Thermal behavior of surface plasmon resonance in dynamic suprastructure multilayer

Delicate thermodynamic control at confined space has been of importance in recent nano/micro-plasmonic sensing to be more accurate and to use lower quantity of specimens than conventional devices. In our study, experimental and computational study on thermal behavior of surface plasmon resonance (SPR) was carried out using various sizes of Au nanoparticles (NPs; 4, 18, and 57 nm) and thermo-reversible polymer, poly(N-isopropylacrylamide) (PNIPAm) on SPR chip. It was interesting that SPR angle shift on temperature was dependent on NP sizes, where the smaller size the better sensitive. It is probable that both plasmonic interaction and polymer dynamicity were collaboratively affected and presumably the latter dominated in the thermal monitoring of SPR signals. The simulations clearly indicated that the interaction between the Au NPs and polymers was strengthened by increasing temperature and NP sizes, resulting in decreasing sensitivity. These results are supportive to develop further accurate devices using plasmonics and polymer dynamics, such as plasmonic sensing devices, thermo-actuators, hybrid organic solar cell, and flexible display.     

Performances of different metals in optical fibre-based surface plasmon resonance sensor

The capability of various metals used in optical fibre-based surface plasmon resonance (SPR) sensing is studied theoretically. Four metals, gold (Au), silver (Ag), copper (Cu) and aluminium (Al) are considered for the present study. The performance of the optical fibre-based SPR sensor with four different metals is obtained numerically and compared in detail. The performance of optical fibre-based SPR sensor has been analysed in terms of sensitivity, signal-to-noise (SNR) ratio and quality parameter. It is found that the performance of optical fibre-based SPR sensor with Au metal is better than that of the other three metals. The sensitivity of the optical fibre-based SPR sensor with 50 nm thick and 10 mm long Au metal film of exposed sensing region is 2.373 μm/RIU with good linearity, SNR is 0.724 and quality parameter is 48.281 RIU^− 1. The thickness of the metal film and the length of the exposed sensing region of the optical fibre-based SPR sensor for each metal are also optimized.     

Nanoindentation of gold nanoparticles functionalized with proteins

The hardness and Young's modulus of 10 and 20 nm gold nanoparticles (Au NPs) modified with bovine serum albumin and streptavidin were measured using a nanoindenter. The Au NPs were immobilized on a semiconductor surface through organic self-assembled monolayers. Changes in mechanical properties occurred when the Au NPs were immobilized on the surface. The hardness and Young's modulus were dependent on the size of the NPs, and the proteins on the particles showed highly plastic and elastic behavior compared to flat surfaces modified with self-assembled monolayers.     

Ultra-elongated depth of focus of plasmonic lenses with concentric elliptical slits under Gaussian beam illumination

In this paper, we discuss the influence of ratio of minor to major axis on the propagation property and focusing performance of a plasmonic lens with variant periodic concentric elliptical slits illuminating under a Gaussian beam. In order to analyse the influence theoretically, a finite-difference time-domain （FDTD） numerical algorithm is adopted for the computational numerical calculation and the design of the plasmonic structure. The structure is flanked with penetrated slits through a 200-nm metal film （Au） which is coated on a quartz substrate. Tunability of focusing capability of the plasmonic lenses is studied by tailoring the ratio. Our calculation results demonstrate that the ratio of the elliptical slits greatly affects the focusing capability of the lense. The plasmonic lenses with concentric elliptical slits illuminating under a Gaussian beam have ultra-elongated depth of focus. These results are very encouraging for the future study of the plasmonic lens-based applications.     

Two-dimensional nanopatterning by PDMS relief structures of polymeric colloidal crystals

A new constructive method of fabricating a nanoparticle self-assembly on the patterned surface of a poly(dimethylsiloxane) (PDMS) relief nanostructure was demonstrated. Patterned PDMS templates with close-packed microwells were fabricated by molding against a self-assembled monolayer of polystyrene spheres. Alkanethiol-functionalized gold nanoparticles with an average particle size of 2.5 nm were selectively deposited onto a hydrophobic self-assembled monolayer printed on the substrate by the micro-contact printing (μCP) of the prepared PDMS microwell, in which the patterned gold nanoparticles consisted of close-packed hexagons with an average diameter of 370 nm. In addition, two-dimensional colloidal crystals derived from PMMA microspheres with a diameter of 380 nm and a negative surface charge were successfully formed on the hemispherical microwells by electrostatic force using positively charged PAH-coated PDMS as a template to produce multidimensional nanostructures.     

