Indium phosphide (InP) quantum dots (QDs) are considered the most promising alternative for Cd and Pb-based QDs for lighting and display applications. However, while core-only QDs of CdSe and CdTe have been prepared with near-unity photoluminescence quantum yield (PLQY), this is not yet achieved for InP QDs. Treatments with HF have been used to boost the PLQY of InP core-only QDs up to 85%. However, HF etches the QDs, causing loss of material and broadening of the optical features. Here, we present a simple postsynthesis HF-free treatment that is based on passivating the surface of the InP QDs with InF_3. For optimized conditions, this results in a PLQY as high as 93% and nearly monoexponential photoluminescence decay. Etching of the particle surface is entirely avoided if the treatment is performed under stringent acid-free conditions. We show that this treatment is applicable to InP QDs with various sizes and InP QDs obtained via different synthesis routes. The optical properties of the resulting core-only InP QDs are on par with InP/ZnSe/ZnS core-shell QDs, with significantly higher absorption coefficients in the blue, and with potential for faster charge transport. These are important advantages when considering InP QDs for use in micro-LEDs or photodetectors.

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Although density functional theory (DFT) calculations have been crucial in our understanding of colloidal quantum dots (QDs), simulations are commonly carried out on QD models that are significantly smaller than those generally found experimentally. While smaller models allow for efficient study of local surface configurations, increasing the size of the QD model will increase the size or number of facets, which can in turn influence the energetics and characteristics of trap formation. Moreover, core-shell structures can only be studied with QD models that are large enough to accommodate the different layers with the correct thickness. Here, we use DFT calculations to study the electronic properties of QDs as a function of size, up to a diameter of ∼4.5 nm. We show that increasing the size of QD models traditionally used in DFT studies leads to a disappearance of the band gap and localization of the HOMO and LUMO levels on facet-specific regions of the QD surface. We attribute this to the lateral coupling of surface orbitals and the formation of surface bands. The introduction of surface vacancies and their a posteriori refilling with Z-type ligands leads to surface reconstructions that widen the band gap and delocalize both the HOMO and LUMO. These results show that the surface geometry of the facets plays a pivotal role in defining the electronic properties of the QD.

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Colloidal nanoplatelets (NPLs) are promising materials for lasing applications. The properties are usually discussed in the framework of 2D materials, where strong excitonic effects dominate the optical properties near the band edge. At the same time, NPLs have finite lateral dimensions such that NPLs are not true extended 2D structures. Here we study the photophysics and gain properties of CdSe/CdS/ZnS core-shell-shell NPLs upon electrochemical n doping and optical excitation. Steady-state absorption and PL spectroscopy show that excitonic effects are weaker in core-shell-shell nanoplatelets due to the decreased exciton binding energy. Transient absorption studies reveal a gain threshold of only one excitation per nanoplatelet. Using electrochemical n doping, we observe the complete bleaching of the band edge exciton transitions. Combining electrochemical doping with transient absorption spectroscopy, we demonstrate that the gain threshold is fully removed over a broad spectral range and gain coefficients of several thousand cm-1 are obtained. These doped NPLs are the best performing colloidal nanomaterial gain medium reported to date, with the lowest gain threshold and broadest gain spectrum and gain coefficients that are 4 times higher than in n-doped colloidal quantum dots. The low exciton binding energy due to the CdS and ZnS shells, in combination with the relatively small lateral size of the NPLs, results in excited states that are effectively delocalized over the entire platelet. Core-shell NPLs are thus on the border between strong confinement in QDs and dominant Coulombic effects in 2D materials. We demonstrate that this limit is in effect ideal for optical gain and that it results in an optimal lateral size of the platelets where the gain threshold per nm2 is minimal.

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Few-layered transition-metal dichalcogenides (TMDs) are increasingly popular materials for optoelectronics and catalysis. Among the various types of TMDs available today, rhenium chalcogenides (ReX2) stand out due to their remarkable electronic structure, such as the occurrence of anisotropic excitons and potential direct band gap behavior throughout multilayered stacks. In this paper, we have analyzed the nature and dynamics of charge carriers in highly crystalline liquid-phase exfoliated ReS2, using a unique combination of optical pump-THz probe and broad-band transient absorption spectroscopy. Two distinct time regimes are identified, both of which are dominated by unbound charge carriers despite the high exciton binding energy. In the first time regime, the unbound charge carriers cause an increase and a broadening of the exciton absorption band. In the second time regime, a peculiar narrowing of the excitonic absorption profile is observed, which we assign to the presence of built-in fields and/or charged defects. Our results pave the way to analyze spectrally complex transient absorption measurements on layered TMD materials and indicate the potential for ReS2 to produce mobile free charge carriers, a feat relevant for photovoltaic applications.

