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1.
J Am Chem Soc ; 141(44): 17617-17628, 2019 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-31610655

RESUMO

Wurtzite CdSe@CdS dot@platelet nanocrystals, dot-shaped CdSe nanocrystals encased within epitaxially grown CdS nanoplatelets, are controllably synthesized with nearly monodisperse size and shape distribution and outstanding photoluminescence (PL) properties. The excellent size and shape control with their lateral to thickness dimension ratio up to 3:1 is achieved by systematically studying the synthetic parameters, which results in a simple, tunable, yet reproducible epitaxy scheme. These special types of core/shell nanocrystals possess two-dimensional emission dipoles with the ab plane of the wurtzite structure. While their near-unity PL quantum yield and monoexponential PL decay dynamics are at the same level of the state-of-art CdSe/CdS core/shell nanocrystals in dot shape, CdSe@CdS dot@platelet nanocrystals possess ∼2 orders of magnitude lower probability for initiating PL blinking at the single-nanocrystal level than the dot-shaped counterparts do.

2.
Angew Chem Int Ed Engl ; 58(49): 17764-17770, 2019 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-31591763

RESUMO

Facet-dependent on-surface reactions are systematically studied on zinc-blende CdSe nanoplatelets with atomically-flat {001} basal facets and small yet non-polar side facets. The on-surface half-reactions between the surface Se sites and Cd carboxylates in the solution are qualitatively equivalent to those on the spheroidal counterparts. Conversely, the on-surface half-reactions between the surface Cd sites and the activated Se precursors in solution show a strong facet-dependence, which includes three distinguishable stages. In the first stage, the Se precursors adsorb onto the small and non-polar side facets of the nanoplatelets. The second stage is initiated by the adsorbed Se precursors at the side-basal plane edges and proceeds from the edges to the center of the basal planes in quasi-zeroth-order kinetics. In the third stage, the nanoplatelets are dismantled, which includes the creation of a hole in the middle and a build-up of thick edges.

3.
J Am Chem Soc ; 141(6): 2288-2298, 2019 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-30649864

RESUMO

Mn2+-doped ZnSe nanocrystals (Mn:ZnSe d-dots) with high optical quality-high dopant emission quantum yield with monoexponential dopant-emission decay dynamics-enable systematic and quantitative studies of temperature- and Mn2+ concentration-dependent optical properties of the dopant emission, especially its relationship with magnetic coupling. While temperature-dependent steady-state and transient dopant emission of d-dots with dilute Mn2+ concentrations originated from isolated Mn2+ ions, and can be quantitatively treated as a result of exciton-phonon coupling of isolated paramagnetic emission centers. Dopant emission of d-dots with high Mn2+ concentrations (up to 50% of Zn2+ ions being replaced by Mn2+ ions in the core nanocrystals) are found solely related to magnetically coupled Mn2+ emission. Magnetic coupling effects on steady-state dopant emission of d-dots with high Mn2+ concentrations are much stronger than those observed for doped bulk semiconductors, which is found to follow a strong and universe shell-thickness dependence for the epitaxial ZnSe and/or ZnS shells of the d-dots. By exciting the magnetically coupled Mn2+ ions directly, dopant-emission of d-dots with high Mn2+ concentrations exhibit monoexponential decay dynamics. In addition to this emission channel, a minor channel with slightly longer decay lifetime appears when the host nanocrystals with high Mn2+ concentrations are excited, which is barely visible at room temperature and increases its fraction by decreasing temperature.

4.
J Org Chem ; 83(19): 11886-11895, 2018 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-30168324

RESUMO

CdSe/CdS core/shell quantum dots (QDs) can be used as stable and highly active photoredox catalysts for efficient transfer hydrogenation of imines to amines with thiophenol as a hydrogen atom donor. This reaction proceeds via a proton-coupled electron transfer (PCET) from the QDs conduction band to the protonated imine followed by hydrogen atom transfer from the thiophenol to the α-aminoalkyl radical. This precious metal free transformation is easy to scale up and can be carried out by a one-pot protocol directly from aldehyde, amine, and thiophenol.  Additional advantageous features of this protocol include a wide substrate scope, high yield of the amine products, extremely low catalyst loading (0.001 mol %), high turnover number (105), and the mild reaction conditions of using visible light or sun light at room temperature in neutral media.

