Stacked organic optoelectronic devices make use of electrode materials with different work functions, leading to efficient large area light emission. In contrast, lateral electrode arrangements offer the possibility to be shaped as resonant optical antennas, radiating light from subwavelength volumes. However, tailoring electronic interface properties of laterally arranged electrodes with nanoscale gaps - to e.g. optimize charge-carrier injection - is rather challenging, yet crucial for further development of highly efficient nanolight sources. Here, we demonstrate site-selective functionalization of laterally arranged micro- and nanoelectrodes by means of different self-assembled monolayers. Upon applying an electric potential across nanoscale gaps, surface-bound molecules are removed selectively from specific electrodes by oxidative desorption. Kelvin-probe force microscopy as well as photoluminescence measurements are employed to verify the success of our approach. Moreover, we obtain asymmetric current–voltage characteristics for metal–organic devices in which just one of the electrodes is coated with 1-octadecanethiol; further demonstrating the potential to tune interface properties of nanoscale objects. Our technique paves the way for laterally arranged optoelectronic devices based on selectively engineered nanoscale interfaces and in principle enables molecular assembly with defined orientation in metallic nano-gaps.
Ochs, Maximilian; Jucker, Laurent; Rödel, Maximilian; Emmerling, Monika; Kullock, René; Pflaum, Jens; Mayor, Marcel; Hecht, Bert
Achieving reliable and quantifiable performance in large-area surface-enhanced Raman spectroscopy (SERS) substrates has long been a formidable challenge. It requires substantial signal enhancement while maintaining a reproducible and uniform response. Conventional SERS substrates are typically made of inhomogeneous materials with random resonator geometries and distributions. As a result, they exhibit several or broadened plasmonic resonances, undesired absorptive losses, and inhomogeneous field enhancement. These limitations diminish the signal strength and hamper reproducibility, making it difficult to conduct comparative studies with high sensitivity. In this study, we propose an approach that utilizes monocrystalline gold flakes to fabricate well-defined gratings composed of plasmonic double-wire resonators, which are fabricated through focused ion-beam lithography. The geometry of the double wire grating substrate (DWGS) was evolutionary optimized to achieve efficient enhancement for both excitation and emission processes. The use of monocrystalline material minimizes absorption losses while enhancing the shape fidelity during the nanofabrication process. The DWGS shows notable reproducibility (RSD=6.6%), repeatability (RSD=5.6%), and large-area homogeneity over areas >104μm2. Moreover, it provides a SERS enhancement factor of ≈106 for 4-Aminothiophenol (4-ATP) analyte and detection capability for sub-monolayer coverage. The DWGS demonstrates reusability, as well as long-term stability on the shelf. Experimental validation with various analytes, in different states of matter, including biological macromolecules, confirms the sensitive and reproducible nature of DWGSs, thereby establishing them as a promising SERS substrate design for future sensing applications.
Sweedan, Amro; Pavan, Mariela J.; Schatz, Enno; Maaß, Henriette; Tsega, Ashageru; Tzin, Vered; Höflich, Katja; Mörk, Paul; Feichtner, Thorsten; Y. Bashouti, Muhammad
Classical electrodynamics describes the optical response of macroscopic systems, where the boundaries between materials is treated as infinitesimally thin. However, due to the quantum nature of electrons, interfaces acquires a finite thickness. To include non-classical surface effects in the framework of Maxwell's equations, surface-response functions can be introduced, also known as Feibelman d-parameters. Surface response impacts systems with strong field localization at interfaces, which is encountered in noble metal nanoparticles supporting surface plasmon polaritons. However, studying surface response is challenging as it necessitates sub-nanometer control of geometric features, e.g. the gap size in a dimer antenna, while minimizing uncertainties in morphology. In contrast, electrical gating is convenient since the static screening charges are confined exclusively to the surface, which alleviates the need for precise control over the morphology. Here, we study the perturbation of Feibelman d-parameters by direct electric charging of a single plasmonic nanoresonator and investigate the resulting changes of the resonance in experiment and theory. The measured change of the resonance frequency matches the theory by assuming a perturbation of the tangential surface current. However, we also observe an unforeseen narrowing in the resonance width when adding electrons to the surface of a plasmonic nanoresonator. These reduced losses cannot be explained by electron spill-out within the local-response approximation (LRA). Such an effect is likely caused by nonlocality and the anisotropy of the perturbed local permittivity. Our findings open up possibilities to reduce losses in plasmonic resonators and to develop ultrafast and extremely small electrically driven plasmonic modulators and metasurfaces by leveraging electrical control over non-classical surface effects.
