Third-order Optical Nonlinearity Research Articles

Enhancement of third-order optical nonlinearity in effective epsilon-near-zero metamaterials of dielectric/metal/dielectric sandwich nanostructures

We report the enhancement of third-order optical nonlinearity in dielectric/metal/dielectric sandwiches driven by the epsilon-near-zero (ENZ) effect. The lithium niobate (LN) and Au are chosen as the typical dielectric and metal, respectively. The sandwich nanostructure consists of two layers of LN film (90 nm) and an insertion of Au layer of different thicknesses (9, 13, and 17 nm). The ENZ wavelength of LN/Au/LN (LAL) sandwiches is experimentally obtained with a modulation from 0.96 μm (Au layer 17 nm) to 1.33 μm (Au layer 9 nm). The nonlinear refractive index n2 and nonlinear absorption coefficient β are determined at variable near infrared wavelengths using the Z-scan method. The maximum n2=2.31×10−14(6.76×10−15)m2/W and β=−9.20×10−8(−1.94×10−8)m/W are obtained in the LAL sandwich with a 13 nm Au layer of ENZ wavelength 1.088 μm at the wavelength 1.064 μm with a pulse duration of 25 ps (120 fs). The n2 is around 19 and 25 times larger than those in the pure LN film of thickness 180 nm measured at the picosecond and femtosecond time domains, respectively. The enhancement of n2 in LAL sandwiches follows the numerical results obtained from the ENZ effect. Especially, the LN layer and the Au layer have comparable contributions to the effective third-order susceptibility χeff(3), which leads to the reconfigurable χeff(3) by changing the thickness of each layer and further to modulate the n2 and β of the samples. The results offer a promising way to attain large and reconfigurable optical nonlinearities for application in all-optical photonic devices at a specified wavelength.

Quantum chemical study of new oxadiazoles as efficient optical and nonlinear optical and photovoltaic materials under gas, PCM and COSMO solvent effects

The science of organic optical and nonlinear optical (NLO) materials has been captivating the scientific community owing to their extensive applications in optoelectronics, OLEDs, and telecommunications. This study presents the design and investigation of novel organic compounds of pyrene and 1,3,4-oxadiazole derivatives (1-oxza to 6-oxza), featuring various push–pull combinations. Quantum chemical calculations were employed to determine linear polarizabilities (α) and third-order NLO polarizabilities (γ). Notably, the largest average third-order NLO polarizability value was found to be 254.9 × 10−36 esu for the finely tuned push–pull system 6-oxza, which is ∼35 times greater than that of the prototype NLO molecule of p-nitroaniline (p-NA). Among the derivatives, 1-oxza exhibits the highest linear isotropic polarizability (αiso) value of 61.59 × 10−24 esu, while 5-oxza displays the highest linear anisotropic polarizability (αaniso) value of 60.09 × 10−24 esu. A notable increase of approximately ∼1 to ∼2 times in < γ > is observed for selected compounds (1-oxza, 4-oxza, 6-oxza), indicating that the Conductor-like Screening Model (COSMO) overestimates the values compared to the polarizable continuum model (PCM) and gas phases. Solvent significantly enhances third-order NLO polarizability amplitudes depending upon solvent polarity and strength of substitution groups. We calculated the frequency-dependent third-order NLO polarizability of 6-oxza at laser wavelengths ranging from 1400 to 1970 nm. The second hyperpolarizability EFISHG process (γ(−2ω; ω, ω, 0)) was calculated at a laser wavelength of 1400 nm, and the γ-amplitude was found to be 400.1 × 10−36 esu. The remarkable hyperpolarizability response in the gas phase is corroborated by TD-DFT calculations, which reveal a larger transition dipole moment of 3.062 and a lower transition energy of 3.780 eV as origin of larger hyperpolarizability for 6-oxza. A comprehensive analysis was performed based on FMOs for designed compounds to elucidate the intramolecular charge transfer (ICT) mechanisms and observed a notable reduction in energy band gap 4.89 eV for 6-oxza, which is responsible for enhanced NLO response. Additionally, DOS maps revealed the quantitative contributions of HOMOs and LUMOs for crucial electronic states related to the efficient ICT process. Additionally, we analyzed the photovoltaic properties and found that 6-oxza has the highest dye regeneration and the lowest open-circuit voltages of 1.89 eV and 2.22 eV, respectively. Our designed model compounds can put real-time such compounds under spotlight of scientific interests which seeks more efficient optical and NLO properties.

