Insights into thiocyanate-enhanced photoluminescence in CsPbBr3 nanocrystals by ultrafast two-dimensional infrared spectroscopy.

Functionalization of perovskite nanocrystal surfaces with thiocyanate anions presents a transformative approach to enhancing stability and photoluminescence quantum yield (PLQY) through surface defect passivation. This study investigates the role of thiocyanate ligands in modifying the optoelectronic properties of CsPbBr3 nanocrystals. We employed ultrafast two-dimensional infrared spectroscopy to investigate the nature of the dynamic interaction of thiocyanate ligands with nanocrystal surfaces, providing insights into the mechanisms underlying the observed increase in PLQY and stability. Our analysis reveals that the thiocyanate ligands efficiently passivate the surface defects, thereby enhancing the PLQY and the stability of the treated nanocrystals. The spectroscopic evidence supports a model where thiocyanate binds to under-coordinated lead atoms, contributing to a stable nanocrystal surface with enhanced optoelectronic performance. This ligand-induced passivation mechanism advances our understanding of surface chemistry's role in optimizing nanomaterials for solar cell and LED applications.

Correction: Atomically flat semiconductor nanoplatelets for light-emitting applications.

Correction for 'Atomically flat semiconductor nanoplatelets for light-emitting applications' by Bing Bai et al., Chem. Soc. Rev., 2023, 52, 318-360, https://doi.org/10.1039/D2CS00130F.

Atomically flat semiconductor nanoplatelets for light-emitting applications.

The last decade has witnessed extensive breakthroughs and significant progress in atomically flat two-dimensional (2D) semiconductor nanoplatelets (NPLs) in terms of synthesis, growth mechanisms, optical and electronic properties and practical applications. Such NPLs have electronic structures similar to those of quantum wells in which excitons are predominantly confined along the vertical direction, while electrons are free to move in the lateral directions, resulting in unique optical properties, such as extremely narrow emission line width, short photoluminescence (PL) lifetime, high gain coefficient, and giant oscillator strength transition (GOST). These unique optical properties make NPLs favorable for high color purity light-emitting applications, in particular in light-emitting diodes (LEDs), backlights for liquid crystal displays (LCDs) and lasers. This review article first introduces the intrinsic characteristics of 2D semiconductor NPLs with atomic flatness. Subsequently, the approaches and mechanisms for the controlled synthesis of atomically flat NPLs are summarized followed by an insight on recent progress in the mediation of core/shell, core/crown and core/crown@shell structures by selective epitaxial growth of passivation layers on different planes of NPLs. Moreover, an overview of the unique optical properties and the associated light-emitting applications is elaborated. Despite great progress in this research field, there are some issues relating to heavy metal elements such as Cd2+ in NPLs, and the ambiguous gain mechanisms of NPLs and others are the main obstacles that prevent NPLs from widespread applications. Therefore, a perspective is included at the end of this review article, in which the current challenges in this stimulating research field are discussed and possible solutions to tackle these challenges are proposed.

Tuning the Colloidal Softness of CsPbBr3 Nanocrystals for Homogeneous Superlattices.

Perovskite nanocrystal superlattices (NC SLs), made from millions of ordered crystals, support collective optoelectronic phenomena. Coupled NC emitters are highly sensitive to the structural and spectral inhomogeneities of the NC ensemble. Free electrons in scanning electron microscopy (SEM) are used to probe the cathodoluminescence (CL) properties of CsPbBr3 SLs with a ∼20 nm spatial resolution. Correlated CL-SEM measurements allow for simultaneous characterization of structural and spectral heterogeneities of the SLs. Hyperspectral CL mapping shows multipole emissive domains within a single SL. Consistently, the edges of the SLs are blue-shifted relative to the central domain by up to 65 meV. We discover a relation between NC building block colloidal softness and the extent of the CL shift. Residual uniaxial compressive strains accompanying SL formation are contributors to these emission shifts. Therefore, precise control over the colloidal softness of the NC building blocks is critical for SL engineering.

