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.     

Extrinsic Ion Distribution Induced Field Effect in CsPbIBr2 Perovskite Solar Cells

Excellent power conversion efficiency (PCE) and stability are the primary forces that propel the all‐inorganic cesium‐based halide perovskite solar cells (PSCs) toward commercialization. However, the intrinsic high density of trap state and internal nonradiative recombination of CsPbIBr₂ perovskite film are the barriers that limit its development. In the present study, a facile additive strategy is introduced to fabricate highly efficient CsPbIBr₂ PSCs by incorporating sulfamic acid sodium salt (SAS) into the perovskite layer. The additive can control the crystallization behaviors and optimize morphology, as well as effectively passivate defects in the bulk perovskite film, thereby resulting in a high‐quality perovskite. In addition, SAS in perovskite has possibly introduced an additional internal electric field effect that favors electron transport and injection due to inhomogeneous ion distribution. A champion PCE of 10.57% (steady‐output efficiency is 9.99%) is achieved under 1 Sun illumination, which surpasses that of the contrast sample by 16.84%. The modified perovskite film also exhibits improved moisture stability. The unencapsulated device maintains over 80% initial PCE after aging for 198 h in air. The results provide a suitable additive for inorganic perovskite and introduce a new conjecture to explain the function of additives in PSCs more rationally.     

In Situ Real‐Time Study of the Dynamic Formation and Conversion Processes of Metal Halide Perovskite Films

Metal halide perovskite solar cells (PSCs) have advanced to the forefront of solution‐processed photovoltaic techniques and made stunning progress in power conversion efficiency (PCE). Further improvements in device performances rely on perfecting the structure and morphology of perovskite films. However, undesirable defects such as pinholes and grain boundaries are often created in film preparations due to lack of knowledge of the precise reaction mechanism. Here, in situ grazing‐incidence X‐ray diffraction (GI‐XRD) investigations are performed, facilitated by other techniques, on the formation of the widely adopted MAPbI₃ (MA = methylammonium) perovskite films from their intermediate adduct (IA) phases. The influences of solvent vapor atmospheres on MAPbI₃ films are also systematically investigated, where the dynamic conversion processes between different phases are visualized in real time. Further in situ GI‐XRD and infrared spectroscopy measurements reveal that the IA phases contain both N,N‐dimethylformamide and dimethyl sulfoxide (DMSO) as coordinating molecules. By tuning the DMSO concentration in perovskite precursors, the ideal perovskite film is formed and the best PCE is achieved for the planar MAPbI₃‐based PSCs. These findings highlight the role of IA phases and the effect of solvent atmospheres on the quality of perovskite films, providing direct insights into their growth mechanism.     

A Novel Conductive Mesoporous Layer with a Dynamic Two‐Step Deposition Strategy Boosts Efficiency of Perovskite Solar Cells to 20%

Lead halide perovskite solar cells (PSCs) with the high power conversion efficiency (PCE) typically use mesoporous metal oxide nanoparticles as the scaffold and electron‐transport layers. However, the traditional mesoporous layer suffers from low electron conductivity and severe carrier recombination. Here, antimony‐doped tin oxide nanorod arrays are proposed as novel transparent conductive mesoporous layers in PSCs. Such a mesoporous layer improves the electron transport as well as light utilization. To resolve the common problem of uneven growth of perovskite on rough surface, the dynamic two‐step spin coating strategy is proposed to prepare highly smooth, dense, and crystallized perovskite films with micrometer‐scale grains, largely reducing the carrier recombination ratio. The conductive mesoporous layer and high‐quality perovskite film eventually render the PSC with a remarkable PCE of 20.1% with excellent reproducibility. These findings provide a new avenue to further design high‐efficiency PSCs from the aspect of carrier transport and recombination.     

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.     

