Au纳米颗粒和CdTe量子点复合体系发光增强和猝灭效应

利用金属蒸发真空多弧离子源注入机, 将Au离子注入到高纯石英玻璃来制备镶嵌有Au 纳米颗粒的衬底材料, 随后将化学方法合成的CdTe量子点旋涂在玻璃衬底上制备了Au纳米颗粒和CdTe量子点复合体系. 通过对镶嵌有Au纳米颗粒的衬底进行热退火处理来控制Au纳米颗粒的生长和分布, 系统研究了Au纳米颗粒的局域表面等离子体共振对CdTe量子点光致发光性能的影响. 利用光学吸收谱、原子力显微镜、透射电子显微镜和光致发光谱对样品进行了表征和测试. 光致发光谱表明, Au纳米颗粒的局域表面等离子体对CdTe量子点的发光有增强效应也有猝灭效应. 深入分析了Au纳米颗粒和CdTe量子点之间的相互作用过程, 提出了关于Au-CdTe 纳米复合体系中CdTe 发光增强和猝灭的新机理. 该实验结果为利用金属纳米颗粒表面等离子体技术制备高发光性能的光电子器件提供了较好的参考.     

不同形貌金纳米粒子的制备及其表面增强拉曼散射效应的研究

不同形状的金纳米粒子在表面增强拉曼散射(surface enhanced Raman scattering,SERS)中有不同的增强效果,多面体金纳米粒子具有多角结构,显示出比金纳米板更为明显的增强效果,近年来对其合成和性质的研究备受关注。该研究探究了十二面体,二十面体,三角板,球形四种形状的金纳米粒子在SERS中不同的增强效果。分别采用硼氢化钠还原法和以N,N-二甲基甲酰胺(DMF)为还原剂制备金三角纳米片和二十面体金纳米粒子,又以二十面体金纳米粒子为种子制备出十二面体金纳米粒子,并分别以以上三种不同形貌的金纳米粒子及球形金溶胶为基底,4-巯基吡啶,对巯基苯甲酸为探针分子检测了其在不同激发波长下的增强效果。透射电子显微镜结果表明金三角纳米板的平均边长为130nm,二十面体和十二面体金纳米粒子的粒径分别为100和120nm。三者的紫外可见吸收峰分别在589,598和544nm处。表面增强拉曼散射结果表明金多面体比金三角纳米板表现出更好的增强效果。     

Assembly of single-walled carbon nanotubes on patterns of Au nanoparticles

We report on the assembly of single-walled carbon nanotubes (SWNTs) and gold nanoparticles (NPs) hybrid structure without any surface modification of SWNTs on patterns of Au nanoparticles (NPs). Microscale Au NP patterns were created on composite self-assembled monolayer (SAM) templates of octadecanethiol (ODT) and octanedithiol (OD) through self-assembly of Au NPs via the thiol-Au chemical bond onto the OD region. On such templates, we observed extensive adhesion and strong affinity of SWNTs on the Au NPs and no SWNT on ODT. We also examined systematically the adhesion of SWNTs on ODT with varying coverage of vapour-deposited Au. We observed little SWNT attachment even when there are high-density of Au clusters on the ODT SAM. Extensive adhesion of SWNTs is observed only when the coverage of ODT by Au is almost complete. Dynamic contact angle measurements of dichlorobenzene on the ODT/Au substrates revealed a direct correlation between the surface wettability and the SWNT assembly on a molecular template.     

High stability of the crystalline configuration of Au nanoparticles embedded in silica under ion and electron irradiation

Au nanoparticles (NPs) with a size in the 2–12 nm range have been grown in silica by 2 MeV Au-ion implantation and a subsequent thermal annealing in air. The as-prepared Au NPs were irradiated with 10 MeV Si ions elongating some of them. From transmission electron microscopy in Z-contrast mode, we observed a narrow size distribution of the minor axis of the deformed NPs, which presents its higher frequency around 6–7 nm and have a saturation about 9 nm. This final result agrees well with the diameter of the track formed by Si ions of 10 MeV in silica, supporting the thermal spike model, which would explain the deformation of the NPs. In this model, the NP melts and creeps along the ion track. Our results show that the NP crystallization is in the fcc structure. On the other hand, a 200 keV electron irradiation provoked roundness on the previously elongated nanoparticles. This effect was observed in situ by high-resolution transmission electron microscopy, showing additionally that, during the roundness process, the fcc structure, as well as its crystalline orientation, remain unchanged. Thus, this study shows how Au NPs embedded in silica, within this size distribution, keep the fcc bulk structure under both ion and electron irradiations.     

