Second-harmonic Response Research Articles

Second-harmonic imaging microscopy for time-resolved investigations of transition metal dichalcogenides

Two-dimensional transition metal dichalcogenides (TMD) have shown promise for various applications in optoelectronics and so-called valleytronics. Their operation and performance strongly depend on the stacking of individual layers. Here, optical second-harmonic generation in imaging mode is shown to be a versatile tool for systematic time-resolved investigations of TMD monolayers and heterostructures in consideration of the material’s structure. Large sample areas can be probed without the need of any mapping or scanning. By means of polarization dependent measurements, the crystalline orientation of monolayers or the stacking angles of heterostructures can be evaluated for the whole field of view. Pump-probe experiments then allow to correlate observed transient changes of the second-harmonic response with the underlying structure. The corresponding time-resolution is virtually limited by the pulse duration of the used laser. As an example, polarization dependent and time-resolved measurements on mono- and multilayer MoS2 flakes grown on a SiO2/ Si(001) substrate are presented.

Wavelength and Polarization Dependence of Second-Harmonic Responses from Gold Nanocrescent Arrays

In the developing field of nonlinear plasmonics, it is important to understand the fundamental relationship between properties of the localized surface plasmon resonance (LSPR) of metallic nanostructures and their nonlinear optical responses. A detailed understanding of nonlinear responses from nanostructures with well-characterized LSPRs is an essential prerequisite for the future design of sophisticated plasmonic systems with advanced functions to control light. In this article, we investigate the second-order harmonic (SH) responses from gold nanocrescent (Au NC) antennas which have wavelength and polarization sensitive LSPRs in the visible and near-infrared wavelength ranges. The wavelength dependence of the SH intensity exhibits spectral profiles different from dipole LSPR bands in absorbance spectra. The incident polarization angle dependence was found to vary significantly when the excitation wavelength was tuned over the dipole band. Finite-difference time-domain calculations coupled with a nonlinear hydrodynamic model were carried out for Au NC arrays to investigate the local field enhancement of the incoming fundamental and emitting SH light. The experimental and theoretical results indicate that the effects of higher-order LSPRs, such as quadrupole and multipole resonances, occurring at SH wavelengths are important in governing the SH generation process. Also, it is shown that the incident polarization angle dependence of SH signals is very strongly sensitive to nanoscale variations in the NC’s shape.

Nanoscale Nonlinear Optical Spectroscopy with Electron Beams

We theoretically demonstrate the ability of electron beams to probe the nonlinear photonic response with nanometer spatial resolution, well beyond the capabilities of existing optical techniques. Although the interaction of electron beams with photonic modes is generally weak, the use of optical pumping produces stimulated electron-light interactions that can reach order-unity probabilities in photon-induded near field electron microscopy (PINEM). Here, we demonstrate that PINEM can locally and quantitatively probe the nonlinear optical response. Specifically, we predict a dependence of PINEM electron spectra on the sample nonlinearity that can reveal the second-harmonic (SH) response of optical materials with nanometer resolution, observed through asymmetries between electron energy losses and gains. We illustrate this concept by showing that PINEM spectra are sensitive to the SH near field of centrosymmetric structures and by finding substantial spectral asymmetries in geometries for which the linear interaction is reduced.

Second-Harmonic Voltage Response for the Magnetic Weyl Semimetal Co3Sn2S2

We experimentally investigate longitudinal and transverse second-harmonic voltage response to ac electrical current for a magnetic Weyl semimetal Co$_3$Sn$_2$S$_2$. In contrast to the previously observed Berry-curvature induced non-linear Hall effect for non-magnetic Weyl and Dirac semimetals, the second-harmonic transverse voltage demonstrates sophisticated interplay of different effects for Co$_3$Sn$_2$S$_2$. In high magnetic fields, it is of Seebeck-like square-B law, while the low-field behavior is found to be linear and sensitive to the direction of sample magnetization. The latter can be expected both for the non-linear Hall effect and for the surface state contribution to the Seebeck effect in Weyl semimetals. Thus, thermoelectric effects are significant in Co$_3$Sn$_2$S$_2$, unlike non-magnetic Weyl and Dirac materials.

