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Time-resolved measurements of changes in the size and shape of nanobiological objects and layers are crucial to understand their properties and optimize their performance. Optical sensing is particularly attractive with high throughput and sensitivity, and label-free operation. However, most state-of-the-art solutions require intricate modeling or multiparameter measurements to disentangle conformational or thickness changes of biomolecular layers from complex interfacial refractive index variations. Here, we present a dual-band nanoplasmonic ruler comprising mixed arrays of plasmonic nanoparticles with spectrally separated resonance peaks. As electrodynamic simulations and model experiments show, the ruler enables real-time simultaneous measurements of thickness and refractive index variations in uniform and heterogeneous layers with sub-nanometer resolution. Additionally, nanostructure shape changes can be tracked, as demonstrated by quantifying the degree of lipid vesicle deformation at the critical coverage prior to rupture and supported lipid bilayer formation. In a broader context, the presented nanofabrication approach constitutes a generic route for multimodal nanoplasmonic optical sensing.

Plasmonic sensors rely on optical resonances in metal nanoparticles and are typically limited by their broad spectral features. This constraint is particularly taxing for optical hydrogen sensors, in which hydrogen is absorbed inside optically-lossy Pd nanostructures and for which state-of-the-art detection limits are only at the low parts-per-million (ppm) range. Here, we overcome this limitation by inversely designing a plasmonic metasurface based on a periodic array of Pd nanoparticles. Guided by a particle swarm optimization algorithm, we numerically identify and experimentally demonstrate a sensor with an optimal balance between a narrow spectral linewidth and a large field enhancement inside the nanoparticles, enabling a measured hydrogen detection limit of 250 parts-per-billion (ppb). Our work significantly improves current plasmonic hydrogen sensor capabilities and, in a broader context, highlights the power of inverse design of plasmonic metasurfaces for ultrasensitive optical (gas) detection., (© 2022. The Author(s).)

The temperature of nanoparticles is a critical parameter in applications that range from biology, to sensors, to photocatalysis. Yet, accurately determining the absolute temperature of nanoparticles is intrinsically difficult because traditional temperature probes likely deliver inaccurate results due to their large thermal mass compared to the nanoparticles. Here we present a hydrogen nanothermometry method that enables a noninvasive and direct measurement of absolute Pd nanoparticle temperature via the temperature dependence of the first-order phase transformation during Pd hydride formation. We apply it to accurately measure light-absorption-induced Pd nanoparticle heating at different irradiated powers with 1 °C resolution and to unravel the impact of nanoparticle density in an array on the obtained temperature. In a wider perspective, this work reports a noninvasive method for accurate temperature measurements at the nanoscale, which we predict will find application in, for example, nano-optics, nanolithography, and plasmon-mediated catalysis to distinguish thermal from electronic effects.

Hydrogen gas is rapidly approaching a global breakthrough as a carbon-free energy vector. In such a hydrogen economy, safety sensors for hydrogen leak detection will be an indispensable element along the entire value chain, from the site of hydrogen production to the point of consumption, due to the high flammability of hydrogen-air mixtures. To stimulate and guide the development of such sensors, industrial and governmental stakeholders have defined sets of strict performance targets, which are yet to be entirely fulfilled. In this Perspective, we summarize recent efforts and discuss research strategies for the development of hydrogen sensors that aim at meeting the set performance goals. In the first part, we describe the state-of-the-art for fast and selective hydrogen sensors at the research level, and we identify nanostructured Pd transducer materials as the common denominator in the best performing solutions. As a consequence, in the second part, we introduce the fundamentals of the Pd-hydrogen interaction to lay the foundation for a detailed discussion of key strategies and Pd-based material design rules necessary for the development of next generation high-performance nanostructured Pd-based hydrogen sensors that are on par with even the most stringent and challenging performance targets.

