Second Harmonic Generation Light Research Articles

Characterizing electric fields in semiconductor devices: effect of second-harmonic light interference.

Characterizing electric fields in semiconductor devices using electric field-induced second-harmonic generation (EFISHG) has opened new opportunities for an advanced device design. However, this new technique still has challenges due to the interference between background second-harmonic generation (SHG) and EFISHG generated light. We demonstrate that interference effects can effectively be eliminated during EFISHG measurements by focusing the laser from the transparent substrate side of a GaN PN diode, enabling straightforward quantitative electric field analysis, in contrast to PN junction interface side measurements. A model based on wave generation and propagation is proposed and highlights the incoherence between background SHG and EFISHG light. This incoherence may be attributed to the depth of focus of the incident laser and phase mismatch between incident and SHG light.

Synthesis, Optical, Dielectric, SHG, Magnetic and Visible Light Driven Catalytic Studies on Compounds Belonging to the Swedenborgite Structure.

A new compound, InBaZn3GaO7, with swedenborgite structure along with transition metal (TM) substituted variants have also been prepared. The structure contains layers of tetrahedral ions (Zn2+/Ga3+) connected by octahedrally coordinated In3+ ion forming the three-dimensional structure with voids where the Ba2+ ions occupy. The TM substituted compounds form with new colors. The origin of the color was understood based on the ligand-field transitions. The near IR reflectivity studies indicate that the Ni - substituted compounds exhibit good near - IR reflectivity behavior, making them possible candidates for 'cool pigments'. The temperature dependent dielectric studies indicate that the InBaZn3GaO7 compound undergoes a phase transition at ~360 °C. The compounds are active towards second harmonic generation (SHG). Magnetic studies show the compounds, InBaZn2CoFeO7 and InBaZn2CuFeO7 to be anti-ferromagnetic in nature. The copper containing compounds were found to be good catalysts, under visible light, for the oxidation of aromatic alkenes. The many properties observed in the swedenborgite structure-based compounds suggests that the mineral structure offers a fertile ground to investigate newer compounds and properties.

Characterization of organic crystals for second-harmonic generation.

Second-harmonic generation (SHG) is a common technique with many applications. Common inorganic single-crystalline materials used to produce SHG light are effective using short IR/visible wavelengths but generally do not perform well at longer, technologically relevant IR wavelengths such as 1300, 1550, and 2000 nm. Efficient SHG materials possess many of the same key material properties as terahertz (THz) generators, and certain single-crystalline organic THz generation materials have been reported to perform at longer IR wavelengths. Consequently, this work focuses on characterizing three efficient organic THz generators for SHG, namely, DAST (trans-4-[4-(dimethylamino)-N-methylstilbazolium] p-tosylate), DSTMS (4-N,N-dimethylamino-4'-N'-methylstilbazolium 2,4,6-trimethylbenzenesulfonate), and the recently discovered generator PNPA ((E)-4-((4-nitrobenzylidene)amino)-N-phenylaniline). All three of these crystals outperform the beta-barium borate (BBO), an inorganic material commonly used for SHG, using IR pump wavelengths (1200-2000 nm).

Ferroelectric Domain Control of Nonlinear Light Polarization in MoS2 via PbZr0.2 Ti0.8 O3 Thin Films and Free-Standing Membranes.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) such as MoS2 exhibit exceptionally strong nonlinear optical responses, while nanoscale control of the amplitude, polar orientation, and phase of the nonlinear light in TMDCs remains challenging. In this work, by interfacing monolayer MoS2 with epitaxial PbZr0.2 Ti0.8 O3 (PZT) thin films and free-standing PZT membranes, the amplitude and polarization of the second harmonic generation (SHG) signal are modulated via ferroelectric domain patterning, which demonstrates that PZT membranes can lead to in-operando programming of nonlinear light polarization. The interfacial coupling of the MoS2 polar axis with either the out-of-plane polar domains of PZT or the in-plane polarization of domain walls tailors the SHG light polarization into different patterns with distinct symmetries, which are modeled via nonlinear electromagnetic theory. This study provides a new material platform that enables reconfigurable design of light polarization at the nanoscale, paving the path for developing novel optical information processing, smart light modulators, and integrated photonic circuits.

