Molecular Configuration Engineering in Hole-Transporting Materials toward Efficient and Stable Perovskite Solar Cells

The development of hole-transporting materials (HTMs) that can passivate defects in perovskite is of great significance in improving the efficiency and long-term stability of perovskite solar cells. To date, the investigation on HTMs mainly focus on exploring new structures, while molecular configuration is seldomly concerned. In this work, two small molecules are developed as HTMs with benzil and phenanthrene quinone as the core structure, respectively. With similar structure and the same defect passivation groups, whereas, the two molecules exhibit different configurations, thus distinct properties. Compared to 3,6-bis(3,6-bis(bis(4-methoxyphenyl)amino)-9H-carbazol-9-yl)phenanthrene-9,10-dione (PQ) with a rigid core structure, the benzil group in 1,2-bis(4-(3,6-bis(bis(4-methoxyphenyl)amino)-9H-carbazol-9-yl)phenyl)ethane-1,2-dione (DB) is flexible and can adjust molecular configuration to efficiently interact with the underlying perovskite material, which is confirmed from both experimental results and theoretical simulations. The DB-based device exhibits a high power conversion efficiency of 22.21% with excellent long-term stability, superior to the PQ-based device (20.22%). This study demonstrates that molecular configuration engineering will directly affect the properties of hole transport materials, as well as their interactions with perovskite, which should also be taken into consideration when devising HTMs.     

Efficient and Stable Perovskite Solar Cells via Dual Functionalization of Dopamine Semiquinone Radical with Improved Trap Passivation Capabilities

Highly efficient planar heterojunction perovskite solar cells (PVSCs) with dopamine (DA) semiquinone radical modified poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) (DA‐PEDOT:PSS) as a hole transporting layer (HTL) were fabricated. A combination of characterization techniques were employed to investigate the effects of DA doping on the electron donating capability of DA‐PEDOT:PSS, perovskite film quality and charge recombination kinetics in the solar cells. Our study shows that DA doping endows the DA‐PEDOT:PSS‐modified PVSCs with a higher radical content and greater perovskite to HTL charge extraction capability. In addition, the DA doping also improves work function of the HTL, increases perovskite film crystallinity, and the amino and hydroxyl groups in DA can interact with the undercoordinated Pb atoms on the perovskite crystal, reducing charge‐recombination rate and increasing charge‐extraction efficiency. Therefore, the DA‐PEDOT:PSS‐modified solar cells outperform those based on PEDOT:PSS, increasing open‐circuit voltage (V _oc) and power conversion efficiency (PCE) to 1.08 V and 18.5%, respectively. Even more importantly, the efficiency of the unencapsulated DA‐PEDOT:PSS‐based PVSCs are well retained with only 20% PCE loss after exposure to air for 250 hours. These in‐depth insights into structure and performance provide clear and novel guidelines for the design of effective HTLs to facilitate the practical application of inverted planar heterojunction PVSCs.     

Phenylhydrazinium Iodide for Surface Passivation and Defects Suppression in Perovskite Solar Cells

In recent years, hybrid perovskite solar cells (HPSCs) have received considerable research attention due to their impressive photovoltaic performance and low‐temperature solution processing capability. However, there remain challenges related to defect passivation and enhancing the charge carrier dynamics of the perovskites, to further increase the power conversion efficiency of HPSCs. In this work, the use of a novel material, phenylhydrazinium iodide (PHAI), as an additive in MAPbI₃ perovskite for defect minimization and enhancement of the charge carrier dynamics of inverted HPSCs is reported. Incorporation of the PHAI in perovskite precursor solution facilitates controlled crystallization, higher carrier lifetime, as well as less recombination. In addition, PHAI additive treated HPSCs exhibit lower density of filled trap states (10¹⁰ cm^?2) in perovskite grain boundaries, higher charge carrier mobility (≈11 × 10^?4 cm² V^?1 s), and enhanced power conversion efficiency (≈18%) that corresponds to a ≈20% improvement in comparison to the pristine devices.     

