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The sustainable identification and efficient degradation of some recessive and seriously toxic pollutants are important issues in practical applications. Herein, a portable platform (EAl/ACN/Ag) constructed by growing AgNPs in situ in the cavities of the alkalized carbon nitride (ACN) coated on the etched Al sheet (EAl) is achieved. Interestingly, on the constructed EAl/ACN/Ag substrate irradiated by light for 3 min, a Raman inactive leuco-malachite green (LMG: a highly toxic and environmentally persistent pollutant that is difficult to be found due to being colorless) can be sensitively and selectively detected by surface-enhanced Raman scattering spectroscopy (SERS). Results demonstrate that the abundant â¢O2-, â¢OH, and h+ active species produced by irradiation of the EAl/ACN/Ag are responsible for the sensitive and selective SERS detection of the Raman-inactive LMG. The green and sustainable initiation in the sensitive SERS detection of LMG is greatly different from those by the traditional chemical process. The limit of detection of LMG can reach 8.99 × 10-13 mol·L-1, which is superior to some other methods for LMG detection in real samples. In addition, the EAl/ACN/Ag substrate displays excellent photocatalytic activity for LMG molecules. The research will provide a new and green way for the sensitive detection and efficient removal of some recessive and toxic pollutants in food fields and environmental analyses.
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The in situ formation of reduced dimensional perovskite layer via post-synthesis ion exchange has been an effective way of passivating organic-inorganic hybrid perovskites. In contrast, cesium ions in Cs-based inorganic perovskite with strong ionic binding energy cannot exchange with those well-known organic cations to form reduced dimensional perovskite. Herein, we demonstrate that tetrabutylammonium (TBA+ ) cation can intercalate into CsPbI3 to effectively substitute the Cs cation and to form one-dimensional (1D) TBAPbI3 layer in the post-synthesis TBAI treatment. Such TBA cation intercalation leads to in situ formation of TBAPbI3 protective layer to heal defects at the surface of inorganic CsPbI3 perovskite. The TBAPbI3 -CsPbI3 perovskite exhibited enhanced stability and lower defect density, and the corresponding perovskite solar cell devices achieved an improved efficiency up to 18.32 % compared to 15.85 % of the control one.
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The reduced dimension perovskite including 2D perovskites are one of the most promising strategies to stabilize lead halide perovskite. A mixed-cation 2D perovskite based on a steric phenyltrimethylammonium (PTA) cation is presented. The PTA-MA mixed-cation 2D perovskite of PTAMAPbI4 can be formed on the surface of MAPbI3 (PTAI-MAPbI3 ) by controllable PTAI intercalation by either spin coating or soaking. The PTAMAPbI4 capping layer can not only passivate PTAI-MAPbI3 perovskite but also act as MA+ locker to inhibit MAI extraction and significantly enhance the stability. The highly stable PTAI-MAPbI3 based perovskite solar cells exhibit a reproducible photovoltaic performance with a champion PCE of 21.16 %. Such unencapsulated devices retain 93 % of initial efficiency after 500â h continuous illumination. This steric mixed-cation 2D perovskite as MA+ locker to stabilize the MAPbI3 is a promising strategy to design stable and high-performance hybrid lead halide perovskites.
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Organometallic halide perovskite solar cells such as MAPbI3 have shown great promise as a low-cost, high-efficiency photovoltaic candidate. Recent studies demonstrated that by substituting an appropriate amount I ions of MAPbI3 with Br ions, the device performance parameters, such as moisture stability or power conversion efficiency, can be further optimized. In this study, using time-resolved optical reflectivity to track the carrier dynamics in MAPb(I1- xBr x)3 films with different Br contents, we found that photocarriers in MAPb(I1- xBr x)3 films with x = 0.01 and 0.02 diffuse much faster than those in films with other Br contents. We suggest that the faster charge carrier diffusion benefits from larger crystal grain size. As a result, this suppresses electron and hole recombination and increases the carrier extraction efficiency, in agreement with the higher power conversion efficiency reported previously.