Thin Layer Buckling in Perovskite CsPbBr3 Nanobelts.

Flexible semiconductor materials, where structural fluctuations and transformation are tolerable and have low impact on electronic properties, focus interest for future applications. Two-dimensional thin layer lead halide perovskites are hailed for their unconventional optoelectronic features. We report structural deformations via thin layer buckling in colloidal CsPbBr3 nanobelts adsorbed on carbon substrates. The microstructure of buckled nanobelts is determined using transmission electron microscopy and atomic force microscopy. We measured significant decrease in emission from the buckled nanobelt using cathodoluminescence, marking the influence of such mechanical deformations on electronic properties. By employing plate buckling theory, we approximate adhesion forces between the buckled nanobelt and the substrate to be Fadhesion ∼ 0.12 µN, marking a limit to sustain such deformation. This work highlights detrimental effects of mechanical buckling on electronic properties in halide perovskite nanostructures and points toward the capillary action that should be minimized in fabrication of future devices and heterostructures based on nanoperovskites.

Manipulating the Transition Dipole Moment of CsPbBr3 Perovskite Nanocrystals for Superior Optical Properties.

Colloidal cesium lead halide perovskite nanocrystals exhibit unique photophysical properties including high quantum yields, tunable emission colors, and narrow photoluminescence spectra that have marked them as promising light emitters for applications in diverse photonic devices. Randomly oriented transition dipole moments have limited the light outcoupling efficiency of all isotropic light sources, including perovskites. In this report we design and synthesize deep blue emitting, quantum confined, perovskite nanoplates and analyze their optical properties by combining angular emission measurements with back focal plane imaging and correlating the results with physical characterization. By reducing the dimensions of the nanocrystals and depositing them face down onto a substrate by spin coating, we orient the average transition dipole moment of films into the plane of the substrate and improve the emission properties for light emitting applications. We then exploit the sensitivity of the perovskite electronic transitions to the dielectric environment at the interface between the crystal and their surroundings to reduce the angle between the average transition dipole moment and the surface to only 14° and maximize potential light emission efficiency. This tunability of the electronic transition that governs light emission in perovskites is unique and, coupled with their excellent photophysical properties, introduces a valuable method to extend the efficiencies and applications of perovskite based photonic devices beyond those based on current materials.

The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver-Bismuth Halide Compositions.

Replacing lead in halide perovskites is of great interest due to concerns about stability and toxicity. Recently, lead free double perovskites in which the unit cell is doubled and two divalent lead cations are substituted by a combination of mono- and trivalent cations have been synthesized as bulk single crystals and as thin films. Here, we study stability and optical properties of all-inorganic cesium silver(I) bismuth(III) chloride and bromide nanocrystals with the double perovskite crystal structure. The cube-shaped nanocrystals are monodisperse in size with typical side lengths of 8 to 15 nm. The absorption spectrum of the nanocrystals presents a sharp peak, which we assign to a direct bismuth s-p transition and not to a quantum confined excitonic transition. Using this spectroscopic handle combined with high-resolution transmission electron microscopy (TEM) based elemental analysis, we conduct stoichiometric studies at the single nanocrystal level as well as decomposition assays in solution and observe that Ag+ diffusion and coalescence is one of the pathways by which this material degrades. Drying the nanocrystals leads to self-assembly into ordered nanocrystal solids, and these exhibit less degradation than nanocrystals in solution. Our results demonstrate that Cs2AgBiX6 (X = Cl, Br) nanocrystals are a useful model system to study structure-function relationships in the search for stable nontoxic halide perovskites.

Strongly Quantum Confined Colloidal Cesium Tin Iodide Perovskite Nanoplates: Lessons for Reducing Defect Density and Improving Stability.

