Nonlinear Optical Response Research Articles

Investigation of thermally induced nonlinear optical response of polyurethane-graphene composite by SSPM method

We conducted a study on composites made of polyurethane and graphene (PU-G). We synthesized these composites and then examined their far-field diffraction patterns at various concentrations of dimethylformamide (DMF) using the spatial self-phase modulation (SSPM) method. By analyzing the intensity-dependent far-field ring patterns, we were able to estimate the samples' thermally induced nonlinear refractive index and thermo-optical coefficient. We found that these variables, as well as other observable phenomena such as the “diffraction ring collapse effect” and “variation in nonlinear refractive index,” depended on the sample's concentration rate. Our results indicate that the laser-induced thermal effect is a significant factor in the SSPM phenomena observed in our experiments. Furthermore, our findings suggest that the PU/G combination in DMF has promising nonlinear optical properties that could be beneficial in a variety of nonlinear optics applications.

Theoretical study on the enhanced nonlinear optical responses of sulflowers and selenosulflowers

To develop highly efficient NLO materials for optoelectronic applications, theoretically, superhalogen-doped sulflower and selenosulflower were studied. The DFT/B3LYP-D3/6–311++G(2d,2p) basis set is used to complete the inquiry. The NLO properties of these complexes were assessed using, vertical ionization energy, and Electron Density Difference Map (EDDM) methods. The EDDM results reveal the electron transfer from sulflower to superhalogens leads to a donor–acceptor mechanism, which enhances hyperpolarizability. Superhalogen-doped sulflowers exhibit more prominent NLO properties than the undoped ligands, including static and dynamic NLO characteristics. This enhancement is due to the distortion of centrosymmetry and charge transfer between the sulflower and the doped superhalogen.

Subcycle dynamics of excitons under strong laser fields.

Excitons play a key role in the linear optical response of two-dimensional (2D) materials. However, their role in the nonlinear response to intense, nonresonant, low-frequency light is often overlooked as strong fields are expected to tear the electron-hole pair apart. Using high-harmonic generation as a spectroscopic tool, we theoretically study their formation and role in the nonlinear optical response. We show that the excitonic contribution is prominent and that excitons remain stable even when the driving laser field surpasses the strength of the Coulomb field binding the electron-hole pair. We demonstrate a parallel between the behavior of strongly laser-driven excitons in 2D solids and strongly driven Rydberg states in atoms, including the mechanisms of their formation and stability. Last, we show how the excitonic contribution can be singled out by encapsulating the 2D material in a dielectric, tuning the excitonic energy and its contribution to the high-harmonic spectrum.

Doping engineering of NiO–Zn nanofilms for modulation of morphological structure and ultrafast nonlinear optical response at 515 nm

In this work, to investigate the metal doping on the third-order nonlinear optical properties of NiO thin films under femtosecond pulsed laser excitation, pure NiO and 2w,4w,6w,8w Zn doped-NiO nanofilms were prepared by DC-RF co-sputtering technique. Then, the nonlinear absorption properties and nonlinear refractive properties of the five samples were investigated using the femtosecond laser at a wavelength of 515 nm. The experimental results show that the nonlinear absorption and nonlinear refractive properties of NiO are enhanced by the doped metal as well as the effect of defects. In addition, by varying the pump light intensity, we observed the transition of nonlinear absorption from the coexistence of saturated absorption and reverse saturated absorption to reverse saturated absorption. We established a multi-energy level system to interpret the nonlinear absorption and nonlinear refractive results, which broadens the application of NiO thin films in the field of nonlinear optics.

Exploring the Third-Order Non-linear Optical Responses and Optical Limiting Properties of p-Nitroaniline Picrate: A Theoretical and Experimental Study

Exploring the Third-Order Non-linear Optical Responses and Optical Limiting Properties of p-Nitroaniline Picrate: A Theoretical and Experimental Study

Tunable nonlinear excitonic optical response in biased bilayer graphene

Tunable nonlinear excitonic optical response in biased bilayer graphene

Ferroelectric nematic fluids as spontaneous polarization field for enhanced orientational-dependent second-harmonic generation

ABSTRACT Second-order nonlinear optical effects have piqued researchers’ interest in fundamental physics and practical perspectives. The ferroelectric nematic liquid crystals (NF LCs) have recently drawn attention to LC nonlinear optical applications due to their relatively high second-harmonic generation output. Further improving the nonlinear optical properties to get closer to the performance of inorganic nonlinear optical materials is challenging. Here, we take a blending strategy to enhance the nonlinear optical response of a prototype NF LC, DIO. We mixed an organic nonlinear optical crystalline material, 3,5,5-trimethyl (cyclohex-2-enylidene) malononitrile (TCM), with DIO and investigated the effects of TCM doping at various concentrations. We quantitatively determined the second-harmonic generation and spontaneous polarization as functions of temperature and concentration. We found that, compared with the pure DIO, the second-harmonic generation performance increased by about 130% at maximum, 93% in maximum for the nonlinear optical coefficient, and 10% in maximum for spontaneous polarization.

