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Controlling the light emitted by individual molecules is instrumental to a number of novel nanotechnologies ranging from super-resolution bio-imaging and molecular sensing to quantum nanophotonics. Molecular emission can be tailored by modifying the local photonic environment, for example by precisely placing a single molecule inside a plasmonic nanocavity with the help of DNA origami. Here, using this scalable approach, we show that commercial fluorophores experience giant Purcell factors and Lamb shifts, reaching values on par with those recently reported in scanning tip experiments. Engineering of plasmonic modes enables cavity-mediated fluorescence far detuned from the zero-phonon-line (ZPL) - at detunings that are up to two orders of magnitude larger than the fluorescence linewidth of the bare emitter and reach into the near-infrared. Our results evidence a regime where the emission linewidth is dominated by the excited state lifetime, as required for indistinguishable photon emission, baring relevance to the development of nanoscale, ultrafast quantum light sources and to the quest toward single-molecule cavity-QED. In the future, this approach may also allow to design efficient quantum emitters at infrared wavelengths, where standard organic sources have a reduced performance., Comment: Supplementary information included

Controlling the flow of excitons between organic molecules holds immense promise for various applications, including energy conversion, spectroscopy, photocatalysis, sensing, and microscopy. DNA nanotechnology has shown promise in achieving this control by using synthetic DNA as a platform for positioning and, very recently, for also orienting organic dyes. In this study, the orientation of doubly-linked dyes in DNA origami structures was manipulated to control energy transfer. By controlling independently the orientation of single donor and acceptor molecules, the average energy transfer efficiency was doubled. This work demonstrates the potential of DNA nanotechnology for precise control of the excitonic energy transfer with implications for artificial light-harvesting antennas., Comment: 19 pages, 4 figures

Nanotechnology has revolutionized the fabrication of hybrid species with tailored functionalities. A milestone in this field is the DNA conjugation of nanoparticles, introduced almost 30 years ago, which typically exploits the affinity between thiol groups and metallic surfaces. Over the last decades, developments in colloidal research have enabled the synthesis of an assortment of non-metallic structures, such as high-index dielectric nanoparticles, with unique properties not previously accessible with traditional metallic nanoparticles. However, to stabilize, integrate and provide further functionality to non-metallic nanoparticles, reliable techniques for their functionalization with DNA will be crucial. Here, we combine well-established dibenzylcyclooctyne-azide click-chemistry with a simple freeze-thaw method to achieve the functionalization of silica and silicon nanoparticles, which form exceptionally stable colloids with a high DNA surface density of 0.2 molecules/nm2. Furthermore, we demonstrate that these functionalized colloids can be self-assembled into high-index dielectric optical antennas with a yield of up to 78% via the use of DNA origami. Finally, we extend this method to functionalize other important nanomaterials, including oxides, polymers, core-shell and metal nanostructures. Our results indicate that the method presented herein serves as a crucial complement to conventional thiol functionalization chemistry and thus greatly expands the toolbox of DNA-functionalized nanoparticles currently available.

Optical nanoantennas can affect the decay rates of nearby emitters by modifying the local density of photonic states around them. In the weak-coupling limit, and according to the Fermi's Golden Rule, the emission spectrum of a dye is given by the energy of all the possible radiative transitions weighted by the probability of each of them to occur. By engineering the resonance of a nanoantenna, one can selectively enhance specific vibronic transitions of a dye molecule, thus shaping its emission spectrum. Since interactions between emitters and nanoantennas are known to be position dependent, we make here use of DNA origami to precisely place an individual dye at different positions around a gold nanorod. We show how this relative position between the nanorod and the emitter affects the emission spectrum of the latter. In particular, we observe the appearance of a second fluorescence peak whose wavelength and intensity are correlated with the fundamental plasmonic resonance of the nanorod, which we extract from its photoluminescence spectrum. This second peak results from the selective enhancement of transitions to different vibrational levels of the excitonic ground state, whose energies are in resonance with the plasmonic one. Furthermore, we argue that the drastic alteration of the fluorescence spectrum in some of our samples cannot be accounted for with Kasha's rule, which indicates that radiative and vibrational relaxation dye lifetimes can become comparable through the coupling to the gold nanorods.

FRET-based approaches are a unique tool for sensing the immediate surroundings and interactions of (bio)molecules. FRET imaging and FLIM (Fluorescence Lifetime Imaging Microscopy) enable the visualization of the spatial distribution of molecular interactions and functional states. However, conventional FLIM and FRET imaging provide average information over an ensemble of molecules within a diffraction-limited volume, which limits the spatial information, accuracy, and dynamic range of the observed signals. Here, we demonstrate an approach to obtain super-resolved FRET imaging based on single-molecule localization microscopy using an early prototype of a commercial time-resolved confocal microscope. DNA Points Accumulation for Imaging in Nanoscale Topography (DNA-PAINT) with fluorogenic probes provides a suitable combination of background reduction and blinking kinetics compatible with the scanning speed of usual confocal microscopes. A single laser is used to excite the donor, a broad detection band is employed to retrieve both donor and acceptor emission, and FRET events are detected from lifetime information.

