Francisco Palazon

X-ray Lithography on Perovskite Nanocrystals Films: From Patterning with Anion-Exchange Reactions to Enhanced Stability in Air and Water

Films of colloidal CsPbX3 (X = I, Br or Cl) nanocrystals, prepared by solution drop-casting or spin-coating on a silicon substrate, were exposed to a low flux of X-rays from an X-ray photoelectron spectrometer source, causing intermolecular C=C bonding of the organic ligands that coat the surface of the nanocrystals. This transformation of the ligand shell resulted in a greater stability of the film, which translated into the following features: (i) Insolubility of the exposed regions in organic solvents which caused instead complete dissolution of the unexposed regions. This enabled the fabrication of stable and strongly fluorescent patterns over millimeter scale areas. (ii) Inhibition of the irradiated regions toward halide anion exchange reactions, when the films were exposed either to halide anions in solution or to hydrohalic vapors. This feature was exploited to create patterned regions of different CsPbIxBryClz compositions, starting from a film with homogeneous CsPbX3 composition. (iii) Resistance of the films to degradation caused by exposure to air and moisture, which represents one of the major drawbacks for the integration of these materials in devices. (iv) Stability of the film in water and biological buffer, which can open interesting perspectives for applications of halide perovskite nanocrystals in aqueous environments.

Polymer-Free Films of Inorganic Halide Perovskite Nanocrystals as UV-to-White Color-Conversion Layers in LEDs

Being considerably more efficient than traditional incandescent bulbs or fluorescent tubes, light-emitting diodes (LEDs) are becoming the main technology for general lighting applications.1,2 In the last years, a variety of white-LEDs have been demonstrated employing, for example, organic molecules (OLEDs)3−7 or inorganic quantum dots (QDs) of different composition.8 A common way of achieving a white-light emission is to couple a near-UV or blue LED with down-conversion materials such as phosphors.9 More recently, QDs have been incorporated into LEDs, replacing conventional phosphors to tune finely the emission spectrum.10 Among the different available QDs, lead halide-based perovskite nanocrystals have recently emerged as very promising candidates for many optoelectronic applications.11−15 Colloidal perovskite nanocrystals can be synthesized and/or transformed postsynthesis, so that samples emitting at different wavelengths throughout the whole visible spectrum, with high photoluminescence quantum yield (PLQY), can be prepared easily. This can be achieved either by changing the chemical composition (by anion-exchange for example)16,17 or the shape (cubes, platelets, sheets, wires).18−21 Also, electroluminescence has been observed from bulk perovskite films,22−25 blended perovskite-in-polymer films,26 as well as from nanocrystals-only films27,28 leading to the first perovskite-based LEDs.

In Situ Transmission Electron Microscopy Study of Electron Beam-Induced Transformations in Colloidal Cesium Lead Halide Perovskite Nanocrystals

An increasing number of studies have recently reported the rapid degradation of hybrid and all-inorganic lead halide perovskite nanocrystals under electron beam irradiation in the transmission electron microscope, with the formation of nanometer size, high contrast particles. The nature of these nanoparticles and the involved transformations in the perovskite nanocrystals are still a matter of debate. Herein, we have studied the effects of high energy (80/200 keV) electron irradiation on colloidal cesium lead bromide (CsPbBr3) nanocrystals with different shapes and sizes, especially 3 nm thick nanosheets, a morphology that facilitated the analysis of the various ongoing processes. Our results show that the CsPbBr3 nanocrystals undergo a radiolysis process, with electron stimulated desorption of a fraction of bromine atoms and the reduction of a fraction of Pb2+ ions to Pb0. Subsequently Pb0 atoms diffuse and aggregate, giving rise to the high contrast particles, as previously reported by various groups. The diffusion is facilitated by both high temperature and electron beam irradiation. The early stage Pb nanoparticles are epitaxially bound to the parent CsPbBr3 lattice, and evolve into nonepitaxially bound Pb crystals upon further irradiation, leading to local amorphization and consequent dismantling of the CsPbBr3 lattice. The comparison among CsPbBr3 nanocrystals with various shapes and sizes evidences that the damage is particularly pronounced at the corners and edges of the surface, due to a lower diffusion barrier for Pb0 on the surface than inside the crystal and the presence of a larger fraction of under-coordinated atoms.

