Cesium Lead Halide Perovskite Nanocrystals Research Articles

Harnessing Pb-S Interactions for Long-Term Water Stability in Cesium Lead Halide Perovskite Nanocrystals.

Lead halide perovskite nanocrystals (LHP NCs) have garnered attention as promising light-harvesting materials for optoelectronics and photovoltaic devices, attributed to their impressive optoelectronic properties. However, their susceptibility to moisture-induced degradation has hindered their practical applications. Despite various encapsulation strategies, challenges persist in maintaining their stability and optoelectronic performance simultaneously. Here, a ligand exchange approach is proposed using (11-mercaptoundecyl)-N,N,N-trimethylammonium bromide (MUTAB) to enhance the stability and dispersibility of CsPbBr3 (CPB) NCs in aqueous environments. MUTAB enables effective surface passivation of the CPB NCs via robust Pb-S interactions at the S-terminal while concurrently directing water molecules through the unbound cationic N-terminal or vice versa, ensuring water dispersibility and stability. Spectroscopic analysis confirms retained structural and optical integrity post-ligand exchange. Crucially, MUTAB-bound CPB NCs exhibit sustained charge transfer properties, demonstrated by aqueous colloidal oxidation reactions. This ligand exchange strategy offers a promising pathway for advancing LHP NCs toward practical optoelectronic and photocatalytic applications.

Selective detection of ascorbic acid by tuning the composition and fluorescence of the cesium lead halide perovskite nanocrystals

Lead halide perovskite nanocrystals (PNCs) have attracted intense attention due to their excellent optoelectronic properties. In this work, a series of water-stable CsPb(Br/I)3 PNCs fluorescent probes were prepared using an anion exchange method. It was found that the PNCs probes could be used to detect ascorbic acid (AA) in water, and interestingly, the FL spectra of the PNCs probes can be adjusted by controlling the concentration of KI in anion exchange to improve the detection selectivity of AA. The high sensitivity and selectivity make CsPb(Br/I)3 PNCs an ideal material for AA sensing. The concentration of AA can be linearly measured in the range from 0.01 to 50 μM, with a detection limit of 4.2 nM. The reason for the enhanced FL of CsPb(Br/I)3 PNCs was studied, and it is considered that AA causes the aggregation of CsPb(Br/I)3 PNCs. This strategy of improving the selectivity of the probe to the substrate by adjusting the spectrum will significantly expand the application of PNCs in the field of analysis and detection.

Tuning the fluorescence emission of water-stable CsPb(Br/I)3 perovskite nanocrystal probes for naked-eye visual detection of mercury ion

All-inorganic cesium lead halide perovskite nanocrystals (PNCs) have rarely been reported in analytical chemistry, especially in water environment analysis, due to their high susceptibility to environmental conditions. Herein, we investigate and report a method of visual detection of Hg2+ concentration in aqueous solution using CsPb(Br/I)3 PNCs. In this strategy, three kinds of CsPb(Br/I)3 PNCs with FL emission peaks of 551 nm, 591 nm, and 617 nm were used to detect Hg2+, and it was found that Hg2+ can quench the fluorescence of CsPb(Br/I)3 PNCs and blue-shift the maximum FL emission peak. We also found that the Hg2+ concentration has a good linear relationship with the fluorescence quenching rate (I0/I) and FL emission peak shift (Δλ) of CsPb(Br/I)3 PNCs. With the red-shift of the probe FL emission peak, the detected concentration range of Hg2+ gradually expanded. Therefore, the possibility of detecting Hg2+ concentration without huge equipment was detailed by examining the red (R), green (G), and blue (B) values of photographs of CsPb(Br/I)3 PNCs with Hg2+. Under a 365 nm ultraviolet (UV) lamp, the solution color of CsPb(Br/I)3 PNCs emission peaks at 591 nm gradually changes from orange to green with the increase of Hg2+ concentration, which has an excellent visualization effect. The method presented here has the potential to establish a new analytical method for the visual detection of Hg2+ in aqueous environments, and may also facilitate the application of all-inorganic cesium lead halide perovskite nanocrystals for analytical detection in aqueous environments.

Blue-Emitting Cs(Pb,Cd)Br3 Nanocrystals Resistant to Electric Field-Induced Ion Segregation.

