Quasi-Guided Modes in Titanium Dioxide Arrays Fabricated via Soft Nanoimprint Lithography.

Reversible quasi-guided modes (QGMs) are observed in titanium dioxide (TiO2) metasurface arrays fabricated via soft nanoimprint lithography. A TiO2 layer between the nanopillar array and the substrate can facilitate the propagation of QGMs. This layer is porous, allowing for the tuning of the layer properties by incorporating another material. The presence of the QGMs is strongly dependent on the refractive index of the TiO2 layer. QGMs are not supported if the refractive index of the porous TiO2 is too low. It is demonstrated that after depositing R6G on the array QGMs can be observed as very strong and narrow reflectance peaks and transmittance dips. Furthermore, as the second material can penetrate through the pores into the layer it can experience the regions of high field enhancement associated with the QGMs. These results are of interest for a wide range of applications including but not limited to sensing, nonlinear optics, and emission control.

Plasmonic nanodiscs on vanadium dioxide thin films for tunable luminescence enhancement.

We propose an alternative method to dynamically tune luminescence enhancement in the near infrared spectral range using noble metal nanostructures on top of phase change material vanadium dioxide (VO2) thin films. The VO2 phase change is used to tune the nanodisc plasmon resonance providing a luminescence modification mechanism. We employ a model to calculate the emission of quantum emitters, such as dye molecules, in hybrid systems comprising single silver (Ag) nanodiscs on top of a thin layer of VO2. The model considers different dipole orientations and positions with respect to the nanostructure-VO2 film and determines the degree of observable luminescence modification. In the NIR spectral region, the observable photoluminescence of Alexa Dyes in the hybrid systems at room temperature is enhanced by more than a factor of 2.5 as compared to the same system without plasmonic particles. An additional photoluminescence enhancement by more than a factor of 2 can be achieved with the Ag nanodisc-VO2 film systems after the phase transition of the VO2. These systems can be used for tunable luminescence modification and for compensation of thermally induced luminescence quenching. Through optimization of the Ag nanodisc-VO2 film system, luminescence enhancements of up to a factor of 4 can be seen in the metallic VO2 compared to the semiconducting phase and would therefore compensate for a thermal quenching of up to 70% between room temperature and 70° C, rendering the hybrid systems as promising candidates for improved photon management in optoelectronic devices where elevated temperatures minimize the efficiencies of such devices.

Plasmon-Assisted Direction- and Polarization-Sensitive Organic Thin-Film Detector.

Utilizing Bragg surface plasmon polaritons (SPPs) on metal nanostructures for the use in optical devices has been intensively investigated in recent years. Here, we demonstrate the integration of nanostructured metal electrodes into an ITO-free thin film bulk heterojunction organic solar cell, by direct fabrication on a nanoimprinted substrate. The nanostructured device shows interesting optical and electrical behavior, depending on angle and polarization of incidence and the side of excitation. Remarkably, for incidence through the top electrode, a dependency on linear polarization and angle of incidence can be observed. We show that these peculiar characteristics can be attributed to the excitation of dispersive and non-dispersive Bragg SPPs on the metal-dielectric interface on the top electrode and compare it with incidence through the bottom electrode. Furthermore, the optical and electrical response can be controlled by the organic photoactive material, the nanostructures, the materials used for the electrodes and the epoxy encapsulation. Our device can be used as a detector, which generates a direct electrical readout and therefore enables the measuring of the angle of incidence of up to 60° or the linear polarization state of light, in a spectral region, which is determined by the active material. Our results could furthermore lead to novel organic Bragg SPP-based sensor for a number of applications.

Influence of Gold Nano-Bipyramid Dimensions on Strong Coupling with Excitons of Monolayer MoS2.

Rabi splitting between the longitudinal plasmon of a gold nano-bipyramid and the A exciton of monolayer MoS2 is observed at room temperature. The dependence of the Rabi splitting on the physical dimensions of the nano-bipyramid is reported. The impact of bipyramid length, aspect ratio, and tip radius on the coupling strength is investigated. The mode volume of the nanoresonator is significantly reduced because of the sharp tips of the bipyramid, and the Rabi splitting increases with tip sharpness. The results also reveal that greater Rabi splitting is observed for larger bipyramids, contrasting with results previously reported for different nanoresonator shapes. This shows, for the first time, how the magnitude of the splitting has a different response for particular nanoresonators when tuning the size, without increasing the number of excitons coupled into the system. The Rabi splitting, at zero energy detuning between plasmon and A exciton, increases from ∼55 meV with a 70 nm-long bipyramid to ∼80 meV with a 100 nm-long bipyramid. The increase in coupling strength with size arises because of increasing confinement of the field enhancement at the bipyramid tip.

