Colloidal nanocrystal synthesis and the organic–inorganic interface
TL;DR: Colloidal nanocrystals are solution-grown, nanometre-sized, inorganic particles that are stabilized by a layer of surfactants attached to their surface, which makes these structures attractive and promising building blocks for advanced materials and devices.
Abstract: Colloidal nanocrystals are solution-grown, nanometre-sized, inorganic particles that are stabilized by a layer of surfactants attached to their surface. The inorganic cores possess useful properties that are controlled by their composition, size and shape, and the surfactant coating ensures that these structures are easy to fabricate and process further into more complex structures. This combination of features makes colloidal nanocrystals attractive and promising building blocks for advanced materials and devices. Chemists are achieving ever more exquisite control over the composition, size, shape, crystal structure and surface properties of nanocrystals, thus setting the stage for fully exploiting the potential of these remarkable materials.
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9,432 citations
TL;DR: Nanocrystals (NCs) discussed in this Review are tiny crystals of metals, semiconductors, and magnetic material consisting of hundreds to a few thousand atoms each that are among the hottest research topics of the last decades.
Abstract: Nanocrystals (NCs) discussed in this Review are tiny crystals of metals, semiconductors, and magnetic material consisting of hundreds to a few thousand atoms each. Their size ranges from 2-3 to about 20 nm. What is special about this size regime that placed NCs among the hottest research topics of the last decades? The quantum mechanical coupling * To whom correspondence should be addressed. E-mail: dvtalapin@uchicago.edu. † The University of Chicago. ‡ Argonne National Lab. Chem. Rev. 2010, 110, 389–458 389
3,720 citations
TL;DR: It is demonstrated that electrical charges on sterically stabilized nanoparticles determine B NSL stoichiometry; additional contributions from entropic, van der Waals, steric and dipolar forces stabilize the variety of BNSL structures.
Abstract: The assembly of nanoparticles of two different materials into a binary nanoparticle superlattice is a promising way of synthesizing a large variety of materials (metamaterials) with precisely controlled chemical composition and tight placement of the components. In theory only a few stable binary superlattice structures can assemble from hard spheres, potentially limiting this approach. But all is not lost because at the nanometre scale there are additional forces (electrostatic, van der Waals and dipolar) that can stabilize binary nanoparticulate structures. Shevchenko et al. now report the synthesis of a dozen novel structures from various combinations of metal, semiconductor, magnetic and dielectric nanoparticles. This demonstrates the potential of self-assembly in designing families of novel materials and metamaterials with programmable physical and chemical properties. Assembly of small building blocks such as atoms, molecules and nanoparticles into macroscopic structures—that is, ‘bottom up’ assembly—is a theme that runs through chemistry, biology and material science. Bacteria1, macromolecules2 and nanoparticles3 can self-assemble, generating ordered structures with a precision that challenges current lithographic techniques. The assembly of nanoparticles of two different materials into a binary nanoparticle superlattice (BNSL)3,4,5,6,7 can provide a general and inexpensive path to a large variety of materials (metamaterials) with precisely controlled chemical composition and tight placement of the components. Maximization of the nanoparticle packing density has been proposed as the driving force for BNSL formation3,8,9, and only a few BNSL structures have been predicted to be thermodynamically stable. Recently, colloidal crystals with micrometre-scale lattice spacings have been grown from oppositely charged polymethyl methacrylate spheres10,11. Here we demonstrate formation of more than 15 different BNSL structures, using combinations of semiconducting, metallic and magnetic nanoparticle building blocks. At least ten of these colloidal crystalline structures have not been reported previously. We demonstrate that electrical charges on sterically stabilized nanoparticles determine BNSL stoichiometry; additional contributions from entropic, van der Waals, steric and dipolar forces stabilize the variety of BNSL structures.
1,981 citations
TL;DR: Mechanistic studies have shown that monodisperse nanocrystals are produced when the burst of nucleation that enables separation of the nucleation and growth processes is combined with the subsequent diffusion-controlled growth process through which the crystal size is determined.
Abstract: Much progress has been made over the past ten years on the synthesis of monodisperse spherical nanocrystals. Mechanistic studies have shown that monodisperse nanocrystals are produced when the burst of nucleation that enables separation of the nucleation and growth processes is combined with the subsequent diffusion-controlled growth process through which the crystal size is determined. Several chemical methods have been used to synthesize uniform nanocrystals of metals, metal oxides, and metal chalcogenides. Monodisperse nanocrystals of CdSe, Co, and other materials have been generated in surfactant solution by nucleation induced at high temperature, and subsequent aging and size selection. Monodisperse nanocrystals of many metals and metal oxides, including magnetic ferrites, have been synthesized directly by thermal decomposition of metal-surfactant complexes prepared from the metal precursors and surfactants. Nonhydrolytic sol-gel reactions have been used to synthesize various transition-metal-oxide nanocrystals. Monodisperse gold nanocrystals have been obtained from polydisperse samples by digestive-ripening processes. Uniform-sized nanocrystals of gold, silver, platinum, and palladium have been synthesized by polyol processes in which metal salts are reduced by alcohols in the presence of appropriate surfactants.
