Band-Edge Energy Levels of Dynamic Excitons in Cube-Shaped CdSe/CdS Core/Shell Nanocrystals.

An electron-hole pair in a cube-shaped CdSe/CdS core/shell nanocrystal exists in the form of dynamic excitons across the strongly and weakly confined regimes under ambient temperatures. Photochemical doping is applied to distinguish the band-edge electron and hole levels, confirming an effective mass model with universal constants. Reduction of the optical bandgap upon epitaxy of the CdS shells is caused by lowering the band-edge electron level and barely affecting the band-edge hole level. Similar shifts of the electron levels, yet retaining the hole levels, can switch the order in energy of the three lowest-energy transitions. Thermal distribution of 1-4 electrons among the two thermally accessible electron levels follows number-counting statistics, instead of Fermi-Dirac distribution.

Selective Formation of Monodisperse Right Trigonal-Bipyramidal and Cube-Shaped CdSe Nanocrystals: Stacking Faults and Facet-Ligand Pairing.

Formation of monodisperse right trigonal-bipyramidal (rTriBP) and cube-shaped CdSe nanocrystals─both being encased with six (100) facets─is found to be dictated by type of stacking faults along the (111) direction of the zinc-blende structure and an ideal facet-ligand pairing for the (100) facets. During growth with little kinetic overdriving, seeds with single twin boundary (TB) and single intrinsic stacking fault (ISF) grow into rTriBP and cube-shaped nanocrystals, respectively, through two consecutive stages. During the facet-formation stage, each seed would grow rapidly into the smallest faceted one to contain the ∼3 nm seed, with cube-shaped ones growing much faster than rTriBP ones because of the stacking-fault-dependent seed location in the final faceted nanocrystals. In the following facet-growth stage, cube-shaped nanocrystals also grow faster, presumably due to the highly reactive stacking fault edges. Consistent with this hypothesis, growth of rTriBP nanocrystals can become faster than that of cube-shaped ones by intentionally introducing additional intrinsic stacking fault(s) in the seeds. Cube-shaped and rTriBP CdSe nanocrystals exhibit distinctive optical properties, representing two classes of optical materials.

Surface Sites and Ligation in Amine-capped CdSe Nanocrystals.

Converting colloidal nanocrystals (NCs) into devices for various applications is facilitated by designing and controlling their surface properties. One key strategy for tailoring surface properties is thus to choose tailored surface ligands. In that context, amines have been universally used, with the goal to improve NCs synthesis, processing and performances. However, understanding the nature of surface sites in amine-capped NCs remains challenging, due to the complex surface compositions as well as surface ligands dynamic. Here, we investigate both surface sites and amine ligation in CdSe NCs by combining advanced NMR spectroscopy and computational modelling. Notably, dynamic nuclear polarization (DNP) enhanced 113 Cd and 77 Se 1D NMR helps to identify both bulk and surface sites of NCs, while 113 Cd 2D NMR spectroscopy enables to resolve amines terminated sites on both Se-rich and nonpolar surfaces. In addition to directly bonding to surface sites, amines are shown to also interact through hydrogen-bonding with absorbed water as revealed by 15 N NMR, augmented with computations. The characterization methodology developed for this work provides unique molecular-level insight into the surface sites of a range of amine-capped CdSe NCs, and paves the way to identify structure-function relationships and rational approaches towards colloidal NCs with tailored properties.

Toward Surface Chemistry of Semiconductor Nanocrystals at an Atomic-Molecular Level.

ConspectusProperties of colloidal semiconductor nanocrystals with a single-crystalline structure are largely dominated by their surface structure at an atomic-molecular level, which is not well understood and controlled, due to a lack of experimental tools. However, if viewing the nanocrystal surface as three relatively independent spatial zones (i.e., crystal facets, inorganic-ligands interface, and ligands monolayer), we may approach an atomic-molecular level by coupling advanced experimental techniques and theoretical calculations.Semiconductor nanocrystals of interest are mainly based on compound semiconductors and mostly in two (or related) crystal structures, namely zinc-blende and wurtzite, which results in a small group of common low-index crystal facets. These low-index facets, from a surface-chemistry perspective, can be further classified into polar and nonpolar ones. Albeit far from being successful, the controlled formation of either polar or nonpolar facets is available for cadmium chalcogenide nanocrystals. Such facet-controlled systems offer a reliable basis for studying the inorganic-ligands interface. For convenience, here facet-controlled nanocrystals refer to a special class of shape-controlled ones, in which shape control is at an atomic level, instead of those with poorly defined facets (e.g., typical spheroids, nanorods, etc).Experimental and theoretical results reveal that type and bonding mode of surface ligands on nanocrystals is facet-specific and often beyond Green's classification (X-type, Z-type, and L-type). For instance, alkylamines bond strongly to the anion-terminated (0001) wurtzite facet in the form of ammonium ions, with three hydrogens of an ammonium ion bonding to three adjacent surface anion sites. With theoretically assessable experimental data, facet-ligands pairing can be identified using density functional theory (DFT) calculations. To make the pairing meaningful, possible forms of all potential ligands in the system need to be examined systematically, revealing the advantage of simple solution systems.Unlike the other two spatial zones, the ligands monolayer is disordered and dynamic at an atomic level. Thus, an understanding of the ligands monolayer on a molecular scale is sufficient for many cases. For colloidal nanocrystals stably coordinated with surface ligands, their solution properties are dictated by the ligands monolayer. Experimental and theoretical results reveal that solubility of a nanocrystal-ligands complex is an interplay between the intramolecular entropy of the ligands monolayer and intermolecular interactions of the ligands/nanocrystals. By introducing entropic ligands, solubility of nanocrystal-ligands complexes can be universally boosted by several orders of magnitude, i.e., up to >1 g/mL in typical organic solvents. Molecular environment in the pseudophase surrounding each nanocrystal plays a critical role in its chemical, photochemical, and photophysical properties.For some cases, such as the synthesis of high-quality nanocrystals, all three spatial zones of the nanocrystal surface must be taken into account. By optimizing nanocrystal surface at an atomic-molecular level, semiconductor nanocrystals with monodisperse size and facet structure become available recently through either direct synthesis or afterward facet reconstruction, implying full realization of their size-dependent properties.

