醋酸铅添加剂在印刷钙钛矿太阳能电池中的应用

印刷钙钛矿太阳能电池采用无机介孔骨架包覆有机无机杂化钙钛矿材料的器件结构,制备工艺简单,原材料成本低廉,且稳定性优异.然而,在介孔骨架中均匀沉积高质量的钙钛矿材料存在一定困难.本研究通过在典型钙钛矿材料甲胺铅碘(MAPbI3)前驱液中引入醋酸铅(Pb(Ac)2)作为添加剂,加快钙钛矿晶体的成核从而改善其在介孔骨架中的生...     

Europium and Acetate Co‐doping Strategy for Developing Stable and Efficient CsPbI2Br Perovskite Solar Cells

All‐inorganic perovskite solar cells have developed rapidly in the last two years due to their excellent thermal and light stability. However, low efficiency and moisture instability limit their future commercial application. The mixed‐halide inorganic CsPbI₂Br perovskite with a suitable bandgap offers a good balance between phase stability and light harvesting. However, high defect density and low carrier lifetime in CsPbI₂Br perovskites limit the open‐circuit voltage (V_oc < 1.2 V), short‐circuit current density (J_sc < 15 mA cm^?2), and fill factor (FF < 75%) of CsPbI₂Br perovskite solar cells, resulting in an efficiency below 14%. For the first time, a CsPbI₂Br perovskite is doped by Eu(Ac)₃ to obtain a high‐quality inorganic perovskite film with a low defect density and long carrier lifetime. A high efficiency of 15.25% (average efficiency of 14.88%), a respectable V_oc of 1.25 V, a reasonable J_sc of 15.44 mA cm^?2, and a high FF of 79.00% are realized for CsPbI₂Br solar cells. Moreover, the CsPbI₂Br solar cells with Eu(Ac)₃ doping demonstrate excellent air stability and maintain more than 80% of their initial power conversion efficiency (PCE) values after aging in air (relative humidity: 35–40%) for 30 days.     

Defect passivation strategy for inorganic CsPbI2Br perovskite solar cell with a high-efficiency of 16.77％

All-inorganic halide perovskite solar cells(PSCs)have acquired great progress,especially CsPbI2Br.However,their photoelectric conversion efficiency(PCE)remains far below the theoretical predictions.Non-radiative recombination is one of the important issues affecting the photoelectric performance of the PSCs,and the defective lead ions derived from the evaporation of halide ions in the inorganic per-ovskite are the principal non-radiative recombination centers.Herein,the non-radiative recombination is effectively suppressed by introducing the N-methyl-2-pyrrolidone(NMP)as a Lewis base molecule to passivate the defective lead ions.Therefore,by adjusting the dosage of NMP,the smooth and pinhole-free CsPbI2Br perovskite film is obtained and the optimized device exhibits a champion PCE of 16.77％with an excellent fill factor(FF)of 0.80.This work proves the effectiveness of passivation using Lewis base molecules to prevent non-radiative recombination defects in inorganic perovskite.     

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.     

Enhancing Crystallization in Hybrid Perovskite Solar Cells Using Thermally Conductive 2D Boron Nitride Nanosheet Additive

Controlling crystallization and grain growth is crucial for realizing highly efficient hybrid perovskite solar cells (PSCs). In this work, enhanced PSC photovoltaic performance and stability by accelerating perovskite crystallization and grain growth via 2D hexagonal boron nitride (hBN) nanosheet additives incorporated into the active perovskite layer are demonstrated. In situ X-ray scattering and infrared thermal imaging during the perovskite annealing process revealed the highly thermally conductive hBN nanosheets promoted the phase conversion and grain growth in the perovskite layer by facilitating a more rapid and spatially uniform temperature rise within the perovskite film. Complementary structural, physicochemical, and electrical characterizations further showed that the hBN nanosheets formed a physical barrier at the perovskite grain boundaries and the interfaces with charge transport layers, passivating defects, and retarding ion migration. As a result, the power conversion efficiency of the PSC is improved from 17.4% to 19.8%, along with enhanced device stability, retaining ≈90% of the initial efficiency even after 500 h ambient air storage. The results not only highlight 2D hBN as an effective additive for PSCs but also suggest enhanced thermal transport as one of the pathways for improved PSC performance by 2D material additives in general.     

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.     