Plasmonic Colour Printing by Light Trapping in Two-Metal Nanostructures.

Structural colour generation by nanoscale plasmonic structures is of major interest for non-bleaching colour printing, anti-counterfeit measures and decoration applications. We explore the physics of a two-metal plasmonic nanostructure consisting of metallic nanodiscs separated from a metallic back-reflector by a uniform thin polymer film and investigate the potential for vibrant structural colour in reflection. We demonstrate that light trapping within the nanostructures is the primary mechanism for colour generation. The use of planar back-reflector and polymer layers allows for less complex fabrication requirements and robust structures, but most significantly allows for the easy incorporation of two different metals for the back-reflector and the nanodiscs. The simplicity of the structure is also suitable for scalability. Combinations of gold, silver, aluminium and copper are considered, with wide colour gamuts observed as a function of the polymer layer thickness. The structural colours are also shown to be insensitive to the viewing angle. Structures of copper nanodiscs with an aluminium back-reflector produce the widest colour gamut.

Plasmonic Horizon in Gold Nanosponges.

An electromagnetic wave impinging on a gold nanosponge coherently excites many electromagnetic hot-spots inside the nanosponge, yielding a polarization-dependent scattering spectrum. In contrast, a hole, recombining with an electron, can locally excite plasmonic hot-spots only within a horizon given by the lifetime of localized plasmons and the speed carrying the information that a plasmon has been created. This horizon is about 57 nm, decreasing with increasing size of the nanosponge. Consequently, photoluminescence from large gold nanosponges appears unpolarized.

Hybrid Multilayered Plasmonic Nanostars for Coherent Random Lasing.

Here, we report that hybrid multilayered plasmonic nanostars can be universally used as feedback agents for coherent random lasing in polar or nonpolar solutions containing gain material. We show that silver-enhancement of gold nanostars reduces the pumping threshold for coherent random lasing substantially for both a typical dye (R6G) and a typical fluorescent polymer (MEH-PPV). Further, we reveal that the lasing intensity and pumping threshold of random lasers based on silver-enhanced gold nanostars are not influenced by the silica coating, in contrast to gold nanostar-based random lasers, where silica-coated gold nanostars support only amplified spontaneous emission but no coherent random lasing.

Anticorrelation of Photoluminescence from Gold Nanoparticle Dimers with Hot-Spot Intensity.

Bulk gold shows photoluminescence (PL) with a negligible quantum yield of ∼10-10, which can be increased by orders of magnitude in the case of gold nanoparticles. This bears huge potential to use noble metal nanoparticles as fluorescent and unbleachable stains in bioimaging or for optical data storage. Commonly, the enhancement of the PL yield is attributed to nanoparticle plasmons, specifically to the enhancements of scattering or absorption cross sections. Tuning the shape or geometry of gold nanostructures (e.g., via reducing the distance between two nanoparticles) allows for redshifting both the scattering and the PL spectra. However, while the scattering cross section increases with a plasmonic redshift, the PL yield decreases, indicating that the common simple picture of a plasmonically boosted gold luminescence needs more detailed consideration. In particular, precise experiments as well as numerical simulations are required. Hence, we systematically varied the distance between the tips of two gold bipyramids on the nanometer scale using AFM manipulation and recorded the PL and the scattering spectra for each separation. We find that the PL intensity decreases as the interparticle coupling increases. This anticorrelation is explained by a theoretical model where both the gold-intrinsic d-band hole recombination probabilities as well as the field strength inside the nanostructure are considered. The scattering cross section or the field strength in the hot-spot between the tips of the bipyramids are not relevant for the PL intensity. Besides, we not only observe PL supported by dipolar plasmon resonances, but also measure and simulate PL supported by higher order plasmonic modes.

Plasmonic Nanostars as Efficient Broadband Scatterers for Random Lasing.

Huge spectral coverage of random lasing throughout the visible up to the infrared range is achieved with star-shaped gold nanoparticles ("nanostars"). As intrinsically broadband scattering centers, the nanostars are suspended in solutions of various laser dyes, forming randomly arranged resonators which support coherent laser modes. The narrow emission line widths of 0.13 nm or below suggest that gold nanostars provide an efficient coherent feedback for random lasers over an extensive range of wavelengths, all together spanning almost a full optical octave from yellow to infrared.

