Andreas Tittl

Palladium-based plasmonic perfect absorber in the visible wavelength range and its application to hydrogen sensing.

We report on the experimental realization of a palladium-based plasmonic perfect absorber at visible wavelengths and its application to hydrogen sensing. Our design exhibits a reflectance <0.5% and zero transmittance at 650 nm and the operation wavelength of the absorber can be tuned by varying its structural parameters. Exposure to hydrogen gas causes a rapid and reversible increase in reflectance on a time scale of seconds. This pronounced response introduces a novel optical hydrogen detection scheme with very high values of the relative intensity response.

A Switchable Mid‐Infrared Plasmonic Perfect Absorber with Multispectral Thermal Imaging Capability

A switchable perfect absorber with multispectral thermal imaging capability is presented. Aluminum nanoantenna arrays above a germanium antimony telluride (GST) spacer layer and aluminum mirror provide efficient wavelength-tunable absorption in the mid-infrared. Utilizing the amorphous-to-crystalline phase transition in GST, this device offers switchable absorption with strong reflectance contrast at resonance and large phase-change-induced spectral shifts.

Active Chiral Plasmonics

Active control over the handedness of a chiral metamaterial has the potential to serve as key element for highly integrated polarization engineering approaches, polarization sensitive imaging devices, and stereo display technologies. However, this is hard to achieve as it seemingly involves the reconfiguration of the metamolecule from a left-handed into a right-handed enantiomer and vice versa. This type of mechanical actuation is intricate and usually neither monolithically realizable nor viable for high-speed applications. Here, enabled by the phase change material Ge3Sb2Te6 (GST-326), we demonstrate a tunable and switchable mid-infrared plasmonic chiral metamaterial in a proof-of-concept experiment. A large tunability range of the circular dichroism response from λ = 4.15 to 4.90 μm is achieved, and we experimentally demonstrate that the combination of a passive bias-type chiral layer with the active chiral metamaterial allows for switchable chirality, that is, the reversal of the circular dichroism sign, in a fully planar, layered design without the need for geometrical reconfiguration. Because phase change materials can be electrically and optically switched, our designs may open up a path for highly integrated mid-IR polarization engineering devices that can be modulated on ultrafast time scales.

Plasmonic Smart Dust for Probing Local Chemical Reactions

Locally probing chemical reactions or catalytic processes on surfaces under realistic reaction conditions has remained one of the main challenges in materials science and heterogeneous catalysis. Where conventional surface interrogation techniques usually require high-vacuum conditions or ensemble average measurements, plasmonic nanoparticles excel in extreme light focusing and can produce highly confined electromagnetic fields in subwavelength volumes without the need for complex near-field microscopes. Here, we demonstrate an all-optical probing technique based on plasmonic smart dust for monitoring local chemical reactions in real time. The silica shell-isolated gold nanoparticles that form the smart dust can work as strong light concentrators and optically report subtle environmental changes at their pinning sites on the probed surface during reaction processes. As a model system, we investigate the hydrogen dissociation and subsequent uptake trajectory in palladium with both dust-on-film and film-on-dust platforms. Using time-resolved single particle measurements, we demonstrate that our technique can in situ encode chemical reaction information as optical signals for a variety of surface morphologies. The presented technique offers a unique scheme for real-time, label-free, and high-resolution probing of local reaction kinetics in a plethora of important chemical reactions on surfaces, paving the way toward the development of inexpensive and high-output reaction sensors for real-world applications.

Spectral shifts in optical nanoantenna-enhanced hydrogen sensors

In this work, we numerically investigate the nature of spectral shifts in antenna-enhanced hydrogen sensing geometries consisting of a gold bowtie antenna next to a palladium nanodisk. We find through extensive finite element (FEM) simulations that the hydrogen-induced spectral behavior of the system is governed by two competing effects: a small blueshift caused by dielectric function changes in the palladium and a much stronger redshift due to an expansion of the palladium lattice. Our findings enable the accurate numerical characterization and especially the optimization of sensitive antenna-enhanced hydrogen sensors. As a first application, we calculate the performance improvement of gap antennas compared to single cut-wire antenna elements.

Magnesium as Novel Material for Active Plasmonics in the Visible Wavelength Range

Investigating new materials plays an important role for advancing the field of nanoplasmonics. In this work, we fabricate nanodisks from magnesium and demonstrate tuning of their plasmon resonance throughout the whole visible wavelength range by changing the disk diameter. Furthermore, we employ a catalytic palladium cap layer to transform the metallic Mg particles into dielectric MgH2 particles when exposed to hydrogen gas. We prove that this transition can be reversed in the presence of oxygen. This yields plasmonic nanostructures with an extinction spectrum that can be repeatedly switched on or off or kept at any intermediate state, offering new perspectives for active plasmonic metamaterials.

