Molecularly Engineered Alicyclic Organic Spacers for 2D/3D Hybrid Tin-based Perovskite Solar Cells.

The high defect density and inferior crystallinity remain great hurdles for developing highly efficient and stable Sn-based perovskite solar cells (PSCs). 2D/3D heterostructures show strong potential to overcome these bottlenecks; however, a limited diversity of organic spacers has hindered further improvement. Herein, a novel alicyclic organic spacer, morpholinium iodide (MPI), is reported for developing structurally stabilized 2D/3D perovskite. Introducing a secondary ammonium and ether group to alicyclic spacers in 2D perovskite enhances its rigidity, which leads to increased hydrogen bonding and intermolecular interaction within 2D perovskite. These strengthened interactions facilitate the formation of highly oriented 2D/3D perovskite with low structural disorder, which leads to effective passivation of Sn and I defects. Consequently, the MP-based PSCs achieved a power conversion efficiency (PCE) of 12.04% with superior operational and oxidative stability. This work presents new insight into the design of organic spacers for highly efficient and stable Sn-based PSCs.

Efficient and Stable Red Perovskite Light-Emitting Diodes via Thermodynamic Crystallization Control.

Efficient and stable red perovskite light-emitting diodes (PeLEDs) demonstrate promising potential in high-definition displays and biomedical applications. Although significant progress has been made in device performance, meeting commercial demands remains a challenge in the aspects of long-term stability and high external quantum efficiency (EQE). Here, an in situ crystallization regulation strategy is developed for optimizing red perovskite films through ingenious vapor design. Mixed vapor containing dimethyl sulfoxide and carbon disulfide (CS2) is incorporated to conventional annealing, which contributes to thermodynamics dominated perovskite crystallization for well-aligned cascade phase arrangement. Additionally, the perovskite surface defect density is minimized by the CS2 molecule adsorption. Consequently, the target perovskite films exhibit smooth exciton energy transfer, reduced defect density, and blocked ion migration pathways. Leveraging these advantages, spectrally stable red PeLEDs are obtained featuring emission at 668, 656, and 648 nm, which yield record peak EQEs of 30.08%, 32.14%, and 29.04%, along with prolonged half-lifetimes of 47.7, 60.0, and 43.7 h at the initial luminances of 140, 250, and 270 cd m-2, respectively. This work provides a universal strategy for optimizing perovskite crystallization and represents a significant stride toward the commercialization of red PeLEDs.

Robust Imidazole-Linked Covalent Organic Framework Enabling Crystallization Regulation and Bulk Defect Passivation for Highly Efficient and Stable Perovskite Solar Cells.

The low crystallinity of the perovskite layers and many defects at grain boundaries within the bulk phase and at interfaces are considered huge barriers to the attainment of high performance and stability in perovskite solar cells (PSCs). Herein, a robust photoelectric imidazole-linked porphyrin-based covalent organic framework (PyPor-COF) is introduced to precisely control the perovskite crystallization process and effectively passivate defects at grain boundaries through a sequential deposition method. The 1D porous channels, abundant active sites, and high crystallization orientation of PyPor-COF offer advantages for regulating the crystallization of PbI2 and eliminating defects. Moreover, the intrinsic electronic characteristics of PyPor-COF endow a more closely matched energy level arrangement within the perovskite layer, which promotes charge transport and thereby suppresses the recombination of photogenerated carriers. The champion PSCs containing PyPor-COF achieved power conversion efficiencies of 24.10% (0.09 cm2) and 20.81% (1.0 cm2), respectively. The unpackaged optimized device is able to maintain its initial efficiency of 80.39% even after being exposed to air for 2000 h. The device also exhibits excellent heating stability and light stability. This work gives a new impetus to the development of highly efficient and stable PSCs via employing COFs.

Reconstruction and Solidification of Dion-Jacobson Perovskite Top and Buried Interfaces for Efficient and Stable Solar Cells.

