Degradation Of Perovskite Solar Cells Research Articles

Predicting Long-Term Stability from Short-Term Measurement: Insights from Modeling Degradation in Perovskite Solar Cells during Voltage Scans and Impedance Spectroscopy.

A drift-diffusion model is used to investigate the effect of device degradation on current-voltage and impedance measurements of perovskite solar cells (PSCs). Modifications are made to the open-source drift-diffusion software IonMonger to model degradation via an increasing recombination rate during the course of characterization experiments. Impedance spectroscopy is shown to be a significantly more sensitive measure of degradation than current-voltage curves, reliably detecting a power conversion efficiency drop of as little as 0.06% over a 4 h measurement. Furthermore, we find that fast degradation occurring during impedance spectroscopy can induce loops lying above the axis in the Nyquist plot, the first time this experimentally observed phenomenon has been replicated in a physics-based model.

Ligand Assisted Hydrogen Bonding: A Game-Changer in Lead Passivation and Stability in Perovskite Solar Cells.

Lead halide perovskite solar cells (PSCs) have demonstrated power conversion efficiencies comparable to silicon-based solar cells, yet their instability under environmental stressors, such as humidity, heat, and light, remains a significant barrier to commercialization. A primary cause of this instability is the uncoordinated lead ions (Pb2+), which accelerates the degradation of PSCs and pose environmental concerns due to potential lead leakage. Recently, the introduction of ligands into PSCs has shown promise in mitigating lead toxicity through effective passivation, primarily by forming hydrogen bonds (H-bonds) between functional groups of the ligands and the perovskite structure. In this minireview, we explore the critical role of H-bonds in stabilizing PSCs by enhancing the structural integrity of the perovskite layer and reducing lead leakage. Furthermore, we discuss the contribution of these ligands in defect passivation, hydrophobicity, self-encapsulation, cross-linking, and self-healing mechanisms. These insights will highlight the multi-functional capabilities of ligands in improving the long-term stability and durability of PSCs, offering pathways to address current challenges in their commercialization.

Ligand Assisted Hydrogen Bonding: A Game‐Changer in Lead Passivation and Stability in Perovskite Solar Cells

Lead halide perovskite solar cells (PSCs) have demonstrated power conversion efficiencies comparable to silicon‐based solar cells, yet their instability under environmental stressors, such as humidity, heat, and light, remains a significant barrier to commercialization. A primary cause of this instability is the uncoordinated lead ions (Pb2+), which accelerates the degradation of PSCs and pose environmental concerns due to potential lead leakage. Recently, the introduction of ligands into PSCs has shown promise in mitigating lead toxicity through effective passivation, primarily by forming hydrogen bonds (H‐bonds) between functional groups of the ligands and the perovskite structure. In this minireview, we explore the critical role of H‐bonds in stabilizing PSCs by enhancing the structural integrity of the perovskite layer and reducing lead leakage. Furthermore, we discuss the contribution of these ligands in defect passivation, hydrophobicity, self‐encapsulation, cross‐linking, and self‐healing mechanisms. These insights will highlight the multi‐functional capabilities of ligands in improving the long‐term stability and durability of PSCs, offering pathways to address current challenges in their commercialization.

Spectral Control by Silver Nanoparticle-Based Metasurfaces for Mitigation of UV Degradation in Perovskite Solar Cells.

Perovskite solar cells are considered to be one of the most promising solar cell designs in terms of photovoltaic efficiency. However, their practical deployment is strongly affected by their short lifetimes, mostly caused by environmental conditions and UV degradation. In this contribution, we present a metasurface made of silver nanoparticles used as a UV filter on a perovskite solar cell. The UV-blocking layer was fabricated and morphologically and compositionally analyzed. Its optical response, in terms of optical transmission, was also experimentally measured. These results were compared with simulations made through the use of a well-proven computational electromagnetism model. After analyzing the discrepancies between the experimental and simulated results and checking those obtained from electron beam microscopy and electron dispersion spectroscopy, we could see that a residue from fabrication, sodium citrate, strongly modified the optical response of the system, generating a redshift of about 50 nm. Then, we proposed and simulated the optical behavior of core-shell nanoparticles made of silver and silica. The calculated spectral absorption at the active perovskite layer shows how the appropriate selection of the geometrical parameters of these core-shell particles is able to tune the absorption at the active layer by removing a significant portion of the UV band and reducing the absorption of the active layer from 90% to 5% at a resonance wavelength of 403 nm.

