Femtosecond-laser nanofabrication onto silicon surface with near-field localization generated by plasmon polaritons in gold nanoparticles with oblique irradiation

Nanohole fabrication process with gold nanoparticles irradiated by femtosecond laser at different incident angles is investigated. Nanoparticles with diameter of 200 nm and laser irradiation with center wavelength of 800 nm are used in the present study. The analysis of the electromagnetic field distribution in the near-field zone of the particle is made by simulations based on finite-differential time domain (FDTD) method. It is shown that when gold nanoparticle is irradiated by laser pulse surface plasmon excitation can be induced, and associated with it, high-intensity near field is produced in a limited area around the particle. It is found that the change of the irradiation conditions by means of irradiation from various incident directions gives a possibility of laser nanoprocessing with tunable characteristics. Our results show that enhanced optical intensity is able to be induced on the substrate surface regardless of incident direction of the laser due to the image charge interaction with the substrate. Furthermore, the use of p-polarized laser irradiation at a certain angle gives a minimum of the spatial dimensions of the enhanced zone on the substrate which is about two times smaller than that obtained at normal incidence.     

High-intensity near-field generation for silicon nanoparticle arrays with oblique irradiation for large-area high-throughput nanopatterning

We present near-field distributions around an isolated 800-nm silica or silicon nanoparticle, and nanoparticle arrays of 800-nm silica or silicon nanoparticles, on a silicon substrate by the finite-difference time-domain method when 800-nm light is irradiated obliquely to the substrate. Nanopatterning mediated with the nanoparticle system is promising for large-area, high-throughput patterning by using an enhanced localized near-field ablation by the nanoscattered light lens effect. The irradiation area cannot be extended for silica nanoparticles, because the optical field enhancement factor is low. Gold nanoparticles can generate highly enhanced near fields, although at present there are no useful ways to arrange the gold nanoparticles on the substrate at a high throughput. Silicon nanoparticles with high dielectric permittivity have optical characteristics of both silica and gold nanoparticles. The particle arrangement on the Si substrate is technically easy using a wet pulling process. From the calculation, high optical field intensity is acquired with oblique s-polarized irradiation to the substrate under silicon nanoparticle arrays, and the intensity is almost the same as that under gold nanoparticle arrays under the same condition. With this method, high-throughput nanopatterning for a large area would be achievable.     

Near field localization mediated by a single gold nanoparticle embedded in transparent matrix: Application for surface modification

In this work the near field properties of a single gold nanoparticle embedded in transparent host medium are investigated theoretically. The analysis of the electromagnetic field in the near field zone is obtained by finite difference time domain (FDTD) simulation technique. The nanoscale system consists of a transparent layer in which a gold particle with diameters of D = 200 or 80 nm is embedded, is situated on a substrate surface. Laser pulse at wavelength of 800 nm irradiates normally this system. It is found that the field in the vicinity of the particle is enhanced, and at a certain condition the zone with the highest enhancement is localized on the substrate surface. Furthermore, the near field characteristics are found to be controllable by the dielectric properties of the host material, substrate, parameters of the incident irradiation and particle size. With the increase of the refractive index of the host medium, both the magnitude of the near field on the substrate and the characteristic size of the field enhanced zone decrease. The influence of the particle size and polarization of the incident laser irradiation on the near filed properties of the system are also presented. The proposed configuration can be applied for a multiple nanoprocessing and an integrated near field source with a spatial resolution of D/3.     