Three-Dimensional Perovskite Methylhydrazinium Lead Chloride with Two Polar Phases and Unusual Second-Harmonic Generation Bistability above Room Temperature

Formation of noncentrosymmetric three-dimensional (3D) lead halide perovskites has been a widely sought after goal because the polar structure opens up new vistas to properties of these materials, e.g., improved charge separation for photovoltaics arising from ferroelectric order. Here, we report growth and unique properties of a new highly distorted 3D perovskite, methylhydrazinium lead chloride (CH3NH2NH2PbCl3, MHyPbCl3). This perovskite crystallizes in polar P21 structure at room temperature, which consists of two types of PbCl6 octahedra: one weakly and another strongly deformed. The unusual deformation of every second perovskite layer is forced by the large size of methylhydrazinium cations and the ability of NH2+ terminal groups of methylhydrazinium cations to form coordination bonds with Pb2+ metal centers. On heating, MHyPbCl3 undergoes a phase transition at 342 K into another polar Pb21m phase with ordered organic cations. Temperature-resolved second-harmonic generation (TR-SHG) measurements confirm acentricity of both phases and show that second-harmonic response is enhanced for the high-temperature Pb21m phase. This intriguing property of MHyPbCl3 has been employed to demonstrate an unprecedented kind of quadratic nonlinear optical switching in which a second-harmonic response is switched between a room-temperature, low-SHG state and a high-temperature, high-SHG state. X-ray diffraction shows that enhancement of polar properties is due to rearrangement of the perovskite’s organic substructure. There is a clear pyrocurrent peak, but switching of the electric polarization could not be observed. Optical studies showed that MHyPbCl3 is a wide-bandgap material with a bandgap of 3.4 eV (365 nm). At low temperatures, it exhibits weak UV emissions at 362 and 369 nm as well as a strong broadband white emission.

Study of phase separation phenomena in half-doped manganites with isovalent substitution of rare-earth cations on example ofSm0.32Pr0.18Sr0.5MnO3

The effect of isovalent substitution of rare-earth cations on the phase separation in half-doped manganites was studied on the example of ${\mathrm{Sm}}_{0.32}{\mathrm{Pr}}_{0.18}{\mathrm{Sr}}_{0.5}{\mathrm{MnO}}_{3}$ by high-resolution neutron powder diffraction, neutron beam depolarization, second-harmonic magnetic response, and magnetization and resistivity measurements from 4 K up to room temperature and higher. A structural phase transition from the orthorhombic $Pbnm$ phase to a mixture of $Pbnm$ and monoclinic $P{2}_{1}/m$ phases was observed upon cooling. The magnetic ground state was found to be phase-separated into three magnetic phases emerging at different temperatures, viz., ferromagnetic (FM) and antiferromagnetic A and charge-ordered CE types. FM clusters arise far above room temperature in the orthorhombic phase and coalesce upon cooling to produce the long-range FM order below 250 K and to arrive at the percolative FM phase below 120 K. The A- and CE-type orders form in the monoclinic phase at the temperatures 200 K and 120 K, respectively. The Sm/Pr isovalent substitution qualitatively changes the phase separation and significantly increases its temperature range compared to the parent compounds. The results obtained give us knowledge of phase separation occurring in systems with strong electron correlations and extend opportunities for fine-tuning of their properties.

Combining photoinduced linkage isomerism and nonlinear optical properties in ruthenium nitrosyl complexes.

The complex trans-[RuNO(NH3)4F]SiF6 was synthesized in quantitative yield and the structure was characterized by X-ray diffraction and spectroscopic methods. The complex crystallizes in the non-centrosymmetric space group Pn. Hirshfeld surface analysis revealed that the dominant intermolecular interactions are of types H...F and F...O, which are likely to be responsible for the packing of the molecules in a non-centrosymmetric structure. Irradiation with blue light leads to the formation of Ru-ON (metastable state MS1) and Ru-η2-(NO) (metastable state MS2) bond isomers, as shown by IR and UV-Vis spectroscopy. The structural features of the MS1 isomer were elucidated by photocrystallography. The complex exhibits exceptionally good thermal stability of the metastable state MS1, such that it can be populated by light at 290-300 K, which is important for potential applications. The second harmonic (SH) emission can be generated by femtosecond-pulsed irradiation of the complex. The generated SH is rather efficient and stable under long-term exposure. Finally, since both metastable states and harmonic generation can be generated at room temperature, an attempt to drive the SH response by photoisomerization of the nitrosyl ligand was made and is discussed.

