Anion-π interactions suppress phase impurities in FAPbI3 solar cells.

Achieving both high efficiency and long-term stability is the key to the commercialization of perovskite solar cells (PSCs)1,2. However, the diversity of perovskite (ABX3) compositions and phases makes it challenging to fabricate high-quality films3-5. Perovskite formation relies on the reaction between AX and BX2, whereas most conventional methods for film-growth regulation are based solely on the interaction with the BX2 component. Herein, we demonstrate an alternative approach to modulate reaction kinetics by anion-π interaction between AX and hexafluorobenzene (HFB). Notably, these two approaches are independent but work together to establish 'dual-site regulation', which achieves a delicate control over the reaction between AX and BX2 without unwanted intermediates. The resultant formamidinium lead halides (FAPbI3) films exhibit fewer defects, redshifted absorption and high phase purity without detectable nanoscale δ phase. Consequently, we achieved PSCs with power conversion efficiency (PCE) up to 26.07% for a 0.08-cm2 device (25.8% certified) and 24.63% for a 1-cm2 device. The device also kept 94% of its initial PCE after maximum power point (MPP) tracking for 1,258 h under full-spectrum AM 1.5 G sunlight at 50 ± 5 °C. This method expands the range of chemical interactions that occur in perovskite precursors by exploring anion-π interactions and highlights the importance of the AX component as a new and effective working site to improved photovoltaic devices with high quality and phase purity.

Tungstate-mediated In-situ Passivation of Grain Boundary Grooves in Perovskite Solar Cells.

Possessed with advantageous optoelectronic properties, perovskites have boosted the rapid development of solution-processed solar cells. The performance of perovskite solar cells (PSCs) is significantly weakened by the carrier loss at grain boundary grooves (GBGs); however, it receives limited attention and there lacks effective approach to solve this issue. Herein, for the first time, we constructed the tungstate/perovskite heterointerface via a "two step" in situ reaction approach that provides effective defect passivation and ensures efficient carrier dynamics at the GBGs. The exposed perovskite at grain boundaries is converted to wide-band-gap PbWO4 via an in-situ reaction between Pb2+ and tungstate ions, which passivate defects due to the strong ionic bonding. Moreover, recombination loss is further suppressed via the heterointerface energetics modification based on an additional transformation from PbWO4 to CaWO4 . PSCs based on this groove modification strategy showed good universality in both normal and inverted structure, with an improved efficiency of 23.25 % in the n-i-p device and 23.33 % in the p-i-n device. Stable power output of the modified device could maintain 91.7 % after around 1100 h, and the device efficiency could retain 92.5 % after aging in air for around 2110 h, and 93.1 % after aging at 85 °C in N2 for 972 h.

Reducing Energy Disorder in Perovskite Solar Cells by Chelation.

In inverted perovskite solar cells (PSCs), the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is a widely used electron transport material. However, a high degree of energy disorder and inadequate passivation of PCBM limit the efficiency of devices, and severe self-aggregation and unstable morphology limit the lifespan of devices. Here, we design a series of fullerene dyads FP-Cn (n = 4, 8, 12) to replace PCBM as an electron transport layer, where [60]fullerene is linked with a terpyridine chelating group via a flexible alkyl chain of different lengths as a spacer. Among three fullerene dyads, FP-C8 shows the most enhanced molecule ordering and adhesion with the perovskite surface due to the balanced decoupling between the chelation effect from terpyridine and the self-assembly of fullerene, leading to lower energy disorder and higher morphological stability relative to PCBM. The FP-C8/C60-based devices using Cs0.05FA0.90MA0.05PbI2.85Br0.15 as a light absorber show a power conversion efficiency of 21.69%, higher than that of PCBM/C60 (20.09%), benefiting from improved electron extraction and transport as well as reduced charge recombination loss. When employing FAPbI3 as a light absorber, the FP-C8/C60-based devices exhibit an efficiency of 23.08%, which is the champion value of inverted PSCs with solution-processed fullerene derivatives. Moreover, the FP-C8/C60-based devices show better moisture and thermal stability than PCBM/C60-based devices and maintain 96% of their original efficiency after 1200 h of operation, while their counterpart PCBM/C60 maintains 60% after 670 h.

