Residual PbI2 Research Articles

Lead iodide secondary growth and π-π stack regulation for sequential perovskite solar cells with 23.62% efficiency

The sequential deposited perovskite solar cells (PSCs) have received widespread attention due to its application potential in large-scale perovskite module and perovskite/silicon tandem solar cells. However, insufficient reaction between organic ammonium salts and PbI2 leads to residual PbI2 and low crystallinity of perovskite films, and the fragile Pb-I bonds easily creates iodine loss and reduces the stability of PbI6 framework. In this work, the 4-fluorobenzylamine (FBA) with C = O and –NH2 is employed in PbI2 precursor solution to regulate the secondary growth process of PbI2 film. Due to the low Gibbs free energy and high crystallinity of porous PbI2 film, sufficient reaction between organic ammonium salts and PbI2 is promoted, which results in large-grain, low-defect perovskite films. At the same time, through hydrogen bonding and π-π stacking interactions, the stability of the PbI6 skeleton is effectively improved, significantly suppressing non-radiative recombination and reducing defect state density. Finally, this strategy increases the power conversion efficiency (PCE) of PSCs from 22.06 % to 23.62 %, and the target PSCs maintain 96 % of their initial PCE after being placed in nitrogen for 1300 h.

Lead Iodide Redistribution Enables In Situ Passivation for Blading Inverted Perovskite Solar Cells with 24.5% Efficiency.

Blade-coating stands out as an alternative for fabricating scalable perovskite solar cells. However, it demands special control of the precursor composition regarding nucleation and crystallization and currently exhibits lower performance than the spin-coating process. It is mainly the resulting film morphology and excess lead iodide (PbI2) distribution that influences the optoelectronic properties. Here, the effectiveness of introducing N-Methyl-2-pyrrolidone (NMP) to regulate the structure of the perovskite layer and the redistribution of PbI2 is found. The introduction of NMP leads to the accumulation of excess PbI2, mainly on the top surface, reducing residual PbI2 at the perovskite buried interface. This not only facilitates the passivation of perovskite grain boundaries but also eliminates the potential degradation of the PbI2 triggered by light illumination in the perovskite buried interface. The optimized NMP-modified inverted perovskite solar cell achieves a champion efficiency of 24.5%, among the highest reported blade-coated perovskite solar cells. Furthermore, 13.68cm2 blading perovskite solar modules are fabricated and demonstrate an efficiency of up to 20.4%. These findings underscore that with proper modulation of precursor composition, blade-coating can be a feasible and superior alternative for manufacturing high-quality perovskite films, paving the way for their large-scale applications in photovoltaic technology.

Bilateral Chemical Linking at NiOx Buried Interface Enables Efficient and Stable Inverted Perovskite Solar Cells and Modules

AbstractInverted NiOx‐based perovskite solar cells (PSCs) exhibit considerable potential because of their low‐temperature processing and outstanding excellent stability, while is challenged by the carriers transfer at buried interface owing to the inherent low carrier mobility and abundant surface defects that directly deteriorates the overall device fill factor. Present work demonstrates a chemical linker with the capability of simultaneously grasping NiOx and perovskite crystals by forming a Ni−S−Pb bridge at buried interface to significantly boost the carriers transfer, based on a rationally selected molecule of 1,3‐dimethyl‐benzoimidazol‐2‐thione (NCS). The constructed buried interface not only reduces the pinholes and needle‐like residual PbI2 at the buried interface, but also deepens the work function and valence band maximum positions of NiOx, resulting in a smaller VBM offset between NiOx and perovskite film. Consequently, the modulated PSCs achieved a high fill factor up to 86.24 %, which is as far as we know the highest value in records of NiOx‐based inverted PSCs. The NCS custom‐tailored PSCs and minimodules (active area of 18 cm2) exhibited a champion efficiency of 25.05 % and 21.16 %, respectively. The unencapsulated devices remains over 90 % of their initial efficiency at maximum power point under continuous illumination for 1700 hours.