Zurak, Luka; Wolff, Christian; Meier, Jessica; Kullock, René; Mortensen, N. Asger; Hecht, Bert; Feichtner, Thorsten
Room-temperature strong coupling of a single quantum emitter and a single resonant plasmonic mode is a key resource for quantum information processing and quantum sensing at ambient conditions. To beat dephasing, ultrafast energy transfer is achieved by coupling single emitters to a plasmonic nanoresonator with an extremely small mode volume and optimal spectral overlap. Typically, normal mode splittings in luminescence spectra of single-emitter strongly-coupled systems are provided as evidence for strong coupling and to obtain rough estimates of the light-matter coupling strength g. However, a complete anticrossing of a single emitter and a cavity mode as well as the characterization of the uncoupled constituents is usually hard to achieve. Here, we exploit the light-induced oxygen-dependent blue-shift of individual CdSe/ZnS semiconductor quantum dots to tune their transition energy across the resonance of a scanning plasmonic slit resonator after characterizing both single emitter and nano resonator in their uncoupled states. Our results provide clear proof of single-emitter strong light-matter coupling at ambient condition as well as a value for the Rabi splitting at zero detuning 100 meV, consistent with modeling, thereby opening the path towards plexitonic devices that exploit single-photon nonlinearities at ambient conditions.
Friedrich, Daniel; Qin, Jin; Schurr, Benedikt; Tufarelli, Tommaso; Groß, Heiko; Hecht, Bert
Plasmonic dimer antennas create strong field enhancement by squeezing light into a nanoscale gap. These optical hotspots are highly attractive for boosting nonlinear processes, such as harmonic generation, photoelectron emission, and ultrafast electron transport. Alongside large field enhancement, such phenomena often require control over the field asymmetry in the hotspot, which is challenging considering the nanometer length scales. Here, by means of strongly enhanced second harmonic generation, we demonstrate unprecedented control over the field distribution in a hotspot by systematically introducing geometrical asymmetry to the antenna gap. We use focused helium ion beam milling of mono-crystalline gold to realize asymmetric-gap dimer antennas in which an ultra-sharp tip with 3 nm apex radius faces a flat counterpart, conserving the bonding antenna mode and the concomitant field enhancement at the fundamental frequency. By decreasing the tip opening angle, we are able to systematically increase both field enhancement and asymmetry, thus enhancing second harmonic radiation to the far-field, which is nearly completely suppressed for equivalent symmetric dimer antennas. Combining these findings with second harmonic radiation patterns as well as quantitative nonlinear simulations, we further obtain remarkably detailed insights into the mechanism of second harmonic generation at the nanoscale. Our results open new opportunities for the realization of novel nonlinear nanoscale systems, where the control over local field asymmetry in combination with large field enhancement is essential to create nonreciprocal functionalities.
Meier, Jessica; Zurak, Luka; Locatelli, Andrea; Feichtner, Thorsten; Kullock, René; Hecht, Bert
Plasmon polaritons (plasmons, for simplicity) have become paramount for tailored nanoscale light–matter interaction, and extensive research has been conducted to monitor and manipulate their spatial3 and spatio-temporal dynamics. These dynamics result from the superposition of various plasmon modes, which are classical wave packets. Beyond this classical picture, plasmon modes are treated as quasiparticles and they are considered essential for the realization of future nanoscale quantum functionality. Implementing and demonstrating such functionality requires access to the quasiparticle’s quantum state to monitor and manipulate its corresponding quantum wave packet dynamics in Hilbert space. Here we report the local detection of nanoscale plasmon quantum wave packets using plasmon-assisted electron emission as a signal in coherent two-dimensional nanoscopy. The observation of a quantum coherence oscillating at the third harmonic of the plasmon frequency is traced back to the superposition of energetically non-adjacent plasmon occupation number states and is therefore a direct fingerprint of the quantum wave packet. Beyond demonstrating the existence of a plasmon quantum wave packet via the coherence between certain occupation number states and providing an improved model for plasmon-assisted electron emission processes, the results may enable time-dependent probing and manipulation of coupled quantum states and dynamics on the nanoscale.
