Modifying Surface Termination of CsPbI3 Grain Boundaries by 2D Perovskite Layer for Efficient and Stable Photovoltaics

It is highly desirable for all-inorganic perovskite solar cells (PVSCs) to have reduced nonideal interfacial charge recombination in order to improve the performance. Although the construction of a 2D capping layer on 3D perovskite is an effective way to suppress interfacial nonradiative recombination, it is difficult to apply it to all-inorganic perovskites because of the resistance of Cs⁺ cesium ions in cation exchange reactions. To alleviate this problem, a simple approach using an ultra-thin 2D perovskite to terminate CsPbI₃ grain boundaries (GBs) without damaging the original 3D perovskite is developed. The 2D perovskite at the GBs not only enhances the charge-carrier extraction and transport but also effectively suppresses nonradiative recombination. In addition, because the 2D perovskite can prevent the moisture and oxygen from penetrating into the GBs and at the same time suppress the ion migration, the 2D terminated CsPbI₃ films exhibit significantly improved stability against humidity. Moreover, the devices without encapsulation can retain ≈81% of its initial power conversion efficiency (PCE) after being stored at 40 ± 5% relative humidity for 84 h. The 2D-based champion device exhibits a high PCE of 18.82% with a high open-circuit voltage of 1.16 V.     

Phenyl Ethylammonium Iodide introduction into inverted triple cation perovskite solar cells for improved VOC and stability

The efficiency of more than 25% in organic-inorganic hybrid perovskite solar cells has made them very attractive in the pursuit of cheaper alternatives to Si-based devices. However, the stability of the perovskite solar cells was challenging, given their high susceptibility to moisture. Very few reports have emerged in this regard that investigated the influence of introducing large cations into a triple cation perovskite (TC-PVS), with several studies limited to single and dual cation perovskites. Further, the crystallization of TC-PVS on a polymer surface such as PEDOT is not straightforward, and their inclusion in inverted solar cell devices was limited. In this work, we investigated the impact of incorporating Phenyl ethyl ammonium cation into FAMACs triple cation composition. We demonstrated improvements in the crystallinity and more uniform coverage with little to no pinholes and smooth morphology for an optimum PEA amount of 1.67% in the precursor solution. The superior morphology, along with a passivation effect from a quasi 2D phase, led to increased photoluminescence and minority carrier lifetimes. Corresponding inverted photovoltaic devices prepared with PEA showed increased open-circuit voltage from 0.89 V for a control sample to 0.95 V for 1.67% PEA and 0.98 V for 5% PEA, doped devices in an inverted configuration. The efficiency, as a result, increased from 11.27% for a control device to 14.85% for a 1.67% PEA doped device. Further, PEA doped devices showed improved operational and thermal stability attributed to the higher moisture tolerance and light-soaking ability of the PEA doped TC-PVS compared to the undoped TC-PVS.     

Synergistic Toughening and Self-Healing Strategy for Highly Efficient and Stable Flexible Perovskite Solar Cells

Halide perovskites are qualified to meet the flexibility demands of optoelectronic field because of their merits of flexibility, lightness, and low cost. However, the intrinsic defects and deformation-induced ductile fracture in both perovskite and buried interface significantly restrict the photoelectric performance and longevity of flexible perovskite solar cells (PVSCs). Here, a dual-dynamic cross-linking network is schemed to boost the photovoltaic efficiency and mechanical stability of flexible PVSCs by incorporating natural polymerizable small molecule α-lipoic acid (LA). The LA therein can be autonomously ring-opening polymerized through dynamic disulfide bonds and hydrogen bonds, concurrently forming coordination bonds to interact with perovskite component. Importantly, the polymerization product can serve as efficacious passivating and toughening agents to simultaneously optimize interfacial contact, enhance perovskite crystallinity and sustain robust mechanical bendability. Subsequently, the rigid (or flexible) p-i-n device realizes a champion efficiency of 22.43% (or 19.03%) with prominent operational stability. Moreover, the dual-dynamic cross-linking network endows PVSCs with bendability and self-healing capacity, allowing the optimized devices to retain >80% efficiency after 3000 bending cycles, and subsequently restore to ≈95% of its initial efficiency under mild heat-treatment. This toughening and self-healing strategy provides a facile and efficient path to prolong operational lifetime of flexible device.     

