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

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

We define the anisotropic structure building unit that encompasses diverse chemical bonds (ABUCB). The ABUCB is highly likely to cause anisotropy in both crystallographic structure and spatial electron distribution, ultimately resulting in enhanced macroscopic optical anisotropy. Accordingly, the (PO3F)2- or (SO3F)- tetrahedron involving the unique P-F or S-F bond serves as such an ABUCB. The distinct chemical bond effectively alters the microscopic nature of the structure building unit, such as polarizability anisotropy, hyperpolarizability, and geometry distortion; this consequently changes the macroscopic second-order nonlinear optical (2nd-NLO) properties of the materials. In this review, we summarize both typical and newly emerged compounds containing ABUCBs. These compounds encompass approximately 90 examples representing six distinct categories, including phosphates, borates, sulfates, silicates, chalcogenides and oxyhalides. Furthermore, we demonstrate that the presence of ABUCBs in DUV/UV NLO compounds contributes to an increase in birefringence and retention of a large band gap, facilitating phase matching in high-energy short-wavelength spectral ranges. On the other hand, the inclusion of ABUCBs in IR NLO compounds offers a feasible method for increasing the band gap and consequently enhancing the larger laser-induced damage threshold. This review consolidates various trial-and-error explorations and presents a novel strategy for designing 2nd-NLO compounds, potentially offering an opportunity for the development of high-performance 2nd-NLO materials. 

Anisotropic structure building unit involving diverse chemical bonds: a new opportunity for high-performance second-order NLO materials

Hg-based chalcogenides, as good candidates for the exploration of high-performance infrared (IR) nonlinear optical (NLO) materials, usually exhibit strong NLO effects, but narrow bandgaps. Herein, an unprecedented wide bandgap Hg-based IR NLO material Zn2 HgP2 S8 (ZHPS) with diamond-like structure is rationally designed and fabricated by a tetrahedron re-organization strategy with the aid of structure and property predictions. ZHPS exhibits a wide bandgap of 3.37 eV, which is the largest one among the reported Hg-based chalcogenide IR NLO materials and first breaks the 3.0 eV bandgap "wall" in this system, resulting in a high laser-induced damage threshold (LIDT) of ≈2.2 × AgGaS2 (AGS). Meanwhile, it shows a large NLO response (1.1 × AGS), achieving a good balance between bandgap (≥3.0 eV) and NLO effect (≥1 × AGS) for an excellent IR NLO material. DFT calculations uncover that, compared to normal [HgS4 ]n , highly distorted [HgS4 ]d tetrahedral units are conducive to generating wide bandgap, and the wide bandgap in ZHPS can be attributed to the strong s-p hybridization between Hg─S bonding in distorted [HgS4 ]d , which gives some insights into the design of Hg-based chalcogenides with excellent properties based on distorted [HgS4 ]d tetrahedra.

Zn2 HgP2 S8 : A Wide Bandgap Hg-Based Infrared Nonlinear Optical Material with Large Second-Harmonic Generation Response.

Recent advances in IR nonlinear optical chalcogenides with well-balanced comprehensive performance

Noncentrosymmetric (NCS) structures are of particular interest owing to their symmetry-dependent physical properties, e.g., pyroelectricity, ferroelectricity, piezoelectricity, and nonlinear optical (NLO) behavior. Among them, chiral materials exhibit polarization rotation and host topological properties. Borates often contribute to NCS and chiral structures via their triangular [BO3] and tetrahedral [BO4] units and their numerous superstructure motifs. However, no chiral compound with the linear [BO2] unit has been reported to date. Herein, an NCS and chiral mixed-alkali-metal borate, NaRb6(B4O5(OH)4)3(BO2), with a linear BO2- unit in the structure was synthesized and characterized. The structure features a combination of three types of basic building units (BBUs), [BO2], [BO3], and [BO4] with sp-, sp2-, and sp3-hybridization of boron atoms, respectively. It crystallizes in the trigonal space group R32 (No. 155), one of the 65 Sohncke space groups. Two enantiomers of NaRb6(B4O5(OH)4)3(BO2) were found, and their crystallographic relationships are discussed. These results not only expand the small family of NCS structures with the rare linear BO2- unit but also prompt recognition to the fact that NLO materials have generally overlooked the existence of two enantiomers in achiral Sohncke space groups.

NaRb6(B4O5(OH)4)3(BO2) Featuring Noncentrosymmetry, Chirality, and the Linear Anionic Group BO2.

Three new chalcohalide nonlinear optical crystals, [ASr4Cl][Ge3S10] (A=Na, K) and [KBa4Cl][Ge3S10] have been successfully designed and synthesized by combining the covalent [Ge3S9] clusters and ionic [AB4Cl] frameworks. Their crystal structures...

[ASr4Cl][Ge3S10] (A=Na, K) and [KBa4Cl][Ge3S10]: New salt-inclusion infrared nonlinear optical crystals with zero-dimensional [Ge3S9] clusters

Chirality and polarity are the two most important and representative symmetry‐dependent properties. For polar structures, all the twofold axes perpendicular to the principal axis of symmetry should be removed. For chiral structures, all the mirror‐related symmetries and inversion axes should be removed. Especially for duality (polarity and chirality), all of the above symmetries should be broken and that also represents the highest‐level challenge. Herein, a new symmetry‐breaking strategy that employs heteroanionic groups to construct hourglass‐like [Sr3OGeS3]2+ and [Sr3SGeS3]2+ groups to design and synthesize a new oxychalcogenide Sr18Ge9O5S31 with chiral‐polar duality is proposed. The presence of two enantiomers of Sr18Ge9O5S31 is confirmed by the single‐crystal X‐ray diffraction. Its optical activity and ferroelectricity are also studied by solid‐state circular dichroism spectroscopy and piezoresponse force microscopy, respectively. Further property measurements show that Sr18Ge9O5S31 possesses excellent nonlinear optical properties, including the strong second harmonic generation efficiency (≈2.5 × AGS), large bandgap (3.61 eV), and wide mid‐infrared transparent region (≈15.3 µm). These indicate that the unique microstructure groups of heteroanionic materials are conducive to realizing symmetry‐breaking and are able to provide some inspiration for exploring the chiral‐polar duality materials.

Chiral and Polar Duality Design of Heteroanionic Compounds: Sr18Ge9O5S31 Based on [Sr3OGeS3]2+ and [Sr3SGeS3]2+ Groups

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NaRb6(B4O5(OH)4)3(BO2) Featuring Noncentrosymmetry, Chirality, and the Linear Anionic Group BO2.

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

[ASr4Cl][Ge3S10] (A=Na, K) and [KBa4Cl][Ge3S10]: New salt-inclusion infrared nonlinear optical crystals with zero-dimensional [Ge3S9] clusters

Chiral and Polar Duality Design of Heteroanionic Compounds: Sr18Ge9O5S31 Based on [Sr3OGeS3]2+ and [Sr3SGeS3]2+ Groups