Zinc is routinely employed in the synthesis of InP quantum dots (QDs) to improve the photoluminescence efficiency and carrier mobility of the resulting In(Zn)P alloy nanostructures. The exact location of Zn in the final structures and the mechanism by which it enhances the optoelectronic properties of the QDs are debated. We use synchrotron X-ray absorbance spectroscopy to show that the majority of Zn in In(Zn)P QDs is located at their surface as Zn carboxylates. However, a small amount of Zn is present inside the bulk of the QDs with the consequent contraction of their lattice, as confirmed by combining high-resolution high-angle annular dark-field imaging scanning transmission electron microscopy with statistical parameter estimation theory. We further demonstrate that the Zn content and its incorporation into the QDs can be tuned by the ligation of commonly employed Zn carboxylate precursors: the use of highly reactive Zn acetate leads to the formation of undesired Zn₃P₂ and the final nanostructures being characterized by broad optical features, whereas Zn carboxylates with longer carbon chains lead to InP crystals with much lower zinc content and narrow optical features. These results can explain the differences between structural and optical properties of In(Zn)P samples reported across the literature and provide a rational method to tune the amount of Zn in InP nanocrystals and to drive the incorporation of Zn either as surface Zn carboxylate, as a substitutional dopant inside the InP crystal lattice, or even predominantly as Zn₃P₂.

Indium phosphide quantum dots (QDs) have drawn attention as alternatives to cadmium- and lead-based QDs that are currently used as phosphors in lamps and displays. The main drawbacks of InP QDs are, in general, a lower photoluminescence quantum yield (PLQY), a decreased color purity, and poor chemical stability. In this research, we attempted to increase the PLQY and stability of indium phosphide QDs by developing lattice matched InP/MgSe core-shell nanoheterostructures. The choice of MgSe comes from the fact that, in theory, it has a near-perfect lattice match with InP, provided MgSe is grown in the zinc blende crystal structure, which can be achieved by alloying with zinc. To retain lattice matching, we used Zn in both the core and shell and we fabricated InZnP/Zn_xMg_1-xSe core/shell QDs. To identify the most suitable conditions for the shell growth, we first developed a synthesis route to Zn_xMg_1-xSe nanocrystals (NCs) wherein Mg is effectively incorporated. Our optimized procedure was employed for the successful growth of Zn_xMg_1-xSe shells around In(Zn)P QDs. The corresponding core/shell systems exhibit PLQYs higher than those of the starting In(Zn)P QDs and, more importantly, a higher color purity upon increasing the Mg content. The results are discussed in the context of a reduced density of interface states upon using better lattice matched Zn_xMg_1-xSe shells.

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.

Indium antimonide (InSb) quantum dots (QDs) have unique and interesting photophysical properties, but widespread experimentation with InSb QDs is lacking due to the difficulty in synthesizing this material. The key experimental challenge in fabricating InSb QDs is preparing a suitable Sb-precursor in the correct oxidation state that reacts with the In-precursor in a controllable manner. Here, we review and discuss the synthetic strategies for making colloidal InSb QDs and present a new reaction scheme yielding small (∼1 nm diameter) InSb QDs. This was accomplished by employing Sb(NMe₂)₃ as the antimony precursor and by screening different reducing agents that can selectively reduce it to stibine in situ. The released SbH₃, subsequently, reacts with In carboxylate to form small InSb clusters. The absorption features are moderately tunable (from 400 nm to 660 nm) by the amount and rate of reductant addition as well as the temperature of injection and subsequent annealing. Optical properties were probed with transient absorption spectroscopy and show complex time and spectral dependencies.

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.