Beam Steering with a Nonlinear Optical Phased Array Antenna.

Transition metal dichalcogenides (TMDCs) exhibit high second harmonic (SH) generation in the visible due to their noncentrosymmetric crystal structure in odd-layered form and direct bandgap transition when thinned down to a monolayer. In order to emit the SH radiation into a desired direction, one requires a means to control the phase of the in-plane nonlinear polarization. Here, we couple the SH response of a monolayer MoS2 to an optical phased array antenna and demonstrate controllable steering of the nonlinear emission. By exploiting the intrinsic SH generation by the phased array antenna we achieve uniform emission efficiency into a broad angular range. Our work has relevance for novel optoelectronic applications, such as programmable optical interconnects and on-chip LIDAR.

Comprehensive characterization of magnetite-based colloid for biomedical applications

An aqueous colloidal solution of dextran-coated magnetite nanoparticles was studied by nonlinear second-harmonic magnetic response (M2), transmission electron microscopy (TEM), dynamic light scattering (DLS) and electron magnetic resonance (EMR). Nanoparticles were found to aggregate. A set of magnetic parameters of the aggregates, such as the mean magnetic moment, the magnetization damping constant, the longitudinal relaxation time, the field and energy of magnetic anisotropy, and others were evaluated from M2 measurements with the data processing formalism based on the Gilbert–Landau–Lifshitz (GLL) equation for the stochastic dynamics of superparamagnetic (SP) particles. Combined with TEM and DLS, the M2 technique additionally enabled the differentiation between magnetic and nonmagnetic components of the colloid. To achieve full numerical consistency between the parameters obtained from the M2 and TEM data, magnetic correlations of nanoparticles inside the aggregates were taken into account and their correlation radius was evaluated. The observed crossover in the magnetic field dependence of the EMR signal occurring due to the break of the dipole–dipole (d–d) coupling between nanoparticles in the aggregates was described using the M2 and TEM data.

Second-harmonic generation in nanostructured metamaterials

We conduct a theoretical and numerical study on the second-harmonic (SH) optical response of a nano-structured metamaterial composed of a periodic array of inclusions. Both the inclusions and their surrounding matrix are made of centrosymmetrical materials, for which SH is strongly suppressed, but by appropriately choosing the shape of the inclusions, we may produce a geometrically non-centrosymmetric system which does allow efficient SH generation. Variations in the geometrical configuration allows tuning the linear and quadratic spectra of the optical response of the system. We develop an efficient scheme for calculating the nonlinear polarization, extending a formalism for the calculation of the macroscopic dielectric function using Haydock's recursion method. We apply the formalism developed here to an array of holes within an Ag matrix, but it can be readily applied to any metamaterial made of arbitrary materials and for inclusions of any geometry within the long-wavelength regime.

Second-harmonic generation as a probe for structural and electronic properties of buried GaP/Si(0 0 1) interfaces

Optical second-harmonic generation is demonstrated to be a sensitive probe of the buried interface between the lattice-matched semiconductors gallium phosphide and silicon with (0 0 1) orientation. Ex situ rotational anisotropy measurements on GaP/Si heterostructures show a strong isotropic component of the second-harmonic response not present for pure Si(0 0 1) or GaP(0 0 1). The strength of the overlaying anisotropic response directly correlates with the quality of the interface as determined by atomically resolved scanning transmission electron microscopy. Systematic comparison of samples fabricated under different growth conditions in metal–organic vapor phase epitaxy reveals that the anisotropy for different polarization combinations can be used as a selective fingerprint for the occurrence of anti-phase domains and twins. This all-optical technique can be applied as an in situ and non-invasive monitor even during growth.