Molecularly Tailored Surface Defect Modifier for Efficient and Stable Perovskite Solar Cells

Surface defects cause non-radiative charge recombination and reduce the photovoltaic performance of perovskite solar cells (PSCs), thus effective passivation of defects has become a crucial method for achieving efficient and stable devices. Organic ammonium halides have been widely used for perovskite surface passivation, due to their simple preparation, lattice matching with perovskite, and high defects passivation ability. Herein, a surface passivator 2,4,6-trimethylbenzenaminium iodide (TMBAI) is employed as the interfacial layer between the spiro-OMeTAD and perovskite layer to modify the surface defect states. It is found that TMBAI treatment suppresses the nonradiative charge carrier recombination, resulting in a 60 mV increase of the open-circuit voltage (V_oc) (from 1.11 to 1.17 V) and raises the fill factor from 76.3% to 80.3%. As a result, the TMBAI-based PSCs device demonstrates a power conversion efficiency (PCE) of 23.7%. Remarkably, PSCs with an aperture area of 1 square centimeter produce a PCE of 21.7% under standard AM1.5 G sunlight. The unencapsulated TMBAI-modified device retains 92.6% and 90.1% of the initial values after 1000 and 550 h under ambient conditions (humidity 55%–65%) and one-sun continuous illumination, respectively.     

Multifunctional Enhancement for Highly Stable and Efficient Perovskite Solar Cells

With a certified efficiency as high as 25.2%, perovskite has taken the crown as the highest efficiency thin film solar cell material. Unfortunately, serious instability issues must be resolved before perovskite solar cells (PSCs) are commercialized. Aided by theoretical calculation, an appropriate multifunctional molecule, 2,2-difluoropropanediamide (DFPDA), is selected to ameliorate all the instability issues. Specifically, the carbonyl groups in DFPDA form chemical bonds with Pb²⁺ and passivate under-coordinated Pb²⁺ defects. Consequently, the perovskite crystallization rate is reduced and high-quality films are produced with fewer defects. The amino groups not only bind with iodide to suppress ion migration but also increase the electron density on the carbonyl groups to further enhance their passivation effect. Furthermore, the fluorine groups in DFPDA form both an effective barrier on the perovskite to improve its moisture stability and a bridge between the perovskite and HTL for effective charge transport. In addition, they show an effective doping effect in the HTL to improve its carrier mobility. With the help of the combined effects of these groups in DFPDA, the PSCs with DFPDA additive achieve a champion efficiency of 22.21% and a substantially improved stability against moisture, heat, and light.     

Interfacial Energy Level Alignment and Defect Passivation by Using a Multifunctional Molecular for Efficient and Stable Perovskite Solar Cells

Tin oxide (SnO₂) is currently the dominating electron transport material (ETL) used in state-of-the-art perovskite solar cells (PSCs). However, there are amounts of defects distributed at the interface between ETL and perovskite to deteriorate PSC performance. Herein, a molecule bridging layer is built by incorporating 2,5-dichloroterephthalic acid (DCTPA) into the interface between the SnO₂ and perovskites to achieve better energy level alignment and superior interfacial contact. The multifunctional molecular bridging layer not only can passivate the trap states of Sn dangling bonds and oxygen vacancies resulting in improved conductivity and the electron extraction of SnO₂ but also can regulate the perovskite crystal growth and reduce defect-assisted nonradiative recombination due to its strong interaction with undercoordinated lead ions. As a result, the DCTPA-modified PSCs achieve champion power conversion efficiencies (PCEs) of 23.25% and 20.23% for an active area of 0.15 cm² device and 17.52 cm² mini-module, respectively. Moreover, the perovskite films and PSCs based on DCTPA modification show excellent long-term stability. The unencapsulated target device can maintain over 90% of the initial PCE after 1000 h under ambient air. This strategy guides design methods of molecule bridging layer at the interface between SnO₂ and perovskite to improve the performance of PSCs .     

Synergistic Crystallization Modulation and Defects passivation via Additive Engineering Stabilize Perovskite Films for Efficient Solar Cells

Organic-inorganic lead halide perovskite are promising photovoltaic materials, but their intrinsic defects and crystalline quality severely deteriorate the solar cells efficiency and stability. Herein, potassium 1,1,2,2,3,3-hexafluoroprop-ane-1,3-disulfonimide (KHFDF) is introduced into PbI₂ precursor solution to passivate various defects and improve the crystalline quality of perovskite films. It is found that KHFDF can inhibit PbI₂ crystallization, thus tuning the crystal orientation and growth of perovskite films. Furthermore, KHFDF with dual-functional sulfonyl group cannot only passivate grain boundaries (GBs), but also passivate the defects at GBs via strong interaction with undercoordinated Pb²⁺ and/or hydrogen bonding with FA⁺, while the K⁺ counter cations allow ionic interaction with undercoordinated I⁻. As a result, the KHFDF-modified films exhibit high quality with a larger grain size and a reduced trap-state density, thereby suppressing the trap-state nonradiative recombination. And the devices show a champion efficiency up to 24.15%, benefiting from a sharp enhancement of open-circuit voltage (V_oc) of 1.183 V and fill factor of 81.78%. In addition, due to the enhanced humidity tolerance and chemical structure stability, the devices exhibit excellent long-term humidity and thermal stability without encapsulation.     