Compositional Engineering for Thermally Stable,Highly Efficient Perovskite Solar Cells Exceeding 20% Power Conversion Efficiency with 85 °C/85% 1000 h Stability

Perovskite solar cells have received great attention because of their rapid progress in efficiency, with a present certified highest efficiency of 23.3%. Achieving both high efficiency and high thermal stability is one of the biggest challenges currently limiting perovskite solar cells because devices displaying stability at high temperature frequently suffer from a marked decrease of efficiency. In this report, the relationship between perovskite composition and device thermal stability is examined. It is revealed that Rb can suppress the growth of PbI₂ even under PbI₂‐rich conditions and decreasing the Br ratio in the perovskite absorber layer can prevent the generation of unwanted RbBr‐based aggregations. The optimized device achieved by engineering perovskite composition exhibits 92% power conversion efficiency retention in a stress test conducted at 85 °C/85% relative humidity (RH) according to an international standard (IEC 61215) while exceeding 20% power conversion efficiency (certified efficiency of 20.8% at 1 cm²). These results reveal the great potential for the practical use of perovskite solar cells in the near future.     

VOC over 1.2 V for Cs2AgBiBr6 solar cells based on formamidinium acetate additive

Cs₂AgBiBr₆ is a lead-free perovskite that shows great potential to solve the toxicity and instability of organic–inorganic lead perovskite. However, because of the poor interface contact and inferior film quality, the open-circuit voltage and the power conversion efficiency of the solar cells are inhibited. Herein, the Cs₂AgBiBr₆ film quality is improved by adding formamidinium acetate into the precursor solution. With additive regulation, the grain size increases and the film surface is more smooth. The crystal structure remains unchanged, and the defect density decreases. Correspondingly, the average power conversion efficiency of the target device increases more than 30% than the control device. The best efficiency approaches 2.09%, and the open-circuit voltage is surprisingly high at 1.23 V, the highest value reported for Cs₂AgBiBr₆ solar cells. Moreover, the device remains more than 90% of its initial efficiency after 40 days of storage under environmental conditions, showing excellent stability. This work is therefore helpful for enhancing the efficiency and stability of inorganic lead-free perovskite solar cells toward future commercialization.

     

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.     

Morphology and Performance Enhancement through the Strong Passivation Effect of Amphoteric Ions in Tin-based Perovskite Solar Cells

Despite the optoelectronic similarities between tin and lead halide perovskites, the performance of tin-based perovskite solar cells remains far behind, with the highest reported efficiency to date being ≈14%. This is highly correlated to the instability of tin halide perovskite, as well as the rapid crystallization behavior in perovskite film formation. In this work, l -Asparagine as a zwitterion plays a dual role in controlling the nucleation/crystallization process and improving the morphology of perovskite film. Furthermore, tin perovskites with l -Asparagine show more favorable energy-level matching, enhancing the charge extraction and minimizing the charge recombination, leading to an enhanced power conversion efficiency of 13.31% (from 10.54% without l -Asparagine) with remarkable stability. These results are also in good agreement with the density functional theory calculations. This work not only provides a facile and efficient approach to controlling the crystallization and morphology of perovskite film but also offers guidelines for further improved performance of tin-based perovskite electronic devices.     

Bidirectional Anions Gathering Strategy Afford Efficient Mixed Pb?Sn Perovskite Solar Cells

Mixed lead-tin (Pb Sn) perovskite solar cells (PSCs) possess low toxicity and adjustable bandgap for both single-junction and all-perovskite tandem solar cells. However, the performance of mixed Pb Sn PSCs still lags behind the theoretical efficiency. The uncontrollable crystallization and the resulting structural defect are important reasons. Here, the bidirectional anions gathering strategy (BAG) is reported by using Methylammonium acetate (MAAc) and Methylammonium thiocyanate (MASCN) as perovskite bulk additives, which Ac⁻ escapes from the perovskite film top surface while SCN⁻ gathers at the perovskite film bottom in the crystallization process. After the optoelectronic techniques, the bidirectional anions movement caused by the top-down gradient crystallization is demonstrated. The layer-by-layer crystallization can collect anions in the next layer and gather at the broader, enabling a controllable crystallization process, thus getting a high-quality perovskite film with better phase crystallinity and lower defect concentration. As a result, PSCs treated by the BAG strategy exhibit outstanding photovoltaic and electroluminescent performance with a champion efficiency of 22.14%. Additionally, it demonstrates excellent long-term stability, which retains ≈92.8% of its initial efficiency after 4000 h aging test in the N₂ glove box.     

