Molecularly Engineered Multifunctional Bridging Layer Derived from Dithiafulavene Capped Spiroxanthene for Stable and Efficient Perovskite Solar Cells.

This study introduces a novel approach centered around the design and synthesis of an interfacial passivating layer in perovskite solar cells (PSCs). This architectural innovation is realized through the development of a specialized material, termed dithiafulvene end-capped Spiro[fluorene-9,9'-xanthene], denoted by the acronym AF32. In this design architecture, dithiafulvene is thoughtfully attached to the spiroxanthene fluorene core with phenothiazine as the spacer unit, possessing multiple alkyl chains. AF32 passivates interfacial defects by coordinating the sulfur constituents of the phenothiazine and dithiafulvene frameworks to the uncoordinated Pb2+ cations on the surface of the perovskite film, and the alkyl chains construct a hydrophobic environment, preventing moisture from entering the hydrophilic perovskite layer and improving the long-term stability of PSCs. Furthermore, this conductive interlayer facilitates hole transport in PSCs due to its well-aligned molecular orbital levels. Such improvements translated into an enhanced power conversion efficiency (PCE) of 22.6% for the device employing 1.5 mg/mL AF32, and it maintained 85% of its initial PCE after more than 1800 h under ambient conditions [illumination and 45 ± 5% relative humidity (RH)]. This study not only marks progress in photovoltaic technology but also expands our understanding of manipulating interfacial properties for optimized device performance and stability.

Eco-Friendly Boost for Perovskite Photovoltaics: Harnessing Cellulose-Modified SnO2 as a High-Performance Electron Transporting Material.

In this study, a passivated tin oxide (SnO2) film is successfully obtained through the implementation of sodium carboxymethyl cellulose (Na-CMC) modifier agent and used as the electron transporting layer (ETL) within the assembly of perovskite solar cells (PSCs). The strategic incorporation of the Na-CMC modifier agent yields discernible enhancements in the optoelectronic properties of the ETL. Among the fabricated cells, the champion cell based on Na-CMC-complexed SnO2 ETL achieves a conversion efficiency of 22.2% with an open-circuit voltage (VOC) of 1.12 V, short-circuit current density (JSC) of 24.57 mA/cm2, and fill factor (FF) of 80.6%. On the other hand, these values are measured for the pristine SnO2 ETL-based control cell as VOC = 1.11 V, JSC = 23.59 mA/cm2, and FF = 76.7% with an efficiency of 20.1%. This improvement can be ascribed to the high charge extraction ability, higher optical transmittance, better conductivity, and decrease in the trap state density associated with the passivated ETL structure. In addition, the cells employing Na-CMC-complexed SnO2 ETL exhibit prolonged stability under ambient conditions during 2000 h. Based on the preliminary results, this study also presents a set of findings that could have substantial implications for the potential use of the Na-CMC molecule in both large-scale perovskite cells and perovskite/Si tandem configuration.

Probing the Low-Frequency Response of Impedance Spectroscopy of Halide Perovskite Single Crystals Using Machine Learning.

Electrochemical impedance spectroscopy (EIS) has emerged as a versatile technique for characterization and analysis of metal halide perovskite solar cells (PSCs). The crucial information about ion migration and carrier accumulation in PSCs can be extracted from the low-frequency regime of the EIS spectrum. However, lengthy measurement time at low frequencies along with material degradation due to prolonged exposure to light and bias motivates the use of machine learning (ML) in predicting the low-frequency response. Here, we have developed an ML model to predict the low-frequency response of the halide perovskite single crystals. We first synthesized high-quality MAPbBr3 single crystals and subsequently recorded the EIS spectra at different applied bias and illumination intensities to prepare the dataset comprising 8741 datapoints. The developed supervised ML model can predict the real and imaginary parts of the low-frequency EIS response with an R2 score of 0.981 and a root mean squared error (RMSE) of 0.0196 for the testing set. From the ground truth experimental data, it can be observed that negative capacitance prevails at a higher applied bias. Our developed model can closely predict the real and imaginary parts at a low frequency (50 Hz-300 mHz). Thus, our method makes recording of EIS more accessible and opens a new way in using the ML techniques for EIS.

