Exogenous Metal Cations in the Synthesis of CsPbBr3 Nanocrystals and Their Interplay with Tertiary Amines.

Current syntheses of CsPbBr3 halide perovskite nanocrystals (NCs) rely on overstoichiometric amounts of Pb2+ precursors, resulting in unreacted lead ions at the end of the process. In our synthesis scheme of CsPbBr3 NCs, we replaced excess Pb2+ with different exogenous metal cations (M) and investigated their effect on the synthesis products. These cations can be divided into two groups: group 1 delivers monodisperse CsPbBr3 cubes capped with oleate species (as for the case when Pb2+ is used in excess) and with a photoluminescence quantum yield (PLQY) as high as 90% with some cations (for example with M = In3+); group 2 yields irregularly shaped CsPbBr3 NCs with broad size distributions. In both cases, the addition of a tertiary ammonium cation (didodecylmethylammonium, DDMA+) during the synthesis, after the nucleation of the NCs, reshapes the NCs to monodisperse truncated cubes. Such NCs feature a mixed oleate/DDMA+ surface termination with PLQY values of up to 97%. For group 1 cations this happens only if the ammonium cation is directly added as a salt (DDMA-Br), while for group 2 cations this happens even if the corresponding tertiary amine (DDMA) is added, instead of DDMA-Br. This is attributed to the fact that only group 2 cations can facilitate the protonation of DDMA by the excess oleic acid present in the reaction environment. In all cases studied, the incorporation of M cations is marginal, and the reshaping of the NCs is only transient: if the reactions are run for a long time, the truncated cubes evolve to cubes.

Cu+ → Mn2+ Energy Transfer in Cu, Mn Coalloyed Cs3ZnCl5 Colloidal Nanocrystals.

In this work, we report the hot-injection synthesis of Cs3ZnCl5 colloidal nanocrystals (NCs) with tunable amounts of Cu+ and Mn2+ substituent cations. All the samples had a rodlike morphology, with a diameter of ∼14 nm and a length of ∼30-100 nm. Alloying did not alter the crystal structure of the host Cs3ZnCl5 NCs, and Cu ions were mainly introduced in the oxidation state +1 according to X-ray photoelectron and electron paramagnetic resonance spectroscopies. The spectroscopic analysis of unalloyed, Cu-alloyed, Mn-alloyed, and Cu, Mn coalloyed NCs indicated that (i) the Cs3ZnCl5 NCs have a large band gap of ∼5.35 eV; (ii) Cu(I) aliovalent alloying leads to an absorption shoulder/peak at ∼4.8 eV and cyan photoluminescence (PL) peaked at 2.50 eV; (iii) Mn(II) isovalent alloying leads to weak Mn PL, which intensifies remarkably in the coalloyed samples, prompted by an energy transfer (ET) process between the Cu and Mn centers, favored by the overlap between the lowest (6A1 → 4T1) transition for tetrahedrally coordinated Mn2+ and the PL profile from Cu(I) species in the Cs3ZnCl5 NCs. The efficiency of this ET process reaches a value of 61% for the sample with the highest extent of Mn alloying. The PL quantum yield (QY) values in these Cu, Mn coalloyed NCs are lower at higher Mn contents. The analysis of the Mn PL dynamics in these samples indicates that this PL drop stems from inter-Mn exciton migration, which increases the likelihood of trapping in defect sites, in agreement with previous studies.

CAT: A Compound Attachment Tool for the Construction of Composite Chemical Compounds.

