金纳米棒状微粒的胶囊模型及吸收光谱

提出了金纳米棒状微粒的胶囊模型,用Waterman发展的T矩阵方法计算了金纳米棒状微粒的吸收光谱.计算谱和实验谱基本符合,520 nm左右处的吸收峰对应于金纳米棒的横向表面等离体子共振（横模）,长波长处的吸收峰对应于金纳米棒的纵向表面等离体子共振（纵模）.随着金纳米棒纵横比的增加,纵模吸收峰表现出显著的红移,横模吸收峰则微弱地蓝移.此外,计算结果表明,金纳米棒状微粒外部介质的介电常数必须随着金纳米棒纵横比的增大非线性地减小.     

Influence of amount of CTAB and ascorbic acid concentration on localized surface plasmon resonance property of gold nanorod

Gold nanorods (AuNRs) are prepared through seeded growth approach. Synthesis parameters of the amount of cetyltrimethylammonium bromide (CTAB), and concentration of ascorbic acid (AA) were studied. We were aiming for an aspect ratio of 3 which could be achieved by a nanorod feature in the range of 45 nm length and 15 nm width. The absorption spectra are observed with an UV–visible NIR spectrophotometer and analysed theoretically. It is known that there are two plasmon resonance peaks for gold nanorod corresponding to transverse surface plasmon resonance (TSPR) and longitudinal surface plasmon resonance (LSPR), respectively. It is found that as the concentration of CTAB increases, the yield of NRs increases. As the concentration of AA increased from 0.05 to 0.2 M, LSP shifts to longer wavelength but upon further increasing the concentration, LSP shifts back to shorter wavelength. A linear relationship between LSPR wavelength and surrounding medium dielectric constant is obtained, which is in good agreement with the theoretical results.     

Seedless synthesis of gold nanorods by using hydrogen peroxide as a weak reducing agent

Abstract

A new seedless wet chemistry synthesis of gold nanorods by using hydrogen peroxide as the weak reducing agent is reported. A reduced concentration of hexadecyltrimethylammonium bromide is used in our experiment, and the synthesized gold nanorods exhibit tunable longitudinal surface plasmon resonance peaks ranging from 725 to 945?nm. The influence on gold nanorods growth by adjusting the amounts of sodium hydroxide, silver nitrate, sodium borohydride, and hexadecyltrimethylammonium bromide were investigated by the visible-near infrared spectroscopy. Under the proper experimental parameters, the longitudinal surface plasmon resonance peaks can be tuned by varying the hydrogen peroxide amounts. Furthermore, it can be seen that the redshift of the longitudinal absorption peak of the prepared gold nanorods with increasing hydrogen peroxide amount is consistent with the increase tendency of the length-to-width aspect ratio obtained from the transmission electron microscopy images. The method provides a facile pathway to prepare gold nanorods with tunable longitudinal surface plasmon resonance peaks, which have potential applications in biomedicine and nanophotonics.     

Combined Facile Synthesis,Purification, and Surface Functionalization Approach Yields Monodispersed Gold Nanorods for Drug Delivery Applications

Synthesizing gold nanorods (AuNRs) by seed-mediated growth method results in the presence of undesired size and shape particles by-products occupying 10–90% of the population. In this study, AuNRs are synthesized by the seed-mediated growth method using cetyltrimethylammonium bromide (CTAB) as a surfactant. AuNRs with redshifted longitudinal localized surface plasmon resonance (LLSPR) peak, localized in the biological “transparency window” (650–1350 nm), are synthesized after optimizing seed solution, silver nitrate solution, and hydrochloric acid solution volumes, based on the published protocols. A two-step purification method, dialysis followed by centrifugation, is applied to remove excess CTAB and collect LLSPR-redshifted AuNRs with high rod purity (>90%). CTAB is subsequently exchanged with polyethylene glycol (PEG) to improve AuNRs biocompatibility. PEGylated AuNRs are confirmed innocuous to both SN4741 cells and B16F10 cells by the modified MTT assay and the modified lactate dehydrogenase (LDH) assay up to 1 nm and 24 h incubation. In this study, a combined facile synthesis, purification, and surface functionalization approach is proposed to obtain water-dispersible monodispersed AuNRs for drug delivery applications.     