Impact of copper and cobalt-based metal-organic framework materials on the performance and stability of hole-transfer layer (HTL)-free perovskite solar cells and carbon-based

This article investigates the impact of metal-organic frameworks (MOFs) on the performance and stability of perovskite solar cells (PSCs), specifically focusing on the type of metal and the morphology of the MOF. Two types of MOFs, copper-benzene-1,3,5-tricarboxylate (Cu-BTC MOF) with spherical morphology and cobalt-benzene-1,3,5-tricarboxylate (Co-BTC MOF) with rod morphology, are synthesized and spin-coated on TiO2 substrates to form FTO/TiO2/MOF/CH3NH3PbI3/C-paste PSCs. The morphology and size of the MOFs are characterized by scanning electron microscopy (SEM), and the crystallinity and residual PbI2 of the perovskite films are analyzed by X-ray diffraction (XRD). The results show that the Co-BTC MOF PSC exhibits the highest power conversion efficiency (PCE) of 10.4% and the best stability, retaining 82% of its initial PCE after 264 h of storage in ambient air. The improved performance and stability are attributed to the enhanced crystallinity and reduced residual PbI2 of the perovskite film after Co-BTC MOF modification. The paper showcases the immense potential of MOF-based interlayers to revolutionize PSC technology, offering a path toward next-generation solar cells with enhanced performance and longevity.

Dual interfacial modification with 1D perovskite for self-assembled monolayer based inverted perovskite solar cells

Recently, self-assembled monolayer (SAM) based inverted perovskite solar cells (PSCs) have been extensively studied due to their remarkable stability and compatibility with large-area devices. Microporesat the SAM/perovskite buried interface are commonly observed, which result in the increased defect density and hindered charge extraction. Herein, a multifunctional organic material, namely 2-(methylthio)-4,5-dihydro-1 H-imidazole ammonium iodide (MTIm), is introduced as an interfacial modification material to react with the residual PbI2, forming one-dimensional (1D) (MTIm)PbI3 small grains. We found that the 1D perovskite distributes at both top and buried interfaces of PSC, achieving dual-interfacial passivation of defects. Moreover, the 1D perovskite leads to a favorable n-type doping at the top interface, and relaxes the lattice strain at the buried interface. As a result, the champion PSC device achieves significantly improved power conversion efficiency from 21.7 % to 23.8 %, and retains over 90 % of its initial PCE after storing in air for 1500 hours.

SnO2 Interacted with Sodium Thiosulfate for Perovskite Solar Cells over 25% Efficiency.

Tin oxide (SnO2) as electron transportation layer (ETL) has demonstrated remarkable performance applied in perovskite solar cells but still accommodated a host of defects such as oxygen vacancies, uncoordinated Sn4+ , and absorbed hydroxyl groups. Here, we use inorganic sodium thiosulfate Na2S2O3 to modify SnO2 nanoparticles in a bulk blending manner. Strong interaction between Na2S2O3 and SnO2 occurs, as reflected from the elemental chemical state change. The interaction has endowed the SnO2 film with better uniformity, increased conductivity, and more matched energy level with perovskite. Moreover, the modified SnO2 film as a substrate could promote the crystallization of perovskite by suppressing unreacted residual PbI2. The trap density from perovskite bulk to the SnO2 film across their interface has been effectively reduced, thus inhibiting the nonradiative recombination and promoting the transportation and extraction of charge carriers. Finally, the solar cell based on modified SnO2 has achieved a champion efficiency of 25.2%, demonstrating the effectiveness and potential of sulfur-containing molecules on optimizing the SnO2 property.

Eliminating Voids and Residual PbI2 beneath a Perovskite Film via Buried Interface Modification for Efficient Solar Cells.

The commercialization process of perovskite solar cells (PSCs) is markedly restricted by the power conversion efficiency (PCE) and long-term stability. During fabrication and operation, the bottom interface of the organic-inorganic hybrid perovskite layer frequently exhibits voids and residual PbI2, while these defects inevitably act as recombination centers and degradation sites, affecting the efficiency and stability of the devices. Therefore, the degradation and nonradiative recombination originating from the buried interface should be thoroughly resolved. Here, we report a multifunctional passivator by introducing malonic dihydrazide as an interfacial chemical bridge between the electron transport layer and the perovskite (PVK) layer. MADH with hydrazine groups improves the surface affinity of SnO2 and provides nucleation sites for the growth of PVK, leading to the reduced residual PbI2 and the voids resulting from the inhomogeneous solvent volatilization at the bottom interface. Meanwhile, the hydrazine group and carbonyl group synergistically coordinate with Pb2+ to improve the crystal growth environment, reducing the number of Pb-related defects. Eventually, the PCE of the PSCs is significantly enhanced benefiting from the reduced interfacial defects and the increased carrier transport. Moreover, the reductive nature of hydrazide further inhibits I2 generation during long-term operation, and the device retains 90% of the initial PCE under a 1 sun continuous illumination exposure of 700 h.

Two-Step Perovskite Solar Cells with > 25% Efficiency: Unveiling the Hidden Bottom Surface of Perovskite Layer.

