for predicting and comparing the polarizability anisotropy of compounds is proposed, which would guide in exploring large birefringent crystals.
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Traditional nonlinear optical (NLO) crystals are exclusively limited to ionic crystals with π-conjugated groups and it is a great challenge to achieve a subtle balance between second-harmonic generation, bandgap, and birefringence for them, especially in the deep-UV spectrum region (Eg > 6.20 eV). Herein, a non-π-conjugated molecular crystal, NH3 BH3 , which realizes such balance with a large second-harmonic generation response (2.0 × KH2 PO4 at 1064 nm, and 0.45 × ß-BaB2 O4 at 532 nm), deep-UV transparency (Eg > 6.53 eV), and moderate birefringence (Δn = 0.056@550 nm) is reported. As a result, NH3 BH3 exhibits a large quality factor of 0.32, which is evidently larger than those of non-π-conjugated sulfate and phosphate ionic crystals. Using an unpolished NH3 BH3 crystal, effective second-harmonic generation outputs are observed at different wavelengths. These attributes indicate that NH3 BH3 is a promising candidate for deep-UV NLO applications. This work opens up a new door for developing high-performance deep-UV NLO crystals.
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Birefringent crystals have important applications in optoelectronics areas due to their ability to modulate and polarize light. Despite increasing discovery of the birefringence potential of new crystals, it remains a great challenge to optimize both birefringence and bandgap simultaneously. Herein, a 1D chain-like hybrid perovskite birefringent crystal designed by 3D-to-1D dimensional tailoring, (GAM)2 PbI7 ·H2 O (GAM = C5 N10 H10 ), is presented, showing enlarged birefringence of 0.49@550 nm and enlarged optical bandgap (2.48 eV). Consequently, the birefringent quality factor of (GAM)2 PbI7 ·H2 O is up to 2.8 times that of the template MAPbI3 . In particular, the birefringence is much larger than those of commercial birefringent crystals and surpasses that of the vast majority of hybrid perovskite known to date. Theoretical calculations reveal that the strongly anisotropic arrangement of (GAM)2.5+ π-conjugated cations and ordered PbI6 octahedra contributes to the large birefringence and wide bandgap of (GAM)2 PbI7 ·H2 O. It is believed that this work will provide a new pathway toward the rational design and synthesis of hybrid perovskite birefringent crystals for compact wide-bandgap polarization dependent devices.
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Birefringence is an important linear optical property of anisotropic crystals that plays a significant role in regulating light polarization. A new bialkali-rare earth metal sulfate, NaRbY2(SO4)4 compound, consisting of non-π-conjugated alkali metals and rare earth metal-centered dodecahedral YO8 has been synthesized. The structure analysis suggests that the three-dimensional (3D) structure of the compound is found to be attributable to the combination of dodecahedral YO8 and tetrahedral SO4 groups with Na+ and Rb+ located in the cavities. The ultraviolet, visible, and near-infrared (UV-vis-NIR) spectra reveal that the compound exhibits transparency at a wavelength of less than 200 nm. The observed birefringence of the compound is 0.045@550 nm, which is comparatively larger than that of most deep-ultraviolet (DUV) birefringent crystals. The birefringence mainly originated from the YO8 dodecahedron, which is suggested by first-principles calculations. This research work can provide a useful perspective to explore new DUV sulfates with excellent birefringence.
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It is in great demand to discover new materials with large birefringence for the miniaturization of optical communication devices. In this work, a new one-dimensional hybrid halide perovskite, (C6 N10 H8 )Pb2 Br6 , is obtained successfully through structural design of dimension reduction from the notable three-dimensional halide perovskite CsPbBr3 . Remarkably, (C6 N10 H8 )Pb2 Br6 exhibits a significantly enhanced birefringence of ∆n = 0.42@550 nm, which is the largest among halide perovskites so far. Furthermore, its birefringence performance is robust in a wide temperature range of 300-440 K. Theoretical calculations reveal that this outstanding birefringence results from the synergistic effect of [PbBr6 ]4- octahedra and [C6 N10 H8 ]2+ cations with expanding π-delocation. According to further structural analyses, the structural dimension reduction cooperating with the increase of [PbBr6 ]4- octahedral distortion leads to the enhanced birefringence. This work uncovers the great promise of hybrid halide perovskites as robust birefringent crystals in future optical communication and would shed useful insights on the design and synthesis of new birefringent crystals.