Photon shifting and trapping in perovskite solar cells for improved efficiency and stability

Advanced light management techniques can enhance the sunlight absorption of perovskite solar cells (PSCs). When located at the front, they may act as a UV barrier, which is paramount for protecting the perovskite layer against UV-enabled degradation. Although it was recently shown that photonic structures such as Escher-like patterns could approach the theoretical Lambertian-limit of light trapping, it remains challenging to also implement UV protection properties for these diffractive structures while maintaining broadband absorption gains. Here, we propose a checkerboard (CB) tile pattern with designated UV photon conversion capability. Through a combined optical and electrical modeling approach, this photonic structure can increase photocurrent and power conversion efficiency in ultrathin PSCs by 25.9% and 28.2%, respectively. We further introduce a luminescent down-shifting encapsulant that converts the UV irradiation into Visible photons matching the solar cell absorption spectrum. To this end, experimentally obtained absorption and emission profiles of state-of-the-art down-shifting materials (i.e., lanthanide-based organic-inorganic hybrids) are used to predict potential gains from harnessing the UV energy. We demonstrate that at least 94% of the impinging UV radiation can be effectively converted into the Visible spectral range. Photonic protection from high-energy photons contributes to the market deployment of perovskite solar cell technology, and may become crucial for Space applications under AM0 illumination. By combining light trapping with luminescent downshifting layers, this work unravels a potential photonic solution to overcome UV degradation in PSCs while circumventing optical losses in ultrathin cells, thus improving both performance and stability.

Recent Progress on Cross-Linkable Fullerene-Based Electron Transport Materials for Perovskite Solar Cells.

Fullerene-based derivatives are frequently used as electron transport materials (ETMs) and interface buffers for perovskite solar cells (PSCs) due to their excellent properties, including high electron affinity and mobility, low recombination energy, tunable energy levels, and solution processability. However, significant challenges arise because fullerene derivatives tend to aggregate and dimerize, which reduces exciton dissociation and charge transport capacity. Additionally, their chemical compatibility with perovskite absorbers facilitates halide diffusion and degradation of PSCs. This overlap causes delamination and dissolution during device fabrication, hindering the performance enhancement of fullerene-based PSCs. To address these issues, researchers have developed cross-linkable fullerene materials. These materials have been shown to not only significantly improve the power conversion efficiency (PCE) of PSCs but also effectively enhance the device stability. In this review, we summarized recent research progress on cross-linkable fullerene derivatives as ETMs for PSCs. We systematically analyze the impact of these cross-linked ETMs on device performance and long-term stability, focusing on their molecular structures and working mechanisms. Finally, we discuss the future challenges that need to be overcome to advance the application of cross-linkable fullerene materials in PSCs.

Biomass Derived Self-Doped Carbon Nanosheets Enable Robust Hole Transport Layers with Ion Buffer for Perovskite Solar Cells.

