Surface Second Harmonic Generation Research Articles

Disentangling the molecular polarizability and first hyperpolarizability of methanol-air interfaces.

Liquid-air interfaces have extensive implications in different areas of interest because the dynamical processes at the interface can be different from those in bulk. Thus, its characterization, understanding, and control may be pivotal in advancing discoveries. However, characterizing the interface requires special and selective tools to avoid signals from the bulk region. This surface specificity and versatility is achieved by using the second harmonic generation (SHG) responses. This study adopts multiscale simulation methods to evaluate the surface SHG responses of methanol-air interfaces with submonolayer resolution tackled by sequentially using classical molecular dynamics simulations under different temperatures and then employing quantum chemistry methods to compute the molecular first hyperpolarizabilities (β). This approach ensures the configurational diversity required to evaluate the average β values. The main achievements are (i) a quasi-absence of surface sensitivity of the mean polarizability 〈α〉 with values about 2% larger than those obtained in bulk, (ii) conversely, smooth variations on the polarizability anisotropy Δα are observed up to the fourth molecular layer at around 20 Å from the interface, and (iii) narrow interfacial effects on the SHG responses, β(-2ω;ω,ω), which are limited to the first molecular layer (∼3.0 Å) and characterized by a high contrast in the βZZZ(-2ω;ω,ω) tensor component between the first and the subsequent layers. Similar trends are obtained at different temperatures or when increasing the number of methanol molecules treated at the quantum chemistry level, indicating the robustness of the approach for describing the dipolar molecular responses of air-liquid interfaces.

Enhanced surface second harmonic generation in nanolaminates.

Second-harmonic generation (SHG) is a second-order nonlinear optical process that is not allowed in media with inversion symmetry. However, due to the broken symmetry at the surface, surface SHG still occurs, but is generally weak. We experimentally investigate the surface SHG in periodic stacks of alternating, subwavelength dielectric layers, which have a large number of surfaces, thus enhancing surface SHG considerably. To this end, multilayer stacks of SiO2/TiO2 were grown by Plasma Enhanced Atomic Layer Deposition (PEALD) on fused silica substrates. With this technique, individual layers of a thickness of less than 2 nm can be fabricated. We experimentally show that under large angles of incidence (> 20 degrees) there is substantial SHG, well beyond the level, which can be observed from simple interfaces. We perform this experiment for samples with different periods and thicknesses of SiO2/TiO2 and our results are in agreement with theoretical calculations.

Enhancement of second harmonic generation from three layers hybrid dielectric/metal/dielectric nanospheres

Due to the significant linear and nonlinear (NL) optical properties, hybridization of high-index dielectric and plasmonic materials can result in generating NL optical phenomena with high efficiency compared to the individual nanostructures made of these materials. The efficient surface second harmonic generation (SSHG) from three layers Si/Au/Si (SAS) nanospheres are investigated by the finite element method. The resonance wavelengths are determined by the numerical calculation of the linear spectral response. Then, by calculating the SSHG from each interface of the SAS at resonance wavelengths, it is shown that the core surface (the middle interface) has the dominant contribution at shorter (longer) wavelengths to enhance the SSHG. Finally, the total SSHG is compared to individual silicon nanosphere (SNS), which shows enhancing the efficiency of SHG up to 50 times at some resonance wavelength. The results of this work can pave the way for investigating and enhancing the efficiency of nano-photonic devices such as nano-lasers and nano-sensors.

Surface vs bulk contribution to the second-harmonic generation in AlGaAs nanoresonators

We address the surface vs bulk origin of the second-order optical nonlinearity in AlGaAs nanocylinders through polarization-resolved measurements. By comparing numerical simulations accounting just for bulk second-order nonlinearity with experimental results, we show that the surface contribution to second-harmonic generation (SHG) cannot be neglected and depends on the resonant conditions of the nanocylinder. Additionally, our analysis suggests that bulk and surface SHG are competing effects, and that their interference might influence the overall efficiency.

Anomalous Second Harmonic Generation from Atomically Thin MnBi2Te4

MnBi2Te4 is a van der Waals topological insulator with intrinsic intralayer ferromagnetic exchange and A-type antiferromagnetic interlayer coupling. Theoretically, it belongs to a class of structurally centrosymmetric crystals whose layered antiferromagnetic order breaks inversion symmetry for even layer numbers, making optical second harmonic generation (SHG) an ideal probe of the coupling between the crystal and magnetic structures. Here, we perform magnetic field and temperature-dependent SHG measurements on MnBi2Te4 flakes ranging from bulk to monolayer thickness. We find that the dominant SHG signal from MnBi2Te4 is unexpectedly unrelated to both magnetic state and layer number. We suggest that surface SHG is the likely source of the observed strong SHG, whose symmetry matches that of the MnBi2Te4-vacuum interface. Our results highlight the importance of considering the surface contribution to inversion symmetry-breaking in van der Waals centrosymmetric magnets.