Speckle Decorrelation in Fundamental and Second-Harmonic Light Scattered from Nonlinear Disorder

Speckle patterns generated in a disordered medium carry a lot of information despite the apparent complete randomness in the intensity pattern. When the medium possesses ${\ensuremath{\chi}}^{(2)}$ nonlinearity, the speckle is sensitive to the phase of the incident fundamental light, as well as the light generated within. Here, we examine the speckle decorrelation in the fundamental and second-harmonic transmitted light as a function of the varying power in the fundamental beam. At low incident powers, the speckle patterns produced by successive pulses exhibit strong correlations, which decrease with increasing power. The average correlation in the second-harmonic speckle decays faster than in the fundamental speckle. Next, we construct a theoretical model, backed up by numerical computations, to obtain deeper physical insights into the faster decorrelations in the second-harmonic light. While providing excellent qualitative agreement with the experiments, the model sheds light on the contribution of two effects in the correlations, namely, the generation of second-harmonic light and the propagation thereof.

Simultaneous Second Harmonic Generation and multiphoton excited photoluminescence in anatase TiO2 nano powders

Second Harmonic Generation (SHG) and Multiphoton Excited Photoluminescence (MEPL) are observed in retro-reflection mode from a 22 nm diameter anatase TiO2 nanoparticle powder. Depth intensity profiles are obtained by scanning the fundamental beam focal point through the TiO2 powder surface into its volume for the energy of the incident photons tuned around the anatase TiO2 band-gap energy of 3.2 eV. Evidence for the appearance of both SHG and MEPL is presented, their relative contribution depending on the conditions of photo-excitation, in particular the fundamental wavelength and the focal point depth location. MEPL dominates at fundamental photon energies matching the band-gap energy whereas below and above the band-gap SHG is clearly seen. Depth intensity profiles exhibiting a rising edge determined by the fundamental laser beam focusing conditions and a decreasing edge determined by extinction and multiphoton scattering strongly differ between SHG and MEPL, SHG profiles being by far narrower than that of MEPL. Re-absorption of the emitted SHG and MEPL light occurs due to the spectral proximity with the TiO2 band gap energy but excitation with fundamental light below band-gap further suggests that the intrinsic difference between the two SHG and MEPL processes is responsible for the contrasted depth profiles. This combined study where both SHG and MEPL occur presents perspectives in the study of the photonic properties of powder materials.

Polytypes of sp2-Bonded Boron Nitride

The sp2-bonded layered compound boron nitride (BN) exists in more than a handful of different polytypes (i.e., different layer stacking sequences) with similar formation energies, which makes obtaining a pure monotype of single crystals extremely tricky. The co-existence of polytypes in a similar crystal leads to the formation of many interfaces and structural defects having a deleterious influence on the internal quantum efficiency of the light emission and on charge carrier mobility. However, despite this, lasing operation was reported at 215 nm, which has shifted interest in sp2-bonded BN from basic science laboratories to optoelectronic and electrical device applications. Here, we describe some of the known physical properties of a variety of BN polytypes and their performances for deep ultraviolet emission in the specific case of second harmonic generation of light.

Modeling the First-Order Molecular Hyperpolarizability Dispersion from Experimentally Obtained One- and Two-Photon Absorption.

The search for optical materials, particularly organic compounds, is still an attractive and essential field for developing several photonic devices and applications. For example, some applications are based on light scattering with twice the energy of the incoming photon for selected compounds, that is, the nonlinear optical effect related to the second-order susceptibility term from the electronic polarization expression. The microscopic interpretation of this phenomenon is called the first-order molecular hyperpolarizability or incoherent second harmonic generation of light. Understanding such phenomena as a function of the incoming wavelength is crucial to improving the optical response of future materials. Still, the experimental apparatus, hyper-Rayleigh scattering, apparently simple, is indeed a challenging task. Therefore, we proposed a proper alternative to obtain the dispersion of the first-order hyperpolarizability using the well-known one- and two-photon absorption techniques. By the spectral analysis of both the spectra, we gathered spectroscopic parameters and applied them for predicting the first-order hyperpolarizability dispersion. This prediction is based on an n-level energy system, taking into account the position and magnitude of transition dipole moments and the difference between the permanent dipole moment of the n-excited states. Moreover, using the presented method, we can avoid underestimating the first-order hyperpolarizability by not suppressing higher-energy transitions. Quantum chemical calculations and the hyper-Rayleigh scattering technique were used to validate the proposed method.

Chemistry, Structure, and Function of Lone Pairs in Extended Solids.

