Surface Of Colloidal Nanocrystals Research Articles

Defect Passivation in Lead‐Halide Perovskite Nanocrystals and Thin Films: Toward Efficient LEDs and Solar Cells

AbstractLead‐halide perovskites (LHPs), in the form of both colloidal nanocrystals (NCs) and thin films, have emerged over the past decade as leading candidates for next‐generation, efficient light‐emitting diodes (LEDs) and solar cells. Owing to their high photoluminescence quantum yields (PLQYs), LHPs efficiently convert injected charge carriers into light and vice versa. However, despite the defect‐tolerance of LHPs, defects at the surface of colloidal NCs and grain boundaries in thin films play a critical role in charge‐carrier transport and nonradiative recombination, which lowers the PLQYs, device efficiency, and stability. Therefore, understanding the defects that play a key role in limiting performance, and developing effective passivation routes are critical for achieving advances in performance. This Review presents the current understanding of defects in halide perovskites and their influence on the optical and charge‐carrier transport properties. Passivation strategies toward improving the efficiencies of perovskite‐based LEDs and solar cells are also discussed.

Defect Passivation in Lead-Halide Perovskite Nanocrystals and Thin Films: Toward Efficient LEDs and Solar Cells.

Lead‐halide perovskites (LHPs), in the form of both colloidal nanocrystals (NCs) and thin films, have emerged over the past decade as leading candidates for next‐generation, efficient light‐emitting diodes (LEDs) and solar cells. Owing to their high photoluminescence quantum yields (PLQYs), LHPs efficiently convert injected charge carriers into light and vice versa. However, despite the defect‐tolerance of LHPs, defects at the surface of colloidal NCs and grain boundaries in thin films play a critical role in charge‐carrier transport and nonradiative recombination, which lowers the PLQYs, device efficiency, and stability. Therefore, understanding the defects that play a key role in limiting performance, and developing effective passivation routes are critical for achieving advances in performance. This Review presents the current understanding of defects in halide perovskites and their influence on the optical and charge‐carrier transport properties. Passivation strategies toward improving the efficiencies of perovskite‐based LEDs and solar cells are also discussed.

Library Design of Ligands at the Surface of Colloidal Nanocrystals

Surfaces-and interfaces-are ubiquitous at the nanoscale. Their relevance to nanoscience and nanotechnology is therefore inherent. Colloidal inorganic nanocrystals (NCs), which can show more than a half of their atoms at the surface, are paradigmatic of the role of surfaces in determining materials' form and functions. Therefore, colloidal NCs may be regarded as soluble surfaces, allowing convenient study of ensemble structure and properties in the solution phase.Colloidal NCs commonly bear chemical species at their surface. Such species (generally referred to as ligands) are introduced already in the synthetic procedures and are added postsynthesis in surface chemistry modification (ligand exchange) reactions. Ligands (i) affect the reactivity and diffusion of the synthetic precursors, (ii) mediate NC interactions with the surroundings, and (iii) contribute to the overall electronic structure. In principle, a vast amount of ligands, as large as our imagination, could be used to coordinate the surface of colloidal NCs. In practice and despite the plethora of studies on NC surface chemistry, a relatively limited number of ligands have been explored. In addition, the importance of designing a set of ligands with tailored features (a ligand library), which may permit comprehensive discussion and explanation of the role of surfaces in the NC structure and properties, is often overlooked. Ligand libraries may also foster heuristic access to novel, unexpected observations.Here, the rational design of ligand libraries is discussed, suggesting that it may be a general method to advance knowledge on colloidal NCs and nanomaterials at large.First, a general ligand framework is introduced. The main subunits are identified: ligands are constituted by a binding group and a pendant moiety, bearing functional substituent groups. On this basis, ligand binding at the NC surface is discussed borrowing concepts from coordination chemistry. Dynamic equilibria at the NC surface are highlighted, revealing the compromise between forming and breaking bonds at interfaces and its intricate interplay with the surroundings. Tailoring of the ligand subunits may impart functions to the whole ligand, eventually transposable to the ligated NC.On these bases, it is shown how ligand design may be exploited to (i) exert control on the size and shape of the NCs, (ii) determine NCs' dispersibility in a solvent and affect their self-assembly, and (iii) tune the NCs' optical and electronic properties. These observations point to a description of colloidal NCs as un-decomposable species: ligands may be conceived as an integral part of the overall chemical and electronic structure of the colloidal NC and should not be considered as mere appendages that weakly perturb the inorganic core features.Finally, a perspective on the ligand library design is given. Function-oriented design of the ligand subunits is foreseen as an effective strategy to explore the chemical diversity space. High-throughput screening processes by using computation may represent a valuable tool for such an exploration. The whole ligand features, which depend on the subunits, can be implemented in the final NCs, providing feedback for refined design, toward a priori materials design. Ligand libraries can be fundamental to enabling colloidal NCs as reliable luminophores and (photo)catalysts.

Nanocrystals in Molten Salts and Ionic Liquids: Experimental Observation of Ionic Correlations Extending beyond the Debye Length.

The nature of the interface between the solute and the solvent in a colloidal solution has attracted attention for a long time. For example, the surface of colloidal nanocrystals (NCs) is specially designed to impart colloidal stability in a variety of polar and nonpolar solvents. This work focuses on a special type of colloids where the solvent is a molten inorganic salt or organic ionic liquid. The stability of such colloids is hard to rationalize because solvents with high density of mobile charges efficiently screen the electrostatic double-layer repulsion, and purely ionic molten salts represent an extreme case where the Debye length is only ∼1 Å. We present a detailed investigation of NC dispersions in molten salts and ionic liquids using small-angle X-ray scattering (SAXS), atomic pair distribution function (PDF) analysis and molecular dynamics (MD) simulations. Our SAXS analysis confirms that a wide variety of NCs (Pt, CdSe/CdS, InP, InAs, ZrO2) can be uniformly dispersed in molten salts like AlCl3/NaCl/KCl (AlCl3/AlCl4-) and NaSCN/KSCN and in ionic liquids like 1-butyl-3-methylimidazolium halides (BMIM+X-, where X = Cl, Br, I). By using a combination of PDF analysis and molecular modeling, we demonstrate that the NC surface induces a solvent restructuring with electrostatic correlations extending an order of magnitude beyond the Debye screening length. These strong oscillatory ion-ion correlations, which are not accounted by the traditional mechanisms of steric and electrostatic stabilization of colloids, offer additional insight into solvent-solute interactions and enable apparently "impossible" colloidal stabilization in highly ionized media.