We introduce and theoretically analyze the concept of manipulating optical chirality via strong coupling of the optical modes of chiral nanostructures with excitonic transitions in molecular layers or semiconductors. With chirality being omnipresent in chemistry and biomedicine, and highly desirable for technological applications related to efficient light manipulation, the design of nanophotonic architectures that sense the handedness of molecules or generate the desired light polarization in an externally controllable manner is of major interdisciplinary importance. Here we propose that such capabilities can be provided by the mode splitting resulting from polaritonic hybridization. Starting with an object with well-known chiroptical response -- here, for a proof of concept, a chiral sphere -- we show that strong coupling with a nearby excitonic material generates two distinct frequency regions that retain the object's chirality density and handedness, which manifest most clearly through anticrossings in circular-dichroism or differential-scattering dispersion diagrams. These windows can be controlled by the intrinsic properties of the excitonic layer and the strength of the interaction, enabling thus the post-fabrication manipulation of optical chirality. Our findings are further verified via simulations of the circular dichroism of a realistic chiral architecture, namely a helical assembly of plasmonic nanospheres embedded in a resonant matrix.

An ideal nanofabrication method should allow the organization of nanoparticles and molecules with nanometric positional precision, stoichiometric control and well-defined orientation. The DNA origami technique has evolved into a highly versatile bottom-up nanofabrication methodology that fulfils almost all of these features. It enables the nanometric positioning of molecules and nanoparticles with stoichiometric control, and even the orientation of asymmetrical nanoparticles along predefined directions. However, orienting individual molecules has been a standing challenge, mainly due to unspecific electrostatic interactions. Here, we show how single molecules, namely Cy5 and Cy3 fluorophores, can be incorporated in a DNA origami with controlled orientation by doubly linking them to oligonucleotide strands that are hybridized while leaving enough unpaired bases to induce a stretching force. Particularly, we explore the effects of leaving 0, 2, 4, 6, and 8 unpaired bases and find extreme orientations for 0 and 8 unpaired bases, corresponding to the molecules being perpendicular and parallel to the DNA double helix, respectively. We foresee that these results will expand the application field of DNA origami towards the fabrication of nanodevices involving a wide range of orientation-dependent molecular interactions, such as energy transfer, intermolecular electron transport, catalysis, exciton delocalization, or the electromagnetic coupling of a molecule to specific resonant nano-antennas modes., Comment: 24 pages, 4 figures

Optical nanoantennas are structures designed to manipulate light-matter interactions at the nanoscale by interfacing propagating light with localized optical fields. In recent years, a plethora of devices have been realized that are able to efficiently tailor the absorption and/or emission rates of fluorophores. By contrast, modifying the spatial characteristics of their radiation fields remains a challenge. Up to date, the designs providing directionality to fluorescence emission have required compound, complex geometries with overall dimensions comparable to the operating wavelength. Here, we present the fabrication and characterization of DNA-templated ultracompact optical antennas, with sub-wavelength sizes and capable of directing single-molecule fluorescence into predefined directions. Using the DNA origami methodology, two gold nanorods are assembled side-to-side with a separation gap of 5 nm. We show that a single fluorescent molecule placed at the tip of one of the nanorods drives the dimer antenna in anti-phase, leading to unidirectional emission.

Controlling directionality of optical emitters is of utmost importance for their application in communication and biosensing devices. Metallic nanoantennas have been proven to affect both excitation and emission properties of nearby emitters, including directionality of their emission. In this regard, optical directional nanoantennas based on a Yagi-Uda design have been demonstrated in the visible range. Despite this impressive proof of concept, their overall size and considerable number of elements represent obstacles for the exploitation of these antennas in nanophotonic applications and for their incorporation onto photonic chips. In order to address these challenges, we investigate an alternative design. In particular, we numerically demonstrate unidirectionality of an ultracompact optical antenna based on two parallel gold nanorods (side-by-side dimer). Our results show that exciting the antiphase mode by an emitter placed in the near-field can lead to unidirectional emission. Furthermore, in order to verify the feasibility of this design, we study the effect on the directionality of several parameters such as shape of the nanorods, possible defects in dimer assembly, and different position and orientation of the emitter. We conclude that this design is robust to changes, making it experimentally achievable.