Effects of solvent on nonlinear absorption properties of tetraphenylporphyrin compounds in the nanosecond regime

The nonlinear absorption properties of tetraphenylporphyrins (TPP) in different solvents and excitation intensities are investigated with nanosecond pulses by the Z-scan technique. The nonlinear absorption behaviour observed presents a distinct difference between in solvent mixtures and in pure solvents. A crossover from reverse saturable absorption (RSA) to saturable absorption (SA) and then again to RSA is observed with the increases of excitation intensity in chloroform and pyridine mixed solvents. However, porphyrin molecules in pure solvents show good RSA behaviour under the studied intensity range, no saturation absorption is observed with nanosecond excitation. Excited state absorption parameters and two-photon absorption coefficients are obtained by theoretical fit using rate equations for population densities in a seven-level energy scheme.     

Nonlinear optical characteristics of self-assembled films of ZnO

In the present work, we have investigated the nonlinear optical properties of self-assembled films formed from ZnO colloidal spheres by z-scan technique. The sign of the nonlinear component of refractive index of the material remains the same; however, a switching from reverse saturable absorption to saturable absorption has been observed as the material changes from colloid to self-assembled film. These different nonlinear characteristics can be mainly attributed to ZnO defect states and electronic effects when the colloidal solution is transformed into self-assembled monolayers. We investigated the intensity, wavelength and size dependence of saturable and reverse saturable absorption of ZnO self-assembled films and colloids. Values of the imaginary part of third-order susceptibility are calculated for particles of size in the range 20–300 nm at different intensity levels ranging from 40 to 325 MW/cm² within the wavelength range of 450–650 nm. PACS 81.16.Dn; 42.65.-k; 42.65.An; 42.70.-a; 42.70.Nq; 78.20.Ci     

有机材料ZnTBP-CA-PhR的非线性吸收和光学限幅性能

报道了一种新型有机材料ZnTBP-CA-PhR的光学非线性吸收特性，此材料在激光作用下，在可见光区域具有反饱和吸收，再反饱和吸收和饱和吸收效应.同时发现该材料优良的光学限幅性能，不仅光限幅的阈值低，而且限幅前光透射呈线性状态没有光学非线性效应.用5能级结构模型及速率方程模拟了饱和及反饱和的实验曲线，分析了非线性吸收等的物理机理.     

Saturable absorption and reverse saturable absorption on silver particles with different shapes

Micro/nanostructured silver particles with different shapes (flower, wire, and rod) have been prepared and characterized. All the open aperture z-scan curves of silver microrods and silver nanoflowers present a typical reverse saturable absorption. With the increase of incident intensity, the nonlinear absorption coefficients and the third-order optical susceptibilities ImX⁽³⁾ of nanoflowers increase, but those of silver microrods decrease. Moreover, the silver nanowires show the conversion from saturable absorption to reverse saturable absorption. There was no definite correlation between incident intensity and nonlinear absorption coefficient (β) under the conditions studied herein. And nonlinear optical properties of micro/nanostructured silver particles are dependent on the particle shape in suspensions at 800 nm.     

Nonresonant and Resonant Nonlinear Absorption of CdSe-Based Nanoplatelets

We present a comprehensive understanding of the nonlinear absorption characteristics of CdSe-based nanoplatelets(NPLs) synthesized by the solution-phase method and the colloidal atomic layer deposition approach through Z-scan techniques at 532 nm with picosecond pulses. The CdSe NPLs exhibit strong two-photon induced free carrier absorption(effective three-photon absorption) upon the nonresonant excitation, resulting in a remarkable optical limiting behavior with the limiting threshold of approximately 75 GW/cm~2. A nonlinear optical switching from saturable absorption(SA) to reverse saturable absorption(RSA) with increasing the laser intensity is observed when coating CdSe NPLs with a monolayer of CdS shell to realize the resonant absorption. The SA behavior originates from the ground state bleaching and the RSA behavior is attributed to the free carrier absorption.These findings explicitly demonstrate the potential applications of CdSe-based NPLs in nonlinear optoelectronics such as optical limiting devices, optical pulse compressors and optical switching devices.     

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.     

Effect of marine derived deoxyribonucleic acid on nonlinear optical properties of PicoGreen dye

We have investigated the effect of DNA on nonlinear absorption of PicoGreen dye using single beam open aperture Z-scan technique in nanosecond regime. We observed reverse saturable absorption at 532 nm for PicoGreen without DNA. In the presence of DNA, the sample begins to behave like saturable absorbers and this effect increased as the concentration of DNA was increased. The dye-intercalated DNA showed SA characteristics near the focus but exhibited RSA characteristics at the focus. Theoretical analysis has been performed using a two-photon absorption model based on nonlinear absorption coefficient and saturation intensity. Such tailoring of optical nonlinear absorption in PicoGreen makes it a potential candidate for photonic application.     

