Dopant‐Free,Amorphous–Crystalline Heterophase SnO2 Electron Transport Bilayer Enables >20% Efficiency in Triple‐Cation Perovskite Solar Cells

Improving the ohmic contact and interfacial morphology between an electron transport layer (ETL) and perovskite film is the key to boost the efficiency of planar perovskite solar cells (PSCs). In the current work, an amorphous–crystalline heterophase tin oxide bilayer (Bi‐SnO₂) ETL is prepared via a low‐temperature solution process. Compared with the amorphous SnO₂ sol–gel film (SG‐SnO₂) or the crystalline SnO₂ nanoparticle (NP‐SnO₂) counterparts, the heterophase Bi‐SnO₂ ETL exhibits improved surface morphology, considerably fewer oxygen defects, and better energy band alignment with the perovskite without sacrificing the optical transmittance. The best PSC device (active area ≈ 0.09 cm²) based on a Bi‐SnO₂ ETL is hysteresis‐less and achieves an outstanding power conversion efficiency of ≈20.39%, which is one of the highest efficiencies reported for SnO₂‐triple cation perovskite system based on green antisolvent. More fascinatingly, large‐area PSCs (active areas of ≈3.55 cm²) based on the Bi‐SnO₂ ETL also achieves an extraordinarily high efficiency of ≈14.93% with negligible hysteresis. The improved device performance of the Bi‐SnO₂‐based PSC arises predominantly from the improved ohmic contact and suppressed bimolecular recombination at the ETL/perovskite interface. The tailored morphology and energy band structure of the Bi‐SnO₂ has enabled the scalable fabrication of highly efficient, hysteresis‐less PSCs.     

Fully High‐Temperature‐Processed SnO2 as Blocking Layer and Scaffold for Efficient,Stable, and Hysteresis‐Free Mesoporous Perovskite Solar Cells

Planar perovskite solar cells (PSCs) based on low‐temperature‐processed (LTP) SnO₂ have demonstrated excellent photovoltaic properties duo to the high electron mobility, wide bandgap, and suitable band energy alignment of LTP SnO₂. However, planar PSCs or mesoporous (mp) PSCs based on high‐temperature‐processed (HTP) SnO₂ show much degraded performance. Here, a new strategy with fully HTP Mg‐doped quantum dot SnO₂ as blocking layer (bl) and a quite thin SnO₂ nanoparticle as mp layer are developed. The performances of both planar and mp PSCs has been greatly improved. The use of Mg‐SnO₂ in planar PSCs yields a high‐stabilized power conversion efficiency (PCE) of close to 17%. The champion of mp cells exhibits hysteresis free and stable performance with a high‐stabilized PCE of 19.12%. The inclusion of thin mp SnO₂ in PSCs not only plays a role of an energy bridge, facilitating electrons transfer from perovskite to SnO₂ bl, but also enhances the contact area of SnO₂ with perovskite absorber. Impedance analysis suggests that the thin mp layer is an “active scaffold” selectively collecting electrons from perovskite and can eliminate hysteresis and effectively suppress recombination. This is an inspiring advance toward high‐performance PSCs with HTP mp SnO₂.     

A Band‐Edge Potential Gradient Heterostructure to Enhance Electron Extraction Efficiency of the Electron Transport Layer in High‐Performance Perovskite Solar Cells

As the key component in efficient perovskite solar cells, the electron transport layer (ETL) can selectively collect photogenerated charge carriers produced in perovskite absorbers and prevent the recombination of carriers at interfaces, thus ensuring a high power conversion efficiency. Compared with the conventional single‐ or dual‐layered ETLs, a gradient heterojunction (GHJ) strategy is more attractive to facilitate charge separation because the potential gradient created at an appropriately structured heterojunction can act as a driving force to regulate the electron transport toward a desired direction. Here, a SnO₂/TiO₂ GHJ interlayer configuration inside the ETL is reported to simultaneously achieve effective extraction and efficient transport of photoelectrons. With such an interlayer configuration, the GHJs formed at the perovskite/ETL interface act collectively to extract photogenerated electrons from the perovskite layer, while GHJs formed at the boundaries of the interconnected SnO₂ and TiO₂ networks throughout the entire ETL layer can extract electron from the slow electron mobility TiO₂ network to the high electron mobility SnO₂ network. Devices based on GHJ ETL exhibit a champion power conversion efficiency of 18.08%, which is significantly higher than that obtained from the compact TiO₂ ETL constructed under the comparable conditions.     

