Engineering topics

Cavanaugh, Paul

Publications and source records attributed to Cavanaugh, Paul.

7 records

DOE OSTI2023

Spectral widths and Stokes shifts in InP-based quantum dots

InP-based quantum dots (QDs) have Stokes shifts and photoluminescence (PL) line widths that are larger than in II–VI semiconductor QDs with comparable exciton energies. The mechanisms responsible for these spectral characteristics are investigated in this paper. Upon comparing different semiconductors, we find the Stokes shift decreases in the following order: InP > CdTe > CdSe. We also find that the Stokes shift decreases with core size and decreases upon deposition of a ZnSe shell. We suggest that the Stokes shift is largely due to different absorption and luminescent states in the angular momentum fine structure. The energy difference between the fine structure levels, and hence the Stokes shifts, are controlled by the electron–hole exchange interaction. Luminescence polarization results are reported and are consistent with this assignment. Spectral widths are controlled by the extent of homogeneous and inhomogeneous broadening. Here, we report PL and PL excitation (PLE) spectra that facilitate assessing the roles of homogeneous and different inhomogeneous broadening mechanisms in the spectra of zinc-treated InP and InP/ZnSe/ZnS particles. There are two distinct types of inhomogeneous broadening: size inhomogeneity and core–shell interface inhomogeneity. The latter results in a distribution of core–shell band offsets and is caused by interfacial dipoles associated with In–Se or P–Zn bonding. Quantitative modeling of the spectra shows that the offset inhomogeneity is comparable to but somewhat smaller than the size inhomogeneity. The combination of these two types of inhomogeneity also explains several aspects of reversible hole trapping dynamics involving localized In 3+ /V Zn 2– impurity states in the ZnSe shells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Reversible Interfacial Charge Transfer and Delayed Emission in InP/ZnSe/ZnS Quantum Dots with Hexadecanethiol

The results in this paper show that holes are rapidly and reversibly transferred from red-emitting InP/ZnSe/ZnS quantum dots (QDs) to adsorbed hexadecanethiol (HDT) forming an equilibrium between the thiols and the QD valence band. Photoexcitation results in populations of holes in the valence band and in slightly higher-energy shell-localized traps. Trap to valence band hole tunneling results in a photoluminescence risetime having time constants varying from 300 ps to 2 ns. The presence of adsorbed HDT eliminates the slower risetime component, indicating that hole transfer from the shell-localized traps that are closest to the particle surface efficiently competes with tunneling to the QD core. This shows that the interfacial charge transfer equilibrium is established in less than 2 ns. The population of the shell-localized traps corresponds to a reservoir of hole states that eventually tunnel to the core-localized valence band, resulting in delayed emission. The amount of delayed emission increases rapidly with ZnSe shell thickness and is slightly blue-shifted from the prompt photoluminescence. We propose an energetic model in which the HDT/valence band equilibrium is affected by the extent of valence band quantum confinement and an electric field produced by core–shell interfacial dipoles. Furthermore, this model explains the core size, shell thickness, and photoluminescence (PL) wavelength dependence of this equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Identity of the reversible hole traps in InP/ZnSe core/shell quantum dots

Density functional theory calculations are combined with time-resolved photoluminescence experiments to identify the species responsible for reversible trapping of holes following photoexcitation of InP/ZnSe/ZnS core/shell/shell quantum dots (QDs) having excess indium in the shell. Several possible assignments are considered, and a substitutional indium adjacent to a zinc vacancy, In 3+ /V Zn 2- , is found to be the most likely. This assignment is consistent with the observation that trapping occurs only when the QD has excess indium and is supported by experiments showing that the addition of zinc oleate or acetate decreases the extent of trapping, presumably by filling some of the vacancy traps. We also show that addition of alkyl carboxylic acids causes increased trapping, presumably by creation of additional zinc vacancies. The calculations show that either a single In 2+ ion or an In 2+ -In 3+ dimer is much too easily oxidized to form the reversible traps observed experimentally, while In 3+ is far too difficult to oxidize. Additional experimental data on InP/ZnSe/ZnS QDs synthesized in the absence of chloride demonstrates that the reversible traps are not associated with Cl - . Furthermore, a zinc vacancy adjacent to a substitutional indium is calculated to have its highest occupied orbitals about 1 eV above the top of the valence band of bulk ZnSe, in the appropriate energy range to act as reversible traps for quantum confined holes in the InP valence band. The associated orbitals are predominantly composed of p orbitals on the Se atoms adjacent to the Zn vacancy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Biexciton and trion dynamics in InP/ZnSe/ZnS quantum dots

