Iridium-Based Selective Emitters for Thermophotovoltaic Applications.

The long-term operation of refractory-metal-based metamaterials is crucial for applications such as thermophotovoltaics. The metamaterials based on refractory metals like W, Mo, Ta, Nb, and Re fail primarily by oxidation. Here, the use of the noble metal Ir is proposed, which is stable to oxidation and has optical properties comparable to gold. The thermal endurance of Ir in a 3-layer-system, consisting of HfO2 /Ir/HfO2 , by performing annealing experiments up to 1240 °C in a pressure range from 2 × 10-6  mbar to 1 bar, is demonstrated. The Ir layer shows no oxidation in a vacuum and inert gas atmosphere. At temperatures above 1100 °C, the Ir layer starts to agglomerate due to the degradation of the confining HfO2 layers. An in situ X-ray diffraction experimental comparison between 1D multilayered Ir/HfO2 and W/HfO2 selective emitters annealed at 1000 °C, 2 × 10-6  mbar, over 100 h, confirms oxidation stability of Ir while W multilayers gradually disappear. The results of this work show that W-based metamaterials are not long-term stable even at 1000 °C. However, the oxidation resistance of Ir can be leveraged for refractory plasmonic metamaterials, such as selective emitters in thermophotovoltaic systems with strong suppression of long wavelength radiation.

Influence of Alumina Addition on the Optical Properties and the Thermal Stability of Titania Thin Films and Inverse Opals Produced by Atomic Layer Deposition.

TiO2 thin films deposited by atomic layer deposition (ALD) at low temperatures (<100 °C) are, in general, amorphous and exhibit a smaller refractive index in comparison to their crystalline counterparts. Nonetheless, low-temperature ALD is needed when the substrates or templates are based on polymeric materials, as the deposition has to be performed below their glass transition or melting temperatures. This is the case for photonic crystals generated via ALD infiltration of self-assembled polystyrene templates. When heated up, crystal phase transformations take place in the thin films or photonic structures, and the accompanying volume reduction as well as the burn-out of residual impurities can lead to mechanical instability. The introduction of cation doping (e.g., Al or Nb) in bulk TiO2 parts is known to alter phase transitions and to stabilize crystalline phases. In this work, we have developed low-temperature ALD super-cycles to introduce Al2O3 into TiO2 thin films and photonic crystals. The aluminum oxide content was adjusted by varying the TiO2:Al2O3 internal loop ratio within the ALD super-cycle. Both thin films and inverse opal photonic crystal structures were subjected to thermal treatments ranging from 200 to 1200 °C and were characterized by in- and ex-situ X-ray diffraction, spectroscopic ellipsometry, and spectroscopic reflectance measurements. The results show that the introduction of alumina affects the crystallization and phase transition temperatures of titania as well as the optical properties of the inverse opal photonic crystals (iPhC). The thermal stability of the titania iPhCs was increased by the alumina introduction, maintaining their photonic bandgap even after heat treatment at 900 °C and outperforming the pure titania, with the best results being achieved with the super-cycles corresponding to an estimated alumina content of 26 wt.%.

Tailoring Disorder and Quality of Photonic Glass Templates for Structural Coloration by Particle Charge Interactions.

To obtain high-quality homogeneous photonic glass-based structural color films over large areas, it is essential to precisely control the degree of disorder of the spherical particles used and reduce the crack density within the films as much as possible. To tailor the disorder and quality of photonic glasses, a heteroaggregation-based process was developed by employing two oppositely charged equal-sized polystyrene (PS) particle types. The influence of the particle size ratio on the extent of heteroaggregation in the suspension mixes is investigated and correlated with both the morphology and the resultant optical properties of the films. The results show that the oppositely charged particle size ratio within the mix greatly influences the assembled structure in the films, affecting their roughness, crack density, and the coffee-ring formation. To better differentiate the morphology of the films, scanning electron microscopy images of the microstructures were classified by a supervised training of a deep convolutional neural network model to find distinctions that are inaccessible by conventional image analysis methods. Selected compositions were then infiltrated with TiO2 via atomic layer deposition, and after removal of the PS spheres, surface-templated inverse photonic glasses were obtained. Different color impressions and optical properties were obtained depending on the heteroaggregation level and thus the quality of the resultant films. The best results regarding the stability of the films and suppression of coffee-ring formation are obtained with a 35 wt % positively charged over negatively charged particle mix, which yielded enhanced structural coloration associated with improved film quality, tailored by the heteroaggregation fabrication process.