Rationalizing the Effect of Polymer-Controlled Growth of Perovskite Single Crystals on Optoelectronic Properties.

To improve and modulate the optoelectronic properties of single-crystal (SC) metal halide perovskites (MHPs), significant progress has been achieved. Polymer-assisted techniques are a great approach to control the growth rate of SCs effectively. However, the resultant optoelectrical properties induced by polymers are ambiguous and need to be taken into the consideration. In this study, we have synthesized methylammonium lead triiodide (MAPbI3) SCs using polyethylene glycol (PEG) and polystyrene (PS) polymers where PEG contains oxygen functionalities and PS does not. We studied the electrical properties of these SCs under dark and illumination conditions. It was observed that PEG-assisted SCs showed few defects with lower photocurrent as compared to the PS-assisted ones because of defect-mediated conductivity. The results are further verified by transient current response, responsivity, and capacitance-frequency measurements. The present study sheds light on the polymer selection for the growth of MHP SCs and their optoelectronic properties.

Facile NaF Treatment Achieves 20% Efficient ETL-Free Perovskite Solar Cells.

Electron transporting layer (ETL)-free perovskite solar cells (PSCs) exhibit promising progress in photovoltaic devices due to the elimination of the complex and energy-/time-consuming preparation route of ETLs. However, the performance of ETL-free devices still lags behind conventional devices because of mismatched energy levels and undesired interfacial charge recombination. In this study, we introduce sodium fluoride (NaF) as an interface layer in ETL-free PSCs to align the energy level between the perovskite and the FTO electrode. KPFM measurements clearly show that the NaF layer covers the surface of rough underlying FTO very well. This interface modification reduces the work function of FTO by forming an interfacial dipole layer, leading to band bending at the FTO/perovskite interface, which facilitates an effective electron carrier collection. Besides, the part of Na+ ions is found to be able to migrate into the absorber layer, facilitating enlarged grains and spontaneous passivation of the perovskite layer. As a result, the efficiency of the NaF-treated cell reaches 20%, comparable to those of state-of-the-art ETL-based cells. Moreover, this strategy effectively enhances the operational stability of devices by preserving 94% of the initial efficiency after storage for 500 h under continuous light soaking at 55 °C. Overall, these improvements in photovoltaic properties are clear indicators of enhanced interface passivation by NaF-based interface engineering.

Organic Ammonium Halide Modulators as Effective Strategy for Enhanced Perovskite Photovoltaic Performance.

Despite rapid improvements in efficiency, long-term stability remains a challenge limiting the future up-scaling of perovskite solar cells (PSCs). Although several approaches have been developed to improve the stability of PSCs, applying ammonium passivation materials in bilayer configuration PSCs has drawn intensive research interest due to the potential of simultaneously improving long-term stability and boosting power conversion efficiency (PCE). This review focuses on the recent advances of improving n-i-p PSCs photovoltaic performance by employing ammonium halide-based molecular modulators. The first section briefly summarizes the challenges of perovskite materials by introducing the degradation mechanisms associated with the hygroscopic nature and ion migration issues. Then, recent reports regarding the roles of overlayers formed from ammonium-based passivation agents are discussed on the basis of ligand and halide effects. This includes both the formation of 2D perovskite films as well as purely organic passivating layers. Finally, the last section provides future perspectives on the use of organic ammonium halides within bilayer-architecture PSCs to improve the photovoltaic performances. Overall, this review provides a roadmap on current demands and future research directions of molecular modulators to address the critical limitations of PSCs, to mitigate the major barriers on the pathway toward future up-scaling applications.

Efficient and Stable Perovskite Solar Cells Enabled by Dicarboxylic Acid-Supported Perovskite Crystallization.

