Optical limiting in fullerenes, colloidal metal solutions, and semiconductors in the field of pico-and nanosecond pulses of an Nd:YAG laser

Optical limiting of pico-and nanosecond pulsed radiation of a Nd:YAG laser (λ=1064 and 532 nm) is studied in solutions of fullerenes (C₆₀ and C₇₀), semiconductor crystals and films (GaAs, As₂S₃, As₂₀S₈₀, 2As₂S₃/As₂Se₃, and 3As₂S₃/As₂Se₃), and colloidal solutions of metals (Au, Ag, Pt, and Cu). The effect of the particle aggregation in silver solutions on the optical limiting is considered. Optical limiting mechanisms, specifically, reverse saturable absorption, two-photon absorption, and self-action effects, are discussed. Nonlinear absorption coefficients of the studied materials are measured.     

OPTICAL LIMITING EFFECT IN TWO PHTHALOCYANINES OBSERVED BY PICOSECOND PULSED LASER

Optical limiting (OL) properties of two phthalocyanines were investigated by using picosecond laser pulses at 532nm. The relative ratios k of the absorption cross section of the first singlet excited state to that of the ground state were approximately obtained by the analysis of the experimental results in which the reverse saturable absorption model of the three-energy-level scheme was employed. A significant comparison with fullerene C₆₀ was presented for OL. The OL mechanisms have been analysed in detail.     

Thermally induced nonlinear optical response and optical power limiting of acid blue 40 dye

We report the investigations of thermally induced third-order nonlinear optical and optical limiting characterizations for various concentrations of acid blue 40 dye in N,N-Dimethyl Formamide, studied by employing z-scan technique under cw He–Ne laser irradiation at 633 nm wavelength. The samples exhibited nonlinear absorption and nonlinear refraction under the experimental conditions. For lower concentration, the samples display both saturable absorption (SA) and reverse saturable absorption (RSA); whereas with increase in concentration, RSA behaviour prevails. The estimated values of the effective coefficients of nonlinear absorption β_eff, nonlinear refraction n₂ and third-order nonlinear susceptibility χ⁽³⁾ were found to be of the order of 10^?2 cm/W, 10^?4 esu and 10^?6 esu respectively. Multiple diffraction rings were observed when the samples were exposed to laser beam due to refractive index change and thermal lensing. The effect of concentration and the laser intensity on the self-diffraction ring patterns was studied experimentally. The acid blue 40 dye also exhibited strong optical limiting properties under cw excitation and reverse saturable absorption is found to be the dominant nonlinear optical process leading to the observed nonlinear behaviour.     

High-efficiency multipass optical limiter

We report experimental results on a highly efficient optical limiter that uses a three-mirror, multipass ring configuration. The optical limiter's enhanced performance is based on the accumulative effect that is achieved when the laser beam passes through the sample several consecutive times. Its feasibility was demonstrated for media with different limiting action processes, namely, reverse saturable absorption, nonlinear scattering, and thermal lensing. We employed a frequency-doubled, Q-switched, 10-ns Nd:YAG laser operating at a 5-Hz repetition rate.     

Optical limiting action of C60 doped poly(dimethylacetylendicarboxylate)

The optical limiting action of poly(dimethylacetylendicarboxylate) polymer doped with fullerene C₆₀ has been investigated under irradiation with 10 ns laser pulses at 532 nm. The optical limiting measurements were performed at four different dopant concentrations. The threshold limiting fluence at 0.3 J/cm² was observed at high doping concentrations, with transmission of about 55%. An explanation based on the combination of two-photon absorption and reverse saturable absorption was proposed for its nonlinear optical absorption behavior.     

Optical limiting action of C60 doped poly(ethylacetylenecarboxylate)

The optical limiting action of C₆₀ doped poly(ethylacetylenecarboxylate) polymer has been carried out using Pulse Nd-YAG laser at 532 nm as the source of excitation. The optical limiting measurements were performed at three different doping concentrations. The optical limiting efficiency of the C₆₀ doped poly(ethylacetylenecarboxylate) polymer was studied at various doping concentrations, the threshold limiting fluence at 0.15 J/cm² was observed with transmission of about 89%. An explanation based on the combination of two-photon absorption and reverse saturable absorption was proposed for its nonlinear optical absorption behavior.     

