Endothermic Charge Separation Occurs Spontaneously in Non-Fullerene Acceptor/Polymer Bulk Heterojunction.

Organic photovoltaics (OPVs) based on non-fullerene acceptors (NFAs) have achieved a power conversion efficiency close to 20%. These NFA OPVs can generate free carriers efficiently despite a very small energy level offset at the donor/acceptor (D/A) interface. Why these NFAs can enable efficient charge separation (CS) with low energy losses remains an open question. Here, the CS process in the PM6:Y6 bulk heterojunction (BHJ) is probed by time-resolved two-photon photoemission (TR-TPPE) spectroscopy. We found that the CS, the conversion from bound charge transfer (CT) excitons to free carriers, is an endothermic process with an enthalpy barrier of 0.15 eV. The CS can occur spontaneously despite being an endothermic process, which implies that it is driven by entropy. We further argue that the morphology of the PM6:Y6 film and the anisotropic electron delocalization restrict the electron and hole wavefunctions within the CT exciton such that they can primarily contact each other through point-like junctions. This configuration can maximize the entropic driving force. This article is protected by copyright. All rights reserved.

Dimensional Regulation from 1D/3D to 2D/3D of Perovskite Interfaces for Stable Inverted Perovskite Solar Cells.

Constructing low-dimensional/three-dimensional (LD/3D) perovskite solar cells can improve efficiency and stability. However, the design and selection of LD perovskite capping materials are incredibly scarce for inverted perovskite solar cells (PSCs) because LD perovskite capping layers often favor hole extraction and impede electron extraction. Here, we develop a facile and effective strategy to modify the perovskite surface by passivating the surface defects and modulating surface electrical properties by incorporating morpholine hydriodide (MORI) and thiomorpholine hydriodide (SMORI) on the perovskite surface. Compared with the PI treatment that we previously developed, the one-dimensional (1D) perovskite capping layer derived from PI is transformed into a two-dimensional (2D) perovskite capping layer (with MORI or SMORI), achieving dimension regulation. It is shown that the 2D SMORI perovskite capping layer induces more robust surface passivation and stronger n-N homotype 2D/3D heterojunctions, achieving a p-i-n inverted solar cell with an efficiency of 24.55%, which retains 87.6% of its initial efficiency after 1500 h of operation at the maximum power point (MPP). Furthermore, 5 × 5 cm2 perovskite mini-modules are presented, achieving an active-area efficiency of 22.28%. In addition, the quantum well structure in the 2D perovskite capping layer increases the moisture resistance, suppresses ion migration, and improves PSCs' structural and environmental stability.

Assessing intra- and inter-molecular charge transfer excitations in non-fullerene acceptors using electroabsorption spectroscopy.

Organic photovoltaic cells using Y6 non-fullerene acceptors have recently achieved high efficiency, and it was suggested to be attributed to the charge-transfer (CT) nature of the excitations in Y6 aggregates. Here, by combining electroabsorption spectroscopy measurements and electronic-structure calculations, we find that the charge-transfer character already exists in isolated Y6 molecules but is strongly increased when there is molecular aggregation. Surprisingly, it is found that the large enhanced charge transfer in clustered Y6 molecules is not due to an increase in excited-state dipole moment, Δµ, as observed in other organic systems, but due to a reduced polarizability change, Δp. It is proposed that such a strong charge-transfer character is promoted by the stabilization of the charge-transfer energy upon aggregation, as deduced from density functional theory and four-state model calculations. This work provides insight into the correlation between molecular electronic properties and charge-transfer characteristics in organic electronic materials.

The role of interfacial donor-acceptor percolation in efficient and stable all-polymer solar cells.

