Friday, February 13, 2015

Nanophotonics and plasmonics: a great look for the International Year of Light

Anna Demming
Publishing Editor, IOP Publishing, Bristol, UK 
Anna Demming 2015 Nanotechnology 26 090201doi:10.1088/0957-4484/26/9/090201
The physics of light has seen many makeovers. It has been described as instantaneous ubiquitous impulses, a vacillating ether, leapfrogging electromagnetic fields, corpuscles and finite velocity photons, as well as some changeling phenomenon that mimics all the above. In recent decades studies of the interactions of light with nanostructures have revealed more weird and wonderful behaviour, and applications of nanophotonics research has already demonstrated promise for new devices for slowing, filtering, trapping, confining and, as highlighted in the topical review in this issue, enhancing light [1].
Biosensing stands to benefit immeasurably from the enhancement of 'Raman signals', indicators of a molecule's vibrational modes in scattered light. Raman signals offer a unique 'fingerprint' of the molecule that is an invaluable resource for identifying substances and their surrounding medium. However with low signal strength—typically 10−14 that of fluorescence signals—the devil is in the detection. Fortunately the same light that activates vibrational modes in the molecule can trigger so-called lightning rod effects and resonant electron oscillations—plasmons—in metal nanostructures nearby. These enhance the local electromagnetic field by several orders of magnitude, while charge transfer 'chemical' processes also contribute to the enhancements. The result is a detectable signal as first demonstrated by David Jeanmaire and Richard van Duyne [2]. Describing their results in 1977 they pointed out, 'The ability to obtain resonance Raman spectra with good signal-to-noise with laser powers less than 1.0 mW, reported here for the first time, opens up possibilities of surface Raman studies with relatively inexpensive laser systems.' These possibilities were neatly demonstrated 20 years later by Katrin Kneipp and colleagues at MIT and the Technical Institute in Berlin who used surface enhanced Raman spectroscopy (SERS) to detect a single molecule [3].
Since then efforts to develop user-friendly SERS techniques have attracted intense research interest. One difficulty in applying the technique is that when Raman probes are attached to metal nanoparticles, the nanoparticles are prone to aggregating and the probes desorb. Ming Li and colleagues at West Virginia University and Ocean Nano Tech in the US and INRS-Énergie in Canada combatted these issues by sandwiching the Raman probe malachite green isothiocyanate between gold nanoparticles and a silica coating [4]. Their objective, as they point out in their report, was 'to develop and optimize a highly sensitive Raman probe that features high sensitivity, good water solubility and stability, low-background fluorescence, and an absence of photobleaching for biological applications.' Experiments and supporting simulations demonstrated the success of their approach.
Monica Potara and colleagues at Babes-Bolyai University in Romania embraced the tendency to aggregate by designing films of silver nanoparticle clusters coated in the biopolymer chitosan [5]. The gaps in the nanoparticle arrangements result in hotspots for extremely high electromagnetic field enhancements while the chitosan coating allows the analyte molecules to diffuse into the film and immobilize on the surface of the silver.
Yet with the inherent variations in geometry and mixing time, reproducibility in SERS is still an issue. In their review [1], Chao Wang and Chenxu Yu from Iowa State University describe the possible solutions offered by integrating SERS with microfluidics, a tool that has already proved useful for highly precise manipulation of small volumes of liquids. Despite the potential applications of the combined approaches in environmental surveillance and assay detection for DNA/RNA and living cells, the approach is not without challenges. Microfluidics systems commonly use the polymer polydimethylsiloxane which is Raman active itself and could interfere with the measured signals. Reproducible intermixing control for colloids and analytes can also be tricky. Wang and Yu describe some of the ways around these and other aspects of SERS-microfluidics, as well as the potential of using continuous flow systems. These could further improve the reproducibility and raise the demand for some sort of optical, electrical or mechanical trapping mechanism to hold samples in the detection area long enough for a signal to be collected.
Plasmonics is an area of nanophotonics that has reached a level of maturity over the past decade. As well as biosensing there are many promising potential applications in communications and photonic circuits as the papers in our 'Plasmonics in optoelectronics' special issue highlight [6]. Yet surprising characteristics in the behaviour of light in plasmonic systems continue to emerge.
By combining plasmonic nanoparticles with photonic crystals, Ali Hatef and colleagues at the University of Western Ontario in Canada and the University of Alabama in Huntsville in the US demonstrated that the absorption of the system could drop dramatically within a given frequency range in a state described as 'plasmonic electromagnetically induced-transparency' [7]. Zhihua Zhu and colleagues from Tianjin University in China, King Abdullah University of Science and Technology in Saudi Arabia, Osaka University in Japan and Oklahoma State University in the US, achieved 'plasmon-induced-transparency', an analogue of electromagnetically induced transparency, by coupling dark mode and light mode resonators in a metamaterial. Moreover they achieved the effect over a broadband spectrum embracing the increasingly important terahertz frequency region of the electromagnetic spectrum with the effect [8].
In 2015 the world celebrates the International Year of Light with a diverse range of events that emphasizes the numerous guises of light that continue to attract interest. Nanotechnology is hosting a focus collection on nanophotonics that will be accepting and publishing papers throughout the year. The collection assembles results of research that continue to push the limits of our understanding and ability to control light interactions with nanomaterials, a topic that seems infinite in its scope for further investigation. As Albert Einstein is said to have commented in 1954, 'All the fifty years of conscious brooding have brought me no closer to answer the question, 'What are light quanta?' Of course today every rascal thinks he knows the answer, but he is deluding himself.'


Wang C and Yu C 2015 Analytical characterization using surface-enhanced Raman scattering (SERS) and microfluidic sampling Nanotechnology 26 092001CrossRef
Jeanmaire D L and van Duyne R P 1977 Surface Raman spectroelectrochemistry: I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode J. Electroanal. Chem. 84 1–20CrossRef
Kneipp K, Wang Y, Kneipp H, Perelman L T, Itzkan I, Dasari R R and Feld M S 1997 Single molecule detection using surface-enhanced Raman scattering (SERS) Phys. Rev. Lett. 78 1667CrossRef
Li M, Cushing S K, Zhang J, Lankford J, Aguilar Z P, Ma D and Wu N 2012 Shape-dependent surface-enhanced Raman scattering in gold–Raman-probe–silica sandwiched nanoparticles for biocompatible applications Nanotechnology 23115501IOPscience
Potara M, Baia M, Farcau C and Astilean S 2012 Chitosan-coated anisotropic silver nanoparticles as a SERS substrate for single-molecule detection Nanotechnology 23 055501IOPscience
Brongersma M and Kim D S 2012 Special issue on plasmonics in optoelectronics devices Editors Nanotechnology 2344
Hatef A, Sadeghi S M and Singh M R 2012 Plasmonic electromagnetically induced transparency in metallic nanoparticle-quantum dot hybrid systems Nanotechnology 23 065701IOPscience
Zhu Z, Yang X, Gu J, Jiang J, Yue W, Tian Z, Tonouchi M, Han J and Zhang W 2013 Broadband plasmon induced transparency in terahertz metamaterials Nanotechnology 24 214003

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