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We studied the dynamics of transfer of photoexcited electronic states in a bilayer of the two-dimensional transition metal dichalcogenide ReS2 and tetracene, with the aim to produce triplets in the latter. This material combination was used as the band gap of ReS2 (1.5 eV) is slightly larger than the triplet energy of tetracene (1.25 eV). Using time-resolved optical absorption spectroscopy, transfer of photoexcited states from ReS2 to triplet states in tetracene was found to occur within 5 ps with an efficiency near 38%. This result opens up new possibilities for heterostructure design of two-dimensional materials with suitable organics to produce long-lived triplets. Triplets are of interest as sensitizers in a wide variety of applications including optoelectronics, photovoltaics, photocatalysis, and photon upconversion.

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Low-dimensional semiconductors have found numerous applications in optoelectronics. However, a quantitative comparison of the absorption strength of low-dimensional versus bulk semiconductors has remained elusive. Here, we report generality in the band-edge light absorptance of semiconductors, independent of their dimensions. First, we provide atomistic tight-binding calculations that show that the absorptance of semiconductor quantum wells equals mπα (m = 1 or 2 with α as the fine-structure constant), in agreement with reported experimental results. Then, we show experimentally that a monolayer (superlattice) of quantum dots has similar absorptance, suggesting an absorptance quantum of mπα per (confined) exciton diameter. Extending this idea to bulk semiconductors, we experimentally demonstrate that an absorptance quantum equal to mπα per exciton Bohr diameter explains their widely varying absorption coefficients. We thus provided compelling evidence that the absorptance quantum πα per exciton diameter rules the band-edge absorption of all direct semiconductors, regardless of their dimension.

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Owing to their widely tuneable optical properties and strong light-matter interaction, colloidal quantum dots[1] (QDs) are considered for next-generation photonic devices such as solution processable lasers[2] and all-optical wavelength converters. Using QDs for this last application, i.e. wavelength conversion, is limited by either slow interband (106-109 s-1) or energy consuming multi-exciton dynamics (109-1012 s−1). Here we show, using white light pump-probe spectroscopy, that the interplay between two intrinsic material properties of PbS QDs, intraband absorption and interband bleach can lead to a very strong modulation of near-infrared light on an ultrafast, picosecond, timescale: A peculiar dynamic arises at the matching wavelength: a strong burst of absorption induced by the pump lasts for roughly 1 picosecond and vanishes, leaving the dots as they were before the pump pulse arrived.@en

Ultrathin two-dimensional (2D) materials have received much attention in the past years for a wide variety of photonic applications because of their pronounced room-temperature excitonic features, leading to unique properties in terms of light-matter interaction. However, only a few studies focus on light amplification and the complex photophysics at high excitation density. The beneficial nature of strong excitonic effects on optical gain remain hence unquantified, and despite the increased binding energies of the excitonic species, it remains unclear what the involvement of 2D excitons would be in optical gain. Here, we use colloidal CdSe nanoplatelets as a model system for colloidal 2D materials and show, using a quantitative and combinatory approach to ultrafast spectroscopy, that several excitation density-dependent optical gain regimes exist. At low density, optical gain originates from excitonic molecules delivering large material gains up to 20 000 cm ^-1 with an Auger limited lifetime of a few hundred picoseconds. At increasing pair density, we observe a persistence of this excitonic gain regime and the unexpected coexistence of blue-shifted and significantly enhanced optical gain up to 10 ⁵ cm ^-1 . We show that this peculiar situation originates from a carrier cooling bottleneck at high density that limits further exciton formation from unbound charge carriers. The insulating (multi-)exciton gas is found to coexist with the conductive phase, indicating the absence of a full Mott transition. Our results shed a new light on the photophysics of excitons in strongly excited 2D materials and pave the way for the development of more efficient (broadband) optical gain media and/or high exciton density applications.