Synthesis, spectral, crystal structure, linear and NLO properties of quinoline Schiff base: Combined experimental and DFT calculations

The study explores the optical and nonlinear optical (NLO) properties of 2-imino [N- (N'-amido phenyl)] chromophore, a compound with potential in photonic applications. The compound was produced and crystallized using a slow evaporation approach using ethanol as solvent, and spectroscopy techniques were used to characterize it. The molecular structure of the compound was determined using FT-IR and NMR spectral methods. The crystal's structure was found via SCXRD analysis, showing a monoclinic system with a P21/c space group. The UV–Vis-NIR spectrum showed good transmittance over the visible region, with lower cutoff wavelengths of 338 nm and optical band gaps of 3.17 eV. The grown crystal exhibited a χ3 value of 2.89 × 10−8esu, making it valuable for non-linear optical applications. Quantum computational analysis was used to investigate molecular architectures, topologies, and molecule-level third-order NLO response. The compound exhibited a planar molecular geometry, with an average third-order NLO polarizability of 69.65 × 10−36 esu. The study also examined quantum chemically computed UV–visible spectra and electron density difference maps, as well as the density of states and molecular electrostatic potentials. In addition to highlighting the relationship between structure and characteristics, our current study of synthesized compounds highlights the potential of photonic applications.

Third-order nonlinear optical properties based on triphenylamine derivative-based covalent organic frameworks

Nonlinear optics (NLO) is an extremely critical research area. In recent years, covalent organic frameworks (COFs) have attracted much attention as a potential NLO material. In this study, a series of COF materials with different D-A effects were successfully synthesized based on the excellent electron-donating properties of the triphenylamine group and were prepared into D-A COFs\\KBr sheet materials that can be used for third-order NLO by the KBr−pressing method. The results of the open-aperture Z-scan technique showed that all COFs\\KBr sheets exhibited saturable absorption (SA) behavior at 3 μJ, with nonlinear absorption coefficients (β) of −1.64, −1.23, and −2.02 × 10−9 mW−1 for PT-PA, PT-BD, and PT-TZ, respectively. Theoretical calculations show that the electron transport distance of PT-PA is shorter than that of PT-BD, while the introduction of S atoms makes the D-A effect of PT-TZ stronger than that of PT-BD, and thus the SA properties of PT-PA and PT-TZ are better than those of PT-BD. These works indicate that the COFs\\KBr sheets have a potential application as high-performance NLO materials and also provide an option for COFs powder application in the field of third-order NLO.

A Porphyrin-Based MOF Thin Film with Oriented Nanosheet Arrays for Optimizing a Nonlinear Optical Response.

Developing two-dimensional (2D) hybrid nanosheet arrays integrating inorganic and organic components is highly significant for third-order nonlinear optical (NLO) applications. Herein, an oriented 2D porphyrin-based MOF (ZnTPyP(Co)) thin film composed of vertically stacked ultrathin nanosheets was fabricated via the liquid-phase epitaxial (LPE) layer-by-layer (LBL) method. The prepared ZnTPyP(Co) thin film exhibits an outstanding third-order NLO response with a high third-order nonlinear susceptibility of ∼2.63 × 10-7 esu, which is ascribed to the hybrid nanosheet array structure. Additionally, experimental Z-scan measurement and theoretical calculations also demonstrate that the substitution of Co metal ions in the porphyrinic core can increase the level of delocalization of the porphyrinic group and contribute to the material's enhanced NLO properties. These findings not only provide new film candidates for NLO application but also highlight the potential of 2D MOF nanosheets in advanced optical devices.