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The controllable growth of CsPbI3 perovskite thin films with desired crystal phase and morphology is crucial for the development of high efficiency inorganic perovskite solar cells (PSCs). The role of dimethylammonium iodide (DMAI) used in CsPbI3 perovskite fabrication was carefully investigated. We demonstrated that the DMAI is an effective volatile additive to manipulate the crystallization process of CsPbI3 inorganic perovskite films with different crystal phases and morphologies. The thermogravimetric analysis results indicated that the sublimation of DMAI is sensitive to moisture, and a proper atmosphere is helpful for the DMAI removal. The time-of-flight secondary ion mass spectrometry and nuclear magnetic resonance results confirmed that the DMAI additive would not alloy into the crystal lattice of CsPbI3 perovskite. Moreover, the DMAI residues in CsPbI3 perovskite can deteriorate the photovoltaic performance and stability. Finally, the PSCs based on phenyltrimethylammonium chloride passivated CsPbI3 inorganic perovskite achieved a record champion efficiency up to 19.03 %.
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The all-inorganic α-CsPbI3 perovskite with the most suitable band gap faces serious challenges of low phase stability and high moisture sensitivity. We discover that a simple phenyltrimethylammonium bromide (PTABr) post-treatment could achieve a bifunctional stabilization including both gradient Br doping (or alloying) and surface passivation. The PTABr treatment on CsPbI3 only induces less than 5 nm blue shift in UV-vis absorbance but significantly stabilize the perovskite phase with much better stability. Finally, the highly stable PTABr treated CsPbI3 based perovskite solar cells exhibit a reproducible photovoltaic performance with a champion efficiency up to 17.06% and stable output of 16.3%. Therefore, this one-step bifunctional stabilization of perovskite through gradient halide doping and surface organic cation passivation presents a novel and promising strategy to design stable and high performance all-inorganic lead halide.
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In this work, the spatially dependent recombination kinetics of mixed-halide hybrid perovskite CH3NH3Pb(Br1- xCl x)3 (0 ≤ x ≤ 0.19) single crystals are investigated using time-resolved photoluminescence spectroscopy with one- and two-photon femtosecond laser excitation. The introduction of chloride by substituting a fraction of the bromide leads to a decreased lattice constant compared to pure bromide perovskite ( x = 0) and a higher concentration of surface defects. The measured kinetics under one-photon excitation (1PE) shows that increasing the chloride addition quenches the photoluminescence (PL) lifetimes, due to substitution-induced surface defects. In stark contrast, upon 2PE, the PL lifetimes measured deeper in the bulk become longer with increasing chloride addition, until the halide substitution reaches the critical concentration of â¼19%. At x = 19% Cl concentration, a significant reversal of this behavior is observed indicating a change in crystal structure beyond the continuous trends observed at lower percentages of halide substitution ( x ≤ 11%). The observed opposing trends, based on 1PE versus 2PE, highlight a dichotomy between extrinsic (surface) and intrinsic (bulk) effects of chloride substitution on the carrier dynamics in lead bromide perovskites. We discuss the physical relation between halide exchange and bulk carrier lifetimes in CH3NH3PbBr3 in terms of the Rashba effect. We propose that the latter is suppressed at the surface due to disorder in the alignment of the MA and that it increases in the bulk with Cl concentration because of the reduction in lattice parameters, which compresses the space available for the MA orientational degrees of freedom.