Janus Doping of Sulfur into Platinum Diselenide Ribbons.

2D platinum diselenide (PtSe2), a novel member of the transition metal dichalcogenides (TMDCs) family, possesses many excellent properties, including a layer-dependent bandgap, high carrier mobility, and broadband response, making it promise for applications in technologies like field-effect transistors and room-temperature photodetectors. Doping represents an effective method to modify the electrical properties of 2D TMDCs and to bestow upon them additional functions. However, to date, little research has been conducted on the successful doping of 2D PtSe2 for modification. In this study, sulfur (S) powder is utilized during the chemical vapor deposition growth process of 2D PtSe2 ribbons and successfully integrated into the PtSe2 lattice through substitutional doping. The Au substrate significantly decreases the substitution energy of Se atoms in the lower layer of PtSe2, resulting in the formation of the Janus PtSSe structure. S-doped PtSe2 ribbons demonstrate significant symmetry breaking and enhanced electrical properties, showcasing a strong nonlinear optical response and certain synaptic plasticity, further simulating some neuromorphological processes. This study not only demonstrates a viable method for controllable doping and modification of 2D PtSe2 but also establishes a platform for exploring the characteristics of Janus TMDCs.

Engineering novel alkalides with superalkali clusters: Ab initio insights into nonlinear optical responses

ABSTRACT We designed novel alkalides such as FLi2-M-OLi3 and FLi2-M-NLi4 (M = Li, Na, K), along with OLi3-M-NLi4 (M = Li, Na) by interacting alkali metal atoms with heterogeneous superalkali clusters in anionic, neutral and cationic configurations. The stability of these superalkali based alkalides are confirmed by its binding energy (Eb ). Utilising QTAIM method, the bond strength and nature of bond have been analysed. NPA charge analysis is conducted to forecast charge transfer and also to confirm the alkalide character of the complex along with the electron localisation function (ELF) analysis. The HOMO–LUMO gap analysis is performed to analyse electrical conductivity and chemical reactivity. The nonlinear optical (NLO) properties have been investigated by polarisability and first-order static hyperpolarizibilty (β0 ), which is found to be as high as 2.77 × 107 a. u. for (OLi3-Li-NLi4)+ complex. The UV-Vis spectra and electronic transitions are used to explain the enhanced NLO responses. The study not only identifies new alkalide candidates but also presents strategies to significantly improve their NLO properties, which may be useful in nonlinear optics and optoelectronics.

Exploring the molecular solvatochromism, stability, reactivity, and non-linear optical response of resveratrol.

This work analyzes the isomerization effects and solvent contributions to the stability, electronic excitations, reactivity, and non-linear optical properties (NLO) of resveratrol molecules within the formalism of the Density Functional Theory. The findings suggest that resveratrol solvatochromism is significantly influenced by solvent polarization. The electronic and free energies (E and G) indicate that trans is the most stable conformer. The system is classified as a strong nucleophile. However, the analysis of the Fukui functions and the Mulliken charges indicate that cis-trans isomerization jointly affects the reactive indices of the carbon and hydrogen atoms. The results also suggest that solvent is relevant to solvatochromism and the NLO response. Both cis and trans conformers present strong excitations that undergo a visible hypsochromic change when the polarity of the solvent increases. Once the absorption spectra are connected to the first hyperpolarization ( ) by the Oudar and Chemla relation, the hypsochromism of resveratrol is the reason for the drop in the generation of the second harmonic when the ambient polarity decreases. The CAM-B3LYP DFT results suggest that resveratrol is interesting for NLO applications. Depending on the choice of solvent, values 50 times those observed for urea ( esu), which is a standard NLO material. The optimized geometries of cis and trans isomers of resveratrol in vacuum were obtained using Density Functional Theory (DFT) with the hybrid exchange-correlation function (CAM-B3LYP) and Pople basis set functions, specifically 6-311++G(d,p). The solvent effect on the geometries of both isomers was included using the polarizable continuum model (PCM) with the same level of QM calculation. Vibrational analysis was conducted to confirm that all optimized geometries correspond to the minimum energy. Various electronic properties, including dipole moments, molecular orbitals, transition energy, dipole polarizabilities, and global reactivity parameters, were calculated using both continuum and discrete solvation models based on the sequential QM/MM methodology. All QM calculations were performed with the Gaussian 09 program and the MC simulations with the DICE program. All NLO analysis was carried out using the Multiwfn code.

