Second Harmonic Generation Signal Research Articles

Time‐Resolved Optical Response of the Dicke's Model via the Nonequilibrium Green's Function Approach

Due to their conceptual appeal and computational convenience, two‐level systems (TLSs) and generalizations are used to investigate nonlinear behavior in quantum optics and assess the applicability of theoretical methods. Herein, the focus is on second‐harmonic generation (SHG) and, as system of interest, on the Dicke model, which consists of several TLSs inside an optical cavity. The main aspect addressed is the scope of nonequilibrium Green's function (NEGF) to describe the effect of inhomogeneities and electron–electron (e–e) interactions on the SHG signal. For benchmarking purposes, exact diagonalization (ED) results are also presented and discussed. SHG spectra obtained with NEGF and ED are found to be in very good mutual agreement in most situations. Furthermore, inhomogeneity in the TLS and e–e interactions reduce the SHG signal, and the reduction is stronger with inhomogeneity than with interactions. This trend is consistently noted across different (small to large) system sizes. Finally, a modified NEGF approach is proposed to account for cavity leakage, where the quantum photon fields are coupled to a bath of classical oscillators. As expected, within this mixed quantum‐classical scheme, a decrease in the intensity of the fluorescent spectra takes place depending on the entity of leakage.

Adequate laser focusing and signal acquisition conditions for 3D measurement of electric-field distribution by the E-FISHG method

Electric field measurement using electric-field-induced second-harmonic generation (E-FISHG) has attracted attention because of its non-invasiveness and high spatiotemporal resolution. In the electric field measurement by the E-FISHG method, the applied electric-field profile along the laser path outside the focal spot affects the second-harmonic generation (SHG) signal. We have proposed a method of calibrating and inferring the applied electric-field profile from the SHG distribution along the laser path. In our previous research, the successful inference of a relatively simple electric-field profile from a series of SHG signals was demonstrated. To measure more complex electric-field profiles, we apply our method to three cases of electric-field profiles: (1) the profile with different sharpness, (2) the profile with two peaks, and (3) the profile with noise superimposed on the SHG signal. The applied electric-field distribution can be inferred within 10% error by adequately choosing the confocal parameter. We also provide guidelines for the required signal acquisition region and measurement pitch when the approximate shape of the applied electric field is known, which are important for actual measurement.

Analysis of age-related changes in the left ventricular myocardium with multiphoton microscopy

Aging induces cardiac remodeling, resulting in an increase in the risk of suffering heart diseases, including heart failure. Collagen deposition increases with age and, together with sarcomeric changes in cardiomyocytes, may lead to ventricular stiffness. Multiphoton (MP) microscopy is a useful technique to visualize and detect variations in cardiac structures in a label free fashion. Here, we propose a method based on MP imaging (both two-photon excitation fluorescence (TPEF) and second harmonic generation (SHG) modalities) to explore and objectively quantify age-related structural differences in various components of cardiac tissues. Results in transmural porcine left ventricle (LV) sections reveal significant differences when comparing samples from young and old animals. Collagen and myosin SHG signals in old specimens are respectively 3.8x and >6-fold larger than in young ones. Differences in TPEF signals from cardiomyocyte were ∼3x. Moreover, the increased amount of collagen in old specimens results in a more organized pattern when compared to young LV tissues. Since changes in collagen and myosin are associated with cardiac dysfunction, the technique used herein might be a useful tool to accurately predict and measure changes associated with age-related myocardium fibrosis, tissue remodeling and sarcomeric alterations, with potential implications in preventing heart disease.

Optical Second Harmonic Generation of Low-Dimensional Semiconductor Materials.

