In CH3NH3PbI3 Perovskite Film,the Surface Termination Layer Dominates the Moisture Degradation Pathway

Theoretical studies have shown that surface terminations, such as MAI or PbI layers, greatly affect the environmental stability of organic–inorganic perovskite. However, until now, there has been little effort to experimentally detect the existence of MAI or PbI terminations on MAPbI₃ grains, let alone disclose their effects on the humidity degradation pathway of perovskite solar cell. Here, we successfully modified and detected the surface terminations of MAI and PbI species on polycrystalline MAPbI₃ films. MAI-terminated perovskite film followed the moisture degradation process from MAPbI₃ to hydrate MAPbI₃⋅H₂O and then into PbI₂, with penetration of water molecules being the main driving force leading to the degradation of MAPbI₃ layer by layer. In contrast, for the PbI-terminated perovskite film in a humid atmosphere, a deprotonation degradation pathway was confirmed, in which the film preferentially degraded directly from MAPbI₃ into PbI₂, here the iodine defects played a key role in promoting the dissociation of water molecules into OH⁻ and further catalyzing the decomposition of perovskite.     

Similar Structural Dynamics for the Degradation of CH3NH3PbI3 in Air and in Vacuum

We investigate the degradation path of MAPbI₃ (MA=methylammonium) films over flat TiO₂ substrates at room temperature by means of X‐ray diffraction, spectroscopic ellipsometry, X‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI₂. We describe how this degradation product is structurally coupled with the original MAPbI₃ lattice through the orientation of its constituent PbI₆ octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH₃NH₂ or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material.     

Ion‐Exchange‐Induced 2D–3D Conversion of HMA1−xFAxPbI3Cl Perovskite into a High‐Quality MA1−xFAxPbI3 Perovskite

High‐quality phase‐pure MA_1?xFA_xPbI₃ 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 FA_xMA_1?xPbI₃ requiring rigid crystallization conditions. Here A 2D–3D conversion to transform compact 2D mixed composition HMA_1?xFA_xPbI₃Cl perovskite precursor films into 3D MA_1?xFA_xPbI₃ (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 MA_1?xFA_xPbI₃ without δ‐FAPbI₃ and MAPbI₃ impurity. In all, we successfully developed a facile one‐step method to fabricate high quality phase‐pure MA_1?xFA_xPbI₃ (x=0.1–0.9) perovskite films by 2D–3D conversion of HMA_1?xFA_xPbI₃Cl perovskite. This 2D–3D conversion is a promising strategy for lead halide perovskite fabrication.     

Influence of Orientational Disorder on the Optical Absorption Properties of the Hybrid Metal-Halide Perovskite CH3NH3PbI3

An experimental and theoretical investigation is reported to analyze the relation between the structural and absorption properties of CH₃NH₃PbI₃ in the tetragonal phase. More than 3000 geometry optimizations were performed to reveal the structural disorder and identify structures with the lowest energies. The electronic structure calculations provide an averaged band gap of 1.674 eV, which is in excellent agreement with the experimental value of about 1.6 eV. The simulations of the absorption spectrum for three representative structures with lowest energy reproduced the absorption shoulders observed in the experimental spectra. These shoulders are assigned to excitations having similar orbital characters and involving transitions between hybridized 6s(Pb)/5p(I) orbitals and 6p(Pb) orbitals. The geometries of the three structures were analyzed and the effects of the inorganic frame and the CH₃NH₃⁺ cations on the absorption properties were estimated. It was found that both changes in the inorganic frame and the CH₃NH₃⁺ cations orientations impact the absorption spectra, by modifying the transitions energies and intensities. This highlights the role of CH₃NH₃⁺ cation in influencing the absorption properties of CH₃NH₃PbI₃ and demonstrates that CH₃NH₃⁺ cation is one of the key elements explaining the broad and nearly constant absorption spectrum in the visible range.     

Steric Mixed‐Cation 2D Perovskite as a Methylammonium Locker to Stabilize MAPbI3

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 500 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.     