C60介质反饱和吸收动力学

采用速率方程理论研究C₆₀分子实现反饱和吸收的动力学过程,以YAG倍频调Q脉冲激光照射C₆₀甲苯溶液,实验验证了理论模拟的正确性。还分析了分子各能级对反饱和吸收的贡献以及不同激光波长和脉宽对反饱和吸收的影响。 关键词：     

Theoretical investigation of the dependence of attenuation of pulsed laser radiation by fullerene-containing solutions on the pulse duration

The dependence of attenuation of laser radiation by fullerene-containing solutions on the laser pulse duration is theoretically studied. The investigation is carried out for a wide range of variations in the pulse durations: from 250×10^?15 to 10^?8 s. The contribution of two mechanisms (reverse saturable absorption and induced scattering associated with thermal nonlinearity) to the attenuation of radiation is studied. It is shown that reverse saturable absorption makes a considerable contribution to the attenuation in the whole range of durations under consideration, whereas induced scattering exists only in the range of durations that are longer than some nanoseconds. It is shown that the law of similarity with respect to the product of the intensity and the pulse duration for attenuation of laser radiation is approximately fulfilled in the whole range of durations, i.e., the attenuation depends on the energy density. Additionally, the elementary theory of reverse saturable absorption is developed and the limiting values of the absorption coefficient and the maximum attenuation are obtained.     

Mechanisms of optical limiting in fullerene-doped π-conjugated organic structures demonstrated with polyimide and COANP molecules

Possible mechanisms of optical limiting of visible radiation in conjugated organic structures based on polyimides and substituted pyridines sensitized with C₆₀ and/or C₇₀ fullerenes are studied using the Z-scan method. It is shown that reverse saturable absorption, two-photon absorption, and complex formation between the donor fragment of a π-conjugated molecule and fullerene contribute to the processes of nonlinear absorption. The absorption cross sections for excited states of the charge transfer complexes based on polyimide 6B-C₇₀ and 2-cyclooctylamino-5-nitropyridine-C₇₀ systems are calculated. The data obtained are quantitatively interpreted and compared with those provided by alternative methods.     

Optical limiting characteristics of Dichloridobis(1-ethyl-2, 6-dimethylpyridinium-4-olate-κO) zinc (II)

A newly synthesized metal-organic co-ordination compound Dichloridobis (1-ethyl-2,6-dimethylpyridinium-4-olate-κO) zinc(II) (EDMPZC) is characterized by FTIR to confirm the molecular structure. It crystallizes in the monoclinic system with the centrosymmetric space group C2/c and the unit cell parameters are determined from the single crystal X-ray diffraction analysis. Optical energy band gap is found to be 3.5 eV by UV-Visible absorption studies. The third order nonlinear optical properties were investigated by open-aperture Z-scan measurements using Nd:YAG laser (532 nm, 5 ns). Two-photon absorption and reverse saturable absorption mechanisms at the excitation wavelength are found to cause the observed optical limiting behavior.     

Investigation of the nonlinear absorption and optical limiting properties of two [Q]2[Cu(C3S5)2] compounds

The nonlinear absorption properties of two organometallic compounds, [(C₂H₅)₄N]₂[Cu(C₃S₅)₂] (DCu1) and [(C₄H₉)₄N]₂[Cu(C₃S₅)₂] (DCu2), have been investigated using an open-aperture Z-scan technique at 1064 nm with 40 ps pulse width and at 1053 nm with 18 ns pulse width. The reverse saturable absorption (RSA) which was observed in both samples with nanosecond pulse excitation was much larger than that observed with picosecond pulse excitation. The nonlinear absorption properties were analyzed theoretically by a five-level model. Optical limiting based on RSA was performed and limiting thresholds were evaluated for both samples under three conditions. DCu1 exhibited the better limiting characteristics because of its stronger RSA response.     

