Third-order NLO Properties Research Articles

Control of second-and third-order nonlinear optical properties of DCM and Znq2 composites fabricated by the physical vapor co-deposition process

In the present work, investigations on the second and third-order NLO properties of, 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM) reddye co-doped bis(8-hydroxyquinoline) Zinc (Znq2) thin films with different concentrations were investigated. The samples have a thickness of 100 nm. They were prepared using the physical vapor deposition (PVD) method under a high vacuum. The morphological properties were studied by atomic force microscopy. The second-order nonlinear susceptibility χ(2) after applying the corona poling technique was estimated using the comparative model of Lee, while the third-order nonlinear susceptibility χ(3) was estimated using the comparative model of Kubodera and Kobayashi. The tested samples varied in terms of the concentration of DCM in the structure, which visibly influenced their nonlinear response. The pure DCM thin film showed a large value of the second and third-order nonlinear susceptibility, while pure Znq2 had only the second harmonic response with a low value. In this study, we have demonstrated that doping with DCM, even with small concentrations, has also strongly enhanced the non-linearity of Znq2. The obtained results show that such compositions can be a good alternative for optoelectronic applications.

Studies on the physico-chemical properties of semi-organic nonlinear optical (NLO) material: 2-CPPC [2-CNPyH][ClO4]

Semi-organic NLO single crystals 2-cyanopyridinium perchlorate (2-CPPC) were successfully grown by the method of slow evaporation of solvent at room temperature (27 °C) by using acetone as a solvent and of dimension 15×12×3mm3. The powder X-ray diffraction (XRD) of the grown crystal has been investigated. The UV–vis study estimates the transmission range, refractive index, extinction coefficient, band gap, and reflectance of the grown 2-CPPC crystal. The fluorescence spectra of the grown crystal were also recorded. The presence of different functional groups and the vibrational modes were confirmed by using FTIR analysis. The crystal's mechanical properties were studied by a Vickers microhardness tester. Single beam Z-scan technique using He–Ne laser is used to study the third-order NLO properties.

Hirshfeld surface analysis, experimental and theoretical evaluation of a new monohydrated organic salt of 2-amino-4‑hydroxy-6-methylpyrimidine (AHMP) and 4-acetamidobenzoic acid (AMBA) for nonlinear optical applications

The organic crystal (AHMP+.AMBA−) of the AHMP and AMBA organic compounds was successfully synthesized and grown by the slow evaporation solution process. The present work focuses on the crystal structure, Hirshfeld surface, spectroscopic and DFT analyses of the title salt. The crystal geometry of AHMP+.AMBA− monohydrated salt was characterized by the single-crystal XRD technique. The synthesized salt crystallizes in the triclinic crystal system and P-1 space group. The identification of the functional groups of the compound has been done by FTIR spectroscopy and DFT/B3LYP-D3/6–311++G(d,p) level of theory. Further, Hirshfeld surface mapping and its associated two-dimensional fingerprint plots predict that the O⋅⋅⋅H and H⋅⋅⋅H interactions are dominant for stabilizing the crystal structure. TG-DTA reveals the crystal is thermally stable up to 168 ºC. The optical studies have been performed by the time-dependent DFT (TD-DFT) and UV–Vis spectroscopic methods. Moreover, the Z-scan experiment has been done to obtain third-order NLO properties. Additionally, the HOMO-LUMO energy gap, MEP maps and theoretical NLO parameters have also been calculated.

Investigation on growth, molecular structure, third-order NLO properties and DFT computational studies of a new creatininium 4-aminobenzoate (C4AB) single crystal

Investigation on growth, molecular structure, third-order NLO properties and DFT computational studies of a new creatininium 4-aminobenzoate (C4AB) single crystal

Studying the Symphonizing Effect of NLO Properties in Hydrated and Non-hydrated Donor Acceptor Complexes Formed Via Charge Transfer.

The present work intended to report the synthesis of newly designed donor-acceptor complexes of the pyrimidine-based system namely TAPHIA 1 and TAPHIA 2, which are symphonized to give the NLO properties. The methodologies adopted for both complexes were different and hence influenced their geometrical properties. The synthesized complexes were characterized using different techniques including SCXRD, FTIR, UV, PXRD, and TGA to confirm their formation. The SCXRD analysis revealed that TAPHIA 1 was crystallized in the Pca21 space group in an orthorhombic system while TAPHIA 2 was crystallized in the P21/c space group in a monoclinic system. The third-order NLO properties of both complexes were explored using the Z-Scan technique by employing a continuous wave (CW) diode laser of 520 nm. The third-order NLO parameters including nonlinear refractive index (n2), nonlinear absorption coefficient (β) and nonlinear optical susceptibility (χ (3)) were calculated at different powers; 40,50 and 60mW at fixed solution concentration (10mM) for both the complexes. Moreover, the experimental properties including NLO, FTIR, and UV were well corroborated with theoretical results obtained at the B3LYP-D3/6-31++G(d,p) level of theory. The analysis of the theoretical and experimental properties of both complexes suggests that TAPHIA 2 is a better applicant to be employed in optical devices than TAPHIA 1 due to the enhanced ability of internal charge transfer.

