An Integrated Deposition and Passivation Strategy for Controlled Crystallization of 2D/3D Halide Perovskite Films.

This work introduces a simplified deposition procedure for multidimensional (2D/3D) perovskite thin films, integrating a phenethylammonium chloride (PEACl)-treatment into the antisolvent step when forming the 3D perovskite. This simultaneous deposition and passivation strategy reduces the number of synthesis steps while simultaneously stabilizing the halide perovskite film and improving the photovoltaic performance of resulting solar cell devices to 20.8%. Using a combination of multimodal in situ and additional ex situ characterizations, it is demonstrated that the introduction of PEACl during the perovskite film formation slows down the crystal growth process, which leads to a larger average grain size and narrower grain size distribution, thus reducing carrier recombination at grain boundaries and improving the device's performance and stability. The data suggests that during annealing of the wet film, the PEACl diffuses to the surface of the film, forming hydrophobic (quasi-)2D structures that protect the bulk of the perovskite film from humidity-induced degradation.

High-Stable Lead-Free Solar Cells Achieved by Surface Reconstruction of Quasi-2D Tin-Based Perovskites.

Tin halide perovskites are an appealing alternative to lead perovskites. However, owing to the lower redox potential of Sn(II)/Sn(IV), particularly under the presence of oxygen and water, the accumulation of Sn(IV) at the surface layer will negatively impact the device's performance and stability. To this end, this work has introduced a novel multifunctional molecule, 1,4-phenyldimethylammonium dibromide diamine (phDMADBr), to form a protective layer on the surface of Sn-based perovskite films. Strong interactions between phDMADBr and the perovskite surface improve electron transfer, passivating uncoordinated Sn(II), and fortify against water and oxygen. In situ grazing incidence wide-angle X-ray scattering (GIWAXS) analysis confirms the enhanced thermal stability of the quasi-2D phase, and hence the overall enhanced stability of the perovskite. Long-term stability in devices is achieved, retaining over 90% of the original efficiency for more than 200 hours in a 10% RH moisture N2 environment. These findings propose a new approach to enhance the operational stability of Sn-based perovskite devices, offering a strategy in advancing lead-free optoelectronic applications.

Unraveling the Role of Perovskite in Buried Interface Passivation.

Interfaces in perovskite solar cells play a crucial role in their overall performance, and therefore, detailed fundamental studies are needed for a better understanding. In the case of the classical n-i-p architecture, TiO2 is one of the most used electron-selective layers and can induce chemical reactions that influence the performance of the overall device stack. The interfacial properties at the TiO2/perovskite interface are often neglected, owing to the difficulty in accessing this interface. Here, we use X-rays of variable energies to study the interface of (compact and mesoporous) TiO2/perovskite in such a n-i-p architecture. The X-ray photoelectron spectroscopy and X-ray absorption spectroscopy methods show that the defect states present in the TiO2 layer are passivated by a chemical interaction of the perovskite precursor solution during the formation of the perovskite layer and form an organic layer at the interface. Such passivation of intrinsic defects in TiO2 removes charge recombination centers and shifts the bands upward. Therefore, interface defect passivation by oxidation of Ti3+ states, the organic cation layer, and an upward band bending at the TiO2/perovskite interface explain the origin of an improved electron extraction and hole-blocking nature of TiO2 in the n-i-p perovskite solar cells.

A systematic discrepancy between the short circuit current and the integrated quantum efficiency in perovskite solar cells.

Halide perovskites solar cells are now approaching commercialisation. In this transition from academic research towards industrialisation, standardized testing protocols and reliable dissemination of performance metrics are crucial. In this study, we analyze data from over 16,000 publications in the Perovskite Database to investigate the assumed equality between the integrated external quantum efficiency and the short circuit current from JV measurements. We find a systematic discrepancy with the JV-values being on average 4% larger. This discrepancy persists across time, perovskite composition, and device architecture, indicating the need to explore new perovskite physics and update reporting protocols and assumptions in the field.

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.

Coordination Chemistry as a Universal Strategy for a Controlled Perovskite Crystallization.

