Matthew T. Frederick

Relaxation of Exciton Confinement in CdSe Quantum Dots by Modification with a Conjugated Dithiocarbamate Ligand

Coordination of phenyldithiocarbamate (PTC) ligands to solution-phase colloidal CdSe quantum dots (QDs) decreases the optical band gap, E(g), of the QDs by up to 220 meV. These values of DeltaE(g) are the largest shifts achieved by chemical modification of the surfaces of solution-phase CdSe QDs and are-by more than an order of magnitude in energy-the largest bathochromic shifts achieved for QDs in either the solution or solid phases. Measured values of DeltaE(g) upon coordination to PTC correspond to an apparent increase in the excitonic radius of 0.26 +/- 0.03 nm; this excitonic delocalization is independent of the size of the QD for radii, R = 1.1-1.9 nm. Density functional theory calculations indicate that the highest occupied molecular orbital of PTC is near resonant with that of the QD, and that the two have correct symmetry to exchange electron density (PTC is a pi-donor, and the photoexcited QD is a pi-acceptor). We therefore propose that the relaxation of exciton confinement occurs through delocalization of the photoexcited hole of the QD into the ligand shell.

Control of exciton confinement in quantum dot-organic complexes through energetic alignment of interfacial orbitals.

This paper describes a method to control the quantum confinement, and therefore the energy, of excitonic holes in CdSe QDs through adsorption of the hole-delocalizing ligand phenyldithiocarbamate, PTC, and para substitutions of the phenyl ring of this ligand with electron-donating or -withdrawing groups. These substitutions control hole delocalization in the QDs through the energetic alignment of the highest occupied orbitals of PTC with the highest density-of-states region of the CdSe valence band, to which PTC couples selectively.

A Molecule to Detect and Perturb the Confinement of Charge Carriers in Quantum Dots

This paper describes unprecedented bathochromic shifts (up to 970 meV) of the optical band gaps of CdS, CdSe, and PbS quantum dots (QDs) upon adsorption of an organic ligand, phenyldithiocarbamate (PTC), and the use of PTC to map the quantum confinement of specific charge carriers within the QDs as a function of their radius. For a given QD material and physical radius, R, the magnitude of the increase in apparent excitonic radius (ΔR) upon delocalization by PTC directly reflects the degree of quantum confinement of one or both charge carriers. The plots of ΔR vs R for CdSe and CdS show that exciton delocalization by PTC occurs specifically through the excitonic hole. Furthermore, the plot for CdSe, which spans a range of R over multiple confinement regimes for the hole, identifies the radius (R∼1.9 nm) at which the hole transitions between regimes of strong and intermediate confinement. This demonstration of ligand-induced delocalization of a specific charge carrier is a first step toward eliminating current-limiting resistive interfaces at organic-inorganic junctions within solid-state hybrid devices. Facilitating carrier-specific electronic coupling across heterogeneous interfaces is especially important for nanostructured devices, which comprise a high density of such interfaces.

Optical properties of strongly coupled quantum dot-ligand systems

This Perspective describes the mechanisms by which organic surfactants, in particular, phenyldithiocarbamates (PTCs), couple electronically to the delocalized states of semiconductor quantum dots (QDs). This coupling reduces the confinement energies of excitonic carriers and, in the case of PTC, the optical band gap of metal chalcogenide QDs by up to 1 eV by selectively delocalizing the excitonic hole. The reduction of confinement energy for the hole is enabled by the creation of interfacial electronic states near the valence band edge of the QD. The PTC case illuminates the general minimal requirements for surfactants to achieve observable bathochromic or hypsochromic shifts of the optical band gap of QDs; these include frontier orbitals with energies near the relevant semiconductor band edge, the correct symmetry to mix with the orbitals of the relevant band, and an adsorption geometry that permits spatial overlap between the orbitals of the ligand and those of the relevant band (Se 4p orbitals for CdSe, for example). The shift is enhanced by energetic resonance of frontier orbitals of the surfactant with a high density of states region of the band, which, for CdSe, is ∼1 eV below the band edge. The Perspective discusses other examples of strong-coupling surfactants and compares the orbital mixing mechanism with other mechanisms of surfactant-induced shifts in the QD band gap.

Surface-amplified ligand disorder in CdSe quantum dots determined by electron and coherent vibrational spectroscopies.

This Article reports measurements of the intra- and intermolecular ordering of tight-binding octylphosphonate ligands on the surface of colloidal CdSe quantum dots (QDs) within solid state films, and the dependence of this order on the size of the QDs. The order of the organic ligands, as probed by vibrational sum frequency generation (SFG) spectroscopy, decreases as the radius of the QDs decreases; this decrease is correlated with a decrease in the order of underlying Cd(2+), as detected by X-ray photoelectron spectroscopy (XPS) line width measurements, for radii of the QDs, R > 2.4 nm, and is independent of the disorder of the Cd(2+) for R < 2.4 nm. We believe that, for R < 2.4, the decreasing order of the ligands with decreasing size is due to an increase in the curvature of the QD surfaces. Disorder in the Cd(2+) results from the presence of a shell of Cd(2+)-surfactant complexes that form during synthesis, so this work demonstrates the possibility for chemical control over molecular order within films of colloidal QDs by changing the surfactant mixture.