Efficient Perovskite Hybrid Solar Cells via Ionomer Interfacial Engineering

The surface of the solution‐processed methylammonium lead tri‐iodide (CH₃NH₃PbI₃) perovskite layer in perovskite hybrid solar cells (pero‐HSCs) tends to become rough during operation, which inevitably leads to deterioration of the contact between the perovskite layer and the charge‐extraction layers. Moreover, the low electrical conductivity of the electron extraction layer (EEL) gives rises to low electron collection efficiency and severe charge carrier recombination, resulting in energy loss during the charge‐extraction and ‐transport processes, lowering the efficiency of pero‐HSCs. To circumvent these problems, we utilize a solution‐processed ultrathin layer of a ionomer, 4‐lithium styrenesulfonic acid/styrene copolymer (LiSPS), to re‐engineer the interface of CH₃NH₃PbI₃ in planar heterojunction (PHJ) pero‐HSCs. As a result, PHJ pero‐HSCs are achieved with an increased photocurrent density of 20.90 mA cm^?2, an enlarged fill factor of 77.80%, a corresponding enhanced power conversion efficiency of 13.83%, high reproducibility, and low photocurrent hysteresis. Further investigation into the optical and electrical properties and the thin‐film morphologies of CH₃NH₃PbI₃ with and without LiSPS, and the photophysics of the pero‐HSCs with and without LiSPS are shown. These demonstrate that the high performance of the pero‐HSCs incorporated with LiSPS can be attributed to the reduction in both the charge carrier recombination and leakage current, as well as more efficient charge carrier collection, filling of the perforations in CH₃NH₃PbI_3, and a higher electrical conductivity of the LiSPS thin layer. These results demonstrate that our method provides a simple way to boost the efficiency of pero‐HSCs.     

Double‐Sided Surface Passivation of 3D Perovskite Film for High‐Efficiency Mixed‐Dimensional Perovskite Solar Cells

Defect‐mediated carrier recombination at the interfaces between perovskite and neighboring charge transport layers limits the efficiency of most state‐of‐the‐art perovskite solar cells. Passivation of interfacial defects is thus essential for attaining cell efficiencies close to the theoretical limit. In this work, a novel double‐sided passivation of 3D perovskite films is demonstrated with thin surface layers of bulky organic cation–based halide compound forming 2D layered perovskite. Highly efficient (22.77%) mixed‐dimensional perovskite devices with a remarkable open‐circuit voltage of 1.2 V are reported for a perovskite film having an optical bandgap of ≈1.6 eV. Using a combination of experimental and numerical analyses, it is shown that the double‐sided surface layers provide effective defect passivation at both the electron and hole transport layer interfaces, suppressing surface recombination on both sides of the active layer. Despite the semi‐insulating nature of the passivation layers, an increase in the fill factor of optimized cells is observed. The efficient carrier extraction is explained by incomplete surface coverage of the 2D perovskite layer, allowing charge transport through localized unpassivated regions, similar to tunnel‐oxide passivation layers used in silicon photovoltaics. Optimization of the defect passivation properties of these films has the potential to further increase cell efficiencies.     

Aryl Diammonium Iodide Passivation for Efficient and Stable Hybrid Organ‐Inorganic Perovskite Solar Cells

Surface passivation is increasingly one of the most prominent strategies to promote the efficiency and stability of perovskite solar cells (PSCs). However, most passivation molecules hinder carrier extraction due to poorly conductive aggregation between perovskite surface and carrier transportation layer. Herein, a novel molecule: p‐phenyl dimethylammonium iodide (PDMAI) with ammonium group on both terminals is introduced, and its passivation effect is systematically investigated. It is found that PDMAI can mitigate defects at the surface and promote carrier extraction from perovskite to the hole transporting layer, leading to a lift of open‐circuit voltage of 40 mV. Profiting from superior PDMAI passivation, the average efficiency of PSCs has been elevated from 19.69% to 20.99%. As demonstrated with density functional theory calculations, PDMAI probably tends to anchor onto the perovskite surface with both ? NH₃I tails, and enhances the adhesion and contact to perovskite layer. The exposed hydrophobic aryl core protects perovskite against detrimental environmental factors. In addition, the alkyl component between aryl and ammonium groups is demonstrated to be essentially vital in triggering passivation function, which offers the guidance for the design of passivation molecules.     