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ConspectusSecond-order nonlinear optical (NLO) materials, producing coherent light by the cascaded frequency conversion, are current hot topics in material chemistry and optics, as they play an important role in diverse fields, such as laser technology, precision measurements, and quantum information as well as future space propulsion. The prerequisite for a second-order NLO material is that it must crystallize in a noncentrosymmetric space group, but it tends to be centrosymmetric in terms of thermodynamical stability. Furthermore, it should simultaneously satisfy strict requirements on second-order NLO coefficients, birefringence, optical transmittance windows, crystal growth, and so on. Therefore, it is still an urgent challenge to rationally assemble high-performance second-order NLO materials. In this Account, we first review the significance and background of second-order NLO materials and some strategies to design new second-order NLO materials controllably. After that, we mainly present our recent studies on the rational assembly of second-order NLO materials by the so-called strategy of "local polarity-induced assembly", including: (1) making use of the coordination habit between specific cations like Li+ or Mg2+ and tetrahedral (PO4)3-, (P2O7)4-, and (SO4)2- units to generate the local polarity, and further inducing the assembly of second-order NLO materials of superb optical properties; (2) by virtue of self-condensation of weakly polarizable units, condensation of different weakly polarizable units and partial substitution of O atoms by F or S atoms in weakly polarizable units of tetrahedral MO4 or octahedral MO6 configuration, enhancing the local polarity to induce the assembly of second-order NLO materials; and (3) introducing strongly polarizable units of stereoactive lone pair electrons into π-conjugated systems to afford the local polarity and inducing second-order NLO materials with enhanced NLO responses. Based on this strategy, we successfully assembled a variety of excellent second-order NLO materials and expanded new sources of second-order NLO materials, like fluorooxosilicophosphates, thiosulfates, and borosulfates. Finally, we will conclude the topic and give some prospects for exploring new excellent second-order NLO materials. We believe that the "local polarity-induced assembly" strategy will not only be useful for understanding the structure-property relationships of second-order NLO materials but also provide researchers with insights into obtaining noncentrosymmetric structures that are essential to other functional materials in piezoelectricity, ferroelectricity, and pyroelectricity, etc.
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Birefringent crystals are essential in the domains of linear and nonlinear optics that need light wave polarization control. Rare earth borate has become a popular study material for ultraviolet (UV) birefringence crystals due to its short cutoff edge in the UV area. RbBaScB6O12, a two-dimensional layered structure compound with the B3O6 group, was effectively synthesized through spontaneous crystallization. The UV cutoff edge of RbBaScB6O12 is shorter than 200 nm, and the experimental birefringence is 0.139 @ 550 nm. Theoretical research indicates that the large birefringence originates from the synergistic impact of the B3O6 group and the ScO6 octahedron. RbBaScB6O12 is an outstanding candidate material for birefringence crystals in the UV and even deep UV regions due to its short UV cutoff edge and significant birefringence.