Within the last several years, metal halide perovskites such as methylammonium lead iodide, CH3NH3PbI3, have come to the forefront of scientific investigation as defect-tolerant, solution-processable semiconductors that exhibit excellent optoelectronic properties. The vast majority of study has focused on Pb-based perovskites, which have limited applications because of their inherent toxicity. To enable the broad application of these materials, the properties of lead-free halide perovskites must be explored. Here, two-dimensional, lead-free cesium tin iodide, (CsSnI3), perovskite nanoplates have been synthesized and characterized for the first time. These CsSnI3 nanoplates exhibit thicknesses of less than 4 nm and exhibit significant quantum confinement with photoluminescence at 1.59 eV compared to 1.3 eV in the bulk. Ab initio calculations employing the generalized gradient approximation of Perdew-Burke-Ernzerhof elucidate that although the dominant intrinsic defects in CsSnI3 do not introduce deep levels inside the band gap, their concentration can be quite high. These simulations also highlight that synthesizing and processing CsSnI3 in Sn-rich conditions can reduce defect density and increase stability, which matches insights gained experimentally. This improvement in the understanding of CsSnI3 represents a step toward the broader challenge of building a deeper understanding of Sn-based halide perovskites and developing design principles that will lead to their successful application in optoelectronic devices.

Ligand Mediated Transformation of Cesium Lead Bromide Perovskite Nanocrystals to Lead Depleted Cs4PbBr6 Nanocrystals.

Lead halide perovskite nanocrystals (NCs) have emerged as attractive nanomaterials owing to their excellent optical and optoelectronic properties. Their intrinsic instability and soft nature enable a post-synthetic controlled chemical transformation. We studied a ligand mediated transformation of presynthesized CsPbBr3 NCs to a new type of lead-halide depleted perovskite derivative nanocrystal, namely Cs4PbBr6. The transformation is initiated by amine addition, and the use of alkyl-thiol ligands greatly improves the size uniformity and chemical stability of the derived NCs. The thermodynamically driven transformation is governed by a two-step dissolution-recrystallization mechanism, which is monitored optically. Our results not only shed light on a decomposition pathway of CsPbBr3 NCs but also present a method to synthesize uniform colloidal Cs4PbBr6 NCs, which may actually be a common product of perovskite NCs degradation.

Atomic Resolution Imaging of Halide Perovskites.

The radiation-sensitive nature of halide perovskites has hindered structural studies at the atomic scale. We overcome this obstacle by applying low dose-rate in-line holography, which combines aberration-corrected high-resolution transmission electron microscopy with exit-wave reconstruction. This technique successfully yields the genuine atomic structure of ultrathin two-dimensional CsPbBr3 halide perovskites, and a quantitative structure determination was achieved atom column by atom column using the phase information of the reconstructed exit-wave function without causing electron beam-induced sample alterations. An extraordinarily high image quality enables an unambiguous structural analysis of coexisting high-temperature and low-temperature phases of CsPbBr3 in single particles. On a broader level, our approach offers unprecedented opportunities to better understand halide perovskites at the atomic level as well as other radiation-sensitive materials.

Ultrathin Colloidal Cesium Lead Halide Perovskite Nanowires.

Highly uniform single crystal ultrathin CsPbBr3 nanowires (NWs) with diameter of 2.2 ± 0.2 nm and length up to several microns were successfully synthesized and purified using a catalyst-free colloidal synthesis method followed by a stepwise purification strategy. The NWs have bright photoluminescence (PL) with a photoluminescence quantum yield (PLQY) of about 30% after surface treatment. Large blue-shifted UV-vis absorption and PL spectra have been observed due to strong two-dimensional quantum confinement effects. A small angle X-ray scattering (SAXS) pattern shows the periodic packing of the ultrathin NWs along the radial direction, demonstrates the narrow radial distribution of the wires, and emphasizes the deep intercalation of the surfactants. Despite the extreme aspect ratios of the ultrathin NWs, their composition and the resulting optical properties can be readily tuned by an anion-exchange reaction with good morphology preservation. These bright ultrathin NWs may be used as a model system to study strong quantum confinement effects in a one-dimensional halide perovskite system.

Surface- vs Diffusion-Limited Mechanisms of Anion Exchange in CsPbBr3 Nanocrystal Cubes Revealed through Kinetic Studies.

