Near field properties of nanoparticle arrays fabricated by laser annealing of thin Au and Ag films

In this work we show the properties of the electromagnetic field in the vicinity of a monolayer nanoparticle array on SiO₂ substrate. The nanoparticle array is produced by a simple experimental procedure, where thin gold and silver films are deposited on a substrate by pulsed laser deposition technique and they are annealed by nanosecond laser pulses. At certain conditions the laser annealing leads to a homogeneous decomposition of the film into nanoparticles with diameters in the range of few tens of nanometers. Using FDTD simulations the near field distribution in array structures taken from SEM images are obtained. The distribution shows presence on “hot spots” where the near field intensity is enhanced more than two orders of magnitude compared to the incident one. The existence of enhanced field intensity is assumed to be the main reason on enhancement of the Raman scattering signal obtained experimentally using the produced structures as active substrates.     

Uniform plasmonic near-field nanopatterning by backward irradiation of femtosecond laser

We present localized optical field distribution properties in the vicinity of gold particles on a silicon substrate by backward and forward irradiation. It is technically difficult to fabricate nanostructures on the surface by a conventional forward laser incident to the substrate because gold nanoparticles easily aggregate to form double-layered particle arrays. We calculated enhanced optical field properties in order to pattern the substrate surface only with a template of the bottom-layered particle arrays in the case that the backward irradiation of a femtosecond laser is used in the system of aggregated double-layered gold nanoparticle arrays. With the backward irradiation, the optical field intensity in the substrate for the double-layered hexagonal arrays is found to be only 30% lower than the mono-layered system. Moreover, a near field cannot be generated with the forward irradiation. As a result, only the backward irradiation scheme is found to be effective for uniform surface nanopatterning at enhanced plasmonic near-field zones.     

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.     

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.     

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.     

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.     

银纳米颗粒阵列的表面增强拉曼散射效应研究

利用具有高密度拉曼热点的金属纳米结构作为表面增强拉曼散射(SERS)基底,可以显著增强吸附分子的拉曼信号.本文通过阳极氧化铝模板辅助电化学法沉积制备了高密度银(Ag)纳米颗粒阵列;利用扫描电子显微镜和反射谱表征了样品的结构形貌和表面等离激元特性;用1, 4-苯二硫醇(1, 4-BDT)为拉曼探针分子,研究了Ag纳米颗粒阵列的SERS效应.通过优化沉积时间,制备出高SERS探测灵敏度的Ag纳米颗粒阵列,检测极限可达10~(-13)mol/L;时域有限差分法模拟结果证实了纳米颗粒间存在强的等离激元耦合作用,且发现纳米颗粒底端的局域场增强更大.研究结果表明Ag纳米颗粒阵列可作为高效的SERS基底.     

Study of electrical field distribution of gold-capped nanoparticle for excitation of localized surface plasmon resonance

The specific optical characteristics which can be observed from noble metal nanostructured materials such as nanoparticles and nanoislands have wide variety of applications such as biosensors, solar cells, and optical circuit. Because, these noble metal nanostructures induce the increment of light absorption efficiency by the enhancing effect of electrical field from localized surface plasmon resonance (LSPR) excitation. However, the enhancing effects of electrical field from LSPR using simple structured noble metal nanostructures for several applications are not satisfactory. To realize the more effective light absorption efficiency by the enhancing effect of electrical field, quite different noble metal nanostructures have been desired for applying to several applications using LSPR. In this study, to obtain the more effective enhancing effect of electrical field, conditions for LSPR excitation using a gold-capped nanoparticle layer substrate are computationally analyzed using finite-difference time-domain (FDTD) method. From the previous research, LSPR excitation using such gold-capped nanoparticle layer substrates has a great potential for application to high-sensitive label-free monitoring of biomolecular interactions. For understanding of detailed LSPR excitation mechanism, LSPR excitation conditions were investigated by analyzing the electrical field distribution using simulation software and comparing the results obtained with experimental results. As a result of computational analysis, LSPR excitation was found to depend on the particle alignment, interparticle distance, and excitation wavelength. Furthermore, the LSPR optical characteristics obtained from the simulation analysis were consistent with experimentally approximated LSPR optical characteristics. Using this gold-capped nanoparticle layer substrate, LSPR can be excited easily more than conventional noble metal nanoparticle-based LSPR excitation without noble metal nanoparticle synthesis. Hence, this structure is detectable a small change of refractive index such as biomolecular interactions for biosensing applications.     

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.     

Influence of local environment on the intensity of the localized surface plasmon polariton of Ag nanoparticles

A combined Ag nanoparticle with an insulating or conductive layer structure has been designed for molecular detection using surface enhanced Raman scattering microscopy. Optical absorption studies revealed localized surface plasmon resonance, which shows regular red shift with increasing environmental dielectric constant. With the combined structure of surface enhanced Raman scattering substrates and rhodamine 6G as a test molecule, the results in this paper show that the absorption has a linear relationship with the local electromagnetic field for insulating substrates, and the electrical property of the substrate has a non-negligible effect on the intensity of the local electromagnetic field and hence the Raman enhancement.     

The Effect of a Silicon Substrate on the Directivity Pattern of Scattered Radiation of a Gold Nanospheroid and on Near-Field Polarization

We studied the radiation-directivity pattern and the near-field polarization of a spheroidal metallic nanoparticle located over a silicon substrate by interaction with a linearly and circularly polarized field. It is shown that the directivity pattern of the spheroidal particle near the silicon substrate becomes strongly asymmetric and forward scattering is predominant compared with the symmetric diagram of a particle in free space. The change of the near-field polarization of the nanoparticle in presence of the substrate is studied for different wavelengths in the vicinity of the plasmonic resonance. The near-field polarization is described using the generalized Stokes parameters, which allow pictorial visualization of results.     