Changing the Dimensionality of Cesium Lead Bromide Nanocrystals by Reversible Postsynthesis Transformations with Amines

by Reversible Postsynthesis Transformations with Amines Francisco Palazon,† Guilherme Almeida,†,§ Quinten A. Akkerman,†,§ Luca De Trizio,† Zhiya Dang,† Mirko Prato,‡ and Liberato Manna*,† †Nanochemistry Department and ‡Materials Characterization Facility, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy Dipartimento di Chimica e Chimica Industriale, Universita ̀ degli Studi di Genova, Via Dodecaneso, 31, 16146 Genova, Italy

Evolution of CsPbBr3 nanocrystals upon post-synthesis annealing under an inert atmosphere

Annealing a film of CsPbBr3 nanocrystals (NCs) leads to the removal of surface ligands and ripening of the NCs below 200 °C. This results in a reduced photoluminescence quantum yield due to the formation of trap states while on the other hand the conductive properties of the films are stabilized, with a significantly stronger photocurrent after annealing.

From CsPbBr3 Nano-Inks to Sintered CsPbBr3–CsPb2Br5 Films via Thermal Annealing: Implications on Optoelectronic Properties

CsPbBr3 nanocrystals passivated with short molecular ligands and deposited on a substrate were annealed from room temperature to 400 °C in inert atmosphere. Chemical, structural, and morphological transformations were monitored in situ and ex situ by different techniques, while optoelectronic properties of the film were also assessed. Annealing at 100 °C resulted in a 1 order of magnitude increase in photocurrent and photoresponse as a result of partial sintering of the NCs and residual solvent evaporation. Beyond 150 °C the original orthorhombic NCs were partially transformed into tetragonal CsPb2Br5 crystals, due to the desorption of weakly bound propionic acid ligands. The photocurrent increased moderately until 300 °C although the photoresponse became slower as a result of the formation of surface trap states. Eventually, annealing beyond 350 °C removed the strongly bound butylamine ligands and reversed the transition to the original orthorhombic phase, with a loss of photocurrent due to the numerous defects induced by the stripping of the passivating butylamine.

Postsynthesis Transformation of Insulating Cs4PbBr6 Nanocrystals into Bright Perovskite CsPbBr3 through Physical and Chemical Extraction of CsBr

Perovskite-related Cs4PbBr6 nanocrystals present a “zero-dimensional” crystalline structure where adjacent [PbBr6]4– octahedra do not share any corners. We show in this work that these nanocrystals can be converted into “three-dimensional” CsPbBr3 perovskites by extraction of CsBr. This conversion drastically changes the optoelectronic properties of the nanocrystals that become highly photoluminescent. The extraction of CsBr can be achieved either by thermal annealing (physical approach) or by chemical reaction with Prussian Blue (chemical approach). The former approach can be simply carried out on a dried film without addition of any chemicals but does not yield a full transformation. Instead, reaction with Prussian Blue in solution achieves a full transformation into the perovskite phase. This transformation was also verified on the iodide counterpart (Cs4PbI6).

Cu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange

Among the different synthesis approaches to colloidal nanocrystals, a recently developed toolkit is represented by cation exchange reactions, where the use of template nanocrystals gives access to materials that would be hardly attainable via direct synthesis. Besides, postsynthetic treatments, such as thermally activated solid-state reactions, represent a further flourishing route to promote finely controlled cation exchange. Here, we report that, upon in situ heating in a transmission electron microscope, Cu2Se or Cu nanocrystals deposited on an amorphous solid substrate undergo partial loss of Cu atoms, which are then engaged in local cation exchange reactions with Cu “acceptor” phases represented by rod- and wire-shaped CdSe nanocrystals. This thermal treatment slowly transforms the initial CdSe nanocrystals into Cu2–xSe nanocrystals, through the complete sublimation of Cd and the partial sublimation of Se atoms. Both Cu “donor” and “acceptor” particles were not always in direct contact with each other; hence, the gradual transfer of Cu species from Cu2Se or metallic Cu to CdSe nanocrystals was mediated by the substrate and depended on the distance between the donor and acceptor nanostructures. Differently from what happens in the comparably faster cation exchange reactions performed in liquid solution, this study shows that slow cation exchange reactions can be performed at the solid state and helps to shed light on the intermediate steps involved in such reactions.