Integrated Tapping Mode Kelvin Probe Force Microscopy with Photoinduced Force Microscopy for Correlative Chemical and Surface Potential Mapping.

Kelvin probe force microscopy (KPFM) is a popular technique for mapping the surface potential at the nanoscale through measurement of the Coulombic force between an atomic force microscopy (AFM) tip and sample. The lateral resolution of conventional KPFM variants is limited to between ≈35 and 100 nm in ambient conditions due to the long-range nature of the Coulombic force. In this article, a novel way of generating the Coulombic force in tapping mode KPFM without the need for an external AC driving voltage is presented. A field-effect transistor (FET) is used to directly switch the electrical connectivity of the tip and sample on and off periodically. The resulting Coulomb force induced by Fermi level alignment of the tip and sample results in a detectable change of the cantilever oscillation at the FET-switching frequency. The resulting FET-switched KPFM delivers a spatial resolution of ≈25 nm and inherits the high operational speed of the AFM tapping mode. Moreover, the FET-switched KPFM is integrated with photoinduced force microscopy (PiFM), enabling simultaneous acquisitions of high spatial resolution chemical distributions and surface potential maps. The integrated FET-switched KPFM with PiFM is expected to facilitate characterizations of nanoscale electrical properties of photoactive materials, semiconductors, and ferroelectric materials.

Interfacial-engineering enhanced performance and stability of ZnO nanowire-based perovskite solar cells.

Perovskite solar cells (PSCs) have attracted extensive attention due to their convenient fabrication and excellent photoelectric characteristics. The highest power conversion efficiency (PCE) of over 25% has been realized. However, ZnO as electron transport layer based PSCs exhibit inferior PCE and stability because of the mismatched energy-band and undesirable interfacial recombination. Here, we introduce a thin layer of SnO2nanocrystals to construct an interfacial engineering with gradient energy band and interfacial passivation via a facile wet chemical process at a low temperature. The best PCE obtained in this study reaches 18.36%, and the stability is substantially improved and maintains a PCE of almost 100% over 500 h. The low-temperature fabrication process facilitates the future application of ZnO/SnO2-based PSCs in flexible and stretchable electronics.

Towards commercialization: the operational stability of perovskite solar cells.

Recently, perovskite solar cells (PSCs) have attracted much attention owing to their high power conversion efficiency (25.2%) and low fabrication cost. However, the short lifetime under operation is the major obstacle for their commercialization. With efforts from the entire PSC research community, significant advances have been witnessed to improve the device operational stability, and a timely summary on the progress is urgently needed. In this review, we first clarify the definition of operational stability and its significance in the context of practical use. By analyzing the mechanisms in established approaches for operational stability improvement, we summarize several effective strategies to extend device lifetime in a layer-by-layer sequence across the entire PSC. These mechanisms are discussed in the contexts of chemical reactions, photo-physical management, technological modification, etc., which may inspire future R&D for stable PSCs. Finally, emerging operational stability standards with respect to testing and reporting device operational stability are summarized and discussed, which may help reliable device stability data circulate in the research community. The main target of this review is gaining insight into the operational stability of PSCs, as well as providing useful guidance to further improve their operational lifetime by rational materials processing and device fabrication, which would finally promote the commercialization of perovskite solar cells.

Strong-bonding hole-transport layers reduce ultraviolet degradation of perovskite solar cells.

The light-emitting diodes (LEDs) used in indoor testing of perovskite solar cells do not expose them to the levels of ultraviolet (UV) radiation that they would receive in actual outdoor use. We report degradation mechanisms of p-i-n-structured perovskite solar cells under unfiltered sunlight and with LEDs. Weak chemical bonding between perovskites and polymer hole-transporting materials (HTMs) and transparent conducting oxides (TCOs) dominate the accelerated A-site cation migration, rather than direct degradation of HTMs. An aromatic phosphonic acid, [2-(9-ethyl-9H-carbazol-3-yl)ethyl]phosphonic acid (EtCz3EPA), enhanced bonding at the perovskite/HTM/TCO region with a phosphonic acid group bonded to TCOs and a nitrogen group interacting with lead in perovskites. A hybrid HTM of EtCz3EPA with strong hole-extraction polymers retained high efficiency and improved the UV stability of perovskite devices, and a champion perovskite minimodule-independently measured by the Perovskite PV Accelerator for Commercializing Technologies (PACT) center-retained operational efficiency of >16% after 29 weeks of outdoor testing.

