Control of thermal radiation at high temperatures is vital for waste heat recovery and for high-efficiency thermophotovoltaic (TPV) conversion. Previously, structural resonances utilizing gratings, thin film resonances, metasurfaces and photonic crystals were used to spectrally control thermal emission, often requiring lithographic structuring of the surface and causing significant angle dependence. In contrast, here, we demonstrate a refractory W-HfO₂ metamaterial, which controls thermal emission through an engineered dielectric response function. The epsilon-near-zero frequency of a metamaterial and the connected optical topological transition (OTT) are adjusted to selectively enhance and suppress the thermal emission in the near-infrared spectrum, crucial for improved TPV efficiency. The near-omnidirectional and spectrally selective emitter is obtained as the emission changes due to material properties and not due to resonances or interference effects, marking a paradigm shift in thermal engineering approaches. We experimentally demonstrate the OTT in a thermally stable metamaterial at high temperatures of 1,000 °C.

High temperature stable selective emitters can significantly increase efficiency and radiative power in thermophotovoltaic (TPV) systems. However, optical properties of structured emitters reported so far degrade at temperatures approaching 1200 °C due to various degradation mechanisms. We have realized a 1D structured emitter based on a sputtered W-HfO₂ layered metamaterial and demonstrated desired band edge spectral properties at 1400 °C. To the best of our knowledge the temperature of 1400 °C is the highest reported for a structured emitter, so far. The spatial confinement and absence of edges stabilizes the W-HfO₂ multilayer system to temperatures unprecedented for other nanoscaled W-structures. Only when this confinement is broken W starts to show the well-known self-diffusion behavior transforming to spherical shaped W-islands. We further show that the oxidation of W by atmospheric oxygen could be prevented by reducing the vacuum pressure below 10⁻⁵ mbar. When oxidation is mitigated we observe that the 20 nm spatially confined W films survive temperatures up to 1400 °C. The demonstrated thermal stability is limited by grain growth in HfO₂, which leads to a rupture of the W-layers, thus, to a degradation of the multilayer system at 1450 °C.

A preparation strategy is developed for monolithic samples of nanoporous gold with a hierarchical structure comprising two nested networks of solid “ligaments” on distinctly different structural length scales. The electrochemical dealloying protocol achieves a large retention of less noble element in a first corrosion step, thereby allowing an extra corrosion step which forms a separate structural hierarchy level. The beneficial impact of adding Pt to the Ag–Au master alloys that are more conventionally used in dealloying approaches to nanoporous gold is demonstrated. At ≈6 nm, the lower hierarchy level ligament size emerges extremely small. Furthermore, Pt favors the retention of Ag during the first dealloying step even when the master alloy has a high Au content. The high Au content reduces the corrosion‐induced shrinkage, mitigating crack formation during preparation and favoring the formation of high‐quality macroscopic (mm‐sized) samples. The corrosion effectively carves out the nanoscale hierarchical ligament structure from the parent crystals tens of micrometers in size. This is revealed by X‐ray as well as electron backscatter diffraction, which shows that the porous crystallites inherit the highly ordered, macroscopic crystal lattice structure of the master alloy.

High-resolution elemental mapping in a transmission electron microscope shows that the residual silver in dealloying-made nanoporous gold (NPG) is aggregated in nanoscale clusters. Kinetic Monte Carlo simulation confirms that these regions are buried relics of the master alloy that have never been exposed to corrosion. The surface of as-dealloyed NPG is covered by at least one atomic monolayer of nearly pure gold. The preferential location of silver in the bulk is relevant when interfaces control the material's function, as in catalysis and sensing. Annealing in air homogenizes the alloy by surface diffusion. GRAPHICAL ABSTRACT IMPACT STATEMENT The residual silver which is typically found in nanoporous gold made by dealloying is localized in clusters that are relics of the original master alloy which have evaded corrosion.