Enhancing the Performance of CdSe/CdS Dot-in-Rod Light-Emitting Diodes via Surface Ligand Modification

The surface ligands on colloidal nanocrystals (NCs) play an important role in the performance of NC-based optoelectronic devices such as photovoltaic cells, photodetectors, and light-emitting diodes (LEDs). On one hand, the NC emission depends critically on the passivation of the surface to minimize trap states that can provide nonradiative recombination channels. On the other hand, the electrical properties of NC films are dominated by the ligands that constitute the barriers for charge transport from one NC to its neighbor. Therefore, surface modifications via ligand exchange have been employed to improve the conductance of NC films. However, in LEDs, such surface modifications are more critical because of their possible detrimental effects on the emission properties. In this work, we study the role of surface ligand modifications on the optical and electrical properties of CdSe/CdS dot-in-rods (DiRs) in films and investigate their performance in all-solution-processed LEDs. The DiR films maintain high photoluminescence quantum yield, around 40-50%, and their electroluminescence in the LED preserves the excellent color purity of the photoluminescence. In the LEDs, the ligand exchange boosted the luminance, reaching a fourfold increase from 2200 cd/m2 for native surfactants to 8500 cd/m2 for the exchanged aminoethanethiol (AET) ligands. Moreover, the efficiency roll-off, operational stability, and shelf life are significantly improved, and the external quantum efficiency is modestly increased from 5.1 to 5.4%. We relate these improvements to the increased conductivity of the emissive layer and to the better charge balance of the electrically injected carriers. In this respect, we performed ultraviolet photoelectron spectroscopy (UPS) to obtain a deeper insight into the band alignment of the LED structure. The UPS data confirm similar flat-band offsets of the emitting layer to the electron- and hole-transport layers in the case of AET ligands, which translates to more symmetric barriers for charge injection of electrons and holes. Furthermore, the change in solubility of the NCs induced by the ligand exchange allows for a layer-by-layer deposition process of the DiR films, which yields excellent homogeneity and good thickness control and enables the fabrication of all the LED layers (except for cathode and anode) by spin-coating.

Writing on Nanocrystals: Patterning Colloidal Inorganic Nanocrystal Films through Irradiation-Induced Chemical Transformations of Surface Ligands

In the past couple of decades, colloidal inorganic nanocrystals (NCs) and, more specifically, semiconductor quantum dots (QDs) have emerged as crucial materials for the development of nanoscience and nanotechnology, with applications in very diverse areas such as optoelectronics and biotechnology. Films made of inorganic NCs deposited on a substrate can be patterned by e-beam lithography, altering the structure of their capping ligands and thus allowing exposed areas to remain on the substrate while non-exposed areas are redispersed in a solvent, as in a standard lift-off process. This methodology can be described as a “direct” lithography process, since the exposure is performed directly on the material of interest, in contrast with conventional lithography which uses a polymeric resist as a mask for subsequent material deposition (or etching). A few reports from the late 1990s and early 2000s used such direct lithography to fabricate electrical wires from metallic NCs. However, the poor conductivity obtained through this process hindered the widespread use of the technique. In the early 2010s, the same method was used to define fluorescent patterns on QD films, allowing for further applications in biosensing. For the past 2–3 years, direct lithography on NC films with e-beams and X-rays has gone through an important development as it has been demonstrated that it can tune further transformations on the NCs, leading to more complex patternings and opening a whole new set of possible applications. This Perspective summarizes the findings of the past 20 years on direct lithography on NC films with a focus on the latest developments on QDs from 2014 and provides different potential future outcomes of this promising technique.