Combining Efficiency and Stability in Mixed Tin–Lead Perovskite Solar Cells by Capping Grains with an Ultrathin 2D Layer

The development of narrow-bandgap (E_g ≈ 1.2 eV) mixed tin–lead (Sn–Pb) halide perovskites enables all-perovskite tandem solar cells. Whereas pure-lead halide perovskite solar cells (PSCs) have advanced simultaneously in efficiency and stability, achieving this crucial combination remains a challenge in Sn–Pb PSCs. Here, Sn–Pb perovskite grains are anchored with ultrathin layered perovskites to overcome the efficiency-stability tradeoff. Defect passivation is achieved both on the perovskite film surface and at grain boundaries, an approach implemented by directly introducing phenethylammonium ligands in the antisolvent. This improves device operational stability and also avoids the excess formation of layered perovskites that would otherwise hinder charge transport. Sn–Pb PSCs with fill factors of 79% and a certified power conversion efficiency (PCE) of 18.95% are reported—among the highest for Sn–Pb PSCs. Using this approach, a 200-fold enhancement in device operating lifetime is achieved relative to the nonpassivated Sn–Pb PSCs under full AM1.5G illumination, and a 200 h diurnal operating time without efficiency drop is achieved under filtered AM1.5G illumination.     

Highly Efficient and Stable Perovskite Solar Cells: Competitive Crystallization Strategy and Synergistic Passivation

Defects of perovskite (PVK) films are one of the main obstacles to achieving high-performance perovskite solar cells (PSCs). Here, the authors fabricated highly efficient and stable PSCs by introducing prolinamide (ProA) into the PbI₂ precursor solution, which improves the performance of PSCs by the competitive crystallization and efficient defect passivation of perovskite. The theoretical and experimental results indicate that ProA forms an adduct with PbI₂, competes with free I⁻ to coordinate with Pb²⁺, leads to the increase of the energy barrier of crystallization, and slows down the crystallization rate. Furthermore, the dual-site synergistic passivation of ProA is revealed by density functional theory (DFT) calculations and experimental results. ProA effectively reduces non-radiative recombination in the resultant films to improve the photovoltaic performance of PSCs. Notably, ProA-assisted PSCs achieve 24.61% power conversion efficiency (PCE) for the champion device and the stability of PSCs devices under ambient and thermal environments is improved.     

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.     

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).     

Advances in cesium lead iodide perovskite solar cells: Processing science matters

The prevailing perovskite solar cells (PSCs) employ hybrid organic–inorganic halide perovskites as light absorbers, but these materials exhibit relatively poor environmental stability, which potentially hinders the practical deployment of PSCs. One important strategy to address this issue is replacing the volatile and hygroscopic organic cations with inorganic cesium cations in the crystal structure, forming all-inorganic halide perovskites. In this context, CsPbI₃ perovskite is drawing phenomenal attention, primarily because it exhibits an ideal bandgap of 1.7 eV for the use in tandem solar cells, and it shows significantly enhanced thermal stability that is the key to the long-term device operation. Within only half a decade, the power conversion efficiency (PCE) of CsPbI₃ PSCs has ramped beyond 20%, which has been driven by inventions of numerous processing methods for high-quality CsPbI₃ perovskite thin films. These methods are broadly classified into three categories: vapor deposition, nanocrystals assembly, and solution deposition. Herein we present a systematic review on these methods and related materials sciences. In particular, we comprehensively discuss the dimethylammonium-additive-based solution deposition, which has resulted into the best-performing CsPbI₃ PSCs. We also present the challenges and prospects on future research towards the realization of the full potential of CsPbI₃ PSCs.     

Superfast Room‐Temperature Activation of SnO2 Thin Films via Atmospheric Plasma Oxidation and their Application in Planar Perovskite Photovoltaics

The power conversion efficiency (PCE) of perovskite solar cells (PSCs) has now exceeded 20%; thus, research focus has shifted to establishing the foundations for commercialization. One of the pivotal themes is to curtail the overall fabrication time, to reduce unit cost, and mass‐produce PSCs. Additionally, energy dissipation during the thermal annealing (TA) stage must be minimized by realizing a genuine low‐temperature (LT) process. Here, tin oxide (SnO₂) thin films (TFs) are formulated at extremely high speed, within 5 min, under an almost room‐temperature environment (<50 °C), using atmospheric Ar/O₂ plasma energy (P‐SnO₂) and are applied as an electron transport layer of a “n–i–p”‐type planar PSC. Compared with a thermally annealed SnO₂ TF (T‐SnO₂), the P‐SnO₂ TF yields a more even surface but also outstanding electrical conductivity with higher electron mobility and a lower number of charge trap sites, consequently achieving a superior PCE of 19.56% in P‐SnO₂‐based PSCs. These findings motivate the use of a plasma strategy to fabricate various metal oxide TFs using the sol–gel route.     

