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.     

Seed‐Assisted Growth for Low‐Temperature‐Processed All‐Inorganic CsPbIBr2 Solar Cells with Efficiency over 10%

All‐inorganic CsPbIBr₂ perovskite has recently received growing attention due to its balanced band gap and excellent environmental stability. However, the requirement of high‐temperature processing limits its application in flexible devices. Herein, a low‐temperature seed‐assisted growth (SAG) method for high‐quality CsPbIBr₂ perovskite films through reducing the crystallization temperature by introducing methylammonium halides (MAX, X = I, Br, Cl) is demonstrated. The mechanism is attributed to MA cation based perovskite seeds, which act as nuclei lowering the formation energy of CsPbIBr₂ during the annealing treatment. It is found that methylammonium bromide treated perovskite (Pvsk‐Br) film fabricated at low temperature (150 °C) shows micrometer‐sized grains and superior charge dynamic properties, delivering a device with an efficiency of 10.47%. Furthermore, an efficiency of 11.1% is achieved for a device based on high‐temperature (250 °C) processed Pvsk‐Br film via the SAG method, which presents the highest reported efficiency for inorganic CsPbIBr₂ solar cells thus far.     

Synergistic Effect of Surface p-Doping and Passivation Improves the Efficiency,Stability, and Reduces Lead Leakage in All-Inorganic CsPbIBr2-Based Perovskite Solar Cells

Wide-bandgap inorganic cesium lead halide CsPbIBr₂ is a popular optoelectronic material that researchers are interested in because of the character that balances the power conversion efficiency and stability of solar cells. It also has great potential in semitransparent solar cells, indoor photovoltaics, and as a subcell for tandem solar cells. Although CsPbIBr₂-based devices have achieved good performance, the open-circuit voltage (V_oc) of CsPbIBr₂-based perovskite solar cells (PSCs) is still lower, and it is critical to further reduce large energy losses (E_loss). Herein, a strategy is proposed for achieving surface p-type doping for CsPbIBr₂-based perovskite for the first time, using 1,5-Diaminopentane dihydroiodide at the perovskite surface to improve hole extraction efficiency. Meanwhile, the adjusted energy levels reduce E_loss and improve V_oc of the CsPbIBr₂ PSCs. Furthermore, the Cs- and Br-vacancies at the interface are filled, reducing structural disorder and defect states and thus improving the quality of the perovskite film. As a result, the target device achieves a high efficiency of 11.02% with a V_oc of 1.33 V, which is among the best values. In addition to the improved performance, the stability of the target device under various conditions is enhanced, and the lead leakage is effectively suppressed.     

Perovskite Solar Cells with Inorganic Electron‐ and Hole‐Transport Layers Exhibiting Long‐Term (≈500 h) Stability at 85 °C under Continuous 1 Sun Illumination in Ambient Air

Despite the high power conversion efficiency (PCE) of perovskite solar cells (PSCs), poor long‐term stability is one of the main obstacles preventing their commercialization. Several approaches to enhance the stability of PSCs have been proposed. However, an accelerating stability test of PSCs at high temperature under the operating conditions in ambient air remains still to be demonstrated. Herein, interface‐engineered stable PSCs with inorganic charge‐transport layers are shown. The highly conductive Al‐doped ZnO films act as efficient electron‐transporting layers as well as dense passivation layers. This layer prevents underneath perovskite from moisture contact, evaporation of components, and reaction with a metal electrode. Finally, inverted‐type PSCs with inorganic charge‐transport layers exhibit a PCE of 18.45% and retain 86.7% of the initial efficiency for 500 h under continuous 1 Sun illumination at 85 °C in ambient air with electrical biases (at maximum power point tracking).     

