Heteroepitaxial growth of core-shell and core-multishell nanocrystals composed of palladium and gold

The heteroepitaxial growth of the core-shell nanocrystals composed of Pd and Au is developed. Pd nanocubes or Au nano-octahedrons are utilized as the cores. The growths of the Au and Pd shells are realized under similar conditions, where the same reducing agent and stabilizing surfactant are employed. The preparation is highly controllable, and the epitaxial growth is repeated up to three times to yield Pd@Au@Pd@Au and Au@Pd@Au@Pd core-trishell nanocrystals. The thickness of each shell is readily varied by changing the amount of the metal salts used for growth. All of the nanocrystal products have narrow size distributions and are single crystalline. The plasmon resonance properties of these nanocrystals are mainly determined by the exterior shell. The plasmon of the Pd-shell-terminated nanocrystals is suppressed, while that of the Au-shell-terminated ones is recovered and is stronger when the Au shell becomes thicker. This growth method can potentially be extended to other metals for the synthetic design of more complex core-multishell metal nanostructures with desirable optical, catalytic, and magnetic properties.     

Formation of Heteroepitaxy in Different Shapes of Au–CdSe Metal–Semiconductor Hybrid Nanostructures

Formation of heteroepitaxy and designing different‐shaped heterostructured nanomaterials of metal and semiconductor in solution remains a frontier area of research. However, it is evident that the synthesis of such materials is not straightforward and needs a selective approach to retain both metal and semiconductor identities in the reaction system during heterostructure formation. Herein, the epitaxial growth of semiconductor CdSe on selected facets of metal Au seeds is reported and different shapes (flower, tetrapod, and core/shell) hetero‐nanostructures are designed. These results are achieved by controlling the reaction parameters, and by changing the sequence and timing for introduction of different reactant precursors. Direct evidence of the formation of heteroepitaxy between {111} facets of Au and (0001) of wurtzite CdSe is observed during the formation of these three heterostructures. The mechanism of the evolution of these hetero‐nanostructures and formation of their heteroepitaxy with the planes having minimum lattice mismatch are also discussed. This shape‐control growth mechanism in hetero‐nanostructures should be helpful to provide more information for establishing the fundamental study of heteroepitaxial growth for designing new nanomaterials. Such metal–semiconductor nanostructures may have great potential for nonlinear optical properties, in photovoltaic devices, and as chemical sensors.     

Fe2o3 shell growth on Pt nanoparticles

Fe2O3 shells have been synthesized around Pt cores to create Pt@Fe2O3 core-shell nanoparticles. The synthesis conditions allow control of the shell shape and allow the preparation of both hexagonal shells and spherical shells. 2D cross-sectional TEM images show that the cores are not positioned at the centers of the shells. By rotating the nanoparticles and monitoring the apparent motions of the cores in the 2D cross-sectional images, it is possible to determine quantitatively the radial position of the Pt core with respect to the center of the Fe2O3 shell. The distribution of core positions within the core-shell structures is bimodal. These observations suggest that the Fe2O3 shells grow on the Pt cores by a nucleation process, rather than layer-by-layer growth.     

Highly luminescent CdSe/ZnSe core-shell quantum dots of one-pot preparation in octadecene

CdSe/ZnSe core-shell quantum dots were synthesized using a new one-pot procedure where the core was prepared in octadecene. A ZnSe shell around a CdSe nanoparticle was formed by the reaction of selenium-richness on the surfaces of CdSe nanoparticles with Zn2+ from the injected zinc stearate precursor. The optical properties, luminescence kinetics, and the effect of shell thickness of as-prepared QDs were studied, which verifies the high quality of the resulting QDs. The new approach is effective not only for preparing core/shell QDs, but also for reducing the complexity of synthesis, toxicity, and reagent cost.     

CdSe/Cd(x)Zn1-xS core/shell nanocrystals: core morphology and luminescent property