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.     

Effective Carrier‐Concentration Tuning of SnO2 Quantum Dot Electron‐Selective Layers for High‐Performance Planar Perovskite Solar Cells

The carrier concentration of the electron‐selective layer (ESL) and hole‐selective layer can significantly affect the performance of organic–inorganic lead halide perovskite solar cells (PSCs). Herein, a facile yet effective two‐step method, i.e., room‐temperature colloidal synthesis and low‐temperature removal of additive (thiourea), to control the carrier concentration of SnO₂ quantum dot (QD) ESLs to achieve high‐performance PSCs is developed. By optimizing the electron density of SnO₂ QD ESLs, a champion stabilized power output of 20.32% for the planar PSCs using triple cation perovskite absorber and 19.73% for those using CH₃NH₃PbI₃ absorber is achieved. The superior uniformity of low‐temperature processed SnO₂ QD ESLs also enables the fabrication of ≈19% efficiency PSCs with an aperture area of 1.0 cm² and 16.97% efficiency flexible device. The results demonstrate the promise of carrier‐concentration‐controlled SnO₂ QD ESLs for fabricating stable, efficient, reproducible, large‐scale, and flexible planar PSCs.     

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.     

Realizing Reduced Imperfections via Quantum Dots Interdiffusion in High Efficiency Perovskite Solar Cells

Realization of reduced ionic (cationic and anionic) defects at the surface and grain boundaries (GBs) of perovskite films is vital to boost the power conversion efficiency of organic–inorganic halide perovskite (OIHP) solar cells. Although numerous strategies have been developed, effective passivation still remains a great challenge due to the complexity and diversity of these defects. Herein, a solid-state interdiffusion process using multi-cation hybrid halide perovskite quantum dots (QDs) is introduced as a strategy to heal the ionic defects at the surface and GBs. It is found that the solid-state interdiffusion process leads to a reduction in OIHP shallow defects. In addition, Cs⁺ distribution in QDs greatly influences the effectiveness of ionic defect passivation with significant enhancement to all photovoltaic performance characteristics observed on treating the solar cells with Cs_0.05(MA_0.17FA_0.83)_0.95PbBr₃ (abbreviated as QDs-Cs5). This enables power conversion efficiency (PCE) exceeding 21% to be achieved with more than 90% of its initial PCE retained on exposure to continuous illumination of more than 550 h.     

A Highly Emissive Surface Layer in Mixed‐Halide Multication Perovskites

Mixed‐halide lead perovskites have attracted significant attention in the field of photovoltaics and other optoelectronic applications due to their promising bandgap tunability and device performance. Here, the changes in photoluminescence and photoconductance of solution‐processed triple‐cation mixed‐halide (Cs_0.06MA_0.15FA_0.79)Pb(Br_0.4I_0.6)₃ perovskite films (MA: methylammonium, FA: formamidinium) are studied under solar‐equivalent illumination. It is found that the illumination leads to localized surface sites of iodide‐rich perovskite intermixed with passivating PbI₂ material. Time‐ and spectrally resolved photoluminescence measurements reveal that photoexcited charges efficiently transfer to the passivated iodide‐rich perovskite surface layer, leading to high local carrier densities on these sites. The carriers on this surface layer therefore recombine with a high radiative efficiency, with the photoluminescence quantum efficiency of the film under solar excitation densities increasing from 3% to over 45%. At higher excitation densities, nonradiative Auger recombination starts to dominate due to the extremely high concentration of charges on the surface layer. This work reveals new insight into phase segregation of mixed‐halide mixed‐cation perovskites, as well as routes to highly luminescent films by controlling charge density and transfer in novel device structures.     

