Defects in Lead Halide Perovskite Nanocrystals: Analogies and (Many) Differences with the Bulk

Understanding the origin of defects in lead halide perovskite nanocrystals is paramount to attaining long-term structural stability and improved optical efficiency, key features for their successful implementation in optoelectronic devices. Unlike other studies, we explore the possible formation of trap states in explicit, nonperiodic CsPbBr3 nanocrystal models about 3 nm in size. Using density functional theory, we compute the defect formation energies of interstitial, vacancy, and antisite defects in different regions of the nanocrystal (center, surface center, and surface edge), demonstrating that the most stable defect position is found at the surface. We ascribe the high defect tolerance of CsPbBr3 nanocrystals to the fact that vacancies, i.e. the loss of surface ligands as ion pairs, are energetically difficult to form and only excessive stripping of surface ligands might be problematic, as their detachment leaves undercoordinated Br– on the crystal surface that only in this case translates into dee..

Chemically triggered formation of two-dimensional epitaxial quantum dot superlattices

Two dimensional superlattices of epitaxially connected quantum dots enable size-quantization effects to be combined with high charge carrier mobilities, an essential prerequisite for highly performing QD devices based on charge transport. Here, we demonstrate that surface active additives known to restore nanocrystal stoichiometry can trigger the formation of epitaxial superlattices of PbSe and PbS quantum dots. More specifically, we show that both chalcogen-adding (sodium sulfide) and lead oleate displacing (amines) additives induce small area epitaxial superlattices of PbSe quantum dots. In the latter case, the amine basicity is a sensitive handle to tune the superlattice symmetry, with strong and weak bases yielding pseudohexagonal or quasi-square lattices, respectively. Through density functional theory calculations and in situ titrations monitored by nuclear magnetic resonance spectroscopy, we link this observation to the concomitantly different coordination enthalpy and ligand displacement potency of the amine. Next to that, an initial similar to 10% reduction of the initial ligand density prior to monolayer formation and addition of a mild, lead oleate displacing chemical trigger such as aniline proved key to induce square superlattices with long-range, square micrometer order; an effect that is the more pronounced the larger the quantum dots. Because the approach applies to PbS quantum dots as well, we conclude that it offers a reproducible and rational method for the formation of highly ordered epitaxial quantum dot superlattices

Phonon-mediated and weakly size-dependent electron and hole cooling in CsPbBr3 nanocrystals revealed by atomistic simulations and ultrafast spectroscopy

We combine state-of-the-art ultrafast photoluminescence and absorption spectroscopy and nonadiabatic molecular dynamics simulations to investigate charge-carrier cooling in CsPbBr3 nanocrystals over a very broad size regime, from 0.8 to 12 nm. Contrary to the prevailing notion that polaron formation slows down charge-carrier cooling in lead-halide perovskites, no suppression of carrier cooling is observed in CsPbBr3 nanocrystals except for a slow cooling (over similar to 10 ps) of "warm" electrons in the vicinity (within similar to 0.1 eV) of the conduction band edge. At higher excess energies, electrons and holes cool with similar rates, on the order of 1 eV ps(-1) carrier(-1), increasing weakly with size. Our ab initio simulations suggest that cooling proceeds via fast phonon-mediated intraband transitions driven by strong and size-dependent electron-phonon coupling. The presented experimental and computational methods yield the spectrum of involved phonons and may guide the development of devices utilizing hot charge carriers

Surface Termination, Morphology and Bright Photoluminescence of Cesium Lead Halide Perovskite Nanocrystals

Colloidal cesium lead halide perovskite nanocrystals (CsPbX3 PNC, X=Cl, Br, I) exhibit important optoelectronic properties that make them amenable for a plethora of applications. The origin of these properties, even for as-synthesized and unpurified PNCs, is however largely unknown. Electronic structure calculations are therefore essential to understand with atomistic detail the properties of these nanomaterials, however finding a model for PNCs that resembles the experiments is a challenging task. Essentially, the main problem is how to correctly terminate the PNC surface that comprises of a large fraction of the atoms that compose the nanocrystal and of ligands employed in the synthesis. Here, we construct nominally trap-free models for PNCs taking into account experimental conditions. With density functional theory we analyze the effect of size, shape and halide composition on the electronic structure of PNCs. We confirm that the PNC crystalline core exhibits an orthorhombic structure and we demonstrat..