High-performance solution-processed perovskite light-emitting diodes (PeLEDs) have emerged as a good alternative to the well-established technology of epitaxially grown AIIIBV semiconductor alloys. Colloidal cesium lead halide perovskite nanocrystals (CsPbX3 NCs) exhibit room-temperature excitonic emission that can be spectrally tuned across the entire visible range by varying the content of different halogens at the X-site. Therefore, they present a promising platform for full color display manufacturing. Engineering of highly efficient PeLEDs based on bromide and iodide perovskite NCs emitting green and red light, respectively, does not face major challenges except low operational stability of the devices. Meanwhile, mixed-halide counterparts demonstrating blue luminescence suffer from the electric field-induced phase separation (ion segregation) phenomenon described by the rearrangement (demixing) of mobile halide ions in the crystal lattice. This phenomenon results in an undesirable temporal redshift of the electroluminescence spectrum. However, to realize spectral tuning and, at the same time, address the issue of ion segregation less mobile Cd2+ ion could be introduced in the lattice at Pb2+-site that leads to the band gap opening. Herein, we report an original synthesis of CsPb0.88Cd0.12Br3 perovskite NCs and study their structural and optical properties, in particular electroluminescence. Multilayer PeLEDs based on the obtained NCs exhibit single-peak emission centered at 485 nm along with no noticeable change in the spectral line shape for 30 min which is a significant improvement of the device performance.

Transition metal ion-doped cesium lead halide perovskite nanocrystals: doping strategies and luminescence design

We herein briefly review the recent advances in transition metal ion-doped cesium lead halide perovskite nanocrystals including the typical strategies for effective doping and optical properties manipulation.

Near-infrared two-photon excited photoluminescence from Yb3+-doped CsPbClxBr3-x perovskite nanocrystals embedded into amphiphilic silica microspheres.

Nonlinear absorption of metal-halide perovskite nanocrystals (NCs) makes them an ideal candidate for applications which require multiphoton-excited photoluminescence. By doping perovskite NCs with lanthanides, their emission can be extended into the near-infrared (NIR) spectral region. We demonstrate how the combination of Yb3+ doping and bandgap engineering of cesium lead halide perovskite NCs performed by anion exchange (from Cl- to Br-) leads to efficient and tunable emitters that operate under two-photon excitation in the NIR spectral region. By optimizing the anion composition, Yb3+-doped CsPbClxBr3-x NCs exhibited high values of two-photon absorption cross-section reaching 2.3 × 105 GM, and displayed dual-band emission located both in the visible (407-493 nm) and NIR (985 nm). With a view of practical applications of bio-visualisation in the NIR spectral range, these NCs were embedded into silica microspheres which were further wrapped with amphiphilic polymer shells to ensure their water-compatibility. The resulting microspheres with embedded NCs could be easily dispersed in both toluene and water, while still exhibiting a dual-band emission in visible and NIR under both one- and two-photon excitation conditions.

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.

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.

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.

Multigram-Scale Synthesis of Luminescent Cesium Lead Halide Perovskite Nanobricks for Plastic Scintillators.

Cesium lead halide perovskite nanocrystals of general formula CsPbX3 are having tremendous impact on a vast array of technologies requiring strong and tunable luminescence across the visible range and solutions processing. The development of plastic scintillators is just one of the many relevant applications. The syntheses are relatively simple but generally unsuitable to produce a large amount of material of reproducible quality required when moving from proof-of-concept scale to industrial applications. Wastes, particularly large amounts of lead-contaminated toxic and flammable organic solvents, are also an open issue. We describe a simple and reproducible procedure enabling the synthesis of luminescent CsPbX3 nanobricks of constant quality on a scale going from 0.12 to 8 g in a single batch. We also show complete recycling of the reaction wastes, leading to dramatically improved efficiency and sustainability.

Flexible, Stretchable, and Luminescent Hydrogels Based on a Polydimethylsiloxane-Coated CsPbBr3 Nanostructure for Elastomers

Cesium lead halide perovskite nanocrystals (PNCs) have attracted great attention in optoelectronic devices due to their excellent optical properties, such as tunable emission wavelengths, long carrier lifetime, and narrow full width at half-maximum (fwhm). However, the poor stability of PNCs in water or humid environments greatly limits their wide-spreading applications. It is challenging to prepare PNCs with long-term stability in water. Herein, we successfully prepared CsPbBr3@PDMS microspheres by using the emulsification method. Due to the protection of the PDMS layer, the CsPbBr3@PDMS microspheres exhibit good optical properties and stability in water, acid, and alkali solutions. In addition, to expand the application of CsPbBr3 NCs in flexible optical devices and wearable devices, we first prepared stretchable, stable, and photoluminescent hydrogel with a CsPbBr3@PDMS microsphere (hydrogel/CsPbBr3@PDMS) by using the emulsification method. The hydrogel/CsPbBr3@PDMS elastomer exhibits good stability and stretchability. Furthermore, the hydrogel/CsPbBr3@PDMS elastomer retains bright green emission and stability under different mechanical deformations. This work provides a method to improve the CsPbBr3 PNCs with high stability by emulsification, which could also expand the applications of PNCs in underwater display, wearable, and flexible optoelectronic devices.

