氧化钛薄膜调控金属铜的表面等离子体共振特性研究

提出了一种利用氧化钛薄膜对金属铜薄膜表面等离子体共振特性调制的想法。实验中首先使用电子束蒸发制备一批同等厚度的氧化钛薄膜,再利用磁控溅射方法在氧化钛薄膜上沉积厚度为5～80 nm不等的金属铜薄膜。测试结果表明,氧化钛膜层对不同厚度的金属铜薄膜表面等离子体共振增强具有不同调制效果,金属铜薄膜厚度小于20 nm时,底层的氧化钛薄膜对Cu薄膜表面等离子体共振增强效果显著,且随着金属Cu膜层厚度增加表面等离子体共振峰发生蓝移,而当金属铜膜层的厚度超过20 nm时,共振增强效果因金属Cu薄膜消光能力的上升而开始减弱。     

Formation of argentic clusters and small Ag nanoparticles in soda-lime silicate glass

The formation of argentic clusters and very small Ag nanoparticles of 0.5 to 2 nm size in commercial soda-lime glass silver-doped by Ag/Na ion exchange in a mixed nitrate melt has been studied by electron microscopy and EXAFS. Particles formation was induced already during the ion exchange procedure, or by subsequent ion irradiation with 1.5 MeV He⁺ or 3 MeV Au⁺. The presence of nanoparticles was also macroscopically revealed by their surface plasmon resonance. The structural characterization indicates that specific configurations of silver oxide-like structures, so-called argentic clusters, are involved in the initial stage of nanoparticles formation.     

Electronic excitations and optical response of metal nanocomposites under heavy ion implantation

The optical transmission and ion-induced luminescence under implantation of copper ions into quartz glass (a-SiO₂) have been measured to study the processes of formation of copper nanoparticles. It is shown that in situ measurements are more informative in comparison with the ordinary approach—investigation of the properties of ion-implanted nanocomposites only after implantation. A series of experiments was performed to prove that the ion-induced luminescence band at 545–550 nm is due to Cu⁺ ions dissolved in a-SiO₂. The combined use of in situ optical techniques makes it possible to monitor the states of implanted copper (metal nanoparticles and dissolved atoms) by the change in the optical absorption near the surface plasmon resonance of nanoparticles and by the intensity of ion-induced luminescence of Cu⁺ states in solid solution. It is shown that the optical bands of defects, dissolved copper, and nanoparticles can be separated within a simple linear approximation. Near the surface plasmon resonance and defect bands, ion-induced transient optical absorption has been revealed. The transient optical absorption near the surface plasmon resonance is explained by the temperature effect. The relationship between the electronic excitation, radiation-induced optical response, and the kinetics of nanoparticle formation is analyzed. Several stages of nanoparticle formation have been established: accumulation of implanted copper in solid solution, nucleation of nanoparticles, coalescence, growth of nanoparticles, and saturation of nanocomposites.     

Polarization dependence of the permanent deformation of silver nanoparticles in glass by ultrashort laser pulses

Glass containing spherical silver nanoparticles has been irradiated with single, intense, ultrashort laser pulses, with a wavelength corresponding to the surface plasmon resonance of the particles. After irradiation with linear polarization, dichroism is observed. Transmission electron microscopy studies reveal that these spectral changes are caused by deformation of the particles to anisotropic (in the TEM projection approximately ellipsoidal) shapes with an additional halo of small silver particles around the central one. The deformed particles are uniformly oriented with their longer axes perpendicular to the laser polarization. Using laser pulses with circular polarization, again a halo is formed around the particles, but the central particles remain spherical, and no dichroism was observed in the optical spectra. Received 30 November 2000     

Electron irradiation induced nanocrystal formation in Cu-borosilicate glass

Nanoscale writing of Cu nanoparticles in glasses is introduced using focused electron irradiation by transmission electron microscopy. Two types of copper borosilicate glasses, one with high and another with low Cu loading, have been tested at energies of 200–300 keV, and formation of Cu nanoparticles in a variety of shapes and sizes using different irradiation conditions is achieved. Electron energy loss spectroscopy analysis, combined with high-resolution transmission electron microscopy imaging, confirmed the irradiation-induced precipitated nanoparticles as metallic, while furnace annealing of the glass triggered dendrite-shaped particles of copper oxide. Unusual patterns of nanoparticle rings and chains under focused electron beam irradiation are also presented. Conclusively, electron beam patterning of Cu-loaded glasses is a promising alternative route to well-established femtosecond laser photoreduction of Cu ions in glass.     