Quasi-two-dimensional (Q-2D) perovskites show great potential in the field of photonic and optoelectronic device applications. However, defects and local lattice dislocation still limit performance and stability improvement by nonradiative recombination, unpreferred phase distribution, and unbonded amines. Here, a low-temperature synergistic strategy for both reconstructing and solidifying the perovskite top and buried interface is developed. By post-treating the 1,4-phenylenedimethanammonium (PDMA) based (PDMA)MA4Pb5I16 films with cesium acetate (CsAc) before thermal annealing, a condensation reaction between R-COO- and -NH2 and ion exchange between Cs+ and MA+ occur. It converts the unbonded amines to amides and passivates uncoordinated Pb2+. Meanwhile, it adjusts film composition and improves the phase distribution without changing the out-of-plane grain orientation. Consequently, performance of 18.1% and much-enhanced stability (e.g., stability for photo-oxygen increased over 10 times, light-thermal for T90 over 4 times, and reverse bias over 3 times) of (PDMA)MA4Pb5I16 perovskite solar cells are demonstrated.

Regulation of Lead Iodide Crystallization and Distribution for Efficient Perovskite Solar Cells.

At present, the power conversion efficiency (PCE) of perovskite solar cells (PSCs) has reached 26.1%. Polycrystalline perovskite films prepared by sequential deposition are often accompanied by excess PbI2. Although excess PbI2 can reduce the internal defects of the perovskites and promote charge transfer, excess PbI2 is unevenly distributed in the perovskites and easily decomposed into the composite center of charge. Therefore, the growth and distribution of PbI2 crystals can be regulated by introducing 4-fluoroaniline (4-FLA) as an additive into the precursor of PbI2. We observe that the presence of an amino group in 4-FLA leads to a reduction in the strength of van der Waals forces between PbI2 layer structures, thereby facilitating the uniform dispersion of excess PbI2 within the perovskites. Additionally, 4-FLA is restricted from being embedded in the PbI2 layer due to the steric hindrance of 4-FLA and the hydrogen bond interaction between nitrogen atoms and PbI2. Therefore, it leads to better dispersion of PbI2, resulting in better passivation and device efficiency. Based on the hydrophobicity of the benzene ring, the modified perovskite film shows excellent hydrophobicity. Ultimately, we achieved 21.63% PCE and 1.16V VOC. This provides an effective strategy for regulating excess PbI2 to achieve efficient and stable PSCs.

Low-Defect-Density Monolayer MoS2 Wafer by Oxygen-Assisted Growth-Repair Strategy.

Atomic chalcogen vacancy is the most commonly observed defect category in two dimensional (2D) transition-metal dichalcogenides, which can be detrimental to the intrinsic properties and device performance. Here a low-defect density, high-uniform, wafer-scale single crystal epitaxial technology by in situ oxygen-incorporated "growth-repair" strategy is reported. For the first time, the oxygen-repairing efficiency on MoS2 monolayers at atomic scale is quantitatively evaluated. The sulfur defect density is greatly reduced from (2.71 ± 0.65) × 1013 down to (4.28 ± 0.27) × 1012 cm-2, which is one order of magnitude lower than reported as-grown MoS2. Such prominent defect deduction is owing to the kinetically more favorable configuration of oxygen substitution and an increase in sulfur vacancy formation energy around oxygen-incorporated sites by the first-principle calculations. Furthermore, the sulfur vacancies induced donor defect states is largely eliminated confirmed by quenched defect-related emission. The devices exhibit improved carrier mobility by more than three times up to 65.2 cm2 V-1 s-1 and lower Schottky barrier height reduced by half (less than 20 meV), originating from the suppressed Fermi-level pinning effect from disorder-induced gap state. The work provides an effective route toward engineering the intrinsic defect density and electronic states through modulating synthesis kinetics of 2D materials.

Lattice Strain Regulation and Halogen Vacancies Passivation Enable High-Performance Formamidine-Based Perovskite Solar Cells.

Formamidinium lead iodide (FAPbI3) perovskite has lately surfaced as the preferred contender for highly proficient and robust perovskite solar cells (PSCs), owing to its favorable bandgap and superior thermal stability. Nevertheless, volatilization and migration of iodide ions (I-) result in non-radiating recombination centers, and the presence of large formamidine (FA) cations tends to cause lattice strain, thereby reducing the power conversion efficiency (PCE) and stability of PSCs. To solve these problems, the lead formate (PbFa) is added into the perovskite solution, which effectively mitigates the halogen vacancy and provides tensile strain outside the perovskite lattice, thereby enhancing its properties. The strong coordination between the C═O of HCOO- and Pb-I backbones effectively immobilizes anions, significantly increases the energy barrier for anion vacancy formation and migration, and reduces the risk of lead ion (Pb2+) leakage, thereby improving the operation and environmental safety of the device. Consequently, the champion PCE of devices with Ag electrodes can be increased from 22.15% to 24.32%. The unencapsulated PSCs can still maintain 90% of the original PCE even be stored in an N2 atmosphere for 1440 h. Moreover, the target devices have significantly improved performance in terms of light exposure, heat, or humidity.

