Surface traps are ubiquitous to nanoscopic semiconductor materials. Understanding their atomistic origin and manipulating them chemically have capital importance to design defect-free colloidal quantum dots and make a leap forward in the development of efficient optoelectronic devices. Recent advances in computing power established computational chemistry as a powerful tool to describe accurately complex chemical species and nowadays it became conceivable to model colloidal quantum dots with realistic sizes and shapes. In this Perspective, we combine the knowledge gathered in recent experimental findings with the computation of quantum dot electronic structures. We analyze three different systems: namely, CdSe, PbS, and CsPbI3 as benchmark semiconductor nanocrystals showing how different types of trap states can form at their surface. In addition, we suggest experimental healing of such traps according to their chemical origin and nanocrystal composition.
Colloidal quantum dots (QDs) stand among the most attractive light-harvesting materials to be exploited for solution-processed optoelectronic applications. To this aim, quantitative replacement of the bulky electrically insulating ligands at the QD surface coming from the synthetic procedure is mandatory. Here we present a conceptually novel approach to design light-harvesting nanomaterials demonstrating that QD surface modification with suitable short conjugated organic molecules permits us to drastically enhance light absorption of QDs, while preserving good long-term colloidal stability. Indeed, rational design of the pendant and anchoring moieties, which constitute the replacing ligand framework leads to a broadband increase of the optical absorbance larger than 300% for colloidal PbS QDs also at high energies (>3.1 eV), which could not be predicted by using formalisms derived from effective medium theory. We attribute such a drastic absorbance increase to ground-state ligand/QD orbital mixing, as inferred by density functional theory calculations; in addition, our findings suggest that the optical band gap reduction commonly observed for PbS QD solids treated with thiol-terminating ligands can be prevalently ascribed to 3p orbitals localized on anchoring sulfur atoms, which mix with the highest occupied states of the QDs. More broadly, we provide evidence that organic ligands and inorganic cores are inherently electronically coupled materials thus yielding peculiar chemical species (the colloidal QDs themselves), which display arising (opto)electronic properties that cannot be merely described as the sum of those of the ligand and core components.
Suitable postsynthesis surface modification of lead-chalcogenide quantum dots (QDs) is crucial to enable their integration in photovoltaic devices. Here we exploit arenethiolate anions to completely replace pristine oleate ligands on PbS QDs in the solution phase, thus preserving the colloidal stability of QDs and allowing their solution-based processability into photoconductive thin films. Complete QD surface modification relies on the stronger acidic character of arenethiols compared to that of alkanethiols and is demonstrated by FTIR and UV−vis−NIR absorption spectroscopy analyses, which provide quantitative evaluation of stoichiometry and thermodynamic stability of the resulting system. Arenethiolate ligands induce a noticeable reduction of the optical band gap of PbS QDs, which is described and explained by charge transfer interactions occurring at the organic/inorganic interface that relax exciton confinement, and a large increase of QD molar absorption coefficient, achieved through the conjugated moiety of the replacing ligands. In addition, surface modification in the solution phase promotes switching of the symmetry of PbS QD self-assembled superlattices from hexagonal to cubic close packing, which is accompanied by further reduction of the optical band gap, ascribed to inter-QD exciton delocalization and dielectric effects, together with a drastic improvement of the charge transport properties in PbS QD solids. As a result, smooth dense-packed thin films of arenethiolatecapped PbS QDs can be integrated in heterojunction solar cells via a single solution-processing step. Such single PbS QD layers exhibit abated cracking upon thermal or chemical postdeposition treatment, and the corresponding devices generate remarkable photocurrent densities and overall efficiencies, thus representing an effective strategy toward low-cost processing for QD-based photovoltaics.
The self-assembly of a blue-emitting light-harvesting organogelator and specifically designed highly fluorescent tetracenes yields nanofibers with tunable emissive properties. In particular, under near-UV excitation, white light emission is achieved in organogels and dry films of nanofibers. Confocal fluorescence microspectroscopy demonstrates that each individual nanofiber emits white light. A kinetic study shows that an energy transfer (ET) occurs between the blue-emitting anthracene derivative and the green- and red-emitting tetracenes, while inter-tetracene ETs also take place. Moreover, microscopy unravels that the nanofibers emit polarized emission in the blue spectral region, while at wavelengths higher than 500 nm the emission is not significantly polarized.
