Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange‐Driven Cation Exchange

Unlike widely used postsynthetic halide exchange for CsPbX₃ (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange‐driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn‐doped CsPb(Cl/Br)₃ NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl₂ molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core–shell structured mid states with triple emission bands, and dopant molecules composition‐dependent doping process. As‐prepared dual‐emitting Mn‐doped CsPb(Cl/Br)₃ NCs are available for ratiometric temperature sensing.     

High‐Brightness Blue and White LEDs based on Inorganic Perovskite Nanocrystals and their Composites

Inorganic metal halide perovskite nanocrystals (NCs) have been employed universally in light‐emitting applications during the past two years. Here, blue‐emission (≈470 nm) Cs‐based perovskite NCs are derived by directly mixing synthesized bromide and chloride nanocrystals with a weight ratio of 2:1. High‐brightness blue perovskite light‐emitting diodes (PeLEDs) are obtained by controlling the grain size of the perovskite films. Moreover, a white PeLED is demonstrated for the first time by blending orange polymer materials with the blue perovskite nanocrystals as the active layer. Exciton transfer from the blue nanocrystals to the orange polymers via Förster or Dexter energy transfer is analyzed through time resolved photoluminescence. By tuning the ratio between the perovskite nanocrystals and polymers, pure white light is achieved with the a CIE coordinate at (0.33,0.34).     

CsPbX3纳米晶稳定性的研究进展

全无机钙钛矿纳米晶具有窄发射、高量子效率及较高的载流子迁移率等优点, 在高清柔性显示器和太阳能电池等领域具有广泛的应用前景。然而, 钙钛矿纳米晶的表面配体处于高度动态结合的状态, 容易在分离和提纯等过程中造成大量配体缺失, 从而导致量子效率和稳定性下降。此外, 钙钛矿材料本身的离子晶体特性使其对极性溶剂非常敏感, 这些问题严重制约了钙钛矿纳米晶在光电器件中的实际应用。本文从钙钛矿纳米晶表面态出发, 结合国内外的研究工作, 分析了路易斯酸、路易斯碱及表面包覆策略对钙钛矿纳米晶光学性质和稳定性的影响, 并对进一步优化提升钙钛矿纳米晶的稳定性进行了展望。     

A New Passivation Route Leading to Over 8% Efficient PbSe Quantum‐Dot Solar Cells via Direct Ion Exchange with Perovskite Nanocrystals

Colloidal quantum dots (QDs) are promising candidate materials for photovoltaics (PV) owing to the tunable bandgap and low‐cost solution processability. Lead selenide (PbSe) QDs are particularly attractive to PV applications due to the efficient multiple‐exciton generation and carrier transportation. However, surface defects arising from the oxidation of the PbSe QDs have been the major limitation for their development in PV. Here, a new passivation method for chlorinated PbSe QDs via ion exchange with cesium lead halide (Br, I) perovskite nanocrystals is reported. The surface chloride ions on the as‐synthesized QDs can be partially exchanged with bromide or iodide ions from the perovskite nanocrystals, hence forming a hybrid halide passivation. Consistent with the improved photoluminescence quantum yield, the champion PV device fabricated with these PbSe QDs achieves a PCE of 8.2%, compared to 7.3% of that fabricated with the untreated QDs. This new method also leads to devices with excellent air‐stability, retaining at least 93% of their initial PCEs after being stored in ambient conditions for 57 d. This is considered as the first reported PbSe QD solar cell with a PCE of over 8% to date.     

Flexible,Printable Soft‐X‐Ray Detectors Based on All‐Inorganic Perovskite Quantum Dots

Metal halide perovskites represent a family of the most promising materials for fascinating photovoltaic and photodetector applications due to their unique optoelectronic properties and much needed simple and low‐cost fabrication process. The high atomic number (Z) of their constituents and significantly higher carrier mobility also make perovskite semiconductors suitable for the detection of ionizing radiation. By taking advantage of that, the direct detection of soft‐X‐ray‐induced photocurrent is demonstrated in both rigid and flexible detectors based on all‐inorganic halide perovskite quantum dots (QDs) synthesized via a solution process. Utilizing a synchrotron soft‐X‐ray beamline, high sensitivities of up to 1450 µC Gy_air^?1 cm^?2 are achieved under an X‐ray dose rate of 0.0172 mGy_air s^?1 with only 0.1 V bias voltage, which is about 70‐fold more sensitive than conventional α‐Se devices. Furthermore, the perovskite film is printed homogeneously on various substrates by the inexpensive inkjet printing method to demonstrate large‐scale fabrication of arrays of multichannel detectors. These results suggest that the perovskite QDs are ideal candidates for the detection of soft X‐rays and for large‐area flat or flexible panels with tremendous application potential in multidimensional and different architectures imaging technologies.     

