Lead Halide Perovskite Nanocrystals Research Articles

In Situ Real-Time Observation of Formation and Self-Assembly of Perovskite Nanocrystals at High Temperature.

All-inorganic cesium lead halide perovskite nanocrystals (NCs) have received much attention due to their outstanding optical and electronic properties, but the underlying growth mechanism remains elusive due to their rapid formation process. Here, we report an in situ real-time study of the growth of Cs4PbBr6 NCs under practical synthesis conditions in a custom-made reactor. Through the synchrotron-based small-angle X-ray scattering technique, we find that the formation of Cs4PbBr6 NCs is accomplished in three steps: the fast nucleation process accompanied by self-focusing growth, the subsequent diffusion-limited Ostwald ripening, and the self-assembly of NCs into the face-centered cubic (fcc) superlattices at high temperature and the termination of growth. The simultaneously collected wide-angle X-ray scattering signals further corroborate the three-step growth model. The influence of superlattice formation is also elucidated, which improves the uniformity of the final NCs.

Influence of Binary Ligands in Designing Cesium Lead Halide (CsPbX3, X = Cl, Br, I) Perovskite Nanocrystals-Oleic Acid and Oleylamine

The surface chemistry of cesium lead halide perovskite nanocrystals has been elaborately studied in recent years and has proved the critical role of carboxylic acids and amines in the formation and stability of the nanocrystals. Specifically, a slight change in the concentration and ratio of the frequently used oleic acid and oleylamine critically influences the resultant phase and physical properties. Thus, understanding the delicate surface of cesium lead halide perovskite nanocrystals mainly relies on chemical bonding and the dynamic ligand environment of these two organic species. In this aspect, this review summarizes experimental findings about the critical role of oleic acid and oleylamine on the nucleation, growth, stability, phase, and morphology of cesium lead halide perovskite nanocrystals and their effect under different circumstances.

Dual-band photoluminescence mechanism of magnetic doped two-dimensional (PEA)2PbBr4 single crystals

Mn2+ doping effectively realizes white light emission in three-dimensional lead halide perovskite nanocrystals. Meanwhile, research on Mn-doped two-dimensional layered perovskite single crystal is limited. We report centimeter-scale Mn-doped PEA2PbBr4 (C6H5CH2CH2NH3+ and PEA+) single crystals prepared by a slow evaporation method. Mn2+ dopants mainly act as substitutional doping and exhibit paramagnetic properties in the crystal at low doping density, while interstitial doping of Mn2+ prevails and induces antiferromagnetic characteristics at high doping density. Mn:PEA2PbBr4 single crystals exhibit dual-band chromacity-tunable blue-orange photoluminescence originating from excitons and Mn2+ emission. The negative temperature quenching effect is achieved by Mn-doping defects for the temperature-dependent exciton photoluminescence. Upon testing in the low-pressure vacuum chamber, the Mn2+ peak of the single crystal shows a dramatic shift from 610 to 690 nm. These results indicate that Mn:PEA2PbBr4 single crystal can serve as a potential and promising luminescent device material that achieves color tunable properties by regulating the systematic changes in the intensity ratio of exciton emission and Mn2+ emission, which will be very helpful for exploring the application of perovskite in magneto-optical devices in the future.

The Impact of Ligand Removal on the Optoelectronic Properties of Inorganic and Hybrid Lead Halide Perovskite Nanocrystal Films

AbstractLigand exchange performed during or after the colloidal synthesis of nanocrystals (NCs) provides an efficient way to produce conductive NC solids for optoelectronics. Herein, a post‐synthetic ligand washing process is developed and applied to two different combinations of ligands and perovskite NCs, namely robust green CsPbBr3 NCs capped by didodecyldimethylammonium bromide and near‐infrared FAPbI3 NCs decorated by weakly bound oleic acid ligands. The impact of such processes on the morphological and optoelectronic NC properties is examined while exploring parameters such as the reaction time and the influence of oxygen and humidity. For the FAPbI3 NCs, ligand washing results in extended NC aggregation and substantial photoluminescence loss, with the treatment becoming more aggressive for air‐exposed films. For the CsPbBr3 NCs, the process is insensitive to the environmental conditions and results in partial ligand shell loss and NC close packing rather than bulk‐like aggregation while affecting less the optical properties. Upon ligand removal, the photoconductance increases by up to ≈90% and ≈60% for FAPbI3 NCs and CsPbBr3 NCs, respectively. THz spectroscopy produces qualitatively similar trends of the conductivity with ligand removal time, with THz mobility values as high as 30 and 6 V−1s−1cm2 for glove box prepared FAPbI3 and CsPbBr3 NCs, respectively.

