Deep strong light-matter coupling in plasmonic nanoparticle crystals.

In the regime of deep strong light-matter coupling, the coupling strength exceeds the transition energies of the material1-3, fundamentally changing its properties4,5; for example, the ground state of the system contains virtual photons and the internal electromagnetic field gets redistributed by photon self-interaction1,6. So far, no electronic excitation of a material has shown such strong coupling to free-space photons. Here we show that three-dimensional crystals of plasmonic nanoparticles can realize deep strong coupling under ambient conditions, if the particles are ten times larger than the interparticle gaps. The experimental Rabi frequencies (1.9 to 3.3 electronvolts) of face-centred cubic crystals of gold nanoparticles with diameters between 25 and 60 nanometres exceed their plasmon energy by up to 180 per cent. We show that the continuum of photons and plasmons hybridizes into polaritons that violate the rotating-wave approximation. The coupling leads to a breakdown of the Purcell effect-the increase of radiative damping through light-matter coupling-and increases the radiative polariton lifetime. The results indicate that metallic and semiconducting nanoparticles can be used as building blocks for an entire class of materials with extreme light-matter interaction, which will find application in nonlinear optics, the search for cooperative effects and ground states, polariton chemistry and quantum technology4,5.

Far-Field Petahertz Sampling of Plasmonic Fields.

The response of metal nanostructures to optical excitation leads to localized surface plasmon (LSP) generation with nanoscale field confinement driving applications in, for example, quantum optics and nanophotonics. Field sampling in the terahertz domain has had a tremendous impact on the ability to trace such collective excitations. Here, we extend such capabilities and introduce direct sampling of LSPs in a more relevant petahertz domain. The method allows to measure the LSP field in arbitrary nanostructures with subcycle precision. We demonstrate the technique for colloidal nanoparticles and compare the results to finite-difference time-domain calculations, which show that the build-up and dephasing of the plasmonic excitation can be resolved. Furthermore, we observe a reshaping of the spectral phase of the few-cycle pulse, and we demonstrate ad-hoc pulse shaping by tailoring the plasmonic sample. The methodology can be extended to single nanosystems and applied in exploring subcycle, attosecond phenomena.

Electron Donor-Specific Surface Interactions Promote the Photocatalytic Activity of Metal-Semiconductor Nanohybrids.

In the past two decades, the application of colloidal semiconductor-metal nanoparticles (NPs) as photocatalysts for the hydrogen generation from water has been extensively studied. The present body of literature studies agrees that the photocatalytic yield strongly depends on the electron donating agent (EDA) added for scavenging the photogenerated holes. The highest reported hydrogen production rates are obtained in the presence of ionic EDAs and at high pH. The large hydrogen production rates are attributed to fast hole transfer from the NP onto the EDAs. However, the present discussions do not treat the influence of EDA-specific surface interactions. This systematic study focuses on that aspect by combining steady-state hydrogen production measurements with time-resolved and static optical spectroscopy, employing 11-mercaptoundecanoic acid-capped, Pt-tipped CdSe/CdS dot-in-rods in the presence of a large set of EDAs. Based on the experimental results, two distinct EDA groups are identified: surface-active and diffusion-limited EDAs. The largest photocatalytic efficiencies are obtained in the presence of surface-active EDAs that induce an agglomeration of the NPs. This demonstrates that the introduction of surface-active EDAs can significantly enhance the photocatalytic activity of the NPs, despite reducing their colloidal stability and inducing the formation of NP networks.

Time-Resolved Single-Particle X-ray Scattering Reveals Electron-Density Gradients As Coherent Plasmonic-Nanoparticle-Oscillation Source.