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Organolead halide perovskites exhibit superior photoelectric properties, which have given rise to the perovskite-based solar cells whose power conversion efficiency has rapidly reached above 20% in the past few years. However, perovskite-based solar cells have also encountered problems such as current-voltage hysteresis and degradation under practical working conditions. Yet investigations into the intrinsic chemical nature of the perovskite material and its role on the performance of the solar cells are relatively rare. In this work, Raman spectroscopy is employed together with CASTEP calculations to investigate the organic-inorganic interactions in CH3NH3PbI3 and CH3NH3PbBr3-xClx perovskite single crystals with comparison to those having ammonic acid as the cations. For Raman measurements of CH3NH3PbI3, a low energy line of 1030 nm is used to avoid excitation of strong photoluminescence of CH3NH3PbI3. Raman spectra covering a wide range of wavenumbers are obtained, and the restricted rotation modes of CH3-NH3(+) embedded in CH3NH3PbBr3 (325 cm(-1)) are overwhelmingly stronger over the other vibrational bands of the cations. However, the band intensity diminishes dramatically in CH3NH3PbBr3-xClx and most of the bands shift towards high frequency, indicating the interaction with the halides. The details of such an interaction are further revealed by inspecting the band shift of the restricted rotation mode as well as the C-N, NH3(+) and CH3 stretching of the CH3NH3(+) as a function of Cl composition and length of the cationic ammonic acids. The results show that the CH3NH3(+) interacts with the PbX3(-) octahedral framework via the NH3(+) end through N(+)-HX hydrogen bonding whose strength can be tuned by the composition of halides but is insensitive to the size of the organic cations. Moreover, an increase of the Cl content strengthens the hydrogen bonding and thus blueshifts the C-N stretching bands. This is due to the fact that Cl is more electronegative than Br and an increase of the Cl content decreases the lattice constant of the perovskite. The findings of the present work are valuable in understanding the role of cations and halides in the performance of MAPbX3-based perovskite solar cells.
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We demonstrate a facile morphology-controllable sequential deposition of planar CH3NH3PbI3 (MAPbI3) film by using a novel volume-expansion-adjustable PbI2·xMAI (x: 0.1-0.3) precursor film to replace pure PbI2. The use of additive MAI during the first step of deposition leads to the reduced crystallinity of PbI2 and the pre-expansion of PbI2 into PbI2·xMAI with adjustable morphology, which result in about 10-fold faster formation of planar MAPbI3 film (without PbI2 residue) and thus minimize the negative impact of the solvent isopropanol on perovskites during the MAI intercalation/conversion step. The best efficiency obtained for a planar perovskite solar cell based on PbI2·0.15MAI is 17.22% (under one sun illumination), which is consistent with the stabilized maximum power output at an efficiency of 16.9%.
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High-quality phase-pure MA1-x FAx PbI3 planar films (MA=methylammonium, FA=formamidinium) with extended absorption and enhanced thermal stability are difficult to deposit by regular simple solution chemistry approaches owing to crystallization competition between the easy-to-crystallize but unwanted δ-FAPbI3 /MAPbI3 and FAx MA1-x PbI3 requiring rigid crystallization conditions. Here A 2D-3D conversion to transform compact 2D mixed composition HMA1-x FAx PbI3 Cl perovskite precursor films into 3D MA1-x FAx PbI3 (x=0.1-0.9) perovskites is presented. The designed Cl/I and H/FA(MA) ion exchange reaction induced fast transformation of compact 2D perovskite film, helping to form the phase-pure and high quality MA1-x FAx PbI3 without δ-FAPbI3 and MAPbI3 impurity. In all, we successfully developed a facile one-step method to fabricate high quality phase-pure MA1-x FAx PbI3 (x=0.1-0.9) perovskite films by 2D-3D conversion of HMA1-x FAx PbI3 Cl perovskite. This 2D-3D conversion is a promising strategy for lead halide perovskite fabrication.
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Revealing the structural impact of lead halide perovskites on photocarrier dynamics is essential for the associated solar cells but deficient in experimental visualization. In this study, with femtosecond spectroscopy, we for the first time explored the contribution of the disorder of the distorted PbX6 octahedrons and A-site cations on the carrier behaviours. It was found that photoinduced carriers recombine almost twice slower and diffuse 20% faster in the disordered, ß-phased samples than in the ordered, γ-phased ones. Yet within the same phase, with a similar PbX6 orientation but various A-site mobility, the carrier diffusion and recombination have no apparent difference. Thus we firmly conclude that lattice disorder effectively influences the carrier dynamics and therein the Pb-X sublattice is worth more than A-site cations, which should inspire future lead halide perovskite design and applications.