Crown Ethers with Different Cavity Diameters Inhibit Ion Migration and Passivate Defects toward Efficient and Stable Lead Halide Perovskite Solar Cells.

Organic-inorganic hybrid metal halide perovskite solar cells have been considered as one of the most promising next-generation photovoltaic technologies. Nevertheless, perovskite defects and Li+ ionic migration will seriously affect the power conversion efficiency and stability of the formal device. Herein, we designed two crown ether derivatives (PC12 and PC15) with different cavity diameters, which selectively bind to different metal cations. It is found that PC15 in perovskite precursor solution can actively regulate the nucleation and crystallization processes and passivate the uncoordinated Pb2+ ions, while PC12 at the interface between the perovskite layer and hole-transporting layer can effectively inhibit the migration of Li+ ions and reduce nonradiative recombination losses. Therefore, PC12 and PC15 can act as "lubricant" and defect passivators, as well as inhibitors of ion migration, when they are synergistically applied at the surface and bulk of perovskite layer. Consequently, the optimized device achieved a champion efficiency of 24.8% with significantly improved humidity, thermal, and light stability.

One-Stone-For-Three-Birds Strategy Using a Fullerene Modifier for Efficient and Stable Inverted Perovskite Solar Cells.

The electron extraction from perovskite/C60 interface plays a crucial role in influencing the photovoltaic performance of inverted perovskite solar cells (PSCs). Here, we develop a one-stone-for-three-birds strategy via employing a novel fullerene derivative bearing triple methyl acrylate groups (denoted as C60-TMA) as a multifunctional interfacial layer to optimize electron extraction at the perovskite/C60 interface. It is found that the C60-TMA not only passivates surface defects of perovskite via coordination interactions between C=O groups and Pb2+ cations but also bridge electron transfer between perovskite and C60. Moreover, it effectively induces the secondary grain growth of the perovskite film through strong bonding effect, and this phenomenon has never been observed in prior art reports on fullerene related studies. The combination of the above three upgrades enables improved perovskite film quality with increased grain size and enhanced crystallinity. With these advantages, C60-TMA treated PSC devices exhibit a much higher power conversion efficiency (PCE) of 24.89% than the control devices (23.66%). Besides, C60-TMA benefits improved thermal stability of PSC devices, retaining over 90% of its initial efficiency after aging at 85 °C for 1200 h, primarily due to the reinforced interfacial interactions and improved perovskite film quality.

Synergy Between Dynamic Behavior of Hydrogen Defects and Non-Radiative Recombination in Metal-Halide Perovskites.

In organic-inorganic hybrid perovskite solar cells (PSCs), hydrogen defects introduce deep-level trap states, significantly influencing non-radiative recombination processes. Those defects are primarily observed in MA-PSCs rather than FA-PSCs. As a result, MA-PSCs demonstrated a lower efficiency of 23.6% compared to 26.1% of FA-PSCs. In this work, both hydrogen vacancy (VH -) and hydrogen interstitial (Hi -) defects in MAPbI3 bulk and on surfaces, respectively are investigated. i) Bulk VH - defects have dramatic impact on non-radiative recombination, with lifetime varying from 67 to 8 ns, depending on whether deprotonated MA0 are ion-bonded or not. ii) Surface H-defects exhibited an inherent self-healing mechanism through a chemical bond between MA0 and Pb2+, indicating a self-passivation effect. iii) Both VH - and Hi - defects can be mitigated by alkali cation passivation; while large cations are preferable for VH - passivation, given strong binding energy of cation/perovskite, as well as, weak band edge non-adiabatic couplings; and small cations are suited for Hi - passivation, considering the steric hindrance effect. The dual passivation strategy addressed diverse experimental outcomes, particularly in enhancing performance associated with cation selections. The dynamic connection between hydrogen defects and non-radiative recombination is elucidated, providing insights into hydrogen defect passivation essential for high-performance PSCs fabrication.