Bridging the Buried Interface with Piperazine Dihydriodide Layer for High Performance Inverted Solar Cells

Given that it is closely related to perovskite crystallization and interfacial trap densities, buried interfacial engineering is crucial for creating effective and stable perovskite solar cells. Compared with the in-depth studies on the defect at the top perovskite interface, exploring the defect of the buried side of perovskite film is relatively complicated and scanty owing to the non-exposed feature. Herein, the degradation process is probed from the buried side of perovskite films with continuous illumination and its effects on morphology and photoelectronic characteristics with a facile lift-off method. Additionally, a buffer layer of Piperazine Dihydriodide (PDI₂) is inserted into the imbedded bottom interface. The PDI₂ buffer layer is able to lubricate the mismatched thermal expansion between perovskite and substrate, resulting in the release of lattice strain and thus a void-free buried interface. With the PDI₂ buffer layer, the degradation originates from the growing voids and increasing non-radiative recombination at the imbedded bottom interfaces are suppressed effectively, leading to prolonged operation lifetime of the perovskite solar cells. As a result, the power conversion efficiency of an optimized p-i-n inverted photovoltaic device reaches 23.47% (with certified 23.42%) and the unencapsulated devices maintain 90.27% of initial efficiency after 800 h continuous light soaking.     

An Air Knife–Assisted Recrystallization Method for Ambient‐Process Planar Perovskite Solar Cells and Its Dim‐Light Harvesting

The photovoltaic performance of perovskite solar cells is highly dependent on the control of morphology and crystallization of perovskite film, which usually requires a controlled atmosphere. Therefore, fully ambient fabrication is a desired technology for the development of perovskite solar cells toward real production. Here, an air‐knife assisted recrystallization method is reported, based on a simple bath‐immersion to prepare high‐quality perovskite absorbers. The resulted film shows a strong crystallinity with pure domains and low trap‐state density, which contribute to the device performance and stability. The proposed method can operate in a wide process window, such as variable relative humidity and bath‐immersion conditions, demonstrating a power conversion efficiency over 19% and 27% under 1 sun and 500–2000 lux dim‐light illumination respectively, which is among the highest performance of ambient‐process perovskite solar cells.     

Interface Engineering for All‐Inorganic CsPbI2Br Perovskite Solar Cells with Efficiency over 14%

In this work, a SnO₂/ZnO bilayered electron transporting layer (ETL) aimed to achieve low energy loss and large open‐circuit voltage (V_oc) for high‐efficiency all‐inorganic CsPbI₂Br perovskite solar cells (PVSCs) is introduced. The high‐quality CsPbI₂Br film with regular crystal grains and full coverage can be realized on the SnO₂/ZnO surface. The higher‐lying conduction band minimum of ZnO facilitates desirable cascade energy level alignment between the perovskite and SnO₂/ZnO bilayered ETL with superior electron extraction capability, resulting in a suppressed interfacial trap‐assisted recombination with lower charge recombination rate and greater charge extraction efficiency. The as‐optimized all‐inorganic PVSC delivers a high V_oc of 1.23 V and power conversion efficiency (PCE) of 14.6%, which is one of the best efficiencies reported for the Cs‐based all‐inorganic PVSCs to date. More importantly, decent thermal stability with only 20% PCE loss is demonstrated for the SnO₂/ZnO‐based CsPbI₂Br PVSCs after being heated at 85 °C for 300 h. These findings provide important interface design insights that will be crucial to further improve the efficiency of all‐inorganic PVSCs in the future.     

