Data-Driven Controlled Synthesis of Oriented Quasi-Spherical CsPbBr3 Perovskite Materials.

Controlled synthesis of lead-halide perovskite crystals is challenging yet attractive because of the pivotal role played by the crystal structure and growth conditions in regulating their properties. This study introduces data-driven strategies for the controlled synthesis of oriented quasi-spherical CsPbBr3, alongside an investigation into the synthesis mechanism. High-throughput rapid characterization of absorption spectra and color under ultraviolet illumination was conducted using 23 possible ligands for the synthesis of CsPbBr3 crystals. The links between the absorption spectra slope (difference in the absorbance at 400 nm and 450 nm divided by a wavelength interval of 50 nm) and crystal size were determined through statistical analysis of more than 100 related publications. Big data analysis and machine learning were employed to investigate a total of 688 absorption spectra and 652 color values, revealing correlations between synthesis parameters and properties. Ex situ characterization confirmed successful synthesis of oriented quasi-spherical CsPbBr3 perovskites using polyvinylpyrrolidone and Acacia. Density functional theory calculations highlighted strong adsorption of Acacia on the (110) facet of CsPbBr3. Optical properties of the oriented quasi-spherical perovskites prepared with these data-driven strategies were significantly improved. This study demonstrates that data-driven controlled synthesis facilitates morphology-controlled perovskites with excellent optical properties.

Colloidal Chiral Carbon Dots: An Emerging System for Chiroptical Applications.

Chiral CDots (c-CDots) not only inherit those merits from CDots but also exhibit chiral effects in optical, electric, and bio-properties. Therefore, c-CDots have received significant interest from a wide range of research communities including chemistry, physics, biology, and device engineers. They have already made decent progress in terms of synthesis, together with the exploration of their optical properties and applications. In this review, the chiroptical properties and chirality origin in extinction circular dichroism (ECD) and circularly polarized luminescence (CPL) of c-CDots is briefly discussed. Then, the synthetic strategies of c-CDots is summarized, including one-pot synthesis, post-functionalization of CDots with chiral ligands, and assembly of CDots into chiral architectures with soft chiral templates. Afterward, the chiral effects on the applications of c-CDots are elaborated. Research domains such as drug delivery, bio- or chemical sensing, regulation of enzyme-like catalysis, and others are covered. Finally, the perspective on the challenges associated with the synthetic strategies, understanding the origin of chirality, and potential applications is provided. This review not only discusses the latest developments of c-CDots but also helps toward a better understanding of the structure-property relationship along with their respective applications.

Introduction to halide perovskite optoelectronics.

An introduction to the Nanoscale themed collection on halide perovskite nanomaterials for optoelectronic applications, featuring a variety of articles that highlight the latest developments to address ongoing challenges in the field.

All-Inorganic Lead-Free Doped-Metal Halides for Bright Solid-State Emission from Primary Colors to White Light.

Metal halides have been explored with the aid of strong photoluminescence for optical and optoelectronic applications. However, the preparation of lead (Pb)-free solid-state emitters with high photoluminescence quantum yields (PLQYs) and tunable emission remains exceptionally challenging. Herein, we report metal ion (Cu(I), Mn(II), and Sn(II))-doped Cs3ZnI5 single crystals that are primary color (violet, green, and orange/red) emitters with extremely high PLQYs. Whereas the Mn-doping leads to bright green emissions with 100% PLQY, the Cu- and Sn-doping give rise to blue and red emissions with PLQYs of 57 and 64%, respectively. Interestingly, higher Mn doping results in white light emissive crystals as a side product, which are found to be Mn-doped CsI single crystals. The bright white light emissive crystals can be synthesized in a pure form in large quantities and exhibit a high color rendering index (CRI) of 78 and CIE coordinates of (0.30, 0.38), which are close to daylight conditions. To the best of our knowledge, this is the first demonstration of white light emission from a complete inorganic system. Importantly, the single crystals of all colors exhibit high long-term stability as their PLQY remains unchanged even after 2 months of preparation, and are thermally stable up to 600 °C.

Toward Chiral Lasing from All-Solution-Processed Flexible Perovskite-Nanocrystal-Liquid-Crystal Membranes.