Computational investigation for electronic, structural, linear/nonlinear optical responses for newly designed organometallic quantum dots

AbstractThe interaction of metallic ($$M^{ + 3}$$ M + 3 )-cations ($$M = {\text{Al}},{\text{Cu}},{\text{Zn}},{\text{In}},{\text{Ga}},{\text{Ge}},{\text{Sb}},{\text{Sn}}$$ M = Al , Cu , Zn , In , Ga , Ge , Sb , Sn ) with an active organic linker result in the formation of organometallic quantum dots (OMQDs). The B3LYP and WB97X interfaces via 6-311G++(d,p) route are used to test the stability, electrical, optical, and nonlinear-optics (NLO) properties. OMQD UV–Vis absorption spectra are computed. Some OMQD have singlet spin states, while others have doublet spin states. Cation mobility and the organic linker nature have a significant impact on both optical and NLO properties. For electron rush via the conduction domain, doublet spins provide more advanced turnabilities than singlets. For singlet-spin Cu-3HPHP QDs, an anomalous NLO response is endorsed. Both Zn-3HPHP and Sn-3HPHP QDs are recognized as the finest contenders. Zn-3HPHP and Sn-3HPHP appear to be the next covenant for highly efficient optoelectronics and avalanche photodetectors.

Manipulating Photogalvanic Effects in Two-Dimensional Multiferroic Breathing Kagome Materials.

Multiferroic materials, known for their multiple tunable orders, present an exceptional opportunity to manipulate nonlinear optical responses that are sensitive to symmetry. In this study, we propose leveraging electric and magnetic fields to selectively control and switch specific types of photogalvanic effects in two-dimensional multiferroic breathing kagome materials. Taking monolayer Nb3I8 as an example, we demonstrate that the shift current, characterized by the real-space shift of electrons and holes, is predominantly unaffected by magnetic order. In contrast, injection current, featured by quantum metric dipole in momentum space, is closely related to valley polarization, which can be controlled by a magnetic field. Furthermore, both photocurrents can be reversed by an out-of-plane electric field via lattice breathing. Our findings reveal the potential of multiferroic breathing kagome structures for multifunctional optoelectronic applications and sensors.

Strain-Induced Structural Rearrangement Towards a White-Light-Emitting Adamantane-Type Cluster Dimer.

Group 14/16 adamantane-type hybrid clusters of the type [(RT)4E6] (T=group 14 element, E=group 16 element, R=organic group) have been reported to emit white-light when irradiated in an amorphous state with a continuous-wave (CW) infrared laser diode. This effect is enhanced if the cluster core is varied from a binary to a more complex composition. To further explore this phenomenon, we synthesized clusters with a multinary R/R'-T/T'-E/E' composition, including isolobal replacement of E with CH2, in [(2-NpSi){CH2Sn(S)Ph}3] (1, Np=naphthyl). When expanding one of the CH2 moieties to a C2H4 group, thus generating a R/R'-T/T'-E/E'/E'' cluster composition, we unexpectedly observed a dimerization of the initially formed, yet non-isolable adamantane-like cluster [(2-NpSi){CH2Sn(S)Ph}2{C2H4Sn(S)Ph}] (2) to [(2-NpSi){CH2Sn(S)Ph}2{C2H4Sn(S)Ph}]2 (3), exhibiting a heretofore unprecedented cluster architecture. Both monomeric 1 and dimeric 3, show white-light emission as thin films. The nonlinear optical response of the compounds was also modelled with DFT methods.