Studies on third-order nonlinear optical properties and reverse saturable absorption in polythiophene/poly (methylmethacrylate) composites

We report here the studies on third-order nonlinear optical properties of two novel polythiophene composite films investigated using the Z-scan technique. The measurements were carried out using a Q-switched, frequency doubled Nd:YAG laser producing 7 nanosecond laser pulses at 532 nm. Z-scan results reveal that the composite films exhibit self-defocusing nonlinearity. The real and imaginary parts of the third-order nonlinear optical susceptibility were of the order 10⁻¹² esu. The effective excited-state absorption cross section was found to be larger than the ground state absorption cross section, indicating that the operating nonlinear mechanism is reverse saturable absorption (RSA). The polythiophene composite films also exhibit good optical power limiting of the nanosecond laser pulses. The nonlinear optical parameters are found to increase on increasing the strength of the electron-donor group, indicating the dependence of χ ⁽³⁾ on the electron-donor/acceptor units of polythiophenes.     

Reverse saturable absorption of a novel rhodamine-B cation fulleride salt at 532 nm

A novel rhodamine-B cation fulleride salt was synthesized by metathetical reaction. Its tetrahydrofuran solution was prepared and the fluence-dependent transmission was measured with 10-ns 532-nm laser pulses in a collimated optical setup. With increases in the input fluence, its transmittance decreased significantly, which indicated reverse saturable absorption behavior. For comparison, the input fluence-dependent transmittance of fullerene C₆₀ and rhodamine-B solution were also measured. The nonlinear optical limiting effect of the fulleride salt in tetrahydrofuran is slightly lower than that of C₆₀ in toluene and the explanations are provided. Received: 25 August 2000 / Accepted: 6 November 2000 / Published online: 3 April 2001     

Influence of Annealing Temperature on Structure, Optical Loss and Laser-Induced Damage Threshold of TiO2 Thin Films

TiO2 thin films are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for 4h, the spectra and XRD patterns of the TiO2 thin film are obtained. Weak absorption of coatings is measured by the surface thermal lensing technique, and laser-induced damage threshold （LIDT） is determined. It is found that with the increasing annealing temperature, the transmittance of TiO2 films decreases. Especially when coatings are annealed at high temperature over 1173K, the optical loss is very serious. Weak absorption detection indicates that the absorption of coatings decreases firstly and then increases, and the absorption and defects play major roles in the LIDT of TiO2 thin films.     

Enhanced cubic optical nonlinearity of oligoazine derivatives

We report a large positive third-order optical nonlinearity of synthesized oligoazine derivatives (OADs) using z-scan technique at 532 nm by Q-switched Nd:YAG laser. Optical band gap of OADs shrinks with increasing repeated units. Origin of large cubic nonlinearity is in the extensive π-electron delocalization. We obtained the values of $\chi_{R}^{(3)} \approx (0.78 - 3.98) \times 10^{ - 11} \,{\text{esu}}$ and $\chi_{I}^{(3)} \approx (0.21 - 1.95) \times 10^{ - 11} \,{\text{esu}}$ in OADs. Moreover, values of optical nonlinearity of OADs show reasonable agreement with the theoretically predicted values. We have shown OADs could be used as good reverse saturable absorber and self-focusing materials. Optical limiting, due to reverse saturable absorption, has also been successfully demonstrated at 532 nm.     

EXCITED-STATE NONLINEAR ABSORPTION AND ITS APPLICATION IN PHOTONIC TECHNOLOGY

The main achievements in our research on the physical phenomena of the excited-state nonlinear absorption in a molecular system and its applications in photonic technology are described. In the first part of this paper, some energy-level models and rate-equations are used to explain various mechanisms of the excited-state nonlinear absorption under differ-ent conditions, such as reverse saturable absorption caused by the triplet and/or the singlet excited-state absorption; saturable absorption due to the first and/or the second singlet excited-state absorption; and the excited-state nonlinear absorption induced by two-photon absorption. The experimental results for metal-organic and C₆₀ materials irradiated by ps and ns laser pulses are consistent with the simulated curves of the transmittance versus flu-ences. In the second part, the applications of excited-state nonlinear absorption in photonic techniques including optical bistability, optical switching, optical limiting, optical modula-tion, optical logic and optical storage are introduced. The working principles of the photonic devices based on the excited-state nonlinear absorption are presented. The experimental characteristic curves are found in good agreement with the theoretical simulations for these devices.     

