Diamond-lattice photonic crystals assembled from DNA origami.

Colloidal self-assembly allows rational design of structures on the micrometer and submicrometer scale. One architecture that can generate complete three-dimensional photonic bandgaps is the diamond cubic lattice, which has remained difficult to realize at length scales comparable with the wavelength of visible or ultraviolet light. In this work, we demonstrate three-dimensional photonic crystals self-assembled from DNA origami that act as precisely programmable patchy colloids. Our DNA-based nanoscale tetrapods crystallize into a rod-connected diamond cubic lattice with a periodicity of 170 nanometers. This structure serves as a scaffold for atomic-layer deposition of high-refractive index materials such as titanium dioxide, yielding a tunable photonic bandgap in the near-ultraviolet.

Catalytic Metasurfaces Empowered by Bound States in the Continuum.

Photocatalytic platforms based on ultrathin reactive materials facilitate carrier transport and extraction but are typically restricted to a narrow set of materials and spectral operating ranges due to limited absorption and poor energy-tuning possibilities. Metasurfaces, a class of 2D artificial materials based on the electromagnetic design of nanophotonic resonators, allow optical absorption engineering for a wide range of materials. Moreover, tailored resonances in nanostructured materials enable strong absorption enhancement and thus carrier multiplication. Here, we develop an ultrathin catalytic metasurface platform that leverages the combination of loss-engineered substoichiometric titanium oxide (TiO2-x) and the emerging physical concept of optical bound states in the continuum (BICs) to boost photocatalytic activity and provide broad spectral tunability. We demonstrate that our platform reaches the condition of critical light coupling in a TiO2-x BIC metasurface, thus providing a general framework for maximizing light-matter interactions in diverse photocatalytic materials. This approach can avoid the long-standing drawbacks of many naturally occurring semiconductor-based ultrathin films applied in photocatalysis, such as poor spectral tunability and limited absorption manipulation. Our results are broadly applicable to fields beyond photocatalysis, including photovoltaics and photodetectors.

Intra- and inter-nanocrystal charge transport in nanocrystal films.

The exploitation of semiconductor nanocrystal (NC) films in novel electronic and optoelectronic applications requires a better understanding of charge transport in these systems. Here, we develop a model of charge transport in NC films, based on a generalization of the concept of transport energy level ET to nanocrystal assemblies, which considers both intra- and inter-NC charge transfer processes. We conclude that the role played by each of these processes can be probed from temperature-dependent measurements of charge carrier density n and mobility µ in the same films. The model also enables the determination of the position of the Fermi energy level EF with respect to ET, an important parameter of charge transport in semiconductor materials, from the temperature dependence of n. Moreover, we provide support to an essentially temperature-independent intra-NC charge carrier mobility, considered in the transport level concept, and consequently the frequently observed temperature dependence of the overall mobility µ in NC films results from a temperature variation of the inter-NC charge transport processes. Importantly, we also conclude that the temperature dependence of conductivity in NC films should result in general from a combination of temperature variations of both n and µ. By applying the model to solution-processed Si NC films, we conclude that transport within each NC is similar to that in amorphous Si (a-Si), with charges hopping along band tail states located below the conduction band edge. For Si NCs, we obtain values of ET - EF of ∼0.25 eV. The overall mobility µ in Si NC films is significantly further reduced with respect to that typically found in a-Si due to the additional transport constraints imposed by inter-NC transfer processes inherent to a nanoparticulate film. Our model accounting for inter- and intra-NC charge transport processes provides a simple and more general description of charge transport that can be broadly applied to films of semiconductor NCs.