Characterization of nanocrystalline gold/DLC composite films synthesized by plasma CVD technique

Composite films containing gold nanoparticles embedded in diamond-like carbon (Au-DLC) matrix were deposited on glass and Si (1 0 0) substrates by using capacitatively coupled plasma (CCP) chemical vapour deposition technique (CVD). Particle size and metal volume fraction were tailored by varying the relative amount of argon in the methane + argon gas mixture in the plasma. Optical constants of the films were evaluated. Bonding environment in these films were obtained from Raman and Fourier transformed infrared spectra (FTIR) studies. Blue-shift of the surface plasmon resonance peak in the optical absorbance spectra of the films could be associated with the reduction of the particle size while red shift was observed with the increase in volume fraction of metal particles in the DLC films. Absorption spectra recorded in the reflection mode indicated dichromatism in these films.     

Tunable surface-plasmon-resonance wavelength of silver island films

This paper experimentally and theoretically investigates the effect of the underlayer medium on tuning of the surface plasmon resonance (SPR) wavelength of silver island films,and the effect of substrate temperature on the morphologies and optical properties of the films.From the absorption spectra of single Ag with various thickness and overcoated (Ag/TiO 2) films deposited on glass substrates at various substrate temperatures by RF magnetron sputtering,we demonstrate that the surface plasmon resonance wavelength can be made tunable by changing the underlayer medium,the thickness of metal layer and the substrate temperature.By varying substrate temperatures,the interparticle coupling effects on plasmon resonances of nanosilver particles enhance as the spacing between the particles reduces.When the substrate temperature is up to 500 C,the absorption peak decreases sharply and shifts to shorter wavelength side due to the severe coalescence between silver islands in the film.     

An ellipsometric investigation of Ag/SiO$\mathsf{_2}$ nanocomposite thin films

Dielectric properties of silver/SiO₂ nanocomposite thin films grown by high-pressure d.c. sputtering technique were studied by spectroscopic ellipsometry (300-800 nm). The dielectric behavior of the nanocomposite thin films largely depended on the particle size, its number density and the surrounding environments. The films showed semiconductor-like behavior up to a critical particle size and concentration, beyond which the films exhibited the typical surface plasmon resonance characteristics in their optical properties. The refractive index was also found to have a strong dependence on the particle size and its dispersion in the matrix. The results were found to be consistent with those obtained from UV-VIS optical absorbance data. Bruggeman effective medium theory was used to explain the experimental results.Received: 3 April 2002, Published online: 23 July 2003PACS:   78.67.-n Optical properties of nanoscale materials and structures - 78.67.Bf Nanocrystals and nanoparticles     

纳米Ag颗粒复合薄膜的制备及其吸收特性

利用磁控溅射分层制备Ag和SiO₂薄膜,通过快速热处理,使Ag颗粒富集在复合薄膜的表面.研究了Ag膜层厚度、退火时间、退火温度和退火方式对Ag颗粒形貌的影响,以及Ag颗粒致密度对其共振吸收的影响.结果表明:通过控制每层Ag膜的厚度,可有效控制Ag颗粒形貌.当每层金属为2 nm、退火温度为500 ℃时,形成的颗粒粒径大小均匀且致密度较高.通过间断退火可有效降低Ag颗粒的粒径.发现Ag颗粒表面等离子共振吸收并没有随颗粒粒径的减小而明显降低,甚至提高.这和以往的报道不同.通过深入研究金属颗粒表面等离子体产生机理,发现其表面等离子共振吸收增强的原因是致密度较高的颗粒表面能级与费米能级差值较大,Ag颗粒内部的电子向颗粒表面迁移越多,形成新的费米能级E'_F的电子数就越多,表面等离子共振吸收就越强.最终得出了金属颗粒共振吸收不单纯依赖于金属粒径、和颗粒的致密度也有很大关系的结论.     

Magnetron and pulsed laser deposition of silver and gold nanoparticles and discontinuous films and their optical properties

Ag and Au nanoparticles are obtained by magnetron sputtering and pulsed laser deposition under different conditions, and the features of their absorption spectra associated with plasmon resonances are investigated. Optimal deposition conditions for obtaining small (5?C10 nm) silver nanoparticles with a high density of surface distribution include an increased argon pressure (2.5 × 10^?2 Torr) and a low discharge voltage (100 V). Gold nanoparticle arrays obtained by pulsed laser deposition at a temperature of 200°C in vacuum are more uniformly distributed on the substrates than those deposited at room temperature in argon. It is shown that the maximum of the plasmon absorption shifts toward shorter wavelengths with a decrease in the equivalent thickness of metal films and depends not only on this thickness but also on the type of substrate, which is responsible for the morphology of nanoparticle arrays.     

