Ou Chen

Compact high-quality CdSe–CdS core–shell nanocrystals with narrow emission linewidths and suppressed blinking

High particle uniformity, high photoluminescence quantum yields, narrow and symmetric emission spectral lineshapes and minimal single-dot emission intermittency (known as blinking) have been recognized as universal requirements for the successful use of colloidal quantum dots in nearly all optical applications. However, synthesizing samples that simultaneously meet all these four criteria has proven challenging. Here, we report the synthesis of such high-quality CdSe-CdS core-shell quantum dots in an optimized process that maintains a slow growth rate of the shell through the use of octanethiol and cadmium oleate as precursors. In contrast with previous observations, single-dot blinking is significantly suppressed with only a relatively thin shell. Furthermore, we demonstrate the elimination of the ensemble luminescence photodarkening that is an intrinsic consequence of quantum dot blinking statistical ageing. Furthermore, the small size and high photoluminescence quantum yields of these novel quantum dots render them superior in vivo imaging agents compared with conventional quantum dots. We anticipate these quantum dots will also result in significant improvement in the performance of quantum dots in other applications such as solid-state lighting and illumination.

Self-assembled colloidal superparticles from nanorods

Beyond Quantum Dots Semiconducting colloidal nanoparticles—quantum dots—are of interest for their unusual properties. One current challenge is the controlled assembly of colloidal particles into larger structures, such as two-dimensional lattices on a substrate, or three-dimensional superparticles. Wang et al. (p. 358) present a two-step self-assembly of CdSe/CdS semiconductor nanorods to form mesoscopic colloidal superparticles. The particles show well-defined super-crystalline domains with dimensions ranging from hundreds of nanometers to several microns, and with the particle morphology controlled by the number of constituent rods. Films of the needle-shaped superparticles were able to act as polarizing light-emitting diodes. Colloidal rods self-assemble into semiconducting superparticles with a shape controlled by the number of rods. Colloidal superparticles are nanoparticle assemblies in the form of colloidal particles. The assembly of nanoscopic objects into mesoscopic or macroscopic complex architectures allows bottom-up fabrication of functional materials. We report that the self-assembly of cadmium selenide–cadmium sulfide (CdSe-CdS) core-shell semiconductor nanorods, mediated by shape and structural anisotropy, produces mesoscopic colloidal superparticles having multiple well-defined supercrystalline domains. Moreover, functionality-based anisotropic interactions between these CdSe-CdS nanorods can be kinetically introduced during the self-assembly and, in turn, yield single-domain, needle-like superparticles with parallel alignment of constituent nanorods. Unidirectional patterning of these mesoscopic needle-like superparticles gives rise to the lateral alignment of CdSe-CdS nanorods into macroscopic, uniform, freestanding polymer films that exhibit strong photoluminescence with a striking anisotropy, enabling their use as downconversion phosphors to create polarized light-emitting diodes.

On Doping CdS/ZnS Core/Shell Nanocrystals with Mn

This paper presents a mechanistic study on the doping of CdS/ZnS core/shell semiconductor nanocrystals with Mn based on a three-step synthesis, which includes host-particle synthesis, Mn-dopant growth, and ZnS-shell growth. We used a combination of electron paramagnetic resonance spectroscopy (EPR) and inductively coupled plasma atomic emission spectroscopy (ICP) to monitor Mn-doping level and growth yield during doping synthesis at both the dopant-growth and ZnS-shell-growth steps. First, our kinetic study shows that Mn adsorption onto the nanocrystal surface includes the formation of weakly and strongly bound Mn. The formation of weakly bound Mn is associated with a chemical equilibrium between adsorbed Mn species on the nanocrystal surface and free Mn species in growth solution, while the formation of strongly bound Mn exhibits first-order kinetics with an activation-energy barrier of 211 +/- 13 kJ/mol. Second, our results demonstrate that both weakly and strongly bound Mn can be removed from the surface of nanocrystals during ZnS-shell growth. The replacement of strongly bound Mn requires a higher temperature than that of weakly bound Mn. The yield of the replacement of strongly bound Mn is strongly dependent on the temperature of ZnS-shell growth. Third, our results show that the Mn-growth yield is not dependent on the size and crystal structure of nanocrystals. All together, these results suggest a mechanism in which nanocrystal doping is determined by the chemical kinetics of three activation-controlled processes: dopant adsorption, replacement, and ZnS-shell growth.

