Giant Second Harmonic Generation Research Articles

Above-Room-Temperature Ferroelectricity and Giant Second Harmonic Generation in 1D vdW NbOI3.

The realization of spontaneous ferroelectricity down to the one-dimensional (1D) limit is both fundamentally intriguing and practically appealing for high-density ferroelectric and nonlinear photonics. However, the 1D vdW ferroelectric materials are not discovered experimentally yet. Here, the first 1D vdW ferroelectric compound NbOI3 with a high Curie temperature TC>450K and giant second harmonic generation (SHG) is reported. The 1D crystalline chain structure of the NbOI3 is revealed by cryo-electron microscopy, whereas the 1D ferroelectric order originated from the Nb displacement along the Nb-O chain (b-axis) is confirmed via obvious electrical and ferroelectric hysteresis loops. Impressively, NbOI3 exhibits a giant SHG susceptibility up to 1572pmV-1 at a fundamental wavelength of 810nm, and a further enhanced SHG susceptibility of 5582pmV-1 under the applied hydrostatic pressure of 2.06GPa. Combing in situ pressure-dependent X-ray diffraction, Raman spectra measurements, and first-principles calculations, it is demonstrated that the O atoms shift along the Nb─O atomic chain under compression, which can lead to the increased Baur distortion of [NbO2I4] octahedra, and hence induces the enhancement of SHG. This work provides a 1D vdW ferroelectric system for developing novel ferroelectronic and photonic devices.

Giant second-harmonic generation in monolayer MoS2 boosted by dual bound states in the continuum

Abstract Dielectric metasurfaces open new avenues in nonlinear optics through their remarkable capability of boosting frequency conversion efficiency of nonlinear optical interactions. Here, a metasurface consisting of a square array of cruciform-shaped silicon building blocks covered by a monolayer MoS2 is proposed. By designing the metasurface so that it supports optical bound states in the continuum (BICs) at the fundamental frequency and second harmonic, nearly 600× enhancement of the second-harmonic generation (SHG) in the MoS2 monolayer as compared to that of the same MoS2 monolayer suspended in air is achieved. To gain deeper insights into the physics of the metasurface-induced enhancement of nonlinear optical interactions, an eigenmode expansion method is employed to analytically investigate the main characteristics of SHG and the results show a good agreement with the results obtained via full-wave numerical simulations. In addition, a versatile nonlinear homogenization approach is used to highlight and understand the interplay between the BICs of the metasurface and the efficiency of the SHG process. This work suggests a promising method to enhance the nonlinear optical processes in two-dimensional materials, enabling the development of advanced photonic nanodevices.

Quasi-BICs enhanced second harmonic generation from WSe2 monolayer

Abstract Quasi-bound states in the continuum (quasi-BICs) offer unique advantages in enhancing nonlinear optical processes and advancing the development of active optical devices. Here, the tunable robust quasi-BICs resonances are experimentally achieved through the engineering of multiple-hole Si-metasurface. Notably, the quasi-BICs mode exhibits flat bands with minimal dispersion at a wide range of incident angles, as demonstrated by the angle-resolved spectroscopy measurements. Furthermore, we demonstrate a giant second-harmonic generation (SHG) enhancement by coupling a WSe2 monolayer to the quasi-BICs hosted in the metasurface. Leveraging the strong local electric field and high state density of the observed quasi-BICs, the SHG from the WSe2 monolayer can be enhanced by more than two orders of magnitude. Our work paves the way for effectively enhancing nonlinear optical processes in two dimensional (2D) materials within the framework of silicon photonics and is expected to be applied in nonlinear optical devices.

Giant Mid‐Infrared Second‐Harmonic Generation Response in a Densely‐Stacked Van Der Waals Transition‐Metal Oxychloride

AbstractSecond‐harmonic generation (SHG) is a fundamental optical property of nonlinear optical (NLO) crystals. Thus far, it has proved difficult to engineer large SHG responses, particularly in the mid‐infrared region, owing to the difficulty in simultaneously controlling the arrangement and density of functional NLO‐active units. Herein, a new assembly strategy employing functional modules only, and aimed at maximizing the density and optimizing the spatial arrangement of highly efficient functional modules, has been applied to the preparation of NLO crystals, affording the van der Waals crystal MoO2Cl2. This exhibits the strongest powder SHG response (2.1×KTiOPO4 (KTP) @ 2100 nm) for a transition‐metal oxyhalide, a wide optical transparency window, and a sufficient birefringence. MoO2Cl2 is the first SHG‐active transition‐metal oxyhalide effective in the infrared region. Theoretical studies and crystal structure analysis suggest that the densely packed, optimally‐aligned [MoO4Cl2] modules within the two‐dimensional van der Waals layers are responsible for the giant SHG response.