Quantum-Confined and Enhanced Optical Absorption of Colloidal PbS Quantum Dots at Wavelengths with Expected Bulk Behavior

Nowadays it is well-accepted to attribute bulk-like optical absorption properties to colloidal PbS quantum dots (QDs) at wavelengths above 400 nm. This assumption permits to describe PbS QD light absorption by using bulk optical constants and to determine QD concentration in colloidal solutions from simple spectrophotometric measurements. Here we demonstrate that PbS QDs experience the quantum confinement regime across the entire near UV-vis-NIR spectral range, therefore also between 350 and 400 nm already proposed to be sufficiently far above the band gap to suppress quantum confinement. This effect is particularly relevant for small PbS QDs (with diameter of ≤4 nm) leading to absorption coefficients that largely differ from bulk values (up to ∼40% less). As a result of the broadband quantum confinement and of the high surface-to-volume ratio peculiar of nanocrystals, suitable surface chemical modification of PbS QDs is exploited to achieve a marked, size-dependent enhancement of the absorption coefficients compared to bulk values (up to ∼250%). We provide empirical relations to determine the absorption coefficients at 400 nm of as-synthesized and ligand-exchanged PbS QDs, accounting for the broadband quantum confinement and suggesting a heuristic approach to qualitatively predict the ligand effects on the optical absorption properties of PbS QDs. Our findings go beyond formalisms derived from Maxwell Garnett effective medium theory to describe QD optical properties and permit to spectrophotometrically calculate the concentration of PbS QD solutions avoiding underestimation due to deviations from the bulk. In perspective, we envisage the use of extended π-conjugated ligands bearing electronically active substituents to enhance light-harvesting in QD solids and suggest the inadequacy of the representation of ligands at the QD surface as mere electric dipoles

Role of Surface Reduction in the Formation of Traps in n-Doped II-VI Semiconductor Nanocrystals: How to Charge without Reducing the Surface

The efficiency of nanocrystal (NC)-based devices is often limited by the presence of surface states that lead to localized energy levels in the bandgap. Yet, a complete understanding of the nature of these traps remains challenging. Although theoretical modeling has greatly improved our comprehension of the NC surface, several experimental studies suggest the existence of metal-based traps that have not yet been found with theoretical methods. Since there are indications that these metal-based traps form in the presence of excess electrons, the present work uses density functional theory (DFT) calculations to study the effects of charging II-VI semiconductor NCs with either full or imperfect surface passivation. It is found that charge injection can lead to trap-formation via two pathways: metal atom ejection from perfectly passivated NCs or metal-metal dimer-formation in imperfectly passivated NCs. Fully passivated CdTe NCs are observed to be stable up to a charge of two electrons. Further reduction leads to charge localization on a surface Cd atom and the formation of in-gap states. The effects of suboptimal passivation are probed by charging NCs where an X-type ligand is removed from the (100) plane. In this case, injection of even one electron leads to Cd-dimerization and trap-formation. Addition of an L-type amine ligand prevents this dimer-formation and is suggested to also prevent trapping of photoexcited electrons in charge neutral NCs. The results presented in this work are generalized to NCs of different sizes and other II-VI semiconductors. This has clear implications for n-doping II-VI semiconductor NCs without introducing surface traps due to metal ion reduction. The possible effect of these metal ion localized traps on the photoluminescence efficiency of neutral NCs is also discussed.ChemE/Opto-electronic Material

