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Post-synthesis phase and shape evolution of CsPbBr3 colloidal nanocrystals: The role of ligands
摘要： The surface chemistry of colloidal cesium lead bromide (CsPbBr3) nanocrystals is decisive in determining the stability and the final morphology of this class of materials, characterized by ionic structure and a high defect tolerance factor. Here, the high sensitivity of purified colloidal nanocubes of CsPbBr3 to diverse environmental condition (solvent dilution, ageing, ligands post synthetic treatment) in ambient atmosphere is investigated by means of a comprehensive morphological (electron microscopy), structural (θ/2θ X-ray diffraction (XRD) and grazing incidence wide angle scattering (GIWAXS)), and spectroscopic chemical (1H nuclear magnetic resonance (NMR), nuclear Overhauser effect spectroscopy (NOESY), absorption and emission spectroscopy) characterization. The aging and solvent dilution contribute to modify the nanocrystal morphology, due to a modification of the ligand dynamic. Moreover, we establish the ability of aliphatic carboxylic acids and alkyl amines ligands to induce, even in a post preparative process at room temperature, structural, morphological and spectroscopic variations. Upon post synthesis alkyl amine addition, in particular of oleyl amine and octyl amine, the highly green emitting CsPbBr3 nanocubes effectively turn into one-dimensional (1D) thin tetragonal nanowires or lead halide deficient rhombohedral zero-dimensional (0D) Cs4PbBr6 structures with a complete loss of fluorescence. The addition of an alkyl carboxylic acid, as oleic and nonanoic acid, produces the transformation of nanocubes into still emitting orthorombic two-dimensional (2D) nanoplates. The acid/base equilibrium between the native and added ligands, the adsorbed/free ligands dynamic in solution and the ligand solubility in non-polar solvent contribute to render CsPbBr3 particularly sensitive to environmental and processing conditions and, therefore prone to undergo to structural, morphological and, hence spectroscopic, transformations.
关键词： lead halide perovskite nanocrystals,surface chemistry,ligands equilibria,long term stability
更新于2025-11-21 11:01:37
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Cesium lead halide perovskite nanocrystals for ultraviolet and blue light blocking
摘要： Direct exposure to ultraviolet (UV) light is closely related to various harmful effects [1-3], ranging from skin injures to cancer originated from DNA damage. Recent years, some studies reported that blue light are also detrimental to humans [4,5], for example, the blue light could cause photochemical lesions to human retinal within the intensity range of the natural light [6]. Furthermore, blue light is responsible for the solar retinitis and may play a role in age-related macular degeneration. Importantly, the harmful effects of blue lights generated from the electronic display devices should also be careful [7]. Thus, the development of new UV and blue light shielding materials has been received much attention [8]. In the past few years, there has been an increased awareness of the importance to develop UV shielding materials. A variety of materials have been used to prevent UV lesions. Organic molecules like avobenzone or oxybenzone have been used as a UV absorber for many years, but the self-degradation limits their usage time. Inorganic materials such as zinc oxide (ZnO) and titanium oxide (TiO2) have been used intensively for UV shielding [9-12]. However, photocatalytic properties and self-degradations of the ZnO and TiO2 based absorbers also hindered their applications [13,14]. Other materials, e.g., graphene oxide-poly(vinyl alcohol) composite film and lanthanide complex functionalized cellulose nanopaper were also reported for UV shielding [15,16]. Whereas, the excellent UV-filtering capability of these films was obtained by sacrificing the visible light transmittance. Therefore, fabricating UV and blue light blocking materials with good photostability and high transparency to the rest of visible light still remains a challenge and is urgently needed to be developed. Recently, because of the outstanding performance in photovoltaic applications, lead halide perovskite APbX3 (where A = CH3NH3+, (NH2)2CH+ and Cs+, X = Cl?, Br? and I?) has become the most noticeable materials [17-22]. These perovskite nanocrystals exhibit intriguing features [23], such as easy tunable band gap, sharp optical absorption edges and high quantum efficiency with narrow emission spectra. These nanocrystals have been studied extensively for various optical applications, especially light emitting diodes and lasers [24-27]. Post modification of perovskite nanocrystals by anion exchange enables the absorbance band gap tuned from ultraviolet to near infrared spectra [28,29]. In addition, the perovskite nanocrystals show large absorption range, which offers the great potential for UV and blue light shielding applications. Although the tunable absorption-band edge of perovskite nanocrystals has already been realized, there have not been reports on developing UV and blue light blocking material with tunable absorption-band edge. Herein, we aim to the development of a simple and easy way to fabricate UV and blue light blocking material by mixing pervoskite nanocrystals and ethyl cellulose (EC). In this study, EC was used as a host material for the CsPb(Cl/Br)3 pervoskite nanocrystals. By tuning the ratio of Br to Cl, the blocked wavelength range could be easily controlled. Using the sharp absorption edges, the material possesses excellent light blocking ability in the range of 200-460 nm and maintains high transparency (95%) to visible light in the range beyond blue light.