Large area laser surface micro/nanopatterning by contact microsphere lens arrays

Laser surface micro/nanopatterning by particle lens arrays is a well-known technique. Enhanced optical fields can be achieved on a substrate when a laser beam passes through a self-assembled monolayer of silica microspheres placed on the substrate. This enhanced optical field is responsible for ablative material removal from the substrate resulting in a patterned surface. Because of the laser ablation, the microspheres are often ejected from the substrate during laser irradiation. This is a major issue impeding this technique to be used for large area texturing. We explored the possibility to retain the spheres on the substrate surface during laser irradiation. A picosecond laser system (wavelength of 515 nm, pulse duration 6.7 ps, repetition rate 400 kHz) was employed to write patterns through the lens array on a silicon substrate. In this experimental study, the pulse energy was found to be a key factor to realize surface patterning and retain the spheres during the process. When the laser pulse energy is set within the process window, the microspheres stay on the substrate during and after laser irradiation. Periodic patterns of nanoholes can be textured on the substrate surface. The spacing between the nanoholes is determined by the diameter of the microspheres. The depth of the nanoholes varies, depending on the number of laser pulses applied and pulse energy. Large area texturing can be made using overlapping pulses obtained through laser beam scanning.     

用于飞秒激光纳米加工的TiO_2粒子阵列诱导多种基底表面近场增强

利用纳米粒子辅助对飞秒激光能量进行空间局域化,使其在基底表面诱导产生纳米尺度的近场增强,这对超衍射极限微结构加工具有重要意义.目前对于粒子阵列诱导飞秒激光纳米孔加工的研究仅限于金属Au粒子及低折射率聚苯乙烯介电粒子等,本文提出并开展了应用高折射率TiO_2介电粒子阵列作为辅助诱导激光近场增强从而进行飞秒激光超衍射纳米孔加工的研究.对TiO_2介电粒子阵列在Si,Pt及SiO_2表面的近场强度分布进行了数值模拟,研究其基底表面近场增强的规律及物理过程.研究结果发现,使用硅基底时,阵列与单一TiO_2球形粒子相比其近场增强仅下降约30%;相对于入射激光强度而言,在直径约为100nm的空间范围内获得140倍的近场增强,这一现象可用于百纳米孔的激光加工.同时在其他典型基底的理论计算结果中也表明,几乎在所有金属及介电材料表面均可以实现良好的百纳米空间范围内的近场增强,并且具有近场随着基底折射率变大而增强的规律.这些现象的产生归因于TiO_2粒子中磁四极振荡产生的激光前向场增强及粒子与基底的耦合作用.进一步引入镜像电荷模型对基底光学参数对其表面近场增强的影响规律进行了分析和解释.本文的模拟结果对飞秒激光近场超衍射极限纳米加工的应用有着重要的意义.     

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.     

Localization of the electromagnetic field in the vicinity of gold nanoparticles: Surface modification of different substrates

Theoretical predictions and experimental results for nanosized modification of metal (Au), semiconductor (Si), or dielectric (soda lime glass) substrates using near-electromagnetic field enhancement in the vicinity of gold nanoparticles are presented. The near field properties for the system consisting of an isolated gold nanoparticle or nanoparticle aggregate deposited on the substrates, which is irradiated by electromagnetic wave, are investigated using Finite Difference Time Domain Simulation technique. The influence of the substrate material on the near field distribution characteristics is predicted. The results reveal that the field on the substrate surface is enhanced in the three investigated cases, but its spatial distribution and magnitude depend on the substrate material. In the case of the metal and semiconductor substrate the enhanced near field is strongly localized in the vicinity of the contact point with the particle, in an area with diameter smaller than the particle's one. The intensity of the enhanced field on the glass is more than an order of magnitude lower than the case of using silicon substrate. The properties of the near field on the substrate surface also depend on the particle arrangement. For a two-dimensional gold nanoparticle array, when the particles are closely arrayed, the intensity of the enhanced field on the substrate surface is minimal. With the increase of the interparticle distance the near field intensity increases. The validity of the obtained theoretical results is confirmed experimentally.     