Fabrication of NIR‐Excitable SERS‐Active Composite Particles Composed of Densely Packed Au Nanoparticles on Polymer Microparticles

A simple fabrication method is demonstrated for surface‐enhanced Raman scattering (SERS)‐active plasmonic nanoballs, which consisted of Au nanoparticles (NPs) and core–shell polystyrene and amino‐terminated poly(butadiene) particles, by heterocoagulation and Au NP diffusion. The amount of Au NPs introduced into the core–shell particles increases with the concentration of Au NPs added to the aqueous dispersion of the core–shell particles. When the amount of Au NPs increases, closely packed, three‐dimensionally arranged and close‐packed Au NPs arrays are formed in the shells. Strong SERS signals from para‐mercaptophenol adsorbed onto composite particles with multilayered Au NPs arrays are obtained by near‐infrared (NIR) light illumination.     

Adjustable surface plasmon resonance with Au,Ag, and Ag@Au core-shell nanoparticles

We report an experimental study on the synthesis of metal nanoparticles （NPs） with adjustable optical density based on surface plasmon resonance （SPR）. Metal NPs prepared by laser ablation in liquid method and the effect of laser parameters on the size, distribution, wavelength of SPR of Ag, Au, and mixture of Ag-Au, and Ag core/Au shell NPs are investigated. Our results show that the adjustable SPR band can be achieved in each class of NPs which is suitable for adjustable optical window applications.     

Coalescence of Cluster Beam Generated Sub‐2 nm Bare Au Nanoparticles and Analysis of Au Film Growth Parameters

In this work is presented the growth model for Au films grown on a carbon substrate at room temperature by using as building blocks Au nanoparticles (NPs) with 1.4 nm mean size generated via remote cluster beam synthesis and soft landing on the substrate. The key results highlighted in this work are that 1) the deposited nanoparticles coalesce at substrate level in such a way that the film growth is 3D, 2) newly formed nanoparticles at substrate level are predominantly magic number clusters and 3) coalescensce takes place as soon as two neighboring nanopartciles come closer than a critical distance. The film growth was investigated by TEM as a function of Au load, in the range 0–1.2 μg/cm². Two distinct regimes are identified: the “landing regime” and the “coalescence regime”. During the latter the film growth is 3D with a dynamic scaling exponent z of 2.13. Particular attention was devoted to the study of the evolution of the NP population from the moment they are generated with the cluster beam generator to the moment they land on the substrate and coalesce with other NPs. Our results show that 1) the NPs generated by the cluster beam are heterogeneous in size and are made by more than 95% by Au Magic numbers, mainly Au₂₀ and Au₅₅ and 2) kinetic processes (coalescence) at substrate level is capable of producing NPs populations made of larger Au magic numbers containing up to several thousands of Au atoms. Experimental and simulation results provide insight into the coalescence mechanism and provide strong evidence that the NPs coalesce when the nearest neighbor distance is below a critical mark. The critical distance is at its minimum 0.4‐0.5 nm and it is still unclear whether it is constant or not although the best matching simulation results seem to point to a superlinear dependence from the NP size difference between two neighboring candidate coalescing NPs. The coalescence phenomenon investigated in this work pinpoints the unique self‐organization properties of these small Au NPs in creating films with a stable edge‐to‐edge mean nearest neighbor distance of the order of 1.4 nm.     

Plasmonic Newton's cradle for low-loss subwavelength energy transport: Homogeneous or heterogeneous nanoparticle chains?