Giant Mid-Infrared Second-Harmonic Generation Response in a Densely-Stacked Van Der Waals Transition-Metal Oxychloride.

Second-harmonic generation (SHG) is a fundamental optical property of nonlinear optical (NLO) crystals. Thus far, it has proved difficult to engineer large SHG responses, particularly in the mid-infrared region, owing to the difficulty in simultaneously controlling the arrangement and density of functional NLO-active units. Herein, a new assembly strategy employing functional modules only, and aimed at maximizing the density and optimizing the spatial arrangement of highly efficient functional modules, has been applied to the preparation of NLO crystals, affording the van der Waals crystal MoO2 Cl2 . This exhibits the strongest powder SHG response (2.1×KTiOPO4 (KTP) @ 2100 nm) for a transition-metal oxyhalide, a wide optical transparency window, and a sufficient birefringence. MoO2 Cl2 is the first SHG-active transition-metal oxyhalide effective in the infrared region. Theoretical studies and crystal structure analysis suggest that the densely packed, optimally-aligned [MoO4 Cl2 ] modules within the two-dimensional van der Waals layers are responsible for the giant SHG response.

Quenching of second-harmonic generation by epsilon-near-zero media

Epsilon-near-zero (ENZ) media were demonstrated to exhibit unprecedented strong nonlinear optical properties including giant second-harmonic generation (SHG) due to their field-enhancement effect. Here, on the contrary, we report the quenching of SHG by the ENZ media. We find that when a tiny nonlinear particle is placed very close to a subwavelength ENZ particle, the SHG from the nonlinear particle can be greatly suppressed. The SHG quenching effect originates from the extraordinary prohibition of electric fields occurring near the ENZ particle due to evanescent scattering waves, which is found to be universal in both isotropic and anisotropic ENZ particles, irrespective of their shapes. Based on this principle, we propose a kind of dynamically controllable optical metasurface exhibiting switchable SHG quenching effect. Our work enriches the understanding of optical nonlinearity with ENZ media and could find applications in optical switches and modulators.

Manipulating Peierls Distortion in van der Waals NbOX2 Maximizes Second-Harmonic Generation.

Two-dimensional (2D) van der Waals (vdW) materials, featuring relaxed phase-matching conditions and highly tunable optical nonlinearity, endow them with potential applications in nanoscale nonlinear optical (NLO) devices. Despite significant progress, fundamental questions in 2D NLO materials remain, such as how structural distortion affects second-order NLO properties, which call for advanced regulation and in situ diagnostic tools. Here, by applying pressure to continuously tune the displacement of Nb atoms in 2D vdW NbOI2, we effectively modulate the polarization and achieve a 3-fold boost of the second-harmonic generation (SHG) at 2.5 GPa. By introducing a Peierls distortion parameter, λ, we establish a quantitative relationship between λ and SHG intensity. Importantly, we further demonstrate that the SHG enhancement can be achieved under ambient conditions by anionic substitution to tune the distortion in NbO(I1-xBrx)2 (x = 0-1) compounds, where the chemical tailoring simulates the pressure effects on the structural optimization. Consequently, NbO(I0.60Br0.40)2 with λ = 0.17 exhibits a giant SHG of over 2 orders of magnitude higher than that in monolayer WSe2, reaching the record-high value among reported 2D vdW NLO materials. This work unambiguously demonstrates the correlation between Peierls distortion and SHG property and, more broadly, opens new paths for the development of advanced NLO materials by manipulating the structure distortions.

