SHINERS and plasmonic properties of Au Core SiO2 shell nanoparticles with optimal core size and shell thickness

Shell‐isolated nanoparticles (NPs)‐enhanced Raman spectroscopy (SHINERS) can be potentially applied to virtually any substrate type and morphology. How to take a step forward to prepare SHINERS NPs (SHINs) with superior performance is critical for the practical applications of surface‐enhanced Raman scattering (SERS) in the breadth and depth. Here, we present a method to obtain 120 nm diameter gold NPs coated with ultrathin silica shells (1–4 nm). The silica shell can be controlled growth through carefully tuning a series of parameters, such as amount of 3‐aminopropyl triethoxysilane used, pH, reaction time, and reaction temperature. We compare the enhancement factor of the obtained 120 nm Au with a 4 nm silica shell NPs to the 55 nm Au with a 4 nm silica shell NPs, and the activity of a 120 nm SHINs is nearly 24 times that the 55 nm SHIN from a single particle view. We also compare the enhancement factor of 1 nm silica shell Au@SiO₂ NPs with the bare Au NPs. The enhancement factor of 1 nm silica shell Au@SiO₂ NPs was found to be about twice that of the bare particles. For a deeper understanding of the source of the giant enhanced electrical field of the 1 nm silica shell Au@SiO₂ NPs, we study the plasmonic property of single 1 nm silica shell Au@SiO₂ NP on a gold film substrate through correlation of the structure of single NP using SEM with its SPR spectroscopy. We find that the multipolar interaction between the single Au@SiO₂ NP and gold film substrate is important for the SERS. Our studies on the performance of 120 nm SHINs and the plasmonic property of these particles can significantly expand the applications of SHINERS technique and improve the understanding of physical nature of SHINs. Copyright © 2013 John Wiley & Sons, Ltd.     

Assembly and interaction of Au/C core-shell nanoparticles

The formation of Au/C core-shell structures from C-supported Au nanoparticles, and their thermally and electron beam induced interactions are studied by real-time TEM. At temperatures below 400 °C no C-shell is assembled, and closely spaced Au nanoparticles interact by coalescence. At high temperatures (400-800 °C) the Au particles are transformed into Au/C core-shell structures via encapsulation into curved, fullerene-like C shells. The shells initially passivate the Au cores and inhibit their coalescence. But under electron irradiation, the Au cores can break free from their shells, and hence can coalesce. Surprisingly, at this stage the assembled C-sheets may actually enhance the coalescence process by driving the directed motion of Au/C particles and causing the efficient contraction of widely spaced particle ensembles.     

The unexpected formation of Au-Si by the resonance neutralization of Ar during the low energy bombardment of Au nanoparticles on c-Si

Nanoscale Au layers, with irregular porosities, have been formed by the low energy Ar⁺ bombardment of Au nanoparticles that were sputter-deposited onto native oxide-covered Si surfaces. High-resolution field emission scanning electron microcopy (FE-SEM) and X-ray photoelectron spectroscopy (XPS) have been used to characterize the formation and evolution of the nanoporous layer. Under Ar⁺ bombardment, the Au nanoparticles that were initially deposited were observed to flatten and spread across the native oxide surface, without diffusing, finally coalescing at their edges to form a nanoporous film having irregular pore dimensions. XPS showed that this evolution was accompanied by the loss of Au as a result of sputtering. The formation of such porous films necessitates strong interfacial bonding to avoid the lateral diffusion of the Au nanoparticles, and their ultimate coalescence into larger nanoparticles.We demonstrated that Ar⁺ beam bombardment invariably caused the formation of Au^δ+-Si^δ− bonding, rather than the expected Au^δ−-Si^δ+ bonding, and we explain this to be due to the resonance neutralization of the Ar⁺ beam on impacting the Au layer. We also reveal that the presumed formation of AuSi_x is not quantifiable by XPS, due to the superposition of the chemical shift of the Au nanoparticles with that of the quantum size effect, during Au loss on sputtering.     