The continuous improvement of computer architectures allows for the simulation of molecular systems of growing sizes. However, such calculations still require the input of initial structures, which are also becoming increasingly complex. In this work, we present CAT, a Compound Attachment Tool (source code available at https://github.com/nlesc-nano/CAT) and Python package for the automatic construction of composite chemical compounds, which supports the functionalization of organic, inorganic, and hybrid organic-inorganic materials. The CAT workflow consists in defining the anchoring sites on the reference material, usually a large molecular system denoted as a scaffold, and on the molecular species that are attached to it, i.e., the ligands. Usually, ligands are pre-optimized in a conformation biased toward more linear structures to minimize interligand(s) steric interactions, a bias that is important when multiple ligands are attached onto the scaffold. The resulting superstructure(s) are then stored in various formats that can be used afterward in quantum chemical calculations or classical force field-based simulations.

Alloying Bi-Doped Cs2Ag1-xNaxInCl6 Nanocrystals with K+ Cations Modulates Surface Ligands Density and Photoluminescence Efficiency.

We show how, in the synthesis of yellow-emissive Bi-doped Cs2Ag1-xNaxInCl6 double perovskite nanocrystals (NCs), preventing the transient formation of Ag0 particles increases the photoluminescence quantum yield (PLQY) of the NCs from ∼30% to ∼60%. Calculations indicate that the presence of even a single Ag0 species on the surface of a NC introduces deep trap states. The PL efficiency of these NCs is further increased to ∼70% by partial replacement of Na+ with K+ ions, up to a 7% K content, due to a lattice expansion that promotes a more favorable ligands packing on the NC surface, hence better surface passivation. A further increase in K+ lowers the PLQY, due to both the activation of nonradiative quenching channels and a lower oscillator strength of the BiCl6→AgCl6 transition (through which PL emission occurs). The work indicates how a deeper understanding of parameters influencing carrier trapping/relaxation can boost the PLQY of double perovskites NCs.

Halide perovskites as disposable epitaxial templates for the phase-selective synthesis of lead sulfochloride nanocrystals.

Colloidal chemistry grants access to a wealth of materials through simple and mild reactions. However, even few elements can combine in a variety of stoichiometries and structures, potentially resulting in impurities or even wrong products. Similar issues have been long addressed in organic chemistry by using reaction-directing groups, that are added to a substrate to promote a specific product and are later removed. Inspired by such approach, we demonstrate the use of CsPbCl3 perovskite nanocrystals to drive the phase-selective synthesis of two yet unexplored lead sulfochlorides: Pb3S2Cl2 and Pb4S3Cl2. When homogeneously nucleated in solution, lead sulfochlorides form Pb3S2Cl2 nanocrystals. Conversely, the presence of CsPbCl3 triggers the formation of Pb4S3Cl2/CsPbCl3 epitaxial heterostructures. The phase selectivity is guaranteed by the continuity of the cationic subnetwork across the interface, a condition not met in a hypothetical Pb3S2Cl2/CsPbCl3 heterostructure. The perovskite domain is then etched, delivering phase-pure Pb4S3Cl2 nanocrystals that could not be synthesized directly.

Cesium Manganese Bromide Nanocrystal Sensitizers for Broadband Vis-to-NIR Downshifting.

Simultaneously achieving both broad absorption and sharp emission in the near-infrared (NIR) is challenging. Coupling of an efficient absorber such as lead halide perovskites to lanthanide emissive species is a promising way to meet the demands for visible-to-NIR spectral conversion. However, lead-based perovskite sensitizers suffer from relatively narrow absorption in the visible range, poor stability, and toxicity. Herein, we introduce a downshifting configuration based on lead-free cesium manganese bromide nanocrystals acting as broad visible absorbers coupled to sharp emission in the NIR-I and NIR-II spectral regions. To achieve this, we synthesized CsMnBr3 and Cs3MnBr5 nanocrystals and attempted to dope them with a series of lanthanides, achieving success only with CsMnBr3. The correlation of the lanthanide emission to the CsMnBr3 visible absorption was confirmed with steady-state excitation spectra and time-resolved photoluminescence measurements, whereas the mechanism of downconversion from the CsMnBr3 matrix to the lanthanides was understood by density functional theory calculations. This study shows that lead-free metal halides with an appropriate phase are effective sensitizers for lanthanides and offer a route to efficient downshifting applications.

