RESUMO
Propagating surface plasmon waves have been used for many applications including imaging and sensing. However, direct in-plane imaging of micro-objects with surface plasmon waves suffers from the lack of simple, two-dimensional lenses, mirrors, and other optical elements. In this paper, we apply lensless digital holographic techniques and leakage radiation microscopy to achieve in-plane surface imaging with propagating surface plasmon waves. As plasmons propagate in two-dimensions and scatter from various objects, a hologram is formed over the surface. Iterative phase retrieval techniques applied to this hologram remove twin image interference for high-resolution in-plane imaging and enable further applications in real-time plasmonic phase sensing.
RESUMO
The front cover artwork is provided by Prof. Sang-Hyun Oh's group at the University of Minnesota. The image shows the optical trapping of chiral nanoparticles using coaxial nano-optical tweezers, devices capable of harnessing light to manipulate objects a few nanometers in size. Read the full text of the Review at 10.1002/cphc.202100004.
RESUMO
Optical tweezers were developed in 1970 by Arthur Ashkin as a tool for the manipulation of micron-sized particles. Ashkin's original design was then adapted for a variety of purposes, such as trapping and manipulation of biological materials[1] and the laser cooling of atoms.[2,3] More recent development has led to nano-optical tweezers, for trapping particles on the scale of only a few nanometers, and holographic tweezers, which allow for dynamic control of multiple traps in real-time. These alternatives to conventional optical tweezers have made it possible to trap single molecules and to perform a variety of studies on them. Presented here is a review of recent developments in nano-optical tweezers and their current and future applications.
RESUMO
We demonstrate dynamic trapping and manipulation of nanoparticles with plasmonic holograms. By tailoring the illumination pattern of an incident light beam with a computer-controlled spatial light modulator, constructive and destructive interference of plasmon waves create a focused hotspot that can be moved across a surface. Specifically, a computer-generated hologram illuminating the perimeter of a silver Bull's Eye nanostructure generates surface plasmons that propagate toward the center. Shifting the phase of the plasmon waves as a function of space gives complete control over the location of the focus. We show that 200 nm diameter nanoparticles trapped in this focus can be moved in arbitrary patterns. This allows, for example, circular motion with linearly polarized light. These results show the versatility of holographically generated surface plasmon waves for advanced trapping and manipulation of nanoparticles.
RESUMO
We present a novel plasmonic antenna structure, a split-wedge antenna, created by splitting an ultrasharp metallic wedge with a nanogap perpendicular to its apex. The nanogap can tightly confine gap plasmons and boost the local optical field intensity in and around these opposing metallic wedge tips. This three-dimensional split-wedge antenna integrates the key features of nanogaps and sharp tips, i.e., tight field confinement and three-dimensional nanofocusing, respectively, into a single platform. We fabricate split-wedge antennas with gaps that are as small as 1 nm in width at the wafer scale by combining silicon V-grooves with template stripping and atomic layer lithography. Computer simulations show that the field enhancement and confinement are stronger at the tip-gap interface compared to what standalone tips or nanogaps produce, with electric field amplitude enhancement factors exceeding 50 when near-infrared light is focused on the tip-gap geometry. The resulting nanometric hotspot volume is on the order of λ3/106. Experimentally, Raman enhancement factors exceeding 107 are observed from a 2 nm gap split-wedge antenna, demonstrating its potential for sensing and spectroscopy applications.
