Highly efficient AlGaN-based deep-ultraviolet light-emitting diodes: from bandgap engineering to device craft.

AlGaN-based light-emitting diodes (LEDs) operating in the deep-ultraviolet (DUV) spectral range (210-280 nm) have demonstrated potential applications in physical sterilization. However, the poor external quantum efficiency (EQE) hinders further advances in the emission performance of AlGaN-based DUV LEDs. Here, we demonstrate the performance of 270-nm AlGaN-based DUV LEDs beyond the state-of-the-art by exploiting the innovative combination of bandgap engineering and device craft. By adopting tailored multiple quantum wells (MQWs), a reflective Al reflector, a low-optical-loss tunneling junction (TJ) and a dielectric SiO2 insertion structure (IS-SiO2), outstanding light output powers (LOPs) of 140.1 mW are achieved in our DUV LEDs at 850 mA. The EQEs of our DUV LEDs are 4.5 times greater than those of their conventional counterparts. This comprehensive approach overcomes the major difficulties commonly faced in the pursuit of high-performance AlGaN-based DUV LEDs, such as strong quantum-confined Stark effect (QCSE), severe optical absorption in the p-electrode/ohmic contact layer and poor transverse magnetic (TM)-polarized light extraction. Furthermore, the on-wafer electroluminescence characterization validated the scalability of our DUV LEDs to larger production scales. Our work is promising for the development of highly efficient AlGaN-based DUV LEDs.

Metasurface-integrated elliptically polarized laser-pumped SERF magnetometers.

The emergence of biomagnetism imaging has led to the development of ultrasensitive and compact spin-exchange relaxation-free (SERF) atomic magnetometers that promise high-resolution magnetocardiography (MCG) and magnetoencephalography (MEG). However, conventional optical components are not compatible with nanofabrication processes that enable the integration of atomic magnetometers on chips, especially for elliptically polarized laser-pumped SERF magnetometers with bulky optical systems. In this study, an elliptical-polarization pumping beam (at 795 nm) is achieved through a single-piece metasurface, which results in an SERF magnetometer with a high sensitivity reaching 10.61 fT/Hz1/2 by utilizing a 87Rb vapor cell with a 3 mm inner diameter. To achieve the optimum theoretical polarization, our design combines a computer-assisted optimization algorithm with an emerging metasurface design process. The metasurface is fabricated with 550 nm thick silicon-rich silicon nitride on a 2 × 2 cm 2 SiO2 substrate and features a 22.17° ellipticity angle (a deviation from the target polarization of less than 2%) and more than 80% transmittance. This study provides a feasible approach for on-chip polarization control of future all-integrated atomic magnetometers, which will further pave the way for high-resolution biomagnetism imaging and portable atomic sensing applications.

Theoretical Prediction of Monolayer BeP2O4H4 with Excellent Nonlinear-Optical Properties in Deep-Ultraviolet Range.

Most 2D nonlinear optical (NLO) materials do not have an ultrawide bandgap, therefore, they are unsuitable for working in the deep-ultraviolet spectral range (< 200 nm). Herein, the theoretical prediction of an excellent monolayer BeP2O4H4 (ML-BPOH) is reported. DFT analyses suggest a low cleavage energy (≈45 meV per atom) from a naturally existed bulk-BPOH material, indicating feasible exfoliation. This novel 2D material exhibits excellent properties including an ultrawide bandgap (Eg) of 7.84 eV, and a strong second-order nonlinear susceptibility ( d b u l k e f f $d_{bulk}^{eff}$ = 0.43 pm V-1), which is comparable to that of benchmark bulk-KBBF crystal (d16 = 0.45 pm V-1). The wide bandgap and large SHG effect of ML-BPOH are mainly derived from the (PO2H2)- tetrahedron. Notably, ML-BPOH exhibits an outstanding 50% variation in dsheet under minor stress stimuli (±3%) due to rotation of structurally rigid (PO2H2)- tetrahedron. This indicates significant potential for application in material deformation monitoring.

Azimuthal rotation-controlled nanoinscribing for continuous patterning of period- and shape-tunable asymmetric nanogratings.