Synthesis, spectroscopical and DFT studies on third order NLO crystal: Sodium bis(malonato)borate monohydrate (SBMBM)

The single crystal of sodium bis(malonato)borate monohydrate (SBMBM) was grown using the Slow Evaporation Solution Technique(SEST). To analyze the crystal lattice parameters of the grown SBMBM crystal, Single Crystal X-Ray Diffraction analysis were used. The results shows that the crystal belongs to Triclinic crystal system with space group P21/n with lattice parameters A = 7.9058 (4) Å, B = 8.2979 (5) Å, and C = 14.6473 (9) Å, where α = 90°, β = 101.565 (2)°, and γ = 90° The theoretical calculation utilizing HF/LANL2DZ and the experimental results agree rather well. The molecular optimized geometry, FT-IR, and the energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were calculated using the HF/LANL2DZ basis set. The several functional groups in the SBMBM crystal are investigated by FT-IR spectrum. Studies of UV–visible NIR transmittance indicate that the crystal has a high transmittance throughout the whole visible spectrum. Using the Z-scan technique, third-order nonlinear optical (NLO) property of SBMBM crystal is analysed, and the linear and nonlinear refractive index are computed. χ3 = 4.49 × 10−6esu is the third-order nonlinear optical susceptibility.

Nonlinear optical properties of La3+-Doped tellurite-zinc glasses: Impact of chemical bonding and physical properties via Raman and XPS

Understanding the connection between the local environments of lanthanum ions in tellurite glasses and their nonlinear optical (NLO) properties is essential for various technological applications. Rare earth ions can serve as probes for the local environments of the host material if the structure-property correlations are well understood. In this study, we investigated glasses with compositions 70TeO2 - (30-x)ZnO - (x)La2O3 (mol%) (x = 0, 5, 7, 9) fabricated by the melt-quenching technique. The capabilities of combined Raman and X-ray photoemission (XPS) spectroscopy were used to identify these glasses and define spectral deconvolution for distinguishing them in the formation of bridging oxygens (BO) and non-bridging oxygens (NBO). NLO properties were evaluated using open-aperture (OA) and closed-aperture (CA) Z-scan measurements with femtosecond (fs) laser pulses (∼220 fs, 750 Hz) at wavelengths ranging from 600 to 1500 nm. Raman spectra revealed a shift to higher frequencies from 731 to 746 cm−1, with increasing of La3+ ions, indicating the conversion of TeO4 polyhedra to TeO3 structural units, affecting the Te-O- Zn2+ or Te=O bonds and resulting in a variation of the polarizability. Besides the conventional analysis of oxidation state and chemical shifts of the core-level peaks, XPS spectroscopy included a careful analysis of the type oxygen bridges and metal-oxygen bond length to distinguish otherwise similar spectral contributions of different TZL glasses. Glasses with a high fraction of Zn2⁺ ions bonded with oxygen form NBO and modify the local structure of the glass network, while La³⁺ ions coordinate with oxygen atoms or interact with the lone pairs of tellurium atoms. By analyzing the correlation in different concentrations of La3+ ions, the Te-O bonds and NBO/(BO + NBO) ratio were clearly demonstrated. These findings suggest charge compensation between the Zn2⁺ and La³⁺ ions, for maintaining structural stability within the glass network. This study also reveals an enhancement of NLO properties as a function of La3+ ions concentration in TZL glasses under fs laser excitation due to resonant nonlinearity. The third-order optical nonlinearities showed an increase in the two-photon absorption coefficient (β) from 0.26 × 10−2 cm GW−1 (TZL5) to 0.62 × 10−2 cm GW−1 (TZL9), along with an increase in the nonlinear refractive index (n2) from 0.32 × 10−18 m2 W−1 to 0.65 × 10−18 m2 W−1. This enhancement is attributed to the increased number of NBOs and the high polarizability of La3+ ions. For all-optical switching (AOS) applications, two figures of merit were applied using the n2, α0, and β coefficients. The results suggest that the TZL glasses studied are potential candidates for AOS devices. Thus, this work not only elucidates the factors underlying the NLO properties but also highlights the promising potential of these glasses for use in AOS devices.

