The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

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Present and Future of Surface-Enhanced Raman Scattering

The importance of the Fano resonance concept is recognized across multiple fields of physics. In this Review, Fano resonance is explored in the context of optics, with particular emphasis on dielectric nanostructures and metasurfaces. Rapid progress in photonics and nanotechnology brings many examples of resonant optical phenomena associated with the physics of Fano resonances, with applications in optical switching and sensing. For successful design of photonic devices, it is important to gain deep insight into different resonant phenomena and understand their connection. Here, we review a broad range of resonant electromagnetic effects by using two effective coupled oscillators, including the Fano resonance, electromagnetically induced transparency, Kerker and Borrmann effects, and parity–time symmetry breaking. We discuss how to introduce the Fano parameter for describing a transition between two seemingly different spectroscopic signatures associated with asymmetric Fano and symmetric Lorentzian shapes. We also review the recent results on Fano resonances in dielectric nanostructures and metasurfaces.

Fano resonances in photonics

Metasurfaces provide opportunities for wavefront control, flat optics, and subwavelength light focusing. We developed an imaging-based nanophotonic method for detecting mid-infrared molecular fingerprints and implemented it for the chemical identification and compositional analysis of surface-bound analytes. Our technique features a two-dimensional pixelated dielectric metasurface with a range of ultrasharp resonances, each tuned to a discrete frequency; this enables molecular absorption signatures to be read out at multiple spectral points, and the resulting information is then translated into a barcode-like spatial absorption map for imaging. The signatures of biological, polymer, and pesticide molecules can be detected with high sensitivity, covering applications such as biosensing and environmental monitoring. Our chemically specific technique can resolve absorption fingerprints without the need for spectrometry, frequency scanning, or moving mechanical parts, thereby paving the way toward sensitive and versatile miniaturized mid-infrared spectroscopy devices.

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Imaging-based molecular barcoding with pixelated dielectric metasurfaces.

Plasmonic colours are structural colours that emerge from resonant interactions between light and metallic nanostructures. The engineering of plasmonic colours is a promising, rapidly emerging research field that could have a large technological impact. We highlight basic properties of plasmonic colours and recent nanofabrication developments, comparing technology-performance indicators for traditional and nanophotonic colour technologies. The structures of interest include diffraction gratings, nanoaperture arrays, thin films, and multilayers and structures that support Mie resonances and whispering-gallery modes. We discuss plasmonic colour nanotechnology based on localized surface plasmon resonances, such as gap plasmons and hybridized disk–hole plasmons, which allow for colour printing with sub-diffraction resolution. We also address a range of fabrication approaches that enable large-area printing and nanoscale lithography compatible with complementary metal-oxide semiconductor technologies, including nanoimprint lithography and self-assembly. Finally, we review recent developments in dynamically reconfigurable plasmonic colours and in the laser-induced post-processing of plasmonic colour surfaces. Plasmonic colours can be used to colour large surfaces, can be mass-produced and dynamically reconfigured, and can provide sub-diffraction resolution. In this Review, basic properties of plasmonic colours, different platforms supporting them and recent developments in the field are discussed.

Plasmonic colour generation

Plasmonic colour printing based on engineered metasurfaces has revolutionized colour display science due to its unprecedented subwavelength resolution and high-density optical data storage. However, advanced plasmonic displays with novel functionalities including dynamic multicolour printing, animations, and highly secure encryption have remained in their infancy. Here we demonstrate a dynamic plasmonic colour display technique that enables all the aforementioned functionalities using catalytic magnesium metasurfaces. Controlled hydrogenation and dehydrogenation of the constituent magnesium nanoparticles, which serve as dynamic pixels, allow for plasmonic colour printing, tuning, erasing and restoration of colour. Different dynamic pixels feature distinct colour transformation kinetics, enabling plasmonic animations. Through smart material processing, information encoded on selected pixels, which are indiscernible to both optical and scanning electron microscopies, can only be read out using hydrogen as a decoding key, suggesting a new generation of information encryption and anti-counterfeiting applications. Here Duanet al. demonstrate dynamic plasmonic colour displays using catalytic magnesium metasurfaces. Controlled hydrogenation and dehydrogenation of the constituent nanoparticles, which serve as dynamic pixels, allow plasmonic colour printing, tuning, erasing, restoration of colour and encoding of information.

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Dynamic plasmonic colour display.

