Dependent Second Harmonic Generation Research Articles

Synthesis, structure, growth, characterization and quantum chemical studies on 2-amino-5-bromopyridinium trichloroacetate: A novel phasematchable organic NLO single crystal

Organic crystals have become excellent candidates towards nonlinear optical (NLO) applications as they possess superior second and third order optical nonlinearities and high electro-optic coefficients when compared with their inorganic counterparts. In this direction, 2-Amino-5-bromopyridinium trichloroacetate (2A5BPT), a new organic second-order nonlinear optical compound is synthesized and optical grade single crystals are formed utilizing a slow evaporation solution growth approach at room temperature while using methanol as the solvent. Single crystal X-ray diffraction study shows that the title compound is assigned to monoclinic crystal system having non-centrosymmetric space group Cc. The crystal is transparent ( ̴ 85%) throughout the whole visible spectrum, according to the Ultraviolet-Visble (UV–Vis) spectra, with a cutoff wavelength of 367 nm and an optical energy band gap Eg of 3.32 eV. The crystal possesses good thermal stability. The compound has a 1.6 times greater powder second harmonic generation (SHG) efficiency than potassium dihydrogen phosphate (KDP). The phase matchability of the 2A5BPT is studied through particle size dependence of SHG. The intermolecular connection demonstrated by numerous inter contacts has been shown by a molecular Hirshfeld surface analysis of the crystal structure, and the related 2-dimensional finger print analysis further evaluates the individual contribution from each atom. In order to examine the first order hyperpolarizability, molecular electrostatic potential, and Highest occupied molecular orbital-Lowest unoccupied molecular orbital (HOMO-LUMO) energies, the quantum chemical calculations for the title molecule (2A5BPT) were carried out by density functional theory (DFT) utilizing the B3LYP/6–311++G(d,p) basis set. According to these results, the 2A5BPT crystal could be suitable for optoelectronic applications.

Second-harmonic generation in 2D moiré superlattices composed of bilayer transition metal dichalcogenides.

Moiré superlattices (MSLs) in twisted two-dimensional van der Waals materials feature twist-angle-dependent crystal symmetry and strong optical nonlinearities. By adjusting the twist angle in bilayer van der Waals materials, the second-harmonic generation (SHG) can be controlled. Here, we focus on exploring the electronic and SHG properties of MSLs in 2D bilayer transition metal dichalcogenides (TMDs) with different twist angles through first-principles calculations. We constructed MSL structures of five TMD materials, including three single-phase materials (MoS2, WS2, and MoSe2) and two heterojunctions (MoS2/MoSe2 and MoS2/WS2) with twist angles of 9.4°, 13.2°, 21.8°, 32.2°, and 42.1° without lattice mismatch. Our findings demonstrate a consistent variation in the SHG susceptibility among different TMD MSLs as a response to twist-angle changes. The underlying reason for the twist-angle dependence of SHG is that the twist angle regulates the interlayer coupling strength, affecting the optical band gap of MSLs and subsequently tuning the SHG susceptibility. Through a comparison of the static SHG susceptibility values, we identified the twist angle of 9.4° as the configuration that yields the highest SHG susceptibility (e.g. 358.5 pm V-1 for the 9.4° MoSe2 MSL). This value is even twice that of the monolayer (173.3 pm V-1 for monolayer MoSe2) and AA'-stacked bilayer structures (139.8 pm V-1 for AA' MoSe2). This high SHG susceptibility is attributed to the strong interlayer coupling in the 9.4° MSL, which enhances the valence band energy (contributed by the antibonding orbitals of chalcogen-pz and transition metal-dz2) and consequently leads to a small optical band gap, thus improving the optical transitions. The findings of this study provide a straightforward way to improve the SHG performance of bilayer TMDs and also throw light on the sensitive relationship between the twist angle, band structure and SHG properties of TMD MSLs.