In recent years, the phenomenon of optical second harmonic generation (SHG) has attracted significant attention as a pivotal nonlinear optical effect in research. Notably, in low-dimensional materials (LDMs), SHG detection has become an instrumental tool for elucidating nonlinear optical properties due to their pronounced second-order susceptibility and distinct electronic structure. This review offers an exhaustive overview of the generation process and experimental configurations for SHG in such materials. It underscores the latest advancements in harnessing SHG as a sensitive probe for investigating the nonlinear optical attributes of these materials, with a particular focus on its pivotal role in unveiling electronic structures, bandgap characteristics, and crystal symmetry. By analyzing SHG signals, researchers can glean invaluable insights into the microscopic properties of these materials. Furthermore, this paper delves into the applications of optical SHG in imaging and time-resolved experiments. Finally, future directions and challenges toward the improvement in the NLO in LDMs are discussed to provide an outlook in this rapidly developing field, offering crucial perspectives for the design and optimization of pertinent devices.

Centrosymmetry-Breaking Morphotropic Phase Boundary: A Pathway to Highly Sensitive and Strong Pressure-Responsive Nonlinear Optical Switches.

The quest for high-performance piezoelectric materials has been synonymous with the pursuit of the morphotropic phase boundary (MPB), yet the full potential of MPBs remains largely untapped outside of the realm of ferroelectrics. In this study, we reveal a new class of MPB by creating continuous molecular-based solid solutions between centro- and noncentrosymmetric compounds, exemplified by (tert-butylammonium)1-x(tert-amylammonium)xFeCl4 (0 ≤ x ≤ 1), where the MPB is formed due to disorder of molecular cations. Near the MPB, we discovered an exceptionally sensitive nonlinear optical material in the centrosymmetric phase, capable of activation at pressures as low as 0.12-0.27 GPa, and producing tunable second-harmonic generation (SHG) signals from zero to 18.8 times that of KH2PO4 (KDP). Meanwhile, synchrotron diffraction experiments have unveiled a third competing phase (P212121) appearing at low pressure, forming a triple-phase point near the MPB, thereby providing insight into the mechanism underpinning the nonlinear optical (NLO) switch behavior. These findings highlight the opportunity to harness exceptional physical properties in symmetry-breaking solid solution systems by strategically designing novel MPBs.

Giant Modulation of the Second Harmonic Generation by Magnetoelectricity in Two-Dimensional Multiferroic CuCrP2S6.

Multiferroic materials have attracted considerable attention owing to their unique magnetoelectric or magnetooptical properties. The recent discovery of few-layer van der Waalsmultiferroic crystals provides a new research direction for controlling the multiferroic properties in the atomic layer limit. However, research on few-layer multiferroic crystals is limited and the effect of thickness-dependent symmetries on those properties is less explored. In this study, the symmetries and magnetoelectric responses of van der Waals multiferroic CuCrP2S6 are investigated by optical second harmonic generation (SHG). Structural and magnetic phase transitions are successfully probed by the temperature-dependent SHG signals, revealing significant changes by applying the magnetic field reflecting the magnetoelectric effect. Moreover, it is found that symmetries and resultant magnetoelectric responses can be modulated by the number of layers. These results offer a new principle of controlling the multiferroicity and indicate that 2D van der Waals multiferroic material is a promising building block for functional nanodevices.

Terahertz-triggered ultrafast nonlinear optical activities in two-dimensional centrosymmetric PtSe2.

The nonlinear mechanisms of polarization and optical fields can induce extensive responses in materials. In this study, we report on two kinds of nonlinear mechanisms in the topological semimetal PtSe2 crystal under the excitation of intense terahertz (THz) pulses, which are manipulated by the real and imaginary parts of the nonlinear susceptibility of PtSe2. Regarding the real part, the broken inversion symmetry of PtSe2 is achieved through a THz-electric-field polarization approach, which is characterized by second harmonic generation (SHG) measurements. The transient THz-laser-induced SHG signal occurs within 100 fs and recombines to the equilibrium state within 1 ps, along with a high signal-to-noise ratio (∼51 dB) and a high on/off ratio (∼102). Regarding the imaginary part, a nonlinear absorption change can be generated in the media. We reveal a THz-induced absorption enhancement in PtSe2 via nonlinear transmittance measurements, and the sheet conductivity can be modulated up to 42% by THz electric fields in our experiment. Therefore, the THz-induced ultrafast nonlinear photoresponse reveals the application potential of PtSe2 in photonic and optoelectronic devices in the THz technology.