5.
J Am Chem Soc ; 140(29): 9174-9183, 2018 07 25.
Artigo em Inglês | MEDLINE | ID: mdl-29956924

RESUMO

On-surface reaction mechanisms during the growth of high-quality CdSe nanocrystals are studied quantitatively and systematically by introducing a cyclic growth scheme. Prior to the repeating growth cycles, presynthesized CdSe QD seeds from a conventional scheme are reacted with an activated Se precursor, which is found to include three elementary steps and generate Se-terminated CdSe QDs. The cyclic growth in amine-octadecene solution includes two repeating half-reactions. The first half-reaction is between cadmium carboxylates in the bulk solution and the Se-terminated QDs, and the other is between the Se precursor in the bulk solution and the Cd-terminated QDs generated by the first half-reaction. While two elementary steps in the Se-surface half-reaction can be quantitatively treated as parallel kinetics, two elementary steps for the Cd-surface half-reaction must be treated as consecutive steps. These elementary steps are found to possess substantially different reaction rates as well as activation energies. Results indicate that, in the growth of compound semiconductor nanocrystals with metal carboxylates as cationic precursor (or ligands), the elementary step between activated anionic precursors in the bulk solution and the cationic sites on the surface of nanocrystals would be the rate-limiting step. This rate-limiting step should be the one that causes nucleation (or formation of small clusters by solution reactions) to be substantially faster than the corresponding growth through on-surface reactions.

6.
Adv Mater ; 30(28): e1801387, 2018 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-29808563

RESUMO

Quantum-dot light-emitting diodes (QLEDs) may combine superior properties of colloidal quantum dots (QDs) and advantages of solution-based fabrication techniques to realize high-performance, large-area, and low-cost electroluminescence devices. In the state-of-the-art red QLED, an ultrathin insulating layer inserted between the QD layer and the oxide electron-transporting layer (ETL) is crucial for both optimizing charge balance and preserving the QDs' emissive properties. However, this key insulating layer demands very accurate and precise control over thicknesses at sub-10 nm level, causing substantial difficulties for industrial production. Here, it is reported that interfacial exciton quenching and charge balance can be independently controlled and optimized, leading to devices with efficiency and lifetime comparable to those of state-of-the-art devices. Suppressing exciton quenching at the ETL-QD interface, which is identified as being obligatory for high-performance devices, is achieved by adopting Zn0.9 Mg0.1 O nanocrystals, instead of ZnO nanocrystals, as ETLs. Optimizing charge balance is readily addressed by other device engineering approaches, such as controlling the oxide ETL/cathode interface and adjusting the thickness of the oxide ETL. These findings are extended to fabrication of high-efficiency green QLEDs without ultrathin insulating layers. The work may rationalize the design and fabrication of high-performance QLEDs without ultrathin insulating layers, representing a step forward to large-scale production and commercialization.

7.
Nat Commun ; 8(1): 1132, 2017 10 26.
Artigo em Inglês | MEDLINE | ID: mdl-29070867

RESUMO

Photonic quantum information requires high-purity, easily accessible, and scalable single-photon sources. Here, we report an electrically driven single-photon source based on colloidal quantum dots. Our solution-processed devices consist of isolated CdSe/CdS core/shell quantum dots sparsely buried in an insulating layer that is sandwiched between electron-transport and hole-transport layers. The devices generate single photons with near-optimal antibunching at room temperature, i.e., with a second-order temporal correlation function at zero delay (g (2)(0)) being <0.05 for the best devices without any spectral filtering or background correction. The optimal g (2)(0) from single-dot electroluminescence breaks the lower g (2)(0) limit of the corresponding single-dot photoluminescence. Such highly suppressed multi-photon-emission probability is attributed to both novel device design and carrier injection/recombination dynamics. The device structure prevents background electroluminescence while offering efficient single-dot electroluminescence. A quantitative model is developed to illustrate the carrier injection/recombination dynamics of single-dot electroluminescence.

