Real-Time In Situ Observation of CsPbBr3 Perovskite Nanoplatelets Transforming into Nanosheets.

The manipulation of nano-objects through heating is an effective strategy for inducing structural modifications and therefore changing the optoelectronic properties of semiconducting materials. Despite its potential, the underlying mechanism of the structural transformations remains elusive, largely due to the challenges associated with their in situ observations. To address these issues, we synthesize temperature-sensitive CsPbBr3 perovskite nanoplatelets and investigate their structural evolution at the nanoscale using in situ heating transmission electron microscopy. We observe the morphological changes that start from the self-assembly of the nanoplatelets into ribbons on a substrate. We identify several paths of merging nanoplates within ribbons that ultimately lead to the formation of nanosheets dispersed randomly on the substrate. These observations are supported by molecular dynamics simulations. We correlate the various paths for merging to the random orientation of the initial ribbons along with the ligand mobility (especially from the edges of the nanoplatelets). This leads to the preferential growth of individual nanosheets and the merging of neighboring ones. These processes enable the creation of structures with tunable emission, ranging from blue to green, all from a single material. Our real-time observations of the transformation of perovskite 2D nanocrystals reveal a route to achieve large-area nanosheets by controlling the initial orientation of the self-assembled objects with potential for large-scale applications.

Impact of the organic cation on the band-edge emission of two-dimensional lead-bromide perovskites.

Organic-inorganic low-dimensional layered metal-halide perovskites are semiconductors in which the optoelectronic properties can be tuned by the material composition and the design of the layered architecture. While the electronic band structure is mainly determined by the inorganic octahedra lattice, the binding and conformation of the organic cations induces related lattice distortions that can break the symmetry and lead to the splitting of the exciton energy levels, and influence the dielectric confinement. Furthermore, organic-induced lattice deformations lead to offsets in k-space (where k is the wavevector) that go along with the exciton energy level splitting. Hence, the electronic transitions between these levels require the momentum contribution of phonons, and contributions of phonons in the exciton recombination dynamics result in thermal broadening of the emission linewidth. In this work, we investigate the band-edge emission of two-dimensional Ruddlesden-Popper lead-bromide perovskites synthesized with different organic cations that vary in their binding head group and their alkyl chain length. We find several peaks in the low-temperature photoluminescence spectra, and the number of peaks in the band-edge emission and their decay dynamics depend strongly on the type of organic cation in the material, which we relate to the difference in the inorganic lattice distortions that the cations induce. For two-dimensional layered perovskites with mainly in-plane distortions, induced by short primary ammonium molecules, we find a two-fold splitting of the band edge emission at low temperatures. If also out-of-plane distortions are present, as for the long-chain primary ammoniums, a three-fold splitting is observed. Interestingly, the low-energy peaks of the split series merge into the highest energy peak with increasing temperature. Thermal broadening analysis of the temperature-dependent photoluminescence linewidth in the structures with out-of-plane distortions yields energies that are larger than those reported for the inorganic lattice phonons. This indicates the involvement of either high-frequency oscillations involving the organic cations, or the broadening might be related to higher order phonon scattering processes in the excitonic recombination process. The strong directionality of the phonon modes in the octahedral lattice could promote the involvement of multiple electron-phonon scattering processes in the exciton relaxation dynamics, for example involving modes with orthogonal directionality.

Stable Sn-Based Hybrid Perovskite-Related Structures with Tunable Color Coordinates via Organic Cations in Low-Temperature Synthesis.

Organic-inorganic Pb-free layered perovskites are efficient broadband emitters and thus are promising materials for lighting applications. However, their synthetic protocols require a controlled atmosphere, high temperature, and long preparation time. This hinders the potential tunability of their emission through organic cations, as is instead common practice in Pb-based structures. Here, we present a set of Sn-Br layered perovskite-related structures that display different chromaticity coordinates and photoluminescence quantum yield (PLQY) up to 80%, depending on the choice of the organic monocation. We first develop a synthetic protocol that is performed under air and at 4 °C, requiring only a few steps. X-ray and 3D electron diffraction analyses show that the structures exhibit diverse octahedra connectivity (disconnected and face-sharing) and thus optical properties, while preserving the organic-inorganic layer intercalation. These results provide key insight into a previously underexplored strategy to tune the color coordinates of Pb-free layered perovskites through organic cations with complex molecular configurations.

Highly Emitting Perovskite Nanocrystals with 2-Year Stability in Water through an Automated Polymer Encapsulation for Bioimaging.

Lead-based halide perovskite nanocrystals are highly luminescent materials, but their sensitivity to humid environments and their biotoxicity are still important challenges to solve. Here, we develop a stepwise approach to encapsulate representative CsPbBr3 nanocrystals into water-soluble polymer capsules. We show that our protocol can be extended to nanocrystals coated with different ligands, enabling an outstanding high photoluminescence quantum yield of ∼60% that is preserved over two years in capsules dispersed in water. We demonstrate that this on-bench strategy can be implemented on an automated platform with slight modifications, granting access to a faster and more reproducible fabrication process. Also, we reveal that the capsules can be exploited as photoluminescent probes for cell imaging at a dose as low as 0.3 µgPb/mL that is well below the toxicity threshold for Pb and Cs ions. Our approach contributes to expanding significantly the fields of applications of these luminescent materials including biology and biomedicine.

