Unraveling the Influence of Solvent on Side Reactions between Formamidinium Lead Triiodide and Methylammonium Cations.

Formamidinium lead triiodide (FAPbI3) perovskite thin films are commonly deposited through a solution process, often incorporating a specific amount of methylammonium halide to stabilize the α-phase or enhance their crystallinity. The precursor solution for such coatings significantly influences the fabrication of perovskite solar cells (PSCs), involving time-dependent aging and byproduct formation. The chemical principle underlying this behavior is believed to be related to the deprotonation of methylamine cations (MA+) and subsequent chemical reactions with FA+ to generate N-methylformamidinium. Nevertheless, the role of the solvent in the side reactions between these organic cations remains unclear. This work systematically investigates the reaction reactivity in three protic solvents and three aprotic solvents. We uncover the hidden role of dimethylamine from the hydrolysis products of N,N-dimethylformamide, promoting the reaction between FA+ and MA+. Additionally, we elucidate the impact of environmental factors, such as water and oxygen, in stabilizing precursor solutions. This work establishes a basic concept and scientific direction for rationalizing high-efficiency, reproducible, and long-term-stable PSCs.

Double-side 2D/3D heterojunctions for inverted perovskite solar cells.

Defects at the top and bottom interfaces of three-dimensional (3D) perovskite photoabsorbers diminish the performance and operational stability of perovskite solar cells owing to charge recombination, ion migration and electric-field inhomogeneities1-5. Here we demonstrate that long alkyl amine ligands can generate near-phase-pure 2D perovskites at the top and bottom 3D perovskite interfaces and effectively resolve these issues. At the rear-contact side, we find that the alkyl amine ligand strengthens the interactions with the substrate through acid-base reactions with the phosphonic acid group from the organic hole-transporting self-assembled monolayer molecule, thus regulating the 2D perovskite formation. With this, inverted perovskite solar cells with double-side 2D/3D heterojunctions achieved a power conversion efficiency of 25.6% (certified 25.0%), retaining 95% of their initial power conversion efficiency after 1,000 h of 1-sun illumination at 85 °C in air.

Deciphering Reaction Products in Formamidine-Based Perovskites with Methylammonium Chloride Additive.

The fabrication of formamidinium lead iodide (FAPbI3) perovskite solar cells (PSCs) involves the addition of methylammonium chloride (MACl) to promote low-temperature α-phase formation and grain growth. However, as the added MACl deprotonates and volatilizes into methylamine (MA0) and HCl for removal, MA0 can chemically interact with formamidinium (FA+), forming methyl formamidinium (MFA+) as a byproduct. Despite its significance, the chemical interactions among FAPbI3 perovskites, MACl additives, and their byproducts remain poorly understood. Our findings reveal that the FA+ and MA0 reaction primarily yields a mixture of cis/trans-N-methyl formamidinium iodide (MFAI) isomers, with cis-MFAI prevailing as the dominant species. Moreover, MFAI subsequently reacts with PbI2 to yield fully formed cis-MFAPbI3 2H-phase perovskite. We elucidated the effects of MFAI on the crystal growth, phase stability, and band gap of formamidine-based perovskites through the growth of single crystals. This research offers valuable insights into the role of these byproducts in influencing the efficiency and long-term stability of future PSCs.

Stabilization of photoactive phases for perovskite photovoltaics.

Interest in photovoltaics (PVs) based on Earth-abundant halide perovskites has increased markedly in recent years owing to the remarkable properties of these materials and their suitability for energy-efficient and scalable solution processing. Formamidinium lead triiodide (FAPbI3)-rich perovskite absorbers have emerged as the frontrunners for commercialization, but commercial success is reliant on the stability meeting the highest industrial standards and the photoactive FAPbI3 phase suffers from instabilities that lead to degradation - an effect that is accelerated under working conditions. Here, we critically assess the current understanding of these phase instabilities and summarize the approaches for stabilizing the desired phases, covering aspects from fundamental research to device engineering. We subsequently analyse the remaining challenges for state-of-the-art perovskite PVs and demonstrate the opportunities to enhance phase stability with ongoing materials discovery and in operando analysis. Finally, we propose future directions towards upscaling perovskite modules, multijunction PVs and other potential applications.

