可溶性高聚物-多壁碳纳米管复合物的吸收光谱和光限幅性能研究

合成了三种可溶性高聚物嫁接的多壁碳纳米管复合物,包括聚乙烯基咔唑-多壁碳纳米管复合物(MWNTs-PVK),聚苯乙烯-多壁碳纳米管复合物(MWNTs-PSt)和聚甲基丙烯酸甲酯-多壁碳纳米管复合物(MWNTs-PMMA)。合成样品的TEM图显示出高聚物成功地包裹在碳纳米管外。样品的氯仿溶液UV-Vis 吸收谱显示,复合物的紫外区与纯的多壁碳纳米管不同,有一些复杂的特征吸收峰,反映了高聚物与碳纳米管共价连接的作用。利用Z扫描技术通过527 nm的纳秒激光脉冲激发研究了这三种复合物的非线性光学性质和光限幅性能。这三种复合物的氯仿溶液的光限幅性能很相似,并且优于纯多壁碳纳米管氯仿悬浮液和C60甲苯溶液。为解释观察到的结果,研究了样品的非线性折射,非线性吸收和非线性散射机制。结果显示,非线性吸收是引起样品光限幅的主要机制。     

Broadband optical limiting performance of polymer-wrapped carbon nanotubes in the orange-NIR region

Soluble multi-walled carbon nanotubes (MWNTs) have been obtained by noncovalent modification with poly [2-methoxy,5-(2′-ethyl-hexyloxy)-p-phenylene vinylene] (MEH-PPV). For the composite MWNT/MEH-PPV, there is π-π interaction between the MEH-PPV and MWNTs in addition to the wrapping of the polymer. The nonlinear optical transmittance was measured using a nanosecond optical parametric oscillator pumped with a Nd:YAG system. Excellent optical limiting performance of the composite MWNT/MEH-PPV was observed both in the visible region of 590-680 nm and at the wavelength of 1064 nm. By means of time-correlated single-photon counting fluorescence measurement, an explanation based on the nonlinear absorption of MWNT dominated by the intermolecular energy transfer was proposed.     

Nonlinear optical response of inorganic metal cluster MoCu3Se4(PPh3)3Cl solution

The pump-probe response of the metal cluster MoCu₃Se₄(PPh₃)₃/CH₂Cl₂ solution is similar to that of CBS, which implies a nonlinear scattering origin of its nonlinearity. To testify how much the nonlinear scattering contributes to the optical limiting process, we employ a method by inserting a light collection lens in a standard OL experimental setup. Results from such an experiment show that nonlinear scattering is important when the concentration is low. For a high-concentration sample, the nonlinear energy loss is mainly related to thermal induced nonlinear absorption.     

Strong optical limiting property of a ball-type supramolecular zinc-phthalocyanine in polymer-phthalocyanine composite film

The nonlinear absorption and optical limiting (OL) performance of a supramolecular hexa-phthalocyaninato-hexazinc (II) with hexylthio substituents in solution and in the solid-state 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 indicated that OL performance of the investigated compound in the polymeric film is much better compared to properties in solution. With the excellent combination of OL parameters the investigated compound in the solid-state is a candidate for the use as optical limiter.     

Optical limiting properties of zinc phthalocyanines in solution and solid PMMA composite films

The nonlinear absorption and optical limiting (OL) performance of tetra- and octasubstituted zinc phthalocyanine complexes were described in solution and in the solid state 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 polymeric films exhibit a much larger effective nonlinear absorption coefficient in comparison with solution. However, the parameters of the ratio of the excited to ground state absorption cross section and energy-dependent saturation in solution are much better compared to properties in the polymeric film. In terms of the ratio of the excited to ground state absorption cross section, the peripherally substituted complexes show better OL performance than the non-peripherally substituted derivative.     

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.     

Optical limiting properties of trimeric metallo-phthalocyanines/polymer composite films

The nonlinear absorption and optical limiting properties of two trimeric metallo-phthalocyanines namely, 2,4,6-tris[2-oxa-9,10,16,17,23,24-hexa(hexylthio) phthalocyaninato M(II)]-s-triazine (M=Zn for compound ZnPc and Cu for compound CuPc) doped polyvinyl chloride (PVC) thin film in the nanosecond regime were investigated by using the open-aperture Z-scan technique. The measurements were performed using 4 ns pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. OL parameters of the ratio of the excited state to ground state absorption cross-sections κ, the effective nonlinear absorption coefficient β_eff, the linear absorption coefficient α₀ and the saturation density or energy density F_sat values were determined. The results show that MPc/PVC composite displays much larger nonlinear absorption coefficient and lower saturable fluence for optical limiting when compared to the same Pc molecules in solution. The results indicated that both compounds exhibited good OL performances. ZnPc shows slightly better OL parameters than that of CuPc.     