Infrared nonlinear optical materials with multiple strongly ionic cations

Infrared nonlinear optical (IR-NLO) crystals with excellent properties are in extensive demand due to their important role in IR laser technology. Currently, it remains a great challenge to obtain IR-NLO materials with both high second harmonic generation (SHG) response and large laser-induced damage thresholds (LIDTs). Some structural design strategies such as ‘structural/functional regions’ have been adopted to develop new high-performance NLO materials. The covalent structural region producing SHG signals has been extensively investigated, whereas the hard cations (alkali, alkaline-earth, and rare-earth metal ions) which are responsible for improving LIDTs, have been relatively neglected. Utilizing the concept of structural/functional regions, we focus on the relation between structural regions and SHG properties in chalcogenides. Combining different kinds of hard cations can change the dimension of structures and affect the stacking of NLO-active groups. Introducing more hard cations and constructing more complex ion regions help to increase the laser damage threshold. Based on the mentioned structural strategies, guidance will be provided for developing high-performance multiple-cation materials for IR NLO applications.

Label-free quantification of imaging features in the extracellular matrix of left and right-sided colon cancer tissues

The molecular pathogenesis of colorectal cancer is known to differ between the right and left side of the colon. Several previous studies have focussed on the differences in clinicopathological features, proteomic and genetic biomarkers, the composition of gut microbiota, response to therapy, and the characteristics of the tumour microenvironment. However, the morphology and density of collagen in the extracellular matrix (ECM) have not been studied intensively. In this study, we employed 2-photon laser scanning microscopy (2PLSM) to visualise the intrinsic second-harmonic generation (SHG) signal emitted by collagen fibres in the heterogeneous ECM of human colon tumour tissues. Through texture analysis of the SHG signal, we quantitatively distinguished the imaging features generated by structural differences of collagen fibres in healthy colon and cancers and found marked differences. The fibres inside of tumours exhibited a loss of organisation, particularly pronounced in right-sided colon cancer (RSCC), where the chaotic regions were significantly increased. In addition, a higher collagen content was found in left-sided colon cancer (LSCC). In future, this might aid in subclassification and therapeutic decisions or even in designing new therapy regimens by taking into account the differences between collagen fibres features between colon tumours located at different sides.

Plasmonic electro-optic modulators on lead zirconate titanate platform

Abstract The advancement in material platforms exhibiting strong and robust electro-optic effects is crucial for further progress in developing highly efficient and miniaturized optoelectronic components with low power consumption for modern optical communication systems. In this work, we investigate thin-film lead zirconate titanate (PZT) substrates grown by a chemical solution deposition technique as a potential platform for on-chip plasmonic electro-optic modulators. A high modulation depth (>40 %) is achieved with 15 μm-long electro-optic directional coupler modulators. An unusual cutoff in the modulation frequency response at ∼200 kHz is observed and further studied with respect to possible reorientation effects. Second-harmonic generation signals are found influenced by the externally applied electric field, indicating that the domain reorientation effect can be responsible for the unusual frequency response observed.

Modulating Polarization in Second Harmonic Generation through Symmetry Evolution in Plasmonic Lattices.

We report a strategy for preparing cost-effective plasmonic square lattices with tunable unit structures of circles, crosses, and circle-cross pairs on a centimeter scale. The asymmetrical electromagnetic (EM) field distribution of the lattice enhances second harmonic generation (SHG) under oblique incidence. The SHG signals are progressively strengthened as the unit symmetry decreases from C∞v (circle) to C4v (cross) to C2v (circle-cross pair). The peak SHG signal is observed from the plasmonic lattice with a circle-cross pair, showcasing a conversion efficiency of 1.0 × 10-2, which is a 7.3-fold enhancement relative to the dielectric lattice comprised of circle units. This notably high conversion efficiency of SHG is on par with that of phase-matched bulk nanostructures under normal incidence, benefiting from the Bloch-surface plasmon polariton (Bloch-SPP) modes associated with the distribution of the photonic local density of states (LDOS). Furthermore, the SHG emission exhibits distinctive directional and polarization characteristics as the unit symmetry is reduced. This work offers valuable insights into a structural symmetry-dependent SHG in plasmonic lattices and the way forward for the design of functional nonlinear plasmonic devices.

