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Many technological applications in photonics require devices to function reliably under extreme conditions, including high temperatures. To this end, materials and structures with thermally stable optical properties are indispensable. State-of-the-art thermal photonic devices based on nanostructures suffer from severe surface diffusion-induced degradation, and the operational temperatures are often restricted. Here, we report on a thermo-optically stable superabsorber composed of bilayer refractory dielectric materials. The device features an average absorptivity ∼95% over >500 nm bandwidth in the near-infrared regime, with minimal temperature dependence up to 1500 °C. Our results demonstrate an alternative pathway to achieve high-temperature thermo-optically stable photonic devices., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The composition-dependent degradation of hybrid organic-inorganic perovskites (HOIPs) due to environmental stressors still precludes their commercialization. It is very difficult to quantify their behavior upon exposure to each stressor by exclusively using trial-and-error methods due to the high-dimensional parameter space involved. We implement machine learning (ML) models using high-throughput, in situ photoluminescence (PL) to predict the response of Cs y FA 1- y Pb(Br x I 1- x ) 3 while exposed to relative humidity cycles. We quantitatively compare three ML models while generating forecasts of environment-dependent PL responses: linear regression, echo state network, and seasonal autoregressive integrated moving average with exogenous regressor algorithms. We achieve accuracy of >90% for the latter, while tracking PL changes over a 50 h window. Samples with 17% of Cs content consistently showed a PL increase as a function of cycle. Our precise time-series forecasts can be extended to other HOIP families, illustrating the potential of data-centric approaches to accelerate material development for clean-energy devices., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Optical materials based on unconventional plasmonic metals (e.g., magnesium) have lately driven rising research interest for the quest of possibilities in nanophotonic applications. Several favorable attributes of Mg, such as earth abundancy, lightweight, biocompatibility/biodegradability, and its active reactions with water or hydrogen, have underpinned its emergence as an alternative nanophotonic material. Here, we experimentally demonstrate a thin film-based optical device composed exclusively of earth-abundant and complementary metal-oxide semiconductor (CMOS)-compatible materials (i.e., Mg, a-Si, and SiO 2 ). The devices can exhibit a spectrally selective and tunable near-unity resonant absorption with an ultrathin a-Si absorbing layer due to the strong interference effect in this high-index and lossy film. Alternatively, they can generate diverse reflective colors by appropriate tuning of the a-Si and SiO 2 layer thicknesses, including all the primary colors for RGB (red, green, blue) and CMY (cyan, magenta, yellow) color spaces. In addition, the reflective hues of the devices can be notably altered in a zero power-consumption fashion by immersing them in water due to the resulted dissolution of the Mg back-reflection layer. These compelling features in combination with the lithography-free and scalable fabrication steps may promise their adoption in various photonic applications including solar energy harvesting, optical information security, optical modulation, and filtering as well as structure reuse and recycling., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Mg shows great potential as a metal hydride for switchable optical response and hydrogen detection due to its ability to stably incorporate significant amounts of hydrogen into its lattice. However, this thermodynamic stability makes hydrogen removal difficult. By alloying Mg with secondary elements, the hydrogenation kinetics can be increased. Here, we report the dynamic optical, loading, and stress properties of three Mg alloy systems (Mg-Al, Mg-Ti, and Mg-Ni) and present several novel phenomena and three distinct device designs that can be achieved with them. We find that these materials all have large deviations in refractive index when exposed to H 2 gas, with a wide range of potential properties in the hydride state. The magnitude and sign of the optical property change for each of the alloys are similar, but the differences have dramatic effects on device design. We show that Mg-Ti alloys perform well as both switchable windows and broadband switchable light absorbers, where Mg 0.87 Ti 0.13 and Mg 0.85 Ti 0.15 can achieve a 40% transmission change as a switchable window and a 55% absorption change as a switchable solar absorber. We also show how different alloys can be used for dynamically tunable color filters, where both the reflected and transmitted colors depend on the hydrogenation state. We demonstrate how small changes in the alloy composition (e.g., with Mg-Ni) can lead to dramatically different color responses upon hydrogenation (red-shifting vs blue-shifting of the resonance). Our results establish the potential for these Mg alloys in a variety of applications relating to hydrogen storage, detection, and optical devices, which are necessary for a future hydrogen economy.