Synthesis of silver nanocomposites by SCF impregnation of matrices of synthetic opal and Vycor glass by the Ag(hfac)COD precursor

Silver-containing nanocomposites were prepared by impregnating Vycor glass (a pore diameter of 4 nm) and synthesized opal matrices (an interstitial void size of 40 nm) with cyclooctadiene complex of silver hexafluoroacetylacetonate (Ag(hfac)COD), a silver precursor, dissolved in supercritical carbon dioxide and were examined by optical absorption spectroscopy, atomic force microscopy, and electron spin-resonance spectroscopy. It was demonstrated that the absorption spectra of Vycor glass and opal matrices impregnated with Ag(hfac)COD molecules and subjected to thermal treatment in air at temperatures above 50°C exhibit plasmon resonances characteristic of Ag nanoparticles at 420–430 nm. The peculiarities of the plasmon resonance band for both types of samples were attributed to the morphology of the pore space in which silver particles are formed. Paramagnetic Cu(hfac)₂ molecules (copper hexafluoroacetylacetonate) were used as a spectroscopic probe for estimating the distribution of the precursor in the pores of Vycor glass and opal matrices during supercritical fluid impregnation.     

Characteristic energy loss spectra of copper crystals with surfaces described by LEED

Energy distributions of electrons back-scattered from copper (100) and (110) surfaces have been obtained for incident electron energies in the range 30 to 350 eV. The relations between optical measurements and the characteristic energy losses, as well as the effect of interband transitions on the bulk and surface plasmon frequencies in metals which do not have ideally free electron plasmas are discussed. By chemisorbing increasing amounts of oxygen on the clean surface, the surface plasmon loss peak was identified in the copper energy loss spectrum from its intensity dependence on the dielectric constant at the surface. This peak has been identified by previous authors as the bulk plasmon loss of a single s-electron plasma oscillation. Our identification of the surface plasmon loss peak implies that the d-electrons in copper do participate in the plasma oscillation and that the bulk plasmon frequency is shifted from its free electron value because of interband transitions.     

Optical and magneto-optical properties in Fe-doped glasses irradiated with femtosecond laser

Optical, magnetic, and magneto-optical properties have been investigated for the α-Fe₂O₃-doped transparent glasses irradiated with an infrared fs laser and subsequently annealed. The values of the saturation magnetization at room temperature for the irradiated glasses were increased compared with the as-prepared samples, which is due to the precipitation of the ferrimagnetic ferrite nanoparticles (NPs). By adding further dopants as precursors of plasmonic metals, Au or Al NPs were space-selectively precipitated together with the ferrite NPs in a confined region after irradiation and thermal annealing. In the case of the glass codoped with Al, magneto-optical Faraday effect was plasmonically enhanced and exhibited a negative distinct peak ascribed to a coupling between the ferrimagnetism of ferrite NPs and the localized surface plasmon resonance of Al NPs, while the glass, in which ferrite and Au NPs were precipitated, showed a positive enhancement of Faraday effect due to a coupling of plasmon resonance with diamagnetism of glass matrix.     

Electron induced modification in poly(ethylene terephthalate)

Abstract

The effect of 100 kGy dose of 2 MeV electron irradiation on Poly(ethylene terepthalate) (PET) has been studied by different characterisation techniques such as the Fourier transformed IR spectroscopy, electron spin resonance spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction analysis. Oxidative degradation leading to amorphisation of the polymer has been observed from spectral analysis. The thermal stability of the polymer was found to decrease due to electron irradiation. The thermal decomposition temperature as well as the melting temperature in case of irradiated PET was found to be decreased due to electron bombardment. A decrease in crystallinity of the polymer has also been observed after irradiation.     