Gold nanosphere propulsion by using femtosecond laser-excited enhanced near field

We propose nanosphere propulsion by using femtosecond laser-excited enhanced near field based on the theoretical calculations and experimental study. The optical intensity distribution and enhancement around a gold nanosphere on a silicon substrate was simulated by a 3D finite-difference time-domain method. The sphere velocities and propelled angles were calculated based on the optical intensity distribution. In our simulation, we calculated the optical intensity for the gold nanospheres with a diameter ranging from 100 to 600 nm. Calculation results show that the sphere velocity was fairly constant for the diameters ranging from 100 to 250 nm, while the velocity decreased for diameters larger than 250 nm. The propelled angle could be controlled up to only 4.6° by varying the incident angles of p-polarized waves. We have demonstrated the gold nanosphere propulsion in experiment. The gold nanospheres with a diameter of 200 nm were used in our experiments. The propelled gold particles have been melted by laser irradiation and deposited on the receiver substrate. The size and spatial distributions of gold particles have been investigated. The decrease in the laser spot size and the gap distance between the donor and receiver substrate would realize the reduction in the existence region of gold particles on the receiver substrate.     

SERS activity of Au nanoparticle films

The core-shell gold nanoparticle film is fabricated by using nanolithography and self-assembly monolayer technology. The film exhibits unique optical properties and has strong surface enhanced Raman scattering （SERS） activity. The relationship between nanostructure and surface electrical field is studied by employing pyridine as the SERS probe. It is found that particle size and inter-particle space are important factors. The enhancement ratio is measured to be more than 10^4.     

Plasmonic laser nanoablation of silicon by the scattering of femtosecond pulses near gold nanospheres

We present the fabrication of nanostructures ablated on silicon(100) by the plasmonic scattering of 780 nm, 220 fs laser pulses in the near-field of gold nanospheres. We take advantage of the enhanced plasmonic scattering of ultrashort laser light in the particle near-field to ablate well-defined nanocraters. Gold nanospheres of 150 nm diameter are deposited onto a silicon surface and irradiated with a single laser pulse. We studied the effect of laser polarization on the morphology of ablated nanostructures and estimated the minimum fluence for plasmonic nanoablation. When the polarization of the incident radiation is directed at a 45° angle into the substrate surface, a near-field enhancement of 23.1±7.6 is measured, reducing the required silicon ablation fluence from 191±14 mJ/cm² to 8.2±2.9 mJ/cm². Enhancements are also measured for laser polarizations parallel to the substrate surface when the substrate is angled 0° and 45° to the incident irradiation, giving enhancements of 6.9±0.6 and 4.1±1.3, respectively. Generated nanocrater morphologies show a direct imprint of the particle dipolar scattering region, as predicted in our theoretical calculations. The measured near-field enhancement values agree well with the maximum field enhancements obtained in our calculations. The agreement between theory and measurements supports that the nanocraters are indeed formed by the enhanced plasmonic scattering in the near-field of the nanoparticles. PACS 42.62.-b; 52.38.Mf; 81.65.Cf; 81.16.-c; 78.67.Bf     

Enhanced cleaning of photoresist film on a transparent substrate by backward irradiation of a Nd:YAG laser

Laser cleaning of a photoresist (PR) on a glass substrate using ns-pulsed Nd:YAG laser was studied. The direction of the substrate facing the laser beam was varied as a main parameter as well as the power of the laser beam. The backward irradiation (BWI) of the third harmonic beam (355 nm) completely removed 1.2 μm thick PR layer with three pulses at 1.5 J/cm² leaving no residues behind; while the forward irradiation (FWI) at the same condition just partially cleaned it. To investigate the difference of removal mechanisms between irradiation directions, the size distributions of particulates generated during laser cleaning were observed using an optical particle counter. The concentration of micron-sized particulates increased with increasing laser fluence up to 1 J/cm² for FWI and 0.5 J/cm² for BWI and then decreased at higher fluences because the target was a very thin film. The concentration of larger particulates for BWI was much higher than that for FWI implying the difference in removal mechanisms. In consideration of the size characteristics of the particulates and the temperature profiles of the PR layer, the most probable distinct mechanism for the BWI would be a blasting due to high temperature at the PR/glass interface. The particulate number concentration decreased rapidly after the completion of cleaning, suggesting that the measurement of the particulate concentration could detect the progress of the cleaning. Our results demonstrated that the backward irradiation will be useful for the laser cleaning of film-type contaminants on an optically transparent substrate.     