We present an azimuthal-rotation-controlled dynamic nanoinscribing (ARC-DNI) process for continuous and scalable fabrication of asymmetric nanograting structures with tunable periods and shape profiles. A sliced edge of a nanograting mold, which typically has a rectangular grating profile, slides over a polymeric substrate to induce its burr-free plastic deformation into a linear nanopattern. During this continuous nanoinscribing process, the "azimuthal angle," that is, the angle between the moving direction of the polymeric substrate and the mold's grating line orientation, can be controlled to tailor the period, geometrical shape, and profile of the inscribed nanopatterns. By modulating the azimuthal angle, along with other important ARC-DNI parameters such as temperature, force, and inscribing speed, we demonstrate that the mold-opening profile and temperature- and time-dependent viscoelastic polymer reflow can be controlled to fabricate asymmetric, blazed, and slanted nanogratings that have diverse geometrical profiles such as trapezoidal, triangular, and parallelogrammatic. Finally, period- and profile-tunable ARC-DNI can be utilized for the practical fabrication of diverse optical devices, as is exemplified by asymmetric diffractive optical elements in this study.

Unlocking Giant Third-Order Optical Nonlinearity in (MA)2CuX4 through Introducing Jahn-Teller Distortion.

Nonlinear absorption coefficient and modulation depth stand as pivotal properties of nonlinear optical (NLO) materials, while the existing NLO materials exhibit limitations such as low nonlinear absorption coefficients and/or small modulation depths, thereby severely impeding their practical application. Here we unveil that introducing Jahn-Teller distortion in a Mott-Hubbard system, (MA)2CuX4 (MA=methylammonium; X=Cl, Br) affords the simultaneous attainment of a giant nonlinear absorption coefficient and substantial modulation depth. The optimized compound, (MA)2CuCl4, demonstrates a nonlinear absorption coefficient of (1.5±0.08)×105 cm GW-1, a modulation depth of 60 %, and a relatively low optical limiting threshold of 1.22×10-5 J cm-2. These outstanding attributes surpass those of most reported NLO materials. Our investigation reveals that a more pronounced distortion of the [CuX6]4- octahedron emerges as a crucial factor in augmenting optical nonlinearity. Mechanism study involving structural and spectral characterization along with theoretical calculations indicates a correlation between the compelling performance and the Mott-Hubbard band structure of the materials, coupled with the Jahn-Teller distortion-induced d-d transition. This study not only introduces a promising category of high-performance NLO materials but also provides novel insights into enhancing the performance of such materials.

Investigation of second-order NLO properties of novel 1,3,4-oxadiazole derivatives: a DFT study.

CONTEXT: In this study, we have developed four new chromophores (TM1-TM4) and performed quantum chemical calculations to explore their nonlinear optical properties. Our focus was on understanding the impact of electron-donating substituents on 1,3,4-oxadiazole derivative chromophores. The natural bond orbital analysis confirmed the interactions between donors and acceptors as well as provided insights into intramolecular charge transfer. We also estimated dipole moment, linear polarizability molecular electrostatic potential, UV-visible spectra, and first hyperpolarizability. Our results revealed that TM1 with a strong and stable electron-donating group exhibited high first hyperpolarizability (ß) 293,679.0178 × 10-34 esu. Additionally, TM1 exhibited a dipolar moment (µ) of 5.66 Debye and polarizability (α) of 110.62 × 10-24 esu when measured in dimethyl sulfoxide (DMSO) solvent. Furthermore, in a benzene solvent, TM1 showed a low energy band gap of 5.33 eV by using the ωB97XD functional with a 6-311 + + G(d, p) basis set. Moreover, our study of intramolecular charge transfers highlighted N, N dimethyl triphenylamine and carbazole as major electron-donating groups among the four 1,3,4-oxadiazole derivative chromophores. This research illustrates the potential applications of these organic molecules in photonics due to their versatile nature. METHODS: The molecules were individually optimized using different functionals, including APFD, B3LYP, CAM B3LYP, and ωB97XD combined with the 6-311 + + G (d, p) basis set in Gaussian 16 software. These methods encompass long-range functionals such as APFD and B3LYP, along with long-range corrected functionals like CAM B3LYP and ωB97XD. The employed functionals of APFD, B3LYP, CAM B3LYP, and ωB97XD with the 6-311 + + G (d,p) basis set were used to extract various properties such as geometrical structures, dipole moment, molecular electrostatic potential, and first hyperpolarizability through precise density functional theory (DFT). Additionally, TD-DFT was utilized for obtaining UV-visible spectra. All studies have been conducted in both gas and solvent phases.

Supramolecular Solid Complexes between Bis-pyridinium-4-oxime and Distinctive Cyanoiron Platforms.

