RESUMEN
We report a highly crystalline self-assembled multilayer (SAMUL) that is fundamentally different from the conventional monolayer or disordered bilayer used for hole-extraction in inverted perovskite solar cells (PSCs). The SAMUL can be easily formed on ITO substrate to form better surface coverage for enhancing the performance and stability of PSCs. A detailed structure-property-performance relationship of molecules used for SAMUL is established through a systematic study of their crystallinity, molecular packing, and hole-transporting properties. These SAMULs are rationally optimized by varying their molecular structures and deposition through thermal evaporation or spin-coating for fabricating PSCs. The CbzNaphPPA-based SAMUL was chosen for fabricating inverted PSCs due to its highest crystallinity and hole mobility derived from the ordered H-aggregation, which resulted in a remarkably high fill factor of 86.45%. This enables a very impressive power conversion efficiency (PCE) of 26.07% to be achieved along with excellent device stability (94% of its initial PCE retained after continuous operation for 1200 h under 1-sun irradiation at maximum power point at 65°C). Additionally, a record-high PCE of 23.50% could be achieved by adopting a thermally evaporated SAMUL. This greatly simplifies and broadens the scope for SAM to be used for large-area devices on diverse substrates.
RESUMEN
Inverted perovskite solar cells (PSCs) are preferred for tandem applications due to their superior compatibility with diverse bottom solar cells. However, the solution processing and low formation energy of perovskites inevitably lead to numerous defects at both the bulk and interfaces. We report a facile and effective strategy for precisely modulating the perovskite by incorporating AlOx deposited by atomic layer deposition (ALD) on the top interface. We find that Al3+ can not only infiltrate the bulk phase and interact with halide ions to suppress ion migration and phase separation but also regulate the arrangement of energy levels and passivate defects on the perovskite surface and grain boundaries. Additionally, ALD-AlOx exhibits an encapsulation effect through a dense interlayer. Consequently, the ALD-AlOx treatment can significantly improve the power conversion efficiency (PCE) to 21.80 % for 1.66 electron volt (eV) PSCs. A monolithic perovskite-silicon TSCs using AlOx-modified perovskite achieved a PCE of 28.5 % with excellent photothermal stability. More importantly, the resulting 1.55â eV PSC and module achieved a PCE of 25.08 % (0.04â cm2) and 21.01 % (aperture area of 15.5â cm2), respectively. Our study provides an effective way to efficient and stable wide-band gap perovskite for perovskite-silicon TSCs and paves the way for large-area inverted PSCs.
RESUMEN
Delicately manipulating nanomorphology is recognized as a vital and effective approach to enhancing the performance and stability of organic solar cells (OSCs). However, the complete removal of solvent additives with high boiling points is typically necessary to maintain the operational stability of the device. In this study, two commercially available organic intermediates, namely thieno[3,2-b]thiophene (TT) and 3,6-dibromothieno[3,2-b]thiophene (TTB) are introduced, as solid additives in OSCs. The theoretical simulations and experimental results indicate that TT and TTB may exhibit stronger intermolecular interactions with the acceptor Y6 and donor PM6, respectively. This suggests that the solid additives (SAs) can selectively intercalate between Y6 and PM6 molecules, thereby improving the packing order and crystallinity. As a result, the TT-treated PM6:Y6 system exhibits a favorable morphology, improved charge carrier mobility, and minimal charge recombination loss. These characteristics contribute to an impressive efficiency of 17.75%. Furthermore, the system demonstrates exceptional thermal stability (T80 > 2800 h at 65 °C) and outstanding photostability. The universal applicability of TT treatment is confirmed in OSCs employing D18:L8-BO, achieving a significantly higher PCE of 18.3%. These findings underscore the importance of using appropriate solid additives to optimize the blend morphology of OSCs, thereby improving photovoltaic performance and thermal stability.
