Second Harmonic Generation Performance Research Articles

Magnetic Switching of Second-Harmonic Generation from Single Cerium-Based Coordination Polymer Microcrystals.

Conventional access and modulation of second-harmonic generation (SHG) require precise control of crystal orientation, which faces great mechanical challenges in the case of micro/nanocrystals. Here, we demonstrate the magnetic-field-tunable SHG performance of lanthanide coordination polymer (Ce-BTC CP) microcrystals through field-aligned orientations. The coordination of Ce ions and organic ligands constructs a noncentrosymmetric structure, which not only contributes to a favorable powder SHG efficiency 3.2 times larger than that of the benchmark KH2PO4 (KDP) but also endows the microcrystals with strong magnetic anisotropy. The SHG efficiency (∼0 to 10 × KDP) depends on the orientation of the crystallographic c-axis, whereas magnetic anisotropy always aligns the c-axis with the magnetic field at a specific angle. Accordingly, the SHG can be magnetically switched by field-induced alignments. The adsorption of dyes by Ce-BTC CPs further facilitates the magnetic switching of multicolor fluorescence that can be excited by the SHG. Our work provides a new pathway for achieving SHG modulation at the microscopic level.

Observation of Anisotropic Second Harmonic Generation in Two-Dimensional Niobium Diselenide.

The intrinsic anisotropy of NbSe2 provides a favorable prerequisite of second harmonic generation (SHG) and rich possibilities for tailoring its nonlinear optical (NLO) properties. Here we report the highly efficient SHG of mechanically exfoliated NbSe2 flakes. The nonlinear optical response changes with excitation wavelengths, layer thicknesses, and polarizations of the excitation laser. The anisotropic SHG response further exhibits the intrinsic non-centrosymmetric crystal structure and could effectively assign the crystalline orientation of NbSe2 flakes. Interestingly, although NbSe2 flakes with tens of nanometers thickness experience attenuations in SHG performance, more efficient SHG anisotropy ratios were obtained, which are around 4 times higher than that of the 5-layer counterpart. The determined second-order nonlinearities of NbSe2 flakes (monolayer: ∼1.0 × 103 pm/V; 3-layer: ∼73 pm/V) are comparable to those of the commonly reported two-dimensional materials (e.g., MoS2, WSe2, graphene) with the same number of layers and much higher than those of commercial nonlinear optical crystals.

Efficient second harmonic generation in a high-Q Fabry-Perot microresonator on x-cut thin film lithium niobate.

Microresonators facilitate enhanced light-matter interactions within a limited space, showing great promise for nonlinear optics. Here, we demonstrate a high-quality (Q) factor Fabry-Perot microresonator (FPR) for second harmonic generation (SHG) on an x-cut thin film lithium niobate (TFLN) platform. The FPR exhibits Q factors of Qpump = 1.09 × 105 and QSH = 1.15 × 104 at the 1560 nm pump wavelength and 780 nm second harmonic wavelength, respectively. Under low pump power, a normalized SHG efficiency of 158.5 ± 18.5%/W is attained. We experimentally verify that increased temperatures mitigate photorefractive effects that degrade SHG performance. This work highlights the immense capabilities of one-dimensional planar optical waveguide resonators for efficient on-chip nonlinear wavelength conversion.

Second harmonic generation of visible vortex laser based on a waveguide-grating emitter in LBO.

In this work, we propose a practical solution to visible vortex laser emission at 532 nm based on second harmonic generation (SHG) in a well-designed waveguide-grating structure. Such an integrated structure is fabricated by femtosecond laser direct writing (FsLDW) in an LBO crystal. Confocal micro-Raman spectroscopy is employed for detailed analysis of FsLDW-induced localized crystalline damage. By optical excitation at 1064 nm, the guiding properties, SHG performance, as well as vortex laser generation of the waveguide-grating hybrid structure are systematically studied. Our results indicate that FsLDW waveguide-grating emitter is a reliable design holding great promise for nonlinear vortex beam generation in integrated optics.

Second-harmonic generation in 2D moiré superlattices composed of bilayer transition metal dichalcogenides.