Second harmonic generation and two photon absorption assisted power limiting mechanism of l-Phenylalanine (LPA) - poly-ethylene-oxide (PEO) electrospun nanofibers

Nanofibers consisting of organic nonlinear optical l-Phenylalanine (LPA) nanocrystals embedded in poly-ethylene-oxide (PEO) polymer were synthesized by the electrospinning technique. The preferred crystallographic orientation of the organic molecules that crystallized inside the nanofibers was demonstrated through X-ray diffraction and calculations show that the average crystallite size is around 28 nm. SEM images clearly show the formation of smooth fibers with average diameter of 246 nm. The emission of green light from the nanofiber powder sample approved the second harmonic generation (SHG) under the excitation of Nd: YAG laser (1064 nm). Further the generation of second harmonic from the fibers was confirmed by nonlinear microscope imaging and power dependent SHG studies, performed using femtosecond fiber laser (1040 nm). The nonlinear absorption and its power limiting characteristics of LPA-PEO electro-spun nanofibers were studied utilizing the Z-scan method employing Q switched Nd: YAG laser as an excitation source (532 nm, 5 ns, 10 Hz). Open aperture Z-scan measurement (with intensity 1.23 × 1012 W/m2 and 2.4623 × 1012 W/m2) revealed the reverse saturable absorption property of LPA-PEO nanofibers. The existence of a sequential two-photon absorption process involving real resonant intermediate states has been demonstrated by the intensity dependent two-photon absorption coefficient. The usefulness of LPA optical fibers as power limiters is ensured by their lower optical limiting threshold than other optical limiting materials.

Nonlinear Optical Properties in an Epitaxial YbFe2O4 Film Probed by Second Harmonic and Terahertz Generation.

An epitaxial film of YbFe2O4, a candidate for oxide electronic ferroelectrics, was fabricated on yttrium-stabilized zirconia (YSZ) substrate by magnetron sputtering technique. For the film, second harmonic generation (SHG), and a terahertz radiation signal were observed at room temperature, confirming a polar structure of the film. The azimuth angle dependence of SHG shows four leaves-like profiles and is almost identical to that in a bulk single crystal. Based on tensor analyses of the SHG profiles, we could reveal the polarization structure and the relationship between the film structure of YbFe2O4 and the crystal axes of the YSZ substrate. The observed terahertz pulse showed anisotropic polarization dependence consistent with the SHG measurement, and the intensity of the emitted terahertz pulse reached about 9.2% of that emitted from ZnTe, a typical nonlinear crystal, implying that YbFe2O4 can be applied as a terahertz wave generator in which the direction of the electric field can be easily switched.

Insights into the mechanism of the symmetry dependent SHG properties in low dimensional KNbO3 structures

The second harmonic generation (SHG) response of low-dimensional nanomaterials is potential dependence on structural symmetry and high-density surface defects, e.g., body contribution and surface contribution.

Mode-Matching Enhancement of Second-Harmonic Generation with Plasmonic Nanopatch Antennas.

Plasmonic enhancement of nonlinear optical processes confront severe limitations arising from the strong dispersion of metal susceptibilities and small interaction volumes that hamper the realization of desirable phase-matching-like conditions. Maximizing nonlinear interactions in nanoscale systems require simultaneous excitation of resonant modes that spatially and constructively overlap at all wavelengths involved in the process. Here, we present a hybrid rectangular patch antenna design for optimal second-harmonic generation (SHG) that is characterized by a non-centrosymmetric dielectric/ferroelectric material at the plasmonic hot spot. The optimization of the rectangular patch allows for the independent tuning of various modes of resonances that can be used to enhance the SHG process. We explore the angular dependence of SHG in these hybrid structures and highlight conditions necessary for the maximal SHG efficiency. Furthermore, we propose a novel configuration with a periodically poled ferroelectric layer for an orders-of-magnitude enhanced SHG at normal incidence. Such a platform may enable the development of integrated nanoscale light sources and on-chip frequency converters.

Spatial mapping of exciton transition energy and strain in composition graded WS2(1−x)Se2x monolayer

We studied the optical properties of a composition graded WS2(1−x)Se2x alloy monolayer. A symmetric gradual composition gradient from a Se-rich center to the relatively less Se-rich edges of an equilateral triangle shaped flake is confirmed by Raman mapping. Photoluminescence (PL) mapping shows a large 100 meV variation in the exciton energy, resulting from the composition dependent bandgap variation and carrier localization. The alloying leads to symmetry breaking and large nonlinear optical susceptibility. Second harmonic generation (SHG) mapping was carried out to study the non-linear properties and additionally to determine the lattice strain of the alloy flake. In contrast to PL and Raman mappings, SHG intensity is found to be spatially uniform. However, polarization dependent SHG reveals a unidirectional strain parallel to the (zigzag) edge of the flake, in addition to the sixfold symmetry expected from the transition metal dichalcogenide (TMD) lattice. Our results suggest potential applications of composition graded TMD alloys as ultra-compact color-tunable light sources and miniaturized spectrometers.

