P. Kepič: Arrays of Plasmonic Nanostructures Made of Phase-Change Materials (BUT, 2019) (bachelor’s thesis)
Fundamentals of cathodoluminescence in a STEM: The impact of sample geometry and electron beam energy on light emission of semiconductors by Michael Stöger-Pollach, Kristýna Bukvišová, Sabine Schwarz, Michal Kvapil, Tomáš Šamořil and Michal Horák
Ultramicroscopy Volume 200, May 2019, Pages 111-124
Link to ORDP experimental dataset
Cathodoluminescence has attracted interest in scanning transmission electron microscopy since the advent of commercial available detection systems with high efficiency, like the Gatan Vulcan or the Attolight Mönch system. In this work we discuss light emission caused by high-energy electron beams when traversing a semiconducting specimen. We nd that it is impossible to directly interpret the spectrum of the emitted light to the inter-band transitions excited by the electron beam, because the Čerenkov effect and the related light guiding modes as well as transition radiation is altering the spectra. Total inner re ection and subsequent interference effects are changing the spectral shape dependent on the sample shape and geometry, sample thickness, and beam energy, respectively. A detailed study on these parameters is given using silicon and GaAs as test materials.
Formation of Tungsten Oxide Nanowires by Electron-Beam-Enhanced Oxidation of WS2 Nanotubes and Platelets by Miroslav Kolíbal, Kristýna Bukvišová, Lukáš Kachtík, Alla Zak, Libor Novák, and Tomáš Šikola
J. Phys. Chem. C, DOI: 10.1021/acs.jpcc.9b00592, March 9 2019
Link to Open access version
Link to ORDP experimental dataset
Oxidation of van der Waals-bonded layered semiconductors plays a key role in deterioration of their superior optical and electronic properties. The oxidation mechanism of these materials is, however, different from non-layered semiconductors in many aspects. Here, we show a rather unusual oxidation of tungsten disulfide (WS2) nanotubes and platelets in a high vacuum chamber at a presence of water vapor and at elevated temperatures. The process results in formation of small tungsten oxide nanowires on the surface of WS2. Utilizing real-time scanning electron microscopy we are able to unravel the oxidation mechanism, which proceeds via reduction of initially formed WO3 phase into W18O49 nanowires. Moreover, we show that the oxidation reaction can be localized and enhanced by an electron beam irradiation, which allows for on-demand growth of tungsten oxide nanowires.
Geometric-Phase Microscopy for Quantitative Phase Imaging of Isotropic, Birefringent and SpaceVariant Polarization Samples by Petr Bouchal; Lenka Štrbková; Zbyněk Dostál; Radim Chmelík, and Zdeněk Bouchal
Scientific Reports 9, Article number: 3608 (2019), March 5 2019 (Open Access)
We present geometric-phase microscopy allowing a multipurpose quantitative phase imaging in which the ground-truth phase is restored by quantifying the phase retardance. The method uses broadband spatially incoherent light that is polarization sensitively controlled through the geometric (Pancharatnam-Berry) phase. The assessed retardance possibly originates either in dynamic or geometric phase and measurements are customized for quantitative mapping of isotropic and birefringent samples or multi-functional geometric-phase elements. The phase restoration is based on the self-interference of polarization distinguished waves carrying sample information and providing pure reference phase, while passing through an inherently stable common-path setup. The experimental configuration allows an instantaneous (single-shot) phase restoration with guaranteed subnanometer precision and excellent ground-truth accuracy (well below 5 nm). The optical performance is demonstrated in advanced yet routinely feasible noninvasive biophotonic imaging executed in the automated manner and predestined for supervised machine learning. The experiments demonstrate measurement of cell dry mass density, cell classification based on the morphological parameters and visualization of dynamic dry mass changes. The multipurpose use of the method was demonstrated by restoring variations in the dynamic phase originating from the electrically induced birefringence of liquid crystals and by mapping the geometric phase of a space-variant polarization directed lens.