Integrated System Built for Small-Molecule Semiconductors via High-Throughput Approaches.

High-throughput synthesis of solution-processable structurally variable small-molecule semiconductors is both an opportunity and a challenge. A large number of diverse molecules provide a possibility for quick material discovery and machine learning based on experimental data. However, the diversity of the molecular structure leads to the complexity of molecular properties, such as solubility, polarity, and crystallinity, which poses great challenges to solution processing and purification. Here, we first report an integrated system for the high-throughput synthesis, purification, and characterization of molecules with a large variety. Based on the principle "Like dissolves like," we combine theoretical calculations and a robotic platform to accelerate the purification of those molecules. With this platform, a material library containing 125 molecules and their optical-electronic properties was built within a timeframe of weeks. More importantly, the high repeatability of recrystallization we design is a reliable approach to further upgrading and industrial production.

Controlled growth of perovskite layers with volatile alkylammonium chlorides.

Controlling the crystallinity and surface morphology of perovskite layers by methods such as solvent engineering1,2 and methylammonium chloride addition3-7 is an effective strategy for achieving high-efficiency perovskite solar cells. In particular, it is essential to deposit α-formamidinium lead iodide (FAPbI3) perovskite thin films with few defects due to their excellent crystallinity and large grain size. Here we report the controlled crystallization of perovskite thin films with the combination of alkylammonium chlorides (RACl) added to FAPbI3. The δ-phase to α-phase transition of FAPbI3 and the crystallization process and surface morphology of the perovskite thin films coated with RACl under various conditions were investigated through in situ grazing-incidence wide-angle X-ray diffraction and scanning electron microscopy. RACl added to the precursor solution was believed to be easily volatilized during coating and annealing owing to dissociation into RA0 and HCl with deprotonation of RA+ induced by RA⋯H+-Cl- binding to PbI2 in FAPbI3. Thus, the type and amount of RACl determined the δ-phase to α-phase transition rate, crystallinity, preferred orientation and surface morphology of the final α-FAPbI3. The resulting perovskite thin layers facilitated the fabrication of perovskite solar cells with a power-conversion efficiency of 26.08% (certified 25.73%) under standard illumination.

Stabilization of the Alkylammonium Cations in Halide Perovskite Thin Films by Water-Mediated Proton Transfer.

The development of alkylammonium lead trihalide perovskite (ALHP) photovoltaics has grown rapidly over the past decade. However, there are remaining critical challenges, such as proton defects, which can lead to the material instability of ALHPs. Although specific strategies, including the use of halide additives, have significantly reduced the defects, a fundamental understanding of the defect passivation mechanism remains elusive. Herein, an approach and mechanism for minimizing proton defects in ALHP crystals by adding ionized halides to the perovskite precursor solution are reported. This work clarifies that the ionized halides induced proton transfer from H2 O to the alkylammonium cation in the precursor solution, stabilizing the ALHP crystals. The fundamental characteristics of ALHP and its precursors are examined by X-ray diffraction, transmittance electron microscopy, in situ extended X-ray absorption fine structure, Fourier transform NMR spectroscopy, and Fourier transform infrared spectroscopy. The findings from this work will guide the development of highly stable ALHP crystals, enabling efficient and stable optoelectronic ALHP devices.

Intrinsic Phase Stability and Inherent Bandgap of Formamidinium Lead Triiodide Perovskite Single Crystals.

Understanding the intrinsic phase stability and inherent band gap of formamidinium lead triiodide (FAPbI3 ) perovskites is crucial to further improve the performance of perovskite solar cells (PSCs). Herein, we explored the α- to δ-phase transition and band gap of FAPbI3 single crystals grown by an inverse temperature solubility method. We found that the residual γ-butyrolactone solvents in the inner empty space of the FAPbI3 single crystal accelerate the phase transition at kinetics. By adopting 2-methoxyethanol as the solvent, over 2000 h of stable α-FAPbI3 crystals could be acquired. This proves that although FAPbI3 is regarded as unstable at thermodynamics, it could own excellent kinetic stability without any doping or additives because of the slow solid to solid phase transition instead of the fast phase transition assisted by the solvents. Furthermore, we revealed that the bulk FAPbI3 single crystal with a size above 100 µm can have an inherent band gap of 1.41 eV. Thus, our work provides key scientific guidance for high-performance FAPbI3 -based PSCs.