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Biomimetic nanohydroxyapatite (nHAp) has long been used as a biocompatible material for bone repair, bone regeneration, and bone reconstruction due to its low toxicity to local or systemic tissues. Various cross-linkers have been employed to maintain the structure of collagen; these include epigallocatechin-3-gallate (EGCG), which can fortify the mechanical properties of collagen and withstand the degradation of collagenase. We hypothesized that EGCG combined with nHAp may promote resin-dentin bonding durability. Here, we examined the effect of epigallocatechin-3-gallate-encapsulated nanohydroxyapatite/mesoporous silica (EGCG@nHAp@MSN) on thermal stability and remineralization capability of dentin collagen. Dentin slices (2 × 2 × 1 mm3 ) were obtained and completely demineralized in a 10% phosphoric acid water solution. The resulting dentin collagen matrix was incubated with deionized water, EGCG, nHAp@MSN, and EGCG@nHAp@MSN. The collagen thermal degradation temperature was assessed utilizing differential scanning calorimetry analysis, which indicated that EGCG, nHAp@MSN, and EGCG@nHAp@MSN reinforced collagen's capability to resist thermal degradation. EGCG@nHAp@MSN resulted in the highest increase in denaturation temperature. Thermogravimetric analysis showed that both nHAp@MSN and EGCG@nHAp@MSN achieved a higher residual mass than the EGCG and control groups. Fourier transform infrared spectroscopy was performed to examine the interaction between EGCG@nHAp@MSN and dentin collagen. The EGCG@nHAp@MSN sample exhibited stronger dentin microhardness and uppermost bond strength after thermocycling. EGCG significantly enhanced collagen's capability to resist thermal degradation. In summary, EGCG and nHAp@MSN may work together to assist the exposed collagen to improve resistance to thermal cycling and promote remineralization while also strengthening the durability of resin-dentin bonds.
Assuntos
Dentina , Dióxido de Silício , Dentina/química , Dióxido de Silício/análise , Colágeno , Água/análise , Água/químicaRESUMO
Perovskite oxides with unique crystal structures and high defect tolerance are promising as atomic surface passivation layers for photoelectrodes for efficient and stable water splitting. However, controllably depositing and crystalizing perovskite-type metal oxides at the atomic level remains challenging, as they usually crystalize at higher temperatures than regular metal oxides. Here, we report a mild solution chemistry approach for the quasi-epitaxial growth of an atomic CaTiO3 perovskite layer on rutile TiO2 nanorod arrays. The high-temperature crystallization of CaTiO3 perovskite is overcome by a sequential hydrothermal conversion of the atomic amorphous TiOx layer to CaTiO3 perovskite. The atomic quasi-epitaxial CaTiO3 layer passivated TiO2 nanorod arrays exhibit more efficient interface charge transfer and high photoelectrochemical performance for water splitting. Such a mild solution-based approach for the quasi-epitaxial growth of atomic metal oxide perovskite layers could be a promising strategy for both fabricating atomic perovskite layers and improving their photoelectrochemical properties.
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The prevalence of sulfonamide residues in aquatic environments poses serious environmental risks, and the sensitive detection and effective degradation of sulfonamides have attracted widespread attention. Here, the environmentally friendly chitosan (CS)/carbon nitride (CN) with three-dimensional porous structure is fabricated by freeze-drying method, and subsequently a new bifunctional flexible substrate (CS/CN/Ag) is prepared by anchoring of small sized AgNPs (6 â¼ 12 nm) on CS/CN. Importantly, the CS/CN/Ag substrate shows high adsorption capacity (â¼ 83.06%) for sulfamethoxazole (SMX) solution within 20 mins and the limit of detection can be as low as 7.46 × 10-9 mol·L-1 with an enhancement factor of 3.3 × 105. Also, the CS/CN/Ag substrate displays highly selective for surface-enhanced Raman spectroscopy (SERS) detection of sulfonamides and also shows excellent SERS response for SMX in hospital wastewater samples. In addition, the photocatalytic degradation efficiency of SMX could reach as high as 99.22% within 20 mins of irradiation and the CS/CN/Ag still maintains outstanding photocatalytic performance after six cycles. Moreover, the Ag content in the CS/CN/Ag substrate is only 2.35%, and also the CS/CN/Ag exhibits good uniformity, repeatability, recyclability and stability. Therefore, this flexible and cost-effectively substrate of CS/CN/Ag shows great potential for the simultaneous SERS detection and photocatalytic degradation of pollutants in actual wastewater samples.