Investigation on Growth, Structural, Spectral, DFT, MEP Computational Studies of Novel Methyl Triphenylphosphonium Bromide HydrateSingle Crystal for Third-Order Nonlinear Optical Limiting Applications

A novel organic nonlinear optical (NLO) single crystal, Methyl Triphenylphosphonium Bromide Hydrate (MTPB), grown for the first time using the slow evaporation solution technique at room temperature. Comprehensive structural analysis by single crystal X-ray diffraction reveals that MTPB crystallizes in the monoclinic system with space group P2₁/n, and its lattice parameters have been accurately determined. Structural refinement was performed using the full matrix least squares technique with the SHELXL-97 program. To characterize the molecular structure and interactions, FT-IR and FT-Raman spectra provided functional group identification, and 2D fingerprint and Hirshfeld surface analyses offered insights into hydrogen bonding interactions within the crystal. The novelty extends to computational analysis, where the molecule's geometry was optimized using DFT-B3LYP with a 6-31++G(d,p) basis set, allowing comparison between theoretical vibrational frequencies and experimental data. Additionally, the third-order NLO properties were assessed via the Z-scan technique, marking the first use of MTPB in optical limiting applications. This work's innovation lies in the successful synthesis, comprehensive characterization, and demonstration of MTPB's significant potential as an optical limiter, paving the way for new NLO applications.

Bismorpholin-4-ium tetrabromo-cadmium metal-organic single crystal delivering Crystal structure, physicochemical properties and Characterizations for Optoelectronic Applications

For the development of nonlinear optical (NLO) materials, compositions of cadmium chloride (CC) and Morpholinium bromide (MB) molecules were utilized to form metal-organic materials. Morpholinium bromide was incorporated with cadmium metal to have electron charge transfer by constructing acentric structures that take advantage of strong third-order nonlinear optical properties. Bis Morpholinium cadmium bromide (BMCB) crystals were synthesized by a slow evaporation method (SEST). The BMCB crystal belongs to monoclinic P21/c space group with four molecules in the unit cell (a = 6.7607(4) Å, b = 16.5811(2) Å, c = 14.9744(2) Å, β=94.136(3) ° and Z = 4). The grown BMCB crystal phase purity and crystallinity were further investigated using powder X-ray diffraction (PXRD) analysis. Using Fourier transform infrared (FTIR) spectroscopy, the functional groups and their vibrational states were evaluated. From the results obtained from UV–vis-NIR spectral analysis, it is clear that the title compound is transparent in the visible range with the lower cut-off wavelength of 254 nm. The TG-DTA measurement has been used to evaluate thermal stability. Microhardness measurements were carried out to evaluate the mechanical stability of the grown crystal. The third-order nonlinear optical (NLO) characteristics were studied using Z-scan technique. The grown crystal exhibits outstanding third-order NLO response and wide laser damage threshold (LDT), which are crucial characteristics for developing practical NLO devices. The findings consequently open a novel path for the logical design of enormous, thermally stable and NLO-active metal-organic complexes for NLO applications.

Study of Solvent Dependent on Third-Order Nonlinear Optical and Thermo-Optic Coefficient of Malachite Green Dye.

This study reveals the solvent dependent third-order nonlinear optical (NLO) features of malachite green (MG) dye using Z-scan technique. MG dye is dissolved in polar solvents, including DMF, DMSO, ethanol, acetone, methanol, and 1-propanol. The study employs the Z-scan instrument, using a continuous wave (CW) laser as the excitation source, operating at a wavelength of 650nm. The closed aperture (CA) and open aperture (OA) Z-scan techniques are used to assess the nonlinear indices of refraction (n2) and nonlinear coefficient of absorption (β) of MG dye. MG dye demonstrates both saturable absorption (SA) and reverse saturable absorption (RSA) in the OA Z-scan results, due to negative and positive NLO absorption coefficients. MG dye proves a self-defocusing NLO refractive index while operating under low-power conditions. The third-order NLO susceptibility (χ3) of MG dye in various liquids are calculated to be the order of 10-6 esu. Multilinear regression fit is applied here to investigate the various intermolecular interactions between the solute and solvent. MG dye exhibited large thermo-optic coefficient of the order of 10- 3 K- 1 is observed. The results give important new information about the characteristics of MG dye and indicate potential sources of material for NLO applications in future.