Solvatochromism effect on third-order NLO properties of Azo dye

Solvatochromism effect on third-order NLO properties of Azo dye

Molecular structure tuning impact on optical linearity and nonlinearity of novel push-pull conjugated organic systems for photonic applications

In the present work, we have designed and synthesized push-pull conjugated (symmetric d-π-A-π-D type) organic chromophores 2-(2,6-bis((E)-2-(anthracen-9-yl) vinyl)-4H-pyran-4-ylidene)malononitrile (M2) and 2-(2,6-bis((E)-2-(pyren-1-yl) vinyl)-4H-pyran-4-ylidene) malononitrile (M3). These chromophores are the derivatives of 2-(2, 6-dimethyl-4H-pyran-4-ylidene) malononitrile (DPM) with DPM acting as an electron acceptor unit whereas anthracene and pyrene substituents are represented as the electron donor units in M2 and M3 respectively. The structural and photophysical properties of these compounds have been analyzed using IR, NMR, UV–Vis absorption and emission spectroscopies. We comparatively investigated the third-order NLO properties of these novel compounds in CHCl3 for different dye solution concentrations and various laser powers. Moreover, the effect of substitution (electron acceptor unit anthracene and pyrene) on the nonlinear optical properties have been discussed based on the structural modification. The quantum chemical calculations (DFT) were performed to obtain optimized geometry, frontier molecular orbitals, natural bond orbitals (NBO), and NLO parameters of these compounds. The time-dependent density functional theory (TD-DFT) was employed for insight into the electronic structure, photophysical, and NLO properties of these compounds. Experimental results have been supported by the obtained theoretical results.

Improvement of third-order NLO properties of vacuum deposited Cd1-xPbxS nanostructured thin films for optoelectronic device applications

A polycrystalline nanostructured cadmium lead sulfide thin film was deposited using the thermal evaporation (PVD) technique (Cd1-xPbxS with x = 0.00, 0.01, 0.05 and 0.1 wt.% of Pb). Structural parameters of as-prepared Cd1-xPbxS thin films have been studied through X-ray diffraction. The optical investigation demonstrates that Cd1-xPbxS film's optical band gap (Eg) may be adjusted from the visible to the near-infrared region. (2.64 - 2.42 eV). The film is substantially more appropriate for absorbing layers in solar cells and optoelectronic applications due to the large decrease in ‘Eg.’ The enhanced Pb doping was found to have altered the surface morphology, verified by Field Emission Scanning Electron Microscopy (FESEM) images. The doped films also showed a significant red shift in the band edge and increased transmittance in the visible and NIR regions. The third-order nonlinear optical (TONLO) parameters of the samples were determined from the Q-switched Nd: YAG laser with 65-ps pulse duration at 1064 nm. The investigated TONLO components such as nonlinear absorption coefficient (β), nonlinear refractive index (n2) and the susceptibility χ(3)were found to be in the range from 1.16 × 10−3 to 4.12 × 10−3 (cmW−1), 1.06 × 10−8 to 3.32 × 10−8 (cm2 W−1) and 1.23 × 10−4 to 5.62 × 10−4 (esu) respectively. The results indicate that Pb-doping on CdS nanostructures on surface morphology can be used to modify NLO characteristics.Cd1-xPbxS thin film is a potential and able material for optoelectronic device applications, as seen by these encouraging NLO results.

Theoretical Model of Polarization Effects on Third-Order NLO Properties of the Stilbazolium Derivative Crystal.

The linear and nonlinear properties of the stilbazolium derivative, 2-[2-(3-hydroxy-4-methoxy-phenyl)-vinyl]-1-methyl-pyridinium naphthalene-2-sulfonate dihydrate crystal (VSNS), were investigated using an iterative electrostatic embedding scheme and density functional theory (DFT). The dipole moment and second hyperpolarizability of the VSNS molecule are sharply influenced by its crystalline phase. Standard DFT global hybrids such as B3LYP and M06 are strongly benefited by the effects of crystalline polarization. The performance can be further improved by making small changes in the amount of Hartree-Fock exchange included in the hybrid, delivering good hyperpolarizability and spectroscopy.