Epitaxial Growth of Lead‐Free Double Perovskite Shell for CsPbX3/Cs2SnX6 (X = Cl, Br, and I) Core/Shell Perovskite Nanocrystals with Enhanced Photoelectric Properties and Stability

AbstractAll‐inorganic lead halide perovskite nanocrystals (NCs) have great optoelectronic properties with promising applications in light‐emitting diodes (LEDs), lasers, photodetectors, solar cells, and photocatalysis. However, the intrinsic toxicity of Pb and instability of the NCs impede their broad applications. Shell‐coating is an effective method for enhanced environmental stability while reducing toxicity by choosing non‐toxic shell materials such as metal oxides, polymers, silica, etc. However, multiple perovskite NCs can be encapsulated within the shell material and a uniform epitaxial‐type shell growth of well‐isolated NCs is still challenging. In this work, lead‐free vacancy‐ordered double perovskite Cs2SnX6 (X = Cl, Br, and I) shells are epitaxially grown on the surface of CsPbX3 NCs by a hot‐injection method. The effectiveness of the non‐toxic double perovskite shell protection is demonstrated by the enhanced environmental and phase stability against UV illumination and water. In addition, the photoluminescence quantum yields (PL QYs) increase for the CsPbCl3 and CsPbBr3 NCs after shelling because of the type I band alignment of the core/shell materials, while enhanced charge transport properties obtained from CsPbI3/Cs2SnI6 core/shell NCs are due to the efficient charge separation in the type II core/shell band alignment.

Synthesis of a water-stable fluorescence CsPbBr3 perovskite by dual-supersaturated recrystallization method and tuning the fluorescence spectrum for selective detection of folic acid

As an excellent fluorescent material, cesium lead halide perovskite nanocrystals (PNCs) is rarely used for analytical purposes because the PNCs are unstable in polar solvents, especially water. Developing a new synthesis method to prepare water-stable PNCs makes it promising for the detection of analytes in aqueous solutions. Herein, by using the solubility difference of the precursors in different solvents, we successfully synthesized water-stable CsPbBr3 PNCs by a dual-supersaturated recrystallization method at room temperature. We also found that the fluorescence of the as-prepared CsPbBr3 PNCs could be quenched by some small organic molecules, such as folic acid (FA) and dopamine (DA). By using a chloride-induced anion exchange reaction method, the fluorescence emission peak of the CsPbBr3 PNCs could be tuned from 518 to 418 nm and the emission color changed from green to blue. The blue emission chloride-exchanged PNCs have a good selectivity for only FA and a good linear relationship is established between the fluorescence quenching rate of the PNCs and concentration of FA from 10.0 to 140.0 μM, with a limit of detection (LOD) of 0.9 μM. This work expanded the applications of PNCs in the field of analytical chemistry and also proposed a new strategy for improving selectivity by tuning the emission spectrum of a fluorescent probe.

Cesium lead bromide perovskite nanocrystals for the visual detection of chloride ions: A review

Lead halide perovskite nanocrystals (NCs) have been extensively studied due to their high quantum yield, high color purity, tunable band gap, and simple preparation methods. Among them, cesium lead bromide perovskite NCs (CsPbBr3 NCs) have the characteristics of good stability performance, better luminous performance, and good halide exchange properties, etc., and a visual sensing system for fluorescence wavelength shift can be constructed by using their spectral tunability. Accordingly, CsPbBr3 has become a potential candidate material for on-site detection of chloride ions, providing possibility for tunable visual analysis, which not only expands the application potential of CsPbBr3 NCs in the detection field, but also greatly improves the visual fluorescence sensing method. On a basis of the halide exchange property of CsPbBr3 NCs, this review introduces the development strategy of perovskites as the probes to detect chloride ions in the environments of liquids, solids, and gases, and summarizes and prospects the new methods of chloride detection over CsPbBr3 NCs. In addition, this review provides an overview of existing challenges, providing reference for the development of highly sensitive and long-term stable chloride probes based on lead halide perovskites.

