Inorganic Ammonium Halide Additive Strategy for Highly Efficient and Stable CsPbI3 Perovskite Solar Cells

All-inorganic perovskite cesium lead iodide (CsPbI₃) exhibits excellent prospects for commercial application as a light absorber in single-junction or tandem solar cells due to its outstanding thermal stability and proper bandgap. However, the device performance of CsPbI₃-based perovskite solar cells (PSCs) is still restricted by the unsatisfactory crystal quality and severe non-radiative recombination. Herein, inorganic additive ammonium halides are introduced into the precursor solution to regulate the nucleation and crystallization of the CsPbI₃ film by exploiting the atomic interaction between the ammonium group and the Pb–I framework. The grain boundaries and interfacial contact of the CsPbI₃ film have been improved, which leads to significant suppression in the non-radiative recombination and an enhancement in the charge transport ability. With these benefits, a high efficiency of 18.7% together with an extraordinarily high fill factor of 0.83–0.84 has been achieved, comparable to the highest records reported so far. Moreover, the cell exhibits ultra-high photoelectrical stability under continuous light illumination and high bias voltage with 96% of its initial power-conversion efficiency being sustained after 2000 h operation, even superior to the world-champion CsPbI₃ solar cell. The findings are promising for the development and application of all-inorganic PSCs using a simple inorganic additive strategy.     

One-Source Strategy Boosting Dopant-Free Hole Transporting Layers for Highly Efficient and Stable CsPbI2Br Perovskite Solar Cells

All-inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their organic–inorganic hybrid counterparts. However, the inferior film quality and doped hole transport layer (HTL) have a strong tendency to degrade the perovskite under high temperatures or harsh operating conditions. To solve these problems, a one-source strategy using the same polymer donor material (PDM) to simultaneously dope CsPbI₂Br perovskite films via antisolvent engineering and fabricating the HTL is proposed. The doping assists perovskite film growth and forms a top–down gradient distribution, generating CsPbI₂Br with enlarged grain size and reduced defect density. The PDM as the HTL suppresses the energy barrier and forms favorable electrical contacts for hole extraction, and assemble into a fingerprint-like morphology that improves the conductivity, facilitating the creation of a dopant-free HTL. Based on this one-source strategy using PBDB-T as PDM, the CsPbI₂Br perovskite solar cell with a dopant-free HTL achieves a power conversion efficiency (PCE) of 16.40%, which is one of the highest PCEs reported among all-inorganic CsPbI₂Br pero-SCs with a dopant-free HTL. Importantly, the devices exhibit the highest thermal stability at 85 °C and operational stability under continuous illumination even with Ag as the top electrode and present good universality.     

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.     

In Situ Growth of 2D Perovskite Capping Layer for Stable and Efficient Perovskite Solar Cells

2D halide perovskites have recently been recognized as a promising avenue in perovskite solar cells (PSCs) in terms of encouraging stability and defect passivation effect. However, the efficiency (less than 15%) of ultrastable 2D Ruddlesden–Popper PSCs still lag far behind their traditional 3D perovskite counterparts. Here, a rationally designed 2D‐3D perovskite stacking‐layered architecture by in situ growing 2D PEA₂PbI₄ capping layers on top of 3D perovskite film, which drastically improves the stability of PSCs without compromising their high performance, is reported. Such a 2D perovskite capping layer induces larger Fermi‐level splitting in the 2D‐3D perovskite film under light illumination, resulting in an enhanced open‐circuit voltage (V_oc) and thus a higher efficiency of 18.51% in the 2D‐3D PSCs. Time‐resolved photoluminescence decay measurements indicate the facilitated hole extraction in the 2D‐3D stacking‐layered perovskite films, which is ascribed to the optimized energy band alignment and reduced nonradiative recombination at the subgap states. Benefiting from the high moisture resistivity as well as suppressed ion migration of the 2D perovskite, the 2D‐3D PSCs show significantly improved long‐term stability, retaining nearly 90% of the initial power conversion efficiency after 1000 h exposure in the ambient conditions with a high relative humidity level of 60 ± 10%.     