Post‐Treatment of CH3NH3PbI3/PbI2 Composite Films with Methylamine to Realize High‐Performance Photoconductor Devices

Organometallic halide perovskites have attracted great research interest as light‐active materials for use in optoelectronics. Here, we report a high‐performance photoconductor based on a methylammonium lead iodide (MAPbI₃) film that was prepared from a methylamine‐treated MAPbI₃/PbI₂ perovskite film. An ultrahigh responsivity of 3.6 A W^?1 and detectivity of 5.4×10¹² Jones were obtained for the film under 0.5 mW cm^?2 white‐light illumination. In addition, under 420 nm light irradiation, the film exhibited its highest responsivity and detectivity of 30 A W^?1 and 2.4×10¹⁴ Jones, respectively. The excellent photo‐response performance results from the improved electronic quality and suppressed nonradiative recombination channels of the treated perovskite thin film.     

Optoelectronic and morphology properties of perovskite/silicon interface layer for tandem solar cell application

Silicon (Si) solar cell has low optical absorption because of the low and indirect bandgap of Si, and the efficiency was trapped at 25% for 15 years. Si solar cell is able to achieve efficiency up to 30% by adding perovskite as multiple bandgap material through tandem formation. In this paper, the Si/perovskite interface layer was characterized to study the compatibility of perovskite on fluorine-doped tin oxide (FTO) glass and p-type Si wafer (p-Si). The single solution deposition step of methyl ammonium lead iodide, CH₃NH₃PbI₃ (MAPbI₃) perovskite film, was spin-coated at different concentration. The physical properties of the MAPbI₃/FTO and MAPbI₃/p-Si were obtained by profilometer, atomic force microscope, X-ray diffraction, and Raman spectroscopy. The optical properties were analyzed by ultraviolet-visible spectroscopy, photoluminescence, and infrared transmission. Then the electrical properties were measured by Hall effect. From the measurement, it is observed that 1.2M concentration of MAPbI₃ thin film has the highest thickness, smoothest film surface, and largest crystallite size compared with 0.8M and 1.0M. It is found that there is an interaction in perovskite/Si interface and caused in a low-wavelength shift, and the increase in concentration of MAPbI₃ helped in intensifying the Raman signal produced. 1.2M MAPbI₃ thin film had the highest enhancement in light trapping property rather than 0.8M and 1.0M. The bulk concentration and conductivity of 1.2M perovskite were higher, but the resistivity was lower than 0.8M MAPbI₃ because of more CH₃NH₃I and PbI₂ concentration within MAPbI₃ perovskite compound.     

Coordination Chemistry Dictates the Structural Defects in Lead Halide Perovskites

We show the influence of species present in precursor solution during formation of lead halide perovskite materials on the structural defects of the films. The coordination of lead by competing solvent molecules and iodide ions dictate the type of complexes present in the films. Depending on the processing conditions all PbIS₅⁺, PbI₂S_4, PbI₃S₃^?, PbI₄S₂^2?, PbI₅S₂^3?, PbI₆^4?and 1D (Pb₂I₄)_n chains are observed by absorption measurements. Different parameters are studied such as polarity of the solvent, concentration of iodide ions, concentration of solvent molecules and temperature. It is concluded that strongly coordinating solvents will preferentially form species with a low number of iodide ions and less coordinative solvents generate high concentration of PbI₆^?. We furthermore propose that all these plumbate ions may act as structural defects determining electronic properties of the photovoltaic films.     