Synthesis of CsPbX3 (X = Cl/Br,Br, and Br/I)@SiO2/PMMA composite films as color-conversion materials for achieving tunable multi-color and white light emission

All-inorganic cesium lead halide based perovskite nanocrystals(PNCs)exhibit promising optoelectronic properties,but their poor stability and anion exchange reaction limit their broad commercial applications.Herein,we demonstrated the successful synthesis of blue-green-red emitting CsPbX₃(X=Cl/Br,Br,and Br/I)PNCs via hot injection method,followed by silica-coating and embedding in poly(methylmethacrylate)(PMMA)matrix.The photoluminescence(PL)spectra of SiO₂/PMMA-coated PNCs can be tuned continuously by regulating precursor composition ratio,from blue(CsPb(Cl_0.5/Br_0.5)₃;460 nm)to red(CsPb(Br_0.4/I_0.6)₃via green(CsPbBr₃;519 nm).The PNCs composite films exhibit improved stability(thermal-,moisture-,and photo-stability)because of the barrier formed by Si0₂/PMMA coating and also displayed exceptional photoluminescent quantum yield(PLQY of blue,green,and red-emitting Si0₂/PMMA coated PNCs are 37%,86%,and 71%,respectively)with longer lifetimes inhibiting anion exchange.Eventually,the PNCs-encapsulated Si0₂/PMMA composite films were integrated into the UV LED chip as down-converting materials to construct a prototype white-peLED unit.The designed white-peLED unit demonstrated bright white light generating CIE coordinates(0.349,0.350),a luminous efficiency(LE)of 39.2%and a color rendering index(CRI)of 84.7.The wide color gamut of 121.47%of NTSC and 98.56%of Rec.2020 is also achieved with the built w-LED system.Therefore,the results demonstrated that CsPbX₃(X=Cl/Br,Br,and Br/I)PNCs@SiO₂/PMMA composite films can be employed as efficient UV to visible color conversion materials for white-LEDs and backlighting.     

Molecule‐Induced p‐Doping in Perovskite Nanocrystals Enables Efficient Color‐Saturated Red Light‐Emitting Diodes

Color‐saturated red light‐emitting diodes (LEDs) with emission wavelengths at around 620–640 nm are an essential part of high‐definition displays. Metal halide perovskites with very narrow emission linewidth are promising emitters, and rapid progress has been made in perovskite‐based LEDs (PeLEDs); however, the efficiency of the current color—pure red PeLEDs—still far lags behind those of other‐colored ones. Here, a simple but efficient strategy is reported to gradually down‐shift the Fermi level of perovskite nanocrystals (NCs) by controlling the interaction between NCs and their surface molecular electron acceptor—benzyl iodide with aromatic rings—and realize p‐doping in the color‐saturated 625 nm emitting NCs, which significantly reduces the hole injection barrier in devices. Besides, both the luminescence efficiency and electric conductivity of perovskite NCs are enhanced as additional advantages as the result of surface defects passivation. As a result, the external quantum efficiency for the resulting LED is increased from 4.5% to 12.9% after benzyl iodide treatment, making this device the best‐performing color‐saturated red PeLED so far. It is further found that the hole injection plays a more critical role than the photoluminescence efficiency of perovskite emitter in determining the LED performance, which implies design principles for efficient thin‐film planar LEDs.     

Perovskite‐Initiated Photopolymerization for Singly Dispersed Luminescent Nanocomposites

Metal halide perovskites have demonstrated rich photophysics and remarkable potential in photovoltaic and electroluminescent devices. However, the photoactivity of perovskite semiconductors in chemical processes remains relatively unexplored. Here, a general approach toward the synthesis of luminescent perovskite–polymer nanocomposites is reported, whereby perovskite nanocrystals are used as photoinitiators in the polymerization of vinyl monomers. The white‐light illumination of a perovskite–monomer mixture triggers a free‐radical chain‐growth polymerization process, giving rise to high molecular weight polymers of ≈200 kDa. The in situ growth of polymer chains from the perovskite crystal surface allows the formation of individually dispersed nanocrystal cores within an encapsulating polymer matrix, and leads to a significant threefold enhancement in photoluminescence quantum yield. This photoluminescence enhancement is attributed to the spatial separation of the perovskite nanocrystals and hence the deactivation of energy transfer to dark crystals. The resulting perovskite–polymer nanocomposites exhibit excellent stability against moisture and are shown to be useful as functional downconversion phosphor films for luminescent displays and lighting.     

