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.

Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline-Earth-Metal Substitution by Tin

Potential optical functional crystals with large birefringence: Recent advances and future prospects

Exploring significant ultraviolet/deep-ultraviolet nonlinear optical (NLO) materials is hindered by rigorous and contradictory requirements, especially, possessing a moderate optical birefringence to meet phase-matching (PM). Except for suitable birefringence, small chromatic dispersion is also crucial to blue-shift the PM wavelength. Here, the introduction of a fluorinated tetrahedral boron-centred chromophore strategy was proposed to optimize the chromatic dispersion. Herein, the [BF4 ]- unit with a large HOMO-LUMO band gap was introduced to the Na-B-O-F system and Na4 B8 O9 F10 was designed and synthesized successfully for the first time. Na4 B8 O9 F10 with an optimized chromatic dispersion can achieve a short second harmonic generation PM wavelength of 240 nm with a relatively small birefringence (0.036@1064 nm). Notably, Na4 B8 O9 F10 is the first acentric crystal with [BF4 ]- units among the reported metal-fluorooxoborate systems, involving isolated [BF4 ]- and novel [B7 O10 F6 ]5- fundamental building blocks. 

Na 4 B 8 O 9 F 10 : A Deep‐Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase‐Matching Wavelength Induced by Optimized Chromatic Dispersion

Birefringent materials play indispensable roles in modulating the polarization of light and are vital in the laser science and technology. Currently, the design of birefringent materials operating in the deep-ultraviolet region (DUV, λ ≤200 nm) is still a great challenge. In this work, we developed a new DUV birefringent crystal LiBO2 based on [BO2]∞ infinite chains in the Li-B-O system, which simultaneously achieves the shortest UV cutoff edge (164 nm) and the largest birefringence (≥0.168 at 266 nm) among all the reported borate-based DUV birefringent materials. Single crystals of LiBO2 with dimensions up to Ø55 × 34 mm3 were grown by the Czochralski method, providing access to large-sized single crystal with low cost. Moreover, it has a high laser damage threshold and stable physicochemical properties. These outstanding characters unambiguously support that LiBO2 can be an excellent birefringent material for DUV application. 

/pdf/an-excellent-deep-ultraviolet-birefringent-material-based-on-1wyp5uwa.pdf

An excellent deep-ultraviolet birefringent material based on [BO2]∞ infinite chains

The combination of Sn(II) or Sb(III) with π, non-π-conjugated units has produced some birefringent crystals with birefringence ranging from 0.005 to 0.468@1064 nm. And it is proven that introducing Sn(II) or Sb(III) into crystals is a feasible strategy to enlarge the birefringence, which not only promotes the miniaturization of fabricated devices, but also effectively modulates polarized light. Herein, recently discovered Sn(II), Sb(III)-based birefringent crystals with birefringence investigated are summarized, including their crystal structure, and optical properties, especially birefringence. This review also presents the influence of Sn(II), Sb(III) with stereochemical activity lone pair on the optical anisotropy. We hope that this work will acquire a clear perspective on the crystal chemistry of Sn(II), Sb(III)-based optical functional crystal and promote the development of new birefringent crystal with large optical anisotropy.

Recent Development of Sn(II), Sb(III)-based Birefringent Material: Crystal Chemistry and Investigation of Birefringence.

RbB3O4F2: a rubidium fluorooxoborate with an unprecedented [B3O5F2]3- functionalized unit and a large birefringence.

A new complex alkaline-earth metal borosilicate chloride Ba3Ca4(BO3)3(SiO4)Cl has been successfully synthesized by the high-temperature solution method. It crystallizes in the space group P63mc (no. 186) of the hexagonal system. Its structure features a 3∞[Ca4(BO3)3(SiO4)] framework formed by interconnected 1∞[Ca4(BO3)3(SiO4)O9] chains with large octagonal star-like channels, in which the 1∞[Ba3Cl] chains are located. The second harmonic generation (SHG) measurement shows that Ba3Ca4(BO3)3(SiO4)Cl has an SHG of about 0.6 times that of KH2PO4 and it is phase matchable. In addition, it melts congruently and exhibits a wide transparent range with the UV cut-off edge below 190 nm. All the above indicates that Ba3Ca4(BO3)3(SiO4)Cl could be regarded as a potential ultraviolet nonlinear optical material.

Ba3Ca4(BO3)3(SiO4)Cl: a new non-centrosymmetric complex alkaline-earth metal borosilicate chloride with a deep-ultraviolet cut-off edge

Tin(II)oxybromide, Sn14O11Br6 (TOB), was synthesized successfully via the high-temperature solution method in a closed system for the first time. Its structure displays two-dimensional [Sn14O11Br6] layers constructed from highly distorted [SnO3]4− and [SnO2Br]3− polyhedra. Besides, TOB possesses good thermal stability and a birefringence larger than 0.248 at 546.1 nm. First-principles calculations reveal that TOB shows giant optical anisotropy of Δn = 0.265 at 546 nm owing to the superior arrangement of highly distorted Sn–O/Br polyhedra.

Sn14O11Br6: a promising birefringent material with a [Sn14O11Br6] layer

A new tin borate fluoride Sn2B7O12F has been successfully synthesized by the high-temperature solution method in a closed system. It crystallizes in the monoclinic space group C2/c. The structure features a new fundamental building block (FBB) [B7O16]11−, which further condenses to an infinite 2∞[B14O24]6− layer extended in the ab plane. The adjacent layers are bridged by the unique isolated [Sn4O12F2]18− clusters, which are constructed from two [Sn2O7F]11− polyhedra sharing a common edge. First-principles calculations have shown that the birefringence of Sn2B7O12F is about 0.07@1064 nm, which originated from the the synergistic contributions of the B–O and Sn–O/F interactions.

Sn2B7O12F with a 2∞[B14O24]6− layer constructed from the unprecedented [B7O16]11− fundamental building block

Multinuclear 3d-4f nano-clusters, consisting of a large number of metal ions, are interesting both structurally and functionally. They attract great research attention, in particluar, because if their significantly magnetocaloric effect....

{Gd44Ni22}: A Gigantic 3d-4f Wheel-like Nanoscale Cluster with Large Magnetocaloric Effect

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