Ultraviolet Nonlinear Optical Materials Research Articles

Unveiling Noncentrosymmetric Pyridine Carboxylates from Centrosymmetric Templates through Motif Configuration Modulation in Zero-Dimensional System.

Developing approaches to induce noncentrosymmetric (NCS) frameworks through atomic-scale structural optimizations is crucial due to the growing need for new ultraviolet (UV) nonlinear optical (NLO) materials. Herein, the first two new NCS pyridine carboxylates, ZnBr(C6H3.5FNO2)2 (1) and Cd(C6H3FNO2)2(H2O)2 (2), were successfully synthesized using centrosymmetric (CS) templates and rational structural reconstructions induced by different ionic radius. Both compounds crystallize in the orthorhombic system and feature metal-centered zero-dimensional (0D) isolated clusters. Substituting the [ZnO2N2O] pyramid in the CS pyridine carboxylate with the [ZnO2N2Br] pyramid in compound 1 breaks the centrality, leading to an NCS framework with a second harmonic generation (SHG) response of 1.7 × KH2PO4 (KDP). Introducing a larger Cd2+ cation results in a trans-to-cis transition of the [MO4N2] (M = Zn, Co, and Ni in CS templates, Cd in 2) octahedra, forming a wing-shaped asymmetric 0D cluster with an SHG response of 2.1 × KDP. These findings indicate an approach that can effectively induce NCS structures of 0D organic-inorganic hybrid materials.

Assembly of π-Conjugated [B3O6] Units by Mer-Isomer [YO3F3] Octahedra to Design a UV Nonlinear Optical Material, Cs2YB3O6F2.

Achieving the extreme balance of the key performance requirements is the crucial to breakthrough the application bottleneck for nonlinear optical (NLO) materials. Herein, by assembly of the π-conjugated [B3O6] functional species with the aid of structure-directing property of mer-isomer [YO3F3] octahedra, a new ultraviolet (UV) NLO material, Cs2YB3O6F2 with aligned arrangement of coplanar [B3O6] groups has been synthesized. The polar material exhibits the rare coexistence of the largest second harmonic generation response of 5.6×KDP, the largest birefringence of 0.091 at 532 nm, the shortest Type I phase-matching down to 200.5 nm and deep-ultraviolet transparency among reported acentric rare-earth borates with [B3O6] groups. Remarkably, benefiting from the enhanced bonding force among functional units [B3O6], a firm three-dimensional framework is constructed, which facilitates the growth of large crystals. This can be proved by a block shape crystal with dimensional of 6×5×4 mm3, indicating that it was a promising UV NLO crystal. This work provides a powerful strategy to design UV NLO materials with good performances.

Assembly of π‐Conjugated [B3O6] Units by Mer‐Isomer [YO3F3] Octahedra to Design a UV Nonlinear Optical Material, Cs2YB3O6F2

AbstractAchieving the extreme balance of the key performance requirements is the crucial to breakthrough the application bottleneck for nonlinear optical (NLO) materials. Herein, by assembly of the π‐conjugated [B3O6] functional species with the aid of structure‐directing property of mer‐isomer [YO3F3] octahedra, a new ultraviolet (UV) NLO material, Cs2YB3O6F2 with aligned arrangement of coplanar [B3O6] groups has been synthesized. The polar material exhibits the rare coexistence of the largest second harmonic generation response of 5.6×KDP, the largest birefringence of 0.091 at 532 nm, the shortest Type I phase‐matching down to 200.5 nm and deep‐ultraviolet transparency among reported acentric rare‐earth borates with [B3O6] groups. Remarkably, benefiting from the enhanced bonding force among functional units [B3O6], a firm three‐dimensional framework is constructed, which facilitates the growth of large crystals. This can be proved by a block shape crystal with dimensional of 6×5×4 mm3, indicating that it was a promising UV NLO crystal. This work provides a powerful strategy to design UV NLO materials with good performances.

