Nanometre-size inorganic dots, tubes and wires exhibit a wide range of electrical and optical properties that depend sensitively on both size and shape, and are of both fundamental and technological interest. In contrast to the syntheses of zero-dimensional systems, existing preparations of one-dimensional systems often yield networks of tubes or rods which are difficult to separate. And, in the case of optically active II-VI and III-V semiconductors, the resulting rod diameters are too large to exhibit quantum confinement effects. Thus, except for some metal nanocrystals, there are no methods of preparation that yield soluble and monodisperse particles that are quantum-confined in two of their dimensions. For semiconductors, a benchmark preparation is the growth of nearly spherical II-VI and III-V nanocrystals by injection of precursor molecules into a hot surfactant. Here we demonstrate that control of the growth kinetics of the II-VI semiconductor cadmium selenide can be used to vary the shapes of the resulting particles from a nearly spherical morphology to a rod-like one, with aspect ratios as large as ten to one. This method should be useful, not only for testing theories of quantum confinement, but also for obtaining particles with spectroscopic properties that could prove advantageous in biological labelling experiments and as chromophores in light-emitting diodes.
We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.
Key limitations of the colloidal semiconductor nanorods that have been reported so far are a significant distribution of lengths and diameters as well as the presence of irregular shapes produced by the current synthetic routes and, finally, the poor ability to fabricate large areas of oriented nanorod arrays. Here, we report a seeded-growth approach to the synthesis of asymmetric core-shell CdSe/CdS nanorods with regular shapes and narrow distributions of rod diameters and lengths, the latter being easily tunable up to 150 nm. These rods are highly fluorescent and show linearly polarized emission, whereby the emission energy depends mainly on the core diameter. We demonstrate their lateral alignment as well as their vertical self-alignment on substrates up to areas of several square micrometers.
The formation of extremely high aspect ratio CdSe nanorods (30:1), as well as arrow-, teardrop-, tetrapod-, and branched tetrapod-shaped nanocrystals of CdSe, has been achieved by growth of the nanoparticles in a mixture of hexylphosphonic acid and trioctylphosphine oxide. The most influential factors in shape control are the ratio of surfactants, injection volume, and time-dependent monomer concentration.
Lead halide perovskites (LHPs) in the form of nanometre-sized colloidal crystals, or nanocrystals (NCs), have attracted the attention of diverse materials scientists due to their unique optical versatility, high photoluminescence quantum yields and facile synthesis. LHP NCs have a 'soft' and predominantly ionic lattice, and their optical and electronic properties are highly tolerant to structural defects and surface states. Therefore, they cannot be approached with the same experimental mindset and theoretical framework as conventional semiconductor NCs. In this Review, we discuss LHP NCs historical and current research pursuits, challenges in applications, and the related present and future mitigation strategies explored.
Nanoscale materials are currently being exploited as active components in a wide range of technological applications in various fields, such as composite materials, chemical sensing, biomedicine, optoelectronics and nanoelectronics. Colloidal nanocrystals are promising candidates in these fields, due to their ease of fabrication and processibility. Even more applications and new functional materials might emerge if nanocrystals could be synthesized in shapes of higher complexity than the ones produced by current methods (spheres, rods, discs). Here, we demonstrate that polytypism, or the existence of two or more crystal structures in different domains of the same crystal, coupled with the manipulation of surface energy at the nanoscale, can be exploited to produce branched inorganic nanostructures controllably. For the case of CdTe, we designed a high yield, reproducible synthesis of soluble, tetrapod-shaped nanocrystals through which we can independently control the width and length of the four arms.
Metal halide perovskites represent a flourishing area of research, which is driven by both their potential application in photovoltaics and optoelectronics and by the fundamental science behind their unique optoelectronic properties. The emergence of new colloidal methods for the synthesis of halide perovskite nanocrystals, as well as the interesting characteristics of this new type of material, has attracted the attention of many researchers. This review aims to provide an up-to-date survey of this fast-moving field and will mainly focus on the different colloidal synthesis approaches that have been developed. We will examine the chemistry and the capability of different colloidal synthetic routes with regard to controlling the shape, size, and optical properties of the resulting nanocrystals. We will also provide an up-to-date overview of their postsynthesis transformations, and summarize the various solution processes that are aimed at fabricating halide perovskite-based nanocomposites. Furthermore, we will review the fundamental optical properties of halide perovskite nanocrystals by focusing on their linear optical properties, on the effects of quantum confinement, and on the current knowledge of their exciton binding energies. We will also discuss the emergence of nonlinear phenomena such as multiphoton absorption, biexcitons, and carrier multiplication. Finally, we will discuss open questions and possible future directions.
Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today's strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. The performance of inorganic NC-based photovoltaic and light-emitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where very few semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. New phenomena are constantly being discovered in the photophysics of NCs and in the electronic properties of NC solids. In this Nano Focus, we review the state of the art in research on colloidal NCs focusing on the most recent works published in the last 2 years.
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