Goethite Quantum Dots as Multifunctional Additives for Highly Efficient and Stable Perovskite Solar Cells

Minimization of defects and ion migration in organic–inorganic lead halide perovskite films is desirable for obtaining photovoltaic devices with high power conversion efficiency (PCE) and long‐term stability. However, achieving this target is still a challenge due to the lack of efficient multifunctional passivators. Herein, to address this issue, n‐type goethite (FeOOH) quantum dots (QDs) are introduced into the perovskite light‐absorption layer for achieving efficient and stable perovskite solar cells (PSCs). It is found that the iron, oxygen, and hydroxyl of FeOOH QDs can interact with iodine, lead, and methylamine, respectively. As a result, the crystallization kinetics process can be retarded, thereby resulting in high quality perovskite films with large grain size. Meanwhile, the trap states of perovskite can be effectively passivated via interaction with the under‐coordinated metal (Pb) cations, halide (I) anions on the perovskite crystal surface. Consequently, the PSCs with FeOOH QDs achieve a high efficiency close to 20% with negligible hysteresis. Most strikingly, the long‐term stability of PSCs is significantly enhanced. Furthermore, compared with the CH₃NH₃PbI₃‐based device, a higher PCE of 21.0% is achieved for the device assembled with a Cs_0.05FA_0.81MA_0.14PbBr_0.45I_2.55 perovskite layer.     

Thermally Stable MAPbI3 Perovskite Solar Cells with Efficiency of 19.19% and Area over 1 cm2 achieved by Additive Engineering

Solution‐processed perovskite (PSC) solar cells have achieved extremely high power conversion efficiencies (PCEs) over 20%, but practical application of this photovoltaic technology requires further advancements on both long‐term stability and large‐area device demonstration. Here, an additive‐engineering strategy is developed to realize a facile and convenient fabrication method of large‐area uniform perovskite films composed of large crystal size and low density of defects. The high crystalline quality of the perovskite is found to simultaneously enhance the PCE and the durability of PSCs. By using the simple and widely used methylammonium lead iodide (MAPbI₃), a certified PCE of 19.19% is achieved for devices with an aperture area of 1.025 cm², and the high‐performing devices can sustain over 80% of the initial PCE after 500 h of thermal aging at 85 °C, which are among the best results of MAPbI₃‐based PSCs so far.     

Suppressed Voltage Deficit and Degradation of Perovskite Solar Cells by Regulating the Mineralization of Lead Iodide

Both the uncoordinated Pb²⁺ and excess PbI₂ in perovskite film will create defects and perturb carrier collection, thus leading to the open-circuit voltage (V_OC) loss and inducing rapid performance degradation of perovskite solar cells (PSCs). Herein, an additive of 3-aminothiophene-2-carboxamide (3-AzTca) that contains amide and amino and features a large molecular size is introduced to improve the quality of perovskite film. The interplay of size effect and adequate bonding strength between 3-AzTca and uncoordinated Pb²⁺ regulates the mineralization of PbI₂ and generates low-dimensional PbI₂ phase, thereby boosting the crystallization of perovskite. The decreased defect states result in suppressed nonradiative recombination and reduced V_OC loss. The power conversion efficiency (PCE) of modified PSC is improved to 22.79% with a high V_OC of 1.22 V. Moreover, the decomposition of PbI₂ and perovskite films is also retarded, yielding enhanced device stability. This study provides an effective method to minimize the concentration of uncoordinated Pb²⁺ and improve the PCE and stability of PSCs.     

Quasi‐Heteroface Perovskite Solar Cells

Perovskite solar cells (PSCs) have attracted unprecedented attention due to their rapidly rising photoelectric conversion efficiency (PCE). In order to further improve the PCE of PSCs, new possible optimization path needs to be found. Here, quasi‐heteroface PSCs (QHF‐PSCs) is designed by a double‐layer perovskite film. Such brand new PSCs have good carrier separation capabilities, effectively suppress the nonradiative recombination of the PSCs, and thus greatly improve the open‐circuit voltage and PCE. The root cause of the performance improvement is the benefit from the additional built‐in electric field, which is confirmed by measuring the external quantum efficiency under applied electric field and Kelvin probe force microscope. Meanwhile, an intermediate band gap perovskite layer can be obtained simply by combining a wide band gap perovskite layer with a narrow band gap perovskite layer. Tunability of the band gap is obtained by varying the film thicknesses of the narrow and wide band gap layers. This phenomenon is quite different from traditional inorganic solar cells, whose band gap is determined only by the narrowest band gap layer. It is believed that these QHF‐PSCs will be an effective strategy to further enhance PCE in PSCs and provide basis to further understand and develop the perovskite materials platform.     