Optical Performance and Nonlinear Scattering of Soluble Polystyrene Grafted Multi-Walled Carbon Nanotubes

Three soluble polystyrene grafted multi-walled carbon nanotube （MWNT） samples are synthesized, and their optical performance and nonlinear scattering properties are investigated by z-scan method using nanosecond pulses of 532 nm from a frequency-doubled Q-switched Nd： YLF laser. Analysis of the experimental results shows that other than nonlinear scattering, nonlinear absorption plays a major role in optical limiting performance of these stable and well-dispersed suspensions. These new synthesized materials which can be better dispersed in common organic solvents than MWNT itself can be considered as potential sources for further optical applications.     

Third-order nonlinear optical properties of graphene composites: A review

Graphene has excellent thirdorder nonlinear optical (NLO) properties due to its unique electronic band structure and wideband gap tunability. This paper focuses on the research progress of graphene and its composite materials in nonlinear optics in recent years. In this review, recent results on graphene (or graphene oxide)-metal nanoparticles (G-MNPs), graphene-metal-oxide nanoparticles (G-MONPs), graphene-metal sulfide nanoparticles (G-MSNPs), and graphene-organic molecular composites (G-OM) have been discussed. In addition, the enhancement mechanism of nonlinear absorption (NLA) and optical limiting (OL) have also been covered.     

A novel optical limiting coordination polymer with ladder-like framework

The optical limiting (OL) properties of a novel coordination polymer {[Et₄N][Ag₂I₃]}_n with a ladder-like framework were investigated using 532-nm nanosecond laser pulses. The coordination polymer in dimethylformamide solution exhibits better OL performance than C₆₀ in toluene. The results were discussed using a phenomenological model based on excited-state nonlinear absorption. PACS 42.70.Mp; 42.65.-k; 42.70.Hj; 36.20.Hb     

Synthesis of anatase titania-carbon nanotubes nanocomposites with enhanced photocatalytic activity through a nanocoating-hydrothermal process

Anatase TiO₂ nanoparticles were covalently anchored onto acid-treated multi-walled carbon nanotubes (MWNTs) through a nanocoating-hydrothermal process to obtain TiO₂-MWNTs nanocomposites. The composition and structural properties of the nanocomposites were characterized by XRD, BET, TG, TEM, HRTEM, EDX, XPS, and FTIR, and the formation of ester-bond linkage between TiO₂ nanoparticles and MWNTs was demonstrated. The enhanced photocatalytic activity of TiO₂-MWNTs nanocomposites was probed by photodegradation reaction of methylene blue under visible-light irradiation.     

碳纳米管/二硒化钼有机玻璃的非线性吸收、非线性散射和光限幅特性

MoSe₂的禁带宽度较窄（1.1–1.5 eV）,且具有可调谐的激子光电效应,这样使其在光致发光、光电晶体管、太阳能电池和光学非线性等方面具有潜在的应用价值.然而,纯的MoSe₂的光生电子空穴复合率较高,限制了其在某些光学领域中的应用.通过设计MoSe₂的复合材料,可以降低材料的光生电子空穴复合率,从而扩展其应用领域.首先,通过热溶剂法合成CNT/MoSe₂复合材料;然后,通过浇铸法将其分散在甲基丙烯酸甲酯（MMA）中制备成有机玻璃,其中MMA会聚合成聚甲基丙烯酸甲酯（PMMA）,并利用改进的Z-扫描技术首次对CNT/MoSe₂/PMMA有机玻璃的非线性吸收、非线性散射和光限幅特性进行了研究.研究表明,随着输入能量的变化,通过调节输入能量,CNT/MoSe₂/PMMA有机玻璃表现出饱和吸收（SA）和从SA到反饱和吸收的转变.结合材料特性及应用条件要求,可以得到CNT/MoSe₂/PMMA有机玻璃在光学设备,如光学限制器和锁模/调Q激光器等方向具有较好的应用前景.     

Multilayer Au/TiO2Composite Films with Ultrafast Third-Order Nonlinear Optical Properties

We report on the ultrafast third-order optical nonlinearity in multilayer Au/TiO2 composite films fabricated on quartz substrates by pulsed laser deposition technique. The linear optical properties of the films are determined and optical absorption peaks due to surface plasmon resonance of Au particles are observed at about 590hm. The third-order optical nonlinearities of the films are investigated by z-scan method using a femtosecond laser （50 fs） at the wavelength of 800 nm. The sample showed fast nonlinear optical responses with nonlinear absorption coefficient and nonlinear refractive index being -3.66 × 10^-10 m/W and -2.95 × 10^-17 m^2/W, respectively. The results also show that the nonlinear optical effects increase with the increasing Au concentration in the composite films.     