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Ba1.09Pb0.91Be2(BO3)2F2 (BPBBF), a previously unreported lead-containing beryllium borate fluoride, has been successfully grown through a high-temperature flux method. Its structure is solved by single-crystal X-ray diffraction (SC-XRD), and it is optically characterized via infrared, Raman, UV-vis-IR transmission, and polarizing spectra as well. SC-XRD data suggests that it can be indexed by a trigonal unit cell (space group P3m1) with lattice parameters a = 4.7478(6) Å, c = 8.3856(12) Å, Z = 1, and V = 163.70(5) Å. This material could be considered as a derivative of the Sr2Be2B2O7 (SBBO) structural motif. It consists of 2D [Be3B3O6F3]∞ layers in the crystallographic ab plane, with divalent Ba2+ or Pb2+ cations serving as spacers among the adjacent layers. Ba and Pb were found to adopt a disordered arrangement in the trigonal prismatic coordination within the BPBBF structural lattice, which is evidenced by both structural refinements against SC-XRD data and energy dispersive spectroscopy. The UV absorption edge (279.1 nm) and birefringence (Δn = 0.054@ 546.1 nm) of BPBBF are confirmed by UV-vis-IR transmission and polarizing spectra, respectively. The discovery of this previous unreported SBBO-type material, BPBBF, along with other reported analogues such as BaMBe2(BO3)2F2 (M = Ca, Mg, and Cd), provide a prodigious example for tuning the bandgap, birefringence, and short UV absorption edge via simple chemical substitution.
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Birefringent crystals that can switch light polarization have important applications in optoelectronics. In the last decades, birefringence is mostly optimized by chemical strategies. Recently, switching birefringence by physical means has attracted much attention. Here, this work reports the observation of heat switching birefringence in a 2D layered hybrid halide perovskite (C2 N3 H4 )2 PbCl4 ((C2 N3 H4 )+ =1,2,4-triazolium). This heat switching birefringence leads to a significant change in the interference color for the crystal plate under the illumination of orthogonal polarized light. Structure analyses reveal a heat dependent structure transition in (C2 N3 H4 )2 PbCl4 , whose birefringence is switched by the change in the distortion degree of PbCl6 octahedron. This discovery may be beneficial to the further development of stimuli-responsive polarization optical devices.
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Common nonlinear optical (NLO) crystals consist of traditional functional building blocks with inherent optical limitation. Herein, inspired by traditional (B3 O6 )3- inorganic building block, we theoretically identified a new type of organic functional building blocks and then successfully synthesized the first cyamelurate NLO crystal, Ba(H2 C6 N7 O3 )2 â 8 H2 O. To our surprise, the constituent (H2 C6 N7 O3 )- building block is not in structurally optimal arrangement, but Ba(H2 C6 N7 O3 )2 â 8 H2 O exhibits excellent optical properties including wide band gap of 4.10â eV, very large birefringence of 0.24@550â nm, and exceptionally strong second-harmonic generation (SHG) response of about 12×KH2 PO4 . Both the SHG response and birefringence are much larger than those of commercial NLO crystal ß-BaB2 O4 with optimally aligned (B3 O6 )3- building block. Theoretical calculations suggest that the expanded π-conjugation delocalization within (H2 C6 N7 O3 )- vs (B3 O6 )3- should be responsible to the enhanced performance. This work implies that there is still much room to develop new NLO crystals with excellent functional building blocks that may be longly neglected.
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Birefringent crystals could modulate the polarization of light and are widely used as polarizers, waveplates, optical isolators, etc. To date, commercial birefringent crystals have been exclusively limited to purely inorganic compounds such as α-BaB2 O4 with birefringence of about 0.12. Herein, we report a new hydrogen bonded supramolecular framework, namely, Cd(H2 C6 N7 O3 )2 â 8 H2 O, which exhibits exceptionally large birefringence up to about 0.60. To the best of our knowledge, the birefringence of Cd(H2 C6 N7 O3 )2 â 8 H2 O is significantly larger than those of all commercial birefringent crystals and is the largest among hydrogen bonded supramolecular framework crystals. First-principles calculations and structural analyses reveal that the exceptional birefringence is mainly ascribed to strong covalent interactions within (H2 C6 N7 O3 )- organic ligands and the perfect coplanarity between them. Given the rich structural diversity and tunability, hydrogen bonded supramolecular frameworks would offer unprecedented opportunities beyond the traditional purely inorganic oxides for birefringent crystals.