Transient absorption (TA) and time-resolved photoluminescence (PL) spectroscopies have been used to elucidate the hole tunneling and Auger dynamics in biexcitons and negative trions in high-quality InP/ZnSe/ZnS quantum dots (QDs). In a previous paper [Nguyen et al., J. Phys. Chem. C 125, 15405–15414 (2021)], we showed that under high-intensity photoexcitation, two types of biexcitons are formed: those having two conduction band electrons and two valence band holes (designated as an XX state) and those having two conduction band electrons, one valence band hole, and an additional trapped hole (designated as an XT state). In the present paper, we show that both types of biexcitons can undergo Auger processes, with those of the XT state being a factor of four to five slower than those of the XX state. In addition, the trapped holes can undergo tunneling into the valence band, converting an XT state to an XX state. The relative amplitudes of the fast (XX) and slow (XT) components are different in the TA and PL kinetics, and these differences can be quantitatively understood in terms of oscillator strengths and electron–hole overlap integrals of each state. XT to XX hole tunneling rates are obtained from the comparison of the XT state lifetimes with those of the negative trions. This comparison shows that the tunneling times decrease with decreasing core size and shell thickness. Furthermore, these times are about 2 ns for the thinnest shell red-emitting QDs and decrease to 330 ps for QDs that luminesce in the yellow.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Radiative dynamics and delayed emission in pure and doped InP/ZnSe/ZnS quantum dots

We have used time-correlated single photon counting to elucidate the radiative dynamics of InP/ZnSe/ZnS core/shell/shell quantum dots (QDs) that differ in the amount and distribution of excess indium. Stoichiometric QDs having an In:P atom ratio very near unity exhibit simple luminescence kinetics. The photoluminescence (PL) rises with the 40 ps instrument response function and exhibits a decay that is close to a single exponential with a time constant that decreases from 32 to 28 ns with increasing shell thickness. QDs having excess indium (In:P ratio of 1.15–1.63) show a significant component of a slower rise time assigned to transient population of indium-based hole traps in the ZnSe shell. They also have a slower PL decay, attributed to an equilibrium between these traps, which are optically dark, and the emissive valence-band state. This results in a radiative lifetime that increases from 32 to 48 ns with increasing shell thickness. Different treatments of the InP cores prior to shell deposition result in different core/shell interfaces as indicated by resonance Raman spectroscopy, as well as differences in the amplitude and timescale of the slow PL rise and the PL decay time. These are interpreted in terms of different radial distributions of the indium-based hole traps, which can be related to differences in the interfacial lattice strain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Auger Dynamics in InP/ZnSe/ZnS Quantum Dots Having Pure and Doped Shells

In this study, we report the negative trion and biexciton Auger dynamics in very high-quality InP/ZnSe/ZnS quantum dots (QDs) having varying amounts of indium-based traps in the ZnSe shell. Negative trion times are determined by time-correlated photon-counting measurements on QDs that have been photoreduced with lithium triethylborohydride. We find that the Auger times vary from 280 to 425 ps and scale linearly with the total particle volume. Excess indium in the ZnSe shell gives rise to hole traps that are transiently populated following photoexcitation. Comparing stoichiometric and nonstoichiometric particles, we find that the negative trion lifetimes are independent of the presence of indium in the ZnSe shell. Biexciton dynamics are determined from transient absorption (TA) bleach recovery measurements. Absorption of two photons results in the formation of two types of biexcitons: those having both holes in the InP core (XX state) and those having one hole trapped in the ZnSe shell (XT state). XX state Auger times are measured in stoichiometric QDs, and for these particles, the Auger times are ~80 ps. Nonstoichiometric QDs show an additional long TA decay component, assigned to Auger recombination of the XT state. Here, a previous study (J. Phys. Chem. C 2021, 125, 4110–4118) found that hole trapping at indium-based shell traps results in a slow photoluminescence (PL) rise component. We find that the fraction of the XT state formed by the absorption of two photons correlates with the product of the fraction of slow PL rise and the rise time constant following one-photon excitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Resonance Raman Study of Shell Morphology in InP/ZnSe/ZnS Core/Shell/Shell Nanocrystals

Resonance Raman spectra and absolute cross sections of InP/ZnSe/ZnS core/shell/shell nanocrystals have been obtained at excitation wavelengths of 501.7, 457.9, and 410 nm. Eight different structures having nearly the same lowest excitonic absorption wavelength but significantly different stoichiometries are compared. The Raman spectra show phonon features attributable to both the InP core and the ZnSe shell. The largest differences among the structures are seen in the ZnSe phonon region by using excitation at 457.9 nm, on the low-energy edge of the absorption features having significant contributions from the ZnSe shell. Here, structures that are nearly stoichiometric (In:P ratio ≈1.0) show a sharp, strongly polarized peak near the bulk ZnSe phonon frequency (~250 cm –1 ) and a weak lower-frequency shoulder with a higher depolarization ratio. Structures having excess indium show a stronger low-frequency shoulder near 225 cm –1 and lower integrated Raman intensities throughout the ZnSe phonon region. These changes are attributed to the presence of indium atoms in the ZnSe shell. Furthermore, these results support a previous assignment of a slow rise component in the time-resolved photoluminescence spectra of nonstoichiometric structures to transient trapping of holes at indium defects in the shell.

77 NANOSCIENCE AND NANOTECHNOLOGY↗