Au-BaTiO3复合薄膜的脉冲激光沉积制备及其非线性光学效应

利用脉冲激光沉积技术制备了掺杂金纳米颗粒的钛酸钡复合薄膜Au-BaTiO3,用高分辨透射电镜和X射线光电子能谱对薄膜进行了表征。从透射电镜照片可以看出,制备的样品中金颗粒大小约为2~3 nm,呈球形,均匀分布在载体介质中。X射线光电子能谱给出了Ba3d、Ti2p和Au4f电子芯能级结合能,结果表明载体介质是以BaTiO3的形式存在,而Au以金属的状态掺杂其中。330~800 nm范围的线性吸收谱表明样品中Au颗粒的共振吸收峰在500 nm附近。用单光束纵向扫描方法测量了样品的三阶非线性光学效应,使用的光源为调Q的YAG激光器,波长为532 nm,脉宽为10 ns,得到的非线性折射率和非线性吸收系数分别为-2.42×10-6esu和2.22×10-6m/W,表明了Au-BaTiO3复合薄膜有较大的非线性光学响应。     

PbS纳米颗粒复合的溶胶凝胶薄膜的飞秒非线性光学特性

通过光Kerr效应研究了PbS半导体纳米颗粒的三阶光学非线性响应。在较低的激发强度下,单激子态的饱和吸收和双激子效应的激发态吸收对非线性的贡献同时存在;而在高激发强度下,双激子效应是主要的。计算了高激发强度下(4mJ/cm²)PbS半导体纳米颗粒的三阶非线性光学极化率为5.1×10^-10esu。     

Effects of the ZnSe concentration on the structural and optical properties of ZnSe/PVA nanocomposite thin film

This study investigated the effects of ZnSe nanoparticles (NPs) on the structural and (linear and nonlinear) optical properties of polyvinyl alcohol (PVA) thin film. Three samples of ZnSe NP-doped PVA thin films with different concentrations of ZnSe were produced on a glass substrate. The ZnSe NPs were synthesized by pulsed laser ablation of the ZnSe bulk target immersed in distilled water using a 1064 nm wavelength and a high frequency pulsed Nd:YAG laser. The optical bandgap energies of the films were extracted from their UV-Vis-NIR absorption spectra. The corresponding energy bandgaps of the nanocomposite films declined as the ZnSe NPs doping concentration increased. X-ray diffraction analysis was used to characterize the crystalline phases of the ZnSe/PVA nanocomposite films. The concentration-dependent nonlinear optical absorption and nonlinear refraction behaviors of the films after exposure to 532-nm nanosecond laser pulses were investigated using the Z-scan technique. The nonlinear absorption response of the films was positive when measured using an open aperture scheme, which was attributed to the two-photon absorption mechanism. In addition, the nonlinear refraction indices had a negative value and they increased as the concentration of ZnSe NPs in the films increased.     

Tuning of optical properties of CdS nanoparticles synthesized in a glass matrix

Attempts were made to provide the data concerning directed synthesis of semiconductor nanoparticles in a dielectric silica-based glass matrix. These attempts involve finding out the connections between the structure, size of CdS nanoparticles, and optical properties of the nanocomposites produced. High-resolution focused ion beam scanning electron microscopy images of CdS nanoparticles incorporated in glass and SAXS results confirm the formation of uniformly distributed spherical CdS nanoparticles with an average diameter of about 6.2 nm. UV–Vis measurements show that CdS composites possess a direct bandgap wider than 2.45 eV depending on the heat treatment conditions; thus, heat treatment can be used to control nanoparticle size in each selected composite. The emission spectra showed a maximum at about 603 nm and a red shift of about 100 nm with increasing annealing temperature that is associated with the presence of defect states in the nanoparticles. In addition, semiconductor phase concentration in the glass matrix was found by using optical absorption data for the first time, which allows understanding the effect of nanocomposite structure on luminescence properties.     

Preparation and nonlinear characterization of zinc selenide nanoparticles embedded in polymer matrix

Nanocomposites of ZnSe nanoparticles embedded in polyvinyl alcohol (PVA) matrix have been prepared by in-situ synthesis. ZnSe/PVA nanocomposites are characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and UV/Vis spectra. The nanocomposite structure is confirmed by the blue-shift of the absorption edge. The nonlinear refractive index and two-photon absorption (TPA) coefficient are measured by the Z-scan technique using low power CW He–Ne laser light. The results show that the ZnSe nanocomposite films show large optical nonlinearity and the magnitude of the third-order nonlinear susceptibility χ⁽³⁾ is calculated to be 2.62×13^?11 m²/V².     