Silicon nanotips formed by self-assembled Au nanoparticle mask

The Au nanoparticle monolayer is formed by self-assembly technology on the Si substrates terminated with different functional groups. Silicon nanotips were fabricated by a self-assembled gold colloidal particle monolayer as an etch mask. The silicon nanotips with high density and uniformity in height and shape were obtained using reactive ion etching (RIE). The Si nanotips on the surface of the 3-aminopropyltrimethoxysilane (APTMS)-treated Si substrate are less-ordered array and uniformity than 3-mercaptopropyltrimethoxysilane (MPTMS)-treated Si substrate at the same etching conditions. The ordered array and uniformity of Si nanotips on the APTMS-modified Si substrate was improved through heat-treatment. This result is implied the different functional groups on the Si surfaces could affect the formation of the Si nanostructures during RIE process. The uniformly nanotip pattern with height of >20 nm is obtained on the etched nanoparticle-coated Si substrate. This method can be applied to patterning a wide variety of thin film materials into tip arrays.     

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.     

Strain relaxation of CdTe films growing on lattice-mismatched substrates

We have deposited CdTe films by laser-assisted epitaxy approach and investigated the influence of substrate and film thickness on the film properties. Grown on Si(001), GaAs(001), and quartz substrates; the CdTe films exhibit preferential orientation along the cubic CdTe(111) direction. When the films are thin (<500 nm), a blueshift of the band gap and splitting of valence bands were observed. These results are attributed to the existence of residual strains induced by mismatch of the film lattice constant with that of the substrate, and by their difference in thermal expansion coefficients. The bulk band-gap energy of 1.5 eV was achieved on the surface of thick CdTe films grown on Si(001) substrate, indicating that strain was almost completely relaxed in this case. Our results demonstrate that by a proper selection of substrate and film thickness it is possible to grow film semiconductors with band gap approaching those of bulk crystals.     

微波合成银包覆金纳米粒子膜的拉曼散射活性研究

采用微波加热加压法和静电吸附自组装法在石英玻璃表面制备了银包覆金纳米粒子薄膜,利用原子力显微镜分析了薄膜的表面形态和结构,测定结晶紫分子在薄膜表面的拉曼光谱。结果表明,银包覆金纳米粒子薄膜具有很强的表面增强拉曼散射效应(SERS)活性和稳定性。     

The formation of sub-10 nm nanohole array on block copolymer thin films on gold surface using surface neutralization based on O2 plasma treatment and self-assembled monolayer

Blockcopolymer (BCP) lithography is an emerging nanolithography technique for fabrications of various nanoscale devices and materials. In this study, self-assembled BCP thin films having cylindrical nanoholes were prepared on gold by surface neutralization using self-assembled monolayer (SAM). Oxygen plasma treatment was investigated as a way to enhance the functionality of Au surface toward SAM formation. After surface neutralization, well-ordered nanoholes with 9 to 20 nm diameters were formed inside BCP thin films on Au surfaces through microphase separation. The effects of oxygen plasma treatment on the formation of BCP nanopattern were investigated using surface analysis techniques including X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. Au nanodot arrays were fabricated on gold film by utilizing the BCP nanotemplate and investigated by atomic force microscopy (AFM).     

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.     

Fabrication and applications of ultraflexible nanostructures using dielectric heating-assisted nanoimprint on PVC films

We developed dielectric heating-assisted nanoimprint method for rapid fabrication of ultraflexible nanostructures. Using spin-coating polyvinyl-chloride (PVC) film on the glass slide, the dielectric heating on PVC film helped the pattern transfer from the mold to PVC film in few seconds. Various kinds of nanostructures were successfully made on PVC films with about 20-μm thickness. We demonstrated the applications of ultraflexible metallic nanostructures for bending measurement using surface plasmon resonance (SPR) and surface enhanced Raman scattering (SERS) on the curved surfaces. For measuring bending angles using SPR on capped nanowire arrays, the minimum detection angle was 2.4 × 10⁻³ degree under 0.02 nm wavelength resolution. For SERS measurement, the nanorod arrays on a curved substrate can increase SERS signals for two times as compared to planar SERS substrate.     

