Hybrid supervised and reinforcement learning for the design and optimization of nanophotonic structures.

From higher computational efficiency to enabling the discovery of novel and complex structures, deep learning has emerged as a powerful framework for the design and optimization of nanophotonic circuits and components. However, both data-driven and exploration-based machine learning strategies have limitations in their effectiveness for nanophotonic inverse design. Supervised machine learning approaches require large quantities of training data to produce high-performance models and have difficulty generalizing beyond training data given the complexity of the design space. Unsupervised and reinforcement learning-based approaches on the other hand can have very lengthy training or optimization times associated with them. Here we demonstrate a hybrid supervised learning and reinforcement learning approach to the inverse design of nanophotonic structures and show this approach can reduce training data dependence, improve the generalizability of model predictions, and significantly shorten exploratory training times. The presented strategy thus addresses several contemporary deep learning-based challenges, while opening the door for new design methodologies that leverage multiple classes of machine learning algorithms to produce more effective and practical solutions for photonic design.

Array-Level Inverse Design of Beam Steering Active Metasurfaces.

We report an array-level inverse design approach to optimize the beam steering performance of active metasurfaces, thus overcoming the limitations posed by nonideal metasurface phase and amplitude tuning. In contrast to device-level topology optimization of passive metasurfaces, the outlined system-level optimization framework relies on the electrical tunability of geometrically identical nanoantennas, enabling the design of active antenna arrays with variable spatial phase and amplitude profiles. Based on this method, we demonstrate high-directivity, continuous beam steering up to 70° for phased arrays with realistic tunable antenna designs, despite nonidealities such as strong covariation of scattered light amplitude with phase. Nonintuitive array phase and amplitude profiles further facilitate beam steering with a phase modulation range as low as 180°. Furthermore, we use the device geometries presented in this work for experimental validation of the system-level inverse design approach of active beam steering metasurfaces. The proposed method offers a framework to optimize nanophotonic structures at the array level that is potentially applicable to a wide variety of objective functions and actively tunable metasurface antenna array platforms.

High Broadband Light Transmission for Solar Fuels Production Using Dielectric Optical Waveguides in TiO2 Nanocone Arrays.

We describe the fabrication and use of arrays of TiO2 nanocones to yield high optical transmission into semiconductor photoelectrodes covered with high surface loadings of light-absorbing electrocatalysts. Covering over 50% of the surface of a light absorber with an array of high-refractive-index TiO2 nanocones imparted antireflective behavior (<5% reflectance) to the surface and allowed >85% transmission of broadband light to the underlying Si, even when thick metal contacts or opaque catalyst coatings were deposited on areas of the light-facing surface that were not directly beneath a nanocone. Three-dimensional full-field electromagnetic simulations for the 400-1100 nm spectral range showed that incident broadband illumination couples to multiple waveguide modes in the TiO2 nanocones, reducing interactions of the light with the metal layer. A proof-of-concept experimental demonstration of light-driven water oxidation was performed using a p+n-Si photoanode decorated with an array of TiO2 nanocones additionally having a Ni catalyst layer electrodeposited onto the areas of the p+n-Si surface left uncovered by the TiO2 nanocones. This photoanode produced a light-limited photocurrent density of ∼28 mA cm-2 under 100 mW cm-2 of simulated air mass 1.5 illumination, equivalent to the photocurrent density expected for a bare planar Si surface even though 54% of the front surface of the Si was covered by an ∼70 nm thick Ni metal layer.

Polarized Single-Particle Quantum Dot Emitters through Programmable Cluster Assembly.

Although fluorescence and lifetimes of nanoscale emitters can be manipulated by plasmonic materials, it is harder to control polarization due to strict requirements on emitter environments. An ability to engineer 3D nanoarchitectures with nanoscale precision is needed for controlled polarization of nanoscale emitters. Here, we show that prescribed 3D heterocluster architectures with polarized emission can be successfully assembled from nanoscale fluorescent emitters and metallic nanoparticles using DNA-based self-assembly methods. An octahedral DNA origami frame serves as a programmable scaffold for heterogeneous nanoparticle assembly into prescribed clusters. Internal space and external connections of the frames are programmed to coordinate spherical quantum dots (QDs) and gold nanoparticles (AuNPs) into heterocluster architectures through site-specific DNA encodings. We demonstrate and characterize assembly of these architectures using in situ and ex situ structural methods. These cluster nanodevices exhibit polarized light emission with a plasmon-induced dipole along the QD-AuNP nanocluster axis, as observed by single-cluster optical probing. Moreover, emittance properties can be tuned via cluster design. Through a systematic study, we analyzed and established the correlation between cluster architecture, cluster orientation, and polarized emission at a single-emitter level. Excellent correspondence between the optical behavior of these clusters and theoretical predictions was observed. This approach provides the basis for rational creation of single-emitter 3D nanodevices with controllable polarization output using a highly customizable DNA assembly platform.