Defect diamond-like tellurides as infrared nonlinear optical materials with giant second-harmonic generation tensor

As promising candidate for mid- and far-infrared (MFIR) nonlinear optical (NLO) materials, diamond-like (DL) chalcogenides have been extensively studied because of their considerable advantages. Among them, tellurides attract our attention as their stronger electron polarization and wider transmittance range than those of sulfides and selenides. Herein, the insightful structural characteristics and NLO properties of defect DL MGa2Te4 (M = Zn, Cd) were studied for the first time at experimental and theoretical level. They crystallize in the non-centrosymmetric I-4 space group (No.82), with a three-dimensional structure consisting of highly oriented [MTe4] and [GaTe4] tetrahedra, which can be viewed as derived from AgGaS2 (AGS). Experimental results illustrate that MGa2Te4 (M = Zn, Cd) exhibits moderate band gaps, strong SHG intensities about 4.9–10.6 times that of AGSe at 90–125 μm, and congruent-melting behavior. Theoretical calculations based on E-field DFPT method indicate that the tremendous SHG tensors d14 of ZnGa2Te4 and CdGa2Te4 are 127.67 and 105.19 pm/V. SHG-density analysis reveals that the lone-pair packets of Te ions in [GaTe4] units are the main source of SHG responses. In addition, calculations on Mulliken bond order index imply that the main difference between these two crystals is the bonding modes of M−Te. Special care was also given to ensure convergence of k-mesh for both conventional and primitive cells of the crystals, with two different methods for calculating linear and non-linear optical properties compared side by side. This work demonstrates the potential applications of these two defect DL tellurides in the MFIR NLO field.

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.

Cd2 Nb2 Te4 O15 : A Novel Pseudo-Aurivillius-Type Tellurite with Unprecedented Nonlinear Optical Properties and Excellent Stability.

Oxides are emerging candidates for mid-infrared (mid-IR) nonlinear optical (NLO) materials. However, their intrinsically weak second harmonic generation (SHG) effects hinder their further development. A major design challenge is to increase the nonlinear coefficient while maintaining the broad mid-IR transmission and high laser-induced damage threshold (LIDT) of the oxides. In this study, it is reported on a polar NLO tellurite, Cd2 Nb2 Te4 O15 (CNTO), featuring a pseudo-Aurivillius-type perovskite layered structure composed of three types of NLO active groups, including CdO6 octahedra, NbO6 octahedra, and TeO4 seesaws. The uniform orientation of the distorted units induces a giant SHG response that is ≈31 times larger than that of KH2 PO4 , the largest value among all reported metal tellurites. Additionally, CNTO exhibits a large band gap (3.75eV), a wide optical transparency window (0.33-14.5µm), superior birefringence (0.12@ 546nm), high LIDT (23×AgGaS2 ), and strong acid and alkali resistance, indicating its potential as a promising mid-IR NLO material.

Giant second-harmonic generation in ferroelectric NbOI2

Implementing nonlinear optical components in nanoscale photonic devices is challenged by phase-matching conditions requiring thicknesses in the order of hundreds of wavelengths, and is disadvantaged by the short optical interaction depth of nanometre-scale materials and weak photon–photon interactions. Here we report that ferroelectric NbOI2 nanosheets exhibit giant second-harmonic generation with conversion efficiencies that are orders of magnitude higher than commonly reported nonlinear crystals. The nonlinear response scales with layer thickness and is strain- and electrical-tunable; a record >0.2% absolute SHG conversion efficiency and an effective nonlinear susceptibility $$\chi _{\mathrm{eff}}^{(2)}$$ in the order of 10−9 m V−1 are demonstrated at an average pump intensity of 8 kW cm–2. Due to the interplay between anisotropic polarization and excitonic resonance in NbOI2, the spatial profile of the polarized SHG response can be tuned by the excitation wavelength. Our results represent a new paradigm for ultrathin, efficient nonlinear optical components. Strained NbOI2 flakes with a thickness of 20 nm exhibit a record SHG absolute conversion efficiency of >0.2% and an effective bulk-like nonlinear susceptibility of 1.1 × 10−9 m V−1 at the fundamental wavelength of 1,050 nm. The spatial profile of the polarized second-harmonic generation response can be tuned by the fundamental wavelength.