关键词： UV blocking,Cesium lead halide nanocrystals,Blue light blocking,Tunable adsorption edge,Perovskite nanocrystals
更新于2025-09-23 15:23:52
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Stark Effect and Environment-Induced Modulation of Emission in Single Halide Perovskite Nanocrystals
摘要： Organic-inorganic halide perovskites have emerged as promising materials for next generation solar cells. In nanostructured form also, these materials are excellent candidates for optoelectronic applications such as lasers and light emitting diodes for displays and lighting. While great progress has been achieved so far in optimizing the intrinsic photophysical properties of perovskite nanocrystals (NCs), in working opto-electronic devices external factors, such as the effects of conducting environment and of the applied electric field on exciton generation and photon emission have been largely unexplored. Here, we use NCs of the all-inorganic perovskite CsPbBr3 dispersed polyvinyl carbazole, a hole-conductor, and in polymethyl methacrylate, an insulator, to examine the effects of applied electric field and conductivity of the matrix on the perovskite photophysics at single-particle level. We found that the conducting environment causes a significant decrease of photoluminescence (PL) brightness of individual NCs due the appearance of intermediate-intensity emitting states with significantly shortened lifetime. Applied electric field has a similar effect and, in addition, causes a non-linear spectral-shift of the PL maxima, a combination of linear and quadratic Stark effect caused by environment-induced polarity and field-related polarizability. The environment and electric field effects are explained by ionization of the NCs through hole transfer and emission of the resulting negatively-charged excitons.
关键词： ionization,halide perovskite nanocrystals,single-particle spectroscopy,Stark effect,blinking
更新于2025-09-23 15:23:52
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Ethanol-Precipitable Silica-Passivated Perovskite Nanocrystals Incorporated into Polystyrene Microspheres for Long-Term Storage and Re-Usage
摘要： Perovskite nanocrystals (PNCs) are emerging luminescent materials due to their fascinating physic-optical properties. However, their sensitive surface chemistry with organic polar solvents, oxygen and moisture greatly hinders their developments towards practical applications. Herein we promote silica-passivated PNCs (SP-PNCs) by in situ hydrolyzing the surface ligands of (3-aminopropyl) triethoxysilane. The resultant SP-PNCs possesses a high quantum yield (QY) of 80% and are precipitable by polar solvents, such as ethanol and acetone, without destroying their surface chemistry or losing QY, which offers an eco-friendly and efficient method for separation, purification and phase transfer of PNCs compared with the traditional solvent evaporation technique. Moreover, we further promoted a swelling-deswelling encapsulation process to incorporate the as-made SP-PNCs into polystyrene microspheres (PMs), which can largely increase the stability of the SP-PNCs against moisture for long-term storage. Besides, the embedded SP-PNCs can also be reused and mono-dispersed by totally dissolving the PMs in suitable solvents for making all-solution-processed devices. We thereby believe this work should open new avenues for greener synthesis, scalable production, and long-term storage of PNCs towards the emerging practical applications.