Experimental Methods for Efficient Solar Hydrogen Production in Microgravity Environment.

Long-term space flights and cis-lunar research platforms require a sustainable and light life-support hardware which can be reliably employed outside the Earth's atmosphere. So-called 'solar fuel' devices, currently developed for terrestrial applications in the quest for realizing a sustainable energy economy on Earth, provide promising alternative systems to existing air-revitalization units employed on the International Space Station (ISS) through photoelectrochemical water-splitting and hydrogen production. One obstacle for water (photo-) electrolysis in reduced gravity environments is the absence of buoyancy and the consequential, hindered gas bubble release from the electrode surface. This causes the formation of gas bubble froth layers in proximity to the electrode surface, leading to an increase in ohmic resistance and cell-efficiency loss due to reduced mass transfer of substrates and products to and from the electrode. Recently, we have demonstrated efficient solar hydrogen production in microgravity environment, using an integrated semiconductor-electrocatalyst system with p-type indium phosphide as the light-absorber and a rhodium electrocatalyst. By nanostructuring the electrocatalyst using shadow nanosphere lithography and thereby creating catalytic 'hot spots' on the photoelectrode surface, we could overcome gas bubble coalescence and mass transfer limitations and demonstrated efficient hydrogen production at high current densities in reduced gravitation. Here, the experimental details are described for the preparations of these nanostructured devices and further on, the procedure for their testing in microgravity environment, realized at the Bremen Drop Tower during 9.3 s of free fall.

Efficient solar hydrogen generation in microgravity environment.

Long-term space missions require extra-terrestrial production of storable, renewable energy. Hydrogen is ascribed a crucial role for transportation, electrical power and oxygen generation. We demonstrate in a series of drop tower experiments that efficient direct hydrogen production can be realized photoelectrochemically in microgravity environment, providing an alternative route to existing life support technologies for space travel. The photoelectrochemical cell consists of an integrated catalyst-functionalized semiconductor system that generates hydrogen with current densities >15 mA/cm2 in the absence of buoyancy. Conditions are described adverting the resulting formation of ion transport blocking froth layers on the photoelectrodes. The current limiting factors were overcome by controlling the micro- and nanotopography of the Rh electrocatalyst using shadow nanosphere lithography. The behaviour of the applied system in terrestrial and microgravity environment is simulated using a kinetic transport model. Differences observed for varied catalyst topography are elucidated, enabling future photoelectrode designs for use in reduced gravity environments.

Advancing semiconductor-electrocatalyst systems: application of surface transformation films and nanosphere lithography.

Photoelectrochemical (PEC) cells offer the possibility of carbon-neutral solar fuel production through artificial photosynthesis. The pursued design involves technologically advanced III-V semiconductor absorbers coupled via an interfacial film to an electrocatalyst layer. These systems have been prepared by in situ surface transformations in electrochemical environments. High activity nanostructured electrocatalysts are required for an efficiently operating cell, optimized in their optical and electrical properties. We demonstrate that shadow nanosphere lithography (SNL) is an auspicious tool to systematically create three-dimensional electrocatalyst nanostructures on the semiconductor photoelectrode through controlling their morphology and optical properties. First results are demonstrated by means of the photoelectrochemical production of hydrogen on p-type InP photocathodes where hitherto applied photoelectrodeposition and SNL-deposited Rh electrocatalysts are compared based on their J-V and spectroscopic behavior. We show that smaller polystyrene particle masks achieve higher defect nanostructures of rhodium on the photoelectrode which leads to a higher catalytic activity and larger short circuit currents. Structural analyses including HRSEM and the analysis of the photoelectrode surface composition by using photoelectron spectroscopy support and complement the photoelectrochemical observations. The optical performance is further compared to theoretical models of the nanostructured photoelectrodes on light scattering and propagation.

Experimental Demonstration of >230° Phase Modulation in Gate-Tunable Graphene-Gold Reconfigurable Mid-Infrared Metasurfaces.