The structural features and optical properties of supramolecular cyanoiron salts containing bis-pyridinium-4-oxime Toxogonin® (TOXO) as an electron acceptor are presented. The properties of the new TOXO-based cyanoiron materials were probed by employing two cyanoiron platforms: hexacyanoferrate(II), [Fe(CN)6]4- (HCF); and nitroprusside, [Fe(CN)5(NO)]2- (NP). Two water-insoluble inter-ionic donor-acceptor phases were characterized: the as-prepared microcrystalline reddish-brown (TOXO)2[Fe(CN)6]·8H2O (1a) with a medium-responsive, hydrochromic character; and the dark violet crystalline (TOXO)2[Fe(CN)6]·3.5H2O (1cr). Complex 1a, upon external stimulation, transforms to the violet anhydrous phase (TOXO)2[Fe(CN)6] (1b), which upon water uptake transforms back to 1a. Using the NP platform resulted in the water-insoluble crystalline salt TOXO[Fe(CN)5(NO)]·2H2O (2). The structures of 1cr and 2, solved by single-crystal X-ray diffraction, along with a comparative spectroscopic (UV-vis-NIR diffuse reflectance, IR, solid-state MAS-NMR, Mössbauer), thermal, powder X-ray diffraction, and microscopic analysis (SEM, TEM) of the isolated materials, provided insight for the supramolecular binding, electron-accepting, and H-bonding capabilities of TOXO in the self-assembly of these functionalized materials.

Tunable and Switchable Thermochromism in Cholesteric Liquid Crystalline Elastomers.

Thermochromic materials have found widespread commercial use in packaging as temperature indicators. Often, these products utilize leuco dyes that are mixed into conventional polymeric resins to prepare coatings or films that exhibit temperature-dependent color change. Here, we consider a distinctive approach to thermochromism via the selective reflection of liquid crystalline elastomers that retain the helicoidal structure of the cholesteric phase (CLCEs). Upon heating, the order of the CLCEs reduces and approaches zero, resulting in a change in birefringence as well as material thickness, both of which manifest as changes in the selective reflection to heating. This examination systematically prepares CLCEs capable of reversible thermochromic response as a function of cross-link density and liquid crystalline composition. A particular focus of this examination is the preparation of CLCEs composed of chiral and achiral liquid crystalline monomers that reduce the strength of the mesogen-mesogen interaction and accordingly reduce the nematic-isotropic transition temperature. The low birefringence of some of the CLCE compositions facilitates thermochromic reflection tuning, followed by switching.

Highly stable CsPbBr3/ PMA perovskite nanocrystals for improved optical performance.

In this study, to address the stability issues, we synthesized a CsPbBr3-coated poly (maleic anhydride-alt-1-octadecene) (CsPbBr3/PMA) using a modified hot-injection method. The CsPbBr3/PMA perovskite nanocrystals (PNCs) exhibited effective green emission at 522 nm with an improved photoluminescence quantum yield (86.8 %) compared to traditional CsPbBr3 PNCs (54.2 %). The ligands in the polymer coating can bond with the uncoordinated Pb and Br ions on the surface of PNCs to minimize surface defects and avoid exposure to the external environment, enhancing the stability of the perovskites. Time-resolved photoluminescence spectra showed longer lifetimes for CsPbBr3/PMA PNCs, while transient absorption measurements provided valuable insights into the intraband hot-exciton relaxation and recombination. We demonstrate the potential application of CSPbBr3/PMA in a down-conversion white-light-emitting diode (LED) by coupling green CsPbBr3/PMA and red K2SiF6:Mn4+ phosphor-coated glass slides onto a 455-nm blue GaN LED. The white LED produced a white light with the International Commission on Illumination color coordinates of (0.323, 0.345), luminous efficiency of 58.4 lm/W, and color rendering index of 83.2. The fabricated, white-LED system obtained a wide color gamut of 125.3 % of the National Television Standards Committee and 98.9 % of Rec. 2020. The findings demonstrate that CsPbBr3/PMA can be an efficient down-conversion material for white LEDs and backlighting.

Steerable mass transport in a photoresponsive system for advanced anticounterfeiting.

