Defect engineering of second-harmonic generation in nonlinear optical semiconductors

Crystal growth is an important branch of solid state physics and material science. The Growth of Nonlinear Optical (NLO) materials crystals receives much importance nowadays because NLO materials have various applications in modern technologies like Laser technology, optoelectronics, and fiber optics, etc. Potassium dihydrogen phosphate (KDP) is a well known nonlinear optical (NLO) material with different applications. Since most of the amino acids exhibit NLO property, it is of interest to dope them in KDP. In the present study, amino acid L-Phenylalanine doped KDP crystals have been grown by slow evaporation solution growth technique. In present study powder XRD analysis was carried out which show that pure and L-Phenylalanine doped KDP crystals have tetragonal symmetry. The doping of L-Phenylalanine was confirmed by FT-IR and paper chromatography. Thermal analysis has been performed on the grown crystals.The SHG efficiency of L-Phenylalanine doped KDP crystals was found to be increasing with a doping concentration of L-Phenylalanine. Introduction. The demand for high quality large size KDP single crystal increases due to its application as frequency conversion crystal in inertial confinement fusion [1, 2]. KDP belongs to scalenohedral (twelve faced) class of tetragonal crystal system [3]. With the aim of improving the second harmonic generation (SHG) efficiency of KDP, researchers have attempted to modify KDP crystals by doping different types of impurities. The non-linear optical (NLO) and other properties of the crystal have been improved by doping of organic impurities [4-9]. KDP doped with amino acids like L-glutamine acid, L-gistidine, and L-valine was reported [10]. Kumaresan et al. [11] has reported the thermal dielectric properties of amino acids such as L-glutamic acid, L-histidine and L-valine doped KDP crystals. They found improved NLO properties of the KDP crystal and modifications in the structural, optical, mechanical, and electrical properties, too. Parikh [12] has reported the SHG efficiency of L-arginine doped KDP crystal. Kumaresan et al. [13] has also reported the effect of metal ion and amino acid doping on the optical properties of KDP crystal. Muley et al. [5] has studied thermal, NLO properties of KDP crystal doped with L-arginine and L-alanine. Suresh Kumar and Rajendrababu [6] studied the effects of L-arginine, L-histidine and glycine on the growth of KDP single crystals and observed that addition of amino acid enhances transparency, thermal stability and NLO efficiency of KDP crystals. Amino acid family crystals are playing an important role in the field of non-linear optical organic molecular crystal. Among them L-Phenylalanine (LPA) with chemical formula (C6H5CH2CH(NH2)COOH) is the α-amino acid with a non-reactive hydrophobic benzyl side chain. The physical, chemical and non-linear optical properties of KDP are enhanced by adding optically active amino acids as dopants.The growth and characterization of Single crystals of KDP doped with amino acids namely glycine, arginine, alanine, tryptophan, histidine have been reported earlier [5-8]. In the present work, single crystals of Potassium dihydrogen phosphate (KDP) added

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If a bucket is to hold more water, its shortest plank must be made longer. This guideline also applies to the exploration of ultraviolet (UV) and deep-UV (DUV) nonlinear optical (NLO) materials that are limited by multiple criteria. Phosphates are one kind of promising candidate for new NLO materials. Unfortunately, the small birefringence, as the shortest plank, severely restricts the phase-matching of second harmonic generation (SHG) in the UV/DUV region. In this work, fluorophosphates are rationally proposed as substitutes for phosphates to break down the limitation of birefringence and simultaneously enhance SHG response and retain wide UV transmittance. The (PO3F)2– and (PO2F2)− groups are confirmed as superior material genomes to achieve the discussed combination properties. Accordingly, (NH4)2PO3F was screened out by density functional theory calculation, and single crystals with centimeter size have been grown. It possesses a powder SHG efficiency of 1 × KH2PO4 (KDP) and is phase-matchable with output of SHG wavelength at 266 nm. To the best of our knowledge, it is the first time that fluorophosphates are identified and developed as new and ideal candidates to new UV/DUV NLO materials by combining theories and experiments.

