Pyrite‐Based Bi‐Functional Layer for Long‐Term Stability and High‐Performance of Organo‐Lead Halide Perovskite Solar Cells

Organo‐lead halide perovskite solar cells (PSCs) have received great attention because of their optimized optical and electrical properties for solar cell applications. Recently, a dramatic increase in the photovoltaic performance of PSCs with organic hole transport materials (HTMs) has been reported. However, as of now, future commercialization can be hampered because the stability of PSCs with organic HTM has not been guaranteed for long periods under conventional working conditions, including moist conditions. Furthermore, conventional organic HTMs are normally expensive because material synthesis and purification are complicated. It is herein reported, for the first time, octadecylamine‐capped pyrite nanoparticles (ODA‐FeS₂ NPs) as a bi‐functional layer (charge extraction layer and moisture‐proof layer) for organo‐lead halide PSCs. FeS₂ is a promising candidate for the HTM of PSCs because of its high conductivity and suitable energy levels for hole extraction. A bi‐functional layer based on ODA‐FeS₂ NPs shows excellent hole transport ability and moisture‐proof performance. Through this approach, the best‐performing device with ODA‐FeS₂ NPs‐based bi‐functional layer shows a power conversion efficiency of 12.6% and maintains stable photovoltaic performance in 50% relative humidity for 1000 h. As a result, this study has the potential to break through the barriers for the commercialization of PSCs.     

Water‐Soluble Triazolium Ionic‐Liquid‐Induced Surface Self‐Assembly to Enhance the Stability and Efficiency of Perovskite Solar Cells

Despite being a promising candidate for next‐generation photovoltaics, perovskite solar cells (PSCs) exhibit limited stability that hinders their practical application. In order to improve the humidity stability of PSCs, herein, a series of ionic liquids (ILs) “1‐alkyl‐4‐amino‐1,2,4‐triazolium” (termed as RATZ; R represents alkyl chain, and ATZ represents 4‐amino‐1,2,4‐triazolium) as cations are designed and used as additives in methylammonium lead iodide (MAPbI₃) perovskite precursor solution, obtaining triazolium ILs‐modified PSCs for the first time (termed as MA/RATZ PSCs). As opposed to from traditional methods that seek to improve the stability of PSCs by functionalizing perovskite film with hydrophobic molecules, humidity‐stable perovskite films are prepared by exploiting the self‐assembled monolayer (SAM) formation of water‐soluble triazolium ILs on a hydrophilic perovskite surface. The mechanism is validated by experimental and theoretical calculation. This strategy means that the MA/RATZ devices exhibit good humidity stability, maintaining around 80% initial efficiency for 3500 h under 40 ± 5% relative humidity. Meanwhile, the MA/RATZ PSCs exhibit enhanced thermal stability and photostability. Tuning the molecule structure of the ILs additives achieves a maximum power conversion efficiency (PCE) of 20.03%. This work demonstrates the potential of using triazolium ILs as additives and SAM and molecular design to achieve high performance PSCs.     

Encapsulation of Printable Mesoscopic Perovskite Solar Cells Enables High Temperature and Long‐Term Outdoor Stability

Perovskite solar cells (PSCs) have achieved high power conversion efficiency on the lab scale, rivaling the other commercialized photovoltaic technologies. However, stability issues have made it difficult for PSCs to achieve comparable or practical lifetimes in outdoor applications. Here, three different types of hot melt films (polyurethane, PU; polyolefin, POE; and ethylene vinyl acetate, EVA) together with glass sheets are employed to encapsulate printable PSCs. The influence of thermal stress and the encapsulation (lamination) process on cell performance is investigated. It is found that POE and EVA, which are the typical encapsulants for silicon and thin film solar cells, are not suitable for the encapsulation of PSCs due to a high laminating temperature (>130 °C) or corrosion of the perovskite absorber. By contrast, encapsulation with PU can be carried out at a relatively mild temperature of 80 °C, and significantly enhance the thermal stability of the cells. When this encapsulation method is applied to large‐area (substrate area 100 cm²) printable PSC submodules, the submodules can maintain 97.52% of the initial efficiency after 2136 h under outdoor conditions (location: 39°19′48″N 114°37′26″E). This work demonstrates the potential of industrially relevant encapsulation techniques to enable the commercial viability of PSCs.     

