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.
We present a plasmon-active hybrid nanomaterial design with electrochemical tunability of the localized surface plasmon resonances. The plasmonic-active nanostructures are composed of silver nanocube ...aggregates embedded into an electrochromic polymer coating on an indium tin oxide electrode with the nanocube aggregation controlled by the surface pressure. Such polymer–nanocube hybrid nanomaterials demonstrated unique tunable plasmonic behavior under an applied electrochemical potential. A significant reversible experimental peak shift of 22 nm at an electrical potential of 200 mV has been achieved in these measurements. Finite-difference time-domain (FDTD) simulations show that, under full oxidation potential, a maximal spectral shift of ca. 80 nm can be potentially achieved, which corresponds to a high sensitivity of 178 nm per refractive index unit. Furthermore, FDTD modeling suggests that the electrochemically controlled tunability of plasmonic peaks is caused by reversible changes in the refractive index of the electrochromic polymer coating caused by oxidation or reduction reactions under external electrical potential. Consequently, we define the orthogonal plasmonic resonance shift as a shift that is orthogonal to the redox process responsible for the refractive index change. On the basis of these results, we suggest that the combination of anisotropic nanostructures and electrochromic matrix has the potential to reversibly electrically tune plasmonic resonances over the full visible spectrum.
Electromagnetic radiation of a certain frequency can excite the collective oscillation of the free electrons in metallic nanostructures using localized surface plasmon resonances (LSPRs), and this ...phenomenon can be used for a variety of optical and electronic functionalities. However, nanostructure design over a large area using controlled LSPR features is challenging and requires high accuracy. In this article, we offer an overview of the efforts made by our group to implement a wrinkle-assisted colloidal particle assembly method to approach this challenge from a different angle. First, we introduce the controlled wrinkling process and discuss the underlying theoretical framework. We then set out how the wrinkled surfaces are utilized to guide the self-assembly of colloidal nanoparticles of various surface chemistry, size, and shape. Subsequently, template-assisted colloidal self-assembly mechanisms and a general guide for particle assembly beyond plasmonics will be presented. In addition, we also discuss the collective plasmonic behavior in depth, including strong plasmonic coupling due to nanoscale gap size as well as magnetic mode excitation and demonstrate the potential applications of wrinkle-assisted colloidal particle assembly method in the field of mechanoresponsive metasurfaces and surface-enhanced spectroscopy. Lastly, a general perspective in the field of template-assisted colloidal assembly with regard to potential applications in plasmonic photocatalysis, solar cells, optoelectronics, and sensing devices is provided.
Dynamic control of circular polarization in chiral metasurfaces is being used in many photonic applications. However, simple fabrication routes to create chiral materials with considerable and fully ...tunable chiroptical responses at visible and near-infrared wavelengths are scarce. Here, we describe a scalable bottom-up approach to construct cross-stacked nanoparticle chain arrays that have a circular dichroism of up to 11°. Due to their layered design, the strong superchiral fields of the inter-layer region are accessible to chiral analytes, resulting in a tenfold enhanced sensitivity in a chiral sensing proof-of-concept experiment. In situ restacking and local mechanical compression enables full control over the entire set of circular dichroism characteristics, namely sign, magnitude and spectral position. Strain-induced reconfiguration opens up an intriguing route towards actively controlled pixel arrays using local deformation, which fosters continuous polarization engineering and multi-channel detection.
We demonstrate a novel colloidal self-assembly approach toward obtaining mechanically tunable, cost-efficient, and low-loss plasmonic nanostructures that show pronounced optical anisotropy upon ...mechanical deformation. Soft lithography and template-assisted colloidal self-assembly are used to fabricate a stretchable periodic square lattice of gold nanoparticles on macroscopic areas. We stress the impact of particle size distribution on the resulting optical properties. To this end, lattices of narrowly distributed particles (∼2% standard deviation in diameter) are compared with those composed of polydisperse ones (∼14% standard deviation). The enhanced particle quality sharpens the collective surface lattice resonances by 40% to achieve a full width at half-maximum as low as 16 nm. This high optical quality approaches the theoretical limit for this system, as revealed by electromagnetic simulations. One hundred stretching cycles demonstrate a reversible transformation from a square to a rectangular lattice, accompanied by polarization-dependent optical properties. On the basis of these findings we envisage the potential applications as strain sensors and mechanically tunable filters.
For many photonic applications, it is important to confine light of a specific wavelength at a certain volume of interest at low losses. So far, it is only possible to use the polarized light ...perpendicular to the solid grid lines to excite waveguide–plasmon polaritons in a waveguide-supported hybrid structure. In our work, we use a plasmonic grating fabricated by colloidal self-assembly and an ultrathin injection layer to guide the resonant modes selectively. We use gold nanoparticles self-assembled in a linear template on a titanium dioxide (TiO2) layer to study the dispersion relation with conventional ultraviolet–visible–near-infrared spectroscopic methods. Supported with finite-difference in time-domain simulations, we identify the optical band gaps as hybridized modes: plasmonic and photonic resonances. Compared to metallic grids, the observation range of hybridized guided modes can now be extended to modes along the nanoparticle chain lines. With future applications in energy conversion and optical filters employing these cost-efficient and upscalable directed self-assembly methods, we discuss also the application in refractive index sensing of the particle-based hybridized guided modes.