飞秒激光所致金纳米粒子析出的玻璃非线性吸收

依据Z-scan技术,使用波长532nm的纳秒脉冲,研究了通过聚焦的飞秒脉冲诱导并辅以热处理得到的金纳米粒子析出的玻璃的非线性吸收.观察到金纳米粒子析出的玻璃具有饱和吸收特性.根据局域场效应,对实验结果拟合,得到在接近表面等离子体共振激发情况下,金纳米粒子三阶极化率虚部分别为Imχ(3)m=57×10-7esu.玻璃样品中金纳米粒子的非线性响应主要起源于热电子贡献. 关键词： 带内跃迁 带间跃迁 热电子贡献     

Probability and shape of the spectral line of a single bulk characteristic energy loss of a fast electron in a medium with electron absorption and strong spatial dispersion

The probability of single characteristic energy loss of a fast electron in a reflection experiment has been calculated. Unlike many works concerning this subject, the bremsstrahlung of bulk plasmons in the non- Cherenkov ranges of frequencies and wavevectors of a plasmon has been taken into account. The contributions to the probability of single loss and to the shape of the spectral line from a quantum correction that is due to the interference of elastic and inelastic electron scattering events have been determined. The probability has been calculated in the kinetic approximation for the relative permittivity, where the short-wavelength range of the plasmon spectrum is correctly taken into account. In view of these circumstances, the expression for the mean free path of the electron with respect to the emission of a bulk plasmon that was obtained by Pines [D. Pines, Elementary Excitations in Solids (Benjamin, New York, 1963)] has been refined. The coherence length of the fast electron in the medium-energy range under consideration has been estimated. The shape of the spectral line of energy losses in the non-Cherenkov frequency range has been determined. It has been shown that the probability of the single emission of the bulk plasmon incompletely corresponds to the Poisson statistics.     

玻璃基底上不规则银纳米结构的生长及其光学性质的研究

以经过硅烷化后玻璃片为基底，之后吸附金纳米种子，采用柠檬酸钠为还原剂，在荧光灯照射条件下还原硝酸银，制备出基底表面具有银纳米粒子聚集结构的材料。采用透射电镜、扫描电镜和紫外可见分光光度计对产物的形貌和性质进行了表征，并考察银纳米粒子的形貌对其薄膜基底SERS活性的影响。结果表明：随着光照时间增加至16 h，金种子长大为平均粒径110 nm的不规则状多晶银纳米粒子，且出现双层粒子堆积。基底上纳米粒子的吸收光谱上出现了由银粒子的表面等离子体激元偶极子耦合引发的强烈吸收峰：随着光照时间的变化，耦合峰在600～813 nm波段内移动。光照时间为12 h后得到的SERS活性基底具有最强的SERS信号。     

玻璃基底上不规则银纳米结构的生长及其光学性质的研究

以经过硅烷化后玻璃片为基底,之后吸附金纳米种子,采用柠檬酸钠为还原剂,在荧光灯照射条件下还原硝酸银,制备出基底表面具有银纳米粒子聚集结构的材料。采用透射电镜、扫描电镜和紫外可见分光光度计对产物的形貌和性质进行了表征,并考察银纳米粒子的形貌对其薄膜基底SERS活性的影响。结果表明：随着光照时间增加至16 h,金种子长大为平均粒径110 nm的不规则状多晶银纳米粒子,且出现双层粒子堆积。基底上纳米粒子的吸收光谱上出现了由银粒子的表面等离子体激元偶极子耦合引发的强烈吸收峰：随着光照时间的变化,耦合峰在600～813 nm波段内移动。光照时间为12 h后得到的SERS活性基底具有最强的SERS信号。     

On the fluorescence enhancement mechanism of Er3+ in germanate glass containing silver particles

The spectral properties of trivalent erbium ions(Er3+) are systematically studied in a melt-quenched germanate glass(60 GeO2-20PbO-10BaO-10K2O-0.1Ag2O) containing silver(Ag) particles.Thermal treatment of the material leads to the precipitation of Ag particles as observed by transmission electron microscopy and confirmed by absorption spectrum for the obvious surface plasmon resonance peak of Ag particles.The fluorescence from Er3+ in the 10-min-annealed sample with Ag particles is found to be 4.2 times enhanced compared with the unannealed sample excited by 488-nm Ar+ laser.A comparison is made between a spectral study performed on the unannealed Er3+-doped sample and the one annealed for 20 min.The data of absorption cross section and Judd-Ofelt intensity parameters show the agreement between the two samples no matter whether there are Ag particles,indicating that the introduction of Ag particles by post-heat treatment has no effect on the crystal field environment of Er3+ ions.The fluorescence enhancement is attributed to the surface plasmon oscillations of Ag particles in germanate glass.     