Cesium Methylammonium Lead Iodide (CsxMA1−xPbI3) Nanocrystals with Wide Range Cation Composition Tuning and Enhanced Thermal Stability of the Perovskite Phase

Cesium methylammonium lead iodide (Cs_xMA_1−xPbI₃) nanocrystals were obtained with a wide range of A-site Cs-MA compositions by post-synthetic, room temperature cation exchange between CsPbI₃ nanocrystals and MAPbI₃ nanocrystals. The alloyed Cs_xMA_1−xPbI₃ nanocrystals retain their photoactive perovskite phase with incorporated Cs content, x, as high as 0.74 and the expected composition-tunable photoluminescence (PL). Excess methylammonium oleate from the reaction mixture in the MAPbI₃ nanocrystal dispersions was necessary to obtain fast Cs-MA cation exchange. The phase transformation and degradation kinetics of films of Cs_xMA_1−xPbI₃ nanocrystals were measured and modeled using an Avrami expression. The transformation kinetics were significantly slower than those of the parent CsPbI₃ and MAPbI₃ nanocrystals, with Avrami rate constants, k, at least an order of magnitude smaller. These results affirm that A-site cation alloying is a promising strategy for stabilizing iodide-based perovskites.     

Theoretical study on halide and mixed halide Perovskite solar cells: Effects of halide atoms on the stability and electronic properties

Increasing the stability of perovskite solar cells is one of the most important tasks in the photovoltaic industry. Thus, the structural, energetic, and electronic properties of pure CH₃NH₃PbI₃ and fully doped compounds (CH₃NH₃PbBr₃ and CH₃NH₃PbCl₃) in cubic and tetragonal phases were investigated using density functional theory calculations. We also considered the effects of mixed halide perovskites CH₃NH₃PbI₂X (where X = Br and Cl) and compared their properties with CH₃NH₃PbI₃. The DFT results indicate that the phase transformation from tetragonal to cubic phase decreases the band gap. The calculated results show that the X‐site ion plays a vital role in the geometrical stability and electronic levels. An increase in the band gap and a reduction in the lattice constants are more apparent in CH₃NH₃PbI₂X compounds (I > Br > Cl).     

Influence of halide mixing on thermal and photochemical stability of hybrid perovskites: XPS studies

The effect of I^–/Cl^–and I^–/Br^–mixing on the thermal and photochemical degradation of organometallic perovskite MeNH₃PbI₃ (MAPbI₃) was studied by X-ray photoelectron spectroscopy, which revealed the opportunity to essentially increase the photo and thermal stabilities of the material depending on the level and position of halide-mixing. The largest positive effect was observed for the small concentration of chloride substituent (MAPbI_2.7Cl_0.3), while the full halide substitution (MAPbBr₃) had a negative effect on the stability of hybrid perovskite.     

Application of Iodide Ion Selective Electrode to the Study of Stepwise Formation Constant and Solubility Product of Lead Iodide

Iodide ion-selective electrode were studied, prepared and applied for the complex formations and solubility product determination. The thermodynamic formation constant of PbI⁺ and the solubility product of PbI₃ were found to be 54 and 9.2 × 10^?9, respectively. The formation constant of PbNO₃⁺ was calculated to be 4.6 from the different formation constant of PbI⁺ in perchlorate and nitrate media.     

Lead‐ and Iodide‐Deficient (CH3NH3)PbI3 (d‐MAPI): The Bridge between 2D and 3D Hybrid Perovskites

3D and 2D hybrid perovskites, which have been known for more than 20 years, have emerged recently as promising materials for optoelectronic applications, particularly the 3D compound (CH₃NH₃)PbI₃ (MAPI). The discovery of a new family of hybrid perovskites called d ‐MAPI is reported: the association of PbI₂ with both methyl ammonium (MA⁺) and hydroxyethyl ammonium (HEA⁺) cations leads to a series of five compounds with general formulation (MA)_1−2.48x(HEA)_3.48x[Pb_1−xI_3−x]. These materials, which are lead‐ and iodide‐deficient compared to MAPI while retaining 3D architecture, can be considered as a bridge between the 2D and 3D materials. Moreover, they can be prepared as crystallized thin films by spin‐coating. These new 3D materials appear very promising for optoelectronic applications, not only because of their reduced lead content, but also in account of the large flexibility of their chemical composition through potential substitutions of MA⁺, HEA⁺, Pb²⁺ and I⁻ ions.     