Compositional dependence of linear and nonlinear optical response in crystalline hafnium zirconium oxide thin films

Composition dependence of second harmonic generation, refractive index, extinction coefficient, and optical bandgap in 20 nm thick crystalline Hf1−xZrxO2 (0 ≤ x ≤ 1) thin films is reported. The refractive index exhibits a general increase with increasing ZrO2 content with all values within the range of 1.98–2.14 from 880 nm to 400 nm wavelengths. A composition dependence of the indirect optical bandgap is observed, decreasing from 5.81 eV for HfO2 to 5.17 eV for Hf0.4Zr0.6O2. The bandgap increases for compositions with x > 0.6, reaching 5.31 eV for Hf0.1Zr0.9O2. Second harmonic signals are measured for 880 nm incident light. The magnitude of the second harmonic signal scales with the magnitude of the remanant polarization in the composition series. Film compositions that display near zero remanent polarizations exhibit minimal second harmonic generation while those with maximum remanent polarization also display the largest second harmonic signal. The results are discussed in the context of ferroelectric phase assemblage in the hafnium zirconium oxide films and demonstrate a path toward a silicon-compatible integrated nonlinear optical material.

Extraordinary Temperature Dependent Second Harmonic Generation in Atomically Thin Layers of Transition‐Metal Dichalcogenides

AbstractAtomically thin transition metal dichalcogenides (TMDs) are important semiconducting materials because of their interesting layer dependent properties. Recently, optical second harmonic generation (SHG) is used to probe layer number, lattice orientation, phase variation, and strain vector in ultrathin TMDs. Here, it is demonstrated that SHG response of ultrathin TMDs is highly sensitive to temperature modulation. Furthermore, temperature dependent SHG is found to show opposite trends for single layer and few odd layers (3L, 5L, 7L, etc.) of TMDs. A remarkable temperature dependent SHG enhancement (25.8%) is found in single layer molybdenum diselenide (MoSe2) using 900 nm laser excitation whereas few odd layers show significant temperature dependent SHG quenching which is found to be ‐55.2%, ‐31.02%, and ‐18.4% in case of 3L, 5L, and 7L of MoSe2. Temperature dependent SHG investigation with other TMDs, like MoS2, WS2, and WSe2, shows the similar trend which reveals an important structural characteristic for TMDs. Second order nonlinear susceptibility calculations considering weak van der Waal forces during thermal expansion in ultrathin TMDs show good agreement with the experimental findings. The results show SHG as a powerful and sensitive approach to investigate thermal variation in ultrathin TMDs.

Quantum-enhanced tunable spin-valley dependent excitonic second harmonic generation in molybdenum disulfide quantum dots

Developing a robust system with a strong tunable nonlinear second harmonic generation (SHG) is desirable. In this work, we calculate SHG arising from the excitonic states of monolayer molybdenum disulfide quantum dots (MoS2 QDs) with a parabolic confinement potential within massive Dirac fermion model using the density matrix formalism. We theoretically demonstrate that MoS2 QDs can exhibit a giant and tunable Spin-Valley dependent excitonic SHG, which can be tuned from 0 to ∼107 pm V−1 and realized by biasing nanostructured gates or by position-dependent doping. Remarkably, the strength of SHG response is more than two orders of magnitude higher than that in monolayer MoS2. Furthermore, robust excitonic effects together with strong spin-valley coupling in monolayer transition metal dichalcogenides quantum dots (TMDC QDs), which are tunable depending on the strength of the quantum confinement, make them as a promising candidate for ultrathin nonlinear optical materials with large nonlinearities. We believe that this study could spark interest in the nonlinear optical properties of TMDC QDs and open up a variety of new avenues for versatile novel 2D nonlinear photonics and optoelectronic nanodevices.

A self-consistent model of second harmonic generation of laser radiation in the periodically poled nonlinear-optical crystal conditioned by its nonuniform heating

We introduce a self-consistent model that describes the process of the second harmonic generation (SHG) of the laser radiation in a nonlinear-optical crystal in conditions of its nonuniform heating induced by optical absorption. A periodically poled crystal pumped by the pulse laser radiation focused into its center was considered. The iteration procedure of solving the SHG problem relies on the interrelated solution of two equation systems describing the temperature dependent SHG and the heat conduction processes. The heat sources are represented by the absorbed power of both pump and generated radiations. Along with the absorption of pump and generated waves the diffraction effect was also taken into account. Eventually the resulting distribution of the crystal temperature should correspond to the radiation intensity distributions of pump and second harmonic.