Manganese doping influence on the plasmon energy of nickel films

Manganese doping in nickel films capped with copper have been prepared by evaporation in vacuum. The films are composed of grains with an average diameter of ~ 20 nm from scanning electron microscope scans. Optical absorption is measured over a wavelength range of 190–450 nm. Two plasmon peaks are observed at 3.30 eV and 4.45 eV for a range of concentrations of films. The 4.45 eV peak is a bulk plasmon peak that is enhanced by increasing the manganese in nickel. The 3.30 eV peak is a surface plasmon peak that increases in width or strength of plasmon resonance with increasing concentration of manganese. This may be a combination effect of charge carrier concentration and dielectric screening from the reformed electronic band structure caused by manganese doping. By adding manganese into nickel, the ferromagnetic order is further destroyed as a transition into a spin glass occurs. This spin glass behavior is seen in a coercivity measurement at 4 K where the coercivity drops precipitously as the doping concentration increases.     

Laser synthesis of Au/Ag colloidal nano-alloys: Optical properties, structure and composition

We have successfully synthesized Au/Ag colloidal nano-alloys with a wide range of compositions by laser ablation of single metal targets in water and a re-irradiation of mixed colloidal suspensions. The optical extinction spectra have been obtained in the plasmon resonance region and their analysis by using the Mie-Gans approach has lead to a quantitative estimation of a number of different structural features for the sols. Some of the obtained results are supported by X-ray photoelectron data and transmission electron microscopy, while others are used to investigate the kinetics of formation of the nano-alloys under laser irradiation.     

功能光学纳米Ag薄膜的制备及其光学特性研究

对以热蒸发法制备的超薄Ag薄膜,扫描电子显微镜结果显示其呈纳米尺度的颗粒状,由透射谱测量发现其具有表面等离子体激元特征.检测到不同条件制备纳米Ag薄膜的表面等离子体共振吸收峰的位移规律,且纳米Ag材料具有选择性的透过、反射特性.通过不同的制备条件,得到了在长波范围内透过率超过90％、在表面等离子体共振峰值位置处反射率接近50％且峰位可调的光学薄膜材料.这种薄膜材料有望成为应用在薄膜太阳电池中间层中具有潜在性光管理功能的光学薄膜材料. 关键词： 热蒸发 纳米Ag薄膜 表面等离子体激元 光管理     

Fabrication of periodical structure and shape-induced modulating spectroscopy of Au nanoparticles

This paper presents optical property of the periodical bowties structure of Au nanoparticles on glass substrate fabricated by high-resolution electron beam lithography. Numerical calculation is used to examine the shape-induced surface plasmon enhancement and extinction spectroscopy by using Finite-Difference Time Domain algorithm and Lorentz model of surface plasmon. The calculated extinction spectra of the periodical nanoparticles are consistent with the experimental results. The influence of the geometrical shape on the spectral properties of bowtie nanoparticles is discussed. This investigation may help one to design plasmonic sub-wavelength devices with desired spectral properties.     

Temperature dependence of the optical properties of ion-beam sputtered ZrN films

The reflectivity of sputtered Zirconium nitride films on glass substrate has been investigated in the spectral energy range of 0.8–6.1 eV as a function of deposition temperature varying between 373 and 723 K. Optical constants of the prepared films have been determined using the Drude analysis. Experimental results showed strong dependency of optical properties of the films, such as optical resistivity on the substrate temperature. The temperature increase of the substrate has shown an increase in both the plasmon frequency and electron scattering time. The electrical behavior of the films showed a good agreement between their optical and electrical resistivity.     

Structural and electrical studies of template synthesized copper nanowires

The template strategy combined with electrodeposition technique has been used to produce copper nanowires in the cylindrical pores of track-etched polycarbonate membranes. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and UV–visible spectroscopy have been used to characterize as-prepared copper nanowires. XRD study shows the face centered cubic crystal structure of copper nanowires. Williamson–Hall (WH) analysis has been used to determine the crystallite size and microstrain induced due to lattice deformation. FESEM results reveal that copper nanowires are continuous, well aligned with uniform diameter and having high aspect ratio. The optical absorption spectra exhibit a strong peak at 568 nm attributed to the surface plasmon resonance. The current–voltage (I–V) characteristics show an ohmic behavior of the fabricated copper nanowires. The increase in resistivity of nanowires than that of bulk counterpart has been attributed to the surface and size effects in nanowires and explained in the light of Fuchs–Sondeimer and Mayadas–Shatzkes models.