Refractory metals have recently garnered significant interest as options for photonic applications due to their superior high-temperature stability and versatile optical properties. However, most previous studies only consider their room-temperature optical properties when analyzing these materials' behavior as optical components. Here, we demonstrate structural color pixels based on three refractory metals (Ru, Ta, and W) for high-temperature applications. We quantify their optical behavior in an oxygenated environment and determine their dielectric functions after heating up to 600 °C. We use in situ oxidation, a fundamental chemical reaction, to form nanometer-scale metal oxide thin-film bilayers on each refractory metal. We fully characterize the behavior of the newly formed thin-film interference structures, which exhibit vibrant color changes upon high-temperature treatment. Finally, we present optical simulations showing the full range of hues achievable with a simple two-layer metal oxide/metal reflector structure. All of these materials have melting points >1100 °C, with the Ta-based structure offering high-temperature stability, and the Ru- and W-based options providing an alternative for reversible color filters, at high temperatures in inert or vacuum environments. Our approach is uniquely suitable for high-temperature photonics, where the oxides can be used as conformal coatings to produce a wide variety of colors across a large portion of the color gamut.

Metal halide perovskite (MHP) photovoltaics may become a viable alternative to standard Si-based technologies, but the current lack of long-term stability precludes their commercial adoption. Exposure to standard operational stressors (light, temperature, bias, oxygen, and water) often instigate optical and electronic dynamics, calling for a systematic investigation into MHP photophysical processes and the development of quantitative models for their prediction. We resolve the moisture-driven light emission dynamics for both methylammonium lead tribromide and triiodide thin films as a function of relative humidity (rH). With the humidity and photoluminescence time series, we train recurrent neural networks and establish their ability to quantitatively predict the path of future light emission with 18% error over 4 h. Together, our in situ rH-PL measurements and machine learning forecasting models provide a framework for the rational design of future stable perovskite devices and, thus, a faster transition toward commercial applications.

Perovskite solar cells (PSC) are a favorable candidate for next-generation solar systems with efficiencies comparable to Si photovoltaics, but their long-term stability must be proven prior to commercialization. However, traditional trial-and-error approaches to PSC screening, development, and stability testing are slow and labor-intensive. In this Perspective, we present a survey of how machine learning (ML) and autonomous experimentation provide additional toolkits to gain physical understanding while accelerating practical device advancement. We propose a roadmap for applying ML to PSC research at all stages of design (compositional selection, perovskite material synthesis and testing, and full device evaluation). We also provide an overview of relevant concepts and baseline models that apply ML to diverse materials problems, demonstrating its broad relevance while highlighting promising research directions and associated challenges. Finally, we discuss our outlook for an integrated pipeline that encompasses all design stages and presents a path to commercialization.

Pd x Au 1- x alloys have recently shown great promise for next-generation optical hydrogen sensors due to their increased chemical durability while their optical sensitivity to small amounts of hydrogen gas is maintained. However, the correlation between chemical composition and the dynamic optical behavior upon hydrogenation/dehydrogenation is currently not well understood. A complete understanding of this relation is necessary to optimize future sensors and nanophotonic devices. Here, we quantify the dynamic optical, chemical, and mechanical properties of thin film Pd x Au 1- x alloys as they are exposed to H 2 by combining in situ ellipsometry with gravimetric and stress measurements. We demonstrate the dynamic optical property dependence of the film upon hydrogenation and directly correlate it with the hydrogen content up to a maximum of 7 bar of H 2 . With this measurement, we find that the thin films exhibit their strongest optical sensitivity to H 2 in the near-infrared. We also discover higher hydrogen-loading amounts as compared to previous measurements for alloys with low atomic percent Pd. Specifically, a measurable optical and gravimetric hydrogen response in alloys as low as 34% Pd is found, when previous works have suggested a disappearance of this response near 55% Pd. This result suggests that differences in film stress and microstructuring play a crucial role in the sorption behavior. We directly measure the thin film stress and morphology upon hydrogenation and show that the alloys have a substantially higher relative stress change than pure Pd, with the pure Pd data point falling 0.9 GPa below the expected trend line. Finally, we use the measured optical properties to illustrate the applicability of these alloys as grating structures and as a planar physical encryption scheme, where we show significant and variable changes in reflectivity upon hydrogenation. These results lay the foundation for the composition and design of next-generation hydrogen sensors and tunable photonic devices.