Designing Strong Polarity and High Configurational Entropy Flexible Units toward Excellent Ultraviolet Nonlinear Optical Materials

AbstractPolar materials play a crucial role in numerous essential fields; however, efficiently synthesizing them remains a significant challenge. In this study, a viable approach is proposed to enhance the probability of discovering polar materials by developing new functional basic units (FBUs) with strong polarity and high configurational entropy. To validate this approach, a site‐modification strategy is applied to the high configurational entropy flexible (C3H2O4)2− FBU, resulting in the development of four new polar‐enhancing FBUs: (C3(CH3)2O4)2−, (C3F2O4)2−, (C3H(OH)O4)2−, and (C3HFO4)2−. Moreover, 11 new compounds through temperature‐driven conformational changes in FBUs are successfully synthesized. Among these, the proportion of polar structures reaches an impressive 54%. Remarkably, all of these novel polar compounds exhibit outstanding nonlinear optical (NLO) properties. The [Li2C3(CH3)2O4]2·3H2O demonstrates the rare coexistence of a moderate birefringence (0.071@514 nm), short UV cutoff edge (210 nm), and the strongest second harmonic generation (SHG) effect (6.5 × KDP) among ionic‐organic fourth harmonic generation crystals. Preliminary laser experiments have also proven its potential practical value as a fourth harmonic generation crystal. This research not only discovers a variety of exceptional UV NLO crystals but also provides a feasible method to increase the likelihood of finding polar materials.

From Cd(SCN)2(CH4N2S)2 to Cd(SCN)2(C4H6N2)2: Controlling Sulfur Content in Thiocyanate Systems Significantly Improves the Overall Performance of UV Nonlinear Optical Materials.

Combining a strong second-order nonlinear optical (NLO) effect (>1×KH2PO4 (KDP)), a large band gap (>4.2 eV), and a moderate birefringence in ultraviolet (UV) NLO crystals remains a formidable challenge. Herein, Cd(SCN)2(C4H6N2)2, the first example of a thiocyanate capable of realizing a phase-matched UV NLO crystal material, is obtained by reducing the sulfur (S) content in the centrosymmetric (CS) structure of Cd(SCN)2(CH4N2S)2. Compared to the "shoulder-to-shoulder" one-dimensional (1D) chain of Cd(SCN)2(CH4N2S)2, Cd(SCN)2(C4H6N2)2 has a different sawtooth 1D chain structure. Cd(SCN)2(CH4N2S)2 has second harmonic generation (SHG) inertia with a band gap of 3.90 eV and a UV cutoff edge of 342 nm, however, it possesses a large birefringence (0.35@546 nm). In contrast, the symmetry center breaking of Cd(SCN)2(C4H6N2)2 leads to remarkably strong SHG intensity (10 times that of KDP). Furthermore, it has a wide band gap (4.74 eV), short UV cutoff edge (234 nm), and moderate birefringence capable of phase matching (0.17@546 nm). This research indicates that thiocyanates are a promising class of UV NLO crystal materials, and that modulation of the sulfur content of CS thiocyanates is an effective strategy for the development of UV NLO crystals with excellent overall performances.

A-site cation manipulation of exemplary second harmonic generation response and optical anisotropy in rare-earth borates.

Ultraviolet nonlinear optical (UV NLO) materials have garnered significant interest for their prospective applications in advanced laser technologies. However, tailoring the desired structure in these materials remains a formidable challenge. Here, we propose a simple yet effective strategy for synthesizing rare-earth borates, K x Na3-x La2B3O9 (x = 2-3), by manipulating the A-site cations to induce structural evolution. Notably, K x Na3-x La2B3O9 undergoes a phase transition from the Pnc2 to the Amm2 space group by adjusting the K+ content to reach x = 2.6. Moreover, the target compounds exhibit strong phase-matching second harmonic generation (SHG) efficiencies, ranging from 1.3 to 3.3 times that of KDP (KH2PO4), and feature short UV cutoff edges of around 204-208 nm. Additionally, the correlation between microscopic polarizability, optical anisotropy, and the structural evolution of these materials was characterized through structural and theoretical analyses. These findings highlight the potential applications of K x Na3-x La2B3O9 as UV NLO materials and underscore the viability of manipulating A-site cations to fabricate NLO crystals with desirable properties.

A bifunctional primitive strategy induces enhancements of large second harmonic generation and wide UV transmittance in rare-earth borates containing [B5O10] groups.