Hot-Electron-Induced Photochemical Properties of CdSe/ZnSe Core/Shell Quantum Dots under an Ambient Environment.

Using CdSe/ZnSe core-shell quantum dots (QDs) as a model, we systematically investigate the photochemical properties of QDs with the ZnSe shells under an ambient environment, which show almost opposite responses to either oxygen or water in comparison with CdSe/CdS core/shell QDs. While the ZnSe shells provide an efficient potential barrier for photoinduced electron transfer from the core to the surface-adsorbed oxygen, they also act as a stepping stone for hot-electron transfer directly from the ZnSe shells to oxygen. The latter process is so effective and competes favorably with ultrafast relaxation of hot electrons from the ZnSe shells to the core QDs, which can completely quench the photoluminescence (PL) with saturated adsorption of oxygen (1 bar) and initiate oxidation of the surface anion sites. Water can slowly eliminate the excess hole to neutralize the positively charged QDs, partially canceling the photochemical effects of oxygen. Alkylphosphines─through two distinctive reaction pathways with oxygen─stop the photochemical effects of oxygen and completely recover PL. With limited thickness (around two monolayers), the ZnS outer shells substantially slow down photochemical effects on CdSe/ZnSe/ZnS core/shell/shell QDs but cannot fully stop PL quenching by oxygen.

Reversible Facet Reconstruction of CdSe/CdS Core/Shell Nanocrystals by Facet-Ligand Pairing.

Synthesis of colloidal semiconductor nanocrystals with defined facet structures is challenging, though such nanocrystals are essential for fully realizing their size-dependent optical and optoelectronic properties. Here, for the mostly developed colloidal wurtzite CdSe/CdS core/shell nanocrystals, facet reconstruction is investigated under typical synthetic conditions, excluding nucleation, growth, and interparticle ripening. Within the reaction time window, two reproducible sets of facets─each with a specific group of low-index facets─can be reversibly reconstructed by switching the ligand system, indicating thermodynamic stability of each set. With a unique <0001> axis, atomic structures of the low-index facets of wurtzite nanocrystals are diverse. Experimental and theoretical studies reveal that each facet in a given set is paired with a common ligand in the solution, namely, either fatty amine and/or cadmium alkanoate. The robust bonding modes of ligands are found to be strongly facet-dependent and often unconventional, instead of following Green's classification. Results suggest that facet-controlled nanocrystals can be synthesized by optimal facet-ligand pairing either in synthesis or after-synthesis reconstruction, implying semiconductor nanocrystal formation with size-dependent properties down to an atomic level.

Synthesis of Weakly Confined, Cube-Shaped, and Monodisperse Cadmium Chalcogenide Nanocrystals with Unexpected Photophysical Properties.

Zinc-blende CdSe, CdS, and CdSe/CdS core/shell nanocrystals with a structure-matched shape (cube-shaped, edge length ≤30 nm) are synthesized via a universal scheme. With the edge length up to five times larger than exciton diameter of the bulk semiconductors, the nanocrystals exhibit novel properties in the weakly confined size regime, such as near-unity single exciton and biexciton photoluminescence (PL) quantum yields, single-nanocrystal PL nonblinking, mixed PL decay dynamics of exciton and free carriers with sub-microsecond monoexponential decay lifetime, and stable yet extremely narrow PL full width at half maximum (FWHM < 0.1 meV) at 1.8 K. Their monodisperse edge length, shape, and facet structure enable demonstration of unexpected yet size-dependent PL properties at room temperature, including unusually broad and abnormally size-dependent PL FWHM (∼100 meV), nonmonotonic size dependence of PL peak energy, and dual-peak single-exciton PL. Calculations suggest that these unusual properties should be originated from the band-edge electron/hole states of the dynamic-exciton, whose exciton binding energy is too small to hold the photogenerated electron-hole pair as a bonded Wannier exciton in a weakly confined nanocrystal.

