3 μm~5 μm中红外激光辐照石墨烯非线性散射实验研究

为了研究石墨烯器件在中红外波段的光限幅机理,采用化学气相沉积法制备出层数可控的石墨烯薄膜CaF2镜片,并基于MgO∶PPLN周期极化晶体搭建了全固态中红外光学参量振荡器,利用3 m~5 m波长可调谐的闲频光开展了石墨烯薄膜散射实验,测量了石墨烯薄膜的散射信号与入射光强度变化的归一化曲线。当闲频光能量超过1 J/cm2时,石墨烯被迅速汽化,电离形成的微小等离子体和石墨烯微片对入射闲频光产生多重非线性散射,散射能量信号呈现出快速非线性增长趋势,并且散射能量信号值的增长率与闲频光的入射波长成反比,与石墨烯的层数成正比关系,从而验证了石墨烯对中红外波段激光较强的非线性散射使其具有光限幅效应。     

碳纳米管悬浮液对532nm激光限幅机理的实验研究

通过光限幅、Z扫描、非线性吸收和散射能量分布实验,研究了碳纳米管悬浮液对532 nm激光的限幅机理以及样品厚度对光限幅机理的影响。结果表明:碳纳米管悬浮液的光限幅机理并非单纯的非线性散射,对低能量入射激光光限幅特性主要源于对入射激光的非线性吸收;对高能量入射激光,碳纳米管的吸收效应和它电离形成的微等离子体以及液体汽化所形成气泡散射效应的共同作用,使其具有较强的光限幅能力,对浓度一定的悬浮液,增加样品厚度虽然会增强其限幅效果,但却会减弱其非线性散射效应。     

酞菁掺杂复合体系光限幅性能的基质效应

采用Sol-gel法将四磺化酞菁镍(NiTSPc)、酞菁铅(PbPc)分别植入二氧化硅凝胶基质,制备出均匀掺杂的复合凝胶玻璃,并对光限幅性能进行了测试.研究结果表明基质的组成、结构和凝胶化过程将改变复合体系中掺杂酞菁存在的微化学环境,进而影响其激发态物理过程和由此决定的光限幅性能,表现出复合体系光限幅性能的基质效应.     

氧化石墨烯-卟啉复合材料光限幅性能的理论研究

利用时域有限差分法数值求解速率-场强方程,研究了一系列共价连接的氧化石墨烯-卟啉复合材料在纳秒时域内的光限幅性质和双光子吸收. 计算结果表明,氧化石墨烯-卟啉复合分子与单独的卟啉分子相比展现出增强的光限幅效应,并且有着更大的双光子吸收截面.与之前得到的含重金属的卟啉分子具有更强非线性光学性质的结论不同,不含金属元素的卟啉分子与氧化石墨烯结合后展现出了更强的非线性光学性质. 理论计算的结果与实验测量符合较好. 此外,着重研究了介质的厚度和脉冲宽度对分子双光子吸收截面的影响. 结果表明,随着介质厚度的增加或者脉宽的变宽分子的动态双光子吸收截面增大.     

四取代4-异丙苯基苯氧基酞菁铅复合凝胶玻璃的结构及光限幅性能研究

采用溶胶-凝胶(Sol-gel)湿化学工艺将四取代4-异丙苯基苯氧基酞菁铅PbPc(CP)4掺入二氧化硅(SiO2)凝胶玻璃基质,制备均匀掺杂的PbPc(CP)4复合凝胶玻璃,并通过紫外-可见(UV-Vis)吸收光谱和透射电镜(TEM)图像对PbPc(CP)4在复合凝胶玻璃中的存在状态及结构进行了表征.对PbPc(CP)4在液相体系和固相体系中的光限幅性能分别进行了测试及对比研究.结果表明PbPc(CP)4以团簇形式存在于复合凝胶玻璃中,并由于钢性结构固相基质的保护作用使其在复合凝胶玻璃相对于液相体系中表现出较强的光限幅特性.     

氯铟酞菁光稳定性及光限幅循环特征研究

借助氯铟酞菁(InPcCl)溶液在激光轰击及日照过程中UV-Vis吸收光谱的改变以研究其光稳定性,并采用开孔Z-扫描技术对其光限幅效应及其循环特性进行跟踪研究.结果表明,InPcCl具有良好的光限幅循环特征和在激光轰击下的稳定性,相反,其在日光照射下的稳定性很差.提出了导致这种差异的原因.     

