Second Harmonic Generation Experiments Research Articles

A Novel Sensing Method to Detect Malachite Green Contaminant on Silicon Substrate Using Nonlinear Optics.

We propose a nonlinear-optics-based nanosensor to detect malachite green (MG) contaminants on semiconductor interfaces such as silicon (Si). Applying the simplified bond hyperpolarizability model (SBHM), we simplified the second-harmonic generation (SHG) analysis of an MG-Si(111) surface and were able to validate our model by reproducing experimental rotational anisotropy (RA) SHG experiments. For the first time, density functional theory (DFT) calculations using ultrasoft pseudopotentials were implemented to obtain the molecular configuration and bond vector orientation required by the SBHM to investigate and predict the second-harmonic generation contribution for an MG-Si 001 surface. We show that the SBHM model significantly reduces the number of independent components in the nonlinear tensor of the MG-Si(111) interface, opening up the possibility for real-time and non-destructive contaminant detection at the nanoscale. In addition, we derive an explicit formula for the SHG far field, demonstrating its applicability for various input polarization angles. Finally, an RASHG signal can be enhanced through a simulated photonic crystal cavity up to 4000 times for more sensitivity of detection. Our work can stimulate more exploration using nonlinear optical methods to detect and analyze surface-bound contaminants, which is beneficial for environmental monitoring, especially for mitigating pollution from textile dyes, and underscores the role of nonlinear optics in real-time ambient-condition applications.

RMS error analysis of spatial uniformity and energy stability of the laser beam in second harmonic generation.

The coupling of the energy stability and spatial uniformity of the laser beam before and after second harmonic generation (SHG) was analyzed. SHG experiments were performed using a Nd:YAG nanosecond laser and LBO crystals, and images, pulse shapes, and energies were measured. The relationship between energy stability and spatial uniformity uses a formula derived from the previous study to analyze changes in energy stability and spatial uniformity of the input beam and converted beam. In addition, the measured input beam shape and energy are compared with the results of applying the SHG converting equation considering pump depletion. Both methods were similar to the experimental results when corrected by empirical factors. Through SHG, it was confirmed that there is an optimal point of energy stability and spatial uniformity of the laser beam near the critical power.

SHG behavior of the solid isomorphic compounds Ni- and Cu-5,10,15,20- tetraphenylporphyrinate. An experimental and theoretical study

We prepared and investigated the SHG behavior in the solid state of the two isomorphic Nickel and Copper 5,10,15,20-tetraphenylporphyrinate, that crystallize in the same acentric I4¯2d space group. The compounds were synthesized and characterized, and the Second Harmonic Generation (SHG) response of powdered samples was measured employing a 1.907 μm pulsed laser radiation. During laser irradiation, for both compounds, a gradual increase of the intensity of the SH signal was observed until, after a few minutes, it reached a plateau of about fifty times (for the Ni-TPP) or ten times (for the Cu-TPP) the initial value. We attempted to understand the origin of this phenomenon both through experimental analysis and theoretical calculations. Absorption and vibrational spectroscopies, in solution and solid state, combined with powder X-ray diffraction, both before and after irradiation, do not evidence any chemical degradation, phase transition or amorphization process. Theoretical calculations on little fragments of the Ni/Cu-TPP structure simulate appropriately the structural features of the complexes and their initial experimental SHG response. Magnetic balance measurement in the solid state before and after irradiation, in conjunction with DFT/B3LYP optimization of excited spin states and TDDFT calculations, highlight a change in the electronic and/or spin state due to the irradiation of the complexes.

Characterization of cracking-healing cycle of asphalt mixture based on air-coupled second harmonic measurement using Duffing-van der pol oscillator

Second harmonic generation (SHG) technique using Rayleigh surface wave has been successfully attempted for the non-destruction evaluation of asphalt mixture during the self-healing process. The air-coupled transducer placement is desirable for the convenient implementation of SHG for the large-scale detection. Nevertheless, the pronounced attenuation of ultrasonic wave by air-coupled propagation will cause the second harmonic induced by microcracks to be barely detectable, particularly under the influence of inevitable noise. In this study, a novel approach by combining Duffing oscillator and van der pol equation is developed to identify and quantify the second harmonic in noise-contained signals based on the phase trajectory and periodic trajectory area exponent. The multi-physics finite element model is first established to simulate the air-asphalt propagation of Rayleigh waves, and proof-of-concept numerical simulations are carried out to estimate the second harmonic amplitude of noise-contaminated signals. The air-coupled SHG experiments are conducted, and the approach of the Duffing-van der pol oscillator is applied to extract the second harmonic in experimental data, and the self-healing behavior of asphalt mixture is analyzed through the variation of the nonlinear parameter of SHG measurements. The results indicate that the contactless SHG method combined with the Duffing-van der pol oscillator can effectively realize the convenient and reliable estimation of the nonlinear ultrasonic signal during the cycle of asphalt deterioration and healing, which is important for the property characterization of asphalt mixture considering its high attenuation to the ultrasonic waves.