Interface Dipole Induced Field-Effect Passivation for Achieving 21.7% Efficiency and Stable Perovskite Solar Cells

Organolead halide hybrid perovskite solar cells (PSCs) have become a shining star in the renewable devices field due to the sharp growth of power conversion efficiency; however, interfacial recombination and carrier-extraction losses at heterointerfaces between the perovskite active layer and the carrier transport layers remain the two main obstacles to further improve the power conversion efficiency. Here, novel field-effect passivation has been successfully induced to effectively suppress the interfacial recombination and improve interfacial charge transfer by incorporating interfacial polarization via inserting a high work function interlayer between perovskite and holes transport layer. The charge dynamics within the device and the mechanism of the field-effect passivation are elucidated in detail. The unique interfacial dipoles reinforce the built-in field and prevent the photogenerated charges from recombining, resulting in power conversion efficiency up to 21.7% with negligible hysteresis. Furthermore, the hydrophobic interlayer also suppresses the perovskite decomposition by preventing the moisture penetration, thereby improving the humidity stability of the PSCs (>91% of the initial power conversion efficiency (PCE) after 30 d in 65 ± 5% humidity). Finally, several promising research perspectives based on field-effect passivation are also suggested for further conversion efficiency improvements and photovoltaic applications.     

Synergistic Passivation and Down-Conversion by Imidazole-Modified Graphene Quantum Dots for High Performance and UV-Resistant Perovskite Solar Cells

Organic–inorganic hybrid perovskite solar cells (PVSCs) have achieved stunning progress during the past decade, which has inspired great potential for future commercialization. However, tin dioxide (SnO₂) as a commonly used electron transport layer with varied defects and energy level mismatch with perovskite contributes to the energy loss and limitation of charge extraction. Herein, imidazole-modified graphene quantum dots (IGQDs) are introduced as the interlayer, which plays a significant role in three aspects: 1) dually passivating the defects of SnO₂ and buried interface of perovskite by first-principles calculations; 2) accelerating the carrier extraction and transfer owing to ideal band alignment; and 3) improving light utilization through down-conversion proved by light intensity measurement. Consequently, the devices based on IGQDs/SnO₂ not only exhibit the champion power conversion efficiency (PCE) of 24.11%, but display a significantly enhanced ultraviolet (UV) stability retaining about 81% of their initial PCEs after continuous UV irradiation (365 nm, 20 mW cm⁻²) for 300 h. Moreover, the unencapsulated modified device remains 82% after storing for 1650 h in air (20–30 °C, RH 45–55%). This work furnishes a novel method for the combination of interfacial passivation and photon management, which holds out for the prospect of employment in other optoelectronic applications.     

Synergistic Toughening and Self-Healing Strategy for Highly Efficient and Stable Flexible Perovskite Solar Cells

Halide perovskites are qualified to meet the flexibility demands of optoelectronic field because of their merits of flexibility, lightness, and low cost. However, the intrinsic defects and deformation-induced ductile fracture in both perovskite and buried interface significantly restrict the photoelectric performance and longevity of flexible perovskite solar cells (PVSCs). Here, a dual-dynamic cross-linking network is schemed to boost the photovoltaic efficiency and mechanical stability of flexible PVSCs by incorporating natural polymerizable small molecule α-lipoic acid (LA). The LA therein can be autonomously ring-opening polymerized through dynamic disulfide bonds and hydrogen bonds, concurrently forming coordination bonds to interact with perovskite component. Importantly, the polymerization product can serve as efficacious passivating and toughening agents to simultaneously optimize interfacial contact, enhance perovskite crystallinity and sustain robust mechanical bendability. Subsequently, the rigid (or flexible) p-i-n device realizes a champion efficiency of 22.43% (or 19.03%) with prominent operational stability. Moreover, the dual-dynamic cross-linking network endows PVSCs with bendability and self-healing capacity, allowing the optimized devices to retain >80% efficiency after 3000 bending cycles, and subsequently restore to ≈95% of its initial efficiency under mild heat-treatment. This toughening and self-healing strategy provides a facile and efficient path to prolong operational lifetime of flexible device.     