Minimal spaser threshold within electrodynamic framework: Shape, size and modes.

It is known (yet often ignored) from quantum mechanical or energetic considerations, that the threshold gain of the quasi-static spaser depends only on the dielectric functions of the metal and the gain material. Here, we derive this result from the purely classical electromagnetic scattering framework. This is of great importance, because electrodynamic modelling is far simpler than quantum mechanical one. The influence of the material dispersion and spaser geometry are clearly separated; the latter influences the threshold gain only indirectly, defining the resonant wavelength. We show that the threshold gain has a minimum as a function of wavelength. A variation of nanoparticle shape, composition, or spasing mode may shift the plasmonic resonance to this optimal wavelength, but it cannot overcome the material-imposed minimal gain. Furthermore, retardation is included straightforwardly into our framework; and the global spectral gain minimum persists beyond the quasi-static limit. We illustrate this with two examples of widely used geometries: Silver spheroids and spherical shells embedded in and filled with gain materials.

Optical Plasmons of Individual Gold Nanosponges.

The search for novel plasmonic nanostructures, which can act simultaneously as optical detectors and stimulators, is crucial for many applications in the fields of biosensing, electro- and photocatalysis, electrochemistry, and biofuel generation. In most of these areas, a large surface-to-volume ratio, as well as high density of active surface sites, is desirable. We investigate sponge-like, that is, fully porous, nanoparticles, called nanosponges, where both the gold and the air phase are fully percolated in three dimensions. We correlate, on a single nanoparticle basis, their optical scattering spectra (using dark field microscopy) with their individual morphology (using electron microscopy). We find that the scattering spectra of nanosponges depend only weakly on their size and outer shape, but are greatly influenced by their unique percolation, in qualitative agreement with numerical simulations.

Giant cross polarization in a nanoimprinted metamaterial combining a fishnet with its Babinet complement.

We present a large area (1 cm2) nanoimprinted metamaterial comprising a fishnet structure and its Babinet complement, which shows giant cross polarization. When illuminated with s-polarized light, the reflected beam can be p-polarized up to 96%, depending on the azimuthal orientation of the sample. This experimental result is close to the result of numerical simulations, which predict 98.7% of cross-polarization. It is further shown, that 95-100% cross polarization is only achieved in the case when the fishnet is combined with its Babinet complement. Each structure alone (either an ordinary fishnet or a plane with metallic rectangles only) shows substantially less polarization conversion.

Random Lasing with Systematic Threshold Behavior in Films of CdSe/CdS Core/Thick-Shell Colloidal Quantum Dots.

While over the past years the syntheses of colloidal quantum dots (CQDs) with core/shell structures were continuously improved to obtain highly efficient emission, it has remained a challenge to use them as active materials in laser devices. Here, we report random lasing at room temperature in films of CdSe/CdS CQDs with different core/shell band alignments and extra thick shells. Even though the lasing process is based on random scattering, we find systematic dependencies of the laser thresholds on morphology and laser spot size. To minimize laser thresholds, optimizing the film-forming properties of the CQDs, proven by small-angle X-ray scattering, was found to be more important than the optical parameters of the CQDs, such as biexciton lifetime and binding energy or fluorescence decay time. Furthermore, the observed systematic behavior turned out to be highly reproducible after storing the samples in air for more than 1 year. These highly reproducible systematic dependencies suggest that random lasing experiments are a valuable tool for testing nanocrystal materials, providing a direct and simple feedback for further development of colloidal gain materials toward lasing in continuous wave operation.

Gold nanostars for random lasing enhancement.

We demonstrate random lasing with star-shaped gold nanoparticles ("nanostars") as scattering centers embedded in a dye-doped gain medium. It is experimentally shown that star-shaped gold nanoparticles outperform those of conventional shapes, such as spherical or prolate nanoparticles. The nanoparticles are randomly distributed within a thin film of gain medium, forming resonators which support coherent laser modes. Driven by single-pulsed excitation, the random lasers exhibit coherent lasing thresholds in the order of 0.9 mJ/cm(2) and spectrally narrow emission peaks with linewidths less than 0.2 nm. The distinguished random laser comprising nanostars is likely to take advantage of the high plasmonic field enhancements, localized at the spiky tips of the nanostars, which improves the feedback mechanism for lasing and increases the emission intensity of the random laser.

Quantitative understanding of the optical properties of a single, complex-shaped gold nanoparticle from experiment and theory.