Polymerization of Y6-type acceptor molecules leads to bulk-heterojunction organic solar cells with both high power-conversion efficiency and device stability, but the underlying mechanism remains unclear. Here we show that the exciton recombination dynamics of polymerized Y6-type acceptors (Y6-PAs) strongly depends on the degree of aggregation. While the fast exciton recombination rate in aggregated Y6-PA competes with electron-hole separation at the donor-acceptor (D-A) interface, the much-suppressed exciton recombination rate in dispersed Y6-PA is sufficient to allow efficient free charge generation. Indeed, our experimental results and theoretical simulations reveal that Y6-PAs have larger miscibility with the donor polymer than Y6-type small molecular acceptors, leading to D-A percolation that effectively prevents the formation of Y6-PA aggregates at the interface. Besides enabling high charge generation efficiency, the interfacial D-A percolation also improves the thermodynamic stability of the blend morphology, as evident by the reduced device "burn-in" loss upon solar illumination.

Mask-inspired moisture-transmitting and durable thermochromic perovskite smart windows.

Thermochromic perovskite smart windows (TPWs) are a cutting-edge energy-efficient window technology. However, like most perovskite-based devices, humidity-related degradation limits their widespread application. Herein, inspired by the structure of medical masks, a unique triple-layer thermochromic perovskite window (MTPW) that enable sufficient water vapor transmission to trigger the thermochromism but effectively repel detrimental water and moisture to extend its lifespan is developed. The MTPW demonstrates superhydrophobicity and maintains a solar modulation ability above 20% during a 45-day aging test, with a decay rate 37 times lower than that of a pristine TPW. It can also immobilize lead ions and significantly reduce lead leakage by 66 times. Furthermore, a significant haze reduction from 90% to 30% is achieved, overcoming the blurriness problem of TPWs. Benefiting from the improved optical performance, extended lifespan, suppressed lead leakage, and facile fabrication, the MTPW pushes forward the wide applications of smart windows in green buildings.

Fluorescent Conversion Agent Embedded in Zinc Oxide as an Electron-Transporting Layer for High-Performance Non-Fullerene Organic Solar Cells with Improved Photostability.

Zinc oxide (ZnO) is widely used as an electron transporting layer (ETL) for organic solar cells (OSCs). Here, a low-cost commercial water/alcohol-soluble fluorescent conversion agent, sodium 2,2'-([1,1'-biphenyl]-4,4'-diyldivinylene)-bis(benzenesulfonate) (CBS), is incorporated into ZnO to develop a novel organic-inorganic hybrid ETL for high-performance OSCs. The photoinduced charge transfer from CBS to ZnO significantly improves the charge transport properties of ZnO, resulting in faster electron extraction and reduced charge recombination in OSC devices with ZnO:CBS ETLs. ZnO:CBS-based devices exhibit higher power conversion efficiencies (PCEs) than their pure ZnO-based counterparts, especially in devices with a thicker ETL, which is more suitable for roll-to-roll and large-area module processing. Furthermore, the strong ultraviolet-light absorption capability of CBS inhibits the photodegradation of the active layer, improving the photostability of ZnO:CBS based OSC devices. Therefore, this work provides a simple and effective strategy for realizing high-performance OSCs with high PCE and good photostability, which can further facilitate the commercialization of OSCs.

Charge injection engineering at organic/inorganic heterointerfaces for high-efficiency and fast-response perovskite light-emitting diodes.

The development of advanced perovskite emitters has considerably improved the performance of perovskite light-emitting diodes (LEDs). However, the further development of perovskite LEDs requires ideal device electrical properties, which strongly depend on its interfaces. In perovskite LEDs with conventional p-i-n structures, hole injection is generally less efficient than electron injection, causing charge imbalance. Furthermore, the popular hole injection structure of NiOx/poly(9-vinylcarbazole) suffers from several issues, such as weak interfacial adhesion, high interfacial trap density and mismatched energy levels. In this work, we insert a self-assembled monolayer of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid between the NiOx and poly(9-vinylcarbazole) layers to overcome these challenges at the organic/inorganic heterointerfaces by establishing a robust interface, passivating interfacial trap states and aligning the energy levels. We successfully demonstrate blue (emission at 493 nm) and green (emission at 515 nm) devices with external quantum efficiencies of 14.5% and 26.0%, respectively. More importantly, the self-assembled monolayer also gives rise to devices with much faster response speeds by reducing interfacial capacitance and resistance. Our results pave the way for developing more efficient and brighter perovskite LEDs with quick response, widening their potential application scope.