Circularly polarized (CP) coherent light sources are of great potential for various advanced optical applications spanning displays/imaging to data processing/encryption and quantum communication. Here, the first demonstration of CP amplified spontaneous emission (ASE)/lasing from a free-standing and flexible membrane device is reported. The membrane device consists of perovskite nanocrystals (PNCs) and cholesteric liquid crystals (CLCs) layers sandwiched within a Fabry-Pérot (F-P) cavity architecture. The chiral liquid crystal cavity enables the generation of CP light from the device. The device is completely solution-processable and displays CP ASE with record dissymmetry factor (glum ) as high as 1.4, which is 3 orders of magnitude higher as compared with glum of CP luminescence of chiral ligand-capped colloidal PNCs. The device exhibits ultraflexibility as the ASE intensity remains unchanged after repeated 100 bending cycles and it is stable for more than 3 months with 80% of its original intensity. Furthermore, the ultraflexibility enables the generation of ASE from various objects of different geometric surfaces covered with the flexible perovskite membrane device. This work not only demonstrates the first CP ASE from a PNCs membrane with extremely high glum but also opens the door toward the fabrication of ultraflexible, extremely stable, and all solution-processable perovskite chiral laser devices.

Nanoimprinted 2D-Chiral Perovskite Nanocrystal Metasurfaces for Circularly Polarized Photoluminescence.

The versatile hybrid perovskite nanocrystals (NCs) are one of the most promising materials for optoelectronics by virtue of their tunable bandgaps and high photoluminescence (PL) quantum yields. However, their inherent crystalline chemical structure limits the chiroptical properties achievable with the material. The production of chiral perovskites has become an active field of research for its promising applications in optics, chemistry, or biology. Typically, chiral halide perovskites are obtained by the incorporation of different chiral moieties in the material. Unfortunately, these chemically modified perovskites have demonstrated moderate values of chiral PL so far. Here, a general and scalable approach is introduced to produce chiral PL from arbitrary nanoemitters assembled into 2D-chiral metasurfaces. The fabrication via nanoimprinting lithography employs elastomeric molds engraved with chiral motifs covering millimeter areas that are used to pattern two types of unmodified colloidal perovskite NC inks: green-emissive CsPbBr3 and red-emissive CsPbBr1 I2 . The perovskite 2D-metasurfaces exhibit remarkable PL dissymmetry factors (glum ) of 0.16 that can be further improved up to glum of 0.3 by adding a high-refractive-index coating on the metasurfaces. This scalable approach to produce chiral photoluminescent thin films paves the way for the seamless production of bright chiral light sources for upcoming optoelectronic applications.

Fast A-Site Cation Cross-Exchange at Room Temperature: Single-to Double- and Triple-Cation Halide Perovskite Nanocrystals.

We report here fast A-site cation cross-exchange between APbX3 perovskite nanocrystals (NCs) made of different A-cations (Cs (cesium), FA (formamidinium), and MA (methylammonium)) at room temperature. Surprisingly, the A-cation cross-exchange proceeds as fast as the halide (X=Cl, Br, or I) exchange with the help of free A-oleate complexes present in the freshly prepared colloidal perovskite NC solutions. This enabled the preparation of double (MACs, MAFA, CsFA)- and triple (MACsFA)-cation perovskite NCs with an optical band gap that is finely tunable by their A-site composition. The optical spectroscopy together with structural analysis using XRD and atomically resolved high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and integrated differential phase contrast (iDPC) STEM indicates the homogeneous distribution of different cations in the mixed perovskite NC lattice. Unlike halide ions, the A-cations do not phase-segregate under light illumination.

Elucidating the Role of Antisolvents on the Surface Chemistry and Optoelectronic Properties of CsPbBrxI3-x Perovskite Nanocrystals.