The third order nonlinear optical characteristics of amorphous vanadium oxide thin film

We studied the nonlinear absorptive characteristics (saturation intensity threshold and effective nonlinear absorption coefficients) and nonlinear refraction in a 50-nm-thick VO _x thin amorphous film prepared by pulsed DC magnetron reactive sputtering. The absorptive and refractive nonlinearities were investigated by pump–probe and Z-scan techniques. The closed-aperture Z-scan results reveal self-defocussing characteristics of the amorphous VO _x thin film for both nanosecond and picosecond pulse durations. Experimental results show that a phase transition does not occur in the range of intensities used for the experiments and the investigated sample can be treated as an amorphous semiconductor structure. The open-aperture Z-scan curves with nanosecond pulses exhibit saturable absorption for all input intensities. On the other hand, the open-aperture Z-scan curves with picosecond pulses exhibit nonlinear absorption/saturable absorption for low/high input intensities, respectively. Saturation intensity thresholds were found to be 15.3 MW/cm² for 4-ns pulse duration and 586 MW/cm² for 65-ps pulse duration.     

Optical limiting response by embedding copper phthalocyanine into polymer host

The multilayer film of PMMA containing mononuclear octakis(mercaptopropylisobutyl-POSS) substituted phthalocyaninato-copper (CuPc) was obtained by spin-coating on quartz substrate. The nonlinear absorption and optical limiting (OL) performance of CuPc have been described using the open-aperture Z-scan technique. The measurements were performed using collimated 4 ns pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. The results indicate that CuPc/PMMA composite exhibits a much larger nonlinear absorption coefficient, a lower saturable fluence and a lower absorption cross-section ratio for optical limiting when compared to the same CuPc molecules in solution. No evidence of film fatigue or degradation was observed in the CuPc/PMMA film after numerous scans at varying laser intensity. This material is a good candidate for optical limiting applications.     

一种新型非晶态分子材料的非线性光学折射率和吸收特性

用单光束扫描法测量了在532nm处一种新型非晶态分子材料5,5′Bis(dimesitylboryl)2,2′bithiophene的非线性折射率和吸收系数样品非线性透射特性的分析表明,在靠近线性吸收区的532nm处有饱和吸收存在由三能级饱和模型和Zscan法确定了饱和强度、非线性折射率的实部和虚部研究结果表明:这种新型非晶态分子材料具有非常好的光子学应用前景.     

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.     

Optical Nonlinearity of Emerging ZrS2 and HfS2 Semiconductors

Compatible with existing processing technology, chemical vapor deposition method is used to synthesize ZrS₂ and HfS₂ films a a large scale. The nonlinear optical properties are characterized by Z-scan measurement with femtosecond pulses at 800 nm. The results show that saturable absorption happens in ZrS₂ owing to the larger ground state absorption than the excited state absorption, while reverse saturable absorption appears in HfS₂ due to the two-photon absorption. The figure of merit values of ZrS₂ (≈4.30 ± 0.12 × 10⁻¹⁵ esu cm) and HfS₂ (≈6.0 ± 1.4 × 10⁻¹⁵ esu cm) are much larger than those of MoS₂ and graphene in ultrafast nonlinear optical performance at the wavelength of 800 nm.     

Effect of self assembly on the nonlinear optical characteristics of ZnO thin films

In the present work, we report the third order nonlinear optical properties of ZnO thin films deposited using self assembly, sol gel process as well as pulsed laser ablation by z scan technique. ZnO thin films clearly exhibit a negative nonlinear index of refraction at 532 nm and the observed nonlinear refraction is attributed to two photon absorption followed by free carrier absorption. Although the absolute nonlinear values for these films are comparable, there is a change in the sign of the absorptive nonlinearity of the films. The films developed by dip coating and pulsed laser ablation exhibit reverse saturable absorption whereas the self assembled film exhibits saturable absorption. These different nonlinear characteristics in the self assembled films can be mainly attributed to the saturation of linear absorption of the ZnO defect states.     

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.     