Direct visual evidence for chemical mechanisms of SERRS via charge transfer in Au20–pyrazine–Au20 junction

The essence of the chemical mechanism for surface‐enhanced resonance Raman scattering (SERRS) is the charge transfer (CT) between the metal and the molecule at the resonant electronic transition, which results in the mode‐selective enhancement in the SERRS spectrum. The site‐orientated CT can directly interpret the mode‐selective chemical enhancement in SERRS. However, it is a great challenge to intutively visualize the orientation and site of the CT. In this paper, for the pyrazine–Au₂ complex, a three‐dimensional (3D) cubic representation is built to provide direct visual evidence for chemical mechanisms of SERRS via CT from the Au₂ cluster to pyrazine at the resonant electronic transition. The relationship between the mode‐selective enhancements in SERRS and the site‐orientated CT was clearly revealed. The intracluster excitation (analog of plasmon excitation in large naonoparticles) was also visualized by the 3D cubic presentation, which provided the direct evidence of local electromagnetic field enhancement of SERRS. To study the quantum size effect and the coupling effect of the nanoparticles, the photoexcitation mechanisms of the Au₂₀–pyrazine complex and the Au₂₀–pyrazine–Au₂₀ junction were also investigated. The tunneling charge transfer from one Au₂₀ cluster to another Au₂₀ cluster outside the pyrazine in Au₂₀–pyrazine–Au₂₀ junction was also revealed visually. The calculated normalized extinction spectra of Au nanoparticles using the generalized Mie theory reveal that the resonance peak is red‐shifted due to the coupling between particles. Copyright © 2009 John Wiley & Sons, Ltd.     

Systematic Control of Size and Morphology in the Synthesis of Gold Nanoparticles

The synthesis of gold nanoparticles (Au NPs) capped by poly(1‐vinylpyrrolidin‐2‐one (PVP, average  = 10 000 kDa) yields moderately dispersed (6–8.5 nm) product with limited morphological control while larger NPs (15–20 nm) are reliably prepared using trisodium citrate (Na₃Cit) as a reductant/capping agent. Excellent size control in the intermediate 10 nm regime is achieved by hybridizing these methodologies, with highly monodisperse, polycrystalline Au NPs forming. For a Na₃Cit:PVP:Au ratio of 3.5:3.5:1, anisotropic NPs with an aspect ratio of 1.8:1 suggest the systematic agglomeration of NP pairs. Enhanced control of NP morphology is allowed by the 1,2‐tetradecanediol reduction of Au^III in the presence of straight chain, molecular anti‐agglomerants. Last, ligand substitution is used to controllably grow preformed Au seeds. In spite of the extended growth phase used, the replacement of phosphine by 1‐pentadecylamine affords highly monodisperse, cuboidal NPs containing a single clearly visible twinning plane. The allowance of particle growth parallel to this close‐packed plane explains the remarkable particle morphology.     

Sputtering of amorphous ice induced by C60 and Au3 clusters

Molecular dynamics simulations were performed to study the behavior of cluster SIMS. Two predominant cluster ion beam sources, C₆₀ and Au₃, were chosen for comparison. An amorphous water ice substrate was bombarded with incident energy of 5 keV. The C₆₀ cluster was observed to shatter upon impact creating a crater of damage approximately 8 nm deep. Although Au₃ was also found to both break apart and form a damage crater, it continued along its initial trajectory causing damage roughly 10 nm deep into the sample and becoming completely imbedded. It is suggested that this difference in behavior is due to the large mass of Au relative to the substrate water molecule.     

Migration-coalescence of Nanoparticles During Deposition of Au,Ag, Cu,and GaAs on Amorphous SiO2

Nanoparticles formed during the initial period of film growth can migrate, coalesce, and may also melt. Nanoparticles of Au, Ag, Cu, and GaAs ranging from 1 to 15nm in diameter were sputter-deposited on amorphous SiO₂ (a-SiO₂). Transmission electron microscopy was used to analyze the time-dependent change of the dispersion of particles on a thin film. The number density of nanoparticles was nearly constant during the deposition of Ag. For Au, Cu, and GaAs, however, the number density decreased with time during the early deposition period. For example, for Au the number density decreased from 2.8×10¹⁶m^–2 (surface coverage ratio of 0.08) to 1.8×10¹⁶m^–2 (surface coverage ratio of 0.14). The surface coverage increased because the particle size increased as the number density decreased. This decrease suggests that migration followed by coalescence occurred. For Au, although we found evidence of migration of 2-nm particles at 500°C, the migration rate was too slow to account for the results from the deposition experiments. These observations indicate an autocatalytic mechanism that migration followed by coalescence liberates energy by the formation of chemical bonds, heats the coalesced particles, and enhances further migration. The strong dependence of the structure of nanoparticle dispersions on the deposition rate is a direct consequence of the deposition mechanism, which is a nonlinear, kinetically-controlled process.     