Pseudo-Stilbene- and Azobenzene-Type Systems for Optical Frequency Conversion: Estimating the First-Order Molecular Hyperpolarizability

This study investigates the potential of a set of pseudo-stilbene and azobenzene molecular structures to become optical frequency converters for optical communications based on a detailed exploration of the first-order molecular hyperpolarizability (βHRS), which is the microscopic counterpart of second harmonic generation (SHG). βHRS values were obtained via quantum chemical calculations using the Gaussian 16 software package in solvent and gas-phase media at different wavelengths, i.e., 1064 nm, 1310 nm, and 1510 nm. The latter two wavelengths are of particular interest for optical communications. Our study focused on discerning how the molecular structure influences the βHRS response, explicitly highlighting the influence of the azomethine group (CH=N). The results revealed that the molecular planarity, affected by this group, plays a crucial role in modulating the optical properties. The highest βHRS value in a solvent medium using the CAM-B3LYP/6-311+G(2d,p) level of theory achieved in this work was around 1400 ×10−30cm4startvolt−1, four orders of magnitude higher than KDP (0.2 ×10−30cm4startvolt−1), which is a reference in SHG experiments at 1064 nm. The highest calculated βHRS value at the same level of theory and solvent at 1310 nm and 1550 nm was 631 × 10−30cm4startvolt−1 and 456 × 10−30cm4startvolt−1, respectively. All these values belong to molecular structures with azo-coupling with donor (4-NMe2) and acceptor (4′-NO2) peripheral groups, designated as AB-3.

Cation Modifies Interfacial Water Structures on Platinum during Alkaline Hydrogen Electrocatalysis.

The molecular details of an electrocatalytic interface play an essential role in the production of sustainable fuels and value-added chemicals. Many electrochemical reactions exhibit strong cation-dependent activities, but how cations affect reaction kinetics is still elusive. We report the effect of cations (K+, Li+, and Ba2+) on the interfacial water structure using second-harmonic generation (SHG) and classical molecular dynamics (MD) simulation. The second- (χH2O(2)) and third-order (χH2O(3)) optical susceptibilities of water on Pt are smaller in the presence of Ba2+ compared to those of K+, suggesting that cations can affect the interfacial water orientation. MD simulation reproduces experimental SHG observations and further shows that the competition between cation hydration and interfacial water alignment governs the net water orientation. The impact of cations on interfacial water supports a cation hydration-mediated mechanism for hydrogen electrocatalysis; i.e., the reaction occurs via water dissociation followed by cation-assisted hydroxide/water exchange on Pt. Our study highlights the role of interfacial water in electrocatalysis and how innocent additives (such as cations) can affect the local electrochemical environment.

Investigating the Photovoltaic Performance in ABO3 Structures via the Nonlinear Bond Model for an Arbitrary Incoming Light Polarization.

ABO3 structures commonly known as perovskite are of high importance in advanced material science due to their interesting optical properties. Applications range from tunable band gaps, high absorption coefficients, and versatile electronic properties, making them ideal for solar cells to light-emitting diodes and even photodetectors. In this work, we present, for the first time, a nonlinear phenomenological bond model analysis of second harmonic generation (SHG) in tetragonal ABO3 with arbitrary input light polarization. We study the material symmetry and explore the strength of the nonlinear generalized third-rank tensorial elements, which can be exploited to produce a high SHG response if the incoming light polarization is correctly selected. We found that the calculated SHG intensity profile aligns well with existing experimental data. Additionally, as the incoming light polarization varies, we observed a smooth shift in the SHG intensity peak along with changes in the number of peaks. These observations confirm the results from existing rotational anisotropy SHG experiments. In addition, we show how spatial dispersion can contribute to the total SHG intensity. Our work highlights the possibility of studying relatively complex structures, such as ABO3, with minimal fitting parameters due to the power of the effective bond vector structure, enabling the introduction of an effective SHG hyperpolarizability rather than a full evaluation of the irreducible SHG tensor by group theoretical analysis. Such a simplification may well lead to a better understanding of the nonlinear properties in these classes of material and, in turn, can improve our understanding of the photovoltaic performance in ABO3 structures.