The diffusion of iodine species and lead leakage during device degradation represent the main obstacles restricting the commercial application of perovskite solar cells (PSCs). Cobalt loaded ultrathin carbon nanosheets (Co(III)-CNS) derived from biomass are prepared as ion buffer material to construct robust hole transport layers (HTLs). The carbon nanosheets containing trivalent cobalt ions can facilitate the oxidation of the hole transport material while preserving the structural integrity and electrical properties of HTLs under thermal stress, thereby ensuring efficient carrier transport. The two-dimensional ultrathin graphitized lamellar structure of Co(III)-CNS is conducive to alleviate the corrosive effects of the outward diffusion of iodine species on HTLs and silver electrodes, while avoiding irreversible degradation of PSCs. With the improvement of HTL composition and the related interfaces, Co(III)-CNS doped devices can maintain intact device structure under thermal stress and remain above 80% of the original power conversion efficiency (PCE) after thermal aging at 85 oC for 720 h. Notably, the chemical interactions between heteroatoms of self-doped carbon nanosheets and the mobile lead ions can effectively alleviate lead leakage and avoid the potential impacts of device degradation on ecosystem. Ultimately, the Co(III)-CNS doped PSCs with enhanced thermal stability exhibit a champion PCE of 22.32%.

Unraveling the Degradation Mechanisms of Perovskite Solar Cells under Mechanical Tensile Loads.

The short longevity of perovskite solar cells (PSCs) is the major hurdle toward their commercialization. In recent years, mechanical stability has emerged as a pivotal aspect in enhancing the overall durability of PSCs, prompting a myriad of strategies devoted to this issue. However, the mechanical degradation mechanisms of PSCs remain largely unexplored, with corresponding studies mainly limited to perovskite single crystals, neglecting the complexity and nuances present in PSC devices based on polycrystalline perovskite thin films. Herein, we reveal the underlying mechanisms of the mechanical degradation of formamidinium-based PSCs, which are the most prevalent high-performance PSC candidates. Under uniaxial tensile loads, we found that the degradation is mainly attributed to the sequential increase in the density of micropores and halide defects within the perovskite films. This phenomenon is consistent across various perovskite compositions and environmental conditions. Our findings elucidate mechanistic insights for more targeted mitigation strategies aimed at addressing the mechanical degradation of PSC devices.

Thermally Stable Perovskite Solar Cells with Fluoropolymer Coating

Halide perovskites are promising as the light absorbers of solar cells with efficient solar power conversion. However, why the degradation of perovskite solar cells (PSCs), especially at high temperatures, happens has not been completely understood to date. Herein, it is shown that evaporation of 4‐tert‐butylpyridine (4‐tBP) from the hole transport layer (HTL) of 2,2',7,7'‐tetrakis(N,N‐di‐p‐methoxyphenylamino)‐9,9'‐spirobifluorene (spiro‐OMeTAD) is one of possible degradation mechanisms in PSCs at a high temperature of 85 °C. In fresh PSCs, the chemical doping of the spiro‐OMeTAD HTL with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is not so efficient because of the formation of a LiTFSI:4‐tBP complex in the HTL. When PSCs are placed at 85 °C, 4‐tBP gradually evaporates from the HTL, resulting in the dissociation of the LiTFSI:4‐tBP complex. This 4‐tBP evaporation enhances the chemical doping of spiro‐OMeTAD by LiTFSI and makes the hole transport level of the spiro‐OMeTAD HTL deeper, thereby impeding hole extraction at the perovskite/spiro‐OMeTAD/Au interfaces. Herein, the 4‐tBP evaporation by covering PSCs with a fluoro‐polymer CYTOP layer, significantly improving the high‐temperature durability of PSCs, is suppressed. The basic understanding obtained in this study would help promote the spread of more thermally durable PSC products in the future.

Engineering the Hole Transport Layer with a Conductive Donor-Acceptor Covalent Organic Framework for Stable and Efficient Perovskite Solar Cells.