The most efficient and stable perovskite solar cells (PSCs) are made from a complex mixture of precursors. Typically, to then form a thin film, an extreme oversaturation of the perovskite precursor is initiated to trigger nucleation sites, e.g., by vacuum, an airstream, or a so-called antisolvent. Unfortunately, most oversaturation triggers do not expel the lingering (and highly coordinating) dimethyl sulfoxide (DMSO), which is used as a precursor solvent, from the thin films; this detrimentally affects long-term stability. In this work, (the green) dimethyl sulfide (DMS) is introduced as a novel nucleation trigger for perovskite films combining, uniquely, high coordination and high vapor pressure. This gives DMS a universal scope: DMS replaces other solvents by coordinating more strongly and removes itself once the film formation is finished. To demonstrate this novel coordination chemistry approach, MAPbI3 PSCs are processed, typically dissolved in hard-to-remove (and green) DMSO achieving 21.6% efficiency, among the highest reported efficiencies for this system. To confirm the universality of the strategy, DMS is tested for FAPbI3 as another composition, which shows higher efficiency of 23.5% compared to 20.9% for a device fabricated with chlorobenzene. This work provides a universal strategy to control perovskite crystallization using coordination chemistry, heralding the revival of perovskite compositions with pure DMSO.

Understanding the impact of surface roughness: changing from FTO to ITO to PEN/ITO for flexible perovskite solar cells.

So far, single-junction flexible PSCs have been lacking in efficiency compared to rigid PSCs. Recently, > 23% have been reported. We therefore focus on understanding the differences between rigid and flexible substrates. One often neglected parameter is the different surface roughness which directly affects the perovskite film formation. Therefore, we adjust the layer thickness of SnO2 and the perovskite layers. Furthermore, we introduce a PMMA layer between the perovskite and the hole transporting material (HTM), spiro-MeOTAD, to mitigate shunting pathways. In addition, the multication perovskite Rb0.02Cs0.05FA0.77MA0.16Pb(I0.83Br0.17)3 is employed, resulting in stabilized performances of 16% for a flexible ITO substrate and 19% on a rigid ITO substrate.

Highly efficient p-i-n perovskite solar cells that endure temperature variations.

Daily temperature variations induce phase transitions and lattice strains in halide perovskites, challenging their stability in solar cells. We stabilized the perovskite black phase and improved solar cell performance using the ordered dipolar structure of ß-poly(1,1-difluoroethylene) to control perovskite film crystallization and energy alignment. We demonstrated p-i-n perovskite solar cells with a record power conversion efficiency of 24.6% over 18 square millimeters and 23.1% over 1 square centimeter, which retained 96 and 88% of the efficiency after 1000 hours of 1-sun maximum power point tracking at 25° and 75°C, respectively. Devices under rapid thermal cycling between -60° and +80°C showed no sign of fatigue, demonstrating the impact of the ordered dipolar structure on the operational stability of perovskite solar cells.

Coevaporation Stabilizes Tin-Based Perovskites in a Single Sn-Oxidation State.

Chemically processed methylammonium tin-triiodide (CH3NH3SnI3) films include Sn in different oxidation states, leading to poor stability and low power conversion efficiency of the resulting solar cells (PSCs). The development of absorbers with Sn [2+] only has been identified as one of the critical steps to develop all Sn-based devices. Here, we report on coevaporation of CH3NH3I and SnI2 to obtain absorbers with Sn being only in the preferred oxidation state [+2] as confirmed by X-ray photoelectron spectroscopy. The Sn [4+]-free absorbers exhibit smooth highly crystalline surfaces and photoluminescence measurements corroborating their excellent optoelectronic properties. The films show very good stability under heat and light. Photoluminescence quantum yields up to 4 × 10-3 translate in a quasi Fermi-level splittings exceeding 850 meV under one sun equivalent conditions showing high promise in developing lead-free, high efficiency, and stable PSCs.

Lamination methods for the fabrication of perovskite and organic photovoltaics.

Perovskite solar cells (PSCs) have shown rapid progress in a decade of extensive research and development, aiming now towards commercialization. However, the development of more facile, reliable, and reproducible manufacturing techniques will be essential for industrial production. Many lamination methods have been initially designed for organic photovoltaics (OPVs), which are conceptually similar to PSCs. Lamination could provide a low-cost and adaptable technique for the roll-to-roll production of solar cells. This review presents an overview of lamination methods for the fabrication of PSCs and OPVs. The lamination of different electrodes consisting of various materials such as metal back contacts, photoactive layers, hole transport layers (HTLs), and electron transport layers (ETLs) is discussed. The efficiency and stability of the laminated devices are also presented. Finally, the challenges and opportunities of laminated solar cells are discussed.

Tin-based halide perovskite materials: properties and applications.

Organic-inorganic hybrid halide perovskite materials have attracted considerable research interest, especially for photovoltaics. In addition, their scope has been extended towards light-emitting devices, photodetectors, or detectors. However, the toxicity of lead (Pb) element in perovskite compositions limits their applications. Therefore, a tremendous research effort on replacing is underway. More specifically, tin-based perovskites have shown the highest potential for this purpose. However, many challenges remain before these materials reach the goals of stability, safety, and eventually commercial application. This perspective considers many aspects and the critical development possibilities of tin-based perovskites, including drawbacks and challenges based on their physical properties. Additionally, it provides insights for future device applications that go beyond solar cells. Finally, the existing challenges and opportunities in tin-based perovskites are discussed.