Enhancing Efficiency and Durability of Perovskite Solar Cells with Chlorine-Functionalized Fully Conjugated Porous Aromatic Framework.

Non-radiative recombination, caused by trap states, significantly hampers the efficiency and stability of perovskite solar cells (PSCs). The emerging porous organic polymers (POPs) show promise as a platform for designing novel defect passivation agents due to their rigid and porous structure. However, the POPs reported so far lack either sufficient stability or clear sites of interactions with the defects. Herein, two chlorine-functionalized, fully conjugated porous aromatic frameworks (PAFs) were constructed via a decarbonylation reaction. The chlorinated PAFs feature unique long-range conjugated networks bearing multiple chlorine atoms, significantly improving the photovoltaic performance and stability of doped solar cells. Combined experimental and theoretical analyses confirmed the strong passivation effects of conjugated structure to the defect through Cl sites. Specifically, PAF-159, bearing a triphenylamine moiety, demonstrated stronger Cl-Pb bonding and higher passivation efficiency due to the presence of π* anti-bonding orbitals, which elevate the HOMO energy level and facilitate Cl-Pb charge transfer. Consequently, we obtained high-performance PAF-159-doped devices with advanced PCE (24.3%), good storage stability (retaining 86% after 3000 hours), and good long-term operational stability (retaining 92% after 350 hours).

Suppressed Defects by Functional Thermally Cross-Linked Fullerene for High-Efficiency Tin-Lead Perovskite Solar Cells.

Mixed tin-lead (Sn-Pb) perovskites have attracted the attention of the community due to their narrow bandgap, ideal for photovoltaic applications, especially tandem solar cells. However, the oxidation and rapid crystallization of Sn2+ and the interfacial traps hinder their development. Here, cross-linkable [6,6]-phenyl-C61-butyric styryl dendron ester (C-PCBSD) is introduced during the quenching step of perovskite thin film processing to suppress the generation of surface defects at the electron transport layer interface and improve the bulk crystallinity. The C-PCBSD has strong coordination ability with Sn2+ and Pb2+ perovskite precursors, which retards the crystallization process, suppresses the oxidation of Sn2+, and improves the perovskite bulk and surface crystallinity, yielding films with reduced nonradiative recombination and enhanced interface charge extraction. Besides, the C-PCBSD network deposited on the perovskite surface displays superior hydrophobicity and oxygen resistance. Consequently, the devices with C-PCBSD obtain PCEs of up to 23.4% and retained 97% of initial efficiency after 2000 h of storage in a N2 atmosphere.

Defect Passivation and Crystallization Regulation for Efficient and Stable Formamidinium Lead Iodide Solar Cells with Multifunctional Amidino Additive.

Amidino-based additives show great potential in high-performance perovskite solar cells (PSCs). However, the role of different functional groups in amidino-based additives have not been well elucidated. Herein, two multifunctional amidino additives 4-amidinobenzoic acid hydrochloride (ABAc) and 4-amidinobenzamide hydrochloride (ABAm) are employed to improve the film quality of formamidinium lead iodide (FAPbI3) perovskites. Compared with ABAc, the amide group imparts ABAm with larger dipole moment and thus stronger interactions with the perovskite components, i.e., the hydrogen bonds between N…H and I- anion and coordination bonds between C = O and Pb2+ cation. It strengthens the passivation effect of iodine vacancy defect and slows down the crystallization process of α-FAPbI3, resulting in the significantly reduced non-radiative recombination, long carrier lifetime of 1.7 µs, uniformly large crystalline grains, and enhances hydrophobicity. Profiting from the improved film quality, the ABAm-treated PSC achieves a high efficiency of 24.60%, and maintains 93% of the initial efficiency after storage in ambient environment for 1200 hours. This work provides new insights for rational design of multifunctional additives regarding of defect passivation and crystallization control toward highly efficient and stable PSCs.

Monoammonium Modified Dion-Jacobson Quasi-2D Perovskite for High Efficiency Pure-Blue Light Emitting Diodes.