Optimizing Crystallization in Wide-Bandgap Mixed Halide Perovskites for High-Efficiency Solar Cells.

Wide-bandgap (WBG) perovskites have attracted considerable attention due to their adjustable bandgap properties, making them ideal candidates for top subcells in tandem solar cells (TSCs). However, WBG perovskites often face challenges such as inhomogeneous crystallization and severe nonradiative recombination loss, leading to high open-circuit voltage (VOC ) deficits and poor stability. To address these issues, a multifunctional phenylethylammonium acetate (PEAAc) additive that enhances uniform halide phase distribution and reduces defect density in perovskite films by regulating the mixed-halide crystallization rate, is introduced. This approach successfully develops efficient WBG perovskite solar cells (PSCs) with reduced VOC loss and enhanced stability. By applying this universal strategy to the FAMACsPb(I1- x Brx )3 system with a range of bandgaps of 1.73, 1.79, 1.85, and 1.92 eV, power conversion efficiencies (PCE) of 21.3%, 19.5%, 18.1%, and 16.2%, respectively, are attained. These results represent some of the highest PCEs reported for the corresponding bandgaps. Furthermore, integrating WBG perovskite with organic photovoltaics, an impressive PCE of over 24% for two-terminal perovskite/organic TSCs, with a record VOC of ≈ 2.2 V is achieved. This work establishes a foundation for addressing phase separation and inhomogeneous crystallization in Br-rich perovskite components, paving the way for the development of high-performance WBG PSCs and TSCs.

Perovskite Smart Windows: The Light Manipulator in Energy-Efficient Buildings.

Uncontrolled sunlight entering through windows contributes to substantial heating and cooling demands in buildings, which leads to high energy consumption from the buildings. Recently, perovskite smart windows have emerged as innovative energy-saving technologies, offering the potential to adaptively control indoor solar heat gain through their impressive sunlight modulation capabilities. Moreover, harnessing the high-efficiency photovoltaic properties of perovskite materials, these windows have the potential to generate power, thereby realizing more advanced windows with combined light modulation and energy harvesting capabilities. This review summarizes the recent advancements in various chromic perovskite materials for achieving light modulation, focusing on both perovskite structures and underlying switching mechanisms. The discussion also encompasses device engineering strategies for smart windows, including the improvement of their optical and transition performance, durability, combination with electricity generation, and the evaluation of their energy-saving performance in building applications. Furthermore, the challenges and opportunities associated with perovskite smart windows are explicated, aimed at stimulating more academic research and advancing their pragmatic implementation for building energy efficiency and sustainability.

Advances in the Application of Perovskite Materials.

Nowadays, the soar of photovoltaic performance of perovskite solar cells has set off a fever in the study of metal halide perovskite materials. The excellent optoelectronic properties and defect tolerance feature allow metal halide perovskite to be employed in a wide variety of applications. This article provides a holistic review over the current progress and future prospects of metal halide perovskite materials in representative promising applications, including traditional optoelectronic devices (solar cells, light-emitting diodes, photodetectors, lasers), and cutting-edge technologies in terms of neuromorphic devices (artificial synapses and memristors) and pressure-induced emission. This review highlights the fundamentals, the current progress and the remaining challenges for each application, aiming to provide a comprehensive overview of the development status and a navigation of future research for metal halide perovskite materials and devices.

Understanding the Role of Removable Solid Additives: Selective Interaction Contributes to Vertical Component Distributions.