Dopant-Free Polymer Hole Transport Materials for Highly Stable and Efficient CsPbI3 Perovskite Solar Cells

All-inorganic perovskite CsPbI₃ contains no volatile organic components and is a thermally stable photoactive material for wide-bandgap perovskite solar cells (PSCs); however, CsPbI₃ readily undergoes undesirable phase transitions due to the hygroscopic nature of the ionic dopants used in commonly used hole transport materials. In the current study, the popular donor material PM6 in organic solar cells is used as a hole transport layer (HTL). The benzodithiophene-based backbone-conjugated polymer requires no dopant and leads to a higher power conversion efficiency (PCE) than 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (Spiro-OMeTAD). Moreover, PM6 also shows priorities in hole mobility, hydrophobicity, cascade energy level alignment, and even defect passivation of perovskite films. With PM6 as the dopant-free HTL, the PSCs achieve a champion PCE of 18.27% with a competitive fill factor of 82.8%. Notably, the present PCE is based on the dopant-free HTL in CsPbI₃ PSCs reported thus far. The PSCs with PM6 as the HTL retain over 90% of the initial PCE stored in a glovebox filled with N₂ for 3000 h. In contrast, the PSCs with Spiro-OMeTAD as the HTL maintain ≈80% of the initial PCE under the same conditions.     

Fine Multi‐Phase Alignments in 2D Perovskite Solar Cells with Efficiency over 17% via Slow Post‐Annealing

Layered Ruddlesden–Popper (RP) phase (2D) halide perovskites have attracted tremendous attention due to the wide tunability on their optoelectronic properties and excellent robustness in photovoltaic devices. However, charge extraction/transport and ultimate power conversion efficiency (PCE) in 2D perovskite solar cells (PSCs) are still limited by the non‐eliminable quantum well effect. Here, a slow post‐annealing (SPA) process is proposed for BA₂MA₃Pb₄I₁₃ (n = 4) 2D PSCs by which a champion PCE of 17.26% is achieved with simultaneously enhanced open‐circuit voltage, short‐circuit current, and fill factor. Investigation with optical spectroscopy coupled with structural analyses indicates that enhanced crystal orientation and favorable alignment on the multiple perovskite phases (from the 2D phase near bottom to quasi‐3D phase near top regions) is obtained with SPA treatment, which promotes carrier transport/extraction and suppresses Shockley–Read–Hall charge recombination in the solar cell. As far as it is known, the reported PCE is so far the highest efficiency in RP phase 2D PSCs based on butylamine (BA) spacers (n = 4). The SPA‐processed devices exhibit a satisfactory stability with <4.5% degradation after 2000 h under N₂ environment without encapsulation. The demonstrated process strategy offers a promising route to push forward the performance in 2D PSCs toward realistic photovoltaic applications.     

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%.     

Mitigating Ion Migration with an Ultrathin Self-Assembled Ionic Insulating Layer Affords Efficient and Stable Wide-Bandgap Inverted Perovskite Solar Cells

Wide-bandgap perovskite solar cells (PSCs) are attracting increasing attention because they play an irreplaceable role in tandem solar cells. Nevertheless, wide-bandgap PSCs suffer large open-circuit voltage (V_OC) loss and instability due to photoinduced halide segregation, significantly limiting their application. Herein, a bile salt (sodium glycochenodeoxycholate, GCDC, a natural product), is used to construct an ultrathin self-assembled ionic insulating layer firmly coating the perovskite film, which suppresses halide phase separation, reduces V_OC loss, and improves device stability. As a result, 1.68 eV wide-bandgap devices with an inverted structure deliver a V_OC of 1.20 V with an efficiency of 20.38%. The unencapsulated GCDC-treated devices are considerably more stable than the control devices, retaining 92% of their initial efficiency after 1392 h storage under ambient conditions and retaining 93% after heating at 65 °C for 1128 h in an N₂ atmosphere. This strategy of mitigating ion migration via anchoring a nonconductive layer provides a simple approach to achieving efficient and stable wide-bandgap PSCs.