银团簇纳米颗粒的制备及其光吸收谱性质

 采用自悬浮定向流技术制备银团簇纳米颗粒，理论分析了银团簇的成核机理与影响因素，实验研究了制备条件和工艺。结果表明：惰性气体的冷却效率、气体流速和压强、金属熔球的温度和大小是控制颗粒尺寸大小及分布的关键条件，制备粒径小于10 nm的团簇颗粒须采用氦气为载流气体；团簇颗粒流速越大，颗粒粒径越小，尺寸分布越窄，但颗粒生成数量越少。性能表征说明：制备的颗粒呈较规则的球形，为面心立方结构，分散均匀，表面纯净无氧化，粒径分布窄。理论与实验研究了银团簇纳米颗粒的光学吸收谱性质，证明表面等离子共振吸收峰与颗粒的尺寸有很强的相关性，随着颗粒尺寸的减小，由于量子尺寸效应，吸收峰将发生宽化和蓝移。     

染料掺杂聚合物薄膜中金纳米颗粒增强的随机激光

基于金属纳米结构而获得随机激光的增强,其独特的性质及其潜在的应用价值具有重要的研究意义,在表面增强荧光、光学开关器件、表面等离子激元激光等方面实现了较多应用。报道一种快捷有效的制备纳米颗粒的手段并基于该纳米颗粒结构分析了染料掺杂聚合物薄膜涂覆的随机激光现象和规律。利用离子溅射沉积和高温热处理在石英基底上制备了Au纳米颗粒,改变溅射时间Au纳米颗粒的尺寸发生可控变化,该方法便捷、工艺简单。研究采用40,80和120 s三种不同的时间进行Au膜溅射并在650 ℃下高温处理,得到粒径尺寸不同的Au纳米颗粒,随着溅射时间延长Au纳米颗粒的尺寸逐渐变大。通过涂覆有机荧光染料DCJTB掺杂的PMMA聚合物薄膜构建光致激射系统,利用纳秒脉冲激光对样品进行激发,得到随机激光并研究其出射光强度和阈值的变化规律特征。40,80和120 s三种溅射时间下所得Au纳米颗粒的平均粒径尺寸分别为230,250和390 nm,在532 nm激光激发下产生随机激光的阈值分别为20.5,17.5和12.5 μJ·pulse-1。Au纳米颗粒尺寸越大、粒子间距越小时,光子散射的平均自由程越短,光在金属颗粒之间可以多次有效散射,从而显著提高散射效率,产生较低阈值的激光发射;Au纳米颗粒的吸收峰与染料的荧光峰恰好匹配时,将会显著增强染料的荧光效应,激发更多染料分子发生能级跃迁,增加光子态密度,获得峰值更高、阈值更低的激射现象;泵浦光不破坏染料分子的情况下,可以多次循环泵浦获得激光,染料分子的发光效率随着多次激发略有降低,有助于随机激光器件的研究开发。实验研究结果与理论分析相一致,进一步明确了Au纳米颗粒对光子散射和等离子共振对光吸收增强的随机激光发射机理。该研究以Au纳米结构对光子的强散射效应为增益,通过理论分析和实验测量获得随机激光,为实现高效率、低阈值的随机激光研究提供了一种便捷的技术手段,有望促进随机激光器件的开发和应用。     

Effects of post-thermal annealing temperature on the optical and structural properties of gold particles on silicon suboxide films

In this work, silicon suboxide (SiO_x) thin films were deposited using a RF magnetron sputtering system. A thin layer of gold (Au) with a thickness of about 10 nm was sputtered onto the surface of the deposited SiO_x films prior to the thermal annealing process at 400 °C, 600 °C, 800 °C and 1000 °C. The optical and structural properties of the samples were studied using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and optical transmission and reflection spectroscopy. SEM analyses demonstrated that the samples annealed at different temperatures produced different Au particle sizes and shapes. SiO_x nanowires were found in the sample annealed at 1000 °C. Au particles induce the crystallinity of SiO_x thin films in the post-thermal annealing process at different temperatures. These annealed samples produced silicon nanocrystallites with sizes of less than 4 nm, and the Au nanocrystallite sizes were in the range of 7-23 nm. With increased annealing temperature, the bond angle of the Si-O bond increased and the optical energy gap of the thin films decreased. The appearance of broad surface plasmon resonance absorption peaks in the region of 590-740 nm was observed due to the inclusion of Au particles in the samples. The results show that the position and intensity of the surface plasmon resonance peaks can be greatly influenced by the size, shape and distribution of Au particles.     