Sequentially deposited organic solar cells (SD-OSCs) have attracted great attention owing to their ability in achieving a more favorable, vertically phase-separated morphology to avoid the accumulation of counter charges at absorber/transporting layer interfaces. However, the processing of SD-OSCs is still quite challenging in preventing the penetration of small-molecule acceptors into the polymer donor layer via erosion or swelling. Herein, solid additives (SAs) with varied electrostatic potential distributions and steric hinderance are introduced into SD-OSCs to investigate the effect of evaporation dynamics and selective interaction on vertical component distribution. Multiple modelings indicate that the π-π interaction dominates the interactions between aromatic SAs and active layer components. Among them, p-dibromobenzene shows a stronger interaction with the donor while 2-chloronaphthalene (2-CN) interacts more preferably with acceptor. Combining the depth-dependent morphological study aided by multiple X-ray scattering methods, it is concluded that the evaporation of SAs can drive the stronger-interaction component upward to the surface, while having minor impact on the overall molecular packing. Ultimately, the 2-CN-treated devices with reduced acceptor concentration at the bottom surface deliver a high power conversion efficiency of 19.2%, demonstrating the effectiveness of applying selective interactions to improve the vertical morphology of OSCs by using SAs with proper structure.

Correlation of Local Isomerization Induced Lateral and Terminal Torsions with Performance and Stability of Organic Photovoltaics.

Organic photovoltaics (OPVs) have achieved great progress in recent years due to delicately designed non-fullerene acceptors (NFAs). Compared with tailoring of the aromatic heterocycles on the NFA backbone, the incorporation of conjugated side-groups is a cost-effective way to improve the photoelectrical properties of NFAs. However, the modifications of side-groups also need to consider their effects on device stability since the molecular planarity changes induced by side-groups are related to the NFA aggregation and the evolution of the blend morphology under stresses. Herein, a new class of NFAs with local-isomerized conjugated side-groups are developed and the impact of local isomerization on their geometries and device performance/stability are systematically investigated. The device based on one of the isomers with balanced side- and terminal-group torsion angles can deliver an impressive power conversion efficiency (PCE) of 18.5%, with a low energy loss (0.528 V) and an excellent photo- and thermal stability. A similar approach can also be applied to another polymer donor to achieve an even higher PCE of 18.8%, which is among the highest efficiencies obtained for binary OPVs. This work demonstrates the effectiveness of applying local isomerization to fine-tune the side-group steric effect and non-covalent interactions between side-group and backbone, therefore improving both photovoltaic performance and stability of fused ring NFA-based OPVs.

Deciphering the Roles of MA-Based Volatile Additives for α-FAPbI3 to Enable Efficient Inverted Perovskite Solar Cells.

Functional additives that can interact with the perovskite precursors to form the intermediate phase have been proven essential in obtaining uniform and stable α-FAPbI3 films. Among them, Cl-based volatile additives are the most prevalent in the literature. However, their exact role is still unclear, especially in inverted perovskite solar cells (PSCs). In this work, we have systematically studied the functions of Cl-based volatile additives and MA-based additives in formamidinium lead iodide (FAPbI3)-based inverted PSCs. Using in situ photoluminescence, we provide clear evidence to unravel the different roles of volatile additives (NH4Cl, FACl, and MACl) and MA-based additives (MACl, MABr, and MAI) in the nucleation, crystallization, and phase transition of FAPbI3. Three different kinds of crystallization routes are proposed based on the above additives. The non-MA volatile additives (NH4Cl and FACl) were found to promote crystallization and lower the phase-transition temperatures. The MA-based additives could quickly induce MA-rich nuclei to form pure α-phase FAPbI3 and dramatically reduce phase-transition temperatures. Furthermore, volatile MACl provides a unique effect on promoting the growth of secondary crystallization during annealing. The optimized solar cells with MACl can achieve an efficiency of 23.1%, which is the highest in inverted FAPbI3-based PSCs.

Influence of Component Properties on the Photovoltaic Performance of Monolithic Perovskite/Organic Tandem Solar Cells: Sub-Cell, Interconnecting Layer, and Photovoltaic Parameters.