ConspectusThe lone pair has been a known feature of the electronic structure of molecules for over 100 years. Beginning with the pioneering work of Lewis and others that was later developed into useful guidelines for predicting molecular structure, lone pairs and their steric consequences are now taught at the very earliest stages of a chemistry education. In the crystalline solid state, lone pairs have perhaps had a less visible yet equally consequential role, with a significant impact on a range of properties and functionalities. Important properties associated with s2 electron-derived lone pairs include their role in creating conditions favorable for ion transport, in the formation and correlation of local dipoles and the resulting polar behavior leading to ferroics and multiferroics, in increasing the refractive index of glass, in reducing the thermal conductivity of thermoelectric materials, and in breaking local symmetry permitting second-harmonic light generation.. In recent years, the role of the lone pair in developing the electronic structure of some topological quantum materials has also been recognized. While structural distortions due to lone pairs have traditionally been characterized through their crystallography, recent advances in scattering and spectroscopy have revealed the presence of local lone pair-driven distortions that do not correlate over long length scales. The role of these crystallographically "hidden" lone pairs, their detection, and their impact on properties have become a growing body of work in the literature. Hidden lone pairs are an effective argument for considering a role for lone pairs that goes beyond their being objects that occupy space in the coordination polyhedra of cations. This Account introduces the chemistry of lone pairs in extended crystalline solids, including a discussion of when they are stereochemically active, how they manifest in the structure, and how their chemistry can be tuned by the chemical environment around them. Eventually, all of these factors work in unison to help develop and tune properties of interest. Certain specific examples of structure-property relationships in materials that are driven by lone pair behavior are described here, including the potential impact of lone pairs on the optical and electronic properties of hybrid halide perovskite compounds that are relevant to their photovoltaic applications. We highlight the role of lone pairs in the dielectric behavior of geometrically frustrated pyrochlores, the temperature-dependent optoelectronic behavior of halide perovskites, the polar phase transitions in lead-free ferroelectric perovskites, and the compositional insulator-to-metal transition in ruthenium pyrochlores. The theme underpinning this Account is that the lone pair can be considered to be a powerful design element for a broad range of material function.

Comparison of the histology and stiffness of ventricles in Anura of different habitats

Vertebrate hearts have undergone marked morphological and structural changes to adapt to different environments and lifestyles as part of the evolutionary process. Amphibians were the first vertebrates to migrate to land. Transition from aquatic to terrestrial environments required the ability to circulate blood against the force of gravity. In this study, we investigated the passive mechanical properties and histology of the ventricles of three species of Anura (frogs and toads) from different habitats, Xenopus laevis (aquatic), Pelophylax nigromaculatus (semiaquatic), and Bufo japonicus formosus (terrestrial). Pressure-loading tests demonstrated stiffer ventricles of P. nigromaculatus and B. j. formosus compared X. laevis ventricles. Histological analysis revealed a remarkable difference in the structure of cardiac tissue: thickening of the compact myocardium layer of P. nigromaculatus and B. j. formosus and enrichment of the collagen fibers of B. j. formosus. The amount of collagen fibers differed among the species, as quantitatively confirmed by second-harmonic generation light microscopy. No significant difference was observed in cardiomyocytes isolated from each animal, and the sarcomere length was almost the same. The results indicate that the ventricles of Anura stiffen during adaptation to life on land.

Second harmonic generation light quantifies the ratio of type III to total (I\u2009+\u2009III) collagen in a bundle of collagen fiber

The ratio of type III to type I collagen is important for properly maintaining functions of organs and cells. We propose a method to quantify the ratio of type III to total (type I + III) collagen (λIII) in a given collagen fiber bundle using second harmonic generation (SHG) light. First, the relationship between SHG light intensity and the λIII of collagen gels was examined, and the slope (k1) and SHG light intensity at 0% type III collagen (k2) were determined. Second, the SHG light intensity of a 100% type I collagen fiber bundle and its diameter (D) were measured, and the slope (k3) of the relationship was determined. The λIII in a collagen fiber bundle was estimated from these constants (k1-3) and SHG light intensity. We applied this method to collagen fiber bundles isolated from the media and adventitia of porcine thoracic aortas, and obtained λIII = 84.7% ± 13.8% and λIII = 17.5% ± 15.2%, respectively. These values concurred with those obtained with a typical quantification method using sodium dodecyl sulfate–polyacrylamide gel electrophoresis. The findings demonstrated that the method proposed is useful to quantify the ratio of type III to total collagen in a collagen fiber bundle.