High-Resolution Quantitative Phase Imaging of Plasmonic Metasurfaces with Sensitivity down to a Single Nanoantenna by Petr Bouchal, Petr Dvořák, Jiří Babocký, Zdeněk Bouchal, Filip Ligmajer, Martin Hrtoň, Vlastimil Křápek, Alexander Fassbender, Stefan Linden, Radim Chmelík, and Tomáš Šikola
Nano Lett. 2019, 19 (2), 1242-1250; DOI: 10.1021/acs.nanolett.8b04776, January 2 2019
Optical metasurfaces have emerged as a new generation of building blocks for multi-functional optics. Design and realization of metasurface elements place ever-increasing demands on accurate assessment of phase alterations introduced by complex nanoantenna arrays, a process referred to as quantitative phase imaging. Despite considerable effort, the widefield (non-scanning) phase imaging that would approach resolution limits of optical microscopy and indicate the response of a single nanoantenna still remains a challenge. Here, we report on a new strategy in incoherent holographic imaging of metasurfaces, in which unprecedented spatial resolution and light sensitivity are achieved by taking full advantage of the polarization selective control of light through the geometric (Pancharatnam-Berry) phase. The measurement is carried out in an inherently stable common-path setup composed of a standard optical microscope and an add-on imaging module. Phase information is acquired from the mutual coherence function attainable in records created in broadband spatially incoherent light by the self-interference of scattered and leakage light coming from the metasurface. In calibration measurements, the phase was mapped with the precision and spatial background noise better than 0.01 rad and 0.05 rad, respectively. The imaging excels at the high spatial resolution that was demonstrated experimentally by the precise amplitude and phase restoration of vortex metalenses and a metasurface grating with 833 lines/mm. Thanks to superior light sensitivity of the method, we demonstrated, for the first time to our knowledge, the widefield measurement of the phase altered by a single nanoantenna, while maintaining the precision well below 0.15 rad.
Preparation of ultrafine fibrous uranium dioxide by electrospinning by Vojtech Kundrat, Ales Patak, and Jiri Pinkas
Journal of Nuclear Materials; available online 1 Nov 2019 DOI: 10.1016/j.jnucmat.2019.151877
We are introducing for the first time a robust method for the preparation of uranium oxide nanofibers with extraordinary thin diameters. We have studied the preparation of U3O8 and UO2 nanofibers by the electrospinning method from uranyl acetylacetonate in mixed organic solvents. Polyvinylpyrrolidone (PVP) was used as a supporting polymer. Besides studying and optimizing the solution systems, we have also examined the effects of collector material on the properties of the fiber mat. We have found that calcination of electrospun green composite fibers deposited on aluminum foil produces U3O8 nanofibers with the lowest average diameter of 20 ± 5 nm as their adhesion prevents fiber shrinking. We have also studied calcination of fibers on ashless paper and freestanding composite mats. Reduction of U3O8 fibers in H2/N2 atmosphere at various temperatures provided uranium dioxide nanofibers with an average diameter of 90 nm.
Non-diffracting light in nature: Anomalously reflected self-healing Bessel beams from jewel scarabs by Petr Bouchal, Josef Kapitán, Martin Konečný, Marek Zbončák a Zdeněk Bouchal
We report a study of spatial light modulation in the photonic structure of jewel scarabs, revealing the interplay of the polarization and phase control of light, which is not possible with the current optical technology. Phase measurements performed on jewel scarabs demonstrate that the polarization anomalous (helicity-preserving) reflection of light occurs together with alteration of the dynamic phase associated with the optical path length. This control of light differs from the operation of artificially prepared polarization-sensitive structures, shaping light through the geometric phase altered by the polarization transformation. Challenging three-dimensional imaging of the cuticle, requiring high-resolution quantitative mapping of steep phase changes, has been achieved owing to the optical performance of recently developed geometric-phase microscopy. We find that the cuticle of jewel scarabs is formed of micrometer-sized axicon cells, generating thousands of Bessel beams with subwavelength spot size. The nondiffracting features and the self-healing ability of the Bessel beams originating from the beetle Chrysina gloriosa are demonstrated experimentally. Considering Bragg reflection and shaping of RGB components of white light Bessel beams, we explain the spatial structuring of colors in microscopic images of jewel scarabs and reveal the conversion of colors when changing the distance from the cuticle. The functionality and performance of the cuticle axicon cells are discussed in comparison with high-aperture dielectric meta-axicons, and potential applications in colorimetric refractive index sensing are outlined.