Structural degradation of tungsten sandwiched in hafnia layers determined by in-situ XRD up to 1520 °C.

The high-temperature stability of thermal emitters is one of the critical properties of thermophotovoltaic (TPV) systems to obtain high radiative power and conversion efficiencies. W and HfO2 are ideal due to their high melting points and low vapor pressures. At high temperatures and given vacuum conditions, W is prone to oxidation resulting in instantaneous sublimation of volatile W oxides. Herein, we present a detailed in-situ XRD analysis of the morphological changes of a 3-layer-system: HfO2/W/HfO2 layers, in a high-temperature environment, up to 1520 °C. These samples were annealed between 300 °C and 1520 °C for 6 h, 20 h, and 40 h at a vacuum pressure below 3 × 10-6 mbar using an in-situ high-temperature X-ray diffractometer, which allows investigation of crucial alterations in HfO2 and W layers. HfO2 exhibits polymorphic behavior, phase transformations and anisotropy of thermal expansion leads to formation of voids above 800 °C. These voids serve as transport channels for the residual O2 present in the annealing chamber to access W, react with it and form volatile tungsten oxides. An activation energy of 1.2 eV is calculated. This study clarifies the limits for the operation of W-HfO2 spectrally selective emitters for TPV in high-temperature applications.

Surface templated inverse photonic glass for saturated blue structural color.

To substitute conventional pigments, which often are toxic or suffer from fading in ultraviolet light, non-iridescent structural colors should demonstrate high spectral selectivity, while being also mechanically stable. However, conventional photonic glass (PhG) shows low color saturation due to the gradual transition in the reflection spectrum and low mechanical stability due to weak interparticle attachment. Here, a PhG with sharp spectral transition in comparison with the conventional full sphere PhG is designed by a conformal coating via atomic layer deposition (ALD) onto an organic PhG template. The ALD deposition allows to control the film thickness precisely for the highly saturated color. This structure can be described by hollow particle motifs with the effective size larger than the interparticle distance. Such unusual PhG is motivated by the achievable features in the spatial Fourier transform of a disordered assembly of such motifs. The surface-templated inverse PhG shows much higher color saturation than the direct PhG from full spheres. Moreover, the dense and solid connected shell will be beneficial for mechanical stability. These results pave the way for highly saturated structural colors. The demonstrated sharp spectral selection feature can be also considered for many related applications such as sunscreens, photovoltaics and radiative cooling by adjusting the reflection transition to the required wavelength. This can be achieved by proportionally scaling the motif and lattice dimensions as well as the film thickness.

Thermal stability of tungsten based metamaterial emitter under medium vacuum and inert gas conditions.

Commercial deployment of thermophotovoltaics (TPV) is lacking behind the implementation of solar PV technology due to limited thermal stability of the selective emitter structures. Most of the TPV emitters demonstrated so far are designed to operate under high vacuum conditions (~10-6 mbar vacuum pressure), whereas under medium vacuum conditions (~10-2 mbar vacuum pressure), which are feasible in technical implementations of TPV, these emitters suffer from oxidation due to significant O2 partial pressure. In this work, the thermal stability of 1D refractory W-HfO2 based multilayered metamaterial emitter structure is investigated under different vacuum conditions. The impact of the O2 partial pressure on thermal stability of the emitters is experimentally quantified. We show that, under medium vacuum conditions, i.e. ~10-2 mbar vacuum pressure, the emitter shows unprecedented thermal stability up to 1300 °C when the residual O2 in the annealing chamber is minimized by encapsulating the annealing chamber with Ar atmosphere. This study presents a significant step in the experimental implementation of high temperature stable emitters under medium vacuum conditions, and their potential in construction of economically viable TPV systems. The high TPV efficiency, ~50% spectral efficiency for GaSb PV cell at 1300 °C, and high temperature stability make this platform well suited for technical application in next-generation TPV systems.

