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

The study of nonlinear optical responses in the mid-infrared(mid-IR)regime is essential for advancing ultrafast mid-IR laser applications.However,nonlinear optical effects under mid-IR excitation are rarely reported due to the lack of suitable nonlinear optical materials.The natural van derWaals heterostructure franckeite,known for its narrow bandgap and stability in air,shows great potential for developing mid-IR nonlinear optical devices.We have experimentally demonstrated that layered franckeite exhibits a broadband wavelength-dependent nonlinear optical response in the mid-IR spectral region.Franckeite nanosheets were prepared using a liquid-phase exfoliation method,and their nonlinear optical response was characterized in the spectral range of 3000 nm to 5000 nm.The franckeite nanosheets exhibit broadband wavelengthdependent third-order nonlinearities,with nonlinear absorption and refraction coefficients estimated to be about 10^(-7)cm/W and 10^(-11)cm^(2)/W,respectively.Additionally,a passively Q-switched fluoride fiber laser operating around a wavelength of 2800 nm was achieved,delivering nanosecond pulses with a signal-to-noise ratio of 43.6 dB,based on the nonlinear response of franckeite.These findings indicate that layered franckeite possesses broadband nonlinear optical characteristics in the mid-IR region,potentially enabling new possibilities for mid-IR photonic devices.

Synthesis of Poly (3-acetylpyrrolyl methine) with Azobenzene Side Groups and Study on Its Third-order Nonlinear Optical Property

A novel soluble π-conjugated polymer, poly [（3-acetylpyrrole-2, 5-diyl） p-（N, N-dimethylamino） azobenzylidene] （PAPDMAABE）, was synthesized by condensation of 3-acetylpyrrole with 4-aldehyde-4＇-dimethylaminoazobenzene （ADMAA）. The chemical structure of PAPDMAABE was characterized by Fourier transform infrared spectroscopy （FTIR）, ^1H-NMR, and UV-Vis-NIR spectra. Transmission electron microscope （TEM） analysis for PAPDMAABE indicates that part of PAPDMAABE is in crystal state, due to the short-range order of the polymer. Thermogravimetric analysis （TGA） curve shows that the polymer has good thermal stability and its decomposition temperature is 248℃. The optical band gap of PAPDMAABE obtained from the optical absorption spectrum is about 1.73 eV. The resonant third-order nonlinear optical property of PAPDMAABE at 532 nm was studied using degenerate four-wave mixing （DFWM） technique. The resonant third-order nonlinear optical susceptibility of the polymer is about 7.48×10^-8 esu.

The Third-Order Nonlinear Optical Properties in Cobalt-Doped ZnO Films

We quantitatively investigate the third-order optical nonlinear response of Co-doped ZnO thin films prepared by magnetron sputtering using the Z-scan method. The two-photon absorption and optical Kerr effect are revealed to contribute to the third-order nonlinear response of the Co-doped ZnO films. The nonlinear absorption coefficient β is determined to be approximately 8.8 × 10-5 cm/W and the third-order nonlinear susceptibility X（3） is 2.93 × 10-6 esu. The defect-associated energy levels within the band gap are suggested to be responsible for the enhanced nonlinear response observed in Co-doped ZnO films.

UV-Vis Spectrum and the Third-order Nonlinear Optical Properties of the Chiral Camphorderived β-diketonate Platinum Complexes

UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.

Electronic Absorption Spectra and Third-Order Nonlinear Optical Property of Dinaphtho[2,3-b:2’,3’-d]Thiophene-5,7,12,13- Tetraone (DNTTRA) and Its Phenyldiazenyl Derivatives: DFT Calculations

Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of Dinaphtho[2,3-b:2’,3’-d]thiophene-5,7,12,13-tetraone (DNTTRA) and its 36 derivatives containing azobenzene were calculated by using density functional theory B3LYP and M06-2X methods at 6-311++g(d, p) level, respectively. Besides, the atomic charges of natural bond orbitals (NBO) were analyzed. The frontier orbitals and electron absorption spectra of A-G5 molecule were calculated by TD-DFT (TD-B3LYP/6-311++g(d, p) and TD-M06-2X/6-311++g(d, p)). The NLO properties were calculated by effective finite field FF method and self-compiled program. The results show that 36 molecules of these six series are D-π-A-π-D structures. The third-order NLO coefficients γ (second-order hyperpolarizability) of the D series molecules are the largest among the six series, reaching 107 atomic units (10-33 esu) of order of magnitude, showing good third-order NLO properties. Last, the third-order NLO properties of the azobenzene ring can be improved by introducing strong electron donor groups (e.g. -N(CH3)2 or -NHCH3) in the azobenzene ring, so that the third-order NLO materials with good performance can be obtained.