Electron‐Transport‐Layer‐Assisted Crystallization of Perovskite Films for High‐Efficiency Planar Heterojunction Solar Cells

Crystal engineering of CH₃NH₃PbI₃ perovskite materials through template‐directed nucleation and growth on PbI₂ nuclei dispersed in a polar fullerene (C₆₀ pyrrolidine tris‐acid, CPTA) electron transport layer (ETL) (CPTA:PbI₂) is proposed as a route for controlling crystallization kinetics and grain sizes. Chemical analysis of the CPTA:PbI₂ template confirms that CPTA carboxylic acid groups can form a monodentate or bidentate chelate with Pb(II), resulting in a lower nucleation barrier that promotes rapid formation of the tetragonal perovskite phase. Moreover, it is demonstrated that a uniform CH₃NH₃PbI₃ film with highly crystalline and large domain sizes can be realized by increasing the spacing between nuclei to retard perovskite crystal growth via careful control of the preferred nucleation site distribution in the CPTA:PbI₂ layer. The improved perovskite morphology possesses a long photoluminescence lifetime and efficient photocarrier transport/separation properties to eliminate the hysteresis effect. The corresponding planar heterojunction photovoltaic yields a high power conversion efficiency (PCE) of 20.20%, with a high fill factor (FF) of 81.13%. The average PCE and FF values for 30 devices are 19.03% ± 0.57% and 78.67% ± 2.13%, respectively. The results indicate that this ETL template‐assisted crystallization strategy can be applied to other organometal halide perovskite‐based systems.     

Achieving 20% Efficiency for Low‐Temperature‐Processed Inverted Perovskite Solar Cells

Low‐temperature‐processed inverted perovskite solar cells (PVSCs) attract increasing attention because they can be fabricated on both rigid and flexible substrates. For these devices, hole‐transporting layers (HTLs) play an important role in achieving efficient and stable inverted PVSCs by adjusting the anodic work function, hole extraction, and interfacial charge recombination. Here, the use of a low‐temperature (≤150 °C) solution‐processed ultrathin film of poly[(9,9‐dioctyl‐fluorenyl‐2,7‐diyl)‐co‐(4,4′‐(N‐(4‐secbutylphenyl) diphenylamine)] (TFB) is reported as an HTL in one‐step‐processed CH₃NH₃PbI₃ (MAPbI₃)‐based inverted PVSCs. The fabricated device exhibits power conversion efficiency (PCE) as high as 20.2% when measured under AM 1.5 G illumination. This PCE makes them one of the MAPbI₃‐based inverted PVSCs that have the highest efficiency reported to date. Moreover, this inverted PVSC also shows good stability, which can retain 90% of its original efficiency after 30 days of storage in ambient air.     

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.     

Hybrid Perovskite Quantum Dot/Non-Fullerene Molecule Solar Cells with Efficiency Over 15%

Organic-inorganic hybrid film using conjugated materials and quantum dots (QDs) are of great interest for solution-processed optoelectronic devices, including photovoltaics (PVs). However, it is still challenging to fabricate conductive hybrid films to maximize their PV performance. Herein, for the first time, superior PV performance of hybrid solar cells consisting of CsPbI₃ perovskite QDs and Y6 series non-fullerene molecules is demonstrated and further highlights their importance on hybrid device design. In specific, a hybrid active layer is developed using CsPbI₃ QDs and non-fullerene molecules, enabling a type-II energy alignment for efficient charge transfer and extraction. Additionally, the non-fullerene molecules can well passivate the QDs, reducing surface defects and energetic disorder. The champion CsPbI₃ QD/Y6-F hybrid device has a record-high efficiency of 15.05% for QD/organic hybrid PV devices, paving a new way to construct solution-processable hybrid film for efficient optoelectronic devices.     

Enhanced Stability of Perovskite Solar Cells with Low‐Temperature Hydrothermally Grown SnO2 Electron Transport Layers

Perovskite solar cells (PSCs) may offer huge potential in photovoltaic conversion, yet their practical applications face one major obstacle: their low stability, or quick degradation of their initial efficiencies. Here, a new design scheme is presented to enhance the PSC stability by using low‐temperature hydrothermally grown hierarchical nano‐SnO₂ electron transport layers (ETLs). The ETL contains a thin compact SnO₂ layer underneath a mesoporous layer of SnO₂ nanosheets. The mesoporous layer plays multiple roles of enhancing photon collection, preventing moisture penetration and improving the long‐term stability. Through such simple approaches, PSCs with power conversion efficiencies of ≈13% can be readily obtained, with the highest efficiency to be 16.17%. A prototypical PSC preserves 90% of its initial efficiency even after storage in air at room temperature for 130 d without encapsulation. This study demonstrates that hierarchical SnO₂ is a potential ETL for fabricating low‐cost and efficient PSCs with long‐term stability.     

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.     

High‐Performance Inverted Planar Heterojunction Perovskite Solar Cells Based on Lead Acetate Precursor with Efficiency Exceeding 18%

Organic–inorganic lead halide perovskites are emerging materials for the next‐generation photovoltaics. Lead halides are the most commonly used lead precursors for perovskite active layers. Recently, lead acetate (Pb(Ac)₂) has shown its superiority as the potential replacement for traditional lead halides. Here, we demonstrate a strategy to improve the efficiency for the perovskite solar cell based on lead acetate precursor. We utilized methylammonium bromide as an additive in the Pb(Ac)₂ and methylammonium iodide precursor solution, resulting in uniform, compact and pinhole‐free perovskite films. We observed enhanced charge carrier extraction between the perovskite layer and charge collection layers and delivered a champion power conversion efficiency of 18.3% with a stabilized output efficiency of 17.6% at the maximum power point. The optimized devices also exhibited negligible current density–voltage (J–V) hysteresis under the scanning conditions.     

