Defect Passivation and Crystallization Regulation for Efficient and Stable Formamidinium Lead Iodide Solar Cells with Multifunctional Amidino Additive.

Amidino-based additives show great potential in high-performance perovskite solar cells (PSCs). However, the role of different functional groups in amidino-based additives have not been well elucidated. Herein, two multifunctional amidino additives 4-amidinobenzoic acid hydrochloride (ABAc) and 4-amidinobenzamide hydrochloride (ABAm) are employed to improve the film quality of formamidinium lead iodide (FAPbI3) perovskites. Compared with ABAc, the amide group imparts ABAm with larger dipole moment and thus stronger interactions with the perovskite components, i.e., the hydrogen bonds between N…H and I- anion and coordination bonds between C = O and Pb2+ cation. It strengthens the passivation effect of iodine vacancy defect and slows down the crystallization process of α-FAPbI3, resulting in the significantly reduced non-radiative recombination, long carrier lifetime of 1.7 µs, uniformly large crystalline grains, and enhances hydrophobicity. Profiting from the improved film quality, the ABAm-treated PSC achieves a high efficiency of 24.60%, and maintains 93% of the initial efficiency after storage in ambient environment for 1200 hours. This work provides new insights for rational design of multifunctional additives regarding of defect passivation and crystallization control toward highly efficient and stable PSCs.

Self-Assembly of Delta-Formamidinium Lead Iodide Nanoparticles to Nanorods: Study of Memristor Properties and Resistive Switching Mechanism.

In the quest for advanced memristor technologies, this study introduces the synthesis of delta-formamidinium lead iodide (δ-FAPbI3) nanoparticles (NPs) and their self-assembly into nanorods (NRs). The formation of these NRs is facilitated by iodide vacancies, promoting the fusion of individual NPs at higher concentrations. Notably, these NRs exhibit robust stability under ambient conditions, a distinctive advantage attributed to the presence of capping ligands and a crystal lattice structured around face-sharing octahedra. When employed as the active layer in resistive random-access memory devices, these NRs demonstrate exceptional bipolar switching properties. A remarkable on/off ratio (105) is achieved, surpassing the performances of previously reported low-dimensional perovskite derivatives and α-FAPbI3 NP-based devices. This enhanced performance is attributed to the low off-state current owing to the reduced number of halide vacancies, intrinsic low dimensionality, and the parallel alignment of NRs on the FTO substrate. This study not only provides significant insights into the development of superior materials for memristor applications but also opens new avenues for exploring low-dimensional perovskite derivatives in advanced electronic devices.

Lead Iodide Redistribution Enables In Situ Passivation for Blading Inverted Perovskite Solar Cells with 24.5% Efficiency.

Blade-coating stands out as an alternative for fabricating scalable perovskite solar cells. However, it demands special control of the precursor composition regarding nucleation and crystallization and currently exhibits lower performance than the spin-coating process. It is mainly the resulting film morphology and excess lead iodide (PbI2) distribution that influences the optoelectronic properties. Here, the effectiveness of introducing N-Methyl-2-pyrrolidone (NMP) to regulate the structure of the perovskite layer and the redistribution of PbI2 is found. The introduction of NMP leads to the accumulation of excess PbI2, mainly on the top surface, reducing residual PbI2 at the perovskite buried interface. This not only facilitates the passivation of perovskite grain boundaries but also eliminates the potential degradation of the PbI2 triggered by light illumination in the perovskite buried interface. The optimized NMP-modified inverted perovskite solar cell achieves a champion efficiency of 24.5%, among the highest reported blade-coated perovskite solar cells. Furthermore, 13.68 cm2 blading perovskite solar modules are fabricated and demonstrate an efficiency of up to 20.4%. These findings underscore that with proper modulation of precursor composition, blade-coating can be a feasible and superior alternative for manufacturing high-quality perovskite films, paving the way for their large-scale applications in photovoltaic technology.

Modulation of Buried Interface by 1-(3-aminopropyl)-Imidazole for Efficient Inverted Formamidinium-Cesium Perovskite Solar Cells.

Considering the direct influence of substrate surface nature on perovskite (PVK) film growth, buried interfacial engineering is crucial to obtain ideal perovskite solar cells (PSCs). Herein, 1-(3-aminopropyl)-imidazole (API) is introduced at polytriarylamine (PTAA)/PVK interface to modulate the bottom property of PVK. First, the introduction of API improves the growth of PVK grains and reduces the Pb2+ defects and residual PbI2 present at the bottom of the film, contributing to the acquisition of high-quality PVK film. Besides, the presence of API can optimize the energy structure between PVK and PTAA, which facilitates the interfacial charge transfer. Density functional theory (DFT) reveals that the electron donor unit (R-C ═ N) of the API prefers to bind with Pb2+ traps at the PVK interface, while the formation of hydrogen bonds between the R-NH2 of API and I- strengthens the above binding ability. Consequently, the optimum API-treated inverted formamidinium-cesium (FA/Cs) PSCs yields a champion power conversion efficiency (PCE) of 22.02% and exhibited favorable stability.