RbBiP2S6: A Promising IR Nonlinear Optical Material with a Giant Second-Harmonic Generation Response Designed by Aliovalent Substitution

RbBiP₂S₆: A Promising IR Nonlinear Optical Material with a Giant Second-Harmonic Generation Response Designed by Aliovalent Substitution

Observation of Giant Surface Second-Harmonic Generation Coupled to Nematic Orders in the van der Waals Antiferromagnet FePS3.

Second-harmonic generation has been applied to study lattice, electronic, and magnetic proprieties in atomically thin materials. However, inversion symmetry breaking is usually required for the materials to generate a large signal. In this work, we report a giant second-harmonic generation that arises below the Néel temperature in few-layer centrosymmetric FePS3. A layer-dependent study indicates the detected signal is from the second-order nonlinearity of the surface. The magnetism-induced surface second-harmonic response is 2 orders of magnitude larger than those reported in other magnetic systems, with the surface nonlinear susceptibility reaching 0.08-0.13 nm2/V in 2-5 L samples. By combing linear dichroism and second-harmonic generation experiments, we further confirm the giant second-harmonic generation is coupled to nematic orders formed by the three possible Zigzag antiferromagnetic domains. Our study shows that the surface second-harmonic generation is also a sensitive tool to study antiferromagnetic states in centrosymmetric atomically thin materials.

Giant Second-Harmonic Generation Response and Large Band Gap in the Partially Fluorinated Mid-Infrared Oxide RbTeMo2O8F.

Strong second-harmonic generation (SHG) and a wide band gap are two crucial but often conflicting parameters that must be optimized for practical nonlinear optical (NLO) materials. We report herein the first d0-transition-metal (TM) tellurite with half of the d0-TM-octahedra partially fluorinated, namely, quinary RbTeMo2O8F, which exhibits giant SHG responses (27 times that of KH2PO4 (KDP) and 2.2 times that of KTiOPO4 (KTP) with 1064 and 2100 nm laser radiation, respectively), the largest SHG values among all reported metal tellurites. RbTeMo2O8F also possesses a large band gap (3.63 eV), a wide optical transparency window (0.34-5.40 μm), and a significant birefringence (Δn = 0.263 at 546 nm). Theoretical calculations and crystal structure analysis demonstrate that the outstanding SHG responses can be definitively attributed to the uniform alignment of the polarized [MoO5F]/[MoO6] octahedra and the seesaw-like [TeO4], and the consequent favorable summative polarization of the three distinct SHG-active polyhedra, both induced by partial fluorine substitution on the [MoO6] octahedra.

Giant Enhancement of Continuous Wave Second Harmonic Generation from Few-Layer GaSe Coupled to High-Q Quasi Bound States in the Continuum.

Two-dimensional (2D) layered materials such as GaSe recently have emerged as novel nonlinear optical materials with exceptional properties. Although exhibiting large nonlinear susceptibilities, the nonlinear responses of 2D materials are generally limited by the short interaction lengths with light, thus further enhancement via resonant photonic nanostructures is highly desired for building high-efficiency nonlinear devices. Here, we demonstrate a giant second-harmonic generation (SHG) enhancement by coupling 2D GaSe flakes to silicon metasurfaces supporting quasi-bound states in the continuum (quasi-BICs) under continuous-wave (CW) operation. Taking advantage of both high-quality factors and large mode areas of quasi-BICs, SHG from a GaSe flake is uniformly enhanced by nearly 4 orders of magnitude, which is promising for high-power coherent light sources. Our work provides an effective approach for enhancing nonlinear optical processes in 2D materials within the framework of silicon photonics, which also brings second-order nonlinearity associated with 2D materials to silicon photonic devices.

Mg2In3Si2P7: A Quaternary Diamond-like Phosphide Infrared Nonlinear Optical Material Derived from ZnGeP2.