Formation of Iodide-Rich Domains During Halide Segregation in Lead-Halide Perovskite Nanocrystals.

Mixed iodide-bromide methylammonium lead perovskite (MAPbIxBr3-x) nanocrystals (NCs) hold promise for use in light-emitting applications owing to the size- and composition-tunability of their bandgap. However, the segregation of halides during light exposure causes their band gaps to become unstable and narrow. Here, we use transient absorption spectroscopy to track excited-state dynamics during photoinduced halide segregation. The Auger recombination dynamics are observed to accelerate as the bandgap narrows, suggesting enhanced electron-hole overlap. We simulate the motion of iodide within the NC and estimate the evolving bandgap and electron-hole overlap during two possible mechanisms of halide segregation. Our results support a segregation mechanism in which iodide anions form a domain within the NC, rather than a mechanism in which iodide anions independently segregate toward the NC surface. Such mechanistic insight will contribute to future NC bandgap stabilization strategies.

Accelerated room temperature synthesis of desired cesium lead halide perovskite nanocrystals via automated microfluidic meta learner

Cesium lead halide perovskite nanocrystals (CLHP NCs) have demonstrated their unique optical properties in next-generation lighting and display devices through controlling the size, shape, and composition. However, achieving their target-specific synthesis with numerous reaction parameters via traditional methods requires long and tedious optimization. Herein, a fully automated microfluidic meta learner (AMML) coupled with coiled flow inverter reactors (CFIR) is developed for facilely synthesizing desired CLHP NCs. CFIR offers a strong support in reagent mixing for AMML, producing high-quality NCs with negligible by-products. By concatenating the model-agnostic meta-learning and feedback control, AMML provides quick and accurate locating of target emission CsPb(BrxI1-x)3 NCs in the wide range from 519 nm to 636 nm based on 3 data points, even in the no-prior-knowledge part. AMML exhibits excellent screening ability (25 experiments in 110 min) of reaction parameters for controllable synthesis of CsPbBr3 NCs. Based on the optimal results, a white light-emitting diode is fabricated with excellent stability and a wide color gamut of 121 % NTSC. AMML offers a novel paradigm for the large-scale synthesis of desired NCs and can be applied to other NCs for intelligent and sustainable discovery.

Dynamic Observations on Formation of Coffee-Ring Structures from the Degradation of Cesium Lead Halide Perovskite Nanocrystals.

Nanomaterials of halide perovskites have attracted increasing attention for their remarkable potential in optoelectronic devices, but their instability to environmental factors is the core issue impeding their applications. In this context, the microscopic understanding of their structural degradation mechanisms upon external stimuli remains incomplete. Herein, we took an emerging member of this material family, Cs4PbBr6 nanocrystals (NCs), as an example and investigated the degradation pathways as well as underlying mechanisms under an electron beam by using in situ transmission electron microscopy. Our atomic-scale study identified the distinct degradation stages for the NCs toward interesting coffee-ring PbBr2 structures, which are caused by the organic surface capping agents as well as surface energy of NCs. Our findings present a fundamental insight for the degradation of halide perovskite NCs and may provide indispensable guidance for their structural design and stability improvement.

Toward the Controlled Synthesis of Lead Halide Perovskite Nanocrystals.