Colloidal lead-halide perovskite nanocrystals (LHP NCs) have emerged over the past decade as leading candidates for efficient next-generation optoelectronic devices, but their properties and performance critically depend on how they are purified. While antisolvents are widely used for purification, a detailed understanding of how the polarity of the antisolvent influences the surface chemistry and composition of the NCs is missing in the field. Here, we fill this knowledge gap by studying the surface chemistry of purified CsPbBrxI3-x NCs as the model system, which in itself is considered a promising candidate for pure-red light-emitting diodes and top-cells for tandem photovoltaics. Interestingly, we find that as the polarity of the antisolvent increases (from methyl acetate to acetone to butanol), there is a blueshift in the photoluminescence (PL) peak of the NCs along with a decrease in PL quantum yield (PLQY). Through transmission electron microscopy and X-ray photoemission spectroscopy measurements, we find that these changes in PL properties arise from antisolvent-induced iodide removal, which leads to a change in halide composition and, thus, the bandgap. Using detailed nuclear magnetic resonance (NMR) and Fourier-transform infrared spectroscopy (FTIR) measurements along with density functional theory calculations, we propose that more polar antisolvents favor the detachment of the oleic acid and oleylamine ligands, which undergo amide condensation reactions, leading to the removal of iodide anions from the NC surface bound to these ligands. This work shows that careful selection of low-polarity antisolvents is a critical part of designing the synthesis of NCs to achieve high PLQYs with minimal defect-mediated phase segregation.

Oleic acid/oleylamine ligand pair: a versatile combination in the synthesis of colloidal nanoparticles.

A variety of colloidal chemical approaches has been developed in the last few decades for the controlled synthesis of nanostructured materials in either water or organic solvents. Besides the precursors, the solvents, reducing agents, and the choice of surfactants are crucial for tuning the composition, morphology and other properties of the resulting nanoparticles. The ligands employed include thiols, amines, carboxylic acids, phosphines and phosphine oxides. Generally, adding a single ligand to the reaction mixture is not always adequate to yield the desired features. In this review, we discuss in detail the role of the oleic acid/oleylamine ligand pair in the chemical synthesis of nanoparticles. The combined use of these ligands belonging to two different categories of molecules aims to control the size and shape of nanoparticles and prevent their aggregation, not only during their synthesis but also after their dispersion in a carrier solvent. We show how the different binding strengths of these two molecules and their distinct binding modes on specific facets affect the reaction kinetics toward the production of nanostructures with tailored characteristics. Additional functions, such as the reducing function, are also noted, especially for oleylamine. Sometimes, the carboxylic acid will react with the alkylamine to form an acid-base complex, which may serve as a binary capping agent and reductant; however, its reducing capacity may range from lower to much lower than that of oleylamine. The types of nanoparticles synthesized in the simultaneous presence of oleic acid and oleylamine and discussed herein include metal oxides, metal chalcogenides, metals, bimetallic structures, perovskites, upconversion particles and rare earth-based materials. Diverse morphologies, ranging from spherical nanoparticles to anisotropic, core-shell and hetero-structured configurations are presented. Finally, the relation between tuning the resulting surface and volume nanoparticle properties and the relevant applications is highlighted.

Enhancing the Intrinsic and Extrinsic Stability of Halide Perovskite Nanocrystals for Efficient and Durable Optoelectronics.

Over the past few years, metal halide perovskite nanocrystals have been at the forefront of colloidal semiconductor nanomaterial research because of their fascinating properties and potential applications. However, their intrinsic phase instability and chemical degradation under external exposures (high temperature, water, oxygen, and light) are currently limiting the real-world applications of perovskite optoelectronics. To overcome these stability issues, researchers have reported various strategies such as doping and encapsulation. The doping improves the optical and photoactive phase stability, whereas the encapsulation protects the perovskite NCs from external exposures. This perspective discusses the rationale of various strategies to enhance the stability of perovskite NCs and suggests possible future directions for the fabrication of optoelectronic devices with long-term stability while maintaining high efficiency.

Revisiting the nontemplate approach for the synthesis of highly green emissive hybrid perovskite nanocrystals: platelets or spheres?

The long-standing debate about the morphology of colloidal methylammonium lead bromide perovskites nanocrystals, manufactured by our nontemplate synthetic strategy reported in 2014, is now resolved; specifically, the highest green emissive single nanoplatelets (of up to 93%) with long-term chemical and photochemical stability have been obtained after suitable purification steps.