Polarization-insensitive terahertz third-harmonic generation from degenerate pairs of mirror-coupled super-BICs

Resonant nanostructures have emerged as versatile photonic platforms for boosting optical nonlinear responses on a subwavelength scale for their ability to confine intense electromagnetic fields while relaxing the phase-matching requirements. Recent significant advances in this field are associated with the utilization of non-radiative eigenmodes above the light cone, termed bound states in the continuum (BICs), which provide a unique mechanism for light trapping to realize excitation of ultrahigh quality (Q) factor resonances. Nevertheless, the current studies on BICs predominantly focus on symmetry-protected BICs (SP-BICs), whose excitation requires symmetry breaking, and Q factors are limited by fabrication imperfections. Here, we demonstrate a simple and feasible scheme for creating degenerate pairs of mirror-coupled super-BICs by harnessing magnetic dipole resonances coupled to their mirror images in adjacent metal films. Unlike trivial SP-BICs, mirror-coupled BICs showcases the huge enhancement of Q factors and are resilient against fabrication imperfections. By combining mirror-coupled resonance with the engineered radiative loss, we obtain a perfect absorber with near-unity absorption and ultra-narrow bandwidth at a critical coupling condition. Finally, we numerically demonstrate the terahertz (THz) regime, polarization-insensitive highly efficient third-harmonic generation benefiting from the maximum field enhancement localized within the perfect absorber. Our work not only paves the way toward unlocking the full potential of BIC resonance but also promise valuable insights for developing efficient THz optoelectronic devices and metadevices across a wide range of fields.

Nonlinear Optical Response of Au/CsPbI3 Quantum Dots and Its Laser Modulation Characteristics at 2.7 μm.

A passively Q-switched Er:YAP laser of 2.7 µm, utilizing Au-doped CsPbI3 quantum dots (QDs) as a saturable absorber (SA), was realized. It was operated stably with a minimum pulse width of 185 ns and a maximum repetition rate of 480 kHz. The maximum pulse energy and the maximum peak power were 0.6 μJ and 2.9 W, respectively, in the Q-switched operation. The results show that the CsPbI3 QDs SA exhibits remarkable laser modulation properties at ~3 μm.

Chiral topological light for detection of robust enantiosensitive observables

The topological response of matter to electromagnetic fields is a highly demanded property in materials design and metrology due to its robustness against noise and decoherence, stimulating recent advances in ultrafast photonics. Embedding topological properties into the enantiosensitive optical response of chiral molecules could therefore enhance the efficiency and robustness of chiral optical discrimination. Here we achieve such a topological embedding by introducing the concept of chiral topological light—a light beam which displays chirality locally, with an azimuthal distribution of its handedness described globally by a topological charge. The topological charge is mapped onto the azimuthal intensity modulation of the non-linear optical response, where enantiosensitivity is encoded into its spatial rotation. The spatial rotation is robust against intensity fluctuations and imperfect local polarization states of the driving field. Our theoretical results show that chiral topological light enables detection of percentage-level enantiomeric excesses in randomly oriented mixtures of chiral molecules, opening a way to new, extremely sensitive and robust chiro-optical spectroscopies with attosecond time resolution.

The nonlinear optical properties of meso-substituted porphyrins using spatial self-phase modulation

Herein, we studied the nonlinear optical properties of four meso-substituted porphyrins (H2MHTPP, H2THTPP, H2DETPP, and H2TETPP) by the spatial self-phase modulation (SSPM) method, using CW lasers with wavelengths of 532 nm and 780 nm. All samples exhibit strong nonlinear response due to the thermal optical nonlinear effect at 532 nm, which corresponds to the strong absorption band. In addition, four porphyrin samples were calculated that have nonlinear refractive index coefficients of the same order of magnitude (10−10 m2/W) at 532 nm. However, four porphyrins exhibited different optical nonlinear responses affected by the type and numbers of peripheral substituents at 780 nm. This work is of significance for reasonably adjusting the structure of compounds and improving their third-order nonlinear optical coefficients.

Prominent Enhancement of Nonlinear Optical Absorption in SnS2 Nanosheets through Controllable Electrodeposition of Porphyrins

AbstractConstructing organic‐inorganic composites presents a promising approach to enhance the nonlinear optical (NLO) response of materials. However, the effectiveness of this approach is impeded by the complexity of synthesis procedures and challenges in controlling the loading amount. Herein, a convenient and controllable electrodeposition method to non‐covalently combine SnS2 with tetracationic porphyrin (TMPyP) and the remarkable enhancement in NLO absorption of the resultant composite, are introduced. Through this method, a series of SnS2/TMPyP thin films are synthesized, allowing for the regulation of porphyrin loading via varying the deposition time. These resultant SnS2/TMPyP composites exhibit prominent nonlinear absorption coefficients when subjected to femtosecond laser irradiation of varying wavelengths. Notably, the compound with an electrochemical deposition time of 30 s achieves the largest third‐order nonlinear absorption coefficient of 6155 ± 243 cm GW−1 under 800 nm laser excitation, marking an 8.9‐fold increase compared to pristine SnS2 nanosheets. Based on the staggered energy level structure between TMPyP and SnS2, effective enhancement of charge separation/transfer is achieved by leveraging the unique π‐conjugated groups of porphyrins, which facilitates the NLO process and improves the NLO performance of films.