RESUMO
Plasmon-enhanced optical transmission through arrays of nano-structured holes has led to the development of a new generation of optical sensors. In this paper, to dramatically simplify the standard optical setups of these sensors, we position the nanoholes, an LED illumination source and a spacer layer directly on top of a CMOS imager chip. Transmitted light diffracts from the nanohole array, spreading into a spectrum over the space of a millimeter to land on the imager as a full spectrum. Our chip is used as a sensor in both a liquid and a gas environment. The spectrum is monitored in real-time and the plasmon-enhanced transmission peaks shift upon exposure to different concentrations of glycerol-in-water solutions or ethanol vapors in nitrogen. While liquids provide good refractive index contrast for sensing, to enhance sensitivity to solvent vapors, we filled the nanoholes with solvatochromic dyes. This on-chip solution circumvents the bulky components (e.g. microscopes, coupling optics, and spectrometers) needed for traditional plasmonic sensing setups, uses the nanohole array as both the sensing surface and a diffraction grating, and maintains good sensitivity. Finally, we show simultaneous sensing from two side-by-side locations, demonstrating potential for multiplexing and lab on a chip integration.
RESUMO
We demonstrate a novel scheme for plasmonic nanofocusing with internally illuminated asymmetric metallic pyramidal tips using linearly polarized light. A wafer-scale array of sharp metallic pyramids is fabricated via template stripping with films of different thicknesses on opposing pyramid facets. This structural asymmetry is achieved through a one-step angled metal deposition that does not require any additional lithography processing and when internally illuminated enables the generation of plasmons using a Kretschmann-like coupling method on only one side of the pyramids. Plasmons traveling toward the tip on one side will converge at the apex, forming a nanoscale "hotspot." The asymmetry is necessary for these focusing effects since symmetric pyramids display destructive plasmon interference at the tip. Computer simulations confirm that internal illumination with linearly polarized light at normal incidence on these asymmetric pyramids will focus optical energy into nanoscale volumes. Far-field optical experiments demonstrate large field enhancements as well as angle-dependent spectral tuning of the reradiated light. Because of the low background light levels, wafer-scale fabrication, and a straightforward excitation scheme, these asymmetric pyramidal tips will find applications in near-field optical microscopy and array-based optical trapping.
Assuntos
Ouro/química , Nanoestruturas/química , Nanotecnologia , Ressonância de Plasmônio de Superfície , Luz , Espalhamento de RadiaçãoRESUMO
The concept of plasmonic "hotspots" is central to the broad field of nanophotonics. In surface-enhanced Raman scattering (SERS), hotspots can increase Raman scattering efficiency by orders of magnitude. Hotspot dimensions may range from a few nanometers down to the atomic scale and are able to generate SERS signals from single molecules. However, these single-molecule SERS signals often show significant fluctuations, and the concept of intense, localized, yet static hotspots has come into question. Recent experiments have shown these SERS intensity fluctuations (SIFs) to occur over an extremely wide range of timescales, from seconds to microseconds, due to the various physical mechanisms causing SERS and the dynamic nature of light-matter interaction at the nanoscale. The underlying source of single-molecule SERS fluctuations is therefore likely to be a complex interplay of several different effects at different timescales. A high-speed acquisition system that captures a full SERS spectrum with microsecond time resolution can therefore provide information about these dynamic processes. Here, we show an acquisition system that collects at a rate of 100,000 SERS spectra per second, allowing high-speed characterization. We find that while each individual SIF event will enhance a different portion of the SERS spectrum, including a single peak, over 10s to 100s of microseconds, the SIF events overall do not favor one region of the spectrum over another. These high-speed SIF events can therefore occur with relatively equal probability over a broad spectral range, covering both the anti-Stokes and the Stokes sides of the spectrum, sometimes leading to anomalously large anti-Stokes peaks. This indicates that both temporally and spectrally transient hotspots drive the SERS fluctuations at high speeds.
RESUMO
Metallic nanostructures now play an important role in many applications. In particular, for the emerging fields of plasmonics and nanophotonics, the ability to engineer metals on nanometric scales allows the development of new devices and the study of exciting physics. This review focuses on top-down nanofabrication techniques for engineering metallic nanostructures, along with computational and experimental characterization techniques. A variety of current and emerging applications are also covered.