Nonreciprocal second harmonic generation in a magnetoelectric material

Mirror symmetries are of particular importance because they are connected to fundamental properties and conservation laws. Spatial inversion and time reversal are typically associated to charge and spin phenomena, respectively. When both are broken, magnetoelectric cross-coupling can arise. In the optical regime, a difference between forward and backward propagation of light may result. Usually, this nonreciprocal response is small. We show that a giant nonreciprocal optical response can occur when transferring from linear to nonlinear optics, specifically second harmonic generation (SHG). CuB2O4 exhibits SHG transmission changes by almost 100% upon reversal of a magnetic field of just ±10 mT. The observed nonreciprocity results from an interference between magnetic-dipole and electric-dipole SHG. Although the former is inherently weaker than the latter, a resonantly enhanced magnetic-dipole transition has a comparable amplitude as a nonresonant electric-dipole transition, thus maximizing the nonreciprocity. Multiferroics and magnetoelectrics are an obvious materials platform to exhibit nonreciprocal nonlinear optical functionalities.

Organic Nanocrystal Fabrication Using the Process of Resonant Second-Harmonic Generation of Light.

Laser ablation with the use of ultra-short laser pulses is a widely used technique for the fabrication of nanoparticles of metals, inorganic and hybrid materials. However, fabrication of fragile organic nanocrystals via laser ablation is rarely used due to easy photodegradation of molecules. The method employing laser irradiation of the target material is beneficial as no other chemicals are used in the production of nanoparticles, except for a given material and a solvent. In this work, we test the concept of formation of nonlinear optical (NLO) organic nanocrystals dispersion in water by irradiation of the microcrystals of the NLO material with nonabsorbed infrared nanosecond light pulses. These pulses, due to a nonlinear optical process active in a noncentrosymmetric organic crystal, such as those studied in this work, DCNP dye (3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole), produce nanosecond pulses of second-harmonic (SH) light. Due to doubling of photon energy, they are reabsorbed in the volume of DCNP microcrystals and thermal shocks fracture them into nanometer size crystals. To the best of our knowledge, such process and its interpretation have not been described yet in the literature.

Symmetry Breaking and Nonlinear Electric Transport in van der Waals Nanostructures

The recent development of artificially fabricated van der Waals nanostructures makes it possible to design and control the symmetry of solids and to find novel physical properties and related functionalities. A characteristic physical property reflecting such symmetry breaking is the nonlinear response, which is typically studied as the second harmonic generation of light, although studies have recently expanded to include various transport phenomena. An important aspect of nonlinear transport for modern condensed matter physics is that it is not only a unique functionality of noncentrosymmetric systems but also an emergent property reflecting underlying physics such as spin–orbit interaction, superconductivity, magnetism, and band geometry/topology. In this article, we review the nonlinear electrical transport in noncentrosymmetric van der Waals nanostructures obtained by exfoliation, nano-structure fabrication, or the application of an electric field, in particular, nonreciprocal transport resulting from inversion symmetry breaking and the bulk photovoltaic effect in nanomaterials without conventional p- n junctions.

Seeing infrared optical vortex arrays with a nonlinear spiral phase filter.

We demonstrate a new method to detect infrared optical vortex arrays efficiently, which is based on simultaneous up-conversion imaging and spiral phase contrast via second-harmonic generation (SHG) in the Fourier domain. In our experiment, we use a spatial light modulator to prepare a variety of 1064nm structured vortex arrays and employ a vortex phase plate of different topological charges to serve as the nonlinear orbital angular momentum (OAM) filter. The SHG is done by mixing the Fourier spectra of input-structured vortices with a single OAM beam in a type-II potassium titanyl phosphate crystal. Then we can convert the input invisible vortex arrays into the visible SHG light fields, and the vortex cores are mapped and seen by bright Gaussian spots, revealing both their positions and topological charges. Our work has potential in the field of infrared imaging and monitoring.

Detection of elemental mercury using a frequency-doubled diode laser with wavelength modulation spectroscopy

We demonstrate a new method for elemental mercury sensing by wavelength modulation spectroscopy (WMS) using a tunable ultraviolet laser generated through a process of second-harmonic generation (SHG). The WMS is implemented by fast modulating the injection current of the Fabry–Perot-type green diode laser equipped with a Littrow grating to increase the laser-mode power density. The technique of correlation spectroscopy is exploited to deal with the signal variations due to mode hops and guarantee the measurement accuracy. According to the performance evaluation, the SHG-WMS system exhibits a better sensitivity (0.15 µg/m3 for 1-m pathlength with an integration time of 10 s) and a comparably high linearity (R2 = 0.9995 within the range of 60 µg/m2) compared with the direct absorption scheme. The employment of WMS significantly simplifies the data processing for extraction of small mercury absorption signals from the large and complex SHG light background, and, thus, give robust measurement results. High-harmonic (4f and 6f) detections are also carried out, showing a great potential for suppression of large residual amplitude modulation background. The proposed SHG-WMS system shows great promise for rapid and sensitive mercury sensing in industrial fields.