While significant efforts in surface engineering have been devoted to the conversion process of lead iodide (PbI2) into perovskite and top surface engineering of perovskite layer with remarkable progress, the exploration of residual PbI2 clusters and the hidden bottom surface on perovskite layer have been limited. In this work, a new strategy involving 1-butyl-3-methylimidazolium acetate (BMIMAc) ionic liquid (IL) additives is developed and it is found that both the cations and the anions in ILs can interact with the perovskite components, thereby regulating the crystallization process and diminishing the residue PbI2 clusters as well as filling vacancies. The introduction of BMIMAc ILs induces the formation of a uniform porous PbI2 film, facilitating better penetration of the second-step organic salt and fostering a more extensive interaction between PbI2 and the organic salt. Surprisingly, the oversized residual PbI2 clusters at the bottom surface of the perovskite layer completely diminish. In addition, advanced depth analysis techniques including depth-resolved grazing-incidence wide-angle X-ray scattering (GIWAXS) and bottom thinning technology are employed for a comprehensive understanding of the reduction in residual PbI2. Leveraging effective PbI2 management and regulation of the perovskite crystallization process, the champion devices achieve a power conversion efficiency (PCE) of 25.06% with long-term stability.

Synthesis and Optical Properties of CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> Nanorods with Defects States

In this work, methylammonium lead halide CH3NH3PbI3 (MAPI3) perovskite nanorods were synthesized by the sol gel-spray ultrasonic method. The XRD pattern exhibits peaks assigned to the tetragonal MAPI3 structure with a residual PbI2 phase. SEM and AFM images show the formation of nanorods like picture with rough surface. The Raman spectrum was visualized to show various vibration modes in the film. Photoluminescence data revealed one emission peak at 786 nm (1.58 eV) in the band gap band, which was confirmed by the UV-Vis spectrum. The slight difference between the found band gap energy and the ideal one is explained in terms of shallow trap states.

Triisocyanate Derived Interlayer and High-Melting-Point Doping Promoter Boost Operational Stability of Perovskite Solar Cells.

Formamidinium lead triiodide serves as the optimal light-absorbing layer in single-junction perovskite solar cells. However, achieving operational stability of high-efficiency n-i-p type devices at elevated temperatures remains challenging. In this work, we implemented effective surface modifications on microcrystalline perovskite films. This involved the nucleophilic addition of formamidinium cations and coordination of residual PbI2 with triphenylmethane triisocyanate as well as subsequent polymerization. The in situ growth of a cross-linking network chemically anchored on the perovskite film in this approach effectively reduced trap densities, favorably altered surface work function, suppressing interface charge recombination and thus enhancing cell efficiency. Coupled with a high-melting-point air-doping promoter, we fabricated n-i-p type perovskite solar cells surpassing 25 % efficiency, demonstrating excellent operational stability at 65 °C.

Triisocyanate Derived Interlayer and High‐Melting‐Point Doping Promoter Boost Operational Stability of Perovskite Solar Cells

AbstractFormamidinium lead triiodide serves as the optimal light‐absorbing layer in single‐junction perovskite solar cells. However, achieving operational stability of high‐efficiency n‐i‐p type devices at elevated temperatures remains challenging. In this work, we implemented effective surface modifications on microcrystalline perovskite films. This involved the nucleophilic addition of formamidinium cations and coordination of residual PbI2 with triphenylmethane triisocyanate as well as subsequent polymerization. The in situ growth of a cross‐linking network chemically anchored on the perovskite film in this approach effectively reduced trap densities, favorably altered surface work function, suppressing interface charge recombination and thus enhancing cell efficiency. Coupled with a high‐melting‐point air‐doping promoter, we fabricated n‐i‐p type perovskite solar cells surpassing 25 % efficiency, demonstrating excellent operational stability at 65 °C.

Synergetic modification on buried and upper surfaces of perovskites with nitrogen-doped carbon quantum dots for efficient and stable solar cells

Tin oxide (SnO2), which is used as an electron transport layer in perovskite solar cells (PSCs), however, has nonnegligible defects. The surface of SnO2 films contains hydroxyl groups (–OH), which increases film defects and affects the quality of the upper perovskite. The energy level mismatch is also found in SnO2, which leads to severe nonradiative recombination and unsatisfactory photovoltaic performance. Meanwhile, excessive PbI2 residues on the perovskite surface serve as catalytic decomposition sites, significantly undermining device stability. In this study, nitrogen-doped carbon quantum dots (N-CQDs) were synthesized by using human hair as a raw material and were employed as an additive for interface between SnO2 and perovskites to improve interfacial charge transport. In addition, these N-CQDs were also used as a surface modifier on top of the perovskite layer to reduce residual PbI2. These results significantly increase the power conversion efficiency (PCE) of the related devices from 19.22% to 21.49%. The CQDs-modified device also shows significantly enhanced operational stability that when exposed to 30% humidity, the PCE of the optimized device retains 86% of its initial value after 1200 h. This study emphasizes the great potential of N-CQDs as a multifunctional interfacial modifier for fabrication of efficient and stable PSCs.