Lead-chelating hole-transport layers for efficient and stable perovskite minimodules.

The defective bottom interfaces of perovskites and hole-transport layers (HTLs) limit the performance of p-i-n structure perovskite solar cells. We report that the addition of lead chelation molecules into HTLs can strongly interact with lead(II) ion (Pb2+), resulting in a reduced amorphous region in perovskites near HTLs and a passivated perovskite bottom surface. The minimodule with an aperture area of 26.9 square centimeters has a power conversion efficiency (PCE) of 21.8% (stabilized at 21.1%) that is certified by the National Renewable Energy Laboratory (NREL), which corresponds to a minimal small-cell efficiency of 24.6% (stabilized 24.1%) throughout the module area. Small-area cells and large-area minimodules with lead chelation molecules in HTLs had a light soaking stability of 3010 and 2130 hours, respectively, at an efficiency loss of 10% from the initial value under 1-sun illumination and open-circuit voltage conditions.

Anion Confinement for Homogeneous Mixed Halide Perovskite Film Growth by Electrospray.

Wide-bandgap perovskites are promising absorbers for state-of-the-art tandem solar cells to feasibly surpass Shockley-Queisser limit with low cost. However, the commonly used mixed halide perovskites suffer from poor stability; particularly, photoinduced phase segregation. Electrospray deposition is developed to bridge the gap of growth rate between iodide and bromide components during film growth by spatially confining the anion diffusion and eliminating the kinetic difference, which universally improves the initial homogeneity of perovskite films regardless of device architectures. It thus promotes the efficiency and stability of corresponding solar cells based on wide-bandgap (1.68 eV) absorbers. Remarkable power conversion efficiencies (PCEs) of 21.44% and 20.77% are achieved in 0.08 cm2 and 1.0 cm2 devices, respectively. In addition, these devices maintain 90% of their initial PCE after 1550 h of stabilized power output (SPO) tracking upon one sun irradiation (LED) at room temperature.

Temperature-Insensitive Efficient Inorganic Perovskite Photovoltaics by Bulk Heterojunctions.

Inorganic perovskite solar cells (IPSCs) emerge as an ideal candidate for applications beyond terrestrial implementation due to their robustness. However, underlying mechanisms regarding their photovoltaic process at different temperatures remain unclear. Based on a stable absorber of CsPbI2.85 (BrCl)0.15 , considerable variation of corresponding device performance is revealed over temperature and further demonstrates a simple approach to an effective reduction of such variation. Interestingly, this absorber is found to be excitonic with poor carrier transport even at an ambient temperature of 285 K and below. With a novel device configuration of a PTB7-th/perovskite bulk heterojunction, exciton dissociation and carrier extraction is facilitated. The resultant solar cell attains a best power conversion efficiency (PCE) of 17.2% with the fill factor of ≈84%, which represents the highest-efficiency γ-phase IPSCs reported to date. Importantly, this device is less sensitive to operation temperature, wherein the PCE variation over the temperature range from 210 to 360 K is 60% suppressed compared with the reference. The approach is effectively extended to other IPSCs with different photoactive phases, which may shed light on realizing highly efficient IPSCs for specific scenarios such as polar regions, near-space, and exoplanet exploration.

Reversible Phase Transition for Durable Formamidinium-Dominated Perovskite Photovoltaics.

