Rational Design of the Alkali Metal Sn-Based Mixed Halides with Large Birefringence and Wide Transparent Range.

Birefringent materials are widely used in various advanced optical systems, owing to their vital role in creating and controlling polarized light. Currently, Sn2+-based compounds containing stereochemically active lone-pair (SCALP) cations are extensively investigated and considered as one class of promising birefringent materials. To solve the problem of relatively narrow bandgap of Sn2+-based compounds, alkali metals and multiple halogens are introduced to widen the bandgap during the research. Based on this strategy, four new Sn2+-based halides, A2Sn2F5Cl and ASnFCl2 (A = Rb and Cs), with large birefringence, short ultraviolet (UV) cutoff edge, and wide transparent range are successfully found. The birefringences of A2Sn2F5Cl (A = Rb and Cs) are 0.31 and 0.28 at 532 nm, respectively, which are among the largest in Sn-based halide family. Remarkably, A2Sn2F5Cl possess relatively shorter UV cutoff edge (<300 nm) and broad infrared (IR) transparent range (up to 16.6 µm), so they can become promising candidates as birefringent materials applied in both UV and IR regions. In addition, a comprehensive analysis on crystal structures and structure-property relationship of metal Sn2+-based halides is performed to fully understand this family. Therefore, this work provides insights into designing birefringent materials with balanced optical properties.

Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep-Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering.

Deep-ultraviolet (UV) birefringent materials are urgently needed to facilitate light polarization in deep-UV lithography. Maximizing anisotropy by regulating the alignment of functional modules is essential for improving the linear optical performance of birefringent materials. In this work, we proposed a strategy to design deep-UV birefringent materials that achieve functional module ordering via weak interactions. Following this strategy, four compounds CN4H7SO3CF3, CN4H7SO3CH3, C(NH2)3SO3CH3, and C(NH2)3SO3CF3 were identified as high-performance candidates for deep-UV birefringent materials. The millimeter-sized crystals of CN4H7SO3CF3, CN4H7SO3CH3, and C(NH2)3SO3CH3 were grown, and the transmittance spectra show that their cutoff edges are below 200 nm. CN4H7SO3CF3 exhibits the largest birefringence (0.149 @ 546 nm, 0.395 @ 200 nm) in the deep-UV region among reported sulfates and sulfate derivatives. It reveals that the hydrogen bond can modulate the module ordering of the heteroleptic tetrahedra and planar π-conjugated cations, thus greatly enhancing the birefringence. Our study not only discovers new deep-UV birefringent materials but also provides an upgraded strategy for optimizing optical anisotropy to achieve efficient birefringence.

An Antimony(III) Fluoride Oxalate with Large Birefringence.

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 546 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.

Circular Phase-Dichroism of Chiral Metasurface Using Birefringent Interference.

Circular phase-dichroism (CPD) has been suggested for the characterization of chiral metasurfaces in supplementing the conventional circular dichroism (CD). Conventional CD probes the bulk properties while the CPD, reported recently in 2D chiral metasurfaces using an air-gap Fabry-Perot setup, is based on the surface properties. Here we propose and demonstrate a robust birefringent interference approach to obtain the CPD by replacing the air-gap with a uniaxial birefringent material in which interference is realized by the difference in the refractive indexes for the ordinary and extraordinary components of the material. We measure the transmission phases of metasurfaces fabricated on birefringent sapphire substrates and obtain clear CPDs for chiral metasurfaces but vanishing for achiral metasurfaces. Importantly, our approach can be applied to metasurfaces fabricated on nonbirefringent substrates by add-on birefringent materials. We confirm our results by a Jones matrix method using data obtained from full-wave simulations, and good agreements with experiments are obtained.

α-SnF2 : A UV Birefringent Material with Large Birefringence and Easy Crystal Growth.

The simple binary fluoride α-SnF2 is shown to be an excellent birefringent material with outstanding birefringence, about 14 times that of MgF2 . Furthermore, it exhibits a shorter UV cutoff edge and easy crystal growth at ambient temperature compared to YVO4 and TiO2 . A novel theoretical calculation mode was established to analyze the stereochemical-activity lone-pair (SCALP) contribution to the birefringence (SCB) based on the SCALP's strength and arrangement, and it was found that the large birefringence of α-SnF2 mainly benefits from well-aligned [SnF5 ] polyhedra with a strong SCALP. The exploration of the α-SnF2 birefringent crystal points out the direction of the future search for excellent birefringent materials.