Ultrashort pulse breaking in optical fiber with third-order dispersion and quintic nonlinearity

The optical wave breaking （OWB） characteristics in terms of the pulse shape, spectrum, and frequency chirp, in the normal dispersion regime of an optical fiber with both the third-order dispersion （TOD） and quintic nonlinearity （QN） are numerically calculated. The results show that the TOD causes the asymmetry of the temporal- and spectral-domain, and the chirp characteristics. The OWB generally appears near the pulse center and at the trailing edge of the pulse, instead of at the two edges of the pulse symmetrically in the case of no TOD. With the increase of distance, the relation of OWB to the TOD near the pulse center increases quickly, leading to the generation of ultra-short pulse trains, while the OWB resulting from the case of no TOD at the trailing edge of the pulse disappears gradually. In addition, the positive （negative） QN enhances （weakens） the chirp amount and the fine structures, thereby inducing the OWB phenomena to appear earlier （later）. Thus, the TOD and the positive （negative） QN are beneficial （detrimental） to the OWB and the generation of ultra-short pulse trains.

Ultrafast third-order optical nonlinearity of several sandwich-type phthalocyaninato and porphyrinato europium complexes

The third-order optical nonlinearity of two sandwich-type phthalocyaninato and porphyrinato europium com- plexes, including double- and triple-deckers （Eu[Pc（OC5H11）8]2, Eu2（Pc）（TPP）2, Pc=phthalocyanine, TPP=5, 10, 15, 20- tetraphenylporphyrinate）, was investigated by using the femtosecond time-resolved optical Kerr gate method at 830 nm wavelength. Their second-order hyperpolarizability is estimated to be 0.74× 10^-30esu and 3.0× 10^-3esu respectively. This exhibits an evident enhancement in comparison with 0.47×10^-30esu for one-decker Eu（Pc）（acac） （acac=acetylacetonate）, which is also measured under the same conditions. The enhancement is attributed to the introduction of lanthanide metal to the large π-conjugated system, intermacrocycle interaction and two-photon resonance etc.

Synthesis, Structure and Third-order Non-linear Optical Properties of Tungsten Dioxo Complex with 8-Hydroxyquinoline Ligand WO_2(C_9H_6NO)_2

Tungsten dioxo complex WO 2(C 9H 6NO) 2 was obtained via the low temperature solid-state reaction of(NH 4) 2WS 4, 8-hydroxyquinoline(8-hq) and(CH 3) 4NI, and it was characterized by means of elemental analyses, IR spectroscopy and X-ray diffraction analysis. The crystal of the title compound belongs to monoclinic, space group C2/c, with the crystal cell parameters: a=1.3316(3) nm, b=0.94444(19) nm, c=1.3485(3) nm, β=109.66(3)°, V=1.5970(6) nm 3, Z=6. The title compound possesses a supramolecular structure formed through hydrogen bonds and π-π stacking interactions. The third-order non-linear optical(NLO) properties of the title compound were also investigated. The third-order non-linear absorption coefficient α 2 and refractive index n 2 are 0.85×10 -11 m/W -1 and -1.5×10 -19 m 2/W, respectively. The third-order non-linear susceptibility χ (3) is 3.03×10 -13 esu for 3.8×10 -5 mol/L sample concentration.

Synthesis of Poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] and Its Third-order Nonlinear Optical Property

A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] (POPNBE), was synthesized by a five-step reaction. As a result of introducing a long acyl to pyrrole at 3-position, the polymer can be easily solved in polar solvents and be processed into films. The chemical structures of the intermediates and POPNBE were characterized by FTIR, 1H NMR, and UV-Vis-NIR spectrometries. The absorption band in the range of 400-600 nm in the UV-Vis-NIR spectrum is due to the π-π * band gap transition. The optical band gap of POPNBE obtained from the optical absorption is about 1.72 eV. The resonant third-order nonlinear optical property of POPNBE at 532 nm was studied by using the degenerate four-wave mixing(DFWM) technique. The resonant third-order nonlinear optical susceptibility of POPNBE is about 3.42×10 -8 esu.