Phase instability is one of the major obstacles to the wide application of formamidinium (FA)-dominated perovskite solar cells (PSCs). An in-depth investigation on relevant phase transitions is urgently needed to explore more effective phase-stabilization strategies. Herein, the reversible phase-transition process of FA1- x Csx PbI3 perovskite between photoactive phase (α phase) and non-photoactive phase (δ phase) under humidity, as well as the reversible healing of degraded devices, is monitored. Moreover, through in situ atomic force microscopy, the kinetic transition between α and δ phase is revealed to be the "nucleation-growth transition" process. Density functional theory calculation implies an enthalpy-driven α-to-δ degradation process during humidity aging and an entropy-driven δ-to-α healing process at high temperatures. The α phase of FA1- x Csx PbI3 can be stabilized at elevated temperature under high humidity due to the increased nucleation barrier, and the resulting non-encapsulated PSCs retain >90% of their initial efficiency after >1000 h at 60 °C and 60% relative humidity. This finding provides a deepened understanding on the phase-transition process of FA1- x Csx PbI3 from both thermodynamics and kinetics points of view, which also presents an effective means to stabilize the α phase of FA-dominated perovskites and devices for practical applications.

Synergistic Effects of Eu-MOF on Perovskite Solar Cells with Improved Stability.

Enhancing device lifetime is one of the essential challenges in perovskite solar cells. The ultrathin Eu-MOF layer is introduced at the interface between the electron-transport layer and the perovskite absorber to improve the device stability. Both Eu ions and organic ligands in the MOF can reduce the defect concentration and improve carrier transport. Moreover, due to the Förster resonance energy transfer effect, Eu-MOF in perovskite films can improve light utilization and reduce the decomposition under ultraviolet light. Meanwhile, Eu-MOF also turns tensile strain to compressive strain in the perovskite films. As a result, the corresponding devices achieve a champion power conversion efficiency (PCE) of 22.16%. In addition, the devices retain 96% of their original PCE after 2000 h under the relative humidity of 30% and 91% of their original PCE after 1200 h after continuous 85 °C aging condition in N2 .

Promoting Energy Transfer via Manipulation of Crystallization Kinetics of Quasi-2D Perovskites for Efficient Green Light-Emitting Diodes.

Quasi-2D (Q-2D) perovskites are promising materials applied in light-emitting diodes (LEDs) due to their high exciton binding energy and quantum confinement effects. However, Q-2D perovskites feature a multiphase structure with abundant grain boundaries and interfaces, leading to nonradiative loss during the energy-transfer process. Here, a more efficient energy transfer in Q-2D perovskites is achieved by manipulating the crystallization kinetics of different-n phases. A series of alkali-metal bromides is utilized to manipulate the nucleation and growth of Q-2D perovskites, which is likely associated with the Coulomb interaction between alkali-metal ions and the negatively charged PbBr6 4- frames. The incorporation of K+ is found to restrict the nucleation of high-n phases and allows the subsequent growth of low-n phases, contributing to a spatially more homogeneous distribution of different-n phases and promoted energy transfer. As a result, highly efficient green Q-2D perovskites LEDs with a champion EQE of 18.15% and a maximum brightness of 25 800 cd m-2 are achieved. The findings affirm a novel method to optimize the performance of Q-2D perovskite LEDs.

Liquid medium annealing for fabricating durable perovskite solar cells with improved reproducibility.

Solution processing of semiconductors is highly promising for the high-throughput production of cost-effective electronics and optoelectronics. Although hybrid perovskites have potential in various device applications, challenges remain in the development of high-quality materials with simultaneously improved processing reproducibility and scalability. Here, we report a liquid medium annealing (LMA) technology that creates a robust chemical environment and constant heating field to modulate crystal growth over the entire film. Our method produces films with high crystallinity, fewer defects, desired stoichiometry, and overall film homogeneity. The resulting perovskite solar cells (PSCs) yield a stabilized power output of 24.04% (certified 23.7%, 0.08 cm2) and maintain 95% of their initial power conversion efficiency (PCE) after 2000 hours of operation. In addition, the 1-cm2 PSCs exhibit a stabilized power output of 23.15% (certified PCE 22.3%) and keep 90% of their initial PCE after 1120 hours of operation, which illustrates their feasibility for scalable fabrication. LMA is less climate dependent and produces devices in-house with negligible performance variance year round. This method thus opens a new and effective avenue to improving the quality of perovskite films and photovoltaic devices in a scalable and reproducible manner.

