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.

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.

Structure,electronic,and nonlinear optical properties of superalkaline M_(3)O(M=Li,Na)doped cyclo[18]carbon

Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.

Electrical and nonlinear optical properties of TGZO transparent conducting films deposited by magnetron sputtering

Thin transparent oxide conducting films(TCOFs)of titanium and gallium substituted zinc oxide(TGZO)were fabricated via radio frequency(RF)magnetron sputtering technique.The effects of RF power on electrical,linear and nonlinear optical characteristics were investigated by Hall tester,Ultraviolet(UV)-visible spectrophotometer and optical characterization method.The results indicate that RF power significantly influences the electrical and optical properties of the deposited films.As RF power raises,the resistivity and Urbach energy fall initially and then rise,while the figure of merit,mean visible transmittance and optical bandgap show the reverse variation trend.At RF power of 190 W,the TGZO sample exhibits the highest electro-optical properties,with the maximum figure of merit(1.14×10^(4)Ω^(-1)∙cm^(-1)),mean visible transmittance(86.9%)and optical bandgap(3.50 eV),the minimum resistivity(6.26×10^(-4)Ω∙cm)and Urbach energy(174.23 meV).In addition,the optical constants of the deposited films were determined by the optical spectrum fitting method,and the RF power dependence of nonlinear optical properties was studied.It is observed that all the thin films exhibit normal dispersion characteristics in the visible region,and the nonlinear optical parameters are greatly affected by the RF power in the ultraviolet region.

Heterometallic copper(Ⅱ) vanadates: synthesis, crystal structures and third-order nonlinear optical properties

Three polymeric heterometallic clusters with 1D, 2D, and 3D frameworks, constructed from a cyclic vanadate {V4O12}4- building block and three geometric constraint ligands, were synthesized by a one-pot self-assembly reaction. Z-scan experiments demonstrated that all the three cluster polymers have large hyperpolarizability y values. TD-DFT calculations afforded insight into the electronic transitions and spectral characterization of these novel NLO molecular materials.

Influence of Waveguide Properties on Wave Prototypes Likely to Accompany the Dynamics of Four-Wave Mixing in Optical Fibers

In this article, we study the impacts of nonlinearity and dispersion on signals likely to propagate in the context of the dynamics of four-wave mixing. Thus, we use an indirect resolution technique based on the use of the iB-function to first decouple the nonlinear partial differential equations that govern the propagation dynamics in this case, and subsequently solve them to propose some prototype solutions. These analytical solutions have been obtained;we check the impact of nonlinearity and dispersion. The interest of this work lies not only in the resolution of the partial differential equations that govern the dynamics of wave propagation in this case since these equations not at all easy to integrate analytically and their analytical solutions are very rare, in other words, we propose analytically the solutions of the nonlinear coupled partial differential equations which govern the dynamics of four-wave mixing in optical fibers. Beyond the physical interest of this work, there is also an appreciable mathematical interest.

Crystal Structure,Electrochemical Properties and Third-order Nonlinear Optical Response of 4-Methyloxy benzaldehyde Thiosemicarbazone and Its Copper(Ⅱ)Complex

The crystal structUre of the title ligand and its copper (Ⅱ) complex was determined bysingle crystal X-ray diffraction. The electrochendcal properties and the third-order nonlinearoptical response of the ligand and its copper (Ⅱ) complex were also studied.

Rational synthesis, structural characterization and the third-order nonlinear optical properties of two new M-Cu-S (M = Mo or W) clusters

By the additional reaction of binuclear compounds (Me4N)2M2S4 (TDT)2 (M = Mo, W; H2TDT= H2CH3GH3S2) with mononuclear cuprous complex, two new M-Cu-S clusters Mo2 Cu2 S4 (TDT)2-(PPh3)2CH3CH2OH (1) and W2Cu2S4 (TDT)2 (PPh3 )2 · 0. 5CH3 CH2 OH·0. 5H2O (2) have been prepared and characterized by IR, UV-Vis, 31P NMR spectroscopy, cyclic voltammetry and single crystal X-ray structure analysis. Both compounds crystallize in space group P 21/ n with lattice parameters a = 1.0956(3), b = 2. 2072(3), c =2.4340(3) nm, β=100.36(2)°, V= 5.790(3) nm3 and Z = 4 for 1 and a = 1.0965(9), b = 2.2135(3), c = 2.4317(4) nm, β = 99. 63(8)°, V = 5.819(8) nm3 and Z = 4 for 2. Both molecular structures contain a cubane-like cluster core [M2Cu2S4] (M= Mo, W) and their skeletons are almost the same except for M atoms. The syntheses, structures and spectrum characterizations of these two clusters are discussed. The third-order nonlinear optical (NLO) property of the two clusters was studied by the technique of forward degenerate four-wave mixing (DFWM) for the first time and these clusters exhibited relatively large nonlinear optical coefficients.