Photoinduced Electron Transfer in a Porphyrin-Fullerene Dyad at a Liquid Interface.

The excited-state properties of an amphiphilic porphyrin-fullerene dyad and of its porphyrin analogue adsorbed at the dodecane/water interface are investigated by using surface second-harmonic generation. Although the porphyrin is formally centrosymmetric, the second-harmonic spectra of both compounds are dominated by the intense Soret band of the porphyrin. Polarization-selective measurements and molecular dynamics simulations suggest an angle of about 45° between the donor-acceptor axis and the interfacial plane, with the porphyrin interacting mostly with the nonpolar phase. Time-resolved measurements reveal a marked concentration dependence of the dynamics of both compounds upon Q-band excitation, indicating the occurrence of intermolecular quenching processes. The significant differences in dynamics and spectra between the dyad and the porphyrin analogue are explained by a self-quenching of the excited dyad via an intermolecular electron transfer.

Second harmonic generation microscopy of otoconia.

The origin of second harmonic generation (SHG) signal in otoconia was investigated. SHG signal intensity from otoconia was compared to pure calcite crystals, given calcite is the primary component of otoconia and is known to emit surface SHG. The SHG intensity from calcite was found to be ∼41× weaker than the SHG intensity from otoconia signifying that the SHG signal from otoconia is likely generated from the organic matrix. Furthermore, the SHG intensity from otoconia increased when treated with a chelating agent known to dissolve calcite which confirms that calcite is not the source of SHG. Additionally, polarization-resolved SHG microscopy imaging revealed that the arrangement of the SHG emitters is radial and can form highly ordered domains.

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.

Discrete Charges at ITIES - Polarisation and Electrochemical Reactions

The role of the discreteness of the charges at ITIES has recently been revisited within the framework of the so-called "Discrete Helmholtz" model. The main conclusion of this model is that the potential drop across an ITIES takes place over a bilayer of correlated ions rather than across two back-to-back diffuse layers as suggested by the Gouy Chapman approach. The experimental signatures from Surface Second Harmonic Generation (SSHG) and electrocapillary measurements are a constant capacitance and a linear relationship between surface charges and applied potential. We shall here discuss polarisation at ITIES and compare the different models. We shall also discuss how the interfacial polarisation acts as a driving force for potential dependant electrochemical reactions such as ion transfer and electron transfer.In the second part of the presentation, we shall discuss water splitting reactions at ITIES using redox photo-electrocatalysis. We shall discuss the different reactions leading to hydrogen evolution and present some very recent data on oxygen evolution.Finally, we shall discuss the feasibility of batch water splitting at ITIES as an industrial process. Figure 1

Modeling of surface-induced second-harmonic generation from multilayer structures by the transfer matrix method.

We analytically and numerically investigate surface second-harmonic generation (SHG) from a stack of dielectric layers. We develop a theoretical formalism based on the transfer matrix method for the calculation of the surface-driven second-harmonic radiation from multilayer structures and elaborate it for the case of ultrathin dielectric layers using a power series expansion to derive the effective surface nonlinear tensor for the whole stack. We show that for deeply subwavelength thicknesses of the layers the surface responses from all interfaces can efficiently sum up, leading to largely enhanced efficiency of SHG. As a result, such surface-driven nonlinearity can become comparable to the bulk nonlinearity in noncentrosymmetric semiconductors and can yield high performance for nonlinear nanophotonic applications.

Optical second harmonic generation from plasmonic nanoshells using the nonlocal hydrodynamic model

In this paper, we investigate the linear and nonlinear optical response of spherical plasmonic nanoshells within the nonlocal hydrodynamical model for conduction electrons. The optical absorption and surface second-harmonic generation (SHG) associated with metallic core-shell nanoparticles is studied on the basis of the hydrodynamic Drude model. The influence of nonlocality on the optical SHG is investigated. We show that nonlocal effects can be applied to boost SHG from plasmonic nanoshells. It is found that the surface SHG radiation from the surface of nanoshells can be achieved by symmetry-breaking and is sensitive to nonlocality of the electron response. It is also shown that nonlocal effects lead to enhancement and shift of the resonant wavelengths of the optical absorption and SHG in metal nanoshells. Keywords: Optical absorption, Second harmonic generation, plasmonic nanoshell, nonlocal effects.