The highly localized sensitivity of metallic nanoparticles sustaining localized surface plasmon resonance (LSPR) enables detection of minute events occurring close to the particle surface and forms the basis for nanoplasmonic sensing. To date, nanoplasmonic sensors typically consist of two-dimensional (2D) nanoparticle arrays and can therefore only probe processes that occur within the array plane, leaving unaddressed the potential of sensing in three dimensions (3D). Here, we present a plasmonic metasurface comprising arrays of stacked Ag nanodisks separated by a thick SiO 2 dielectric layer, which, through rational design, exhibit two distinct and spectrally separated LSPR sensing peaks and corresponding spatially separated sensing locations in the axial direction. This arrangement thus enables real-time plasmonic sensing in 3D. As a proof-of-principle, we successfully determine in a single experiment the layer-specific glass transition temperatures of a bilayer polymer thin film of poly(methyl methacrylate), PMMA, and poly(methyl methacrylate)/poly(methacrylic acid), P(MMA-MAA). Our work thus demonstrates a strategy for nanoplasmonic sensor design and utilization to simultaneously probe local chemical or physical processes at spatially different locations. In a wider perspective, it stimulates further development of sensors that employ multiple detection elements to generate distinct and spectrally individually addressable LSPR modes.

Organic solar cells are thought to suffer from poor thermal stability of the active layer nanostructure, a common belief that is based on the extensive work that has been carried out on fullerene-based systems. We show that a widely studied non-fullerene acceptor, the indacenodithienothiophene-based acceptor ITIC, crystallizes in a profoundly different way as compared to fullerenes. Although fullerenes are frozen below the glass-transition temperature T g of the photovoltaic blend, ITIC can undergo a glass-crystal transition considerably below its high T g of ∼180 °C. Nanoscopic crystallites of a low-temperature polymorph are able to form through a diffusion-limited crystallization process. The resulting fine-grained nanostructure does not evolve further with time and hence is characterized by a high degree of thermal stability. Instead, above T g , the low temperature polymorph melts, and micrometer-sized crystals of a high-temperature polymorph develop, enabled by more rapid diffusion and hence long-range mass transport. This leads to the same detrimental decrease in photovoltaic performance that is known to occur also in the case of fullerene-based blends. Besides explaining the superior thermal stability of non-fullerene blends at relatively high temperatures, our work introduces a new rationale for the design of bulk heterojunctions that is not based on the selection of high- T g materials per se but diffusion-limited crystallization. The planar structure of ITIC and potentially other non-fullerene acceptors readily facilitates the desired glass-crystal transition, which constitutes a significant advantage over fullerenes, and may pave the way for truly stable organic solar cells.

Hydrogen sensors are a prerequisite for the implementation of a hydrogen economy due to the high flammability of hydrogen-air mixtures. They are to comply with the increasingly stringent requirements set by stakeholders, such as the automotive industry and manufacturers of hydrogen safety systems, where sensor deactivation is a severe but widely unaddressed problem. In response, we report intrinsically deactivation-resistant nanoplasmonic hydrogen sensors enabled by a rationally designed ternary PdAuCu alloy nanomaterial, which combines the identified best intrinsic attributes of the constituent binary Pd alloys. This way, we achieve extraordinary hydrogen sensing metrics in synthetic air and poisoning gas background, simulating real application conditions. Specifically, we find a detection limit in the low ppm range, hysteresis-free response over 5 orders of magnitude hydrogen pressure, subsecond response time at room temperature, long-term stability, and, as the key, excellent resistance to deactivating species like carbon monoxide, notably without application of any protective coatings. This constitutes an important step forward for optical hydrogen sensor technology, as it enables application under demanding conditions and provides a blueprint for further material and performance optimization by combining and concerting intrinsic material assets in multicomponent nanoparticles. In a wider context, our findings highlight the potential of rational materials design through alloying of multiple elements for gas sensor development, as well as the potential of engineered metal alloy nanoparticles in nanoplasmonics and catalysis.

