Room‐Temperature Partial Conversion of α‐FAPbI3 Perovskite Phase via PbI2 Solvation Enables High‐Performance Solar Cells

The two‐step conversion process consisting of metal halide deposition followed by conversion to hybrid perovskite has been successfully applied toward producing high‐quality solar cells of the archetypal MAPbI₃ hybrid perovskite, but the conversion of other halide perovskites, such as the lower bandgap FAPbI₃, is more challenging and tends to be hampered by the formation of hexagonal nonperovskite polymorph of FAPbI₃, requiring Cs addition and/or extensive thermal annealing. Here, an efficient room‐temperature conversion route of PbI₂ into the α‐FAPbI₃ perovskite phase without the use of cesium is demonstrated. Using in situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) and quartz crystal microbalance with dissipation (QCM‐D), the conversion behaviors of the PbI₂ precursor from its different states are compared. α‐FAPbI₃ forms spontaneously and efficiently at room temperature from P₂ (ordered solvated polymorphs with DMF) without hexagonal phase formation and leads to complete conversion after thermal annealing. The average power conversion efficiency (PCE) of the fabricated solar cells is greatly improved from 16.0(±0.32)% (conversion from annealed PbI₂) to 17.23(±0.28)% (from solvated PbI₂) with a champion device PCE > 18% due to reduction of carrier recombination rate. This work provides new design rules toward the room‐temperature phase transformation and processing of hybrid perovskite films based on FA⁺ cation without the need for Cs⁺ or mixed halide formulation.     

δ‐CsPbI3 Intermediate Phase Growth Assisted Sequential Deposition Boosts Stable and High‐Efficiency Triple Cation Perovskite Solar Cells

Cs/FA/MA triple cation perovskite films have been well developed in the antisolvent dripping method, attributable to its outstanding photovoltaic and stability performances. However, a facile and effective strategy is still lacking for fabricating high‐quality large‐grain triple cation perovskite films via sequential deposition method a, which is one of the key technologies for high efficiency perovskite solar cells. To address this issue, a δ‐CsPbI₃ intermediate phase growth (CsPbI₃‐IPG) assisted sequential deposition method is demonstrated for the first time. The approach not only achieves incorporation of controllable cesium into (FAPbI₃)_1–x(MAPbBr₃)_x perovskite, but also enlarges the perovskite grains, manipulates the crystallization, modulates the bandgap, and improves the stability of final perovskite films. The photovoltaic performances of the devices based on these Cs/FA/MA perovskite films with various amounts of the δ‐CsPbI₃ intermediate phase are investigated systematically. Benefiting from moderate cesium incorporation and intermediate phase‐assisted grain growth, the optimized Cs/FA/MA perovskite solar cells exhibit a significantly improved power conversion efficiency and operational stability of unencapsulated devices. This facile strategy provides new insights into the compositional engineering of triple or quadruple cation perovskite materials with enlarged grains and superior stability via a sequential deposition method.     

A Dual‐Retarded Reaction Processed Mixed‐Cation Perovskite Layer for High‐Efficiency Solar Cells

Mixed‐cation perovskite solar cells (PSCs) have become of enormous interest because of their excellent efficiency, which is now crossing 23.7%. Their broader absorption, relatively high stability with low fabrication cost compared to conventional single phase ABX₃ perovskites (where A: organic cation; B: divalent metal ion; and X: halide anion) are key properties of mixed‐halide mixed‐cation perovskites. However, the controlling reaction rate and formation of extremely dense, textured, smooth, and large grains of perovskite layer is a crucial task in order to achieve highly efficient PSCs. Herein, a new simple dual‐retarded reaction processing (DRP) method is developed to synthesize a high‐quality mixed‐cation (FAPbI₃)_0.85(MAPbBr₃)_0.15 (where MAPbBr₃ stands for methylammonium lead bromide and FAPbI₃ stands for formamidinium lead iodide) perovskite thin film via intermediate phase and incorporation of nitrogen‐doped reduced graphene oxide (N‐rGO). The reaction rate is retarded via two steps: first the formation of intermediate phase and second the interaction of the nitrogen groups on N‐rGO with hydrogen atoms from formamidinium cations. This DRP process allows for the fabrication of PSCs with maximum conversion efficiency higher than 20.3%.     