Lead halide perovskite nanocrystals (LHP NCs) have rapidly emerged as one of the most promising materials for optical sources, photovoltaics, and sensor fields. The controlled synthesis of LHP NCs with high monodispersity and precise size tunability has been a subject of intensive research in recent years. However, due to their ionic nature, LHP NCs are usually formed instantaneously, and the corresponding nucleation and growth are difficult to monitor and regulated. In this Perspective, we summarize the representative attempts to achieve controlled synthesis of LHP NCs. We first highlight the burst nucleation and rapid growth characteristics of conventional synthesis methods. Afterward, we introduce the scheme of changing the LHP NCs into kinetically dominant, continuously size-tunable synthesis via nucleation-growth decoupling. We also summarize methods to eliminate undesired ripening effects and achieve homogeneous size distribution through rational ligand selection and solvent engineering. We hope this Perspective will facilitate the development of controlled LHP NCs synthesis protocols and advance the understanding of crystal growth fundamentals of perovskite materials.

Tailoring the Electron and Hole Landé Factors in Lead Halide Perovskite Nanocrystals by Quantum Confinement and Halide Exchange.

The tunability of the optical properties of lead halide perovskite nanocrystals makes them highly appealing for applications. Halide anion exchange and quantum confinement enable tailoring of the band gap. For spintronics, the Landé g-factors of electrons and holes are essential. Using empirical tight-binding and k·p methods, we calculate them for nanocrystals of all-inorganic lead halide perovskites CsPbX3 (X = I, Br, Cl). The hole g-factor band gap dependence follows the universal law found for bulk perovskites, while for electrons, a considerable modification is predicted. Based on the k·p analysis, we conclude that this difference arises from the interaction of the bottom conduction band with the spin-orbit split electron states. These predictions are confirmed experimentally for electron and hole g-factors in CsPbI3 nanocrystals in a glass matrix, measured by time-resolved Faraday ellipticity in a magnetic field at cryogenic temperatures.

Pt-CsPbBr3 Perovskite Nanocrystal Heterostructures: All Epitaxial.

Designing heterostructures of soft ionic nanocrystals with metallic or covalent nanostructures having epitaxial junctions in solution poses several fundamental challenges. Hence, in spite of large successes in developing lead halide perovskite nanocrystals, the chemistry of formation of their facet-directive epitaxial growth of noble metals cannot be explored yet. To address this, herein, epitaxial heterostructures of orthorhombic CsPbBr3 and cubic Pt in multiple directional approaches are reported. Appropriate facets of perovskite nanocrystals and high-temperature reaction are the key parameters for obtaining such nanocrystal heterostructures. Interfacial planes at the junctions having ideal lattice matching helped in establishing the epitaxial relations of (110) of orthorhombic (space group Pbnm) CsPbBr3 with {020} of cubic Pt and again (011) of CsPbBr3 with {111} of Pt. These results provided strong fundamental insights that ionic halide perovskite nanostructures and materials having different crystal phases can be placed in a single building block with continuous sublattice structures.

Ultrafast and Radiation-Hard Lead Halide Perovskite Nanocomposite Scintillators.

The use of scintillators for the detection of ionizing radiation is a critical aspect in many fields, including medicine, nuclear monitoring, and homeland security. Recently, lead halide perovskite nanocrystals (LHP-NCs) have emerged as promising scintillator materials. However, the difficulty of affordably upscaling synthesis to the multigram level and embedding NCs in optical-grade nanocomposites without compromising their optical properties still limits their widespread use. In addition, fundamental aspects of the scintillation mechanisms are not fully understood, leaving the scientific community without suitable fabrication protocols and rational guidelines for the full exploitation of their potential. In this work, we realize large polyacrylate nanocomposite scintillators based on CsPbBr3 NCs, which are synthesized via a novel room temperature, low waste turbo-emulsification approach, followed by their in situ transformation during the mass polymerization process. The interaction between NCs and polymer chains strengthens the scintillator structure, homogenizes the particle size distribution and passivates NC defects, resulting in nanocomposite prototypes with luminescence efficiency >90%, exceptional radiation hardness, 4800 ph/MeV scintillation yield even at low NC loading, and ultrafast response time, with over 30% of scintillation occurring in the first 80 ps, promising for fast-time applications in precision medicine and high-energy physics. Ultrafast radioluminescence and optical spectroscopy experiments using pulsed synchrotron light further disambiguate the origin of the scintillation kinetics as the result of charged-exciton and multiexciton recombination formed under ionizing excitation. This highlights the role of nonradiative Auger decay, whose potential impact on fast timing applications we anticipate via a kinetic model.