Complex k-uniform tilings by a simple bitopic precursor self-assembled on Ag(001) surface by Lukáš Kormoš, Pavel Procházka, Anton O. Makoveev and Jan Čechal
The realization of complex long-range ordered structures in a Euclidean plane presents a significant challenge en route to the utilization of their unique physical and chemical properties. Recent progress in on-surface supramolecular chemistry has enabled the engineering of regular and semi-regular tilings, expressing translation symmetric, quasicrystalline, and fractal geometries. However, the k-uniform tilings possessing several distinct vertices remain largely unexplored. Here, we show that these complex geometries can be prepared from a simple bitopic molecular precursor – 4,4’-biphenyl dicarboxylic acid (BDA) – by its controlled chemical transformation on the Ag(001) surface. The realization of 2- and 3-uniform tilings is enabled by partially carboxylated BDA mediating the seamless connection of two distinct binding motifs in a single long-range ordered molecular phase. These results define the basic self-assembly criteria, opening way to the utilization of complex supramolecular tilings.
Multi-Electrode Array with a Planar Surface for Cell Patterning by Microprinting by Jan Slavík; Josef Skopalík; Ivo Provazník; and Jaromír Hubálek
Multielectrode arrays (MEAs) are devices for non-invasive electrophysiological measurements of cell populations. This paper describes a novel fabrication method of MEAs with a fully planar surface. The surface of the insulation layer and the surface of the electrodes were on one plane; we named this device the planar MEA (pMEA). The main advantage of the pMEA is that it allows uniform contact between the pMEA surface and a substrate for positioning of microfluidic channels or microprinting of a cell adhesive layer. The fabrication of the pMEA is based on a low adhesive Au sacrificial peel-off layer. In divergence from conventional MEAs with recessed electrodes, the electrodes of the pMEA lead across the sloped edge of the insulation layer. To make this, the profile of the edge of the insulation layer was measured and the impedance of the planar electrodes was characterized. The impedance of the pMEA was comparable with the impedance of conventional MEA electrodes. The pMEA was tested for patterning HL-1 cells with a combination of imprinting fibronectin and coating by antifouling poly (l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG). The HL-1 cells remained patterned even at full confluency and presented spontaneous and synchronous beating activity.
Low temperature selective growth of GaN single crystals on pre-patterned Si substrates by Jindřich Mach, Jakub Piastek, Jaroslav Maniš, Vojtěch Čalkovský, Tomáš Šamořil, Jana Damková, Miroslav Bartošík, Stanislav Voborný, Martin Konečný and Tomáš Šikola
We report on a hybrid method for fabrication of arrays of GaN nanocrystals by low-temperature UHV selective growth on pre-patterned silicon substrates covered by native oxide. Patterning of the substrates was performed by using a gallium focused ion beam (FIB). To get GaN nanocrystals at specific positions, Ga droplets were created at FIB patterned sites by evaporation of Ga atoms at 280 °C substrate temperature first, and then modified by their post-nitridation using an ultra-low energy (50 eV) nitrogen ion–beam at a sample temperature of 200 °C. To get larger arrays of GaN nanocrystals (≈150 nm and 200 nm in diameter), such a sequential process was repeated in several cycles at slightly modified operation conditions. The quality of the nanocrystals was checked by measurement of their photoluminescence properties which proved the occurrence of the peak of a band edge emission at around 367 nm (3.38 eV).
Independent engineering of individual plasmon modes in plasmonic dimers with conductive and capacitive coupling by Vlastimil Křápek; Andrea Konečná; Michal Horák; Filip Ligmajer; Michael Stöger-Pollach; Martin Hrtoň; Jiří Babocký; and Tomáš Šikola
We revisit plasmon modes in nanoparticle dimers with conductive or insulating junction resulting in conductive or capacitive coupling. In our study, which combines electron energy loss spectroscopy, optical spectroscopy, and numerical simulations, we show the coexistence of strongly and weakly hybridised modes. While the properties of the former ones strongly depend on the nature of the junction, the properties of the latter ones are nearly unaffected. This opens up a prospect for independent engineering of individual plasmon modes in a single plasmonic antenna. In addition, we show that Babinet’s principle allows to engineer the near field of plasmon modes independent of their energy. Finally, we demonstrate that combined electron energy loss imaging of a plasmonic antenna and its Babinet-complementary counterpart allows to reconstruct the distribution of both electric and magnetic near fields of localised plasmon resonances supported by the antenna, as well as charge and current antinodes of related charge oscillations.