Polarization-resolved super-resolution second-harmonic generation imaging based on multifocal structured illumination microscopy.

Polarization-resolved second-harmonic generation (PSHG) microscopy is widely used in investigating the structural and morphological alterations of collagen. However, the resolution of second-harmonic generation (SHG) imaging remains constrained by optical diffraction, resulting in the polarization extraction of collagen characteristics from the average properties of collagen fibers. In this study, multifocal structured illumination microscopy (MSIM) was combined with PSHG to achieve polarization-resolved super-resolution imaging of second-harmonic generation signals. For the first time to our knowledge, periodic structures with an average pitch of 277 nm were observed in mouse tail tendons using optical microscopy, and the orientation angle of fibrils within each period was found to exhibit an alternating arrangement along the axis in a regular pattern.

Global imaging for polarization resolved second harmonic generation of WS2 monolayers

Second-harmonic generation (SHG) is a nonlinear optical effect enhanced by broken crystallin symmetry and is very sensitive to electronic structures. SHG has recently been applied to two-dimensional transition metals dichalcogenides (2D-TMDs). 2D-TMDs have been the focus of much recent research due to their ultrathin scale, high quantum confinement, and energy gap toning ability that results in unique linear or nonlinear optical and electrical properties. WS2 monolayers are well-known 2D TMDs with strong SHG. They have attracted a great deal of interest due to their potential applications in fundamental material characterization and nanophotonic device development. In this study, we grew WS2 monolayers using the chemical vapor deposition (CVD) technique and characterized them with Raman and photoluminescence (PL) spectroscopy. The intense direct excitonic peak A at 630 nm was identified in the PL spectra, while the Raman spectra exhibited the two distinctive modes A1g (at 418 cm−1) and E2g (at 356 cm−1). The monolayers were pumped by an 830 nm circularly polarized and defused pulsed laser to produce the SHG image. global one-shot SH images for different growth shapes were obtained and crystalline domains were identified using polarization-resolved second-harmonic generation imaging (PRSHGI). The defect level was observed to clearly enhance the SHG signal following the increase in broken crystalline centrosymmetric and relaxing the optical selection roles at the valley degree of freedom.

Coherent control of enhanced second-harmonic generation in a plasmonic nanocircuit using a transition metal dichalcogenide monolayer

Nonlinear nanophotonic circuits, renowned for their compact form and integration capabilities, hold potential for advancing high-capacity optical signal processing. However, limited practicality arises from low nonlinear conversion efficiency. Transition metal dichalcogenides (TMDs) could present a promising avenue to address this challenge, given their superior optical nonlinear characteristics and compatibility with diverse device platforms. Nevertheless, this potential remains largely unexplored, with current endeavors predominantly focusing on the demonstration of TMDs’ coherent nonlinear signals via free-space excitation and collection. In this work, we perform direct integration of TMDs onto a plasmonic nanocircuitry. By controlling the polarization angle of the input laser, we show selective routing of second-harmonic generation (SHG) signals from a MoSe2 monolayer within the plasmonic circuit. Routing extinction ratios of 14.86 dB are achieved, demonstrating good coherence preservation in this hybrid nanocircuit. Additionally, our characterization indicates that the integration of TMDs leads to a 13.8-fold SHG enhancement, compared with the pristine nonlinear plasmonic nanocircuitry. These distinct features—efficient SHG generation, coupling, and controllable routing—suggest that our hybrid TMD-plasmonic nanocircuitry could find immediate applications including on-chip optical frequency conversion, selective routing, switching, logic operations, as well as quantum operations.

Supramolecular Metal Halide Complexes for High-Temperature Nonlinear Optical Switches.