石墨烯在中红外波段的光限幅效应研究

利用纳秒级脉冲量激光的Z 扫描方法对不同层数石墨烯薄膜在3 m~5 m中红外波段的光限幅效应开展了研究,获得的开孔Z扫描曲线均呈现出单一谷结构,而闭孔Z扫描曲线没有明显的峰谷对称结构。通过对开孔Z扫描实验数据进行数值模拟,分别得到3层石墨烯在3.010 m、3.522 m、4.326 m和4.880 4 m 4个中心波长处的三阶非线性吸收系数和光限幅阈值分别为11.3910-7cm/W、10.6110-7cm/W、9.7510-7cm/W、8.8110-7cm/W和3.49 J/cm2、3.75 J/cm2、4.11 J/cm2、4.55 J/cm2;3层、5层和7层石墨烯在3.522 m中心波长处的三阶非线性吸收系数和光限幅阈值分别为10.6110-7 cm/W、11.3210-7 cm/W、11.9510-7 cm/W和3.75 J/cm2、3.41 J/cm2、3.32 J/cm2。实验数据表明,石墨烯在中红外波段产生了较强的非线性反饱和吸收而具有明显的光限幅效应。     

可溶性多壁碳纳米管光限幅机理研究

根据光限幅与Z扫描实验研究了可溶性多壁碳纳米管的光限幅机理.通过现象分析、数据处理以及类比研究,证实材料的光限幅特征符合非线性吸收效应.对厚样品的独特现象进行了解释,讨论了其他机理的影响.根据Z扫描公式,计算了实验材料的三阶非线性系数.通过分析证实了非线性吸收在可溶性多壁碳纳米管的光限幅中发挥着主要作用.对厚介质的特殊现象进行的分析和计算表明,对于较厚介质和激光连续加热的情况下,其他机理的影响并不能完全否定,其特殊现象可能与微气泡的气穴作用有关.     

氧化石墨烯与水溶性酞菁铜的表面增强拉曼散射光谱特性研究

采用氧化石墨烯(GO)作为表面增强拉曼散射的基底,水溶性酞菁铜(TSCuPc)作为探针分子,实验探究了氧化石墨烯薄膜的层数和TSCuPc薄膜的厚度对拉曼散射增强的影响。首先配制了不同浓度的GO溶液,利用旋涂法在玻璃基底上制备了不同层数的GO膜,然后通过调节TSCuPc薄膜的旋涂转速,制备了GO和TSCuPc的复合薄膜。实验结果表明,当增加GO薄膜层数时,由GO和TSCuPc产生的π-π共轭所感应的分子极化率和由GO含氧官能团感应的局域电场均增大,因此TSCuPc分子的拉曼强度增大,且随着层数的增加,增强呈现饱和趋势;而随着TSCuPc薄膜厚度的增加,由于其自身分子间也存在π-π共轭,TSCuPc分子的拉曼光谱强度呈近似线性增加,且由TSCuPc薄膜厚度引起的首层效应并不是很明显。选用的可以溶液法成膜的TSCuPc分子,通常被用作有机光电子器件的空穴注入材料,研究GO与TSCuPc的表面增强拉曼光谱特性,为优化器件参数以提高有机光电子器件的电荷转移效率等性能具有重要的意义。     

表面修饰基团对金纳米颗粒非线性光学效应的影响研究

采用两相法分别制备一级硫醇修饰和二级十六烷基三甲基溴化铵(CTAB) 修饰的金纳米颗粒,通过透射电子显微镜和紫外-可见吸收光谱表征了其结构和线性光学性质. 采用开孔Z扫描技术,研究表面修饰对金纳米颗粒在532 nm波长激光作用下的非线性光学效应及光限幅性能的影响行为.结果表明,二级CTAB的修饰增强了颗粒在激光照射下的局域场作用, 并提高了热电子对非线性光学效应的贡献程度,从而有效地提高了金纳米颗粒的光限幅性能.     

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.     

Enhanced optical limiting effect in fluorine-functionalized graphene oxide

Nonlinear optical absorption of fluorine-functionalized graphene oxide (F-GO) solution was researched by the open-aperture Z-scan method using 1064 and 532 nm lasers as the excitation sources. The F-GO dispersion exhibited strong optical limiting property and the fitted results demonstrated that the optical limiting behavior was the result of a two-photon absorption process. For F-GO nanosheets, the two-photon absorption coefficients at 1064 nm excitation are 20% larger than the values at 532 nm excitation and four times larger than that of pure GO nanosheets. It indicates that the doping of fluorine can effectively improve the nonlinear optical property of GO especially in infrared waveband, and fluorine-functionalized graphene oxide is an excellent nonlinear absorption material in infrared waveband.     

Physical properties and device applications of graphene oxide

Graphene oxide (GO), the functionalized graphene with oxygenated groups (mainly epoxy and hydroxyl), has attracted resurgent interests in the past decade owing to its large surface area, superior physical and chemical properties, and easy composition with other materials via surface functional groups. Usually, GO is used as an important raw material for mass production of graphene via reduction. However, under different conditions, the coverage, types, and arrangements of oxygen-containing groups in GO can be varied, which give rise to excellent and controllable physical properties, such as tunable electronic and mechanical properties depending closely on oxidation degree, suppressed thermal conductivity, optical transparency and fluorescence, and nonlinear optical properties. Based on these outstanding properties, many electronic, optical, optoelectronic, and thermoelectric devices with high performance can be achieved on the basis of GO. Here we present a comprehensive review on recent progress of GO, focusing on the atomic structures, fundamental physical properties, and related device applications, including transparent and flexible conductors, field-effect transistors, electrical and optical sensors, fluorescence quenchers, optical limiters and absorbers, surface enhanced Raman scattering detectors, solar cells, light-emitting diodes, and thermal rectifiers.     

