Method for measurements of second-order nonlinear optical coefficient based on Z-scan

The method for measuring second-order nonlinear optical coefficients based on well-known Z-scan is presented. The influence of linear absorption coefficients on normalized transmittance is discussed. Using this method, we obtained the second-order nonlinear coefficient d₃₁(5%MgO:LiNbO₃) = 4.5 × 10⁻¹² m/v at 1064 nm, which agrees well with theoretical calculations and previous well-known values.     

Theoretical study on stability of Z-scan technique by use of quasi-one-dimensional slit beam

The modified Z-scan technique using the quasi-one-dimensional slit (QODS) beam for characterizing the third-order optical nonlinearity has been reported recently. In the present work, we investigate the effect of the finite length of the slit in the QODS beam Z-scan for the practical experimental conditions, and then give an empirical expression that allows the direct estimation of nonlinear refraction coefficient from the measured normalized peak-valley transmittance difference. In particular, we explore relatively in detail the influences of the sample imperfection on the Z-scan traces, such as the hollow hole of the sample and the nonuniform nonlinearity. Compared with the other Z-scan techniques, such as the top-hat and Gaussian-beam Z-scans, we find that the QODS beam Z-scan has the great improvement for the sample imperfections. The results suggest that the QODS beam Z-scan is a more promising and useful technique for characterizing the optical nonlinearity of an imperfect sample.     

Effects of metallization and bromination on nonlinear optical properties of diphenylporphyrins

Nonlinear refraction and nonlinear absorption of diphenylporphyrins with bromination and metallization were studied by Z-scan technique in nanosecond and picosecond regimes. Results show that both metallization and bromination of diphenylporphyrins can cause the regular change of magnitude and sign of nonlinear absorption. The transition between saturable absorption and reverse saturable absorption happens as bromine increases and metal ion changes. The effect of bromination on nonlinear refraction is small, the change of nonlinear refraction is mainly attributed to the metallization. Influences of photophysical parameters on nonlinear absorption and nonlinear refraction have been elucidated using five-level models.     

Third order nonlinear optical studies of bromocresol purple in liquid and solid media

The quest for materials exhibiting high nonlinear refraction and absorption are required for photonic device application. In this paper we report a simplified Z-scan technique, to study the optical nonlinearity of the dye bromocresol purple in methanol and ethanol for different concentration and dye doped polymer film at the wavelength 532 nm of Nd:YAG laser. The experimental results show that the investigated organic dye molecule exhibits saturation absorption and negative nonlinearity. The nonlinear absorption co-efficient and the nonlinear refractive index were measured for the dye doped film, and for dye in methanol and ethanol at the concentration of 0.03 mM and 0.05 mM. The measured third order susceptibility was found to be of the order of 10⁻⁶ e.s.u. in both solid and liquid medium. The result shows that the dye has potential applications in nonlinear optics.     

Measurement of nonlinear properties and optical limiting ability of Rhodamine6G doped silica and polymeric samples

The third order nonlinear optical properties of Rhodamine6G (Rh6G) doped silica and polymeric samples have been investigated using single beam z-scan technique under excitation by the second harmonic of Nd:YAG laser beam (532 nm). The nonlinear refractive index, nonlinear absorption coefficient, real and imaginary parts of third order nonlinear susceptibility in the samples of silica and poly-methylmethacrylate (PMMA) matrices are measured. Thermal contribution to the nonlinear refractive index in case of undoped silica samples has been calculated in order to have better accuracy of the material response contribution to third order nonlinearity. The comparative study of the optical limiting performance of Rh6G doped silica and polymeric samples show that Rh6G doped silica is relatively superior for optical limiting applications.     

Nonlinear optical studies of a newly synthesized copolymer containing oxadiazole and substituted thiophenes

We investigated the third-order nonlinear optical properties of a newly synthesized soluble copolymer containing oxadiazole and thiophene units using Z-scan and Degenerate Four Wave Mixing (DFWM) techniques. The measurements were performed at 532 nm with 7 ns pulses from a Nd:YAG laser. We found a good agreement between the values of χ⁽³⁾ determined from both experiments. Z-scan results indicate a negative nonlinear refractive index, n₂, whose magnitude is of the order of 10⁻¹⁰ esu. The copolymer exhibits strong nonlinear absorption and good optical limiting properties at 532 nm, and hence may be a potential material for optical limiting applications.     