强非线性吸收下Z扫描衍射模型及实验研究

根据光的衍射理论,建立了非线性光学介质对高斯光束的开孔Z 扫描理论模型.数值计算表明,当相移比值Γ≤0.15,出射光功率随入射光功率的增加出现振荡衰减现象;当Γ>0.15,在输入光强低于某一个值时,输出随输入的增加而线性增加;当输入光强超过该值后,输出功率不再增加甚至趋于零.实验采用Nd∶YAG脉冲激光,在波长为532 nm,脉宽8 ns条件下,对含3.5%和7.0%碳纳米管的聚苯胺/碳纳米管复合体薄膜（PANI/MWCNT）的非线性吸收特性进行了研究.计算表明,该类化合物的激发态吸收截面积远大于其基态吸收截面积,具有很强的反饱和吸收.     

Nonlinear optical properties of silver colloidal solution by in situ synthesis technique

The silver colloidal solutions were prepared by in situ synthesis technique in the presence of the Polymethyl Methacrylate, which was polymerized by reversible addition-fragmentation transfer. The UV–VIS spectra and transmission electron microscopy had shown the formation of sphere silver nanoparticles with average size of 10 nm. Nonlinear optical properties as a function of silver concentration were studied using Z-scan technique with 13 ns pulse duration at 532 nm. The optical nonlinearity enhancement was observed by increasing the concentration. The third-order nonlinear susceptibility χ⁽³⁾ was measured to 1.045 × 10⁻¹¹ esu when the concentration was 2.13 mg/ml. Besides, the sample was founded to exhibit a shift from saturable absorption to reverse saturable absorption at higher incident laser energy. The reverse saturable absorption was observed to be responsible for the optical limiting characteristics in our experiments.     

High-quality, large-area monolayer graphene for efficient bulk laser mode-locking near 1.25 μm

High-quality monolayer graphene as large as 1.2×1.2?cm² was synthesized by chemical vapor deposition and used as a transmitting saturable absorber for efficient passive mode-locking of a femtosecond bulk solid-state laser. The monolayer graphene mode-locked Cr:forsterite laser was tunable around 1.25?μm and delivered sub-100?fs pulses with output powers up to 230?mW. The nonlinear optical characteristics of the monolayer graphene saturable absorber and the mode-locked operation were then compared with the case of the bilayer graphene saturable absorber.     

Nonlinear optical properties of an exciton bound to an ionized donor impurity in quantum dots

In this study, a detailed investigation of the nonlinear optical properties of the (D⁺,X) complex in a disc-like parabolic quantum dot has been carried out by using the matrix diagonalization method and the compact density-matrix approach. First, the numeric calculations and analysis of the oscillator strength of intersubband quantum transition from the ground state into the first excited state at the varying confinement frequency have been performed. Second, the linear, third-order nonlinear, and total absorption coefficients and refractive indices have been investigated. It is observed that the confinement frequency of QDs and the intensity of the illumination have drastic effects on the nonlinear optical properties. In addition, we find that all kinds of absorption coefficients and refractive indices of an exciton in QDs shift to lower energies and their peak values have considerably decreases induced by the impurity.     

Flexible alteration of optical nonlinearities of iodine charge-transfer complexes in solutions

The type of donor used is found to influence greatly the optical nonlinearities of iodine charge-transfer (CT) complexes in solutions for several solvents. The magnitude and sign changes of nonlinear absorption of iodine CT complexes for different solvents as donors are observed, which implies the transition from saturable absorption to reverse saturable absorption. Compared with C60 in toluene, iodine CT complexes with toluene and benzene demonstrate larger reverse saturable absorption. Meanwhile, flexible alteration of optical nonlinearities is easily obtained by adjusting the mixture ratio of different solvents, yielding a prospective means of constructing a nonlinear medium with a large nonlinear coefficient.     

Optical limiting and pulse reshaping of picosecond pulse trains by fullerene C60

We present a dynamical theory of nonlinear absorption and propagation of a laser pulse train that contains 20 subpulses with an individual pulse width of 100 ps. It is shown that the accumulative nonlinearity and the reverse saturation absorption play important roles in the optical limiting performance and pulse shaping. When the incident field is not too strong, the population transfer reveals a slow response process, and the periodic sequence of short light pulses can be regarded as a continuous long pulse. The general theory is applied to fullerence C₆₀, which is a popular reverse saturable absorption material and a good limiter because of its larger excited-state absorption cross-section compared with that of the ground state. The propagation of the front subpulses is mainly affected by the linear transition between the ground state and the first excited singlet state, while the latter subpulses are attenuated by the excited-state absorption. Moreover, these two different kinds of absorption mechanisms result in different radial distributions for different subpulses. The pulse propagation is studied by solving numerically the coupled rate equations and the propagation equation of the optical pulse intensity, using experimental parameters as input. We suggest a new method to measure the lifetime of the triplet state.