Effect of deposition angle on fabrication of plasmonic gold nanocones and nanodiscs by Jiří Liška, Filip Ligmajer, Pedro V. Pinho N., Lukáš Kejík, Michal Kvapil, Petr Dvořák, Michal Horký, Nikolaus S. Leitner, Erik Reimhult, and Tomáš Šikola; Microelectronic Engineering, Volume 228, 1 May 2020, 111326.
Metal nanocones can exhibit several strong plasmonic resonances, which are associated with intense and accessible electromagnetic hot spots. They can thus be used to enhance light–matter interactions or to facilitate location-specific sensing while enabling separation of some non-specific contributions towards the sensing signal. Nanocones and similar 3D structures are often fabricated with the use of the so-called self-shading effect, which occurs during the evaporation of a metal film into circular nanowells. Unfortunately, a full description of a successful deposition process with all the essential details is currently missing in literature. Here we present a detailed view of the fabrication of ordered arrays of conical gold nanostructures using electron beam lithography and gold electron beam evaporation. We show that the symmetry of the fabricated nanostructures is influenced by the lateral position of the substrate on the sample holder during the deposition. Off-axis deposition or tilt of the sample leads to asymmetric nanostructures. When the deposited film is thick enough, or the nanowells narrow enough, the entrance aperture is clogged, and nanocones with sharp tips are formed. In contrast, flat-top truncated cones are produced for thinner films or wider nanowells. All these findings help to identify inherent limits for the production of wafer-scale arrays of such non-planar nanostructures. On the other hand, they also suggest new fabrication possibilities for more complicated structures such as mutually connected nanocones for electrically addressable chips.
Vacuum Rabi splitting of a dark plasmonic cavity mode revealed by fast electrons by Ora Bitton; Satyendra Nath Gupta; Lothar Houben; Michal Kvapil; Vlastimil Křápek; Tomáš Šikola; and Gilad Haran
Recent years have seen a growing interest in strong coupling between plasmons and excitons, as a way to generate new quantum optical testbeds and influence chemical dynamics and reactivity. Strong coupling to bright plasmonic modes has been achieved even with single quantum emitters. Dark plasmonic modes fare better in some applications due to longer lifetimes, but are difficult to probe as they are subradiant. Here, we apply electron energy loss (EEL) spectroscopy to demonstrate that a dark mode of an individual plasmonic bowtie can interact with a small number of quantum emitters, as evidenced by Rabi-split spectra. Coupling strengths of up to 85 meV place the bowtie-emitter devices at the onset of the strong coupling regime. Remarkably, the coupling occurs at the periphery of the bowtie gaps, even while the electron beam probes their center. Our findings pave the way for using EEL spectroscopy to study exciton-plasmon interactions involving non-emissive photonic modes.
Single-layer graphene on epitaxial FeRh thin films by Vojtěch Uhlíř; Federico Pressacco; Jon Ander Arregi; Pavel Procházka; Stanislav Průša; Michal Potoček; Tomáš Šikola; Jan Čechal; Azzedine Bendounan; and Fausto Sirotti
Graphene is a 2D material that displays excellent electronic transport properties with prospective applications in many fields. Inducing and controlling magnetism in the graphene layer, for instance by proximity of magnetic materials, may enable its utilization in spintronic devices. This paper presents fabrication and detailed characterization of single-layer graphene formed on the surface of epitaxial FeRh thin films. The magnetic state of the FeRh surface can be controlled by temperature, magnetic field or strain due to interconnected order parameters. Characterization of graphene layers by X-ray Photoemission and X-ray Absorption Spectroscopy, Low-Energy Ion Scattering, Scanning Tunneling Microscopy, and Low-Energy Electron Microscopy shows that graphene is single-layer, polycrystalline and covers more than 97% of the substrate. Graphene displays several preferential orientations on the FeRh(0 0 1) surface with unit vectors of graphene rotated by 30°, 15°, 11°, and 19° with respect to FeRh substrate unit vectors. In addition, the graphene layer is capable to protect the films from oxidation when exposed to air for several months. Therefore, it can be also used as a protective layer during fabrication of magnetic elements or as an atomically thin spacer, which enables incorporation of switchable magnetic layers within stacks of 2D materials in advanced devices.
