Borophosphates are very known for the short ultraviolet (UV) cutoff edge and have become the promising UV and deep-UV functional crystals candidates; however, tetrahedral [PO4] and [BO4] groups own weak anisotropy of polarizability and are not conducive to large birefringence, which hinders their application in the short-wavelength region. Improving their birefringence without compromising the band gap is the main research objective. By introducing the excellent birefringent functional groups, such as [B2O5], [BO2]∞ chain, [B2Ox(OH)5-x], and so forth into borophosphates, seven borophosphates with improved birefringence were successfully synthesized (Δn > 0.05@532 nm). Remarkably, among them, the centimeter-sized crystal of Rb3B8PO16 with a short deep-UV cutoff edge (175 nm) and large birefringence (Δn(exp.) ∼ 0.072@589.3 nm) exhibits the shortest phase-matching wavelength (222 nm), which makes Rb3B8PO16 a promising UV NLO crystal, while KB6PO10(OH)4 with deep-UV cutoff edge features the largest birefringence (Δn(exp.) ∼ 0.103@546 nm) in the reported borophosphate system, making KB6PO10(OH)4 a promising deep-UV birefringent crystal. This study not only provides feasible strategies for increasing the birefringence of borophosphates but also pushes phase-matching into the short-wavelength region.

Enhancement of Birefringence in Borophosphate Pushing Phase-Matching into the Short-Wavelength Region.

Deep-ultraviolet nonlinear optical (DUV NLO) crystals are indispensable for solid-state lasers to produce coherent light with wavelengths shorter than 200 nm, yet their structure design still faces great challenges because two groups of conflicting properties must be satisfied simultaneously, i.e., "large second harmonic generation (SHG) response-large band gap" and "large birefringence-weak growth anisotropy". Clearly, hitherto, no crystal can perfectly satisfy these properties, including KBe2BO3F2. Herein, we design a new mixed-coordinated borophosphate Cs3[(BOP)2(B3O7)3] (CBPO) by optimizing the matching of cation and anion groups, which unprecedentedly achieves a balance for two groups of contradictions concurrently for the first time. In the structure of CBPO, it has the coplanar and π-conjugated B3O7 groups, which can make it possess a large SHG response (3 × KDP) and large birefringence (0.075@532 nm). Then, terminal O atoms of these B3O7 groups are connected by BO4 and PO4 tetrahedra, which eliminates all dangling bonds and blue shifts the UV absorption edge to the DUV region (165 nm). More importantly, owing to the judicious selection of cations, the size of cations and void of anion groups is a perfect match, which makes CBPO possess a very stable three-dimensional anion framework and thus reduces the crystal growth anisotropy. A CBPO single crystal with a size of up to 20 × 17 × 8 mm3 has been successfully grown, through which a DUV coherent light has also been achieved in Be-free DUV NLO crystals for the first time. These indicate CBPO will be the next generation of DUV NLO crystals.

Cs3[(BOP)2(B3O7)3]: A Deep-Ultraviolet Nonlinear Optical Crystal Designed by Optimizing Matching of Cation and Anion Groups.

Recent progress in the design of IR nonlinear optical materials by partial chemical substitution: Structural evolution and performance optimization

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.

The [B3O6] group as a prime functional unit provides borates with intrinsic properties that are modified by coordination to cations. Inherent [B3O6] cluster structures in borates exclusively made of them have a near-plane configuration, with more than 90% of them having a maximum dihedral angle of zero and the remaining ones being less than 13°. Although such an inherent configuration can produce considerable birefringence for good phase-matching ability, this is not conducive to obtaining high conversion efficiency and beam quality due to the walk-off effects in the nonlinear optical process. In this article, two new borate halides Ca2B3O6X (X = Cl and Br) were reported, in which the confinement effects of distorted halogen-centered secondary building blocks compress the existence space of [B3O6] primitives, resulting in the nonparallel arrangement between [B3O6] clusters in this series. Both compounds show large second harmonic generation effects, and more importantly, the broken inherent interarrangement of [B3O6] clusters makes them a moderate birefringence and small walk-off angle. Their moderate birefringence is due to the large angular alignment between [B3O6] clusters, resulting from the orbital hybridization between the Ca s and the O p orbitals of the terminal O atoms on [B3O6] clusters. Our model supports this viewpoint and offers guidelines for rearranging [B3O6] clusters' arrangements in borates.