Moiré superlattices (MSLs) in twisted two-dimensional van der Waals materials feature twist-angle-dependent crystal symmetry and strong optical nonlinearities. By adjusting the twist angle in bilayer van der Waals materials, the second-harmonic generation (SHG) can be controlled. Here, we focus on exploring the electronic and SHG properties of MSLs in 2D bilayer transition metal dichalcogenides (TMDs) with different twist angles through first-principles calculations. We constructed MSL structures of five TMD materials, including three single-phase materials (MoS2, WS2, and MoSe2) and two heterojunctions (MoS2/MoSe2 and MoS2/WS2) with twist angles of 9.4°, 13.2°, 21.8°, 32.2°, and 42.1° without lattice mismatch. Our findings demonstrate a consistent variation in the SHG susceptibility among different TMD MSLs as a response to twist-angle changes. The underlying reason for the twist-angle dependence of SHG is that the twist angle regulates the interlayer coupling strength, affecting the optical band gap of MSLs and subsequently tuning the SHG susceptibility. Through a comparison of the static SHG susceptibility values, we identified the twist angle of 9.4° as the configuration that yields the highest SHG susceptibility (e.g. 358.5 pm V-1 for the 9.4° MoSe2 MSL). This value is even twice that of the monolayer (173.3 pm V-1 for monolayer MoSe2) and AA'-stacked bilayer structures (139.8 pm V-1 for AA' MoSe2). This high SHG susceptibility is attributed to the strong interlayer coupling in the 9.4° MSL, which enhances the valence band energy (contributed by the antibonding orbitals of chalcogen-pz and transition metal-dz2) and consequently leads to a small optical band gap, thus improving the optical transitions. The findings of this study provide a straightforward way to improve the SHG performance of bilayer TMDs and also throw light on the sensitive relationship between the twist angle, band structure and SHG properties of TMD MSLs.

Second harmonic generation in anisotropic stratified media: a generalization of the Berreman method and its application to photonic materials.

We have developed a numerical method for calculating the second-harmonic generation (SHG) generated by an anisotropic material whose optical properties present an arbitrary modulation in one dimension. The method is based on the Berreman 4 × 4 matrix formalism, which is generalized to include nonlinear optical phenomena. It can be used under oblique incidences of the input beam, and is valid even when the SHG frequency is close to photonic bands, where the usual slowly-varying-amplitude approximation breaks down. As an example of application, we have studied the SHG performance of ferroelectric and helielectric fluids. The obtained results indicate that the present procedure may contribute to improving the structural design and enlarging the variety of nonlinear optical materials for application in optical devices.

Achiral Fluorinated Aromatic Ligands Based Chiral Hybrid Antimony Halides with High‐Efficiency Second‐Harmonic Generation

AbstractHybrid organic−inorganic metal halides (HOMHs) have emerged as an ideal platform for the construction of semiconductor materials with promising optoelectronic properties. A number of HOMHs based on different metals including Sb3+ have been demonstrated with second‐harmonic generation (SHG) properties, but their nonlinear optical (NLO) performances including effective conversion wavelength range, optical stability, and NLO coefficients are not yet satisfactory. Here, by adopting a molecular design involving fluorine‐substitution on the achiral organic ammonium, this work has synthesized single crystals of two new chiral noncentrosymmetric HOMHs, (2‐FPEA)2SbX5 (X = Cl and Br), with large polarization ratios and outstanding optical transparency. The second‐order NLO coefficients of (2‐FPEA)2SbCl5 and (2‐FPEA)2SbBr5 are determined to be ≈24.3 and 21.6 pm V−1. Significantly, the Sb3+‐based HOMHs enable very high thermal stability and laser resistance. The distinguished laser‐induced damage thresholds (LDTs) have been estimated to be as high as 3.44 mJ cm−2 for (2‐FPEA)2SbCl5 and 3.32 mJ cm−2 for (2‐FPEA)2SbBr5, higher than that of the reported HOMHs. Such a highly efficient SHG performance and stability indicate the promising future of these Sb3+‐based metal halides for nonlinear photonic applications.