Au@碳球复合结构中Au颗粒位置调控光吸收

采用时域有限差分（FDTD）法研究Au纳米颗粒@碳球（AuNPs@CS）复合结构的光吸收控制。发现Au纳米颗粒@碳球复合结构中Au颗粒的位置可以控制复合结构光吸收。模型计算中选取两粒Au纳米颗粒以最佳深度（0 nm）嵌入碳球表面。当两粒Au颗粒球心与碳球球心夹角为22.5°和45°时,复合结构光吸收较单一碳球光吸收明显增强;当夹角为315°、270°、180°、90°时,光吸收增量逐渐减小;当夹角为337.5°时,光吸收量低于单一碳球。这一结果主要归因于Au纳米颗粒位置变化可引起表面等离子体光强度和光散射方向的变化。改变碳球表面Au纳米颗粒的数量和位置,可以进一步调节AuNPs@CS复合结构的光吸收。     

Modeling and identification on nonlinear saturable and reverse-saturable absorptions of gold nanorods using femtosecond Z-scan technique

An improved Z-scan analysis approach is proposed by establishing and solving the saturable absorption (SA) and reverse-SA (RSA) models, respectively. Near-infrared femtosecond Z-scans are carried out on the synthesized gold nanorods (NRs) possessing the average length of 46 nm using a femtosecond laser operated at the wavelength of 800 nm, which is close to the peak position of longitudinal surface plasmon resonance (SPR) (710 nm) of gold NRs. At lower input intensity of less than 400 GW/cm2 , the normalized transmission exhibits only SA phenomenon; however, when it exceeds 400 GW/cm2 , both SA and RSA are observed. By using the presented Z-scan modeling and theory, the three-photon absorption (3PA) is identified in the material, and the 3PA cross-section is determined to be 1.58×1071 cm6s2 .     

银纳米棒光学性质的离散偶极近似计算

利用离散偶极近似 (Discretedipoleapproximation ,简称DDA)的方法 ,从理论上对粒子的形状、尺寸及周围介质等因素对银纳米粒子 ,特别是银纳米棒的光学性质的影响进行了较系统的研究 .计算表明 ,置于空气中的棒状银纳米粒子的光学性质与其形状密切相关 ,纵向表面等离子体共振吸收峰的位置随纳米棒长径比的增加呈现线性红移关系 .给出了空气中银纳米棒纵向表面等离子体共振吸收峰的位置随长径比变化的DDA拟合公式 .如果将金属纳米粒子置于折射率更高的介电环境中 ,其纵向等离子体共振吸收峰的位置进一步呈现线性红移关系 .合成的银纳米粒子的TEM图像及相关的UV VIS消光光谱显示DDA计算结果与实验值相当一致 .DDA算法与Mie′s理论在计算球状银纳米粒子的消光系数时给出很接近的结果 ,这表明用DDA的方法来分析银的光学性质是准确可靠的 ;而DDA算法对银纳米棒消光特性的成功拟合则表明 ,该算法相对Gans′理论而言 ,在研究纳米粒子的光学性质时具有更广的适用性及更高的准确性 .     

Shape and size transformation of gold nanorods (GNRs) via oxidation process: A reverse growth mechanism

The anisotropic shape transformation of gold nanorods (GNRs) with H₂O₂ was observed in the presence of “cethyl trimethylammonium bromide” (CTAB). The adequate oxidative dissolution of GNR is provided by the following autocatalytic scheme with H₂O₂: Au⁰ → Au⁺, Au⁰ + Auⁿ⁺ → 2Au³⁺, n = 1 and 3. The shape transformation of the GNRs was investigated by UV-vis spectroscopy and transmission electron microscopy (TEM). As-synthesised GNRs exhibit transverse plasmon band (TPB) at 523 nm and longitudinal plasmon band (LPB) at 731 nm. Upon H₂O₂ oxidation, the LPB showed a systematic hypsochromic (blue) shift, while TPB stays at ca. 523 nm. In addition, a new emerging peak observed at ca. 390 nm due to Au(III)-CTAB complex formation during the oxidation. TEM analysis of as-synthesised GNRs with H₂O₂ confirmed the shape transformation to spherical particles with 10 nm size in 2 h, whereas centrifuged nanorod solution showed no changes in the aspect ratio under the same condition. Au³⁺ ions produced from oxidation, complex with excess free CTAB and approach the nanorods preferentially at the end, leading to spatially directed oxidation. This work provides some information to the crystal stability and the growth mechanism of GNRs, as both growth and shortening reactions occur preferentially at the edge of single-crystalline GNRs, all directed by Br⁻ ions.     

