Highly Efficient and Stable Perovskite Solar Cells: Competitive Crystallization Strategy and Synergistic Passivation

Defects of perovskite (PVK) films are one of the main obstacles to achieving high-performance perovskite solar cells (PSCs). Here, the authors fabricated highly efficient and stable PSCs by introducing prolinamide (ProA) into the PbI₂ precursor solution, which improves the performance of PSCs by the competitive crystallization and efficient defect passivation of perovskite. The theoretical and experimental results indicate that ProA forms an adduct with PbI₂, competes with free I⁻ to coordinate with Pb²⁺, leads to the increase of the energy barrier of crystallization, and slows down the crystallization rate. Furthermore, the dual-site synergistic passivation of ProA is revealed by density functional theory (DFT) calculations and experimental results. ProA effectively reduces non-radiative recombination in the resultant films to improve the photovoltaic performance of PSCs. Notably, ProA-assisted PSCs achieve 24.61% power conversion efficiency (PCE) for the champion device and the stability of PSCs devices under ambient and thermal environments is improved.     

Precise Control of Crystallization and Phase-Transition with Green Anti-Solvent in Wide-Bandgap Perovskite Solar Cells with Open-Circuit Voltage Exceeding 1.25 V

Wide-bandgap perovskite solar cells (PSCs) have attracted a lot of attention due to their application in tandem solar cells. However, the open-circuit voltage (V_OC) of wide-bandgap PSCs is dramatically limited by high defect density existing at the interface and bulk of the perovskite film. Here, an anti-solvent optimized adduct to control perovskite crystallization strategy that reduces nonradiative recombination and minimizes V_OC deficit is proposed. Specifically, an organic solvent with similar dipole moment, isopropanol (IPA) is added into ethyl acetate (EA) anti-solvent, which is beneficial to form PbI₂ adducts with better crystalline orientation and direct formation of α-phase perovskite. As a result, EA-IPA (7-1) based 1.67 eV PSCs deliver a power conversion efficiency of 20.06% and a V_OC of 1.255 V, which is one of the remarkable values for wide-bandgap around 1.67 eV. The findings provide an effective strategy for controlling crystallization to reduce defect density in PSCs.     

Suppressing Excess Lead Iodide Aggregation and Reducing N-Type Doping at Perovskite/HTL Interface for Efficient Perovskite Solar Cells

Excess lead iodide (PbI₂) aggregation at the charge carrier transport interface leads to energy loss and acts as unstable origins in perovskite solar cells (PSCs). Here, a strategy is reported to modulate the interfacial excess PbI₂ by introducing π-conjugated small-molecule semiconductors 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (TAPC) into perovskite films through an antisolvent addition method. The coordination of TAPC to Pb I units through the electron-donating triphenylamine groups and π-Pb²⁺ interactions allows for a compact perovskite film with reduced excess PbI₂ aggregates. Besides, preferred energy level alignment is achieved due to the suppressed n-type doping effect at the hole transport layer (HTL) interfaces. As a result, the TAPC-modified PSC based on Cs_0.05(FA_0.85MA_0.15)_0.95Pb(I_0.85Br_0.15)₃ triple-cation perovskite achieved an improved PCE from 18.37% to 20.68% and retained ≈90% of the initial efficiency after 30 days of aging under ambient conditions. Moreover, the TAPC-modified device based on FA_0.95MA_0.05PbI_2.85Br_0.15 perovskite produced an improved efficiency of 23.15% compared to the control (21.19%). These results provide an effective strategy for improving the performance of PbI₂-rich PSCs.     

Dual Defect-Passivation Using Phthalocyanine for Enhanced Efficiency and Stability of Perovskite Solar Cells

Semiconducting molecules have been employed to passivate traps extant in the perovskite film for enhancement of perovskite solar cells (PSCs) efficiency and stability. A molecular design strategy to passivate the defects both on the surface and interior of the CH₃NH₃PbI₃ perovskite layer, using two phthalocyanine (Pc) molecules (NP-SC₆-ZnPc and NP-SC₆-TiOPc) is demonstrated. The presence of lone electron pairs on S, N, and O atoms of the Pc molecular structures provides the opportunity for Lewis acid–base interactions with under-coordinated Pb²⁺ sites, leading to efficient defect passivation of the perovskite layer. The tendency of both NP-SC₆-ZnPc and NP-SC₆-TiOPc to relax on the PbI₂ terminated surface of the perovskite layer is also studied using density functional theory (DFT) calculations. The morphology of the perovskite layer is improved due to employing the Pc passivation strategy, resulting in high-quality thin films with a dense and compact structure and lower surface roughness. Using NP-SC₆-ZnPc and NP-SC₆-TiOPc as passivating agents, it is observed considerably enhanced power conversion efficiencies (PCEs), from 17.67% for the PSCs based on the pristine perovskite film to 19.39% for NP-SC₆-TiOPc passivated devices. Moreover, PSCs fabricated based on the Pc passivation method present a remarkable stability under conditions of high moisture and temperature levels.     