Quasi-2D perovskites exhibit impressive optoelectronic properties and hold significant promise for future light-emitting devices. However, the efficiency of perovskite light-emitting diodes (PeLEDs) is seriously limited by defect-induced nonradiative recombination and imbalanced charge injection. Here, the defect states are passivated and charge injection balance is effectively improved by introducing the additive cyclohexanemethylammonium (CHMA) to bromide-based Dion-Jacobson (D-J) structure quasi-2D perovskite emission layer. CHMA participates in the crystallization of perovskite, leading to high quality film composed of compact and well-contacted grains with enhanced hole transportation and less defects. As a result, the corresponding PeLEDs exhibit stable pure blue emission at 466 nm with a maximum external quantum efficiency (EQE) of 9.22%. According to current knowledge, this represents the highest EQE reported for pure-blue PeLEDs based on quasi-2D bromide perovskite thin films. These findings underscore the potential of quasi-2D perovskites for advanced light-emitting devices and pave the way for further advancements in PeLEDs.

Natural Chelating Agent-Treated Electron Transfer Layer for Friendly Environmental and Efficient Perovskite Solar Cells.

In perovskite solar cells (PSCs), the electron transfer layer (ETL) characteristics have significant effects on the photoelectric conversion efficiency (PCE) of the devices. Herein, a natural chelating agent polymer polyaspartic acid (PASP) is doped into the SnO2 precursor solution attributed to a strong interaction between PASP molecules and SnO2, which strengthens the interface contact and passivates the vacancy oxygen trap of the obtained SnO2 ETL, thus promoting the transfer of electrons. In addition, PASP can also regulate the growth of perovskite crystals, leading to an improved crystal quality of the perovskite films. Meanwhile, there is an excellent chelate anchoring of PASP to uncoordinated Pb2+, facilitating the reduction of trap defects at the interface, improving the stability of device, and suppressing the leakage of toxic Pb. Finally, the photovoltaic performance of the optimized device was greatly improved, and the PCE was increased from 21.22 to 23.49%, with outstanding environmental stability. This work provides an inexpensive and efficient treatment strategy that improves the performance and stability of friendly environmental PSCs.

Large-Area Perovskite Solar Modules Based on Uniformity Engineering of Perovskite Films: The Critical Role of Methyldiphenylphosphine Oxide Additive.

Perovskite solar cells (PSCs) have led to distinguished achievements and become one of the state-of-the-art photovoltaic technologies. Undoubtedly, reliable preparation of large area high-quality perovskite (PVK) films with uniform optoelectronic properties has become a critical and challenging task to transition PSCs from lab to market. Here, methyldiphenylphosphine oxide (MDPPO) is employed as an additive in a PVK precursor solution to promote uniform conductivity and carrier transport of PVK films. More important, to check its compatibility with the upscaling process, the MDPPO additive strategy was further applied to doctor-blade large-area PVK films. As a result, benefit from the favorable role of MDPPO additive, the power conversion efficiencies (PCEs) of small-area PSCs reach 23.85% with superb open circuit voltage (Voc) of 1.15 V and fill factor of 81.21%, while an impressive PCE of 19.22% was achieved for the large-area PSC minimodules with active area of 61.48 cm2. Remarkably, the MDPPO modified device exhibits significantly improved operational stability, maintaining an initial efficiency of 68% even after 750 h under continuous 1-sun illumination. Our achievements will provide profound insight and further guidance for the scale-up process of PSCs from lab to large-scale modules.

Improving FAPbBr3 Perovskite Crystal Quality via Additive Engineering for High Voltage Solar Cell over 1.5 V.

Lead bromide-based perovskites are promising materials as the top cells of tandem solar cells and for application in various fields requiring high voltages owing to their wide band gaps and excellent environmental resistances. However, several factors, such as the formation of bulk and surface defects, impede the performances of corresponding devices, thereby limiting the efficiencies of these devices as single-junction devices. To reduce the number of defect sites, urea is added to the formamidinium lead bromide (FAPbBr3) perovskite material to increase its grain size. Nevertheless, urea undesirably reacts with lead(II) bromide (PbBr2) in the perovskite structure, creating unfavorable impurities in the device. To solve this problem, herein, in addition to urea, we introduced formamidinium chloride (FACl) into FAPbBr3. Owing to the synergistic effect of urea and FACl, the FAPbBr3 film quality effectively improved due to suppression of the generation of impurities and stabilization of film crystallinity. Consequently, the FAPbBr3 single-junction solar cell constructed using FACl and urea as additives demonstrated a power conversion efficiency of 9.6% and an open-circuit voltage of 1.516 V with negligible hysteresis. This study provides new insights into the use of additive engineering for overcoming the energy losses caused by defects in perovskite films.