Stabilization of Perovskite Solar Cells: Recent Developments and Future Perspectives.

Exceptional power conversion efficiency (PCE) of 25.7% in perovskite solar cells (PSCs) has been achieved, which is comparable with their traditional rivals (Si-based solar cells). However, commercialization-worthy efficiency and long-term stability remain a challenge. In this regard, there are increasing studies focusing on the interface engineering in PSC devices to overcome their poor technical readiness. Herein, the roles of electrode materials and interfaces in PSCs are discussed in terms of their PCEs and perovskite stability. All the current knowledge on the factors responsible for the rapid intrinsic and external degradation of PSCs is presented. Then, the roles of carbonaceous materials as substitutes for noble metals are focused on, along with the recent research progress in carbon-based PSCs. Furthermore, a sub-category of PSCs, that is, flexible PSCs, is considered as a type of exceptional power source due to their high power-to-weight ratios and figures of merit for next-generation wearable electronics. Last, the future perspectives and directions for research in PSCs are discussed, with an emphasis on their commercialization.

Rethinking the A cation in halide perovskites.

The A cation in ABX3 organic-inorganic lead halide perovskites (OLHPs) was conventionally believed to hardly affect their optoelectronic properties. However, more recent developments have unraveled the critical role of the A cation in the regulation of the physicochemical and optoelectronic properties of OLHPs. We review the important breakthroughs enabled by the versatility of the A cation and highlight potential opportunities and unanswered questions related to the A cation in OLHPs.

Towards environmental friendly multi-step processing of efficient mixed-cation mixed halide perovskite solar cells from chemically bath deposited lead sulphide.

Organic-inorganic hybrid perovskite is the most promising active layer for new generation of solar cells. Despite of highly efficient perovskite active layer conventionally fabricated by spin coating methods, the need for using toxic solvents like dimethylformamide (DMF) required for dissolving low soluble metal precursors as well as the difficulties for upscaling the process have restricted their practical development. To deal with these shortcomings, in this work, lead sulphide as the lead metal precursor was produced by aqueous chemical bath deposition. Subsequently, PbS films were chemically converted to PbI2 and finally to mixed-cation mixed halide perovskite films. The microstructural, optical and solar cell performance of mixed cation mixed halide perovskite films were examined. Results show that controlling the morphology of PbI2 platelets achieved from PbS precursor films enabled efficient conversion to final perovskite films. Using this processing technique, smooth and pin hole-free perovskite films having columnar grains of about 800 nm and a bandgap of 1.55 eV were produced. The solar cell performance consisting of such perovskite layers gave rise to a notable power conversion efficiency of 11.35% under standard solar conditions. The proposed processing technique is very promising towards an environmentally friendly method for the production of large-scale high efficient perovskite solar cells.

Efficient and Stable Antimony Selenoiodide Solar Cells.

Although antimony selenoiodide (SbSeI) exhibits a suitable bandgap as well as interesting physicochemical properties, it has not been applied to solar cells. Here the fabrication of SbSeI solar cells is reported for the first time using multiple spin-coating cycles of SbI3 solutions on Sb2Se3 thin layer, which is formed by thermal decomposition after depositing a single-source precursor solution. The performance exhibits a short-circuit current density of 14.8 mA cm-2, an open-circuit voltage of 473.0 mV, and a fill factor of 58.7%, yielding a power conversion efficiency (PCE) of 4.1% under standard air mass 1.5 global (AM 1.5 G, 100 mW cm-2). The cells retain ≈90.0% of the initial PCE even after illuminating under AM 1.5G (100 mW cm-2) for 2321 min. Here, a new approach is provided for combining selenide and iodide as anions, to fabricate highly efficient, highly stable, green, and low-cost solar cells.

Impact of strain relaxation on performance of α-formamidinium lead iodide perovskite solar cells.