Wide-bandgap perovskite sub-cells (WPSCs)-based tandem solar cells attract considerable interest because of their capability to surpass the Shockley-Queisser limit. Monolithic perovskite/organic tandem solar cells (POTSCs) integrating WPSCs and small-bandgap organic sub-cells (SOSCs) are famous compositions owing to their simple fabrication method and compatibility with flexible devices. Most studies on POTSCs focus on enhancing device efficiency by modifying one or two of the device components (WPSCs, SOSCs, and interconnecting layers). The characteristics of POTSCs are not extensively investigated so far, especially in terms of the influence of the device structure and component properties on the tandem device photovoltaic performance. In this study, the existing p-i-n type WPSC-based p-i-n POTSCs and n-i-p type WPSC-based n-i-p POTSCs are reviewed and their advantages and limitations are highlighted. Furthermore, the influence of the tandem device component properties (optical, electrical, and photovoltaic properties) on the photovoltaic parameters (open-circuit voltage, short-circuit current density, fill factor, and power conversion efficiency) and the existing device modification methods are discussed to provide comprehensive guidance for the development of POTSCs.

Low-voltage-modulated perovskite/organic dual-band photodetectors for visible and near-infrared imaging.

Visible and near-infrared (NIR) light dual-band photodetectors (PDs) have potential applications in signal detection, bioimaging, optical communications and safety monitoring. Herein, we report an ultrafast perovskite/organic heterojunction dual-mode PD with a voltage-modulated photoresponse range in visible and NIR spectra. The PD, comprising a perovskite layer to absorb visible light (500-810 nm) and an organic bulk heterojunction layer for NIR light absorption (810-950 nm), exhibited a switchable spectral response in the visible or NIR bands. The voltage-modulated visible and NIR photoresponses of the PD were attributable to controlled charge photogeneration in perovskite and organic blend thin films under different bias polarities. The device exhibited peak responsivities of 93.5 and 102.2 mA/W in the visible and NIR bands, respectively; a high detectivity of 4.3 × 109 Jones (at forward bias of 0.7 V and incident 625 nm light) and 1.6 × 1012 Jones (at reverse bias of -1.5 V and incident 900 nm light); a fast microsecond response time; and a wide dynamic range (>120 dB) both in the visible mode and NIR mode. Also, this voltage-modulated dual-band PD shows promising applications in visible light and NIR imaging, which is proven by demonstrating a PD array with 25 pixels (5 × 5).

High efficiency pure blue perovskite quantum dot light-emitting diodes based on formamidinium manipulating carrier dynamics and electron state filling.

Achieving high efficiency and stable pure blue colloidal perovskite quantum dot (QD) light-emitting diodes (LEDs) is still an enormous challenge because blue emitters typically exhibit high defect density, low photoluminescence quantum yield (PLQY) and easy phase dissociation. Herein, an organic cation composition modification strategy is used to synthesize high-performance pure blue perovskite quantum dots at room temperature. The synthesized FA-CsPb(Cl0.5Br0.5)3 QDs show a bright photoluminescence with a high PLQY (65%), which is 6 times higher than the undoped samples. In addition, the photophysical properties of the FA cation doping was deeply illustrated through carrier dynamics and first principal calculation, which show lower defects, longer lifetime, and more reasonable band gap structure than undoped emitters. Consequently, pure blue FA-CsPb(Cl0.5Br0.5)3 QDs light-emitting devices were fabricated and presented a maximum luminance of 1452 cd m-2, and an external quantum efficiency of 5.01 % with an emission at 474 nm. The excellent photoelectric properties mainly originate from the enhanced blue QDs emitter and effective charge injection and exciton radiation. Our finding underscores this easy and feasible room temperature doping approach as an alternative strategy to blue perovskite QD LED development.

Molecularly Functionalized SnO2 Films by Carboxylic Acids for High-Performance Perovskite Solar Cells.