金纳米粒子的制备及其表面增强拉曼散射效应的研究

采用多巴胺化学还原法制备了分散性良好的纳米金溶胶,并检测了其作为表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)基底的性质。粒度和透射电子显微镜测试结果表明金溶胶为平均粒径30nm左右的球形颗粒,并且紫外-可见特征吸收峰出现在520nm,为典型的金纳米颗粒特征吸收峰。以罗丹明6G(R6G)为探针分子证明了金溶胶良好的SERS增强效果,用金溶胶对除草剂敌草快(DQ)进行检测,最低检测限可达1×10-7 mol/L。结果表明所制备的金溶胶具有良好的表面增强拉曼散射活性。     

High–Yield Production of Uniform Gold Nanoparticles with Sizes from 31 to 577 nm via One‐Pot Seeded Growth and Size‐Dependent SERS Property

In this work, uniform, quasi‐spherical gold nanoparticles (Au NPs) with sizes of 31–577 nm are prepared via one‐pot seeded growth with the aid of tris‐base (TB). Distinct from the seeded growth methods available in literature, the present method can be simply implemented by subsequently adding the aqueous dispersion of the 17 nm Au‐NP seeds and the aqueous solution of HAuCl₄ into the boiling aqueous TB solution. It is found that at the optimal pH range, the sizes of the final Au NPs and their concentrations are simply controlled by either the particle number of the Au seed dispersion or the concentration of the HAuCl₄ solution, while the latter enables us to produce large Au NPs at very high concentration. Moreover, as‐prepared Au NPs of various sizes are coated on glass substrates to test their surface‐enhanced Raman scattering (SERS) activities by using 4‐aminothiophenol (4‐ATP) molecules as probes, which exhibit “volcano type” dependence on the Au NP sizes at fixed excitation wavelength. Furthermore, the Au NPs with sizes of ≈97 and 408 nm exhibit the largest SERS enhancement at the excitation wavelength of 633 and 785 nm, respectively.     

Spontaneous formation of size-selected bimetallic nanoparticle arrays

An original physical route is proposed to organize size-selected bimetallic nanoparticles on graphite surfaces. This approach is based on the soft landing of preformed clusters and is demonstrated for bimetallic Au_xPt_1 ? x clusters of different compositions. Particle coalescence is avoided thanks to cluster surface reactivity, leading to a self-assembly with a well-defined inter-particle separation (~ 1 nm).     

First-principles studies: Thiolated Au2Cr and Au6Cr clusters

The structural, energetic and magnetic properties of thiol-passivating Au₂Cr and Au₆Cr clusters are investigated by performing first-principles calculation based on density functional theory. We find that the adsorption of thiolate is energetically more favorable than thiol and that the thiolates favor “top” site adsorption on Cr atom in one methanethiolate adsorbed Au₂Cr cluster while they favor “bridge” site adsorption on top of the middle point of Cr–Au bonds in three methanethiolates adsorbed Au₂Cr cluster. In thiol-passivating Au₆Cr cluster, the thiol favor “top” site adsorption on top of atom Au while the thiolate favor “bridge” site adsorption on top of the middle point of Au–Au bonds. The energetics of the reactions indicates that these thiol-passivating Au₂Cr or Au₆Cr clusters can be used as hydrogen storage materials. There are large and positive spin populations on atom Cr. The spin populations of atoms Au, S and H are attributed to both the spin delocalization and the spin polarization mechanisms.     

Self-organization of bimetallic PdAu nanoparticles on SiO<Subscript>2</Subscript> surface

Bimetallic PdAu nanoparticles on SiO₂ substrate were produced by a sequential room-temperature sputtering deposition method. By the atomic force microscopy technique we studied the nanoparticles self-organization mechanisms in various conditions. First, Pd nucleation and growth proceeds at the substrate defects and the Pd nanoparticles density increase rapidly. During the second sputtering deposition, Au atoms adsorb on the SiO₂ and diffuse toward Pd nanoparticles without forming new nuclei. The Au atoms are trapped by the preformed Pd nanoparticles, forming PdAu bimetallic nanoparticles which size increases. Furthermore, fixing the amount of deposited Pd and increasing the amount of deposited Au, we analyzed the evolution of the PdAu film surface morphology: we observe that the PdAu grows initially as three-dimensional islands; then the PdAu film morphology evolves from compact three-dimensional islands to partially coalesced worm-like structures, followed by a percolation morphology and finally to a continuous and rough film. The application of the interrupted coalescence model allowed us to evaluate the critical mean island diameter R _c ≈ 2.8 nm for the partial coalescence process. The application of the dynamic scaling theory of growing interfaces allowed us to evaluate the dynamic growth exponent β = 0.21 ± 0.01 from the evolution of the film surface roughness. Finally, fixing the amount of deposited Pd and Au we studied the self-organization mechanism of the PdAu nanoparticles induced by thermal processes performed in the 973–1173 K temperature range. The observed kinetic growth mechanism is consistent with a surface diffusion-limited ripening of the nanoparticles with a temperature-dependent growth exponent. The dependence of the growth exponent on the temperature is supposed to be linked to the variation with the temperature of the characteristics of the PdAu alloy. The activation energy for the surface diffusion process was evaluated in 0.54 ± 0.03 eV.     