Linear Schrödinger equation with temporal evolution for front induced transitions.

The nonlinear Schrödinger equation based on slowly varying approximation is usually applied to describe the pulse propagation in nonlinear waveguides. However, for the case of the front induced transitions (FITs), the pump effect is well described by the dielectric constant perturbation in space and time. Thus, a linear Schrödinger equation (LSE) can be used. Also, in waveguides with weak dispersion the spatial evolution of the pulse temporal profile is usually tracked. Such a formulation becomes impossible for optical systems for which the group index or higher dispersion terms diverge as is the case near the band edge of photonic crystals. For the description of FITs in such systems a linear Schrödinger equation can be used where temporal evolution of the pulse spatial profile is tracked instead of tracking the spatial evolution. This representation provides the same descriptive power and can easily deal with zero group velocities. Furthermore, the Schrödinger equation with temporal evolution can describe signal pulse reflection from both static and counter-propagating fronts, in contrast to the Schrödinger equation with spatial evolution which is bound to forward propagation. Here, we discuss the two approaches and apply the LSE with temporal evolution for systems close to the band edge where the group velocity vanishes by simulating intraband indirect photonic transitions. We also compare the numerical results with the theoretical predictions from the phase continuity criterion for complete transitions.

Transparency induced in opals via nanometer thick conformal coating.

Self-assembled periodic structures out of monodisperse spherical particles, so-called opals, are a versatile approach to obtain 3D photonic crystals. We show that a thin conformal coating of only several nanometers can completely alter the reflection properties of such an opal. Specifically, a coating with a refractive index larger than that of the spherical particles can eliminate the first photonic band gap of opals. To explain this non-intuitive effect, where a nm-scaled coating results in a drastic change of optical properties at wavelengths a hundred times bigger, we split the permittivity distribution of the opal into a lattice function convoluted with that of core-shell particles as a motif. In reciprocal space, the Bragg peaks that define the first Brillouin zone can be eliminated if the motif function, which is multiplied, assumes zero at the Bragg peak positions. Therefore, we designed a non-monotonic refractive index distribution from the center of the particle through the shell into the background and adjusted the coating thickness. The theory is supported by simulations and experiments that a nanometer thin TiO2 coating via atomic layer deposition (ALD) on synthetic opals made from polystyrene particles induces nearly full transparency at a wavelength range where the uncoated opal strongly reflects. This effect paves the way for sensing applications such as monitoring the thicknesses growth in ALD in-situ and in real time as well as measuring a refractive index change without spectral interrogation.

Metamaterial emitter for thermophotovoltaics stable up to 1400 °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.

Free-carrier detection in a silicon slab via absorption measurement in 2D integrating cells.

2D integrating cells provide long optical path lengths on a chip by multiple reflections at highly reflective mirrors similar to integrating spheres in free space. Therefore, they build a promising platform for integrated optical absorption sensing. Here, we present first absorption measurements of free carriers generated by a modulated pump laser inside a 2D integrating cell in a silicon slab. The results can be used to evaluate the lifetimes of free carriers in silicon slabs for integrated optics. Employing a silicon-on-insulator platform with a silicon thickness of 220 nm, we demonstrate measurements of the access free-carrier concentration on the order of 1-8·1015 cm-3 with lifetimes on the order of 0.1-1 µs governed by surface recombination at the silicon interfaces. The measured lifetimes are dependent on free-carrier concentration, which confirms previous observations. The presented free-carrier absorption experiment verifies the sensitivity of 2D integrating cells to changes in the absorption coefficient and thus demonstrates the potential of 2D integrating cells for absorption sensing.

Backscattering design for a focusing grating coupler with fully etched slots for transverse magnetic modes.

