Noah J. Orfield

Electrical Control of near-Field Energy Transfer between Quantum Dots and Two-Dimensional Semiconductors

We investigate near-field energy transfer between chemically synthesized quantum dots (QDs) and two-dimensional semiconductors. We fabricate devices in which electrostatically gated semiconducting monolayer molybdenum disulfide (MoS2) is placed atop a homogeneous self-assembled layer of core-shell CdSSe QDs. We demonstrate efficient nonradiative Förster resonant energy transfer (FRET) from QDs into MoS2 and prove that modest gate-induced variation in the excitonic absorption of MoS2 leads to large (∼500%) changes in the FRET rate. This in turn allows for up to ∼75% electrical modulation of QD photoluminescence intensity. The hybrid QD/MoS2 devices operate within a small voltage range, allow for continuous modification of the QD photoluminescence intensity, and can be used for selective tuning of QDs emitting in the visible-IR range.

Elimination of Hole–Surface Overlap in Graded CdSxSe1–x Nanocrystals Revealed by Ultrafast Fluorescence Upconversion Spectroscopy

Interaction of charge carriers with the surface of semiconductor nanocrystals plays an integral role in determining the ultimate fate of the excited state. The surface contains a dynamic ensemble of trap states that can localize excited charges, preventing radiative recombination and reducing fluorescence quantum yields. Here we report quasi-type-II band alignment in graded alloy CdSxSe1-x nanocrystals revealed by femtosecond fluorescence upconversion spectroscopy. Graded alloy CdS(x)Se(1-x) quantum dots are a compositionally inhomogeneous nano-heterostructure designed to decouple the exciton from the nanocrystal surface. The large valence band offset between the CdSe-rich core and CdS-rich shell separates the excited hole from the surface by confining it to the core of the nanocrystal. The small conduction band offset, however, allows the electron to delocalize throughout the entire nanocrystal and maintain overlap with the surface. Indeed, the ultrafast charge carrier dynamics reveal that the fast 1-3 ps hole-trapping process is fully eliminated with increasing sulfur composition and the decay constant for electron trapping (∼ 20-25 ps) shows a slight increase. These findings demonstrate progress toward highly efficient nanocrystal fluorophores that are independent of their surface chemistry to ultimately enable their incorporation into a diverse range of applications without experiencing adverse effects arising from dissimilar environments.

Correlation of atomic structure and photoluminescence of the same quantum dot: pinpointing surface and internal defects that inhibit photoluminescence.

In a size regime where every atom counts, rational design and synthesis of optimal nanostructures demands direct interrogation of the effects of structural divergence of individuals on the ensemble-averaged property. To this end, we have explored the structure-function relationship of single quantum dots (QDs) via precise observation of the impact of atomic arrangement on QD fluorescence. Utilizing wide-field fluorescence microscopy and atomic number contrast scanning transmission electron microscopy (Z-STEM), we have achieved correlation of photoluminescence (PL) data and atomic-level structural information from individual colloidal QDs. This investigation of CdSe/CdS core/shell QDs has enabled exploration of the fine structural factors necessary to control QD PL. Additionally, we have identified specific morphological and structural anomalies, in the form of internal and surface defects, that consistently vitiate QD PL.

Interplay of structural and compositional effects on carrier recombination in mixed-halide perovskites

In this work, we investigate the effects of grain structure and bromide content on charge transport in methylammonium lead iodide/bromide (MAPb(I1−xBrx)3) perovskites by examining the steady-state (ss-PL) and time-resolved (tr-PL) photoluminescence of planar films with varying grain size and bromide content. We controlled the perovskite grain structure via solvent engineering with N,N-dimethylformamide (DMF) or dimethyl sulfoxide : γ-butyrolactone (DMSO : GBL), and the resultant grain morphology was independent of Br doping between 0–33%. Carrier lifetimes ranged from 29–52 ns with increasing Br content for DMF-produced perovskite films, and from 2–9 ns for films obtained with DMSO : GBL. Analysis of XRD and photoluminescence data suggests this order-of-magnitude difference in lifetimes is attributable to the nature of iodide-rich recombination nuclei within the bulk perovskite. By modulating the precursor solvent and Br composition, the influence of low-bandgap recombination nuclei can be minimized to enhance charge transport and lengthen the carrier lifetime in mixed-halide perovskite films.

Design of a Hole Trapping Ligand

A new ligand that covalently attaches to the surface of colloidal CdSe/CdS nanorods and can simultaneously chelate a molecular metal center is described. The dithiocarbamate-bipyridine ligand system facilitates hole transfer through energetic overlap at the inorganic-organic interface and conjugation through the organic ligand to a chelated metal center. Density functional theory calculations show that the coordination of the free ligand to a CdS surface causes the formation of two hybridized molecular states that lie in the band gap of CdS. The further chelation of Fe(II) to the bipyridine moiety causes the presence of seven midgap states. Hole transfer from the CdS valence band to the midgap states is dipole allowed and occurs at a faster rate than what is experimentally known for the CdSe/CdS band-edge radiative recombination. In the case of the ligand bound with iron, a two-step process emerges that places the hole on the iron, again at rates much faster than band gap recombination. The system was experimentally assembled and characterized via UV-vis absorbance spectroscopy, fluorescence spectroscopy, time-resolved photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. Theoretically predicted red shifts in absorbance were observed experimentally, as well as the expected quench in photoluminescence and lifetimes in time-resolved photoluminescence.