Polymer‐Passivated Inorganic Cesium Lead Mixed‐Halide Perovskites for Stable and Efficient Solar Cells with High Open‐Circuit Voltage over 1.3 V

Cesium‐based trihalide perovskites have been demonstrated as promising light absorbers for photovoltaic applications due to their superb composition stability. However, the large energy losses (E_loss) observed in inorganic perovskite solar cells has become a major hindrance impairing the ultimate efficiency. Here, an effective and reproducible method of modifying the interface between a CsPbI₂Br absorber and polythiophene hole‐acceptor to minimize the E_loss is reported. It is demonstrated that polythiophene, deposited on the top of CsPbI₂Br, can significantly reduce electron‐hole recombination within the perovskite, which is due to the electronic passivation of surface defect states. In addition, the interfacial properties are improved by a simple annealing process, leading to significantly reduced energy disorder in polythiophene and enhanced hole‐injection into the hole‐acceptor. Consequently, one of the highest power conversion efficiency (PCE) of 12.02% from a reverse scan in inorganic mixed‐halide perovskite solar cells is obtained. Modifying the perovskite films with annealing polythiophene enables an open‐circuit voltage (V_OC) of up to 1.32 V and E_loss of down to 0.5 eV, which both are the optimal values reported among cesium‐lead mixed‐halide perovskite solar cells to date. This method provides a new route to further improve the efficiency of perovskite solar cells by minimizing the E_loss.     

Hole transporting materials in inorganic CsPbI3−xBrx solar cells: Fundamentals,criteria and opportunities

Inorganic cesium lead halide (i.e., CsPbI_3−xBr_x) perovskite solar cells have made great breakthroughs in the last years with power conversion efficiency beyond 20%, thermal and photo stability reaching hundreds of hours. Hole transporting materials, as important building blocks in perovskite solar cells, present significant influences on both performance and stability. Understanding the energy loss mechanisms and failure pathways of inorganic perovskite solar cells that are originated from the hole transporting layer and the adjacent interfaces paves the way to enhance the efficiency towards Shockley-Queisser limit and to approach the long-term stability requirement. In this review, we first briefly overview the fundamentals of inorganic perovskites and solar cells, particularly on the criteria for designing and engineering efficient hole transporting materials. Second, we give a comprehensive review of recent advances on inorganic, small molecular and polymeric hole transporting materials. Finally, we discuss the challenges of state-of-the-art inorganic perovskite solar cells in view of the hole transporting materials and conclude this review by providing perspective on development of advanced hole transporting materials towards next-generation efficient and stable inorganic PSCs.     

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.     

2D-Antimonene-assisted hetero-epitaxial growth of perovskite films for efficient solar cells

There are many grain boundaries and defects in polycrystalline perovskite films, resulting in sacrificed efficiency and instability for perovskite solar cells (PSCs). By regulating the growth of perovskite grains along the vertical direction through epitaxial growth, one may expect fewer grain-boundaries, effective charge transport, improved crystalline quality, and reduced defect density. However, there is still no suitable epitaxial growth substrate for perovskite. Here, we developed an electrochemical lithiation intercalation and ultrasonication method to prepare high-quality antimonene nanosheets (ANs). It is found that the perovskite film grows preferentially along the (012) planes of the ANs that have perfect lattice match with the (001) planes of the perovskite, leading to a high-quality perovskite film with a preferential orientation along the [001] direction and greatly enlarged grain size. Consequently, the oriented perovskite-based PSC achieves a remarkable PCE of 24.54% and shows an enhanced stability under ambient conditions, thermal annealing or light illumination. This work opens an effective avenue to effectively control the oriented growth of perovskite film for high-performance perovskite optoelectrical devices.     

A Nontoxic Bifunctional (Anti)Solvent as Digestive-Ripening Agent for High-Performance Perovskite Solar Cells

The preparation of high-quality perovskite films is important for achieving high-performance perovskite solar cells (PSCs). The effective balance between solvent and antisolvent is an essential factor for regulating high-quality perovskite film during the spin-coating and thermal-annealing steps. In this work, a greener, nonhalogenated, nontoxic bifunctional (anti)solvent, methyl benzoate (MB), is developed not only as an antisolvent to rapidly generate crystal seeds at the perovskite spin-coating step, but also as a digestive-ripening solvent for the perovskite precursors, which can prevent the loss of organic components during the thermal-annealing stage and effectively suppress the formation of miscellaneous lead halide phases. As a result, this novel bifunctional (anti)solvent is employed in planar n–i–p PSCs for engineering high-quality perovskite layers and thus achieving a power conversion efficiency up to 22.37% with negligible hysteresis and >1300 h stability. Moreover, due to the high boiling point and low-volatility characteristic of MB, high-performance PSCs are achieved reproducibly at different operating temperatures (22–34 °C). Therefore, this developed bifunctional solvent system can provide a promising platform toward globally upscaling and commercializing PSCs in all seasons and regions.     

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.