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Title: Inverse design of nanoparticles for enhanced Raman scattering
We show that topology optimization (TO) of metallic resonators can lead to ∼102 × improvement in surface-enhanced Raman scattering (SERS) efficiency compared to traditional resonant structures such as bowtie antennas. TO inverse design leads to surprising structures very different from conventional designs, which simultaneously optimize focusing of the incident wave and emission from the Raman dipole. We consider isolated metallic particles as well as more complicated configurations such as periodic surfaces or resonators coupled to dielectric waveguides, and the benefits of TO are even greater in the latter case. Our results are motivated by recent rigorous upper bounds to Raman scattering enhancement, and shed light on the extent to which these bounds are achievable.
There is tremendous interest in employing collective excitations of the lattice, spin, charge, and orbitals to tune strongly correlated electronic phenomena. We report such an effect in a ruthenate, Ca3Ru2O7, where two phonons with strong electron-phonon coupling modulate the electronic pseudogap as well as mediate charge and spin density wave fluctuations. Combining temperature-dependent Raman spectroscopy with density functional theory reveals two phonons,B2PandB2M, that are strongly coupled to electrons and whose scattering intensities respectively dominate in the pseudogap versus the metallic phases. TheB2Psqueezes the octahedra along the out of planec-axis, while theB2Melongates it, thus modulating the Ru 4d orbital splitting and the bandwidth of the in-plane electron hopping; Thus,B2Popens the pseudogap, whileB2Mcloses it. Moreover, theB2phonons mediate incoherent charge and spin density wave fluctuations, as evidenced by changes in the background electronic Raman scattering that exhibit unique symmetry signatures. The polar order breaks inversion symmetry, enabling infrared activity of these phonons, paving the way for coherent light-driven control of electronic transport.
2D freestanding nanocrystal superlattices represent a new class of advanced metamaterials in that they can integrate mechanical flexibility with novel optical, electrical, plasmonic, and magnetic properties into one multifunctional system. The freestanding 2D superlattices reported to date are typically constructed from symmetrical constituent building blocks, which have identical structural and functional properties on both sides. Here, a general ligand symmetry‐breaking strategy is reported to grow 2D Janus gold nanocrystal superlattice sheets with nanocube morphology on one side yet with nanostar on the opposite side. Such asymmetric metallic structures lead to distinct wetting and optical properties as well as surface‐enhanced Raman scattering (SERS) effects. In particular, the SERS enhancement of the nanocube side is about 20‐fold of that of the nanostar side, likely due to the combined “hot spot + lightening‐rod” effects. This is nearly 700‐fold of SERS enhancement as compared with the symmetric nanocube superlattices without Janus structures.
Nyamekye, Charles K. A.; Weibel, Stephen C.; Smith, Emily A.(
, Journal of Raman Spectroscopy)
Abstract
The gold–sulfur (Au–S) and silver–sulfur (Ag–S) bonds are integral to the surface modification of metal films with alkanethiol monolayers. Although the metal–sulfur bond can be characterized with surface‐enhanced Raman spectroscopy (SERS) at roughened metal films, some applications require or perform better when using a smooth metal surface, which is not suitable for SERS signal enhancement. Directional‐surface‐plasmon‐coupled Raman scattering (directional Raman scattering) is an approach to measure metal–sulfur bonds on smooth metal films with sub‐monolayer sensitivity. The metal–sulfur bonds formed from a benzenethiol monolayer on smooth planar gold or silver films are observed in the directional Raman scattering spectra between 240 and 270 cm−1; the signal‐to‐noise ratio of the Au–S Raman peak is 60. Importantly, the directional Raman scattering signal measured with smooth metal surfaces can be simply modeled and easily compared across many samples. Directional Raman scattering can also be measured at roughened metal films, which makes it applicable for many analyses.
Whereas electron-phonon scattering relaxes the electron’s momentum in metals, a perpetual exchange of momentum between phonons and electrons may conserve total momentum and lead to a coupled electron-phonon liquid. Such a phase of matter could be a platform for observing electron hydrodynamics. Here we present evidence of an electron-phonon liquid in the transition metal ditetrelide, NbGe2, from three different experiments. First, quantum oscillations reveal an enhanced quasiparticle mass, which is unexpected in NbGe2with weak electron-electron correlations, hence pointing at electron-phonon interactions. Second, resistivity measurements exhibit a discrepancy between the experimental data and standard Fermi liquid calculations. Third, Raman scattering shows anomalous temperature dependences of the phonon linewidths that fit an empirical model based on phonon-electron coupling. We discuss structural factors, such as chiral symmetry, short metallic bonds, and a low-symmetry coordination environment as potential design principles for materials with coupled electron-phonon liquid.
Surface-enhanced Raman scattering (SERS) spectroscopy is a popular technique for detecting chemicals in small quantities. Rough metallic surfaces with nanofeatures are some of the most widespread and commercially successful substrates for efficient SERS measurements. A rough metallic surface creates a high-density random distribution of so-called “hot spots” with local optical field enhancement causing Raman signal to increase. In this Letter, we revisit the classic SERS experiment [Surf. Sci.158,229(1985)SUSCAS0039-602810.1016/0039-6028(85)90297-3] with rough metallic surfaces covered by a thin layer of copper phthalocyanine molecules. As a modification to the classic configuration, we apply an adaptive wavefront correction of a laser beam profile. As a result, we demonstrate an increase in brightness of local SERS hot spots and redistribution of Raman signal over the substrate area. We hypothesize that the improvement is due to optimal coupling of the shaped laser beam to the random plasmonic nanoantenna configurations. We show that the proposed adaptive-SERS modification is independent of the exact structure of the surface roughness and topography, works with many rough surfaces, and gives brighter Raman hot spots in comparison with conventional SERS measurements. We prove that the adaptive SERS is a powerful instrument for improving SERS sensitivity.
Christiansen, Rasmus_E, Michon, Jérôme, Benzaouia, Mohammed, Sigmund, Ole, and Johnson, Steven_G.
"Inverse design of nanoparticles for enhanced Raman scattering". Optics Express 28 (4). Country unknown/Code not available: Optical Society of America. https://doi.org/10.1364/OE.28.004444.https://par.nsf.gov/biblio/10133034.
@article{osti_10133034,
place = {Country unknown/Code not available},
title = {Inverse design of nanoparticles for enhanced Raman scattering},
url = {https://par.nsf.gov/biblio/10133034},
DOI = {10.1364/OE.28.004444},
abstractNote = {We show that topology optimization (TO) of metallic resonators can lead to ∼102 × improvement in surface-enhanced Raman scattering (SERS) efficiency compared to traditional resonant structures such as bowtie antennas. TO inverse design leads to surprising structures very different from conventional designs, which simultaneously optimize focusing of the incident wave and emission from the Raman dipole. We consider isolated metallic particles as well as more complicated configurations such as periodic surfaces or resonators coupled to dielectric waveguides, and the benefits of TO are even greater in the latter case. Our results are motivated by recent rigorous upper bounds to Raman scattering enhancement, and shed light on the extent to which these bounds are achievable.},
journal = {Optics Express},
volume = {28},
number = {4},
publisher = {Optical Society of America},
author = {Christiansen, Rasmus_E and Michon, Jérôme and Benzaouia, Mohammed and Sigmund, Ole and Johnson, Steven_G},
}
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