Water molecules bonded to the carboxylate groups at the inorganic-organic interface of an inorganic nanocrystal coated with alkanoate ligands.

High-quality colloidal nanocrystals are commonly synthesized in hydrocarbon solvents with alkanoates as the most common organic ligand. Water molecules with an approximately equal number of surface alkanoate ligands are identified at the inorganic-organic interface for all types of colloidal nanocrystals studied, and investigated quantitatively using CdSe nanocrystals as the model system. Carboxylate ligands are coordinated to the surface metal ions and the first monolayer of water molecules is found to bond to the carboxylate groups of alkanoate ligands through hydrogen bonds. Additional monolayer(s) of water molecules can further be adsorbed through hydrogen bonds to the first monolayer of water molecules. The nearly ideal environment for hydrogen bonding at the inorganic-organic interface of alkanoate-coated nanocrystals helps to rapidly and stably enrich the interface-bonded water molecules, most of which are difficult to remove through vacuum treatment, thermal annealing and chemical drying. The water-enriched structure of the inorganic-organic interface of high-quality colloidal nanocrystals must be taken into account in order to understand the synthesis, processing and properties of these novel materials.

Monodisperse CdSe Quantum Dots Encased in Six (100) Facets via Ligand-Controlled Nucleation and Growth.

Zinc-blende CdSe quantum dots (QDs) encased in six equal (100) facets are synthesized in a noncoordinating solvent. Their monodispersed size, unique facet structure, and single crystallinity render the narrowest ensemble photoluminescence for CdSe QDs (full width at half-maximum being 52 meV). The nucleation stage can selectively form small-size CdSe QDs (≤3 nm) as seeds suited for the growth of cube-shaped QDs by reducing the concentration of cadmium carboxylates (Cd(RCOO)2) as the sole source of ligands. While resulting in poorly controlled nucleation, chloride-ion ligands introduced in the form of soluble CdClx(RCOO)1-x (x = 0.1∼0.2) would thermodynamically stabilize the cadmium-terminated (100) facets yet kinetically accelerate the deposition of selenium ions onto the (100) facets. Results suggest that it is fully feasible to synthesize QDs simultaneously with monodisperse size and surface structure through ligand-controlled nucleation and growth.

Facet-Dependent On-Surface Reactions in the Growth of CdSe Nanoplatelets.

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.

Identification of Facet-Dependent Coordination Structures of Carboxylate Ligands on CdSe Nanocrystals.

Aliphatic carboxylates are the most common class of surface ligands to stabilize colloidal nanocrystals. The widely used approach to identify the coordination modes between surface cationic sites and carboxylate ligands is based on the empirical infrared (IR) spectroscopic assignment, which is often ambiguous and thus hampers the practical control of surface structures. In this report, multiple techniques based on nuclear magnetic resonance (NMR) and IR spectra are applied to distinguish the different coordination structures in a series of zinc-blende CdSe nanocrystals with unique facet structures, including nanoplatelets dominated with {100} basal planes, hexahedrons with only three types of low-index facets (i.e., {100}, {110}, and {111}), and spheroidal dots without well-defined facets. Interpretation and assignment of NMR and IR signals were assisted by density functional theory (DFT) calculations. In addition to the identification of facet-sensitive bonding modes, the present methods also allow a nondestructive quantification of mixed ligands.

Quantitative Identification of Basic Growth Channels for Formation of Monodisperse Nanocrystals.

Different mechanisms are proposed to account formation of monodisperse nanocrystals in literature, each of which is usually proposed to explain one set of experimental observations. Here, a general model based on mass conservation is developed to fully describe all possible channels including free growth by direct incorporation of the monomers converted from the precursors, growth by dissolution of a portion of the regular nanocrystals in solution, and growth by dissolution of the clusters in solution. The new model provides convenient yet quantitative methods to determine the channel ratios at a given time. Experimentally, an automated microreactor system is developed and applied for synthesis of monodisperse CdS nanocrystals, which is coupled with liquid-phase Fourier transform infrared and UV-vis measurements to, respectively, determine precursor conversion and size/concentration of nanocrystals with high reproducibility (<1%) and proper time resolution (<1 s). Different from the most-accepted model for formation of monodisperse nanocrystals, a burst of nucleation followed by growth of all nuclei by direct incorporation of the monomers converted from the precursors (or "focusing of size distribution"), all three basic channels are found to coexist during growth of monodisperse CdS nanocrystals. While the new theory and experimental methods are applied to study growth of monodisperse nanocrystals, they can be extended to offer a full kinetic picture for formation of colloidal nanocrystals.