Efficient and Stable Quasi-2D Perovskite Solar Cells Enabled by Thermal-Aged Precursor Solution

Quasi-2D perovskites have received wide attention in photovoltaics owing to their excellent materials robustness and merits in the device stability. However, the highest power conversion efficiency (PCE) reported on quasi-2D perovskite solar cells (PSCs) still lags those of the 3D counterparts, mainly caused by the relatively high voltage loss. Here, a study is presented on the mitigation of voltage loss in quasi-2D PSCs via usage of thermal-aged precursor solutions (TAPSs). Based on the (AA)₂MA₄Pb₅I₁₆ (n = 5) quasi-2D perovskite absorber with a bandgap of ≈1.60 eV, a record-high open-circuit voltage of 1.24 V is obtained, resulting in boosting the PCE to 18.68%. The enhanced photovoltaic performance afforded by TAPS is attributed to the thermal-aged solution processing that triggers colloidal aggregations to reduce the nucleation sites inside the solution. As a result, formation of high-quality perovskite films featuring compact morphology, preferential crystal orientation, and lowered trap density is allowed. Of importance, with the improved film quality, the corrosion of Ag electrode induced by ion migrations is effectively restrained, which leads to a satisfactory storage stability with <2% degradation after 1200 h under nitrogen environment without encapsulation.     

Integrated Quasi-2D Perovskite/Organic Solar Cells with Efficiency over 19% Promoted by Interface Passivation

Integrated perovskite/organic solar cells (IPOSCs) have shown great potential in broadening the light absorption range and improving the photovoltaic performance. However, the severe interface charge recombination and unmatched energy levels between perovskite and organic photoactive layers hinder their performance improvement. Here, an efficient interface passivation strategy for IPOSCs based on a layered Ruddlesden–Popper (RP) perovskite and high photovoltaic performance is successfully demonstrated. It is found that an ultrathin conjugated polymer (PM6) layer could passivate the surface defects of perovskite film, tuning the energy level and suppress the nonradiative recombination loss, leading to efficient interface contact between RP perovskite and organic photoactive layers, boosting the open-circuit voltage from 1.06 to 1.12 V and the efficiency from 17.23% to 19.15%. Importantly, the optimized device shows extended photocurrent response to 930 nm with a peak intensity close to 50% from 800 to 931 nm. The results indicate that interface passivation using a functionalized polymer could be an efficient strategy to improve the photovoltaic performance of integrated devices.     

Universal Bottom Contact Modification with Diverse 2D Spacers for High-Performance Inverted Perovskite Solar Cells

Although the 2D spacer modification is widely studied in perovskite solar cells (PVSCs), the energy level alignment between the 2D/3D interfaces makes it unfavorable for top surface passivation in the inverted p-i-n device structure. To address this issue, the effect of bottom interface modification is studied with three representative 2D spacers, i.e., the Ruddlesden-Popper 2D spacer, Dion-Jacobson 2D spacer, and strong passivation 2D spacer, in inverted p-i-n PVSCs. After optimization, the PVSCs with these 2D spacer modifications universally exhibit the best efficiencies of ≈21.6%, which constitutes dramatic improvement compared to the control device (20.7%). By lifting off the perovskite layer, the optoelectronic properties of the bottom surface are studied, and the mechanism underlying the improved device performance is unveiled to be uniformly originated from the formation of 2D/3D heterojunction, where the cascade valence band facilitates the hole collection and electron back scattering field suppresses the charge recombination at the anode interface. Besides, the unencapsulated device retains 90% of initial efficiency after 30 days of storage in ambient air with a relative humidity of 30 ± 5%, indicating excellent stability against moisture and oxygen. This study provides insight into the bottom interface modification with diverse 2D spacers for high-performance p-i-n structured PVSC devices.     