Tailoring C60 for Efficient Inorganic CsPbI2Br Perovskite Solar Cells and Modules

Although inorganic perovskite solar cells (PSCs) are promising in thermal stability, their large open-circuit voltage (V_OC) deficit and difficulty in large-area preparation still limit their development toward commercialization. The present work tailors C₆₀ via a codoping strategy to construct an efficient electron-transporting layer (ETL), leading to a significant improvement in V_OC of the inverted inorganic CsPbI₂Br PSC. Specifically, tris(pentafluorophenyl)borane (TPFPB) is introduced as a dopant to lower the lowest unoccupied molecular orbital (LUMO) level of the C₆₀ layer by forming a Lewis acidic adduct. The enlarged free energy difference provides a favorable enhancement in electron injection and thereby reduces charge recombination. Subsequently, a nonhygroscopic lithium salt (LiClO₄) is added to increase electron mobility and conductivity of the film, leading to a reduction in the device hysteresis and facilitating the fabrication of a large-area device. Finally, the as-optimized inorganic CsPbI₂Br PSCs gain a champion power conversion efficiency (PCE) of 15.19%, with a stabilized power output (SPO) of 14.21% (0.09 cm²). More importantly, this work also demonstrates a record PCE of 14.44% for large-area inorganic CsPbI₂Br PSCs (1.0 cm²) and reports the first inorganic perovskite solar module with the excellent efficiency exceeding 12% (10.92 cm²) by a self-developed quasi-curved heating method.     

The Role of Bulk and Interface Recombination in High‐Efficiency Low‐Dimensional Perovskite Solar Cells

2D Ruddlesden–Popper perovskite (RPP) solar cells have excellent environmental stability. However, the power conversion efficiency (PCE) of RPP cells remains inferior to 3D perovskite‐based cells. Herein, 2D (CH₃(CH₂)₃NH₃)₂(CH₃NH₃)_n?1Pb_nI_3n+1 perovskite cells with different numbers of [PbI₆]^4? sheets (n = 2–4) are analyzed. Photoluminescence quantum yield (PLQY) measurements show that nonradiative open‐circuit voltage (V_OC) losses outweigh radiative losses in materials with n > 2. The n = 3 and n = 4 films exhibit a higher PLQY than the standard 3D methylammonium lead iodide perovskite although this is accompanied by increased interfacial recombination at the top perovskite/C₆₀ interface. This tradeoff results in a similar PLQY in all devices, including the n = 2 system where the perovskite bulk dominates the recombination properties of the cell. In most cases the quasi‐Fermi level splitting matches the device V_OC within 20 meV, which indicates minimal recombination losses at the metal contacts. The results show that poor charge transport rather than exciton dissociation is the primary reason for the reduction in fill factor of the RPP devices. Optimized n = 4 RPP solar cells had PCEs of 13% with significant potential for further improvements.     

Mitigating Ion Migration with an Ultrathin Self-Assembled Ionic Insulating Layer Affords Efficient and Stable Wide-Bandgap Inverted Perovskite Solar Cells

Wide-bandgap perovskite solar cells (PSCs) are attracting increasing attention because they play an irreplaceable role in tandem solar cells. Nevertheless, wide-bandgap PSCs suffer large open-circuit voltage (V_OC) loss and instability due to photoinduced halide segregation, significantly limiting their application. Herein, a bile salt (sodium glycochenodeoxycholate, GCDC, a natural product), is used to construct an ultrathin self-assembled ionic insulating layer firmly coating the perovskite film, which suppresses halide phase separation, reduces V_OC loss, and improves device stability. As a result, 1.68 eV wide-bandgap devices with an inverted structure deliver a V_OC of 1.20 V with an efficiency of 20.38%. The unencapsulated GCDC-treated devices are considerably more stable than the control devices, retaining 92% of their initial efficiency after 1392 h storage under ambient conditions and retaining 93% after heating at 65 °C for 1128 h in an N₂ atmosphere. This strategy of mitigating ion migration via anchoring a nonconductive layer provides a simple approach to achieving efficient and stable wide-bandgap PSCs.     