8.
J Am Chem Soc ; 139(9): 3302-3311, 2017 03 08.
Artigo em Inglês | MEDLINE | ID: mdl-28170239

RESUMO

Colloidal quantum dots are promising optical and optoelectronic materials for various applications, whose performance is dominated by their excited-state properties. This article illustrates synthetic control of their excited states. Description of the excited states of quantum-dot emitters can be centered around exciton. We shall discuss that, different from conventional molecular emitters, ground-state structures of quantum dots are not necessarily correlated with their excited states. Synthetic control of exciton behavior heavily relies on convenient and affordable monitoring tools. For synthetic development of ideal optical and optoelectronic emitters, the key process is decay of band-edge excitons, which renders transient photoluminescence as important monitoring tool. On the basis of extensive synthetic developments in the past 20-30 years, synthetic control of exciton behavior implies surface engineering of quantum dots, including surface cation/anion stoichiometry, organic ligands, inorganic epitaxial shells, etc. For phosphors based on quantum dots doped with transition metal ions, concentration and location of the dopant ions within a nanocrystal lattice are found to be as important as control of the surface states in order to obtain bright dopant emission with monoexponential yet tunable photoluminescence decay dynamics.

9.
J Am Chem Soc ; 138(26): 8134-42, 2016 07 06.
Artigo em Inglês | MEDLINE | ID: mdl-27312799

RESUMO

Electronic traps at the inorganic-organic interface of colloidal quantum dots (QDs) are detrimental to their luminescent properties. Several types of interface traps were identified for single-crystalline CdSe/CdS core/shell QDs, which were all found to be extrinsic to either the core/shell structure or their optical performance. The electron traps-presumably excess or unpassivated Cd surface sites-are shallow ones and could be readily isolated from the electron wave function of the excitons with more than ∼2 monolayers of CdS shell. There were two identifiable deep hole traps within the bandgap of the QDs, i.e., the surface adsorbed H2S and unpassivated surface S sites. The surface adsorbed H2S could be removed by either degassing processes or photochemical decomposition of H2S without damaging the QDs. The unpassivated surface S sites could be removed by surface treatment with cadmium carboxylates. Understanding of the surface traps enabled establishment of new phosphine-free synthetic schemes for either single-precursor or successive-ion-layer-adsorption-and-reaction approach, which yielded CdSe/CdS core/shell QDs with near-unity photoluminescence quantum yield and monoexponential photoluminescence decay dynamics with 2-10 monolayers of CdS shell.

10.
ACS Cent Sci ; 2(1): 32-9, 2016 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-27163024

RESUMO

Transition metal doped semiconductor nanocrystals (d-dots) possess fundamentally different emission properties upon photo- or electroexcitation, which render them as unique emitters for special applications. However, in comparison with intrinsic semiconductor nanocrystals, the potential of d-dots has been barely realized, because many of their unique emission properties mostly rely on precise control of their photoluminescence (PL) decay dynamics. Results in this work revealed that it would be possible to obtain bright d-dots with nearly single-exponential PL decay dynamics. By tuning the number of Mn(2+) ions per dot from ∼500 to 20 in Mn(2+) doped ZnSe nanocrystals (Mn:ZnSe d-dots), the single-exponential PL decay lifetime was continuously tuned from ∼50 to 1000 µs. A synthetic scheme was further developed for uniform and epitaxial growth of thick ZnS shell, ∼7 monolayers. The resulting Mn:ZnSe/ZnS core/shell d-dots were found to be essential for necessary environmental durability of the PL properties, both steady-state and transient ones, for the d-dot emitters. These characteristics combined with intense absorption and high PL quantum yields (70 ± 5%) enabled greatly simplified schemes for various applications of PL lifetime multiplexing using Mn:ZnSe/ZnS core/shell d-dots.

11.
J Am Chem Soc ; 138(20): 6475-83, 2016 05 25.
Artigo em Inglês | MEDLINE | ID: mdl-27144923

RESUMO

CdSe magic-size clusters with close-shell surface and fixed molecular formula are well-known in the size range between ∼1 and 3 nm. By applying high concentration of cadmium alkanoates as ligands, a conventional synthetic system for CdSe nanocrystals was tuned to discriminate completion from initiation of atomic flat facets. This resulted in ∼4-13 nm CdSe nanocrystals with hexahedral shape terminated with low-index facets, namely three (100), one (110), and two (111) facets. These low-symmetry (Cs group with single mirror plane) yet monodisperse hexahedra were found to be persistent not only in a broad size range but also under typical synthetic temperatures for growth of both CdSe and CdS. Atomic motion on the surface of the nanocrystals under enhanced ligand dynamics initiated intraparticle ripening without activating interparticle ripening, which converted the hexahedral nanocrystals to monodisperse spherical ones. This new synthetic strategy rendered optimal color purity of photoluminescence (PL) of the CdSe and CdSe/CdS core/shell nanocrystals, with the ensemble PL peak width comparable with that of a corresponding single dot.

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