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In recent years, it is urgent to develop bi-functional materials for highly sensitive SERS detection and photocatalytic degradation of contaminants in water of fish pond. Herein, using 5-mercapto-1-methyltetrazole as the ligand, the tree-trunk like zeolitic imidazolate framework (ZIF-8) is induced and in-situ grown on the surface of aluminum/flower carbon nitride (Al/f-C3N4). Then, AgNPs are tightly anchored in ZIF-8 of Al/f-C3N4/ZIF-8 by strong Ag-N and Ag-S bonds, and a portable architecture of Al/f-C3N4/ZIF-8/Ag is successfully prepared. Results indicate that the Al/f-C3N4/ZIF-8/Ag architecture exhibits excellent SERS activity and the detection limit can as low as 2.15 × 10-11 molâ L-1 for crystal violet (CV, a typical fungicide). Also, the Al/f-C3N4/ZIF-8/Ag substrate presents good photocatalytic activity for CV molecule, and the degradation efficiency reaches 98.58% after illumination for 90 min. This is mainly due to the good adsorption capacity of ZIF-8 which can enrich more CV molecules and pull them to "hot spots" generated by Ag in Al/f-C3N4/ZIF-8/Ag, and thus SERS response are enhanced significantly. Besides, the strong synergistic effect of f-C3N4, ZIF-8 and AgNPs is also important which facilitates the separation of photogenerated electrons and holes. Thus, the designed portable and bi-functional substrate could be used as a potential material for the detection and removal of CV in practical application.
Assuntos
Fungicidas Industriais , Nanopartículas Metálicas , Estruturas Metalorgânicas , Zeolitas , Animais , Prata/química , Nanopartículas Metálicas/química , Zeolitas/químicaRESUMO
This study aimed to explore the therapy role of procyanidin B2 (PB2) in inhibiting angiogenesis and cell growth in oral squamous cell carcinoma. After oral mucosa epithelial cell (OMEC) and human oral squamous cell carcinoma (OSCC) cell line (SCC-25) were treated with PB2 or SCC-25 were treated with PB2 and rhVEGF, cell counting kit-8 (CCK-8) assay was used to determine the cell viability. The apoptosis, migration, invasion and angiogenesis of SCC-25 after indicated treatment were detected by Tunel, wound healing, transwell and tube formation assays. The protein expression related to apoptosis, metastasis and epithelial-mesenchymal transition (EMT) and changed expression of vascular endothelial growth factor (VEGF)/VEGF receptor 2 (VEGFR2) signaling was analyzed by Western blot. As a result, PB2 inhibited viability, invasion, migration and EMT and promoted apoptosis of SCC-25 cells. In addition, PB2 inhibited VEGF/VEGFR2 signaling and tumor itangiogenesis in OSCC. As expected, activation of VEGF/VEGFR2 signaling suppressed the effect of PB2 on growth and metastasis of OSCC cells. In conclusion, PB2 inhibited the VEGF/VEGFR2 pathway to suppress the angiogenesis and cell growth of SCC-25 cells.
Assuntos
Biflavonoides/farmacologia , Catequina/farmacologia , Neoplasias Bucais , Proantocianidinas/farmacologia , Carcinoma de Células Escamosas de Cabeça e Pescoço , Fator A de Crescimento do Endotélio Vascular/metabolismo , Receptor 2 de Fatores de Crescimento do Endotélio Vascular/metabolismo , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Humanos , Neoplasias Bucais/metabolismo , Neoplasias Bucais/patologia , Neovascularização Patológica/metabolismo , Carcinoma de Células Escamosas de Cabeça e Pescoço/metabolismo , Carcinoma de Células Escamosas de Cabeça e Pescoço/patologiaRESUMO
Inorganic CsPbI3 perovskite with high chemical stability is attractive for efficient deep-red perovskite light-emitting diodes (PeLEDs) with high color purity. Compared to PeLEDs based on ex-situ-synthesized CsPbI3 nanocrystals/quantum dots suffering from low conductivity and efficiency droop under high current densities, in situ deposited 3D CsPbI3 films from precursor solutions can maintain high conductivity but show high trap density. Here, it is demonstrated that introducing diammonium iodide can increase the size of colloids in the precursor solution, retard the phase-transition rate, and passivate trap states of the in-situ-formed cuboid crystallites. The PeLED based on the one-step-formed 3D CsPbI3 cuboid crystallite films shows a peak external quantum efficiency (EQE) value up to 15.03% because of the high conductivity and reduced trap states. Furthermore, this one-step method also has a wide processing window, which is attractive for flow-line production of large-area PeLED modules. The fabrication of a 9 cm2 PeLED that exhibits a peak EQE of 10.30% is successfully demonstrated.