Ruling over the surface chemistry of metal halide perovskite nanocrystals (NCs) is crucial to access reliable luminophores. Here, we provide an atomic-level description of the surface of colloidal CsPbBr3 NCs, achieving an effective passivation strategy that leads to near-unity photoluminescence quantum yield. To this end, we used two different types of CsPbBr3 NCs, which had been synthesized with an outer shell of either oleylammonium bromide ion pairs or Cs-oleate complexes. We perturbed the dynamic equilibria at the NCs’ surface with ligands from a comprehensive library, including amines (and their conjugated acids) with different basicities, chain lengths, and steric encumbrances. We demonstrate that control of both ligand binding affinity and ligand-to-NC molar ratio is essential to attain thermodynamically stable coordination of the NC surface. We thus present a reliable protocol for managing the surface chemistry of colloidal CsPbBr3 NCs and for selectively addressing their ligand-induced morphological (and structural) transformations.
Colloidal quantum dots are composed of nanometer-sized crystallites of inorganic semiconductor materials bearing organic molecules at their surface. The organic/inorganic interface markedly affects forms and functions of the quantum dots, therefore its description and control are important for effective application. Herein we demonstrate that archetypal colloidal PbS quantum dots adapt their interface to the surroundings, thus existing in solution phase as equilibrium mixtures with their (metal-)organic ligand and inorganic core components. The interfacial equilibria are dictated by solvent polarity and concentration, show striking size dependence (leading to more stable ligand/core adducts for larger quantum dots), and selectively involve nanocrystal facets. This notion of ligand/core dynamic equilibrium may open novel synthetic paths and refined nanocrystal surface-chemistry strategies.
Excitonic/electronic coupling and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a collective low energy emission peak with accelerated dynamics. Here we report that similar spectroscopic features could appear as a result of the nanocrystal reactivity within the self-assembled superlattices. This is demonstrated by using CsPbBr3 nanocrystal superlattices under room temperature and cryogenic micro-photoluminescence spectroscopy. It is shown that keeping such structures under vacuum, a gradual contraction of the superlattices and subsequent coalescence of the nanocrystals occurs over several days. As a result, a narrow, low energy emission peak is observed at 4 K with a concomitant shortening of the photoluminescence lifetime due to the energy transfer between nanocrystals. When exposed to air, self-assembled CsPbBr3 nanocrystals develop bulk-like CsPbBr3 particles on top of the superlattices. At 4 K, these particles produce a distribution of narrow, low energy emission peaks with short lifetimes and excitation fluence-dependent, oscillatory decays, resembling the features of superfluorescence. Overall, the reactivity of CsPbBr3 nanocrystals dramatically alters the emission of their assemblies, which should not be overlooked when studying collective optoelectronic properties nor confused with superfluorescence effects.
Abstract.Hybrid composites obtained upon blending conjugated polymers and colloidal semiconductor nanocrystals are regarded as attractive photoactive materials for optoelectronic applications.Here we demonstrate that tailoring nanocrystal surface chemistry permits to control noncovalent and electronic interactions between organic and inorganic components. We show that the pending moieties of organic ligands at the nanocrystal surface do not merely confer colloidal stability while hindering charge separation and transport, but drastically impact morphology of hybrid composites during formation from blend solutions. The relevance of our approach to photovoltaic applications is demonstrated for composites based on poly(3-hexylthiophene) and lead sulfide nanocrystals, considered as inadequate until this report, which enable the fabrication of hybrid solar cells displaying a power conversion efficiency that reaches 3 %. By investigating (quasi)steady-state and time-resolved photo-induced processes in the nanocomposites and their constituents, we ascertain that electron transfer occurs at the hybrid interface yielding long-lived separated charge carriers, whereas interfacial hole transfer appears hindered. Here we provide a reliable alternative aiming to gain control over macroscopic optoelectronic properties of polymer/nanocrystal composites by mediating their non-covalent interactions via ligands' pending moieties, thus opening new possibilities towards efficient solution-processed hybrid solar cells.3
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