Nonlinear optical (NLO) switching materials, which exhibit reversible intensity modulation in response to thermal stimuli, have found extensive applications across diverse fields including sensing, photoelectronics, and photonic applications. While significant progress has been made in solid-state NLO switching materials, these materials typically showcase their highest NLO performance near room temperature. However, this performance drastically deteriorates upon heating, primarily due to the phase transition undergone by the materials from noncentrosymmetric to centrosymmetric phase. Here, we introduce a new class of NLO switching materials, solid-state supramolecular compounds 18-Crown-6 ether@Cu2Cl4·4H2O (1·4H2O), exhibiting reversible and stable NLO switching when subjected to near-infrared (NIR) photoexcitation and/or thermal stimuli. The reversible crystal structure in response to external stimuli is attributed to the presence of a weakly coordinated bridging water molecule facilitated by hydrogen bonding/chelation interactions between the metal halide and crown-ether supramolecules. We observed an exceptionally high second-harmonic generation (SHG) signal under continuous photoexcitation, even at temperatures exceeding 110 °C. In addition, the bridging water molecules within the complex can be released and recaptured in a fully reversible manner, all without requiring excessive energy input. This feature allows for precise control of SHG signal activation and deactivation through structural transformations, resulting in a high-contrast off/on ratio, reaching values in the million-fold range.

1D Tin(II)‐Based Chiral Hybrid Perovskite Single Crystals with Extremely Distorted Inorganic Chains for Second Harmonic Generation

AbstractThe organic–inorganic hybrid metal halides with chiral structures have attracted great attentions in the field of optoelectronic functional materials, especially for nonlinear optics. To date, second harmonic generation (SHG) properties of several classes of chiral hybrid halides with different metal ions have been reported. However, SHG‐active tin(II)‐based chiral materials are rarely explored, hindering deep understandings of the relationship between their structures and SHG properties. Herein, Sn2+ ions are successfully introduced into chiral hybrid perovskites, and four new species of chiral hybrid perovskites (R/S‐α‐PEA)SnX3 (X = Cl and Br, PEA = phenylethylammonium) are obtained. The as‐grown crystals are in P212121 space group, with highly distorted [SnX6] octahedral units forming 1D chain structures in the lattice, due to the effect of stereochemically active lone pair 5s2 electrons in Sn2+. Such crystals have an SHG response of ≈1.4× Y‐cut α‐quartz for (S‐α‐PEA)SnBr3 and ≈0.9× Y‐cut α‐quartz for (S‐α‐PEA)SnCl3 at 1020 nm excitation, with high polarization ratio of SHG signals as well as wide bandgaps and transparency windows in the meanwhile. This work opens up a new platform for discovering more novel tin(II)‐based chiral perovskites with superior nonlinear optical properties in the future.

Excited States Dynamics at Pentacene/Perfluoropentacene Interfaces: A Femtosecond Time-Resolved Second Harmonic Generation Study.

Understanding the dynamics of excited states after optical excitation at donor-acceptor (D/A) interfaces is of paramount importance for improving the efficiency and performance of optoelectronic devices. Here, we studied the ultrafast excited state dynamics after optical excitation at interfaces between the electron donor (D) pentacene (PEN) and the electron acceptor (A) perfuoropentacene (PFP) as well as within the single compounds (PEN and PFP) using femtosecond (fs) time-resolved second harmonic generation (SHG). In the single compounds singlet fission is observed on a time scale of around 200 fs. In the bilayer systems a huge SHG intensity rise is observed due to the creation of charge transfer states at the interface and accordingly to formation of a local electric field within tens of picoseconds. The local electric field and therefore the SHG signal intensity from the interface of PEN/PFP bilayer is much more intense compared to the PFP/PEN system because the PFP and PEN intermixing at the PEN/PFP interface is higher. Accordingly a population of defect states on a time scale of 55±12 ps has been proposed for PEN/PFP. Our study provides important insights into D/A charge transfer properties, which is needed for the understanding of the interfacial photophysics of pentacene-based organic compounds.