CdSe cores with rod (an aspect ratio of 1.8, d-5 nm) and spherical (an aspect ratio of 1, d-5 nm) morphologies were fabricated by two kinds of organic approaches through adjusting growth processes. Because of large difference of size and morphology, two kinds of cores revealed different absorption spectra. However, these cores exhibited almost same photoluminescence (PL) spectra with a red-emitting PL peak of around 625 nm. This is ascribed that they have a similar size in diameter. A graded Cd(x)Zn1-xS shell of larger band gap was grown around CdSe rods and spheres using oleic acid as a capping agent. Based on the growth kinetics of CdS and ZnS, interfacial segregation was created to preferentially deposit CdS near the core, providing relaxation of the strain at the core/shell interface. For spherical CdSe cores, the homogeneous deposition of the Cd(x)Zn1-xS shell created spherical core/shell nanocrystals (NCs) with a size of 7.1 nm in diameter. In the case of using CdSe cores with rod morphology, the anisotropic aggregation behaviors of CdS monomers on CdSe rods led to the size (approximately 10 nm in diameter) of spherical CdSe/Cd(x)Zn1-xS core/shell NCs with a small difference to the length of the CdSe rod (approximately 8.9 nm). The resulting spherical core/shell NCs created by the rod and spherical cores exhibited almost same PL peak wavelength (652 and 653 nm for using rod and spherical cores, respectively), high PL efficiency up to 50%, and narrow PL spectra (36 and 28 nm of full with at half maximum of PL spectra for the core/shell NCs with CdSe spheres and rods, respectively). These core/shell NCs provide an opportunity for the study of the evolution of PL properties as the shape of semiconductor NCs.     

Thermally induced structural and morphological changes of CdSe/CdS octapods

Branched nanostructures are of great interest because of their promising optical and electronic properties. For successful and reliable integration in applications such as photovoltaic devices, the thermal stability of the nanostructures is of major importance. Here the different domains (CdSe cores, CdS pods) of the heterogeneous octapods are shown to have different thermal stabilities, and heating is shown to induce specific shape changes. The octapods are heated from room temperature to 700 °C, and investigated using (analytical and tomographic) transmission electron microscopy (TEM). At low annealing temperatures, pure Cd segregates in droplets at the outside of the octapods, indicating non-stochiometric composition of the octapods. Furthermore, the tips of the pods lose their faceting and become rounded. Further heating to temperatures just below the sublimation temperature induces growth of the zinc blende core at the expense of the wurtzite pods. At higher temperatures, (500-700 °C), sublimation of the octapods is observed in real time in the TEM. Three-dimensional tomographic reconstructions reveal that the four pods pointing into the vacuum have a lower thermal stability than the four pods that are in contact with the support.     

High‐Gain 200 ns Photodetectors from Self‐Aligned CdS–CdSe Core–Shell Nanowalls

1D core–shell heterojunction nanostructures have great potential for high‐performance, compact optoelectronic devices owing to their high interface area to volume ratio, yet their bottom‐up assembly toward scalable fabrication remains a challenge. Here the site‐controlled growth of aligned CdS–CdSe core–shell nanowalls is reported by a combination of surface‐guided vapor–liquid–solid horizontal growth and selective‐area vapor–solid epitaxial growth, and their integration into photodetectors at wafer‐scale without postgrowth transfer, alignment, or selective shell‐etching steps. The photocurrent response of these nanowalls is reduced to 200 ns with a gain of up to 3.8 × 10³ and a photoresponsivity of 1.2 × 10³ A W^?1, the fastest response at such a high gain ever reported for photodetectors based on compound semiconductor nanostructures. The simultaneous achievement of sub‐microsecond response and high‐gain photocurrent is attributed to the virtues of both the epitaxial CdS–CdSe heterojunction and the enhanced charge‐separation efficiency of the core–shell nanowall geometry. Surface‐guided nanostructures are promising templates for wafer‐scale fabrication of self‐aligned core–shell nanostructures toward scalable fabrication of high‐performance compact photodetectors from the bottom‐up.     

Sequential synthesis of type II colloidal CdTe/CdSe core-shell nanocrystals

Colloidal type II CdTe/CdSe nanocrystals were synthesized by sequential addition of a tri-n-octylphosphine telluride (TOPTe)/TOP solution and several shell-precursor solutions to a CdO/TOP solution; the shell-precursor solutions consisted of CdO and TOPSe in TOP. For the growth of the CdTe core, the TOPTe/TOP solution was swiftly added to the CdO/TOP solution at a higher temperature (300 degrees C) than the growth temperature (250 degrees C). For the growth of the CdSe shell, in contrast, the CdO/TOPSe/TOP solution was slowly added to the CdTe/TOP solution at a lower temperature than the growth temperature (200-240 degrees C). The temporal evolution of the optical properties of the growing core-shell nanocrystals was monitored in detail. During the growth of the CdSe shell, the core-shell nanocrystals exhibited interesting changes in photoluminescence (PL) properties. The highest PL efficiency (approximately 38 %) was detected from core-shell nanocrystals with a CdSe shell thickness of 0.4-0.5 nm (indicated by TEM); the formation of the first monolayer is proposed. Our synthetic approach is well suited to a practical realization of engineering materials with bandgaps in the near-IR and IR spectral ranges.     