Bis(4,4′-dimethyl-2,2′-bipyridine)ruthenium(II) Complexes Containing 2-Arylimidazo-phenanthroline: Syntheses, Characterization and Third-order Nonlinear Optical Properties

Four novel mononuclear ruthenium(II) complexes [Ru-(dmb) 2L] 2+ [dmb=4,4′-dimethyl-2,2′-bipyridine, L=imid-azo-[4,5-f]phenanthroline (IP), 2-phenylimidazo-phenanthroline (PIP), 2-(4′-hydroxyphenyl)imidazo-phenanthroline (HOP), 2-(4′-dimethylami- nophenyl)imidazo-phenanthroline (DMNP)] were synthesized and characterized by ES-MS, 1H NMR, UV-vis and electrochemistry. The nonlinear optical properties of the ruthenium(II) complexes were investigated by Z-scan techniques with 12 ns laser pulse at 540 nm, and all of them exhibit both nonlinear optical (NLO) absorption and self-defocusing effect. The corresponding effective NLO susceptibility |χ 3| of the complexes is in the range of 2.68×10 -12-4.57×10 -12 esu.

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.

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.

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.

All-optical switching and nonlinear optical properties of HBT in ethanol solution

This paper demonstrates an all-optical switching model system comprising a single pulsed pump beam at 355 nm and a CW He-Ne signal beam at 632.8 nm with 2-（2＇-hydroxyphenyl）benzothiazole （HBT） in ethanol solution. The origins of the optical switching effect were discussed. By the study of nonlinear optical properties for HBT in ethanol solvent, this paper verified that the excited-state intramolecular proton transfer （ESIPT） effect of HBT and the thermal effect of solvent worked on quite different time scales and together induced the change of the refractive index of HBT solution, leading to the signal beam deflection. The results indicated that the HBT molecule could be an excellent candidate for high-speed and high-sensitive optical switching devices.

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.

Crystal Structure and the Third-order Nonlinear Optical Property of a Cadmium(Ⅱ) Complex Based on a D-π-A Structural Organic Ligand

A triphenylamine-containing Schiff base ligand(L), namely, N-(4-(1 H-imidazol-1-yl)benzylidene)-N,N-diphenylbenzene-1,4-diamine, was synthesized and characterized. By coordination of the ligand with CdI2, a complex CdI2 L2 was obtained. The structure of the complex was analyzed through single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 25.277(5), b = 11.176(5), c = 17.912(5) ?, β = 106.056(5)°, V = 4863(3) ?3, Z = 4, Dc =1.633 Mg/m3, F(000) = 2360, Μr = 1195.19, μ = 1.766 mm-1, the final R = 0.0323 and wR = 0.0758 for 33414 observed reflections with I > 2?(I). The linear absorption spectra of the complex were experimentally and theoretically studied. And the third-order nonlinear optical(NLO) property of the complex was also measured through Z-scan technique.

New Application of bond Function Basis Sets──ab initio Calculations of Nonlinear OpticalProperties of Ch_4-1nF_n(n=1,2,3)

On the basis of adding the bond functions (3s 3p 2d) to the basis sets 6-311G ( 2d 2p ) for increasing the efficiency of the basis sets , we have carried out the MP2 calculations of nonlinear optical properties includintg dipole moment uo,polarizibili- ty ao and hyperpolarizability , for CH4-nFn (n = 1 , 2 , 3). The results are in good a- greement with those of experimentsl The roles of the bond functions in the calcula- tions are shown , i. e., the improved values of the properties are about 2%-7% at the SCF level and about 6%-30% at the correlated level (MP2). It is shown that the more important role of the bond functions in calculating is the im- provement of the effects of the corrections of electronic correlations and the increase of the effects is in the order of. In addition , it is also shown that the cal-, culated value of a property does not change with the bond-function location in our calculations except for the regions close to the nuclei in a molecule.

Theoretical Investigation on the Second-order Nonlinear Optical Properties of Chiral Amino Acid Zinc(Ⅱ) Porphyrins

Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipola- rizabilities, and they may be ascribed as the “mixture” of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic χ (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.

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.

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.