Silver nanorods used to promote SERS as a quantitative analytical tool

We have fabricated silver nanorod arrays by electrodepositing the nanorods evenly in the shallow pores of porous anodic aluminum oxide (AAO) templates. The diameter and length were 28 and 44 nm, respectively. The maxima of the transverse and longitudinal modes of the surface plasmon were near 417 and 511 nm, respectively. A good surface‐enhanced Raman scattering (SERS) spectrum was observed by excitation with the 514.5‐nm laser line. The SERS intensity increased almost linearly upon malachite green isothiocyanate adsorption on the tips of the silver nanorods as the concentration of the mother solutions increased. Our results show that silver nanorods fabricated on AAO templates could be used as an SERS substrate for quantitative analyses. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermal tuning of surface plasmon resonance: Ag gratings on barium strontium titanate thin films

Surface plasmon tuning via thermally induced refractive index changes in ferroelectrics is investigated. Epitaxial (Ba_0.7Sr_0.3)TiO₃ (BST) thin films were deposited on MgO (001) substrates by pulsed laser deposition. The refractive index of BST thin films measured by the prism-coupling technique was found to increase from 2.3932 (TE)/1.9945 (TM) at room temperature to 2.3949 (TE)/1.9965 (TM) at 66°C. Then 30-nm-Ag gratings with periodicity 750 nm and width 300 nm were fabricated on BST by soft ultraviolet nanoimprint lithography and subsequent lift-off process. The reflection spectra from 500 to 1000 nm with incident angle from 5° to 60° were measured at room temperature and 66°C, with a collimated and p-polarized light incident perpendicularly to the grating direction. Several modes were observed from the spectra. At 66°C, a red shift of a dip at about 850 nm by 2 nm was obtained at an incident angle of 15°. Calculations confirmed that the observed modes belong to the (−1), (2), (−2) and (3) surface plasmon modes from the Ag and BST interfaces and localized mode; the red shift by thermal tuning is also confirmed. The results indicate the feasibility of active modulation in surface plasmon resonance in solid-state structures.     

Utilization of surface plasmon resonance of Au/Pt nanoparticles for highly photosensitive ZnO nanorods network based plasmon field effect transistor

Hydrothermally processed highly photosensitive ZnO nanorods based plasmon field effect transistors (PFETs) have been demonstrated utilizing the surface plasmon resonance coupling of Au and Pt nanoparticles at Au/Pt and ZnO interface. A significantly enhanced photocurrent was observed due to the plasmonic effect of the metal nanoparticles (NPs). The Pt coated PFETs showed I_on/I_off ratio more than 3 × 10⁴ under the dark condition, with field-effect mobility of 26 cm² V⁻¹ s⁻¹ and threshold voltage of −2.7 V. Moreover, under the illumination of UV light (λ = 350 nm) the PFET revealed photocurrent gain of 10⁵ under off-state (−5 V) of operation. Additionally, the electrical performance of PFETs was investigated in detail on the basis of charge transfer at metal/ZnO interface. The ZnO nanorods growth temperature was preserved at 110 °C which allowed a low temperature, economical and simple method to develop highly photosensitive ZnO nanorods network based PFETs for large scale production.     

Fluorescence Correlation Spectroscopy of Gold Nanoparticles

Diffusion dynamics of gold nanoparticles (GNPs) was studied by fluorescence correlation spectroscopy (FCS). The fluorescence was studied by exciting the particles by green laser (532 nm), which is far from longitudinal plasmon band of nanorods. Transmission electron microscope (TEM) and UV-Vis-NIR spectrometer were used to characterize the gold nanoparticles. Despite their low quantum yields, GNPs possess the native fluorescence. The excellent antiphotobleaching behavior of gold nanorods leads to prospects of using FCS for its detailed studies. Using FCS, dynamic information can be extracted from the fluorescence fluctuations in the system by autocorrelation function. Maximum entropy method (MEMFCS) was used to identify the number of distinct components present in the system. The particle sizes obtained from FCS were found to be higher (by few orders of magnitude) compared to TEM analysis. This might be due to the possible contributions from cetyltrimethyl ammonium bromide (CTAB) capping in the system.     