Metallic materials with engineered optical properties have the potential to enhance the performance of energy harvesting and storage devices operating at the macro- and nanoscale, such as solar cells, photocatalysts, water splitting, and hydrogen storage systems. For both thin films and subwavelength nanostructures, upon illumination, the coherent oscillation of charge carriers at the interface with a dielectric material gives rise to resonances named surface plasmon polariton (SPP) and localized surface plasmon resonance (LSPR), respectively. These resonances result in unique light absorption, scattering, and transmission responses over the electromagnetic spectrum, which, in turn, can be exploited to tailor the behavior of active metallic components in optoelectronic devices containing Ag, Au, Cu, Al, Mg, among other metals. The wavelength in which the resonances occur primarily depends on the metal itself (i.e., the dielectric function or permittivity), the dielectric medium surrounding the metals, and the size, geometry, and periodicity of the metallic nanostructures. Nevertheless, the aforementioned parameters allow a limited modulation of both SPP and LSPR over a narrow window of frequencies. To overcome this constraint, we have proposed and realized the alloying of metals via physical deposition methods as a paradigm to almost arbitrarily tuning their optical behavior in the UV-NIR, which leads to permittivity values currently not available. Our approach offers an additional knob, chemical composition, to engineer light-matter interactions in metallic materials. This Account highlights recent progress in using alloying as a pathway to control the optical behavior of metallic thin films and nanostructures for energy harvesting and storage applications, including (photo)catalysis, photovoltaics, superabsorbers, hydrogen storage, among other systems. We choose to primarily focus on the optical properties of the metallic mixtures and in their near- to far-field responses in the UV-NIR range of the spectrum as they represent key parameters for materials' selection for the devices above. By alloying, it is possible to obtain metallic materials with LSPR not available for pure metals, which can enable the further control of the electromagnetic spectrum. First, we discuss how the permittivity of binary mixtures of coinage metals (Au, Ag, and Cu) can be tailored based on the chemical composition of their pure counterparts. Second, we present how novel metallic materials can be designed through band structure engineering through density functional theory (DFT), a paradigm that could benefit from artificial intelligence methods. Concerning alloyed thin films, we discuss the promise of earth-abundant metals and provide an example of the superior performance of AlCu in superabsorbers. In the realm of nanostructures, we focus the discussion on physical deposition methods, where we provide a detailed analysis of how chemical composition can affect the far- and near-field responses of metallic building blocks. Finally, we provide a brief outlook of promising next steps in the field.

Pd-containing alloys are promising materials for catalysis. Yet, the relationship of the structure-property performance strongly depends on their chemical composition, which is currently not fully resolved. Herein, we present a physical vapor deposition methodology for developing Pd x Au 1- x alloys with fine control over the chemical composition. We establish direct correlations between the composition and these materials' structural and electronic properties with its catalytic activity in an ethanol (EtOH) oxidation reaction. By combining X-ray diffraction (XRD) and X-ray photelectron spectroscopy (XPS) measurements, we validate that the Pd content within both bulk and surface compositions can be finely controlled in an ultrathin-film regime. Catalytic oxidation of EtOH on the Pd x Au 1- x electrodes presents the largest forward-sweeping current density for x = 0.73 at ∼135 mA cm -2 , with the lowest onset potential and largest peak activity of 639 A g Pd -1 observed for x = 0.58. Density functional theory (DFT) calculations and XPS measurements demonstrate that the valence band of the alloys is completely dominated by Pd particularly near the Fermi level, regardless of its chemical composition. Moreover, DFT provides key insights into the Pd x Au 1- x ligand effect, with relevant chemisorption activity descriptors probed for a large number of surface arrangements. These results demonstrate that alloys can outperform pure metals in catalytic processes, with fine control of the chemical composition being a powerful tuning knob for the electronic properties and, therefore, the catalytic activity of ultrathin Pd x Au 1- x catalysts. Our high-throughput experimental methodology, in connection with DFT calculations, provides a unique foundation for further materials' discovery, including machine-learning predictions for novel alloys, the development of Pd-alloyed membranes for the purification of reformate gases, binder-free ultrathin electrocatalysts for fuel cells, and room temperature lithography-based development of nanostructures for optically driven processes.