Interaction of C60 with Methylammonium Lead Iodide Perovskite Surfaces: Unveiling the Role of C60 in Surface Engineering.

Understanding the interaction between fullerene (C60) and perovskite surfaces is pivotal for advancing the efficiency and stability of perovskite solar cells. In this study, we investigate the adsorption behavior of C60 on methylammonium lead iodide (MAPbI3) surfaces using periodic density functional theory calculations. We explore various surface terminations and defect configurations to elucidate the influence of surface morphology on the C60-perovskite interaction, computing the adsorption energy and transfer of charge. Our results reveal distinct adsorption energies and charge transfer mechanisms for different surface terminations, shedding light on the role of surface defects in modifying the electronic structure and stability of perovskite materials. Furthermore, we provide insights into the potential of C60 to passivate surface defects, playing a relevant role in the surface reconstruction after the formation of defects. This comprehensive understanding of C60-perovskite interactions offers valuable guidelines about the role of fullerenes on surface structure and reconstruction.

Polyfluorinated Organic Diammonium Induced Lead Iodide Arrangement for Efficient Two-Step-Processed Perovskite Solar Cells.

The inefficient conversion of lead iodide to perovskite has become one of the major challenges in further improving the performance of perovskite solar cells fabricated by the two-step method. Herein, the discontinuous lead iodide layer realized by introduction of a polyfluorinated organic diammonium salt, octafluoro-([1,1'-biphenyl]-4,4'-diyl)-dimethanaminium (OFPP) iodide which does not form low-dimensional perovskites, can enable the satisfactory conversion of lead iodide into perovskite, leading to meliorated crystallinity and enlarged grains in the OFPP modulated perovskite (OFPP-PVK) film. Combined with the effective defect passivation, the OFPP-PVK films show enhanced charge mobility and suppressed charge recombination. Accordingly, the OFPP-based perovskite solar cells exhibit a champion efficiency of 24.76 % with better device stability. Moreover, a superior efficiency of 21.04 % was achieved in a large-area perovskite module (100 cm2). Our work provides a unique insight into the function of organic diammonium additive in boosting photovoltaic performance.

Formamidinium Lead Iodide-Based Inverted Perovskite Solar Cells with Efficiency over 25 % Enabled by An Amphiphilic Molecular Hole-Transporter.

Formamidinium lead iodide (FAPbI3) represents an optimal absorber material in perovskite solar cells (PSCs), while the application of FAPbI3 in inverted-structured PSCs has yet to be successful, mainly owing to its inferior film-forming on hydrophobic or defective hole-transporting substrates. Herein, we report a substantial improvement of FAPbI3-based inverted PSCs, which is realized by a multifunctional amphiphilic molecular hole-transporter, (2-(4-(10H-phenothiazin-10-yl)phenyl)-1-cyanovinyl)phosphonic acid (PTZ-CPA). The phenothiazine (PTZ) based PTZ-CPA, carrying a cyanovinyl phosphonic acid (CPA) group, forms a superwetting hole-selective underlayer that enables facile deposition of high-quality FAPbI3 thin films. Compared to a previously established carbazole-based hole-selective material (2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl)phosphonic acid (MeO-2PACz), the crystallinity of FAPbI3 is enhanced and the electronic defects are passivated by the PTZ-CPA more effectively, resulting in remarkable increases in photoluminescence quantum yield (four-fold) and Shockley-Read-Hall lifetime (eight-fold). Moreover, the PTZ-CPA shows a larger molecular dipole moment and improved energy level alignment with FAPbI3, benefiting the interfacial hole-collection. Consequently, FAPbI3-based inverted PSCs achieve an unprecedented efficiency of 25.35 % under simulated air mass 1.5 (AM1.5) sunlight. The PTZ-CPA based device shows commendable long-term stability, maintaining over 90 % of its initial efficiency after continuous operation at 40 °C for 2000 hours.

Correlation between Interfacial Structures and Device Performance: The Double-Edged Sword Effect of Lead Iodide in Perovskite Solar Cells.