RESUMEN
A considerable efficiency gap exists between large-area perovskite solar modules and small-area perovskite solar cells. The control of forming uniform and large-area film and perovskite crystallization is still the main obstacle restricting the efficiency of PSMs. In this work, we adopted a solid-liquid two-step film formation technique, which involved the evaporation of a lead iodide film and blade coating of an organic ammonium halide solution to prepare perovskite films. This method possesses the advantages of integrating vapor deposition and solution methods, which could apply to substrates with different roughness and avoid using toxic solvents to achieve a more uniform, large-area perovskite film. Furthermore, modification of the NiOx/perovskite buried interface and introduction of Urea additives were utilized to reduce interface recombination and regulate perovskite crystallization. As a result, a large-area perovskite film possessing larger grains, fewer pinholes, and reduced defects could be achieved. The inverted PSM with an active area of 61.56 cm2 (10 × 10 cm2 substrate) achieved a champion power conversion efficiency of 20.56% and significantly improved stability. This method suggests an innovative approach to resolving the uniformity issue associated with large-area film fabrication.
RESUMEN
The meta-stable active layer morphology of organic solar cells (OSCs) is identified as the main cause of the rapid burn-in loss of power conversion efficiency (PCE) during long-term device operation. However, effective strategies to eliminate the associated loss mechanisms from the initial stage of device operation are still lacking, especially for high-efficiency material systems. Herein, the introduction of molecularly engineered dimer acceptors with adjustable thermal transition properties into the active layer of OSCs to serve as supramolecular stabilizers for regulating the thermal transitions and optimizing the crystallization of the absorber composites is reported. By establishing intimate π-π interactions with small-molecule acceptors, these stabilizers can effectively reduce the trap-state density (Nt) in the devices to achieve excellent PCEs over 19%. More importantly, the low Nt associated with an initially optimized morphology can be maintained under external stresses to significantly reduce the PCE burn-in loss in devices. This research reveals a judicious approach to improving OPV stability by establishing a comprehensive correlation between material properties, active-layer morphology, and device performance, for developing burn-in-free OSCs.
RESUMEN
Crystallization orientation plays a crucial role in determining the performance and stability of perovskite solar cells (PVSCs), whereas effective strategies for realizing oriented perovskite crystallization is still lacking. Herein, a facile and efficient top-down strategy is reported to manipulate the crystallization orientation via treating perovskite wet film with propylamine chloride (PACl) before annealing. The PA+ ions tend to be adsorbed on the (001) facet of the perovskite surface, resulting in the reduced cleavage energy to induce (001) orientation-dominated growth of perovskite film and then reduce the temperature of phase transition, meanwhile, the penetrating Cl ions further regulate the crystallization process. As-prepared (001)-dominant perovskite films exhibit the ameliorative film homogeneity in terms of vertical and horizontal scale, leading to alleviated lattice mismatch and lowered defect density. The resultant PVSC devices deliver a champion power conversion efficiency (PCE) of 25.07% with enhanced stability, and the unencapsulated PVSC device maintains 95% of its initial PCE after 1000 h of operation at the maximum power point under simulated AM 1.5G illumination.
RESUMEN
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.
RESUMEN
All-small-molecule organic solar cells with good batch-to-batch reproducibility combined with non-halogen solvent processing show great potential for commercialization. However, non-halogen solvent processing of all-small-molecule organic solar cells are rarely reported and its power conversion efficiencies are very difficult to improve. Herein, we designed and synthesized a small molecule donor BM-ClEH that can take advantage of strong aggregation property induced by intramolecular chlorine-sulfur non-covalent interaction to improve molecular pre-aggregation in tetrahydrofuran and corresponding micromorphology after film formation. Tetrahydrofuran-fabricated all-small-molecule organic solar cells based on BM-ClEH:BO-4Cl achieved high power conversion efficiencies of 15.0% in binary device and 16.1% in ternary device under thermal annealing treatment. In contrast, weakly aggregated BM-HEH without chlorine-sulfur non-covalent bond is almost inefficient under same processing conditions due to poor pre-aggregation induced disordered π-π stacking, indistinct phase separation and exciton dissociation. This work promotes the development of non-halogen solvent processing of all-small-molecule organic solar cells and provides further guidance.