High-Efficiency Second-Harmonic Generation Using Quasi-Bound State in LiNbO3 Metasurface

We numerically demonstrated a high-efficiency second-harmonic generation (SHG) using quasi-bound state in the continuum (quasi–BIC) in thin film LiNbO3 (TFLN) metasurface. The TFLN possessed exceptionally high second-order nonlinear coefficients, contributing to the enhanced SHG performance. An eccentric cylinder unit cell was presented to achieve high Q–factor resonances associated with the asymmetric parameter introduced. Simulations showed that the high efficiency of the second-harmonic conversion was obtained by using the high Q–factor of the asymmetric dielectric cylinder metasurface, and it achieved a high SHG efficiency of 6.5% at pump intensities as low as 1 MW/cm2 at a normal incident. Furthermore, the simulation results indicated that breaking the symmetry through oblique incidence was more effective in achieving a higher Q–factor compared to altering the structural parameters. Specifically, under 1° oblique incidences, the conversion efficiency could reach 1.2% at an incident power of 1 kW/cm². We have proposed a method to achieve a high conversion efficiency of second-harmonic generation in low-refractive-index materials. Our work not only offers theoretical support but also provides valuable insights for the advancement of efficient nonlinear frequency doubling technology, optical communication, and sensing applications.

Extraordinary second harmonic generation modulated by divergent strain field in pressurized monolayer domes

The most prominent form of nonlinear optical (NLO) frequency conversion is second harmonic generation (SHG), where incident light interacts with a nonlinear medium producing photons at double the input frequency, which has vast applications in material and biomedical science. Emerging two-dimensional nonlinear optical materials led by transition metal dichalcogenides (TMDs) have fascinating optical and mechanical properties and are highly anticipated to overcome the technical limitations imposed by traditional bulky NLO materials. However, the atomic scale interaction length and low conversion efficiency in TMD materials prevent their further implementation in NLO applications. While some uniaxial strain-engineering studies intensively investigated the anisotropic SHG response in TMDs, they did not realize giant SHG enhancement by exploiting the opto-mechanical characteristics. Herein, we employ proton (H+) irradiation to successfully fabricate large pressurized monolayer TMD domes (d ≥ 10 μm) and conduct a comprehensive investigation and characterization of their SHG performance enhancement. We show that the intensity of SHG is effectively enhanced by around two orders of magnitude at room temperature. Such giant enhancement arises from the distinct separation distance induced by capped pressurized gas and the hemi-spherical morphology, enabling constructive optical interference. Moreover, the unique divergent strain field in TMD domes promotes the first experimental study on the anisotropic nonlinear optical behavior based on biaxial strain conditions in terms of varying strain orientation and relative weights. Our work demonstrates a promising system with enhanced NLO performance and well-preserved biocompatibility, paving a way toward the future nano-scaled quantum optics design and biomedical applications.

Femtosecond Laser Micromachining of Cladding Waveguides in KTiOAsO4 Crystal for Second‐Harmonic Generation

Second‐harmonic generation (SHG) of green lasers generated in KTiOAsO4 (KTA) cladding waveguides fabricated by femtosecond laser direct writing (FsLDW) is reported. The minimum propagation loss of the fabricated waveguides is determined to be 2.39 ± 0.24 dB cm−1 at 1064 nm. The SHG performance is characterized by utilizing a 1064 nm pulsed laser. The maximum SHG conversion efficiency reaches 13.67%. This work suggests potential applications of KTA crystals and FsLDW technology in definition of compact waveguide devices for integrated nonlinear optics.

High-Performance Second-Harmonic-Generation (SHG) Materials: New Developments and New Strategies.

