High-Speed Spectral Characterization of Single-Molecule SERS Fluctuations.

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.

Nano-Optical Tweezers: Methods and Applications for Trapping Single Molecules and Nanoparticles.

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.

Nano-Optical Tweezers: Methods and Applications for Trapping Single Molecules and Nanoparticles.

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.

Digital plasmonic holography with iterative phase retrieval for sensing.

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.

High-Speed Fluctuations in Surface-Enhanced Raman Scattering Intensities from Various Nanostructures.

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.

High-speed imaging of surface-enhanced Raman scattering fluctuations from individual nanoparticles.

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.

Real-Time Sensing with Patterned Plasmonic Substrates and a Compact Imager Chip.

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.

Digital plasmonic holography.

We demonstrate digital plasmonic holography for direct in-plane imaging with propagating surface-plasmon waves. Imaging with surface plasmons suffers from the lack of simple in-plane lenses and mirrors. Lens-less digital holography techniques, however, rely on digitally decoding an interference pattern between a reference wave and an object wave. With far-field diffractive optics, this decoding scheme provides a full recording, i.e., a hologram, of the amplitude and phase of the object wave, giving three-dimensional information from a two-dimensional recording. For plasmonics, only a one-dimensional recording is needed, and both the phase and amplitude of the propagating plasmons can be extracted for high-resolution in-plane imaging. Here, we demonstrate lens-less, point-source digital plasmonic holography using two methods to record the plasmonic holograms: a dual-probe near-field scanning optical microscope and lithographically defined circular fluorescent screens. The point-source geometry gives in-plane magnification, allowing for high-resolution imaging with relatively lower-resolution microscope objectives. These results pave the way for a new form of in-plane plasmonic imaging, gathering the full complex wave, without the need for plasmonic mirrors or lenses.

Holographic Plasmonic Nanotweezers for Dynamic Trapping and Manipulation.

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.

Chemically imaging bacteria with super-resolution SERS on ultra-thin silver substrates.

Plasmonic hotspots generate a blinking Surface Enhanced Raman Spectroscopy (SERS) effect that can be processed using Stochastic Optical Reconstruction Microscopy (STORM) algorithms for super-resolved imaging. Furthermore, by imaging through a diffraction grating, STORM algorithms can be modified to extract a full SERS spectrum, thereby capturing spectral as well as spatial content simultaneously. Here we demonstrate SERS and STORM combined in this way for super-resolved chemical imaging using an ultra-thin silver substrate. Images of gram-positive and gram-negative bacteria taken with this technique show excellent agreement with scanning electron microscope images, high spatial resolution at <50 nm, and spectral SERS content that can be correlated to different regions. This may be used to identify unique chemical signatures of various cells. Finally, because we image through as-deposited, ultra-thin silver films, this technique requires no nanofabrication beyond a single deposition and looks at the cell samples from below. This allows direct imaging of the cell/substrate interface of thick specimens or imaging samples in turbid or opaque liquids since the optical path doesn't pass through the sample. These results show promise that super-resolution chemical imaging may be used to differentiate chemical signatures from cells and could be applied to other biological structures of interest.

Split-Wedge Antennas with Sub-5 nm Gaps for Plasmonic Nanofocusing.

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.

Direct spectral imaging of plasmonic nanohole arrays for real-time sensing.

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.

Polarization interferometry for real-time spectroscopic plasmonic sensing.

We present quantitative, spectroscopic polarization interferometry phase measurements on plasmonic surfaces for sensing applications. By adding a liquid crystal variable wave plate in our beam path, we are able to measure phase shifts due to small refractive index changes on the sensor surface. By scanning in a quick sequence, our technique is extended to demonstrate real-time measurements. While this optical technique is applicable to different sensor geometries-e.g., nanoparticles, nanogratings, or nanoapertures-the plasmonic sensors we use here consist of an ultrasmooth gold layer with buried linear gratings. Using these devices and our phase measurement technique, we calculate a figure of merit that shows improvement over measuring only surface plasmon resonance shifts from a reflected intensity spectrum. To demonstrate the general-purpose versatility of our phase-resolved measurements, we also show numerical simulations with another common device architecture: periodic plasmonic slits. Since our technique inherently measures both the intensity and phase of the reflected or transmitted light simultaneously, quantitative sensor device characterization is possible.

Squeezing millimeter waves through a single, nanometer-wide, centimeter-long slit.

We demonstrate broadband non-resonant squeezing of terahertz (THz) waves through an isolated 2-nm-wide, 2-cm-long slit (aspect ratio of 10(7)), representing a maximum intensity enhancement factor of one million. Unlike resonant nanogap structures, a single, effectively infinitely-long slit passes incident electromagnetic waves with no cutoff, enhances the electric field within the gap with a broad 1/f spectral response, and eliminates interference effects due to finite sample boundaries and adjacent elements. To construct such a uniform, isolated slit that is much longer than the millimeter-scale spot of a THz beam, we use atomic layer lithography to pattern vertical nanogaps in a metal film over an entire 4-inch wafer. We observe an increasing field enhancement as the slit width decreases from 20 nm to 2 nm, in agreement with numerical calculations.