A Modified Sequential Deposition Route for High-Performance Carbon-Based Perovskite Solar Cells under Atmosphere Condition

Carbon-based hole transport material (HTM)-free perovskite solar cells have exhibited a promising commercialization prospect, attributed to their outstanding stability and low manufacturing cost. However, the serious charge recombination at the interface of the carbon counter electrode and titanium dioxide (TiO₂) suppresses the improvement in the carbon-based perovskite solar cells’ performance. Here, we propose a modified sequential deposition process in air, which introduces a mixed solvent to improve the morphology of lead iodide (PbI₂) film. Combined with ethanol treatment, the preferred crystallization orientation of the PbI₂ film is generated. This new deposition strategy can prepare a thick and compact methylammonium lead halide (MAPbI₃) film under high-humidity conditions, which acts as a natural active layer that separates the carbon counter electrode and TiO₂. Meanwhile, the modified sequential deposition method provides a simple way to facilitate the conversion of the ultrathick PbI₂ capping layer to MAPbI₃, as the light absorption layer. By adjusting the thickness of the MAPbI₃ capping layer, we achieved a power conversation efficiency (PCE) of 12.5% for the carbon-based perovskite solar cells.     

A thioacetamide additive-based hybrid (MA0.5FA0.5)PbI3 perovskite solar cells crossing 21 % efficiency with excellent long term stability

An additive in hybrid perovskite is playing a vital role in the increment of power conversion efficiency (PCE), stability, and reproducibility of perovskite solar cells (PVSCs). Although, single-phase α-FAPbI₃ perovskite has an ideal band gap but is continuously transforming to δ–FAPbI₃, which is non-photoactive. Here, we controlled the methylammonium (MA) and formamidinium (FA) ratio in the (MA_xFA_1-x)PbI₃ perovskite composition and tuned its morphology with the help of the thioacetamide (TAA) Lewis base additive. The optimum MA:FA ratio and fine-tuning of TAA additive result in a highly crystalline, large grain size and smooth surface of the (MA_0.5FA_0.5)PbI₃ perovskite film. These highly uniform thin films with 850 nm grain size offered a superior interaction between the perovskite material and the electron transport layer (ETL) and a longer lifetime yielding a high PCE. The (MA_0.5FA_0.5)PbI₃+1% TAA-based champion device exhibited the highest PCE of 21.29% for a small area (0.09 cm²) and 18.32% PCE for a large area (1 cm²). The TAA-assisted devices exhibited high stability with >85% retention over 500 h. These results suggest that the (MA_0.5FA_0.5)PbI₃ along with the 1% TAA additive is a promising absorber layer that can produce >21% PCE.     

Thin films of MAPbI3 and MA0.15FA0.75Cs0.1PbI3 perovskites under femtosecond laser irradiation: nonlinear optical absorption and kinetics of photodegradation

The thin MAPbI₃ and MA_0.15FA_0.75Cs_0.1PbI₃ perovskite films have strong nonlinear absorption with coefficients of 443 ± 20 and 830 ± 50 cm GW^–1, respectively, due to two-photon absorption at 1064 nm. The photochemical degradation of perovskite films was observed upon irradiation with femtosecond pulses at 532 nm, and the depth of photodegradation decreased in perovskite films protected with a PMMA polymer layer.     

Enhanced Stability and Optical Absorption in the Perovskite-Based Compounds MA1−xCsxPbI3−yBry

Organometal halide perovskites have been outstanding from enormous amount of functional materials thanks to their highly cost-effective processability and prominent light harvesting capacity. Unfortunately, poor long-term stability seriously hinders their further development. The recent experimental observations suggest that Cesium is a promising candidate to enhance the stability of MAPbI₃. To explore the inherent mechanism, a first-principles investigation based on density functional theory, including hybrid functional, has been performed to analyze the electronic and optical properties of perovskite series MA_0.75Cs_0.25PbI_3−yBr_y. The results indicate that perovskite compound MA_0.75Cs_0.25PbI₂Br is significantly superior to the other doped series in terms of optical absorption within the visible-light range. In the meanwhile, both Bader charge analysis and charge density distribution show that the compound of MA_0.75Cs_0.25PbI₂Br is the most stable among all the doped perovskite series. Moreover, it is clearly manifested that the impact of cesium is mainly embodied in the enhancement of the stability rather than in the improvement of optical absorption. Our study sheds a new light on screening new-type light harvesting materials, and provides theoretical insight into the rationale design of highly efficient and stable photovoltaic devices based on these functional materials.     