Efficient and Stable Mesoscopic Perovskite Solar Cells Using PDTITT as a New Hole Transporting Layer

Stability is the main challenge in the field of organic–inorganic perovskite solar cells (PSCs). Finding low‐cost and stable hole transporting layer (HTL) is an effective strategy to address this issue. Here, a new donor polymer, poly(5,5‐didecyl‐5H‐1,8‐dithia‐as‐indacenone‐alt‐thieno[3,2‐b]thiophene) (PDTITT), is synthesized and employed as an HTL in PSCs, which has a suitable band alignment with respect to the double‐A cation perovskite film. Using PDTITT, the hole extraction in PSCs is greatly improved as compared to commonly used HTLs such as 2,2′,7,7′‐tetrakis[N,N‐di(4‐methoxyphenyl)amino]‐9,9′‐spirobifluorene (spiro‐OMeTAD), addressing the hysteresis issue. After careful optimization, an efficient PSC is achieved based on mesoscopic TiO₂ electron transporting layer with a maximum power conversion efficiency (PCE) of 18.42% based on PDTITT HTL, which is comparable with spiro‐OMeTAD‐based PSC (19.21%). Since spiro‐based PSCs suffer from stability issue, the operational stability in the PSC with PDTITT HTL is studied. It is found that the device with PDTITT retains 88% of its initial PCE value after 200 h under illumination, which is better than the spiro‐based PSC (54%).     

Constructing All-Inorganic Perovskite/Fluoride Nanocomposites for Efficient and Ultra-Stable Perovskite Solar Cells

Organic-inorganic hybrid perovskite solar cells (PSCs) have rapidly developed over the past decade and have achieved the latest certified power conversion efficiency (PCE) up to 25.5%. However, unsatisfactory long-term operational stability for these hybrid PSCs remains a huge obstacle to further development and commercialization. Herein, a unique hetero-structured CsPbI₃/CaF₂ perovskite/fluoride nanocomposites (PFNCs) is fabricated via a newly developed facile two-step hetero-epitaxial growth strategy to deliver efficient and ultra-stable PSCs. After being incorporated into the crystal lattice of α-phase CsPbI₃ perovskite, the cubic-phase CaF₂ in the resultant CsPbI₃/CaF₂ PFNCs can not only passivate the intrinsic defects of CsPbI₃ perovskite itself but also effectively suppress the notorious ion migration in hybrid perovskite Cs_0.05FA_0.81MA_0.14PbI_2.55Br_0.45 (CsFAMA) thin-films of PSCs. As such, the CsFAMA PSC devices based on CsPbI₃/CaF₂-deposited perovskite thin-film achieve a mean PCE of 20.45%, in sharp contrast to 19.33% of the control devices without deposition. Specifically, the CsPbI₃/CaF₂-deposited PSC retains 85% of its original PCE after 1000 h continuous operation at the maximum power point under AM 1.5G solar light, far better than those of the control and CsPbI₃-deposited PSCs with a device T₈₅ lifetime of 315 and 125 h, respectively.     

Inorganic Electron Transport Materials in Perovskite Solar Cells

In the past decade, the perovskite solar cell (PSC) has attracted tremendous attention thanks to the substantial efforts in improving the power conversion efficiency from 3.8% to 25.5% for single-junction devices and even perovskite-silicon tandems have reached 29.15%. This is a result of improvement in composition, solvent, interface, and dimensionality engineering. Furthermore, the long-term stability of PSCs has also been significantly improved. Such rapid developments have made PSCs a competitive candidate for next-generation photovoltaics. The electron transport layer (ETL) is one of the most important functional layers in PSCs, due to its crucial role in contributing to the overall performance of devices. This review provides an up-to-date summary of the developments in inorganic electron transport materials (ETMs) for PSCs. The three most prevalent inorganic ETMs (TiO₂, SnO_2, and ZnO) are examined with a focus on the effects of synthesis and preparation methods, as well as an introduction to their application in tandem devices. The emerging trends in inorganic ETMs used for PSC research are also reviewed. Finally, strategies to optimize the performance of ETL in PSCs, effects the ETL has on J–V hysteresis phenomenon and long-term stability with an outlook on current challenges and further development are discussed.     