Colloidal Metal-Halide Perovskite Nanoplatelets: Thickness-Controlled Synthesis, Properties, and Application in Light-Emitting Diodes.

Colloidal metal-halide perovskite nanocrystals (MHP NCs) are gaining significant attention for a wide range of optoelectronics applications owing to their exciting properties, such as defect tolerance, near-unity photoluminescence quantum yield, and tunable emission across the entire visible wavelength range. Although the optical properties of MHP NCs are easily tunable through their halide composition, they suffer from light-induced halide phase segregation that limits their use in devices. However, MHPs can be synthesized in the form of colloidal nanoplatelets (NPls) with monolayer (ML)-level thickness control, exhibiting strong quantum confinement effects, and thus enabling tunable emission across the entire visible wavelength range by controlling the thickness of bromide or iodide-based lead-halide perovskite NPls. In addition, the NPls exhibit narrow emission peaks, have high exciton binding energies, and a higher fraction of radiative recombination compared to their bulk counterparts, making them ideal candidates for applications in light-emitting diodes (LEDs). This review discusses the state-of-the-art in colloidal MHP NPls: synthetic routes, thickness-controlled synthesis of both organic-inorganic hybrid and all-inorganic MHP NPls, their linear and nonlinear optical properties (including charge-carrier dynamics), and their performance in LEDs. Furthermore, the challenges associated with their thickness-controlled synthesis, environmental and thermal stability, and their application in making efficient LEDs are discussed.

Dimensionality Control of Inorganic and Hybrid Perovskite Nanocrystals by Reaction Temperature: From No-Confinement to 3D and 1D Quantum Confinement.

This work focuses on the systematic investigation of the shape, size, and composition-controlled synthesis of perovskite nanocrystals (NCs) under inert gas-free conditions and using pre-synthesized precursor stock solutions. In the case of CsPbBr3 NCs, we find that the lowering of reaction temperature from ∼175 to 100 °C initially leads to a change of morphology from bulk-like 3D nanocubes to 0D nanocubes with 3D-quantum confinement, while at temperatures below 100 °C the reaction yields 2D nanoplatelets (NPls) with 1D-quantum confinement. However, to our surprise, at higher temperatures (∼215 °C), the reaction yields CsPbBr3 hexapod NCs, which have been rarely reported. The synthesis is scalable, and their halide composition is tunable by simply using different combinations of precursor solutions. The versatility of the synthesis is demonstrated by applying it to relatively less explored shape-controlled synthesis of FAPbBr3 NCs. Despite the synthesis carried out in the air, both the inorganic and hybrid perovskite NCs exhibit nearly-narrow emission without applying any size-selective separation, and it is precisely tunable by controlling the reaction temperature.

Coherent vibrational dynamics reveals lattice anharmonicity in organic-inorganic halide perovskite nanocrystals.

The halide ions of organic-inorganic hybrid perovskites can strongly influence the interaction between the central organic moiety and the inorganic metal halide octahedral units and thus their lattice vibrations. Here, we report the halide-ion-dependent vibrational coherences in formamidinium lead halide (FAPbX3, X = Br, I) perovskite nanocrystals (PNCs) via the combination of femtosecond pump-probe spectroscopy and density functional theory calculations. We find that the FAPbX3 PNCs generate halide-dependent coherent vibronic wave packets upon above-bandgap non-resonant excitation. More importantly, we observe several higher harmonics of the fundamental modes for FAPbI3 PNCs as compared to FAPbBr3 PNCs. This is likely due to the weaker interaction between the central FA moiety and the inorganic cage for FAPbI3 PNCs, and thus the PbI64- unit can vibrate more freely. This weakening reveals the intrinsic anharmonicity in the Pb-I framework, and thus facilitating the energy transfer into overtone and combination bands. These findings not only unveil the superior stability of Br-based PNCs over I-based PNCs but are also important for a better understanding of their electronic and polaronic properties.

Defect Passivation in Lead-Halide Perovskite Nanocrystals and Thin Films: Toward Efficient LEDs and Solar Cells.