Strong second-harmonic generation (SHG) and a short ultraviolet (UV) cutoff edge are two crucial yet often conflicting parameters that must be finely tuned in the exploration of nonlinear optical (NLO) materials. In this study, two new rare earth borate NLO crystals, K7BaSc2B15O30 (KBSBO) and Rb21Sr3.8Sc5.2B45O90 (RSSBO), were rationally designed through a bifunctional primitive strategy to achieve an optimized balance between favorable SHG efficiency and UV transparency. As anticipated, both KBSBO and RSSBO exhibit a wide UV transparency window below 190 nm. Notably, these tailored crystals display strong SHG responses, with RSSBO achieving a remarkable enhancement in SHG efficiency (2 × KDP), surpassing that of most deep-UV rare earth borates containing [B5O10] groups known to date. Theoretical calculations and structural analyses reveal that the impressive SHG activities primarily stem from the [B5O10] groups and [ScO6] polyhedra. These findings suggest promising potential for KBSBO and RSSBO crystals as beryllium-free deep UV NLO materials.

Hydrogen bonding bolstered head-to-tail ligation of functional chromophores in a 0D SbF3·glycine adduct for a short-wave ultraviolet nonlinear optical material.

The key properties of nonlinear optical (NLO) materials highly rely on the quality of functional chromophores (FCs) and their optimized interarrangement in the lattice. Despite the screening of various FCs, significant challenges persist in optimizing their arrangement within specific structures. Generally, FC alignment is achieved by designing negatively charged 2D layers or 3D frameworks, further regulated by templating cations. In this study, a novel 0D adduct NLO material, SbF3·glycine, is reported. Neutrally charged 0D [SbF3C2H5NO2] FCs, comprising [SbF3] pyramids and zwitterionic glycine, are well-aligned in the structure. The alignment is facilitated by the hydrogen bonding, reinforcing a 'head-to-tail' ligation of [SbF3C2H5NO2] FCs. Consequently, the title compound exhibits favorable NLO properties, including a large second-harmonic generation efficiency (3.6 × KDP) and suitable birefringence (cal. 0.057 @ 1064 nm). Additionally, its short absorption cut-off edge (231 nm) positions it as a promising short-wave ultraviolet NLO material. Importantly, the binary SbF3-amino acid system is expected to serve as a new resource for exploring ultraviolet NLO crystals, owing to the abundance of the amino acid family.

Discovery of excellent ultraviolet nonlinear optical materials in chlorates and bromates with highly stereochemically active lone pairs

The long-neglected stereochemically active lone pair groups ClO3− and BrO3− are demonstrated to be important UV NLO functional motifs based on the fact that AClO3 and ABrO3 possess high SHG effects and short λPM and are promising UV NLO materials.

A Deep-Ultraviolet Nonlinear-Optical Material with Wide Band Gap and Large Static Dielectric Polarizability Coefficient: Na6Si3F18

A silicon based noncentrosymmetric deep ultraviolet nonlinear optical material Na6Si3F18 has been synthesized through hydrothermal method. Na6Si3F18 possesses a [SiNa9F42] group, which constructed by an isolated [SiF6] octahedron and nine...

Prediction of ultraviolet optical materials in the K2O-B2O3 system.

Ultraviolet (UV) birefringent crystals play a crucial role in various fields, such as laser technologies, optical telecommunications, and advanced scientific instrumentation. Alkali metal borates, with their diverse structures and remarkable ultraviolet optical properties, have garnered significant attention in recent years. In this study, employing the evolutionary crystal structure prediction algorithm USPEX, in conjunction with ionic substitutions and first-principles calculations, we systematically explored the pseudo-binary K2O-B2O3 system and predicted two stable structures (oP56-K3BO3 and mC44-K4B2O5) previously unreported, and twelve metastable structures in the K2O-B2O3 system. A comprehensive analysis of their structural, electronic and optical properties is conducted. The coplanar arrangement of BO3 and B3O6 groups is found to enhance optical anisotropy, thereby increasing the birefringence. In the K2O-B2O3 system, six structures with wide band gaps and high birefringence (mP28-1-K3BO3, tR72-KBO2, oP112-1-KB5O8, oP112-2-KB5O8, mC220-K5B19O31, and hR21-K3BO3) are found to be possible candidates for UV optical materials. Importantly, hR21-K3BO3, the only non-centrosymmetric structure in this system, exhibits a significant frequency doubling coefficient (about 4.6 KDP) and a moderate birefringence index (0.056@1064 nm), marking it a promising UV nonlinear optical material.