Multifunctional Cross-Linked Polyurethane Polymer as Interface Layer for Efficient and Stable Perovskite Solar Cells

In the past decade, perovskite solar cells (PSCs) have made remarkable progress in improving power conversion efficiency (PCE). In order to further improve the photovoltaic performance and long-term stability of PSCs, the interface layer is essential. A multifunctional cross-linked polyurethane (CLPU) is designed and synthesized via the spontaneous quaternization of polyurethane and 1, 6-diiodohexane on the surface of the perovskite layer. CLPU layer cannot only effectively induce secondary crystallization and passivate the surface defects of perovskite, reduce the non-radiative recombination, but also effectively block the moisture invasion. By this strategy, Cs_0.05FA_0.95PbI₃ PSCs with excellent reproducibility, is realized, achieving a PCE of 23.14% with an open-circuit voltage of 1.11 V, a short-circuit current density of 25.69 mA cm⁻², and a fill factor of 0.81. In addition, the unencapsulated devices show enhanced stability in 35 ± 5% relative humidity (RH) near 3000 h and in 65 ± 5% RH over 700 h. This study provides valuable insights into the role of CLPU interface layer in PSCs, which are essential for the design of high-performance devices.     

Efficient and Thermally Stable Wide Bandgap Perovskite Solar Cells by Dual-Source Vacuum Deposition

Wide bandgap perovskites are being widely studied in view of their potential applications in tandem devices and other semitransparent photovoltaics. Vacuum deposition of perovskite thin films is advantageous as it allows the fabrication of multilayer devices, fine control over thickness and purity, and it can be upscaled to meet production needs. However, the vacuum processing of multicomponent perovskites (typically used to achieve wide bandgaps) is not straightforward, because one needs to simultaneously control several thermal sources during the deposition. Here a simplified dual-source vacuum deposition method to obtain wide bandgap perovskite films is shown. The solar cells obtained with these materials have similar or even larger efficiency as those including multiple A-cations, but are much more thermally stable, up to 3500 h at 85 °C for a perovskite with a bandgap of 1.64 eV. With optimized thickness, record efficiency of >19% and semitransparent devices with stabilized power output in excess of 17% are achieved.     

P3HT为空穴传输层的碳基钙钛矿太阳电池

碳电极具有成本低、印刷方便、可有效隔离水氧等优点,因此有望利用碳电极材料实现低成本、高稳定性的钙钛矿太阳电池。无空穴传输层的传统碳基钙钛矿太阳电池面临着空穴提取率低、电子逆向传输,钙钛矿和碳电极界面的载流子复合等问题。文章引入聚(3-己基噻吩)(P3HT)作为器件的空穴传输层,使碳基钙钛矿太阳电池ITO/SnO₂/MAPbI₃/P3HT/Carbon的光伏性能得到了显著改善:器件的光电转化效率从11.16% 提高到13.37%。在氮气环境下,连续光照1000h,太阳电池的光电转化效率可保持初始值的87%,而传统器件在光照500h后,其光电转化效率已下降至初始值的60%。     

Organic Ionic Plastic Crystals as Hole Transporting Layer for Stable and Efficient Perovskite Solar Cells

Organic ionic plastic crystals (OIPCs) are synthesized through a simple metal‐free, cost‐effective approach. The strategized synchronization of electron‐rich phenoxazine with benzimidazolium iodide (OIPC‐I) and bromide (OIPC‐Br) salts lead to enhanced hole mobility and conductivity of OIPCs which is suitable for an efficient alternative to conventional organic hole transporting materials (HTMs) for stable perovskite solar cells (PSCs). The fabricated PSCs with OIPC‐I as hole transporting layer yielded a power conversion efficiency of 15.0% and 18.1% without and with additive (Li salt) respectively, which are comparable with spiro‐OMeTAD based devices prepared under similar conditions. Furthermore, the PSCs with OIPCs show good stability compared to the spiro‐OMeTAD with or without additives. Here, first time benzimidazolium‐based OIPCs have been used as an alternative organic HTM for perovskite solar cells, which opens a window for the design of effective OIPCs for highly efficient PSCs with long‐term stability.     

Controlled n‐Doping in Air‐Stable CsPbI2Br Perovskite Solar Cells with a Record Efficiency of 16.79%

Cesium‐based inorganic perovskites, such as CsPbI₂Br, are promising candidates for photovoltaic applications owing to their exceptional optoelectronic properties and outstanding thermal stability. However, the power conversion efficiency of CsPbI₂Br perovskite solar cells (PSCs) is still lower than those of hybrid PSCs and inorganic CsPbI₃ PSCs. In this work, passivation and n‐type doping by adding CaCl₂ to CsPbI₂Br is demonstrated. The crystallinity of the CsPbI₂Br perovskite film is enhanced, and the trap density is suppressed after adding CaCl₂. In addition, the Fermi level of the CsPbI₂Br is changed by the added CaCl₂ to show heavy n‐type doping. As a result, the optimized CsPbI₂Br PSC shows a highest open circuit voltage of 1.32 V and a record efficiency of 16.79%. Meanwhile, high air stability is demonstrated for a CsPbI₂Br PSC with 90% of the initial efficiency remaining after more than 1000 h aging in air.     