Highly Efficient and Stable GABr-Modified Ideal-Bandgap (1.35 eV) Sn/Pb Perovskite Solar Cells Achieve 20.63% Efficiency with a Record Small Voc Deficit of 0.33 V

1.5–1.6 eV bandgap Pb-based perovskite solar cells (PSCs) with 30–31% theoretical efficiency limit by the Shockley–Queisser model achieve 21–24% power conversion efficiencies (PCEs). However, the best PCEs of reported ideal-bandgap (1.3–1.4 eV) Sn–Pb PSCs with a higher 33% theoretical efficiency limit are <18%, mainly because of their large open-circuit voltage (V_oc) deficits (>0.4 V). Herein, it is found that the addition of guanidinium bromide (GABr) can significantly improve the structural and photoelectric characteristics of ideal-bandgap (≈1.34 eV) Sn–Pb perovskite films. GABr introduced in the perovskite films can efficiently reduce the high defect density caused by Sn²⁺ oxidation in the perovskite, which is favorable for facilitating hole transport, decreasing charge-carrier recombination, and reducing the V_oc deficit. Therefore, the best PCE of 20.63% with a certificated efficiency of 19.8% is achieved in 1.35 eV PSCs, along with a record small V_oc deficit of 0.33 V, which is the highest PCE among all values reported to date for ideal-bandgap Sn–Pb PSCs. Moreover, the GABr-modified PSCs exhibit significantly improved environmental and thermal stability. This work represents a noteworthy step toward the fabrication of efficient and stable ideal-bandgap PSCs.     

Efficient Bifacial Passivation with Crosslinked Thioctic Acid for High-Performance Methylammonium Lead Iodide Perovskite Solar Cells

Defects, inevitably produced within bulk and at perovskite-transport layer interfaces (PTLIs), are detrimental to power conversion efficiency (PCE) and stability of perovskite solar cells (PSCs). It is demonstrated that a crosslinkable organic small molecule thioctic acid (TA), which can simultaneously be chemically anchored to the surface of TiO₂ and methylammonium lead iodide (MAPbI₃) through coordination effects and then in situ crosslinked to form a robust continuous polymer (Poly(TA)) network after thermal treatment, can be introduced into PSCs as a new bifacial passivation agent for greatly passivating the defects. It is also discovered that Poly(TA) can additionally enhance the charge extraction efficiency and the water-resisting and light-resisting abilities of perovskite film. These newly discovered features of Poly(TA) make PSCs herein achieve among the best PCE of 20.4% ever reported for MAPbI₃ with negligible hysteresis, along with much enhanced ultraviolet, air, and operational stabilities. Density functional theory calculations reveal that the passivation of MAPbI₃ bulk and PTLIs by Poly(TA) occurs through the interaction of functional groups ( COOH,  C S) in Poly(TA) with under-coordinated Pb²⁺ in MAPbI₃ and Ti⁴⁺ in TiO₂, which is supported by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy.     

High‐Performance Inverted Planar Perovskite Solar Cells Enhanced by Thickness Tuning of New Dopant‐Free Hole Transporting Layer

A new hole transporting material (HTM) named DMZ is synthesized and employed as a dopant‐free HTM in inverted planar perovskite solar cells (PSCs). Systematic studies demonstrate that the thickness of the hole transporting layer can effectively enhance the morphology and crystallinity of the perovskite layer, leading to low series resistance and less defects in the crystal. As a result, the champion power conversion efficiency (PCE) of 18.61% with J_SC = 22.62 mA cm^?2, V_OC = 1.02 V, and FF = 81.05% (an average one is 17.62%) is achieved with a thickness of ≈13 nm of DMZ (2 mg mL^?1) under standard global AM 1.5 illumination, which is ≈1.5 times higher than that of devices based on poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT:PSS). More importantly, the devices based on DMZ exhibit a much better stability (90% of maximum PCE retained after more than 556 h in air (relative humidity ≈ 45%–50%) without any encapsulation) than that of devices based on PEDOT:PSS (only 36% of initial PCE retained after 77 h in same conditions). Therefore, the cost‐effective and facile material named DMZ offers an appealing alternative to PEDOT:PSS or polytriarylamine for highly efficient and stable inverted planar PSCs.     