The Reactivity of CsPbBr3 Nanocrystals toward Acid/Base Ligands.

The interaction of lead bromide perovskite nanocrystals with charged ligands, such as salts, zwitterions, or acid-base pairs, has been extensively documented over the past few years. On the other hand, little is known about the reactivity of perovskite nanocrystals toward neutral ligands. To fill this gap, in this work we study the interaction of CsPbBr3 nanocrystals passivated with didodecyldimethylammonium bromide (DDABr) toward a series of exogenous acid/base ligands using a combined computational and experimental approach. Our analysis indicates that DDABr-capped nanocrystals are inert toward most ligands, except for carboxylic, phosphonic, and sulfonic acids. In agreement with the calculations, our experimental results indicate that the higher the acidity of the ligands employed in the treatment, the more etching is observed. In detail, dodecylbenzenesulfonic acid (pKa = -1.8) is found to etch the nanocrystals, causing their complete degradation. On the other hand, oleic and oleylphosphonic acids (pKa 9.9 and 2, respectively) interact with surface-bound DDA molecules, causing their displacement as DDABr in various amounts, which can be as high as 40% (achieved with oleylphosphonic acid). Despite the stripping of DDA ligands, the optical properties of the nanocrystals, as well as structure and morphology, remain substantially unaffected, empirically demonstrating the defect tolerance characterizing such materials. Our study provides not only a clear overview on the interaction between perovskite nanocrystals and neutral ligands but also presents an effective ligand stripping strategy.

Sb-Doped Metal Halide Nanocrystals: A 0D versus 3D Comparison.

We synthesize colloidal nanocrystals (NCs) of Rb3InCl6, composed of isolated metal halide octahedra ("0D"), and of Cs2NaInCl6 and Cs2KInCl6 double perovskites, where all octahedra share corners and are interconnected ("3D"), with the aim to elucidate and compare their optical features once doped with Sb3+ ions. Our optical and computational analyses evidence that the photoluminescence quantum yield (PLQY) of all these systems is consistently lower than that of the corresponding bulk materials due to the presence of deep surface traps from under-coordinated halide ions. Also, Sb-doped "0D" Rb3InCl6 NCs exhibit a higher PLQY than Sb-doped "3D" Cs2NaInCl6 and Cs2KInCl6 NCs, most likely because excitons responsible for the PL emission migrate to the surface faster in 3D NCs than in 0D NCs. We also observe that all these systems feature a large Stokes shift (varying from system to system), a feature that should be of interest for applications in photon management and scintillation technologies. Scintillation properties are evaluated via radioluminescence experiments, and re-absorption-free waveguiding performance in large-area plastic scintillators is assessed using Monte Carlo ray-tracing simulations.

An Overview of Computational Studies on Colloidal Semiconductor Nanocrystals.

In the last two decades, colloidal semiconductor nanocrystals have emerged as a phenomenal research topic due to their size-dependent optoelectronic properties and to their outstanding versatility in many technological applications. In this review, we provide an historical account of the most relevant computational works that have been carried out to understand atomistically the electronic structure of these materials, including the main requirements needed for the preparation of nanocrystal models that align well with the experiments. We further discuss how the advancement of these computational tools has affected the analysis of these nanomaterials over the years. We focus our review on the three main families of colloidal semiconductor nanocrystals: group II-VI and IV-VI metal chalcogenides, group III-V metal pnictogenides and metal halides, in particular lead-based halide perovskites. We discuss the most recent research frontiers and outline the future outlooks expected in this field from a computational perspective.

The Future of Ligand Engineering in Colloidal Semiconductor Nanocrystals.