Grating couplers are a fundamental building block of integrated optics as they allow light to be coupled from free-space to on-chip components and vice versa. A challenging task in designing any grating coupler is represented by the need for reducing back reflections at the waveguide-grating interface, which introduce additional losses and undesirable interference fringes. Here, we present a design approach for focusing TM grating couplers that minimizes these unwanted reflections by introducing a modified slot that fulfills an anti-reflection condition. We show that this antireflection condition can be met only for the Bloch mode of the grating that concentrates in the dielectric. As a consequence the light is scattered from the grating coupler with a negative angle, referred to as "backscattering design". Our analytic model shows that the anti-reflection condition is transferrable to grating couplers on different waveguide platforms and that it applies for both TE and TM polarizations. Our experimentally realized focusing grating coupler for TM-modes on the silicon photonics platform has a coupling loss of (3.95 ± 0.15) dB at a wavelength of 1.55 µm. It has feature sizes above 200 nm and fully etched slots. The reflectivity between the grating coupler and the connected waveguide is suppressed to below 0.16%.

Dataset of ptychographic X-ray computed tomography of inverse opal photonic crystals produced by atomic layer deposition.

This data article describes the detailed parameters for synthesizing mullite inverse opal photonic crystals via Atomic Layer Deposition (ALD), as well as the detailed image analysis routine used to interpret the data obtained by the measurement of such photonic crystals, before and after the heat treatment, via Ptychographic X-ray Computed Tomography (PXCT). The data presented in this article are related to the research article by Furlan and co-authors entitled "Photonic materials for high-temperature applications: Synthesis and characterization by X-ray ptychographic tomography" (Furlan et al., 2018). The data include detailed information about the ALD super-cycle process to generate the ternary oxides inside a photonic crystal template, the raw data from supporting characterization techniques, as well as the full dataset obtained from PXCT. All the data herein described is publicly available in a Mendeley Data archive "Dataset of synthesis and characterization by PXCT of ALD-based mullite inverse opal photonic crystals" located at https://data.mendeley.com/datasets/zn49dsk7x6/1 for any academic, educational, or research purposes.

Coupling between multimode fibers and slab waveguides.

In guided-wave optics, using gratings to couple between single mode waveguides and single mode fibers and vice versa is well-established. In contrast, the coupling between multimode waveguides is more complex and a much less understood topic, even though multimode coupling is essential for the excitation of guided modes from spatially incoherent sources or for the extraction of spatially incoherent radiation from a guided-wave platform. Here, we present the design for a grating that couples multiple modes of a 2D slab waveguide into a multimode fiber and vice versa and discuss the corresponding challenges. We highlight the importance of matching mode numbers and scattering angles and show that the coupling efficiency can readily drop to low values. We present a rudimentary design that illustrates the key issues by demonstrating the coupling from a multimode fiber into a waveguide slab and back into another fiber, which achieves a total efficiency of -34 dB. By modeling the same geometry, we achieve good agreement, which allows us to explain the physics of the coupler and to suggest improvements. Future options are discussed to improve the coupling elements with a better directivity in order to achieve a maximal coupling efficiency. Our findings can be exploited for improving the multimode light injection into and out of integrated guided-wave optical systems.

Author Correction: Reflection from a free carrier front via an intraband indirect photonic transition.

The original version of this article contained an error in first sentence of the Acknowledgements, which incorrectly read 'M.A.G, D.J., A.Y.P. and M.E. acknowledge the support of the German Research Foundation under grant no. EI 391/13-2, and appreciate the support of CST, Darmstadt, Germany, with their Microwave Studio Software.' The correct version states '261759120' in place of 'EI 391/13-2'. This has been corrected in both the PDF and HTML versions of the article.

Photonic glass for high contrast structural color.

