Valerie M. Nichols

Hybrid Molecule-Nanocrystal Photon Upconversion Across the Visible and Near-Infrared.

The ability to upconvert two low energy photons into one high energy photon has potential applications in solar energy, biological imaging, and data storage. In this Letter, CdSe and PbSe semiconductor nanocrystals are combined with molecular emitters (diphenylanthracene and rubrene) to upconvert photons in both the visible and the near-infrared spectral regions. Absorption of low energy photons by the nanocrystals is followed by energy transfer to the molecular triplet states, which then undergo triplet-triplet annihilation to create high energy singlet states that emit upconverted light. By using conjugated organic ligands on the CdSe nanocrystals to form an energy cascade, the upconversion process could be enhanced by up to 3 orders of magnitude. The use of different combinations of nanocrystals and emitters shows that this platform has great flexibility in the choice of both excitation and emission wavelengths.

Observation of Multiple, Identical Binding Sites in the Exchange of Carboxylic Acid Ligands with CdS Nanocrystals.

We study ligand exchange between the carboxylic acid group and 5.0 nm oleic-acid capped CdS nanocrystals (NCs) using fluorescence resonance energy transfer (FRET). This is the first measurement of the initial binding events between cadmium chalcogenide NCs and carboxylic acid groups. The binding behavior can be described as an interaction between a ligand with single binding group and a substrate with multiple, identical binding sites. Assuming Poissonian binding statistics, our model fits both steady-state and time-resolved photoluminescence (SSPL and TRPL, respectively) data well. A modified Langmuir isotherm reveals that a CdS nanoparticle has an average of 3.0 new carboxylic acid ligands and binding constant, Ka, of 3.4 × 10(5) M(-1).

Ligand Binding to Distinct Sites on Nanocrystals Affecting Energy and Charge Transfer.

Hybrid optoelectronic devices are attractive because they offer the promise of low-cost, roll-to-roll fabrication. Despite this, energy transfer between organic and inorganic interfaces is not well understood. Device engineering on this class of solution-processed materials generally focuses on replacing the long insulating ligands with short ones. Here, we show that energy and charge transfer between an inorganic nanocrystal (NC) donor and organic molecular acceptor is acutely sensitive to the chemical moiety linking the two species. Our results reveal that the CdS NCs have distinct binding sites for different chemical species because only resonance energy transfer (RET) is observed for the carboxylic-acid-functionalized ligand, while both RET and charge transfer are observed for the amine-functionalized ligand. We observe that the equilibrium constant for this static quenching term increases with decreasing particle size. This finding offers a new approach in the design of hybrid thin films for devices and NC probes based on RET used for imaging, sensing, signal transduction, and photon management.

Robust singlet fission in pentacene thin films with tuned charge transfer interactions

Singlet fission, the spin-allowed photophysical process converting an excited singlet state into two triplet states, has attracted significant attention for device applications. Research so far has focused mainly on the understanding of singlet fission in pure materials, yet blends offer the promise of a controlled tuning of intermolecular interactions, impacting singlet fission efficiencies. Here we report a study of singlet fission in mixtures of pentacene with weakly interacting spacer molecules. Comparison of experimentally determined stationary optical properties and theoretical calculations indicates a reduction of charge-transfer interactions between pentacene molecules with increasing spacer molecule fraction. Theory predicts that the reduced interactions slow down singlet fission in these blends, but surprisingly we find that singlet fission occurs on a timescale comparable to that in pure crystalline pentacene. We explain the observed robustness of singlet fission in such mixed films by a mechanism of exciton diffusion to hot spots with closer intermolecular spacings.Singlet fission is desirable for highly efficient solar cells, yet the details of the process remain elusive. Here, Broch et al. show that the changes in bulk intermolecular interactions can have little effect on the singlet fission rate in a mixture of pentacene and weakly interacting spacer molecules.