Isabell Thomann

Plasmon Enhanced Solar-to-Fuel Energy Conversion

Future generations of photoelectrodes for solar fuel generation must employ inexpensive, earth-abundant absorber materials in order to provide a large-scale source of clean energy. These materials tend to have poor electrical transport properties and exhibit carrier diffusion lengths which are significantly shorter than the absorption depth of light. As a result, many photoexcited carriers are generated too far from a reactive surface and recombine instead of participating in solar-to-fuel conversion. We demonstrate that plasmonic resonances in metallic nanostructures and multilayer interference effects can be engineered to strongly concentrate sunlight close to the electrode/liquid interface, precisely where the relevant reactions take place. On comparison of spectral features in the enhanced photocurrent spectra to full-field electromagnetic simulations, the contribution of surface plasmon excitations is verified. These results open the door to the optimization of a wide variety of photochemical processes by leveraging the rapid advances in the field of plasmonics.

Direct Plasmon-Driven Photoelectrocatalysis

Harnessing the energy from hot charge carriers is an emerging research area with the potential to improve energy conversion technologies.1-3 Here we present a novel plasmonic photoelectrode architecture carefully designed to drive photocatalytic reactions by efficient, nonradiative plasmon decay into hot carriers. In contrast to past work, our architecture does not utilize a Schottky junction, the commonly used building block to collect hot carriers. Instead, we observed large photocurrents from a Schottky-free junction due to direct hot electron injection from plasmonic gold nanoparticles into the reactant species upon plasmon decay. The key ingredients of our approach are (i) an architecture for increased light absorption inspired by optical impedance matching concepts,4 (ii) carrier separation by a selective transport layer, and (iii) efficient hot-carrier generation and injection from small plasmonic Au nanoparticles to adsorbed water molecules. We also investigated the quantum efficiency of hot electron injection for different particle diameters to elucidate potential quantum effects while keeping the plasmon resonance frequency unchanged. Interestingly, our studies did not reveal differences in the hot-electron generation and injection efficiencies for the investigated particle dimensions and plasmon resonances.

Self-assembly based plasmonic arrays tuned by atomic layer deposition for extreme visible light absorption.

Achieving complete absorption of visible light with a minimal amount of material is highly desirable for many applications, including solar energy conversion to fuel and electricity, where benefits in conversion efficiency and economy can be obtained. On a fundamental level, it is of great interest to explore whether the ultimate limits in light absorption per unit volume can be achieved by capitalizing on the advances in metamaterial science and nanosynthesis. Here, we combine block copolymer lithography and atomic layer deposition to tune the effective optical properties of a plasmonic array at the atomic scale. Critical coupling to the resulting nanocomposite layer is accomplished through guidance by a simple analytical model and measurements by spectroscopic ellipsometry. Thereby, a maximized absorption of light exceeding 99% is accomplished, of which up to about 93% occurs in a volume-equivalent thickness of gold of only 1.6 nm. This corresponds to a record effective absorption coefficient of 1.7 × 10(7) cm(-1) in the visible region, far exceeding those of solid metals, graphene, dye monolayers, and thin film solar cell materials. It is more than a factor of 2 higher than that previously obtained using a critically coupled dye J-aggregate, with a peak width exceeding the latter by 1 order of magnitude. These results thereby substantially push the limits for light harvesting in ultrathin, nanoengineered systems.

Light Trapping for Solar Fuel Generation with Mie Resonances

The implementation of solar fuel generation as a clean, terawatt-scale energy source is critically dependent on the development of high-performance, inexpensive photocatalysts. Many candidate materials, including for example α-Fe2O3 (hematite), suffer from very poor charge transport with minority carrier diffusion lengths that are significantly shorter (nanometer scale) than the absorption depth of light (micrometer scale near the band edge). As a result, most of the photoexcited carriers recombine rather than participate in water-splitting reactions. For this reason, there is a tremendous opportunity for photon management. Plasmon-resonant nanostructures have been employed to effectively enhance light absorption in the near-surface region of photocatalysts, but this approach suffers from intrinsic optical losses in the metal. Here, we circumvent this issue by driving optical resonances in the active photocatalyst material itself. We illustrate that judiciously nanopatterned photocatalysts support optical Mie and guided resonances capable of substantially enhancing the photocarrier generation rate within 10-20 nm from the water/photocatalyst interface.

Plasmons and rust for solar energy conversion

We will present progress towards the use of plasmonic metal nanostructures to enhance the efficiency of solar fuel generation [1]. In the past, solar-to-fuel-efficiencies have been limited because of a large mismatch in the length scales for optical absorption and carrier extraction. Future generations of photoelectrodes must employ cheap, earth-abundant absorber materials in order to provide a large-scale source of clean energy. These materials will likely have relatively poor electrical properties, so progress must be made in optimizing their absorption properties [2, 3]. We chose iron oxide (β-Fe2O3; hematite) [4] as a prototype system that shares many features with other candidate materials for future large-scale solar fuel production, and therefore anticipate that the results obtained in this study will be applicable to other materials systems as well. Hematite has relatively weak absorption in the 500–600 nm range (0.1 – 1 µm absorption length), very long compared to its minority carrier diffusion length on the order of 2–4 nm [5] or 20 nm [6].