Next-generation colloidal semiconductor nanocrystals featuring enhanced optoelectronic properties and processability are expected to arise from complete mastering of the nanocrystals' surface characteristics, attained by a rational engineering of the passivating ligands. This aspect is highly challenging, as it underlies a detailed understanding of the critical chemical processes that occur at the nanocrystal-ligand-solvent interface, a task that is prohibitive because of the limited number of nanocrystal syntheses that could be tried in the lab, where only a few dozen of the commercially available starting ligands can actually be explored. However, this challenging goal can be addressed nowadays by combining experiments with atomistic calculations and machine learning algorithms. In the last decades we indeed witnessed major advances in the development and application of computational software dedicated to the solution of the electronic structure problem as well as the expansion of tools to improve the sampling and analysis in classical molecular dynamics simulations. More recently, this progress has also embraced the integration of machine learning in computational chemistry and in the discovery of new drugs. We expect that soon this plethora of computational tools will have a formidable impact also in the field of colloidal semiconductor nanocrystals.In this Account, we present some of the most recent developments in the atomistic description of colloidal nanocrystals. In particular, we show how our group has been developing a set of programs interfaced with available computational chemistry software packages that allow the thermodynamic controlling factors in the nanocrystal surface chemistry to be captured atomistically by including explicit solvent molecules, ligands, and nanocrystal sizes that match the experiments. At the same time, we are also setting up an infrastructure to automate the efficient execution of thousands of calculations that will enable the collection of sufficient data to be processed by machine learning.To fully capture the power of these computational tools in the chemistry of colloidal nanocrystals, we decided to embed the thermodynamics behind the dissolution/precipitation of nanocrystal-ligand complexes in organic solvents and the crucial process of binding/detachment of ligands at the nanocrystal surface into a unique chemical framework. We show that formalizing this mechanism with a computational bird's eye view helps in deducing the critical factors that govern the stabilization of colloidal dispersions of nanocrystals in an organic solvent as well as the definition of those key parameters that need to be calculated to manipulate surface ligands. This approach has the ultimate goal of engineering surface ligands in silico, anticipating and driving the experiments in the lab.

Halide Perovskite-Lead Chalcohalide Nanocrystal Heterostructures.

We report the synthesis of colloidal CsPbX3-Pb4S3Br2 (X = Cl, Br, I) nanocrystal heterostructures, providing an example of a sharp and atomically resolved epitaxial interface between a metal halide perovskite and a non-perovskite lattice. The CsPbBr3-Pb4S3Br2 nanocrystals are prepared by a two-step direct synthesis using preformed subnanometer CsPbBr3 clusters. Density functional theory calculations indicate the creation of a quasi-type II alignment at the heterointerface as well as the formation of localized trap states, promoting ultrafast separation of photogenerated excitons and carrier trapping, as confirmed by spectroscopic experiments. Postsynthesis reaction with either Cl- or I- ions delivers the corresponding CsPbCl3-Pb4S3Br2 and CsPbI3-Pb4S3Br2 heterostructures, thus enabling anion exchange only in the perovskite domain. An increased structural rigidity is conferred to the perovskite lattice when it is interfaced with the chalcohalide lattice. This is attested by the improved stability of the metastable γ phase (or "black" phase) of CsPbI3 in the CsPbI3-Pb4S3Br2 heterostructure.

Compositional Tuning of Carrier Dynamics in Cs2Na1-x Ag x BiCl6 Double-Perovskite Nanocrystals.