The peculiar SHG behaviour of Co-5,10,15,20-tetraphenilporphyrinate in the solid state. An experimental and theoretical study

We prepared and investigated the SHG behavior in the solid state of the Cobalt 5,10,15,20-tetraphenylporphyrinate that crystallizes in the acentric I4¯2d space group. The compound was synthesized and characterized, and the Second Harmonic Generation (SHG) response of a powdered sample was measured through a 1.907 μm pulsed laser radiation. During laser irradiation, a gradual increase of the intensity of the SH signal was observed until, after a few minutes, it reached a plateau of about fifty times the initial value. We attempted to understand the origin of this peculiar SHG behavior, both through experimental analysis and theoretical calculations. Mass spectrometry, absorption, emission, and vibrational spectroscopies in solution combined with powder X-ray diffraction analysis in solid state, both before and after irradiation, do not evidence any chemical degradation, phase transition or amorphization process. Theoretical calculations on little fragments of the Co-TPP structure simulate appropriately the structural feature of the complex and its initial experimental SHG response. UV–VIS and EPR spectra collected in the solid state before and after irradiation, in conjunction with DFT/B3LYP optimization of excited spin states and TDDFT calculation, highlight a change in the electronic and/or spin state due to the irradiation of the complex.

Strong Nonlinear Optical Response and Transient Symmetry Switch in Type‐II Weyl Semimetal β‐WP2

AbstractThe topological Weyl semimetals (WSMs) with peculiar band structures exhibit novel nonlinear optical enhancement phenomena, even for light at optical wavelengths. While many intriguing nonlinear optical effects are constantly uncovered in type‐I WSMs, few experimental works focuse on basic nonlinear optical properties in type‐II WSMs. Here a static and time‐resolved second harmonic generation (SHG) is performed on the 3D type‐II WSM candidate β‐WP2. Although β‐WP2 exhibits extremely high conductivity and a high carrier density (≈1021 cm−3), the SHG is unscreened by conduction electrons, and a rather strong SHG response is observed, comparing with non‐topological polar metals. Additionally, the time‐resolved SHG experiment traces ultrafast symmetry switch and reveals that polar metal β‐WP2 tends to form an inversion symmetric metastable state after photo‐excitation. Intense femtosecond laser pulse can optically drive symmetry switch and tune nonlinear optical response on ultrafast timescales although the interlayer coupling of β‐WP2 is very strong. These findings are illuminating for the polar metal nonlinear optics and provide a new perspective for future ultrafast topological optoelectronic devices.

Revisiting the structure of (±)-[Co(en)3]I3·H2O – X-ray crystallographic and second-Harmonic results

Abstract As described in the Introduction, we became interested in the existing literature for the crystallization behavior of (±)-[Co(en)3]I3·H2O and the absolute configuration of its enantiomers because of our project on the historical sequence of chemical studies leading Werner to formulate his Theory of Coordination Chemistry. In so doing, we discovered a number of interesting facts, including the possibility that the published “Pbca” structure of the (±)-[Co(en)3]I3·H2O was incorrect, and that it really crystallizes as a kryptoracemate in space group P212121. Other equally interesting facts concerning the crystallization behavior of [Co(en)3]I3·H2O are detailed below, together with an explanation why Platon incorrectly selects, in this case, the space group Pbca instead of the correct choice, P212121. As for the Flack parameter, (±)-[Co(en)3]I3·H2O provides an example long sought by Flack himself – a challenging case, differing from the norm. For that purpose, data sets (for the pure enantiomer and for the racemate) were collected at 100 K with R-factors of 4.24 and 2.82%, respectively, which are ideal for such a test. The fact that Pbca is unacceptable in this case is documented by the results of Second-Harmonic Generation experiments. CCDC nos: 1562401 for compound (I) and 1562403 for compound (II).

Surface Activity and Aggregation Behavior of Polyhydroxylated Fullerenes in Aqueous Solutions.