Shaping nanoparticles and their optical spectra with photons

An experimental method to tailor the shape and the optical absorption spectra of metallic nanoparticles is presented. It exploits the influence of laser irradiation on particle growth by self-assembly of atoms deposited on a substrate surface. By applying nanosecond light pulses of appropriate fluence and three different wavelengths, oblate silver particles with three fixed axial ratios have been fabricated. Their optical extinction spectra were measured with s- and p-polarized light and are dominated by plasmon resonances at fixed photon energies determined by the axial ratio. Possible applications of such tailormade nanoclusters include catalytic converters and optical components with narrow-band extinction, the magnitude and center frequency of which can be specified in advance. Received: 9 September 1999 / Published online: 20 October 1999     

Influence of substrate temperature on growth of a-Si:H films by reactive facing target sputtering deposition

Hydrogenated amorphous silicon(a-Si:H) films were deposited by reactive facing target sputtering(FTS) technique with a mixture of Ar and H2 reaction gas.Fourier transform infrared(FTIR) absorption,Raman scattering and ultraviolet-visible optical absorption are used to investigate the microstructure and optical properties of the deposited films.The decrease of the concentration of bonded hydrogen,especially that of(Si-H2)n with increasing substrate temperature(Ts),was observed in FTIR spectra,suggesting the ...     

Size-controlled aerosol synthesis of silver nanoparticles for plasmonic materials

Aerosol techniques were used to synthesize spherical and monodisperse silver nanoparticles for plasmonic materials. The particles were generated with an evaporation-condensation technique followed by size selection and sintering with a differential mobility analyzer and a tube furnace, respectively. Finally, the nanoparticles were collected on a glass substrate with an electrostatic precipitator. The particle size distributions were measured with a scanning mobility particle sizer and verified with a transmission electron microscope. A spectrophotometer was used to measure the optical extinction spectra of the prepared samples, which contained particles with diameters of approximately 50, 90 and 130?nm. By controlling the particle size, the dipolar peak of the localized surface plasmon resonance was tuned between wavelengths of 398 and 448?nm. In addition, quadrupolar resonances were observed at shorter wavelengths as predicted by the simplified theoretical model used to characterize the measured spectra.     

Absorption and Scattering of Light by Silver and Gold Nanodisks and Nanoprisms

We study the influence of the shape of silver and gold nanoparticles on the spectra of absorption and scattering of the optical-range electromagnetic radiation. We perform numerical calculations of the cross sections of absorption and scattering of light on the basis of the FDTD method for the particles having the shape of a disk and a triangular prism. We establish that the positions of plasmon resonance peaks and the spectral distributions of intensities differ significantly for nanoparticles of different shapes even when the characteristic sizes of the particles are equal. The calculations carried out thus demonstrate that, along with the size and material of the plasmonic particle, its shape is yet another factor that essentially determines its optical features. The results of the study can be utilized in the development of the spectroscopic method of determining the shape of the metal nanoparticles and the quantitative estimate of their characteristic sizes.     

Desorption of metal atoms with laser light of different polarization

Laser-induced desorption of metal atoms from the surface of small metal particles has been investigated as a function of the shape of the particles and the polarization of the incident laser light. The particles were supported on LiF, quartz or sapphire substrates. In a first set of experiments, the shape of the particles was determined by recording optical transmission spectra with s- and p-polarized light incident under an angle of typically 40° with respect to the surface normal. The metal particles turn out to be oblate, the ratio of the axes perpendicular and parallel to the substrate surface being on the order of 0.5. This ratio decreases with increasing particle size. Also, the particles change shape if the temperature is raised. In further experiments, s- and p-polarized light has been used to stimulate desorption of atoms via surface plasmon excitation. It is found that the desorption rate markedly depends on the polarization of the light. This is explained by excitation of the collective electron oscillation along different axes of the non-spherical particles.     