Crystal Structure and Third-order Nonlinear Optical Property Studies on Copper(Ⅱ) Complex Containing NS Donor Ligand

A novel Schiff base ligand (HL) derived from S-methyldithiocabazate and pmethoxylbenzaldehyde was prepared and characterized. The Schiff base ligand acts as a single negatively charged bidentate ligand fondng D-M-D type comPlex (D=donor, M=metal). Single crystal X-ray diffraction analysis of the copper(Ⅱ) complex established that the geometry around Cu (Ⅱ) is square-planar with two equivalent M-N and M-S bonds. The two phenyl rings and the coordinated plane are almost in one plane fotheng an electronic delocalization system. Their thirdorder response was also studied.

Nonlinear Optical Susceptibility and Refractive Index of Two Polyaniline Families

By use of the Keldysh non-equilibrium Green’s-function methods, the third harmonic susceptibilities of two polyaniline families, PANI-HCl and PANI-H 3PO 4, are calculated [ x (3) ( ω )≈10 -12 esu]. It was found that the third harmonic susceptibility of polyaniline strongly depends on the delocalization of the electrons. The refractive indices n ( λ =589 nm) of PANI-HCl and PANI-H 3PO 4 are calculated by use of three common methods (the Lorentz-Lorentz theoretical model, the Gladstone-Dale group contribution and the Vogel group correlation) based on group contributions to molar refraction. The calculated n values are varied from 1.31 to 1.42 for PANI-HCl and 1.36 to 1.45 for PANI-H 3PO 4.

Big Third-order Nonlinear Optical Properties of Two Poly[(3-alkylthiophene-2, 5-diyl)-(benzylidenequinomethane-2, 5-diyl)] Derivatives

Two novel poly[(3-alkylthiophene-2,5-diyl)-(benzylidenequinomethane-2,5-diyl)s] derivatives, poly[ (3-butylthiophene-2,5-diyl)-( p-N,N-dimethylamino) benzylidenequinomethane-2,5-diyl) ] ( PBTDMABQ) and poly [( 3-octylthiophene2,5-diyl) -(p-N, N-dimethylamino ) benzylidenequinomethane-2, 5-diyl)] (POTDMABQ), were synthesized.The band gaps of the two polymers are calculated as 1. 75 eV for PBTDMABQ and 1. 69 eV for POTDMABQ,respectively. The homogenous films of the two polymers were prepared and their third-ordernonlinear optical properties were studied by the backward degenerate four-wave mixing at 532 nm. Byusing the relative measurement technique, the third-order nonlinear optical susceptibilities ofPBTDMABQ and POTDMABQ are calculated as 5. 62 X 10^(-9) and 1. 22 X 10^(-8) ESU, respectively. It isfound that substituted alky groups have strong effects on the band gap and nonlinear opticalproperties of the two polymers. The relatively big third-order nonlinear optical susceptibilitiesand small band gap of POTDMABQ resulted mainly from the longer alkyl with strong electron-donatingability can enhance the delocation degree of conjugated π electronics.

Third-Order Nonlinear Optical Response near the Plasmon Resonance Band of Cu2-xSe Nanocrystals

The third-order nonlinear optical properties of water-soluble Cu Se nanocrystals are studied in the near infrared range of 700-980 nm using a femtosecond pulsed laser by the Z-scan technique. It is observed that the nonlinear optical response of Cu Se nanocrystals is sensitively dependent on the excitation wavelength and exhibits the enhanced nonlinearity compared with other selenides such as ZnSe and CdSe. The W-shaped Z-scan trace, a mixture of the reversed saturated absorption and saturated absorption, is observed near the plasmon resonance band of Cu Se nanocrystals, which is attributed to the state-filling of free carriers generated by copper vacancies (self-doping effect) of Cu Se nanocrystals as well as the hot carrier thermal effect upon intense femtosecond laser excitation. The large nonlinear optical response and tunable plasmonic band make Cu Se nanocrystals promising materials for applications in ultra-fast all-optical switching devices as well as nonlinear nanosensors.

Effect of Substituting Group on the Calculated Nonlinear Second－Order Optical Susceptibilities of Substituted Thiophene Derivatives with Quinoidlike Conformation

alculations of the nonlinear second-order optical susceptlbilities(β_(ijk))for sub- stituted tl1iophene derivative;with quinoidlike conformation are reported.These systetems possess small dipole moment;and large differences between dipole mo- ments of ground and first-excited states.Geometry optimizations of the molecules investigated were carried out using AM 1 method.The calculations were performed using INDO/CI method comboned with a sum-over-states expression for β_(jik). The calculated results sbw that the second-order susceptibility is a function of the na- ture and location of substituents and is larger for disubstituted molecules than monosubstituted molecules. Bipolymeric thiophenemetmne with NH_2/NO_2 groups was calctilated to have a β_μof 79. 920 × 10￣(-30) esu. It was found that the NH_2 and NO_2 groups in above disubstituted molecules are pull-pull groups in ground states,but are usual push-pull groups in the first excited states.