Polyhydroxylated fullerene (PHF) surface activity and aggregation behavior at the air-water interface were examined using surface tension and resonance-enhanced second harmonic generation (SHG). Surface tension data showed that PHFs are surface active with a limiting surface excess corresponding to 130 Å2/molecule in aqueous (Millipore water) solutions. Increasing the solution-phase ionic strength (through the addition of NaCl) reduces the PHF surface excess. Conductivity measurements show that PHFs carry a single charge, presumably negative. Surface-specific SHG experiments show a small but measurable fixed wavelength, nonlinear response from solutions having surface excess coverages as low as ∼400 Å2/molecule. The SHG response of PHF solutions in the low-concentration limit shows unexpected behavior, implying that at bulk concentrations below 0.06 mg/mL, PHF monomers adsorb to the surface and interfere destructively with the intrinsic nonlinear susceptibility of the aqueous/vapor interface, leading to a ∼75% reduction in the SH signal. Above a PHF concentration of 0.0.06 mg/mL, the SH signal begins to rise in the Millipore and 50 mM NaCl solutions but remains very low in the 500 mM NaCl solutions. From this behavior, we infer that an increased nonlinear optical response is due to adsorbed aggregates.

High-efficiency broadband second-harmonic-generation of YCa4O(BO3)3 crystal

High-efficiency broadband second-harmonic-generation (SHG) of YCa4O(BO3)3 (YCOB) crystal was demonstrated for the first time. The theoretical calculation predicted that the retracing point wavelength for type-I SHG of YCOB crystal was at around 1650 nm, which was proved by the followed phase-matching experiment. With a tunable femtosecond laser as the light source, the type-I SHG experiments of YCOB crystal were performed in the range of 1550–1700 nm. Compared with other broadband SHG crystals, YCOB crystal presented the highest optical conversion efficiency of 58%, the largest spectral bandwidth conversion ratio of 65%, and the broadest wavelength acceptance bandwidth of 118.8 nm·cm1/2.

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.

Monitoring of stress variation of strands in prestressed concrete by second harmonic generation measurements based on piezoelectric sensors

The stress loss of prestressed concrete may cause the ultimate failure of structures and the monitoring of stress variation of prestressed structures is therefore important to ensure the service safety. This paper developed a nondestructive evaluation method of nonlinear ultrasonic second harmonic generation (SHG) based on piezoelectric (PZT) sensors and applied for the distinction of different stress level of post-tensioned steel strands in concrete. The nonlinear ultrasonic behavior of both free strand and embedded strand having different length is studied with the developed SHG technique and a defined nonlinear parameter is introduced in SHG experiments to correlate with the tension stress in the strand. It is found that the nonlinear parameter has a negative correlation with the increasing stress of strand in both free and embedded case, indicating the nonlinear ultrasonic behavior is getting weak corresponding to the increasing contact force among strand wires. In addition, the decreasing ratio of nonlinear parameter is very close to each other regardless of the length of steel strand, indicating the possibility of replacing the large-scale on-site testing with scaled down samples in laboratory. The experimental results of this research demonstrate that the SHG technique based on PZT sensors could be useful for the stress monitoring of prestressed reinforced concrete with consideration of the relatively high sensitivity of nonlinear parameter to the variation of contact force of strand wires.

Three-dimensional stacking of canted antiferromagnetism and pseudospin current in undoped Sr2IrO4 : Symmetry analysis and microscopic model realization

Recent optical second-harmonic generation experiments observed unexpected broken spatial symmetries in the undoped spin-orbit Mott insulator Sr$_2$IrO$_4$, leading to intensive debates on the nature of its ground state. We propose that it is a canted antiferromagnetism with a hidden order of circulating staggered pseudospin current. Symmetry analysis shows that a proper $c$-axis stacking of the canted antiferromagnetism and the pseudospin current lead to a magnetoelectric coexistence state that breaks the two-fold rotation, inversion, and time-reversal symmetries, consistent with experimental observations. We construct a three-dimensional Hubbard model with spin-orbit coupling for the five localized 5$d$ Wannier orbitals centered at Ir sites, and demonstrate the microscopic realization of the desired coexistence state in a wide range of band parameters via a combination of self-consistent Hartree-Fock and variational calculations.

Guest-Mediated Hierarchical Self-Assembly of Dissymmetric Organic Cages to Form Supramolecular Ferroelectrics

Guest-Mediated Hierarchical Self-Assembly of Dissymmetric Organic Cages to Form Supramolecular Ferroelectrics

Crystal structure or chemical composition of salt–sugar-based metal–organic frameworks: what are the nonlinear optical properties due to?