ConspectusSecond-harmonic-generation (SHG) causes the frequency doubling of light, which is very useful for generating high-energy lasers with specific wavelengths. Noncentrosymmetry (NCS) is the first requirement for an SHG process because the SHG coefficient is zero (χ2 = 0) in all centrosymmetric structures. At this stage, developing novel NCS crystals is a crucial scientific topic. Assembling polar units in an addictive fashion can facilely form NCS crystals with outstanding SHG performance. In this way, our group has obtained many different NCS crystals with extremely large SHG intensities (>5 × KDP or 1 × KTP). In this Account, we first provide a brief review of the development of SHG materials and concisely highlight the features of the excellent SHG materials. Then, we present four facile and rational molecular design strategies: (1) Traditional BO33--based crystals feature short absorption edges but usually suffer from relatively weak SHG performance (<5 × KDP). The combination of two types of pure π-conjugated anions (BO33- and NO3-) in a parallel fashion in the same compound has afforded a metal borate nitrate with a strong SHG effect. (2) To overcome the problems of the weak SHG effect and small birefringence in the less anisotropic QO4-based compounds, highly polarizable cations such as Hg2+ and Bi3+ are introduced into these systems, which greatly enhances both SHG effects and birefringence. (3) Iodate anions can be condensed into polynuclear iodate anions with a higher density of I5+ per unit cell, hence polyiodate anions can serve as excellent SHG-active groups. We developed a novel synthesis method for hydrothermal reactions under a phosphoric acid medium and obtained a series of metal polyiodates with strong SHG effects. In addition, as the number of iodate groups increases, the structural configuration of the polyiodate anion changes from linear to bent. (4) We introduce the concept of aliovalent substitution which features site-to-site atomic displacement at the structural level. Such aliovalent substitution led to new materials that have the same chemical stoichiometries or structural features as their parent compounds. Thus, aliovalent substitution can provide more experimental opportunities and afford new high-performance SHG materials. The introduction of a fluoride anion and the replacement of metal cations in the MO6 octahedron can result in new metal iodates with balanced properties including a large SHG effect, a wide band gap, and a high laser-induced damage threshold (LIDT) value. Finally, we briefly discuss several problems associated with the studies of SHG materials and give some prospects for SHG materials in the future.

Series of Luminescent Lanthanide MOFs with Regular SHG Performance.

Second-harmonic generation (SHG) is a kind of nonlinear optical phenomenon which has been widely used in optical devices, and factors influencing its signal are very complex. Here, taking advantage of excellent structural designability and overcoming the limitations of various coordinations of lanthanide metals, for the first time a series of lanthanide metal-organic frameworks (Ln-MOFs) with one particular ligand were synthesized and structurally characterized to study the interference of the SHG signal. The optical performance including single-photon fluorescence and SHG was collected and analyzed. It is found that all 13 kinds of Ln-MOFs can be divided into 2 crystal configurations by their individual space groups and Ln-MOFs with coordinated metal atoms from La to Tb possessing the noncentrosymmetric C2 space group exhibit the SHG property, the intensity of which depends on the type of metal atoms, the pumping wavelength, and the size of the single-crystal particles. This is the first time that the relationship between the nonlinear optical properties and the structure, metal atoms, pumping wavelength, crystal size of the whole series of Ln-MOFs is studied systematically, providing a lot of interesting results and enriching the research scope of nonlinear optics and materials science.

Chirality-Dependent Second Harmonic Generation of MoS2 Nanoscroll with Enhanced Efficiency.

Materials with high second harmonic generation (SHG) efficiency and reduced dimensions are favorable for integrated photonics and nonlinear optical applications. Here, we fabricate MoS2 nanoscrolls with different chiralities and study their SHG performances. As a 1D material, MoS2 nanoscroll shows reduced symmetry and strong chirality dependency in the polarization-resolved SHG characterizations. This SHG performance can be well explained by the superposition theory of second harmonic field of the nanoscroll walls. MoS2 nanoscrolls with certain chiralities and diameters in our experiment can have SHG intensity up to 95 times stronger than that of monolayer MoS2, and the full potential can still be further exploited. The same chirality-dependent SHG can be expected for nanoscrolls or nanotubes composed of other noncentrosymmetric 2D materials, such as WS2, WSe2, and hBN. The characterization and analysis results presented here can also be exploited as a nondestructive technique to determine the chiralities of these nanoscrolls and nanotubes.