In this contribution, the optical losses and gains attributed to periodic nanohole array electrodes in polymer solar cells are systematically studied. For this, thin gold nanomeshes with hexagonally ...ordered holes and periodicities (P) ranging from 202 nm to 2560 nm are prepared by colloidal lithography. In combination with two different active layer materials (P3HT:PC
BM and PTB7:PC
BM), the optical properties are correlated with the power conversion efficiency (PCE) of the solar cells. A cavity mode is identified at the absorption edge of the active layer material. The resonance wavelength of this cavity mode is hardly defined by the nanomesh periodicity but rather by the absorption of the photoactive layer. This constitutes a fundamental dilemma when using nanomeshes as ITO replacement. The highest plasmonic enhancement requires small periodicities. This is accompanied by an overall low transmittance and high parasitic absorption losses. Consequently, larger periodicities with a less efficient cavity mode, yet lower absorptive losses were found to yield the highest PCE. Nevertheless, ITO-free solar cells reaching ~77% PCE compared to ITO reference devices are fabricated. Concomitantly, the benefits and drawbacks of this transparent nanomesh electrode are identified, which is of high relevance for future ITO replacement strategies.
We report a facile synthesis of Au-based cubic nanoboxes as small as 20 nm for the outer edge length, together with well-defined openings at the corners and walls fewer than 10 atomic layers (or <2 ...nm) in thickness. The success relies on the selective formation of Ag2O at the corners of Ag nanocubes, followed by the conformal deposition of Au on the side faces in a layer-by-layer fashion. When six atomic layers of Au are formed on the side faces to generate Ag@Au6L core–shell nanocubes, we can selectively remove the Ag2O patches at the corner sites using a weak acid, making it possible to further remove the Ag core by H2O2 etching without breaking the ultrathin Au shell. This synthetic approach works well for Ag nanocubes of 38 and 18 nm in edge length, and the wall thickness of the nanoboxes can be controlled down to 2 nm. The resultant Au nanoboxes exhibit strong plasmonic absorption in the near-infrared region, consistent with computational simulations.
Hollow and porous core–shell nanostructures with defined interior nanogaps are of great significance in the field of surface-enhanced Raman scattering (SERS) applications because of the presence of ...intrinsic electromagnetic (EM) hot spots, multipolar resonances, and multiple facets. Further, nanomaterials having extinction in the near-infrared (NIR) region are particularly important for SERS and biomedical applications, and thus it is highly desirable to synthesize NIR-active plasmonic nanostructures. Herein, we report the synthesis of gold nanocapsules having a solid Au bead as core and a thin-porous rod-shaped shell with extinction in both NIR I and NIR II regions. Thermally induced twinned seeds were used for the silver-free synthesis of pentatwinned Au bead, which served as the foundation for the directed growth of Ag nanorods, which was finally converted to Au nanocapsules following galvanic replacement reaction (GRR). Detailed investigation was carried out to understand the effect of thermal treatment duration in the seed morphology and its subsequent growth to anisotropic Au beads. Ag overgrowth on Au beads yielded uniform Au-bead@Ag nanorods whose size can be tuned by varying the Ag precursor. Five different sized Au-bead@Ag nanorods were studied, and they were converted to Au nanocapsules following GRR. We explored the size-dependent SERS activity of the prepared Au nanocapsules along with their comparison with solid pentatwinned Au beads and found that the smallest sized Au nanocapsules were the best SERS performers. Finite-difference time-domain simulation revealed the presence of intense EM hot spots in the smallest sized Au nanocapsule and corroborated the experimental SERS data. Finally, we fabricated a simple flexible cellulose-based SERS substrate by using the smallest sized Au nanocapsules and investigated its SERS sensing ability for the detection of 2-napthalenethiol (2-NT), as a model analyte, and were able to achieve its detection down to 1 fM concentration.
Metallic nanostructures exhibit strong interactions with electromagnetic radiation, known as the localized surface plasmon resonance. In recent years, there is significant interest and growth in the ...area of coupled metallic nanostructures. In such assemblies, short‐ and long‐range coupling effects can be tailored and emergent properties, e.g., metamaterial effects, can be realized. The term “plasmonic metasurfaces” is used for this novel class of assemblies deposited on planar surfaces. Herein, the focus is on plasmonic metasurfaces formed from colloidal particles. These are formed by self‐assembly and can meet the demands of low‐cost manufacturing of large‐area, flexible, and ultrathin devices. The advances in high optical quality of the colloidal building blocks and methods for controlling their self‐assembly on surfaces will lead to novel functional devices for dynamic light modulators, pulse sharpening, subwavelength imaging, sensing, and quantum devices. This progress report focuses on predicting optical properties of single colloidal building blocks and their assemblies, wet‐chemical synthesis, and directed self‐assembly of colloidal particles. The report concludes with a discussion of the perspectives toward expanding the colloidal plasmonic metasurfaces concept by integrating them with quantum emitters (gain materials) or mechanically responsive structures.
Self‐assembly concepts for colloidal metasurfaces via incremental increase in the number of particles are reviewed here: from colloidal particles as building blocks, to unit cells from few colloids dominated by near‐field coupling, over 1D plasmonic “polymers,” to collective coupling within particle clusters, and 2D plasmonic lattices with long‐distance coupling.
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