Amine-releasable Mediator In situ Repair Perovskites for Efficient and Stable Perovskite Solar Cells.

Residual lead iodide (PbI2) is deemed to a double-edged sword in perovskite film as small amounts of PbI2 are beneficial to the photovoltaic performance, but excessive will cause degradation of photovoltaic performance and stability. Herein, an in situ repair strategy has been developed by introducing amine-releasable mediator (methylammonium pyridine-2-carboxylic, MAPyA) to eliminate over-residual PbI2 and regulate the crystal quality of perovskite film. Notably, MAPyA can be partially decomposed into methylamine (MA) gas and pyridine-2-carboxylic (PyA) during high temperature annealing. The released MA can locally form liquid intermediate phase, facilitating the reconstruction of perovskite microcrystals and residual PbI2. Moreover, the leftover PyA is confirmed to effectively passivate the uncoordinated lead ions in final perovskite film. Based upon this, superior perovskite film with optimized crystal structure and holistic negligible PbI2 is acquired. The assembled device realizes outstanding efficiency of 24.06 %, and exhibits a remarkable operational stability that maintaining 87 % of its origin efficiency after continuous illumination for 1480 h. And the unencapsulated MAPyA-treated devices present significant uplift in humidity stability (maintaining ~93 % of the initial efficiency over 1500 h, 50-60 % relative humidity). Furthermore, the further optimization of this strategy with nanoimprint technology proves its superiority in the amplificative preparation for perovskite films.

Amine‐releasable Mediator In situ Repair Perovskites for Efficient and Stable Perovskite Solar Cells

AbstractResidual lead iodide (PbI2) is deemed to a double‐edged sword in perovskite film as small amounts of PbI2 are beneficial to the photovoltaic performance, but excessive will cause degradation of photovoltaic performance and stability. Herein, an in situ repair strategy has been developed by introducing amine‐releasable mediator (methylammonium pyridine‐2‐carboxylic, MAPyA) to eliminate over‐residual PbI2 and regulate the crystal quality of perovskite film. Notably, MAPyA can be partially decomposed into methylamine (MA) gas and pyridine‐2‐carboxylic (PyA) during high temperature annealing. The released MA can locally form liquid intermediate phase, facilitating the reconstruction of perovskite microcrystals and residual PbI2. Moreover, the leftover PyA is confirmed to effectively passivate the uncoordinated lead ions in final perovskite film. Based upon this, superior perovskite film with optimized crystal structure and holistic negligible PbI2 is acquired. The assembled device realizes outstanding efficiency of 24.06 %, and exhibits a remarkable operational stability that maintaining 87 % of its origin efficiency after continuous illumination for 1480 h. And the unencapsulated MAPyA‐treated devices present significant uplift in humidity stability (maintaining ~93 % of the initial efficiency over 1500 h, 50–60 % relative humidity). Furthermore, the further optimization of this strategy with nanoimprint technology proves its superiority in the amplificative preparation for perovskite films.

High performance wide bandgap perovskite solar cell with low VOC deficit less than 0.4 V

Wide bandgap perovskite solar cells (PSCs) have attracted significant attention because they can be applied to the top cells of tandem solar cells. However, high open-circuit voltage (VOC) deficit (>0.4 V) result from poor crystallization and high non-radiative recombination losses become a serious limitation in the pursuit of high performance. Here, the relevance between different PbI2 proportions and performance parameters are revealed through analysis of surface morphology, residual stress, and photostability. The increase of PbI2 proportion promotes crystal growth and reduces the work function of the perovskite film surface and promotes the energy level alignment with the carrier transport layer, which decreased the VOC deficit. However, residual PbI2 exacerbated the stress level of perovskite film, and the resulting lattice disorder deteriorated the photostability of the device. Ultimately, after the synergistic passivation of residual PbI2 and PEAI, the VOC achieves 1.266 V and VOC deficit is less than 0.4 V, the record value in wide bandgap PSCs.