Ion-exchange transformations allow access to nanocrystalline materials with compositions that are inaccessible via direct synthetic routes. However, additional mechanistic insight into the processes that govern these reactions is needed. We present evidence for the presence of two distinct mechanisms of exchange during anion exchange in CsPbX3 nanocrystals (NCs), ranging in size from 6.5 to 11.5 nm, for transformations from CsPbBr3 to CsPbCl3 or CsPbI3. These NCs exhibit bright luminescence throughout the exchange, allowing their optical properties to be observed in real time, in situ. The iodine exchange presents surface-reaction-limited exchanges allowing all anionic sites within the NC to appear chemically identical, whereas the chlorine exchange presents diffusion-limited exchanges proceeding through a more complicated exchange mechanism. Our results represent the first steps toward developing a microkinetic description of the anion exchange, with implications not only for understanding the lead halide perovskites but also for nanoscale ion exchange in general.

Synthesis of Composition Tunable and Highly Luminescent Cesium Lead Halide Nanowires through Anion-Exchange Reactions.

Here, we demonstrate the successful synthesis of brightly emitting colloidal cesium lead halide (CsPbX3, X = Cl, Br, I) nanowires (NWs) with uniform diameters and tunable compositions. By using highly monodisperse CsPbBr3 NWs as templates, the NW composition can be independently controlled through anion-exchange reactions. CsPbX3 alloy NWs with a wide range of alloy compositions can be achieved with well-preserved morphology and crystal structure. The NWs are highly luminescent with photoluminescence quantum yields (PLQY) ranging from 20% to 80%. The bright photoluminescence can be tuned over nearly the entire visible spectrum. The high PLQYs together with charge transport measurements exemplify the efficient alloying of the anionic sublattice in a one-dimensional CsPbX3 system. The wires increased functionality in the form of fast photoresponse rates and the low defect density suggest CsPbX3 NWs as prospective materials for optoelectronic applications.

Highly Luminescent Colloidal Nanoplates of Perovskite Cesium Lead Halide and Their Oriented Assemblies.

Anisotropic colloidal quasi-two-dimensional nanoplates (NPLs) hold great promise as functional materials due to their combination of low dimensional optoelectronic properties and versatility through colloidal synthesis. Recently, lead-halide perovskites have emerged as important optoelectronic materials with excellent efficiencies in photovoltaic and light-emitting applications. Here we report the synthesis of quantum confined all inorganic cesium lead halide nanoplates in the perovskite crystal structure that are also highly luminescent (PLQY 84%). The controllable self-assembly of nanoplates either into stacked columnar phases or crystallographic-oriented thin-sheet structures is demonstrated. The broad accessible emission range, high native quantum yields, and ease of self-assembly make perovskite NPLs an ideal platform for fundamental optoelectronic studies and the investigation of future devices.

Couples of colloidal semiconductor nanorods formed by self-limited assembly.

Colloidal nanocrystal synthesis provides a powerful approach for creating unique nanostructures of relevance for applications. Here, we report that wurtzite ZnSe nanorod couples connected by twinning structures can be synthesized by means of a self-limited assembly process. Unlike for individual nanorods, the band-edge states calculated for the nanorod couples are predominantly confined to the short edges of the structure and this leads to low photoluminescence polarization anisotropy, as confirmed by single-particle fluorescence. Through a cation-exchange approach, the composition of nanorod couples can be readily expanded to additional materials, such as CdSe and PbSe. We anticipate that this family of nanorod-couple structures with distinct compositions and controlled properties will constitute an ideal system for the investigation of electronic coupling effects between individual nanorod components on the nanoscale, with relevance to applications in optics, photocatalysis and optoelectronic devices.

[Unique mechanism in heart-shaped balloon burst resulting in blunt ocular injury].