Performance Enhancement of Tri‐Cation and Dual‐Anion Mixed Perovskite Solar Cells by Au@SiO2 Nanoparticles

Tri‐cation and dual‐anion mixed perovskites have been widely utilized in perovskite solar cell (PSC) applications due to their novel properties such as high absorption, high stability, and low cost. To commercialize the PSCs, further improving the device performance without detrimentally changing the device configuration is important at present. Herein, Au@SiO₂ nanoparticles (NPs) are introduced to modify the interface between mesoporous TiO₂ (mp‐TiO₂) and mixed perovskite with increased main photovoltaic parameters of the device, resulting in a ≈29% enhancement of power conversion efficiency (PCE) from 15.8% to 20.3%. The origins of the enhancement have been studied by exploring the optical absorption, optical power distribution, and charge carrier behaviors within the system. The small perturbation transient photovoltage measurement exhibits prolonged charge carrier lifetimes after the Au@SiO₂ NPs incorporation, and time of flight photoconductivity measurement shows that charge carrier mobilities of this system are also enhanced. These characteristics make metallic nanostructures a promising functional material in facile tuning of the charge carriers transport and further boosting the PCE of the PSCs.     

24.64%-Efficiency MA-Free Perovskite Solar Cell with Voc of 1.19 V Enabled by a Hinge-Type Fluorine-Rich Complex

High density of defects at interface severely affects the performance of perovskite solar cells (PSCs). Herein, cobalt (II) hexafluoro-2,4-pentanedionat (CoFAc), a hinge-type fluorine-rich complex, is introduced onto the surface of formamidinium cesium lead iodide (FACsPbI₃) film to address the issues of perovskite/Spiro-OMeTAD interface. The existence of CoFAc passivates both organic cation and halide anion vacancies by establishing powerful hydrogen bonds with HC(NH₂)₂⁺ (FA⁺) and strong ionic bonds with Pb²⁺ in perovskite films. In addition, CoFAc serves as a connecting link to enhance interfacial hole-transport kinetics via interacting with Spiro-OMeTAD. Consequently, FACsPbI₃ PSCs with CoFAc modification display a champion power conversion efficiency (PCE) of 24.64% with a charming open-circuit voltage (V_OC) of 1.191 V, which is the record V_OC among all the reported organic-inorganic hybrid PSCs with TiO₂ as electron transport layer. Furthermore, CoFAc-modified devices exhibit an outstanding long-term stability, which can maintain 95% of their initial PCEs after exposure to ambient atmosphere for 1500 h without any encapsulation.     

Improving the Extraction of Photogenerated Electrons with SnO2 Nanocolloids for Efficient Planar Perovskite Solar Cells

Great attention to cost‐effective high‐efficiency solar power conversion of trihalide perovskite solar cells (PSCs) has been hovering at high levels in the recent 5 years. Among PSC devices, admittedly, TiO₂ is the most widely used electron transport layer (ETL); however, its low mobility which is even less than that of CH₃NH₃PbI₃ makes it not an ideal material. In principle, SnO₂ with higher electron mobility can be regarded as a positive alternative. Herein, a SnO₂ nanocolloid sol with ≈3 nm in size synthesized at 60 °C was spin‐coated onto the fuorine‐doped tin oxide (FTO) glass as the ETL of planar CH₃NH₃PbI₃ perovskite solar cells. TiCl₄ treatment of SnO₂‐coated FTO is found to improve crystallization and increase the surface coverage of perovskites, which plays a pivotal role in improving the power conversion efficiency (PCE). In this report, a champion efficiency of 14.69% (J_sc = 21.19 mA cm^?2, V_oc = 1023 mV, and FF = 0.678) is obtained with a metal mask at one sun illumination (AM 1.5G, 100 mW cm^?2). Compared to the typical TiO₂, the SnO₂ ETL efficiently facilitates the separation and transportation of photogenerated electrons/holes from the perovskite absorber, which results in a significant enhancement of photocurrent and PCE.     

