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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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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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Exploring the surface chemistry of cesium lead halide perovskite nanocrystals
摘要： Colloidal nanocrystals (NCs) of cesium lead halide perovskites (CsPbX3, X = Cl, Br or I) are emerging as an exciting class of optoelectronic materials, but the retention of their colloidal and structural integrity during isolation, purification and handling still represents a critical issue. The impelling questions concerning their intrinsic chemical instability are connected to the dynamic nature of the bonding between the inorganic surface and the long-chain capping ligands. However, the key aspects of CsPbX3's surface chemistry that directly impact their stability remain elusive. In this contribution, we provide an in-depth investigation of the surface properties of differently composed CsPbX3 NCs, prepared by traditional hot-injection methods. The study, mainly relying on solution NMR spectroscopy, is backed up by elemental analysis as well as morphological, structural and optical investigations. We ascertained that the nature of the ligand adsorption/desorption processes at the NC surface is dependent on its elemental composition, thus explaining the origin of the instability afflicting CsPbI3 NCs. We also evaluated the effect of NC purification as well as of the degradation pathways involving the organic shell on the surface chemistry of CsPbX3 NCs. This study paves the way for new post-functionalization strategies for this promising class of nanomaterials.
关键词： surface chemistry,colloidal stability,degradation pathways,cesium lead halide perovskite nanocrystals,purification,ligand adsorption/desorption,NMR spectroscopy
更新于2025-09-19 17:15:36
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Room-temperature synthesis of Mn2+-doped cesium lead halide perovskite nanocrystals via a transformation doping method
摘要： Currently, Mn2+-doped cesium lead halide perovskite nanocrystals have attracted research interests. Here, we report a novel room-temperature transformation doping method for the synthesis of Mn2+-doped CsPbCl3 and CsPb(Br/Cl)3 nanocrystals. Innovatively, the transformation of Cs4PbX6 (X=Cl, Br) phase which has no excitation emission to CsPbX3 phase which has strong luminescence was used in this mechanism. Simply injecting MnCl2 precursor into Cs4PbX6 solution could result in the full transformation of Cs4PbX6 phase to CsPbX3 phase and Mn2+-doped CsPbCl3 or CsPb(Br/Cl)3 were obtained. The basic idea for the transformation doping method is that MnCl2 can not only drive the transformation of the two structures but also Mn2+ can substitute Pb2+. In this reaction, the concentration of Mn precursor is a key influence factor. Moreover, instead of the ligand of OA, the acetic acid was used in our method. Through the adjustment of the ligand in precursor, not just the photoluminescence quantum yields of as-prepared Mn2+-doped CsPbCl3 nanocrystals were improved from 7.8 to 32.6% (Mn2+-doped CsPb(Br/Cl)3 nanocrystals even could reach to 42.7%), the nanocrystals also retained outstanding stability. We propose a combination of structure transformation and ion doping as a perovskite doping mechanism. Our doping method is a novel strategy for lead halide perovskite nanocrystals doping project and it could provide more possibilities in the future.
关键词： photoluminescence quantum yields,Cs4PbX6,Mn2+-doped cesium lead halide perovskite nanocrystals,CsPbX3,room-temperature transformation doping method
更新于2025-09-09 09:28:46
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Rationalizing and Controlling the Surface Structure and Electronic Passivation of Cesium Lead Halide Nanocrystals
摘要： Colloidal lead halide perovskite nanocrystals (NCs) have recently emerged as versatile photonic sources. Their processing and luminescent properties are challenged by the lability of their surfaces, i.e. the interface of the NC core and the ligand shell. On the example of CsPbBr3 NCs, we model the nanocrystal surface structure and its effect on the emergence of trap states using density functional theory. We rationalize the typical observation of a degraded luminescence upon aging or the luminescence recovery upon post-synthesis surface treatments. The conclusions are corroborated by the elemental analysis. We then propose a strategy for healing the surface trap states and for improving the colloidal stability by the combined treatment with didodecyldimethyl ammonium bromide and lead bromide and validate this approach experimentally. This simple procedure results in robust colloids, which are both highly pure and exhibit high photoluminescence quantum yields of up to 95-98%, retained even after 3-4 rounds of washing.
关键词： trap states,didodecyldimethyl ammonium bromide,luminescence recovery,photoluminescence quantum yields,lead bromide,CsPbBr3 NCs,density functional theory,Colloidal lead halide perovskite nanocrystals,surface structure
更新于2025-09-09 09:28:46
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Trap-Mediated Two-Step Sensitization of Manganese Dopants in Perovskite Nanocrystals
摘要： Halide perovskite nanocrystals hold promise for printable optoelectronic and photonic applications. Doping enhances their functionalities and is being investigated for substituting lead with environmentally friendlier elements. The most investigated dopant is Mn2+ that acts as a color center sensitized by the host excitons. The sensitization mechanism is far from understood and no comprehensive picture of the energy-transfer process has been proposed. Similarly, the role of shallow states - particularly abundant in defect tolerant materials - is still unknown. Here, we address this problem via spectroscopic studies at controlled excitation density and temperature on Mn:CsPbCl3 nanocrystals. Our results indicate a two-step process involving exciton localization in a shallow metastable state that mediates the thermally-assisted sensitization of the Mn2+-emission, which is completely quenched for T<200K. At T≤60K, however, such emission surprisingly reappears, suggesting direct energy-transfer from band-edge states. Electron spin resonance supports this picture revealing the signatures of conformational rearrangements below 70K, possibly removing the potential barrier for sensitization. Our results demystify anomalous behaviors of the exciton-to-Mn2+ energy-transfer mechanism and highlight the role of shallow defects in the photophysics of doped perovskite nanostructures.
关键词： Halide perovskite nanocrystals,energy-transfer,spectroscopic studies,Mn2+ dopants,shallow states
更新于2025-09-09 09:28:46