In Situ Observation of Crystallization Dynamics and Grain Orientation in Sequential Deposition of Metal Halide Perovskites

Metal halide perovskites have revolutionized the development of highly efficient, solution‐processable solar cells. Further advancements rely on improving perovskite film qualities through a better understanding of the underlying growth mechanism. Here, a systematic in situ grazing‐incidence X‐ray diffraction investigation is performed, facilitated by other techniques, on the sequential deposition of formamidinium lead iodide (FAPbI₃)‐based perovskite films. The active chemical reaction, composition distribution, phase transition, and crystal grain orientation are all visualized following the entire perovskite formation process. Furthermore, the influences of additive ions on the crystallization speed, grain orientation, and morphology of FAPbI₃‐based films, along with their photovoltaic performances, are fully evaluated and optimized, which leads to highly reproducible and efficient perovskite solar cells. The findings provide key insights into the perovskite growth mechanism and suggest the fabrication of high‐quality perovskite films for widespread optoelectronic applications.     

Humidity‐Induced Degradation via Grain Boundaries of HC(NH2)2PbI3 Planar Perovskite Solar Cells

The sensitivity of organic–inorganic perovskites to environmental factors remains a major barrier for these materials to become commercially viable for photovoltaic applications. In this work, the degradation of formamidinium lead iodide (FAPbI₃) perovskite in a moist environment is systematically investigated. It is shown that the level of relative humidity (RH) is important for the onset of degradation processes. Below 30% RH, the black phase of the FAPbI₃ perovskite shows excellent phase stability over 90 d. Once the RH reaches 50%, degradation of the FAPbI₃ perovskite occurs rapidly. Results from a Kelvin probe force microscopy study reveal that the formation of nonperovskite phases initiates at the grain boundaries and the phase transition proceeds toward the grain interiors. Also, ion migration along the grain boundaries is greatly enhanced upon degradation. A post‐thermal treatment (PTT) that removes chemical residues at the grain boundaries which effectively slows the degradation process is developed. Finally, it is demonstrated that the PTT process improves the performance and stability of the final device.     

Octadecylamine‐Functionalized Single‐Walled Carbon Nanotubes for Facilitating the Formation of a Monolithic Perovskite Layer and Stable Solar Cells

Organic–inorganic lead halide perovskites have shown great future for application in solar cells owing to their exceptional optical and electronic properties. To achieve high‐performance perovskite solar cells, a perovskite light absorbing layer with large grains is desirable in order to minimize grain boundaries and recombination during the operation of the device. Herein, a simple yet efficient approach is developed to synthesize perovskite films consisting of monolithic‐like grains with micrometer size through in situ deposition of octadecylamine functionalized single‐walled carbon nanotubes (ODA‐SWCNTs) onto the surface of the perovskite layer. The ODA‐SWCNTs form a capping layer that controls the evaporation rate of organic solvents in the perovskite film during the postthermal treatment. This favorable morphology in turn dramatically enhances the short‐circuit current density of the perovskite solar cells and almost completely eliminates the hysteresis. A maximum power conversion efficiency of 16.1% is achieved with an ODA‐SWCNT incorporated planar solar cell using (FA_0.83MA_0.17)_0.95Cs_0.05Pb(I_0.83Br_0.17)₃ as light absorber. Furthermore, the perovskite solar cells with ODA‐SWCNT demonstrate extraordinary stability with performance retention of 80% after 45 d stability testing under high humidity (60–90%) environment. This work opens up a new avenue for morphology manipulation of perovskite films and enhances the device stability using carbon material.     

NbF5: A Novel α‐Phase Stabilizer for FA‐Based Perovskite Solar Cells with High Efficiency

The HC(NH₂)₂⁺(FA⁺) is a well‐known substitute to CH₃NH₃⁺(MA⁺) for its capability to extend light utilization for improved power conversion efficiency for perovskite solar cells; unfortunately, the dark cubic phase (α‐phase) can easily transition to the yellow orthorhombic phase (δ‐phase) at room temperature, an issue that prevents its commercial application. In this report, an inorganic material (NbF₅) is developed to stabilize the desired α‐phase perovskite material by incorporating NbF₅ additive into the perovskite films. It is found that the NbF₅ additive effectively suppresses the formation of the yellow δ‐phase in the perovskite synthesis and aging process, thus enhancing the humidity and light‐soaking stability of the perovskite film. As a result, the perovskite solar cells with the NbF₅ additive exhibit improved air stability by tenfold, retaining nearly 80% of their initial efficiency after aging in air for 50 d. In addition, under full‐sun AM 1.5 G illumination of a xenon lamp without any UV‐reduction, the perovskite solar cells with the NbF₅ additive also show fivefold improved illumination stability than the control devices without NbF₅.     