One-Step Thermal Gradient- and Antisolvent-Free Crystallization of All-Inorganic Perovskites for Highly Efficient and Thermally Stable Solar Cells.

All-inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their heat-sensitive hybrid organic-inorganic counterparts. In particular, CsPbI2 Br shows the highest potential for developing thermally-stable perovskite solar cells (PSCs) among all-inorganic compositions. However, controlling the crystallinity and morphology of all-inorganic compositions is a significant challenge. Here, a simple, thermal gradient- and antisolvent-free method is reported to control the crystallization of CsPbI2 Br films. Optical in situ characterization is used to investigate the dynamic film formation during spin-coating and annealing to understand and optimize the evolving film properties. This leads to high-quality perovskite films with micrometer-scale grain sizes with a noteworthy performance of 17% (≈16% stabilized), fill factor (FF) of 80.5%, and open-circuit voltage (VOC ) of 1.27 V. Moreover, excellent phase and thermal stability are demonstrated even after extreme thermal stressing at 300 °C.

Isometric and Anisometric Contraction Relationships with Surface Electromyography.

The isometric contraction is the most investigated muscle contraction, however most tasks in daily life involve anisometric contractions. Most hand prostheses studies [1] use sEMG features to directly relate the exerted force as a means of intuitive control. It may thus be expected that similar sEMG-velocity relationships characterizing anisometric contractions may also contribute towards intuitive prosthetic hand control. While different contraction type relationships have been studied separately, in this work anisometric and isometric contraction experiments on the biceps brachii muscle were carried out using the same sEMG electrode system and the motor unit activity was then related to limb velocities and limb forces, to respectively characterize the isometric and anisometric contractions. This muscle was chosen as a simpler alternative to the synergistic hand muscles as an initial test of the general concept.Clinical Relevance- These contraction characterizations with sEMG may be used to afford prosthetic intuitive control and to assist in motor impairment diagnosis and rehabilitation.

Encapsulation Strategies for Highly Stable Perovskite Solar Cells under Severe Stress Testing: Damp Heat, Freezing, and Outdoor Illumination Conditions.

A key direction toward managing extrinsic instabilities in perovskite solar cells (PSCs) is encapsulation. Thus, a suitable sealing layer is required for an efficient device encapsulation, preventing moisture and oxygen ingression into the perovskite layer. In this work, a solution-based, low-cost, and commercially available bilayer structure of poly(methyl methacrylate)/styrene-butadiene (PMMA/SB) is investigated for PSCs encapsulation. Encapsulated devices retained 80% of the initial power conversion efficiency (PCE) at 85 °C temperature and 85% relative humidity after 100 h, while reference devices without SB (only PMMA) suffer from rapid and intense degradation after only 2 h, under the same condition. In addition, encapsulated devices retained 95% of the initial PCE under -15 °C freezing temperature after 6 h and retained ∼80% of the initial PCE after immersion in HCl (37%) for 90 min. Moreover, applying an additional aluminum metal sheet on the PMMA/SB protective bilayer leads to the improvement of device stability up to 500 h under outdoor illumination, retaining almost 90% of the initial PCE. Considering the urge to develop reliable, scalable, and simple encapsulation for future large-area PSCs, this work establishes solution-based bilayer encapsulation, which is applicable for flexible solar modules as well as other optoelectronic devices such as light-emitting devices and photodetectors.improvement of device stability up to 500 h under outdoor illumination, retaining almost 90% of the initial PCE. Considering the urge to develop reliable, scalable, and simple encapsulation for future large-area PSCs, this work establishes solution-based bilayer encapsulation, which is applicable for flexible solar modules as well as other optoelectronic devices such as light-emitting devices and photodetectors.

Mechanism of ultrafast energy transfer between the organic-inorganic layers in multiple-ring aromatic spacers for 2D perovskites.

Lead halide based perovskite semiconductors self-assemble with distinct organic cations in natural multi-quantum-well structures. The emerging electronic properties of these two-dimensional (2D) materials can be controlled by the combination of the halide content and choice of chromophore in the organic layer. Understanding the photophysics of the perovskite semiconductor materials is critical for the optimization of stable and efficient optoelectronic devices. We use femtosecond transient absorption spectroscopy (fs-TAS) to study the mechanism of energy transfer between the organic and inorganic layers in a series of three lead-based mixed-halide perovskites such as benzylammonium (BA), 1-naphthylmethylammonium (NMA), and 1-pyrenemethylammonium (PMA) cations in 2D-lead-based perovskite thin films under similar experimental conditions. After optical excitation of the 2D-confined exciton in the lead halide layer, ultrafast energy transfer is observed to organic singlet and triplet states of the incorporated chromophores. This is explained by an effective Dexter energy transfer, which operates via a correlated electron exchange between the donating 2D-confined exciton and the accepting chromophore under spin conservation.