Sn2 PO4 I: An Excellent Birefringent Material with Giant Optical Anisotropy in Non π-Conjugated Phosphate.

Exploring non π-conjugated phosphate birefringent crystal with a large birefringence has been a great challenge. Herein, based on the unique two-dimensional layered structure in KBe2 BO3 F2 (KBBF), two new compounds, Sn2 PO4 I and Sn2 BO3 I, were designed and synthesized successfully, maintaining the layer structural feature and enhancing the optical anisotropy of crystals. In particular, the birefringence of Sn2 PO4 I is larger than or equal to 0.664 @546 nm, which is largest among the reported borates and phosphates, even surpassing commercial birefringent crystals YVO4 and TiO2 . This work indicates that a breakthrough in birefringence of inorganic compound was achieved. Also, it provides a guiding idea for exploring large birefringence materials in the future.

An Exceptional Peroxide Birefringent Material Resulting from d-π Interactions.

Birefringent materials, which can modulate the polarization of light, are almost exclusively limited to oxides. Peroxides have long been overlooked as birefringent materials, because they are usually not stable in air. Now, the first peroxide birefringent material Rb2 VO(O2 )2 F is reported, the single crystals of which keep transparency after being exposed in the air for two weeks. Interestingly, Rb2 VO(O2 )2 F does not feature an optimal anisotropic structure, but its birefringence (Δn=0.189 at 546 nm) exceeds those of the majority of oxides. According to the first-principles calculations, this exceptional birefringence should be attributed to the strong electronic interactions between localized π orbital of O2 2- anions and V5+ 3d orbitals, which may be also favorable to the stability in the air for Rb2 VO(O2 )2 F. These findings distinguish peroxides as a brand-new class of birefringent materials that may possess birefringence superior to the traditional oxides.

An Unprecedented Antimony(III) Borate with Strong Linear and Nonlinear Optical Responses.

Antimony(III) borates with a stereochemical active lone pair remained unknown, although the first antimony borate was reported more than twenty years ago. Now, the first antimony(III) borate in a closed system is successfully synthesized, namely SbB3 O6 . Remarkably, SbB3 O6 not only exhibits an exceptional linear optical response, that is, birefringence of Δn=0.290 at the wavelength of 546 nm, which is the largest among borates, but also has a strong nonlinear optical response of 3.5 times larger than the benchmark KH2 PO4 , exceeding those of most borates. Theoretical calculations reveal that the coexistence of strong linear and nonlinear optical responses in SbB3 O6 should be attributable to the synergistic effect of π-conjugated B-O anionic groups and Sb3+ with stereochemically active lone pair. This work provides a new class of optical bi-functional materials with potential prospects in integrated optical devices.

Sn2 B5 O9 Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline-Earth-Metal Substitution by Tin.

The excellent birefringent materials are needed for optical systems. Herein, we reported a new compound, the first tin borate chloride, Sn2 B5 O9 Cl (SBOC) with a large birefringence (0.168 at 546 nm) measured by the polarizing microscope. Its birefringence is 16 times that of the isostructural Ba2 B5 O9 Cl (BBOC) compound (0.010@ at 546 nm). The results show that the birefringence enhancement originates mainly from the Sn2+ polyhedra. We propose that the birefringence can be enlarged by substituting the alkaline-earth metal cation by the Sn2+ cation in the isostructural borate with small birefringence. This strategy will guide the discovery of large birefringent materials in the future.

Time-Resolved Four-Channel Jones Matrix Measurement of Birefringent Materials Using an Ultrafast Laser.

A method for ultrafast time-resolved four-channel Jones matrix measurement of birefringent materials using an ultrafast laser is investigated. This facilitated the acquisition of a four-channel angular multiplexing hologram in a single shot. The Jones matrix information of a birefringent sample was retrieved from the spatial spectrum of a hologram. The feasibility of this approach was established by measuring the Jones matrix of starch granules in microfluidic chips and the complex amplitude distribution and phase delay distribution of liquid crystal cell at different voltages. Moreover, when the picosecond laser was switched to a femtosecond laser, ultrafast measurements were possible provided that the time interval between two detection pulses was larger than the pulse width.