Nanostructuring of thin Au films by means of short UV laser pulses

The particle size distribution, morphology and optical properties of the Au nanoparticle (NP) structures for surface enhanced Raman signal (SERS) application are investigated in dependence on their preparation conditions. The structures are produced from relatively thin Au films (10–20 nm) sputtered on fused silica glass substrate and irradiated with several pulses (6 ns) of laser radiation at 266 nm and at fluencies in the range of 160–412 mJ/cm². The SEM inspection reveals nearly homogeneously distributed, spherical gold particles. Their initial size distribution of the range of 20–60 nm broadens towards larger particle diameters with prolonged irradiation. This is accompanied by an increase in the uncovered surface of the glass substrate and no particle removal is observed. In the absorption profiles of the nanostructures, the broad peak centred at 546 nm is ascribed to resonant absorption of surface plasmons (SPR). The peak position, halfwidth and intensity depend on the shape, size and size distribution of the nanostructured particles in agreement with literature. From peak intensities of the Raman spectra recorded for Rhodamine 6G in the range of 300–1800 cm⁻¹, the relative signal enhancement by factor between 20 and 603 for individual peaks is estimated. The results confirm that the obtained structures can be applied for SERS measurements and sensing.     

金和银纳米粒子二维周期阵列的光学性质

本文利用离散点偶极子近似方法(DDA)研究了金和银纳米粒子二维周期阵列的光学性质。研究结果表明二维周期阵列的消光性质及其表面等离子共振(SPR)波长受到阵列内粒子组成材料、粒子形状尺寸、阵列周期和阵列排布方式等因素的影响。对于二维正方阵列,当周期较小时(一般小于300 nm),阵列的共振波长主要取决于粒子组成材料和形状尺寸;当周期与阵列单体的共振波长附近时,阵列的消光谱中会出现极窄且锐的SPR共振峰,峰位只与阵列的周期值相关。改变阵列在平行和垂直于入射光偏振方向的周期,可以方便地调节二维长方阵列的共振峰的峰位和峰宽。     

Direct writing of micro/nano-scale patterns by means of particle lens arrays scanned by a focused diode pumped Nd:YVO4 laser

A practical approach to a well-known technique of laser micro/nano-patterning by optical near fields is presented. It is based on surface patterning by scanning a Gaussian laser beam through a self-assembled monolayer of silica micro-spheres on a single-crystalline silicon (Si) substrate. So far, the outcome of this kind of near-field patterning has been related to the simultaneous, parallel surface-structuring of large areas either by top hat or Gaussian laser intensity distributions. We attempt to explore the possibility of using the same technique in order to produce single, direct writing of features. This could be of advantage for applications in which only some areas need to be patterned (i.e. local area selective patterning) or single lines are required (e.g. a particular micro/nano-fluidic channel). A diode pumped Nd:YVO₄ laser system (wavelength of 532 nm, pulse duration of 8 ns, repetition rate of 30 kHz) with a computer-controlled 3 axis galvanometer beam scanner was employed to write user-defined patterns through the particle lens array on the Si substrate. After laser irradiation, the obtained patterns which are in the micro-scale were composed of sub-micro/micro-holes or bumps. The micro-pattern resolution depends on the dimension of both the micro-sphere’s diameter and the beam’s spot size. The developed technique could potentially be employed to fabricate photonic crystal structures mimicking nature’s butterfly wings and anti-reflective “moth eye” arrays for photovoltaic cells.     