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Low-bandgap formamidinium-cesium (FA-Cs) perovskites of FA1-x Cs x PbI3 (x < 0.1) are promising candidates for efficient and robust perovskite solar cells, but their black-phase crystallization is very sensitive to annealing temperature. Unfortunately, the low heat conductivity of the glass substrate builds up a temperature gradient within from bottom to top and makes the initial annealing temperature of the perovskite film lower than the black-phase crystallization point (~150°C). Herein, we take advantage of such temperature gradient for the diffusional growth of high-quality FA-Cs perovskites by introducing a thermally unstable MA+ cation, which would firstly form α-phase FA-MA-Cs mixed perovskites with low formation energy at the hot bottom of the perovskite films in the early annealing stage. The natural gradient annealing temperature and the thermally unstable MA+ cation then lead to the bottom-to-top diffusional growth of highly orientated α-phase FA-Cs perovskite, which exhibits 10-fold of enhanced crystallinity and reduced trap density (~3.85 × 1015 cm-3). Eventually, such FA-Cs perovskite films were fabricated into stable solar cell devices with champion efficiency up to 23.11%, among the highest efficiency of MA-free perovskite solar cells.
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Research on chemically stable inorganic perovskites has achieved rapid progress in terms of high efficiency exceeding 19% and high thermal stabilities, making it one of the most promising candidates for thermodynamically stable and high-efficiency perovskite solar cells. Among those inorganic perovskites, CsPbI3 with good chemical components stability possesses the suitable bandgap (≈1.7 eV) for single-junction and tandem solar cells. Comparing to the anisotropic organic cations, the isotropic cesium cation without hydrogen bond and cation orientation renders CsPbI3 exhibit unique optoelectronic properties. However, the unideal tolerance factor of CsPbI3 induces the challenges of different crystal phase competition and room temperature phase stability. Herein, the latest important developments regarding understanding of the crystal structure and phase of CsPbI3 perovskite are presented. The development of various solution chemistry approaches for depositing high-quality phase-pure CsPbI3 perovskite is summarized. Furthermore, some important phase stabilization strategies for black phase CsPbI3 are discussed. The latest experimental and theoretical studies on the fundamental physical properties of photoactive phase CsPbI3 have deepened the understanding of inorganic perovskites. The future development and research directions toward achieving highly stable CsPbI3 materials will further advance inorganic perovskite for highly stable and efficient photovoltaics.
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5-Ammonium valeric acid iodide (AVAI) has been widely known as a stabilizer to enhance the stability of MAPbI3 perovskite, but its role and function is still under exploration. The typical 2D perovskites of AVA2PbI4 have been proposed as the capping layer for stabilization. Here, a novel AVA-MA mixed-cation perovskite of AVAMAPbI4 is found to show a more even and compact coverage than the typical 2D perovskite of AVA2PbI4. A simple post-treatment on MAPbI3 films by using AVAI isopropanol solution can fabricate such a mixed-cation 2D perovskite capping layer on the MAPbI3 sample. This AVAMAPbI4 capping layer effectively passivates surface defects of MAPbI3 perovskite films and reduces the charge-carrier recombination, enabling AVAI-MAPbI3 perovskite films to exhibit improved stability against thermal and moisture stress. Finally, the AVAI-MAPbI3-based perovskite solar cells also show an enhanced photovoltaic performance with a champion PCE up to 20.05% with enhanced stability.