In the last few decades optical imaging techniques based on nonlinear optical properties have been of interest for biosensing applications. This work focuses on two isostructural and isomorphous sugar-derived metal–organic frameworks (MOFs) with second-harmonic generation (SHG) properties, in order to investigate their possible application as biosensors in view of their high biocompatibility. Combining 2-deoxy-D-galactose with the metal halogenides CaX 2 (X = Br, I), two new isomorphous MOFs of formula [Ca(C6H12O5)2]X 2 were obtained and characterized through single-crystal X-ray diffraction. The first-order static hyperpolarizability and second-order susceptibility were estimated by in vacuo and in-crystal density functional theory calculations, and compared with the experimental SHG response of powdered samples. The parameters influencing the SHG response of these compounds were investigated by comparison with similar previously analysed MOFs, to understand how to design more efficient materials to be used as nanoprobes by exploiting crystal engineering techniques.

Influence of the spatial extent of the space-charge region in c-Si on the electric-field-induced second-harmonic-generation effect

Second-harmonic-generation (SHG) spectroscopy can be used as an all-optical probe of space-charge regions (SCR) in semiconductors such as c - S i by exploiting the electric-field-induced second-harmonic-generation (EFISH) effect. To do so accurately, a thorough understanding of the EFISH effect is needed, and here a detailed model is presented, taking into account the so-far neglected spatial extent of the SCR on the spectral shape of the EFISH contribution. This shows that the spatial extent causes a significant phase shift in the EFISH contribution ranging from 0.1 π r a d to 0.4 π r a d with decreasing SCR strength. This predicted phase shift was verified by dedicated measurements of the spectral SHG phase and intensity of a series of samples covering the typical range of SCR strengths. The spectral SHG response of these samples indeed showed the predicted phase shift in the EFISH contribution and demonstrated that the extent of the SCR cannot be neglected. The obtained insights can result in improved accuracy in the determination of built-in charges near a c - S i interface, which is of interest in the context of semiconductor devices using SHG spectroscopy. Moreover, this refined understanding of the EFISH effect is beneficial in SHG experiments on 2D materials with c - S i serving as a substrate of Si-based photonic devices.

Solvent-dependent morphology and anisotropic microscopic dynamics of cellulose nanocrystals under electric fields.

Cellulose nanocrystals (CNCs) are interesting for the construction of biomaterials for energy delivery and packaging purposes. The corresponding processing of CNCs can be optimized through the variation of intercellulose interactions by employing different types of solvents, and thereby varying the degree of cellulose hydrogen bonding. The aim of this work is (i) to show how different types of solvents affect the self-assembled morphology of CNCs, (ii) to study the microscopic dynamics and averaged orientations on the CNCs in aqueous suspensions, including the effect of externally imposed electric fields, and (iii) to explore the nonlinear optical response of CNCs. The homogeneity of self-assembled chiral-nematic phase depends on both the polarity of the solvent and the CNC concentration. The variation of the chiral-nematic pitch length with concentration, as determined from real-space and Fourier images, is found to be strongly solvent dependent. The anisotropic microdynamics of CNCs suspension exhibits two modes, related to diffusion parallel and perpendicular to the (chiral-) nematic director. We have found also the coupling between translational and orientational motion, due to existing correlation length of twisted nematic elasticity. Preliminary second-harmonic generation experiments are performed, which reveal that relatively high field strengths are required to reorient chiral-nematic domains of CNCs.

Second Harmonic Generation of 266 nm Laser Beam Using BBO Nonlinear Crystal

Second harmonic generation (SHG) is a phenomenon observed in nonlinear optics that leads to frequency duplication for a high intensity laser incident on nonlinear crystal using BBO crystal. The SHG yield is achieved when the photons interact with a nonlinear optical material and effectively combine to form new photons with double frequency, and therefore double energy and half wavelength. This paper is concerned with the establishment of an SHG experiment to govern the process of producing half-wavelength laser beam from the input one. The theoretical effort was extended to compute the efficiency by using MATLAB software based on mathematical relationships. The values of the conversion maximum efficiencies, which were computed as a function of the input and output powers of the theoretical computations, were 15.6% and 16% at input and output power values of 0.6 and 0.1, respectively. The experimental results of the laser source of 532nm wavelength (fundamental frequency was 0.563x1015s-1) gave a half wavelength of 266nm (double frequency was 1.126x1015s-1). The conversion efficiencies, computed as a function of the input and output powers of the experimental measurements, were 14.32% and 12.97%, respectively.