Co-doping effect of Amaranth and EDTA on bulk growth, optical, structural properties and second harmonic generation of KDP crystals grown by Sankaranarayanan-Ramasamy (SR) technique

KDP (Potassium dihydrogen phosphate) single crystals co-doped with Amaranth dye and EDTA (Ethylenediaminetetraacetic acid disodium salt) with concentrations of 0.005 mol% and 1 mol% respectively in the solution were grown from seeds by the method of temperature reduction and Sankaranarayanan-Ramasamy (SR) technique. The seeds were mounted vertically and in a direction of 59° from the vertical. The latter orientation of the seed made second harmonic generation (SHG) efficiency of KDP crystal with the 1064 nm laser reach its maximum value. Bulk growth, optical, and structural properties of the crystals were assessed by UV–Vis spectroscopy, X-ray diffraction (XRD) analysis, and photoluminescence. The elemental composition of crystals was also determined by Energy-dispersive X-ray (EDX) spectroscopy. Amaranth and EDTA additives have improved the SHG performance of pure KDP crystals by up to 168%, which probably could not be achieved by doping either with Amaranth or EDTA. Finally, three different parts of the crystal rods grown by SR technique were not homogeneous in the optical, structural properties and the degree of being dyed.

Ionothermal Synthesis of Metal Chalcogenides M2Ag3Sb3S7 (M = Rb, Cs) Displaying Nonlinear Optical Activity in the Infrared Region

Two interesting non-centrosymmetric metal chalcogenides, Rb2Ag3Sb3S7 and Cs2Ag3Sb3S7, were synthesized by an ionothermal approach. Crystals of compounds Rb2Ag3Sb3S7 and Cs2Ag3Sb3S7 possess isomorphic configuration, consisting of two-dimensional (2D) anionic networks ∞[Ag3Sb3S7]2-, which are split by alkali-metal M+ cations. The band gaps are 2.11 and 2.02 eV for Rb2Ag3Sb3S7 and Cs2Ag3Sb3S7, respectively. Second-harmonic generation (SHG) studies revealed that Rb2Ag3Sb3S7 affords a powder SHG performance of ∼0.5 × AgGaS2 with type-I phase matching, while Cs2Ag3Sb3S7 shows a slightly stronger SHG performance of ∼0.6 × AgGaS2 with type-I phase matching. Both compounds possess broad transparency ranges (∼0.6-20 μm), suggesting their potential as infrared (IR) nonlinear optical (NLO) materials. The laser damage thresholds (LDTs) of both Rb2Ag3Sb3S7 and Cs2Ag3Sb3S7 are about 2.3 × AgGaS2. The calculated birefringence indexes Δn are 0.1885 and 0.1944 at 1.064 μm, respectively, which are sufficiently large enough to achieve phase matching. Theoretical studies using density functional theory have been implemented to further understand the relationship between their NLO properties and band structures.

Annealing stability of the domain structure in periodically poled MgO doped lithium niobate single crystals

The stability of periodical domain structure during high-temperature annealing was studied in MgO doped lithium niobate single crystals by analysis of efficiency and homogeneity of the second harmonic generation (SHG) signal and optical visualization of the domain pattern. Annealing at temperatures up to 600 °C with up to 50 heating/cooling cycles resulted in weak changes of SHG performance and domain structure, while annealing at 1000 °C resulted in eight times decrease in the average SHG power and two times decrease in the effective periodical domain structure depth. Backswitching was attributed to the action of electric field induced by the crystal composition gradient caused by Li out-diffusion.

Type-II second-harmonic-generation properties of YCOB and GdCOB single crystals.

As excellent nonlinear optical (NLO) crystals, YCa(4)O(BO(3))(3) (YCOB) and GdCa(4)O(BO(3))(3) (GdCOB) have been paid much attention since their first appearance in 1990's. From that time to now, almost all of related researches and applications have focused on their type-I phase-matching (PM) configurations which possess large effective NLO coefficient (d(eff)). In this paper, type-II second-harmonic-generation (SHG) properties of these two crystals are reported, including PM curve, d(eff), angular acceptance and walk-off angle. Both of the type-II SHG experiments for 1064 and 1320 nm have indicated that the optimum directions which have maximum d(eff) locate in the second octant, i.e. (90° < θ< 180°, 0° < ϕ < 90°). For a (112°, 81.3°)-cut, 24 mm long YCOB crystal, the largest type-II SHG conversion efficiency of a 1064 nm Nd:YAG pico-second laser is 55%, which reaches the same level of the optimum type-I sample. To our knowledge this is the first time that type-II SHG performance of YCOB and GdCOB crystals is investigated intensively. Our research has shown that the smaller d(eff) of type-II PM can be compensated by its larger angular acceptance and less beam walk-off. The same level SHG conversion efficiency implies for such type crystals the type-II components have the potential to replace type-I ones and obtain important NLO applications in the future.