Functional 2D Phases in Mixed Dimensional Perovskite Photovoltaics

Organic-inorganic hybrid perovskite solar cells (PSCs) with unique properties exhibit their powerful competitiveness in the photovoltaic field over the past few years. However, the challenges of stability for perovskite devices limit the commercialization and further development. The 2D/3D hybrid structures combine the superior efficiency of bulk perovskites and the superior stability of layered perovskites and gradually get hotspots of the photovoltaic field. In addition, there remains a lack of comprehensive understanding and systematic summary of the function of 2D perovskite attributed to the complex nature of 2D/3D structures. Here, the latest progress of 2D/3D hybrid structures and focus on the functionality of 2D phases in mixed structures and the underlying mechanism from the perspective of their different distributions in the perovskite layer is summarized. Then, the insight and vital factors for overall improvements in the stability of 2D/3D structures are thoroughly discussed. Finally, it is expected that this review will contribute to the present challenges and future research prospects in the photovoltaic industry.     

Efficient and Ambient‐Air‐Stable Solar Cell with Highly Oriented 2D@3D Perovskites

3D organic–inorganic lead halide perovskites have shown great potential in efficient photovoltaic devices. However, the low stability of the 3D perovskite layer and random arrangement of the perovskite crystals hinder its commercialization road. Herein, a highly oriented 2D@3D ((AVA)₂PbI₄@MAPbI₃) perovskite structure combining the advantages of both 2D and 3D perovskite is fabricated through an in situ route. The highest power conversion efficiency (PCE) of 18.0% is observed from a 2D@3D perovskite solar cell (PSC), and it also shows significantly enhanced device stability under both inert (90% of initial PCE for 32 d) and ambient conditions (72% of initial PCE for 20 d) without encapsulation. The high efficiency of 18.0% and nearly twofold improvement of device stability in ambient compared with pure 3D PSCs confirm that such 2D@3D perovskite structure is an effective strategy for high performance and increasing stability and thus will enable the timely commercialization of PSCs.     

Transparent and Reusable Nanostencil Lithography for Organic–Inorganic Hybrid Perovskite Nanodevices

Organic—inorganic hybrid perovskites have attracted considerable attention for developing novel optoelectronic devices owing to their excellent photoresponses. However, conventional nanolithography of hybrid perovskites remains a challenge because they undergo severe damage in standard lithographic solvents, which prohibits device miniaturization and integration. In this study, a novel transparent stencil nanolithography (t-SL) technique is developed based on focused ion beam (FIB)-assisted polyethylene terephthalate (PET) direct patterning. The proposed t-SL enables ultrahigh lithography resolution down to 100 nm and accurate stencil mask alignment. Moreover, the stencil mask can be reused more than ten times, which is cost-effective for device fabrication. By applying this lithographic technique to hybrid perovskites, a high-performance 2D hybrid perovskite heterostructure photodetector is fabricated. The responsivity and detectivity of the proposed heterostructure photodetector can reach up to 28.3 A W⁻¹ and 1.5 × 10¹³ Jones, respectively. This t-SL nanolithography technique based on FIB-assisted PET direct patterning can effectively support the miniaturization and integration of hybrid-perovskite-based electronic devices.     

Hystersis mechanism in perovskite photovoltaic devices and its potential application for multi-bit memory devices

The hysteresis in perovskites devices puzzled researchers because it was a big hurdle for device stability and the origin of it was still a riddle for people to solve. Here we reported our analysis in mechanism of the hysteresis based on the trap states in the perovskites film surface. We tried to explain the current hysteresis through the dynamic charge trapping–detrapping processes and the conclusion applied both in porous and planar structure devices. However, the proportion of deep traps and shallow traps are different in planar structure device and in porous structure device. Furthermore, we found perovskite devices has potentials of serving as memory devices due to the photocurrent hysteresis. The on/off ratio of memory based on perovskite can be higher than 60 and the write time was as low as 0.54 s as memory. It also had a very low read bias near 0 V. Moreover, the devices show multi-bit property and a multi-bit organic memory came forward as a novel application of perovskite devices.     