Dynamics of optically excited plasmonic nanoparticles are presently understood as a series of scattering events involving the initiation of nanoparticle breathing oscillations. According to established models, these are caused by statistical heat transfer from thermalized electrons to the lattice. An additional contribution by hot-electron pressure accounts for phase mismatches between theory and experimental observations. However, direct experimental studies resolving the breathing-oscillation excitation are still missing. We used optical transient-absorption spectroscopy and time-resolved single-particle X-ray diffractive imaging to access the electron system and lattice. The time-resolved single-particle imaging data provided structural information directly on the onset of the breathing oscillation and confirmed the need for an additional excitation mechanism for thermal expansion. We developed a new model that reproduces all of our experimental observations. We identified optically induced electron density gradients as the initial driving source.

Theory of radial oscillations in metal nanoparticles driven by optically induced electron density gradients.

We provide a microscopic approach to describe the onset of radial oscillation of a silver nanoparticle. Using the Heisenberg equation of motion framework, we find that the coupled ultrafast dynamics of coherently excited electron occupation and the coherent phonon amplitude initiate periodic size oscillations of the nanoparticle. Compared to the established interpretation of experiments, our results show a more direct coupling mechanism between the field intensity and coherent phonons. This interaction triggers a size oscillation via an optically induced electron density gradient occurring directly with the optical excitation. This source is more efficient than the incoherent heating process currently discussed in the literature and well-describes the early onset of the oscillations in recent experiments.

Carrier localization in zero-dimensional and one-dimensional CdSe-CdS heterostructures.

Mobile charge carriers in heterostructured nanoparticles are relevant for applications requiring charge separation and extraction. We investigate the benchmark systems CdSe-CdS core-shell quantum dots and quantum dots in quantum rods by optical and THz pump-probe spectroscopy. We relate photoconductivity and carrier location and observe that only shell-located electrons in quantum rods contribute to an observable photoconductivity. Despite the shallow electron confinement in the quasi-type II heterostructures, core-located carriers are bound into immobile excitons that respond on external electrical fields by polarization.

Dark plasmon modes for efficient hot electron generation in multilayers of gold nanoparticles.

The excitation of dark plasmons, i.e., coupled plasmon modes with a vanishing net dipole, is expected to favor Landau damping over radiative damping. Dark plasmon excitation might, therefore, lead to an increased absorption of energy within gold nanoparticles, resulting in a strong generation of hot electrons compared to the generation via bright plasmons. We performed transient-absorption spectroscopy on gold nanoparticle films to assess the initial electronic temperature before thermalization. We observe a significant increase in the electron-phonon coupling time when dark plasmon modes are excited in these films. The results indicate an efficient energy absorption due to the suppressed radiative decay of dark plasmon modes and a subsequent energy transformation into hot electrons.

Inter-individual variability in spring phenology of temperate deciduous trees depends on species, tree size and previous year autumn phenology.

We explored the inter-individual variability in bud-burst and its potential drivers, in homogeneous mature stands of temperate deciduous trees. Phenological observations of leaves and wood formation were performed weekly from summer 2017 to summer 2018 for pedunculate oak, European beech and silver birch in Belgium. The variability of bud-burst was correlated to previous' year autumn phenology (i.e. the onset of leaf senescence and the cessation of wood formation) and tree size but with important differences among species. In fact, variability of bud-burst was primarily related to onset of leaf senescence, cessation of wood formation and tree height for oak, beech and birch, respectively. The inter-individual variability of onset of leaf senescence was not related to the tree characteristics considered and was much larger than the inter-individual variability in bud-burst. Multi-species multivariate models could explain up to 66% of the bud-burst variability. These findings represent an important advance in our fundamental understanding and modelling of phenology and tree functioning of deciduous tree species.

Resonant Energy Transfer can Trigger Multiexciton Recombination in Dense Quantum Dot Ensembles.

Core/shell quantum dots/quantum rods are nanocrystals with typical application scenarios as ensembles. Resonance energy transfer is a possible process between adjacent nanocrystals. Highly excited nanocrystals can also relax energy by multiexciton recombination, competing against the energy transfer. The two processes have different dependencies and can be convolved, resulting in collective properties different from the superposition of the individual nanocrystals. A platform to study the interplay of energy transfer and multiexciton recombination is presented. CdSe/CdS quantum dot/quantum rods encapsulated in amphiphilic micelles with an interparticle distance control by spacer ligands are used for time-resolved photoluminescence and transient absorption experiments. At exciton populations around one, the ensemble starts to be in a state where energy transfer can trigger multiexciton Auger recombination, altering the collective dynamics.