Mg(C3 O4 H2 )(H2 O)2 : A New Ultraviolet Nonlinear Optical Material Derived from KBe2 BO3 F2 with High Performance and Excellent Water-Resistance.

Acquiring high-performance ultraviolet (UV) nonlinear optical (NLO) materials that simultaneously exhibit a strong second harmonic generation (SHG) coefficients, as short as possible SHG phase-matching (PM) wavelength and non-hygroscopic properties has consistently posed a significant challenge. Herein, through multicomponent modification of KBe2 BO3 F2 (KBBF), an excellent UV NLO crystal, Mg(C3 O4 H2 )(H2 O)2 , was successfully synthesized in malonic system. This material possesses a unique 2D NLO-favorable electroneutral [Mg(C3 O4 H2 )3 (H2 O)2 ]∞ layer, resulting in the rare coexistence of a strong SHG response of 3×KDP (@1064 nm) and short PM wavelength of 200 nm. More importantly, it exhibits exceptional water resistance, which is rare among ionic organic NLO crystals. Theoretical calculations revealed that its excellent water-resistant may be originated from its small available cavity volumes, which is similar to the famous LiB3 O5 (LBO). Therefore, excellent NLO properties and stability against air and moisture indicate it should be a promising UV NLO crystal.

Mg(C3O4H2)(H2O)2: A New Ultraviolet Nonlinear Optical Material Derived from KBe2BO3F2 with High Performance and Excellent Water‐Resistance

AbstractAcquiring high‐performance ultraviolet (UV) nonlinear optical (NLO) materials that simultaneously exhibit a strong second harmonic generation (SHG) coefficients, as short as possible SHG phase‐matching (PM) wavelength and non‐hygroscopic properties has consistently posed a significant challenge. Herein, through multicomponent modification of KBe2BO3F2 (KBBF), an excellent UV NLO crystal, Mg(C3O4H2)(H2O)2, was successfully synthesized in malonic system. This material possesses a unique 2D NLO‐favorable electroneutral [Mg(C3O4H2)3(H2O)2]∞ layer, resulting in the rare coexistence of a strong SHG response of 3×KDP (@1064 nm) and short PM wavelength of 200 nm. More importantly, it exhibits exceptional water resistance, which is rare among ionic organic NLO crystals. Theoretical calculations revealed that its excellent water‐resistant may be originated from its small available cavity volumes, which is similar to the famous LiB3O5 (LBO). Therefore, excellent NLO properties and stability against air and moisture indicate it should be a promising UV NLO crystal.

Two noncentrosymmetric alkali metal phosphates MZnPO4 (M = Rb, Cs) with honeycomb-like structures

In recent years, phosphates have become a research hotspot to explore new ultraviolet (UV) nonlinear optical (NLO) materials. Herein, two NLO materials MZnPO4 (M = Rb, Cs) are synthesized by cation substitution in alkali-zinc orthophosphates. Although they crystallize in different space groups P21 and Imm2, respectively, they both have a honeycomb-like topological structure consisting of corner-shared PO4 and ZnO4 tetrahedra and separated by "M" cations. Two compounds exhibit mild powder second harmonic generation (SHG) responses (1.2 and 0.5 × KDP for RbZnPO4 and CsZnPO4, respectively) with type I phase matching behaviors and short absorption edges (226 nm for RbZnPO4 and 231 nm for CsZnPO4). Furthermore, their thermal properties, infrared (IR) spectra and theoretical calculations are also mentioned in the paper. The synthesis and structure-property relationship described in the system will enable discovery of new NLO materials.

Ba4B14O25: A Deep Ultraviolet Transparent Nonlinear Optical Crystal with Strong Second Harmonic Generation Response Achieved by a Boron-Rich Closed-Loop Strategy.