HPbI3: A New Precursor Compound for Highly Efficient Solution‐Processed Perovskite Solar Cells

Recently, there have been extensive research efforts on developing high performance organolead halide based perovskite solar cells. While most studies focused on optimizing the deposition processes of the perovskite films, the selection of the precursors has been rather limited to the lead halide/methylammonium (or formamidium) halide combination. In this work, we developed a new precursor, HPbI₃, to replace lead halide. The new precursor enables formation of highly uniform formamidium lead iodide (FAPbI₃) films through a one‐step spin‐coating process. Furthermore, the FAPbI₃ perovskite films exhibit a highly crystalline phase with strong (110) preferred orientation and excellent thermal stability. The planar heterojunction solar cells based on these perovskite films exhibit an average efficiency of 15.4% and champion efficiency of 17.5% under AM 1.5 G illumination. By comparing the morphology and formation process of the perovskite films fabricated from the formamidium iodide (FAI)/HPbI₃, FAI/PbI₂, and FAI/PbI₂ with HI additive precursor combinations, it is shown that the superior property of the HPbI₃ based perovskite films may originate from 1) a slow crystallization process involving exchange of H⁺ and FA⁺ ions in the PbI₆ octahedral framework and 2) elimination of water in the precursor solution state.     

Air‐Stable Highly Crystalline Formamidinium Perovskite 1D Structures for Ultrasensitive Photodetectors

State‐of‐the‐art optoelectronic devices based on metal‐halide perovskites demand solution‐processed structures with high crystallinity, controlled crystallographic orientation, and enhanced environmental stability. Formamidinium lead iodide (α‐FAPbI₃) possesses a suitable bandgap of 1.48 eV and enhanced thermal stability, whereas perovskite‐type polymorph (α‐phase) is thermodynamically instable at ambient temperatures. Stable α‐FAPbI₃ perovskite 1D structure arrays with high crystallinity and ordered crystallographic orientation are developed by controlled nucleation and growth in capillary bridges. By surface functionalization with phenylethylammonium ions (PEA⁺), FAPbI₃ wires sustain a stable α‐phase after 28 day storage in the ambient environment with a relative humidity of 50%. Enhanced photoluminescence (PL) intensity and elongated PL lifetime demonstrate suppressed trap density and high crystallinity in these 1D structures, which is also reflected by the enhanced diffraction density and pure (001) crystallographic orientation in the grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) pattern. Based on these high‐quality 1D structures, sensitive photodetectors are achieved with average responsivities of 5282 A W^?1, average specific detectivities of more than 1.45 × 10¹⁴ Jones, and a fast response speed with a 3 dB bandwidth of 15 kHz.     

Inorganic Rubidium Cation as an Enhancer for Photovoltaic Performance and Moisture Stability of HC(NH2)2PbI3 Perovskite Solar Cells

Perovskite solar cells (PSCs) based on organic monovalent cation (methylammonium or formamidinium) have shown excellent optoelectronic properties with high efficiencies above 22%, threatening the status of silicon solar cells. However, critical issues of long‐term stability have to be solved for commercialization. The severe weakness of the state‐of‐the‐art PSCs against moisture originates mainly from the hygroscopic organic cations. Here, rubidium (Rb) is suggested as a promising candidate for an inorganic–organic mixed cation system to enhance moisture‐tolerance and photovoltaic performances of formamidinium lead iodide (FAPbI₃). Partial incorporation of Rb in FAPbI₃ tunes the tolerance factor and stabilizes the photoactive perovskite structure. Phase conversion from hexagonal yellow FAPbI₃ to trigonal black FAPbI₃ becomes favored when Rb is introduced. The authors find that the absorbance and fluorescence lifetime of 5% Rb‐incorporated FAPbI₃ (Rb_0.05FA_0.95PbI₃) are enhanced than bare FAPbI₃. Rb_0.05FA_0.95PbI₃‐based PSCs exhibit a best power conversion efficiency of 17.16%, which is much higher than that of the FAPbI₃ device (13.56%). Moreover, it is demonstrated that the Rb_0.05FA_0.95PbI₃ film shows superior stability against high humidity (85%) and the full device made with the mixed perovskite exhibits remarkable long‐term stability under ambient condition without encapsulation, retaining the high performance for 1000 h.     