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SO4 tetrahedral groups have weak polarization anisotropy, which thus results in the small birefringence of sulfates. Here, we report new sulfate CsY(SO4)2·4H2O with unprecedented birefringence among deep-ultraviolet (deep-UV) sulfates. Its single crystal (10 mm × 3.5 mm × 1.5 mm) was simply grown by an aqueous solution evaporation technique, and it features a rare layered structure composed of YO9 polyhedra, SO4 tetrahedra, and H2O molecules. Interestingly, each SO4 group donates two oxygen atoms to edge-share with one adjacent YO9 polyhedron and thus causes severe distortion of these groups. The characteristic edge-sharing mode gives CsY(SO4)2·4H2O a large birefringence of â¼0.045@546 nm, which is the maximum among deep-UV sulfates and phosphates with similar non-π-conjugated anionic groups. The ultraviolet-visible-near-infrared diffuse reflection and transmission spectra, infrared spectrum, thermal stability, and theoretical calculations are also presented. The fascinating results will improve our understanding of sulfates and may provide useful insights into the exploration of deep-UV sulfates with large birefringence.
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Birefringent crystals that can modulate the polarization of light play a significant role in modern optical devices including polarizing microscopes, optical isolators, and achromatic quarter-wave plates. To date, commercial birefringent crystals are exclusively limited to purely inorganic compounds. Here we report a new organic-inorganic hybrid halide, MLAPbBr4 (MLA=melamine), which features a (110)-oriented layered perovskite structure. Although the 6s2 lone-pair electrons of Pb2+ cations are stereochemically inert, MLAPbBr4 exhibits a birefringence of 0.322@550â nm, which exceeds those of all commercial birefringent crystals. The first-principles calculations reveal that this birefringence should be ascribed to the highly dislocated π-conjugation of MLA cations and high distortion of PbBr6 octahedra. This work highlights the persistently neglected great potential of hybrid halide perovskites as birefringent crystals.
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Birefringent materials are highly demanded for high-performance polarized optics. As compared with artificial anisotropic metamaterials, anisotropic crystals have advantages of low optical losses and easy processing, but their birefringence is still limited. Herein, based on first-principles studies, we identified a new type of functional anion units, (Hx C6 N9 )(3-x)- (x=0, 1, 2), and then successfully synthesized a new anisotropic crystal, namely, CsH2 C6 N9 â H2 O (I), whose crystal structure consists of (H2 C6 N9 )- anions. Remarkably, I is ultraviolet transparent and exhibits very large birefringence of about 0.55@550â nm, which is much larger than those of commercial birefringent crystals. These results make I a candidate for highly efficient manipulation of optics and light in optical modulation devices. Theoretical calculations reveal that large birefringence mainly arises from the cooperative π orbitals in (H2 C6 N9 )- anions. This work provides a new insight on the underlying structure-property relationships of anisotropic crystals.
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Antiperovskites have been studied since the 1980s because of their rich physical and chemical properties, but their linear and second-order nonlinear optical responses remain largely unknown. Here we report a new polar crystal, Cs3 Cl(HC3 N3 S3 ) (I), which features a quasi-one-dimensional antiperovskite structure composed of ClCs6 polyhedra and A-site [HC3 N3 S3 ]2- rings. To our best knowledge, this kind of antiperovskite structure is reported for the first time. Remarkably, I exhibits a very strong nonlinear optical response up to 11.4 times that of the benchmark KH2 PO4 and exceptionally large birefringence of 0.52. The first-principles calculations and structural analyses reveal that [HC3 N3 S3 ]2- is the "material gene" while the antiperovskite structural feature making it in a favorable arrangement. This work provides a new structural platform for the rational design of integrated optoelectronic materials with linear and second-order nonlinear optical responses.
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Discovering new functional genes and developing high-performance materials are the goals being pursued by scientists. In this work, we successfully obtained a second-order nonlinear optical (NLO) material via the aqueous solution method, Y[N(CN)2 ]4 [NH(C2 H5 )3 ] â 3H2 O, which is the first NLO material with the anionic group N(CN)2 - . Remarkably, this material is not only strongly NLO-active at 1064â nm with a response of about 2.8 × KH2 PO4 , but also possesses a short UV absorption edge of 250â nm. In-depth first-principles calculations illustrate well that the optical properties are mainly from the strong interaction of N, C and Y atoms. This result indicates that the N(CN)2 - anion may be a new NLO functional gene. This work enriches the diversity of NLO functional genes and materials.
