Precursor Chemistry of Lead Bromide Perovskite Nanocrystals.

We investigate the early stages of cesium lead bromide perovskite formation through absorption spectroscopy of stopped-flow reactions, high-throughput mapping, and direct synthesis and titration of potential precursor species. Calorimetric and spectroscopic measurements of lead bromide complex titrations combined with theoretical calculations suggest that bromide complexes with higher coordination numbers than previously considered for nonpolar systems can better explain observed behaviors. Synthesis mapping of binary lead halides reveals multiple lead bromide species with absorption peaks higher than 300 nm, including a previously observed species with a peak at 313 nm and two species with peaks at 345 and 370 nm that also appear as reaction intermediates during the formation of lead bromide perovskites. Based on theoretical calculations of excitonic energies that match within 50 meV, we give a preliminary assignment of these species as two-dimensional magic-sized clusters with side lengths of 2, 3, and 4 unit cells. Kinetic measurements of the conversion of benzoyl bromide precursor are connected to stopped-flow measurements of product formation and demonstrate that the formation of complexes and magic-sized clusters (i.e., nucleation) is controlled by precursor decomposition, whereas the growth rate of 2D and 3D perovskites is significantly slower.

Evidence and Structural Insights into a Ligand-Mediated Phase Transition in the Solvated Ligand Shell of Quantum Dots.

As synthesized, nanocrystal surfaces are typically covered in coordinating organic ligands, and the degree of packing and order of these ligands are ongoing questions in the field of colloidal nanocrystals, particularly in the solution state. Recently, isothermal titration calorimetry coupled with 1H NMR has been used to probe ligand exchanges on colloidal quantum dots, revealing the importance of the composition of the ligand shell on exchange thermodynamics. Previous work has shown that the geometry and length of a ligand's aliphatic chain can influence the thermodynamics of exchange. This has been attributed to interligand interactions, and the use of a modified Ising model simulation to account for these collective effects has been critical in describing these reactions. In this report, we explore the reaction between indium phosphide quantum dots and zinc chloride on a size series of nanocrystals capped with two different lengths of aliphatic, straight-chain carboxylate ligands to investigate the effect that nanocrystal size has on these interligand interactions. We demonstrate that interligand interactions increase as the nanocrystal size increases, changing the thermodynamics of the ligand exchange reaction. Critically, we show that a self-consistent model of these ligand exchanges does not fit the data without the use of a phase transition term in the model and that the strength of this phase transition depends on the nanocrystal size. Combined with solution state X-ray diffraction, these results provide indirect evidence that ligands are ordered on nanocrystals in the solution state.

Observation of negative surface and interface energies of quantum dots.

Surface energy is a fundamental property of materials and is particularly important in describing nanomaterials where atoms or molecules at the surface constitute a large fraction of the material. Traditionally, surface energy is considered to be a positive quantity, where atoms or molecules at the surface are less thermodynamically stable than their counterparts in the interior of the material because they have fewer bonds or interactions at the surface. Using calorimetric methods, we show that the surface energy is negative in some prototypical colloidal semiconductor nanocrystals, or quantum dots with organic ligand coatings. This implies that the surface atoms are more thermodynamically stable than those on the interior due to the strong bonds between these atoms and surfactant molecules, or ligands, that coat their surface. In addition, we extend this work to core/shell indium phosphide/zinc sulfide nanocrystals and show that the interfacial energy between these materials is highly thermodynamically favorable in spite of their large lattice mismatch. This work challenges many of the assumptions that have guided thinking about colloidal nanomaterial thermodynamics, investigates the fundamental stability of many technologically relevant colloidal nanomaterials, and paves the way for future experimental and theoretical work on nanocrystal thermodynamics.

Observation of ordered organic capping ligands on semiconducting quantum dots via powder X-ray diffraction.

Powder X-ray diffraction is one of the key techniques used to characterize the inorganic structure of colloidal nanocrystals. The comparatively low scattering factor of nuclei of the organic capping ligands and their propensity to be disordered has led investigators to typically consider them effectively invisible to this technique. In this report, we demonstrate that a commonly observed powder X-ray diffraction peak around [Formula: see text] observed in many small, colloidal quantum dots can be assigned to well-ordered aliphatic ligands bound to and capping the nanocrystals. This conclusion differs from a variety of explanations ascribed by previous sources, the majority of which propose an excess of organic material. Additionally, we demonstrate that the observed ligand peak is a sensitive probe of ligand shell ordering. Changes as a function of ligand length, geometry, and temperature can all be readily observed by X-ray diffraction and manipulated to achieve desired outcomes for the final colloidal system.

Thermodynamics of Composition Dependent Ligand Exchange on the Surfaces of Colloidal Indium Phosphide Quantum Dots.

