Efficient Hole Transporting Materials with Two or Four N,N‐Di(4‐methoxyphenyl)aminophenyl Arms on an Ethene Unit for Perovskite Solar Cells

Novel steric bulky hole transporting materials (HTMs) with two or four N,N‐di(4‐methoxyphenyl)aminophenyl units have been synthesized. When the EtheneTTPA was used as a hole transporting material in perovskite solar cell, the power conversion efficiency afforded 12.77 % under AM 1.5 G illumination, which is comparable to the widely used spiro‐OMeTAD based solar cell (13.28 %).     

Dimethylammonium Cation-Induced 1D/3D Heterostructure for Efficient and Stable Perovskite Solar Cells

Mixed-dimensional perovskite engineering has been demonstrated as a simple and useful approach to achieving highly efficient and more-durable perovskite solar cells (PSCs), which have attracted increasing research interests worldwide. In this work, 1D/3D mixed-dimensional perovskite has been successfully obtained by introducing DMAI via a two-step deposition method. The additive DMA⁺ can facilitate the crystalline growth and form 1D DMAPbI₃ at grain boundaries of 3D perovskite, leading to improved morphology, longer charge carrier lifetime, and remarkably reduced bulk trap density for perovskite films. Meanwhile, the presence of low-dimension perovskite is able to prevent the intrusion of moisture, resulting in enhanced long-term stability. As a result, the PSCs incorporated with 1D DMAPbI₃ exhibited a first-class power conversion efficiency (PCE) of 21.43% and maintained 85% of their initial efficiency after storage under ambient conditions with ~45% RH for 1000 h.     

In Quest of Environmentally Stable Perovskite Solar Cells: A Perspective

Inorganic-organic halide perovskites pose a once-in-a-generation opportunity to revolutionize photovoltaic technology as they are excellent semiconductor candidates with a combination of many desirable attributes. Specifically, halide perovskite solar cells with extremely high device efficiency are easily fabricated and present great promise for commercialization in the near future. However, their non-ideal environmental stability under real operating conditions can limit their further development. Both the academic and industrial research communities have been devoting considerable effort to overcome this critical deficiency through material and device engineering. Significant progress has been reported in this direction, and in this perspective, we review the recent strategies that promise to improve solar cell stability focusing on two interwoven topics. The first one is the development of environmentally stable semiconductor materials, while the second one is dedicated to the reported progress in improving solar cell device stability. Although, the currently adopted methods have not resolved the above problems, yet they build a foundation of principles for future advances to overcome them. In this regard, we believe commercial perovskite-related photovoltaics might indeed be on the horizon, not only replacing the currently commercially available ones, but also improving them.     

Stabilization of Highly Efficient and Stable Phase‐Pure FAPbI3 Perovskite Solar Cells by Molecularly Tailored 2D‐Overlayers

As a result of their attractive optoelectronic properties, metal halide APbI₃ perovskites employing formamidinium (FA⁺) as the A cation are the focus of research. The superior chemical and thermal stability of FA⁺ cations makes α‐FAPbI₃ more suitable for solar‐cell applications than methylammonium lead iodide (MAPbI₃). However, its spontaneous conversion into the yellow non‐perovskite phase (δ‐FAPbI₃) under ambient conditions poses a serious challenge for practical applications. Herein, we report on the stabilization of the desired α‐FAPbI₃ perovskite phase by protecting it with a two‐dimensional (2D) IBA₂FAPb₂I₇ (IBA=iso‐butylammonium overlayer, formed via stepwise annealing. The α‐FAPbI₃/IBA₂FAPb₂I₇ based perovskite solar cell (PSC) reached a high power conversion efficiency (PCE) of close to 23 %. In addition, it showed excellent operational stability, retaining around 85 % of its initial efficiency under severe combined heat and light stress, that is, simultaneous exposure with maximum power tracking to full simulated sunlight at 80 °C over 500 h.     

A Purified,Solvent‐Intercalated Precursor Complex for Wide‐Process‐Window Fabrication of Efficient Perovskite Solar Cells and Modules

A high‐purity methylammonium lead iodide complex with intercalated dimethylformamide (DMF) molecules, CH₃NH₃PbI₃?DMF, is introduced as an effective precursor material for fabricating high‐quality solution‐processed perovskite layers. Spin‐coated films of the solvent‐intercalated complex dissolved in pure dimethyl sulfoxide (DMSO) yielded thick, dense perovskite layers after thermal annealing. The low volatility of the pure DMSO solvent extended the allowable time for low‐speed spin programs and considerably relaxed the precision needed for the antisolvent addition step. An optimized, reliable fabrication method was devised to take advantage of this extended process window and resulted in highly consistent performance of perovskite solar cell devices, with up to 19.8 % power‐conversion efficiency (PCE). The optimized method was also used to fabricate a 22.0 cm², eight‐cell module with 14.2 % PCE (active area) and 8.64 V output (1.08 V/cell).     