RESUMEN
Dielectric constant of non-fullerene acceptors plays a critical role in organic solar cells in terms of exciton dissociation and charge recombination. Current acceptors feature a dielectric constant of 3-4, correlating to relatively high recombination loss. We demonstrate that selenium substitution on acceptor central core can effectively modify molecule dielectric constant. The corresponding blend film presents faster hole-transfer of ~5 ps compared to the sulfur-based derivative (~10 ps). However, the blends with Se-acceptor also show faster charge recombination after 100 ps upon optical pumping, which is explained by the relatively disordered stacking of the Se-acceptor. Encouragingly, dispersing the Se-acceptor in an optimized organic solar cell system can interrupt the disordered aggregation while still retain high dielectric constant. With the improved dielectric constant and optimized fibril morphology, the ternary device exhibits an obvious reduction of non-radiative recombination to 0.221 eV and high efficiency of 19.0%. This work unveils heteroatom-substitution induced dielectric constant improvement, and the associated exciton dynamics and morphology manipulation, which finally contributes to better material/device design and improved device performance.
RESUMEN
Organic solar cells (OSCs) have achieved remarkable power conversion efficiencies (PCEs) of over 19 % in the past few years due to the rapid development of non-fullerene acceptors (NFAs). However, the operational stability remains a great challenge that inhibits their commercialization. Recently, oligomeric NFAs (ONFAs) have attracted great attention, which not only can deliver excellent device performance, but also improve the thermal-/photo- stability of OSCs. This is attributed to the suppressed molecular diffusion of ONFAs associated with their high glass-transition temperature (Tg) and improved thermodynamic properties of ONFAs. Herein, we focus on investigating the correction between the ONFA chemical structure, material properties, device performance, and stability. In addition, we also try to point out the challenges in synthesizing ONFAs and provide potential directions for future ONFA designs.
RESUMEN
Self-assembled monolayers (SAMs) have been widely employed as the bottom-contact hole-selective layer (HSL) in inverted perovskite solar cells (PSCs). Besides manipulating the electrical properties, molecularly engineering the SAM provides an opportunity to modulate the perovskite buried interface. Here, we successfully introduced Lewis-basic oxygen and sulfur heteroatoms through rational molecular design of asymmetric SAMs to obtain two novel multifunctional SAMs, CbzBF and CbzBT. Detailed characterization of single-crystal structures and device interfaces shows that enhanced packing, more effective ITO work function adjustment, and buried interface passivation were successfully achieved. Consequently, the champion PSC employing CbzBT showed an excellent power conversion efficiency (PCE) of 24.0% with a high fill factor of 84.41% and improved stability. This work demonstrates the feasibility of introducing defect-passivating heterocyclic groups into SAM molecules to help passivate the interfacial defects in PSCs. The insights gained from this molecular design strategy will accelerate the development of new multifunctional SAM HSLs for efficient PSCs.
RESUMEN
Self-assembled monolayers (SAMs) emerging as promising hole-selective layers (HSLs) are advantageous for facile processability, low cost, and minimal material consumption in the fabrication of both perovskite solar cells (PSCs) and organic solar cells (OSCs). However, owing to the different nature between perovskites and organic semiconductors, few SAMs were reported to effectively accommodate both PSCs and OSCs at the same time. In this regard, a universally applicable SAM that can accommodate both perovskites and organic semiconductors could be desirable for simplifying cell manufacturing, especially from an industrial perspective. In this work, we designed a SAM, TDPA-Cl by introducing chlorinated phenothiazine as the headgroup and linking with anchor phosphonic acid through a butyl chain. The resulting dense SAM was carefully characterized in terms of molecular bonding, surface morphology, and packing density, and its functions in OSCs and PSCs were discussed from the aspects of interactions with the absorber layer, energy level alignment, and charge-selective dipoles. The PM6:Y6-based OSCs with TDPA-Cl SAM as the HSL showed a superior performance to those with PEDOT:PSS. Furthermore, the universality was proved with an efficiency of 17.4% in the D18:Y6 system. In PSCs, the TDPA-Cl-based devices delivered a better performance of 22.4% than the PTAA-based devices (20.8%) with improved processability and reproducibility. This work represents a SAM with reasonably good compromise between the differing requirements of OSCs and PSCs.