Self‐Crystallized Multifunctional 2D Perovskite for Efficient and Stable Perovskite Solar Cells

Recently, perovskite solar cells (PSC) with high power‐conversion efficiency (PCE) and long‐term stability have been achieved by employing 2D perovskite layers on 3D perovskite light absorbers. However, in‐depth studies on the material and the interface between the two perovskite layers are still required to understand the role of the 2D perovskite in PSCs. Self‐crystallization of 2D perovskite is successfully induced by deposition of benzyl ammonium iodide (BnAI) on top of a 3D perovskite light absorber. The self‐crystallized 2D perovskite can perform a multifunctional role in facilitating hole transfer, owing to its random crystalline orientation and passivating traps in the 3D perovskite. The use of the multifunctional 2D perovskite (M2P) leads to improvement in PCE and long‐term stability of PSCs both with and without organic hole transporting material (HTM), 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenyl‐amine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) compared to the devices without the M2P.     

Highly Efficient and Stable Wide-Bandgap Perovskite Solar Cells via Strain Management

Wide-bandgap (WBG) perovskite solar cells (PSCs) with high performance and stability are in considerable demand to boost tandem solar cell efficiencies. Perovskite bandgap broadening results in a high barrier for enhancing the efficiency of PSCs and phase segregation in perovskite. In this study, it is shown that the residual strain is the key factor affecting the WBG perovskite device efficiency and stability. The dimethyl sulfoxide addition helps lead halide with opening the layer spacing to form intermediate phases that provide more nucleation sites to eliminate lattice mismatch with organic components, which dominates the strain effects on the WBG perovskite growth in a sequential deposition. By minimizing the strain, 1.67 and 1.77 eV nip devices with record efficiencies of 22.28% and 20.45%, respectively, can be achieved. The greatly suppressed phase segregation enables the devices with retained 90–95% of initial efficiency over 4000 h of damp stability and 80–90% of initial efficiency over 700 h of maximum-power-point (MPP) stability. Besides, the 1.67 eV pin devices can achieve a competitive 22.3% efficiency with considerable damp-heat, pre-ultraviolet (pre-UV) aging and MPP tracking stability according to IEC 61215. The final efficiency of more than 28.3% for the perovskite/Si tandem is obtained.     

Metal Oxide Charge Transport Layers for Efficient and Stable Perovskite Solar Cells

Currently, the efficiency of perovskite solar cells (PSCs) is ≈24%. For the fabrication of such high efficiency PSCs, it is necessary to use both electron and hole transport layers to effectively separate the charges generated by light absorption of the perovskite layer and selectively transfer the separated electrons and holes. In addition to the efficiency, the materials used for transporting charges must be resilient to light, heat, and moisture to ensure long‐term stability of PSCs; furthermore, low‐cost fabrication is required to form a charge transport layer at low temperatures by a solution process. For this purpose, metal oxides are best suited as charge transport materials for PSCs because of their advantages such as low cost, long‐term stability, and high efficiency. In this Review, the metal oxide electron and hole transport materials used in PSCs are reviewed and preparation of these materials is summarized. Finally, the challenges and future research direction for metal oxide‐based charge transport materials are described.     

Efficient and Stable Inverted Wide-Bandgap Perovskite Solar Cells and Modules Enabled by Hybrid Evaporation-Solution Method

Wide-bandgap perovskite solar cells (WBG-PSCs), when partnered with Si bottom cells in tandem configuration, can provide efficiencies up to 44%; yet, the development of stable, efficient, and scalable WBG-PSCs is required. Here, the utility of the hybrid evaporation-solution method (HESM) is investigated to meet these demanding requirements via its unique advantages including ease of control and reproducibility. A PbI₂/CsBr layer is co-evaporated followed by coating of organic-halide solutions in a green solvent. Bandgaps between 1.55–1.67 eV are systematically screened by varying CsBr and MABr content. Champion efficiencies of 21.06% and 20.35% in cells and 19.83% and 18.73% in mini-modules (16 cm²) for perovskites with 1.64 and 1.67 eV bandgaps are achieved, respectively. Additionally, 18.51%-efficient semi-transparent WBG-PSCs are implemented in 4T perovskite/bifacial silicon configuration, reaching a projected power output of 30.61 mW cm⁻² based on PD IEC TS 60904-1-2 (BiFi200) protocol. Despite similar bandgaps achieved by incorporating Br via MABr solution and/or CsBr evaporation, PSCs having a perovskite layer without MABr addition show significantly higher thermal and moisture stability. This study proves scalable, high-performance, and stable WBG-PSCs are enabled by HESM, hence their use in tandems and in emerging applications such as indoor photovoltaics are now within reach.     