Nanocube Superlattices of Cesium Lead Bromide Perovskites and Pressure‐Induced Phase Transformations at Atomic and Mesoscale Levels

Lead halide perovskites are promising materials for a range of applications owing to their unique crystal structure and optoelectronic properties. Understanding the relationship between the atomic/mesostructures and the associated properties of perovskite materials is crucial to their application performances. Herein, the detailed pressure processing of CsPbBr₃ perovskite nanocube superlattices (NC‐SLs) is reported for the first time. By using in situ synchrotron‐based small/wide angle X‐ray scattering and photoluminescence (PL) probes, the NC‐SL structural transformations are correlated at both atomic and mesoscale levels with the band‐gap evolution through a pressure cycle of 0 ? 17.5 GPa. After the pressurization, the individual CsPbBr₃ NCs fuse into 2D nanoplatelets (NPLs) with a uniform thickness. The pressure‐synthesized perovskite NPLs exhibit a single cubic crystal structure, a 1.6‐fold enhanced photoluminescence quantum yield, and a longer emission lifetime than the starting NCs. This study demonstrates that pressure processing can serve as a novel approach for the rapid conversion of lead halide perovskites into structures with enhanced properties.     

Metal Halide Perovskite Nanorods: Shape Matters

Quasi-1D metal halide perovskite nanorods (NRs) are emerging as a type of materials with remarkable optical and electronic properties. Research into this field is rapidly expanding and growing in the past several years, with significant advances in both mechanistic studies of their growth and widespread possible applications. Here, the recent advances in 1D metal halide perovskite nanocrystals (NCs) are reviewed, with a particular emphasis on NRs. At first, the crystal structures of perovskites are elaborated, which is followed by a review of the major synthetic approaches toward perovskite NRs, such as wet-chemical synthesis, substrate-assisted growth, and anion exchange reactions, and discussion of the growth mechanisms associated with each synthetic method. Then, thermal and aqueous stability and the linear polarized luminescence of perovskite NRs are considered, followed by highlighting their applications in solar cells, light-emitting diodes, photodetectors/phototransistors, and lasers. Finally, challenges and future opportunities in this rapidly developing research area are summarized.     

Oxalic Acid Enabled Emission Enhancement and Continuous Extraction of Chloride from Cesium Lead Chloride/Bromide Perovskite Nanocrystals

All‐inorganic cesium lead halide perovskite nanocrystals (NCs) have demonstrated excellent optical properties and an encouraging potential for optoelectronic applications; however, mixed‐halide perovskites, especially CsPb(Cl/Br)₃ NCs, still show lower photoluminescence quantum yields (PL QY) than the corresponding single‐halide materials. Herein, anhydrous oxalic acid is used to post‐treat CsPb(Cl/Br)₃ NCs in order to initially remove surface defects and halide vacancies, and thus, to improve their PL QY from 11% to 89% for the emission of 451 nm. Furthermore, due to the continuous chelating reaction with the oxalate ion, chloride anions from the mixed‐halide CsPb(Cl/Br)₃ perovskite NCs could be extracted, and green emitting CsPbBr₃ NCs with PL QY of 85% at 511 nm emission are obtained. Besides being useful to improve the emission of CsPb(Cl/Br)₃ NCs, the oxalic acid treatment strategy introduced here provides a further tool to adjust the distribution of halide anions in mixed‐halide perovskites without using any halide additives.     