Perovskite solar cells that incorporate small concentrations of Cs in their A-site have shown increased lifetime and improved device performance. Yet, the development of fully stable devices operating near the theoretical limit requires understanding how Cs influences perovskites' electrical properties at the nanoscale. Here, we determine how the chemical composition of three perovskites (MAPbBr 3 , MAPbI 3 , and Cs-mixed) affects their short- and long-term voltage stabilities, with <50 nm spatial resolution. We map an anomalous irreversible electrical signature on MAPbBr 3 at the mesoscale, resulting in local V oc variations of ∼400 mV, and in entire grains with negative contribution to the V oc . These measurements prove the necessity of high spatial resolution mapping to elucidate the fundamental limitations of this emerging material. Conversely, we capture the fully reversible voltage response of Cs-mixed perovskites, composed by Cs 0.06 (MA 0.17 FA 0.83 ) 0.94 Pb(I 0.83 Br 0.17 ) 3 , demonstrating that the desired electrical output persists even at the nanoscale. The Cs-mixed material presents no spatial variation in V oc , as ion motion is restricted. Our results show that the nanoscale electrical behavior of the perovskites is intimately connected to their chemical composition and macroscopic response.

The spatial resolution of atomic force microscopy (AFM) needed to resolve material interfaces is limited by the tip-sample separation ( d) dependence of the force used to record an image. Here, we present a new multiscale functional imaging technique that allows for in situ tunable spatial resolution, which can be applied to a wide range of inhomogeneous materials, devices, and interfaces. Our approach uses a multifrequency method to generate a signal whose d-dependence is controlled by mixing harmonics of the cantilever's oscillation with a modulated force. The spatial resolution of the resulting image is determined by the signal's d-dependence. Our measurements using harmonic mixing (HM) show that we can change the d-dependence of a force signal to improve spatial resolution by up to a factor of two compared to conventional methods. We demonstrate the technique with both Kelvin probe force microscopy (KPFM) and bimodal AFM to show its generality. Bimodal AFM with harmonic mixing actuation separates conservative from dissipative forces and is used to identify the regions of adhesive residue on exfoliated graphene. Our electrostatic measurements with open-loop KPFM demonstrate that multiple force modulations may be applied at once. Further, this method can be applied to any tip-sample force that can be modulated, for example, electrostatic, magnetic, and photoinduced forces, showing its universality. Because HM enables in situ switching between high sensitivity and high spatial resolution with any periodic driving force, we foresee this technique as a critical advancement for multiscale functional imaging.

Hybrid organic-inorganic perovskites containing Cs are a promising new material for light-absorbing and light-emitting optoelectronics. However, the impact of environmental conditions on their optical properties is not fully understood. Here, we elucidate and quantify the influence of distinct humidity levels on the charge carrier recombination in Cs x FA 1- x Pb(I y Br 1- y ) 3 perovskites. Using in situ environmental photoluminescence (PL), we temporally and spectrally resolve light emission within a loop of critical relative humidity (rH) levels. Our measurements show that exposure up to 35% rH increases the PL emission for all Cs (10-17%) and Br (17-38%) concentrations investigated here. Spectrally, samples with larger Br concentrations exhibit PL redshift at higher humidity levels, revealing water-driven halide segregation. The compositions considered present hysteresis in their PL intensity upon returning to a low-moisture environment due to partially reversible hydration of the perovskites. Our findings demonstrate that the Cs/Br ratio strongly influences both the spectral stability and extent of light emission hysteresis. We expect our method to become standard when testing the stability of emerging perovskites, including lead-free options, and to be combined with other parameters known for affecting material degradation, e.g., oxygen and temperature.