Assuntos
Nanopartículas Metálicas , Nanotecnologia/métodos , Técnicas Biossensoriais , Engenharia , Nanopartículas Metálicas/química , Nanopartículas Metálicas/ultraestrutura , Fenômenos Ópticos , Pontos Quânticos , Análise Espectral Raman , Ressonância de Plasmônio de SuperfícieRESUMO
While atomic layer deposition (ALD) has been used for many years as an industrial manufacturing method for microprocessors and displays, this versatile technique is finding increased use in the emerging fields of plasmonics and nanobiotechnology. In particular, ALD coatings can modify metallic surfaces to tune their optical and plasmonic properties, to protect them against unwanted oxidation and contamination, or to create biocompatible surfaces. Furthermore, ALD is unique among thin-film deposition techniques in its ability to meet the processing demands for engineering nanoplasmonic devices, offering conformal deposition of dense and ultra-thin films on high-aspect-ratio nanostructures at temperatures below 100 °C. In this review, we present key features of ALD and describe how it could benefit future applications in plasmonics, nanosciences, and biotechnology.
RESUMO
We demonstrate precise three-dimensional integration of smooth bumps, grooves, and apertures in optically thick metal films using template stripping. Patterned silicon wafers are used as high-quality, reusable templates. The heights or depths of the metallic features are controlled to within 2 nm, giving continuously tunable optical properties with sharp and intense plasmonic resonances. Furthermore, we demonstrate a pick-and-place template stripping method in situ, enabling versatile three-dimensional micromanipulation, imaging, and characterization of nanoscale devices.
Assuntos
Técnicas Biossensoriais/métodos , Nanotecnologia/métodos , Técnicas Biossensoriais/instrumentação , Desenho de Equipamento , Íons , Metais , Microscopia Eletrônica de Varredura/métodos , Óptica e Fotônica , Silício/químicaRESUMO
This perspective gives an overview of recent developments in surface-enhanced Raman scattering (SERS) for biosensing. We focus this review on SERS papers published in the last 10 years and to specific applications of detecting biological analytes. Both intrinsic and extrinsic SERS biosensing schemes have been employed to detect and identify small molecules, nucleic acids, lipids, peptides, and proteins, as well as for in vivo and cellular sensing. Current SERS substrate technologies along with a series of advancements in surface chemistry, sample preparation, intrinsic/extrinsic signal transduction schemes, and tip-enhanced Raman spectroscopy are discussed. The progress covered herein shows great promise for widespread adoption of SERS biosensing.
Assuntos
Técnicas Biossensoriais/métodos , Análise Espectral Raman/métodos , Anticorpos/química , Anticorpos/imunologia , Aptâmeros de Nucleotídeos/química , DNA/química , Enzimas/química , Nanopartículas Metálicas/química , Peptídeos/química , Proteínas/químicaRESUMO
Nanometric gaps in noble metals can harness surface plasmons, collective excitations of the conduction electrons, for extreme subwavelength localization of electromagnetic energy. Positioning molecules within such metallic nanogaps dramatically enhances light-matter interactions, increasing absorption, emission, and, most notably, surface-enhanced Raman scattering (SERS). However, the lack of reproducible high-throughput fabrication techniques with nanometric control over the gap size has limited practical applications. Here we show sub-10-nm metallic nanogap arrays with precise control of the gap's size, position, shape, and orientation. The vertically oriented plasmonic nanogaps are formed between two metal structures by a sacrificial layer of ultrathin alumina grown using atomic layer deposition. We show increasing local SERS enhancements of up to 10(9) as the nanogap size decreases to 5 nm. Because these sub-10-nm gaps can be fabricated at high densities using conventional optical lithography over an entire wafer, these results will have significant implications for spectroscopy and nanophotonics.
RESUMO
We demonstrate three-dimensional plasmonic nanofocusing of light with patterned metallic pyramids obtained via template stripping. Gratings on the faces of these pyramids convert linearly polarized light into plasmons that propagate toward and converge at a approximately 10 nm apex. Experiments and computer simulations confirm that optical energy is focused into a nanoscale volume (5 x 10(-5) wavelength(3)). Because these structures are easily and reproducibly fabricated, our results could benefit many applications, including imaging, sensing, lithography, and nonlinear spectroscopy.
