Nonlinear Optical Properties of 2D Materials and their Applications.

2D materials are a subject of intense research in recent years owing to their exclusive photoelectric properties. With giant nonlinear susceptibility and perfect phase matching, 2D materials have marvelous nonlinear light-matter interactions. The nonlinear optical properties of 2D materials are of great significance to the design and analysis of applied materials and functional devices. Here, the fundamental of nonlinear optics (NLO) for 2D materials is introduced, and the methods for characterizing and measuring second-order and third-order nonlinear susceptibility of 2D materials are reviewed. Furthermore, the theoretical and experimental values of second-order susceptibility χ(2) and third-order susceptibility χ(3) are tabulated. Several applications and possible future research directions of second-harmonic generation (SHG) and third-harmonic generation (THG) for 2D materials are presented.

Harmonic Imaging of Stem Cells in Whole Blood at GHz Pixel Rate.

The pre-clinical validation of cell therapies requires monitoring the biodistribution of transplanted cells in tissues of host organisms. Real-time detection of these cells in the circulatory system and identification of their aggregation state is a crucial piece of information, but necessitates deep penetration and fast imaging with high selectivity, subcellular resolution, and high throughput. In this study, multiphoton-based in-flow detection of human stem cells in whole, unfiltered blood is demonstrated in a microfluidic channel. The approach relies on a multiphoton microscope with diffractive scanning in the direction perpendicular to the flow via a rapidly wavelength-swept laser. Stem cells are labeled with metal oxide harmonic nanoparticles. Thanks to their strong and quasi-instantaneous second harmonic generation (SHG), an imaging rate in excess of 10 000 frames per second is achieved with pixel dwell times of 1 ns, a duration shorter than typical fluorescence lifetimes yet compatible with SHG. Through automated cell identification and segmentation, morphological features of each individual detected event are extracted and cell aggregates are distinguished from isolated cells. This combination of high-speed multiphoton microscopy and high-sensitivity SHG nanoparticle labeling in turbid media promises the detection of rare cells in the bloodstream for assessing novel cell-based therapies.

Low Temperature Synthesis of 2D p-Type α-In2Te3 with Fast and Broadband Photodetection.

2D A 2 III B 3 VI ${\mathrm{A}}_2^{{\mathrm{III}}}{\mathrm{B}}_3^{{\mathrm{VI}}}$ compounds (A = Al, Ga, In, and B = S, Se, and Te) with intrinsic structural defects offer significant opportunities for high-performance and functional devices. However, obtaining 2D atomic-thin nanoplates with non-layered structure on SiO2/Si substrate at low temperatures is rare, which hinders the study of their properties and applications at atomic-thin thickness limits. In this study, the synthesis of ultrathin, non-layered α-In2Te3 nanoplates is demonstrated using a BiOCl-assisted chemical vapor deposition method at a temperature below 350 °C on SiO2/Si substrate. Comprehensive characterization results confirm the high-quality single crystal is the low-temperature cubic phase α-In2Te3 , possessing a noncentrosymmetric defected ZnS structure with good second harmonic generation. Moreover, α-In2Te3 is revealed to be a p-type semiconductor with a direct and narrow bandgap value of 0.76 eV. The field effect transistor exhibits a high mobility of 18 cm2 V-1 s-1, and the photodetector demonstrates stable photoswitching behavior within a broadband photoresponse from 405 to 1064 nm, with a satisfactory response time of τrise = 1 ms. Notably, the α-In2Te3 nanoplates exhibit good stability against ambient environments. Together, these findings establish α-In2Te3 nanoplates as promising candidates for next-generation high-performance photonics and electronics.

Stereo-Active Lone Pairs Induced Second Harmonic Generation Responses and Electrocatalytic Activity in Hybrid Material.

The lone pair electrons in the electronic structure of molecules have been a prominent research focus in chemistry for more than a century. Stable s2lone pair electrons significantly influence material properties, including thermoelectric properties, nonlinear optical properties, ferroelectricity, and electro(photo)catalysis.While major advances have been achieved in understanding the influence of lone pair electrons on material characteristics, research on this effect in organic-inorganic hybrid materials is in its initial stage. In this work, we successfully obtained a novel organic-inorganic hybrid material incorporating Ge with 4s2 lone pair electrons, (MeHDabco)2[GeBr3]4-H2O (MeHDabco = N-methyl-1,4-diazabicyclo[2.2.2]octane) (1). Driven by the stereochemically active lone pair electrons on the Ge2+, 1 crystallizes in the noncentrosymmetric space group P21 at room temperature and exhibits good second harmonic generation (SHG) responses. Interestingly, 1 also shows electrocatalytic activity for the hydrogen evolution reaction due to the existence of lone pair electrons on Ge2+ cations. The electrochemical experiment combined with the DFT calculations revealed the lone pair electrons act as both an active site for proton adsorption and facilitate the ionization of water. This work not only emphasizes the important role of lone pair electrons in material properties and functions but also provides new insight for designing novel Ge-based hybrid materials.