Efficient Hot Electron Transfer in Quantum Dot-Sensitized Mesoporous Oxides at Room Temperature

Hot carrier cooling processes represent one of the major efficiency losses in solar energy conversion. Losses associated with cooling can in principle be circumvented if hot carrier extraction toward selective contacts is faster than hot carrier cooling in the absorber (in so-called hot carrier solar cells). Previous work has demonstrated the possibility of hot electron extraction in quantum dot (QD)-sensitized systems, in particular, at low temperatures. Here we demonstrate a room-temperature hot electron transfer (HET) with up to unity quantum efficiency in strongly coupled PbS quantum dot-sensitized mesoporous SnO₂. We show that the HET efficiency is determined by a kinetic competition between HET rate (<i>K</i>_HET) and the thermalization rate (<i>K</i>_TH) in the dots. <i>K</i>_HET can be modulated by changing the excitation photon energy; <i>K</i>_TH can be modified through the lattice temperature. DFT calculations demonstrate that the HET rate and efficiency are primarily determined by the density of the state (DoS) of QD and oxide. Our results provide not only a new way to achieve efficient hot electron transfer at room temperature but also new insights on the mechanism of HET and the means to control it

Near-edge ligand stripping and robust radiative exciton recombination in CdSe/CdS core/crown nanoplatelets

We address the relation between surface chemistry and optoelectronic properties in semiconductor nanocrystals using core/crown CdSe/CdS nanoplatelets passivated by cadmium oleate (Cd(Ol)(2)) as model systems. We show that addition of butylamine to a nanoplatelet (NPL) dispersion maximally displaces similar to 40% of the original Cd(Ol)(2) capping. On the basis of density functional theory simulations, we argue that this behavior reflects the preferential displacement of Cd(Ol)(2) from (near)-edge surface sites. Opposite from CdSe core NPLs, core/crown NPL dispersions can retain 45% of their initial photoluminescence efficiency after ligand displacement, while radiative exciton recombination keeps dominating the luminescent decay. Using electron microscopy observations, we assign this robust photoluminescence to NPLs with a complete CdS crown, which prevents charge carrier trapping in the near-edge surface sites created by ligand displacement. We conclude that Z-type ligands such as cadmium carboxylates can provide full electronic passivation of (100) facets yet are prone to displacement from near-edge surface sites

Colloidal CdSe nanoplatelets, a model for surface chemistry/optoelectronic property relations in semiconductor nanocrystals

While the surface termination of quasi-spherical metal chalcogenide nanocrystals or quantum dots has been widely investigated, it remains unclear whether the ensuing surface chemistry models apply to similar nanocrystals with anisotropic shapes. In this work, we report on the surface-chemistry of 2D CdSe nanoplatelets, where we make use of an improved synthesis strategy that yields stable and aggregation free nanoplatelet suspensions with a photoluminescence quantum yield as high as 55%. We confirm that such nanoplatelets are enriched in Cd and, by means of H-1 nuclear magnetic resonance spectroscopy, we show that the Cd-rich surface is terminated by X-type carboxylate ligands. Not unlike CdSe quantum dots (QDs), entire cadmium carboxylate entities can be displaced by the addition of amines, and the desorption isotherm points toward a considerable binding site heterogeneity. Moreover, we find that even the slightest displacement of cadmium carboxylate ligands quenches the nanoplatelet photoluminescence. These experimental findings are further confirmed by density functional theory (DFT) calculations on a 5 monolayer model CdSe nanoplatelet. These simulations show that the most labile ligands are located in the vicinity of facet edges, and that the displacement of ligands from such edge sites creates midgap states that can account for the observed photoluminescence quenching. Next to extending surface chemistry insights from colloidal QDs to nanoplatelets, this work indicates that CdSe nanoplatelets constitute a unique nanocrystal model system to establish a comprehensive description of midgap trap states, which includes their structural, chemical, and electronic properties