Nonlinear Diffraction in Asymmetric Dielectric Metasurfaces.

Metasurfaces provide new and promising mechanisms with which to control and manipulate light at the nanoscale. While most metasurfaces are designed to operate in the linear regime, it was recently shown that such metasurfaces may also generate nonlinear signals by manipulation of the higher-order susceptibility terms. As such, metasurfaces can generate additional harmonics without the need for light propagation, as typically occurs in nonlinear crystals. While such demonstrations typically rely on the nonlinear properties of metals, we hereby report the design, fabrication, and experimental characterization of a resonant dielectric metasurface made of amorphous silicon to create and manipulate second harmonic light and control its diffraction patterns. As shown in the paper, the second harmonic generation of light follows selection rules that rely on the asymmetry of the meta-atom. Given the fact that silicon crystals are centrosymmetric, the generation of the second harmonic signal in amorphous silicon is intriguing. In fact, the second harmonic signal is generated mostly from the surface of the meta-atom. It is the use of nanostructures that increases the surface-to-volume ratio and enables second harmonic generation. Additionally, the meta-atom is designed to exploit its spectral resonances in the principal and the second harmonic frequencies for providing electromagnetic field enhancement, which assists in boosting the generation of second harmonic signals.

Polarization-resolved second-harmonic-generation imaging of dermal collagen fiber in prewrinkled and wrinkled skins of ultraviolet-B-exposed mouse.

.Skin wrinkling is a typical symptom of cutaneous photoaging; however, the skin wrinkling depends on not only the actual age but also exposure history to ultraviolet B (UVB) rays in individuals. Therefore, there is considerable need for its assessment technique in vivo in skin cosmetics and antiaging dermatology. Wrinkles always appear as linear grooves in the skin, and dermal collagen fibers play an important role to determine the morphology and mechanical properties of the skin. Therefore, an optical probe sensitive to dermal collagen fiber and its orientation will be useful. Polarization-resolved second-harmonic-generation (SHG) microscopy is a promising approach for in vivo evaluation of collagen fiber orientation because the efficiency of SHG light is sensitive to collagen fiber orientation when the incident light is linearly polarized. We investigate orientation change of dermal collagen fiber in prewrinkled and wrinkled skins of the UVB-exposed mouse model using polarization-resolved SHG microscopy. A polarization anisotropic image of the SHG light indicates that the change of collagen fiber orientation starts in the prewrinkled skin of UVB-exposed mice, then the wrinkle appears. Furthermore, the dominant direction of collagen fiber orientation in the prewrinkled skin is significantly parallel to the wrinkle direction in the wrinkled skin. This result implies that the change of collagen fiber orientation is a trigger of wrinkling in cutaneous photoaging.

Second Harmonic Generation in CdSiP2 Nanowires in the Optical Frequency Regime

We report on the second harmonic generation of light in a cadmium silicon phosphide (CdSiP2, CSP) nanowire waveguide excited at the telecommunication wavelength of 1550 nm. This frequency-conversion process is studied by means of time-domain simulations that solve for the full vector fields of Maxwell’s equations and which incorporate the complete second-order nonlinear coefficient tensor of the CSP crystal. Over the short length of 30 $\mu \text{m}$ , the CSP nanowire waveguide produces electric field pulses having a peak-to-peak value of 116 kV/cm at a conversion efficiency of $1.6\times 10^{-3}$ . This electric field value is five times larger than that obtained in a lithium niobate nanowire waveguide having the same footprint, whereas the conversion efficiency value is 11 times higher than what is achieved in the lithium niobate nanowire. These results suggest that CSP nanowire waveguides have the potential to be used for on-chip sources of coherent optical radiation that are highly efficient given their compact structure.

Intrinsic second harmonic generation from un-poled doped silica multilayered thin films

Second harmonic light generation (SHG) was observed from as-deposited silica glass thin films suitable for waveguiding, without the need for an inversion symmetry-breaking poling treatment. Thin film stacks of up to 16 layers of alternating 2% phosphorus-doped and undoped silica glass on silica substrates were prepared and probed with a pulsed Nd:YAG laser at 1064 nm. We observed that even though these structures were not poled, they possess a net second order non-linearity with a value of the order of 0.03 pm/V. The SHG increased with the number of layers (total thicknesses between 4 and 9.6 µm have been tested) and also depended on the thickness ratio between the doped and undoped layers. Annealing at 800°C for 4 hours removed the nonlinearity completely.