Abstract:In this paper, we review recent progresses on colloidal growth of 2D nanocrystals.We identify four main sources of anisotropy which lead to the formation of plate-and sheetlike colloidal nanomaterials. Defect induced anisotropy is a growth method which relies on the presence of topological defects at the nanoscale to induce 2D shapes objects. Such a method is particularly important in the growth of metallic nanoobjects. Another way to induce anisotropy is based on ligand engineering. The availability of some nanocrystal facets can be tuned by selectively covering the surface with ligands of tunable thickness. Cadmium chalcogenides nanoplatelets (NPLs) strongly rely on this method which offers atomic control in the thinner direction, down to a few monolayers. 2D objects can also be obtained by post or in situ self-assembly of nanocrystals. This growth method differs from the previous ones in the sense that the elementary objects are not molecular precursors, and is a common method for lead chalcogenide compounds. Finally, anisotropy may simply rely on the lattice anisotropy itself as it is common for rod-like nanocrystals. Colloidally grown Transition Metal DiChalcogenides (TMDC) in particular result from such process. We also present hybrid syntheses which combine several of the previously described methods and other paths, such as cation exchange, which expand the range of available materials. Finally, we discuss in which sense 2D-objects differ from 0D nanocrystals and review some of their applications in optoelectronics, including lasing and photodetection, and biology.
CONSPECTUS: Semiconductors are at the basis of electronics. Up to now, most devices that contain semiconductors use materials obtained from a top down approach with semiconductors grown by molecular beam epitaxy or chemical vapor deposition. Colloidal semiconductor nanoparticles have been synthesized for more than 30 years now, and their synthesis is becoming mature enough that these nanoparticles have started to be incorporated into devices. An important development that recently took place in the field of colloidal quantum dots is the synthesis of two-dimensional (2D) semiconductor nanoplatelets that appear as free-standing nanosheets. These 2D colloidal systems are the newborn in the family of shaped-controlled nanoparticles that started with spheres, was extended with rods and wires, continued with tetrapods, and now ends with platelets. From a physical point of view, these objects bring 1D-confined particles into the colloidal family. It is a notable addition, since these platelets can have a thickness that is controlled with atomic precision, so that no inhomogeneous broadening is observed. Because they have two large free interfaces, mirror charges play an important role, and the binding energy of the exciton is extremely large. These two effects almost perfectly compensate each other, it results in particles with unique spectroscopic properties such as fast fluorescent lifetimes and extreme color purity (narrow full width at half-maximum of their emission spectra). These nanoplatelets with extremely large confinement but very simple and well-defined chemistry are model systems to check and further develop, notably with the incorporation in the models of the organic/inorganic interface, various theoretical approaches used for colloidal particles. From a chemical point of view, these colloidal particles are a model system to study the role of ligands since they have precisely defined facets. In addition, the synthesis of these highly anisotropic objects triggered new research to understand at a mechanistic level how this strong anisotropy could be generated. Luckily, some of the chemical know-how built with the spherical and rod-shaped particles is being transferred, with some adaptation, to 2D systems, so that 2D core/shell and core/crown heterostructures have recently been introduced. These objects are very interesting because they suggest that multiple quantum wells could be grown in solution. From the application point of view, 2D colloidal nanoplatelets offer interesting perspectives when color purity, charge conductivity, or field tunable absorption are required. In this Account, we review the chemical synthesis, the physical properties, and the applications of colloidal semiconductor nanoplatelets with an emphasis on the zinc-blende nanoplatelets that were developed more specifically in our group.
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