Synthesis of core-shell Au@polypyrrole nanocomposite using a dendrimer-template approach

Conducting polymeric nanostructures have been reported recently, which were produced from polypyrrole (PPy), including hollow nanocapsules, nanofibers, nanoporous membranes, nanowires, and nanofilms. In most cases, new synthetic routes were used aimed at controlling specific properties of these conducting nanostructures at the molecular level. In this communication we present a new chemical route to synthesize polypyrrole-based nanocomposites, in which polyamidoamine (PAMAM) dendrimers encapsulating Au nanoparticles are used as template. The two-step synthesis comprises the reduction of Au nanoparticles inside PAMAM molecules followed by PPy polymerization around the PAMAM-Au nanoparticles. The structure of the core-shell PAMAM-gold@polypyrrole nanospheres comprises a 40 nm PPy shell enclosing a core of 3 nm gold nanoparticles, as revealed by Transmission Electronic Microscopy (TEM). This new, environmentally-friendly approach may be suitable to produce hybrid nanomaterials for applications in catalysis, batteries, sensors, and micro/nanoelectronic devices.     

Synthesis of silica/Au core-shell nanostructures by galvanic replacement of silica/Ag in aqueous and alkaline medium

We present here a facile one-step method for the synthesis of silica/Au core-shell nanostructures by exploiting the potential difference of AuCl₄^? and Ag in aqueous as well as alkaline media. Initially, silica/Ag core-shell nanostructures were synthesised by coating Ag nanoparticles on silica core (size ～150 nm) in a two-step process (seeding and growth) and were characterised for their morphological, structural and optical behaviours. A complete coverage of silica core with Ag nanoparticles was seen from scanning electron microscope and transmission electron microscope images. The presence of resonance peaks in the optical spectrum manifests the nature of the shell (thin shell ～413 and 650 nm, thick shell ～434 nm). Galvanic replacement of silica/Ag core-shell nanostructures in chloroauric acid solution (HAuCl₄) was studied in both the aqueous and alkaline medium, where an aqueous environment results into fast and effective replacement as compared to an alkaline medium, which has been confirmed from optical absorption studies. The optical studies showed that in an alkaline environment, on galvanic replacement of Ag with Au, the individual absorption peak of Ag (～414 nm) and Au (～520 nm) disappeared, whereas new absorption wavelengths in higher region (600–800 nm) of electromagnetic spectrum were observed. A detailed mechanism is proposed for the same to explain this behaviour. A range of novel new plasmonic core-shell nanomaterials can be synthesised as an intermediate of this facile one-step reaction.     

Charge transfer and retention in directly coupled Au-CdSe nanohybrids

The energy and charge transfer dynamics of directly coupled Au-CdSe hybrid nanocrystals have been studied using time-resolved photoluminescence (PL) techniques. The PL of such nanohybrids was found to be quenched dramatically compared to that of both CdSe quantum dots and mixtures of CdSe quantum dots with Au nanoparticles. Fluorescence decay curves of the Au-CdSe nanohybrids show three distinct decay channels with the fastest one associated with the transfer of electrons from the CdSe portion to the Au portion. The holes on the CdSe portion created by such charge transfer were then quickly taken away by the solution, while the electrons on the Au portion slowly leaked into the solution as well, thus serving as a reductant for redox reactions. Using a model reaction based on the reduction of methylene blue by the leaking electrons, our photocatalytic experiments indicate that the electrons can be temporarily retained in the Au portion (most likely at the Au-capping agent interface) for a dramatically long timescale, up to 100 min. Finally, by merging all of the observations in the time-resolved PL measurements, we were able to figure out a relatively complete picture of charge transfer and retention in the Au-CdSe nanohybrids. This picture is expected to guide researchers in designing modern photocatalysts and solar cells constructed from nanoscale metal-semiconductor hybrids.      

Road Map for the Controlled Synthesis of CdSe Nanowires,Nanobelts, and Nanosaws—A Step Towards Nanomanufacturing

One‐dimensional (1D) nanostructures of CdSe have been found to exhibit morphologies of nanowires, nanobelts, and nanosaws, but their synthesis is by trial and error. To meet the needs of large‐scale, controlled, and designed synthesis of nanostructures, it is imperative to systematically find experimental conditions under which the desired nanostructures are synthesized reproducibly, in large quantity, and with controlled morphology. This article reports the first systematic study on the growth of 1D CdSe nanostructures by a vapor–liquid–solid (VLS) process by varying a wide range of experimental conditions. Over 150 experiments have been conducted to investigate the morphology dependence of three different types of nanostructures: nanowires, nanobelts, and nanosaws, over various substrate temperatures and pressures. The results of this work yield a road map for the controlled growth of 1D CdSe nanostructures. This research serves as a guidance and “menu” for scaling up of the synthesis of CdSe nanostructures. This is a key step towards the controlled synthesis of nanostructures to meet the needs of many industrial applications of nanomanufacturing.     