Liquid‐solid‐Interpenetration Surface Reconstruction of Monodisperse Water Stabilized CsPbBr3/CsPb2Br5 Core/Shell Perovskite Nanocrystals

AbstractAll‐inorganic lead halide perovskite nanocrystals (NCs) have shown great potential in various optoelectronic device applications due to their excellent optoelectronic properties, but their poor stability remains a key obstacle to widespread application. The preparation of core/shell NCs is developed to improve their stability, but most of the coating for single NCs is incomplete, and the crystal orientation and interface binding of core/shell structures are still unclear. Here, a surface reconstruction strategy to synthesize CsPbBr3/CsPb2Br5 core/shell NCs with uniform coating structure is reported. The concentration of [PbBr8]6− monomer in the system is regulated by creating local low H2O concentration conditions to balance the erosion of perovskite by water and the overall heterogeneous nucleation reaction system, resulting in single encapsulated and well‐edged perovskite core/shell NCs. More importantly, advanced characterization tools are used to reveal the core/shell structural features of CsPbBr3/CsPb2Br5 core/shell NCs at the atomic scale, which has not been reported before, and the interface matching of the two‐phase binding is simulated by density functional theory calculations, which confirm that the CsPb2Br5 (116) facet can bind to the CsPbBr3 (100) facet with the lowest binding energy. The prepared core/shell perovskite NCs can still retain photoluminescence emission after >30 days in water.

One-step synthesis of all-inorganic high-entropy dual-phase Cs‘B’Br3/Cs‘B’2Br5 perovskite nanocrystals by high-energy ball milling

All-inorganic lead halide perovskite nanocrystals (NCs) have attracted considerable attention in field of optoelectronics due to their excellent properties such as high PLQY, tunable emission spectra in visible light region, and narrow emission peaks. However, problems existing in the research of all-inorganic lead halide perovskite materials are high lead content, low stability, and complex synthesis processes. Those problems need to be solved urgently. Therefore, dual-phase Cs‘B’Br3/Cs‘B’2Br5 perovskite material (Cs(Pb1/5Mn1/5Ni1/5Zn1/5Cd1/5)Br3/Cs(Pb1/5Mn1/5Ni1/5Zn1/5Cd1/5)2Br5) was synthesized by doping the B-site of CsPbBr3 and CsPb2Br5 using high-energy ball milling in this thesis. This dual-phase perovskite material has maximum absorption edge of 540 nm, a band gap width of 2.22 eV, the maximum emission peak at 600 nm with FWHM of 72 nm, PLQY of 24.50%, and an average fluorescence lifetime of 227.87 μs. After 21 days at room temperature, luminescent intensity of NCs increased to 156%, and still retained 109% at 120 days. After treatment at 150 °C, luminescent intensity decreased to 47%. Results show that this high-entropy dual-phase perovskite has great stability in different temperature. This proves that synthesis of high-entropy dual-phase halide perovskite by high-energy ball milling is feasible, and has great significance in solving poor stability and high lead content of all-inorganic lead halide perovskite in the future.

Unraveling the Relevance of Electron and Hole Transfer in Lead Halide Perovskite Nanocrystals on Current Conduction.

Optimization of perovskite-based optoelectronic performance demands prudent engineering in the device architecture with facile transport of generated charge carriers. Herein, we explore the charge transfer (CT) kinetics in perovskite nanocrystals (PNCs), CsPbBr3, with two redox-active quinones, menadione (MD) and anthraquinone (AQ), and its alteration in halide exchanged CsPbCl3. With a series of spectroscopic and microscopic measurements, we infer that both electron and hole transfer (ET-HT) prevail in CsPbCl3 with quinones, resulting in a faster CT, while ET predominates for CsPbBr3. Furthermore, current-sensing atomic force microscopy measurements demonstrate that the conductance across a metal-PNC-metal nanojunction is improved in the presence of quinones. The contributions of ET and HT to current conduction across PNCs are well supported and validated by theoretical calculations of the density of states. These outcomes convey a new perspective on the relevance of ET and HT in the optimal current conduction and optoelectronic device engineering of perovskites.