Sb2Se3‐Sensitized Inorganic–Organic Heterojunction Solar Cells Fabricated Using a Single‐Source Precursor

The photovoltaic performance of Sb₂Se₃‐sensitized heterojunction solar cells, which were fabricated by a simple deposition of Sb₂Se₃ on mesoporous TiO₂ by an approach that features multiple cycles of spin coating with a single‐source precursor solution and thermal decomposition, is reported. Poly[2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7(2,1,3‐benzothioadiazole)] was used as the hole‐transporting material. The most efficient cell exhibited a short‐circuit current density of 22.3 mA cm^?2, an open‐circuit voltage of 304.5 mV, and a fill factor of 47.2 %, yielding a power conversion efficiency of 3.21 % under standard test conditions (irradiation of 1000 W m^?2, air mass=1.5 G). The results of this study imply that the developed approach has a high potential as a simple and effective route for the fabrication of efficient and inexpensive solar cells.     

Observing Defect Passivation of the Grain Boundary with 2‐Aminoterephthalic Acid for Efficient and Stable Perovskite Solar Cells

Metal halide perovskite solar cells (PSCs), with their exceptional properties, show promise as photoelectric converters. However, defects in the perovskite layer, particularly at the grain boundaries (GBs), seriously restrict the performance and stability of PSCs. Now, a simple post‐treatment procedure involves applying 2‐aminoterephthalic acid to the perovskite to produce efficient and stable PSCs. By optimizing the post‐treatment conditions, we created a device that achieved a remarkable power conversion efficiency (PCE) of 21.09 % and demonstrated improved stability. This improvement was attributed to the fact that the 2‐aminoterephthalic acid acted as a cross‐linking agent that inhibited the migration of ions and passivated the trap states at GBs. These findings provide a potential strategy for designing efficient and stable PSCs regarding the aspects of defect passivation and crystal growth.     

阴极界面修饰层改善平面p-i-n型钙钛矿太阳能电池的光伏性能

有机/无机杂化金属卤化物钙钛矿半导体材料结合了有机材料良好的溶液可加工性以及无机材料优越的光电特性,近几年受到了热捧,成为太阳能电池领域一颗耀眼的明星. 伴随着钙钛矿薄膜结晶过程和形貌的优化、器件结构的改进以及电极界面材料的开发,这类有机/无机杂化金属卤化物钙钛矿太阳能电池的光电转换效率从最初的3.8%迅速提高到目前最高的22.1%. 其中界面工程在提升器件性能上发挥着极其重要的作用. 本文总结了平面p-i-n型钙钛矿太阳能电池中阴极界面修饰层（CBL）的研究进展. CBL从材料上讲可分为无机金属氧化物、金属或金属盐以及有机材料,从构成上讲可分为单层CBL、双层CBLs以及共混型CBL. 本文对这些类型的CBL分别给予详细的介绍. 最后,我们归纳出CBL在改善器件效率和稳定性上所起的作用以及理想CBL所应满足的要求,希望能为以后阴极界面修饰材料的设计提供一定的借鉴.     

Stabilization of Highly Efficient and Stable Phase-Pure FAPbI3 Perovskite Solar Cells by Molecularly Tailored 2D-Overlayers

As a result of their attractive optoelectronic properties, metal halide APbI₃ perovskites employing formamidinium (FA⁺) as the A cation are the focus of research. The superior chemical and thermal stability of FA⁺ cations makes α-FAPbI₃ more suitable for solar-cell applications than methylammonium lead iodide (MAPbI₃). However, its spontaneous conversion into the yellow non-perovskite phase (δ-FAPbI₃) under ambient conditions poses a serious challenge for practical applications. Herein, we report on the stabilization of the desired α-FAPbI₃ perovskite phase by protecting it with a two-dimensional (2D) IBA₂FAPb₂I₇ (IBA=iso-butylammonium overlayer, formed via stepwise annealing. The α-FAPbI₃/IBA₂FAPb₂I₇ based perovskite solar cell (PSC) reached a high power conversion efficiency (PCE) of close to 23 %. In addition, it showed excellent operational stability, retaining around 85 % of its initial efficiency under severe combined heat and light stress, that is, simultaneous exposure with maximum power tracking to full simulated sunlight at 80 °C over 500 h.     