Direct measurement of free carrier nonlinearity in semiconductor-doped glass with picosecond pump-probe Z-scan experiment

We report the direct measurement of free carrier nonlinearity in a semiconductor-doped glass with picosecond pump-probe Z-scan experiment. A strong Z-scan signal from a weak and time delayed probe beam is observed. The probe beam Z-scan signal is comparable in magnitude to the Z-scan signal of the intense pump beam, clearly showing the dominance of the effective fifth order nonlinearity due to the pump beam generated free carriers in the overall nonlinear response of semiconductor-doped glass. The estimated magnitude of the fifth order nonlinearity is consistent with that obtained from earlier reported experiments.     

Investigation of nonlinear optical properties of organic dye by Z-scan technique using He-Ne laser

The third-order nonlinear optical properties of Basic Green 1 dye were measured by the Z-scan technique and measurements were carried out at different concentrations and several incident intensities. The results showed that the Basic Green 1 dye exhibited large nonlinear refractive coefficient () and nonlinear absorption coefficient () at the wavelength 632.8 nm of He-Ne. The negative sign of the nonlinear refractive index n₂ indicates that this material exhibits self-defocusing optical nonlinearity. These results show that Basic Green 1 dye has potential applications in nonlinear optics.     

Preparation and the optical nonlinearity of surface chemistry improved titania nanoparticles in poly(methyl methacrylate)-titania hybrid thin films

With 800-nm, 120-fs laser pulses, optical nonlinearity has been studied in a series of thin films containing poly(methyl methacrylate) (PMMA), filled with surfactant acetylacetone (Acac) capped TiO₂ nanoparticles, which were synthesized by a simple in situ sol-gel/polymerization process, assisted by spin coating and multi-step baking. The resulting nanohybrid thin films have highly optical transparency and demonstrate a unique nonlinear optical (NLO) response. The highest nonlinear refractive index (n₂) is observed up to 6.55 × 10⁻² cm² GW⁻¹ in the nanohybrid thin film of 60 wt% Ti(OBu)₄ in PMMA, with a negligible two-photon absorption (TPA), as confirmed by the Z-scan technique. The titanium precursor loading combined with the nature of the capping molecules are used to influence the ability of nanoparticles to nonlinear optical response. Indeed, the ligands at the nanoparticles’ surface can not only control the extent of the interaction between the organic molecules and the embedded nanoparticles but also influence the optical nonlinearities of nanoparticles.     

High sensitive measurements of absorption coefficient and optical nonlinearities

Accurate knowledge of absorption coefficient of a sample is a prerequisite for measuring the third-order optical nonlinearity of materials, which can be a serious limitation for unknown samples. We introduce a method, which measures both the absorption coefficient and the third-order optical nonlinearity of materials with high sensitivity in a single experimental arrangement. We use a dual-beam pump-probe experiment and conventional single-beam z-scan under different conditions to achieve this goal with communication relevant wavelength. We also demonstrate a counterintuitive coupling of the non-interacting probe-beam with the pump-beam in pump-probe z-scan experiment.     

Z-scan studies and optical limiting of nanosecond laser pulses in neutral red dye

The nonlinear optical absorption, refraction and optical limiting behaviour of an organic dye, neutral red, were investigated under excitation with nanosecond laser pulses at 532 nm. The nonlinear optical responses of the material were studied both in solution and solid film, made in methanol and polyvinyl alcohol, respectively, using single-beam Z-scan technique. The open aperture Z-scans of the solution samples displayed a switch over from saturable absorption to enhanced absorption with increase in input intensity. Theoretical fit to the experimental data indicated that the dominant mechanism of nonlinear absorption is two-photon absorption. The closed aperture Z-scans of both the samples denoted positive nonlinearity, which was three orders larger in magnitude in solid film, compared with that in solution. The results of optical limiting experiments revealed that neutral red exhibited strong optical limiting of nanosecond laser pulses with a threshold lower than that of C₆₀ in toluene.     