关键词： stability,perovskite nanocrystals,surface engineering,encapsulation,polar environment
更新于2025-09-23 15:23:52
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Blue Electrogenerated Chemiluminescence from Halide Perovskite Nanocrystals
摘要： Electrogenerated chemiluminescence (ECL) has been extensively used in ultrasensitive electroanalysis because it can be generated electrochemically without using expensive optics and light sources. Visible ECL emission can be obtained with a reasonable quantum yield and stability. Blue ECL is rare and often suffers from stability and poor quantum efficiency. Blue ECL emission at 473 nm from organometallic halide perovskite nanocrystals (PNCs), CH3NH3PbCl1.08Br1.92, is reported here for the first time using tripropylamine (TPrA) as co-reactant. The blue ECL emission peak resembles its photoluminescence peak position. In addition to this blue emission peak, the ECL spectra of CH3NH3PbCl1.08Br1.92 PNCs also showed a broad ECL peak at 745 nm. Generation of the second ECL peak at 745 nm from CH3NH3PbCl1.08Br1.92 PNCs was can be explained by the existence of surface trap states on as-synthesized PNC due to incomplete surface passivation. Halide anion tunability of ECL emission from CH3NH3PbX3 (X: Cl, Br, I) PNCs is also demonstrated. The fluorescence microscopy image of single PNC and stability of selected single PNCs are presented in this with simultaneous acquisition of fluorescence spectra using 405-nm laser excitation. The photoluminescence (PL) decay was described by PL lifetime (τ) of 1.2 ns. The effect of the addition of surfactants (oleic acid and n-octylamine) on the fluorescence intensity and stability of CH3NH3PbCl1.08Br1.92 PNCs is also discussed.
关键词： Surfactants,Blue light emission,ECL (electrogenerated chemiluminescence),Photoluminescence (PL),Perovskite nanocrystals (PNCs),Photoluminescence quantum yield (PLQY)
更新于2025-09-23 15:23:52
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Achieving Near-Unity Photoluminescence Efficiency for Blue-violet Emitting Perovskite Nanocrystals
摘要： While the perovskite nanocrystals (NCs) have shown great promise as materials for efficient light emitting diodes (LEDs), low photoluminescence quantum yield (PLQY) of the blue-emitting perovskites is an impediment to the development of white LEDs of which blue is an essential component. Herein, we report that room temperature post-synthetic treatment of weakly blue-violet emitting (PLQY 3%) CsPbCl3 NCs with CdCl2 results in an instantaneous enhancement of the PLQY to near-unity without affecting the PL peak position (406 nm) and spectral width. The time-resolved PL and ultrafast transient absorption measurements confirm the removal of nonradiative defect states of the CsPbCl3 NCs in treated sample. The elemental composition and structural data of the treated sample reveal facile doping of Cd2+ into the crystal lattice without affecting the size and shape of the NCs. Extraordinary PLQY, high air- and photo-stability and ease of preparation of this Cd-doped CsPbCl3 make it by far the most attractive blue-emitting perovskite for development of efficient blue and white LEDs.
关键词： photoluminescence quantum yield,blue-emitting perovskites,perovskite nanocrystals,CdCl2 treatment,white LEDs
更新于2025-09-23 15:21:21
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Interface Engineering of CsPbBr <sub/>3</sub> Nanocrystal Light-Emitting Diodes via Atomic Layer Deposition
摘要： Perovskite nanocrystal (PNC) suffers from solution corrosion and water/oxygen oxidation when used in light-emitting diodes (LEDs). Atomic layer deposition (ALD) is applied to introduce Al2O3 infilling and interface engineering for the CsPbBr3 nanocrystal emission layers, and the inorganic electron transport layer-based CsPbBr3–ZnMgO LED device is fabricated. The introduction of Al2O3 ALD layers significantly improves the tolerance of CsPbBr3 PNC thin films to polar solvents ethanol of ZnMgO during spin coating. The operation lifetime of ALD-treated CsPbBr3 PNC–ZnMgO LED is prolonged to about two orders of magnitude greater than that of the CsPbBr3 PNC-TPBi LED device with a largely improved external quantum efficiency (EQE) value. Moreover, the infilling of Al2O3 into the CsPbBr3 layer boosts the carrier mobility for more than 40 times inside the light-emission layer. However, the interfacial carrier transport between different functional layers is hindered by the insulated Al2O3 layer, which provides an effective barrier for excess electron transport. Such a favorable band alignment facilitates the carrier balance of the device and contributes to the improved electroluminescent performance of the device with ALD Al2O3 interface engineering, which is further supported by theoretical device modeling. Herein, a facile method is provided to fabricate PNC-LED devices with both high efficiency and long-term lifetime.