Quantum dot surfaces can have a substantial effect on their physical, chemical, and optoelectronic properties. When the chemistry that occurs at the surface of nanocrystals is studied, critical insights can be gained into the fundamental structural, thermodynamic, and optical properties of quantum dot materials providing a valuable guide for how to best adapt them for desired applications. Colloidal quantum dots are often terminated with organic ligands that consist of a long aliphatic chain and a head group that binds tightly to the nanocrystal surface. While extensive work has been done to understand how ligand head groups influence quantum dot properties, studies to unravel the influence of the organic ligand tail on ligands and surface reaction equilibria are incomplete. To further investigate the driving forces of quantum dot surface modification, a series of ligand exchange reactions with oleic acid were performed on indium phosphide quantum dots, initially terminated with straight-chain carboxylates of variable lengths. The reaction was monitored using isothermal titration calorimetry and 1H NMR to determine the extent of each reaction and its associated thermodynamics. From these measurements, interligand interactions were observed to be dependent on the length of the straight-chain ligand. A modified Ising model was used to investigate the enthalpic and entropic effects contributing to these ligand exchanges and reveal that interligand interactions play a much larger role than previously thought. Additional experimentation with phosphonic acid ligand exchange reveals complexity in the reaction mechanism but further illustrates the significant impact of ligand tail group length on thermodynamics, even in cases where there is a large difference in head group binding energy.

Thermodynamic Investigation of Increased Luminescence in Indium Phosphide Quantum Dots by Treatment with Metal Halide Salts.

Increasing the quantum yields of InP quantum dots is important for their applications, particularly for use in consumer displays. While several methods exist to improve quantum yield, the addition of inorganic metal halide salts has proven promising. To further investigate this phenomenon, InP quantum dots dispersed in tetrahydrofuran were titrated with ZnCl2, ZnBr2, and InCl3. The optical properties were observed, and the reactions were studied by using quantitative 1H NMR and thermodynamic measurements from isothermal titration calorimetry. These measurements contradict the previously hypothesized reaction mechanism in which metal halide salts, acting as Z-type ligands, passivate undercoordinated anions on the surface of the quantum dots. This work provides evidence for a newly proposed mechanism wherein the metal halide salts undergo a ligand exchange with indium myristate. Thermodynamic measurements prove key to supporting this new mechanism, particularly in describing the organic ligand interactions on the surface. An Ising model was used to simulate the quantum dot surface and was fit by using thermodynamic and 1H NMR data. Together, these data and the proposed exchange mechanism provide greater insight into the surface chemistry of quantum dots.

Tracking the Effects of Ligands on Oxidative Etching of Gold Nanorods in Graphene Liquid Cell Electron Microscopy.

Surface ligands impact the properties and chemistry of nanocrystals, but observing ligand binding locations and their effect on nanocrystal shape transformations is challenging. Using graphene liquid cell electron microscopy and the controllable, oxidative etching of gold nanocrystals, the effect of different ligands on nanocrystal etching can be tracked with nanometer spatial resolution. The chemical environment of liquids irradiated with high-energy electrons is complex and potentially harsh, yet it is possible to observe clear evidence for differential binding properties of specific ligands to the nanorods' surface. Exchanging CTAB ligands for PEG-alkanethiol ligands causes the nanorods to etch at a different, constant rate while still maintaining their aspect ratio. Adding cysteine ligands that bind preferentially to nanorod tips induces etching predominantly on the sides of the rods. This etching at the sides leads to Rayleigh instabilities and eventually breaks apart the nanorod into two separate nanoparticles. The shape transformation is controlled by the interplay between atom removal and diffusion of surface atoms and ligands. These in situ observations are confirmed with ex situ colloidal etching reactions of gold nanorods in solution. The ability to monitor the effect of ligands on nanocrystal shape transformations will enable future in situ studies of nanocrystals surfaces and ligand binding positions.

Thermodynamic Evidence of Structural Transformations in CO2-Loaded Metal-Organic Framework Zn(MeIm)2 from Heat Capacity Measurements.

Metal-organic frameworks are a class of porous compounds with potential applications in molecular sieving, gas sequestration, and catalysis. One family of MOFs, zeolitic imidizolate frameworks (ZIFs), is of particular interest for carbon dioxide sequestration. We have previously reported the heat capacity of the sodalite topology of the zinc 2-methylimidazolate framework (ZIF-8), and in this Article we present the first low-temperature heat capacity measurements of ZIF-8 with various amounts of sorbed CO2. Molar heat capacities from 1.8 to 300 K are presented for samples containing up to 0.99 mol of CO2 per mol of ZIF-8. Samples with at least 0.56 mol of CO2 per mol of ZIF-8 display a large, broad anomaly from 70 to 220 K with a shoulder on the low-temperature side, suggesting sorption-induced structural transitions. We attribute the broad anomaly partially to a gate-opening transition, with the remainder resulting from CO2 rearrangement and/or lattice expansion. The measurements also reveal a subtle anomaly from 0 to 70 K in all samples that does not exist in the sorbate-free material, which likely reflects new vibrational modes resulting from sorbate/ZIF-8 interactions. These results provide the first thermodynamic evidence of structural transitions induced by CO2 sorption in the ZIF-8 framework.