Polymer Doping for High‐Efficiency Perovskite Solar Cells with Improved Moisture Stability

Each component layer in a perovskite solar cell plays an important role in the cell performance. Here, a few types of polymers including representative p‐type and n‐type semiconductors, and a classical insulator, are chosen to dope into a perovskite film. The long‐chain polymer helps to form a network among the perovskite crystalline grains, as witnessed by the improved film morphology and device stability. The dewetting process is greatly suppressed by the cross‐linking effect of the polymer chains, thereby resulting in uniform perovskite films with large grain sizes. Moreover, it is found that the polymer‐doped perovskite shows a reduced trap‐state density, likely due to the polymer effectively passivating the perovskite grain surface. Meanwhile the doped polymer formed a bridge between grains for efficient charge transport. Using this approach, the solar cell efficiency is improved from 17.43% to as high as 19.19%, with a much improved stability. As it is not required for the polymer to have a strict energy level matching with the perovskite, in principle, one may use a variety of polymers for this type of device design.     

Mixed 3D–2D Passivation Treatment for Mixed‐Cation Lead Mixed‐Halide Perovskite Solar Cells for Higher Efficiency and Better Stability

Layered low‐dimensional perovskite structures employing bulky organic ammonium cations have shown significant improvement on stability but poorer performance generally compared to their 3D counterparts. Here, a mixed passivation (MP) treatment is reported that uses a mixture of bulky organic ammonium iodide (iso‐butylammonium iodide, iBAI) and formammidinium iodide (FAI), enhancing both power conversion efficiency and stability. Through a combination of inactivation of the interfacial trap sites, characterized by photoluminescence measurement, and formation of an interfacial energetic barrier by which ionic transport is reduced, demonstrated by Kelvin probe force microscopy, MP treatment of the perovskite/hole transport layer interface significantly suppresses photocurrent hysteresis. Using this MP treatment, the champion mixed‐halide perovskite cell achieves a reverse scan and stabilized power conversion efficiency of 21.7%. Without encapsulation, the devices show excellent moisture stability, sustaining over 87% of the original performance after 38 d storage in ambient environment under 75 ± 20% relative humidity. This work shows that FAI/ i BAI, is a new and promising material combination for passivating perovskite/selective‐contact interfaces.     

Stability and Dark Hysteresis Correlate in NiO‐Based Perovskite Solar Cells

In perovskite solar cells (PSCs), the interfaces are a weak link with respect to degradation. Electrochemical reactivity of the perovskite's halides has been reported for both molecular and polymeric hole selective layers (HSLs), and here it is shown that also NiO brings about this decomposition mechanism. Employing NiO as an HSL in p–i–n PSCs with power conversion efficiency (PCE) of 16.8%, noncapacitive hysteresis is found in the dark, which is attributable to the bias‐induced degradation of perovskite/NiO interface. The possibility of electrochemically decoupling NiO from the perovskite via the introduction of a buffer layer is explored. Employing a hybrid magnesium‐organic interlayer, the noncapacitive hysteresis is entirely suppressed and the device's electrical stability is improved. At the same time, the PCE is improved up to 18% thanks to reduced interfacial charge recombination, which enables more efficient hole collection resulting in higher V_oc and FF.     

Incorporating CsF into the PbI2 Film for Stable Mixed Cation‐Halide Perovskite Solar Cells

Adding a small amount of CsI into mixed cation‐halide perovskite film via a one‐step method has been demonstrated as an excellent strategy for high‐performance perovskite solar cells (PSCs). However, the one‐step method generally relies on an antisolvent washing process, which is hard to control and not suitable for fabricating large‐area devices. Here, CsF is employed and Cs is incorporated into perovskite film via a two‐step method. It is revealed that CsF can effectively diffuse into the PbI₂ seed film, and drastically enhances perovskite crystallization, leading to high‐quality Cs‐doped perovskite film with a very long photoluminescence carrier lifetime (1413 ns), remarkable light stability, thermal stability, and humidity stability. The fabricated PSCs show power conversion efficiency (PCE) of over 21%, and they are highly thermally stable: in the aging test at 60 °C for 300 h, 96% of the original PCE remains. The CsF incorporation process provides a new avenue for stable high‐performance PSCs.     