关键词： light emitting diodes,working stability,interface engineering,atomic layer deposition,CsPbBr3 perovskite nanocrystals
更新于2025-09-23 15:21:01
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Morphological and optoelectronic investigations of CsPbBr3 nanocrystals chelating diphenylammonium halide ligands via low temperature synthesis
摘要： In this study, the low temperature method was adopted to synthesize all-inorganic cesium lead bromide CsPbBr3 nanocrystals (NCs) as the active layer in light-emitting devices. In order to improve film-forming and optoelectronic properties of CsPbBr3 NCs, a surface ligand diphenylammonium bromide (DPABr) was added from 0 to 0.15 mole fraction in proportion to the amount of oleylamine. The experimental results showed that introducing 0.1 mole fraction of DPABr in CsPbBr3 NCs brought the best performance. The SEM and AFM results revealed that smooth and pinhole-free films of CsPbBr3 NCs were formed by introducing DPABr with a low surface roughness of 4.6 nm. The introduced bromide ions can passivate the surface vacancies of CsPbBr3 NCs and improve photoluminescence quantum yield (PLQY) from 38% to 72% compared with the pristine CsPbBr3 NCs. Moreover, shorter and π electron-rich phenyl groups help to increase carrier injection into nanocrystalline core, preventing carriers from being hindered by oleic acid and oleylamine with longer alkyl chains. Therefore, the conductivity of the resulting CsPbBr3 NCs was augmented. The maximum brightness and current efficiency of the optimized device based on CsPbBr3 NCs with 0.1 mole fraction of DPABr were enhanced 2.3- and 3.3-fold, respectively, relative to the pristine one.
关键词： perovskite nanocrystals,low temperature method,photoluminescence quantum yield,surface passivation,diphenylammonium bromide
更新于2025-09-23 15:21:01
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Annealing CsPbX <sub/>3</sub> (X = Cl and Br) Perovskite Nanocrystals at High Reaction Temperatures: Phase Change and Its Prevention
摘要： Annealing perovskite nanocrystals at high reaction temperature changes their crystal phase, shape, and optical properties. Carrying out reactions between 180 and 250 °C, the impact of thermal annealing for CsPbCl3 and CsPbBr3 nanocrystals in a reaction ?ask was investigated here. At higher temperature, a phase change was observed instantly, which could not be trapped even with ice-bath cooling. Interestingly, using a calculated amount of preformed alkylammonium halides as dual passivating agents, the nanocrystals of both CsPbCl3 and CsPbBr3 could even be stabilized for hours of annealing at 250 °C. CsPbCl3, which was reported to be a poor emissive nanocrystal in comparison to CsPbBr3, could sustain even more than 5 h of annealing at 250 °C and recorded ～51% absolutely quantum yield. Details of the interface chemistry and the role of the used dual passivating agent for providing thermal stability are studied and reported in this Letter.
关键词： thermal annealing,quantum yield,phase change,dual passivating agents,perovskite nanocrystals
更新于2025-09-23 15:21:01
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Surface Engineering of Alla??Inorganic Perovskite Quantum Dots with Quasi Corea??Shell Technique for Higha??Performance Photodetectors
摘要： All-inorganic lead halide perovskites with good surface morphology show substantial prospect for optoelectronic devices. However, the anion exchange of coordinated alkylamine ligands (e.g., oleic acid and oleylamine) can detach ligands and induce more interface trap sites, subsequently to reduce device performance. In this paper, therefore, a simple solution-processed route is presented to synthesize quasi coreshell CsPbBr3formamidinium iodide (FAI = CH(NH2)2I) colloidal quantum dots (CQDs), and then it is applied as the active layer for photodetectors by finely controlling the ligands exchange. The presence of FAI = CH(NH2)2I on CsPbBr3 is confirmed by Fourier transform infrared spectroscopy. As a result, the photodetector ITO/ZnO (100 nm)/CsPbBr3 (150 nm)/Au show an enhanced specific detectivity over 1013 Jones with a responsivity of 19 A W1 under 3 mW cm2 405 nm illumination at 1.5 V. The experimental data show that the enhanced device performance is due to the improved crystallinity and less surface defects of CsPbBr3 CQDs, as the result of less alkylamine ligands is detached during its FAI passivation, thus the charge carriers’ mobility of the film is improved. Therefore, it provides a promising way for high-performance solution-processed all-inorganic CsPbBr3 based optoelectronic devices.
关键词： CsPbBr3 perovskite nanocrystals,solution-processed,surface passivation,recombination process
更新于2025-09-23 15:19:57