Surface-enhanced absorption by self-organized silver films with aciniform-like nanoaggregates at elevated temperatures

Morphological evolution of silver nanocomposite films prepared by the wet colloidal route and surface-enhanced phenomena on aggregate nanostructures evolved during annealing were investigated. Dramatic changes in morphologies of particles and pores incurred by rearragement, coarsening, premelting, and dewetting of the silver clusters at different concentrations (i.e., mass thicknesses). At a higher mass thickness, the morphological transitions from self-organized nanoaggregates with aciniform pattern at 300 °C to elongated and coarsened particles with circular holes at 400 °C to island clusters at 500 °C occurred in the films. The peculiar absorption with a much redder and broader surface plasmon feature, which gone far beyond the theoretical prediction, induced by the formation of aciniform nanoaggregates embedded in the porous polymer matrix at a critical mass thickness of 9.6 nm during partial degradation of the PVP polymer and rearrangement of silver clusters at 300 °C. The surface-enhanced absorption was dramatically reduced by the elemination of the aggregate nanostructures and the spontaneous formation of the silver nanoisland film at the dewetting temperature of 500 °C.     

Effect of annealing temperature on optical and electrochemical properties of chitosan–ZnO nanostructure

Chitosan–ZnO nanostructures were prepared by chemical precipitation method using different concentration of zinc chloride and sodium hydroxide solutions. Nanorod-shaped grains with hexagonal structure for samples annealed at 300 °C and porous structure with amorphous morphology for samples annealed at 600 °C were revealed in SEM analysis. X-ray diffraction patterns confirmed the hexagonal phase ZnO with crystallite size found to be in the range of ~24.15–34.83 nm. Blue shift of UV–Vis absorption shows formation of nanocrystals/nanorods of ZnO with marginal increase in band gap. Photoluminescence spectra show that blue–green emission band at 380–580 nm. The chitosan–ZnO nanostructures used on surface of a glassy carbon electrode gives the oxidation peak potential at ~0.6 V. The electrical conductivity of chitosan–ZnO composites were observed at 2.1?×?10^?5 to 2.85?×?10^?5?S/m. The nanorods with high surface area and nontoxicity nature of chitosan–ZnO nanostructures observed in samples annealed at 300 °C were suitable as a potential material for biosensing.     

Optical properties of ZnO and Al2O3 implanted with silver ions

ZnO and Al₂O₃ samples implanted with 30-keV silver ions with fluences in the interval (0.25–1.00) × 10¹⁷ ions/cm² are studied by the method of optical photometry in the visible part of the spectrum. The optical transmission spectra of the implanted samples exhibit a selective band associated with surface plasmon resonance absorption of silver nanoparticles. The intensity of this band nonmonotonically depends on the implantation fluence. The silver ion depth distribution in the samples is calculated. It is shown that the non-monotonicity observed in experiments is due to an increase in the substrate sputtering ratio with increasing implantation fluence. It is found that vacuum thermal annealing of the implanted Al₂O₃ layers up to 700°C causes a considerable narrowing of the plasmon absorption bandwidth without a tangible change in its intensity. At higher annealing temperatures, the plasmon absorption band broadens and its intensity drops. Annealing of the ZnO films under such conditions causes their complete vaporization.     

Anisotropic nonlinear optical absorption of gold nanorods in a silica matrix

Nanocomposite films consisting of gold nanospheres or gold nanorods embedded in a silica matrix have been prepared using a hybrid deposition technique consisting of plasma-enhanced chemical vapor deposition of SiO₂ and co-sputtering of gold, followed by annealing at 900 °C. Subsequent irradiation with 30 MeV heavy ions (Cu⁵⁺) was used to form gold nanorods. Linear and nonlinear optical properties of this material are closely related with the surface plasmon resonance in the visible. The nonlinear absorption coefficient (α₂@532 nm) for the films containing gold nanospheres was measured by Z-scan and P-scan techniques, and it was found to be isotropic and equal to −4.8 × 10⁻² cm/W. On the contrary, gold nanorods films exhibited two distinct surface plasmon resonance absorption bands giving rise to a strong anisotropic behavior, namely a polarization-dependent linear absorption and saturable absorption. Z-scan and P-scan measurements using various light polarization directions yielded nonlinear absorption coefficient (α₂@532 nm) values varying from −0.9 × 10⁻² cm/W up to −3.0 × 10⁻² cm/W. Linearity of the P-scan method in the context of nanocomposite saturable absorption is also discussed.     