Gradient Energy Alignment Engineering for Planar Perovskite Solar Cells with Efficiency Over 23%

An electron-transport layer (ETL) with appropriate energy alignment and enhanced charge transfer is critical for perovskite solar cells (PSCs). However, interfacial energy level mismatch limits the electrical performance of PSCs, particularly the open-circuit voltage (V_OC). Herein, a simple low-temperature-processed In₂O₃/SnO₂ bilayer ETL is developed and used for fabricating a new PSC device. The presence of In₂O₃ results in uniform, compact, and low-trap-density perovskite films. Moreover, the conduction band of In₂O₃ is shallower than that of Sn-doped In₂O₃ (ITO), enhancing the charge transfer from perovskite to ETL, thus minimizing V_OC loss at the perovskite and ETL interface. A planar PSC with a power conversion efficiency of 23.24% (certified efficiency of 22.54%) is obtained. A high V_OC of 1.17 V is achieved with the potential loss at only 0.36 V. In contrast, devices based on single SnO₂ layers achieve 21.42% efficiency with a V_OC of 1.13 V. In addition, the new device maintains 97.5% initial efficiency after 80 d in N₂ without encapsulation and retains 91% of its initial efficiency after 180 h under 1 sun continuous illumination. The results demonstrate and pave the way for the development of efficient photovoltaic devices.     

Record Efficiency Stable Flexible Perovskite Solar Cell Using Effective Additive Assistant Strategy

Even though the power conversion efficiency (PCE) of rigid perovskite solar cells is increased to 22.7%, the PCE of flexible perovskite solar cells (F‐PSCs) is still lower. Here, a novel dimethyl sulfide (DS) additive is developed to effectively improve the performance of the F‐PSCs. Fourier transform infrared spectroscopy reveals that the DS additive reacts with Pb²⁺ to form a chelated intermediate, which significantly slows down the crystallization rate, leading to large grain size and good crystallinity for the resultant perovskite film. In fact, the trap density of the perovskite film prepared using the DS additive is reduced by an order of magnitude compared to the one without it, demonstrating that the additive effectively retards transformation kinetics during the thin film formation process. As a result, the PCE of the flexible devices increases to 18.40%, with good mechanical tolerance, the highest reported so far for the F‐PSCs. Meanwhile, the environmental stability of the F‐PSCs significantly enhances by 1.72 times compared to the device without the additive, likely due to the large grain size that suppresses perovskite degradation at grain boundaries. The present strategy will help guide development of high efficiency F‐PSCs for practical applications.     

FA0.88Cs0.12PbI3−x(PF6)x Interlayer Formed by Ion Exchange Reaction between Perovskite and Hole Transporting Layer for Improving Photovoltaic Performance and Stability

Interface engineering to form an interlayer via ion exchange reaction is reported. A FA_0.88Cs_0.12PbI₃ formamidinium (FA) perovskite layer is first prepared, then FAPF₆ solution with different concentrations is spin‐coated on top of the perovskite film, which leads to a partial substitution of iodide by PF₆^? ion. The second phase with nominal composition of FA_0.88Cs_0.12PbI_3?x(PF₆)_x is grown at the grain boundary, which has island morphology and its size depends on the FAPF₆ solution concentration. The lattice is expanded and bandgap is reduced due to inclusion of larger PF₆^? ions. The power conversion efficiency (PCE) is significantly enhanced from 17.8% to 19.3% as a consequence of improved fill factor and open‐circuit voltage (V_oc). In addition, current–voltage hysteresis is reduced. Post‐treatment with FAPF₆ reduces defect density and enhances carrier lifetime, which is responsible for the improved photovoltaic performance and reduced hysteresis. The unencapsulated device with post‐treated perovskite film demonstrates better stability than the pristine perovskite, where the initial PCE retains over 80% after 528 h exposure under relative humidity of around 50–70% in the dark and 92% after 360 h under one sun illumination.     