Linear and Nonlinear Intersubband Optical Absorptions and Refractive Index Changes in InGaN Strained Single Quantum Wells： Strong Built-in Electric Field Effects

Considering the strong built-in electric field （BEF） effects due to the spontaneous and piezoelectric polarizations, the intersubband optical absorptions and refractive index changes for an InxGa1-xN/AlyGa1-yN strained single quantum well are studied theoretically within the framework of the density matrix method and effective-mass approximation. The linear, third-order nonlinear and total absorption coefficients and refractive index changes are calculated as a function of the incident optical intensity and photon energy. Our results show that both the incident optical intensity and the strong BEF have great influence on the total absorptions and refractive index cllanges. The results are significant for designing some important photodetectors and the photonic crystal devices with adjustable photonic band structures.     

可溶性聚噻吩甲烯包覆碳纳米管的三阶非线性光学响应

采用原位聚合的方法合成了聚(3-己基噻吩)-2,5-二(4-羟基-3-甲氧基苯甲烯)包覆的多壁碳纳米管(PHTHMOBQ/MWNTs). 荧光光谱分析表明, PHTHMOBQ/MWNTs复合体中, 碳纳米管与共轭聚合物PHTHMOBQ之间形成光致电子转移体系, 使得π电子离域程度增加, 并且导致荧光量子效率降低. 根据E_g与入射光子能量hν的关系, 拟合了PHTHMOBQ/MWNTs薄膜的光学禁带宽度. 发现随着碳纳米管含量的增加, E_g逐步减小. 采用简并四波 关键词： 共轭聚合物 碳纳米管 光致电子转移 三阶非线性光学效应     

Enhanced optical limiting properties in suspensions of CdO nanowires

Optical limiting (OL) properties of CdO nanowires in water and ethanol were investigated by using nanosecond laser pulses at 532 nm. Experimental results show that suspension of CdO nanowires in ethanol exhibits better OL property than solution of C₆₀ in toluene and suspension of CdO nanowires in water. The dominant mechanism for the observed enhanced optical limiting in ethanol suspensions of CdO nanowires is due to nonlinear scattering.     

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：     

The nonlinear refraction and nonlinear absorption in 4-(4,6-diaminopyrimidin-2-ylthio) substituted double-decker Lu(III) phthalocyanine

A 4-(4,6-diaminopyrimidin-2-ylthio) substituted double-decker Lu(III) phthalocyanines (4) have been prepared and characterized by elemental analysis, IR, UV-vis and ¹H NMR spectroscopies. The nonlinear refractive index, nonlinear absorption and the optical limiting (OL) performance of the compound 4 in a 0.5 mm spectroscopic cell in DMF solution were investigated by using 4 ns pulse laser at 532 nm. Z-scan experiments have been conducted between 0.24 and 2.39 GW/cm² peak intensities for 10 Hz repetition rate and also between 2.39 and 23.89 GW/cm² peak intensities for 1 Hz repetition rate. The thermal effect contributes to the nonlinear response of the material higher than 0.72 GW/cm² peak intensity at 10 Hz. We measured the effective nonlinear refractive index of the material as 1.2×10⁻¹¹ esu at 3.5×10⁻⁴ M concentration with the peak intensity less than 0.72 GW/cm² and we found that nonlinear absorption was very small. On the other hand, when concentration is increased to 2.4×10⁻³ M material's nonlinear absorption becomes dominant mechanism for the nonlinear response and the compound 4 indicates OL behavior at 2.4×10⁻³ M concentration.     

钒氧酞菁与萘酞菁的光限幅循环特性及光稳定性研究

采用Z-扫描测试技术及UV/Vis吸收光谱研究钒氧酞菁(VOPcs)与萘酞菁(VONcs)的光限幅循环特性及光稳定性。结果表明,钒氧2,11,20,29-四取代叔丁基-2,3-萘酞菁最初表现出最好的光限幅效应,但光稳定性较差。钒氧2,9,16,23-四取代苯氧基-29H,31H-酞菁具有较强的光限幅效应和良好的光稳定性,是一种有应用前景的光限幅材料。探讨了VOPcs与VONcs的光解机理。     

氧化石墨烯/壳聚糖复合薄膜材料的制备及其非线性光限幅效应的研究

石墨烯及其衍生物作为新型碳纳米结构,由于其优异的光限幅性能而受到广泛关注,但现有的工作多侧重于其在液相体系中光限幅效应及其起因研究.本文以壳聚糖为成膜基质,将氧化石墨烯(GO)与壳聚糖(CS)在液相中均匀共混后成膜,对比研究GO溶液和GO-CS复合膜的光限幅效应及其起因.结果表明在线性透过率相同的情况下,GO在固相基质中表现出比液相基质更强的光限幅效应和更弱的非线性散射.这说明不同于碳纳米管简单的非线性散射,在GO中可能存在多种非线性光学效应.