3,4‐Phenylenedioxythiophene (PheDOT) Based Hole‐Transporting Materials for Perovskite Solar Cells

Two new electron‐rich molecules based on 3,4‐phenylenedioxythiophene (PheDOT) were synthesized and successfully adopted as hole‐transporting materials (HTMs) in perovskite solar cells (PSCs). X‐ray diffraction, absorption spectra, photoluminescence spectra, electrochemical properties, thermal stabilities, hole mobilities, conductivities, and photovoltaic parameters of PSCs based on these two HTMs were compared with each other. By introducing methoxy substituents into the main skeleton, the energy levels of PheDOT‐core HTM were tuned to match with the perovskite, and its hole mobility was also improved (1.33×10^?4 cm² V^?1 s^?1, being higher than that of spiro‐OMeTAD, 2.34×10^?5 cm² V^?1 s^?1). The PSC based on MeO‐PheDOT as HTM exhibits a short‐circuit current density (J_sc) of 18.31 mA cm^?2, an open‐circuit potential (V_oc) of 0.914 V, and a fill factor (FF) of 0.636, yielding an encouraging power conversion efficiency (PCE) of 10.64 % under AM 1.5G illumination. These results give some insight into how the molecular structures of HTMs affect their performances and pave the way for developing high‐efficiency and low‐cost HTMs for PSCs.     

Stable and Low‐Cost Mesoscopic CH3NH3PbI2Br Perovskite Solar Cells by using a Thin Poly(3‐hexylthiophene) Layer as a Hole Transporter

Mesoscopic perovskite solar cells using stable CH₃NH₃PbI₂Br as a light absorber and low‐cost poly(3‐hexylthiophene) (P3HT) as hole‐transporting layer were fabricated, and a power conversion efficiency of 6.64 % was achieved. The partial substitution of iodine with bromine in the perovskite led to remarkably prolonged charge carrier lifetime. Meanwhile, the replacement of conventional thick spiro‐MeOTAD layer with a thin P3HT layer has significantly reduced the fabrication cost. The solar cells retained their photovoltaic performance well when they were exposed to air without any encapsulation, presenting a favorable stability. The combination of CH₃NH₃PbI₂Br and P3HT may render a practical and cost‐effective solid‐state photovoltaic system. The superior stability of CH₃NH₃PbI₂Br is also promising for other photoconversion applications.     

Unconventional Route to Oxygen‐Vacancy‐Enabled Highly Efficient Electron Extraction and Transport in Perovskite Solar Cells

The ability to effectively transfer photoexcited electrons and holes is an important endeavor toward achieving high‐efficiency solar energy conversion. Now, a simple yet robust acid‐treatment strategy is used to judiciously create an amorphous TiO₂ buffer layer intimately situated on the anatase TiO₂ surface as an electron‐transport layer (ETL) for efficient electron transport. The facile acid treatment is capable of weakening the bonding of zigzag octahedral chains in anatase TiO₂, thereby shortening staggered octahedron chains to form an amorphous buffer layer on the anatase TiO₂ surface. Such amorphous TiO₂‐coated ETL possesses an increased electron density owing to the presence of oxygen vacancies, leading to efficient electron transfer from perovskite to TiO₂. Compared to pristine TiO₂‐based devices, the perovskite solar cells (PSCs) with acid‐treated TiO₂ ETL exhibit an enhanced short‐circuit current and power conversion efficiency.     

Hexaazatrinaphthylene Derivatives: Efficient Electron‐Transporting Materials with Tunable Energy Levels for Inverted Perovskite Solar Cells

Hexaazatrinaphthylene (HATNA) derivatives have been successfully shown to function as efficient electron‐transporting materials (ETMs) for perovskite solar cells (PVSCs). The cells demonstrate a superior power conversion efficiency (PCE) of 17.6 % with negligible hysteresis. This study provides one of the first nonfullerene small‐molecule‐based ETMs for high‐performance p–i–n PVSCs.     

Efficient Hole‐Transporting Materials with Triazole Core for High‐Efficiency Perovskite Solar Cells

Efficient hole‐transporting materials (HTMs), TAZ‐[MeOTPA]₂ and TAZ‐[MeOTPATh]₂ incorporating two electron‐rich diphenylamino side arms, through direct linkage or thiophen bridges, respectively, on the C3‐ and C5‐positions of a 4‐phenyl‐1,2,4‐triazole core were synthesized. These synthetic HTMs with donor–acceptor type molecular structures exhibited effective intramolecular charge transfer for improving the hole‐transporting properties. The structural modification of HTMs by thiophene bridging might increase intermolecular π–π stacking in the solid state and afford a better spectral response because of their increased π‐conjugation length. Perovskite‐based cells using TAZ‐[MeOTPA]₂ and TAZ‐[MeOTPATh]₂ as HTMs afforded high power conversion efficiencies of 10.9 % and 14.4 %, respectively, showing a photovoltaic performance comparable to that obtained using spiro‐OMeTAD. These synthetically simple and inexpensive HTMs hold promise for replacing the more expensive spiro‐OMeTAD in high‐efficiency perovskite solar cells.     

