Brian P. Bloom

Spin Selective Charge Transport through Cysteine Capped CdSe Quantum Dots

This work demonstrates that chiral imprinted CdSe quantum dots (QDs) can act as spin selective filters for charge transport. The spin filtering properties of chiral nanoparticles were investigated by magnetic conductive-probe atomic force microscopy (mCP-AFM) measurements and magnetoresistance measurements. The mCP-AFM measurements show that the chirality of the quantum dots and the magnetic orientation of the tip affect the current-voltage curves. Similarly, magnetoresistance measurements demonstrate that the electrical transport through films of chiral quantum dots correlates with the chiroptical properties of the QD. The spin filtering properties of chiral quantum dots may prove useful in future applications, for example, photovoltaics, spintronics, and other spin-driven devices.

Eliminating Fermi-level pinning in PbS quantum dots using an alumina interfacial layer

Through a systematic approach we show that the insertion of a thin alumina layer in between a PbS QD layer and an Au substrate can eliminate Fermi level pinning. In this study band edge energies of different sized PbS QD monolayers with different cross-linkers were measured by using ultraviolet photoelectron spectroscopy and electrochemistry. When PbS QDs were immobilized directly on the Au, the measured valence band maximum was found to be insensitive to changes in the QD size or cross-linker indicating Fermi level pinning of the QD valence band to the Au Fermi level. After insertion of a thin film of alumina in between the PbS quantum dot monolayer film and the Au substrate, the measured valence band position revealed a shift that depended on ligand and QD size. These results identify a general method for eliminating Fermi level pinning in QDs and an approach for predictably controlling the energetics at QD–metal interfaces which is beneficial for improving the performance of QD based solar cells.

Chirality Control of Electron Transfer in Quantum Dot Assemblies

Electron spin and molecular chirality are emerging as factors that can be used effectively to direct charge flow at the molecular scale. We report order of magnitude effects of molecular chirality on electron-transfer rates between quantum dots (QDs) in chiral QD assemblies. Indeed, both the circular polarization of the light that excites the electron donor and the imprinted chirality of the acceptor QDs affect the dot-to-dot electron-transfer kinetics. We define a polarization for the electron-transfer rate constant and show that it correlates with the strength of the acceptor QD circular dichroism (CD) spectrum. These findings imply that the CD strength of the QD exciton transition(s) may be used as a predictor for the spin-dependent electron transfer, indicating that chiral imprinting of the dots may lie at the origin of this phenomenon.

Electron Transfer in Nanoparticle Dyads Assembled on a Colloidal Template

This work shows how to create covalently bound nanoparticle dyad assemblies on a colloidal template and studies photoinduced charge transfer in them. New results are reported for how the electron-transfer rate changes with the inter-nanoparticle distance and the energy band offset of the nanoparticles (reaction Gibbs energy). The experimental findings show that the distance dependence is consistent with an electron tunneling mechanism. The dependence of the rate on the energy band offset is found to be consistent with Marcus theory, as long as one performs a sum over final electronic states. These results indicate that our understanding of electron transfer in molecular donor-bridge-acceptor assemblies can be translated to describe nanoparticle-bridge-nanoparticle assemblies.

Through-Solvent Tunneling in Donor–Bridge–Acceptor Molecules Containing a Molecular Cleft

Photoinduced electron transfer is used to investigate the solvent-mediated electron tunneling between electron donor and acceptor groups in polar solvents. Bis-peptide scaffolds are used to control the spatial positioning of electron donor and acceptor groups and create a molecular cleft. The photoinduced electron transfer is studied for two different cleft sizes, and the electronic coupling is found to be controlled by the nature of the solvent and the ability of the molecular cleft to accommodate it, as well as interact directly with it. These studies demonstrate the importance of electron tunneling through nonbonded contacts and reveal a strategy for examining such tunneling pathways in polar solvents.

Imprinting Chirality onto the Electronic States of Colloidal Perovskite Nanoplatelets

The direct synthesis of chiroptical organic-inorganic methylammonium lead bromide perovskite nanoplatelets that are passivated by R- or S-phenylethylammonium ligands is reported. The circular dichroism spectra can be divided into two components: (1) a region associated with a charge transfer transition between the ligand and the nanoplatelet, 300-350 nm, and (2) a region corresponding to the excitonic absorption maximum of the perovskite, 400-450 nm. The temperature- and concentration-dependent circular dichroism spectra indicate that the chiro-optical response arises from chiral imprinting by the ligand on the electronic states of the quantum-confined perovskite rather than chiral ligand-induced stereoselective aggregation.