Non-iridescent structural colors based on disordered arrangement of monodisperse spherical particles, also called photonic glass, show low color saturation due to gradual transition in the reflectivity spectrum. No significant improvement is usually expected from particles optimization, as Mie resonances are broad for small dielectric particles with moderate refractive index. Moreover, the short range order of a photonic glass alone is also insufficient to cause sharp spectral features. We show here, that the combination of a well-chosen particle geometry with the short range order of a photonic glass has strong synergetic effects. Using a first-order approximation and an Ewald sphere construction the reflectivity of such structures can be related to the Fourier transform of the permittivity distribution. The Fourier transform required for a highly saturated color can be achieved by tailoring the substructure of the motif. We show that this can be obtained by choosing core-shell particles with a non-monotonous refractive index distribution from the center of the particle through the shell and into the background material. The first-order theoretical predictions are confirmed by numerical simulations.

Ewald sphere construction for structural colors.

Disordered structures producing a non-iridescent color impression have been shown to feature a spherically shaped Fourier transform of their refractive-index distribution. We determine the direction and efficiency of scattering from thin films made from such structures with the help of the Ewald sphere construction which follows from first-order scattering approximation. This way we present a simple geometrical argument why these structures are well suited for creating short wavelength colors like blue but are hindered from producing long wavelength colors like red. We also numerically synthesize a model structure dedicated to produce a sharp spherical shell in reciprocal space. The reflectivity of this structure as predicted by the first-order approximation is compared to direct electromagnetic simulations. The results indicate the Ewald sphere construction to constitute a simple geometrical tool that can be used to describe and to explain important spectral and directional features of the reflectivity. It is shown that total internal reflection in the film in combination with directed scattering can be used to obtain long wavelength structural colors.

Reflection from a free carrier front via an intraband indirect photonic transition.

The reflection of light from moving boundaries is of interest both fundamentally and for applications in frequency conversion, but typically requires high pump power. By using a dispersion-engineered silicon photonic crystal waveguide, we are able to achieve a propagating free carrier front with only a moderate on-chip peak power of 6 W in a 6 ps-long pump pulse. We employ an intraband indirect photonic transition of a co-propagating probe, whereby the probe practically escapes from the front in the forward direction. This forward reflection has up to 35% efficiency and it is accompanied by a strong frequency upshift, which significantly exceeds that expected from the refractive index change and which is a function of group velocity, waveguide dispersion and pump power. Pump, probe and shifted probe all are around 1.5 µm wavelength which opens new possibilities for "on-chip" frequency manipulation and all-optical switching in optical telecommunications.

A ferroelectric liquid crystal confined in cylindrical nanopores: reversible smectic layer buckling, enhanced light rotation and extremely fast electro-optically active Goldstone excitations.

The orientational and translational order of a thermotropic ferroelectric liquid crystal (2MBOCBC) imbibed in self-organized, parallel, cylindrical pores with radii of 10, 15, or 20 nm in anodic aluminium oxide monoliths (AAO) are explored by high-resolution linear and circular optical birefringence as well as neutron diffraction texture analysis. The results are compared to experiments on the bulk system. The native oxidic pore walls do not provide a stable smectogen wall anchoring. By contrast, a polymeric wall grafting enforcing planar molecular anchoring results in a thermal-history independent formation of smectic C* helices and a reversible chevron-like layer buckling. An enhancement of the optical rotatory power by up to one order of magnitude of the confined compared to the bulk liquid crystal is traced to the pretransitional formation of helical structures at the smectic-A*-to-smectic-C* transformation. A linear electro-optical birefringence effect evidences collective fluctuations in the molecular tilt vector direction along the confined helical superstructures, i.e. the Goldstone phason excitations typical of the para-to-ferroelectric transition. Their relaxation frequencies increase with the square of the inverse pore radii as characteristic of plane-wave excitations and are two orders of magnitude larger than in the bulk, evidencing an exceptionally fast electro-optical functionality of the liquid-crystalline-AAO nanohybrids.

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.

Blackbody Theory for Hyperbolic Materials.

The blackbody theory is revisited in the case of thermal electromagnetic fields inside uniaxial anisotropic media in thermal equilibrium with a heat bath. When these media are hyperbolic, we show that the spectral energy density of these fields radically differs from that predicted by Planck's blackbody theory and that the maximum of the spectral energy density determined by Wien's law is redshifted. Finally, we derive the Stefan-Boltzmann law for hyperbolic media which becomes a quadratic function of the heat bath temperature.