Notable third-order optical nonlinearities of a Keplerate-type polyoxometalate in solution and in thin films of PMMA

The third-order nonlinear optical properties of a Keplerate-type polyoxometalate (NH₄)₁₈[(Bu₄N]₂₄[Mo₁₃₂O₃₇₂(H₂O)₇₂(CH₃COO)₃₀]?ca.7NH₄CH₃COO?ca.173H₂O (denoted Bu₄N-{Mo₁₃₂}) in solution and in films of poly(methylmethacrylate) (denoted PMMA) matrix have been studied by the Z-scan method at 532 nm with a pulse duration of 20 ps. Experimental results show that both the solution and the solid films of Bu₄N-{Mo₁₃₂} have nonlinear self-defocusing effects and notable nonlinear reverse saturable absorption. Embedding Bu₄N-{Mo₁₃₂} as inclusion into PMMA host significantly improves the nonlinear absorption coefficient β, while it reduces the nonlinear refractive coefficient as a result of the higher concentration of Bu₄N-{Mo₁₃₂} in PMMA matrix than in solution. The magnitude of β for solid-state Bu₄N-{Mo₁₃₂} in films increases with the increasing amount of incorporated Bu₄N-{Mo₁₃₂}, while the third-order nonlinear refractive index n ₂ decreases. Experimental results prove the high stability of Bu₄N-{Mo₁₃₂} in PMMA films in inorganic acidic and basic solutions. These studies indicate that Bu₄N-{Mo₁₃₂} in thin solid films of PMMA are potential candidates for fabricating nonlinear optical devices.     

Optical and nonlinear optical characteristics of the Ge and GaAs nanoparticle suspensions prepared by laser ablation

The laser ablation of Ge and GaAs targets placed in water and ethanol was carried out using the fundamental radiation of nanosecond Nd:YLF laser. The results of preparation and the optical and nonlinear optical characterization of the Ge and GaAs nanoparticle suspensions are presented. The considerable shift of the band gap energy of the nanoparticles compared to the bulk semiconductors was observed. The distribution of nanoparticle sizes was estimated in the range of 1.5-10 nm on the basis of the TEM and spectral measurements. The nonlinear refractive indices and nonlinear absorption coefficients of Ge and GaAs nanoparticles were defined by the z-scan technique using second harmonic radiation of picosecond Nd:YAG laser (λ = 532 nm).     

Nonlinear optical absorption and fluorescence of phosphine-substituted bithiophenes in the violet-blue spectral region

The nonlinear optical absorptions of two 5,5′-bis(diphenylphosphino)-2,2′-bithiophene derivatives, Ph₂(X)P(C₄H₂S)₂P(X)Ph₂ (X = O, 1; S, 2), have been investigated by direct transmission measurement with both picosecond and nanosecond laser pulses from 420 nm to 480 nm. Saturated dichloromethane solutions of 1 and 2 exhibit strong nonlinear optical absorptions in this violet-blue spectral region with that of 2 being stronger at all wavelengths. In the picosecond regime, at 420 nm, the transmittance rapidly falls to 50% when the incident fluence is 0.22 J/cm² for 1 and 0.11 J/cm² for 2. Two-photon absorption appears to be the primary mechanism for this nonlinear absorption. The two-photon absorption coefficients β for 1 (2.1 cm/GW) and 2 (4.4 cm/GM) were obtained by fitting the measurement of transmittance as the function of incident beam intensity at 420 nm. These β values are comparable with some of the best results obtained for organic materials in the green, red and infrared spectral region. Both compounds also show fluorescence with an emission peak at 390 nm for 1 and 400 nm for 2. The fluorescence of 1 is considerably stronger than is that of 2. The combination of the wide band gap and strong fluorescence emission of 1 makes it a promising candidate as a host material for blue organic light emitting diodes.     

Synthesis, characterization and optical limiting effect of nickel complexes of multi-sulfur 1,2-dithiolene

Three nickel complexes with a new multi-sulfur 1,2-dithiolene ligand, (n-Bu₄N)[Ni(cddt)₂] 1, (Ph₄P)[Ni(cddt)₂] 2 and [Ni(cddt)₂] 3 (cddt=4a, 6, 7, 7a-5H-cyclopenta[b]-1,4-dithiin-2,3-dithiolate), have been synthesized and characterized by electrochemical measurements, IR, EPR and UV-Vis-NIR spectroscopies. The crystal structure of complex 2 is determined. Their optical nonlinearities are measured by the Z-scan technique with an 8 ns pulsed laser at 532 nm and all exhibit NLO absorptive abilities. Complexes 1 and 2 both exhibit effective self-defocusing performance (n₂=−5.81×10⁻¹⁰ esu for 1 and −4.51×10⁻¹⁰ esu for 2). The optical limiting (OL) effects were observed with nanosecond and picosecond laser pulses. The OL capability of complex 3 is superior to C₆₀ at the same experimental condition in ns measurements.     