Numerous anticounterfeiting platforms using photoresponsive materials have been designed to improve information security, enabling applications in anticounterfeiting technology. However, fabricating sophisticated micro/nanostructures using bidirectional mass transport to achieve advanced anticounterfeiting remains challenging. Here, we propose one strategy to achieve steerable mass transport in a photoresponsive system with the assistance of solvent vapor at room temperature. Upon optimizing the host-guest ratio and the width of photoisomerized areas, wettability gradient is acquired just photo-patterning once, then bidirectional mass transport is realized due to the competition of mass transport induced by surface energy gradient of the material itself and flow of the solvent on the film surface with wettability gradient. Taking advantage of the interaction between solvent and film surface with wettability gradient, this bidirectional polymer flow has been successfully applied in multi-mode anticounterfeiting. This work paves a promising avenue toward high-level information storage in soft materials, demonstrating the potential applications in anticounterfeiting.

Laser-assisted direct roller imprinting of large-area microstructured optical surfaces.

In this study, a high-throughput fabrication method called laser-assisted direct roller imprinting (LADRI) was developed to lower the cost of nanoimprinting large-area polymer films and to address problems associated with nanoimprinting, namely, microstructural damage and precision in flatness of entire film. With LADRI, the laser directly heats the microstructured surface of the roller mold, which heats and melts the surface of a polymethyl methacrylate (PMMA) film to replicate the microstructures on the mold rapidly. In this study, the effects of laser power density, scanning speed, size of the microstructures, and contact pressure on the replication speed were investigated experimentally. The replication speed increased as the power and scanning speed increased. However, because the film required heating until it filled the entire depth of the microstructure, an appropriate replication speed was necessary. This result was supported by simulation of the temperature distribution inside the mold and the PMMA using transient heat conduction analyses. To demonstrate the applications of LADRI, two different optical surfaces were replicated: an antireflection (AR) structure with conical structures sized several hundred nanometers and a light-extraction structure with a microlens array (MLA) comprising 10 µm lenses, for display and illumination, respectively. The replication degree of the MLA was governed by the contact pressure. Polymer flow simulation indicated that the heat conduction and flow speeds of the melted PMMA surface were comparable within several tens of micrometers. In addition, the reflectivity of the AR structure decreased from 4 to 0.5%, and the light intensity of the light-extraction structure increased by a factor of 1.47.

Unearthing Superior Inorganic UV Second-Order Nonlinear Optical Materials: A Mineral-Inspired Method Integrating First-Principles High-Throughput Screening and Crystal Engineering.

Natural minerals, with their adaptable framework structures exemplified by perovskite and lyonsite, have sparked substantial interest as potential templates for the design of advanced functional solid-state materials. Nonetheless, the quest for new materials with desired properties remains a substantial challenge, primarily due to the scarcity of effective and practical synthetic approaches. In this study, we have harnessed a synergistic approach that seamlessly integrates first-principles high-throughput screening and crystal engineering to reinvigorate the often-overlooked fresnoite mineral, Ba2 TiOSi2 O7 . This innovative strategy has culminated in the successful synthesis of two superior inorganic UV nonlinear optical materials, namely Rb2 TeOP2 O7 and Rb2 SbFP2 O7 . Notably, Rb2 SbFP2 O7 demonstrates a comprehensive enhancement in nonlinear optical performance, featuring a shortened UV absorption edge (260 nm) and a more robust second-harmonic generation response (5.1×KDP). Particularly striking is its significantly increased birefringence (0.15@546 nm), which is approximately 30 times higher than the prototype Ba2 TiOSi2 O7 (0.005@546 nm). Our research has not only revitalized the potential of the fresnoite mineral for the development of new high-performance UV nonlinear optical materials but has also provided a clearly defined roadmap for the efficient exploration of novel structure-driven functional materials with targeted properties.

Ca2 Ln(BS3 )(SiS4 ) (Ln = La, Ce, and Gd): Mixed Metal Thioborate-Thiosilicates as Well-Performed Infrared Nonlinear Optical Materials.

The first examples of thioborate-thiosilicates, namely Ca2 Ln(BS3 )(SiS4 ) (Ln = La, Ce, and Gd), are synthesized by rationally designed high-temperature solid-state reactions. They crystalize in the polar space group P63 mc and feature a novel three-dimensional crystal structure in which the discrete [BS3 ]3- and [SiS4 ]4- anionic groups are linked by Ca2+ and Ln3+ cations occupying the same atomic site. Remarkably, all three compounds show comprehensive properties required as promising infrared nonlinear optical materials, including phase-matchable strong second harmonic generation (SHG) responses at 2.05 µm (1.1-1.2 times that of AgGaS2 ), high laser-induced damage thresholds (7-10 times that of AgGaS2 ), wide light transmission range (0.45-11 µm), high thermal stabilities (>800 °C), and large calculated birefringence (0.126-0.149 @1064 nm), which justify the material design strategy of combining [BS3 ]3- and [SiS4 ]4- active units. Theoretical calculations suggest that their large SHG effects originate mainly from the synergy effects of the LnS6 , BS3 , and SiS4 groups. This work not only broadens the scope of research on metal chalcogenides but also provides a new synthetic route for mixed anionic thioborates.