Formation of CdSe/CdS/ZnS-Au/SiO2 dual-yolk/shell nanostructures through a Trojan-type inside-out etching strategy

In this work we report the development of a rapid and selective etching strategy to synthesize a dual-yolk/shell nanostructure consisting of semiconductor-metal hybrid nanocrystals and hollow SiO₂ for the first time. By utilizing CdSe/CdS/ZnS quantum dot (CSSQD)/SiO₂ core/shell nanoparticles as the template and aurate hydroxyl complexes [Au(OH) ₄ ^? ] as the Trojan-type inside-out etching agent, rapid formation of CSSQD-Au hybrid nanocrystal dual-yolk and SiO₂ hollow shell occur during the reduction of Au(OH) ₄ ^? on CSSQD cores accompanied by localized hydroxyl-liberation from Au(OH) ₄ ^? at the interface between silica and CSSQD. Unlike surface-protected etching strategies, a selective as well as directional etching takes place from the silica internal surface and the thickness of the silica shell can be controlled by varying the etching time. Moreover, the size of attached Au nanoclusters can be tuned by subsequent light exposure. Consequently, the resulting platform offers a number of attractive features: (1) a new, directional, and rapid etching approach toward the formation of hollow silica nanostructures in solution; (2) semiconductor/metal hybrid nanocrystals as yolks within hollow silica nanospheres have been reported for the first time; and (3) the ability, through light exposure, to tune the size of the attached metal nanoclusters on the encapsulated CSSQD within the hollow silica nanospheres. Most importantly, the synthetic method has the capability of introducing additional guest species (e.g. metals) into a primary yolk (e.g. semiconductor) of hollow silica nanoparticles, potentially leading to many promising applications in fuel cells, photocatalysis, bioimaging, and cancer therapy.      

A novel route to cysteine capped Au–CdSe hybrid nanoparticles

We report the synthesis of cysteine Au–CdSe hybrid core–shell nanoparticles via a facile ‘green’, solution based route. The absorption spectrum of the hybrid particles displays unique excitonic features that vary from CdSe and Au. The X-ray diffraction pattern shows peaks attributed to both the parent materials. The transmission electron microscopy (TEM) images shows well aligned particles with an average size of 15 ± 3 nm. The High Resolution TEM image confirms the core/shell structure of the particles.     

Preparation of a ZnS shell on CdSe quantum dots using a single-molecular ZnS precursor

A simple synthetic route to the preparation of a thin ZnS shell on CdSe quantum dot cores from the air-stable, single-molecular precursor zinc diethyldithiocarbamate, Zn(S(2)CNEt(2))(2), in the three-component solvent system octadec-1-ene/oleylamine/tri-n-octylphosphine (ODE/OLA/TOP) is presented. The one-pot synthesis proceeds through heating of the solution of CdSe cores and the amount of crystalline Zn(S(2)CNEt(2))(2) corresponding to a shell thickness of two monolayers of ZnS to 110-120 °C for 1-2 h. The role of the surfactants OLA and TOP and the significance of the temperature and the amount of Zn(S(2)CNEt(2))(2) have been investigated with optical absorption and luminescence spectroscopy. We show that the presence of both OLA and TOP is crucial for the low-temperature growth and that the amount of precursor corresponding to two monolayers of ZnS results in the highest quality of core/shell CdSe/ZnS quantum dots.     

Fabricating a Homogeneously Alloyed AuAg Shell on Au Nanorods to Achieve Strong,Stable, and Tunable Surface Plasmon Resonances