Fast and Controllable Electric‐Field‐Assisted Reactive Deposited Stable and Annealing‐Free Perovskite toward Applicable High‐Performance Solar Cells

Recently, organic–inorganic hybrid perovskite materials have drawn great attention for their outstanding performance in high‐efficiency solar cells. Successful synthesis has been realized either in solution‐based chemical deposition or vapor deposition. However, conflicts have never ceased among quality control, growth rate, process complexity, and instrument requirement, which have limited their development toward real applications. In this work, the first electrochemical fabrication of perovskite toward high‐efficiency and scalable perovskite solar cells (PSCs) is established. The morphology and crystallization of the CH₃NH₃PbI₃ film can be effectively controlled by simply modulating a few physical parameters. A detailed study on its optoelectronic properties reveals significantly improved film quality and interfacial conditions. Aided by this, the total process does not require standard annealing, which greatly reduces the total growth time from hours to minutes. Up to now, an efficiency of 15.65% has been achieved in planar PSCs under 1 sun AM 1.5 condition, with small hysteresis and efficiency loss under longtime exposure to air. Moreover, high efficiency (10.45%) can be easily attained for large cells (2 cm²). This result will hopefully facilitate research for applicable high‐efficiency PSCs and other multicomponent materials as well.     

Dual Interfacial Modification Engineering with 2D MXene Quantum Dots and Copper Sulphide Nanocrystals Enabled High‐Performance Perovskite Solar Cells

The performance of perovskite solar cells (PSCs) strongly depends on the electron transport layer (ETL), perovskite absorber, hole transport layer (HTL), and their interfaces. Herein, the first approach to utilize ultrathin 2D titanium‐carbide MXenes (Ti₃C₂T_x quantum dots, TQD) by engineering the perovskite/TiO₂ ETL interface and perovskite absorber and introducing Cu_1.8S nanocrystals to perfect the Spiro‐OMeTAD HTL is represented. A significant hysteresis‐free power conversion efficiency improvement from 18.31% to 21.64% of PSCs is achieved after modifications with the enhanced short‐circuit current density, open‐circuit voltages, and fill factor. Various advanced characterizations, including femtosecond transient absorption spectroscopy, electrochemical impedance spectroscopy, and ultraviolet photoelectron spectroscopy, elucidate that the TQD/Cu_1.8S significantly contribute to the improved crystalline quality of the perovskite film with its large grain size and improved electron/holes extraction efficiencies at perovskite/ETL and perovskite/HTL interfaces. Furthermore, the long‐time ambient and light stability of PSCs are largely boosted through the TQD and/or Cu_1.8S nanocrystals doping, originating from the better crystallization of perovskite, suppressing the film aggregation and crystallization of HTL, and inhibiting the ultraviolet‐induced photocatalysis of the ETL. The findings highlight the TQD and Cu_1.8S can act as a superfast electrons and holes tunnel for the optoelectronic devices.     