Subpicosecond excimer laser ablation of thick gold films of ultra-fine particles generated by a gas deposition technique

The results of UV laser ablation of gold nanoparticle films on glass substrates using femtosecond pulses are presented. Films of ultra-fine gold particles were prepared by an inert gas evaporation and deposition technique, resulting in a well-defined log-normal particle size distribution of (7ǃ) nm. The pulse length of the laser was 500 fs at a wavelength of 248 nm. Ablation thresholds, ablation rates at different fluxes, and the morphology of the ablated structures are presented. For the nanoparticle films studied an ablation rate five times higher than that of gold films prepared by the conventional evaporation technique was found. The ablation thresholds and rates are supposed to depend on the particle size and also on the evaporation pressure. These results are explained by taking into account the energy transport properties of nanocrystalline and conventionally evaporated gold films.     

Influence of groove depth and surface profile on fluorescence enhancement by grating-coupled surface plasmon resonance

The fluorescence intensity of a sample placed on a metal grating pattern is enhanced due to excitation by the electric field of the grating-coupled surface plasmon resonance (GC-SPR). The dependence of the enhancement on groove depth and surface profile was studied with the aim of improving the sensitivity of fluorescence detection. The enhancement was found to depend on the groove depth, with intensity most enhanced on grating substrate of about 20 nm depth, which produced an intensity about 30 times greater than that on a flat borosilicate glass substrate. Rigorous coupled wave analysis calculation showed that the shape of the groove influenced GC-SPR, suggesting that controlling not only the depth but also the shape of the grating surface profile can be an important factor in improving the sensitivity of detection by fluorescence microscopy.     

Self-assembly of length-tunable gold nanoparticle chains in organic solvents

The one-dimensional coagulation of gold colloidal particles dispersed in organic solvent was investigated with transmission electron microscopy. The results indicate that the length of the nanoparticle chains can be modulated by changing the concentration of the solutions. It was also demonstrated that the wetting of the substrate surface hardly influenced the morphology of the nanoparticle chains, which revealed that the particle chains had been formed in the solution before deposition on the substrates. A general theoretical interpretation is provided to explain the linear coagulation of gold colloidal particles, on the basis of the asymmetrical distribution of the charges absorbed on the surface of the gold colloidal particles, as well as the action of the solvent molecules. Received: 8 April 2002 / Accepted: 1 July 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-025/361-9983, E-mail: jhliao@seu.edu.cn     

Plasmonic structure and electromagnetic field enhancements in the metallic nanoparticle-film system

We investigate the plasmonic structure of a metallic nanoparticle near a metallic thin film. We show that in the thin film limit, a virtual plasmon resonance composed of delocalized thin film plasmons is induced. We investigate how the physical properties of the virtual state depend on polarization, film thickness and nanoparticle-film separation. We show that the electromagnetic field enhancements associated with the virtual plasmon resonance are large, suggesting applications of metallic nanoparticle/thin film systems as substrates for surface enhanced spectroscopies and surface enhanced scanning probe microscopies. PACS 78.67.Bf; 73.20.Mf; 78.30.-j     

Self-assembling of metal nanoparticles on patterned semiconductor surfaces (Au/GaAs)

The fabrication of selectively deposited arrays of metal nanoparticles on textured semiconductor surfaces is reported. Gold nanoparticles were grown on previously textured surfaces using photostimulated chemical deposition from an aqueous solution of AuCl₃ salt. Surfaces with random and periodic microreliefs were used as templates of sites for nanoparticle deposition. Dendrite-like and quasi-grating-like microreliefs were produced by anisotropic etching of GaAs (100) substrates. Periodic reliefs (diffraction gratings and bi-gratings) were fabricated by the holographic photochemical etching of the same substrates. Our results from AFM, SEM and EDX show that gold predominantly locates on the tops of the microreliefs. Since the surface relief strongly affects the topology of metal deposition, the use of microprofiling of semiconductor surfaces allows designing nanostructure deposition.     

Nanophotonics of isolated spherical particles

The problem of extreme focusing of an optical beam into the spatial region with wavelength dimensions is considered with the use of the special features of radiation interaction with isolated spherical particles. Results of numerical computations of the optical field intensity at the surface of silver particles of different radii upon exposure to laser radiation with different wavelengths are presented. It is demonstrated that the relative intensity of the plasmon optical field on the nanoparticle surface increases and the field focusing region decreases with increasing particle radius. Results of numerical computations illustrating the influence of the shell of composite nanoparticles comprising a dielectric core and a metal shell on the optical field intensity in the vicinity of the particle are presented. The problem of local optical foci of a transparent microparticle (photonic nanojets) is investigated. It is established that variation of the micron particle size, its optical properties, and laser radiation parameters allows the amplitude and spatial characteristics of the photonic nanojet region to be controlled efficiently.     

Surface-enhanced Raman scattering effect of gold nanoparticle arrays: The influence of annealing temperature,excitation power and array thickness

Gold nanoparticle arrays are fabricated for surface-enhanced Raman scattering (SERS) and the effect of the annealing temperature, the thickness of nanoparticle array and the exciting power on the SERS signals are investigated. The particle distribution and particle size are dense and uniform on the glass substrate when the 10 nm gold film was annealed at 250 °C and strong SERS signals for Rhodamine 6G were achieved via a 532 nm excitation with a 10 mW power. The SERS signal at 1650 cm⁻¹ is enhanced more than 10 times as compared to that of the gold film without annealing. The strong SERS behavior of gold nanoparticle arrays may broaden the SERS applications in biomedical and analytical chemistry.     

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.