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527nm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。     

Optical Limiting Properties of Two Soluble Polymer/Multi-Walled Carbon Nanotube Composites

Two soluble polymer grafted multi-walled carbon nanotubes （MWNTs）, including poly（N-vinylcarbazole）-MWNTs and poly（methyl methacrylate）-MWNTs, are synthesized. Their nonlinear optical properties and opticaJ limiting （OL） performances are investigated by z-scan method with 527nm nanosecond laser pulses. These grafted MWNTs dissolved in chloroform show much better optical limiting performance than those of MWNTs and C60 in toluene solution. Nonlinear absorption and nonlinear scattering mechanism are taken into consideration for explaining the observed results. The comparison of the experimental results shows that nonlinear absorption is the dominant mechanism for OL performance of these new samples.     

Synthesis and Characterization of Poly(vinyl pyrrolidone)/Reduced Graphene Oxide Nanocomposite

Poly(vinyl pyrrolidone) (PVP)/reduced graphene oxide (RGO) nanocomposites were synthesized by reducing graphene oxide in the polymer matrix at different temperatures. The effects of the GO content on the properties of the nanocomposites were investigated by Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The degree of dispersion of GO in the PVP matrix was examined by field-emission scanning electron microscopy. The results showed that both GO and RGO were well dispersed in the PVP matrix. Under low filler content, the improvement of onset decomposition temperatures of PVP nanocomposites was not obviously observed, but the amounts of residual char of the PVP nanocomposites were clearly increased. In addition, the decomposition temperature peak values of the PVP nanocomposites were increased, while the peak was broadened.     

Electron interactions and scaling relations for optical excitations in carbon nanotubes

Recent fluorescence spectroscopy experiments on single wall carbon nanotubes reveal substantial deviations of observed absorption and emission energies from predictions of noninteracting models of the electronic structure. Nonetheless, the data for nearly armchair nanotubes obey a nonlinear scaling relation as a function of the tube radius R. We show that these effects can be understood in a theory of large radius tubes, derived from the theory of two dimensional graphene where the Coulomb interaction leads to a logarithmic correction to the electronic self-energy and marginal Fermi liquid behavior. Interactions on length scales larger than the tube circumference lead to strong self-energy and excitonic effects that compete and nearly cancel so that the observed optical transitions are dominated by the graphene self-energy effects.     

Enhanced Fluorescence of Graphene Oxide by Well-Controlled Au@SiO2 Core-Shell Nanoparticles

Graphene and graphene derivatives, including graphene oxide (GO) and reduced GO (rGO), have attracted remarkable attention in different fields due to their unique electronic, thermal, and mechanical properties, whereas the fluorescence property is rarely been studied. This paper reports on metal-enhanced fluorescence Au@SiO₂ composite nanoparticles adsorbed graphene oxide nanosheets, where the silica-shell is used to control the distance between gold-core and fluorophore GO, and a positively charged polyelectrolyte poly(allylamine hydrochloride) (PAH) is used to adsorb the negatively charged silica-shell and GO by layer-by-layer assembly (LbL) approach. The silica-shell around the 80 nm gold-core can be well-controlled by ending the reaction at different times. Various analytical techniques were applied to characterize the morphology and optical characters of the as-prepared particles. A more than three-fold increase of the fluorescence intensity of GO was obtained.     

Difference in formation of carbon cluster cations by laser ablation of graphene and graphene oxide

The distributions of positive carbon cluster ions produced by laser ablation of graphene (G) and graphene oxide (GO) are found to be quite different. Under a typical experimental condition, narrow distributions of even-numbered clusters from C60+ to C162+ were observed for G, and broad distributions including even-numbered clusters from C100+ to C400+ and odd-numbered clusters from C189+ to C395+ were observed for GO. The threshold of laser energy for G is lower than that of GO. Further results of collision-activated dissociation mass spectrometry indicate that the cluster ions generated from G are structurally similar but are different with those generated from GO or nanodiamonds. It is proposed that the experimentally observed difference can be attributed to the different mechanisms behind the process. A top-down mechanism including both direct transformation of G to fullerene and fragmentation of large-sized fullerenes is suggested for the generation of carbon cluster cations in the process of laser ablation of G. For GO, the experimental results are close to those of nanodiamonds and other materials reported previously and can be explained by the generally accepted bottom-up mechanism.