A Theoretical Study of Nonlinear Second-Order Optical Properties of Substituted Silanes

On the basis of ZINDO method and according to the sum over states(SOS) expression, the program is devised for the calculation of nonlinear second order optical susceptibilites β ijk and studying how different substituents on the phenyl ring attached to the atom silicon influence on the nonlinear second order optical properties of substituted silane series of molecules. The properties of (CH 3) 3Si? ?has been studied particularly. The effect of the length of silica chains on the calculated values has been studied too. The regularity summarized from the calculated results has been explained micromechanically.

Nonlinear optical properties of [（CH3）4N]Au（dmit）2 using Z-scan technique

The third-order optical nonlinearities of [（CH3）4N]Au（dmit）2 （dmit = 4,5-dithiolate-1,3-dithiole-2-thione） at 532 nm and 1064 nm are investigated using the Z-scan technique with pulses of picoseconds duration. The Z-scan spectra reveal a strong nonlinear absorption （reverse saturable absorption） and a negative nonlinear refraction at 532 nm. No nonlinear absorption is observed at 1064 nm. The molecular second-order hyperpolarizability γ for the [（CH3）4N]Au（dmit）2 molecule at 532nm is estimated to be as high as （2.1 ±0.1） × 10^-31 esu, which is nearly three times larger than that at 1064 nm. The mechanism responsible for the difference between the results is analysed. Nonlinear transmission measurements suggest that this material has potential applications in optical limiting.

Nonlinear optical properties of Au/PVP composite thin films

Colloidal Au and poly（vinylpyrrolidone） （PVP） composite thin films are fabricated by spin-coating method. Linear optical absorption measurements of the Au/PVP composite films indicate an absorption peak around 530 nm due to the surface plasmon resonance of gold nanoparticles. Nonlinear optical properties are studied using standard Z-scan technique, and experimental results show large optical nonlinearities of the Au/PVP composite films. A large value of χ^（3）/α up to 0.56× 10-^10esu·cm is obtained, which is comparable to the best values reported in metal/oxlde composite films.

Nonlinear Optical Properties in Bismuth-based Glasses

A series of glasses with high Bi2O3 content of Bi2O3-B2O3-WO3 ternary system were chosen and prepared .Their densities and linear refractive indices increase with increasing WO3 content. The optical band gaps Eopt of glasses obtained from ultraviolet absorption edges decreases with increase of WO3 content. Z-scan technique was carried out to investigate the third-order nonlinear optical properties of the glasses. It is found that the nonlinear refraction γ increases with decreasing the optical band gap Eopt, since an increase of WO3 content can promote the non-bridging oxygen ion content, and the highest γ value of samples is 1.173×10-14 cm2/W. The results show that these glasses are potential materials in the application of third-order nonlinear optics field.

Nonlinear optical behaviors in a silver nanoparticle array at different wavelengths

The optical nonlinearities of an Ag nanoparticle array are investigated by performing Z-scan measurements at the selected wavelengths （400, 600, 650, and 800 nm）. The nonlinear refraction index in the resonant region （around 400 nm） exhibits a significant enhancement by two orders compared with that in the off-resonant region （around 800 nm））, and exhibits an sign alternation of the resonant nonlinear absorption, which results in a negligible nonlinear absorption at a certain excitation intensity. Moreover, a low degree of nonlinear absorption was measured at the edges of the resonant region （600 and 650 nm）, which is attributed to the competition of the saturated absorption and the two-photon absorption processes.

THIRD ORDER NONLINEAR OPTICAL PROPERTIES OF PERNIGRANILINE SOLUTION IN CONCENTRATED SULFURIC ACID

The fully oxidized state of polyaniline (PANI), pernigraniline (PN), was synthesized by oxidation of the emeraldine base form of PAM dissolved in NMP solvent with m-chloroperoxybenzoic acid. The resulted PN was characterized by FTIR and UV-Visible spectra. The third-order nonlinear optical properties of PN in concentrated sulfuric acid (PN/H2SO4) were measured by a degenerated four wave mixing (DFWM) method. The results obtained suggest that the soliton-pair intermediate state associated with the degenerated state does not play a major role in the third order nonlinear optical properties of PANI.