We have previously shown that heart-shaped balloons have a different explosion mechanism than spherical balloons in which the former splits into two rubber parts still attached to the balloon base with a backward whiplash motion. This backward whiplash motion may cause significant blunt ocular trauma if the balloon is inflated by mouth. In this article, the energy of the blunt ocular trauma is estimated by the high speed camera photos analysis of the balloon burst. Furthermore, we describe the followup of eight patients with ocular trauma following inflation of heart-shaped balloons.

Bright Innovations: Review of Next-Generation Advances in Scintillator Engineering.

This review focuses on modern scintillators, the heart of ionizing radiation detection with applications in medical diagnostics, homeland security, research, and other areas. The conventional method to improve their characteristics, such as light output and timing properties, consists of improving in material composition and doping, etc., which are intrinsic to the material. On the contrary, we review recent advancements in cutting-edge approaches to shape scintillator characteristics via photonic and metamaterial engineering, which are extrinsic and introduce controlled inhomogeneity in the scintillator's surface or volume. The methods to be discussed include improved light out-coupling using photonic crystal (PhC) coating, dielectric architecture modification producing the Purcell effect, and meta-materials engineering based on energy sharing. These approaches help to break traditional bulk scintillators' limitations, e.g., to deal with poor light extraction efficiency from the material due to a typically large refractive index mismatch or improve timing performance compared to bulk materials. In the Outlook section, modern physical phenomena are discussed and suggested as the basis for the next generations of scintillation-based detectors and technology, followed by a brief discussion on cost-effective fabrication techniques that could be scalable.

Colloidal Synthesis of (PbBr2)2(AMTP)2PbBr4 a Periodic Perovskite "Heterostructured" Nanocrystal.

Heterostructures in nanoparticles challenge our common understanding of interfaces due to quantum confinement and size effects, giving rise to synergistic properties. An alternating heterostructure in which multiple and reoccurring interfaces appear in a single nanocrystal is hypothesized to accentuate such properties. We present a colloidal synthesis for perovskite layered heterostructure nanoparticles with a (PbBr2)2(AMTP)2PbBr4 composition. By varying the synthetic parameters, such as synthesis temperature, solvent, and selection of precursors, we control particle size, shape, and product priority. The structures are validated by X-ray and electron diffraction techniques. The heterostructure nanoparticles' main optical feature is a broad emission peak, showing the same range of wavelengths compared to the bulk sample.

Controlling localized surface plasmon resonances in GeTe nanoparticles using an amorphous-to-crystalline phase transition.

Infrared absorption measurements of amorphous and crystalline nanoparticles of GeTe reveal a localized surface plasmon resonance (LSPR) mode in the crystalline phase that is absent in the amorphous phase. The LSPR mode emerges upon crystallization of amorphous nanoparticles. The contrasting plasmonic properties are elucidated with scanning tunneling spectroscopy measurements indicating a Burstein-Moss shift of the band gap in the crystalline phase and a finite density of electronic states throughout the band gap in the amorphous phase that limits the effective free carrier density.

How Does Local Strain Affect Stokes Shifts in Halide Double Perovskite Nanocrystals?

Lead-free perovskite nanocrystals are of interest due to their nontoxicity and potential application in the display industry. However, engineering their optical properties is nontrivial and demands an understanding of emission from both self-trapped and free excitons. Here, we focus on tuning silver-based double perovskite nanocrystals' optical properties via two iso-valent dopants, Bi and Sb. The photoluminescence quantum yield of the intrinsic Cs2Ag1-yNayInCl6 perovskite increased dramatically upon doping. However, the two dopants affect the optical properties very differently. We hypothesize that the differences arise from their differences in electronic level contributions and ionic sizes. This hypothesis is validated through absorption and temperature dependence photoluminescence measurements, namely, by employing the Huang-Rhys factor, which indicates the coupling of the exciton to the lattice environment. The larger ionic size of Bi also plays a role in inducing significant microstraining verified via synchrotron measurements. These differences make Bi more sensitive to doping concentration over antimony which displays brighter emission (QY ∼40%). Such understanding is important for engineering optical properties in double perovskites, especially in light of recent achievements in boosting the photoluminescence quantum yield.