Third-order optical nonlinearities of an organometallic complex: Bis(tetra-n-propylammonium)bis(2-thioxo-1,3-dithiole-4,5-dithiolato)cuprate(II) doped in solid PMMA films

An organometallic complex, bis(tetra-n-propylammonium)bis(2-thioxo-1,3-dithiole-4,5-dithiolato)cuprate(II), [(C₃H₇)₄N]₂[Cu(dmit)₂] (dmit^2?=4,5-dithiolate-1,3-dithiole-2-thione), abbreviated as PrCu, was synthesized. The films of PrCu were prepared using spin coating method. The third-order nonlinear optical properties of PrCu in acetone solution and PMMA films were investigated by Z-scan technique at 1064 nm with laser duration of 20 ps. The Z-scan spectra reveal that the composite films exhibit large negative nonlinear refractive indices of the order of 10^?15 m²/W, which are three orders larger than that in acetone solution. The nonlinear absorption coefficients were calculated to be 9.416×10^?10 m/W. For the composite films, the figure of merit, W and T, meet the requirement of all-optical switching devices. The experimental results show that the PrCu-doped PMMA films have potential applications for nonlinear optical devices.     

Third-order optical nonlinearity of (Ba0.7Sr0.3)TiO3 ferroelectric thin films fabricated by soft solution processing

(Ba_0.7Sr_0.3)TiO₃ (BST) ferroelectric thin films with perovskite crystal structure were fabricated by soft solution processing on a quartz substrate. The third-order nonlinear optical properties were investigated by using Z-scan technique. Positive nonlinear refractive index and nonlinear absorption coefficient were determined to be 4×10⁻⁷ esu and 1.2×10⁻⁶ m/w, respectively. The real part and imaginary part of third-order optical nonlinear susceptibility were calculated and the values were 6.43×10⁻⁸ and 5.14×10⁻⁸ esu, respectively. All of these results show ferroelectric BST thin film is promising for applications in nonlinear optical devices.     

Nonlinear optical characteristics of polymethine dyes

Nonlinear refraction, nonlinear absorption, and saturated absorption of a number of polymethine dyes are studied and their nonlinear optical parameters are measured by the Z-scan method (λ=1064 nm). Simultaneous occurrence of several nonlinear optical processes in the case of excitation of dye solutions by picosecond pulses is analyzed. Saturated absorption of dye solutions is considered in terms of different models.     

Structure and thermal behaviors of organic crystals based on substituted 1,3,4-thiadiazoles

The crystalline structure of some compounds containing the 1,3,4-thiadiazole moiety, (1) 5-ethyl-2-amino-1,3,4- thiadiazole (EATZ), (2) 5-benzylsulfany-2-amino-1,3,4-thiadiazole (BSATZ) and (3) 2,5-bis-benzylsulfanyl-1,3,4-thiadiazole (BBSTZ) were determined. Both EATZ and BBSTZ show orthorhombic structures with space group Pbca and BSATZ a monoclinic system with space group C2/c. The lattice parameters: a=0.72280 (14), b=1.0811 (2), c=1.6210 (3) nm for 1, a=2.5282 (5), b=0.59083 (12), c=1.5390 (3) nm for 2 and a=0.87530 (18), b=1.0365 (2), c=3.6098 (7) nm for 3. To compare the intra- and intermolecular interactions in thiadiazole containing organic crystals, thermal analysis studies on each crystal is performed using DSC and TG in N₂ atmosphere to describe the thermal behaviors. Based on the results, the changing regularity of melting point and decomposition temperature of these compounds is educed     

Determinations of the transient thermal lensing effect in metal cluster Polymer {WS4Cu4I2(bpe)3}n solution by the use of the Z-scan

The nonlinear optical (NLO) properties of a novel cluster Polymer {WS₄Cu₄I₂(bpe)₃}_n solution are studied by using Z-scan technique with laser pulses of 4.5 ns pulse-width at a wavelength of 532 nm. The results show that the cluster solution possesses strong nonlinear absorption and refraction. Nonlinear refraction of the cluster is composed of third-order nonlinear refraction and transient thermal effect. The thermal effect is mainly due to the strong nonlinear absorption. Numerical simulations obtained by solving simultaneously photo-acoustic and electromagnetic wave equations, agrees basically with experimental results.