Chiral Stereoisomer Engineering of Electron Transporting Materials for Efficient and Stable Perovskite Solar Cells

A series of chiral stereoisomers of electron transporting materials with two chiral substituents is rationally designed and synthesized, and the influence of stereoisomerism on their physical and electronic properties is investigated to demonstrate highly efficient and stable perovskite solar cells (PSCs). Compared to mesomeric naphthalene diimide (NDI) derivatives, which have heterochiral side groups with centrosymmetric molecular packing of symmetric‐shaped conformers in the crystalline state, enantiomeric NDI derivatives have homochiral side groups that exhibit non‐centrosymmetric molecular packing of asymmetric‐shaped conformers in the crystalline state and exhibit better solution processability based on one order of magnitude higher solubility. A similar trend is observed in different rylene diimide stereoisomers based on larger semiconducting core perylene diimide. The PSCs based on NDI enantiomers with good film‐forming ability and a very high lowest phase transition temperature (T_lowest) of 321 °C exhibit a high and uniform average power conversion efficiency (PCE) of 19.067 ± 0.654%. These PSCs also have a high temporal device stability, with less than 10% degradation of the PCE at 100 °C for 1000 h without encapsulation. Therefore, chiral stereoisomer engineering of charge transporting materials is a potential approach to achieve high solution processability, excellent performance, and significant temporal stability in organic electronic devices.     

Chemical Reduction of Iodine Impurities and Defects with Potassium Formate for Efficient and Stable Perovskite Solar Cells

The performance of perovskite solar cells (PSCs) is negatively affected by iodine (I₂) impurities generated from the oxidation of iodide ions in the perovskite precursor powder, solution, and perovskite films. In this study, the use of potassium formate (HCOOK) as a reductant to minimize the presence of detrimental I₂ impurities is presented. It is demonstrated that HCOOK can effectively reduce I₂ back to I⁻ in the precursor solution as well as in the devices under external conditions. Furthermore, the introduced formate anion (HCOO⁻) and alkali metal cation (K⁺) can reduce the defect density within the perovskite film by modulating perovskite growth and passivating electronic defects, significantly prolonging the carrier lifetime and reducing the J–V hysteresis. Consequently, the maximum efficiency of the HCOOK-doped planar n–i–p PSCs reaches 23.8%. After 1000 h of operation at maximum power point tracking under continuous 1 sun illumination, the corresponding encapsulated devices retain 94% of their initial efficiency.     

Side-Chain Functionalized Polymer Hole-Transporting Materials with Defect Passivation Effect for Highly Efficient Inverted Quasi-2D Perovskite Solar Cells

Compared with inverted 3D perovskite solar cell (PSCs), inverted quasi-2D PSCs have advantages in device stability, but the device efficiency is still lagging behind. Constructing polymer hole-transporting materials (HTMs) with passivation functions to improve the buried interface and crystallization properties of perovskite films is one of the effective strategies to improve the performance of inverted quasi-2D PSCs. Herein, two novel side-chain functionalized polymer HTMs containing methylthio-based passivation groups are designed, named PVCz-SMeTPA and PVCz-SMeDAD, for inverted quasi-2D PSCs. Benefited from the non-conjugated flexible backbone bearing functionalized side-chain groups, the polymer HTMs exhibit excellent film-forming properties, well-matched energy levels and improved charge mobility, which facilitates the charge extraction and transport between HTM and quasi-2D perovskite layer. More importantly, by introducing methylthio units, the polymer HTMs can enhance the contact and interactions with quasi-2D perovskite, and further passivating the buried interface defects and assisting the deposition of high-quality perovskite. Due to the suppressed interfacial non-radiative recombination, the inverted quasi-2D PSCs using PVCz-SMeTPA and PVCz-SMeDAD achieve impressive power conversion efficiency (PCE) of 21.41% and 20.63% with open-circuit voltage of 1.23 and 1.22 V, respectively. Furthermore, the PVCz-SMeTPA based inverted quasi-2D PSCs also exhibits negligible hysteresis and considerably improved thermal and long-term stability.     