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.     

Stable and High-Efficiency Methylammonium-Free Perovskite Solar Cells

Organic–inorganic metal halide perovskite solar cells (PSCs) have achieved certified power conversion efficiency (PCE) of 25.2% with complex compositional and bandgap engineering. However, the thermal instability of methylammonium (MA) cation can cause the degradation of the perovskite film, remaining a risk for the long-term stability of the devices. Herein, a unique method is demonstrated to fabricate highly phase-stable perovskite film without MA by introducing cesium chloride (CsCl) in the double cation (Cs, formamidinium) perovskite precursor. Moreover, due to the suboptimal bandgap of bromide (Br⁻), the amount of Br⁻ is regulated, leading to high power conversion efficiency. As a result, MA-free perovskite solar cells achieve remarkable long-term stability and a PCE of 20.50%, which is one of the best results for MA-free PSCs. Moreover, the unencapsulated device retains about 80% of the original efficiencies after a 1000 h aging study. These results provide a feasible approach to enhance solar cell stability and performance simultaneously, paving the way for commercializing PSCs.     

Defect‐Engineering‐Enabled High‐Efficiency All‐Inorganic Perovskite Solar Cells

The emergence of cesium lead iodide (CsPbI₃) perovskite solar cells (PSCs) has generated enormous interest in the photovoltaic research community. However, in general they exhibit low power conversion efficiencies (PCEs) because of the existence of defects. A new all‐inorganic perovskite material, CsPbI₃:Br:InI₃, is prepared by defect engineering of CsPbI₃. This new perovskite retains the same bandgap as CsPbI₃, while the intrinsic defect concentration is largely suppressed. Moreover, it can be prepared in an extremely high humidity atmosphere and thus a glovebox is not required. By completely eliminating the labile and expensive components in traditional PSCs, the all‐inorganic PSCs based on CsPbI₃:Br:InI₃ and carbon electrode exhibit PCE and open‐circuit voltage as high as 12.04% and 1.20 V, respectively. More importantly, they demonstrate excellent stability in air for more than two months, while those based on CsPbI₃ can survive only a few days in air. The progress reported represents a major leap for all‐inorganic PSCs and paves the way for their further exploration in order to achieve higher performance.     

Methodologies toward Highly Efficient Perovskite Solar Cells

A perovskite solar cell (PSC) employing an organic–inorganic lead halide perovskite light harvester, seeded in 2009 with power conversion efficiency (PCE) of 3.8% and grown in 2011 with PCE of 6.5% in dye‐sensitized solar cell structure, has received great attention since the breakthrough reports ≈10% efficient solid‐state PCSs demonstrating 500 h stability. Developments of device layout and high‐quality perovskite film eventually lead to a PCE over 22%. As of October 31, 2017, the highest PCE of 22.7% is listed in an efficiency chart provided by NREL. In this Review, the methodologies to obtain highly efficient PSCs are described in detail. In order to achieve a PCE of over 20% reproducibly, key technologies are disclosed from the viewpoint of precursor solution chemistry, processing for defect‐free perovskite films, and passivation of grain boundaries. Understanding chemical species in precursor solution, crystal growth kinetics, light–matter interaction, and controlling defects is expected to give important insights into not only reproducible production of high PCE over 20% but also further enhancement of the PCE of PCSs.     

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.     

Co-Solvent Engineering Contributing to Achieve High-Performance Perovskite Solar Cells and Modules Based on Anti-Solvent Free Technology

The pinhole-free and defect-less perovskite film is crucial for achieving high efficiency and stable perovskite solar cells (PSCs), which can be prepared by widely used anti-solvent crystallization strategies. However, the involvement of anti-solvent requires precise control and inevitably brings toxicity in fabrication procedures, which limits its large-scale industrial application. In this work, a facile and effective co-solvent engineering strategy is introduced to obtain high- quality perovskite film while avoiding the usage of anti-solvent. The uniform and compact perovskite polycrystalline films have been fabricated through the addition of co-solvent that owns strong coordination capacity with perovskite components , meanwhile possessing the weaker interaction with main solvent . With those strategies, a champion power conversion efficiency (PCE) of 22% has been achieved with the optimal co-solvent, N-methylpyrrolidone (NMP) and without usage of anti-solvent. Subsequently, PSCs based on NMP show high repeatability and good shelf stability (80% PCE remains after storing in ambient condition for 30 days). Finally, the perovskite solar module (5 × 5 cm) with 7 subcells connects in series yielding champion PCE of 16.54%. This strategy provides a general guidance of co-solvent selection for PSCs based on anti-solvent free technology and promotes commercial application of PSCs.     

