Narrow bandgap lead-tin perovskites are essential components of next-generation all-perovskite multi-junction solar cells. However, their poor stability under operating conditions hinders successful implementation. In this work, we systematically investigate the underlying mechanisms of this instability under combined heat and light stress (ISOS L-2 conditions) by measuring changes in phase, conductivity, recombination and current-voltage characteristics. We find an increased impact of the redistribution of mobile ions during device operation to be the primary driver of performance loss during stressing, with further losses caused by a slower increase in non-radiative recombination and background hole density. Crucially, the dominant degradation mode changes with different hole transport materials, which we attribute to variations in iodine vacancy generation rates. By quantifying the impact of these mechanisms on device performance, we provide critical insights for improving the operational stability of lead-tin perovskite solar cells.

Perovskite solar cells (PSCs) offer an efficient, inexpensive alternative to current photovoltaic technologies, with the potential for manufacture via high-throughput coating methods. However, challenges for commercial-scale solution-processing of metal-halide perovskites include the use of harmful solvents, the expense of maintaining controlled atmospheric conditions, and the inherent instabilities of PSCs under operation. Here, we address these challenges by introducing a high volatility, low toxicity, biorenewable solvent system to fabricate a range of 2D perovskites, which highly effective precursor phases for subsequent transformation to alpha-formamidinium lead triiodide (FAPbI3), fully processed under ambient conditions. PSCs utilising our FAPbI3 reproducibly show remarkable stability under illumination and elevated temperature (ISOS-L-2) and "damp heat" (ISOS-D-3) stressing, surpassing other state-of-the-art perovskite compositions. We determine that this enhancement is a consequence of the 2D precursor phase crystallisation route, which simultaneously avoids retention of residual low-volatility solvents (such as DMF and DMSO) and reduces the rate of degradation of FA+ in the material. Our findings highlight both the critical role of the initial crystallisation process in determining the operational stability of perovskite materials, and that neat FA+-based perovskites can be competitively stable despite the inherent metastability of the alpha-phase.

AbstractPerovskite solar cells (PSCs) offer an efficient, inexpensive alternative to current photovoltaic technologies, with the potential for manufacture via high-throughput coating methods. However, challenges for commercial-scale solution-processing of metal-halide perovskites include the use of harmful solvents, the expense of maintaining controlled atmospheric conditions, and the inherent instabilities of PSCs under operation. Here, we address these challenges by introducing a high volatility, low toxicity, biorenewable solvent system to fabricate a range of 2D perovskites, which we use as highly effective precursor phases for subsequent transformation to α-formamidinium lead triiodide (α-FAPbI3), fully processed under ambient conditions. PSCs utilising our α-FAPbI3 reproducibly show remarkable stability under illumination and elevated temperature (ISOS-L-2) and “damp heat” (ISOS-D-3) stressing, surpassing other state-of-the-art perovskite compositions. We determine that this enhancement is a consequence of the 2D precursor phase crystallisation route, which simultaneously avoids retention of residual low-volatility solvents (such as DMF and DMSO) and reduces the rate of degradation of FA+ in the material. Our findings highlight both the critical role of the initial crystallisation process in determining the operational stability of perovskite materials, and that neat FA+-based perovskites can be competitively stable despite the inherent metastability of the α-phase.