Photovoltaic and Amplified Spontaneous Emission Studies of High‐Quality Formamidinium Lead Bromide Perovskite Films

This study demonstrates the formation of extremely smooth and uniform formamidinium lead bromide (CH(NH₂)₂PbBr₃ = FAPbBr₃) films using an optimum mixture of dimethyl sulfoxide and N,N‐dimethylformamide solvents. Surface morphology and phase purity of the FAPbBr₃ films are thoroughly examined by field emission scanning electron microscopy and powder X‐ray diffraction, respectively. To unravel the photophysical properties of these films, systematic investigation based on time‐integrated and time‐dependent photoluminescence studies are carried out which, respectively, bring out relatively lower nonradiative recombination rates and long lasting photogenerated charge carriers in FAPbBr₃ perovskite films. The devices based on FTO/TiO₂/FAPbBr₃/spiro‐OMeTAD/Au show highly reproducible open‐circuit voltage (V_oc) of 1.42 V, a record for FAPbBr₃‐based perovskite solar cells. V_oc as a function of illumination intensity indicates that the contacts are very selective and higher V_oc values are expected to be achieved when the quality of the FAPbBr₃ film is further improved. Overall, the devices based on these films reveal appreciable power conversion efficiency of 7% under standard illumination conditions with negligible hysteresis. Finally, the amplified spontaneous emission (ASE) behavior explored in a cavity‐free configuration for FAPbBr₃ perovskite films shows a sharp ASE threshold at a fluence of 190 μJ cm^?2 with high quantum efficiency further confirming the high quality of the films.     

Introduction of Hydrophobic Ammonium Salts with Halogen Functional Groups for High‐Efficiency and Stable 2D/3D Perovskite Solar Cells

2D perovskites have attracted extensive attention due to their excellent stability compared with 3D perovskites. However, the intrinsic hydrophilicity of introduced alkylammonium salts effects the humidity stability of 2D/3D perovskites. Devices based on longer chain alkylammonium salts show improvement in hydrophobicity but lower efficiency due to the poorer charge transport among various layers. To solve this issue, two hydrophobic short‐chain alkylammonium salts with halogen functional groups (2‐chloroethylamine, CEA⁺ and 2‐bromoethylamine, BEA⁺) are introduced into (Cs_0.1FA_0.9)Pb(I_0.9Br_0.1)₃ 3D perovskites to form 2D/3D perovskite structure, which achieve high‐quality perovskite films with better crystallization and morphology. The optimal 2D/3D perovskite solar cells (PSCs) with 5% CEA⁺ display a power conversion efficiency (PCE) as high as 20.08% under 1 sun irradiation. Because of the notable hydrophobicity of alkylammonium cations with halogen functional groups and the formed 2D/3D perovskite structure, the optimal PSCs exhibit superior moisture resistance and retain 92% initial PCE after aging at 50 ± 5% relative humidity for 2400 h. This work opens up a new direction for the design of new‐type 2D/3D PSCs with improved performance by employing proper alkylammonium salts with different functional groups.     

Review on the Application of SnO2 in Perovskite Solar Cells

SnO₂ has been well investigated in many successful state‐of‐the‐art perovskite solar cells (PSCs) due to its favorable attributes such as high mobility, wide bandgap, and deep conduction band and valence band. Several independent studies show the performances of PSCs with SnO₂ are higher than that with TiO₂, especially in device stability. In 2015, the first planar PSCs were reported with a power conversion efficiency over 17% using a low temperature sol‐derived SnO₂ nanocrystal electron transport layer (ETL). Since then, many other groups have also reported high performance PSCs based on SnO₂ ETLs. SnO₂ planar PSCs show currently the highest performance in planar configuration devices (21.6%) and are close to the record holder of TiO₂ mesoporous PSCs, suggesting their high potential as ETLs in PSCs. The main concerns with the application of SnO₂ as ETL are that it suffers from degradation in high temperature processes and that its much lower conduction band compared to perovskite may result in a voltage loss of PSCs. Here, notable achievements to date are outlined, the unique attributes of SnO₂ as ETLs in PSCs are described, and the challenges facing the successful development of PSCs and approaches to the problems are discussed.     