Triamine‐Based Aromatic Cation as a Novel Stabilizer for Efficient Perovskite Solar Cells

Operational stability of perovskite solar cells has been a challenge from the beginning of perovskite research. In general, humidity and heat are the most well‐known degradation sources for perovskites, requiring ideal design of perovskite chemistry to withstand them. Although triple‐cation perovskite (Cs_0.05(FA_0.85MA_0.15)_0.95Pb(I_0.85Br_0.15)₃) has been already introduced as the stable perovskite material, the high reactivity of methylammonium and formamidinium in the cation sites demands further modification. Herein, 1,2,4‐triazole is suggested as an effective cation solute to improve the performance and stability of perovskite solar cells. 1,2,4‐Triazole is an aromatic cation with low dipole moment that is stable under humidity and heat. It also possesses three nitrogen atoms, forming additional hydrogen bonds in the lattice, stabilizing the material. In this study, the solar cell utilizing 1,2,4‐triazole alloying achieves a power conversion efficiency of 20.9% with superior stability under extreme condition (85 °C/85% of relative humidity (RH), encapsulated) for 700 h. The 1,2,4‐triazole‐alloyed perovskite exhibits reduced trap density and film roughness and enhanced carrier lifetime with electrical conductivity, suggesting an ideal perovskite structure for efficient and stable optoelectronic applications.     

Heteroatom Effect on Star‐Shaped Hole‐Transporting Materials for Perovskite Solar Cells

Three new star‐shaped hole‐transporting materials (HTMs) incorporating benzotripyrrole, benzotrifuran, and benzotriselenophene central cores endowed with three‐armed triphenylamine moieties ( BTP‐1 , BTF‐1 , and BTSe‐1 , respectively) are designed, synthesized, and implemented in perovskite solar cells (PSCs). The impact that the heteroatom‐containing central scaffold has on the electrochemical and photophysical properties, as well as on the photovoltaic performance, is systematically investigated and compared with their sulfur‐rich analogue ( BTT‐3 ). The new HTMs exhibit suitable highest‐occupied molecular orbitals (HOMO) levels regarding the valence band of the perovskite, which ensure efficient hole extraction at the perovskite/HTM interface. The molecular structures of BTF‐1 , BTT‐3 , and BTSe‐1 are fully elucidated by single‐crystal X‐ray crystallography as toluene solvates. The optimized (FAPbI₃)_0.85(MAPbBr₃)_0.15‐based perovskite solar cells employing the tailor‐made, chalcogenide‐based HTMs exhibit remarkable power conversion efficiencies up to 18.5%, which are comparable to the devices based on the benchmark spiro‐OMeTAD. PSCs with BTP‐1 exhibit a more limited power conversion efficiency of 15.5%, with noticeable hysteresis. This systematic study indicates that chalcogenide‐based derivatives are promising HTM candidates to compete efficiently with spiro‐OMeTAD.     

Constructing CsPbBr3 Cluster Passivated‐Triple Cation Perovskite for Highly Efficient and Operationally Stable Solar Cells

Ion migration and phase segregation, in mixed‐cation/anion perovskite materials, raises a bottleneck for its stability improvement in solar cells operation. Here, the synergetic effect of electric field and illumination on the phase segregation of Cs_0.05FA_0.80MA_0.15Pb(I_0.85Br_0.15)₃ (CsFAMA) perovskite is demonstrated. CsFAMA perovskite with a CsPbBr₃‐clusters passivated structure is realized, in which CsPbBr₃‐clusters are located at the surface/interface of CsFAMA grains. This structure is realized by introducing a CsPbBr₃ colloidal solution into the CsFAMA precursor. It is found that CsPbBr₃ passivation greatly suppresses phase segregation in CsFAMA perovskite. The resultant passivated CsFAMA also exhibits a longer photoluminescence lifetime due to reduced defect state densities, produces highly efficient TiO₂‐based planar solar cells with 20.6% power conversion efficiency and 1.195 V open‐circuit voltage. The optimized devices do not suffer from a fast burn‐in degradation and retain 90% of their initial performance at maximum power under one‐sun illumination at 25 °C (65 °C) exceeding 500 h (100 h) of continuous operation. This result represents the most stable output among CsFAMA solar cells in a planar structure with Spiro‐OMeTAD.     

