Nonclassical Mechanism of Metal-Enhanced Photoluminescence of Quantum Dots.

Metal-enhanced photoluminescence is able to provide a robust signal even from a single emitter and is promising in applications in biosensors and optoelectronic devices. However, its realization with semiconductor nanocrystals (e.g., quantum dots, QDs) is not always straightforward due to the hidden and not fully described interactions between plasmonic nanoparticles and an emitter. Here, we demonstrate nonclassical enhancement (i.e., not a conventional electromagnetic mechanism) of the QD photoluminescence at nonplasmonic conditions and correlate it with the charge exchange processes in the system, particularly with high efficiency of the hot-hole generation in gold nanoparticles and the possibility of their transfer to QDs. The hole injection returns a QD from a charged nonemitting state caused by hole trapping by surface and/or interfacial traps into an uncharged emitting state, which leads to an increased photoluminescence intensity. These results open new insights into metal-enhanced photoluminescence, showing the importance of the QD surface states in this process.

Unraveling the Chirality Transfer from Circularly Polarized Light to Single Plasmonic Nanoparticles.

Due to their broken symmetry, chiral plasmonic nanostructures have unique optical properties and numerous applications. However, there is still a lack of comprehension regarding how chirality transfer occurs between circularly polarized light (CPL) and these structures. Here, we thoroughly investigate the plasmon-assisted growth of chiral nanoparticles from achiral Au nanocubes (AuNCs) via CPL without the involvement of any chiral molecule stimulators. We identify the structural chirality of our synthesized chiral plasmonic nanostructures using circular differential scattering (CDS) spectroscopy, which is correlated with scanning electron microscopy imaging at both the single-particle and ensemble levels. Theoretical simulations, including hot-electron surface maps, reveal that the plasmon-induced chirality transfer is mediated by the asymmetric distribution of hot electrons on achiral AuNCs under CPL excitation. Furthermore, we shed light on how this plasmon-induced chirality transfer can also be utilized for chiral growth in bimetallic systems, such as Ag or Pd on AuNCs. The results presented here uncover fundamental aspects of chiral light-matter interaction and have implications for the future design and optimization of chiral sensors and chiral catalysis, among others.

DNA-Assembled Chiral Satellite-Core Nanoparticle Superstructures: Two-State Chiral Interactions from Dynamic and Static Conformations.

A significant challenge exists in obtaining chiral nanostructures that are amenable to both solution-phase self-assembly and solid-phase preservation, which enable the observation of unveiled optical responses impacted by the dynamic or static conformation and the incident excitations. Here, to meet this demand, we employed DNA origami technology to create quasi-planar chiral satellite-core nanoparticle superstructures with an intermediate geometry between the monolayer and the double layer. We disentangled the complex chiral mechanisms, which include planar chirality, 3D chirality, and induced chirality transfer, through combined theoretical studies and thorough experimental measurements of both solution- and solid-phase samples. Two distinct states of optical responses were demonstrated by the dynamic and static conformations, involving a split or nonsplit circular dichroism (CD) line shape. More importantly, our study on chiral nanoparticle superstructures on a substrate featuring both a dominant 2D geometry and a defined 3D represents a great leap toward the realization of colloidal chiral metasurfaces.

Chiral Generation of Hot Carriers for Polarization-Sensitive Plasmonic Photocatalysis.

Mastering the manipulation of chirality at the nanoscale has long been a priority for chemists, physicists, and materials scientists, given its importance in the biochemical processes of the natural world and in the development of novel technologies. In this vein, the formation of novel metamaterials and sensing platforms resulting from the synergic combination of chirality and plasmonics has opened new avenues in nano-optics. Recently, the implementation of chiral plasmonic nanostructures in photocatalysis has been proposed theoretically as a means to drive polarization-dependent photochemistry. In the present work, we demonstrate that the use of inorganic nanometric chiral templates for the controlled assembly of Au and TiO2 nanoparticles leads to the formation of plasmon-based photocatalysts with polarization-dependent reactivity. The formation of plasmonic assemblies with chiroptical activities induces the asymmetric formation of hot electrons and holes generated via electromagnetic excitation, opening the door to novel photocatalytic and optoelectronic features. More precisely, we demonstrate that the reaction yield can be improved when the helicity of the circularly polarized light used to activate the plasmonic component matches the handedness of the chiral substrate. Our approach may enable new applications in the fields of chirality and photocatalysis, particularly toward plasmon-induced chiral photochemistry.