We present the concept of electrostatic field-driven supra-molecular translation within electrically connected plasmonic nano-antennas. The antenna serves as an anchoring point for the mechanically interlocked molecules, as an electrode for the electrostatic field, and as an amplifier of the antenna-enhanced fluorescence. The synthesis of a push–pull donor–π–acceptor chromophore with optical properties aligned to the antenna resonance is described and its immobilization on the surface is demonstrated. Photoluminescence experiments of the chromophore on a gold nano-antenna are shown, highlighting the molecule–antenna coupling and resulting emission intensity increase. The successful synthesis of an electrostatic field-sensitive rotaxane in water is described and the tightrope walk between functionality and water solubility is illustrated by unsuccessful designs. In solution, an enhanced fluorescence quantum yield is observed for the chromophore comprising the mechanically interlocked rotaxane in water and DMSO compared to the reference rod, ideal for future experiments in plasmonic nano-antennas.
L. Jucker, M. Ochs, R. Kullock, Y. Aeschi, B. Hecht, M. Mayor
Organic Materials, 4, 127-136 (2022)
The control of nonlinear optical signals in nanostructured systems is pivotal to develop functional devices suitable for integration in optical platforms. A possible control mechanism is exploiting coherent interactions between different nonlinear optical processes. Here, this concept is implemented by taking advantage of the strong field enhancement and high optical non-linearity provided by plasmonic nanostructures. Two beams, one at the angular frequency ω, corresponding to the telecom wavelength λ= 1551 nm, and the other at 2ω, are combined to generate a sum-frequency signal at 3ω from single asymmetric gold nanoantennas. This nonlinear signal interferes with the third-harmonic radiation generated by the beam at ω, resulting in a modulation up to 50% of the total signal at 3ω depending on the relative phase between the beams. Such a large intensity modulation of the nonlinear signal is accompanied by a rotation of its polarization axis, due to the lack of central symmetry of the nanostructure. The demonstration that the nonlinear emission can be coherently controlled through the phase difference of the two-color illumination represents a promising route toward all-optical logic operations at the nanoscale through nonlinear optical signal manipulation.
A. D. Francescantonio, A. Locatelli, X. Wu, A. Zilli, T. Feichtner, P. Biagioni, L. Duò, D. Rocco, C. D. Angelis, M. Celebrano, B. Hecht and M. Finazzi
Adv. Optical Mater, 2200757 (2022)
Visible and infrared photons can be detected with a broadband response via the internal photoeffect. By using plasmonic nanostructures, i.e. nanoantennas, wavelength selectivity can be introduced to such detectors through geometry-dependent resonances. Also, additional functionality, like electronic responsivity switching and polarization detection have been realized. However, previous devices consisted of large arrays of nanostructures to achieve detectable photocurrents. Here we show that this concept can be scaled down to a single antenna level, resulting in detector dimensions well below the resonance wavelength of the device. Our design consists of a single electrically-connected plasmonic nanoantenna covered with a wide-bandgap semiconductor allowing broadband photodetection in the VIS/NIR via injection of hot carriers. We demonstrate electrical switching of the color sensitivity as well as polarization detection. Our results hold promise for the realization of ultra small, highly integratable photodetectors with advanced functionality.
P. Pertsch, R. Kullock, V. Gabriel, L. Zurak, M. Emmerling, B. Hecht
Nano Lett. 2022, 22, 17, 6982–6987
When photons interact with matter, forces and torques occur due to the transfer of linear and angular momentum, respectively. The resulting accelerations are small for macroscopic objects but become substantial for microscopic objects with small masses and moments of inertia, rendering photon recoil very attractive to propel micro- and nano-objects. However, until now, using light to control object motion in two or three dimensions in all three or six degrees of freedom has remained an unsolved challenge. Here we demonstrate light-driven microdrones (size roughly 2 μm and mass roughly 2 pg) in an aqueous environment that can be manoeuvred in two dimensions in all three independent degrees of freedom (two translational and one rotational) using two overlapping unfocused light fields of 830 and 980 nm wavelength. To actuate the microdrones independent of their orientation, we use up to four individually addressable chiral plasmonic nanoantennas acting as nanomotors that resonantly scatter the circular polarization components of the driving light into well-defined directions. The microdrones are manoeuvred by only adjusting the optical power for each motor (the power of each circular polarization component of each wavelength). The actuation concept is therefore similar to that of macroscopic multirotor drones. As a result, we demonstrate manual steering of the microdrones along complex paths. Since all degrees of freedom can be addressed independently and directly, feedback control loops may be used to counteract Brownian motion. We posit that the microdrones can find applications in transport and release of cargos, nanomanipulation, and local probing and sensing of nano and mesoscale objects.