High-efficiency lead halide perovskite solar cells (PSCs) have been fabricated with α-phase formamidinium lead iodide (FAPbI3) stabilized with multiple cations. The alloyed cations greatly affect the bandgap, carrier dynamics, and stability, as well as lattice strain that creates unwanted carrier trap sites. We substituted cesium (Cs) and methylenediammonium (MDA) cations in FA sites of FAPbI3 and found that 0.03 mol fraction of both MDA and Cs cations lowered lattice strain, which increased carrier lifetime and reduced Urbach energy and defect concentration. The best-performing PSC exhibited power conversion efficiency >25% under 100 milliwatt per square centimeter AM 1.5G illumination (24.4% certified efficiency). Unencapsulated devices maintained >80% of their initial efficiency after 1300 hours in the dark at 85°C.

Carbazole-Based Spiro[fluorene-9,9'-xanthene] as an Efficient Hole-Transporting Material for Perovskite Solar Cells.

For the practical application of perovskite solar cells (PSC), it is desirable to have high efficiency, long-term stability, and low manufacturing cost. Therefore, it is required to develop inexpensive and well-performing hole-transporting materials (HTMs). In this study, we synthesized SFXDAnCBZ, which is a new carbazole-based spiro[fluorene-9,9'-xanthene] (SFX) derivative, where the central core and end-cap units consist of SFX and N3,N6-bis(di-4-anisylamino)-9H-carbazole (DAnCBZ), respectively, as an efficient and low-cost HTM for PSCs. Photoluminescence quenching at the SFXDAnCBZ/perovskite interface was more effective than at the perovskite/Spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxy-phenyl-amine) 9,9'spiro-bifluorene) interface. We fabricated a PSC with a power conversion efficiency (PCE) of 20.87% under 1 sun illumination (100 mW cm-2) using SFXDAnCBZ as an HTM. This value is comparable to that measured for the benchmark Spiro-OMeTAD. Thus, this result confirms that SFX core-based materials can be a new kind of HTMs for high-efficiency and low-cost PSCs.

Unveiling the Relationship between the Perovskite Precursor Solution and the Resulting Device Performance.

For the fabrication of perovskite solar cells (PSCs) using a solution process, it is essential to understand the characteristics of the perovskite precursor solution to achieve high performance and reproducibility. The colloids (iodoplumbates) in the perovskite precursors under various conditions were investigated by UV-visible absorption, dynamic light scattering, photoluminescence, and total internal reflection fluorescence microscopy techniques. Their local structure was examined by in situ X-ray absorption fine structure studies. Perovskite thin films on a substrate with precursor solutions were characterized by transmission electron microscopy, X-ray diffraction analysis, space-charge-limited current, and Kelvin probe force microscopy. The colloidal properties of the perovskite precursor solutions were found to be directly correlated with the defect concentration and crystallinity of the perovskite film. This work provides guidelines for controlling perovskite films by varying the precursor solution, making it possible to use colloid-engineered lead halide perovskite layers to fabricate efficient PSCs.

Enhanced Moisture Stability by Butyldimethylsulfonium Cation in Perovskite Solar Cells.

Many organic cations in halide perovskites have been studied for their application in perovskite solar cells (PSCs). Most organic cations in PSCs are based on the protic nitrogen cores, which are susceptible to deprotonation. Here, a new candidate of fully alkylated sulfonium cation (butyldimethylsulfonium; BDMS) is designed and successfully assembled into PSCs with the aim of increasing humidity stability. The BDMS-based perovskites retain the structural and optical features of pristine perovskite, which results in the comparable photovoltaic performance. However, the fully alkylated aprotic nature of BDMS shows a much more pronounced effect on the increase in humidity stability, which emphasizes a generic electronic difference between protic ammonium and aprotic sulfonium cation. The current results would pave a new way to explore cations for the development of promising PSCs.

Strain Tuning via Larger Cation and Anion Codoping for Efficient and Stable Antimony-Based Solar Cells.