Balancing the second-harmonic generation (SHG) coefficient, band gap, and birefringence is a vital but addressable challenge for designing infrared nonlinear optical materials. By applying a "rigidity-flexibility coupling" strategy, a quaternary diamond-like phosphide, Mg2In3Si2P7, with wurtzite-type superstructure was successfully designed and synthesized. Remarkably, it achieved the rare coexistence of giant second-harmonic generation (2 × ZnGeP2 and 7.1 × AgGaS2), suitable band gap (2.21 eV), moderate birefringence (0.107), and wide IR transparent range (0.56-16.4 μm). First-principles calculations revealed that the giant SHG response and large birefringence can be attributed to the synergy of arrangement-aligned [InP4] and [SiP4] tetrahedra. This work not only opens a new avenue for designing advanced infrared nonlinear optical materials but also may spur more explorations on quaternary diamond-like pnictides.

Phase-matched optical second harmonic generation in a hyperbolic metamaterial based on silver nanorods

Artificial hyperbolic metamaterials (HMM) are perspective for the nonlinear optical applications, their exciting functionality being due to the hyperbolic dispersion induced by a strong shape anisotropy. Here we study the second harmonic generation (SHG) in HMM formed by arrays of silver nanorods in anodic alumina. In the hyperbolic dispersion regime, giant SHG is observed associated with the fulfillment of the phase-matching conditions supported by the epsilon-near-pole resonance at the SHG wavelength, and an increase in the pump field in the epsilon-near-zero (ENZ) spectral range. We predict a strong increase in the SHG efficiency for metamaterials with the ENZ resonance at the second harmonic frequency.

Nonreciprocal Terahertz Second-Harmonic Generation in Superconducting NbN under Supercurrent Injection.

Giant second-harmonic generation in the terahertz (THz) frequency range is observed in a thin film of an s-wave superconductor NbN, where the time-reversal (T) and space-inversion (P) symmetries are simultaneously broken by supercurrent injection. We demonstrate that the phase of the second-harmonic signal flips when the direction of supercurrent is inverted; i.e., the signal is ascribed to the nonreciprocal response that occurs under broken P and T symmetries. The temperature dependence of the SH signal exhibits a sharp resonance, which is accounted for by the vortex motion driven by the THz electric field in an anharmonic pinning potential. The maximum conversion ratio η_{SHG} reaches ≈10^{-2} in a thin film NbN with the thickness of 25nm after the field cooling with a very small magnetic field of ≈1 Oe, for a relatively weak incident THz electric field of 2.8 kV/cm at 0.48THz.

Chiral Second-Harmonic Generation from Monolayer WS2/Aluminum Plasmonic Vortex Metalens.

Two-dimensional spiral plasmonic structures have emerged as a versatile approach to generate near-field vortex fields with tunable topological charges. We demonstrate here a far-field approach to observe the chiral second-harmonic generation (SHG) at designated visible wavelengths from a single plasmonic vortex metalens. This metalens comprises an Archimedean spiral slit fabricated on atomically flat aluminum epitaxial film, which allows for precise tuning of plasmonic resonances and subsequent transfer of two-dimensional materials on top of the spiral slit. The nonlinear optical measurements show a giant SHG circular dichroism. Furthermore, we have achieved an enhanced chiral SHG conversion efficiency (about an order of magnitude greater than the bare aluminum lens) from monolayer tungsten disulfide (WS2)/aluminum metalens, which is designed at the C-exciton resonance of WS2. Since the C-exciton is not a valley exciton, the enhanced chiral SHG in this hybrid system originates from the plasmonic vortex field-enhanced SHG under the optical spin-orbit interaction.

Data-driven prediction of diamond-like infrared nonlinear optical crystals with targeting performances

Combining high-throughput screening and machine learning models is a rapidly developed direction for the exploration of novel optoelectronic functional materials. Here, we employ random forests regression (RFR) model to investigate the second harmonic generation (SHG) coefficients of nonlinear optical crystals with distinct diamond-like (DL) structures. 61 DL structures in Inorganic Crystallographic Structure Database (ICSD) are selected, and four distinctive descriptors, including band gap, electronegativity, group volume and bond flexibility, are used to model and predict second-order nonlinearity. It is demonstrated that the RFR model has reached the first-principles calculation accuracy, and gives validated predictions for a variety of representative DL crystals. Additionally, this model shows promising applications to explore new crystal materials of quaternary DL system with superior mid-IR NLO performances. Two new potential NLO crystals, Li2CuPS4 with ultrawide bandgap and Cu2CdSnTe4 with giant SHG response, are identified by this model.