Lead-halide perovskites (LHPs), in the form of both colloidal nanocrystals (NCs) and thin films, have emerged over the past decade as leading candidates for next-generation, efficient light-emitting diodes (LEDs) and solar cells. Owing to their high photoluminescence quantum yields (PLQYs), LHPs efficiently convert injected charge carriers into light and vice versa. However, despite the defect-tolerance of LHPs, defects at the surface of colloidal NCs and grain boundaries in thin films play a critical role in charge-carrier transport and nonradiative recombination, which lowers the PLQYs, device efficiency, and stability. Therefore, understanding the defects that play a key role in limiting performance, and developing effective passivation routes are critical for achieving advances in performance. This Review presents the current understanding of defects in halide perovskites and their influence on the optical and charge-carrier transport properties. Passivation strategies toward improving the efficiencies of perovskite-based LEDs and solar cells are also discussed.

An Expanded Surface-Enhanced Raman Scattering Tags Library by Combinatorial Encapsulation of Reporter Molecules in Metal Nanoshells.

Raman-encoded gold nanoparticles (NPs) have been widely employed as photostable multifunctional probes for sensing, bioimaging, multiplex diagnostics, and surface-enhanced Raman scattering (SERS)-guided tumor therapy. We report a strategy toward obtaining a particularly large library of Au nanocapsules encoded with Raman codes defined by the combination of different thiol-free Raman reporters, encapsulated at defined molar ratios. The fabrication of SERS tags with tailored size and predefined codes is based on the in situ incorporation of Raman reporter molecules inside Au nanocapsules during their formation via galvanic replacement coupled to seeded growth on Ag NPs. The hole-free closed-shell structure of the nanocapsules is confirmed by electron tomography. The unusually wide encoding possibilities of the obtained SERS tags are investigated by means of either wavenumber-based encoding or Raman frequency combined with signal intensity, leading to an outstanding performance as exemplified by 26 and 54 different codes, respectively. We additionally demonstrate that encoded nanocapsules can be readily bioconjugated with antibodies for applications such as SERS-based targeted cell imaging and phenotyping.

Templated-Assembly of CsPbBr3 Perovskite Nanocrystals into 2D Photonic Supercrystals with Amplified Spontaneous Emission.

Perovskite nanocrystals (NCs) have revolutionized optoelectronic devices because of their versatile optical properties. However, controlling and extending these functionalities often requires a light-management strategy involving additional processing steps. Herein, we introduce a simple approach to shape perovskite nanocrystals (NC) into photonic architectures that provide light management by directly shaping the active material. Pre-patterned polydimethylsiloxane (PDMS) templates are used for the template-induced self-assembly of 10 nm CsPbBr3 perovskite NC colloids into large area (1 cm2 ) 2D photonic crystals with tunable lattice spacing, ranging from 400 nm up to several microns. The photonic crystal arrangement facilitates efficient light coupling to the nanocrystal layer, thereby increasing the electric field intensity within the perovskite film. As a result, CsPbBr3 2D photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near-IR, in contrast to equivalent flat NC films prepared using the same colloidal ink. This improvement is attributed to the enhanced multi-photon absorption caused by light trapping in the photonic crystal.

Thickness-Dependence of Exciton-Exciton Annihilation in Halide Perovskite Nanoplatelets.

Exciton-exciton annihilation (EEA) and Auger recombination are detrimental processes occurring in semiconductor optoelectronic devices at high carrier densities. Despite constituting one of the main obstacles for realizing lasing in semiconductor nanocrystals (NCs), the dependencies on NC size are not fully understood, especially for those with both weakly and strongly confined dimensions. Here, we use differential transmission spectroscopy to investigate the dependence of EEA on the physical dimensions of thickness-controlled 2D halide perovskite nanoplatelets (NPls). We find the EEA lifetimes to be extremely short on the order of 7-60 ps. Moreover, they are strongly determined by the NPl thickness with a power law dependence according to τ2 ∝ d5.3. Additional measurements show that the EEA lifetimes also increase for NPls with larger lateral dimensions. These results show that a precise control of the physical dimensions is critical for deciphering the fundamental laws governing the process especially in 1D and 2D NCs.