Local magnetostriction measurement in a cobalt thin film using scanning probe microscopy

The local magnetostriction measurement has become an emerging issue because strain-mediated nanocomposites have received considerable attention due to their potential applications for high sensitivity sensors and high density energy harvesters. Compared to many instruments capable of measuring nanometric magnetic domains, techniques for measuring local magnetostriction have been rarely reported. Here, we introduce a local magnetostriction measurement method by modifying an atomic force microscope (AFM) by combing a solenoid to apply an external ac magnetic field and induce magnetostrictive excitation. The distribution of magnetostrictive response is mapped by contact mode AFM and lock-in detection techniques with a few nanometer lateral resolution. We have found that a few micrometer-size domains of a cobalt film showing different amplitude and phase signals of the magnetostrictive response are observed by the second-harmonic response of the ac magnetic field frequency, which is not detected in a linear response signal. We suggest that the phase and amplitude signals observed in each domain are related to magnetic-easy-axis directions. Our findings provide a unique pathway to understand the local magnetostrictive response based on scanning probe microscopy.

Understanding the Second-Harmonic Generation Enhancement and Behavior in Metal Core–Dielectric Shell Nanoparticles

To explain recently observed up to 50-fold enhancement of the second harmonic (SH) signal from gold nanoparticles after depositing of a thin dielectric layer, we perform an analytical study of the SH generation by metal core–dielectric shell spherical nanoparticles (NPs). We derive analytical expressions for the SH intensity accounting for electric dipole and quadrupole impacts. On this basis, we discuss the SH response spectrum of coated gold and silver nanoparticles. The possibility of adjusting the SH scattering regime to dipole or quadrupole resonant mode by varying the shell thickness is shown. We demonstrate that the thin, up to several NPs radii, dielectric cover of the NPs gives a significant advantage in the SH intensity in a line with the resonant enhancement. This effect is most pronounced in gold nanoparticles and even dominates resonant enhancement of the SH generation. This new result in nonlinear plasmonics provides a simple recipe for gold nanoparticles: thicker dielectric coating–higher t...

Label-free and charge-sensitive dynamic imaging of lipid membrane hydration on millisecond time scales

Biological membranes are highly dynamic and complex lipid bilayers, responsible for the fate of living cells. To achieve this function, the hydrating environment is crucial. However, membrane imaging typically neglects water, focusing on the insertion of probes, resonant responses of lipids, or the hydrophobic core. Owing to a recent improvement of second-harmonic (SH) imaging throughput by three orders of magnitude, we show here that we can use SH microscopy to follow membrane hydration of freestanding lipid bilayers on millisecond time scales. Instead of using the UV/VIS resonant response of specific membrane-inserted fluorophores to record static SH images over time scales of >1,000 s, we SH imaged symmetric and asymmetric lipid membranes, while varying the ionic strength and pH of the adjacent solutions. We show that the nonresonant SH response of water molecules aligned by charge-dipole interactions with charged lipids can be used as a label-free probe of membrane structure and dynamics. Lipid domain diffusion is imaged label-free by means of the hydration of charged domains. The orientational ordering of water is used to construct electrostatic membrane potential maps. The average membrane potential depends quadratically on an applied external bias, which is modeled by nonlinear optical theory. Spatiotemporal fluctuations on the order of 100-mV changes in the membrane potential are seen. These changes imply that membranes are very dynamic, not only in their structure but also in their membrane potential landscape. This may have important consequences for membrane function, mechanical stability, and protein/pore distributions.

Plasmonic second-harmonic generation in gold:lithium niobate thin films

Using a sample consisting of a thin gold film on lithium niobate, the plasmonic second-harmonic response of gold is measured simultaneously with the optical second-harmonic response of lithium niobate. The non-phase-matched, bulk optical second-harmonic response of the lithium niobate is used to calibrate the plasmonic signal, and these are found to be of comparable intensity over the short propagation distances that arise in this system.