Ternary Boron Carbon Nitride nanosheets with improved and controllable linear and nonlinear optical response for efficient photocatalytic performance

This work reports the systematic variation of linear and nonlinear optical (NLO) properties of ternary boron carbon nitride (BCN) nanosheets with varying carbon concentrations. These nanosheets are synthesized by the thermal substitutional method to modulate the band-gap of BCN nanosheets by varying the hBN and graphene domain ratios which is confirmed through UV–Vis absorption spectroscopy. The third-order optical nonlinearity of nanosheets was explored through the Z-scan technique. With increases in both carbon content and laser power, samples' NLO properties have shifted from saturable absorption to reverse saturable absorption. The enhanced nonlinearity with carbon concentration in BCN samples was responsible for higher photoinduced charge separation time. In UV–Vis driven photoreduction of organic pollutants, BCN nanosheets with a decreased bandgap and an increased charge separation time show higher catalytic efficiency. Therefore, based on the combined effect of many processes, the results revealed that the BCN nanosheets displayed greater potential for photoinduced reduction.

Growth, characterization and cognition of 2-cyanopyridinium perchlorate single crystals for nonlinear optical applications.

The fascinating electronic applications attracted researchers to explore the field of nonlinear optical (NLO) materials. The slow evaporation of solvent technique (SEST) was employed to grow the 2-cyanopyridinium perchlorate (2-CPPC) NLO single crystals. The cell parameters of the grown 2-CPPC crystal are confirmed by the single crystal X-ray diffraction (SCXRD) study. The powder X-ray diffraction studies confirm the crystallinity of 2-CPPC crystals, and the peaks were indexed. The computation for the geometry optimization, HOMO-LUMO energy gap, global reactivity parameters, natural bond orbital (NBO) analysis, polarizability, and hyperpolarizability of the 2-CPPC molecule was done using B3LYP (6-311G basis set) functional of DFT method. The experimental FTIR and UV-Vis results of the 2-CPPC compound were compared with the simulated results. The second harmonic generation (SHG) study for the 2-CPPC crystal was employed using Kurtz-Perry powder technique. Single beam Z-scan technique using He-Ne laser is used to study the third-order NLO properties.

Modulation of High-Intensity Optical Properties in CdS/CdSe/CdS Spherical Quantum Wells by CdSe Layer Thickness.

Spherical quantum wells (SQWs) have proven to be excellent materials for suppressing Auger recombination due to their expanded confinement volume. However, research on the factors and mechanisms of their high-intensity optical properties, such as multiexciton properties and third-order optical nonlinearities, remains incomplete, limiting further optimization of these properties. Here, a series of CdS/CdSe (xML)/CdS SQWs with varying CdSe layer thicknesses were prepared. The modulation effects of CdSe shell variations on the PL properties, defect distribution, biexciton binding energy, and third-order optical nonlinearities of the SQWs were investigated, and their impact on the material's multiexciton properties was further analyzed. Results showed that the typical CdS/CdSe(3ML)/CdS sample exhibited a large volume-normalized two-photon absorption cross-section (18.17 × 102 GM/nm3) and favorable biexciton characteristics. Optical amplification was observed at 12.4 μJ/cm2 and 1.02 mJ/cm2 under one-photon (400 nm) and two-photon (800 nm) excitation, respectively. Furthermore, different amplified spontaneous emission spectra were observed for the first time under one/two-photon excitation. This phenomenon was attributed to thermal effects overcoming the biexciton binding energy. This study provides valuable insights for further optimizing multiexciton gain characteristics in SQWs and developing optical gain applications.

