Hydrogen-air mixtures are highly flammable. Hydrogen sensors are therefore of paramount importance for timely leak detection during handling. However, existing solutions do not meet the stringent performance targets set by stakeholders, while deactivation due to poisoning, for example by carbon monoxide, is a widely unsolved problem. Here we present a plasmonic metal-polymer hybrid nanomaterial concept, where the polymer coating reduces the apparent activation energy for hydrogen transport into and out of the plasmonic nanoparticles, while deactivation resistance is provided via a tailored tandem polymer membrane. In concert with an optimized volume-to-surface ratio of the signal transducer uniquely offered by nanoparticles, this enables subsecond sensor response times. Simultaneously, hydrogen sorption hysteresis is suppressed, sensor limit of detection is enhanced, and sensor operation in demanding chemical environments is enabled, without signs of long-term deactivation. In a wider perspective, our work suggests strategies for next-generation optical gas sensors with functionalities optimized by hybrid material engineering.

Efficient adhesion of gold thin films on dielectric or semiconductor substrates is essential in applications and research within plasmonics, metamaterials, 2D materials, and nanoelectronics. As a consequence of the relentless downscaling in nanoscience and technology, the thicknesses of adhesion layer and overlayer have reached tens of nanometers, and it is unclear if our current understanding is sufficient. In this report, we investigated how Cr and Ti adhesion layers influence the nanostructure of 2-20 nm thin Au films by means of high-resolution electron microscopy, complemented with atomic force microscopy and X-ray photoelectron spectroscopy. Pure Au films were compared to Ti/Au and Cr/Au bilayer systems. Both Ti and Cr had a striking impact on grain size and crystal orientation of the Au overlayer, which we interpret as the adhesion layer-enhanced wetting of Au and the formation of chemical bonds between the layers. Ti formed a uniform layer under the Au overlayer. Cr interdiffused with the Au layer forming a Cr-Au alloy. The crystal orientation of the Au layers was mainly [111] for all thin-film systems. The results showed that both adhesion layers were partially oxidized, and oxidation sources were scrutinized and found. A difference in bilayer electrical resistivity between Ti/Au and Cr/Au systems was measured and compared. On the basis of these results, a revised and more detailed adhesion layer model for both Ti/Au and Cr/Au systems was proposed. Finally, the implications of the results were analyzed, and recommendations for the selection of adhesion layers for nano-optics and nanoelectronics applications are presented.

Grain boundaries separate crystallites in solids and influence material properties, as widely documented for bulk materials. In nanomaterials, however, investigations of grain boundaries are very challenging and just beginning. Here, we report the systematic mapping of the role of grain boundaries in the hydrogenation phase transformation in individual Pd nanoparticles. Employing multichannel single-particle plasmonic nanospectroscopy, we observe large variation in particle-specific hydride-formation pressure, which is absent in hydride decomposition. Transmission Kikuchi diffraction suggests direct correlation between length and type of grain boundaries and hydride-formation pressure. This correlation is consistent with tensile lattice strain induced by hydrogen localized near grain boundaries as the dominant factor controlling the phase transition during hydrogen absorption. In contrast, such correlation is absent for hydride decomposition, suggesting a different phase-transition pathway. In a wider context, our experimental setup represents a powerful platform to unravel microstructure–function correlations at the individual-nanoparticle level.

[1] The magnetic properties of olivine-hosted Fe-Ni particles have been studied to assess the potential of "dusty olivine" to retain a pre-accretionary remanence in chondritic meteorites. Both body-centered (bcc) and face-centered cubic (fcc) Fe-Ni phases were formed by reduction of a terrestrial olivine precursor. The presence of Ni complicates the magnetic properties during heating and cooling due to the fcc-bcc martensitic transition. First-order reversal curve (FORC) diagrams contain a central ridge with a broad coercivity distribution extending to 600 mT, attributed to non-interacting single-domain (SD) particles, and a "butterfly" structure extending to 250 mT, attributed to single-vortex (SV) states. SD and SV states were imaged directly using electron holography. The location of the SD/SV boundary is broadly consistent with theoretical predictions. A method to measure the volume of individual SD particles using electron holography is presented. Combining the volume information with constraints on coercivity, we calculate the thermal relaxation characteristics of the particles and demonstrate that the high-coercivity component of remanance would remain stable for 4.6 Ga, even at temperatures approaching the Curie temperature of pure Fe. The high coercivity of the particles, together with the chemical protection offered by the surrounding olivine, is likely to make them resistant to shock remagnetization, isothermal remagnetization and terrestrial weathering, making dusty olivine a credible recorder of pre-accretionary magnetic fields.