Breaking the Inherent Interarrangement of [B3O6] Clusters for Nonlinear Optics with Orbital Hybridization Enhancement.

The inorganic heteroanionic materials are attracting increasing attention for exploring new nonlinear optical (NLO) materials because they could better satisfy the necessary but conflicting properties of NLO crystals, e.g. large SHG response and wide band-gap. Up to now, the reports on heteroanionic NLO materials are mainly focused on ultraviolet or visible oxide-based fluoroborates, fluorophosphates, borate-phosphates and borate-iodates. However, the chalcogenide containing different kinds of anionic groups is barely reported. Herein, we have synthesized the first oxychalcogenide-carbonate, Sr3[SnOSe3][CO3] that contains two different kinds of anionic groups, [SnOSe3] and [CO3]. It crystallizes in noncentrosymmetric space group and exhibits fascinating NLO properties, including large SHG response (~1×AGS), sufficient birefringence (0.12 @1064 nm), wide band-gap (3.46 eV) and high laser damage threshold (240 MW/cm2). These make Sr3[SnOSe3][CO3]  a promising NLO crystal.

Sr3[SnOSe3][CO3]: A Heteroanionic Nonlinear Optical Material Containing Planar π-conjugated [CO3] and Heteroleptic [SnOSe3] Anionic Groups.

Oxychalcogenides capable of exhibiting excellent balance among large second‐harmonic generation (SHG) response, wide band gap (Eg), and suitable birefringence (Δn) are ideal materials class for infrared nonlinear optical (IR NLO) crystals. However, rationally designing a new high‐performance oxychalcogenide IR NLO crystal still faces a huge challenge because it requires the optimal orientations of the heteroanionic groups in oxychalcogenide. Herein, a series of antiperovskite‐type oxychalcogenides, Ae3Q[GeOQ3] (Ae = Ba, Sr; Q = S, Se), which were synthesized by employing the antiperovskite‐type Ba3S[GeS4] as the structure template. Their structures feature novel three‐dimensinoal frameworks constructed by distorted [QAe6] octahedra, which are further filled by [GeOQ3] tetrahedra to form antiperovskite‐type structures. Based on the unique antiperovskite‐type structures, the favorable alignment of the polarizable [GeOQ3] tetrahedra and distorted [QAe6] octahedra have been achieved. These contribute the ideal combination of large SHG response (0.7–1.5 times that of AgGaS2), wide Eg (3.52–4.10 eV), and appropriate Δn (0.017–0.035) in Ae3Q[GeOQ3]. Theoretical calculations and crystal structure analyses revealed that the strong SHG and wide Eg could be attributed to the polarizable [GeOQ3] tetrahedra and distorted [QAe6] octahedra. This research provides a new exemplification for the design of high‐performance IR NLO materials.

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/advs.202204755

The Antiperovskite‐Type Oxychalcogenides Ae3Q[GeOQ3] (Ae = Ba, Sr; Q = S, Se) with Large Second Harmonic Generation Responses and Wide Band Gaps

Oxychalcogenides with the performance-advantages of both chalcogenides and oxides are emerging materials class for infrared (IR) nonlinear optical (NLO) crystals that can expand the wavelength of solid-state lasers to IR regions and are of importance in industrial and civil applications. But rationally designing a high-performance oxychalcogenide NLO crystal remains a great challenge. Herein, we chose the melilite-type Sr2ZnSi2O7 as the structure template. Through part isovalent substitution of S2− for O2− anions, the first hetero-anionic thiostannate Sr2ZnSn2OS6 with wide IR transmission has been synthesized. More importantly, compared to the maternal oxide, Sr2ZnSi2O7, the second harmonic generation (SHG) response of Sr2ZnSn2OS6 is enhanced by two orders of magnitude. In addition, Sr2ZnSn2OS6 can exhibit a large band-gap and high laser damage threshold. These advantages make Sr2ZnSn2OS6 a promising IR NLO crystal. Our research will provide insights into the rational design of new IR NLO crystals.

/pdf/rational-design-of-a-promising-oxychalcogenide-infrared-2j954fw5.pdf

Rational design of a promising oxychalcogenide infrared nonlinear optical crystal

NH4(B6PO10(OH)4)·H2O: exhibiting the largest birefringence in borophosphates.

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