Cesium Lead Inorganic Solar Cell with Efficiency beyond 18% via Reduced Charge Recombination

Cesium‐based inorganic perovskite solar cells (PSCs) are promising due to their potential for improving device stability. However, the power conversion efficiency of the inorganic PSCs is still low compared with the hybrid PSCs due to the large open‐circuit voltage (V_OC) loss possibly caused by charge recombination. The use of an insulated shunt‐blocking layer lithium fluoride on electron transport layer SnO₂ for better energy level alignment with the conduction band minimum of the CsPbI_3‐xBr_x and also for interface defect passivation is reported. In addition, by incorporating lead chloride in CsPbI_3‐xBr_x precursor, the perovskite film crystallinity is significantly enhanced and the charge recombination in perovksite is suppressed. As a result, optimized CsPbI_3‐xBr_x PSCs with a band gap of 1.77 eV exhibit excellent performance with the best V_OC as high as 1.25 V and an efficiency of 18.64%. Meanwhile, a high photostability with a less than 6% efficiency drop is achieved for CsPbI_3‐xBr_x PSCs under continuous 1 sun equivalent illumination over 1000 h.     

Amide‐Catalyzed Phase‐Selective Crystallization Reduces Defect Density in Wide‐Bandgap Perovskites

Wide‐bandgap (WBG) formamidinium–cesium (FA‐Cs) lead iodide–bromide mixed perovskites are promising materials for front cells well‐matched with crystalline silicon to form tandem solar cells. They offer avenues to augment the performance of widely deployed commercial solar cells. However, phase instability, high open‐circuit voltage (V_oc) deficit, and large hysteresis limit this otherwise promising technology. Here, by controlling the crystallization of FA‐Cs WBG perovskite with the aid of a formamide cosolvent, light‐induced phase segregation and hysteresis in perovskite solar cells are suppressed. The highly polar solvent additive formamide induces direct formation of the black perovskite phase, bypassing the yellow phases, thereby reducing the density of defects in films. As a result, the optimized WBG perovskite solar cells (PSCs) (E_g ≈ 1.75 eV) exhibit a high V_oc of 1.23 V, reduced hysteresis, and a power conversion efficiency (PCE) of 17.8%. A PCE of 15.2% on 1.1 cm² solar cells, the highest among the reported efficiencies for large‐area PSCs having this bandgap is also demonstrated. These perovskites show excellent phase stability and thermal stability, as well as long‐term air stability. They maintain ≈95% of their initial PCE after 1300 h of storage in dry air without encapsulation.     

Nanoporous p-type NiOx electrode for p-i-n inverted perovskite solar cell toward air stability

Designing air-stable perovskite solar cells (PSCs) is a recent trend in low-cost photovoltaic technology. Metal oxide-based electron transporting layers (ETLs) and hole transporting layers (HTLs) have attracted tremendous attention in PSCs, because of their excellent air stability, high electron mobility, and optical transparency. Herein, we report a co-precipitation method for the synthesis of p-type nanoporous nickel oxide (np-NiOx) thin films as the HTL for inverted (p-i-n) PSCs. The best-performing p-i-n PSC having np-NiOx HTL, (FAPbI₃)_0.85(MAPbBr₃)_0.15 (herein FAPbI₃ stands for formamidinium lead iodide and MAPbBr₃ stands for methylammonium lead bromide) perovskite and phenyl-C₆₁-butyric acid methyl ester (PCBM)/ZnO ETL exhibited a 19.10% (±1%) power conversion efficiency (PCE) with a current density (J_SC) of 22.76?mA?cm^?2, open circuit voltage (V_OC) of 1.076?V and fill factor (FF) of 0.78 under 1?sun (100?mW?cm^?2). Interestingly, the developed p-i-n PSCs based on p-type NiOx and n-type ZnO could retain >80% efficiency after 160?days, which is much higher than conventional PEDOT:PSS HTL-based PSCs. Our findings provide air-stable perovskite solar cells with high efficiency.     

Highly Efficient 2D/3D Hybrid Perovskite Solar Cells via Low‐Pressure Vapor‐Assisted Solution Process