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Colloidal quantum dots (QDs) raise more and more interest as solution-processable and tunable optical gain materials. However, especially for infrared active QDs, optical gain remains inefficient. Since stimulated emission involves multifold degenerate band-edge states, population inversion can be attained only at high pump power and must compete with efficient multi-exciton recombination. Here, we show that mercury telluride (HgTe) QDs exhibit size-tunable stimulated emission throughout the near-infrared telecom window at thresholds unmatched by any QD studied before. We attribute this unique behaviour to surface-localized states in the bandgap that turn HgTe QDs into 4-level systems. The resulting long-lived population inversion induces amplified spontaneous emission under continuous-wave optical pumping at power levels compatible with solar irradiation and direct current electrical pumping. These results introduce an alternative approach for low-threshold QD-based gain media based on intentional trap states that paves the way for solution-processed infrared QD lasers and amplifiers.

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Carrier multiplication is a process in which one absorbed photon excites two or more electrons. This is of great promise to increase the efficiency of photovoltaic devices. Until now, the factors that determine the onset energy of carrier multiplication have not been convincingly explained. We show experimentally that the onset of carrier multiplication in lead chalcogenide quantum confined and bulk crystals is due to asymmetric optical transitions. In such transitions most of the photon energy in excess of the band gap is given to either the hole or the electron. The results are confirmed and explained by theoretical tight-binding calculations of the competition between impact ionization and carrier cooling. These results are a large step forward in understanding carrier multiplication and allow for a screening of materials with an onset of carrier multiplication close to twice the band gap energy. Such materials are of great interest for development of highly efficient photovoltaic devices.

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One of the greatest challenges in the field of semiconductor nanomaterials is to make trap-free nanocrystalline structures to attain a remarkable improvement of their optoelectronic performances. In semiconductor nanomaterials, a very high number of atoms is located on the surface and these atoms form the main source of electronic traps. The relation between surface atom coordination and electronic structure, however, remains largely unknown. Here, we use density functional theory to unveil the surface structure/electronic property relations of zincblende II-VI CdSe model nanocrystals, whose stoichiometry and surface termination agree with recent experimental findings. On the basis of the analysis of the surface geometry and the recent classification of the ligand surface coordination in terms of L-, X-, and Z-type ligands, we show that, contrary to expectations, most under-coordinated "dangling" atoms do not form traps and that L- and X-type ligands are benign to the nanocrystal electronic structure. On the other hand, we find clear evidence that Z-type displacement induces midgap states, localized on the 4p lone pair of 2-coordinated selenium surface atoms. We generalize our findings to the whole family of II-VI metal chalcogenide nanocrystals of any size and shape and propose a new schematic representation of the chemical bond in metal chalcogenide nanocrystals that includes explicitly the coordination number of surface atoms. This work results in a detailed understanding of the formation of surface traps and provides a clear handle for further optimization of colloidal nanocrystals for optoelectronics applications.

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All-optical approaches to change the wavelength of a data signal are considered more energy-and cost-effective than current wavelength conversion schemes that rely on back and forth switching between the electrical and optical domains. However, the lack of cost-effective materials with sufficiently adequate optoelectronic properties hampers the development of this so-called all-optical wavelength conversion. Here, we show that the interplay between intraband and band gap absorption in colloidal quantum dots leads to a very strong and ultrafast modulation of the light absorption after photoexcitation in which slow components linked to exciton recombination are eliminated. This approach enables all-optical wavelength conversion at rates matching state-of-the-art convertors in speed, yet with cost-effective solution-processable materials. Moreover, the stronger light-matter interaction allows for implementation in small-footprint devices with low switching energies. Being a generic property, the demonstrated effect opens a pathway toward low-power integrated photonics based on colloidal quantum dots as the enabling material.

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The cooling dynamics of hot charge carriers in colloidal lead chalcogenide nanocrystals is studied by white light transient absorption spectroscopy. We demonstrate a transient accumulation of charge carriers at a high-energy critical point in the Brillouin zone. Using a theoretical study of the cooling rate in lead chalcogenides, we attribute this slowing down of charge carrier cooling to a phonon scattering bottleneck around this critical point. Our approach allows for the first ever determination of hot carrier cooling rates, relevant in e.g. modeling of multiple exciton generation.@en