Coarsening of mass-selected Au clusters on amorphous carbon at room temperature

Low-energy cluster beam deposition was used to deposit mass-selected Au_n clusters (n = 4, 6, 13 and 20) on amorphous carbon (a-C) substrates. The resulting samples were stored at room temperature under ambient conditions for time periods up to 32 months to analyze the coarsening behaviour of the clusters. Cluster-size distributions were measured in regular time intervals by transmission electron microscopy (TEM). The TEM experiments show a significant increase of the average cluster size with time analogous to classical surface Ostwald ripening (OR). The coarsening of Au clusters can be well described by steady-state diffusion-limited kinetics. The derived surface mass-transport diffusion coefficients at room temperature range between 1.1 and 3.8·10⁻²⁵ m² s⁻¹ for our samples. A detailed analysis of values suggests that, the rate of the surface OR for mass-selected Au_n clusters increases with the cluster size in the sequence: Au₄ ≈ Au₆ < Au₁₃ < Au₂₀ for the investigated range of Au clusters. Given that the initial, on-surface cluster-size distributions are nominally monodisperse, classical OR with cluster coarsening based only on the Gibbs-Thomson effect cannot explain the observed coarsening. The activation of the coarsening process is rationalized by initial variations of the cluster sizes due to the deposition process itself and/or the interaction of the clusters with the substrate. Moreover, the presence of initial deposited Au clusters as different isomers with slightly different chemical potential on the substrate, may also initiate the coarsening by surface OR. Furthermore, we find that the coarsening is most pronounced for the paucidispersed sample with Au_m (10 ? m ? 20) clusters. A possible explanation of this behaviour is the presence of an initial distribution of different cluster sizes directly after deposition.     

A novel method for the synthesis of monodisperse gold-coated silica nanoparticles

Monodisperse silica nanoparticles were synthesised by the well-known Stober protocol, then dispersed in acetonitrile (ACN) and subsequently added to a bisacetonitrile gold(I) coordination complex ([Au(MeCN)₂]⁺) in ACN. The silica hydroxyl groups were deprotonated in the presence of ACN, generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)₂]⁺ complex to undergo ligand exchange with the silica nanoparticles and form a surface coordination complex with reduction to metallic gold (Au⁰) proceeding by an inner sphere mechanism. The residual [Au(MeCN)₂]⁺ complex was allowed to react with water, disproportionating into Au⁰ and Au(III), respectively, with the Au⁰ adding to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of Au(III) to Au⁰ by ascorbic acid (ASC). This process generated a thin and uniform gold coating on the silica nanoparticles. The silica NPs batches synthesised were in a size range from 45 to 460 nm. Of these silica NP batches, the size range from 400 to 480 nm were used for the gold-coating experiments.     

On the interstitial and substitutional distribution of Au dissolved in solid Pb

It has been proposed that Au, when dissolved in solid Pb, exists as isolated atoms (Au₁) and small clusters of two (Au₂) and four (Au₄) atoms. In this paper three sets of data are analyzed: (1) the volume change of Pb(Au) accompanying Au precipitation at room temperature, (2) the difference in lattice parameter between Pb and Pb(Au), and (3_) the equilibrium distribution of Au in Pb in a centrifugal field. On the basis of this analysis it is concluded that Au₁ is predominantly substitutional and Au in the quenched-in Au₄ state is either mostly substitutional (each Au atom occupying a former Pb site) or vacancies are created during cluster formation and survive the quench.     

Efficiency Improvement in Polymer Light‐Emitting Diodes by “Far‐Field” Effect of Gold Nanoparticles

The “far‐field” effect of metal nanoparticles (NPs), when chromophores localized nearby metal NPs (typically the distance >λ/10), is an important optical effect to enhance emission in photoluminescence. The far‐field effect originates mainly from the interaction between origin emission and mirror‐reflected emission, resulting in the increased irradiative rate of chromophores on the mirror‐type substrate. Here, the far‐field effect is used to improve emission efficiency of polymer light‐emitting diodes (PLEDs). A universal performance improvement is achieved for the full visible light (red, green, blue) PLEDs, utilizing gold (Au) NPs to modify the indium tin oxide (ITO) substrates; this is shown by experimental and theoretical simulation to mainly come from the far‐field effect. The optimized distance, between the NPs and chromophores with visible light emission ranging from 400 to 700 nm, is 80–120 nm. Thus the scope of the far‐field may overlap the light‐emitting profile very well to enhance the efficiency of optoelectronic devices. The 30–40% enhancement is obtained for different color‐emitting materials through distance optimization. The far‐field effect is demonstrated to enhance device performance for materials in the full‐visible spectral range, which extends the optoelectric applications of Au NPs.     