New Strategies for Defect Passivation in High‐Efficiency Perovskite Solar Cells

Lead halide perovskite solar cells now show excellent efficiencies and encouraging levels of stability. Further improvements in performance require better control of the trap states which are considered to be associated with vacancies and defects at crystallite surfaces. Herein, a reflection on the ways in which these traps can be mitigated is presented by improving the quality of the perovskite layer and interfaces in fully assembled device configurations. In this review, the most recent design strategies reported in the literature, which have been explored to tune grain orientation, to passivate defects, and to improve charge‐carrier lifetimes, are presented. Specifically, the advances made with single‐cation, mixed‐cation and/or mixed‐halide, and 3D/2D bilayer‐based light absorbers are discussed. The interfacial, compositional, and band alignment engineering along with their consequent effects on the open‐circuit voltage, power conversion efficiency, and stability are a particular focus.     

Development of Next‐Generation Organic‐Based Solar Cells: Studies on Dye‐Sensitized and Perovskite Solar Cells

Next‐generation organic solar cells such as dye‐sensitized solar cells (DSSCs) and perovskite solar cells (PSCs) are studied at the National Institute of Advanced Industrial Science and Technology (AIST), and their materials, electronic properties, and fabrication processes are investigated. To enhance the performance of DSSCs, the basic structure of an electron donor, π‐electron linker, and electron acceptor, i.e., D–π–A, is suggested. In addition, special organic dyes containing coumarin, carbazole, and triphenylamine electron donor groups are synthesized to find an effective dye structure that avoids charge recombination at electrode surfaces. Meanwhile, PSCs are manufactured using both a coating method and a laser deposition technique. The results of interfacial studies demonstrate that the level of the conduction band edge (CBE) of a compact TiO₂ layer is shifted after TiCl₄ treatment, which strongly affects the solar cell performance. Furthermore, a special laser deposition system is developed for the fabrication of the perovskite layers of PSCs, which facilitates the control over the deposition rate of methyl ammonium iodide used as their precursor.     

Enhanced Stability of Perovskite Solar Cells Incorporating Dopant‐Free Crystalline Spiro‐OMeTAD Layers by Vacuum Sublimation

The main handicap still hindering the eventual exploitation of organometal halide perovskite‐based solar cells is their poor stability under prolonged illumination, ambient conditions, and increased temperatures. This article shows for the first time the vacuum processing of the most widely used solid‐state hole conductor (SSHC), i.e., the Spiro‐OMeTAD [2,2′,7,7′‐tetrakis (N,N‐di‐p‐methoxyphenyl‐amine) 9,9′‐spirobifluorene], and how its dopant‐free crystalline formation unprecedently improves perovskite solar cell (PSC) stability under continuous illumination by about two orders of magnitude with respect to the solution‐processed reference and after annealing in air up to 200 °C. It is demonstrated that the control over the temperature of the samples during the vacuum deposition enhances the crystallinity of the SSHC, obtaining a preferential orientation along the π–π stacking direction. These results may represent a milestone toward the full vacuum processing of hybrid organic halide PSCs as well as light‐emitting diodes, with promising impacts on the development of durable devices. The microstructure, purity, and crystallinity of the vacuum sublimated Spiro‐OMeTAD layers are fully elucidated by applying an unparalleled set of complementary characterization techniques, including scanning electron microscopy, X‐ray diffraction, grazing‐incidence small‐angle X‐ray scattering and grazing‐incidence wide‐angle X‐ray scattering, X‐ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy.     

3D–2D–0D Interface Profiling for Record Efficiency All‐Inorganic CsPbBrI2 Perovskite Solar Cells with Superior Stability

All‐inorganic CsPbBrI₂ perovskite has great advantages in terms of ambient phase stability and suitable band gap (1.91 eV) for photovoltaic applications. However, the typically used structure causes reduced device performance, primarily due to the large recombination at the interface between the perovskite, and the hole‐extraction layer (HEL). In this paper, an efficient CsPbBrI₂ perovskite solar cell (PSC) with a dimensionally graded heterojunction is reported, in which the CsPbBrI₂ material is distributed within bulk–nanosheet–quantum dots or 3D–2D–0D dimension‐profiled interface structure so that the energy alignment is optimized in between the valence and conduction bands of both CsPbBrI₂ and the HEL layers. Specifically, the valence‐/conduction‐band edge is leveraged to bend with synergistic advantages: the graded combination enhances the hole extraction and conduction efficiency with effectively decreased recombination loss during the hole‐transfer process, leading to an enhanced built‐in electric field, hence a high V_OC of as much as 1.19 V. The profiled structure induces continuously upshifted energy levels, resulting in a higher J_SC of as much as 12.93 mA cm^?2 and fill factor as high as 80.5%, and therefore record power conversion efficiency (PCE) of 12.39%. As far as it is known, this is the highest PCE for CsPbBrI₂ perovskite‐based PSC.     