Breaking Through the Trade-Off Between Wide Band Gap and Large SHG Coefficient in Mercury-Based Chalcogenides for IR Nonlinear Optical Application.

It is substantially challenging for non-centrosymmetric (NCS) Hg-based chalcogenides for infrared nonlinear optical (IR-NLO) applications to realize wide band gap (Eg > 3.0 eV) and sufficient phase-matching (PM) second-harmonic-generation intensity (deff > 1.0 × benchmark AgGaS2 ) simultaneously due to the inherent incompatibility. To address this issue, this work presents a diagonal synergetic substitution strategy for creating two new NCS quaternary Hg-based chalcogenides, AEHgGeS4 (AE = Sr and Ba), based on the centrosymmetric (CS) AEIn2 S4 . The derived AEHgGeS4 displays excellent NLO properties such as a wide Eg (≈3.04-3.07 eV), large PM deff (≈2.2-3.0 × AgGaS2 ), ultra-high laser-induced damage threshold (≈14.8-15 × AgGaS2 ), and suitable Δn (≈0.19-0.24@2050 nm), making them highly promising candidates for IR-NLO applications. Importantly, such excellent second-order NLO properties are primarily attributed to the synergistic combination of tetrahedral [HgS4 ] and [GeS4 ] functional primitives, as supported by detailed theoretical calculations. This study reports the first two NCS Hg-based materials with well-balanced comprehensive properties (i.e., Eg > 3.0 eV and deff > 1.0 × benchmark AgGaS2 ) and puts forward a new design avenue for the construction of more efficient IR-NLO candidates.

Excellent Nonlinear Optical M[M4 Cl][Ga11 S20 ] (M = A/Ba, A = K, Rb) Achieved by Unusual Cationic Substitution Strategy.

The typical chalcopyrite AgGaQ2 (Q = S, Se) are commercial infrared (IR) second-order nonlinear optical (NLO) materials; however, they suffer from unexpected laser-induced damage thresholds (LIDTs) primairy due to their narrow band gaps. Herein, what sets this apart from previously reported chemical substitutions is the utilization of an unusual cationic substitution strategy, represented by [[SZn4 ]S12 + [S4 Zn13 ]S24 + 11ZnS4 ⇒ MS12 + [M4 Cl]S24 + 11GaS4 ], in which the covalent Sx Zny units in the diamond-like sphalerite ZnS are synergistically replaced by cationic Mx Cly units, resulting in two novel salt-inclusion sulfides, M[M4 Cl][Ga11 S20 ] (M = A/Ba, A = K, 1; Rb, 2). As expected, the introduction of mixed cations in the GaS4 anionic frameworks of 1 and 2 leads to wide band gaps (3.04 and 3.01 eV), which exceeds the value of AgGaS2 , facilitating the improvement of high LIDTs (9.4 and 10.3 × AgGaS2 @1.06 µm, respectively). Furthermore, compounds 1 and 2 exhibit moderate second-harmonic generation intensities (0.84 and 0.78 × AgGaS2 @2.9 µm, respectively), mainly originating from the orderly packing tetrahedral GaS4 units. Importantly, this study demonstrates the successful application of the cationic substitution strategy based on diamond-like structures to provide a feasible chemical design insight for constructing high-performance NLO materials.

Rational Design and Biological Application of Hybrid Fluorophores.

Fluorophores are considered powerful tools for not only enabling the visualization of cell structures, substructures, and biological processes, but also making for the quantitative and qualitative measurement of various analytes in living systems. However, most fluorophores do not meet the diverse requirements for biological applications in terms of their photophysical and biological properties. Hybridization is an important strategy in molecular engineering that provides fluorophores with complementarity and multifunctionality. This review summarizes the basic strategies of hybridization with four classes of fluorophores, including xanthene, cyanine, coumarin, and BODIPY with a focus on their structure-property relationship (SPR) and biological applications. This review aims to provide rational hybrid ideas for expanding the reservoir of knowledge regarding fluorophores and promoting the development of newly produced fluorophores for applications in the field of life sciences.