One‐Step Preparation of Ion‐Doped Cesium Lead Halide Perovskite Nanocrystals by Ultrasonication

AbstractCsPbX3 (X = Cl, Br, I) nanocrystals (NCs) are competitive materials for a wide range of applications because of their outstanding optoelectronic properties. Ion doping has been demonstrated as one powerful method for improving the optical properties of CsPbX3 NCs. However, the conventional ion‐doping approaches are tedious, and generally performed under an inert atmosphere and high temperature. In this work, a one‐step ultrasonic‐assisted approach is demonstrated to prepare doped CsPbX3 NCs. To demonstrate the universality of the ultrasonic‐assisted ion‐doping approach, three ion‐doped perovskite NCs are prepared, which represent three common improvements effects of ion doping on perovskite NCs, namely improved stability, PL emission, and photoluminescence quantum yields (PLQYs) of perovskite NCs. Sr‐doped CsPbI3 NCs showed improved phase stability. Mn‐doped CsPbCl3 NCs showed dual‐color emissions at 406 and 580 nm. The PLQYs of the as‐prepared Ni‐doped CsPbCl3 NCs are greatly improved, from 10.1% to 71%. Such a simple and versatile ion‐doping approach may promote the practical applications of all‐inorganic perovskite NCs.

Effects of ion-exchange and post-thermal annealing on the precipitation of cesium lead halide nanocrystals in glasses

Ion-exchange has been widely employed to modify the composition and structure of glasses. In this work, Cs–K ion-exchange was carried out to facilitate the precipitation of cesium lead halide perovskite nanocrystals in the surface layer of glasses. Both Cs4PbBr6 and CsPbBr3 perovskite nanocrystals and KBr nanocrystals can be precipitated through ion-exchange in nitrate salt. Content of Cs4PbBr6 and CsPbBr3 perovskite nanocrystals is strongly dependent on the composition of nitrate salt, ion-exchange conditions, and post-thermal annealing. High concentration of Cs in nitrate salt, long ion-exchange duration, and post-thermal annealing are effective to promote the formation of CsPbBr3 perovskite nanocrystals. Results reported is valuable for the developing of cesium lead halide perovskite nanocrystals embedded glass for light converters.

Elastic Phonon Scattering Dominates Dephasing in Weakly Confined Cesium Lead Bromide Nanocrystals at Cryogenic Temperatures.

Cesium lead halide perovskite nanocrystals (PNCs) have emerged as a potential next-generation single quantum emitter (QE) material for quantum optics and quantum information science. Optical dephasing processes at cryogenic temperatures are critical to the quality of a QE, making a mechanistic understanding of coherence losses of fundamental interest. We use photon-correlation Fourier spectroscopy (PCFS) to obtain a lower bound to the optical coherence times of single PNCs as a function of temperature. We find that 20 nm CsPbBr3 PNCs emit nearly exclusively into a narrow zero-phonon line from 4 to 13 K. Remarkably, no spectral diffusion is observed at time scales of 10 μs to 5 ms. Our results suggest that exciton dephasing in this temperature range is dominated by elastic scattering from phonon modes with characteristic frequencies of 1-3 meV, while inelastic scattering is minimal due to weak exciton-phonon coupling.

Energy Funneling from Water-Dispersed Perovskites to Chromophores

Cesium lead halide perovskite nanocrystals (PNCs) have enjoyed enormous attention in optoelectronics and photovoltaics. However, instability under polar conditions and limited energy/charge transport due to long-chain capping ligands restrict their large-scale applications. We have engineered a short-chain multidentate bolaamphiphilic ligand (NKE-3), which provides synergistic passivation of the perovskite surface by one multidentate ionic terminal and localizes water molecules by another multidentate ionic terminal, leading to a water-suspended colloidal solution of PNCs. NKE-3 allows efficient long-range dipole-based fluorescence resonance energy transfer (FRET) from perovskites to Rhodamine B isothiocyanate (RITC) in water, with FRET efficiencies ranging from 96% to 98%. We calculated the FRET rate using the acceptor’s rise-time component, as it ensures no contamination from FRET-inactive donors. Moreover, we tuned the emission maxima of PNCs through halide exchange to optimize FRET efficiency. Such energy funneling to a suitable molecular photocatalyst is imperative for PNCs’ potential applications.