Magneto-fluorescent core-shell supernanoparticles

Magneto-fluorescent particles have been recognized as an emerging class of materials that exhibit great potential in advanced applications. However, synthesizing such magneto-fluorescent nanomaterials that simultaneously exhibit uniform and tunable sizes, high magnetic content loading, maximized fluorophore coverage at the surface, and a versatile surface functionality has proven challenging. Here we report a simple approach for co-assembling magnetic nanoparticles with fluorescent quantum dots to form colloidal magneto-fluorescent supernanoparticles. Importantly, these supernanoparticles exhibit a superstructure consisting of a close packed magnetic nanoparticle “core” which is fully surrounded by a “shell” of fluorescent quantum dots. A thin layer of silica-coating provides high colloidal stability and biocompatiblity and a versatile surface functionality. We demonstrate that after surface pegylation, these silica-coated magneto-fluorescent supernanoparticles can be magnetically manipulated inside living cells while being optically tracked. Moreover, our silica-coated magneto-fluorescent supernanoparticles can also serve as an in vivo multi-photon and magnetic resonance dual-modal imaging probe.

Surface-functionalization-dependent optical properties of II-VI semiconductor nanocrystals.

We report a study of the surface-functionalization-dependent optical properties of II-VI zinc-blende semiconductor nanocrystals on the basis of ligand-exchange chemistry, isomaterial core/shell growth, optical spectroscopy, transmission electron microscopy, and X-ray powder diffraction. Our results show that the transition energy and extinction coefficient of the 2S(h3/2)1S(e) excitonic band of these nanocrystals can be strongly modified by their surface ligands as well as ligand associated surface atomic arrangement. The oleylamine exchange of oleate-capped zinc-blende II-VI nanocrystals narrows the energy gap between their first and second excitonic absorption bands, and this narrowing effect is size-dependent. The oleylamine exchange results in the quenching, subsequent recovery, and even enhancing of the photoluminescence emission of these II-VI semiconductor nanocrystals. In addition, the results from our X-ray powder diffraction measurements and simulations completely rule out the possibility that oleate-capped zinc-blende CdSe nanocrystals can undergo zinc-blende-to-wurtzite crystal transformation upon ligand exchange with oleylamine. Moreover, our theoretical modeling results suggest that the surface-functionalization-dependent optical properties of these semiconductor nanocrystals can be caused by a thin type II isomaterial shell that is created by the negatively charged ligands (e.g., oleate and octadecyl phosphonate). Taking all these results together, we provide the unambiguous identification that II-VI semiconductor nanocrystals exhibit surface-functionalization-dependent excitonic absorption features.

Cylindrical Superparticles from Semiconductor Nanorods

In this communication, we report a synthesis of anisotropic colloidal superparticles (SPs) from CdSe/CdS semiconductor nanorods. These anisotropic SPs are cylindrical disks or stacked-disk arrays. We attribute the major driving forces controlling the SP shape to interparticle interactions between nanorods and solvophobic interactions between a superparticle and its surrounding solvent. According to their sizes (or volumes), the SPs adopt either single- or multilayered structures. In addition, these SPs exhibit linearly polarized emissions, demonstrating their potential role as useful components in devices such as polarized light-emitting diodes and electrooptical modulators.

Direct probe of spectral inhomogeneity reveals synthetic tunability of single-nanocrystal spectral linewidths

The spectral linewidth of an ensemble of fluorescent emitters is dictated by the combination of single-emitter linewidths and sample inhomogeneity. For semiconductor nanocrystals, efforts to tune ensemble linewidths for optical applications have focused primarily on eliminating sample inhomogeneities, because conventional single-molecule methods cannot reliably build accurate ensemble-level statistics for single-particle linewidths. Photon-correlation Fourier spectroscopy in solution (S-PCFS) offers a unique approach to investigating single-nanocrystal spectra with large sample statistics and high signal-to-noise ratios, without user selection bias and at fast timescales. With S-PCFS, we directly and quantitatively deconstruct the ensemble linewidth into contributions from the average single-particle linewidth and from sample inhomogeneity. We demonstrate that single-particle linewidths vary significantly from batch to batch and can be synthetically controlled. These findings delineate the synthetic challenges facing underdeveloped nanomaterials such as InP and InAs core-shell particles and introduce new avenues for the synthetic optimization of fluorescent nanoparticles.