Deep-UV nonlinear optical (NLO) materials have attracted much academic and technical attention due to their capability of producing coherent light of wavelengths below 200 nm. As a well-known branch of NLO materials, researchers have obtained many deep-UV NLO crystals with superior properties in π-conjugated system materials (such as borate systems and carbonate systems). However, due to structural and property limitations, the research developments have encountered difficulties in balancing NLO properties. Recently, scientists started to pay attention to the non-π-conjugated system of deep-UV NLO materials. As far as we know, the non-π-conjugated deep-UV NLO materials could be divided into six categories: phosphates, sulfates, borophosphates, borosilicates, fluorides, and silicates. This review focuses on the research advances of deep-UV NLO materials with non-π-conjugated functional groups and summarizes and discusses the deep-UV NLO crystals on the basis of the performance criteria of “deep-UV transmission–large NLO effect–large birefringence”. By analyzing the structure–property relationships of these materials, we summarize the microscopic mechanism restricting the balance of properties and new functional groups, which may provide new ideas and help the explorations of deep-UV NLO materials.

Second-order nonlinear optical (NLO) materials have drawn enormous academic and technological attention attributable to their indispensable role in laser frequency conversion and other greatly facilitated applications. The exploration of new NLO materials with high performances thus has long been an intriguing research field for chemists and material scientists. However, an ideal NLO material should simultaneously satisfy quite a few fundamental yet rigorous criteria including a noncentrosymmetric structure, large NLO coefficients, desired transparent range, large birefringence, high laser damage threshold, and availability of a large-size single crystal. Therefore, the identification of promising compound systems, targeted design, and experience-based syntheses are crucial to discover novel NLO materials working in the spectral region of interest. As an important family of mixed-anion compounds, versatile metal oxyhalides containing metal-centered oxyhalide functional units ([MOmXn] (X = F, Cl, Br, and I)) are becoming a marvelous branch for interesting NLO materials. Especially, when the central metals are d0/d10 transition metals or heavy post-transition metals, a number of novel NLO materials with superior functionalities are expected. Our thorough review on the recent achievements of metal oxyhalides for NLO materials are divided into the fast-growing NLO metal oxyhalides with single type halogen anions and the newly identified NLO metal oxyhalides with mixed halogen anions. Here we mainly focus on the design strategy, structural chemistry, NLO-related properties, and structure–property correlation of the metal oxyhalides with relatively large NLO responses. We hope this review can provide an insight on the rational design and future development of emerging metal oxyhalides for NLO and other applications.

UV nonlinear optical materials require the simultaneous achievement of a large second harmonic generation (SHG) coefficient (≥1 × KH2PO4 (KDP), dij > 0.39 pmV−1), wide bandgap (λ < 300 nm, Eg > 4.2 eV), and moderate birefringence (0.05‐0.10@1064 nm) in a single structure. Therefore, designing UV nonlinear optical materials with excellent comprehensive performance is a challenging task. Herein, four UV transparent selenite materials are successfully obtained, namely, Al2(SeO3)3(H2O)3 (1), Ga2(SeO3)3(H2O)3 (2), NaGa3(HSeO3)6(SeO3)2 (3), and Cd5Ga4(HSeO3)2(SeO3)10 (4), through rational design and screening in the pure selenite system. Al2(SeO3)3(H2O)3 (1) and Ga2(SeO3)3(H2O)3 (2) are UV nonlinear optical materials with balanced properties, exhibiting moderate SHG responses (1.2 and 1.1 × KDP), appropriate birefringence (0.084 and 0.076@1064 nm), and wide bandgaps (5.5 and 5.3 eV). Such bandgaps are the largest in the reported pure selenite nonlinear optical (NLO) materials. This work further demonstrates that pure selenite is a good candidate for UV NLO materials.