Defect Passivation Results in the Stability of Cesium Lead Halide Perovskite Nanocrystals

Nanoheterostructures (NHSs) based on lead halide perovskites (LHPs) and chalcogenide quantum dots have proved to be promising candidates for photovoltaic device applications. However, understanding the defect chemistry at the interfaces of LHPs and chalcogenides is essential to stabilize them and further tune their optoelectronic properties. Here, we demonstrate a route for designing CsPbBr3–PbSe NHSs and other derivatives of LHP-based NHSs using defect-rich MoSe2 nanosheets (NSs) and study the effect of the size of PbSe NPs on their optical properties. In this synthesis route, PbSe nanoparticles (NPs) are formed at an early stage of the reaction through a unique cation displacement reaction, over which CsPbBr3 nanocrystals (NCs) are epitaxially grown. Using this methodology, a nearly 3-fold enhancement in photoluminescence (PL) is achieved, whereas other selenium precursors, which form larger PbSe NPs, result in negligible PL enhancement with respect to the pure CsPbBr3 NCs. Detailed density functional theory (DFT) calculations suggest that the PbSe NPs are responsible for passivating the surface defects that consequently enhance the PL intensity. However, in the case of larger PbSe NPs, the associated valence and conduction bands lie within the band-gap region of CsPbBr3, creating a type-I heterostructure between the two materials, thereby affecting the luminescence properties. Strong passivation of surface defects in CsPbBr3–PbSe NHSs is also evidenced from low-temperature PL studies. Furthermore, the resulting CsPbBr3–PbSe NHSs demonstrate enhanced stability in the presence of water and do not degrade under ambient conditions for several months.

Stability Effects of Selective Anion Abstraction from Cesium Lead Halide Perovskite Nanocrystals

The dynamic surface chemistry and stabilization of cesium lead halide perovskite nanocrystals (NCs) remain principal challenges for the use of these materials in many applications. Here, trimethylsilyl trifluoromethanesulfonate (Me3SiOTf) was used as a Lewis acidic reagent for quantitative and irreversible silylation and removal of anionic ligands from colloidal oleate- and oleylamine-capped CsPbBr3 and CsPbCl3 NCs. 1H NMR and FTIR spectroscopies, combined with elemental analysis, show strong binding of a population of anionic ligands to the NC surfaces. Surface anion exchange for trifluoromethanesulfonate also results in an increase in photoluminescence quantum yields. For CsPbCl3 NCs, Me3SiOTf treatment abstracts chlorides and destabilizes the NC lattice. The thermodynamic differences between these reactions and their implications are discussed.

CsPbBr3@PbBrOH 3D/1D molecular matrix for a high-performance scintillator

All-inorganic cesium lead halide perovskite nanocrystals (NCs) have become highly sought-after materials for X-ray detection and imaging because of their outstanding intrinsic electronic and optical properties. However, because of their highly ionic crystal structure, perovskite materials suffer severe moisture, thermal, and photo instability problems, which hinder their commercialization. To resolve this annoying problem, three-dimensional (3D)/1D CsPbBr3@PbBrOH composite structures in terms of molecular structure are designed by incorporating highly luminescent 3D CsPbBr3 NCs into a 1D PbBrOH matrix to form an “emitter-in-matrix”. The prepared CsPbBr3@PbBrOH exhibits excellent stability without sacrificing photoluminescence quantum yield. Meanwhile, 1D PbBrOH can be considered a perfect host, and the presence of heavy atom Pb in its matrix enhances X-ray absorption. The luminescent CsPbBr3 NCs embedded in an inert PbBrOH host are subjected to X-ray detection and imaging. The CsPbBr3@PbBrOH scintillator shows bright radiation luminescence and sensitive response to X-ray signals. In addition, the scintillator is made into a thin film screen for imaging, obtaining a clear image of the transmission electron microscopy grid hidden inside the capsule, and the resolution of CsPbBr3@PbBrOH film is calculated to be as high as 50 lp mm−1. This property of CsPbBr3@PbBrOH scintillators demonstrates their promising application prospects for ionizing radiation detection, particularly for X-ray imaging.