Defect states at surfaces and grain boundaries as well as poor anchoring of perovskite grains hinder the charge transport ability by acting as nonradiative recombination centers, thus resulting in undesirable phenomena such as low efficiency, poor stability, and hysteresis in perovskite solar cells (PSCs). Herein, a linear dicarboxylic acid-based passivation molecule, namely, glutaric acid (GA), is introduced by a facile antisolvent additive engineering (AAE) strategy to concurrently improve the efficiency and long-term stability of the ensuing PSCs. Thanks to the two-sided carboxyl (-COOH) groups, the strong interactions between GA and under-coordinated Pb2+ sites induce the crystal growth, improve the electronic properties, and minimize the charge recombination. Ultimately, champion-stabilized efficiency approaching 22% is achieved with negligible hysteresis for GA-assisted devices. In addition to the enhanced moisture stability of the devices, considerable operational stability is achieved after 2400 h of aging under continuous illumination at maximum power point (MPP) tracking.

Moisture-Resistant FAPbI3 Perovskite Solar Cell with 22.25 % Power Conversion Efficiency through Pentafluorobenzyl Phosphonic Acid Passivation.

Perovskite solar cells (PSCs) have shown great promise for photovoltaic applications, owing to their low-cost assembly, exceptional performance, and low-temperature solution processing. However, the advancement of PSCs towards commercialization requires improvements in efficiency and long-term stability. The surface and grain boundaries of perovskite layer, as well as interfaces, are critical factors in determining the performance of the assembled cells. Defects, which are mainly located at perovskite surfaces, can trigger hysteresis, carrier recombination, and degradation, which diminish the power conversion efficiencies (PCEs) of the resultant cells. This study concerns the stabilization of the α-FAPbI3 perovskite phase without negatively affecting the spectral features by using 2,3,4,5,6-pentafluorobenzyl phosphonic acid (PFBPA) as a passivation agent. Accordingly, high-quality PSCs are attained with an improved PCE of 22.25 % and respectable cell parameters compared to the pristine cells without the passivation layer. The thin PFBPA passivation layer effectively protects the perovskite layer from moisture, resulting in better long-term stability for unsealed PSCs, which maintain >90 % of the original efficiency under different humidity levels (40-75 %) after 600 h. PFBPA passivation is found to have a considerable impact in obtaining high-quality and stable FAPbI3 films to benefit both the efficiency and the stability of PSCs.

Poly(N,N'-bis-4-butylphenyl-N,N'-bisphenyl)benzidine-Based Interfacial Passivation Strategy Promoting Efficiency and Operational Stability of Perovskite Solar Cells in Regular Architecture.

The failure of perovskite solar cells (PSCs) to maintain their maximum efficiency over a prolonged time is due to the deterioration of the light harvesting material under environmental factors such as humidity, heat, and light. Systematically elucidating and eliminating such degradation pathways are critical to imminent commercial use of this technology. Here, a straightforward approach is introduced to reduce the level of defect-states present at the perovskite and hole transporting layer interface by treating the various perovskite surfaces with poly(N,N'-bis-4-butylphenyl-N,N'-bisphenyl)benzidine (polyTPD) molecules. This strategy significantly suppresses the defect-mediated non-radiative recombination in the ensuing devices and prevents the penetration of degrading agents into the inner layers by passivating the perovskite surface and grain boundaries. Suppressed non-radiative recombination and improved interfacial hole extraction result in PSCs with stabilized efficiency exceeding 21% with negligible hysteresis (≈19.1% for control device). Moreover, ultra-hydrophobic polyTPD passivant considerably alleviates moisture penetration, showing ≈91% retention of initial efficiencies after 300 h storage at high relative humidity of 80%. Similarly, passivated device retains 94% of its initial efficiency after 800 h under operational conditions (maximum power point tracking under continuous illumination at 60 °C). In addition to interfacial passivation function, hole-selective role of dopant-free polyTPD is also evaluated and discussed in this study.

Minimizing the Trade-Off between Photocurrent and Photovoltage in Triple-Cation Mixed-Halide Perovskite Solar Cells.

Its lower bandgap makes formamidinium lead iodide (FAPbI3) a more suitable candidate for single-junction solar cells than pure methylammonium lead iodide (MAPbI3). However, its structural and thermodynamic stability is improved by introducing a significant amount of MA and bromide, both of which increase the bandgap and amplify trade-off between the photocurrent and photovoltage. Here, we simultaneously stabilized FAPbI3 into a cubic lattice and minimized the formation of photoinactive phases such as hexagonal FAPbI3 and PbI2 by introducing 5% MAPbBr3, as revealed by synchrotron X-ray scattering. We were able to stabilize the composition (FA0.95MA0.05Cs0.05)Pb(I0.95Br0.05)3, which exhibits a minimal trade-off between the photocurrent and photovoltage. This material shows low energetic disorder and improved charge-carrier dynamics as revealed by photothermal deflection spectroscopy (PDS) and transient absorption spectroscopy (TAS), respectively. This allowed the fabrication of operationally stable perovskite solar cells yielding reproducible efficiencies approaching 22%.