Five closely spaced Au or Ag NPs are linearly arranged in analogy with Newton's cradle, forming various homogeneous and heterogeneous NP chains. Using small NPs, the Au–Ag–Ag–Ag–Au heterochain has the lowest propagation loss (17.6%) at short resonance wavelengths. When the NP diameter is increased to 80 nm, the dominant resonance is shifted to longer wavelengths. As low as 6% of the total energy dissipates in the intermediate NP component, and there seems to be little difference between the Au–Ag–Ag–Ag–Au heterochain and the Ag–Ag–Ag–Ag–Ag homochain. Besides the wavelength-dependent intrinsic loss (i.e., the imaginary part of the permittivity) in metals, the real part of the permittivity also plays a critical role in determining the propagation loss. Considering the high fabrication cost of the heterochain, the homochain composed of moderately large Ag NPs (<100 nm) may be an optimal choice for low-loss subwavelength energy transport in practice.     

Seed-mediated growth of gold nanoparticles using self-assembled monolayer of polystyrene microspheres as nanotemplate arrays

Arrays of noble metal nanoparticles show potential applications in (bio-)sensing, optical storage, surface-enhanced spectroscopy, and waveguides. For all such potential devices, controlling the size, morphology, and interparticle spacing of the nanoparticles is very important. Here, we combine seed-mediated growth with nanosphere lithography to study the controllable growth of gold nanoparticles (Au NPs), in which the self-assembly monolayer of polystyrene (PS) on a silicon surface is used to guide the modification of alkanesilanes and the subsequent adsorption of gold seeds; seed-mediated growth is applied to controlling the morphology and size of Au NPs. The size of adsorption region (determining the number of adsorbed gold seeds) is controlled by etching PS microspheres with oxygen plasma or annealing PS microspheres at the glass transition temperature. The size and morphology of the Au NPs are controlled by changing growth conditions. In such a way, we have achieved the dual control of the obtained Au NPs. Preliminary results show that this strategy holds a great promise. This approach can also be extended to a wide range of materials and substrates.     

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.     

Design of Enhanced Catalysts by Coupling of Noble Metals (Au,Ag) with Semiconductor SnO2 for Catalytic Reduction of 4‐Nitrophenol

The reduction of 4‐nitrophenol (Nip) into 4‐aminophenol (Amp) by NaBH₄, which is catalyzed by both binary and ternary yolk–shell noble‐metal/SnO₂ heterostructures, is reported. The binary heterostructures contain individual Au or Ag nanoparticles (NPs) and the ternary heterostructures contain both Au and Ag NPs. The Au@SnO₂ yolk–shell NPs are synthesized via a silica seeds‐mediated hydrothermal method. Subsequently, the Au@SnO₂@Ag and Au@SnO₂@Au yolk–shell–shell (YSS) NPs are synthesized, whereby SnO₂ is located between the Au and Ag NPs. The morphology, composition, and optical properties of the as‐prepared samples are analyzed. For the binary heterostructures, the rate of the reduction reaction increases with decreasing particle size. The catalytic results demonstrate the synergistic effect of Au and Ag in the ternary metal–semiconductor heterostructures, which is beneficial to the catalytic reduction of Nip into Amp. Both the binary and ternary heterostructures exhibit significantly better catalytic performances than the corresponding bare Au and Ag NPs. It is envisaged that the current synthesized strategy will promote further interest in the field of bimetal NP‐based catalysis.     

Plasmonic enhancement of the vanadium dioxide phase transition induced by low-power laser irradiation