20.67%-Efficiency Inorganic CsPbI3 Solar Cells Enabled by Zwitterion Ion Interface Treatment

All-inorganic CsPbI₃ perovskite solar cells (PSCs) have been extensively studied due to their high thermal stability and unprecedented rise in power conversion efficiency (PCE). Recently, the champion PCE of CsPbI₃ PSCs has reached up to 21%; however, it is still much lower than that of organic–inorganic hybrid PSCs. Interface modification to passivate surface defects and minimize charge recombination and trapping is important to further improve the efficiency of CsPbI₃ PSCs. Herein, a new zwitterion ion is deposited at the interface between electron transporting layer (ETL) and perovskite layer to passivate the defects therein. The zwitterion ions can not only passivate oxygen vacancy (V_O) and iodine vacancy (V_I) defects, but also improve the band alignment at the ETL-perovskite interface. After the interface treatment, the PCE of CsPbI₃ device reaches up to 20.67%, which is among the highest values of CsPbI₃ PSCs so far. Due to the defect passivation and hydrophobicity improvement, the PCE of optimized device remains 94% of its original value after 800 h storing under ambient condition. These results provide an efficient way to improve the quality of ETL-perovskite interface by zwitterion ions for achieving high performance inorganic CsPbI₃ PSCs.     

Methylammonium Chloride as a Double-Edged Sword for Efficient and Stable Perovskite Solar Cells

The additive engineering strategy promotes the efficiency of solution-processed perovskite solar cells (PSCs) over 25%. However, compositional heterogeneity and structural disorders occur in perovskite films with the addition of specific additives, making it imperative to understand the detrimental impact of additives on film quality and device performance. In this work, the double-edged sword effects of the methylammonium chloride (MACl) additive on the properties of methylammonium lead mixed-halide perovskite (MAPbI_3-xCl_x ) films and PSCs are demonstrated. MAPbI_3-xCl_x films suffer from undesirable morphology transition during annealing, and its impacts on the film quality including morphology, optical properties, structure, and defect evolution are systematically investigated, as well as the power conversion efficiency (PCE) evolution for related PSCs. The FAX (FA = formamidinium, X = I, Br, and Ac) post-treatment strategy is developed to inhibit the morphology transition and suppress defects by compensating for the loss of the organic components, a champion PCE of 21.49% with an impressive open-circuit voltage of 1.17 V is obtained, and remains over 95% of the initial efficiency after storing over 1200 hours. This study elucidates that understanding the additive-induced detrimental effects in halide perovskites is critical to achieve the efficient and stable PSCs.     

Inorganic lead-based halide perovskites: From fundamental properties to photovoltaic applications

Compared with organic–inorganic hybrid halide perovskites (OIHPs), inorganic cesium lead halide perovskites (CsPbX₃) possess superior intrinsic stability for high temperatures and are considered one of the most attractive research hotspots in the perovskite photovoltaic (PV) field in the past several years. The PCE of CsPbX₃ inorganic perovskite solar cells (IPSCs) has increased from 2.9% in 2015 to more than 20% with excellent stability. There are still many on-going studies on the properties of perovskite materials and their applications in PV technology, thereby needing a thorough understanding. Here, the progress of inorganic perovskites is systematically introduced, including the fundamental properties of CsPbX₃ materials and CsPbX₃-based PV devices. The origins of stability and instability of CsPbX₃ and defects in CsPbX₃ are discussed. CsPbI₃-, CsPbI₂Br-, CsPbIBr₂- and CsPbBr₃-based PV devices and performance are comprehensively reviewed. The stabilization methods and mechanism for the photoactive phases of inorganic perovskites with low bandgap are emphasized. Reported strategies to boost the performance of CsPbX₃-based IPSCs are summarized. In the end, the potential of inorganic perovskites is evaluated, which opens up new prospects for the commercialization of IPSCs.     