Discrete Helmholtz charge distribution at liquid-liquid interfaces: Electrocapillarity, capacitance and non-linear spectroscopy studies

The structure of the polarised interface between two immiscible electrolyte solutions (ITIES) has usually been deduced from electrocapillarity and capacitance measurements. However, these two methods only offer an indirect access to the surface change density, by differentiation and integration. In this work, we analyse the dependence on the potential difference and the organic phase electrolyte concentration of the surface charge density of the polarised ITIES. Our study is based on electrocapillarity, capacitance and surface second harmonic generation (SHG). This spectroscopic approach allows us to probe directly ionic concentrations and hence surface charge density. By comparing the results provided by these different methods, we confirm that integration of the capacitance curves yields too large values of the charge density. On the other hand, electrocapillarity and SHG provide consistent results over a large potential range. These results depict an ITIES weakly affected by the organic electrolyte concentration. Furthermore, the surface charge density depends quasi-linearly on the potential difference, at all concentrations. Altogether, these results support the model of a polarised ITIES made of two ionic face-to-face layers and devoid of diffuse layer, the so-called discrete Helmholtz model.

Optical surface second harmonic generation from plasmonic graphene-coated nanoshells: influence of shape, size, dielectric core and embedding medium

We study optical surface second-harmonic generation (SHG) from the plasmonic nanoshells because they can improve and enhance nonlinear optical effects. We also investigate the SHG from the surface of spherical and cylindrical core-shell nanoparticles coated with a strong nonlinear material such as graphene due to its attractive plasmonic behaviour and unique properties of the surface plasmons in graphene. We demonstrate theoretically a giant and tunable second-order harmonic radiation which enhanced through the excitation of the surface plasmon resonance, can be observed at the surface of both spherical and cylindrical nanoshells because of symmetry-breaking at interface, which makes SHG as a valuable and powerful technique for applications in sensing and surface spectroscopy. We present the surface SHG strongly depends on the particle shape and size, the dielectric of embedding medium and core, the type of metal and graphene as a coating nonlinear material.

Restoring the silenced surface second-harmonic generation in split-ring resonators by magnetic and electric mode matching.

Surface second-harmonic generation (SHG) in plasmonic metal nanostructures provides a promising approach to design compact and ultrafast nonlinear nanophotonics devices. However, typical plasmonic nanostructures, such as those with tiny gaps that provide strong near-field-amplified nonlinear sources, often suffer from the cancellation of nonlinear fields in the gaps, which results in the so-called silenced SHG and consequently attenuates the overall nonlinear conversion efficiency. In this study, we propose and demonstrate that the silenced SHG in a gold split-ring resonator can be effectively restored by carefully tailoring its gap geometry to avoid the cancellation of nonlinear fields in the gap and simultaneously achieve both spatial and frequency mode matching between the magnetic and the electric dipolar resonances. As a result, the effective nonlinear sources in the gap can be dramatically amplified and the surface second-harmonic emissions can be efficiently coupled out, leading to an SHG intensity enhancement of 7 times compared to a conventional split-ring resonator. The overall SHG conversion efficiency can thus be enlarged to about 1.49 × 10-8 in the near-infrared excitation region. Importantly, the restored surface second-harmonic emission exhibits the scattering characteristics of an ideal electric dipole, which can be very useful for nonlinear far-field manipulation such as beam steering and holograms.

Surface second-harmonic generation from metallic-nanoparticle configurations: A transformation-optics approach

We study surface second-harmonic generation (SHG) from a singular plasmonic structure consisting of touching metallic wires. We use the technique of transformation optics and relate the structure to a rather simpler geometry, a slab waveguide. This allows us to obtain an analytical solution to the problem, revealing rich physical insights. We identify various conditions that govern the SHG efficiency. Importantly, our analysis demonstrates that apart from the mode-matching condition, phase-matching condition is relevant even for this sub-wavelength structure. Furthermore, we identify a geometric factor which was not identified before. We support our analysis with numerical simulations.

