Pavel N. Dyachenko

Controlling thermal emission with refractory epsilon-near-zero metamaterials via topological transitions

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.

Tungsten band edge absorber/emitter based on a monolayer of ceramic microspheres.

We report on a band edge absorber/emitter design for high-temperature applications based on an unstructured tungsten substrate and a monolayer of ceramic microspheres. The absorber was fabricated as a monolayer of ZrO(2) microparticles on a tungsten layer with a HfO(2) nanocoating. The band edge of the absorption is based on critically coupled microsphere resonances. It can be tuned from visible to near-infrared range by varying the diameter of the microparticles. The absorption properties were found to be stable up to 1000°C.

Facile Deposition of YSZ-Inverse Photonic Glass Films

An alternative all-colloidal and single-step deposition method of yttrium-stabilized zirconia (YSZ)-infiltrated polymeric photonic glass films is presented. Heterocoagulation of oppositely charged polystyrene (PS) microspheres and YSZ nanocrystals in aqueous dispersions created PS/YSZ core-shell spheres. These composite particles were deposited on glass substrates by a simple drop-coating process. Heterocoagulation impaired self-assembly of the particles, resulting in a disordered structure. Burn-out of the polymer yielded a random array of YSZ shells. The effect of the filling fraction of YSZ between these shells was explored. YSZ-inverse photonic glass films with a thickness below 40 μm achieved 70% reflectance of the incident radiation over a broad wavelength range between 0.4 and 2.2 μm. The YSZ structures demonstrated structural stability up to 1000 °C and maintained high reflectance up to 1200 °C for several hours, thus enabling applications as broadband reflectors at elevated temperatures.

Yttria-stabilized zirconia microspheres: novel building blocks for high-temperature photonics

Zirconia-based ceramics cover a huge variety of applications, including refractories, electro- and bioceramics, fuel cells, catalysts, and many more. For various photonic applications considered for energy systems and heat management, zirconia microspheres are interesting building blocks due to their high refractive index, as well as their chemical and mechanical robustness. However, instabilities caused by thermally-induced phase transitions and grain growth at temperatures above ∼1000 °C preclude high-temperature applications of pure zirconia particles. Here, we present a synthetic route for yttria-stabilized zirconia microparticles with significantly improved thermal stability. With these particles we conducted the first study on their thermal stability as a function of the yttrium content and at temperatures up to 1500 °C. Using X-ray diffraction and scanning electron microscopy, the optimum Y content was determined to be 8–10%, which was marked by stabilization of the tetragonal or cubic phase and significantly attenuated grain growth. Furthermore, with diameters ranging from 2 to 5 μm, the particles covered a size range perfectly suited for photonic applications in the IR spectral range. To demonstrate this, photonic glass coatings were prepared with these particles and their IR reflectivity and microstructural stability was studied after subjecting them to various heating cycles. While heating beyond 1200 °C led to failure and delamination of undoped particle films, films doped with 6 and 10% Y displayed quite stable broadband IR reflection of up to 80% in the wavelength range from 1–5 μm, even after prolonged heating at 1400 °C. A detailed analysis of the X-ray diffraction patterns revealed that prolonged heating at 1400 °C resulted in phase decomposition due to Y segregation into Y-lean and Y-rich domains, confirming the presence of the solute-drag effect.

Perfect narrow-band absorber based on a monolayer of metallodielectric microspheres

We have studied how two-dimensional arrays of metallodielectric core-shell microspheres on a metal substrate can efficiently absorb infrared electromagnetic radiation in a narrow wavelength range under normal incidence. Our simulations indicate that perfect absorption efficiencies can be achieved for resonance wavelengths. The influence of core-shell microspheres geometry and lattice geometry is studied on absorption properties. For wavelength from 1.2 μm to 2.6 μm, an optimal combination of sphere and core radius was obtained to provide perfect absorption which can be wavelength adjusted.

Bottom-up Fabrication of Multilayer Stacks of 3D Photonic Crystals from Titanium Dioxide

A strategy for stacking multiple ceramic 3D photonic crystals is developed. Periodically structured porous films are produced by vertical convective self-assembly of polystyrene (PS) microspheres. After infiltration of the opaline templates by atomic layer deposition (ALD) of titania and thermal decomposition of the polystyrene matrix, a ceramic 3D photonic crystal is formed. Further layers with different sizes of pores are deposited subsequently by repetition of the process. The influence of process parameters on morphology and photonic properties of double and triple stacks is systematically studied. Prolonged contact of amorphous titania films with warm water during self-assembly of the successive templates is found to result in exaggerated roughness of the surfaces re-exposed to ALD. Random scattering on rough internal surfaces disrupts ballistic transport of incident photons into deeper layers of the multistacks. Substantially smoother interfaces are obtained by calcination of the structure after each infiltration, which converts amorphous titania into the crystalline anatase before resuming the ALD infiltration. High quality triple stacks consisting of anatase inverse opals with different pore sizes are demonstrated for the first time. The elaborated fabrication method shows promise for various applications demanding broadband dielectric reflectors or titania photonic crystals with a long mean free path of photons.

Refractory absorber/emitter using monolayer of ceramic microparticles

We present a self-assembled refractory absorber/emitter without the necessity to structure the metallic surface itself, still retaining the feature of tailored optical properties for visible light emission and thermophotovoltaic (TPV) applications. We have demonstrated theoretically and experimentally that monolayers of zirconium dioxide (ZrO2) microparticles on a tungsten layer can be used as large area, efficient and thermally stable selective absorbers/emitters. The band edge of the absorption is based on critically coupled microsphere resonances. It can be tuned from visible to near-infrared range by varying the diameter of the microparticles. We demonstrated the optical functionality of the structure after annealing up to temperatures of 1000°C under vacuum conditions. In particular it opens up the route towards high efficiency TPV systems with emission matched to the photovoltaic cell.

Radiative engineering with refractory epsilon-near-zero metamaterials(Conference Presentation)

Improvement in high-temperature stable spectrally selective absorbers and emitters is integral for the further development of thermophotovoltaic (TPV), lighting and solar thermal applications. However, the high operational temperatures (T>1000oC) required for efficient energy conversion, along with application specific criteria such as the operational range of low bandgap semiconductors, greatly restrict what can be accomplished with natural materials. Motivated by this challenge, we demonstrate the first example of high temperature thermal radiation engineering with metamaterials. By employing the naturally selective thermal excitation of radiative modes that occurs near topological transitions, we show that thermally stable highly selective emissivity features are achieved for temperatures up to 1000°C with low angular dependence in a sub-micron thick refractory tungsten/hafnium dioxide epsilon-near-zero (ENZ) metamaterial. We also investigate the main mechanisms of thermal degradation of the fabricated refractory metamaterial both in terms of optical performance and structural stability using spectral analysis and energy-dispersive X-ray spectroscopy (EDS) techniques. Importantly, we observe chemical stability of the constituent materials for temperatures up to 1000°C and structural stability beyond 1100°C. The scalable fabrication, requiring magnetron sputtering, and thermally robust optical properties of this metamaterial approach are ideally suited to high temperature emitter applications such as lighting or TPV. Our findings provide a first concrete proof of radiative engineering with high temperature topological transition in ENZ metamaterials, and establish a clear path for implementation in TPV energy harvesting applications.