Efficient Perovskite Solar Cells Fabricated Through CsCl‐Enhanced PbI2 Precursor via Sequential Deposition

The fabrication of high‐quality perovskite film highly relies on chemical composition and the synthesis method of perovskite. So far, sequentially deposited MA_0.03FA_0.97Pb(I_0.97Br_0.03)₃ polycrystalline film is adopted to produce high‐performance perovskite solar cells with record power conversion efficiency (PCE). Fewer grain boundaries and incorporation of inorganic cation (e.g., cesium) would further increase device performance via sequential deposition. Here, cesium chloride (CsCl) is introduced into lead iodide (PbI₂) precursor solution that beneficially modulates the property of PbI₂ film, leading to larger grains with cesium incorporation in the resulting perovskite film. The enlarged crystal grains originate from a slower nucleation process for CsCl‐containing PbI₂ film when reacting with formamidine iodide, confirmed by in situ confocal photoluminescence imaging. Photovoltaic devices based on CsCl‐containing PbI₂ film demonstrate a higher averaging efficiency of 21.3% than 20.3% of the devices without CsCl additives for reverse scan. More importantly, the device stability is improved by CsCl additives that retain over 90% of their initial PCE value after 4000 min tracking at maximum power point under 1‐sun illumination. This work paves a way to further improve the photovoltaic performance of mixed‐cation‐halide perovskite solar cells via a sequential deposition method.     

Graded Heterojunction Engineering for Hole‐Conductor‐Free Perovskite Solar Cells with High Hole Extraction Efficiency and Conductivity

Despite great progress in the photovoltaic conversion efficiency (PCE) of inorganic–organic hybrid perovskite solar cells (PSCs), the large‐scale application of PSCs still faces serious challenges due to the poor‐stability and high‐cost of the spiro‐OMeTAD hole transport layer (HTL). It is of great fundamental importance to rationally address the issues of hole extraction and transfer arising from HTL‐free PSCs. Herein, a brand‐new PSC architecture is designed by introducing multigraded‐heterojunction (GHJ) inorganic perovskite CsPbBr_x I_3?x layers as an efficient HTL. The grade adjustment can be achieved by precisely tuning the halide proportion and distribution in the CsPbBr_x I_3?x film to reach an optimal energy alignment of the valance and conduction band between MAPbI₃ and CsPbBr_x I_3?x . The CsPbBr_x I_3?x GHJ as an efficient HTL can induce an electric field where a valance/conduction band edge is leveraged to bend at the heterojunction interface, boosting the interfacial electron–hole splitting and photoelectron extraction. The GHJ architecture enhances the hole extraction and conduction efficiency from the MAPbI₃ to the counter electrode, decreases the recombination loss during the hole transfer, and benefits in increasing the open‐circuit voltage. The optimized HTL‐free PCS based on the GHJ architecture demonstrates an outstanding thermal stability and a significantly improved PCE of 11.33%, nearly 40% increase compared with 8.16% for pure HTL‐free devices.     

具有2D-EDAPbI4薄覆盖层的环境稳定的FAPbI3基钙钛矿太阳能电池（英文）

二维(2D)卤化铅钙钛矿材料是钙钛矿太阳能电池(PSC)中最有前途的吸光材料之一,具有优异的稳定性和缺陷钝化作用.然而,这些稳定的二维PSC的转换效率仍远远落后于三维钙钛矿电池.在本文中我们通过原位生长的方法将2D EDAPbI4层成功制备在3D FAPbI3层表面。这种合理设计的2D-3D钙钛矿薄膜分层结构可以明显提高电池的效率.另外,由于EDAPbI4层的高抗湿性和抑制迁移, 2D-3D电池器件显示出明显增强的长期稳定性,在200 h内一直保持初始转换效率,甚至在500 h后仍能保持其初始转化效率的90%.