Formation of Heterodimer Nanocrystals: UO2/In2O3 and FePt/In2O3

This Article reports a mechanistic study on the formation of colloidal UO(2)/In(2)O(3) and FePt/In(2)O(3) heterodimer nanocrystals. These dimer nanocrystals were synthesized via the growth of In(2)O(3) as the epitaxial material onto the seed nanocrystals of UO(2) or FePt. The resulting dimer nanocrystals were characterized using X-ray powder diffraction (XRD), energy dispersion spectroscopy, transmission electron microscopy (TEM), scanning transmission electron microscopy, and high-resolution TEM (HRTEM). The results from XRD and HRTEM clearly show that lattice strains exist in both of these dimer nanocrystals. Interestingly, the lattice of In(2)O(3) expands in UO(2)/In(2)O(3) dimers, whereas FePt/In(2)O(3) dimers exhibit compressed In(2)O(3) lattices. Using HRTEM and nanocrystal structure simulations, we have identified the crystallographic orientation of the attachment of the two segments in these two types of dimers. An unconventional Miller index was introduced to describe the crystallographic orientation of these heterodimer nanocrystals. On the basis of the results herein as well as those from other researchers, we propose an empirical law for the determination of the crystallographic attachment orientation in heterodimers: instead of growth on the facet of the seed nanocrystals where lattice mismatch is minimized, the growth of an epitaxial material often chooses the crystal facets where the first atomic monolayer of this material has the strongest affinity for the seed nanocrystals.

Next-generation in vivo optical imaging with short-wave infrared quantum dots

For in vivo imaging, the short-wavelength infrared region (SWIR; 1000–2000 nm) provides several advantages over the visible and near-infrared regions: general lack of autofluorescence, low light absorption by blood and tissue, and reduced scattering. However, the lack of versatile and functional SWIR emitters has prevented the general adoption of SWIR imaging by the biomedical research community. Here, we introduce a class of high-quality SWIR-emissive indium-arsenide-based quantum dots (QDs) that are readily modifiable for various functional imaging applications, and that exhibit narrow and size-tunable emission and a dramatically higher emission quantum yield than previously described SWIR probes. To demonstrate the unprecedented combination of deep penetration, high spatial resolution, multicolor imaging and fast-acquisition-speed afforded by the SWIR QDs, we quantified, in mice, the metabolic turnover rates of lipoproteins in several organs simultaneously and in real time as well as heartbeat and breathing rates in awake and unrestrained animals, and generated detailed three-dimensional quantitative flow maps of the mouse brain vasculature.

Evolution of the Single-Nanocrystal Photoluminescence Linewidth with Size and Shell: Implications for Exciton–Phonon Coupling and the Optimization of Spectral Linewidths

The optimization of photoluminescence spectral linewidths in semiconductor nanocrystal preparations involves minimizing both the homogeneous and inhomogeneous contributions to the ensemble spectrum. Although the inhomogeneous contribution can be controlled by eliminating interparticle inhomogeneities, far less is known about how to synthetically control the homogeneous, or single-nanocrystal, spectral linewidth. Here, we use solution photon-correlation Fourier spectroscopy (S-PCFS) to measure how the sample-averaged single-nanocrystal emission linewidth of CdSe core and core/shell nanocrystals change with systematic changes in the size of the cores and the thickness and composition of the shells. We find that the single-nanocrystal linewidth at room temperature is heavily influenced by the nature of the CdSe surface and the epitaxial shell, which have a profound impact on the internal electric fields that affect exciton-phonon coupling. Our results explain the wide variations, both experimental and theoretical, in the magnitude and size dependence in previous reports on exciton-phonon coupling in CdSe nanocrystals. Moreover, our findings offer a general pathway for achieving the narrow spectral linewidths required for many applications of nanocrystals.