Shape and size dependence of the surface plasmon resonance of gold nanoparticles studied by Photoacoustic technique

We report on the optical absorption properties of as prepared gold naoparticles of different shapes and sizes measured by photoacoustic (PA) method. The gold nanoparticles of two different shapes (dots, rods) have been prepared using the seed mediated growth method. The shape and the size of these different nanoparticles were determined by STM measurements. PA spectra show the splitting of the surface plasmon resonance (SPR) into two modes (transverse and longitudinal) in case of gold nanorods. The increase in the aspect ratio of the nanorods leads to clear redshifts of the longitudinal SPR. These shifts were used to determine the dielectric constant of the surrounding medium and its variation with the aspect ratios.     

Attenuation,scattering, and depolarization of light by gold nanorods with silver shells

Gold nanoparticles with silver nanoshells are obtained by synthesizing gold nanorods in a growing solution containing cetyltrimethylammonium bromide, subsequent separation in a concentration gradient of glycerol, and reduction of silver nitrate by ascorbic acid under alkaline conditions in the presence of polyvinylpyrrolidone. The formation of silver nanoshells was monitored by the shift of plasmon resonances of extinction and differential light scattering, by the appearance of characteristics peaks of silver in the energy dispersive X-ray (EDX) spectra of samples, by the data of transmission electron microscopy, and by visual changes in the color of colloids. The spectrum of the intensity ratio of the co- and cross-polarized compo- nents of light scattered by gold-silver nanorods is measured for the first time, and it is observed that the maximum is shifted by 80–100 nm compared to previously published spectra of gold nanorods (Khlebtsov et al., J. Phys. Chem. C 112, 12760 (2008)). The extinction and light scattering spectra are calculated by the method of separation of variables using the model of a confocal two-layer spheroid and these calculations are found to agree with spectral measurements. A method for determining the thickness of a silver nanolayer by the spectral shift of an extinction longitudinal resonance is described. The obtained data of optical spectroscopy and transmission electron microscopy and estimations of the mass of the deposited metal show that the aver-age thickness of the silver layer varies from 0.12 to 4 nm as the Ag/Au ratio changes from 2/80 to 90/80 μg/μg.     

Minimizing structural deformation of gold nanorods in plasmon-enhanced dye-sensitized solar cells

Plasmonic metal nanoparticles have shown great promise in enhancing the light absorption of organic dyes and thus improving the performance of dye-sensitized solar cells (DSSCs). However, as the plasmon resonance of spherical nanoparticles is limited to a single wavelength maximum (e.g., ~ 520 nm for Au nanoparticles), we have here utilized silica-coated gold nanorods (Au@SiO₂ NRs) to improve the performance at higher wavelengths as well. By adjusting the aspect ratio of the Au@SiO₂ NRs, we can shift their absorption maxima to better match the absorption spectrum of the utilized dye (here we targeted the 600–800 nm range). The main challenge in utilizing anisotropic nanoparticles in DSSCs is their deformation during the heating step required to sinter the mesoporous TiO₂ photoanode and we show that the Au@SiO₂ NRs start to deform already at temperatures as low as 200 °C. In order to circumvent this problem, we incorporated the Au@SiO₂ NRs in a TiO₂ nanoparticle suspension that does not need high sintering temperatures to produce a functional photoanode. With various characterization methods, we observed that adding the plasmonic particles also affected the structure of the produced films. Nonetheless, utilizing this low-temperature processing protocol, we were able to minimize the structural deformation of the gold nanorods and preserve their characteristic plasmon peaks. This allowed us to see a clear redshift of the maximum in the incident photon-to-current efficiency spectra of the plasmonic devices (Δλ ~ 14 nm), which further proves the great potential of utilizing Au@SiO₂ NRs in DSSCs.

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Graphical Abstract Undeformed gold nanorods provide an enhanced performance of dye-sensitized solar cells at high wavelengths