Temperature-Switch-Controlled Second Harmonic Mode Sensor for Brain-Tissue Detection.

Identifying brain-tissue types holds significant research value in the biomedical field of non-contact brain-tissue measurement applications. In this paper, a layered metastructure is proposed, and the second harmonic generation (SHG) in a multilayer metastructure is derived using the transfer matrix method. With the SHG conversion efficiency (CE) as the measurement signal, the refractive index ranges that can be distinguished are 1.23~1.31 refractive index unit (RIU) and 1.38~1.44 RIU, with sensitivities of 0.8597 RIU-1 and 1.2967 RIU-1, respectively. It can distinguish various brain tissues, including gray matter, white matter, and low-grade glioma, achieving the function of a second harmonic mode sensor (SHMS). Furthermore, temperature has a significant impact on the SHG CE, which can be used to define the switch signal indicating whether the SHMS is functioning properly. When the temperature range is 291.4~307.9 Kelvin (K), the temperature switch is in the "open" state, and the optimal SHG CE is higher than 0.298%, indicating that the SHMS is in the working state. For other temperature ranges, the SHG CE will decrease significantly, indicating that the temperature switch is in the "off" state, and the SHMS is not working. By stimulating temperature and using the response of SHG CE, the temperature-switch function is achieved, providing a new approach for temperature-controlled second harmonic detection.

Compact Metasurface-Based Optical Pulse-Shaping Device.

Dispersion is present in every optical setup and is often an undesired effect, especially in nonlinear-optical experiments where ultrashort laser pulses are needed. Typically, bulky pulse compressors consisting of gratings or prisms are used to address this issue by precompensating the dispersion of the optical components. However, these devices are only able to compensate for a part of the dispersion (second-order dispersion). Here, we present a compact pulse-shaping device that uses plasmonic metasurfaces to apply an arbitrarily designed spectral phase delay allowing for a full dispersion control. Furthermore, with specific phase encodings, this device can be used to temporally reshape the incident laser pulses into more complex pulse forms such as a double pulse. We verify the performance of our device by using an SHG-FROG measurement setup together with a retrieval algorithm to extract the dispersion that our device applies to an incident laser pulse.

Plasmonic Nonlinear Energy Transfer Enhanced Second Harmonic Generation Nanoscopy.

Nonlinear optical response is a fingerprint of various physicochemical properties of materials related to symmetry, including crystallography, interfacial configuration, and carrier dynamics. However, the intrinsically weak nonlinear optical susceptibility and the diffraction limit of far-field optics restrict probing deep-subwavelength-scale nonlinear optics with measurable signal-to-noise ratio. Here, we propose an alternative approach toward efficient second harmonic generation (SHG) nanoscopy for SHG-active sample (zinc oxide nanowire; ZnO NW) using an SHG-active plasmonic nanotip. Our full-wave simulation suggests that the experimentally observed high near-field SHG contrast is possible when the nonlinear response of ZnO NW is enhanced and/or that of the tip is suppressed. This result suggests possible evidence of quantum mechanical nonlinear energy transfer between the tip and the sample, modifying the nonlinear optical susceptibility. Further, this process probes the nanoscale corrosion of ZnO NW, demonstrating potential use in studying various physicochemical phenomena in nanoscale resolution.

From Cd(SCN)2(CH4N2S)2 to Cd(SCN)2(C4H6N2)2: Controlling Sulfur Content in Thiocyanate Systems Significantly Improves the Overall Performance of UV Nonlinear Optical Materials.

Combining a strong second-order nonlinear optical (NLO) effect (>1×KH2PO4 (KDP)), a large band gap (>4.2 eV), and a moderate birefringence in ultraviolet (UV) NLO crystals remains a formidable challenge. Herein, Cd(SCN)2(C4H6N2)2, the first example of a thiocyanate capable of realizing a phase-matched UV NLO crystal material, is obtained by reducing the sulfur (S) content in the centrosymmetric (CS) structure of Cd(SCN)2(CH4N2S)2. Compared to the "shoulder-to-shoulder" one-dimensional (1D) chain of Cd(SCN)2(CH4N2S)2, Cd(SCN)2(C4H6N2)2 has a different sawtooth 1D chain structure. Cd(SCN)2(CH4N2S)2 has second harmonic generation (SHG) inertia with a band gap of 3.90 eV and a UV cutoff edge of 342 nm, however, it possesses a large birefringence (0.35@546 nm). In contrast, the symmetry center breaking of Cd(SCN)2(C4H6N2)2 leads to remarkably strong SHG intensity (10 times that of KDP). Furthermore, it has a wide band gap (4.74 eV), short UV cutoff edge (234 nm), and moderate birefringence capable of phase matching (0.17@546 nm). This research indicates that thiocyanates are a promising class of UV NLO crystal materials, and that modulation of the sulfur content of CS thiocyanates is an effective strategy for the development of UV NLO crystals with excellent overall performances.