Chiral Photomelting of DNA-Nanocrystal Assemblies Utilizing Plasmonic Photoheating.

Chiral plasmonic nanostructures exhibit anomalously strong chiroptical signals and offer the possibility to realize asymmetric photophysical and photochemical processes controlled by circularly polarized light. Here, we use a chiral DNA-assembled nanorod pair as a model system for chiral plasmonic photomelting. We show that both the enantiomeric excess and consequent circular dichroism can be controlled with chiral light. The nonlinear chiroptical response of our plasmonic system results from the chiral photothermal effect leading to selective melting of the DNA linker strands. Our study describes both the single-complex and collective heating regimes, which should be treated with different models. The chiral asymmetry factors of the calculated photothermal and photomelting effects exceed the values typical for the chiral molecular photochemistry at least 10-fold. Our proposed mechanism can be used to develop chiral photoresponsive systems controllable with circularly polarized light.

Local Growth Mediated by Plasmonic Hot Carriers: Chirality from Achiral Nanocrystals Using Circularly Polarized Light.

Plasmonic nanocrystals and their assemblies are excellent tools to create functional systems, including systems with strong chiral optical responses. Here we study the possibility of growing chiral plasmonic nanocrystals from strictly nonchiral seeds of different types by using circularly polarized light as the chirality-inducing mechanism. We present a novel theoretical methodology that simulates realistic nonlinear and inhomogeneous photogrowth processes in plasmonic nanocrystals, mediated by the excitation of hot carriers that can drive surface chemistry. We show the strongly anisotropic and chiral growth of oriented nanocrystals with lowered symmetry, with the striking feature that such chiral growth can appear even for nanocrystals with subwavelength sizes. Furthermore, we show that the chiral growth of nanocrystals in solution is fundamentally challenging. This work explores new ways of growing monolithic chiral plasmonic nanostructures and can be useful for the development of plasmonic photocatalysis and fabrication technologies.

Influence of the CTAB surfactant layer on optical properties of single metallic nanospheres.

We evaluate experimentally and theoretically the role of the residual ligands and ambient environment refractive index in the optical response of a single spherical gold nanoparticle on a substrate and demonstrate the changes in the near- and far-field properties of its hybridized modes in the presence of the cetyltrimethylammonium bromide (CTAB) layer. Particularly, we show that the conventional bilayer scheme for CTAB is not relevant for colloidal nanoparticles deposited on a substrate. We show that this CTAB layer considerably changes the amplitude and localization of the confinement of the electric field, which is of prime importance in the design of plasmonic complex systems coupled to emitters. Moreover, we numerically study the influence of the CTAB layer on the modification of sensitivity of plasmonic resonances of a gold nanopshere to local refractive index changes.

Extinction measurements of metallic nanoparticles arrays as a way to explore the single nanoparticle plasmon resonances.

The optical characterization of a single metallic nanostructure has a strong interest in the scientific community owing to its localized surface plasmon resonances. For a single nano-object, the simplest and the accepted optical characterization technique is dark-field spectroscopy, even if there are many drawbacks and a certain complexity to operate it. We propose here using extinction spectroscopy of nanoparticles ensembles to characterize optically a single nanostructure. The scattering spectrum of a single gold nanocylinder and the extinction spectrum of a well-chosen array show similar results. We perform an experimental and numerical comparative study to draw parallels between both techniques.

Quantum plasmonics pushes chiral sensing limit to single molecules: a paradigm for chiral biodetections.