掺杂CdS纳米粒子聚合物的光折变效应研究

研究了掺杂CdS纳米粒子的有机聚合物体系的光折变效应,体系中以CdS纳米粒子为光敏剂,聚乙烯咔唑(PVK)为载流子输运剂,4-(4-硝基苯偶氮)苯胺染料(DO3)为非线性生色团,9-乙基咔唑(ECZ)为增塑剂。反胶束法合成的CdS胶束颗粒采用紫外可见吸收光谱和透射电子显微镜(TEM)表征,结果表明,具有纳米尺寸和量子限制效应。研究了PVK-CdS薄膜的光电导特性,实验结果表明,CdS纳米粒子与PVK之间的电荷转移可以有效的提高PVK的光电导率。双光束耦合实验证明了该体系的光折变特性,在无外加电场下,获得二波耦合增益系数78.4 cm-1,分析表明聚合物薄膜具有强的光致取向增强效应;样品在两相干光束作用下,可建立折射率光栅,其衍射效率达到4.4%。     

反应前驱物中n(S)∶n(Cd)对CdS薄膜结构及发光特性的影响

采用化学水浴以CdCl2·H2O、CS( NH2)2、NH4Cl、NH3·H2O和去离子水作为反应前驱物制备CdS纳米晶薄膜.采用扫描电镜( SEM)、X射线衍射(XRD)、透射光谱和稳态荧光光谱,研究了反应前驱物中不同的n(S)∶n(Cd)对所制备的CdS薄膜的形貌、结构和光学性能的影响.结果表明:反应前驱物中n(S...     

LARGE AND EXTREMELY FAST THIRD-ORDER NON-LINEARITY OF Ag NANOPARTICLES EMBEDDED INTO A CsxO SEMICONDUCTOR MATRIX

The third-order optical nonlinearity of Ag-O-Cs thin films, where Ag nanoparticles are embedded into a Cs_xO semiconductor matrix, was measured by the femtosecond optical Kerr technique. The third-order nonlinear optical susceptibility, χ⁽³⁾, of the thin films was estimated to be 1.1×10^-9 esu at the incident wavelength of 820 nm. The response time, i.e. the full width at half-maximum of the Kerr signal, is as fast as 114 fs only. The intrinsic third-order optical nonlinearity can be attributed to the intraband transition of electrons from the occupied state near the Fermi level to the unoccupied state. It is suggested that such a nonlinearity is further enhanced by the local field effect that is present in the metallic nanoparticles composite thin films.     

Third-order nonlinear optical response of Au-core CdS-shell composite nanoparticles embedded in BaTiO<Subscript>3</Subscript> thin films

Au-core CdS-shell composite nanoparticles were synthesized by a direct self-assembly process and integrated into BaTiO₃ thin films. Characterization by transmission electron microscopy showed that the average diameter of these composite nanoparticles was about 8 nm. Using the femtosecond time-resolved optical Kerr effect method, we investigated the third-order nonlinear optical response of the Au@CdS nanoparticles embedded in the BaTiO₃ thin films at a wavelength of 800 nm. An ultrafast nonlinear response and a large effective third-order nonlinear susceptibility of χ⁽³⁾=7.7×10^-11 esu were observed. We attributed the enhancement of the third-order optical nonlinearity to a localized electric field effect originating from the core-shell structure under off-surface-plasmon resonance conditions. Received: 13 May 2002 / Revised version: 23 October 2002 / Published online: 3 April 2003 RID="*" ID="*"Corresponding author. Fax: +86-21/6510-4949, E-mail: sxqian@fudan.ac.cn     

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 optical properties of Au/SiO2 nanocomposite prepared by P123

Mesoporous silica thin films loaded with gold nanoparticles are synthesized in the presence of EO20PO70EO20（P123）.Transmission electron microscope images show that the matrix of the nanocomposite is an ordered porous structure with a two-dimensional hexagonal phase.The wide-angle X-ray diffraction pattern implies that the nanocomposite contains gold crystals.These metallic nanoparticleembedded solid thin films show some linear and nonlinear optical properties due to their special structure and composition.Gold nanoparticles bring about surface plasmon resonance,and an absorption peak stemming from this effect has been observed.The linear absorption property is analyzed by a quantum mechanism,and the results show that it is influenced by the size and volume fraction of gold nanoparticles. Furthermore,it shows an obviously clear nonlinear optical property measured by the z-scan technique.The magnitude of the nonlinear refractive index of the nanocomposite is estimated to be about 10？ 10 cm 2 /W.     