Yttrium Hydride Nanoantennas for Active Plasmonics

A key challenge for the development of active plasmonic nanodevices is the lack of materials with fully controllable plasmonic properties. In this work, we demonstrate that a plasmonic resonance in top-down nanofabricated yttrium antennas can be completely and reversibly turned on and off using hydrogen exposure. We fabricate arrays of yttrium nanorods and optically observe, in extinction spectra, the hydrogen-induced phase transition between the metallic yttrium dihydride and the insulating trihydride. Whereas the yttrium dihydride nanostructures exhibit a pronounced particle plasmon resonance, the transition to yttrium trihydride leads to a complete vanishing of the resonant behavior. The plasmonic resonance in the dihydride state can be tuned over a wide wavelength range by simply varying the size of the nanostructures. Furthermore, we develop an analytical diffusion model to explain the temporal behavior of the hydrogen loading and unloading trajectories observed in our experiments and gain information about the thermodynamics of our device. Thus, our nanorod system serves as a versatile basic building block for active plasmonic devices ranging from switchable perfect absorbers to active local heating control elements.

Plasmonic Gas and Chemical Sensing

Abstract Sensitive and robust detection of gases and chemical reactions constitutes a cornerstone of scientific research and key industrial applications. In an effort to reach progressively smaller reagent concentrations and sensing volumes, optical sensor technology has experienced a paradigm shift from extended thin-film systems towards engineered nanoscale devices. In this size regime, plasmonic particles and nanostructures provide an ideal toolkit for the realization of novel sensing concepts. This is due to their unique ability to simultaneously focus light into subwavelength hotspots of the electromagnetic field and to transmit minute changes of the local environment back into the farfield as a modulation of their optical response. Since the basic building blocks of a plasmonic system are commonly noble metal nanoparticles or nanostructures, plasmonics can easily be integrated with a plethora of chemically or catalytically active materials and compounds to investigate processes ranging from hydrogen absorption in palladium to the detection of trinitrotoluene (TNT). In this review, we will discuss a multitude of plasmonic sensing strategies, spanning the technological scale from simple plasmonic particles embedded in extended thin films to highly engineered complex plasmonic nanostructures. Due to their flexibility and excellent sensing performance, plasmonic structures may open an exciting pathway towards the detection of chemical and catalytic events down to the single molecule level.

Quantitative Angle-Resolved Small-Spot Reflectance Measurements on Plasmonic Perfect Absorbers: Impedance Matching and Disorder Effects

Plasmonic devices with absorbance close to unity have emerged as essential building blocks for a multitude of technological applications ranging from trace gas detection to infrared imaging. A crucial requirement for such elements is the angle independence of the absorptive performance. In this work, we develop theoretically and verify experimentally a quantitative model for the angular behavior of plasmonic perfect absorber structures based on an optical impedance matching picture. To achieve this, we utilize a simple and elegant k-space measurement technique to record quantitative angle-resolved reflectance measurements on various perfect absorber structures. Particularly, this method allows quantitative reflectance measurements on samples where only small areas have been nanostructured, for example, by electron-beam lithography. Combining these results with extensive numerical modeling, we find that matching of both the real and imaginary parts of the optical impedance is crucial to obtain perfect absorption over a large angular range. Furthermore, we successfully apply our model to the angular dispersion of perfect absorber geometries with disordered plasmonic elements as a favorable alternative to current array-based designs.

Large-area fabrication of TiN nanoantenna arrays for refractory plasmonics in the mid-infrared by femtosecond direct laser writing and interference lithography [Invited]

Robust plasmonic nanoantennas at mid-infrared wavelengths are essential components for a variety of nanophotonic applications ranging from thermography to energy conversion. Titanium nitride (TiN) is a promising candidate for such cases due to its high thermal stability and metallic character. Here, we employ direct laser writing as well as interference lithography to fabricate large-area nanoantenna arrays of TiN on sapphire and silicon substrates. Our lithographic tools allow for fast and homogeneous preparation of nanoantenna geometries on a polymer layer, which is then selectively transferred to TiN by subsequent argon ion beam etching followed by a chemical wet etching process. The antennas are protected by an additional Al2O3 layer which allows for high-temperature annealing in argon flow without loss of the plasmonic properties. Tailoring of the TiN antenna geometry enables precise tuning of the plasmon resonances from the near to the mid-infrared spectral range. Due to the advantageous properties of TiN combined with our versatile large-area and low-cost fabrication process, such refractory nanoantennas will enable a multitude of high-temperature plasmonic applications such as thermophotovoltaics in the future.