Showing papers by "Moungi G. Bawendi published in 2023"

Narrow Intrinsic Line Widths and Electron-Phonon Coupling of InP Colloidal Quantum Dots.

Abstract: InP quantum dots (QDs) are the material of choice for QD display applications and have been used as active layers in QD light-emitting diodes (QDLEDs) with high efficiency and color purity. Optimizing the color purity of QDs requires understanding mechanisms of spectral broadening. While ensemble-level broadening can be minimized by synthetic tuning to yield monodisperse QD sizes, single QD line widths are broadened by exciton-phonon scattering and fine-structure splitting. Here, using photon-correlation Fourier spectroscopy, we extract average single QD line widths of 50 meV at 293 K for red-emitting InP/ZnSe/ZnS QDs, among the narrowest for colloidal QDs. We measure InP/ZnSe/ZnS single QD emission line shapes at temperatures between 4 and 293 K and model the spectra using a modified independent boson model. We find that inelastic acoustic phonon scattering and fine-structure splitting are the most prominent broadening mechanisms at low temperatures, whereas pure dephasing from elastic acoustic phonon scattering is the primary broadening mechanism at elevated temperatures, and optical phonon scattering contributes minimally across all temperatures. Conversely for CdSe/CdS/ZnS QDs, we find that optical phonon scattering is a larger contributor to the line shape at elevated temperatures, leading to intrinsically broader single-dot line widths than for InP/ZnSe/ZnS. We are able to reconcile narrow low-temperature line widths and broad room-temperature line widths within a self-consistent model that enables parametrization of line width broadening, for different material classes. This can be used for the rational design of more spectrally narrow materials. Our findings reveal that red-emitting InP/ZnSe/ZnS QDs have intrinsically narrower line widths than typically synthesized CdSe QDs, suggesting that these materials could be used to realize QDLEDs with high color purity.

Controlled Assembly and Anomalous Thermal Expansion of Ultrathin Cesium Lead Bromide Nanoplatelets.

Abstract: Quantum confined lead halide perovskite nanoplatelets are anisotropic materials displaying strongly bound excitons with spectrally pure photoluminescence. We report the controlled assembly of CsPbBr3 nanoplatelets through varying the evaporation rate of the dispersion solvent. We confirm the assembly of superlattices in the face-down and edge-up configurations by electron microscopy, as well as X-ray scattering and diffraction. Polarization-resolved spectroscopy shows that superlattices in the edge-up configuration display significantly polarized emission compared to face-down counterparts. Variable-temperature X-ray diffraction of both face-down and edge-up superlattices uncovers a uniaxial negative thermal expansion in ultrathin nanoplatelets, which reconciles the anomalous temperature dependence of the emission energy. Additional structural aspects are investigated by multilayer diffraction fitting, revealing a significant decrease in superlattice order with decreasing temperature, with a concomitant expansion of the organic sublattice and increase of lead halide octahedral tilt.

Elastic Phonon Scattering Dominates Dephasing in Weakly Confined Cesium Lead Bromide Nanocrystals at Cryogenic Temperatures.

Abstract: Cesium lead halide perovskite nanocrystals (PNCs) have emerged as a potential next-generation single quantum emitter (QE) material for quantum optics and quantum information science. Optical dephasing processes at cryogenic temperatures are critical to the quality of a QE, making a mechanistic understanding of coherence losses of fundamental interest. We use photon-correlation Fourier spectroscopy (PCFS) to obtain a lower bound to the optical coherence times of single PNCs as a function of temperature. We find that 20 nm CsPbBr3 PNCs emit nearly exclusively into a narrow zero-phonon line from 4 to 13 K. Remarkably, no spectral diffusion is observed at time scales of 10 μs to 5 ms. Our results suggest that exciton dephasing in this temperature range is dominated by elastic scattering from phonon modes with characteristic frequencies of 1-3 meV, while inelastic scattering is minimal due to weak exciton-phonon coupling.

Lead Halide Perovskite Nanocrystals with Low Inhomogeneous Broadening and High Coherent Fraction through Dicationic Ligand Engineering.

Abstract: Lead halide perovskite nanocrystals (LHP NCs) are an emerging materials system with broad potential applications, including as emitters of quantum light. We apply design principles aimed at the structural optimization of surface ligand species for CsPbBr3 NCs, leading us to the study of LHP NCs with dicationic quaternary ammonium bromide ligands. Through the selection of linking groups and aliphatic backbones guided by experiments and computational support, we demonstrate consistently narrow photoluminescence line shapes with a full-width-at-half-maximum below 70 meV. We observe bulk-like Stokes shifts throughout our range of particle sizes, from 7 to 16 nm. At cryogenic temperatures, we find sub-200 ps lifetimes, significant photon coherence, and the fraction of photons emitted into the coherent channel increasing markedly to 86%. A 4-fold reduction in inhomogeneous broadening from previous work paves the way for the integration of LHP NC emitters into nanophotonic architectures to enable advanced quantum optical investigation.