Supramolecular Assembly of Nitrogen-Containing Curved π-Conjugated Molecules to Polar Crystal

The chemistry of curved π-conjugated molecules has been extensively studied because of the development of their synthetic approach. Among the numerous studies, we have been engaged in nitrogen-containing curved π-conjugated molecules. These molecules have extended optical properties, redox-active behaviors, and electron-donating ability due to the electron-rich nature of nitrogen atoms. Recently, we have focused on the supramolecular assembling behavior of these compounds. For example, we have reported buckycatcher consisted of two azabuckybowls, providing two-photon absorbing host-guest complexes with fullerenes. In this presentation, we would like to show the packing behavior using π-extended azahelicenes and azabuckybowls. Our group has developed π-extended aza[5]helicene derivatives, showing brilliant emissive features. Recently, we succeeded in the synthesis of unsymmetrically substituted azahelicenes. We found that their stackings in the crystal were dependent on the substituent. X-ray diffraction analysis for all products showed π-stacked conformation with each other in the crystal (Figure 1b). In particular, azahelicenes with triisopropylsilyl groupswere found to align their dipole moments to form a one-dimensional columnar structure in the crystal. Polar crystals are expected to have applications in ferroelectric, piezoelectric, and nonlinear optical response materials. This is the first example of a polar crystal with helicenes, paving the way for novel piezoelectric organic materials.The second topic is related to azabuckybowl. In the crystal, azabuckybowl forms a face-to-face dimer by concave-convex interaction. In this study, we prepared two types of azabuckybowl perylene bisimide (PBI) dyads connected with alkyne linkages. PBIs have also been reported to show columnar stacking in solution. We anticipated that the segregate stacking should be achieved by recognizing the difference in structures between the bowl and planar geometry. The UV/vis absorption spectra revealed the presence of intramolecular charge-transfer interaction. In addition, the concentration-dependent absorption spectra and 1H NMR spectra indicated PBI and azabuckybowl units stacked with each other independently in solution (Figure 1a). Here, we would like to discuss about the effect of the effect of molecular shape on the supramolecular assembly with the data obtained using these compounds. Figure 1

Exploring the ON/OFF nonlinear optical (NLO) response in tetracene-based chromophores: A DFT study on solvent and frequency-dependent NLO properties for switching applications

Tetracene-based nonlinear optical (NLO) materials are an ambient field of interest in optoelectronic technology. Inspired by this material, we theoretically designed D-D-A framework molecules (ZO and ZO-1 to ZO-16) with auxiliary donor and acceptor screening of solo tetracene linear surface and investigated their reactivity, electrical properties, solvent-dependent optical and ON/OFF NLO properties utilizing DFT simulations. The CPCM and IEFPCM model is used to examine how entire spectrum of medium polarity, ranging from less polar to more polar solvents (chloroform (ε = 4.71) < tetrahydrofuran (ε = 7.43) < DMSO (ε = 46.83 < water (ε = 78.36)) affect the optical absorption and NLO characteristics (βtot, αtot, and μtot) of suggested compounds (ZO and ZO-1 to ZO-16). Furthermore, natural bond orbital analysis (NBO) and topological analysis (MEP, ELF, and LOL) were used to explain the NLO results. Regarding the charge transfer robustness, ZO-9, a promising tetracene derivative, is identified as an appealing second-order NLO candidate, with the lowest energy gap (1.642 eV) and largest λmax (546.692 nm) among all investigated derivatives. Moreover, the solvent-dependent optical absorption spectrum shows that polar solvent (THF) alleviates the λmax from 273.081 nm to 707.511 nm in ZO-11. Similarly, solvent also influences the NLO properties in all designed compounds, especially in ZO-9, which displayed giant βtotal = 7.244 × 105 in chloroform, 8.640 × 105 in THF, 1.153 × 106 in DMSO, and 1.180 × 106 in water as well as in gas (1.993 × 105). Additionally, the results of the second harmonic generation (SHG) β(−2ω, ω, ω) and the electro-optical Pockels effect (EOPE) β(−ω,ω,0) computed at the frequencies of ω = 1064 nm (0.0428 au) and ω = 532 nm (0.0856 au) validates that all tetracene based derivatives are excellent NLO candidates for laser working condition and switching applications.