Strain induced by lattice distortion is one of the key factors that affect the photovoltaic performance via increasing defect densities. The unsatisfied power conversion efficiencies (PCEs) of solar cells based on antimony chalcogenides (Sb-Chs) are owing to their photoexcited carriers being self-trapped by the distortion of Sb2S3 lattice. However, strain behavior in Sb-Chs-based solar cells has not been investigated. Here, strain tuning in Sb-Chs is demonstrated by simultaneously replacing Sb and S with larger Bi and I ions, respectively. Bi/I codoped Sb2S3 cells are fabricated using poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-enzothiadiazole)] as the hole-transporting layer. Codoping reduced the bandgap and rendered a bigger tension strain (1.76 × 10-4) to a relatively smaller compression strain (-1.29 × 10-4). The 2.5 mol% BiI3 doped Sb2S3 cell presented lower trap state energy level than the Sb2S3 cell; moreover, this doping amount effectively passivated the trap states. This codoping shows a similar trend even in the low bandgap Sb2(SxSe1-x)3 cell, resulting in 7.05% PCE under the standard illumination conditions (100 mW cm-2), which is one of the top efficiencies in solution processing Sb2(SxSe1-x)3 solar cells. Furthermore, the doped cells present higher humidity, thermal and photo stability. This study provides a new strategy for stable Pb-free solar cells.

Efficient, stable solar cells by using inherent bandgap of α-phase formamidinium lead iodide.

In general, mixed cations and anions containing formamidinium (FA), methylammonium (MA), caesium, iodine, and bromine ions are used to stabilize the black α-phase of the FA-based lead triiodide (FAPbI3) in perovskite solar cells. However, additives such as MA, caesium, and bromine widen its bandgap and reduce the thermal stability. We stabilized the α-FAPbI3 phase by doping with methylenediammonium dichloride (MDACl2) and achieved a certified short-circuit current density of between 26.1 and 26.7 milliamperes per square centimeter. With certified power conversion efficiencies (PCEs) of 23.7%, more than 90% of the initial efficiency was maintained after 600 hours of operation with maximum power point tracking under full sunlight illumination in ambient conditions including ultraviolet light. Unencapsulated devices retained more than 90% of their initial PCE even after annealing for 20 hours at 150°C in air and exhibited superior thermal and humidity stability over a control device in which FAPbI3 was stabilized by MAPbBr3.

Multifaceted Role of a Dibutylhydroxytoluene Processing Additive in Enhancing the Efficiency and Stability of Planar Perovskite Solar Cells.

Significant research efforts are currently being devoted to improving both the crystalline quality and stability of lead halide perovskite absorbers to advance the commercial prospects of perovskite-based solar cells. Herein, we report a simple one-step dibutylhydroxytoluene (BHT) additive-based approach for simultaneously improving the crystallinity and resistance of perovskite films under adverse degradation conditions. We found that BHT, commonly known for its antioxidant properties, can considerably improve the performance of methylammonium lead iodide perovskite solar cells by modulating the chemical environment within the precursor medium to form intermediate complexes, and it can also suppress photooxidation, which results in perovskite degradation under environmental operating conditions. Consequently, a device exhibited a significant power conversion efficiency improvement to 18.1% with the BHT-additive-based perovskite absorber, exceeding the 17.1% efficiency achieved for the control device. The BHT additive also improved the perovskite stability by quenching intermediate reactions resulting in perovskite degradation to an undesirable lead iodide phase, as evidenced by detailed analysis of absorption spectra, grazing-incidence wide-angle X-ray scattering, X-ray photoelectron spectra, and photoluminescence measurements.

Mutual Insight on Ferroelectrics and Hybrid Halide Perovskites: A Platform for Future Multifunctional Energy Conversion.

An insight into the analogies, state-of-the-art technologies, concepts, and prospects under the umbrella of perovskite materials (both inorganic-organic hybrid halide perovskites and ferroelectric perovskites) for future multifunctional energy conversion and storage devices is provided. Often, these are considered entirely different branches of research; however, considering them simultaneously and holistically can provide several new opportunities. Recent advancements have highlighted the potential of hybrid perovskites for high-efficiency solar cells. The intrinsic polar properties of these materials, including the potential for ferroelectricity, provide additional possibilities for simultaneously exploiting several energy conversion mechanisms such as the piezoelectric, pyroelectric, and thermoelectric effect and electrical energy storage. The presence of these phenomena can support the performance of perovskite solar cells. The energy conversion using these effects (piezo-, pyro-, and thermoelectric effect) can also be enhanced by a change in the light intensity. Thus, there lies a range of possibilities for tuning the structural, electronic, optical, and magnetic properties of perovskites to simultaneously harvest energy using more than one mechanism to realize an improved efficiency. This requires a basic understanding of concepts, mechanisms, corresponding material properties, and the underlying physics involved with these effects.