Growth morphology of nanoscale sputter-deposited Au films on amorphous soft polymeric substrates

The growth of a room-temperature sputter-deposited thin Au film on two soft polymeric substrates, polystyrene (PS) and poly(methyl methacrylate) (PMMA), from nucleation to formation of a continuous film is investigated by means of atomic force microscopy. In particular, we studied the surface morphology evolution of the film as a function of the deposition time observing an initial Au three-dimensional island-type growth. Then the Au film morphology evolves, with increasing deposition time, from hemispherical islands to partially coalesced worm-like island structures, to percolation, and finally to a continuous and rough film. The overall Au morphology evolution is discussed in the framework of the interrupted coalescence model, allowing us to evaluate the island critical radius for the partial coalescence R _c=8.7±0.9 nm for Au on PS and R _c=7.6±0.8 nm for Au on PMMA. Furthermore, the application of the kinetic freezing model allows us to evaluate the room-temperature surface diffusion coefficient D _s≈1.8×10⁻¹⁸ m²/s for Au on PS and D _s≈1.1×10⁻¹⁸ m²/s for Au on PMMA. The application of the Vincent model allows us, also, to evaluate the critical coverage (at which the percolation occurs) P _c=61% for Au on PS and P _c=56% for Au on PMMA. Finally, the dynamic scaling theory of a growing interface was applied to characterize the kinetic roughening of the Au film on both PMMA and PS. Such analyses allow us to evaluate the dynamic scaling, growth, and roughness exponents z=3.8±0.4, β=0.28±0.03, α=1.06±0.05 for the growth of Au on PS and z=4.3±0.3, β=0.23±0.03, α=1.03±0.05 for the growth of Au on PMMA, in agreement with a non-equilibrium but conservative and linear growth process in which the surface diffusion phenomenon plays a key role.     

Experimental study on the coalescence process of SiO2 supported colloidal Au nanoparticles

We report on an experimental study of the coalescence-driven grow process of colloidal Au nanoparticles on SiO₂ surface. Nanoparticles with 30, 50, 80, 100 nm nominal diameters on a SiO₂ substrate were deposited, from solutions, by the drop-casting method. Then, annealing processes, in the 573–1173 K temperature range and 900–3600 s time range, were performed. Using scanning electron microscopy analyses, the temporal evolution of the nanoparticles sizes has been studied. In particular, for all classes of nanoparticles, the experimental-obtained diameters distributions evidenced double-peak shapes (i. e. bimodal distributions): a first peak centered (and unchanged changing the annealing temperature and/or time) at the nominal diameter of the as-deposited nanoparticles, 〈D₀〉, and a second peak shifting at higher mean diameters, 〈D_C〉, increasing the annealing temperature and/or time. This observation suggested us a coalescence-driven growth process of a nanoparticles sub-population. As a consequence, the temporal evolution of 〈D_C〉 (for each class of nanoparticles and each annealing temperature), within the well-established particles coalescence theoretical framework, has been analyzed. In particular, by the analyses of the experimental data using relations as prescribed by the theoretical model, a characteristic size-dependent activation energy for the Au nanoparticles coalescence process has been evaluated.     

Synthesis and microstructure of metal oxide thin films containing metal nanoparticles by liquid phase deposition (LPD) method

Au nanoparticles dispersed SiO₂-TiO₂ composite films have been prepared by a novel wet process, Liquid Phase Deposition (LPD) method. The composite films were characterized by XRD, XPS, TEM, ICP, SEM and UV-VIS absorption spectroscopy. The results showed that the SiO₂-TiO₂ composite films containing Au^III and Au^I ionic species were co-deposited from a mixed solution of ammonium silicofluoride, ammonium hexafluorotitanate, boric acid and tetrachloroauric acid. The heat treatment induced the reduction of Au ions and formation of Au nanoparticles in the film. TEM observation revealed that the Au nanoparticles with 5-10 nm in diameter were found to be dispersed uniformly in the SiO₂-TiO₂ matrix. The optical absorption band due to the surface plasmon resonance of dispersed Au particles were observed at the wavelength of 550 nm and shifted toward longer wavelength with increasing heat treatment temperature. Received 28 November 2000     

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。