Stability of narrow bandgap lead-tin perovskite material and photovoltaic devicesFlorine Rombach a, Akash Dasgupta a, Manuel Kober-Czerny a, James Ball a, Joel Smith a, Heon Jin a, Michael Farrer a, Henry Snaith aa Department of Physics, University of Oxford, UKInternational Conference on Hybrid and Organic PhotovoltaicsProceedings of International Conference on Hybrid and Organic Photovoltaics (HOPV24)València, Spain, 2024 May 12th - 15thOrganizer: Bruno EhrlerOral, Florine Rombach, presentation 045DOI: https://doi.org/10.29363/nanoge.hopv.2024.045Publication date: 6th February 2024Narrow bandgap perovskite solar cells based on mixed lead-tin perovskites tend to suffer from poor stability under operating conditions. This impedes the development of stable all-perovskite multi-junction solar cells. We explore the causes of this instability under extended periods of combined 65°C thermal and illumination stressing using a range of structural, optical, and electronic characterization techniques on lead-tin perovskite films, half-stacks and devices. We show that the bulk phase, absorbance, mobility and background carrier density of lead-tin perovskite films are stable on timescales that exceed those of device degradation. We also find that non-radiative recombination rates in the perovskite increase moderately during the first few hundred hours of stressing. However, through a combination of device simulations and variable rate current-voltage (J-V) scanning we demonstrate that this change can only account for a small portion of the observed device performance loss. Ultimately, we identify a rapidly increasing impact of mobile ions during aging as the major cause of the observed device degradation. A close investigation of the J-V characteristics of devices reveals the formation of a charge extraction barrier during aging, which is hugely reduced in very fast J-V scans where mobile ions are less able to aggregate at interfaces. We quantify the increasing impact of mobile ions on device performance during aging, and furthermore demonstrate that this impact can be significantly mitigated by an alternative hole transport layer choice. Over longer timescales, we additionally identify the growth of a non-perovskite degradation phase as well as HTL-dependent changes in optoelectronic properties. We quantify the impact of these changes on device performance in comparison to the effects from mobile ions, demonstrating that the dominant effect can change with aging time and device architecture. Thus, we are able to closely identify the various processes that limit the stability of lead-tin perovskite solar cells and make recommendations to overcome these challenges. © FUNDACIO DE LA COMUNITAT VALENCIANA SCITOnanoGe is a prestigious brand of successful science conferences that are developed along the year in different areas of the world since 2009. Our worldwide conferences cover cutting-edge materials topics like perovskite solar cells, photovoltaics, optoelectronics, solar fuel conversion, surface science, catalysis and two-dimensional materials, among many others.MATSUSPreviously nanoGe Spring Meeting (NSM) and nanoGe Fall Meeting (NFM), MATSUS is a multiple symposia conference focused on a broad set of topics of advanced materials preparation, their fundamental properties, and their applications, in fields such as renewable energy, photovoltaics, lighting, semiconductor quantum dots, 2-D materials synthesis, charge carriers dynamics, microscopy and spectroscopy semiconductors fundamentals, etc.International Conference on Hybrid and Organic PhotovoltaicsInternational Conference on Hybrid and Organic Photovoltaics (HOPV) is celebrated yearly in May. The main topics are the development, function and modeling of materials and devices for hybrid and organic solar cells. The field is now dominated by perovskite solar cells but also other hybrid technologies, as organic solar cells, quantum dot solar cells, and dye-sensitized solar cells and their integration into devices for photoelectrochemical solar fuel production.Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and OptoelectronicsThe main topics of the Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and Optoelectronics (IPEROP) are discussed every year in Asia-Pacific for gathering the recent advances in the fields of material preparation, modeling and fabrication of perovskite and hybrid and organic materials. Photovoltaic devices are analyzed from fundamental physics and materials properties to a broad set of applications. The conference also covers the developments of perovskite optoelectronics, including light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling.International Conference on Perovskite Thin Film Photovoltaics Perovskite Photonics and OptoelectronicsThe International Conference on Perovskite Thin Film Photovoltaics Perovskite Photonics and Optoelectronics (NIPHO) is the best place to hear the latest developments in perovskite solar cells as well as on recent advances in the fields of perovskite light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling.

Multijunction photovoltaics (PVs) are gaining prominence owing to their superior capability of achieving power conversion efficiencies (PCEs) beyond the radiative limit of single-junction cells1-8, for which improving narrow-bandgap (NBG) tin-lead perovskites is critical for thin-film devices9. Here, with a focus on understanding the chemistry of tin-lead perovskite precursor solutions, we find that Sn(II) species dominate interactions with precursors and additives and uncover the exclusive role of carboxylic acid in regulating solution colloidal properties and film crystallization and ammonium in improving film optoelectronic properties. Materials that combine these two functional groups, amino acid salts, considerably improve the semiconducting quality and homogeneity of perovskite films, surpassing the effect of the individual functional groups when introduced as part of separate molecules. Our enhanced tin-lead perovskite layer allows us to fabricate solar cells with PCEs of 23.9%, 29.7% (certified 29.26%) and 28.7% for single-junction, double-junction and triple-junction devices, respectively. Our 1-cm2 triple-junction devices show PCEs of 28.4% (certified 27.28%). Encapsulated triple-junction cells maintain 80% of their initial efficiencies after 860 h maximum power point tracking (MPPT) in ambient. We further fabricate quadruple-junction devices and obtain PCEs of 27.9% with the highest open-circuit voltage of 4.94 V. This work establishes a new benchmark for multijunction PVs.