Detection of heterogeneous deposits on the surface of metal structures using nonlinear acoustic resonance technology

Failures caused by carbon deposits have always been a challenge in hydrocarbon processes. In this paper, a nonlinear acoustic resonance technique was investigated to characterize heterogeneous deposits on the surface of metal structures. The amplitude-frequency curves of the fundamental and second-harmonic responses were measured at various excitation levels. Experimental results indicated that the dependence of the resonant spectrum of the second harmonic response on the excitation level is based on the status of the deposit. Moreover, two hysteretic nonlinear parameters related to the second harmonic, the hysteretic elastic nonlinearity and the hysteretic dissipative nonlinearity, were proposed for the quantitative characterization of the deposited layers. The developed nonlinear acoustic resonance method in the megahertz region was used for quantitative evaluation of carbon deposits in a pipe, and the feasibility of the method for assessing carbon deposits was demonstrated.

Observation of Nonlinear Harmonic Generation of Bulk Modes in SAW Devices.

Nonlinear generation of harmonics is measured on the wafer level on temperature compensated surface-acoustic-wave resonators on lithium niobate. The second-harmonic response features strong peaks looking like multiple resonant modes. The product of the frequency difference between the successive peaks to the substrate thickness is found to remain almost constant. The results also show that the level of the harmonic signal strongly depends on the roughness of the back side of the substrate. Due to these findings, it was assumed that the signal is due to nonlinear generation of a bulk mode. This assumption is confirmed experimentally by measuring the second-harmonic wave field on the back side of the substrate with an interferometer. Possible nonlinear mechanisms explaining these results are discussed.

Probing the Near-Field of Second-Harmonic Light around Plasmonic Nanoantennas.

We introduce a new concept that enables subwavelength polarization-resolved probing of the second-harmonic near-field distribution of plasmonic nanostructures. As a local sensor, this method utilizes aluminum nanoantennas, which are resonant to the second-harmonic wavelength and which allow to efficiently scatter the local second-harmonic light to the far-field. We place these sensors into the second-harmonic near-field generated by plasmonic nanostructures and carefully vary their position and orientation. Observing the second-harmonic light resonantly scattered by the aluminum nanoantennas provides polarization-resolved information about the local second-harmonic near-field distribution. We then investigate the polarization-resolved second-harmonic near-field of inversion symmetric gold dipole nanoantennas. Interestingly, we find strong evidence that the second-harmonic dipole is predominantly oriented perpendicular to the gold nanoantenna long axis, although the excitation laser is polarized parallel to the nanoantennas. We believe that our investigations will help to disentangle the highly debated origin of the second-harmonic response of inversion symmetric plasmonic structures. Furthermore, we believe that our new method, which enables the measurement of local nonlinear electric fields, will find widespread implementation and applications in nonlinear near-field optical microscopy.

Relative SHG measurements of metal thin films: Gold, silver, aluminum, cobalt, chromium, germanium, nickel, antimony, titanium, titanium nitride, tungsten, zinc, silicon and indium tin oxide

We have experimentally measured the surface second-harmonic generation (SHG) of sputtered gold, silver, aluminum, zinc, tungsten, copper, titanium, cobalt, nickel, chromium, germanium, antimony, titanium nitride, silicon and indium tin oxide thin films. The second-harmonic response was measured in reflection using a 150fs p-polarized laser pulse at 1561nm. We present a clear comparison of the SHG intensity of these films relative to each other. Our measured relative intensities compare favorably with the relative intensities of metals with published data. We also report for the first time to our knowledge the surface SHG intensity of tungsten and antimony relative to that of well known metallic thin films such as gold and silver.

Surface and bulk second-harmonic responses from a glass slide using tightly focused radially polarized light.

The radially polarized beam is tightly focused by a high numerical aperture microscope objective with adjustable cover glass correction. The intensities of a second-harmonic (SH) signal as a function of the focal position inside a glass slide for different settings of cover glass correction are measured. As compared to linear polarization illumination, the surface responses at the two surfaces of the glass slide are more easily observed in the case of radial polarization. For the first time, to the best of our knowledge, we present the experimental demonstration that surface and bulk SH responses from solid centrosymmetric materials can be separately addressed by adjusting the cover glass correction thickness and the position of the focal exciting field.