We devised a hot-injection synthesis to prepare colloidal double-perovskite Cs2NaBiCl6 nanocrystals (NCs). We also examined the effects of replacing Na+ with Ag+ cations by preparing and characterizing Cs2Na1-x Ag x BiCl6 alloy NCs with x ranging from 0 to 1. Whereas Cs2NaBiCl6 NCs were not emissive, Cs2Na1-x Ag x BiCl6 NCs featured a broad photoluminescence band at ∼690 nm, Stokes-shifted from the respective absorption by ≥1.5 eV. The emission efficiency was maximized for low Ag+ amounts, reaching ∼3% for the Cs2Na0.95Ag0.05BiCl6 composition. Density functional theory calculations coupled with spectroscopic investigations revealed that Cs2Na1-x Ag x BiCl6 NCs are characterized by a complex photophysics stemming from the interplay of (i) radiative recombination via trapped excitons localized in spatially connected AgCl6-BiCl6 octahedra; (ii) surface traps, located on undercoordinated surface Bi centers, behaving as phonon-assisted nonradiative decay channels; and (iii) a thermal equilibrium between trapping and detrapping processes. These results offer insights into developing double-perovskite NCs with enhanced optoelectronic efficiency.

Nanocrystals of Lead Chalcohalides: A Series of Kinetically Trapped Metastable Nanostructures.

We report the colloidal synthesis of a series of surfactant-stabilized lead chalcohalide nanocrystals. Our work is mainly focused on Pb4S3Br2, a chalcohalide phase unknown to date that does not belong to the ambient-pressure PbS-PbBr2 phase diagram. The Pb4S3Br2 nanocrystals herein feature a remarkably narrow size distribution (with a size dispersion as low as 5%), a good size tunability (from 7 to ∼30 nm), an indirect bandgap, photoconductivity (responsivity = 4 ± 1 mA/W), and stability for months in air. A crystal structure is proposed for this new material by combining the information from 3D electron diffraction and electron tomography of a single nanocrystal, X-ray powder diffraction, and density functional theory calculations. Such a structure is closely related to that of the recently discovered high-pressure chalcohalide Pb4S3I2 phase, and indeed we were able to extend our synthesis scheme to Pb4S3I2 colloidal nanocrystals, whose structure matches the one that has been published for the bulk. Finally, we could also prepare nanocrystals of Pb3S2Cl2, which proved to be a structural analogue of the recently reported bulk Pb3Se2Br2 phase. It is remarkable that one high-pressure structure (for Pb4S3I2) and two metastable structures that had not yet been reported (for Pb4S3Br2 and Pb3S2Cl2) can be prepared on the nanoscale by wet-chemical approaches. This highlights the important role of colloidal chemistry in the discovery of new materials and motivates further exploration into metal chalcohalide nanocrystals.

Colloidal Bi-Doped Cs2Ag1-x Na x InCl6 Nanocrystals: Undercoordinated Surface Cl Ions Limit their Light Emission Efficiency.

Understanding and tuning the ligand shell composition in colloidal halide perovskite nanocrystals (NCs) has been done systematically only for Pb-based perovskites, while much less is known on the surface of Pb-free perovskite systems. Here, we reveal the ligand shell architecture of Bi-doped Cs2Ag1-x Na x InCl6NCs via nuclear magnetic resonance analysis. This material, in its bulk form, was found to have a photoluminescence quantum yield (PLQY) as high as 86%, a record value for halide double perovskites. Our results show that both amines and carboxylic acids are present and homogeneously distributed over the surface of the NCs. Notably, even for an optimized surface ligand coating, achieved by combining dodecanoic acid and decylamine, a maximum PLQY value of only 37% is reached, with no further improvements observed when exploiting post-synthesis ligand exchange procedures (involving Cs-oleate, different ammonium halides, thiocyanates and sulfonic acids). Our density functional theory calculations indicate that, even with the best ligands combination, a small fraction of unpassivated surface sites, namely undercoordinated Cl ions, is sufficient to create deep trap states, opposite to the case of Pb-based perovskites that exhibit much higher defect tolerance. This was corroborated by our transient absorption measurements, which showed that an ultrafast trapping of holes (most likely mediated by surface Cl-trap states) competes with their localization at the AgCl6 octahedra, from where, instead, they can undergo an optically active recombination yielding the observed PL emission. Our results highlight that alternative surface passivation strategies should be devised to further optimize the PLQY of double perovskite NCs, which might include their incorporation inside inorganic shells.