Synthesis and Characterization of a Soluble A–D–A Molecule Containing a 2D Conjugated Selenophene‐Based Side Group for Organic Solar Cells

A new acceptor–donor–acceptor (A–D–A) small molecule based on benzodithiophene (BDT) and diketopyrrolopyrrole (DPP) is synthesized via a Stille cross‐coupling reaction. A highly conjugated selenophene‐based side group is incorporated into each BDT unit to generate a 2D soluble small molecule (SeBDT‐DPP). SeBDT‐DPP thin films produce two distinct absorption peaks. The shorter wavelength absorption (400 nm) is attributed to the BDT units containing conjugated selenophene‐based side groups, and the longer wavelength band is due to the intramolecular charge transfer between the BDT donor and the DPP acceptor. SeBDT‐DPP thin films can harvest a broad solar spectrum covering the range 350–750 nm and have a low bandgap energy of 1.63 eV. Solution‐processed field‐effect transistors fabricated with this small molecule exhibit p‐type organic thin film transistor characteristics, and the field‐effect mobility of a SeBDT‐DPP device is measured to be 2.3 × 10⁻³ cm² V⁻¹ s⁻¹. A small molecule solar cell device is prepared by using SeBDT‐DPP as the active layer is found to exhibit a power conversion efficiency of 5.04% under AM 1.5 G (100 mW cm⁻²) conditions.

     

Stability of Perovskite Solar Cells: A Prospective on the Substitution of the A Cation and X Anion

In recent years, organometal trihalide perovskites have emerged as promising materials for low‐cost, flexible, and highly efficient solar cells. Despite their processing advantages, before the technology can be commercialized the poor stability of the organic–inorganic hybrid perovskite materials with regard to humidity, heat, light, and oxygen has be to overcome. Herein, we distill the current state‐of‐the‐art and highlight recent advances in improving the chemical stability of perovskite materials by substitution of the A‐cation and X‐anion. Our hope is to pave the way for the rational design of perovskite materials to realize perovskite solar cells with unprecedented improvement in stability.     

Lowering Molecular Symmetry To Improve the Morphological Properties of the Hole‐Transport Layer for Stable Perovskite Solar Cells

Inspired by the structural feature of the classical hole‐transport material (HTM), Spiro‐OMeTAD, many analogues based on a highly symmetrical spiro‐core were reported for perovskite solar cells (PSCs). However, these HTMs were prone to crystallize because of the high molecular symmetry, forming non‐uniform films, unfavorable for the device stability and large‐area processing. By lowering the symmetry of spiro‐core, we report herein a novel spirobisindane‐based HTM, Spiro‐I, which could form amorphous films with high uniformity and morphological stability. Compared to the Spiro‐OMeTAD‐based PSCs, those containing Spiro‐I exhibit similar efficiencies for small area but higher ones for large area (1 cm²), and especially much higher air stability (retaining 80 % of initial PCE after 2400 h storage without encapsulation). Moreover, the Spiro‐I can be synthesized from a cheap starting material bisphenol A and used with a small amount for the device fabrication.     

钛掺杂钙钛矿制备高效率钙钛矿太阳能电池

采用钛离子掺杂钙钛矿薄膜的方法修饰钙钛矿晶界缺陷。研究表明钛离子富集在晶界处,有效地钝化了晶界缺陷,同时有助于连续、平整、高质量薄膜的形成。经过钛离子掺杂后的钙钛矿太阳能电池电流(JSC)达到22.3 mA·cm~(-2),开路电压(VOC)达1.1 V,填充因子(FF)高达72.4%,光电转换效率(PCE)优化至17.4%,远高于未掺杂钙钛矿太阳能电池。     

Facile Synthesis of a Furan–Arylamine Hole‐Transporting Material for High‐Efficiency,Mesoscopic Perovskite Solar Cells

A novel hole‐transporting molecule (F101) based on a furan core has been synthesized by means of a short, high‐yielding route. When used as the hole‐transporting material (HTM) in mesoporous methylammonium lead halide perovskite solar cells (PSCs) it produced better device performance than the current state‐of‐the‐art HTM 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD). The F101‐HTM‐based device exhibited both slightly higher J_sc (19.63 vs. 18.41 mA cm^?2) and V_oc (1.1 vs. 1.05 V) resulting in a marginally higher power conversion efficiency (PCE) (13.1 vs. 13 %). The steady‐state and time‐resolved photoluminescence show that F101 has significant charge extraction ability. The simple molecular structure, short synthesis route with high yield and better performance in devices makes F101 an excellent candidate for replacing the expensive spiro‐OMeTAD as HTM in PSCs.