We present ensembles of surface-ordered nanoparticle arrangements, which are formed by template-assisted self-assembly of monodisperse, protein-coated gold nanoparticles in wrinkle templates. Centimeter-squared areas of highly regular, linear assemblies with tunable line width are fabricated and their extinction cross sections can be characterized by conventional UV/vis/NIR spectroscopy. Modeling based on electrodynamic simulations shows a clear signature of strong plasmonic coupling with an interparticle spacing of 1–2 nm. We find evidence for well-defined plasmonic modes of quasi-infinite chains, such as resonance splitting and multiple radiant modes. Beyond elementary simulations on the individual chain level, we introduce an advanced model, which considers the chain length distribution as well as disorder. The step toward macroscopic sample areas not only opens perspectives for a range of applications in sensing, plasmonic light harvesting, surface enhanced spectroscopy, and information technology but also eases the investigation of hybridization and metamaterial effects fundamentally.
Inspired by the concept of living polymerization reaction, we are able to produce silver–gold–silver nanowires with a precise control over their total length and plasmonic properties by establishing a constant silver deposition rate on the tips of penta-twinned gold nanorods used as seed cores. Consequently, the length of the wires increases linearly in time. Starting with ∼210 nm × 32 nm gold cores, we produce nanowire lengths up to several microns in a highly controlled manner, with a small self-limited increase in thickness of ∼4 nm, corresponding to aspect ratios above 100, whereas the low polydispersity of the product allows us to detect up to nine distinguishable plasmonic resonances in a single colloidal solution. We analyze the spatial distribution and the nature of the plasmons by electron energy loss spectroscopy and obtain excellent agreement between measurements and electromagnetic simulations, clearly demonstrating that the presence of the gold core plays a marginal role, except for relatively short wires or high-energy modes.
In this work, we investigate the ligand exchange of cetyltrimethylammonium bromide (CTAB) with bovine serum albumin for gold nanorods. We demonstrate by surface-enhanced Raman scattering measurements that CTAB, which is used as a shape-directing agent in the particle synthesis, is completely removed from solution and particle surface. Thus, the protein-coated nanorods are suitable for bioapplications, where cationic surfactants must be avoided. At the same time, the colloidal stability of the system is significantly increased, as evidenced by spectroscopic investigation of the particle longitudinal surface plasmon resonance, which is sensitive to aggregation. Particles are stable at very high concentrations (cAu 20 mg/mL) in biological media such as phosphate buffer saline or Dulbecco’s Modified Eagle’s Medium and over a large pH range (2–12). Particles can even be freeze-dried (lyophilized) and redispersed. The protocol was applied to gold nanoparticles with a large range of aspect ratios and sizes with main absorption frequencies covering the visible and the near-IR spectral range from 600 to 1100 nm. Thus, these colloidally stable and surfactant-free protein-coated nanoparticles are of great interest for various plasmonic and biomedical applications.
We investigate the effect of surfactant-mediated, asymmetric silver overgrowth of gold nanorods on their intrinsic optical properties. From concentration-dependent experiments, we established a close correlation of the extinction in the UV/vis/NIR frequency range and the morphological transition from gold nanorods to Au@Ag cuboids. Based on this correlation, a generic methodology for in situ monitoring of the evolution of the cuboid morphology was developed and applied in time-dependent experiments. We find that growth rates are sensitive to the substitution of the surfactant headgroup by comparison of benzylhexadecyldimethylammonium chloride (BDAC) with hexadecyltrimethylammonium chloride (CTAC). The time-dependent overgrowth in BDAC proceeds about 1 order of magnitude slower than in CTAC, which allows for higher control during silver overgrowth. Furthermore, silver overgrowth results in a qualitatively novel optical feature: Upon excitation inside the overlap region of the interband transition of gold and intraband of silver, the gold core acts as a retarding element. The much higher damping of the gold core compared to the silver shell in Au@Ag cuboids induces mirror charges at the core/shell interface as shown by electromagnetic simulations. Full control over the kinetic growth process consequently allows for precise tailoring of the resonance wavelengths of both modes. Tailored and asymmetric silver-overgrown gold nanorods are of particular interest for large-scale fabrication of nanoparticles with intrinsic metamaterial properties. These building blocks could furthermore find application in optical sensor technology, light harvesting, and information technology.
Here, a new surface enhanced Raman spectroscopy (SERS) platform suitable for gas phase sensing based on the extended organization of poly-N-isopropylacrylamide (pNIPAM)-coated nanostars over large areas is presented. This system yields high and homogeneous SERS intensities, and simultaneously traps organic chemical agents as pollutants from the gas phase. pNIPAM-coated gold nanostars were organized into parallel linear arrays. The optical properties of the fabricated substrates are investigated, and applicability for advanced sensing is demonstrated through the detection in the gas phase of pyrene traces, a well-known polyaromatic hydrocarbon.
We demonstrate the large-scale organisation of anisotropic nanoparticles into linear assemblies displaying optical anisotropy on macroscopic areas. Monodisperse gold nanorods with a hydrophilic protein shell are arranged by dip-coating on wrinkled surfaces and subsequently transferred to indium tin oxide (ITO) substrates by capillary transfer printing. We elucidate how tuning the wrinkle amplitude enables us to precisely adjust the assembly morphology and fabricate single, double and triple nanorod lines. For the single lines, we quantify the order parameter of the assemblies as well as interparticle distances from scanning electron microscopy (SEM) images. We find an order parameter of 0.97 and a mean interparticle gap size of 7 nm. This combination of close to perfect uni-axial alignment and close-packing gives rise to pronounced macroscopic anisotropic optical properties due to strong plasmonic coupling. We characterise the optical response of the assemblies on ITO-coated glass via UV/vis/NIR spectroscopy and determine an optical order parameter of 0.91. The assemblies are thus plasmonic metamaterials, as their periodicity and building block sizes are well below the optical wavelength. The presented approach does not rely on lithographic patterning and provides access to functional materials, which could have applications in subwavelength waveguiding, photovoltaics, and for large-area metamaterial fabrication.
Modern‐day wonders of the world: Nanostructured films of plasmonic pyramid arrays (see picture) were prepared by the simple stamping of preformed homogeneous nanocolloids. These materials show very high efficiency as optical enhancers and can be exploited for the design of quantitative, cheap, portable, and ultrasensitive optical sensors with excellent reversibility.
Nanorattles are metallic core-shell particles with core and shell separated by a dielectric spacer. These nanorattles have been identified as a promising class of nanoparticles, due to their extraordinary high electric-field enhancement inside the cavity. Limiting factors are reproducibility and loss of axial symmetry owing to the movable metal core; movement of the core results in fluctuation of the nanocavity dimensions and commensurate variations in enhancement factor. We present a novel synthetic approach for the robust fixation of the central gold rod within a well-defined box, which results in an axisymmetric nanorattle. We determine the structure of the resulting axisymmetric nanorattles by advanced transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Optical absorption and scattering cross-sections obtained from UV-vis-NIR spectroscopy quantitatively agree with finite-difference time-domain (FDTD) simulations based on the structural model derived from SAXS. The predictions of high and homogenous field enhancement are evidenced by scanning TEM electron energy loss spectroscopy (STEM-EELS) measurement on single-particle level. Thus, comprehensive understanding of structural and optical properties is achieved for this class of nanoparticles, paving the way for photonic applications where a defined and robust unit cell is crucial.
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