Nucleation and Crystallization Control via Polyurethane to Enhance the Bendability of Perovskite Solar Cells with Excellent Device Performance

Solar cells based on mixed organic–inorganic halide perovskites are promising photovoltaic technologies with low‐cost and fantastic power conversion efficiency (PCE). Enhancing the nucleation and regulating the crystallization rate of perovskite films and improving the bendability of brittle hybrid grains are crucial to improving the photovoltaic performance of flexible perovskite solar cells (PVSCs). Here, a simple approach is first introduced for fabricating perovskite films with full coverage and larger crystalline size by incorporating the elastomer polyurethane (PU) into the perovskite precursor solution to both retard the crystallization rate and improve the bendability. Shiny, smooth perovskite films are obtained with compact, micrometer‐sized crystalline grains that exhibit excellent photoelectric performances. The PVSCs fabricated by incorporating PU into the perovskite precursor offer an impressive PCE of 18.7% with almost no photocurrent hysteresis and excellent stability in ambient air. More importantly, the elastomer PU additive crosslinks the grain boundaries between neighboring perovskite crystals to form a PU network that effectively improves the bendability of the perovskite films.     

Low temperature fabrication of hybrid solar cells using co-sensitizer of perovskite and lead sulfide nanoparticles

Our cost-effective approach for hybridizing methylammonium lead iodide and PbS nanoparticles at low temperature (≤100 °C) for photovoltaic devices is introduced. As employed into a perovskite based solar cell platform, effects of PbS on the device performance were investigated. Through experimental observations under simulated air-mass 1.5G illumination (irradiation intensity of 100 mWcm⁻²), the efficiency of a perovskite:PbS device is 11% higher than that of a pristine perovskite solar cell under the same fabrication conditions as a result of the broadened absorption range in the infrared region. The highest photovoltaic performance was observed at a PbS concentration of 2% with an open-circuit voltage, short-circuit current density, fill factor, and power-conversion efficiency of 0.557 V, 22.841 mA cm⁻², 0.55, and 6.99%, respectively. Furthermore, PbS NPs could induce hydrophobic modification of the perovskite surface, leading to an improvement of the device stability in the air. Finally, the low-temperature and cost-effective fabrication process of the hybrid solar cells is a good premise for developing flexible/stretchable cells as well as future optoelectronic devices.     

Scalable,Template Driven Formation of Highly Crystalline Lead-Tin Halide Perovskite Films

Low bandgap lead-tin halide perovskites are predicted to be candidates to maximize the performance of single junction and tandem solar cells based on metal halide perovskites. In spite of the tremendous progress in lab-scale device efficiency, devices fabricated with scalable techniques fail to reach the same efficiencies, which hinder their potential industrialization. Herein, a method is proposed that involves a template of a 2D perovskite deposited with a scalable technique (blade coating), which is then converted in situ to form a highly crystalline 3D lead-tin perovskite. These templated grown films are alloyed with stoichiometric ratio and are highly oriented with the (l00) planes aligning parallel to the substrate. The low surface/volume ratio of the obtained single-crystal-like films contributes to their enhanced stability in different environments. Finally, the converted films are demonstrated as active layer for solar cells, opening up the opportunity to develop this scalable technique for the growth of highly crystalline hybrid halide perovskites for photovoltaic devices.     

Synthesis of 0D Manganese-Based Organic–Inorganic Hybrid Perovskite and Its Application in Lead-Free Red Light-Emitting Diode

Lead-based perovskite light-emitting diodes (PeLEDs) have exhibited excellent purity, high efficiency, and good brightness. In order to develop nontoxic, highly luminescent metal halide perovskite materials, tin, copper, germanium, zinc, bismuth, and other lead-free perovskites have been developed. Here, a novel 0D manganese-based (Mn-based) organic–inorganic hybrid perovskite with the red emission located at 629 nm, high photoluminescence quantum yield of 80%, and millisecond level triplet lifetime is reported. When applied as the emissive layer in the PeLEDs, the maximum recording brightness of devices after optimization is 4700 cd m⁻², and the peak external quantum efficiency is 9.8%. The half-life of the device reaches 5.5 h at 5 V. The performance and stability of Mn-based PeLEDs are one order of magnitude higher than those of other lead-free PeLEDs. This work clearly shows that the Mn-based perovskite will provide another route to fabricate stable and high-performance lead-free PeLEDs.     