The interfacial electronic structure of perovskite layers and transport layers is critical for the performance and stability of perovskite solar cells (PSCs). The device performance of PSCs can generally be improved by adding a slight excess of lead iodide (PbI2 ) to the precursor solution. However, its underlying working mechanism is controversial. Here, we performed a comprehensive study of the electronic structures at the interface between CH3 NH3 PbI3 and C60 with and without the modification of PbI2 using in situ photoemission spectroscopy measurements. The correlation between the interfacial structures and the device performance was explored based on performance and stability tests. We found that there is an interfacial dipole reversal, and the downward band bending is larger at the CH3 NH3 PbI3 /C60 interface with the modification of PbI2 as compared to that without PbI2 . Therefore, PSCs with PbI2 modification exhibit faster charge carrier transport and slower carrier recombination. Nevertheless, the modification of PbI2 undermines the device stability due to aggravated iodide migration. Our findings provide a fundamental understanding of the CH3 NH3 PbI3 /C60 interfacial structure from the perspective of the atomic layer and insight into the double-edged sword effect of PbI2 as an additive.

Tuned Transport Path of Perovskite MAPbI3 -based Memristor Structure.

In this study, the features of resistive random access memory (RRAM) employing a straightforward Cr/MAPbI3 /FTO three-layer structure have been examined and clarified. The device displays various resistance switching (RS) behavior at various sweep voltages between 0.5 and 5 V. The RS effect has a conversion in the direction of the SET and RESET processes during sweeping for a number of cycles at a specific voltage. The directional change of the RS processes corresponds to the dominant transition between the generation/recombination of iodide ion and vacancy in the MAPbI3 perovskite layer and the electrochemical metallization of the Cr electrode under the influence of an electric field, which results in the conductive filament (CF) formation/rupture. At each stage, these processes are controlled by specific charge conduction mechanisms, including Ohmic conduction, space-charge-limited conduction (SCLC), and variable-range hopping (VRH). By identifying the biased voltage and the quantity of voltage sweep cycles, one can take a new approach to control or modulate the pathways for effective charge transport. This new approach is made possible by an understanding of the RS characteristics and the corresponding mechanisms causing the variation of RS behavior in the structure.

Interfacial Interaction Enables Enhanced Mobility in Hybrid Perovskite-Conjugated Polymer Transistors with High-k Fluorinated Polymer Dielectrics.

The charge carrier mobility of organic field-effect transistors (OFETs) has been remarkably improved through several engineering approaches and techniques by targeting pivotal parts. Herein, an ultrathin perovskite channel layer that boosts the field-effect mobility of conjugated polymer OFETs by forming perovskite-conjugated polymer hybrid semiconducting channel is introduced. The optimized lead-iodide-based perovskite-conjugated polymer hybrid channel transistors show enhanced hole mobility of over 4 cm2  V-1  s-1 (average = 2.10 cm2  V-1  s-1 ) with high reproducibility using a benchmark poly(3-hexylthiophene) (P3HT) polymer and employing high-k fluorinated polymer dielectrics. A significant hole carrier mobility enhancement of ≈200-400% in benzo[1,2-b:4,5:b']dithiophene (BDT)-based conjugated polymers is also demonstrated by exploring certain interactive groups with perovskite. This significant enhancement in the transistor performance is attributed to the increased charge carrier density in the hybrid semiconducting channel and the perovskite-polymer interactions. The findings of this paper demonstrate an exceptional engineering approach for carrier mobility enhancement in hybrid perovskite-conjugated-polymer-based electronic devices.

Managing Excess Lead Iodide with Functionalized Oxo-Graphene Nanosheets for Stable Perovskite Solar Cells.

Stability issues could prevent lead halide perovskite solar cells (PSCs) from commercialization despite it having a comparable power conversion efficiency (PCE) to silicon solar cells. Overcoming drawbacks affecting their long-term stability is gaining incremental importance. Excess lead iodide (PbI2 ) causes perovskite degradation, although it aids in crystal growth and defect passivation. Herein, we synthesized functionalized oxo-graphene nanosheets (Dec-oxoG NSs) to effectively manage the excess PbI2 . Dec-oxoG NSs provide anchoring sites to bind the excess PbI2 and passivate perovskite grain boundaries, thereby reducing charge recombination loss and significantly boosting the extraction of free electrons. The inclusion of Dec-oxoG NSs leads to a PCE of 23.7 % in inverted (p-i-n) PSCs. The devices retain 93.8 % of their initial efficiency after 1,000 hours of tracking at maximum power points under continuous one-sun illumination and exhibit high stability under thermal and ambient conditions.