1,765 citations
TL;DR: A ligand-assisted reprecipitation strategy is developed to fabricate brightly luminescent and color-tunable colloidal CH3NH3PbX3 quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies, expected to exhibit interesting nanoscale excitonic properties.
Abstract: Organometal halide perovskites are inexpensive materials with desirable characteristics of color-tunable and narrow-band emissions for lighting and display technology, but they suffer from low photoluminescence quantum yields at low excitation fluencies. Here we developed a ligand-assisted reprecipitation strategy to fabricate brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies. To illustrate the photoluminescence enhancements in these quantum dots, we conducted comprehensive composition and surface characterizations and determined the time- and temperature-dependent photoluminescence spectra. Comparisons between small-sized CH3NH3PbBr3 quantum dots (average diameter 3.3 nm) and corresponding micrometer-sized bulk particles (2–8 μm) suggest that the intense increased photoluminescence quantum yield originates from the increase of exciton binding energy due to size reduction as well a...
1,756 citations
Cites background from "Colloidal nanocrystal synthesis and..."
...33 Introduction of capping ligands on the surface of nanoparticles has been extensively investigated and has become an increasingly mature strategy to control their size and morphology.(34,35) This inspired us to control the crystallization of CH3NH3PbX3 in the reprecipitation process by varying the surface ligands....
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References
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TL;DR: In this article, the authors focus on the properties of quantum dots and their ability to join the dots into complex assemblies creates many opportunities for scientific discovery, such as the ability of joining the dots to complex assemblies.
Abstract: Current research into semiconductor clusters is focused on the properties of quantum dots-fragments of semiconductor consisting of hundreds to many thousands of atoms-with the bulk bonding geometry and with surface states eliminated by enclosure in a material that has a larger band gap. Quantum dots exhibit strongly size-dependent optical and electrical properties. The ability to join the dots into complex assemblies creates many opportunities for scientific discovery.
10,737 citations
"Colloidal nanocrystal synthesis and..." refers background in this paper
...Organic–inorganic interface and dynamic solvation Surfactant-coated nanocrystals, in which an inorganic core is surrounded by a ‘monolayer’ of organic molecules, hold the potential for the creation of new material...
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TL;DR: Semiconductor nanocrystals prepared for use as fluorescent probes in biological staining and diagnostics have a narrow, tunable, symmetric emission spectrum and are photochemically stable.
Abstract: Semiconductor nanocrystals were prepared for use as fluorescent probes in biological staining and diagnostics. Compared with conventional fluorophores, the nanocrystals have a narrow, tunable, symmetric emission spectrum and are photochemically stable. The advantages of the broad, continuous excitation spectrum were demonstrated in a dual-emission, single-excitation labeling experiment on mouse fibroblasts. These nanocrystal probes are thus complementary and in some cases may be superior to existing fluorophores.
8,542 citations
"Colloidal nanocrystal synthesis and..." refers background in this paper
...These colloidal quantum dots are now widely employed as targeted fluorescent labels in biomedical research application...
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TL;DR: In this paper, a simple route to the production of high-quality CdE (E=S, Se, Te) semiconductor nanocrystallites is presented, based on pyrolysis of organometallic reagents by injection into a hot coordinating solvent.
Abstract: A simple route to the production of high-quality CdE (E=S, Se, Te) semiconductor nanocrystallites is presented. Crystallites from ∼12 A to ∼115 A in diameter with consistent crystal structure, surface derivatization, and a high degree of monodispersity are prepared in a single reaction. The synthesis is based on the pyrolysis of organometallic reagents by injection into a hot coordinating solvent. This provides temporally discrete nucleation and permits controlled growth of macroscopic quantities of nanocrystallites. Size selective precipitation of crystallites from Portions of the growth solution isolates samples with narrow size distributions (<5% rms in diameter). High sample quality results in sharp absorption features and strong «band-edge» emission which is tunable with particle size and choice of material
8,374 citations
TL;DR: The new generations of qdots have far-reaching potential for the study of intracellular processes at the single-molecule level, high-resolution cellular imaging, long-term in vivo observation of cell trafficking, tumor targeting, and diagnostics.
Abstract: Research on fluorescent semiconductor nanocrystals (also known as quantum dots or qdots) has evolved over the past two decades from electronic materials science to biological applications. We review current approaches to the synthesis, solubilization, and functionalization of qdots and their applications to cell and animal biology. Recent examples of their experimental use include the observation of diffusion of individual glycine receptors in living neurons and the identification of lymph nodes in live animals by near-infrared emission during surgery. The new generations of qdots have farreaching potential for the study of intracellular processes at the single-molecule level, high-resolution cellular imaging, long-term in vivo observation of cell trafficking, tumor targeting, and diagnostics.
7,499 citations
"Colloidal nanocrystal synthesis and..." refers background in this paper
...These colloidal quantum dots are now widely employed as targeted fluorescent labels in biomedical research application...
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