We report on a combined study of Rayleigh and Raman scattering spectroscopy, 3D electron tomography, and discrete dipole approximation (DDA) calculations of a single, complex-shaped gold nanoparticle (NP). Using the exact reconstructed 3D morphology of the NP as input for the DDA calculations, the experimental results can be reproduced with unprecedented precision and detail. We find that not only the exact NP morphology but also the surroundings including the points of contact with the substrate are of crucial importance for a correct prediction of the NP optical properties. The achieved accuracy of the calculations allows determining how many of the adsorbed molecules have a major contribution to the Raman signal, a fact that has important implications for analyzing experiments and designing sensing applications.

120 nm resolution and 55 nm structure size in STED-lithography.

Two-photon direct laser writing (DLW) lithography is limited in the achievable structure size as well as in structure resolution. Adding stimulated emission depletion (STED) to DLW allowed overcoming both restrictions. We now push both to new limits. Using visible light for two-photon DLW (780 nm) and STED (532 nm), we obtain lateral structure sizes of 55 nm, a Sparrow limit of around 100 nm and we present two clearly separated lines spaced only 120 nm apart. The photo-resist used in these experiments is a mixture of tri- and tetra-acrylates and 7-Diethylamino-3-thenoylcoumarin as a photo-starter which can be readily quenched via STED.

Spectral and directional reshaping of fluorescence in large area self-assembled plasmonic-photonic crystals.

Spectral and directional reshaping of fluorescence from dye molecules embedded in self-assembled hybrid plasmonic-photonic crystals has been examined. The hybrid crystals comprise two-dimensional hexagonal arrays of dye-doped dielectric nanospheres, capped with silver semishells. Comparing the reshaped fluorescence spectra with measured transmission/reflection spectra and numerical calculations reveals that the spectral and directional reshaping of fluorescence is the result of its coupling to photonic crystal Bloch modes and to void plasmons localized inside the silver caps.

Dye-doped spheres with plasmonic semi-shells: Lasing modes and scattering at realistic gain levels.

We numerically simulate the compensation of absorption, the near-field enhancement as well as the differential far-field scattering cross section for dye-doped polystyrene spheres (radius 195 nm), which are half-covered by a silver layer of 10-40 nm thickness. Such silver capped spheres are interesting candidates for nanoplasmonic lasers, so-called spasers. We find that spasing requires gain levels less than 3.7 times higher than those in commercially available dye-doped spheres. However, commercially available concentrations are already apt to achieve negative absorption, and to narrow and enhance scattering by higher order modes. Narrowing of the plasmonic modes by gain also makes visible higher order modes, which are normally obscured by the broad spectral features of the lower order modes. We further show that the angular distribution of the far-field scattering of the spasing modes is by no means dipole-like and is very sensitive to the geometry of the structure.

Triggering the volume phase transition of core-shell Au nanorod-microgel nanocomposites with light.

We have coated gold nanorods (NRs) with thermoresponsive microgel shells based on poly(N-isopropylacrylamide) (pNIPAM). We demonstrate by simultaneous laser-heating and optical extinction measurements that the Au NR cores can be simultaneously used as fast optothermal manipulators (switchers) and sensitive optical reporters of the microgel state in a fully externally controlled and reversible manner. We support our results with optical modeling based on the boundary element method and 3D numerical analysis on the temperature distribution. Briefly, we show that due to the sharp increase in refractive index resulting from the optothermally triggered microgel collapse, the longitudinal plasmon band of the coated Au NRs is significantly red-shifted. The optothermal control over the pNIPAM shell, and thereby over the optical response of the nanocomposite, is fully reversible and can be simply controlled by switching on and off a NIR heating laser. In contrast to bulk solution heating, we demonstrate that light-triggering does not compromise colloidal stability, which is of primary importance for the ultimate utilization of these types of nanocomposites as remotely controlled optomechanical actuators, for applications spanning from drug delivery to photonic crystals and nanoscale motion.

Selective excitation of individual plasmonic hotspots at the tips of single gold nanostars.

Plasmonic hotspots in single gold nanostars are located at the tips and can be excited selectively by laser light as evidenced by photoelectron emission microscopy. Selectivity is achieved through wavelength and polarization of the excitation light. Comparing photoelectron emission intensity and dark-field scattering spectra of the same individual nanostars reveals differences in terms of observable plasmon resonance wavelengths and field enhancements. Differences are explained with the underlying near- and far-field processes of the two techniques.