Assuntos
Nanotecnologia/instrumentação , Ressonância de Plasmônio de Superfície/instrumentação , Simulação por Computador , LuzRESUMO
The observation of single molecule events using surface-enhanced Raman scattering (SERS) is a well-established phenomenon. These events are characterized by strong fluctuations in SERS intensities. High-speed SERS intensity fluctuations (in the microsecond time scale) have been reported for experiments involving single metallic particles. In this work, the high-speed SERS behavior of six different types of nanostructured metal systems (Ag nanoshells, Ag nanostars, Ag aggregated spheres, Au aggregated spheres, particle-on-mirror, and Ag deposited on microspheres) was investigated. All systems demonstrated high-speed SERS intensity fluctuations. Statistical analysis of the duration of the SERS fluctuations yielded tailed distributions with average event durations around 100 µs. Although the characteristics of the fluctuations seem to be random, the results suggest interesting differences between the system that might be associated with the strength distribution and density of the localized SERS hotspots. For instance, systems with more localized fields, such as nanostars, present faster fluctuation bursts compared to metallic aggregates that support spread-out fields. The results presented here appear to confirm that high-speed SERS intensity fluctuations are a fundamental characteristic of the SERS effect.
RESUMO
We present nanohole arrays in thin gold films as sub-micron resolution surface plasmon resonance (SPR) imaging pixels in a microarray format. With SPR imaging, the resolution is not limited by diffraction, but by the propagation of surface plasmon waves to adjacent sensing areas, or nanohole arrays, causing unwanted interference. For ultimate scalability, several issues need to be addressed, including: (1) as several nanohole arrays are brought close to each other, surface plasmon interference introduces large sources of error; and (2) as the size of the nanohole array is reduced, i.e. fewer holes, detection sensitivity suffers. To address these scalability issues, we surround each biosensing pixel (a 3-by-3 nanohole array) with plasmonic Bragg mirrors, blocking interference between adjacent SPR sensing pixels for high-density packing, while maintaining the sensitivity of a 50 x larger footprint pixel (a 16-by-16 nanohole array). We measure real-time, label-free streptavidin-biotin binding kinetics with a microarray of 600 sub-micron biosensing pixels at a packing density of more than 10(7) per cm(2).
Assuntos
Dispositivos Lab-On-A-Chip , Nanotecnologia/instrumentação , Ressonância de Plasmônio de Superfície/instrumentação , Biotina/metabolismo , Dimetilpolisiloxanos/química , Cinética , Microscopia de Força Atômica , Microscopia Eletrônica de Varredura , Sensibilidade e Especificidade , Estreptavidina/metabolismoRESUMO
We present nanohole arrays in a gold film integrated with a six-channel microfluidic chip for parallel measurements of molecular binding kinetics. Surface plasmon resonance effects in the nanohole arrays enable real-time, label-free measurements of molecular binding events in each channel, while adjacent negative reference channels can record measurement artifacts such as bulk solution index changes, temperature variations, or changing light absorption in the liquid. With the use of this platform, streptavidin-biotin specific binding kinetics are measured at various concentrations with negative controls. A high-density microarray of 252 biosensing pixels is also demonstrated with a packing density of 10(6) sensing elements/cm(2), which can potentially be coupled with a massively parallel array of microfluidic channels for protein microarray applications.