Chiral sensing of single molecules is vital for the understanding of chirality and their applications in biomedicine. However, current technologies face severe limitations in achieving single-molecule sensitivity. Here we overcome these limitations by designing a tunable chiral supramolecular plasmonic system made of helical oligoamide sequences (OS) and nanoparticle-on-mirror (NPoM) resonator, which works across the classical and quantum regimes. Our design enhances the chiral sensitivity in the quantum tunnelling regime despite of the reduced local E-field, which is due to the strong Coulomb interactions between the chiral OSs and the achiral NPoMs and the additional enhancement from tunnelling electrons. A minimum of four molecules per single-Au particle can be detected, which allows for the detection of an enantiomeric excess within a monolayer, manifesting great potential for the chiral sensing of single molecules.

Collective chiroptical activity through the interplay of excitonic and charge-transfer effects in localized plasmonic fields.

The collective light-matter interaction of chiral supramolecular aggregates or molecular ensembles with confined light fields remains a mystery beyond the current theoretical description. Here, we programmably and accurately build models of chiral plasmonic complexes, aiming to uncover the entangled effects of excitonic correlations, intra- and intermolecular charge transfer, and localized surface plasmon resonances. The intricate interplay of multiple chirality origins has proven to be strongly dependent on the site-specificity of chiral molecules on plasmonic nanoparticle surfaces spanning the nanometer to sub-nanometer scale. This dependence is manifested as a distinct circular dichroism response that varies in spectral asymmetry/splitting, signal intensity, and internal ratio of intensity. The inhomogeneity of the surface-localized plasmonic field is revealed to affect excitonic and charge-transfer mixed intermolecular couplings, which are inherent to chirality generation and amplification. Our findings contribute to the development of hybrid classical-quantum theoretical frameworks and the harnessing of spin-charge transport for emergent applications.

Local Photochemical Nanoscopy of Hot-Carrier-Driven Catalytic Reactions Using Plasmonic Nanosystems.

Nanoscale investigation of the reactivity of photocatalytic systems is crucial for their fundamental understanding and improving their design and applicability. Here, we present a photochemical nanoscopy technique that unlocks the local spatial detection of molecular products during plasmonic hot-carrier-driven photocatalytic reactions with nanometric precision. By applying the methodology to Au/TiO2 plasmonic photocatalysts, we experimentally and theoretically determined that smaller and denser Au nanoparticle arrays present lower optical contribution with quantum efficiency in hot-hole-driven photocatalysis closely related to the population heterogeneity. As expected, the highest quantum yield from a redox probe oxidation is achieved at the plasmon peak. Investigating a single plasmonic nanodiode, we unravel the areas where oxidation and reduction products are evolved with subwavelength resolution (∼200 nm), illustrating the bipolar behavior of such nanosystems. These results open the way to quantitative investigations at the nanoscale to evaluate the photocatalytic reactivity of low-dimensional materials in a variety of chemical reactions.

Engineering of the Photon Local Density of States: Strong Inhibition of Spontaneous Emission near the Resonant and High-Refractive Index Dielectric Nano-objects.

Metallic or dielectric nano-objects change the photon local density of states of closely placed emitters, particularly when plasmon or Mie resonances are present. Depending on the shape and material of these nano-objects, they may induce either a decrease or an increase in decay rates of the excited states of the emitter. In this work, we consider the reduction of the probability of optical transitions in emitters near high-refractive index dielectric (silicon and zinc selenide) nanoparticles. We tune the spectral positions of magnetic and electric modes of nanocylinders to obtain the largest overlap of the valleys in the total decay rate spectra for differently oriented dipoles and, in this way, find the highest inhibition of about 80% for randomly oriented emitters. The spectral positions of these valleys are easy to control since the wavelengths of the modes depend on the height and diameter of nanocylinders. The inhibition value is robust to the distance between the emitter and the nanoparticle in the range of nearly 50 nm, which is crucially important for the applications, such as selective optical transition engineering and photovoltaics.