Li metal is the preferred anode material for all-solid-state Li batteries. However, a stable plating and stripping of Li metal at the anode-solid electrolyte interface remains a significant challenge particularly at practically feasible current densities. This problem usually relates to high and/or inhomogeneous Li-electrode-electrolyte interfacial impedance and formation and growth of high-aspect-ratio dendritic Li deposits at the electrode-electrolyte interface, which eventually shunt the battery. To better understand details of Li metal plating, we use operando electron microscopy and Auger spectroscopy to probe nucleation, growth, and stripping of Li metal during cycling of a model solid-state Li battery as a function of current density and oxygen pressure. We find a linear correlation between the nucleation density of Li clusters and the charging rate in an ultrahigh vacuum, which agrees with a classical nucleation and growth model. Moreover, the trace amount of oxidizing gas (≈10 -6 Pa of O 2 ) promotes the Li growth in a form of nanowires due to a fine balance between the ion current density and a growth rate of a thin lithium-oxide shell on the surface of the metallic Li. Interestingly, increasing the partial pressure of O 2 to 10 -5 Pa resumes Li plating in a form of 3D particles. Our results demonstrate the importance of trace amounts of preexisting or ambient oxidizing species on lithiation processes in solid-state batteries.

Hybrid organic-inorganic perovskites based on methylammonium lead (MAPbI 3 ) are an emerging material with great potential for high-performance and low-cost photovoltaics. However, for perovskites to become a competitive and reliable solar cell technology their instability and spatial variation must be understood and controlled. While the macroscopic characterization of the devices as a function of time is very informative, a nanoscale identification of their real-time local optoelectronic response is still missing. Here, we implement a four-dimensional imaging method through illuminated heterodyne Kelvin probe force microscopy to spatially (<50 nm) and temporally (16 s/scan) resolve the voltage of perovskite solar cells in a low relative humidity environment. Local open-circuit voltage (V oc ) images show nanoscale sites with voltage variation >300 mV under 1-sun illumination. Surprisingly, regions of voltage that relax in seconds and after several minutes consistently coexist. Time-dependent changes of the local V oc are likely due to intragrain ion migration and are reversible at low injection level. These results show for the first time the real-time transient behavior of the V oc in perovskite solar cells at the nanoscale. Understanding and controlling the light-induced electrical changes that affect device performance are critical to the further development of stable perovskite-based solar technologies.

To increase the power conversion efficiency of solar cells, improved antireflection coatings are needed to couple light into the cell with minimal parasitic loss. Here, we present measurements and simulations of an antireflection coating based on silicon dioxide (SiO2) nanospheres that improve solar cell absorption by coupling light from free space into the absorbing layer through excitation of modes within the nanospheres. The deposited monolayer of nanospheres leads to a significant increase in light absorption within an underlying semiconductor on the order of 15-20%. When the periodicity and spacing between the nanospheres are varied, whispering gallery-like modes can be excited and tuned throughout the visible spectrum. The coating was applied to a Si solar cell containing a Si3N4 antireflection layer, and an additional increase in the spectral current density of ∼5% was found. The fabrication process, involving Meyer rod rolling, is scalable and inexpensive and could enable large-scale manufacturability of microresonator-based photovoltaics.

The local collection characteristics of grain interiors and grain boundaries in thin-film CdTe polycrystalline solar cells are investigated using scanning photocurrent microscopy. The carriers are locally generated by light injected through a small aperture (50-300 nm) of a near-field scanning optical microscope in an illumination mode. Possible influence of rough surface topography on light coupling is examined and eliminated by sculpting smooth wedges on the granular CdTe surface. By varying the wavelength of light, nanoscale spatial variations in external quantum efficiency are mapped. We find that the grain boundaries (GBs) are better current collectors than the grain interiors (GIs). The increased collection efficiency is caused by two distinct effects associated with the material composition of GBs. First, GBs are charged, and the corresponding built-in field facilitates the separation and the extraction of the photogenerated carriers. Second, the GB regions generate more photocurrent at long wavelength corresponding to the band edge, which can be caused by a smaller local band gap. Resolving carrier collection with nanoscale resolution in solar cell materials is crucial for optimizing the polycrystalline device performance through appropriate thermal processing and passivation of defects and surfaces.