Photoelectrochemical Water-Splitting Using CuO-Based Electrodes for Hydrogen Production: A Review.

The cost-effective, robust, and efficient electrocatalysts for photoelectrochemical (PEC) water-splitting has been extensively studied over the past decade to address a solution for the energy crisis. The interesting physicochemical properties of CuO have introduced this promising photocathodic material among the few photocatalysts with a narrow bandgap. This photocatalyst has a high activity for the PEC hydrogen evolution reaction (HER) under simulated sunlight irradiation. Here, the recent advancements of CuO-based photoelectrodes, including undoped CuO, doped CuO, and CuO composites, in the PEC water-splitting field, are comprehensively studied. Moreover, the synthesis methods, characterization, and fundamental factors of each classification are discussed in detail. Apart from the exclusive characteristics of CuO-based photoelectrodes, the PEC properties of CuO/2D materials, as groups of the growing nanocomposites in photocurrent-generating devices, are discussed in separate sections. Regarding the particular attention paid to the CuO heterostructure photocathodes, the PEC water splitting application is reviewed and the properties of each group such as electronic structures, defects, bandgap, and hierarchical structures are critically assessed.

Emerging perovskite monolayers.

The library of two-dimensional (2D) materials has been enriched over recent years with novel crystal architectures endowed with diverse exciting functionalities. Bulk perovskites, including metal-halide and oxide systems, provide access to a myriad of properties through molecular engineering. Their tunable electronic structure offers remarkable features from long carrier-diffusion lengths and high absorption coefficients in metal-halide perovskites to high-temperature superconductivity, magnetoresistance and ferroelectricity in oxide perovskites. Emboldened by the 2D materials research, perovskites down to the monolayer limit have recently emerged. Like other 2D species, perovskites with reduced dimensionality are expected to exhibit new physics and to herald next-generation multifunctional devices. In this Review, we critically assess the preliminary studies on the synthetic routes and inherent properties of monolayer perovskite materials. We also discuss how to exploit them for widespread applications and provide an outlook on the challenges and opportunities that lie ahead for this enticing class of 2D materials.

Defect Passivation in Lead-Halide Perovskite Nanocrystals and Thin Films: Toward Efficient LEDs and Solar Cells.

Lead-halide perovskites (LHPs), in the form of both colloidal nanocrystals (NCs) and thin films, have emerged over the past decade as leading candidates for next-generation, efficient light-emitting diodes (LEDs) and solar cells. Owing to their high photoluminescence quantum yields (PLQYs), LHPs efficiently convert injected charge carriers into light and vice versa. However, despite the defect-tolerance of LHPs, defects at the surface of colloidal NCs and grain boundaries in thin films play a critical role in charge-carrier transport and nonradiative recombination, which lowers the PLQYs, device efficiency, and stability. Therefore, understanding the defects that play a key role in limiting performance, and developing effective passivation routes are critical for achieving advances in performance. This Review presents the current understanding of defects in halide perovskites and their influence on the optical and charge-carrier transport properties. Passivation strategies toward improving the efficiencies of perovskite-based LEDs and solar cells are also discussed.

Shaping Perovskites: In Situ Crystallization Mechanism of Rapid Thermally Annealed, Prepatterned Perovskite Films.

Understanding and controlling the crystallization of organic-inorganic perovskite materials is important for their function in optoelectronic applications. This control is particularly delicate in scalable single-step thermal annealing methods. In this work, the crystallization mechanisms of flash infrared-annealed perovskite films, grown on substrates with lithographically patterned Au nucleation seeds, are investigated. The patterning enables the in situ observation to study the crystallization kinetics and the precise control of the perovskite nucleation and domain growth, while retaining the characteristic polycrystalline micromorphology with larger crystallites at the boundaries of the crystal domains, as shown by electron backscattering diffraction. Time-resolved photoluminescence measurements reveal longer charge carrier lifetimes in regions with large crystallites on the domain boundaries, relative to the domain interior. By increasing the nucleation site density, the proportion of larger crystallites is increased. This study shows that the combination of rapid thermal annealing with nucleation control is a promising approach to improve perovskite crystallinity and thereby ultimately the performance of optoelectronic devices.