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.     

Mass spectroscopy and ablation characteristics of nylon 6.6 in the ultraviolet

We report on the mass spectroscopic and the laser ablative characteristics of nylon 6.6 [-NH-(CH₂)₆-NH-CO-(-CH₂)₄-CO-] at 193 and 248 nm, using the ArF and KrF excimer lasers. The characteristic parameters of the laser ablative process, such as etch rate at different fluences, the threshold fluence, and the absorption coefficient for both wavelengths were determined. Even at low laser energy, there was a complete breaking of the polymeric chain bonds. The following photofragments were observed at 248 nm: H, H₂, C, CH, CH₂, N, NH, O, OH, H₂O, C₂H, C₂H₂, CN, C₂H₃, HCN, N₂, CO, C₂H₄, COH, C₂H₅, N₂H, NO, C₂H₆, H₂CO, N₂H₂, C₂, CH₂NH, O₂, C₃H₃, C₃H₄, C₃H₅, C₃H₆, CNO, HCNO, and H₂CNO. At 193 nm no photofragments were observed for m/e larger than 30 amu. The photofragments with two carbon atoms have a relatively higher probability to be dissociated from the parent monomer, than heavier photofragments with four carbon atoms. The mass spectroscopic studies and the absorption spectrum of nylon 6.6 in the ultraviolet, suggest photochemical bond-breaking at 248 and 193 nm. The monomer dissociates into fragments with the predominant mass at 28 amu for both laser wavelengths. Therefore the amide group is mainly involved in the photodissociation process of nylon 6.6 in the ultraviolet. The experimental results suggest that the photochemical dissociation of the polymeric chain is the dominant mechanism of the laser ablation of nylon 6.6 at 193 and 248 nm.     

萘酞菁铅化合物的光限幅特性研究

应用调Q倍频ns/ps Nd：YAG脉冲激光,在波长为532nm,脉冲宽度为8ns,重复频率为1Hz的条件下,研究了溶于二甲基亚砜(DMSO)中的萘酞菁铅溶液的反饱和吸收和光限幅特性。实验表明,萘酞菁铅具有良好的光限幅特性,它的有效激发态吸收截面与基态吸收截面的比值约为15．21,大于萘酞菁铜。研究结果表明,萘酞菁铅的光限幅特性优于C60,激发态吸收是其主要的光限幅机理。实验结果证实了重原子效应可以通过增强系际跃迁而使三重态的反饱和吸收增强,从而提高光限幅的能力。     

Third-order optical nonlinearities of α,ω-dithienylpolyenes and oligo(thienylvinylene)

α,ω-Dithienylpolyenes and oligo(thienylvinylene) are interesting third-order nonlinear optical materials for a variety of device applications. To better understand the third-order nonlinear response of these materials, the third-order susceptibilities (χ⁽³⁾) and nonlinear absorption behaviors of two α,ω-dithienylpolyenes with different conjugation length and two oligo(thienylvinylene) with different substituents on the thiophene rings have been studied using degenerate four wave mixing (DFWM) and nonlinear transmission techniques at 532 nm. The χ⁽³⁾ values of 1×10⁻³ mol/l solutions are all of the order of 10⁻¹³ esu. The χ⁽³⁾ values increase with the increase of the linear absorption coefficient. In addition, these compounds exhibit reverse saturable absorption for nanosecond laser pulses. The strength of reverse saturable absorption varies when the conjugation length and substituents change. Moreover, the nonlinear absorption characteristics of these compounds in the picosecond regime differ from those in the nanosecond regime. The different nonlinear absorption behavior is due to the relative contributions from excited singlet–singlet and triplet–triplet absorption. The strong reverse saturable absorption characteristics of two of the compounds suggest that they could be potential candidates for optical limiting applications in the nanosecond regime.