Defect Passivation in Perovskite Solar Cells by Cyano‐Based π‐Conjugated Molecules for Improved Performance and Stability

Defects at the surface and grain boundaries of metal–halide perovskite films lead to performance losses of perovskite solar cells (PSCs). Here, organic cyano‐based π‐conjugated molecules composed of indacenodithieno[3,2‐b]thiophene (IDTT) are reported and it is found that their cyano group can effectively passivate such defects. To achieve a homogeneous distribution, these molecules are dissolved in the antisolvent, used to initiate the perovskite crystallization. It is found that these molecules are self‐anchored at the grain boundaries due to their strong binding to undercoordinated Pb²⁺. On a device level, this passivation scheme enhances the charge separation and transport at the grain boundaries due to the well‐matched energetic levels between the passivant and the perovskite. Consequently, these benefits contribute directly to the achievement of power conversion efficiencies as high as 21.2%, as well as the improved environmental and thermal stability of the PSCs. The surface treatment provides a new strategy to simultaneously passivate defects and enhance charge extraction/transport at the device interface by manipulating the anchoring groups of the molecules.     

Benzodithiophene Hole‐Transporting Materials for Efficient Tin‐Based Perovskite Solar Cells

Developing efficient interfacial hole transporting materials (HTMs) is crucial for achieving high‐performance Pb‐free Sn‐based halide perovskite solar cells (PSCs). Here, a new series of benzodithiophene (BDT)‐based organic small molecules containing tetra‐ and di‐triphenyl amine donors prepared via a straightforward and scalable synthetic route is reported. The thermal, optical, and electrochemical properties of two BDT‐based molecules are shown to be structurally and energetically suitable to serve as HTMs for Sn‐based PSCs. It is reported here that ethylenediammonium/formamidinium tin iodide solar cells using BDT‐based HTMs deliver a champion power conversion efficiency up to 7.59%, outperforming analogous reference solar cells using traditional and expensive HTMs. Thus, these BDT‐based molecules are promising candidates as HTMs for the fabrication of high‐performance Sn‐based PSCs.     

A Thienothiophene-Based Cation Treatment Allows Semitransparent Perovskite Solar Cells with Improved Efficiency and Stability

Perovskite surface treatment with additives has been reported to improve charge extraction, stability, and/or surface passivation. In this study, treatment of a 3D perovskite ((FAPbI₃)_1−x(MAPbBr₃)_x) layer with a thienothiophene-based organic cation (TTMAI), synthesized in this work, is investigated. Detailed analyses reveal that a 2D (n = 1) or quasi-2D layer does not form on the PbI₂-rich surface 3D perovskite. TTMAI-treated 3D perovskite solar cells (PSCs) fabricated in this study show improved fill factors, providing an increase in their power conversion efficiencies (PCEs) from 17% to over 20%. It is demonstrated that the enhancement is due to better hole extraction by drift-diffusion simulations. Furthermore, thanks to the hydrophobic nature of the TTMAI, PSC maintains 82% of its initial PCE under 15% humidity for over 380 h (the reference retains 38%). Additionally, semitransparent cells are demonstrated reaching 17.9% PCE with treated 3D perovskite, which is one of the highest reported efficiencies for double cationic 3D perovskites. Moreover, the semitransparent 3D PSC (TTMAI-treated) maintains 87% of its initial efficiency for six weeks (>1000 h) when kept in the dark at room temperature. These results clearly show that this study fills a critical void in perovskite research where highly efficient and stable semitransparent perovskite solar cells are scarce.     

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.     

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.     

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.     

21.41%-Efficiency CsPbI3 Perovskite Solar Cells Enabled by an Effective Redox Strategy with 4-Fluorobenzothiohydrazide in Precursor Solution

To simultaneously stabilize cesium lead triiodide (CsPbI₃) precursor solution and passivate the defects in CsPbI₃ film is greatly significant for achieving highly stable and efficient CsPbI₃ perovskite solar cells (PSCs). Herein, an effective redox 4-fluorobenzothiohydrazide (FBTH) is developed to stabilize the precursor solution and passivate iodine/lead-related defects for high-quality CsPbI₃ film. The comprehensive research confirms that 1) a new compound FBTH-I is obtained from an effective redox interaction between FBTH and molecular iodine (I₂) in perovskite precursor solution, which can effectively impede the formation of I₂ molecule and restrain I⁻ migration in perovskite film by forming N–H···I bond; 2) FBTH-I can also passivate Pb-related defects via forming S···Pb interaction. Consequently, the CsPbI₃ PSC based on FBTH-treated precursor solution exhibits a fascinating power conversion efficiency (PCE) of 21.41%, which is one of the highest PCE values among the reported pure CsPbI₃ PSCs so far, and an outstanding stability against the harsh conditions, such as thermal annealing and continuous light-illumination.