Precursor Engineering for All‐Inorganic CsPbI2Br Perovskite Solar Cells with 14.78% Efficiency

The optoelectronic properties of perovskite films are closely related to the film quality, so depositing dense, uniform, and stable perovskite films is crucial for fabricating high‐performance perovskite solar cells (PSCs). CsPbI₂Br perovskite, prized for its superb stability toward light soaking and thermal aging, has received a great deal of attention recently. However, the air instability and poor performance of CsPbI₂Br PSCs are hindering its further progress. Here, an approach is reported for depositing high‐quality CsPbI₂Br films via the Lewis base adducts PbI₂(DMSO) and PbBr₂(DMSO) as precursors to slow the crystallization of the perovskite film. This process produces CsPbI₂Br films with large‐scale crystalline grains, flat surfaces, low defects, and long carrier lifetimes. More interestingly, PbI₂(DMSO) and PbBr₂(DMSO) adducts could significantly improve the stability of CsPbI₂Br films in air. Using films prepared by this technique, a power conversion efficiency (PCE) of 14.78% is obtained in CsPbI₂Br PSCs, which is the highest PCE value reported for CsPbI₂Br‐based PSCs to date. In addition, the PSCs based on DMSO adducts show an extended operational lifetime in air. These excellent performances indicate that preparing high‐quality inorganic perovskite films by using DMSO adducts will be a potential method for improving the performance of other inorganic PSCs.     

Piezoelectric‐Effect‐Enhanced Full‐Spectrum Photoelectrocatalysis in p–n Heterojunction

Photoelectrochemical (PEC) water splitting offers a promising strategy for converting solar energy to chemical fuels. Herein, a piezoelectric‐effect–enhanced full‐spectrum photoelectrocatalysis with multilayered coaxial titanium dioxide/barium titanate/silver oxide (TiO₂/BTO/Ag₂O) nanorod array as the photoanode is reported. The vertically grown nanorods ensure good electron conductivity, which enables fast transport of the photogenerated electrons. Significantly, the insertion of a piezoelectric BaTiO₃ (BTO) nanolayer at the p‐type Ag₂O and n‐type TiO₂ interface created a polar charge‐stabilized electrical field. It maintains a sustainable driving force that attract the holes of TiO₂ and the electrons of Ag₂O, resulting in greatly increased separation and inhibited recombination of the photogenerated carriers. Furthermore, Ag₂O as a narrow bandgap semiconductor has a high ultraviolet–visible–near infrared (UV–vis–NIR) photoelectrocatalytic activity. The TiO₂/BTO/Ag₂O, after poling, successfully achieves a prominent photocurrent density, as high as 1.8 mA cm^?2 at 0.8 V versus Ag/Cl, which is about 2.6 times the TiO₂ nanorod photoanode. It is the first time that piezoelectric BaTiO₃ is used for tuning the interface of p‐type and n‐type photoelectrocatalyst. With the enhanced light harvesting, efficient photogenerated electron–hole pairs' separation, and rapid charge transfer at the photoanode, an excellent photoelectrocatalytic activity is realized.     

Highly Improved Photocurrent Density and Efficiency of Perovskite Solar Cells via Inclined Fluorine Sputtering Process (Adv. Funct. Mater. 25/2023)

Increase in incident light and surface modification of the charge transport layer are powerful routes to achieve high-performance efficiency of perovskite solar cells (PSCs) by improving the short-circuit current density (J_SC) and charge transport characteristics, respectively. However, few techniques are studied to reduce reflection loss and simultaneously improve the electrical performance of the electron transport layer (ETL). Herein, an inclined fluorine (F) sputtering process to fabricate high-performance PSCs is proposed. The proposed process simultaneously implements the antireflection effect of F coating and the effect of F doping on a TiO₂ ETL, which increases the amount of light transmitted into the PSC due to the extremely low refractive index (≈1.39) and drastically improves the electrical properties of TiO₂. Consequently, the J_SC of the F coating and doping perovskite solar cell (F-PSC) increased from 25.05 to 26.01 mA cm⁻², and the power conversion efficiency increased from 24.17% to 25.30%. The unencapsulated F-PSC exhibits enhanced air stability after 900 h of exposure to ambient environment atmosphere (30% relative humidity, 25 °C under dark condition). The inclined F sputtering process in this study can become a universal method for PSCs from the development stage to commercialization in the future.     