Molecular structure and third-order non-linear optical properties of two novel tetralone-based chalcone derivatives: Promising materials for optical limiting applications

Two novel tetralone-based chalcone derivatives (2E)-2-(3,4-dimethoxybenzylidene]-3,4-dihydro-2H-napthalen-1-one (DMDN) and (2E)-2-(3,4-dimethoxybenzylidene]-6-methoxy-3,4-dihydro-2H-napthalen-1-one (DM6MDN) have been synthesized via a Claisen–Schmidt condensation reaction. Single crystals were obtained using a slow evaporation solution growth method. Structural characterization was carried out using single crystal X-ray diffraction study. Non-centrosymmetric DMDN crystallized in the orthorhombic system with a P212121 space group. Centrosymmetric DM6MDN crystallized in the monoclinic system with a P21/c space group. Hirshfield analysis of both crystals revealed the existence of C–H···π and π···π interactions, which play an important role in creating supramolecular structures. Our TG-DSC study revealed that DM6MDN has higher thermal stability than DMDN. The linear absorption coefficient of DMDN and DM6MDN were calculated from our UV spectral analysis and their respective optical band gaps were calculated to be 2.88 and 3.05 eV, respectively. The photoluminescence spectra show emission peaks in the blue region. DMDN exhibits SHG activity and a large β value when compared to DM6MDN. The third-order NLO properties of the chalcone derivatives was investigated using the Z-scan technique. The obtained crystals show strong non-linear absorption (NLA) and negative non-linear refraction (NLR) for DMDN and a positive NLR for DM6MDN. The third-order non-linear susceptibility (χ(3)) was of the order 10−7 esu. DMDN and DM6MDN also exhibit optical limiting (OL) and optical switching behavior under continuous wave excitation. The static NLO parameters, such as dipole moment (μ), polarizability (α) and first order hyperpolarizability (β), were computed using the B3LYP/6–31++G(d,p) level of theory. The Donor-π-Acceptor-π-Donor (D-π-A-π -D) system of DMDN and DM6MDN also makes them promising materials for NLO applications.

Correlation between structural studies and third-order NLO properties of three new semi-organic compounds

Correlation between structural studies and third-order NLO properties of three new semi-organic compounds

Colloidal semiconductor nanocrystals: synthesis, optical nonlinearity, and related device applications

This review provides the recent advances of colloidal semiconductor NCs in nonlinear optics and ultrafast photonics. Synthesis, third-order NLO properties, and related nonlinear photonic device applications of several NCs are discussed.

Exploration of CH⋯F & CF⋯H mediated supramolecular arrangements into fluorinated terphenyls and theoretical prediction of their third-order nonlinear optical response.

In the present study, three novel fluorinated terphenyl compounds i.e., 2′,4,4′′,5′-tetrafluoro-1,1':4′,1′′-terphenyl (1), 2′,5′-difluoro-1,1':4′,1′′-terphenyl (2) and 2′,5′-difluro-4,4′′-diphenoxy-1,1:4′,1′′-terphenyl (3) have been synthesized by Suzuki Miyaura method. Single crystal XRD study reveals ð-ð stacking stabilization in molecular packing along with F⋯H and F⋯C interactions. This computational quantum chemical exploration was also done by using density functional theory (DFT) methods. The comparison of experimental (SC-XRD) and theoretical (DFT) investigations on structural parameters have been reported which shows reasonable agreements. Hirshfeld surface analysis explores the strength of intermolecular interactions present in the synthesized compounds. A substantial computational analysis of synthesized compounds is done for their optoelectronic and third-order nonlinear optical properties. The third-order NLO study was performed at M06/6-311G* level of theory. A comparative analysis of third-order polarizability of studied compounds is done with that of para-nitroaniline (p-NA) molecule which is often considered as a prototype NLO molecule. The third-order NLO analysis results suggest that all investigated compounds 1, 2 and 3 have significant potential as efficient third-order NLO molecules as compared to p-NA. The studied compounds 1, 2 and 3 possess about 13.7 times, 5.2 times and 5.17 times larger third-order polarizability amplitudes than that of p-NA (25.45 × 10−36 esu) as calculated at same M06/6-311G* levels of theory. Time-dependent density functional theory (TD-DFT) calculations are performed for electronic excitation energies and their oscillator strengths. The studies of frontier molecular orbitals (FMO) analysis, total and partial density of states (DOS) were performed to investigate the intramolecular charge transfer (ICT) process in the entitled compounds.

One-dimensional and two-dimensional coordination polymers from cluster modular construction

Cluster module construction of W/Cu/S cluster-based coordination polymers and their third-order NLO properties were investigated.