Amino acid salt induced PbI2 crystal orientation optimization for high-efficiency perovskite solar cells with long-term stability

By introducing potassium l-glutamate, residual PbI2 at the buried perovskite interface is eliminated, leading to enhanced photoelectric performance in perovskite solar cells.

Advancing high-throughput combinatorial aging studies of hybrid perovskite thin films via precise automated characterization methods and machine learning assisted analysis.

To optimize material stability, automated high-throughput workflows are of increasing interest. However, many of those workflows either employ synthesis techniques not suitable for large-area depositions or are carried out in ambient conditions, which limits the transferability of the results. While combinatorial approaches based on vapour-based depositions are inherently scalable, their potential for controlled stability assessments has yet to be exploited. Based on MAPbI3 thin films as a prototypical system, we demonstrate a combinatorial inert-gas workflow to study intrinsic materials degradation, closely resembling conditions in encapsulated devices. Specifically, we probe the stability of MAPbI3 thin films with varying residual PbI2 content. A comprehensive set of automated characterization techniques is used to investigate the structure and phase constitution of pristine and aged thin films. A custom-designed in situ UV-Vis aging setup is used for real-time photospectroscopy measurements of the material libraries under relevant aging conditions, such as heat or light-bias exposure. These measurements are used to gain insights into the degradation kinetics, which can be linked to intrinsic degradation processes such as autocatalytic decomposition. Despite scattering effects, which complicate the conventional interpretation of in situ UV-Vis results, we demonstrate how a machine learning model trained on the comprehensive characterization data before and after the aging process can link changes in the optical spectra to phase changes during aging. Consequently, this approach does not only enable semi-quantitative comparisons of material stability but also provides detailed insights into the underlying degradation processes which are otherwise mostly reported for investigations on single samples.

Supramolecular interactions using β-cyclodextrin in controlling perovskite solar cell performance

By incorporating β-cyclodextrin, mitigation of residual PbI2 crystallization, control of perovskite chemistry, and uniform crystal growth, leading to improved solar cell performance and stability were demonstrated.

Toward efficient and industrially compatible fully textured perovskite silicon tandem solar cells: Controlled process parameters for reliable perovskite formation

AbstractCapitalizing on the existing silicon industry, fully textured perovskite‐silicon tandem solar cells have a great potential to penetrate the electricity market. While the use of textured silicon with large pyramid size (> 1 μm) enhances the power conversion efficiency (PCE), it also presents process complications. To achieve high performance, meticulous control of deposition parameters on textured silicon is required. This study provides a guideline for the use of the hybrid evaporation/spin‐coating route to form high‐quality perovskite absorbers. Using various characterization techniques, we highlight intrinsic differences between perovskite growth on flat versus textured substrates. Furthermore, we provide pathways to ensure a high perovskite phase purity, reveal mitigation strategies to avoid the formation of undesired dendritic perovskite structures, give guidelines to ensure photostability, and discuss the “misleading” effect of residual PbI2 on the perovskite photoluminescence response. A good understanding of the perovskite growth on textured silicon enables the fabrication of a tandem device with a PCE > 26% (without employing additives or surface treatments) and a good operational stability. The comprehensive guidelines in this study provide a better understanding of perovskite formation on textured silicon and can be transferred when upscaling the hybrid route perovskite deposition.

Intermediate Phase Modification Enables High‐Performance Iodine‐Rich Inorganic Perovskite Solar Cells with 3000‐Hour Stability

AbstractThe presence of excess secondary‐phase PbI2 in perovskite films shows a negative impact on their long‐term stability. Herein, an intermediate phase modification (IPM) strategy is proposed to eliminate residual PbI2 for improved quality of all‐inorganic CsPbI3‐type perovskite films, wherein the extrinsic agent is introduced to address the intermediate phase. By transforming residual PbI2 into a novel 1D perovskite phase, the IPM strategy acts as a patch to suture grain boundaries in the inorganic perovskite films. In addition, the IPM strategy not only enhances the quality of perovskite films but also mitigates energy disorder, reduces trap state density, and prolongs carrier lifetime by expediting the intermediate phase conversion process and passivating surface defects. As such, the perovskite solar cells (PSCs) with a high power conversion efficiency (PCE) of ≈20% and a high fill factor of 83.3% are considered to be very efficient, with excellent shelf stability of 3000 h of exposure in air without any encapsulation. This work not only exhibits a novel optimization route for inorganic perovskite but also emphasizes the crucial role of eliminating residual PbI2 in inorganic perovskites.