Nanosphere dispersion on a large glass substrate by low dose ion implantation for localized surface plasmon resonance

Dispersing nanospheres on a large glass substrate is the key to fabricate noble metal nanostructures for localized surface plasmon resonance through dispersed nanosphere lithography. This article reports that by modifying the glass surface with low dose ion implantation and successively dip coating the surface with poly(diallyldimethyl ammonium chloride) (PDDA), polystyrene or silica nanospheres can be dispersed on a large glass substrate. Investigation shows that several kinds of ions, such as silicon, boron, argon, and arsenic, can improve the nanosphere dispersion on glass, attributed to the ion bombardment-caused silicon increment. Ion implantation imposes no surface roughness or optical loss to the glass substrate, thus this method is suitable for localized surface plasmon resonance application. Experiments show silicon ion implantation can best disperse the nanospheres. For the gold nanostructures obtained by obliquely evaporating 30 nm of gold film onto the polystyrene nanospheres, which are dispersed on a silicon ion implanted glass substrate, a localized surface plasmon resonance sensitivity of 242 nm/RIU is achieved.     

亚微米聚苯乙烯微球在气-液界面组装的机理研究

系统地研究了亚微米聚苯乙烯微球在气-液界面的组装机理.聚苯乙烯微球在介质对流的带动下会到达悬浮液的表面并在气-液界面组装，气-液界面处聚苯乙烯微球间由弯液面产生的毛细管力是组装的推动力.界面处聚苯乙烯微球在干燥过程中其润湿性发生了转变，由完全润湿到部分润湿并最终变成不润湿，相应的聚苯乙烯微球与分散介质间接触角也逐渐增大.研究表明，只有接触角达到或超过某数值θ′_critical时，才能够出现气-液界面组装现象.考虑到PS胶粒晶体的表面是“规则”粗糙的表面，由Wenzel公式知θ′_critical大于测量值θ＝22°.聚苯乙烯微球润湿性的转变是界面组装发生和持续进行的关键性因素. 关键词： 自组装 胶粒晶体 聚苯乙烯微球 润湿性     

Improvement of plasmonic field-matter interaction by subwavelength dielectric gratings

We experimentally and theoretically investigate that detection sensitivity in surface plasmon resonance (SPR) biosensors can be significantly enhanced by employing subwavelength dielectric gratings deposited on a gold film. The enhancement originates from an improvement of field-matter interaction: enhanced evanescent field intensity at the binding region and increased surface reaction area. Using a large-area SiO₂ grating array fabricated by nanoimprint lithography, experimental sensor performance measured by parylene film coating shows that the SPR substrates combined with a dielectric grating provide a notable sensitivity improvement compared to a conventional bare gold film. We also demonstrate that plasmon field can be more confined and enhanced at the dielectric gratings with a larger width. The proposed SPR structure could potentially be useful in a variety of plasmonic applications including high-sensitivity biosensors.     

K9和石英玻璃基片上Au膜真空紫外反射特性研究

采用离子束溅射法,分别在经过不同前期清洗方法处理过的K9及石英玻璃光学基片上,选择不同的镀膜参量,镀制了多种厚度的Au膜。对镀制的Au膜在真空紫外波段较宽波长范围内的反射率进行了连续测量。测试结果表明:辅助离子源的使用方式、Au膜厚度对反射镜的反射率有重大影响。基片材料、镀前基片表面清洗工艺等对反射率也有一定影响。采用镀前离子轰击,可显著提高Au膜反射率及膜与基底的粘合力;获得最高反射率时的最佳膜厚与基片材料、镀膜工艺密切相关。对经过离子清洗的石英基片,膜厚在30 nm左右反射率最高;比较而言,石英基片可获得更高的反射率;辅助离子源的使用还显著影响获得最高反射率时对应的最佳膜厚值,且对K9基片的影响更显著。     

Optical properties and ultrafast electron dynamics in gold–silver alloy and core–shell nanoparticles