Synthesis of nanocrystalline CdS thin film by SILAR and their characterization

Cadmium sulphide (CdS) thin film was prepared by successive ion layer adsorption and reaction (SILAR) technique using ammonium sulphide as anionic precursor. Characterization techniques of XRD, SEM, TEM, FTIR and EDX were utilized to study the microstructure of the films. Structural characterization by x-ray diffraction reveals the polycrystalline nature of the films. Cubic structure is revealed from X-ray diffraction and selected area diffraction (SAD) patterns. The particle size estimated using X-ray line broadening method is approximately 7 nm. Instrumental broadening was taken into account while particle size estimation. TEM shows CdS nanoparticles in the range 5–15 nm. Elemental mapping using EFTEM reveals good stoichiometric composition of CdS. Characteristic stretching vibration mode of CdS was observed in the absorption band of FTIR spectrum. Optical absorption study exhibits a distinct blue shift in band gap energy value of about 2.56 eV which confirms the size quantization.     

Optical Properties of CdS–PVA Nanocomposites

Semiconductor–polymer nanocomposites, with good control over the nanoparticle size and their dispersion within the polymer matrix, can have applications in many optical and luminescent display devices. Cadmium sulphide (CdS) is the most popular semiconductor nanoparticle exhibiting size dependent properties due to its large exciton binding energy and its suitability for large scale production. The nanoparticles need to be passivated against aggregation with suitable capping agents, without sacrificing the desirable properties like transparency and flexibility of the polymer. Cadmium sulphide nanoparticles capped with polyvinyl pyrrolidone (PVP) are synthesized using cadmium nitrate (Cd(NO₃)₂) and hydrogen sulphide (H₂S) as Cd²⁺ and S^2– sources, respectively. CdS particles with sizes in the range of 5–6 nm are prepared in methanol and the solvent is removed using a rotary evaporator. CdS powder is dispersed in polyvinyl alcohol (PVA) solution with dimethyl formamide (DMF) as solvent to get (PVP–CdS)–PVA nanocomposite film of about 0.2 mm thickness. This has been characterized by powder X-ray diffraction (XRD), optical absorption studies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and photoluminescence (PL). Particle size does not change due to incorporation in the polymer matrix and the polymer retains its transparency and flexibility. The nanocomposite shows good photoluminescence property with stronger band edge emission than defect related emission. The latter could be quenched completely by optimizing the PVP content. Irradiation of the nanocomposite with 8 MeV electrons at a dose of 100 kGy could effectively quench the defect related emission.     

Effect of swift heavy ion irradiation on photoluminescence properties of ZnO/PMMA nanocomposite films

We report a study on the SHI induced modifications on structural and optical properties of ZnO/PMMA nanocomposite films. The ZnO nanoparticles were synthesized by the chemical route using 2-mercaptoethanol as a capping agent. The structure of ZnO nanoparticles was confirmed by XRD, SEM and TEM. These ZnO nanoparticles were dispersed in the PMMA matrix to form ZnO/PMMA nanocomposite films by the solution cast method. These ZnO/PMMA nanocomposite films were then irradiated by swift heavy ion irradiation (Ni⁸⁺ ion beam, 100 MeV) at a fluence of 1×10¹¹ ions/cm². The nanocomposite films were then characterized by XRD, UV-vis absorption spectroscopy and photoluminescence spectroscopy. As revealed from the absorption spectra, absorption edge is not changed by the irradiation but the optical absorption is increased. Enhanced green luminescence at about 527 nm and a less intense blue emission peak around 460 nm were observed after irradiation with respect to the pristine ZnO/PMMA nanocomposite film.     

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.     

Synthesis and characterization of CdS/PVA nanocomposite films

A series CdS/PVA nanocomposite films with different amount of Cd salt have been prepared by means of the in situ synthesis method via the reaction of Cd²⁺-dispersed poly vinyl-alcohol (PVA) with H₂S. The as-prepared films were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) spectra, Fourier transform infrared spectroscope (FTIR) and thermogravimetric analysis (TGA). The XRD results indicated the formation of CdS nanoparticles with hexagonal phase in the PVA matrix. The primary FTIR spectra of CdS/PVA nanocomposite in different processing stages have been discussed. The vibrational absorption peak of CdS bond at 405 cm⁻¹ was observed, which further testified the generation of CdS nanoparticles. The TGA results showed incorporation of CdS nanoparticles significantly altered the thermal properties of PVA matrix. The photoluminescence and UV-vis spectroscopy revealed that the CdS/PVA films showed quantum confinement effect.     