2D/3D Heterostructure for Semitransparent Perovskite Solar Cells with Engineered Bandgap Enables Efficiencies Exceeding 25% in Four‐Terminal Tandems with Silicon and CIGS

Wide‐bandgap perovskite solar cells (PSCs) with optimal bandgap (E_g) and high power conversion efficiency (PCE) are key to high‐performance perovskite‐based tandem photovoltaics. A 2D/3D perovskite heterostructure passivation is employed for double‐cation wide‐bandgap PSCs with engineered bandgap (1.65 eV ≤ E_g ≤ 1.85 eV), which results in improved stabilized PCEs and a strong enhancement in open‐circuit voltages of around 45 mV compared to reference devices for all investigated bandgaps. Making use of this strategy, semitransparent PSCs with engineered bandgap are developed, which show stabilized PCEs of up to 25.7% and 25.0% in four‐terminal perovskite/c‐Si and perovskite/CIGS tandem solar cells, respectively. Moreover, comparable tandem PCEs are observed for a broad range of perovskite bandgaps. For the first time, the robustness of the four‐terminal tandem configuration with respect to variations in the perovskite bandgap for two state‐of‐the‐art bottom solar cells is experimentally validated.     

Spidermen Strategy for Stable 24% Efficiency Perovskite Solar Cells

The interface energetics-modification plays an important role in improving the power conversion efficiency (PCE) among the perovskite solar cells (PSCs). Considering the low carrier mobility caused by defects in PSCs, a double-layer modification engineering strategy is adopted to introduce the “spiderman” NOBF₄ (nitrosonium tetrafluoroborate) between tin dioxide (SnO₂ and perovskite layers. NO⁺, as the interfacial bonding layer, can passivate the oxygen vacancy in SnO₂, while BF₄⁻ can optimize the defects in the bulk of perovskite. This conclusion is confirmed by theoretical calculation and transmission electron microscopy (TEM). The synergistic effect of NO⁺ and BF₄⁻ distinctly heightens the carrier extraction efficiency, and the PCE of PSCs is 24.04% with a fill factor (FF) of 82.98% and long-term stability. This study underlines the effectiveness of multifunctional additives in improving interface contact and enhancing PCE of PSCs.     

Efficient and Ambient‐Air‐Stable Solar Cell with Highly Oriented 2D@3D Perovskites

3D organic–inorganic lead halide perovskites have shown great potential in efficient photovoltaic devices. However, the low stability of the 3D perovskite layer and random arrangement of the perovskite crystals hinder its commercialization road. Herein, a highly oriented 2D@3D ((AVA)₂PbI₄@MAPbI₃) perovskite structure combining the advantages of both 2D and 3D perovskite is fabricated through an in situ route. The highest power conversion efficiency (PCE) of 18.0% is observed from a 2D@3D perovskite solar cell (PSC), and it also shows significantly enhanced device stability under both inert (90% of initial PCE for 32 d) and ambient conditions (72% of initial PCE for 20 d) without encapsulation. The high efficiency of 18.0% and nearly twofold improvement of device stability in ambient compared with pure 3D PSCs confirm that such 2D@3D perovskite structure is an effective strategy for high performance and increasing stability and thus will enable the timely commercialization of PSCs.     

Preparation of Tortuous 3D γ‐CsPbI3 Films at Low Temperature by CaI2 as Dopant for Highly Efficient Perovskite Solar Cells