Polarization dependence of second harmonic generation from plasmonic nanoprism arrays

The second order nonlinear optical response of gold nanoprisms arrays is investigated by means of second harmonic generation (SHG) experiments and simulations. The polarization dependence of the nonlinear response exhibits a 6-fold symmetry, attributed to the local field enhancement through the excitation of the surface plasmon resonances in bow-tie nanoantennas forming the arrays. Experiments show that for polarization of the input light producing excitation of the plasmonic resonances in the bow-tie nanoantennas, the SHG signal is enhanced; this despite the fact that the linear absorption spectrum is not dependent on polarization. The results are confirmed by electrodynamic simulations which demonstrate that SHG is also determined by the local field distribution in the nanoarrays. Moreover, the maximum of SHG intensity is observed at slightly off-resonance excitation, as implemented in the experiments, showing a close relation between the polarization dependence and the structure of the material, additionally revealing the importance of the presence of non-normal electric field components as under focused beam and oblique illumination.

Optical second harmonic generation in a ferromagnetic liquid crystal.

A comparative experimental investigation of the dependence of second harmonic generation (SHG) on an applied external voltage between a standard nematic liquid crystalline material and an analogue ferromagnetic nematic liquid crystalline material was performed by using a fundamental optical beam at an 800 nm wavelength. For the ferromagnetic material, the dependence of SHG on an applied magnetic field was also examined. Three different polarization combinations of the fundamental and the second harmonic radiation were analysed. The SHG signal observed in the former material is attributed to a combination of electric field-induced SHG (EFISHG) and flexoelectric deformation-induced SHG, while the SHG signal observed in the latter material is attributed solely to flexoelectric deformation-induced SHG. The obtained dependences of the SHG signal on the associated optical retardation show that, in the most favourable polarization combination, the two contributions generate about the same effective nonlinear optical susceptibility.

Second harmonic generation in strained transition metal dichalcogenide monolayers: MoS2, MoSe2, WS2, and WSe2

Second-harmonic generation (SHG) is a powerful measurement technique to analyze the symmetry properties of crystals. Mechanical strain can reduce the symmetry of a crystal and even weak strain can have a considerable impact on the SHG intensity along different polarization directions. The impact of strain on the SHG can be modeled with a second-order nonlinear photoelastic tensor. In this work, we determined the photoelastic tensors at a fundamental wavelength of 800 nm for four different transition metal dichalcogenide (TMD) monolayers: MoS2, MoSe2, WS2, and WSe2. Strain is applied using a three-point bending scheme, and the polarization-resolved SHG pattern is measured in backscattering geometry. Furthermore, we connected the strain dependent SHG with the strain dependence of the A-exciton energy. With the second-order nonlinear photoelastic tensor, full strain information can be accurately extracted from polarization-resolved SHG measurements. Accordingly, uniaxial strain, induced by polydimethylsiloxan (PDMS) exfoliation and transfer, is measured. We find that TMD monolayers fabricated with PDMS are strained by ∼0.2%. With the experimentally determined nonlinear photoelastic tensors, it will be possible to optically probe arbitrary strain fields in TMD monolayers.

Electric Field Effect on Optical Second-harmonic Generation of Amphoteric Megamolecule Aggregates

We have detected second-order nonlinear optical response from an amphoteric mega-saccharides named sacran under a needle/ring electrode stimulus by using an optical second harmonic generation (SHG) microscope. SHG was observed from sacran in the neighborhood of the negatively biased needle electrode below -4.5 V with respect to the outer ring electrode. From the incident light polarization dependence of SHG, this sacran was suggested to be oriented toward the electrode needle. SHG of the sacran polymer was judged to be induced by sacran aggregates with net positive charge.