Nanocomposites consisting of gold nanoparticle (NP) arrays and vanadium dioxide (VO₂) thin films are noteworthy for the tunability of both their thermal and optical properties. The localized surface plasmon resonance (LSPR) of the Au can be tuned when its dielectric environment is modulated by the semiconducting-to-metal phase transition (SMT) of the VO₂; the LSPR itself can be altered by changing the shape of the NPs and the pitch of the NP array. In principle, then it should be possible to choose a combination of VO₂ film and Au LSPR properties that maximizes the overall optical response of the nanocomposite. To demonstrate this effect, transient transmission measurements were conducted on lithographically fabricated arrays of Au NPs of diameter 140?nm, array spacing 350 nm, and covered with a 60?nm thick films of VO₂ via pulsed laser deposition. Both Au::VO₂ nanocomposites and bare VO₂ film were irradiated with a shuttered 785?nm pump laser, and their optical response was probed at 1550?nm by a fixed-frequency diode laser. The Au::VO₂ nanocomposite exhibited an increased effective absorption coefficient 1.5 times that of the plain film and required 37?% less laser power to induce the SMT. The time-dependent temperature rise in the film as a function of laser intensity was calculated from these measurements and compared with both analytic and finite-element models. Our results suggest that Au::VO₂ nanocomposites may be useful in applications such as thermal-management coatings for energy efficient ??smart?? windows.     

Tunable long-distance light transportation along Au nanoparticle chains: promising for optical interconnect

Tunable light resonance transportation along a single long Au hemisphere nanoparticles (NPs) chain was studied. The realistic experimentally determined gold dielectric function was used for the simulation of Au localized surface plasmon polariton (LSPPs) effect. The resonance light energy with minimized attenuation and its bandwidth were quantitatively analyzed by inducing the effective mass which was observed to increase only with the length of Au NPs between the source and the test point. The geometric ratio g/r of NP size and gap were investigated at 5 µm far of NPs with different gaps from 0 to 70 nm. Strongest resonance can be achieved with g/r = 1.2 by the factor of 1.5 than the connected NPs. This resonance mode falls in the wavelength λ = 555 nm (green light), which is exactly the maximum sensitivity of a light-adapted eye of human beings.     

Study of the Optical Properties of CdZnSe/ZnS-Quantum Dot–Au-Nanoparticle Complexes

The interaction of gold nanoparticles (NPs) and semiconductor alloyed CdZnSe/ZnS quantum dots (QDs) in colloidal solutions is studied. It is shown that the photoluminescence intensity of QDs in a mixture decreases compared to that in the initial QD solution, which is caused by resonance nonradiative energy transfer from QDs to Au NPs in spontaneously formed aggregates. To control the formation of pairs of interacting QDs and Au NPs, we proposed have a method for creating QD–Au NP complexes bound by special molecules—ligands. It is shown that the morphology and optical properties of the samples obtained depend on the method of their preparation, in particular, on the chemical environment of QDs. It is found that the complexes form in the case of addition of hydrophilic Au NPs to hydrophobic QDs and that this almost does not change the optical properties of the latter compared to those of quasi-isolated QDs in colloidal solution.     

Al纳米颗粒表面等离激元对ZnO光致发光增强的研究

基于聚苯乙烯球自组装法,在P型氮化镓(P-GaN)衬底上制备了有序致密的掩模板;采用热蒸发法在该模板上沉积金属Al薄膜,通过甲苯溶液去除聚苯乙烯球,得到了金属Al纳米颗粒阵列;采用原子层沉积法,在Al纳米颗粒阵列表面依次沉积氧化铝(Al_2O_3)和氧化锌(ZnO).通过测试Al纳米颗粒阵列的消光谱以及ZnO薄膜的光致发光谱,研究了Al纳米颗粒表面等离激元与ZnO薄膜激子之间的耦合效应.实验结果表明:引入Al纳米颗粒后,在约380 nm位置附近的ZnO近带边发光峰积分强度增强了1.91倍.对Al纳米颗粒表面等离激元增强ZnO光致发光的机理进行探讨.     

On the spectral difference between electroluminescence and photoluminescence of Si nanocrystals: a mechanism study of electroluminescence

A highly dense and uniform layer of Au nanoparticles (NPs) on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film has been produced by the pulsed laser deposition (PLD) technique toward the production of an improved efficiency photovoltaic device. The advantage of PLD over other techniques is the easy and precise control of the Au NPs size and spatial distribution, without needing of further NP surface functionalization. The efficiency enhancement factor related to Au NPs doping has been evaluated in a solar cell based on poly-(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) diffused bilayer. The short-circuit current density, J _SC, increases by 18 % and the power conversion efficiency by 22 %, respectively, in comparison with an equivalent device without Au NPs. The optical and morphological properties of the Au NPs layer have been selected in order to evaluate the contribution of the surface plasmon resonance as enhancement factor of the solar cell efficiency, in a range size where light scattering is negligible.     