Inorganic cubic CsPbI₃ perovskite (α‐CsPbI₃) has been widely explored for perovskite solar cells (PSCs) due to its thermal stability and suitable bandgap of 1.73 eV. However, α‐CsPbI₃ usually requires high synthesis temperatures (>320 °C). Additionally, it usually undergoes phase transition to the nonperovskite structure phase (β‐CsPbI₃), which results in poor photoelectric performance in devices. In this study, it is first found that the tortuous 3D CsPbI₃ phase (γ‐CsPbI₃) can be prepared and used for PSCs by solution process without any additive at low temperature (60 °C). The γ‐CsPbI₃ exhibits suitable bandgap of 1.75 eV and favorable photoelectric properties. However, γ‐CsPbI₃ is a metastable phase and easily transforms into β‐CsPbI₃ in ambient moisture. In order to improve the stability of γ‐CsPbI₃, calcium ions (Ca²⁺) with a relatively small radius of 100 pm are used to partially substitute lead ions (119 pm). This research proves that Ca²⁺ can effectively improve the stability of the γ‐CsPbI₃ at room temperature. By optimizing the doping concentration of Ca²⁺ (CsPb_1?xCa_xI₃, x is from 0% to 2%), the Ca²⁺‐doped γ‐CsPbI₃ PSCs achieve a hysteresis‐free J–V curve and a maximum power conversion efficiency (PCE) of 9.20%.     

Nonfullerene Electron Transporting Material Based on Naphthalene Diimide Small Molecule for Highly Stable Perovskite Solar Cells with Efficiency Exceeding 20%

This study reports a new nonfullerene electron transporting material (ETM) based on naphthalene diimide (NDI) small molecules for use in high‐performance perovskite solar cells (PSCs). These solar cells simultaneously achieve high power conversion efficiency (PCE) of over 20% and long‐term stability. New NDI‐ID (N,N′‐Bis(1‐indanyl)naphthalene‐1,4,5,8‐tetracarboxylic diimide) consisting of an N‐substituted indane group having simultaneous alicyclic and aromatic characteristics is synthesized by a low‐cost, one‐step reaction, and facile purification method. The partially flexible characteristics of an alicyclic cyclopentene group on indane groups open the possibility of low‐temperature solution processing. The conformational rigidity and aromaticity of phenyl and alicyclic groups contribute to high temporal stability by strong secondary bonds. NDI‐ID has herringbone packed semiconducting NDI cores that exhibit up to 0.2 cm² V^?1 s^?1 electron mobility in field effect transistors. The inverted PSCs based on CH(NH₂)₂PbI_3–xBr_x with NDI‐ID ETM exhibit very high PCEs of up to 20.2%, which is better than that of widely used PCBM (phenyl‐C61‐butyric acid methyl ester) ETM‐based PSCs. Moreover, NDI‐ID‐based PSCs exhibit very high long‐term temporal stability, retaining 90% of the initial PCE after 500 h at 100 °C with 1 sun illumination without encapsulation. Therefore, NDI‐ID is a promising ETM for highly efficient, stable PSCs.     

Synergistic Coassembly of Highly Wettable and Uniform Hole‐Extraction Monolayers for Scaling‐up Perovskite Solar Cells

All organic charge‐transporting layer (CTL)‐featured perovskite solar cells (PSCs) exhibit distinct advantages, but their scaling‐up remains a great challenge because the organic CTLs underneath the perovskite are too thin to achieve large‐area homogeneous layers by spin‐coating, and their hydrophobic nature further hinders the solution‐based fabrication of perovskite layer. Here, an unprecedented anchoring‐based coassembly (ACA) strategy is reported that involves a synergistic coadsorption of a hydrophilic ammonium salt CA‐Br with hole‐transporting triphenylamine derivatives to acquire scalable and wettable organic hole‐extraction monolayers for p–i–n structured PSCs. The ACA route not only enables ultrathin organic CTLs with high uniformity but also eliminates the nonwetting problem to facilitate large‐area perovskite films with 100% coverage. Moreover, incorporation of CA‐Br in the ACA strategy can distinctly guarantee a high quality of electronic connection via the cations' vacancy passivation. Consequently, a high power‐conversion‐efficiency (PCE) of 17.49% is achieved for p–i–n structured PSCs (1.02 cm²), and a module with an aperture area of 36 cm² shows PCE of 12.67%, one of the best scaling‐up results among all‐organic CTL‐based PSCs. This work demonstrates that the ACA strategy can be a promising route to large‐area uniform interfacial layers as well as scaling‐up of perovskite solar cells.