Narrow bandgap mixed lead-tin perovskites are critical for efficient all-perovskite multi-junction solar cells, but their poor stability under operating conditions represents a major barrier to implementation. In this work, we explore the causes of this instability under combined heat and light stress (ISOS L-2 conditions). The phase, absorbance, morphology, and background hole density in lead-tin perovskite films are observed to be stable beyond the usual timescales associated with device degradation. We measure a moderate increase in non-radiative recombination during stressing, but device simulations demonstrate that this can only account for a small portion of the observed steady-state performance loss. Variable rate current-voltage scanning of devices instead reveals an increasing impact of mobile ions to be the major cause of early-time performance degradation. This impact is found to be significantly mitigated by selecting an alternative hole transport layer. Over longer aging times, we also identify the growth of impurity phases as well as hole transport material-dependent changes in the electronic properties of the perovskite. By quantifying the impact of these changes on device performance, we identify the most dominant degradation pathway at each aging time for different device architectures, defining a clear direction for future stability improvements.

Mixed lead‐tin (Pb:Sn) halide perovskites are promising absorbers with narrow‐bandgaps (1.25–1.4 eV) suitable for high‐efficiency all‐perovskite tandem solar cells. However, solution processing of optimally thick Pb:Sn perovskite films is notoriously difficult in comparison with their neat‐Pb counterparts. This is partly due to the rapid crystallization of Sn‐based perovskites, resulting in films that have a high degree of roughness. Rougher films are harder to coat conformally with subsequent layers using solution‐based processing techniques leading to contact between the absorber and the top metal electrode in completed devices, resulting in a loss of V OC , fill factor, efficiency, and stability. Herein, this study employs a non‐continuous layer of alumina nanoparticles distributed on the surface of rough Pb:Sn perovskite films. Using this approach, the conformality of the subsequent electron‐transport layer, which is only tens of nanometres in thickness is improved. The overall maximum‐power‐point‐tracked efficiency improves by 65% and the steady‐state V OC improves by 28%. Application of the alumina nanoparticles as an interfacial buffer layer also results in highly reproducible Pb:Sn solar cell devices while simultaneously improving device stability at 65 °C under full spectrum simulated solar irradiance. Aged devices show a six‐fold improvement in stability over pristine Pb:Sn devices, increasing their lifetime to 120 h.

In this work, we couple theoretical and experimental approaches to understand and reduce the losses of wide bandgap Br-rich perovskite pin devices at open-circuit voltage (VOC) and short-circuit current (JSC) conditions. A mismatch between the internal quasi-Fermi level splitting (QFLS) and the external VOC is detrimental for these devices. We demonstrate that modifying the perovskite top-surface with guanidinium-Br and imidazolium-Br forms a low-dimensional perovskite phase at the n-interface, suppressing the QFLS-VOC mismatch, and boosting the VOC. Concurrently, the use of an ionic interlayer or a self-assembled monolayer at the p-interface reduces the inferred field screening induced by mobile ions at JSC, promoting charge extraction and raising the JSC. The combination of the n- and p-type optimizations allows us to approach the thermodynamic potential of the perovskite absorber layer, resulting in 1 cm2 devices with performance parameters of VOCs up to 1.29 V, fill factors above 80% and JSCs up to 17 mA/cm2, in addition to a thermal stability T80 lifetime of more than 3500 h at 85 °C.

Perovskite solar cells deliver high efficiencies, but are often made from high‐cost bespoke chemicals, such as the archetypical hole‐conductor, 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxy‐phenylamine)‐9‐9′‐spirobifluorene (spiro‐OMeTAD). Herein, new charge‐transporting carbazole‐based enamine molecules are reported. The new hole conductors do not require chemical oxidation to reach high power conversion efficiencies (PCEs) when employed in n‐type‐intrinsic‐p‐type perovskite solar cells; thus, reducing the risk of moisture degrading the perovskite layer through the hydrophilicity of oxidizing additives that are typically used with conventional hole conductors. Devices made with these new undoped carbazole‐based enamines achieve comparable PCEs to those employing doped spiro‐OMeTAD, and greatly enhanced stability under 85 °C thermal aging; maintaining 83% of their peak efficiency after 1000 h, compared with spiro‐OMeTAD‐based devices that degrade to 26% of the peak PCE within 24 h. Furthermore, the carbazole‐based enamines can be synthesized without the use of organometallic catalysts and complicated purification techniques, lowering the material cost by one order of magnitude compared with spiro‐OMeTAD. As a result, we calculate that the overall manufacturing costs of future photovoltaic (PV) modules are reduced, making the levelized cost of electricity competitive with silicon PV modules.