Highly efficient phase-matched second harmonic generation using an asymmetric plasmonic slot waveguide configuration in hybrid polymer-silicon photonics

We theoretically investigate the possible increase of the second harmonic generation (SHG) efficiency in silicon compatible waveguides by considering an asymmetrical plasmonic slot waveguide geometry and a χ((2)) nonlinear polymer infiltrating the slot. The needed phase matching condition is satisfied between the fundamental waveguide mode at the fundamental frequency (FF) and second-order waveguide mode at the second harmonic frequency (SHF) by an appropriate design of the waveguide opto-geometrical parameters. The SHG signal generated in our starting waveguide is three orders of magnitude higher than those previously reported for a FF corresponding to λ = 1550 nm. Then, the SHG performance was further improved by increasing the asymmetry of the structure where nonlinear coupling coefficients as large as 292 psm(-1)W(-1/2) are predicted. The device length is shorter than 20 µm and the normalized SHG conversion efficiency comes up to more than 1 × 10(5) W(-1)cm(-2).

Back Cover: Efficient second harmonic generation by birefringent phase matching in femtosecond‐laser‐inscribed KTP cladding waveguides (Phys. Status Solidi RRL 7/2012)

KTiOPO4 (KTP) is a widely used nonlinear crystal for frequency conversion. Nonlinear optical waveguides play significant roles in the promising micro photonic devices owing to the combination of nonlinear features of bulks and waveguide compact geometries. Femtosecond laser inscription has become a unique and powerful technique to fabricate waveguides in many optical materials. In the Letter on pp. 306–308, Dong et al. report on a novel nonlinear KTP waveguide structure by using femtosecond laser writing. Different from the well investigated stress-induced “double-line” waveguides, the fabricated KTP waveguide is confined in the circular core region surrounded by the fs-laser-induced low-refractive-index tracks. Such a cladding waveguide supports the guidance of two transverse polarizations well, and the large diameter (∼100 μm) of the cross section of the waveguide matches the scale of the optical fiber. Efficient guided-wave phase-matched second harmonic generation (SHG) at 532 nm has been realized under a pulsed 1064 nm laser pump, reaching a conversion efficiency as high as 45.6%, showing SHG performance superior to the stress-induced KTP waveguide. This work offers a new approach to build efficient nonlinear waveguides in optical crystals by using femtosecond laser inscription.

Growth and optical properties of a new nonlinear Na_3La_9O_3(BO_3)_8 crystal

New nonlinear crystals Na(3)La(9)O(3)(BO(3))(8) (abbreviated as NLBO) with desired morphologies, high quality and weight exceeding 40g have been grown along different directions, such as [001], [110], and [100], by top-seeded solution growth(TSSG) method. The refractive indices were accurately measured over the full transmission range, and the second-order nonlinear optical coefficients were determined by the Maker fringe technique. The optimal phase-matching (PM) conditions and the corresponding effective nonlinear coefficient were calculated for second harmonic generation (SHG) at different wavelengths. In order to confirm the correctness of our calculation, we also performed the SHG experiments under 1064 and 800 nm pumping, respectively. In addition, we directly compared the SHG performance of NLBO with that of LBO under the same experimental conditions with the 1064 nm pumping source. As the results, a conversion efficiency of 58.3% at 532 nm was obtained for NLBO, and whereas only 21.5% was obtained for LBO, indicating that NLBO is a highly attractive nonlinear material for frequency conversion of pulses into the visible and ultraviolet.