Colloidal metal nanocrystals with strong, stable, and tunable localized surface plasmon resonances (SPRs) can be useful in a corrosive environment for many applications including field‐enhanced spectroscopies, plasmon‐mediated catalysis, etc. Here, a new synthetic strategy is reported that enables the epitaxial growth of a homogeneously alloyed AuAg shell on Au nanorod seeds, circumventing the phase segregation of Au and Ag encountered in conventional synthesis. The resulting core–shell structured bimetallic nanorods (AuNR@AuAg) have well‐mixed Au and Ag atoms in their shell without discernible domains. This degree of mixing allows AuNR@AuAg to combine the high stability of Au with the superior plasmonic activity of Ag, thus outperforming seemingly similar nanostructures with monometallic shells (e.g., Ag‐coated Au NRs (AuNR@Ag) and Au‐coated Au NRs (AuNR@Au)). AuNR@AuAg is comparable to AuNR@Ag in plasmonic activity, but that it is markedly more stable toward oxidative treatment. Specifically, AuNR@AuAg and AuNR@Ag exhibit similarly strong signals in surface‐enhanced Raman spectroscopy that are some 30‐fold higher than that of AuNR@Au. When incubated with a H₂O₂ solution (0.5 m ), the plasmonic activity of AuNR@Ag immediately and severely decayed, whereas AuNR@AuAg retained its activity intact. Moreover, the longitudinal SPR frequency of AuNR@AuAg can be tuned throughout the red wavelengths (≈620–690 nm) by controlling the thickness of the AuAg alloy shell. The synthetic strategy is versatile to fabricate AuAg alloyed shells on different shaped Au, with prospects for new possibilities in the synthesis and application of plasmonic nanocrystals.     

Breakdown of volume scaling in Auger recombination in CdSe/CdS heteronanocrystals: the role of the core-shell interface

Spatial confinement of electronic excitations in semiconductor nanocrystals (NCs) results in a significant enhancement of nonradiative Auger recombination (AR), such that AR processes can easily dominate the decay of multiexcitons. AR is especially detrimental to lasing applications of NCs, as optical gain in these structures explicitly relies on emission from multiexciton states. In standard NCs, AR rates scale linearly with inverse NC volume. Here, we investigate multiexciton dynamics in hetero-NCs composed of CdSe cores and CdS shells of tunable thickness. We observe a dramatic decrease in the AR rates at the initial stage of shell growth, which cannot be explained by traditional volume scaling alone. Rather, fluorescence-line-narrowing studies indicate that the suppression of AR correlates with the formation of an alloy layer at the core-shell interface suggesting that this effect derives primarily from the "smoothing" of the confinement potential associated with interfacial alloying. These data highlight the importance of NC interfacial structure in the AR process and provide general guidelines for the development of new nanostructures with suppressed AR for future lasing applications.     

Preparation of controllable core-shell gold nanoparticles and its application in detection of silver ions

We report a novel shell technique to prepare controllable core-shell nanoparticles. In this technique, the shell is formed when the core reacts with metal ions and Na(2)S(2)O(3) and the size of the core and thickness of the shell can be controlled. Transmission electron microscopy and X-ray diffraction reveal that the shell consists of insoluble complex salts comprising Au(2)S, AuAgS, and Ag(3)AuS(2). The resulting core-shell nanoparticles obtained at different reaction stages demonstrate that the formation of Au(2)S, AuAgS, and Ag(3)AuS(2) shell proceeds from the outside. The morphological evolution of the particles changes significantly with reaction time demonstrating that formation of the shell results from diffusion in the solid shell. The core-shell nanoparticles produced by this technique can be used as nanosensors to detect Ag(+) in aqueous media with high selectivity and sensitivity. The excellent selectivity for Ag(+) is demonstrated by comparing the response to other metal ions. In addition, our evaluation indicates that gold nanorods offer higher sensitivity than gold nanospheres.     

CdSe/Cd1−x Zn x S core/shell quantum dots with tunable emission: growth and morphology evolution

We demonstrate an organic synthesis to fabricate hydrophobic core/shell CdSe/Cd_1?x Zn _x S quantum dots (QDs) with tunable photoluminescence (PL) between green and red at relatively low temperature using trioctylphosphine S reacted directly with cadmium and zinc acetate. A seeded growth strategy was used for preparing large CdSe cores. Large CdSe cores revealed a rod-like morphology while small one exhibited a spherical shape. Being coated with a Cd_1?x Zn _x S shell on spherical CdSe cores with an average size of 3.9 nm in diameter, core/shell QDs exhibited a cubic morphology (a length of 5 nm). In contrast, the core/shell QDs created using a small core (3.3 nm in diameter) show a spherical morphology. Namely, the anisotropic aggregation behavior of CdS monomers on CdSe cores occurs when the rod-like core is coated with a Cd_1?x Zn _x S shell. CdS interlayer plays an important role for such morphology evolution because all CdSe cores with a pure ZnS shell exhibited a spherical morphology. The PL properties of CdSe/Cd_1?x Zn _x S core/shell QDs depended strongly on the size and morphology of the cores. The QDs revealed a narrow and tunable PL spectrum. It is believed that this facile strategy can be extended to synthesize other core–shell QDs at low temperature.