Nonlinear optical (NLO) materials that can achieve frequency conversion and coherent light emission have garnered significant interest owing to their promising applications in laser technology and advanced photonic systems. In this study, the first-principles high-throughput screening pipeline (FHSP) was employed to systematically explore nonlinear optical materials within vanadate-based systems. A total of 204 vanadates were calculated in the Inorganic Crystal Structure Database (ICSD). Eventually, BiCa2VO6 was screened out and synthesized by a traditional high-temperature solid-state method. BiCa2VO6 exhibits an outstanding second harmonic generation (SHG) response (11.2 × KDP@1064 nm and 1.67 × AGS@2.09 μm), a wide band gap (3.25 eV), and a suitable birefringence (0.123@1064 nm). The work provides a complete perspective for vanadate as a nonlinear optical material and serves as a valuable reference for future research.

Nonlinear optical (NLO) materials are of great importance in modern optics and industry because of their intrinsic capability of wavelength conversion. Bandgap is a key property of NLO crystals. In recent years, machine learning (ML) has become a powerful tool to predict the bandgaps of compounds before synthesis. However, the shortage of available experimental data of NLO crystals poses a significant challenge for the exploration of new NLO materials using ML. In this work, we proposed a new multi-fidelity ML approach based on the multilevel descriptors developed by us (Z.-Y. Zhang, X. Liu, L. Shen, L. Chen and W.-H. Fang, J. Phys. Chem. C, 2021, 125, 25175-25188) and the gradient boosting regression tree algorithm. The calculated and experimental bandgaps of NLO crystals were collected as the low- and high-fidelity labels, respectively. The experimental values were predicted based on chemical compositions of crystals without prior knowledge about crystal structures. The multi-fidelity ML model overcame the performance of single-fidelity predictor. Furthermore, it was observed that less accurate predictions on the low-fidelity label may result in more accurate prediction on the high-fidelity label, at least in the present case. Using the multi-fidelity ML model with the best performance in this work, the mean absolute error on the test set of experimental bandgaps was 0.293 eV, which is smaller than that using the single-fidelity model (0.355 eV). It is far from perfect but accurate enough as an effective computational tool in the first step to discover novel NLO materials.

Effective design and synthesis of second-order nonlinear optical (NLO) materials hold immense significance in driving modern science and technology advancements. In this study, we synthesized a new acentric mercury nitrate, (C5H12N2S)Hg(NO3)2, by regulating the coordination of the Hg atom through the introduction of a heteroatom. It exhibits an unprecedented [(C5H12N2S)2Hg2(NO3)4]∞ chain composed of Hg2+, NO3-, and organic molecule C5H12N2S. Notably, (C5H12N2S)Hg(NO3)2 demonstrates an unprecedented HgO3S unit and a second harmonic generation (SHG) intensity of 1.3 × KDP at 1064 nm, presenting the second-order nonlinear mercury nitrate constructed by organic molecule. Theoretical calculations suggest that the HgO3S unit and organic molecule C5H12N2S significantly contribute to the SHG effect. This study demonstrates that the incorporation of heteroatoms is an effective strategy for the development of new NLO materials.

Fluorooxoborates have inspired investigations of deep‐ultraviolet (DUV) nonlinear optical (NLO) materials that can meet the multiple criteria. Herein, five stable structures with the composition of BaB2O3F2 (I–V) are discovered using the ab initio evolutionary algorithm. Among them, BaB2O3F2‐I has been synthesized experimentally and confirms the reliability of the method. All of the predicted structures possess extremely wide band gaps (8.1–9.0 eV). Moreover, four new structures exhibit giant second harmonic generation (SHG) coefficients (>3×KDP, d36=0.39 pm V−1). A novel type of the [BOF] layer with BO3:BO3F ratio of [1:1] is found in BaB2O3F2‐II and BaB2O3F2‐III. While BaB2O3F2‐IV and BaB2O3F2‐V are solely composed of the BO3F group and have colossal SHG coefficients (ca. 4×KDP). It gives the direct evidence that the BO3F group could generate strong SHG effect. Most importantly, the influences of BO3:BO3F ratio and their number density on band gap, birefringence and SHG effects are investigated.