Stabilization of Highly Efficient and Stable Phase-Pure FAPbI3 Perovskite Solar Cells by Molecularly Tailored 2D-Overlayers.

As a result of their attractive optoelectronic properties, metal halide APbI3 perovskites employing formamidinium (FA+ ) as the A cation are the focus of research. The superior chemical and thermal stability of FA+ cations makes α-FAPbI3 more suitable for solar-cell applications than methylammonium lead iodide (MAPbI3 ). However, its spontaneous conversion into the yellow non-perovskite phase (δ-FAPbI3 ) under ambient conditions poses a serious challenge for practical applications. Herein, we report on the stabilization of the desired α-FAPbI3 perovskite phase by protecting it with a two-dimensional (2D) IBA2 FAPb2 I7 (IBA=iso-butylammonium overlayer, formed via stepwise annealing. The α-FAPbI3 /IBA2 FAPb2 I7 based perovskite solar cell (PSC) reached a high power conversion efficiency (PCE) of close to 23 %. In addition, it showed excellent operational stability, retaining around 85 % of its initial efficiency under severe combined heat and light stress, that is, simultaneous exposure with maximum power tracking to full simulated sunlight at 80 °C over 500 h.

Inorganic CuFeO2 Delafossite Nanoparticles as Effective Hole Transport Materials for Highly Efficient and Long-Term Stable Perovskite Solar Cells.

The regular architecture (n-i-p) of perovskite solar cells (PSCs) has attracted increasing interest in the renewable energy field, owing to high certified efficiencies in the recent years. However, there are still serious obstacles of PSCs associated with spiro-OMeTAD hole transport material (HTM), such as (i) prohibitively expensive material cost (∼150-500 $/g) and (ii) operational instability at elevated temperatures and high humidity levels. Herein, we have reported the highly photo, thermal, and moisture-stable and cost-effective PSCs employing inorganic CuFeO2 delafossite nanoparticles as a HTM layer, for the first time. By exhibiting superior hole mobility and additive-free nature, the best-performing cell achieved a power conversion efficiency (PCE) of 15.6% with a negligible hysteresis. Despite exhibiting a lower PCE as compared to the spiro-OMeTAD-based control cell (19.1%), nonencapsulated CuFeO2-based cells maintained above 85% of their initial efficiency, while the PCE of control cells dropped to ∼10% under continuous illumination at maximum power point tracking after 1000 h. More importantly, the performance of control cells was quickly degraded at above 70 °C, whereas CuFeO2-based cells, retaining ∼80% of their initial efficiency after 200 h, were highly stable even at 85 °C in ambient air under dark conditions. Besides showing significant improvement in stability against light soaking and thermal stress, CuFeO2-based cells exhibited superior shelf stability even at 80 ± 5% relative humidity and retained over 90% of their initial PCE. Overall, we strongly believe that this study highlights the potential of inorganic HTMs for the commercial deployment of long-term stable and low-cost PSCs.

Low-Cost and Highly Efficient Carbon-Based Perovskite Solar Cells Exhibiting Excellent Long-Term Operational and UV Stability.

Today's perovskite solar cells (PSCs) mostly use components, such as organic hole conductors or noble metal back contacts, that are very expensive or cause degradation of their photovoltaic performance. For future large-scale deployment of PSCs, these components need to be replaced with cost-effective and robust ones that maintain high efficiency while ascertaining long-term operational stability. Here, a simple and low-cost PSC architecture employing dopant-free TiO2 and CuSCN as the electron and hole conductor, respectively, is introduced while a graphitic carbon layer deposited at room temperature serves as the back electrical contact. The resulting PSCs show efficiencies exceeding 18% under standard AM 1.5 solar illumination and retain ≈95% of their initial efficiencies for >2000 h at the maximum power point under full-sun illumination at 60 °C. In addition, the CuSCN/carbon-based PSCs exhibit remarkable stability under ultraviolet irradiance for >1000 h while under similar conditions, the standard spiro-MeOTAD/Au based devices degrade severely.