Despite the incredible progress made, the highest efficiency perovskite solar cells are still restricted to small areas (<1 cm2). In large part, this stems from a poor understanding of the widespread spatial heterogeneity in devices. Conventional techniques to assess heterogeneities can be time consuming, operate only at microscopic length scales, and demand specialized equipment. We overcome these limitations by using luminescence imaging to reveal large, millimeter-scale heterogeneities in the inferred electronic properties. We determine spatially resolved maps of "charge collection quality", measured using the ratio of photoluminescence intensity at open and short circuit. We apply these methods to quantify the inhomogeneities introduced by a wide range of transport layers, thereby ranking them by suitability for upscaling. We reveal that top-contacting transport layers are the dominant source of heterogeneity in the multilayer material stack. We suggest that this methodology can be used to accelerate the development of highly efficient, large-area modules, especially through high-throughput experimentation.

Vacuum deposition is a solvent-free method suitable for growing thin films of metal halide perovskite (MHP) semiconductors. However, most reports of high-efficiency solar cells based on such vacuum-deposited MHP films incorporate solution-processed hole transport layers (HTLs), thereby complicating prospects of industrial upscaling and potentially affecting the overall device stability. In this work, we investigate organometallic copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc) as alternative, low-cost, and durable HTLs in all-vacuum-deposited solvent-free formamidinium-cesium lead triodide [CH(NH2)2]0.83Cs0.17PbI3 (FACsPbI3) perovskite solar cells. We elucidate that the CuPc HTL, when employed in an "inverted" p-i-n solar cell configuration, attains a solar-to-electrical power conversion efficiency of up to 13.9%. Importantly, unencapsulated devices as large as 1 cm2 exhibited excellent long-term stability, demonstrating no observable degradation in efficiency after more than 5000 h in storage and 3700 h under 85 °C thermal stressing in N2 atmosphere.

Achieving the long-term stability of perovskite solar cells is arguably the most critical challenge to enabling their widespread commercialization. Understanding the perovskite crystallization process and its direct impact on device stability is essential to achieve this goal. Surprisingly, we find that intermediate phases that occur during the crystallization process strongly influence the long-term perovskite device stability. The commonly employed dimethyl formamide/dimethyl sulfoxide (DMF/DMSO) solvent system preparation method results in poor crystal quality and microstructure of the polycrystalline perovskite films. In this work, we introduce a high-temperature DMSO-free processing method that utilizes dimethylammonium chloride (DMACl) as an additive to control the perovskite intermediate precursor phases accurately. By precisely controlling the 2H to 3C perovskite phase crystallization sequence, we tune the grain size, texturing, orientation (corner-up vs face-up), and crystallinity of the formamidinium (FA)yCs1-yPb(IxBr1-x)3 perovskite system. Encapsulated devices show significantly improved operational stability, with a champion device showing a T80 of 490 hours under simulated sunlight at 85 °C in air, under open circuit conditions. Our work introduces a new processing method that allows higher overall perovskite device stability by controlling the intermediate phase domains during the perovskite formation. This work highlights the importance of material quality to achieve long-term operational stability of perovskite optoelectronic devices.

Many optoelectronic properties have been reported for lead halide perovskite polycrystalline films. However, ambiguities in the evaluation of these properties remain, especially for long-range lateral charge transport, where ionic conduction can complicate interpretation of data. Here we demonstrate a new technique to measure the long-range charge carrier mobility in such materials. We combine quasi-steady-state photo-conductivity measurements (electrical probe) with photo-induced transmission and reflection measurements (optical probe) to simultaneously evaluate the conductivity and charge carrier density. With this knowledge we determine the lateral mobility to be 2 cm2/Vs for CH3NH3PbI3 (MAPbI3) polycrystalline perovskite films prepared from the acetonitrile/methylamine solvent system. Furthermore, we present significant differences in long-range charge carrier mobilities, from 2.2 to 0.2 cm2/Vs, between films of contemporary perovskite compositions prepared via different fabrication processes, including solution and vapour phase deposition techniques. Arguably, our work provides the first accurate evaluation of the long-range lateral charge carrier mobility in lead halide perovskite films, with charge carrier density in the range typically achieved under photovoltaic operation.