Tailored Supramolecular Interactions in Host-Guest Complexation for Efficient and Stable Perovskite Solar Cells and Modules.

Host-guest complexation offers a promising approach for mitigating surface defects in perovskite solar cells (PSCs). Crown ethers are the most widely used macrocyclic hosts for complexing perovskite surfaces, yet their supramolecular interactions and functional implications require further understanding. Here we show that the dipole moment of crown ethers serves as an indicator of supramolecular interactions with both perovskites and precursor salts. A larger dipole moment, achieved through the substitution of heteroatoms, correlates with enhanced coordination with lead cations. Perovskite films incorporating aza-crown ethers as additives exhibited improved morphology, reduced defect densities, and better energy-level alignment compared to those using native crown ethers. We report power-conversion efficiencies (PCEs) exceeding 25 % for PSCs, which show enhanced long-term stability, and a record PCE of 21.5 % for host-guest complexation-based perovskite solar modules with an active area of 14.0 cm2.

Elucidating the Role of Alkali Metal Carbonates in Impact on Oxygen Vacancies for Efficient and Stable Perovskite Solar Cells.

Effectively suppressing nonradiative recombination at the SnO2/perovskite interface is imperative for perovskite solar cells. Although the capabilities of alkali salts at the SnO2/perovskite interface have been acknowledged, the effects and optimal selection of alkali metal cations remain poorly understood. Herein, a novel approach for obtaining the optimal alkali metal cation (A-cation) at the interface is investigated by comparatively analyzing different alkali carbonates (A2CO3; Li2CO3, Na2CO3, K2CO3, Rb2CO3, and Cs2CO3). Theoretical calculations demonstrate that A2CO3 coordinates with undercoordinated Sn and O on the surface, effectively mitigating oxygen vacancy (VO) defects with increasing A-cation size, whereas Cs2CO3 exhibits diminished preferability owing to enhanced steric hindrance. The experimental results highlight the crucial role of Rb2CO3 in actively passivating VO defects, forming a robust bond with SnO2, and facilitating Rb+ diffusion into the perovskite layer, thereby enhancing charge extraction, alleviating deep-level trap states and structural distortion in the perovskite film, and significantly suppressing nonradiative recombination. X-ray absorption spectroscopy analyses further reveal the effect of Rb2CO3 on the local structure of the perovskite film. Consequently, a Rb2CO3-treated device with aperture area of 0.14 cm2 achieves a notable efficiency of 22.10%, showing improved stability compared to the 20.11% achieved for the control device.

Nitrogen-rich carbon dots as the antisolvent additive for perovskite-based photovoltaic devices.

Solution-processed perovskite solar cells (PSCs) have demonstrated a tremendous growth in power conversion efficiency (PCE). A high-quality, defect-free perovskite-based active layer is a key point to enhance PSC performance. Introduction of additives and interlayers have proved to be an effective tool to passivate surface defects, control crystal growth, and improve PSC stability. Antisolvent engineering has emerged recently as a new approach, which aims to adjust perovskite layer properties and enhance the PCE and stability of PSC devices. Here, we demonstrate that carbon dots (CDs) may serve as a prospective additive for antisolvent engineering. Nitrogen-rich amphiphilic CDs were synthesized from amines by a solvothermal method and used as an additive to chlorobenzene for a perovskite layer fabrication. The interaction between perovskite and functional groups in CDs promotes improved crystallization of an active perovskite layer and defects passivation, bringing higher PSCs efficiency, stability, and suppressed hysteresis. Under optimized CD concentration, the maximum PCE increased by 34% due to the improved short-circuit current and fill factor, and the device maintains 87% of its initial efficiency after 6 d of storage under ambient conditions.