Spiro-OMeTAD doped with lithium-bis(trifluoromethylsulfonyl)-imide (Li-TFSI) and tertbutyl-pyridine (t-BP) is widely used as a hole transport layer (HTL) in n-i-p perovskite solar cells (PSCs). Spiro-OMeTAD based PSCs typically show poor stability owing to the agglomeration of Li-TFSI, the migration of lithium ions (Li+), and the existence of potential mobile defects originating from the perovskite layer. Thus, it is necessary to search for a strategy that suppresses the degradation of PSCs and overcomes the Shockley Queisser efficiency limit via harvesting excess energy from hot charge carrier. Herein, two covalent organic frameworks (COFs) including BPTA-TAPD-COF and a well-defined donor-acceptor COF (BPTA-TAPD-COF@TCNQ) were developed and incorporated into Spiro-OMeTAD HTL. BPTA-TAPD-COF and BPTA-TAPD-COF@TCNQ could act as multifunctional additives of Spiro-OMeTAD HTL, which improve the photovoltaic performance and stability of the PSC device by accelerating charge-carrier extraction, suppressing the Li+ migration and Li-TFSI agglomeration, and capturing mobile defects. Benefiting from the increased conductivity, the addition of BPTA-TAPD-COF@TCNQ in the device led to the highest power conversion efficiency of 24.68% with long-term stability in harsh conditions. This work provides an example of using COFs as additives of HTL to enable improvements of both efficiency and stability for PSCs.

Method to Study Potential‐Induced Degradation of Perovskite Solar Cells and Modules in an Inert Environment

The efficiency of perovskite solar cells (PSCs) is advancing rapidly, yet their sensitivity to ambient conditions poses challenges. An additional degradation mechanism, potential‐induced degradation (PID), can emerge during field operation, but the understanding of PID within perovskite devices is limited. To exclude environmental stressors, this study is conducted in an inert environment at room temperature. PSCs and mini‐modules are subjected to a 324 h PID stress test at −1000 V, revealing relative efficiency losses of around 29% and 24% for the PSCs and mini‐modules, respectively, exposing subtle degradation differences. These degradation rates are notably lower than reported in the literature, suggesting possible additional degradation pathways arising from suboptimal encapsulation combined with ambient conditions. Subsequently, half of the stressed samples are subject to +1000 V for 523 h and recover to a reduced efficiency loss of 15% and 7.7% for the PSCs and module, respectively. In contrast, storing the stressed samples on the shelf increased the efficiency losses to 32% (PSCs) and 41% (module). Therefore, the post‐PID rates differ significantly between both groups, whereas both effects of voltage recovery and progressed degradation are more pronounced in modules compared to cells. This study contributes to a robust method for PID research.

Tracking deep-level defects in degrading perovskite solar cells with a multifactorial approach

In this work, we provide a mechanistic understanding of the degradation of perovskite solar cells in operation by focusing on methylammonium lead triiodide (CH3NH3PbI3 or MAPbI3) and tracking the evolution of electronic defects via photo-induced current transient spectroscopy (PICTS). Moreover, we also record the degradation of its photovaltaic characteristics over time under various electric load and temperature conditions. Using PICTS, we found that bands of trap states, initially highly localized deep within the band gap of the perovskite, widened over the exposure period. This effect was exacerbated with increasing temperature. Further, using the design of experiment methodology for this multifactorial study, we found that two interaction factors (temperature× load & temperature× time) were significant in the degradation of the perovskite cells, validating the importance of our holistic approach. Through these observations, we establish a mechanistic link between deep-level traps and photovoltaic characteristics.

Improved perovskite photostability via application of TiO2, ZnO and AZO thin films by pulsed laser deposition

The UV-induced degradation of perovskite solar cells has been a barrier to commercialization. Thin film encapsulation represents a promising solution for extending perovskite solar cell lifetimes. Three materials with suitable bandgaps for blocking UV light are identified: TiO2, ZnO and AZO. Herein, the optical properties of TiO2, ZnO and AZO thin films grown by pulsed laser deposition at room-temperature are optimized by varying the oxygen partial pressure between 2, 5 and 20 mTorr during deposition. UV–Vis spectroscopy reveals facile bandgap tuning via the PLD O2 pressure for maximized UV light absorption/reflection. In particular, the TiO2 bandgap is found to narrow with decreasing O2 partial pressure as a result of an increase in oxygen vacancies and Ti3+ interstitials. Conversely, the AZO bandgap widens with decreasing O2 partial pressure, as explained by the Burstein-Moss effect. Finally, ZnO films have stable optical properties at all investigated oxygen pressures. The analysis finds that ZnO, TiO2, and AZO coatings exhibit maximum percentages of absorbed/reflected UV-A light of 72.13 ± 3.05%, 52.30 ± 2.72%, and 52.06 ± 2.20% at 5, 2 and 20 mTorr O2, respectively. Accelerated UV-aging experiments find that the films which screen the most UV light are also most effective in delaying perovskite degradation. A comparison of TiO2, ZnO and AZO photoprotective coatings concludes that ZnO is most suitable for perovskite solar cell encapsulation since it provides a ∼ 50% reduction in UV-degradation without significantly compromising visible light transmittance.