Future photonic devices require efficient, multifunctional, electrically driven light sources with directional emission properties and subwavelength dimensions. Electrically driven plasmonic nanoantennas have been demonstrated as enabling technology. Here, we present the concept of a nanoscale organic light-emitting antenna (OLEA) as a color- and directionality-switchable point source. The device consists of laterally arranged electrically contacted gold nanoantennas with their gap filled by the organic semiconductor zinc phthalocyanine (ZnPc). Since ZnPc shows preferred hole conduction in combination with gold, the recombination zone relocates depending on the polarity of the applied voltage and couples selectively to either of the two antennas. Thereby, the emission characteristics of the device also depend on polarity. Contrary to large-area OLEDs where recombination at metal contacts significantly contributes to losses, our ultracompact OLEA structures facilitate efficient radiation into the far-field rendering transparent electrodes obsolete. We envision OLEA structures to serve as wavelength-scale pixels with tunable color and directionality for advanced display applications.
P. Grimm, S. Zeißner, M. Rödel, S. Wiegand, S. Hammer, M. Emmerling, E. Schatz, R. Kullock, J Pflaum, B. Hecht
Nano Lett., 1c03994 (2022)
Coupling N identical emitters to the same field mode is a well-established method to enhance light-matter interaction. However, the resulting √N boost of the coupling strength comes at the cost of a “linearized” (effectively semiclassical) dynamics. Here, we instead demonstrate a new approach for enhancing the coupling constant of a single quantum emitter, while retaining the nonlinear character of the light-matter interaction. We consider a single quantum emitter with N nearly degenerate transitions that are collectively coupled to the same field mode. We show that in such conditions an effective Jaynes-Cummings model emerges with a boosted coupling constant of order √N. The validity and consequences of our general conclusions are analytically demonstrated for the instructive case N=2. We further observe that our system can closely match the spectral line shapes and photon autocorrelation functions typical of Jaynes-Cummings physics, proving that quantum optical nonlinearities are retained. Our findings match up very well with recent broadband plasmonic nanoresonator strong-coupling experiments and will, therefore, facilitate the control and detection of single-photon nonlinearities at ambient conditions.
T. Tufarelli, D. Friedrich, H. Groß, J. Hamm, O. Hess, B. Hecht
Phys. Rev. Research 3, 033103 (2021)
The electrical excitation of guided plasmonic modes at the nanoscale enables integration of optical nanocircuitry into nanoelectronics. In this context, exciting plasmons with a distinct modal field profile constitutes a key advantage over conventional single-mode integrated photonics. Here, we demonstrate the selective electrical excitation of the lowest-order symmetric and antisymmetric plasmonic modes in a two-wire transmission line. We achieve mode selectivity by precisely positioning nanoscale excitation sources, i.e., junctions for inelastic electron tunneling, within the respective modal field distribution. By using advanced fabrication that combines focused He-ion beam milling and dielectrophoresis, we control the location of tunnel junctions with sub-10 nm accuracy. At the far end of the two-wire transmission line, the guided plasmonic modes are converted into far-field radiation at separate spatial positions showing two distinct orthogonal polarizations. Hence, the resulting device represents the smallest electrically driven light source with directly switchable polarization states with possible applications in display technology.
M. Ochs, L. Zurak, E. Krauss, J. Meier, M. Emmerling, R. Kullock, B. Hecht
Coherent perfect absorption (CPA) describes the absence of all outgoing modes from a lossy resonator, driven by lossless incoming modes. Here, we show that for nanoresonators that also exhibit radiative losses, e.g., plasmonic nanoantennas, a generalized version of CPA (gCPA) can be applied. In gCPA outgoing modes are suppressed only for a subset of (guided plasmonic) modes while other (radiative) modes are treated as additional loss channels - a situation typically referred to as perfect impedance matching. Here we make use of gCPA to show how to achieve perfect impedance matching between a single nanowire plasmonic waveguide and a plasmonic nanoantenna. Antennas with both radiant and subradiant characteristics are considered. We further demonstrate potential applications in background-free sensing.