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 (3.75 eV), a wide optical transparency window (0.33-14.5 µm), superior birefringence (0.12@ 546 nm), high LIDT (23 × AgGaS2 ), and strong acid and alkali resistance, indicating its potential as a promising mid-IR NLO material.

Nonlinear All-Optical Coherent Generation and Read-Out of Valleys in Atomically Thin Semiconductors.

With conventional electronics reaching performance and size boundaries, all-optical processes have emerged as ideal building blocks for high speed and low power consumption devices. A promising approach in this direction is provided by valleytronics in atomically thin semiconductors, where light-matter interaction allows to write, store, and read binary information into the two energetically degenerate but non-equivalent valleys. Here, nonlinear valleytronics in monolayer WSe2 is investigated and show that an individual ultrashort pulse with a photon energy tuned to half of the optical band-gap can be used to simultaneously excite (by coherent optical Stark shift) and detect (by a rotation in the polarization of the emitted second harmonic) the valley population.

Polarization-Independent Second Harmonic Generation in 2D Van Der Waals Kagome Nb3 SeI7 Crystals.

Second harmonic generation (SHG) of 2D crystals has been of great interest due to its advantages of phase-matching and easy integration into nanophotonic devices. However, the polarization-dependence character of the SHG signal makes it highly troublesome but necessary to match the laser polarization orientation relative to the crystal, thus achieving the maximum polarized SHG intensity. Here, it is demonstrated a polarization-independent SHG, for the first time, in the van der Waals Nb3 SeI7 crystals with a breathing Kagome lattice. The Nb3 triangular clusters and Janus-structure of each Nb3 SeI7 layer are confirmed by the STEM. Nb3 SeI7 flake shows a strong SHG response due to its noncentrosymmetric crystal structure. More interestingly, the SHG signals of Nb3 SeI7 are independent of the polarization of the excitation light owing to the in-plane isotropic arrangement of nonlinear active units. This work provides the first layered nonlinear optical crystal with the polarization-independent SHG effect, providing new possibilities for nonlinear optics.

Controlling the Nonlinear Optical Behavior and Structural Transformation with A-Site Cation in α-AZnPO4 (A = Li, K).

Regulating the crystal structure by A-site cation substitution is one of the effective methods to explore high-performance nonlinear optical (NLO) materials. Herein, two non-centrosymmetric (NCS) compounds, α-MZnPO4 (M = Li, K) with short UV absorption edges 221 and 225 nm, are obtained by performing A-site cation substitution method. It is noteworthy that α-LiZnPO4 (α-LZPO) achieves >10 times second harmonic generation (SHG) response (2.3 × KDP) enhancement compared with that of α-KZnPO4 (α-KZPO) (0.2 × KDP), which is the only case among phosphates with different A-site cations. By structural comparison, it is found that the A-site cations play important roles for anion rearrangements, and further the structure features of the two compounds by designing two suppositional crystal models as well as performing other theoretical calculations are analyzed. The study confirms the feasibility to design promising NLO materials with strengthen SHG response and structural stability in orthophosphate system.

Polarity and Dielectric Property Control Triggered by a Coordinated Solvent Molecule Exchange in Luminescent Mononuclear Aluminium(III) Complexes.

The development of molecule-based multifunctional switchable materials that exhibit a switch of polarity and dielectric property are extremely limited. We have demonstrated solvent-vapour-induced reversible molecular rearrangements between nonpolar crystals [Al(sap)(acac)(sol)] (H2 sap=2-salicylideneaminophenol, acac=acetylacetonate, sol=MeOH (1), EtOH (2)) and polar crystal [Al(sap)(acac)(DMSO)] (3). This crystal-to-crystal structural transformation was accompanied by a switch of second harmonic generation (SHG) and dielectric properties, including the formation of ferroelectric domains, thus reflecting the SHG-active polar Cc space group of 3. This is the first reported example of dielectric properties and polarity switching in luminescent mononuclear aluminium(III) complexes, which exhibit strong green emission in the solid state.