Over the years, scientists have identified various synthetic "handles" while developing wet chemical protocols for achieving a high level of shape and compositional complexity in colloidal nanomaterials. Halide ions have emerged as one such handle which serve as important surface active species that regulate nanocrystal (NC) growth and concomitant physicochemical properties. Halide ions affect the NC growth kinetics through several means, including selective binding on crystal facets, complexation with the precursors, and oxidative etching. On the other hand, their presence on the surfaces of semiconducting NCs stimulates interesting changes in the intrinsic electronic structure and interparticle communication in the NC solids eventually assembled from them. Then again, halide ions also induce optoelectronic tunability in NCs where they form part of the core, through sheer composition variation. In this review, we describe these roles of halide ions in the growth of nanostructures and the physical changes introduced by them and thereafter demonstrate the commonality of these effects across different classes of nanomaterials.

Nanoscale materials have long promised to revolutionize science and technology, with claims being sustained by both the advances in their fabrication and by the many fundamental studies that have been carried out to date, which have revealed fascinating properties when materials dimensions shrink all the way down to a few hundreds/thousands of atoms. In this ongoing hype, on one side we have the futuristic views and promises of ubiquitous devices in which the operating units will be eventually scaled down to individual atoms or molecules. On the other side, we have the more realistic (and already unfolding) scenario represented by nanoscale materials making their way in a wide variety of applications (not always and not necessarily flagged as “high-tech”) where downsizing truly brings about new or improved features that can be immediately exploited for some practical use. These applications have encompassed fields as disparate as medicine, biology, energy conversion and storage, catalysis, sensing, nanocomposite engineering, cosmetics, to cite the most popular ones. For a new technology to be pervasive and disruptive, the costs associated to the fabrication, the characterization and the assemblage of its key components have to drop quickly over time, while at the same time the material quality and the reproducibility of the various processes must keep improving. In the case of nanomaterials, we have not yet witnessed such an ubiquitous revolution, and one of the reasons is probably the lack of straightforward and reproducible synthetic protocols providing large amounts of nanomaterials and thus capable of efficient up-scaling to fulfil industrial needs. Another reason likely resides in the growing concern that nanomaterials will pose new threats to the environment, but this aspect will not be investigated here. In this review, we will touch upon the critical feature of nanomaterials science and engineering dealing with the high throughput synthesis, with a focus on materials prepared in the liquid phase, where the expertise of the authors of this review lays. As a note of caution to the reader, we will not cover in depth all existing approaches to large scale syntheses. Our discussion will be instead a broad summary of the main types of synthetic approaches developed to date, and which we believe will be useful to scientists and engineers who are approaching the fabrication of nanomaterials with an eye on their use in large-scale, industrial applications. The review has been written according to the principle “from the simple to the complex”: it begins with the simplest one-batch heat-up synthesis approach, followed by hot-injection methods and ends by discussing the more sophisticated continuous flow syntheses of nanoparticles. Similarly, in each section, wherever possible, the discussion will start from simpler compounds, (for example, one-component noble metal nanocrystals), and will then move on to more complex structures (from binary to ternary and even quaternary compounds, which will be mainly metal oxides and chalcogenides).

Colloidal quantum dots (QDs) show great promise as LED phosphors due to their tunable narrow-band emission and ability to produce high-quality white light. Currently, the most suitable QDs for lighting applications are based on cadmium, which presents a toxicity problem for consumer applications. The most promising cadmium-free candidate QDs are based on InP, but their quality lags much behind that of cadmium based QDs. This is not only because the synthesis of InP QDs is more challenging than that of Cd-based QDs, but also because the large lattice parameter of InP makes it difficult to grow an epitaxial, defect-free shell on top of such material. Here, we propose a viable approach to overcome this problem by alloying InP nanocrystals with Zn²⁺ ions, which enables the synthesis of In_xZn_yP alloy QDs having lattice constant that can be tuned from 5.93 Å (pure InP QDs) down to 5.39 Å by simply varying the concentration of the Zn precursor. This lattice engineering allows for subsequent strain-free, epitaxial growth of a ZnSe_zS_1-z shell with lattice parameters matching that of the core. We demonstrate, for a wide range of core and shell compositions (i.e.; varying x, y, and z), that the photoluminescence quantum yield is maximal (up to 60%) when lattice mismatch is minimal.