Silver and gold are the two most popular metals used for many nanoparticle applications, such as surface enhanced Raman scattering or surface enhanced fluorescence, in which the local field enhancement associated with the excitation of the localized surface-plasmon–polariton resonance (SPR) is exploited. Therefore, tunability of the SPR over a wide energy range is required. For this purpose we have investigated core–shell nanoparticles composed of gold and silver with different shell thicknesses as well as the impact of alloying on these nanoparticles due to a tempering process. The nanoparticles were prepared by subsequent deposition of Au and Ag atoms or vice versa on quartz substrates followed by diffusion and nucleation. Their linear extinction spectra were measured as a function of shell thickness and annealing temperature. It turned out that different gold shell thicknesses on silver cores allow a tuning of the SPR position from 2.79 to 2.05 eV, but interestingly without a significant change on the extinction amplitude. Heating of core–shell nanoparticles up to only 540 K leads to the formation of alloy nanoparticles, accompanied by a back shift of the SPR to 2.60 eV. Calculations performed in quasi-static approximation describe the experimental results quite well and prove the structural assignments of the samples. In additional experiments, we applied the well-established persistent spectral hole burning technique to the alloy nanoparticles in order to determine the ultrafast dephasing time T ₂. We obtained a dephasing time of T ₂=(8.1±1.6) fs, in good agreement with the dephasing time of T _2,∞=8.9 fs, which is already included in the dielectric function of the bulk.     

Large enhancement of Faraday rotation by localized surface plasmon resonance in Au nanoparticles embedded in Bi:YIG film

A large enhancement of the Faraday rotation, which is associated with localized surface plasmon resonance (LSPR), was obtained in a sample with Au nanoparticles embedded in a Bi-substituted yttrium iron garnet (Bi:YIG) film. On a quartz substrate, Au nanoparticles were formed by heating an Au thin film, and a Bi:YIG film was then deposited on them. A sample containing the Au nanoparticles produced by 1000 °C heating showed a resonant attenuation with narrower bandwidth in the transmission spectrum than nanoparticles of other samples formed by low-temperature heating. The sharp resonant Faraday rotation angle was 4.4 times larger than the estimated intrinsic Bi:YIG film at the LSPR wavelength; the angular difference was 0.14°. A discrepancy in the bandwidth between the transmission attenuation and the resonant Faraday rotation is discussed.     

Surface plasmon resonance detection using amorphous carbon/Au multilayer structure

Surface plasmon resonance (SPR) can be used to detect the change in reflective index on a metal surface. In this report, we propose detection of the SPR can easily be applied to estimate the thickness of the amorphous carbon (a-C:H) films. To detect changes in film thickness using SPR, devices with an a-C:H/Au structure were fabricated. The a-C:H films were deposited by electron cyclotron resonance plasma chemical vapor deposition (ECR-CVD) and sputtering, and the obtained film densities were 1.4 and 1.6 g/cm³, respectively. By the deposition of an 11-nm thick a-C:H film on a Au layer by sputtering, the SPR angle changed from 44.90° to 47.05°. For a-C:H deposited by ECR-CVD, the SPR angle was shifted from 44.24° for Au without the a-C:H layer to 58.44° after deposition of 45 nm thick a-C:H film. In both systems of the SPR angle increased with increasing the film thickness. The rate at which the SPR angle shifted depended on the a-C:H film density. These results show that the thickness of an a-C:H film can be determined by the SPR angle shift on an a-C:H layer using a-C:H/Au device with an a-C:H film of the same density.     

Large-scale protein/antibody patterning with limiting unspecific adsorption

A simple synthetic route based on nanosphere lithography has been developed in order to design a large-scale nanoarray for specific control of protein anchoring. This technique based on two-dimensional (2D) colloidal crystals composed of polystyrene spheres allows the easy and inexpensive fabrication of large arrays (up to several centimeters) by reducing the cost. A silicon wafer coated with a thin adhesion layer of chromium (15 nm) and a layer of gold (50 nm) is used as a substrate. PS spheres are deposited on the gold surface using the floating-transferring technique. The PS spheres were then functionalized with PEG-biotin and the defects by self-assembly monolayer (SAM) PEG to prevent unspecific adsorption. Using epifluorescence microscopy, we show that after immersion of sample on target protein (avidin and anti-avidin) solution, the latter are specifically located on polystyrene spheres. Thus, these results are meaningful for exploration of devices based on a large-scale nanoarray of PS spheres and can be used for detection of target proteins or simply to pattern a surface with specific proteins.