Organic‐inorganic hybrids based on phenanthrene‐functionalized gold nanoparticles for OLEDs

The electroluminescence intensity of the phenanthrene‐functionalized gold nanoparticles, PMPT‐Au nanoparticles/CPB: Ir(PIA)₂ (acac) film, was increased by 4.9 times compared with control device, CPB: Ir(PIA)₂ (acac) due to coupling between the excitons of emissive layer and localized surface plasmonic resonance of PMPT‐Au NPs. The maximum luminous efficiencies of devices II to IV with PMPT‐Au NPs were 39.2 cd A^?1 (11.8 V), 40.1 cd A^?1 (10.5 V), and 43.1 cd A^?1 (9.0 V), respectively. The increment of current efficiency with PMPT‐Au NP coated devices was strongly related to the energy transfer between the radiated light generated from CBP: Ir(PIA)₂ (acac) emissive layer and localized surface plasmonic resonance excited by PMPT‐Au NP layer.     

Peptide‐Targeted Gold Nanoparticles for Photodynamic Therapy of Brain Cancer

Targeted drug delivery using epidermal growth factor peptide‐targeted gold nanoparticles (EGF_pep‐Au NPs) is investigated as a novel approach for delivery of photodynamic therapy (PDT) agents, specifically Pc 4, to cancer. In vitro studies of PDT show that EGF_pep‐Au NP‐Pc 4 is twofold better at killing tumor cells than free Pc 4 after increasing localization in early endosomes. In vivo studies show that targeting with EGF_pep‐Au NP‐Pc 4 improves accumulation of fluorescence of Pc 4 in subcutaneous tumors by greater than threefold compared with untargeted Au NPs. Targeted drug delivery and treatment success can be imaged via the intrinsic fluorescence of the PDT drug Pc 4. Using Pc 4 fluorescence, it is demonstrated in vivo that EGF_pep‐Au NP‐Pc 4 impacts biodistribution of the NPs by decreasing the initial uptake by the reticuloendothelial system (RES) and by increasing the amount of Au NPs circulating in the blood 4 h after IV injection. Interestingly, in vivo PDT with EGF_pep‐Au NP‐Pc 4 results in interrupted tumor growth when compared with EGF_pep‐Au NP control mice when selectively activated with light. These data demonstrate that EGF_pep‐Au NP‐Pc 4 utilizes cancer‐specific biomarkers to improve drug delivery and therapeutic efficacy over untargeted drug delivery.     

Energy transfer between excitons and plasmons in semiconductor-metal hybrid nanostructures

We summarized our recent optical studies on semiconductor nanoparticle (NP) based hybrid nanostructures: isolated CdSe NPs on Au substrates, close-packed CdSe NP monolayers on Au substrates, and close-packed monolayers of mixed CdSe/Au NPs. Luminescence properties of semiconductor-metal hybrid nanostructures were studied by space-resolved optical imaging spectroscopy and time-resolved luminescence spectroscopy. The luminescence spectra and dynamics of isolated and assembled NPs depend on the local environments. We discuss exciton-plasmon interactions in semiconductor-metal hybrid nanostructures.     

Self‐Assembly of Functionalized Gold Nanoparticles with Rigid and Flexible Multifunctional Linkers

The interparticle spacing of carboxyl functionalized gold nanoparticles (Au–COOH) was mediated by rigid cross‐linkers, octa(3‐aminopropyl)octasilsesquioxane (POSS–NH₃ ⁺) and poly(amidoamine) dendrimer terminated with hydroxyl groups (PAMAM–OH), and a flexible polymeric linker, poly(hexanyl viologen) (6‐VP). Regular interparticle spacing was achieved by utilizing POSS–NH₃ ⁺ and PAMAM–OH dendrimer as cross‐linkers, whereas size growth of Au–COOH was observed featuring no interparticle spacing by utilizing 6‐VP as the cross‐linker.