Defective crystalline semiconductor plays a significant role in photocatalytic nitrogen fixation, however the rapid recombination of photoexcited electron/hole pairs largely reduces the efficiency. Spontaneous polarization of the nonlinear optical (NLO) material has emerged as a promising strategy for addressing the problem. Herein, a defects-rich NLO crystalline LiNbO3 modulated by natural nano-mineral palygorskite (LiNbO3/Pal) has been synthesized via sol–gel method. The intrinsic polarization of LiNbO3/Pal is investigated by second harmonic generation (SHG) measurements, which indicates an intensity of about 3.1 times that of typical NLO material KH2PO4 (KDP). The strong polarization can facilitate the separation of photogenerated charge carriers in the bulk phase and on the surface of LiNbO3/Pal. The existence of oxygen vacancies in LiNbO3/Pal may originate from doping of metal ions and active groups on the surface of Pal during crystallization of LiNbO3, which shortens the bandgap of LiNbO3 and facilitates the absorption and activation of N2 molecules. As a result, the polarization effect and rich oxygen vacancies make the LiNbO3/Pal an exceptional photocatalyst for N2 fixation. The 40 wt% LiNbO3/Pal composite achieves an average rate of photocatalytic NH4+ production of 52.57 μmol gcat−1 h−1 under simulated solar light, which is about sixfold higher than that of bulk LiNbO3. This work not only presents a new perspective on mineral modification of NLO material but also offers a cost-effective photocatalyst for nitrogen fixation.

Inorganic adducts are an emerging class of infrared nonlinear optical (NLO) materials. However, although the reported NLO adducts have sufficient birefringences and significant laser‐induced damage thresholds (LIDTs), they commonly suffer from weak second harmonic generation (SHG) responses. In this work, a series of polar phosphorus chalcogenide cage molecules with strong hyperpolarizabilities were theoretically screened out to enhance the SHG responses of adducts. Accordingly, (CuI)3(P4S4), (CuI)3(P4Se4), (CuBr)7(P4S3)3 and (CuBr)7(P4Se3)3 with target polar cage molecules were successfully synthesized. As expected, they exhibit enhanced SHG responses while keeping moderate birefringences and high LIDTs. Notably, (CuBr)7(P4Se3)3 possesses the largest SHG response (3.5×AGS@2.05 μm) among the known inorganic NLO adducts. Our study confirms that introducing NLO‐active cage molecules into adducts is an efficient strategy for high‐performance NLO materials.

Structural, thermal, mechanical and optical properties of l-arginine diiodate crystal: A new nonlinear optical material

Inherent law of SHG and phase-matching in 0D NLO materials: Permutation tetra-coordinated groups

Fluorine-containing compounds have stimulated the exploration of ultraviolet/deep-ultraviolet nonlinear optical (NLO) materials. Alkali/alkaline-earth metal phosphates are one of the important potential systems as NLO materials, while the common small birefringence limits the phase-matching (PM) ability in the ultraviolet/deep-ultraviolet region. Herein, by applying a "fluorination synergy-induced enhancement of optical property" strategy, novel structures of phosphate fluoride/fluorophosphate in BePO3F with good thermodynamic/dynamic stability and promising NLO-related properties are discovered via performing crystal structure prediction combined with first-principles calculations. BePO3F-I-VI exhibit relatively large birefringence of 0.025, 0.048, 0.049, 0.049, 0.059, and 0.063 at 1064 nm, respectively. Simultaneously, BePO3F-I (Pc) is a new thermodynamically stable phosphate fluoride which possesses a wide band gap (Eg = 8.03 eV), large second-harmonic generation (SHG) coefficient (d11 = 0.67 pm/V, 1.7 × KDP), and the shortest PM wavelength of 292 nm. Other five thermodynamically metastable noncentrosymmetric (NCS) BePO3F structures (II-VI) belong to fluorophosphates and exhibit deep-ultraviolet PM wavelengths of 187, 183, 186, 188, and 196 nm. It reveals that the aligned nonbonding O 2p orbitals of [BeO2F2] and [PO4] units lead to a large SHG coefficient in the phosphate fluoride BePO3F-I. For fluorophosphates (BePO3F-II-VI), the synergy of [BeO3] planar units and [PO3F] units induces relatively large birefringence. Our research results provide an idea for exploring novel high-performance NLO materials.