Solution-phase single-particle spectroscopy for probing multi-polaronic dynamics in quantum emitters at femtosecond resolution

Abstract: The development of many optical quantum technologies depends on the availability of solid-state single quantum emitters with near-perfect optical coherence. However, a standing issue that limits systematic improvement is the significant sample heterogeneity and lack of mechanistic understanding of microscopic energy flow at the single emitter level and ultrafast timescales. Here we develop solution-phase single-particle pump-probe spectroscopy with photon correlation detection that captures sample-averaged dynamics in single molecules and/or defect states with unprecedented clarity at femtosecond resolution. We apply this technique to single quantum emitters in two-dimensional hexagonal boron nitride, which suffers from significant heterogeneity and low quantum efficiency. From millisecond to nanosecond timescales, the translation diffusion, metastable-state-related bunching shoulders, rotational dynamics, and antibunching features are disentangled by their distinct photon-correlation timescales, which collectively quantify the normalized two-photon emission quantum yield. Leveraging its femtosecond resolution, spectral selectivity and ultralow noise (two orders of magnitude improvement over solid-state methods), we visualize electron-phonon coupling in the time domain at the single defect level, and discover the acceleration of polaronic formation driven by multi-electron excitation. Corroborated with results from a theoretical polaron model, we show how this translates to sample-averaged photon fidelity characterization of cascaded emission efficiency and optical decoherence time. Our work provides a framework for ultrafast spectroscopy in single emitters, molecules, or defects prone to photoluminescence intermittency and heterogeneity, opening new avenues of extreme-scale characterization and synthetic improvements for quantum information applications.

Fast detection of liver fibrosis with collagen-binding single-nanometer iron oxide nanoparticles via T1-weighted MRI.

Abstract: SNIO-CBP, a single-nanometer iron oxide (SNIO) nanoparticle functionalized with a type I collagen-binding peptide (CBP), was developed as a T1-weighted MRI contrast agent with only endogenous elements for fast and noninvasive detection of liver fibrosis. SNIO-CBP exhibits 6.7-fold higher relaxivity compared to a molecular gadolinium-based collagen-binding contrast agent CM-101 on a per CBP basis at 4.7 T. Unlike most iron oxide nanoparticles, SNIO-CBP exhibits fast elimination from the bloodstream with a 5.7 min half-life, high renal clearance, and low, transient liver enhancement in healthy mice. We show that a dose of SNIO-CBP that is 2.5-fold lower than that for CM-101 has comparable imaging efficacy in rapid (within 15 min following intravenous injection) detection of hepatotoxin-induced liver fibrosis using T1-weighted MRI in a carbon tetrachloride-induced mouse liver injury model. We further demonstrate the applicability of SNIO-CBP in detecting liver fibrosis in choline-deficient L-amino acid-defined high-fat diet mouse model of nonalcoholic steatohepatitis. These results provide a platform with potential for the development of high relaxivity, gadolinium-free molecular MRI probes for characterizing chronic liver disease.

Metal Oxide Interlayers Enable Lower-Cost Electrodes in PbS QD Solar Cells

Abstract: PbS quantum dots (QDs) are an emerging light-absorbing material for thin-film solar cells. However, state-of-the-art solar cell architectures rely on a gold electrode, which raises material costs to 3× more than the 2030 US DOE SunShot target module price. Here, we enable both aluminum and copper electrodes to replace gold through a NiOx interlayer. An additional indium tin oxide (ITO) buffer layer between the NiOx interlayer and electrode further enables longer shelf lifetimes. By combining these layers, we lower electrode material costs in PbS QD solar cells by a factor of 130000 without compromising power conversion efficiency or stability.

Rational Design of A Chemical Bath Deposition Based Tin Oxide Electron Transport Layer for Perovskite Photovoltaics.

Abstract: Chemical bath deposition is widely used to deposit SnOx as an electron transport layer in perovskite solar cells (PSCs). The conventional recipe uses thioglycolic acid (TGA) to facilitate attachments of SnOx particles onto the substrate. However, nonvolatile TGA has been reported to harm the operational stability of PSCs. In this work, we introduced a volatile oxalic acid (OA) as an alternative to TGA. OA, a dicarboxylic acid, functions as a chemical linker for the nucleation and attachment of particles to the substrate in the chemical bath. Moreover, OA can be readily removed through thermal annealing followed by a mild H2 O2 treatment, as shown by FTIR measurements. Synergistically, the mild H2 O2 treatment selectively oxidizes the surface of the SnOx layer, minimizing nonradiative interface carrier recombination. EELS (electron-energy-loss-spectroscopy) confirms that the SnOx surface is dominated by Sn4+ , while the bulk is a mixture of Sn2+ and Sn4+ . This rational design of a CBD SnOx layer leads to devices with T85∼1,500 h, a significant improvement over the TGA-based device with T80∼250 h. Our champion device reached a power conversion efficiency of 24.6%. This work offers a rationale for optimizing the complex parameter space of CBD SnOx to achieve efficient and stable PSCs. This article is protected by copyright. All rights reserved.

Quantum Shell in a Shell: Engineering Colloidal Nanocrystals for a High-Intensity Excitation Regime.

Abstract: Many optoelectronic processes in colloidal semiconductor nanocrystals (NCs) suffer an efficiency decline under high-intensity excitation. This issue is caused by Auger recombination of multiple excitons, which converts the NC energy into excess heat, reducing the efficiency and life span of NC-based devices, including photodetectors, X-ray scintillators, lasers, and high-brightness light-emitting diodes (LEDs). Recently, semiconductor quantum shells (QSs) have emerged as a promising NC geometry for the suppression of Auger decay; however, their optoelectronic performance has been hindered by surface-related carrier losses. Here, we address this issue by introducing quantum shells with a CdS-CdSe-CdS-ZnS core-shell-shell-shell multilayer structure. The ZnS barrier inhibits the surface carrier decay, which increases the photoluminescence (PL) quantum yield (QY) to 90% while retaining a high biexciton emission QY of 79%. The improved QS morphology allows demonstrating one of the longest Auger lifetimes reported for colloidal NCs to date. The reduction of nonradiative losses in QSs also leads to suppressed blinking in single nanoparticles and low-threshold amplified spontaneous emission. We expect that ZnS-encapsulated quantum shells will benefit many applications exploiting high-power optical or electrical excitation regimes.