Well‐Defined Cobalt Catalyst with N‐Doped Carbon Layers Enwrapping: The Correlation between Surface Atomic Structure and Electrocatalytic Property

Admittedly, the surface atomic structure of heterogenous catalysts toward the electrochemical oxygen reduction reaction (ORR) are accepted as the important features that can tune catalytic activity and even catalytic pathway. Herein, a surface engineering strategy to controllably synthesize a carbon‐layer‐wrapped cobalt‐catalyst from 2D cobalt‐based metal–organic frameworks is elaborately demonstrated. Combined with synchrotron radiation X‐ray photoelectron spectroscopy, the soft X‐ray absorption near‐edge structure results confirmed that rich covalent interfacial Co? N? C bonds are efficiently formed between cobalt nanoparticles and wrapped carbon‐layers during the polydopamine‐assisted pyrolysis process. The X‐ray absorption fine structure and corresponding extended X‐ray absorption fine structure spectra further reveal that the wrapped cobalt with Co–N coordinations shows distinct surface distortion and atomic environmental change of Co‐based active sites. In contrast to the control sample without coating layers, the 800 °C‐annealed cobalt catalyst with N‐doped carbon layers enwrapping achieves significantly enhanced ORR activity with onset and half‐wave potentials of 0.923 and 0.816 V (vs reversible hydrogen electrode), highlighting the important correlation between surface atomic structure and catalytic property.     

Thermoresponsive Emission Switching via Lower Critical Solution Temperature Behavior of Organic–Inorganic Perovskite Nanoparticles

Lead halide perovskites have shown much promise for high‐performing solar cells due to their inherent electronic nature, and though the color of bright‐light emitters based on perovskite nanoparticles can be tuned by halide mixing and/or size control, dynamic switching using external stimuli remains a challenge. This article reports an unprecedented lower critical solution temperature (LCST) for toluene solutions containing methylammonium lead bromide (MAPbBr₃), oleic acid, alkylamines, and dimethylformamide. The delicate interplay of these molecules and ions allows for the reversible formation and decomposition of MAPbBr₃ nanoparticles upon heating and cooling, which is accompanied by green and blue photoemissions at each state. An intermediate 1D crystal with PbBr₂‐amine coordination is found to play pivotal role in this, and a mechanistic insight is provided based on a three‐state model. In addition to a high quantum yield (up to 85%), this system allows for control over the cloud point (30?80 °C) through compositional engineering and the luminescent color (blue to red) via halogen exchange, thus making it a versatile solution for developing functional molecular organic–inorganic LCST quantum dots.     

Light Generation in Lead Halide Perovskite Nanocrystals: LEDs,Color Converters,Lasers, and Other Applications

Facile solution processing lead halide perovskite nanocrystals (LHP‐NCs) exhibit superior properties in light generation, including a wide color gamut, a high flexibility for tuning emissive wavelengths, a great defect tolerance and resulting high quantum yield; and intriguing electric feature of ambipolar transport with moderate and comparable mobility. As a result, LHP‐NCs have accomplished great achievements in various light generation applications, including color converters for lighting and display, light‐emitting diodes, low threshold lasing, X‐ray scintillators, and single photon emitters. Herein, the considerable progress that has been made thus far is reviewed along with the current challenges and future prospects in the light generation applications of LHP‐NCs.     

In-situ fabricated anisotropic halide perovskite nanocrystals in polyvinylalcohol nanofibers: Shape tuning and polarized emission

Nano Research - We report an in-situ fabrication of halide perovskite (CH3NH3PbX3, CH3NH3 = methylammonium, MA, X= Cl, Br, I) nanocrystals in polyvinylalcohol (PVA) nanofibers (MAPbX3@PVA...     

Recent Progress and Development in Inorganic Halide Perovskite Quantum Dots for Photoelectrochemical Applications

Inorganic halide perovskite quantum dots (IHPQDs) have recently emerged as a new class of optoelectronic nanomaterials that can outperform the existing hybrid organometallic halide perovskite (OHP), II–VI and III–V groups semiconductor nanocrystals, mainly due to their relatively high stability, excellent photophysical properties, and promising applications in wide‐ranging and diverse fields. In particular, IHPQDs have attracted much recent attention in the field of photoelectrochemistry, with the potential to harness their superb optical and charge transport properties as well as spectacular characteristics of quantum confinement effect for opening up new opportunities in next‐generation photoelectrochemical (PEC) systems. Over the past few years, numerous efforts have been made to design and prepare IHPQD‐based materials for a wide range of applications in photoelectrochemistry, ranging from photocatalytic degradation, photocatalytic CO₂ reduction and PEC sensing, to photovoltaic devices. In this review, the recent advances in the development of IHPQD‐based materials are summarized from the standpoint of photoelectrochemistry. The prospects and further developments of IHPQDs in this exciting field are also discussed.     