Enhanced Incorporation of Guanidinium in Formamidinium‐Based Perovskites for Efficient and Stable Photovoltaics: The Role of Cs and Br

Recently, incorporating guanidium (GA) cations into organolead halide perovskites is shown to effectively improve the stability and performance of the solar cells. However, the underlying mechanisms that govern the GA incorporation have remained unclear. Here, FAPbI₃ is used as a basic framework to investigate experimentally and theoretically the role of cesium (Cs) and bromine (Br) substitutions in GA⁺ incorporation. It is found that simultaneous introduction of the small‐size Cs⁺ and Br^– in the FAPbI₃ lattice is critical to create sufficient space for the large GA⁺ and that the presence of the Cs⁺ prevents the formation of a GA‐contained low‐dimensional phase, which both assist GA⁺ incorporation. Upon entering the perovskite lattice, the GA⁺ can stabilize the lattice structure via forming strong hydrogen bonds with their neighboring halide ions. Such structure modification suppresses halide vacancy formation, thus leading to improved material properties. Compared to the GA‐free perovskite reference samples, the optimal system GA_0.05Cs_0.15FA_0.8Pb(I_0.85Br_0.15)₃ exhibits substantially improved thermal and photothermal stability, as well as increased photocarrier lifetime. Solar cells fabricated with the optimal material system show an excellent photovoltaic performance, with the champion device reaching a power conversion efficiency of 21.3% and an open circuit voltage of 1.229 V.     

Sulfate‐Assisted Interfacial Engineering for High Yield and Efficiency of Triple Cation Perovskite Solar Cells with Alkali‐Doped TiO2 Electron‐Transporting Layers

Facile electron injection and extraction are two key attributes desired in electron transporting layers to enhance the efficiency of planar perovskite solar cells. Herein it is demonstrated that the incorporation of alkali metal dopants in mesoporous TiO₂ can effectively modulate electronic conductivity and improve the charge extraction process by counterbalancing oxygen vacancies acting as nonradiative recombination centers. Moreover, sulfate bridges (SO₄^2?) grafted on the surface of K‐doped mesoporous titania provide a seamless integration of absorber and electron‐transporting layers that accelerate overall transport kinetics. Potassium doping markedly influences the nucleation of the perovskite layer to produce highly dense films with facetted crystallites. Solar cells made from K:TiO₂ electrodes exhibit power conversion efficiencies up to 21.1% with small hysteresis despite all solution coating processes conducted under ambient air conditions (controlled humidity: 25–35%). The higher device efficiencies are attributed to intrinsically tuned electronic conductivity and chemical modification of grain boundaries enabling uniform coverage of perovskite films with large grain size.     

Conjugated Small Molecule for Efficient Hole Transport in High‐Performance p‐i‐n Type Perovskite Solar Cells

The π‐conjugated organic small molecule 4,4′‐cyclohexylidenebis[N,N‐bis(4‐methylphenyl) benzenamine] (TAPC) has been explored as an efficient hole transport material to replace poly(3,4‐ethylenedio‐xythiophene):poly(styrenesulfonate) (PEDOT:PSS) in the preparation of p‐i‐n type CH₃NH₃PbI₃ perovskite solar cells. Smooth, uniform, and hydrophobic TAPC hole transport layers can be facilely deposited through solution casting without the need for any dopants. The power conversion efficiency of perovskite solar cells shows very weak TAPC layer thickness dependence across the range from 5 to 90 nm. Thermal annealing enables improved hole conductivity and efficient charge transport through an increase in TAPC crystallinity. The perovskite photoactive layer cast onto thermally annealed TAPC displays large grains and low residual PbI₂, leading to a high charge recombination resistance. After optimization, a stabilized power conversion efficiency of 18.80% is achieved with marginal hysteresis, much higher than the value of 12.90% achieved using PEDOT:PSS. The TAPC‐based devices also demonstrate superior stability compared with the PEDOT:PSS‐based devices when stored in ambient circumstances, with a relatively high humidity ranging from 50 to 85%.     

Precursor Solution Annealing Forms Cubic‐Phase Perovskite and Improves Humidity Resistance of Solar Cells

Solar cells with light‐absorbing layers comprising organometal halide perovskites have recently exceeded 22% efficiency. Despite high power‐conversion efficiencies, the stability of these devices, particularly when exposed to humidity and oxygen, remains poor. In the current study, a pathway to increase the stability of methylammonium lead iodide (CH₃NH₃PbI₃) based solar cells towards humidity is demonstrated, while maintaining the simplicity and solution‐processability of the active layers. Thermal annealing of the precursor solution prior to deposition induces the formation of cubic‐phase perovskite films in the solid state at room temperature. The experiments demonstrate that this improved ambient stability is correlated with the presence of the cubic phase at device operating temperatures, with the cubic phase resisting the formation of perovskite monohydrate—a pathway of degradation in conventionally processed perovskite thin films—on exposure to humidity.     