Supramolecular Aza Crown Ether Modulator for Efficient and Stable Perovskite Solar Cells

Molecular modulators have been demonstrated to be an effectual strategy for reducing the defect at the interface and in bulk of perovskite and ameliorating the performance and stability of perovskite solar cells (PSCs). Herein, 1-aza-15-crown 5-ether (A15C5), with a unique nitrogen heterocyclic structure as a molecular modulator is introduced at the interface between perovskite layer and hole transport layer of PSCs. Multiple supramolecular synergistic interaction between A15C5 and perovskite dramatically suppress and passivate defects, resulting in a 38% decrease in electron trap-state density in perovskite. The formation of two-dimensional/th3D perovskite heterojunctions induced by planar A15C5 releases residual strain of perovskite film, optimizes the match of energy level array and boosts the stability of devices. Consequently, A15C5-modulated PSC achieves an impressing efficiency of 24.13% along with excellent humidity, light and thermal stability. This work provides a typical strategy to utilize supramolecular crown ether in PSCs.     

Self‐Crystallized Multifunctional 2D Perovskite for Efficient and Stable Perovskite Solar Cells

Recently, perovskite solar cells (PSC) with high power‐conversion efficiency (PCE) and long‐term stability have been achieved by employing 2D perovskite layers on 3D perovskite light absorbers. However, in‐depth studies on the material and the interface between the two perovskite layers are still required to understand the role of the 2D perovskite in PSCs. Self‐crystallization of 2D perovskite is successfully induced by deposition of benzyl ammonium iodide (BnAI) on top of a 3D perovskite light absorber. The self‐crystallized 2D perovskite can perform a multifunctional role in facilitating hole transfer, owing to its random crystalline orientation and passivating traps in the 3D perovskite. The use of the multifunctional 2D perovskite (M2P) leads to improvement in PCE and long‐term stability of PSCs both with and without organic hole transporting material (HTM), 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenyl‐amine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) compared to the devices without the M2P.     

Multi-Site Intermolecular Interaction for In Situ Formation of Vertically Orientated 2D Passivation Layer in Highly Efficient Perovskite Solar Cells

Surface passivation via 2D perovskite is critical for perovskite solar cells (PSCs) to achieve remarkable performances, in which the applied spacer cations play an important role on structural templating. However, the random orientation of 2D perovskite always hinder the carrier transport. Herein, multiple nitrogen sites containing organic spacer molecule (1H-Pyrazole-1-carboxamidine hydrochloride, PAH) is introduced to form 2D passivation layer on the surface of formamidinium based (FAPbI₃) perovskite. Deriving from the interactions between PAH and PbI₂, the defects of FAPbI₃ perovskite are effectively passivated. Interestingly, due to the multiple-site interactions, the 2D nanosheets are found to grow perpendicularly to the substrate for promotion of charge transfer. Therefore, an impressive power conversion efficiency of 24.6% and outstanding long-term stability are achieved for the 2D/3D perovskite devices. The findings further provide a perspective in structure design of novel organic halide salts for the fabrication of efficient and stable PSCs.     

The Synergistic Effect of Pemirolast Potassium on Carrier Management and Strain Release for High-Performance Inverted Perovskite Solar Cells

The quality of the perovskite absorption layer is critical for the high efficiency and long-term stability of perovskite solar cells (PSCs). The inhomogeneity due to local lattice mismatch causes severe residual strain in low-quality perovskite films, which greatly limits the availability of high-performance PSCs. In this study, a multi-active-site potassium salt, pemirolast potassium (PP), is added to perovskite films to improve carrier dynamics and release residual stress. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) measurements suggest that the proposed multifunctional additive bonds with uncoordinated Pb²⁺ through the carbonyl group/tetrazole N and passivated I atom defects. Moreover, the residual stress release is effective from the surface to the entire perovskite layer, and carrier extraction/transport is promoted in PP-modified perovskite films. As a result, a champion power conversion efficiency (PCE) of 23.06% with an ultra-high fill factor (FF) of 84.36% is achieved in the PP-modified device, which ranks among the best in formamidinium-cesium (FACs) PSCs. In addition, the PP-modified device exhibits excellent thermal stability due to the inhibited phase separation. This work provides a reliable way to improve the efficiency and stability of PSCs by releasing residual stress in perovskite films through additive engineering.