RESUMEN
Interfacial engineering has long been a vital means of improving thin-film device performance, especially for organic electronics, perovskites, and hybrid devices. It greatly facilitates the fabrication and performance of solution-processed thin-film devices, including organic field effect transistors (OFETs), organic solar cells (OSCs), perovskite solar cells (PVSCs), and organic light-emitting diodes (OLEDs). However, due to the limitation of traditional interfacial materials, further progress of these thin-film devices is hampered particularly in terms of stability, flexibility, and sensitivity. The deadlock has gradually been broken through the development of self-assembled monolayers (SAMs), which possess distinct benefits in transparency, diversity, stability, sensitivity, selectivity, and surface passivation ability. In this review, we first showed the evolution of SAMs, elucidating their working mechanisms and structure-property relationships by assessing a wide range of SAM materials reported to date. A comprehensive comparison of various SAM growth, fabrication, and characterization methods was presented to help readers interested in applying SAM to their works. Moreover, the recent progress of the SAM design and applications in mainstream thin-film electronic devices, including OFETs, OSCs, PVSCs and OLEDs, was summarized. Finally, an outlook and prospects section summarizes the major challenges for the further development of SAMs used in thin-film devices.
RESUMEN
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.
RESUMEN
The power conversion efficiencies (PCEs) of perovskite solar cells have recently developed rapidly compared to crystalline silicon solar cells. To have an effective way to control the crystallization of perovskite thin films is the key for achieving good device performance. However, a paradox in perovskite crystallization is from the mismatch between nucleation and Oswald ripening. Usually, the large numbers of nucleation sites tend to weak Oswald ripening. Here, we proposed a new mechanism to promote the formation of nucleation sites by reducing surface energy from 44.9â mN/m to 36.1â mN/m, to spontaneously accelerate the later Oswald ripening process by improving the grain solubility through the elastic modulus regulation. The ripening rate is increased from 2.37â Åm â s-1 to 4.61â Åm â s-1 during annealing. Finally, the solar cells derived from the optimized films showed significantly improved PCE from 23.14 % to 25.32 %. The long-term stability tests show excellent thermal stability (the optimized device without encapsulation maintaining 82 % of its initial PCE after 800â h aging at 85 °C) and an improved light stability under illumination. This work provides a new method, the elastic modulus regulation, to enhance the ripening process.
RESUMEN
Additive engineering is widely utilized to optimize film morphology in active layers of organic solar cells (OSCs). However, the role of additive in film formation and adjustment of film morphology remains unclear at the molecular level. Here, taking high-efficiency Y6-based OSC films as an example, this work thus employs all-atom molecular-dynamics simulations to investigate how introduction of additives with different π-conjugation degree thermodynamically and dynamically impacts nanoscale molecular packings. These results demonstrate that the van der Waals (vdW) interactions of the Y6 end groups with the studied additives are strongest. The larger the π-conjugation degree of the additive molecules, the stronger the vdW interactions between additive and Y6 molecules. Due to such vdW interactions, the π-conjugated additive molecules insert into the neighboring Y6 molecules, thus opening more space for relaxation of Y6 molecules to trigger more ordered packing. Increasing the interactions between the Y6 end groups and the additive molecules not only accelerates formation of the Y6 ordered packing, but also induces shorter Y6-intermolecular distances. This work reveals the fundamental molecular-level mechanism behind film formation and adjustment of film morphology via additive engineering, providing an insight into molecular design of additives toward optimizing morphologies of organic semiconductor films.