Direct optical excitation of dark plasmons for hot electron generation.

An ideal plasmonic system for hot-electron generation allows the optical excitation of plasmons, limits radiation losses, exhibits strong non-radiative electron damping, and is made from scalable and cost-effective materials. Here we demonstrate the optical excitation of dark interlayer plasmons in bilayers of colloidal gold nanoparticles. This excitation is created by an antiparallel orientation of the dipole moments in the nanoparticle layers; it is expected to exhibit strongly reduced radiative damping. Despite the vanishing dipole moment, an incoming electromagnetic wave that is propagating normal to the surface will excite the dark mode due to field retardation. We observe a strong peak in the absorption spectrum of a colloidal gold bilayer (nanoparticle diameter = 46 nm); this peak is absent for a nanoparticle monolayer. The full width at half maximum of the dark mode is 230 meV for an ideal nanoparticle crystal and 320 meV for the structure produced by self-assembly out of solution. The position and width of the dark plasmon are efficiently tailored by the interparticle distance within the layer, nanoparticle size and layer number. We present time-resolved pump and probe experiments of hot-electron generation by bright and dark bilayer nanoparticle modes.

Kinetics of pressure-induced nanocrystal superlattice formation.

Colloidal nanocrystals (NC) are known to self-organize into superlattices that promise many applications ranging from medicine to optoelectronics. Recently, the formation of high-quality PEGylated gold NC was reported at high hydrostatic pressure and high salt concentrations. Here, we study the formation kinetics of these superlattices after pressure jumps beyond their crystallisation pressure by means of small-angle X-ray scattering with few ms experimental resolution. The timescale of NC formation was found to be reduced the larger the width of the pressure jump. This is connected to an increase of crystal quality, i.e., the faster the NC superlattice forms, the better the crystal quality. In contrast to the formation kinetics, the melting of the NC superlattice is approximately one order of magnitude slower and shows linear kinetics.

Strain in InP/ZnSe, S core/shell quantum dots from lattice mismatch and shell thickness-Material stiffness influence.

We investigate the buildup of strain in InP quantum dots with the addition of shells of the lower-lattice constant materials ZnSe and ZnS by Raman spectroscopy. Both materials induce compressive strain in the core, which increases with increasing shell volume. We observe a difference in the shell behavior between the two materials: the thickness-dependence points toward an influence of the material stiffness. ZnS has a larger Young's modulus and requires less material to develop stress on the InP lattice at the interface, while ZnSe requires several layers to form a stress-inducing lattice at the interface. This hints at the material stiffness being an additional parameter of relevance for designing strained core/shell quantum dots.

Nonlinear dynamics of river runoff elucidated by horizontal visibility graphs.

Horizontal Visibility Graphs (HVGs) are a recently developed method to construct networks from time series. The values of the time series are considered as the nodes of the network and are linked to each other if there is no larger value between them, such as they can "see" each other. The network properties reflect the nonlinear dynamics of the time series. For some classes of stochastic processes and for periodic time series, analytical results can be obtained for network-derived quantities such as the degree distribution, the local clustering coefficient distribution, the mean path length, and others. HVGs have the potential to discern between deterministic-chaotic and correlated-stochastic time series. Here, we investigate the sensitivity of the HVG methodology to properties and pre-processing of real-world data, i.e., time series length, the presence of ties, and deseasonalization, using a set of around 150 runoff time series from managed rivers at daily resolution from Brazil with an average length of 65 years. We show that an application of HVGs on real-world time series requires a careful consideration of data pre-processing steps and analysis methodology before robust results and interpretations can be obtained. For example, one recent analysis of the degree distribution of runoff records reported pronounced sub-exponential "long-tailed" behavior of North American rivers, whereas another study of South American rivers showed hyper-exponential "short-tailed" behavior resembling correlated noise. We demonstrate, using the dataset of Brazilian rivers, that these apparently contradictory results can be reconciled by minor differences in data-preprocessing (here: small differences in subtracting the seasonal cycle). Hence, data-preprocessing that is conventional in hydrology ("deseasonalization") changes long-term correlations and the overall runoff dynamics substantially, and we present empirical consequences and extensive simulations to investigate these issues from a HVG methodological perspective. After carefully accounting for these methodological aspects, the HVG analysis reveals that the river runoff dataset shows indeed complex behavior that appears to stem from a superposition of short-term correlated noise and "long-tailed behaviour," i.e., highly connected nodes. Moreover, the construction of a dam along a river tends to increase short-term correlations in runoff series. In summary, the present study illustrates the (often substantial) effects of methodological and data-preprocessing choices for the interpretation of river runoff dynamics in the HVG framework and its general applicability for real-world time series.