Enhanced near field mediated nanohole fabrication on silicon substrate by femtosecond laser pulse

Investigation of the process of nanohole formation on silicon surface mediated with near electromagnetic field enhancement in vicinity of gold particles is described. Gold nanospheres with diameters of 40, 80 and 200 nm are used. Irradiation of the samples with laser pulse at fluences below the ablation threshold for native Si surface, results in a nanosized surface modification. The nanostructure formation is investigated for the fundamental (λ = 800 nm, 100 fs) and the second harmonic (λ = 400 nm, 250 fs) of the laser radiation generated by ultrashort Ti:sapphire laser system. The near electric field distribution is analyzed by an Finite Difference Time Domain (FDTD) simulation code. The properties of the produced morphological changes on the Si surface are found to depend strongly on the polarization and the wavelength of the laser irradiation. When the laser pulse is linearly polarized the produced nanohole shape is elongated in the E-direction of the polarization. The shape of the hole becomes symmetrical when the laser radiation is circularly polarized. The size of the ablated holes depends on the size of the gold particles, as the smallest holes are produced with the smallest particles. The variation of the laser fluence and the particle size gives possibility of fabricating structures with lateral dimensions ranging from 200 nm to below 40 nm. Explanation of the obtained results is given on the basis simulations of the near field properties using FDTD model and Mie's theory.     

Optical properties of Ag@cicada wing substrate deposited by Ag nanoparticles

In this paper, Ag nanoparticles were deposited on Ag@cicada wing array by using the cicada wings as templates to study its optical properties, including surface enhanced Raman scattering (SERS), polarization and surface enhanced fluorescence (SEF). The nanogaps between adjacent conical protrusion can be well dominated by adjusting the sputtering time and the optimal substrate AgNPs@Ag@cicada wing arrays have a noteworthy enhancement of SERS signal. Characterization of the prepared optimal substrate certified that it possesses the excellent SERS performances. Basically consistent SERS signal strength at the different polarization angles of the optimal substrate indicates that its polarization-independence. The SEF spectra shows that the optimal substrate has a slightly lower and unstable enhancement at this initial stage of repeated examination due to the weak adhesion between the Ag@cicada wing arrays and Ag nanoparticles. The outstanding optical properties indicate that it has enormous potential in the label-free detection and biological analytes determination.     

The surface plasmon resonance of metal-film nanohole arrays

In this paper we investigated the enhanced transmission and surface plasmon resonance through a thin gold film with a periodic array of subwavelength nanoholes. Both freestanding gold-film nanohole arrays and gold-film nanohole arrays deposited on a gallium arsenide (GaAs) substrate are considered. Periodic arrays of nanoholes exhibit two different surface plasmon resonance features: localized waveguide resonance and the well-recognized photonic crystal resonance. The tangential electric field component $Ey$ is nonzero only in the hole region for a freestanding gold-film nanohole array, but it can exist in the hole region and in the metallic region for a gold-film nanohole array deposited on a GaAs substrate.     

膜结构对金纳米线阵列表面增强拉曼散射的影响

金纳米线阵列作为表面增强拉曼散射的基底能够产生有效的增强效应,金纳米线阵列通过金线之间的电场耦合产生增强的拉曼信号。在实验中,制备出金纳米线阵列与金纳米刷,两种样品结构不同,金纳米刷的一面带有金膜。用巯基吡啶作为探针分子,金纳米刷的SERS实验显示出很好的增强效应,增强因子为106,不同位点的SERS谱具有区域不均一的特征。而相同实验条件下的金纳米线阵列的增强因子只有102。光学吸收谱表明这两种结构均发生了共振吸收增强电场,对其结构的分析表明,这两种结构具有不同的电场局域化分布,同时金纳米刷中金线上端强烈的电场耦合,这是其具有更好的增强效用的原因。同时,4-MP的表面增强拉曼谱的变化特征体现了化学增强效应的影响。     

Intracavity changes in the field statistics of Raman fiber lasers

We present an experiment in which intracavity optical power spectra of a Raman fiber laser are precisely measured both in the forward and in the backward propagation directions near the cavity mirrors. The statistical properties of the intracavity Stokes field are found to be very different before and after reflection on the cavity mirrors. The influence of both the dispersion and the spectral filtering actions of fiber Bragg grating mirrors are discussed.