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ÂnionsRESUMO
Birefringent materials play a key role in modulating the polarization of light and thus in optical communication as well as in laser techniques and science. Designing new, excellent birefringent materials remains a challenge. In this work, we designed and synthesized the first antimony(III) fluoride oxalate birefringent material, KSb2 C2 O4 F5 , by a combination of delocalized π-conjugated [C2 O4 ]2- groups, stereochemical active Sb3+ cations, and the most electronegative element, fluorine. The [C2 O4 ]2- groups are not in an optimal arrangement in the crystal structure of KSb2 C2 O4 F5 ; nonetheless, KSb2 C2 O4 F5 exhibits a large birefringence (Δn=0.170 at 546â nm) that is even better than that of the well-known commercial birefringent material α-BaB2 O4 , even though the latter features an optimal arrangement of π-conjugated [B3 O6 ]3- groups. Based on first-principles calculations, this prominent birefringence should be attributed to the alliance of planar π-conjugated [C2 O4 ]2- anions, highly distorted SbO2 F2 and SbOF3 polyhedra with a stereochemically active lone pair. The combination of lone-pair electrons and π-conjugated systems boosts the birefringence to a large extent and will help the development of high-performance birefringent materials.
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Birefringence, an important optical performance parameter for optoelectronic functional materials, is mainly influenced by the types of anion groups and their spatial arrangement. Inspired by the relationship between the structure and properties of chalcogenides, combined with the dimensional transformation, we successfully synthesized a sulfide compound (Cs2ZnSn3S8) with a two-dimensional layered structure and a large birefringence. The experimental results showed that, compared with Rb10Zn4Sn4S17, Cs2ZnSn3S8 achieved the structural transition from a zero-dimensional arrangement to a two-dimensional lamellar arrangement and achieved a breakthrough of birefringence from 0 to 0.12, which was determined by both experiments and first-principles calculations. These findings demonstrated that Cs2ZnSn3S8 was a potential birefringent material and provided instructions for the study of the synthesis of birefringent materials.
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Accurately designing and synthesizing new deep-ultraviolet (deep-UV) nonlinear optical (NLO) crystals that are limited by the so-called "200 nm wall" on their transparency windows remain challenging. On the basis of a bandgap-directed computer-aided material design approach, two new NLO sulfates, KMgSO4F and KZnSO4F, are designed and successfully synthesized. They feature three-dimensional frameworks closely related to the commercial NLO crystal, KTiOPO4 (KTP). Remarkably, the transmittance spectrum based on a single crystal indicates that the transparency window of KZnSO4F is significantly blue-shifted to <190 nm from 350 nm for KTP. The microscopic origin of this significant transparent window blue shift is illustrated well by first-principles calculations. This work pushes the transparency windows of KTP-like NLO sulfates into the deep-UV spectral region for the first time and will pave a prospective way to the accurate design and synthesis of new deep-UV NLO materials.
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It remains a challenge to develop UV nonlinear optical (NLO) crystals that can achieve a desirable trade-off on UV absorption edge, second harmonic generation (SHG), and birefringence. Here we report a thiosulfate UV NLO crystal of a 2D van der Waals layered structure, [C(NH2)3]2SO3S. Remarkably, this thiosulfate realizes the desired trade-off, with a short absorption edge of 254 nm, a strong SHG response of approximately 2.8 times that of the benchmark KH2PO4, and a sufficient birefringence of 0.073 at the wavelength of 546 nm. In addition, it exhibits strong in-plane anisotropy of the SHG intensity. According to the first-principles calculations, the non-π-conjugated [SO3S]2- anion is the dominant SHG functional gene, while the π-conjugated [C(NH2)3]+ cation serves as the functional gene of birefringence. This is different from common UV NLO materials whose functionals of SHG and birefringence are the same. These findings indicate that combining different function genes may be an effective strategy to develop outstanding NLO materials with the desirable property trade-off.