Size-Dependent Phase Transfer Functionalization of Gold Nanoparticles To Promote Well-Ordered Self-Assembly.

We present a route for the functionalization of gold nanoparticles (AuNP) based on phase transfer functionalization in order to optimize the stability and the potential for self-assembly. Depending on the desired size, different ligand exchanges have to be employed: The maximum AuNP size that can be stabilized without concentration loss is 46 nm for polystyrene-based ligands with 5 and 10 kDa. Small particles <12 nm are better stabilized by smaller ligands. We are able to demonstrate that well-ordered close-packed monolayers of 28 nm AuNP covering at least 400 µm2 are possible with a potential for much larger areas. Such monolayers are of great interest for various fundamental experiments in the context of plasmonics and SERS and for sensor applications.

Metal-Semiconductor Nanoparticle Hybrids Formed by Self-Organization: A Platform to Address Exciton-Plasmon Coupling.

Hybrid nanosystems composed of excitonic and plasmonic constituents can have different properties than the sum of of the two constituents, due to the exciton-plasmon interaction. Here, we report on a flexible model system based on colloidal nanoparticles that can form hybrid combinations by self-organization. The system allows us to tune the interparticle distance and to combine nanoparticles of different sizes and thus enables a systematic investigation of the exciton-plasmon coupling by a combination of optical spectroscopy and quantum-optical theory. We experimentally observe a strong influence of the energy difference between exciton and plasmon, as well as an interplay of nanoparticle size and distance on the coupling. We develop a full quantum theory for the luminescence dynamics and discuss the experimental results in terms of the Purcell effect. As the theory describes excitation as well as coherent and incoherent emission, we also consider possible quantum optical effects. We find a good agreement of the observed and the calculated luminescence dynamics induced by the Purcell effect. This also suggests that the self-organized hybrid system can be used as platform to address quantum optical effects.

Ligand Layer Engineering To Control Stability and Interfacial Properties of Nanoparticles.

The use of mixed ligand layers including poly(ethylene glycol)-based ligands for the functionalization of nanoparticles is a very popular strategy in the context of nanomedicine. However, it is challenging to control the composition of the ligand layer and maintain high colloidal and chemical stability of the conjugates. A high level of control and stability are crucial for reproducibility, upscaling, and safe application. In this study, gold nanoparticles with well-defined mixed ligand layers of α-methoxypoly(ethylene glycol)-ω-(11-mercaptoundecanoate) (PEGMUA) and 11-mercaptoundecanoic acid (MUA) were synthesized and characterized by ATR-FTIR spectroscopy and gel electrophoresis. The colloidal and chemical stability of the conjugates was tested by dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and UV/vis spectroscopy based experiments, and their interactions with cells were analyzed by elemental analysis. We demonstrate that the alkylene spacer in PEGMUA is the key feature for the controlled synthesis of mixed layer conjugates with very high colloidal and chemical stability and that a controlled synthesis is not possible using regular PEG ligands without the alkylene spacer. With the results of our stability tests, the molecular structure of the ligands can be clearly linked to the colloidal and chemical stabilization. We expect that the underlying design principle can be generalized to improve the level of control in nanoparticle surface chemistry.