Metasurfaces offer significant potential to control far-field light propagation through the engineering of the amplitude, polarization, and phase at an interface. We report here the phase modulation of an electronically reconfigurable metasurface and demonstrate its utility for mid-infrared beam steering. Using a gate-tunable graphene-gold resonator geometry, we demonstrate highly tunable reflected phase at multiple wavelengths and show up to 237° phase modulation range at an operating wavelength of 8.50 µm. We observe a smooth monotonic modulation of phase with applied voltage from 0° to 206° at a wavelength of 8.70 µm. Based on these experimental data, we demonstrate with antenna array calculations an average beam steering efficiency of 23% for reflected light for angles up to 30° for this range of phases, confirming the suitability of this geometry for reconfigurable mid-infrared beam steering devices. By incorporating all nonidealities of the device into the antenna array calculations including absorption losses which could be mitigated, 1% absolute efficiency is achievable up to 30°.

Efficiency limits for photoelectrochemical water-splitting.

Theoretical limiting efficiencies have a critical role in determining technological viability and expectations for device prototypes, as evidenced by the photovoltaics community's focus on detailed balance. However, due to their multicomponent nature, photoelectrochemical devices do not have an equivalent analogue to detailed balance, and reported theoretical efficiency limits vary depending on the assumptions made. Here we introduce a unified framework for photoelectrochemical device performance through which all previous limiting efficiencies can be understood and contextualized. Ideal and experimentally realistic limiting efficiencies are presented, and then generalized using five representative parameters-semiconductor absorption fraction, external radiative efficiency, series resistance, shunt resistance and catalytic exchange current density-to account for imperfect light absorption, charge transport and catalysis. Finally, we discuss the origin of deviations between the limits discussed herein and reported water-splitting efficiencies. This analysis provides insight into the primary factors that determine device performance and a powerful handle to improve device efficiency.

Modeling, Simulation, and Implementation of Solar-Driven Water-Splitting Devices.

An integrated cell for the solar-driven splitting of water consists of multiple functional components and couples various photoelectrochemical (PEC) processes at different length and time scales. The overall solar-to-hydrogen (STH) conversion efficiency of such a system depends on the performance and materials properties of the individual components as well as on the component integration, overall device architecture, and system operating conditions. This Review focuses on the modeling- and simulation-guided development and implementation of solar-driven water-splitting prototypes from a holistic viewpoint that explores the various interplays between the components. The underlying physics and interactions at the cell level is are reviewed and discussed, followed by an overview of the use of the cell model to provide target properties of materials and guide the design of a range of traditional and unique device architectures.

Near-unity broadband absorption designs for semiconducting nanowire arrays via localized radial mode excitation.

We report design methods for achieving near-unity broadband light absorption in sparse nanowire arrays, illustrated by results for visible absorption in GaAs nanowires on Si substrates. Sparse (<5% fill fraction) nanowire arrays achieve near unity absorption at wire resonant wavelengths due to coupling into 'leaky' radial waveguide modes of individual wires and wire-wire scattering processes. From a detailed conceptual development of radial mode resonant absorption, we demonstrate two specific geometric design approaches to achieve near unity broadband light absorption in sparse nanowire arrays: (i) introducing multiple wire radii within a small unit cell array to increase the number of resonant wavelengths, yielding a 15% absorption enhancement relative to a uniform nanowire array and (ii) tapering of nanowires to introduce a continuum of diameters and thus resonant wavelengths excited within a single wire, yielding an 18% absorption enhancement over a uniform nanowire array.

Mesoscale modeling of photoelectrochemical devices: light absorption and carrier collection in monolithic, tandem, Si|WO3 microwires.

We analyze mesoscale light absorption and carrier collection in a tandem junction photoelectrochemical device using electromagnetic simulations. The tandem device consists of silicon (E(g,Si) = 1.1 eV) and tungsten oxide (E(g,WO3) = 2.6 eV) as photocathode and photoanode materials, respectively. Specifically, we investigated Si microwires with lengths of 100 µm, and diameters of 2 µm, with a 7 µm pitch, covered vertically with 50 µm of WO3 with a thickness of 1 µm. Many geometrical variants of this prototypical tandem device were explored. For conditions of illumination with the AM 1.5G spectra, the nominal design resulted in a short circuit current density, J(SC), of 1 mA/cm(2), which is limited by the WO3 absorption. Geometrical optimization of photoanode and photocathode shape and contact material selection, enabled a three-fold increase in short circuit current density relative to the initial design via enhanced WO3 light absorption. These findings validate the usefulness of a mesoscale analysis for ascertaining optimum optoelectronic performance in photoelectrochemical devices.