arXiv subjects

Jessica Kline

Publications and source records attributed to Jessica Kline.

5 recordsLinked to original sources

arXiv2025

Trion Formation Hampers Single Quantum Dot Performance in Silane-Coated FAPbBr3 Quantum Dots

We explore silane-coated formamidinium lead bromide (FAPbBr3) quantum dots as single photon emitters and compare them to FAPbBr3 quantum dots passivated with a phosphoethylammonium derivative (PEAC8C12), which represents current state-of-the-art in zwitterionic molecular surface ligand passivation. We compare properties including single-photon purity (g2(t)), linewidth, blinking, and photostability. We find that at room temperature, these silane-coated dots perform comparably to the PEAC8C12 passivation in terms of single-photon performance metrics, while exhibiting improvements in photostability. However, we find that at 4K, silane-coated FAPbBr3 quantum dots perform worse than the PEAC8C12-passivated samples, exhibiting faster blue-shifting and photobleaching under illumination. Analysis of fluorescence lifetime intensity distributions from the photon-counting data indicates increased efficiency of fast non-radiative processes in the silane-coated quantum dots at 4K. We propose a trion related degradation pathway at low temperatures that is consistent with the observed kinetics and estimate that at 4K with 6.1 uJ/cm2, 472 nm excitation the silane-coated quantum dots build up double the trion population of their PEAC8C12-passivated counterparts.

cond-mat.mtrl-sci↗

arXiv2024

Emissive Surface Traps Lead to Asymmetric Photoluminescence Line Shape in Spheroidal CsPbBr3 Quantum Dots

The morphology of quantum dots plays an important role in governing their photophysics. Here, we explore the photoluminescence of spheroidal CsPbBr3 quantum dots synthesized via the room-temperature trioctlyphosphine oxide/PbBr2 method. Despite photoluminescence quantum yields nearing 100%, these spheroidal quantum dots exhibit an elongated red photoluminescence tail not observed in typical cubic quantum dots synthesized via hot injection. We explore this elongated red tail through structural and optical characterization including small-angle x-ray scattering, transmission electron microscopy and time-resolved, steady-state, and single quantum dot photoluminescence. From these measurements we conclude that the red tail originates from emissive surface traps. We hypothesize that these emissive surface traps are located on the (111) surfaces and show that the traps can be passivated by adding phenethyl ammonium bromide, resulting in a more symmetric line shape

cond-mat.mtrl-sci↗

arXiv2024

Increased Brightness and Reduced Efficiency Droop in Perovskite Quantum Dot Light-Emitting Diodes using Carbazole-Based Phosphonic Acid Interface Modifiers

We demonstrate the use of [2-($\textit{9H}$-carbazol-9-yl)ethyl]phosphonic acid (2PACz) and [2-(3,6-di-$\textit{tert}$-butyl-$\textit{9H}$-carbazol-9-yl)ethyl]phosphonic acid (t-Bu-2PACz) as anode modification layers in metal-halide perovskite quantum dot light-emitting diodes (QLEDs). Compared to conventional QLED structures with PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate)/PVK (poly(9-vinylcarbazole)) hole-transport layers, QLEDs made with phosphonic acid (PA)-modified indium tin oxide (ITO) anodes show an over 7-fold increase in brightness, achieving a brightness of 373,000 cd m$^{-2}$, one of the highest brightnesses reported to date for colloidal perovskite QLEDs. Importantly, the onset of efficiency roll-off, or efficiency droop, occurs at ~1000-fold higher current density for QLEDs made with PA-modified anodes compared to control QLEDs made with conventional PEDOT:PSS/PVK hole transport layers, allowing the devices to sustain significantly higher levels of external quantum efficiency at a brightness of >10$^{5}$ cd m$^{-2}$. Steady-state and time-resolved photoluminescence measurements indicate these improvements are due to a combination of multiple factors, including reducing quenching of photoluminescence at the PEDOT:PSS interface and reducing photoluminescence efficiency loss at high levels of current density.

cond-mat.mtrl-sci↗

arXiv2024

Ligand Equilibrium Influences Photoluminescence Blinking in CsPbBr3: A Change Point Analysis of Widefield Imaging Data

Photoluminescence intermittency remains one of the biggest challenges to realizing perovskite quantum dots (QDs) as scalable single photon emitters. We compare CsPbBr3 QDs capped with different ligands, lecithin, and a combination of oleic acid and oleylamine, to elucidate the role of surface chemistry on photoluminescence intermittency. We employ widefield photoluminescence microscopy, sampling the blinking behavior of hundreds of QDs. Using change point analysis, we achieve the robust classification of blinking trajectories, and we analyze representative distributions from large numbers of QDs (Nlecithin = 1308, Noleic acid/oleylamine =1317). We find that lecithin suppresses blinking in CsPbBr3 QDs compared to oleic acid/oleylamine. Under common experimental conditions, lecithin-capped QDs are 7.5 times more likely to be non-blinking and spend 2.5 times longer in their most emissive state, despite both QDs having nearly identical solution photoluminescence quantum yields. We measure photoluminescence as a function of dilution and show that the differences between lecithin and oleic acid/oleylamine capping emerge at low concentrations during preparation for single particle experiments. From experiment and first principles calculations, we attribute the differences in lecithin and oleic acid/oleylamine performance to differences in their ligand binding equilibria. Consistent with our experimental data, density functional theory calculations suggest a stronger binding affinity of lecithin to the QD surface compared to oleic acid/oleylamine, implying a reduced likelihood of ligand desorption during dilution. These results suggest that using more tightly binding ligands is a necessity for surface passivation and consequently, blinking reduction in perovskite QDs used for single particle and quantum light experiments.

cond-mat.mtrl-sci↗

arXiv2020

Isoenergetic Two-Photon Excitation Enhances Solvent-to-Solute Excited-State Proton Transfer

Two-photon excitation is an attractive means for controlling chemistry in both space and time. Isoenergetic one- and two-photon excitations (OPE and TPE) in non-centrosymmetric molecules are often assumed to reach the same excited state and, hence, to produce similar excited-state reactivity. We compare the solvent-to-solute excited-state proton transfer of the super photobase FR0-SB following isoenergetic OPE and TPE. We find up to 62 % increased reactivity following TPE compared to OPE. From steady-state spectroscopy, we rule out the involvement of different excited states and find that OPE and TPE spectra are identical in non-polar solvents but not in polar ones. We propose that differences in the matrix elements that contribute to the two-photon absorption cross sections lead to the observed enhanced isoenergetic reactivity, consistent with the predictions of our high-level coupled-cluster-based computational protocol. We find that polar solvent configurations favor greater dipole moment change between ground and excited states, which enters the probability for two-photon excitations as the absolute value squared. This, in turn, causes a difference in the Franck-Condon region reached via TPE compared to OPE. We conclude that a new method has been found for controlling chemical reactivity via the matrix elements that affect two-photon cross sections, which may be of great utility for spatial and temporal precision chemistry.

physics.chem-ph↗