Thermal properties of Ag@Ni core-shell nanoparticles by Vít Vykoukal, František Zelenka, Jiří Bursík, Tomáš Kaňa, Aleš Kroupa, and Jiří Pinkas
We synthesized Ag@Ni core-shell nanoparticles by the solvothermal hot injection method and characterized them as for their shape and size by dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). We previously demonstrated their core-shell structure by scanning transmission electron microscopy with energy dispersive spectroscopy (STEM-EDS). The silver/nickel phase diagram was calculated by the CALPHAD method, and the melting points of 10, 15, and 20 nm silver nanoparticles were predicted at 930.2, 940.7, and 946.0 °C, respectively. We took advantage of the nickel shell to avoid silver sintering and to confirm the calculated melting point depression (MPD). The results obtained from the differential scanning calorimetry (DSC) experiments revealed the melting points of 11–15 nm nanoparticles at 944–949 °C in agreement with calculated values.
Preparation of thorium dioxide nanofibers by electrospinning by Vojtěch Kundrát; Zdeněk Moravec and Jiří Pinkas
Journal of Nuclear Materials; available online 14 April 2020 DOI: 10.1016/j.jnucmat.2020.152153
For the first time, we report the preparation of thorium dioxide with nanofibrous morphology by the electrospinning method. Two approaches were employed with different electrospun solution compositions and inorganic precursors. Thorium nitrate with polyvinyl alcohol (PVA) as a supporting polymer was successfully electrospun from an aqueous solution resulting in green composite fibers that were calcined at 773 K to pure ThO2 nanofibers of diameter 76 ± 25 nm. Another precursor solution was based on organic solvents and thorium acetylacetonate complex with polyvinylpyrrolidone (PVP). Green fibers were calcined at 673 K to porous nanofibers of ThO2 with an average diameter of 34 ± 18 nm and surface area of 85 m2 g-1 . The prepared materials were characterized by TGA-DSC, SEM, TEM, PXRD, and BET methods.
Using Čerenkov radiation for measuring the refractive index in thick samples by interferometric cathodoluminescence by Michael Stöger-Pollach, Stefan Löffler, Niklas Maurer, and Kristýna Bukvišová
Link to ORDP experimental dataset (coming soon)
Cathodoluminescence (CL) has evolved into a standard analytical technique in (scanning) transmission electron microscopy. CL utilizes light excited due to the interactions between the electron-beam and the sample. In the present study we focus on Cˇerenkov radiation. We make use of the fact that the electron transparent specimen acts as a Fabry-Pérot interferometer for coherently emitted radiation. From the wavelength dependent interference pattern of thickness dependent measurements we calculate the refractive index of the studied material. We describe the limits of this approach and compare it with the determination of the refractive index by using valence electron energy loss spectrometry (VEELS).
Magnetic Near Field Imaging with Electron Energy Loss Spectroscopy Based on Babinet's Principle by Michal Horák, Vlastimil Křápek, Martin Hrtoň, Andrea Konečná, Filip Ligmajer, Michael Stöger-Pollach and Tomáš Šikola
Conference paper in the proceedings of Microscopy & Microanalysis 2020 (4th–7th August, Milwaukee, USA, held in a virtual form) published as a supplement of impact journal Microscopy and Microanalysis.
Optical topography of rough surfaces using vortex localization of fluorescent markers by Petr Schovánek, Petr Bouchal, and Zdeněk Bouchal
Measuring rough surfaces is challenging because the proven topographic methods are impaired by the adverse effects of diffuse light. In our method, the measured surface is marked by fluorescent nanobeads allowing a complete suppression of diffuse light by bandpass filtering. Light emitted by each fluorescent bead is shaped to a double-helix point spread function used for three-dimensional bead localization on the surface. This non-interferometric measurement of rough surface topography is implemented in a vibration resistant setup. The comparison of our method with vertical scanning interferometry shows that a commercial profiler is surpassed when ground glass surfaces with steep slopes are measured.
