ABSTRACT
Lead halide perovskites have been of paramount interest for solution-processable solar cells, reaching power conversion efficiencies larger than 25%. In this spotlight, we will provide a systematic overview of the influence of different solution-based processing routes of lead halide perovskites on their phase transformation and conversion as revealed through in-situ X-ray-scattering experiments. These experiments were performed in conditions closely mimicking thin film processing methods and conditions used for thin film solar cell device fabrication and therefore provide critical information about the mechanism of the phase transformation, its onset, the kinetics, as well as the emergence and disappearance of various (meso)phases along the way. The measurements capture the overall solidification and conversion process of lead halide perovskite inks into solid films via so-called one-step and two-step spin-coating processes as well as blade coating and hot casting. Processing routes are applied to films based on basic components as well as mixtures of different anions and cations, solvents, and antisolvents, all of which deeply affect the thin film microstructure and morphology of the light-absorbing semiconductor and associated solar cell devices.
ABSTRACT
Eco-friendly printing is important for mass manufacturing of thin-film photovoltaic (PV) devices to preserve human safety and the environment and to reduce energy consumption and capital expense. However, it is challenging for perovskite PVs due to the lack of eco-friendly solvents for ambient fast printing. In this study, we demonstrate for the first time an eco-friendly printing concept for high-performance perovskite solar cells. Both the perovskite and charge transport layers were fabricated from eco-friendly solvents via scalable fast blade coating under ambient conditions. The perovskite dynamic crystallization during blade coating investigated using in situ grazing incidence wide-angle X-ray scattering (GIWAXS) reveals a long sol-gel window prior to phase transformation and a strong interaction between the precursors and the eco-friendly solvents. The insights enable the achievement of high quality coatings for both the perovskite and charge transport layers by controlling film formation during scalable coating. The excellent optoelectronic properties of these coatings translate to a power conversion efficiency of 18.26% for eco-friendly printed solar cells, which is on par with the conventional devices fabricated via spin coating from toxic solvents under inert atmosphere. The eco-friendly printing paradigm presented in this work paves the way for future green and high-throughput fabrication on an industrial scale for perovskite PVs.
ABSTRACT
Perovskite solar cells based on two-dimensional/three-dimensional (2D/3D) hierarchical structure have attracted significant attention in recent years due to their promising photovoltaic performance and stability. However, obtaining a detailed understanding of interfacial mechanism at the 2D/3D heterojunction, for example, the ligand-chemistry-dependent nature of the 2D/3D heterojunction and its influence on charge collection and the final photovoltaic outcome, is not yet fully developed. Here we demonstrate the underlying 3D phase templates growth of quantum wells (QWs) within a 2D capping layer, which is further influenced by the fluorination of spacers and compositional engineering in terms of thickness distribution and orientation. Better QW alignment and faster dynamics of charge transfer at the 2D/3D heterojunction result in higher charge mobility and lower charge recombination loss, largely explaining the significant improvements in charge collection and open-circuit voltage (VOC) in complete solar cells. As a result, 2D/3D solar cells with a power-conversion efficiency of 21.15% were achieved, significantly higher than the 3D counterpart (19.02%). This work provides key missing information on how interfacial engineering influences the desirable electronic properties of the 2D/3D hierarchical films and device performance via ligand chemistry and compositional engineering in the QW layer.
ABSTRACT
Perovskite solar cells increasingly feature mixed-halide mixed-cation compounds (FA1- x - y MAx Csy PbI3- z Brz ) as photovoltaic absorbers, as they enable easier processing and improved stability. Here, the underlying reasons for ease of processing are revealed. It is found that halide and cation engineering leads to a systematic widening of the anti-solvent processing window for the fabrication of high-quality films and efficient solar cells. This window widens from seconds, in the case of single cation/halide systems (e.g., MAPbI3 , FAPbI3 , and FAPbBr3 ), to several minutes for mixed systems. In situ X-ray diffraction studies reveal that the processing window is closely related to the crystallization of the disordered sol-gel and to the number of crystalline byproducts; the processing window therefore depends directly on the precise cation/halide composition. Moreover, anti-solvent dripping is shown to promote the desired perovskite phase with careful formulation. The processing window of perovskite solar cells, as defined by the latest time the anti-solvent drip yields efficient solar cells, broadened with the increasing complexity of cation/halide content. This behavior is ascribed to kinetic stabilization of sol-gel state through cation/halide engineering. This provides guidelines for designing new formulations, aimed at formation of the perovskite phase, ultimately resulting in high-efficiency perovskite solar cells produced with ease and with high reproducibility.
ABSTRACT
The two-dimensional (2D) perovskites stabilized by alternating cations in the interlayer space (ACI) define a new type of structure with different physical properties than the more common Ruddlesden-Popper counterparts. However, there is a lack of understanding of material crystallization in films and its influence on the morphological/optoelectronic properties and the final photovoltaic devices. Herein, we undertake in situ studies of the solidification process for ACI 2D perovskite (GA)(MA) nPb nI3 n+1 (⟨ n⟩ = 3) from ink to solid-state semiconductor, using solvent mixture of DMSO:DMF (1:10 v/v) as the solvent and link this behavior to solar cell devices. The in situ grazing-incidence X-ray scattering (GIWAXS) analysis reveals a complex journey through disordered sol-gel precursors, intermediate phases, and ultimately to ACI perovskites. The intermediate phases, including a crystalline solvate compound and the 2D GA2PbI4 perovskite, provide a scaffold for the growth of the ACI perovskites during thermal annealing. We identify 2D GA2PbI4 to be the key intermediate phase, which is strongly influenced by the deposition technique and determines the formation of the 1D GAPbI3 byproducts and the distribution of various n phases of ACI perovskites in the final films. We also confirm the presence of internal charge transfer between different n phases through transient absorption spectroscopy. The high quality ACI perovskite films deposited from solvent mixture of DMSO:DMF (1:10 v/v) deliver a record power conversion efficiency of 14.7% in planar solar cells and significantly enhanced long-term stability of devices in contrast to the 3D MAPbI3 counterpart.
ABSTRACT
The trap states at grain boundaries (GBs) within polycrystalline perovskite films deteriorate their optoelectronic properties, making GB engineering particularly important for stable high-performance optoelectronic devices. It is demonstrated that trap states within bulk films can be effectively passivated by semiconducting molecules with Lewis acid or base functional groups. The perovskite crystallization kinetics are studied using in situ synchrotron-based grazing-incidence X-ray scattering to explore the film formation mechanism. A model of the passivation mechanism is proposed to understand how the molecules simultaneously passivate the Pb-I antisite defects and vacancies created by under-coordinated Pb atoms. In addition, it also explains how the energy offset between the semiconducting molecules and the perovskite influences trap states and intergrain carrier transport. The superior optoelectronic properties are attained by optimizing the molecular passivation treatments. These benefits are translated into significant enhancements of the power conversion efficiencies to 19.3%, as well as improved environmental and thermal stability of solar cells. The passivated devices without encapsulation degrade only by ≈13% after 40 d of exposure in 50% relative humidity at room temperature, and only ≈10% after 24 h at 80 °C in controlled environment.