Enhanced Photocatalytic Activity and Photoluminescence of ZnO Nano-Wires Coupled with Aluminum Nanostructures.

In this study, we fabricated a hybrid plasmonic/semiconductor material by combining the chemical bath deposition of zinc oxide nanowires (ZnONWs) with the physical vapor deposition of aluminum nanostructures (AlNSs) under controlled temperature and atmosphere. The morphological and the optical properties of the ZnONWs/AlNSs hybrid material fabricated at different temperatures (250, 350, and 450 °C) and thicknesses (5, 7, and 9 nm) of Al layers were investigated. By adjusting the deposition and annealing parameters, it was possible to tune the size distribution of the AlNSs. The resonant coupling between the plasmonic AlNSs and ZnONWs leads to an enhanced photoluminescence response. The photocatalytic activity was studied through photodegradation under UV-light irradiation of methylene blue (MB) adsorbed at the surface of ZnO. The MB photodegradation experiment reveals that the ZnONWs covered with 7 nm aluminum film and annealed at 450 °C exhibit the highest degradation efficiency. The comparison between ZnONws and ZnONws/AlNSs shows a photoluminescence enhancement factor of 1.7 and an increase in the kinetics constant of photodegradation with a factor of 4.

Refractive index mediated plasmon hybridization in an array of aluminium nanoparticles.

The arrangement of plasmonic nanoparticles in a non-symmetrical environment can feature far-field and/or near-field interactions depending on the distance between the objects. In this work, we study the hybridization of three intrinsic plasmonic modes (dipolar, quadrupolar and hexapolar modes) sustained by one elliptical aluminium nanocylinder, as well as behavior of the hybridized modes when the nanoparticles are organized in arrays or when the refractive index of the surrounding medium is changed. The position and the intensity of these hybridized modes were shown to be affected by the near-field and far-field interactions between the nanoparticles. In this work, two hybridized modes were tuned in the UV spectral range to spectrally coincide with the intrinsic interband excitation and emission bands of ZnO nanocrystals. The refractive index of the ZnO nanocrystal layer influences the positions of the plasmonic modes and increases the role of the superstrate medium, which in turn results in the appearance of two separate modes in the small spectral region. Hence, the enhancement of ZnO nanocrystal photoluminescence benefits from the simultaneous excitation and emission enhancements.

Large-Scale and Low-Cost Fabrication of Silicon Mie Resonators.

High index dielectric nanoparticles have been proposed for many different applications. However, widespread utilization in practice also requires large-scale production methods for crystalline silicon nanoparticles, with engineered optical properties in a low-cost manner. Here, we demonstrate a facile, low-cost, and large-scale fabrication method of crystalline silicon colloidal Mie resonators in water, using a blender. The obtained nanoparticles are polydisperse with an almost spherical shape and the diameters controlled in the range 100-200 nm by a centrifugation process. Then the size distribution of silicon nanoparticles enables broad extinction from UV to near-infrared, confirmed by Mie theory when considering the size distribution in the calculations. Thanks to photolithographic and drop-cast deposition techniques to locate the position on a substrate of the colloidal nanoparticles, we experimentally demonstrate that the individual silicon nanoresonators show strong electric and magnetic Mie resonances in the visible range.

Photochromic control of a plasmon-quantum dots coupled system.

The control of quantum dot (QD) photoluminescence (PL) is a challenge for many applications. It is well known that plasmonic resonances can enhance this PL. In this work, we couple QDs with silver nanoparticles and immerse the system in a photochromic organic material. As these molecules are optical switches going from a transparent to a colored isomer by absorbing UV light, we observe on one hand a Förster Resonant Energy Transfer (FRET) between the QD emission and the absorbing isomer and on the other hand a plasmonic PL enhancement. The photochromic transition leads to the optical control of the FRET, allowing us to control the QD de-excitation preferences (radiative or non-radiative) and so the emitted light.