Collector Droplet Behavior during Formation of Nanowire Junctions by Yanming Wang, Tomáš Šikola, and
Formation of nanowire networks is an appealing strategy for demonstrating novel phenomena at the nanoscale, e.g., detection of Majorana Fermions, as well as an essential step in realizing complex nanowire-based architectures. However, a detailed description of mechanisms taking place during growth of such complex structures is lacking. Here, the experimental observations of gold-catalyzed germanium nanowire junction formation are explained utilizing phase field modeling corroborated with real-time in situ scanning electron microscopy. When the two nanowires collide head on during the growth, we observe two scenarios. (i) Two catalytic droplets merge into one, and the growth continues as a single nanowire. (ii) The droplets merge and subsequently split again, giving rise to the growth of two daughter nanowires. Both the experiments and modeling indicate the critical importance of the liquid–solid growth interface anisotropy and the growth kinetics in facilitating the structural transition during the nanowire merging process.
Mechanism and Suppression of Physisorbed-Water-Caused Hysteresis in Graphene FET Sensors by Miroslav Bartošík, Jindřich Mach, Jakub Piastek, David Nezval, Martin Konečný, Vojtěch Švarc, Klaus Ensslin, and Tomáš Šikola
JACS Sensors 2020 5 (9), 2940-2949 - open access version
Hysteresis is a problem in field-effect transistors (FETs) often caused by defects and charge traps inside a gate isolating (e.g., SiO2) layer. This work shows that graphene-based FETs also exhibit hysteresis due to water physisorbed on top of graphene determined by the relative humidity level, which naturally happens in biosensors and ambient operating sensors. The hysteresis effect is explained by trapping of electrons by physisorbed water, and it is shown that this hysteresis can be suppressed using short pulses of alternating gate voltages.
Fundamental Limit of Plasmonic Cathodoluminescence by Franz-Philipp Schmidt, Arthur Losquin,
Michal Horák, Ulrich Hohenester, Michael Stöger-Pollach, and Joachim R. Krenn
We use cathodoluminescence (CL) spectroscopy in a transmission electron microscope to probe the radial breathing mode of plasmonic silver nanodisks. A two-mirror detection system sandwiching the sample collects the CL emission in both directions, that is, backward and forward with respect to the electron beam trajectory. We unambiguously identify a spectral shift of about 8 nm in the CL spectra acquired from both sides and show that this asymmetry is induced by the electron beam itself. By numerical simulations, we confirm the observations and identify the underlying physical effect due to the interference of the CL emission patterns of an electron-beam-induced dipole and the breathing mode. This effect can ultimately limit the achievable fidelity in CL measurements on any system involving multiple excitations and should therefore be considered with care in high-precision experiments.
Tungsten disulfide polycrystalline microfibers were successfully synthesized by a process involving electrospinning, calcination, and sulfidation steps. We used an aqueous solution of silicotungstic acid (H4SiW12O40) and polyvinyl alcohol as precursors for the synthesis of composite fibers by the needle-less electrospinning technique. The obtained green composite fibers (av. diam. 460 nm) were converted by calcination in air to tungsten oxide WO3 fibers with traces of SiO2 and a smaller diameter (av. diam. 335 nm). The heat treatment of the WO3 fibers under flowing H2/H2S/N2 stream led to conversion to tungsten disulfide WS2 with retention of the fibrous morphology (av. diam. 196 nm). Characterization of the intermediate and final fibers was performed by the XRD, SEM, TEM, HAADF STEM EDS, elemental analyses ICP-OES, and IR spectroscopy methods.
Complex plasmon-exciton dynamics revealed through quantum dot light emission in a nanocavity by Satyendra Nath Gupta, Ora Bitton, Tomas Neuman, Ruben Esteban, Lev Chuntonov, Javier Aizpurua & Gilad Haran
Link to ORDP experimental dataset (coming soon)
Plasmonic cavities can confine electromagnetic radiation to deep sub-wavelength regimes. This facilitates strong coupling phenomena to be observed at the limit of individual quantum emitters. Here, we report an extensive set of measurements of plasmonic cavities hosting one to a few semiconductor quantum dots. Scattering spectra show Rabi splitting, demonstrating that these devices are close to the strong coupling regime. Using Hanbury Brown and Twiss interferometry, we observe non-classical emission, allowing us to directly determine the number of emitters in each device. Surprising features in photoluminescence spectra point to the contribution of multiple excited states. Using model simulations based on an extended Jaynes-Cummings Hamiltonian, we find that the involvement of a dark state of the quantum dots explains the experimental findings. The coupling of quantum emitters to plasmonic cavities thus exposes complex relaxation pathways and emerges as an unconventional means to control dynamics of quantum states.