Optical Properties of Cationic Perylenediimide Nanowires in Aqueous Medium: Experimental and Computational Studies.

Cationic perylenediimide derivative, namely N,N'-di(2-(trimethylammoniumiodide)ethylene) perylenediimide (TAIPDI), has been synthesized and characterized in an aqueous medium by using dynamic light scattering (DLS), X-ray diffraction (XRD), fourier-transform infrared (FTIR), scanning electron microscope (SEM), and high-resolution transmission electron microscopy (HRTEM) techniques. The optical absorption and fluorescence spectra of TAIPDI revealed the formation of aggregated TAIPDI nanowires in water, but not in organic solvents. In order to control the aggregation behavior, the optical properties of TAIPDI have been examined in different aqueous media, namely cetyltrimethylammonium bromide (CTAB), and sodium dodecyl sulfate (SDS). Furthermore, the utilization of the examined TAIPDI for constructing supramolecular donor-acceptor dyad has been achieved by combining the electron accepting TAIPDI with the electron donating 4,4'-bis (2-sulfostyryl)-biphenyl disodium salt (BSSBP). The formed supramolecular dyad TAIPDI-BSSBP through the ionic and electrostatic π-π interactions have been well examined by various spectroscopic techniques, e.g., steady-state absorption and fluorescence, cyclic voltammetry, and time-correlated single-photon counting (TCSPC), and first principle computational chemistry methods. Experimental results suggested the occurring of intra-supramolecular electron transfer from BSSBP to TAIPDI with rate constant and efficiency of 4.76 × 109 s-1 and 0.95, respectively. The ease of construction, absorption in the UV-Visible region, and fast electron transfer process render the supramolecular TAIPDI-BSSBP complex as a donor-acceptor material for optoelectronic devices.

Temperature-Dependent Color-Tunable Afterglow in Zirconium-Doped CsCdCl3 Perovskite for Advanced Anti-Counterfeiting and Thermal Distribution Detection.

Persistent luminescence (PersL) materials exhibit thermal-favored optical behavior, enabling their unique applications in security night vision signage, in vivo bioimaging, and optical anti-counterfeiting. Therefore, developing efficient and color-tunable PersL materials is significantly crucial in promoting advanced practical use. In this study, hexagonal Zr4+ -doped CsCdCl3 perovskite is synthesized via a hydrothermal reaction with a tunable photoluminescent (PL) behavior through heterovalent substitution. Moreover, the incorporation of Zr4+ ions result in an extra blue emission band, originating from the enhanced excitonic recombination in D3d octahedrons. Furthermore, the afterglow performances of the samples are dramatically improved, along with the noticeable temperature-dependent PersL as well as the thermo-luminescence with tunable color output. Detailed analysis reveals that the unique temperature-dependent PersL and thermo-luminescence color change are attributed to the presence of multiple luminous centers and abundant traps. Overall, this work facilitates the development of optical intelligence platforms and novel thermal distribution probes with the as-developed halides perovskite for its superior explored PersL characteristic.

Deep-Ultraviolet Transparent Mixed Metal Sulfamates with Enhanced Nonlinear Optical Properties and Birefringence.

Enhancing anisotropy through the controlled arrangement of anionic groups is essential for improving the nonlinear optical (NLO) performance of non-π-conjugated NLO materials. In this study, we present the successful synthesis of the first examples of mixed alkali metal-alkaline earth metal sulfamate materials, including noncentrosymmetric Cs2 Mg(NH2 SO3 )4 ⋅ 4H2 O (1), as well as centrosymmetric K2 Ca(NH2 SO3 )4 (2) and Rb2 Ca(NH2 SO3 )4 (3). All three compounds feature promising deep ultraviolet cut-off edges, notably 1 with a cut-off edge below 180 nm. The synergy of Cs+ and Mg2+ cations in 1 facilitated the successful alignment of polar [NH2 SO3 ] tetrahedra in a uniform orientation. Remarkably, 1 stands as the sole instance among reported sulfamate compounds with a co-parallel anionic arrangement, yielding a very large dipole moment compared to other non-π-conjugated NLO materials. Moreover, the substantial dipole moment of 1 yields an enhanced second harmonic generation response, approximately 2.3 times that of KH2 PO4 , and a large birefringence of 0.054 at 546.1 nm. The approach of regulating the arrangement of anionic groups using aliovalent cations holds promise for advancing the exploration of non-π-conjugated 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 (<200 nm), 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.