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Register a new userBreaking the Selection Rules of Spin-Forbidden Molecular Absorption in Plasmonic Nanocavities
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Controlling absorption and emission of organic molecules is crucial for efficient light-emitting diodes, organic solar cells and single-molecule spectroscopy. Here, a new molecular absorption is activated inside a gold plasmonic nanocavity, and found to break selection rules via spin-orbit coupling. Photoluminescence excitation scans reveal absorption from a normally spin-forbidden singlet to triplet state transition, while drastically enhancing the emission rate by several thousand fold. The experimental results are supported by density functional theory, revealing the manipulation of molecular absorption by nearby metallic gold atoms.
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Structured light are custom light fields where the phase, polarization, and intensity vary with position. It has been used for nanotweezers, nanoscale imaging, and quantum information technology, but its role in exciting optical transitions in materials has been little examined so far. Here we use group theory to derive the optical selection rules for nanosystems that get excited by structured light. If the size of the nanostructure is comparable to the light wavelength, it will sample the full beam profile during excitation with profound consequences on optical excitations. Using nanooligomers as model nanosystems, we show that structured light excites optical transitions that are forbidden for linearly polarized or unpolarized light. Such dipole forbidden modes have longer lifetimes and narrower resonances than dipole allowed transitions. We derive symmetry-adapted eigenmodes for nanooligomers containing up to six monomers. Our study includes tables with selection rules for cylindrical vector beams, for beams with orbital angular momentum, and for field retardation along the propagation direction. We discuss multi-photon processes of nonlinear optics in addition to one-photon absorption. Structured light will unlock a broad range of excitations in nanooligomers and other nanostructures that are currently inaccessible to optical studies.
Prospects of using metal hole arrays for the enhanced optical detection of molecular chirality in nanosize volumes are investigated. Light transmission through the holes filled with an optically active material is modeled and the activity enhancement by more than an order of magnitude is demonstrated. The spatial resolution of the chirality detection is shown to be of a few tens of nanometers. From comparing the effect in arrays of cylindrical holes and holes of complex chiral shape, it is concluded that the detection sensitivity is determined by the plasmonic near field enhancement. The intrinsic chirality of the arrays due to their shape appears to be less important.
Immense field enhancement and nanoscale confinement of light are possible within nanoparticle-on-mirror (NPoM) plasmonic resonators, which enable novel optically-activated physical and chemical phenomena, and render these nanocavities greatly sensitive to minute structural changes, down to the atomic scale. Although a few of these structural parameters, primarily linked to the nanoparticle and the mirror morphology, have been identified, the impact of molecular assembly and organization of the spacer layer between them has often been left uncharacterized. Here, we experimentally investigate how the complex and reconfigurable nature of a thiol-based self-assembled monolayer (SAM) adsorbed on the mirror surface impacts the optical properties of the NPoMs. We fabricate NPoMs with distinct molecular organizations by controlling the incubation time of the mirror in the thiol solution. Afterwards, we investigate the structural changes that occur under laser irradiation by tracking the bonding dipole plasmon mode, while also monitoring Stokes and anti-Stokes Raman scattering from the molecules as a probe of their integrity. First, we find an effective decrease in the SAM height as the laser power increases, compatible with an irreversible change of molecule orientation caused by heating. Second, we observe that the nanocavities prepared with a densely packed and more ordered monolayer of molecules are more prone to changes in their resonance compared to samples with sparser and more disordered SAMs. Our measurements indicate that molecular orientation and packing on the mirror surface play a key role in determining the stability of NPoM structures and hence highlight the under-recognized significance of SAM characterization in the development of NPoM-based applications.
Lasers are ubiquitous for information storage, processing, communications, sensing, biological research, and medical applications [1]. To decrease their energy and materials usage, a key quest is to miniaturize lasers down to nanocavities [2]. Obtaining the smallest mode volumes demands plasmonic nanocavities, but for these, gain comes from only single or few emitters. Until now, lasing in such devices was unobtainable due to low gain and high cavity losses [3]. Here, we demonstrate a plasmonic nanolaser approaching the single-molecule emitter regime. The lasing transition significantly broadens, and depends on the number of molecules and their individual locations. We show this can be understood by developing a theoretical approach [4] extending previous weak-coupling theories [5]. Our work paves the way for developing nanolaser applications [2, 6, 7] as well as fundamental studies at the limit of few emitters [5, 8, 9].
Recent results have shown unprecedented control over separation distances between two metallic elements hundreds of nanometers in size, underlying the effects of free-electron nonlocal response also at mid-infrared wavelengths. Most of metallic systems however, still suffer from some degree of inhomogeneity due to fabrication-induced surface roughness. Nanoscale roughness in such systems might hinder the understanding of the role of microscopic interactions. Here we investigate the effect of surface roughness in coaxial nanoapertures resonating at mid-infrared frequencies. We show that although random roughness shifts the resonances in an unpredictable way, the impact of nonlocal effects can still be clearly observed. Roughness-induced perturbation on the peak resonance of the system shows a strong correlation with the effective gap size of the individual samples. Fluctuations due to fabrication imperfections then can be suppressed by performing measurements on structure ensembles in which averaging over a large number of samples provides a precise measure of the ideal systems optical properties.
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