A Thermodynamically Favored Crystal Orientation in Mixed Formamidinium/Methylammonium Perovskite for Efficient Solar Cells.

Crystal orientation has a great impact on the properties of perovskite films and the resultant device performance. Up to now, the exquisite control of crystal orientation (the preferred crystallographic planes and the crystal stacking mode with respect to the particular planes) in mixed-cation perovskites has received limited success, and the underlying mechanism that governs device performance is still not clear. Here, a thermodynamically favored crystal orientation in formamidinium/methylammonium (FA/MA) mixed-cation perovskites is finely tuned by composition engineering. Density functional theory calculations reveal that the FA/MA ratio affects the surface energy of the mixed perovskites, leading to the variation of preferential orientation consequently. The preferable growth along the (001) crystal plane, when lying parallel to the substrates, affects their charge transportation and collection properties. Under the optimized condition, the mixed-cation perovskite (FA1- x MAx PbI2.87 Br0.13 (Cl)) solar cells deliver a champion power conversion efficiency over 21%, with a certified efficiency of 20.50 ± 0.50%. The present work not only provides a vital step in understanding the intrinsic properties of mixed-cation perovskites but also lays the foundation for further investigation and application in perovskite optoelectronics.

Impacts of alkaline on the defects property and crystallization kinetics in perovskite solar cells.

Further minimizing the defect state density in the semiconducting absorber is vital to boost the power conversion efficiency of solar cells approaching Shockley-Queisser limit. However, it lacks a general strategy to control the precursor chemistry for defects density reduction in the family of iodine based perovskite. Here the alkaline environment in precursor solution is carefully investigated as an effective parameter to suppress the incident iodine and affects the crystallization kinetics during film fabrication, via rationale adjustment of the alkalinity of additives. Especially, a 'residual free' weak alkaline is proposed not only to shrink the bandgap of the absorber by modulating the stoichiometry of organic cation, but also to improve the open circuit voltage in the resultant device. Consequently, the certified efficiency of 20.87% (Newport) is achieved with one of the smallest voltage deficits of 413 mV in the planar heterojunction perovskite solar cell.

A Eu3+-Eu2+ ion redox shuttle imparts operational durability to Pb-I perovskite solar cells.

The components with soft nature in the metal halide perovskite absorber usually generate lead (Pb)0 and iodine (I)0 defects during device fabrication and operation. These defects serve as not only recombination centers to deteriorate device efficiency but also degradation initiators to hamper device lifetimes. We show that the europium ion pair Eu3+-Eu2+ acts as the "redox shuttle" that selectively oxidized Pb0 and reduced I0 defects simultaneously in a cyclical transition. The resultant device achieves a power conversion efficiency (PCE) of 21.52% (certified 20.52%) with substantially improved long-term durability. The devices retained 92% and 89% of the peak PCE under 1-sun continuous illumination or heating at 85°C for 1500 hours and 91% of the original stable PCE after maximum power point tracking for 500 hours, respectively.

Strain engineering in perovskite solar cells and its impacts on carrier dynamics.

The mixed halide perovskites have emerged as outstanding light absorbers for efficient solar cells. Unfortunately, it reveals inhomogeneity in these polycrystalline films due to composition separation, which leads to local lattice mismatches and emergent residual strains consequently. Thus far, the understanding of these residual strains and their effects on photovoltaic device performance is absent. Herein we study the evolution of residual strain over the films by depth-dependent grazing incident X-ray diffraction measurements. We identify the gradient distribution of in-plane strain component perpendicular to the substrate. Moreover, we reveal its impacts on the carrier dynamics over corresponding solar cells, which is stemmed from the strain induced energy bands bending of the perovskite absorber as indicated by first-principles calculations. Eventually, we modulate the status of residual strains in a controllable manner, which leads to enhanced PCEs up to 20.7% (certified) in devices via rational strain engineering.