Correlating Symmetries of Low-Frequency Vibrations and Self-Trapped Excitons in Layered Perovskites for Light Emission with Different Colors.

The soft hybrid organic-inorganic structure of two-dimensional layered perovskites (2DLPs) enables broadband emission at room temperature from a single material, which makes 2DLPs promising sources for solid-state white lighting, yet with low efficiency. The underlying photophysics involves self-trapping of excitons favored by distortions of the inorganic lattice and coupling to phonons, where the mechanism is still under debate. 2DLPs with different organic moieties and emission ranging from self-trapped exciton (STE)-dominated white light to blue band-edge photoluminescence are investigated. Detailed insights into the directional symmetries of phonon modes are gained using angle-resolved polarized Raman spectroscopy and are correlated to the temperature-dependence of the STE emission. It is demonstrated that weak STE bands at low-temperature are linked to in-plane phonons, and efficient room-temperature STE emission to more complex coupling to several phonon modes with out-of-plane components. Thereby, a unique view is provided into the lattice deformations and recombination dynamics that are key to designing more efficient materials.

Engineering the Optical Emission and Robustness of Metal-Halide Layered Perovskites through Ligand Accommodation.

The unique combination of organic and inorganic layers in 2D layered perovskites offers promise for the design of a variety of materials for mechatronics, flexoelectrics, energy conversion, and lighting. However, the potential tailoring of their properties through the organic building blocks is not yet well understood. Here, different classes of organoammonium molecules are exploited to engineer the optical emission and robustness of a new set of Ruddlesden-Popper metal-halide layered perovskites. It is shown that the type of molecule regulates the number of hydrogen bonds that it forms with the edge-sharing [PbBr6 ]4- octahedra layers, leading to strong differences in the material emission and tunability of the color coordinates, from deep-blue to pure-white. Also, the emission intensity strongly depends on the length of the molecules, thereby providing an additional parameter to optimize their emission efficiency. The combined experimental and computational study provides a detailed understanding of the impact of lattice distortions, compositional defects, and the anisotropic crystal structure on the emission of such layered materials. It is foreseen that this rational design can be extended to other types of organic linkers, providing a yet unexplored path to tailor the optical and mechanical properties of these materials and to unlock new functionalities.

Mechanical switching of orientation-related photoluminescence in deep-blue 2D layered perovskite ensembles.

The synergy between the organic component of two-dimensional (2D) metal halide layered perovskites and flexible polymers offers an unexplored window to tune their optical properties at low mechanical stress. Thus, there is a significant interest in exploiting their PL anisotropy by controlling their orientation and elucidating their interactions. Here, we apply this principle to platelet structures of micrometre lateral size that are synthesized in situ into free-standing polymer films. We study the photoluminescence of the resulting films under cyclic mechanical stress and observe an enhancement in the emission intensity up to ∼2.5 times along with a switch in the emission profile when stretching the films from 0% to 70% elongation. All the films recovered their initial emission intensity when releasing the stress throughout ca. 15 mechanical cycles. We hypothesize a combined contribution from reduced reabsorption, changes on in-plane and out-of-plane dipole moments that stem from different orientation of the platelets inside the film, and relative sliding of platelets within oriented stacks while stretching the films. Our results reveal how low-mechanical stress affects 2D layered perovskite aggregation and orientation, an open pathway toward the design of strain-controlled emission.

Directional Anisotropy of the Vibrational Modes in 2D-Layered Perovskites.

The vibrational modes in organic/inorganic layered perovskites are of fundamental importance for their optoelectronic properties. The hierarchical architecture of the Ruddlesden-Popper phase of these materials allows for distinct directionality of the vibrational modes with respect to the main axes of the pseudocubic lattice in the octahedral plane. Here, we study the directionality of the fundamental phonon modes in single exfoliated Ruddlesden-Popper perovskite flakes with polarized Raman spectroscopy at ultralow frequencies. A wealth of Raman bands is distinguished in the range from 15 to 150 cm-1 (2-15 meV), whose features depend on the organic cation species, on temperature, and on the direction of the linear polarization of the incident light. By controlling the angle of the linear polarization of the excitation laser with respect to the in-plane axes of the octahedral layer, we gain detailed information on the symmetry of the vibrational modes. The choice of two different organic moieties, phenethylammonium (PEA) and butylammonium (BA), allows us to discern the influence of the linker molecules, evidencing strong anisotropy of the vibrations for the (PEA)2PbBr4 samples. Temperature-dependent Raman measurements reveal that the broad phonon bands observed at room temperature consist of a series of sharp modes and that such mode splitting strongly differs for the different organic moieties and vibrational bands. Softer molecules such as BA result in lower vibrational frequencies and splitting into fewer modes, while more rigid molecules such as PEA lead to higher frequency oscillations and larger number of Raman peaks at low temperature. Interestingly, in distinct bands the number of peaks in the Raman bands is doubled for the rigid PEA compared to the soft BA linkers. Our work shows that the coupling to specific vibrational modes can be controlled by the incident light polarization and choice of the organic moiety, which could be exploited for tailoring exciton-phonon interaction, and for optical switching of the optoelectronic properties of such 2D layered materials.