Assuntos
Análise em Microsséries/instrumentação , Nanotecnologia/instrumentação , Ressonância de Plasmônio de Superfície/instrumentação , Biotina/metabolismo , Simulação por Computador , Injeções , Cinética , Lasers , Técnicas Analíticas Microfluídicas , Modelos Moleculares , Estreptavidina/metabolismo , Técnica de Subtração , TemperaturaRESUMO
We present a simple and massively parallel nanofabrication technique to produce self-assembled periodic nanohole arrays over a millimeter-sized area of metallic film, with a tunable hole shape, diameter, and periodicity. Using this method, 30 x 30 microm(2) defect-free areas of 300 nm diameter or smaller holes were obtained in silver; this area threshold is critical because it is larger than the visible wavelength propagation length of surface plasmon waves ( approximately 27 microm) in the silver film. Measured optical transmission spectra show highly homogeneous characteristics across the millimeter-size patterned area, and they are in good agreement with FDTD simulations. The simulations also reveal intense electric fields concentrated near the air/silver interface, which was used for surface-enhanced Raman spectroscopy (SERS). Enhancement factors (EFs) measured with different hole shape and excitation wavelengths on the self-assembled nanohole arrays were 10(4)-10(6). With an additional Ag electroless plating step, the EF was further increased up to 3 x 10(6). The periodic nanohole arrays produced using this tunable self-assembly method show great promise as inexpensive SERS substrates as well as surface plasmon resonance biosensing platforms.
Assuntos
Nanoestruturas/química , Ressonância de Plasmônio de Superfície/métodos , Técnicas Biossensoriais/métodos , Microscopia de Força Atômica , Nanoestruturas/ultraestrutura , Nanotecnologia/métodos , Análise Espectral RamanRESUMO
Optical sensing is an important research field due to its proven ability to be extremely sensitive, nondestructive, and applicable to sensing a wide range of chemical, thermal, electric, or magnetic phenomena. Beyond traditional optical sensors that often rely on bulky setups, plasmonic nanostructures can offer many advantages based on their sensitivity, compact form, cost-effectiveness, multiplexing compatibility, and compatibility with many standard semiconductor nanofabrication techniques. In particular, plasmon-enhanced optical transmission through arrays of nanostructured holes has led to the development of a new generation of optical sensors. In this chapter we present a simple fabrication technique to use plasmonic nanostructures as compact sensors. We position the nanohole array, an LED illumination source, and a spacer layer directly on top of a standard complementary metal-oxide-semiconductor (CMOS) imager chip. This setup is a viable sensor platform in both liquid and gas environments. These devices could operate as low-cost sensors for environmental monitoring, security, food safety, or monitoring small-molecule binding to extract affinity information and binding constants.
Assuntos
Nanoestruturas/química , Nanotecnologia/métodos , Dispositivos Ópticos , Tecnologia de Sensoriamento Remoto/instrumentação , Semicondutores , Metais/química , Miniaturização/métodos , Nanotecnologia/economia , Óxidos/química , Tecnologia de Sensoriamento Remoto/economia , Fatores de TempoRESUMO
The concept of plasmonic hotspots is central to the interpretation of the surface-enhanced Raman scattering (SERS) effect. Although plasmonic hotspots are generally portrayed as static features, single-molecule SERS (SM-SERS) is marked by characteristic time-dependent fluctuations in signal intensity. The origin of those fluctuations can be assigned to a variety of dynamic and complex processes, including molecular adsorption or desorption, surface diffusion, molecular reorientation and metal surface reconstruction. Since each of these mechanisms simultaneously contributes to a fluctuating SERS signal, probing their relative impact in SM-SERS remains an experimental challenge. Here, we introduce a super-resolution imaging technique with an acquisition rate of 800,000 frames per second to probe the spatial and temporal features of the SM-SERS fluctuations from single silver nanoshells. The technique has a spatial resolution of ~7 nm. The images reveal short ~10 µs scattering events localized in various regions on a single nanoparticle. Remarkably, even a fully functionalized nanoparticle was 'dark' more than 98% of the time. The sporadic SERS emission suggests a transient hotspot formation mechanism driven by a random reconstruction of the metallic surface, an effect that dominates over any plasmonic resonance of the particle itself. Our results provide the SERS community with a high-speed experimental approach to study the fast dynamic properties of SM-SERS hotspots in typical room-temperature experimental conditions, with possible implications in catalysis and sensing.