Efficient photon upconversion enabled by strong coupling between silicon quantum dots and anthracene.

Hybrid structures formed between organic molecules and inorganic quantum dots can accomplish unique photophysical transformations by taking advantage of their disparate properties. The electronic coupling between these materials is typically weak, leading photoexcited charge carriers to spatially localize to the dot or to a molecule at its surface. However, we show that by converting a chemical linker that covalently binds anthracene molecules to silicon quantum dots from a carbon-carbon single bond to a double bond, we access a strong coupling regime where excited carriers spatially delocalize across both anthracene and silicon. By pushing the system to delocalize, we design a photon upconversion system with a higher efficiency (17.2%) and lower threshold intensity (0.5 W cm-2) than that of a corresponding weakly coupled system. Our results show that strong coupling between molecules and nanostructures achieved through targeted linking chemistry provides a complementary route for tailoring properties in materials for light-driven applications.

Multidimensional Nano-Imaging of Structure, Coupling, and Disorder in Molecular Materials.

A hierarchy of intramolecular and intermolecular interactions controls the properties of biomedical, photophysical, and novel energy materials. However, multiscale heterogeneities often obfuscate the relationship between microscopic structure and emergent function, and they are generally difficult to access with conventional optical and electron microscopy techniques. Here, we combine vibrational exciton nanoimaging in variable-temperature near-field optical microscopy (IR s-SNOM) with four-dimensional scanning transmission electron microscopy (4D-STEM), and vibrational exciton modeling based on density functional theory (DFT), to link local microscopic molecular interactions to macroscopic three-dimensional order. In the application to poly(tetrafluoroethylene) (PTFE), large spatio-spectral heterogeneities with C-F vibrational energy shifts ranging from sub-cm-1 to ≳25 cm-1 serve as a molecular ruler of the degree of local crystallinity and disorder. Spatio-spectral-structural correlations reveal a previously invisible degree of highly variable local disorder in molecular coupling as the possible missing link between nanoscale morphology and associated electronic, photonic, and other functional properties of molecular materials.

The Motion of Trapped Holes on Nanocrystal Surfaces.

This Perspective discusses the phenomenon of trapped-hole diffusion in colloidal semiconductor nanocrystals. Surface charge-carrier traps are ubiquitous in nanocrystals and often dictate the fate of photoexcited carriers. New measurements and calculations are unveiling the nature of the nanocrystal surface, but many challenges to understanding the dynamics of trapped carriers remain. In contrast to the view that trapped holes are stationary, we have put forward a series of reports demonstrating that trapped holes on the surfaces of CdS and CdSe nanocrystals are mobile and move between traps in a sequence of hops. We summarize how these findings advance the understanding of carrier dynamics in colloidal nanocrystals and how they may impact a broad set of excited-state behaviors in these materials.

On the Nature of Trapped-Hole States in CdS Nanocrystals and the Mechanism of Their Diffusion.

Recent transient absorption experiments on CdS nanorods suggest that photoexcited holes rapidly trap to the surface of these particles and then undergo diffusion along the rod surface. In this Letter, we present a semiperiodic density functional theory model for the CdS nanocrystal surface, analyze it, and comment on the nature of both the hole-trap states and the mechanism by which the holes diffuse. Hole states near the top of the valence band form an energetic near continuum with the bulk and localize to the nonbonding sp3 orbitals on surface sulfur atoms. After localization, the holes form nonadiabatic small polarons that move between the sulfur orbitals on the surface of the particle in a series of uncorrelated, incoherent, thermally activated hops at room temperature. The surface-trapped holes are deeply in the weak-electronic coupling limit and, as a result, undergo slow diffusion.