\u03bcMAPPS: a novel phasor approach to second harmonic analysis for in vitro-in vivo investigation of collagen microstructure

Second Harmonic Generation (SHG) is a label-free imaging method used to monitor collagen organization in tissues. Due to its sensitivity to the incident polarization, it provides microstructural information otherwise unreachable by other intensity based imaging methods. We develop and test a Microscopic Multiparametric Analysis by Phasor projection of Polarization-dependent SHG (μMAPPS) that maps the features of the collagen architecture in tissues at the micrometer scale. μMAPPS retrieves pixel-by-pixel the collagen fibrils anisotropy and orientation by operating directly on two coupled phasor spaces, avoiding direct fitting of the polarization dependent SHG signal. We apply μMAPPS to fixed tissue sections and to the study of the collagen microscopic organization in tumors ex-vivo and in-vivo. We develop a clustering algorithm to automatically group pixels with similar microstructural features. μMAPPS can perform fast analyses of tissues and opens to future applications for in-situ diagnosis of pathologies and diseases that could assist histo-pathological evaluation.

Second-order nonlinear optical microscopy of spider silk

Asymmetric $\rm \beta$-sheet protein structures in spider silk should induce nonlinear optical interaction such as second harmonic generation (SHG) which is experimentally observed for a radial line and dragline spider silk by using an imaging femtosecond laser SHG microscope. By comparing different spider silks, we found that the SHG signal correlates with the existence of the protein $\rm \beta$-sheets. Measurements of the polarization dependence of SHG from the dragline indicated that the $\rm \beta$-sheet has a nonlinear response depending on the direction of the incident electric field. We propose a model of what orientation the $\rm \beta$-sheet takes in spider silk.

A study on the l-lysine-iodic acid: semi organic non linear optical single crystals for electro-optic applications

Non linear optical single crystals of l-lysine-iodic acid (LLI) of dimensions upto 24 × 14 × 5 mm3 have been grown successfully by slow evaporation technique from aqueous solution. The crystal structure of the grown material was solved by single crystal X-ray diffraction analysis and it was found that the LLI crystal belongs to monocinic system with space group P21. Functional groups of the grown crystal were identified by Fourier Transform Infrared (FTIR) spectral analysis. The UV–Vis spectral analysis was carried out to measure the transparent range of the LLI crystal which is nearly 85% and the band gap energy is found to be 5.51 eV. Thermal stability and decomposition temperature of LLI crystal was found by means of TGA and DTA analyses. The mechanical behavior of the grown crystal has been employed using Vicker’s micro hardness technique. The Second Harmonic Generation (SHG) efficiency of the crystal was investigated and it was found to be 3.2 times of KDP. The particle size dependent SHG studies of LLI crystals were performed using Nd:YAG laser. The laser damage threshold value of LLI crystal is found to be 8.54 GW/cm2. Dielectric study indicates the reasonable dielectric constant and low dielectric loss of LLI crystal which are essential properties to develop optoelectronic devices. The ac and dc electrical conductivity measurements were carried out at various temperatures. Photoconductivity study exhibits the negative photoconductivity nature of the LLI crystal and the results are discussed for the first time.

Second-harmonic generation in quaternary atomically thin layered AgInP2S6 crystals

Nonlinear effects in two-dimensional (2D) atomic layered materials have attracted increasing interest. Here, we report the observation of optical second-harmonic generation (SHG) in two-dimensional atomically thin silver indium phosphorus sulfide (AgInP2S6) crystals, with odd layer thickness. The nonlinear signal facilitates the use of thickness-dependent SHG intensity to investigate the stacking type of this material, while the crystal-orientation dependent SHG intensity of the monolayer sample reveals the rotational symmetry of the AgInP2S6 lattice in plane. Our studies expand the 2D crystal family in nonlinear effect field, which opened considerable promise to the functionalities and potential applications of 2D materials.

(Invited) Non-Destructive Characterization of Dielectric - Semiconductor Interfaces by Second Harmonic Generation

Here we present the characterization of dielectric - semiconductor interfaces using optical second harmonic generation (SHG). The technique is contactless, which makes it useful for non-destructive monitoring of ultra-thin dielectrics. The generated second harmonic is sensitive to material parameters and charges near interfaces. The signal exhibits time dependence due to charging of traps with carriers generated by the incident laser during the measurement. Quantitative models are applied to the time dependent SHG signals in the Al2O3 stacks, which provide trapping kinetics information, and thus Al2O3 film quality. Al2O3 films are commonly used for passivating Si in photovoltaic stacks. To further demonstrate that time dependent behavior is due to changes in the electric field across the semiconductor/dielectric interface, additional systems are presented for comparison: SiNx on silicon, passivated and non-passivated silicon-on-insulator substrates. Results confirm the value of SHG as a quality control method for multiple thin film dielectrics.