An official website of the United States government
Cadmium chalcogenide nanoplatelets (NPLs) and their heterostructures have been reported to have low gain thresholds and large gain coefficients, showing great potential for lasing applications. However, the further improvement of the optical gain properties of NPLs is hindered by a lack of models that can account for their optical gain characteristics and predict their dependence on the properties (such as lateral size, concentration, and/or optical density). Herein, we report a systematic study of optical gain (OG) in 4-monolayer thick CdSe NPLs by both transient absorption spectroscopy study of colloidal solutions and amplified spontaneous emission (ASE) measurement of thin films. We showed that comparing samples with the same optical density at the excitation, the OG threshold is not dependent of the NPL lateral area, while the saturation gain amplitude is dependent on the NPL lateral area when comparing samples with the same optical density at the excitation wavelength. Both the OG and ASE thresholds increase with the optical density at the excitation wavelength for samples of the same NPL thickness and lateral area. We proposed an OG model for NPLs that can successfully account for the observed lateral area and optical density dependences. The model reveals that OG originates from stimulated emission from the bi-exciton states and the OG threshold is reached when the average number of excitons per NPL is about half the occupation of the band-edge exciton states. The model can also rationalize the much lower OG thresholds in the NPLs compared to QDs. This work provides a microscopic understanding of the dependence of the OG properties on the morphology of the colloidal nanocrystals and important guidance for the rational optimization of the lasing performance of NPLs and other 1- and 2-dimensional nanocrystals.
more »
« less
Efficient 2D to 0D Energy Transfer in HgTe Nanoplatelet-Quantum Dot Heterostructures through High-Speed Exciton Diffusion
Large area absorbers with localized defect emission are of interest for energy concentration via the antenna effect. Transfer between 2D and 0D quantum-confined structures is advantageous as it affords maximal lateral area antennas with continuously tunable emission. We report the quantum efficiency of energy transfer in in situ grown HgTe nanoplatelet (NPL)/quantum dot (QD) heterostructures to be near unity (>85%), while energy transfer in separately synthesized and well separated solutions of HgTe NPLs to QDs only reaches 47 ± 11% at considerably higher QD concentrations. Using Kinetic Monte Carlo simulations, we estimate an exciton diffusion constant of 1–10 cm2/s in HgTe NPLs, the same magnitude as that of 2D semiconductors. We also simulate in-solution energy transfer between NPLs and QDs, recovering an R–4 dependence consistent with 2D-0D near-field energy transfer even in randomly distributed NPL/QD mixtures. This highlights the advantage of NPLs 2D morphology and the efficiency of NPL/QD heterostructures and mixtures for energy harvesting.
more »
« less
- Award ID(s):
- 1945572
- PAR ID:
- 10489672
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry Letters
- Volume:
- 14
- Issue:
- 42
- ISSN:
- 1948-7185
- Page Range / eLocation ID:
- 9456 to 9463
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Photon upconversion is a process that combines low-energy photons to form useful high-energy photons. There are potential applications in photovoltaics, photocatalysis, biological imaging, etc. Semiconductor quantum dots (QDs) are promising for the absorption of these low-energy photons due to the high extinction coefficient of QDs, especially in the near infrared (NIR). This allows the intriguing use of diffuse light sources such as solar irradiation. In this review, we describe the development of this organic-QD upconversion platform based on triplet-triplet annihilation, focusing on the dark exciton in QDs with triplet character. Then we introduce the underlying energy transfer steps, starting from QD triplet photosensitization, triplet exciton transport, triplet-triplet annihilation, and ending with the upconverted emission. Design principles to improve the total upconversion efficiency are presented. We end with limitations in current reports and proposed future directions. This review provides a guide for designing efficient organic-QD upconversion platforms for future applications, including overcoming the Shockley-Queisser limit for more efficient solar energy conversion, NIR-based phototherapy, and diagnostics in vivo.more » « less
-
Hybrid materials combining the optoelectronic absorption and tunability of quantum dots (QDs) with the high surface area, chemical functionality, and porosity of metal-organic frameworks (MOFs) are emerging as systems with unique optoelectronic properties relevant to applications in catalysis, sensing, and energy conversion and storage. A key component of the electronic interaction between QDs and MOFs is the transfer of charge between the two materials. This review examines the mechanisms driving charge transfer at the QD/MOF interfaces and the effects that both physical and chemical composition have on this process. We provide an overview of the key experimental approaches, including spectroscopic and electrochemical techniques, which have been used for probing charge transfer dynamics in this hybrid system. Challenges in controlling interfacial structure, distinguishing between charge and energy transfer, and optimizing stability are also discussed. This review highlights recent work on the preparation and characterization of QD/MOF hybrid materials, as well as fundamental studies advancing the understanding of charge transfer processes that occur in these systems.more » « less
-
Abstract Driven by tensile strain, GaAs quantum dots (QDs) self-assemble on In0.52Al0.48As(111)A surfaces lattice-matched to InP substrates. In this study, we show that the tensile-strained self-assembly process for these GaAs(111)A QDs unexpectedly deviates from the well-known Stranski-Krastanov (SK) growth mode. Traditionally, QDs formed via the SK growth mode form on top of a flat wetting layer (WL) whose thickness is fixed. The inability to tune WL thickness has inhibited researchers’ attempts to fully control QD-WL interactions in these hybrid 0D-2D quantum systems. In contrast, using microscopy, spectroscopy, and computational modeling, we demonstrate that for GaAs(111)A QDs, we can continually increase WL thickness with increasing GaAs deposition, even after the tensile-strained QDs (TSQDs) have begun to form. This anomalous SK behavior enables simultaneous tuning of both TSQD size and WL thickness. No such departure from the canonical SK growth regime has been reported previously. As such, we can now modify QD-WL interactions, with future benefits that include more precise control of TSQD band structure for infrared optoelectronics and quantum optics applications.more » « less
-
We demonstrate a low-temperature synthesis of ultrasmall (<2 nm) HgTe quantum dots (QDs) with superlative optical properties in the near and shortwave infrared. The tunable cold-injection synthesis produces HgTe QDs ranging from 1.7 to 2.3 nm in diameter, with photoluminescence maxima ranging from 900 to 1180 nm and a full-width at half-maximum of ∼100 nm (∼130 meV). The synthesized quantum dots display high photoluminescence quantum yields (PLQY) ranging from 80 to 95% based on both relative and absolute methods. Furthermore, samples retain their high PLQY (∼60%) in the solid state, allowing for first-of-their-kind photoluminescence imaging and blinking studies of HgTe QDs. The facile synthesis allows for the isolation of small, photostable HgTe quantum dots, which can provide valuable insight into the extremes of quantum confinement.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.jpclett.3c02168