Clustering of CdSe/CdS Quantum Dot/Quantum Rods into Micelles Can Form Bright, Non-blinking, Stable, and Biocompatible Probes.

We investigate clustered CdSe/CdS quantum dots/quantum rods, ranging from single to multiple encapsulated rods within amphiphilic diblock copolymer micelles, by time-resolved optical spectroscopy. The effect of the clustering and the cluster size on the optical properties is addressed. The clusters are bright and stable and show no blinking while retaining the fundamental optical properties of the individual quantum dots/quantum rods. Cell studies show neither unspecific uptake nor morphological changes of the cells, despite the increased sizes of the clusters.

Solid-State Chemistry on the Nanoscale: Ion Transport through Interstitial Sites or Vacancies?

How can ion-exchange process occur in nanocrystals without the size and shape changing and why is the ion transport much faster than in classical interdiffusion processes in macrocrystalline solids? We have investigated these processes at the molecular level by means of high-resolution and analytical electron microscopy in temperature-dependent kinetic experiments for several model reactions. The results clearly show a diffusion process that proceeds exclusively through the interstitial lattice positions with a subsequent "kick out" to remove individual ions from lattice sites without the formation of vacancies. This mechanism has not been observed in nanocrystalline systems before.

Out-of-equilibrium dynamics of a grid-like Fe(ii) spin crossover dimer triggered by a two-photon excitation.

The application of two-photon excitation (TPE) in the study of light-responsive materials holds immense potential due to its deeper penetration and reduced photodamage. Despite these benefits, TPE has been underutilised in the investigation of the photoinduced spin crossover (SCO) phenomenon. Here, we employ TPE to delve into the out-of-equilibrium dynamics of a SCO FeII dimer of the form [FeII(HL)2]2(BF4)4·2MeCN (HL = 3,5-bis{6-(2,2'-bipyridyl)}pyrazole). Optical transient absorption (OTA) spectroscopy in solution proves that the same dynamics take place under both one-photon excitation (OPE) and TPE. The results show the emergence of the photoinduced high spin state in less than 2 ps and with a lifetime of 147 ns. Time-resolved photocrystallography (TRXRD) reveals a single molecular reorganisation within the first 500 ps following TPE. Additionally, variable temperature single crystal X-ray diffraction (VTSCXRD) and magnetic susceptibility measurements confirm that the thermal transition is silenced by the solvent. While the results of the OTA and TRXRD utilising TPE are intriguing, the high pump fluencies required to excite enough metal centres to the high spin state may impair its practical application. Nonetheless, this study sheds light on the potential of TPE for the investigation of the out-of-equilibrium dynamics of SCO complexes.

Resolving Nonequilibrium Shape Variations among Millions of Gold Nanoparticles.

Nanoparticles, exhibiting functionally relevant structural heterogeneity, are at the forefront of cutting-edge research. Now, high-throughput single-particle imaging (SPI) with X-ray free-electron lasers (XFELs) creates opportunities for recovering the shape distributions of millions of particles that exhibit functionally relevant structural heterogeneity. To realize this potential, three challenges have to be overcome: (1) simultaneous parametrization of structural variability in real and reciprocal spaces; (2) efficiently inferring the latent parameters of each SPI measurement; (3) scaling up comparisons between 105 structural models and 106 XFEL-SPI measurements. Here, we describe how we overcame these three challenges to resolve the nonequilibrium shape distributions within millions of gold nanoparticles imaged at the European XFEL. These shape distributions allowed us to quantify the degree of asymmetry in these particles, discover a relatively stable "shape envelope" among nanoparticles, discern finite-size effects related to shape-controlling surfactants, and extrapolate nanoparticles' shapes to their idealized thermodynamic limit. Ultimately, these demonstrations show that XFEL SPI can help transform nanoparticle shape characterization from anecdotally interesting to statistically meaningful.