Efficient and Stable Inverted Perovskite Solar Cells with TOASiW12-Modified Al as a Cathode

Inexpensive metal Al is scarcely utilized as the cathode in the perovskite solar cells (PVSCs) because its violent reaction with perovskite active layer results in poor device stability in air. It is urgent to improve the efficiency and stability of PVSCs with Al as the cathode for mass production of low-cost PVSCs. Herein, a novel solution-processed cathode interlayer material, surfactant-encapsulated polyoxometalate complex [(C₈H₁₇)₄N]₄[SiW₁₂O₄₀] (TOASiW₁₂) is reported. Using TOASiW₁₂-modified Al as the cathode, the power conversion efficiency (PCE) of 20.64% has been achieved in the inverted PVSCs. The findings demonstrate that a thin TOASiW₁₂ layer can effectively obstruct the chemical reaction between Al and perovskite layer, and significantly enhance the device stability. The unencapsulated devices with TOASiW₁₂-modified Al retain more than 80% of the initial PCE after 350 h storage in the ambient atmosphere at 45% relative humidity. This study provides an excellent alternative cathode interlayer material for efficient and stable inverted PVSCs.     

Side-Chain Functionalized Polymer Hole-Transporting Materials with Defect Passivation Effect for Highly Efficient Inverted Quasi-2D Perovskite Solar Cells

Compared with inverted 3D perovskite solar cell (PSCs), inverted quasi-2D PSCs have advantages in device stability, but the device efficiency is still lagging behind. Constructing polymer hole-transporting materials (HTMs) with passivation functions to improve the buried interface and crystallization properties of perovskite films is one of the effective strategies to improve the performance of inverted quasi-2D PSCs. Herein, two novel side-chain functionalized polymer HTMs containing methylthio-based passivation groups are designed, named PVCz-SMeTPA and PVCz-SMeDAD, for inverted quasi-2D PSCs. Benefited from the non-conjugated flexible backbone bearing functionalized side-chain groups, the polymer HTMs exhibit excellent film-forming properties, well-matched energy levels and improved charge mobility, which facilitates the charge extraction and transport between HTM and quasi-2D perovskite layer. More importantly, by introducing methylthio units, the polymer HTMs can enhance the contact and interactions with quasi-2D perovskite, and further passivating the buried interface defects and assisting the deposition of high-quality perovskite. Due to the suppressed interfacial non-radiative recombination, the inverted quasi-2D PSCs using PVCz-SMeTPA and PVCz-SMeDAD achieve impressive power conversion efficiency (PCE) of 21.41% and 20.63% with open-circuit voltage of 1.23 and 1.22 V, respectively. Furthermore, the PVCz-SMeTPA based inverted quasi-2D PSCs also exhibits negligible hysteresis and considerably improved thermal and long-term stability.     

Water‐Resistant and Flexible Perovskite Solar Cells via a Glued Interfacial Layer

Perovskite solar cells (PVSCs) are promising photovoltaic technologies for realizing power sources with outstanding power conversion efficiency (PCE) and low‐cost properties. However, the extraordinary photovoltaic performance can be maximized only if an extremely stabilized device structure is developed. Here, a novel glued poly(ethylene‐co‐vinyl acetate) (EVA) interfacial layer is introduced to fabricate highly efficient and stable PVSCs with excellent waterproofness and flexibility. This strategy can effectively passivate the perovskite surface, reduce defect density, and balance charge transfer, which leads to a champion PCE of 19.31% for a 0.1 cm² device and 11.73% for a 25 cm² solar module. More importantly, the formation of a glued EVA thin layer on the surface of perovskite can inhibit ionic migration to the Ag electrode, form favorable interfacial contact and adhesive interaction with the perovskite/[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester to sustain mechanical bending, and produce significant waterproofness from moisture invasion, thus facilitating improvement in the operational stability of the PVSCs. The EVA‐treated PVSCs exhibit superior PCE values of 15.12% for a flexible device (0.1 cm²) and 8.95% for a flexible module (25 cm²), as well as over 85% retention after 5000 bending cycles, which opens up a new strategy for the practical application of PVSCs in portable and wearable electronics.     