Anion Tuned Structural Modulation and Nonlinear Optical Effects of Metal-Ion Directed 310 -Helix Networks.

Metals play an important role in the structure and functions of various proteins. The combination of metal ions and peptides have been emerging as an attractive field to create advanced structures and biomaterials. Here, we are reporting the anion-influenced, silver ion coordinated diverse networks of designed short tripeptide 310 -helices with terminal pyridyl groups. The short peptides adopted classical right-handed, left-handed and 310 EL -helical conformations in the presence of different silver salts. The peptides have displayed conformational flexibility to accommodate different sizes and interactions of anions to yield a variety of metal-coordinated networks. The complexes of metal ions and peptides have shown different porous networks, right- and left-handed helical polymers, transformation of helix into superhelix and 2 : 2 metal-peptide macrocycles. Further, the metal-peptide crystals with inherent dipoles of helical peptides gave striking second harmonic generation response. The optical energy upconversion from NIR to red and green light is demonstrated. Overall, we have shown the utilization of short 310 -helices for the construction of diverse metal-coordinated helical networks and notable non-linear optical effects.

In-depth polarisation resolved SHG microscopy in biological tissues using iterative wavefront optimisation.

Polarised nonlinear microscopy has been extensively developed to study molecular organisation in biological tissues, quantifying the response of nonlinear signals to a varying incident linear polarisation. Polarisation Second harmonic Generation (PSHG) in particular is a powerful tool to decipher sub-microscopic modifications of fibrillar collagen organisation in type I and III collagen-rich tissues. The quality of SHG imaging is however limited to about one scattering mean free path in depth (typically 100 micrometres in biological tissues), due to the loss of focus quality, induced by wavefront aberrations and scattering at even larger depths. In this work, we study how optical depth penetration in biological tissues affects the quality of polarisation control, a crucial parameter for quantitative assessment of PSHG measurements. We apply wavefront shaping to correct for SHG signal quality in two regimes, adaptive optics for smooth aberration modes corrections at shallow depth, and wavefront shaping of higher spatial frequencies for optical focus correction at larger depths. Using nonlinear SHG active nanocrystals as guide stars, we quantify the capabilities of such optimisation methods to recover a high-quality linear polarisation and investigate how this approach can be applied to in-depth PSHG imaging in tissues, namely tendon and mouse cranial bone.

Enhanced second harmonic generation from a quasi-periodic silver dendritic metasurface.

The preparation of the vast majority of nonlinear optical metal metasurfaces currently relies on complex top-down methods such as electron beam or ion beam etching, which are expensive and difficult to meet the requirement of large area preparation. In this paper, an easily prepared quasi-periodic silver dendritic metasurface model with highQfactor is established in the near-infrared band based on a simple and easy-to-operate electrochemical deposition method. The simulations prove that the silver dendritic metasurface has a highQfactor (exceeds 104) because of its strong electric field localization ability, which is analogous to the superposition of multiple split-ring resonators. It is demonstrated that the second harmonic generation (SHG) intensity of the dendritic metasurface at a large incident angle (such as 85°) is about 30 times that of the metasurface at a small incident angle when thex-polarized pump light is incident obliquely to break the centrosymmetry of the metasurface. The influences of the incident angle or dendritic structure's dimensions on theQfactor and SHG efficiency have also been researched through a lot of simulation. This easily prepared quasi-periodic silver dendritic metasurface SHG device may provide a new avenue for the development and application of miniature, integratable nonlinear optical devices.

Synthesis, Structural, Spectroscopic, Fluorescence, and Dielectric Studies of Bis-(4-Aminopyridine)-Zinc(II) Acetate: A Metal-Organic Crystal.

The advancement of crystalline growth and characterization tools allows us to investigate novel nonlinear optical substances suitable for photonic applications. Bis-(4-aminopyridine)-zinc(II) acetate (B4AZA), a metal-organic crystal was produced in this study using the slow evaporation procedure at room temperature. Analytical studies such as X-ray crystallography, Fourier transform infrared (FT-IR), UV-visible (UV-Vis), fluorescence, second harmonic generation (SHG), and dielectric tests were used to characterize the as-grown B4AZA crystals. According to the solubility data, the sample has a positive temperature coefficient of solubility. The crystallographic findings show that the B4AZA crystallized in a monoclinic structure with the P21/n space group. Molecular vibrations and functional groups in the substance were determined using the FT-IR technique. The UV-Vis absorbance and transmittance spectra have shown the wide transparency and minimum absorbance of the B4AZA in the near UV and entire visible regions of the electromagnetic spectrum. The bandgap of the B4AZA has been calculated using the Tauc relation and found to be 4.32 eV. The fluorescence spectra have shown a prominent emission peak at 584 nm with an excitation wavelength of 280 nm. The larger Stokes shift found in the fluorescence spectra is advantageous for practical applications. The SHG study revealed that the powdered B4AZA samples generated a second harmonic output. The dielectric test revealed frequency-dependent changes in the dielectric constant and loss factor. Both the dielectric constant and the loss factor decrease exponentially as frequency increases, reaching low values at higher frequencies. The experimental results illustrate the suitability of the B4AZA crystals for photonic applications.