Unfolding B?O?B Bonds for an Enhanced ORR Performance in ABO3‐Type Perovskites

Identifying the relationship between catalytic performance and material structure is crucial to establish the design principle for highly active catalysts. Deficiency in B? O bond covalency induced by lattice distortion severely restricts the oxygen reduction reaction (ORR) performance for ABO₃‐type perovskite oxides. Herein, a rearrangement of hybridization mode for B? O bond is used to tune the overlap of the electron cloud between B 3d and O 2p through A‐stie doping with larger radius ions. The B? O bond covalency is strengthened with a B? O? B bond angle recovered from intrinsic structural distortion. As a result, the adsorption and the reduction process for O₂ on the oxide surface can be promoted via shifting the O‐2p band center toward the Fermi Level. Simultaneously, the spin electrons in the Mn 3d orbit become more parallel. It will lead to a high electrical conductivity by the enhanced double exchange process and thereof mitigate the ORR efficiency loss. Further density functional theory calculation reveals that a flat [BO₂] plane will make contribution to the charge transfer process from lattice oxygen to adsorbed oxygen (mediated with B ions). Through such exploration of the effect of crystal structure on the electronic state of perovskite oxides, a novel insight into design of highly active ORR catalysts is offered.     

Kinetic Stabilization of the Sol–Gel State in Perovskites Enables Facile Processing of High‐Efficiency Solar Cells

Perovskite solar cells increasingly feature mixed‐halide mixed‐cation compounds (FA_1?x?yMA_xCs_yPbI_3?zBr_z) as photovoltaic absorbers, as they enable easier processing and improved stability. Here, the underlying reasons for ease of processing are revealed. It is found that halide and cation engineering leads to a systematic widening of the anti‐solvent processing window for the fabrication of high‐quality films and efficient solar cells. This window widens from seconds, in the case of single cation/halide systems (e.g., MAPbI₃, FAPbI₃, and FAPbBr₃), to several minutes for mixed systems. In situ X‐ray diffraction studies reveal that the processing window is closely related to the crystallization of the disordered sol–gel and to the number of crystalline byproducts; the processing window therefore depends directly on the precise cation/halide composition. Moreover, anti‐solvent dripping is shown to promote the desired perovskite phase with careful formulation. The processing window of perovskite solar cells, as defined by the latest time the anti‐solvent drip yields efficient solar cells, broadened with the increasing complexity of cation/halide content. This behavior is ascribed to kinetic stabilization of sol–gel state through cation/halide engineering. This provides guidelines for designing new formulations, aimed at formation of the perovskite phase, ultimately resulting in high‐efficiency perovskite solar cells produced with ease and with high reproducibility.     

Advances in metal halide perovskite nanocrystals: Synthetic strategies,growth mechanisms,and optoelectronic applications

Metal halide perovskite nanocrystals, as a new class of light-harvesting and light-emitting materials, have recently attracted a lot of attention for an impressive variety of optoelectronic applications. Some advantages of perovskite nanocrystals include there being low-cost, easy-to-perform synthetic routes, convenient solution processability, precise bandgap tunability over the entire visible spectral range, and exceptionally high photoluminescence quantum yields. In this review, we summarize recent advances of perovskite nanocrystals with an emphasis on the synthetic methods, growth mechanisms, optical properties, and related applications. The focus is placed on emerging new results in terms of the increasing diversity in the synthetic methodologies, ability to control nanoparticle shapes, stability enhancement strategies (including direct syntheses in water), and on the particle formation mechanisms. The basic design principles and up-to-date performance of optoelectronic devices based on perovskite nanocrystals are considered, with a main focus on light-emitting diodes, but also touching upon solar cells, photodetectors, and lasers. We finish the review with a critical outlook into the open issues and future perspective of this versatile, still rapidly developing field.     

Synthesis and Photocatalytic Application of Stable Lead‐Free Cs2AgBiBr6 Perovskite Nanocrystals

Lead halide perovskite nanocrystals (NCs) have demonstrated great potential as appealing candidates for advanced optoelectronic applications. However, the toxicity of lead and the intrinsic instability toward moisture hinder their mass production and commercialization. Herein, to solve such thorny problems, novel lead‐free Cs₂AgBiBr₆ double perovskite NCs fabricated via a simple hot‐injection method are reported, which exhibit impressive stability in moisture, light, and temperature. Such materials are then applied into photocatalytic CO₂ reduction, achieving a total electron consumption of 105 µmol g^?1 under AM 1.5G illumination for 6 h. This study offers a reliable avenue for Cs₂AgBiBr₆ perovskite nanocrystals preparation, which holds a great potential in the further photochemical applications.