Synergetic Exterior and Interfacial Approaches by Colloidal Carbon Quantum Dots for More Stable Perovskite Solar Cells Against UV.

The achievement of both efficiency and stability in perovskite solar cells (PSCs) remains a challenging and actively researched topic. In particular, among different environmental factors, ultraviolet (UV) photons play a pivotal role in contributing to device degradation. In this work, by harvesting simultaneously both the optical and the structural properties of bottom-up-synthesized colloidal carbon quantum dots (CQDs), a cost-effective means is provided to circumvent the UV-induced degradation in PSCs without scarification on their power conversion efficiencies (PCEs). By exploring and optimizing the number of CQDs and the different locations/interfaces of the solar cells where CQDs are applied, a synergetic configuration is achieved where the photovoltaic performance drop due to optical loss is completely compensated by the increased perovskite crystallinity due to interfacial modification. As a result, on the optimized configurations where CQDs are applied both on the exterior front side as an optical layer and at the interface between the electron transport layer and the perovskite absorber, unencapsulated PSCs with PCEs >20% are fabricated which can maintain up to ≈94% of their initial PCE after 100h of degradation in ambient air under continuous UV illumination (5mWcm-2).

Ion-induced field screening as a dominant factor in perovskite solar cell operational stability

AbstractThe presence of mobile ions in metal halide perovskites has been shown to adversely affect the intrinsic stability of perovskite solar cells (PSCs). However, the actual contribution of mobile ions to the total degradation loss compared with other factors such as trap-assisted recombination remains poorly understood. Here we reveal that mobile ion-induced internal field screening is the dominant factor in the degradation of PSCs under operational conditions. The increased field screening leads to a decrease in the steady-state efficiency, often owing to a large reduction in the current density. Instead, the efficiency at high scan speeds (>1,000 V s−1), where the ions are immobilized, is much less affected. We also show that the bulk and interface quality do not degrade upon ageing, yet the open-circuit voltage decreases owing to an increase in the mobile ion density. This work reveals the importance of ionic losses for intrinsic PSC degradation before chemical or extrinsic mechanical effects manifest.

Unraveling the rapid ion migration in perovskite solar cells by circuit-switched transient photoelectric technique.

Ion migration activated by illumination is a critical factor responsible for the performance decline and stability degradation of perovskite solar cells (PSCs). While ion migration has been widely believed to be much slower than charge transport, recent research suggests that, despite the lack of understanding of the mechanism, it may also be involved in a series of rapid photoelectric responses of PSCs. Here, we report an improved circuit-switched transient photoelectric technique with nanosecond temporal resolution, which enables quantitative characterization of ion migration dynamics in PSCs across a fairly broad time window. Specifically, ion migration occurring within microseconds after illumination (corresponding to a diffusion length of ∼10-7cm) is unambiguously identified. In conjunction with the composition engineering protocol, we justify that it arises from the short-range migration of halide anions and organic cations around the contact/perovskite interface. The rapid ion migration kinetics revealed in this work strongly complement the well-established ion migration model, which offers new insights into the mechanism of ion-carrier interaction in PSC devices.

Understanding and Mitigating Atomic Oxygen-Induced Degradation of Perovskite Solar Cells for Near-Earth Space Applications.