Solution-Mediated Hybrid FAPbI3 Perovskite Quantum Dots for Over 15% Efficient Solar Cell

Organic–inorganic formamidinium lead triiodide (FAPbI₃) hybrid perovskite quantum dot (QD) is of great interest to photovoltaic (PV) community due to its narrow band gap, higher ambient stability, and long carrier lifetime. However, the surface ligand management of FAPbI₃ QD is still a key hurdle that impedes the design of high-efficiency solar cells. Herein, this study first develops a solution-mediated ligand exchange (SMLE) for preparing FAPbI₃ QD film with enhanced electronic coupling. By dissolving optimal methylammonium iodide (MAI) into antisolvent to treat the FAPbI₃ QD solution, the SMLE can not only effectively replace the long-chain ligands, but also passivate the A- and X-site vacancies. By combining experimental and theoretical results, this study demonstrates that the SMLE engineered FAPbI₃ QD exhibits lower defect density, which is beneficial for fabricating high-quality QD arrays with desired morphology and carrier transport. Consequently, the SMLE FAPbI₃ QD based solar cell outputs a champion efficiency of 15.10% together with improved long-term ambient storage stability, which is currently the highest reported value for hybrid perovskite QD solar cells. These results would provide new design principle of hybrid perovskite QDs toward high-performance optoelectronic application.     

Charge‐Carrier Dynamics,Mobilities, and Diffusion Lengths of 2D–3D Hybrid Butylammonium–Cesium–Formamidinium Lead Halide Perovskites

Perovskite solar cells (PSCs) have improved dramatically over the past decade, increasing in efficiency and gradually overcoming hurdles of temperature‐ and humidity‐induced instability. Materials that combine high charge‐carrier lifetimes and mobilities, strong absorption, and good crystallinity of 3D perovskites with the hydrophobic properties of 2D perovskites have become particularly promising candidates for use in solar cells. In order to fully understand the optoelectronic properties of these 2D–3D hybrid systems, the hybrid perovskite BA_x(FA_0.83Cs_0.17)_1‐xPb(I_0.6Br_0.4)₃ is investigated across the composition range 0 ≤ x ≤ 0.8. Small amounts of butylammonium (BA) are found that help to improve crystallinity and appear to passivate grain boundaries, thus reducing trap‐mediated charge‐carrier recombination and enhancing charge‐carrier mobilities. Excessive amounts of BA lead to poor crystallinity and inhomogeneous film formation, greatly reducing effective charge‐carrier mobility. For low amounts of BA, the benevolent effects of reduced recombination and enhanced mobilities lead to charge‐carrier diffusion lengths up to 7.7 µm for x = 0.167. These measurements pave the way for highly efficient, highly stable PSCs and other optoelectronic devices based on 2D–3D hybrid materials.     

Boosting Photovoltaic Performance for Lead Halide Perovskites Solar Cells with BF4− Anion Substitutions

Composition engineering is a particularly simple and effective approach especially using mixed cations and halide anions to optimize the morphology, crystallinity, and light absorption of perovskite films. However, there are very few reports on the use of anion substitutions to develop uniform and highly crystalline perovskite films with large grain size and reduced defects. Here, the first report of employing tetrafluoroborate (BF₄^?) anion substitutions to improve the properties of (FA = formamidinium, MA = methylammonium (FAPbI₃)_0.83(MAPbBr₃)_0.17) perovskite films is demonstrated. The BF₄^? can be successfully incorporated into a mixed‐ion perovskite crystal frame, leading to lattice relaxation and a longer photoluminescence lifetime, higher recombination resistance, and 1–2 orders magnitude lower trap density in prepared perovskite films and derived solar cells. These advantages benefit the performance of perovskite solar cells (PVSCs), resulting in an improved power conversion efficiency (PCE) of 20.16% from 17.55% due to enhanced open‐circuit voltage (V_OC) and fill factor. This is the highest PCE for BF₄^? anion substituted lead halide PVSCs reported to date. This work provides insight for further exploration of anion substitutions in perovskites to enhance the performance of PVSCs and other optoelectronic devices.