Nikolai Strohfeldt

Thermodynamics of the hybrid interaction of hydrogen with palladium nanoparticles.

Palladium-hydrogen is a prototypical metal-hydrogen system. It is therefore not at all surprising that a lot of attention has been devoted to the absorption and desorption of hydrogen in nanosized palladium particles. Several seminal articles on the interaction of H with Pd nanocubes and nanoparticles have recently been published. Although each article provides for the first time detailed data on specific aspects of hydrogen in nanoparticles, they individually do not contain enough information to draw firm conclusions about the involved mechanisms. Here, we show that the large body of data available so far in literature exhibits general patterns that lead to unambiguous conclusions about the processes involved in H absorption and desorption in Pd nanoparticles. On the basis of a remarkably robust scaling law for the hysteresis in absorption-desorption isotherms, we show that hydrogen absorption in palladium nanoparticles is consistent with a coherent interface model and is thus clearly different from bulk Pd behaviour. However, H desorption occurs fully coherently only for small nanoparticles (typically smaller than 50 nm) at temperatures sufficiently close to the critical temperature. For larger particles it is partially incoherent, as in bulk, where dilute α-PdHx and high concentration β-PdHx phases coexist.

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.

Nonlinear Refractory Plasmonics with Titanium Nitride Nanoantennas

Titanium nitride (TiN) is a novel refractory plasmonic material which can sustain high temperatures and exhibits large optical nonlinearities, potentially opening the door for high-power nonlinear plasmonic applications. We fabricate TiN nanoantenna arrays with plasmonic resonances tunable in the range of about 950-1050 nm by changing the antenna length. We present second-harmonic (SH) spectroscopy of TiN nanoantenna arrays, which is analyzed using a nonlinear oscillator model with a wavelength-dependent second-order response from the material itself. Furthermore, characterization of the robustness upon strong laser illumination confirms that the TiN antennas are able to endure laser irradiation with high peak intensity up to 15 GW/cm(2) without changing their optical properties and their physical appearance. They outperform gold antennas by one order of magnitude regarding laser power sustainability. Thus, TiN nanoantennas could serve as promising candidates for high-power/high-temperature applications such as coherent nonlinear converters and local heat sources on the nanoscale.

Long-term stability of capped and buffered palladium-nickel thin films and nanostructures for plasmonic hydrogen sensing applications

One of the main challenges in optical hydrogen sensing is the stability of the sensor material. We found and studied an optimized material combination for fast and reliable optical palladium-based hydrogen sensing devices. It consists of a palladium-nickel alloy that is buffered by calcium fluoride and capped with a very thin layer of platinum. Our system shows response times below 10 s and almost no short-term aging effects. Furthermore, we successfully incorporated this optimized material system into plasmonic nanostructures, laying the foundation for a stable and sensitive hydrogen detector.

Sensitivity engineering in direct contact palladium-gold nano-sandwich hydrogen sensors [Invited]

In recent years, plasmonic hydrogen sensing schemes using complex hybrid Pd@Au nanostructures have attracted significant attention. However, so far, most studies have focused on investigating the sensing performance of nanosensor geometries where the constituent materials are laterally coupled. In contrast to such planar hybrid systems, which often require complex multi-step fabrication approaches, sensing devices where the materials are stacked directly on top of each other can be fabricated in a single lithography step, enabling straightforward high-throughput processing. Here, we demonstrate a novel hydrogen sensing scheme which incorporates complex hybrid plasmonic nanostructures consisting of stacked gold and palladium nanodisks. In particular, we study the influence of stacking order and geometry, experimentally and numerically, to find an optimal arrangement for a hydrogen sensor device. With an optimized sensing geometry – a stack of gold as lower and palladium as upper disk – we obtain spectral shifts as large as 30 nm at 4 vol.% H2, which is a strong improvement compared to previous indirect sensing designs. Our samples yield large absorption and scattering signals and are fabricated by low-cost hole-mask colloidal lithography and therefore yield sample sizes over areas of 1 cm2.

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 behaviour of the hydrogen loading and unloading process 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.

Nanoscale Hydrogenography on Single Magnesium Nanoparticles

Active plasmonics is enabling novel devices such as switchable metasurfaces for active beam steering or dynamic holography. Magnesium with its particle plasmon resonances in the visible spectral range is an ideal material for this technology. Upon hydrogenation, metallic magnesium switches reversibly into dielectric magnesium hydride (MgH2), turning the plasmonic resonances off and on. However, up until now, it has been unknown how exactly the hydrogenation process progresses in the individual plasmonic nanoparticles. Here, we introduce a new method, namely nanoscale hydrogenography, that combines near-field scattering microscopy, atomic force microscopy, and single-particle far-field spectroscopy to visualize the hydrogen absorption process in single Mg nanodisks. Using this method, we reveal that hydrogen progresses along individual single-crystalline nanocrystallites within the nanostructure. We are able to monitor the spatially resolved forward and backward switching of the phase transitions of several individual nanoparticles, demonstrating differences and similarities of that process. Our method lays the foundations for gaining a better understanding of hydrogen diffusion in metal nanoparticles and for improving future active nano-optical switching devices.

Modeling of pressure-composition isotherms and diffusion dynamics of a plasmonic palladium sensor for hydrogen detection

In this contribution, we present a physically motivated dynamic model for a plasmonic hydrogen sensor based on a multilayer sample design with palladium nanodisks, which exhibits near-perfect absorption at visible wavelengths. This plasmonic gas sensor enables detection of low hydrogen concentrations providing the advantages of optical measurement principles and may be produced cost-effectively as a miniaturizable system. However, the response is highly temperature-dependent and exhibits a nonlinear relationship between the external hydrogen pressure and the output. Furthermore, the response time depends on the hydrogen concentration and it can take up to several minutes until the steady state is reached and the sensor response can be evaluated. By deriving a dynamic model of the sensor behavior, it is possible to compensate these unfavorable properties of the sensing system. The model derived in this paper consists of a model for the pressure-composition isotherms, which describes the relationship between the external hydrogen pressure and the stationary atomic ratio H/Pd in the palladium crystal using thermodynamic relations, a diffusion model with a concentration-dependent diffusion coefficient and a linear model for the optical response. The parameters of the dynamic model are identified based on literature research and measured data. Finally the dynamic model is validated using experimental data at 30°C, 50°C and 90°C.