Combining high efficiency with good radiation tolerance, perovskite solar cells (PSCs) are promising candidates to upend expanding space photovoltaic (PV) technologies. Successful employment in a Near-Earth space environment, however, requires high resistance against atomic oxygen (AtOx). This work unravels AtOx-induced degradation mechanisms of PSCs with and without phenethylammonium iodide (PEAI) based 2D-passivation and investigates the applicability of ultrathin silicon oxide (SiO) encapsulation as AtOx barrier. AtOx exposure for 2h degraded the average power conversion efficiency (PCE) of devices without barrier encapsulation by 40% and 43% (w/o and with 2D-PEAI-passivation) of their initial PCE. In contrast, devices with a SiO-barrier retained over 97% of initial PCE. To understand why 2D-PEAI passivated devices degrade faster than less efficient non-passivated devices, various opto-electrical and structural characterications are conducted. Together, these allowed to decouple different damage mechanisms. Notably, pseudo-J-V curves reveal unchanged high implied fill factors (pFF) of 86.4% and 86.2% in non-passivated and passivated devices, suggesting that degradation of the perovskite absorber itself is not dominating. Instead, inefficient charge extraction and mobile ions, due to a swiftly degrading PEAI interlayer are the primary causes of AtOx-induced device performance degradation in passivated devices, whereas a large ionic FF loss limits non-passivated devices.

Unraveling Interface-Driven and Loss Mechanism-Centric Phenomena in 3D/2D Halide Perovskites: Prospects for Optoelectronic Applications.

In recent years, organic-inorganic metal halide perovskite solar cells (PSCs) have attracted considerable interest due to their remarkable and rapidly advancing efficiencies. Over the past decade, PSC efficiencies have significantly approached those of state-of-the-art silicon-based photovoltaics, making them a promising material. Currently, the scientific community widely recognizes the performance of 3D-PSCs and 2D-PSCs individually. However, when both are combined to form a heterostructure, the lattice and charge dynamics at the interface undergo a multitude of mechanisms that affect their performance. The interface between heterostructures facilitates the degradation of PSCs. The degradation pathways can be attributed to lattice distortions, inhomogeneous energy landscapes, interlayer ion migration, nonradiative recombination, and charge accumulation. This Review is dedicated to examining the phenomena that arise at the interface of 3D/2D halide perovskites and their related photophysical properties and loss mechanism processes. We mainly focus on the impact of lattice mismatch, energy level alignment, anomalous carrier dynamics, and loss mechanisms. We propose a "cause-impact-identify-rectify" approach to gain a comprehensive understanding of the ultrafast processes occurring within the material. Finally, we highlight the importance of advanced spectroscopic and imaging techniques in unraveling these intricate mechanisms. This discussion delves into the future possibilities of fabricating 3D/2D heterostructure-based optoelectronic devices, pushing the boundaries of performance across diverse fields. It envisions the creation of devices with unparalleled capabilities, exceeding the limitations of current technologies.

Melatonin treatment as an anti-aging therapy for UV-related degradation of perovskite solar cells

With the ability to absorb UV light and scavenge radicals, the melatonin modified perovskite exhibits enhanced anti-aging and resistance to UV-related degradation.

Barrier Strategy for Strain-Free Encapsulation of Perovskite Solar Cells.

The performance loss caused by encapsulation has been an obstacle to guarantee the excellent power conversion efficiency of perovskite solar cells (PSCs) in practical application. This work revealed that the encapsulation-induced performance loss is highly related to the tensile strains imposed on the functional layers of the device when the PSC is exposed directly to the deformed encapsulant. A barrier strategy is developed by employing a nonadhesive barrier layer to isolate the deformed encapsulant from the PSC functional layer, achieving a strain-free encapsulation of the PSCs. The encapsulated device with a barrier layer effectively reduced the relative performance loss from 21.4% to 5.7% and dramatically improved the stability of the device under double 85 environment conditions. This work provides an effective strategy to mitigate the negative impact of encapsulation on the performance of PSCs as well as insight into the underlying mechanism of the accelerated degradation of PSCs under external strains.