Managing Secondary Phase Lead Iodide in Hybrid Perovskites via Surface Reconstruction for High-Performance Perovskite Solar Cells with Robust Environmental Stability.

Rationally managing the secondary-phase excess lead iodide (PbI2 ) in hybrid perovskite is of significance for pursuing high performance perovskite solar cells (PSCs), while the challenge remains on its conversion to a homogeneous layer that is robust stable against environmental stimuli. We herein demonstrate an effective strategy of surface reconstruction that converts the excess PbI2 into a gradient lead sulfate-silica bi-layer, which substantially stabilizes the perovskite film and reduces interfacial charge transfer barrier in the PSCs device. The perovskite films with such bi-layer could bear harsh conditions such as soaking in water, light illumination at 70 % relative humidity, and the damp-thermal (85 °C and 30 % humidity) environment. The resulted PSCs deliver a champion efficiency up to 24.09 %, as well as remarkable environmental stability, e.g., retaining 78 % of their initial efficiency after 5500 h of shelf storage, and 82 % after 1000 h of operational stability testing.

Carrier recombination in CH3NH3PbI3: why is it a slow process?

In methylammonium lead iodide (MAPbI3), a slow recombination process of photogenerated carriers has often been considered to be the most intriguing property of the material resulting in high-efficiency perovskite solar cells. In spite of intense research over a decade or so, a complete understanding of carrier recombination dynamics in MAPbI3has remained inconclusive. In this regard, several microscopic processes have been proposed so far in order to explain the slow recombination pathways (both radiative and non-radiative), such as the existence of shallow defects, a weak electron-phonon coupling, presence of ferroelectric domains, screening of band-edge charges through the formation of polarons, occurrence of the Rashba splitting in the band(s), and photon-recycling in the material. Based on the up-to-date findings, we have critically assessed each of these proposals/models to shed light on the origin of a slow recombination process in MAPbI3. In this review, we have presented the interplay between the mechanisms and our views/perspectives in determining the likely processes, which may dictate the recombination dynamics in the material. We have also deliberated on their interdependences in decoupling contributions of different recombination processes.

Passivating Defects at the Bottom Interface of Perovskite by Ethylammonium to Improve the Performance of Perovskite Solar Cells.

The interface of perovskite solar cells (PSCs) plays a significant role in influencing their performance, yet there is still scarce research focusing on their difficult-to-expose bottom interfaces. Herein, ethylammonium bromide (EABr) is introduced into the bottom interface and its passivation effects are studied directly. First, EABr can improve substrate wettability, which is beneficial for the perovskite-film deposition. By lifting off the perovskite film spontaneously from the substrate, it is found that EABr can significantly reduce the amount of unreacted PbI2 at the bottom interface. These PbI2 crystals have been recently identified as a major defect source and degradation site for perovskite film. Meanwhile, EABr also lifts the valence band maximum at the bottom side of perovskite from -5.38 to -5.09 eV, facilitating better hole transfer. Such a improvement is also verified by the study of charge carrier dynamics. Through introducing EABr, all photovoltaic parameters of the inverted PSCs are improved, and their power conversion efficiency (PCE) increases from 20.41% to 21.06%. The study highlights the importance of direct characterization of the bottom interface for a better passivation effect.

Precursor engineering for efficient and stable perovskite solar cells.

The perovskite film prepared by the two-step spin coating method is widely used in photovoltaic devices due to its good film morphology and great reproducibility. However, there usually exists excessive lead iodide (PbI2) in the perovskite film for this method, which is believed to passivate the grain boundaries (GBs) to increase the efficiency of the perovskite solar cells. Nevertheless, the excessive PbI2at the GBs of perovskite is believed to induce the decomposition of the perovskite film and undermine the long-term stability of devices. In this study, we utilize precursor engineering to realize the preparation of perovskite solar cells with high efficiency and stability. The concentration of organic salts (AX: A = MA+, FA+; X = I-, Cl-) in the precursor solution for the second step of the two-step spin coating method is adjusted to optimize the perovskite light-absorbing layer so that the excessive PbI2is converted into perovskite to obtain a smooth and pinhole-free perovskite film with high performance. Our results indicate that by adjusting the concentration of AX in the precursor solution, PbI2in the film could be completely converted into perovskite without excessive AX residue. Both the efficiency and stability of the perovskite solar cells without excessive PbI2have been significantly improved. A planar perovskite solar cell with the highest power conversion efficiency (PCE) of 21.26% was achieved, maintaining about 90% of the initial PCE after 300 h of storage in a dry air environment and in the dark, about 76% of the initial PCE after 300 h of continuous illumination of 1 Sun.