Label-free 3D characterization of cardiac fibrosis in muscular dystrophy using SHG imaging of cleared tissue.

BACKGROUND INFORMATION: Duchenne muscular dystrophy (DMD) is a neuromuscular disease caused by mutations in the gene encoding dystrophin. It leads to repeated cycles of muscle fiber necrosis and regeneration and progressive replacement of fibers by fibrotic and adipose tissue, with consequent muscle weakness and premature death. Fibrosis and, in particular, collagen accumulation are important pathological features of dystrophic muscle. A better understanding of the development of fibrosis is crucial to enable better management of DMD. Three-dimensional (3D) characterization of collagen organization by second harmonic generation (SHG) microscopy has already proven a highly informative means of studying the fibrotic network in tissue. RESULTS: Here, we combine for the first-time tissue clearing with SHG microscopy to characterize in depth the 3D cardiac fibrosis network from DMDmdx rat model. Heart sections (1-mm-thick) from 1-year-old wild-type (WT) and DMDmdx rats were cleared using the CUBIC protocol. SHG microscopy revealed significantly greater collagen deposition in DMDmdx versus WT sections. Analyses revealed a specific pattern of SHG+ segmented objects in DMDmdx cardiac muscle, characterized by a less elongated shape and increased density. Compared with the observed alignment of SHG+ collagen fibers in WT rats, profound fiber disorganization was observed in DMDmdx rats, in which we observed two distinct SHG+ collagen fiber profiles, which may reflect two distinct stages of the fibrotic process in DMD. CONCLUSION AND SIGNIFICANCE: The current work highlights the interest to combine multiphoton SHG microscopy and tissue clearing for 3D fibrosis network characterization in label free organ. It could be a relevant tool to characterize the fibrotic tissue remodeling in relation to the disease progression and/or to evaluate the efficacy of therapeutic strategies in preclinical studies in DMD model or others fibrosis-related cardiomyopathies diseases.

Organization of collagen fibers and tissue hardening: Markers of fibrotic scarring after spinal cord injury in mice revealed by multiphoton-atomic force microscopy imaging.

Spinal cord injury is a dramatic disease leading to severe motor, sensitive and autonomic impairments. After injury the axonal regeneration is partly inhibited by the glial scar, acting as a physical and chemical barrier. The scarring process involves microglia, astrocytes and extracellular matrix components, such as collagen, constructing the fibrotic component of the scar. To investigate the role of collagen, we used a multimodal label-free imaging approach combining multiphoton and atomic force microscopy. The second harmonic generation signal exhibited by fibrillar collagen enabled to specifically monitor it as a biomarker of the lesion. An increase in collagen density and the formation of more tortuous fibers over time after injury are observed. Nano-mechanical investigations revealed a noticeable hardening of the injured area, correlated with collagen fibers' formation. These observations indicate the concomitance of important structural and mechanical modifications during the fibrotic scar evolution.

The Effect of Diabetes Mellitus Type 1 on the Energy Metabolism of Hepatocytes: Multiphoton Microscopy and Fluorescence Lifetime Imaging.

A decrease in the regenerative potential of the liver during the development of non-alcoholic fatty liver disease (NAFLD), which is observed in the vast majority of patients with diabetes mellitus type 1, significantly increases the risk of postoperative liver failure. In this regard, it is necessary to develop new approaches for the rapid intraoperative assessment of the condition of liver tissue in the presence of concomitant liver pathology. A modern label-free approach based on multiphoton microscopy, second harmonic generation (SHG), and fluorescence lifetime imaging microscopy (FLIM) allow for the evaluation of the structure of liver tissue as well as the assessment of the metabolic state of hepatocytes, even at the cellular level. We obtained optical criteria and identified specific changes in the metabolic state of hepatocytes for a reduced liver regenerative potential in the presence of induced diabetes mellitus type 1. The obtained criteria will expand the possibilities for the express assessment of the structural and functional state of liver tissue in clinical practice.