RESUMEN
The buried interface of the perovskite layer has a profound influence on its film morphology, defect formation, and aging resistance from the outset, therefore, significantly affects the film quality and device performance of derived perovskite solar cells. Especially for FAPbI3 , although it has excellent optoelectronic properties, the spontaneous transition from the black perovskite phase to nonperovskite phase tends to start from the buried interface at the early stage of film formation then further propagate to degrade the whole perovskite. In this work, by introducing âNH3 + rich proline hydrochloride (PF) with a conjugated rigid structure as a versatile medium for buried interface, it not only provides a solid α-phase FAPbI3 template, but also prevents the phase transition induced degradation. PF also acts as an effective interfacial stress reliever to enhance both efficiency and stability of flexible solar cells. Consequently, a champion efficiency of 24.61% (certified 23.51%) can be achieved, which is the highest efficiency among all reported values for flexible perovskite solar cells. Besides, devices demonstrate excellent shelf-life/light soaking stability (advanced level of ISOS stability protocols) and mechanical stability.
RESUMEN
The heterogeneity of perovskite film crystallization along the vertical direction leads to voids and traps at the buried interfaces, hampering both efficiency and stability of perovskite solar cells. Here, bovine serum albumin-functionalized Au nanoclusters (ABSA), combined with heavy gravity, high surface charge density, and strong interactions with the electron transport layer, are designed to reconstruct the buried interfaces for not only high-quality crystallization, but also improved carrier transfer. The ABSA macromolecules with amine function groups and larger surface charge density interact with the perovskite to improve the crystallinity, and gradually migrate towards the buried interface, healing the defective voids, hence suppressing surface recombination velocity from 3075 to 452 cm s-1 . The healed buried interface and the higher surface potential of ABSA-modified TiO2 lead to improved carrier extraction at the interface. The resulting solar cell attains a power conversion efficiency of 25.0% with negligible hysteresis and remarkable stability, maintaining 92.9% of their initial efficiency after 3200 h of exposure to the ambient atmosphere, they also exhibit better continuous irradiation stability compared to control devices. These findings provide a new metal-protein complex to eliminate the deleterious voids and defects at the buried interface for improved photovoltaic performance and stability.
RESUMEN
Organic solar cells (OSCs) represent one of the most important emerging photovoltaic technologies that can implement solar energy conversion efficiently. The chemical structure of organic semiconductors deployed in the active layer of OSCs plays a critical role in the photovoltaic performance and chemical/physical stability of relevant devices. With the structure innovation of organic semiconductors, especially nonfullerene acceptors (NFAs), the performance of OSCs have been promoted rapidly in recent years, with state-of-the-art power conversion efficiencies (PCEs) exceeding 19.5%. Compared with other photovoltaics like perovskite, the shortcoming of OSCs mainly lies in the high nonradiative recombination loss. However, the photocurrent density is superior in OSCs owing to the easy modulation of the NFA band gap toward the near-infrared region. In these regards, the effort to further boost the PCE of OSCs to achieve a milestone >21% should be devoted to reducing the nonradiative loss while further broadening the absorption band. Developing organic semiconductors with biaxially extended conjugated structures has provided a potential solution to achieve these goals. Herein, we summarize the design rules and performance progress of biaxially extended conjugated materials for OSCs. The descriptions are divided into two major categories, i.e., polymers and NFAs. For p-type polymers, we focus on the biaxial conjugation on some representative building blocks, e.g., polythiophene, triphenylamine, and quinoxaline. Whereas for n-type polymers, some structures with large conjugated planes in the normal direction are presented. We also elaborate on the biaxial conjugation strategies in NFAs with modification site at either the π-core or side-group. The general structure-property relationships are further retrieved within these materials, with focus on the short-wavelength absorption and nonradiative energy loss. Finally, we provide an outlook for the further structure modification strategies of biaxially conjugated materials toward highly efficient, stable, and industry-compatible OSCs.