Synthesis of Zwitterionic CsPbBr3 Nanocrystals with Controlled Anisotropy using Surface-Selective Ligand Pairs.

Mechanistic studies of the morphology of lead halide perovskite nanocrystals (LHP-NCs) are hampered by a lack of generalizable suitable synthetic strategies and ligand systems. Here, the synthesis of zwitterionic CsPbBr3 NCs is presented with controlled anisotropy using a proposed "surface-selective ligand pairs" strategy. Such a strategy provides a platform to systematically study the binding affinity of capping ligand pairs and the resulting LHP morphologies. By using zwitterionic ligands (ZwL) with varying structures, majority ZwL-capped LHP NCs with controlled morphology are obtained, including anisotropic nanoplatelets and nanorods, for the first time. Combining experiments with density functional theory calculations, factors that govern the ligand binding on the different surface facets of LHP-NCs are revealed, including the steric bulkiness of the ligand, the number of binding sites, and the charge distance between binding moieties. This study provides guidance for the further exploration of anisotropic LHP-NCs.

Anion Exchanges of Water-Stable Perovskite Nanocrystals in the Pure Water Phase and Applications in Detecting Halide Ions via a Smartphone-Based Sensing Platform.

Recently, the newly emerging lead halide perovskite nanocrystals (PNCs) have been intensely researched in many fields, such as light-emitting diodes (LEDs), solar cells, lasers, and display devices. The extremely high fluorescence quantum yield (near 100%) of PNCs over classic fluorescent materials would enable good applications of PNCs in sensing. However, the study on PNCs for bio- and chemical sensing, especially for detecting targets that exist in aqueous medium, faces great challenges due to the well-known instability of PNCs in polar solvents, especially water. Although the encapsulation of polymers or inorganic materials can efficiently protect PNCs from decomposition in aqueous solution, the sensing based on the interaction between PNCs and targets is severely hindered by the compact protection coating at the surfaces of PNCs. In this work, novel water-dispersed PNCs (W-PNCs), i.e., CsPbBr3@CsPb2Br5 PNCs, with strong fluorescence and excellent water stability were synthesized from OAm-capped CsPbBr3 PNCs by a simple "oil-solid-water" phase transition. The W-PNCs without being encapsulated with compact polymers or inorganic materials can sensitively and stably sense targets in the pure water phase via direct chemical reactions. For the first time, ion exchanges between PNCs and halide ions and their effects on the fluorescence wavelength of PNCs were investigated in the pure water phase, on the basis of which a new, visualized, selective, and sensitive smartphone-based sensing platform for halide ions has been established by the integration of the conveniently prepared W-PNC nanoprobe and the portable mobile phone. It is envisioned that the uncoated but extremely water-stable and highly fluorescent W-PNCs have promising applications in chemical sensing, biosensing, and bioimaging of targets in aqueous medium.

Synthesis of CsPbBr3 in Micro Total Reaction System: Fast Operation Space Mapping and Subsecond Growth Process Monitoring.

Lead halide perovskite nanocrystals (LHP NCs) have the characteristics of fast reaction kinetics and crystal instability due to the intrinsically highly ionic bonding between the respective ions, which bring challenges for revealing the growth kinetics and practical applications. Compared with conventional batch synthesis methods, the single-function microreactor can achieve precise and stable control of the NCs synthesis process, but it still has the shortcoming of not being able to obtain information about the growth process. In this study, a micro Total Reaction System (μTRS) with remote control, online detection, and rapid data analysis functions is designed. μTRS can sample the photoluminescence information of CsPbBr3 NCs growth in ligand-assisted reprecipitation method. CsPbBr3 NCs with an emission range of 435-492 nm are successfully detected, which breaks the record of the smallest size of CsPbBr3 NCs synthesized directly from precursors. The real-time feature of μTRS enables the construction of an automated close-loop synthesis system. Besides, the rapid acquisition and timely processing of product information enable the rapid mapping of the operation space for CsPbBr3 NCs preparation, which provides a reliable and learnable data set for designing a fully autonomous microreaction system capable of synthesizingNCs.