Electron dynamics in supported metal nanoparticles: relaxation and charge transfer studied by time-resolved photoemission

Resonant excitation of the plasmon polariton in supported nanoparticles leads to a strong enhancement of the multiphoton photoemission yield and consequently, the total yield is dominated by the emission from the nanoparticles although they cover only a minor fraction of the surface. This allows investigation of the electron dynamics in supported nanoparticles, directly in the time domain. Here, Ag nanoparticles grown on graphite are used to demonstrate that the transient shape of the photoemission spectrum in time-resolved two-color multiphoton photoemission spectroscopy, reveals the electron relaxation within the nanoparticle, and the dynamic charge transfer between substrate and nanoparticle. The photoemission spectra map the transient electron energy distribution and exhibit a transient shift that is attributed to a dynamic charging of the nanoparticle. The comparison with model calculations comprising the full relaxation cascade in the nanoparticle and substrate, shows that the dynamic charge transfer accounts for almost half of the total deposited energy in the nanoparticle. PACS 78.67.Bf; 73.22.-f; 67.40.Fd; 78.47.+p     

(Au,Si)/SiO2复合纳米颗粒薄膜的光谱特性

采用复合靶共溅射法制备了(Au，Si)／SiO2复合纳米颗粒薄膜样品，并对其荧光谱作了测量．在理论上分别计算了在强限域效应下和弱限域效应下Si纳晶吸收光谱的峰值位置与晶粒尺寸之间的关系，并采用Drude理论计算了Au／SiO2复合体系的吸收峰的峰值位置与微粒尺寸的关系．给出了(Au，Si)／SiO2体系复合薄膜共振吸收峰的位置随Au和Si的掺杂浓度比和微粒尺寸的相关特征．     

Ag-SiO2复合薄膜形貌和吸收特性的研究

通过分层镀膜的方式制备Ag和SiO₂的分层结构，经过快速热退火后，Ag颗粒扩散到复合薄膜的表面附近. 通过改变Ag颗粒扩散的距离(SiO₂的膜厚)，可很好地控制Ag颗粒在复合薄膜表面附近的大小，浓度和形貌，进而对共振吸收特性产生影响. 在实验中，根据Ag颗粒扩散的长度来调节退火的时间. 发现经过足够长的时间(17.5min)后，Ag颗粒会形成平行于衬底的平面团簇. 由于Ag原子在平面团簇之间容易扩散，使得Ag颗粒的粒径平均值变小并趋于某一特定的半径，且粒径分布范围变小，导致吸收谱发生蓝移，吸收带变窄，且强度增加. 关键词： 复合薄膜 共振吸收 平面团簇     

金属纳米颗粒LSPR光纤生物传感DDA方法研究

研究了金属纳米颗粒的局部表面等离子体共振(LSPR)行为,并讨论了其在光纤生物传感领域的应用.采用离散偶极近似(DDA)的方法,从理论上分析了金属纳米颗粒的尺寸、形状对其传感灵敏度的影响.计算结果显示,金属纳米颗粒的等离子共振吸收峰同时受到颗粒尺寸和形状的影响,但形状对其传感灵敏度的影响最为明显,计算结果与实验数据能较好地吻合.     

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。     

Te/TeO2-SiO2复合薄膜的吸收和非线性光学特性研究

应用分光光度计测量Te/TeO₂-SiO₂复合薄膜的透射光谱和吸收光谱, 在480nm附近观察到Te颗粒引起的等离子体共振吸收峰; 采用Z扫描技术研究了共振(激发波长为532 nm)和非共振情况下(激发波长1064 nm) 不同电位制备薄膜的Te颗粒状态与复合薄膜的三阶非线性极化率的关系. 基于有效介质理论对复合薄膜的三阶非线性效应进行分析, 研究Te颗粒大小对Te/TeO₂-SiO₂复合薄膜的非线性光学性质的影响及其产生机理. 结果表明薄膜制备过电位增大, Te的粒径减小, 颗粒数量多, 颗粒分布趋于均匀, 使得金属颗粒的表面等离子体共振峰红移, 吸收强度增强, 导致三阶非线性光学效应增强, χ⁽³⁾由1064 nm的5.12×10^-7 esu增大为532 nm的8.11×10^-7 esu. 关键词： 碲 二氧化碲 复合薄膜 三阶非线性     

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。