Hysteresis-Free Planar Perovskite Solar Cells with a Breakthrough Efficiency of 22% and Superior Operational Stability over 2000 h.

Understanding the transport loss and the ways to improving optoelectronic properties of the charge transporting layers is critical to fabricate highly efficient, long-term stable, and hysteresis-free perovskite solar cells (PSCs). Herein, we report success in suppressing hysteresis and boosting the performance of operationally stable planar solar cells using a ruthenium (Ru) doped tin oxide (SnO2) electron transport layer (ETL) and Zn-TFSI2 doped spiro-OMeTAD hole transport layer (HTL). Apparently, the incorporation of Ru drastically shifts the Fermi level of SnO2 ETL upward, which provides a facile route to tailor the ETL/perovskite band-offset to improve built-in electric fields of devices for improving VOC and electron extraction simultaneously. Meanwhile, rapid injection of the photogenerated electrons from perovskite into ETL with reduced trap density is also observed when Ru doped SnO2 is employed as ETL. On the other hand, the conception of Zn-TFSI2 incorporation into HTL not only further boosts the photovoltaic performance but also prolongs the photostability of the devices. Consequently, a breakthrough efficiency of 22% (average 21.8%) with a JSC of 24.6 mA cm-2, VOC of 1.15 V, and FF of 0.78 has been obtained in planar-type PSCs with a loss in efficiency of only ∼3% at maximum power point tracking over 2000 h.

Ultrahydrophobic 3D/2D fluoroarene bilayer-based water-resistant perovskite solar cells with efficiencies exceeding 22.

Preventing the degradation of metal perovskite solar cells (PSCs) by humid air poses a substantial challenge for their future deployment. We introduce here a two-dimensional (2D) A2PbI4 perovskite layer using pentafluorophenylethylammonium (FEA) as a fluoroarene cation inserted between the 3D light-harvesting perovskite film and the hole-transporting material (HTM). The perfluorinated benzene moiety confers an ultrahydrophobic character to the spacer layer, protecting the perovskite light-harvesting material from ambient moisture while mitigating ionic diffusion in the device. Unsealed 3D/2D PSCs retain 90% of their efficiency during photovoltaic operation for 1000 hours in humid air under simulated sunlight. Remarkably, the 2D layer also enhances interfacial hole extraction, suppressing nonradiative carrier recombination and enabling a power conversion efficiency (PCE) >22%, the highest reported for 3D/2D architectures. Our new approach provides water- and heat-resistant operationally stable PSCs with a record-level PCE.

Site-selective Synthesis of ß-[70]PCBM-like Fullerenes: Efficient Application in Perovskite Solar Cells.

We report on the site-selective synthesis of PCBM-like [70]fullerene site-isomers, where the elusive ß-site-isomers are, for the first time, the major product in a (cyclo)addition chemical reaction involving [70]fullerene. The reaction involves an straightforward cyclopropanation of [70]fullerene from sulfonium salts, affording a mixture of α and ß site-isomers in good yields. Amazingly, the preference for the α- or ß-site-isomer can be efficiently controlled by means of the solvent polarity! DFT theoretical calculations (DMF and toluene) nicely predict that, although the formation of the α-adduct is, as expected, thermodynamically favored, the selectivity of the process is determined by the energy difference of the respective transition states. Furthermore, the employ of α or/and ß site-isomers, as pure materials or as a mixture of them, used as templating agent, has been evaluated in perovskite solar cells. The positive influence of the [70]fullerenes by passivating the voids/pin-holes and/or deep slits, is reflected in highly efficient and stable bulk heterojunction perovskite solar cells, whose performance (around 20 %) is slightly but consistently depending on the isomeric fullerene composition. These experimental findings pave the way to investigate a new reactivity on C70 and to explore the properties of the less-known ß-derivatives.