The optical properties and energy transition process in nanocomposite of polyvinyl-pyrrolidone polymer and Mn-doped ZnS

This study has been carried out on the optical properties of polyvinyl-pyrrolidone (PVP), the energy transition process in nanocomposite of PVP capped ZnS:Mn nanocrystalline and the influence of the PVP concentration on the optical properties of the PVP capped ZnS:Mn nanocrystalline thin films synthesized by the wet chemical method. The microstructures of the samples were investigated by X-ray diffraction, the atomic absorption spectroscopy, and transmission electron microscopy. The results showed that the prepared samples belonged to the sphalerite structure with the average particle size of about 2–3 nm. The optical properties of samples are studied by measuring absorption, photoluminescence (PL) spectra and time-resolved PL spectra in the wavelength range from 200 to 700 nm at 300 K. From data of the absorption spectra, the absorption edge of PVP polymer was found about of 230 nm. The absorption edge of PVP capped ZnS:Mn nanoparticles shifted from 322 to 305 nm when the PVP concentration increases. The luminescence spectra of PVP showed a blue emission with peak maximum at 394 nm. The luminescence spectra of ZnS:Mn–PVP exhibits a blue emission with peak maximum at 437 nm and an orange–yellow emission of ion Mn²⁺ with peak maximum at 600 nm. While the PVP coating did not affect the microstructure of ZnS:Mn nanomaterial, the PL spectra of the PVP capped ZnS:Mn samples were found to be affected strongly by the PVP concentration.     

纳米银颗粒掺杂铋酸盐玻璃的光谱与三阶非线性光学特性研究

采用新型的热化学还原法,制备了银纳米颗粒掺杂的铋酸盐复合玻璃材料。利用紫外-可见吸收光谱观察到了银纳米颗粒表面等离子谐振(SPR)吸收的峰值位移特性,用拉曼光谱表征了引入银纳米颗粒后玻璃的结构变化。借助飞秒激光脉冲激发下的Z扫描与光克尔闸技术,在近红外波段下研究了材料的三阶非线性光学特性。研究结果表明银纳米颗粒铋酸盐复合材料有着亚皮秒级的非线性响应时间,并且其非线性折射率γ在纳米颗粒的热电子效应以及局部场效应的影响下,较基质玻璃最高可以提升29倍。     

聚电解质/硫化镉薄膜的层-层组装及其光谱分析

以六偏磷酸钠为稳定剂,采用硝酸镉和硫化钠合成了硫化镉纳米颗粒,利用层-层组装技术制备了聚电解质与硫化镉胶体的复合薄膜.吸收光谱显示,硫化镉胶体的吸收带边相对其体相有明显蓝移,并可观察到激子吸收峰,显示出量子尺寸效应.复合薄膜的荧光光谱上出现2个发光带,随着薄膜的组装层数的增加,复合薄膜的带带跃迁发光和表面态发光都相应减弱.     

Effect of gamma irradiation on the structural and optical properties of PVA/CdS nanocomposite films prepared by ex-situ technique

ABSTRACT

For a comprehensive understanding of the PVA/CdS nanocomposite properties, it is essential to select the suitable method for their preparation as well as elucidate the interfacial interactions, which still need support. CdS nanoparticles have been prepared by thermolysis method under the flow of nitrogen. Rietveld refinement of x-ray data shows that all the CdS samples have both cubic and hexagonal structures. Then PVA/CdS films were prepared by ex-situ technique. Samples from PVA/CdS nanocomposite have been irradiated with gamma doses in the range 10–120?kGy. The implanting of CdS NPs into PVA matrix was confirmed by XRD hand in hand with UV–vis and FTIR spectroscopic techniques. UV/VIS absorption spectra confirm the formation of hybridized film CdS/PVA nanocomposite with a refractive index in the range of 1.32–1.48 (at 500?nm). UV/VIS measurements were also used in calculating different optical parameters such as refractive index, extinction coefficient and optical band gap energy. Additionally, Tauc’s relation was used to determine the type of electronic transition. It is found that the gamma irradiation in the dose range 30-90?kGy led to a more compact structure of PVA/CdS nanocomposite and causes proper dispersion of CdS nanoparticles in the PVA matrix. This led to the formation of coordination reaction between OH of PVA and CdS nanoparticles, resulted in an increase in refractive index and the amorphous phase. Also, the gamma irradiation reduces the optical energy gap from 4.53 to 2.19?eV, and accompanied with an increase in the Urbach energy from 2.28 to 4.46?eV, at that dose range which could be attributed to the increase in structural disorder of the irradiated PVA/CdS nanocomposites due to crosslinking. Further, the color intensity ΔE, which is the color difference between the non-irradiated sample and the irradiated ones, was increased, from 0 to 10.8, with increasing the gamma dose, convoyed by an increase in the red and yellow color components.