Building Blocks of Hybrid Perovskites: A Photoluminescence Study of Lead-Iodide Solution Species

In this work, we present a detailed investigation of the optical properties of hybrid perovskite building blocks, [PbI_2+n]ⁿ⁻, that form in solutions of CH₃NH₃PbI₃ and PbI₂. The absorbance, photoluminescence (PL) and photoluminescence excitation (PLE) spectra of CH₃NH₃PbI₃ and PbI₂ solutions were measured in various solvents and a broad concentration range. Both CH₃NH₃PbI₃ and PbI₂ solutions exhibit absorption features attributed to [PbI₃]¹⁻ and [PbI₄]²⁻ complexes. Therefore, we propose a new mechanism for the formation of polymeric polyiodide plumbates in solutions of pristine PbI₂. For the first time, we show that the [PbI_2+n]ⁿ⁻ species in both solutions of CH₃NH₃PbI₃ and PbI₂ exhibit a photoluminescence peak at about 760 nm. Our findings prove that the spectroscopic properties of both CH₃NH₃PbI₃ and PbI₂ solutions are dominated by coordination complexes between Pb²⁺ and I⁻. Finally, the impact of these complexes on the properties of solid-state perovskite semiconductors is discussed in terms of defect formation and defect tolerance.     

First-Principles Study of Aziridinium Lead Iodide Perovskite for Photovoltaics

The long-term stability remains one of the main challenges for the commercialization of the rapidly developing hybrid organic-inorganic perovskite solar cells. Herein, we investigate the electronic and optical properties of the recently reported hybrid halide perovskite (CH₂)₂NH₂PbI₃ (AZPbI₃), which exhibits a much better stability than the popular halide perovskites CH₃NH₃PbI₃ and HC(NH₂)₂PbI₃, by using density functional theory (DFT). We find that AZPbI₃ possesses a band gap of 1.31 eV, ideal for single-junction solar cells, and its optical absorption is comparable with those of the popular CH₃NH₃PbI₃ and HC(NH₂)₂PbI₃ materials in the whole visible-light region. In addition, the conductivity of AZPbI₃ can be tuned from efficient p-type to n-type, depending on the growth conditions. Besides, the charge-carrier mobilities and lifetimes are unlikely hampered by deep transition energy levels, which have higher formation energies in AZPbI₃ according to our calculations. Overall, we suggest that the perovskite AZPbI₃ is an excellent candidate as a stable high-performance photovoltaic absorber material.     

A Layered Hybrid Perovskite Solar‐Cell Absorber with Enhanced Moisture Stability

Two‐dimensional hybrid perovskites are used as absorbers in solar cells. Our first‐generation devices containing (PEA)₂(MA)₂[Pb₃I₁₀] ( 1 ; PEA=C₆H₅(CH₂)₂NH₃⁺, MA=CH₃NH₃⁺) show an open‐circuit voltage of 1.18 V and a power conversion efficiency of 4.73 %. The layered structure allows for high‐quality films to be deposited through spin coating and high‐temperature annealing is not required for device fabrication. The 3D perovskite (MA)[PbI₃] ( 2 ) has recently been identified as a promising absorber for solar cells. However, its instability to moisture requires anhydrous processing and operating conditions. Films of 1 are more moisture resistant than films of 2 and devices containing 1 can be fabricated under ambient humidity levels. The larger bandgap of the 2D structure is also suitable as the higher bandgap absorber in a dual‐absorber tandem device. Compared to 2 , the layered perovskite structure may offer greater tunability at the molecular level for material optimization.