Discovering new deep ultraviolet (DUV) nonlinear optical (NLO) materials is the current research hotspot. However, how to perfectly integrate several stringent performances into a crystal is a great challenge because of the natural incompatibility among them, particularly wide band gap and large NLO coefficient. To tackle the challenge, a boron-rich closed-loop strategy is supposed, based on which a new barium borate, Ba4B14O25, is designed and synthesized successfully via the high-temperature solid-state melting method. It features a highly polymeric 3D geometry with the closed-loop anionic framework [B14O25]8- constructed by the fundamental building blocks [B14O33]24-. The high-density π-conjugated [BO3]3- groups and the fully closed-loop B-O-B connections make Ba4B14O25 possess excellent NLO properties, including short UV cutoff edge (<200nm), large second harmonic generation response (3.0 × KDP) and phase-matching capability, being a promising DUV-transparent NLO candidate material. The work provides a creative design strategy for the exploration of DUV NLO crystals.

New Functional Groups Design toward High Performance Ultraviolet Nonlinear Optical Materials.

ConspectusThe invention of the laser is a pivotal milestone in the evolution of modern science and technology. Second-order nonlinear optical (NLO) crystals, which possess the ability to convert frequencies, have found widespread applications in laser science, information transmission, industrial Internet, and other cutting-edge fields within materials and optics. As modern science and technology continue to advance at a rapid pace, existing ultraviolet (UV) and deep ultraviolet (DUV) NLO crystals struggle to meet the ever-growing demands of various applications. Consequently, the development of novel UV and DUV NLO crystals has become an urgent necessity. For a UV NLO crystal to be considered outstanding in the UV/DUV range, it must exhibit three fundamental yet crucial properties: large second-order NLO coefficients, suitable birefringence, and short UV cutoff edge corresponding to a wide band gap. However, these key factors often conflict with one another, making it challenging to achieve a harmonious balance within a single crystal. It is widely believed that these mutually constrained optical properties are codetermined by microscopic NLO-active units and macroscopic structure features. Therefore, how to design high performance UV NLO-active groups to balance these three key properties is an essential scientifically question and serious challenge. In this Account, we present three strategies for designing high-performance UV NLO-active groups: (1) The "tetrahedron partial substitution" strategy by employing various substituents to replace one or more atoms in the traditional nonpolar tetrahedral groups, might achieve the aim of increasing the polarizability anisotropy and hyperpolarizability of the newly formed polar tetrahedral functional groups, such as from SO4 to SO3NH2 or SO3CH3 groups. (2) The "structure-analogue" strategy to develop a range of organic functional groups exhibiting more strong polarizability anisotropy and hyperpolarizability by using inorganic π-conjugated groups, such as BO3 and B3O6 groups, as templates. (3) The "two in one" strategy for integrating groups featuring planar triangle configurations and tetrahedrons to create NLO-active functional groups possessing large band gaps, strong hyperpolarizability, and moderate polarizability anisotropy. These three strategies successfully guide us to design and explore various kinds of organic-inorganic composite NLO crystal materials with excellent performances, like Ba(SO3CH3)2, M(SO3NH2)2 (M = Sr, Ba), C(NH2)3SO3F, KLi(HC3N3O3)·2H2O, KLi(C3H2O4)·H2O, and so on. Finally, we briefly conclude these strategies and propose some prospects for exploring new excellent UV/DUV NLO materials with practical applications. These findings could inspire novel thoughts for researchers designing new UV/DUV NLO materials and providing abundant materials used in UV/DUV regions.

Sr(NH2SO3)(NO3)·H2O: An Ultraviolet Nonlinear Optical Material Exhibiting Strong Second-Harmonic Generation Response and Sufficient Birefringence.

Second-harmonic generation (SHG) response and birefringence stand as fundamental optical properties for nonlinear optical (NLO) materials. Up to now, engineering a strong SHG response and substantial birefringence in the sulfamate system has proven to be exceedingly challenging. A novel noncentrosymmetric compound, Sr(NH2SO3)(NO3)·H2O, has been meticulously designed by introducing the (NO3)- group characterized by significant polarizability anisotropy and hyperpolarizability into the polar non-π-conjugated (NH2SO3)- system. This compound exhibits a robust SHG response (5.2 × KDP), ample birefringence (0.077 at 546.1 nm), and a short ultraviolet (UV) absorption edge (290 nm). The linear and nonlinear optical properties can be attributed to the (NO3)- group and the (NH2SO3)- group. This study presents an effective approach that contributes to the design of more composite anionic UV NLO materials with excellent and balanced optical properties.