Fabricating MAPbI3/MoS2 Composites for Improved Photocatalytic Performance.

Although lead halide perovskites are demonstrated to be promising photocatalysts for hydrogen evolution from hydrogen halide splitting, it still remains challenging to fabricate efficient and stable catalysts. Here MoS2 nanoflowers with abundant active sites are assembled with methylammonium lead iodide (MAPbI3) microcrystals to form a new heterostructure. Its hydrogen evolution rate can reach up to about 30 000 µmol g-1 h-1, which is more than 1000-fold higher than pristine MAPbI3 under visible light irradiation (λ ≥ 420 nm). Importantly, the solar HI splitting efficiency reaches 7.35%, one of the highest efficiencies so far. The introduction of MoS2 with proper band alignment and unsaturated species can efficiently promote the charge separation and afford more active sites for H2 production. This finding not only provides a highly efficient and stable photocatalyst for hydrogen evolution but also offers a useful modification strategy on lead halide perovskites.

Tuning Hybrid exciton-Photon Fano Resonances in Two-Dimensional Organic-Inorganic Perovskite Thin Films.

As easy-to-grow quantum wells with narrow excitonic features at room temperature, two-dimensional (2D) Ruddleson-Popper perovskites are promising for realizing novel nanophotonic devices based on exciton-photon interactions. Here, we demonstrate a distinct hybrid exciton-photon Fano resonance in (C4H9NH3)2PbI4 thin films prepared via spin coating. Using a classical coupled-oscillator model and finite-difference time-domain simulations, we link the Fano interference to the coupling of the exciton with the Rayleigh-like scattering of the film microstructure. Combining colloidal plasmonic cavities with the 2D perovskite films, we demonstrate tuning of the Fano resonance. In combination with silver nanoparticles, the exciton-photon Fano interference couples to the in-plane plasmonic modes with indications of Rabi splitting. By creating a nanoparticle on mirror geometry, we address the out-of-plane excitonic component, reaching an intermediate coupling regime. These structures suggest possible photonic targets for biomolecular self-assembly applications.

Thermodynamic Study of Formamidinium Lead Iodide (CH5N2PbI3) from 5 to 357 K.

In the present study, the molar heat capacity of solid formamidinium lead iodide (CH5N2PbI3) was measured over the temperature range from 5 to 357 K using a precise automated adiabatic calorimeter. In the above temperature interval, three distinct phase transitions were found in ranges from 49 to 56 K, from 110 to 178 K, and from 264 to 277 K. The standard thermodynamic functions of the studied perovskite, namely the heat capacity C°p(T), enthalpy [H0(T) - H0(0)], entropy S0(T), and [G°(T) - H°(0)]/T, were calculated for the temperature range from 0 to 345 K based on the experimental data. Herein, the results are discussed and compared with those available in the literature as measured by nonclassical methods.

Deeper Insight into the Role of Organic Ammonium Cations in Reducing Surface Defects of the Perovskite Film.

Organic ammonium salts (OASs) have been widely used to passivate perovskite defects. The passivation mechanism is usually attributed to coordination of OASs with unpaired lead or halide ions, yet ignoring their interaction with excess PbI2 on the perovskite film. Herein, we demonstrate that OASs not only passivate defects by themselves, but also redistribute excess aggregated PbI2 into a discontinuous layer, augmenting its passivation effect. Moreover, alkyl OAS is more powerful to disperse PbI2 than a F-containing one, leading to better passivation and device efficiency because F atoms restrict the intercalation of OAS into PbI2 layers. Inspired by this mechanism, exfoliated PbI2 nanosheets are adopted to provide better dispersity of PbI2 , further boosting the efficiency to 23.14 %. Our finding offers a distinctive understanding of the role of OASs in reducing perovskite defects, and a route to choosing an OAS passivator by considering substitution effects rather than by trial and error.

The Influence of Oxygen Plasma on Methylammonium Lead Iodide (MAPbI3) Film Doped with Lead Cesium Triiodide (CsPbI3).

In recent years, the study of organic-inorganic halide perovskite as an optoelectronics material has been a significant line of research, and the power conversion efficiency of solar cells based on these materials has reached 25.5%. However, defects on the surface of the film are still a problem to be solved, and oxygen plasma is one of the ways to passivate surface defects. In order to avoid destroying the methylammonium lead iodide (MAPbI3), the influence of plasma powers on film was investigated and the cesium triiodide (CsPbI3) quantum dots (QDs) were doped into the film. In addition, it was found that oxygen plasma can enhance the mobility and carrier concentration of the MAPbI3 film.