Exploring the impact of heterocyclic bridges for tuning the amplitudes of Nonlinear optical properties under Gas, IEFPCM and COSMO solvent models

Nonlinear optical (NLO) materials are a distinctive class of materials due to their NLO response and wide range of applications. We present a systematic quantum chemical study for designing triphenylamine based derivatives (1Ph to 3PhDTDZ) by modifying central bridge with various size and types of heterocyclic rings. Density functional theory (DFT) method is used to calculate the NLO properties including linear and third-order NLO polarizabilities (α and γ) by using M06-2X functional coupled with the 6-311G** basis set. The calculation results predict that among the designed compounds, 1PhDTDZ has the highest third-order NLO polarizability of 2347.7 x 10−36 esu and lowest transition energy of 1.828 eV. On the other hand, 3PhDTDZ has a greater amplitude (108.5 x 10−24 esu) of static linear polarizability (αiso). We also computed frequency-dependent third-order NLO polarizability values at various laser wavelengths (1500 nm to 1970 nm). This provides valuable information about the complex interaction between light and matter. Dynamic second hyperpolarizability of electro-optic Pockels effect (EOPE effect, (γ (−ω; ω,0,0)) is calculated at 1500 nm laser wavelength with a larger γ-amplitude of 36708.4 x 10−36 esu. The effect of solvent on α and γ has also been the primary focus of this research. An extensive solvation impact has been studied using integral equation formalism Polarizable Continuum Model (IEFPCM) and Conductor-like Screening Model (COSMO). Magnitudes of αiso and 〈γ〉 have shown variation from gas to solvent methods. While among solvents, amplitudes are seen 3.87 % to 11.29 % greater under the effect of COSMO-methanol than PCM-methanol. The Frontier molecular orbital (FMO) studies found a significant decrease in energy band gaps from 5.75 eV to 2.98 eV. Since our systems exhibit remarkable photovoltaic properties, they can be used as dye-sensitized solar cells (DSSCs). Their open circuit voltage (VOC) ranging from 1 eV to 4 eV. Thus, our designed triphenylamine based derivatives with distinct central heterocyclic bridges showcase remarkable efficiency as NLO materials, with additional benefits of exhibiting good photovoltaic properties.

Structural and ultrafast third-order nonlinearities of methyl and methoxy substituted anthracene chalcones: Z-scan, four-wave mixing, and DFT approaches

We report on the structural, thermal, linear, and ultrafast third-order nonlinear optical (NLO) properties of two novel anthracene chalcones: (2E)-1-(anthracen-9-yl)-3-(5-methylthiophen-2-yl)prop-2-en-1-one (5ML2SANC) and (2E)-1-(9-anthryl)-3-(2,4,5-trimethoxyphenyl)prop-2-en-1-one (245TMANC). The chalcones were synthesized by Claisen-Schmidt condensation reaction, and the single crystals were grown by the solvent evaporation method. The molecular structure was confirmed by FTIR and NMR spectroscopy, while the crystal structure was determined using the single crystal XRD. Both crystals belong to centrosymmetric monoclinic crystal system with space group P21/n. The Hirshfeld surface was analyzed to understand intermolecular interactions, and the band structures - including HOMO-LUMO levels, excited state energies, GCRDs and MEPs-were studied using DFT. The ultrafast third-order NLO properties were investigated by Z-scan and degenerate four-wave mixing (DFWM) techniques using Ti: Sapphire amplifier laser delivering ∼50 fs pulses at 800 nm (1 kHz, ∼4 mJ, 2 W). Two-photon absorption, positive nonlinear refraction, optical limiting and optical switching behaviors were observed by Z-scan measurements. The time-resolved DFWM show that the decay time of 5ML2SANC is ∼127 fs, while for 245TMANC it is ∼142 fs. The second hyperpolarizability (γ) measured by Z-scan, DFWM and the estimations from the DFT theory are found to be in good agreement (∼10−34 esu). The ultrafast optical response, significant NLO properties and thermal stability of the synthesized chalcones demonstrate their potential suitability in optical limiting and switching applications.

Integration of Open Metal Sites in an Amino-Functionalized Sm(III)-Organic Framework toward Enhanced Third-Order Nonlinear Optical Property.