Bond model of second-harmonic generation in wurtzite ZnO(0002) structures with twin boundaries

We describe second-harmonic generation (SHG) in ZnO(0002) wurtzite structures with [11¯00]/(1102) twin boundaries using the simplified bond hyperpolarizability model (SBHM). We show explicitly how the reflective second-harmonic generation (RSHG) intensity profile for the s-incoming fundamental and s-outgoing SHG polarized light arise via superposition of the SHG dipole fields. The nonlinear fields originate from anharmonic motions of electric charges along each bond. The total dipole fields from within the ZnO bulk sum up to zero but produce a constructive SHG radiation from the unreduced surface and twin boundary. In addition, we compare the third-order susceptibility tensor obtained from group theory and the SBHM and calculate the values for the nonzero components. We found that the off-resonance RSHG intensity data in diatomic wurtzite structures even with the presence of twin boundaries can be modeled using only three independent fitting parameters, namely, the effective bulk, reduced surface, and twin boundary SHG hyperpolarizability. The results show that the SBHM can be used to investigate impurities and surface defects in ZnO as well as their contribution to nonlinear radiation with potential application to frequency conversion in nanoscale optical circuitry.

Analytical model of surface second-harmonic generation

The process of second-harmonic generation (SHG) in a finite one-dimensional nonlinear medium is analyzed in parallel by the Green-function technique and the Fourier-transform method. Considering the fundamental pump field propagating along a given direction and eliminating back-reflections at the boundaries the terms giving the surface second-harmonic fields in the particular solution of the wave equation are uniquely identified. Using these terms the flow of energy corresponding to the surface second-harmonic fields is analyzed in the vicinity of the boundaries. The formula giving the depth of the nonlinear medium contributing to the surface SHG is obtained. Both approaches for describing the SHG are compared considering complexity and quantization of the interacting fields. In addition, a theoretical model of surface SHG in centrosymmetric media is proposed. The model is built upon assumption that the second-order nonlinearity decays exponentially with distance from the boundary. As an important example, the generation of surface SHG from a thin dielectric nonlinear layer placed on a silicon substrate is analyzed by the proposed model.

Second-harmonic generation from supported carbon nanotube films grown by chemical vapor deposition on fused silica

Surface second-harmonic generation (SHG) is shown to be observable for carbon nanotube (CNT) films grown by CVD on fused silica. The SHG intensity ratio for incident radiation polarized perpendicular and parallel to the plane of incidence at the fundamental radiation (1064 nm) is observed to have typical values for the two kinds of grown film: a film with aligned CNTs and a film with randomly oriented CNTs lying on a substrate sheet. SHG is discussed to originate not from the CNT bulk but from the film surface. The polarization ratio obtained for the two kinds of film was consistent with that calculated for a composite film of spheroidal particles with varying diameters employed to approximate the actual CNT films. The present findings may be applied to in situ evaluation of the initial stage in the CVD growth process of CNTs.

Hierarchical microstructures with high spatial frequency laser induced periodic surface structures possessing different orientations created by femtosecond laser ablation of silicon in liquids

High spatial frequency laser induced periodic surface structures (HSFLs) on silicon substrates are often developed on flat surfaces at low fluences near ablation threshold of 0.1 J/cm2, seldom on microstructures or microgrooves at relatively higher fluences above 1 J/cm2. This work aims to enrich the variety of HSFLs-containing hierarchical microstructures, by femtosecond laser (pulse duration: 457 fs, wavelength: 1045 nm, and repetition rate: 100 kHz) in liquids (water and acetone) at laser fluence of 1.7 J/cm2. The period of Si-HSFLs in the range of 110–200 nm is independent of the scanning speeds (0.1, 0.5, 1 and 2 mm/s), line intervals (5, 15 and 20 μm) of scanning lines and scanning directions (perpendicular or parallel to light polarization direction). It is interestingly found that besides normal HSFLs whose orientations are perpendicular to the direction of light polarization, both clockwise or anticlockwise randomly tilted HSFLs with a maximal deviation angle of 50° as compared to those of normal HSFLSs are found on the microstructures with height gradients. Raman spectra and SEM characterization jointly clarify that surface melting and nanocapillary waves play important roles in the formation of Si-HSFLs. The fact that no HSFLs are produced by laser ablation in air indicates that moderate melting facilitated with ultrafast liquid cooling is beneficial for the formation of HSFLs by LALs. On the basis of our findings and previous reports, a synergistic formation mechanism for HSFLs at high fluence was proposed and discussed, including thermal melting with the concomitance of ultrafast cooling in liquids, transformation of the molten layers into ripples and nanotips by surface plasmon polaritons (SPP) and second-harmonic generation (SHG), and modulation of Si-HSFLs direction by both nanocapillary waves and the localized electric field coming from the excited large Si particles.

Quasi-Phase-Matching Method Based on Coupling Compensation for Surface Second-Harmonic Generation in Optical Fiber Nanowire Coupler

Efficient second harmonic generation (SHG) employing quasi-phase-matching (QPM) method based on the spatial modulation of mode intensity has been demonstrated experimentally and theoretically in th...