Quadruple‐Bidentate Nitrate‐Ligated A2Hg(NO3)4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence

AbstractThe design of efficient nonlinear optical (NLO) crystals continues to pose significant challenges due to the difficulty of assembling polar NLO‐active modules in an optimal additive fashion. We report herein the first NLO‐active mercuric nitrates A2Hg(NO3)4 (A=(KHNO), Rb (RHNO)), for which assembly is induced by ionic polarization of the d10 cations. The two new crystalline compounds are isostructural, featuring interesting pseudo‐diamond‐like structures with parallel [Hg(NO3)4] modules, and leading to strong powder second‐harmonic generation (SHG) responses of 9.2 (KHNO) and 8.8 (RHNO) times that of KH2PO4. In combination with the simple solution preparation of centimeter‐scale crystals, sufficient birefringence, and short ultraviolet (UV) cutoff edges, these attributes make KHNO and RHNO promising candidates for UV NLO materials. Theoretical calculations and single‐crystal structure analysis reveal that the newly‐developed highly condensed and distorted [Hg(NO3)4] module, with an Hg2+ cation that is quadruply bidentate nitrate‐ligated, is crucial for the significant SHG responses. This work highlights the potential importance of modules with multiple bidentate ligands for the development of high‐performing next‐generation NLO materials.

Quadruple-Bidentate Nitrate-Ligated A2 Hg(NO3 )4 (A=K, Rb): Strong Second-Harmonic Generation and Sufficient Birefringence.

The design of efficient nonlinear optical (NLO) crystals continues to pose significant challenges due to the difficulty of assembling polar NLO-active modules in an optimal additive fashion. We report herein the first NLO-active mercuric nitrates A2 Hg(NO3 )4 (A=(KHNO), Rb (RHNO)), for which assembly is induced by ionic polarization of the d10 cations. The two new crystalline compounds are isostructural, featuring interesting pseudo-diamond-like structures with parallel [Hg(NO3 )4 ] modules, and leading to strong powder second-harmonic generation (SHG) responses of 9.2 (KHNO) and 8.8 (RHNO) times that of KH2 PO4 . In combination with the simple solution preparation of centimeter-scale crystals, sufficient birefringence, and short ultraviolet (UV) cutoff edges, these attributes make KHNO and RHNO promising candidates for UV NLO materials. Theoretical calculations and single-crystal structure analysis reveal that the newly-developed highly condensed and distorted [Hg(NO3 )4 ] module, with an Hg2+ cation that is quadruply bidentate nitrate-ligated, is crucial for the significant SHG responses. This work highlights the potential importance of modules with multiple bidentate ligands for the development of high-performing next-generation NLO materials.

Hg3(SeO3)2(SO4): A UV Nonlinear Optical Mercury Selenite Sulfate Constructed by Neat [Hg6O8(SeO3)4]∞ Layers and SO4 Tetrahedra.

A novel mercury selenite sulfate named Hg3(SeO3)2(SO4) has been successfully synthesized under a mild hydrothermal method. Hg3(SeO3)2(SO4) crystallizes in a monoclinic space group P21 and features a unique three-dimensional (3D) frame structure formed by [Hg6O8(SeO3)4]∞ layers and SO4 tetrahedra, which enables it to exhibit a comprehensive performance of a moderate second-harmonic generation (SHG) response of approximately 1.3 times that of baseline KH2PO4 (KDP), a moderate birefringence (0.118@546 nm), and a wide band gap (4.70 eV), which indicates that it has potential for application as an ultraviolet (UV) nonlinear optical material. Detailed theoretical calculations show that the Hg2+-based polyhedra with large polarizability and deformability and the SeO3 groups with stereochemically active lone pair (SCALP) electrons are the main contributors to moderate optical properties.