Second harmonic generation in an anisotropic lithium niobate metasurface governed by quasi-BICs

Resonant metasurfaces can greatly trap the light fields, so that they are widely used to enhance light–matter interactions at the nanoscale, such as promoting nonlinear effects of materials. Lithium niobate (LN) is an excellent nonlinear optical material and is often employed to generate harmonic signals. In this Letter, we numerically study the second harmonic generation (SHG) characteristics of the LN metasurface based on the quasi-bound states in the continuum (QBIC). The designed BIC and excited QBIC metasurfaces always hold C4v symmetry, and the BIC is demonstrated to degenerate into two BICs due to the anisotropic characteristics of LN. Moreover, the excited two high Q-factor QBICs can effectively enhance the SHG in LN, although the device maintains C4v symmetry, the SHG signal still shows polarization dependence. In addition, with the increase of Q-factor of quasi-BIC, the power and conversion efficiency (η) of SHG increase significantly. The calculated η can reach 6.04 × 10−3 and can be further improved when the resonance mode is closer to BIC. These results have important implications for high-quality nonlinear light sources based on LN materials.

A Universal Strategy for Synthesis of 2D Ternary Transition Metal Phosphorous Chalcogenides.

The 2D ternary transition metal phosphorous chalcogenides (TMPCs) have attracted extensive research interest due to their widely tunable band gap, rich electronic properties, inherent magnetic and ferroelectric properties. However, the synthesis of TMPCs via chemical vapor deposition (CVD) is still challenging since it is difficult to control reactions among multi-precursors. Here, a subtractive element growth mechanism is proposed to controllably synthesize the TMPCs. Based on the growth mechanism, the TMPCs including FePS3 , FePSe3 , MnPS3 , MnPSe3 , CdPS3 , CdPSe3 , In2 P3 S9 , and SnPS3 are achieved successfully and further confirmed by Raman, second-harmonic generation (SHG), and scanning transmission electron microscopy (STEM). The typical TMPCs-SnPS3 shows a strong SHG signal at 1064nm, with an effective nonlinear susceptibility χ(2) of 8.41×10-11 mV-1 , which is about 8 times of that in MoS2 . And the photodetector based on CdPSe3 exhibits superior detection performances with responsivity of 582mAW-1 , high detectivity of 3.19×1011 Jones, and fast rise time of 611µs, which is better than most previously reported TMPCs-based photodetectors. These results demonstrate the high quality of TMPCs and promote the exploration of the optical properties of 2D TMPCs for their applications in optoelectronics.

Mask R-CNN provides efficient and accurate measurement of chondrocyte viability in the label-free assessment of articular cartilage

ObjectiveChondrocyte viability (CV) can be measured with the label-free method using second harmonic generation (SHG) and two-photon excitation autofluorescence (TPAF) imaging. To automate the image processing for the label-free CV measurement, we previously demonstrated a two-step deep-learning method: Step 1 used a U-Net to segment the lacuna area on SHG images; Step 2 used dual CNN networks to count live cells and the total number of cells in extracted cell clusters from TPAF images. This study aims to develop one-step deep learning methods to improve the efficiency of CV measurement. MethodTPAF/SHG images were acquired simultaneously on cartilage samples from rats and pigs using two-photon microscopes and were merged to form RGB color images with red, green, and blue channels assigned to emission bands of oxidized flavoproteins, reduced forms of nicotinamide adenine dinucleotide, and SHG signals, respectively. Based on the Mask R-CNN, we designed a deep learning network and its denoising version using Wiener deconvolution for CV measurement. ResultsUsing training and test datasets from rat and porcine cartilage, we have demonstrated that Mask R-CNN-based networks can segment and classify individual cells with a single-step processing flow. The absolute error (difference between the measured and the ground-truth CV) of the CV measurement using the Mask R-CNN with or without Wiener deconvolution denoising reaches 0.01 or 0.08, respectively; the error of the previous CV networks is 0.18, significantly larger than that of the Mask R-CNN methods. ConclusionsMask R-CNN-based deep-learning networks improve efficiency and accuracy of the label-free CV measurement.