Dynamic placement of plasmonic hotspots for super-resolution surface-enhanced Raman scattering.

In this paper, we demonstrate dynamic placement of locally enhanced plasmonic fields using holographic laser illumination of a silver nanohole array. To visualize these focused "hotspots", the silver surface was coated with various biological samples for surface-enhanced Raman spectroscopy (SERS) imaging. Due to the large field enhancements, blinking behavior of the SERS hotspots was observed and processed using a stochastic optical reconstruction microscopy algorithm enabling super-resolution localization of the hotspots to within 10 nm. These hotspots were then shifted across the surface in subwavelength (<100 nm for a wavelength of 660 nm) steps using holographic illumination from a spatial light modulator. This created a dynamic imaging and sensing surface, whereas static illumination would only have produced stationary hotspots. Using this technique, we also show that such subwavelength shifting and localization of plasmonic hotspots has potential for imaging applications. Interestingly, illuminating the surface with randomly shifting SERS hotspots was sufficient to completely fill in a wide field of view for super-resolution chemical imaging.

Template-stripped asymmetric metallic pyramids for tunable plasmonic nanofocusing.

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.

Fabrication of smooth patterned structures of refractory metals, semiconductors, and oxides via template stripping.

The template-stripping method can yield smooth patterned films without surface contamination. However, the process is typically limited to coinage metals such as silver and gold because other materials cannot be readily stripped from silicon templates due to strong adhesion. Herein, we report a more general template-stripping method that is applicable to a larger variety of materials, including refractory metals, semiconductors, and oxides. To address the adhesion issue, we introduce a thin gold layer between the template and the deposited materials. After peeling off the combined film from the template, the gold layer can be selectively removed via wet etching to reveal a smooth patterned structure of the desired material. Further, we demonstrate template-stripped multilayer structures that have potential applications for photovoltaics and solar absorbers. An entire patterned device, which can include a transparent conductor, semiconductor absorber, and back contact, can be fabricated. Since our approach can also produce many copies of the patterned structure with high fidelity by reusing the template, a low-cost and high-throughput process in micro- and nanofabrication is provided that is useful for electronics, plasmonics, and nanophotonics.

Atomic layer lithography of wafer-scale nanogap arrays for extreme confinement of electromagnetic waves.

Squeezing light through nanometre-wide gaps in metals can lead to extreme field enhancements, nonlocal electromagnetic effects and light-induced electron tunnelling. This intriguing regime, however, has not been readily accessible to experimentalists because of the lack of reliable technology to fabricate uniform nanogaps with atomic-scale resolution and high throughput. Here we introduce a new patterning technology based on atomic layer deposition and simple adhesive-tape-based planarization. Using this method, we create vertically oriented gaps in opaque metal films along the entire contour of a millimetre-sized pattern, with gap widths as narrow as 9.9 Å, and pack 150,000 such devices on a 4-inch wafer. Electromagnetic waves pass exclusively through the nanogaps, enabling background-free transmission measurements. We observe resonant transmission of near-infrared waves through 1.1-nm-wide gaps (λ/1,295) and measure an effective refractive index of 17.8. We also observe resonant transmission of millimetre waves through 1.1-nm-wide gaps (λ/4,000,000) and infer an unprecedented field enhancement factor of 25,000.

Plasmonic nanofocusing with a metallic pyramid and an integrated C-shaped aperture.

We demonstrate the design, fabrication and characterization of a near-field plasmonic nanofocusing probe with a hybrid tip-plus-aperture design. By combining template stripping with focused ion beam lithography, a variety of aperture-based near-field probes can be fabricated with high optical performance. In particular, the combination of large transmission through a C-shaped aperture aligned to the sharp apex (<10 nm radius) of a template-stripped metallic pyramid allows the efficient delivery of light--via the C-shaped aperture--while providing a nanometric hotspot determined by the sharpness of the tip itself.

Highly reproducible near-field optical imaging with sub-20-nm resolution based on template-stripped gold pyramids.

With a template-stripping fabrication technique, we demonstrate the mass fabrication of high-quality, uniform, ultrasharp (10 nm) metallic probes suitable for single-molecule fluorescence imaging, tip-enhanced Raman spectroscopy (TERS), and other near-field imaging techniques. We achieve reproducible single-molecule imaging with sub-20-nm spatial resolution and an enhancement in the detected fluorescence signal of up to 200. Similar results are obtained for TERS imaging of carbon nanotubes. We show that the large apex angle (70.5°) of our pyramidal tip is well suited to scatter the near-field optical signal into the far-field, leading to larger emission enhancement and hence to a larger quantum yield. Each gold or silver pyramidal probe is used on-demand, one at a time, and the unused tips can be stored for extended times without degradation or contamination. The high yield (>95%), reproducibility, durability, and massively parallel fabrication (1.5 million identical probes over a wafer) of the probes hold promise for reliable optical sensing and detection and for cementing near-field optical imaging and spectroscopy as a routine characterization technique.