The fabrication of multidimensional organometallic halide perovskite via a low‐pressure vapor‐assisted solution process is demonstrated for the first time. Phenyl ethyl‐ammonium iodide (PEAI)‐doped lead iodide (PbI₂) is first spin‐coated onto the substrate and subsequently reacts with methyl‐ammonium iodide (MAI) vapor in a low‐pressure heating oven. The doping ratio of PEAI in MAI‐vapor‐treated perovskite has significant impact on the crystalline structure, surface morphology, grain size, UV–vis absorption and photoluminescence spectra, and the resultant device performance. Multiple photoluminescence spectra are observed in the perovskite film starting with high PEAI/PbI₂ ratio, which suggests the coexistence of low‐dimensional perovskite (PEA₂MA_n?1Pb_nI_3n+1) with various values of n after vapor reaction. The dimensionality of the as‐fabricated perovskite film reveals an evolution from 2D, hybrid 2D/3D to 3D structure when the doping level of PEAI/PbI₂ ratio varies from 2 to 0. Scanning electron microscopy images and Kelvin probe force microscopy mapping show that the PEAI‐containing perovskite grain is presumably formed around the MAPbI₃ perovskite grain to benefit MAPbI₃ grain growth. The device employing perovskite with PEAI/PbI₂ = 0.05 achieves a champion power conversion efficiency of 19.10% with an open‐circuit voltage of 1.08 V, a current density of 21.91 mA cm^?2, and a remarkable fill factor of 80.36%.     

Detrimental Effect of Unreacted PbI2 on the Long-Term Stability of Perovskite Solar Cells

Excess/unreacted lead iodide (PbI₂) has been commonly used in perovskite films for the state-of-the-art solar cell applications. However, an understanding of intrinsic degradation mechanisms of perovskite solar cells (PSCs) containing unreacted PbI₂ has been still insufficient and, therefore, needs to be clarified for better operational durability. Here, it is shown that degradation of PSCs is hastened by unreacted PbI₂ crystals under continuous light illumination. Unreacted PbI₂ undergoes photodecomposition under illumination, resulting in the formation of lead and iodine in films. Thus, this photodecomposition of PbI₂ is one of the main reasons for accelerated device degradation. Therefore, this work reveals that carefully controlling the formation of unreacted PbI₂ crystals in perovskite films is very important to improve device operational stability for diverse opto-electronic applications in the future.     

Fine Multi‐Phase Alignments in 2D Perovskite Solar Cells with Efficiency over 17% via Slow Post‐Annealing

Layered Ruddlesden–Popper (RP) phase (2D) halide perovskites have attracted tremendous attention due to the wide tunability on their optoelectronic properties and excellent robustness in photovoltaic devices. However, charge extraction/transport and ultimate power conversion efficiency (PCE) in 2D perovskite solar cells (PSCs) are still limited by the non‐eliminable quantum well effect. Here, a slow post‐annealing (SPA) process is proposed for BA₂MA₃Pb₄I₁₃ (n = 4) 2D PSCs by which a champion PCE of 17.26% is achieved with simultaneously enhanced open‐circuit voltage, short‐circuit current, and fill factor. Investigation with optical spectroscopy coupled with structural analyses indicates that enhanced crystal orientation and favorable alignment on the multiple perovskite phases (from the 2D phase near bottom to quasi‐3D phase near top regions) is obtained with SPA treatment, which promotes carrier transport/extraction and suppresses Shockley–Read–Hall charge recombination in the solar cell. As far as it is known, the reported PCE is so far the highest efficiency in RP phase 2D PSCs based on butylamine (BA) spacers (n = 4). The SPA‐processed devices exhibit a satisfactory stability with <4.5% degradation after 2000 h under N₂ environment without encapsulation. The demonstrated process strategy offers a promising route to push forward the performance in 2D PSCs toward realistic photovoltaic applications.     

Multifunctional Polymer-Regulated SnO2 Nanocrystals Enhance Interface Contact for Efficient and Stable Planar Perovskite Solar Cells

Perovskite solar cells (PSCs) have rapidly developed and achieved power conversion efficiencies of over 20% with diverse technical routes. Particularly, planar-structured PSCs can be fabricated with low-temperature (≤150 °C) solution-based processes, which is energy efficient and compatible with flexible substrates. Here, the efficiency and stability of planar PSCs are enhanced by improving the interface contact between the SnO₂ electron-transport layer (ETL) and the perovskite layer. A biological polymer (heparin potassium, HP) is introduced to regulate the arrangement of SnO₂ nanocrystals, and induce vertically aligned crystal growth of perovskites on top. Correspondingly, SnO₂–HP-based devices can demonstrate an average efficiency of 23.03% on rigid substrates with enhanced open-circuit voltage (V_OC) of 1.162 V and high reproducibility. Attributed to the strengthened interface binding, the devices obtain high operational stability, retaining 97% of their initial performance (power conversion efficiency, PCE > 22%) after 1000 h operation at their maximum power point under 1 sun illumination. Besides, the HP-modified SnO₂ ETL exhibits promising potential for application in flexible and large-area devices.