Enabling Efficient Blue-Emissive Circularly Polarized Luminescence by In Situ Crafting of Chiral Quasi-2D Perovskite Nanosheets within Polymer Nanofibers

Chiral perovskite materials have intrigued enormous interests because of their appealing chiroptical properties and tailorable non-centrosymmetric structures. However, it remains challenging to realize high-efficiency blue emissive circularly polarized luminescence (CPL) of intrinsic chiral perovskite nanomaterials at room temperature. Herein, a robust and versatile electrospinning strategy is reported for in situ construction of chiral 2D and quasi-2D perovskite nanosheets (PNSs) protected in polymer hybrid nanofibers. It is found that quasi-2D chiral PNS/polymer possesses inherent chirality and enhanced CPL properties at room temperature compared to 2D counterparts. Notably, CPL emission color of chiral quasi-2D PNS/polymer can be tuned from deep blue to sky blue, and a high luminescence dissymmetry values up to −8.0 × 10⁻³ can be achieved. Different perovskites, polymers, and nanofibrous structures are expanded to explore the universality of polymer protected PNSs. Significantly, compared to spin-coated film, the stabilities of quasi-2D PNS/polymer film are greatly improved due to the effective protection of polymer. The obtained PNS/polymer hybrid nanofiber films can be conveniently implemented for circularly polarized light emitting diode devices. This study may open up a new avenue for the scalable fabrication of chiral perovskite nanomaterials of interest and their applications in the CPL related fields.     

Low‐Dimensional Lead‐Free Inorganic Perovskites for Resistive Switching with Ultralow Bias

3D organic–inorganic and all‐inorganic lead halide perovskites have been intensively pursued for resistive switching memories in recent years. Unfortunately, instability and lead toxicity are two foremost challenges for their large‐scale commercial applications. Dimensional reduction and composition engineering are effective means to overcome these challenges. Herein, low‐dimensional inorganic lead‐free Cs₃Bi₂I₉ and CsBi₃I₁₀ perovskite‐like films are exploited for resistive switching memory applications. Both devices demonstrate stable switching with ultrahigh on/off ratios (≈10⁶), ultralow operation voltages (as low as 0.12 V), and self‐compliance characteristics. 0D Cs₃Bi₂I₉‐based device shows better retention time and larger reset voltage than the 2D CsBi₃I₁₀‐based device. Multilevel resistive switching behavior is also observed by modulating the current compliance, contributing to the device tunability. The resistive switching mechanism is hinged on the formation and rupture of conductive filaments of halide vacancies in the perovskite films, which is correlated with the formation of AgI_x layers at the electrode/perovskite interface. This study enriches the library of switching materials with all‐inorganic lead‐free halide perovskites and offers new insights on tuning the operation of solution‐processed memory devices.     

Air‐Stable Cesium Lead Iodide Perovskite for Ultra‐Low Operating Voltage Resistive Switching

CsPbX₃ (X = halide, Cl, Br, or I) all‐inorganic halide perovskites (IHPs) are regarded as promising functional materials because of their tunable optoelectronic characteristics and superior stability to organic–inorganic hybrid halide perovskites. Herein, nonvolatile resistive switching (RS) memory devices based on all‐inorganic CsPbI₃ perovskite are reported. An air‐stable CsPbI₃ perovskite film with a thickness of only 200 nm is successfully synthesized on a platinum‐coated silicon substrate using low temperature all‐solution process. The RS memory devices of Ag/polymethylmethacrylate (PMMA)/CsPbI₃/Pt/Ti/SiO₂/Si structure exhibit reproducible and reliable bipolar switching characteristics with an ultralow operating voltage (<+0.2 V), high on/off ratio (>10⁶), reversible RS by pulse voltage operation (pulse duration < 1 ms), and multilevel data storage. The mechanical flexibility of the CsPbI₃ perovskite RS memory device on a flexible substrate is also successfully confirmed. With analyzing the influence of phase transition in CsPbI₃ on RS characteristics, a mechanism involving conducting filaments formed by metal cation migration is proposed to explain the RS behavior of the memory device. This study will contribute to the understanding of the intrinsic characteristics of IHPs for low‐voltage resistive switching and demonstrate the huge potential of them for use in low‐power consumption nonvolatile memory devices on next‐generation computing systems.