A variety of new inorganic and organic materials have emerged to advance laser technologies and optical engineering. A rational design approach can contribute significantly to fabricating nonlinear optically active metal-organic frameworks (MOFs) by considering the underlying structure-property linkage. Here, it has been embarked on a study of novel samarium(III) MOF, ([Sm2(ata)3(DMF)4]·DMF (ata2-: 2-aminoterephthalate), abbreviated as NH2-Sm-MUM-4) with enhanced nonlinear optical (NLO) properties. The crystal structure of this MOF represents a 6-connected framework with a pcu topology and distinctive characteristics, including open metal sites, free amine groups, and great stability, making it suitable for third-order NLO activity. The nonlinear index of refraction (n2) revealed the self-focusing impacts of NH2-Sm-MUM-4 at different incident intensities. The highest value of n2 and β related to 10 mw power of incident intensity are 5.15 cm2/W and 2.65 cm/W, respectively. As far as the authors know, this is the first study examining the potential systematic structural-property associations in Sm-MOFs considering improved third-order NLO properties.

Topochemical Polymerization at Diacetylene Metal-Organic Framework Thin Films for Tuning Nonlinear Optics.

Developing the topochemical polymerization of metal-organic frameworks (MOFs) is of pronounced significance for expanding their functionalities but is still a challenge on third-order nonlinear optics (NLO). Here, we report diacetylene MOF (CAS-1-3) films prepared using a stepwise deposition method and film structural transformation approach, featuring dynamic structural diversity. The MOF structures were determined by the three-dimensional electron diffraction (3D ED) method from nanocrystals collected from the films, which provides a reliable strategy for determining the precise structure of unknown MOF films. We demonstrate the well-aligned diacetylene groups in the MOFs can promote topological polymerization to produce a highly conjugated system under thermal stimulation. As a result, the three MOF films have distinct NLO properties: the CAS-1 film exhibits saturable absorption (SA) while CAS-2 and CAS-3 films exhibit reverse saturable absorption (RSA). Interestingly, due to the topochemical polymerization of the MOF films, a transition from SA to RSA response was observed with increasing temperatures, and the optical limiting effect was significantly enhanced (∼46 times). This study provides a new strategy for preparing NLO materials and thermally regulation of nonlinear optics.

Boosting third-order optical nonlinearity in ITO/Au multilayer films via interfacial effects.

We present the enhancement of third-order optical nonlinearity in indium tin oxide (ITO)/Au multilayer films via interfacial effects. The overall thickness of prepared ITO and Au layer was kept as 200 nm and 14 nm, respectively, and thus multilayers are 214 nm, i.e., for the sandwich structure ITO/Au/ITO, the thickness of ITO and Au is 100 nm and 14 nm, respectively, while the thickness of ITO and Au is 40 nm and 3.5 nm in the nine-layer films composed of five layers of ITO and four layers of Au. The measured nonlinear refractive index (n2) and absorption coefficient (β) of the multilayers rise as the number of layers increases. The maximum n2 and β in the nine-layer film are 2.6×10-14 m2/W and -3.7×10-8 m/W, which are 3.8 and 2.3 times larger than the values in the pure ITO film, respectively. Such enhancement of optical nonlinearity as the number of layers increases originates from the increase of carrier concentrations in multilayers due to contact of metals/semiconductors (interfacial effects), not following the traditional effective media theory and epsilon-near-zero effect. The results pave a way to modulate the optical nonlinearity in special metal-dielectric multilayers of interfacial effects and indicates the promising applications in nonlinear photonics.

Broadband third-order optical nonlinearities of layered franckeite towards mid-infrared regime

Broadband third-order optical nonlinearities of layered franckeite towards mid-infrared regime

Giant ultrafast dichroism and birefringence with active nonlocal metasurfaces

Switching of light polarization on the sub-picosecond timescale is a crucial functionality for applications in a variety of contexts, including telecommunications, biology and chemistry. The ability to control polarization at ultrafast speed would pave the way for the development of unprecedented free-space optical links and of novel techniques for probing dynamical processes in complex systems, as chiral molecules. Such high switching speeds can only be reached with an all-optical paradigm, i.e., engineering active platforms capable of controlling light polarization via ultrashort laser pulses. Here we demonstrate giant modulation of dichroism and birefringence in an all-dielectric metasurface, achieved at low fluences of the optical control beam. This performance, which leverages the many degrees of freedom offered by all-dielectric active metasurfaces, is obtained by combining a high-quality factor nonlocal resonance with the giant third-order optical nonlinearity dictated by photogenerated hot carriers at the semiconductor band edge.