The interesting luminescence behavior and rare nonlinear optical properties of the {Ag55Mo6} nanocluster.

The remarkably reversible thermochromic luminescence behavior and the rare nonlinear optical (NLO) properties of the [Ag55(MoO4)6(C Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> CtBu)24(CH3COO)18(CH3COO)]·2H2O ({Ag55Mo6} for short) nanocluster reported were investigated experimentally. The important contributions of Ag+, CC− ions and MoO42− groups to the NLO properties were proved by further density functional theory (DFT) calculations.

Structural parametersversusthird-order optical susceptibility of zinc porphyrin molecules

Third-order NLO properties of Zn porphyrins are correlated to their structures by combining experiments and DFT calculations adopting six strategies. Molecules of lesser π-electron conjugation are also shown to have higher NLO characteristics.

Highly broadband NLO response of acceptor–donor–acceptor materials with a planar conformation

The third-order NLO properties of A–D–A molecules originally derived from organic photovoltaic (OPV) devices are studied. The results show that NLO performance of planar molecule (O-IDTBR) is better than that of twisted molecule (IDFBR) in solution or film state.

Two Polyoxometalate-Based Hybrid Compounds Modified by Iron Schiff Base Complexes: Syntheses, Crystal structures, Cyclic Voltametric Studies and Nonlinear Optical Properties.

Two new polyoxometalate (POM)-based hybrid compounds modified by a Schiff base, [Fe(DAPSC)(H2 O)2 ]2 [HPMo2 V Mo10 VI O40 ] ⋅ 5H2 O (1) and [Fe(DAPSC)(H2 O)]2 [HPV3 IV Mo4 V Mo7 VI O42 ] ⋅ 6H2 O (2), (DAPSC=2,6-diacetylpyridine bis-(semicarbazone)), have been successfully constructed from typical Keggin POMs, iron ions, and DAPSC ligands under hydrothermal condition. Structural analysis demonstrates that the Fe-Schiff base ligand units are free from polyacid anions in compound 1. While in compound 2, the Fe-Schiff base ligand units are bridged with polyacid anions via Fe-O bonds to emerge a stable double-supported skeleton. Noticeably, owing to the introduction of vanadium in H5 PMo10 V2 O40 ⋅ 32.5H2 O, a divanadium-capped configuration is shaped in compound 2. Besides, the third-order nonlinear optical (NLO) properties of two compounds were explored. It should be noted that both compounds 1 and 2 have two-photon absorption properties, which indicates that the two compounds are potential nonlinear optical materials.

Crystal growth and characterization of Benzimidazolium salicylate single crystal for nonlinear optical studies and antibacterial activity

Organic non-linear optical Benzimidazolium salicylate (BISA) single crystals have been harvested from methanol solution by slow evaporation method. The grown crystals belong to the monoclinic crystal system with space group P21/c. Good crystalline nature of grown BISA crystal was confirmed by PXRD. The FTIR spectrum analysis affirms the presence of functional groups in BISA crystal. From the UV‒Vis-Absorption spectrum, the lower cut-off wavelength (356 nm) and its energy band gap and linear refractive index were calculated. Luminescence spectrum was recorded to explore the emission peak at 426 nm. The mechanical strength of BISA crystal was determined by Vickers microhardness tester and mechanical parameters like C11, Hk, Kc, and Bi were calculated for the first time. Dielectric properties of grown crystals were systematically investigated for different temperatures. Further, electronic polarizability (α) were calculated using Penn analysis and Clausius‒Mossotti equation. Z‒scan measurement was taken to explore the third-order NLO properties of BISA crystal. For the first attempt, the BISA crystals were tested against five human pathogenic bacterial, i.e. Bacillus cereus, Staphylococcus aureus, Shigella flexneri, Vibrio cholerae, and Klebsiella pneumoniae. Existing results established that Benzimidazolium salicylate crystals might find useful applications in nonlinear optics and antimicrobial field.

Third order non linear optical properties of novel furan based organic crystal

A crystal for potential nonlinear optical applications, namely 1-(furan-2-yl)-3-(3, 4, 5-trimethoxyphenyl) prop-2-en-1-one (FT3MP), has been synthesized using slow evaporation technique. The functional groups present in the compound have been studied with Fourier transform infrared spectroscopy. The Z-scan technique with the single beam was used to examine the third-order NLO properties of the crystal. The measured nonlinear optical absorption coefficient (β), nonlinear refractive index (n2) and the third order nonlinear optical susceptibility (χ(3)) of FT3MP suggest that the crystal is good for possible photonic applications.