Temperature-Driven Transformation of CsPbBr3 Nanoplatelets into Mosaic Nanotiles in Solution through Self-Assembly.

Two-dimensional colloidal halide perovskite nanocrystals are promising materials for light-emitting applications. Recent studies have focused on nanoplatelets that are able to self-assemble and transform on solid substrates. However, the mechanism behind the process and the atomic arrangement of their assemblies remain unclear. Here, we present a detailed analysis of the transformation of self-assembled stacks of CsPbBr3 nanoplatelets in solution over a period of a few months by using ex situ transmission electron microscopy and surface analysis. We demonstrate that the transformation mechanism can be understood as oriented attachment, proceeding through the following steps: (i) desorption of the ligands from the surfaces of the particles, causing the seamless atomic merging of nanoplatelet stacks into nanobelts; (ii) merging of neighboring nanobelts that form more extended nanoplates; and (iii) attachment of nanobelts and nanoplates, forming objects with an atomic structure that resembles a mosaic made of broken nanotiles. We reveal that aged nanobelts and nanoplates, which are mainly stabilized by amine/ammonium ions, link through a bilayer of CsBr, with the atomic columns of neighboring perovskite lattices shifted by a half-unit-cell, forming Ruddlesden-Popper planar faults. We also show, via in situ monitoring of the nanocrystal photoluminescence combined with transmission electron microscopy analysis, that the transformation is temperature driven and that it can take place within tens of minutes in solution and in spin-coated films. Understanding this process gives crucial information for the design and fabrication of perovskite materials, where control over the type and density of defects is desired, stimulating the development of perovskite nanocrystal structures with tailored electronic properties.

Simple fabrication of layered halide perovskite platelets and enhanced photoluminescence from mechanically exfoliated flakes.

Rapid progress on the fabrication of lead halide perovskite crystals has led to highly promising performance in optoelectronic devices, particularly from three-dimensional crystals. Recently, these efforts have been extended to layered perovskite structures, motivated in part by their good environmental stability. Furthermore, layered perovskites represent a nanocrystal system with micron-size extensions and strong confinement in one dimension that is highly appealing for studying fundamental photophysics. Here, we report a facile route for the growth of single-layered perovskite platelets, which is demonstrated using four different organic cations acting as spacers, providing a layer interdistance from approx. 1.3 nm to 2.4 nm. The resulting ensembles of platelets exhibit a strong emission band in the deep blue spectral region characterized by two emission peaks and a photoluminescence quantum yield (PLQY) up to 15%. Thin 2D layered perovskite flakes can be readily obtained by mechanical exfoliation, and their emission shows a PLQY as high as 42%, which can be related to reduced reabsorption in the exfoliated crystals. Furthermore, the low energy peak that was observed in the double peak emission from the platelet ensembles is suppressed in the exfoliated flakes. Therefore, the exfoliated flakes manifest a more colour-pure blue emission with strongly increased radiative rate as compared to the dried platelet aggregates obtained directly from the synthesis. The straightforward fabrication strategy that employs solely polar solvents with low environmental impact provides a highly appealing route towards two-dimensional perovskite systems with bright and stable emission in the blue spectral range.

Hybrid carbon nanostructured fibers: stepping stone for intelligent textile-based electronics.

The journey of smart textile-based wearable technologies first started with the attachment of sensors to fabrics, followed by embedding sensors in apparels. Presently, garments themselves can be transformed into sensors, which demonstrates the tremendous growth in the field of smart textiles. Wearable applications demand flexible materials that can withstand deformation for their practical use on par with conventional textiles. To address this, we explore the potential reasons for the enhanced performance of wearable devices realized from the fabrication of carbon nanostructured fibers with the use of graphene, carbon nanotubes and other two-dimensional materials. This review presents a brief introduction on the fabrication strategies to form carbon-based fibers and the relationship between their properties and characteristics of the resulting materials. The likely mechanisms of fiber-based electronic and storage devices, focusing mainly on transistors, nano-generators, solar cells, supercapacitors, batteries, sensors and therapeutic devices are also presented. Finally, the future perspectives of this research field of flexible and wearable electronics are discussed. The present study supplements novel ideas not only for beginners aiming to work in this booming area, but also for researchers actively engaged in the field of fiber-based electronics, dealing with advanced electronics and wide range of functionalities integrated into textile fibers.