Nanostructured metal hydrides are able to efficiently detect hydrogen in optical sensors. In the literature, two nanostructured systems based on metal hydrides have been proposed for this purpose each with its own detection principle: continuous sub-100 nm thin films read out via optical reflectance/transmittance changes and nanoparticle arrays for which the detection relies on localized surface plasmon resonance. Despite their apparent similarities, their optical and structural response to hydrogen has never been directly compared. In response, for the case of Pd 1- y Au y ( y = 0.15-0.30) alloys, we directly compare these two systems and establish that they are distinctively different. We show that the dissimilar optical response is not caused by the different optical readout principles but results from a fundamentally different structural response to hydrogen due to the different nanostructurings. The measurements empirically suggest that these differences cannot be fully accounted by surface effects but that the nature of the film-substrate interaction plays an important role and affects both the hydrogen solubility and the metal-to-metal hydride transition. In a broader perspective, our results establish that the specifics of nanoconfinement dictate the structural properties of metal hydrides, which in turn control the properties of nanostructured devices including the sensing characteristics of optical hydrogen sensors and hydride-based active plasmonic systems.

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.

We demonstrate the transfer of arrays of nanofabricated noble metal and alloy nanostructures obtained by high-temperature annealing on a flat parent support onto optical fibers, to create a hysteresis-free fiber optic nanoplasmonic hydrogen sensor. This work enables the integration of complex nanofabricated structures and their arrangements in tailored arrays with fiber optics to realize optical sensors, which will find application in a wide range of disciplines.

Hydride-forming metal nanoparticles sustaining localized surface plasmon resonance have emerged as prototypical material to study the fundamentals of hydrogen-induced phase transformations. They have also been proposed as signal transducers in next-generation hydrogen sensors. However, despite high current interest in hydrogen sorption by nanomaterials in general and such sensors in particular, the correlations between nanoparticle size, shape, and composition, the amount of hydrogen absorbed, and the obtained optical response have not been systematically experimentally studied. Focusing on hydrogenated Pd, PdAu- and PdCu-alloy nanoparticles, which are of particular interest in hysteresis-free plasmonic hydrogen sensing, we find that at practically important Au/Pd and Cu/Pd ratios the optical response to hydrogen concentration is linear and, more interestingly, can be described by a single universal linear trend if constructed as a function of the H/Pd ratio, independent of alloy composition. In addition to this correlation, we establish that the amplitude of optical signal change is defined solely by the spectral plasmon resonance position in the non-hydrogenated state for a specific nanoparticle composition. Thus, it can be maximized by red-shifting the LSPR into the NIR spectral range via tailoring the particle size and shape. These findings further establish plasmonic sensing as an effective tool for studying metal-hydrogen interactions in nanoparticles of complex chemical composition. They also represent universal design rules for metal-hydride-based plasmonic hydrogen sensors, and our theoretical analysis predicts that they are applicable not only to the H/Pd/Au or H/Pd/Cu system investigated here but also to other H/Pd/Metal combinations.

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.

Nanoplasmonic sensors typically comprise arrangements of noble metal nanoparticles on a dielectric support. Thus, they are intrinsically characterized by surface topography with corrugations at the 10-100 nm length scale. While irrelevant in some bio- and chemosensing applications, it is also to be expected that the surface topography significantly influences the interaction between solids, fluids, nanoparticles and (bio)molecules, and the nanoplasmonic sensor surface. To address this issue, we present a wafer-scale nanolithography-based fabrication approach for high-temperature compatible, chemically inert, topographically flat, and laterally homogeneous nanoplasmonic sensor chips. We demonstrate their sensing performance on three different examples, for which we also carry out a direct comparison with a traditional nanoplasmonic sensor with representative surface corrugation. Specifically, we (i) quantify the film-thickness dependence of the glass transition temperature in poly(methyl metacrylate) thin films, (ii) characterize the adsorption and specific binding kinetics of the avidin-biotinylated bovine serum albumin protein system, and (iii) analyze supported lipid bilayer formation on SiO 2 surfaces.