Metal oxides are commonly employed as electron transport layers (ETLs) for n-i-p perovskite solar cells (PSCs), but the presence of surface traps and their mismatched energy alignment with perovskites limits the corresponding device performance. Therefore, the interfacial modification of ETLs by functional molecules becomes an important strategy for tailoring the interfacial properties and facilitating an efficient charge extraction and transport in PSCs. However, an in-depth understanding of the influences of their molecular structures on the surface chemistry and electronic properties of ETLs is rarely discussed. Herein, three carboxylic acid-based molecules with different chemical structures were employed to modify the SnO2 ETL and their effects on the performance of PSCs were systematically investigated. We found that the alkyl-chain length and carboxyl number in molecular structures can dramatically alter their binding strength to SnO2, providing a good strategy to fine-tune their film quality, electron mobility, and energy offset at the cathode interface. Benefiting from the optimal coordination ability of citric acid (CA) to SnO2, the corresponding PSCs show better charge transport properties and suppressed nonradiative recombination, leading to a champion efficiency of 23.1% with much improved environmental stability, highlighting the potential of rational design of molecular modifiers for high-performance ETLs applied in PSCs.

Identifying structure-absorption relationships and predicting absorption strength of non-fullerene acceptors for organic photovoltaics.

Non-fullerene acceptors (NFAs) are excellent light harvesters, yet the origin of their high optical extinction is not well understood. In this work, we investigate the absorption strength of NFAs by building a database of time-dependent density functional theory (TDDFT) calculations of ∼500 π-conjugated molecules. The calculations are first validated by comparison with experimental measurements in solution and solid state using common fullerene and non-fullerene acceptors. We find that the molar extinction coefficient (ε d,max) shows reasonable agreement between calculation in vacuum and experiment for molecules in solution, highlighting the effectiveness of TDDFT for predicting optical properties of organic π-conjugated molecules. We then perform a statistical analysis based on molecular descriptors to identify which features are important in defining the absorption strength. This allows us to identify structural features that are correlated with high absorption strength in NFAs and could be used to guide molecular design: highly absorbing NFAs should possess a planar, linear, and fully conjugated molecular backbone with highly polarisable heteroatoms. We then exploit a random decision forest algorithm to draw predictions for ε d,max using a computational framework based on extended tight-binding Hamiltonians, which shows reasonable predicting accuracy with lower computational cost than TDDFT. This work provides a general understanding of the relationship between molecular structure and absorption strength in π-conjugated organic molecules, including NFAs, while introducing predictive machine-learning models of low computational cost.

Renewed Prospects for Organic Photovoltaics.

Organic photovoltaics (OPVs) have progressed steadily through three stages of photoactive materials development: (i) use of poly(3-hexylthiophene) and fullerene-based acceptors (FAs) for optimizing bulk heterojunctions; (ii) development of new donors to better match with FAs; (iii) development of non-fullerene acceptors (NFAs). The development and application of NFAs with an A-D-A configuration (where A = acceptor and D = donor) has enabled devices to have efficient charge generation and small energy losses (Eloss < 0.6 eV), resulting in substantially higher power conversion efficiencies (PCEs) than FA-based devices. The discovery of Y6-type acceptors (Y6 = 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]-thiadiazolo[3,4-e]-thieno[2″,3″:4',5']thieno-[2',3':4,5]pyrrolo-[3,2-g]thieno-[2',3':4,5]thieno-[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) with an A-DA' D-A configuration has further propelled the PCEs to go beyond 15% due to smaller Eloss values (∼0.5 eV) and higher external quantum efficiencies. Subsequently, the PCEs of Y6-series single-junction devices have increased to >19% and may soon approach 20%. This review provides an update of recent progress of OPV in the following aspects: developments of novel NFAs and donors, understanding of the structure-property relationships and underlying mechanisms of state-of-the-art OPVs, and tasks underpinning the commercialization of OPVs, such as device stability, module development, potential applications, and high-throughput manufacturing. Finally, an outlook and prospects section summarizes the remaining challenges for the further development of OPV technology.