Tailoring Multifunctional Self-Assembled Hole Transporting Molecules for Highly Efficient and Stable Inverted Perovskite Solar Cells

The self-assembled hole transporting molecules (SAHTMs) bearing anchoring groups have been established as the hole transporting layers (HTLs) for highly efficient p–i–n perovskite solar cells (PSCs), yet their stability and engineering at the molecular level remain challenging. A topological design of highly anisotropic aligned SAHTM-based HTLs for operationally stable PSCs that exhibit exceptional solar-to-electric power conversion efficiencies (PCEs) is demonstrated. The judiciously designed multifunctional self-assembled molecules comprise the donor–acceptor subunit for hole transporting and the phosphonic acid group for anchoring, realizing face-on π-stacking parallel to the transparent conductive oxide substrate. The high affinity of SAHTMs to the multi-crystalline perovskite thin film benefits passivating the perovskite buried interface, strengthening interfacial contact while facilitating interfacial hole transfer. Consequently, highly efficient p–i–n PSC devices are obtained with a champion PCE of 23.24% and outstanding operational stability toward various environmental factors including long-term full sunlight soaking at evaluated temperatures. Perovskite solar modules with a champion efficiency approaching 20% are also fabricated for an active device area above 17 cm².     

Multifunctional Enhancement for Highly Stable and Efficient Perovskite Solar Cells

With a certified efficiency as high as 25.2%, perovskite has taken the crown as the highest efficiency thin film solar cell material. Unfortunately, serious instability issues must be resolved before perovskite solar cells (PSCs) are commercialized. Aided by theoretical calculation, an appropriate multifunctional molecule, 2,2-difluoropropanediamide (DFPDA), is selected to ameliorate all the instability issues. Specifically, the carbonyl groups in DFPDA form chemical bonds with Pb²⁺ and passivate under-coordinated Pb²⁺ defects. Consequently, the perovskite crystallization rate is reduced and high-quality films are produced with fewer defects. The amino groups not only bind with iodide to suppress ion migration but also increase the electron density on the carbonyl groups to further enhance their passivation effect. Furthermore, the fluorine groups in DFPDA form both an effective barrier on the perovskite to improve its moisture stability and a bridge between the perovskite and HTL for effective charge transport. In addition, they show an effective doping effect in the HTL to improve its carrier mobility. With the help of the combined effects of these groups in DFPDA, the PSCs with DFPDA additive achieve a champion efficiency of 22.21% and a substantially improved stability against moisture, heat, and light.     

A Regularity-Based Fullerene Interfacial Layer for Efficient and Stable Perovskite Solar Cells via Blade-Coating

The electron transport layer (ETL) plays a crucial part in extracting electron carriers while optimizing the interfacial contact of perovskite/electrode in planar heterojunction perovskite solar cells (PVSCs). Despite various ETLs being designed for efficient PVSCs, there exists hardly any research on the effect of molecular stacking order on device performance. Herein, poly(ethylene-co-vinyl acetate) (EVA) is employed as the [6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM) solution additive. The strong binding energy between EVA with PC₆₁BM promotes the molecular stacking order of ETLs, which alleviates the morphology inhomogeneity, possesses a matched energy level, blocks ion migration, and improves the water–oxygen barrier of perovskite devices. The blade-coated MAPbI₃-based PVSCs achieve a power conversion efficiency (PCE) of 19.32% with positive reproducibility and negligible hysteresis, as well as maintain 90% and 80% of the initial PCE after storage under inert and ambient conditions (52% humidity) for 1500 h without encapsulation. This strategy also improves the champion PCE of CsFAMA-based PVSCs to 20.33%. These findings demonstrate that the regulation of molecular stacking order is a valid approach to optimize interfacial charge-carrier recombination in PVSCs, which meet the demand for high-performance ETL in large-area PVSCs and improve the upscaling of the fabrication technology toward practical applications.