Precursor Engineering for Ambient‐Compatible Antisolvent‐Free Fabrication of High‐Efficiency CsPbI2Br Perovskite Solar Cells

High temperature stable inorganic CsPbX₃ (X: I, Br, or mixed halides) perovskites with their bandgap tailored by tuning the halide composition offer promising opportunities in the design of ideal top cells for high‐efficiency tandem solar cells. Unfortunately, the current high‐efficiency CsPbX₃ perovskite solar cells (PSCs) are prepared in vacuum, a moisture‐free glovebox or other low‐humidity conditions due to their poor moisture stability. Herein, a new precursor system (HCOOCs, HPbI₃, and HPbBr₃) is developed to replace the traditional precursors (CsI, PbI₂, and PbBr₂) commonly used for solar cells of this type. Both the experiments and calculations reveal that a new complex (HCOOH?Cs⁺) is generated in this precursor system. The new complex is not only stable against aging in humid air ambient at 91% relative humidity, but also effectively slows the perovskite crystallization, making it possible to eliminate the popular antisolvent used in the perovskite CsPbI₂Br film deposition. The CsPbI₂Br PSCs based on the new precursor system achieve a champion efficiency of 16.14%, the highest for inorganic PSCs prepared in ambient air conditions. Meanwhile, high air stability is demonstrated for an unencapsulated CsPbI₂Br PSC with 92% of the original efficiency remaining after more than 800 h aging in ambient air.     

Emerging 2D Layered Materials for Perovskite Solar Cells

Perovskite solar cells (PSCs) are now at the forefront of the state‐of‐the‐art photovoltaic technologies due to their high efficiency and low fabrication costs. To further realize the potential of this fascinating class of solar cells, nanostructured functional materials have been playing important roles. 2D layered materials have attracted a great deal of interest due to their fascinating properties and unique structure. Recently, the exploration of a wide range of novel 2D materials for use in PSCs has seen considerable progress, but still a lot remains to be done in this field. In this progress report, the advancements that have recently been made in the application of these emerging 2D materials, beyond graphene, for PSCs are presented. Both the advantages and challenges of these 2D materials for PSCs are highlighted. Finally, important directions for the future advancements toward efficient, low‐cost, and stable PSCs are outlined.     

High‐Performance Thickness Insensitive Perovskite Solar Cells with Enhanced Moisture Stability

High‐performance perovskite solar cells (PVSCs) with absorber layer thickness insensitive features are important for practical fabrication, however these features are difficult to be realized. There are very few reports of the fabrication of polycrystalline PVSCs with power conversion efficienies (PCE) insensitive to film thickness beyond 600 nm. The main reason lies in more serious recombination of the thick perovskite layer compared to the thin layer. Herein, this challenge is addressed by a simple hot casting method to formulate high‐quality perovskite film with enlarged grain size, high carrier mobility, and reduced defects. It is found that increasing the temperature to 70 °C can dramatically increase the film thickness and enlarge the perovskite crystal, therefore boost the efficiency from ≈16% to ≈19%. Notably, a record PCE of 19.54% is achieved with 850 nm thick perovskite film, which is among the highest efficiency for thick‐film PVSCs. The PCE remains steady around 19% when modifying the perovskite layer from 700 to 1150 nm. Moreover, these thick‐film PVSCs show good stability with 80% of its initial efficiency after 30 d in air with a humidity of 50%. Overall, this simple yet effective method has a great potential in the mass manufacture of PVSCs.     

Self‐Assembly Atomic Stacking Transport Layer of 2D Layered Titania for Perovskite Solar Cells with Extended UV Stability

A novel atomic stacking transporting layer (ASTL) based on 2D atomic sheets of titania (Ti_1?δO₂) is demonstrated in organic–inorganic lead halide perovskite solar cells. The atomically thin ASTL of 2D titania, which is fabricated using a solution‐processed self‐assembly atomic layer‐by‐layer deposition technique, exhibits the unique features of high UV transparency and negligible (or very low) oxygen vacancies, making it a promising electron transporting material in the development of stable and high‐performance perovskite solar cells. In particular, the solution‐processable atomically thin ASTL of 2D titania atomic sheets shows superior inhibition of UV degradation of perovskite solar cell devices, compared to the conventional high‐temperature sintered TiO₂ counterpart, which usually causes the notorious instability of devices under UV irradiation. The discovery opens up a new dimension to utilize the 2D layered materials with a great variety of homostructrual or heterostructural atomic stacking architectures to be integrated with the fabrication of large‐area photovoltaic or optoelectronic devices based on the solution processes.