Aluminum is an abundant and high-quality material for plasmonics with potential for large-area, low-cost photonic technologies. Here we examine aluminum nanoclusters with plasmonic Fano resonances that can be tuned from the near-UV into the visible region of the spectrum. These nanoclusters can be designed with specific chromaticities in the blue-green region of the spectrum and exhibit a remarkable spectral sensitivity to changes in the local dielectric environment. We show that such structures can be used quite generally for colorimetric localized surface plasmon resonance (LSPR) sensing, where the presence of analytes is detected by directly observable color changes rather than through photodetectors and spectral analyzers. To quantify our results and provide a metric for optimization of such structures for colorimetric LSPR sensing, we introduce a figure of merit based on the color perception ability of the human eye.

Fano Resonant Aluminum Nanoclusters for Plasmonic Colorimetric Sensing.

Surface-enhanced infrared absorption (SEIRA) spectroscopy has outstanding potential in chemical detection as a complement to surface-enhanced Raman spectroscopy (SERS), yet it has historically lagged well behind SERS in detection sensitivity. Here we report a new ultrasensitive infrared antenna designed to bring SEIRA spectroscopy into the few-molecule detection range. Our antenna consists of a bowtie-shaped Au structure with a sub-3 nm gap, positioned to create a cavity above a reflective substrate. This three-dimensional geometry tightly confines incident mid-infrared radiation into its ultrasmall junction, yielding a hot spot with a theoretical SEIRA enhancement factor of more than 107, which can be designed to span the range of frequencies useful for SEIRA. We quantitatively evaluated the IR detection limit of this antenna design using mixed monolayers of 4-nitrothiophenol (4-NTP) and 4-methoxythiolphenol (4-MTP). The optimized antenna structure allows the detection of as few as ∼500 molecules of 4-NT...

Nanogapped Au Antennas for Ultrasensitive Surface-Enhanced Infrared Absorption Spectroscopy

While there has been a tremendous increase of recent interest in noble metal-based antennas as substrates for surface-enhanced infrared absorption spectroscopy, more abundant and manufacturable metals may offer similar or additional opportunities for this mid-infrared sensing modality. Here we examine the feasibility of aluminum antennas for SEIRA, by designing and fabricating asymmetric aluminum cross antennas with nanometer-scale gaps. The asymmetric cross design enables the simultaneous detection of multiple infrared vibrational resonances over a broad region of the mid-infrared spectrum. The presence of the Al2O3 amorphous surface oxide layer not only passivates the metal antenna structures but also enables a very straightforward covalent binding chemistry for analyte molecules to the antenna through multiple approaches, in this case by the use of carboxylic acid functional groups. The aluminum–oxygen stretching mode of the oxide can be used as a self-calibration standard to quantify the number of ana...

Asymmetric Aluminum Antennas for Self-Calibrating Surface-Enhanced Infrared Absorption Spectroscopy

Plasmonic hot-carrier-based photodetectors detect light at frequencies below the semiconductor bandgap with room temperature operation and can exhibit spectrally narrowband behavior, potentially el...

Combining Plasmonic Hot Carrier Generation with Free Carrier Absorption for High-Performance Near-Infrared Silicon-Based Photodetection

The ability to image the optical near-fields of nanoscale structures, map their morphology, and concurrently obtain spectroscopic information, all with high spatiotemporal resolution, is a highly sought-after technique in nanophotonics. As a step toward this goal, we demonstrate the mapping of electromagnetic forces between a nanoscale tip and an optically excited sample consisting of plasmonic nanostructures with an imaging platform based on atomic force microscopy. We present the first detailed joint experimental–theoretical study of this type of photoinduced force microscopy. We show that the enhancement of near-field optical forces in gold disk dimers and nanorods follows the expected plasmonic field enhancements with strong polarization sensitivity. We then introduce a new way to evaluate optically induced tip–sample forces by simulating realistic geometries of the tip and sample. We decompose the calculated forces into in-plane and out-of-plane components and compare the calculated and measured forc...

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Benjamin Cerjan

Papers

Fano Resonant Aluminum Nanoclusters for Plasmonic Colorimetric Sensing.

Nanogapped Au Antennas for Ultrasensitive Surface-Enhanced Infrared Absorption Spectroscopy

Asymmetric Aluminum Antennas for Self-Calibrating Surface-Enhanced Infrared Absorption Spectroscopy

Combining Plasmonic Hot Carrier Generation with Free Carrier Absorption for High-Performance Near-Infrared Silicon-Based Photodetection

Photoinduced force mapping of plasmonic nanostructures