As perovskite-based photovoltaics near commercialization, it is imperative to develop industrial-scale defect-passivation techniques. Vapor deposition is a solvent-free fabrication technique that is widely implemented in industry and can be used to fabricate metal-halide perovskite thin films. We demonstrate markably improved growth and optoelectronic properties for vapor-deposited [CH(NH2)2]0.83Cs0.17PbI3 perovskite solar cells by partially substituting PbI2 for PbCl2 as the inorganic precursor. We find the partial substitution of PbI2 for PbCl2 enhances photoluminescence lifetimes from 5.6 ns to over 100 ns, photoluminescence quantum yields by more than an order of magnitude, and charge-carrier mobility from 46 cm2/(V s) to 56 cm2/(V s). This results in improved solar-cell power conversion efficiency, from 16.4% to 19.3% for the devices employing perovskite films deposited with 20% substitution of PbI2 for PbCl2. Our method presents a scalable, dry, and solvent-free route to reducing nonradiative recombination centers and hence improving the performance of vapor-deposited metal-halide perovskite solar cells.

Charge transport in three-dimensional metal-halide perovskite semiconductors is due to a complex combination of ionic and electronic contributions, and its study is particularly relevant in light of their successful applications in photovoltaics as well as other opto- and microelectronic applications. Interestingly, the observation of field effect at room temperature in transistors based on solution-processed, polycrystalline, three-dimensional perovskite thin films has been elusive. In this work, we study the time-dependent electrical characteristics of field-effect transistors based on the model methylammonium lead iodide semiconductor and observe the drastic variations in output current, and therefore of apparent charge carrier mobility, as a function of the applied gate pulse duration. We infer this behavior to the accumulation of ions at the grain boundaries, which hamper the transport of carriers across the FET channel. This study reveals the dynamic nature of the field effect in solution-processed metal-halide perovskites and offers an investigation methodology useful to characterize charge carrier transport in such emerging semiconductors.

Space-charge-limited current (SCLC) measurements have been widely used to study the charge carrier mobility and trap density in semiconductors. However, their applicability to metal halide perovskites is not straightforward, due to the mixed ionic and electronic nature of these materials. Here, we discuss the pitfalls of SCLC for perovskite semiconductors, and especially the effect of mobile ions. We show, using drift-diffusion (DD) simulations, that the ions strongly affect the measurement and that the usual analysis and interpretation of SCLC need to be refined. We highlight that the trap density and mobility cannot be directly quantified using classical methods. We discuss the advantages of pulsed SCLC for obtaining reliable data with minimal influence of the ionic motion. We then show that fitting the pulsed SCLC with DD modeling is a reliable method for extracting mobility, trap, and ion densities simultaneously. As a proof of concept, we obtain a trap density of 1.3 × 1013 cm–3, an ion density of 1.1 × 1013 cm–3, and a mobility of 13 cm2 V–1 s–1 for a MAPbBr3 single crystal.

Metal halide perovskite semiconductors have sprung to the forefront of research into optoelectronic devices and materials, largely because of their remarkable photovoltaic efficiency records above 25% in single-junction devices and 28% in tandem solar cells, achieved within a decade of research. Despite this rapid progress, ionic conduction within the semiconductor still puzzles the community and can have a significant impact on all metal halide perovskite-based optoelectronic devices because of its influence upon electronic and optoelectronic processes. This phenomenon thus also makes the interpretation of electrical characterization techniques, which probe the fundamental properties of these materials, delicate and complex. For example, space-charge limited current measurements are widely used to probe defect densities and carrier mobilities in perovskites. However, the influence of mobile ions upon these measurements is significant but has yet to be considered. Here we report the effect of mobile ions upon electronic conductivity during space-charge limited current measurements of MAPbBr(3) single crystals and show that conventional interpretations deliver erroneous results. We introduce a pulsed-voltage space-charge limited current procedure to achieve reproducible current-voltage characteristics without hysteresis. From this revised pulsed current-voltage sweep, we elucidate a lower bound trap-density value of 2.8 +/- 1.8 x 10(12) cm(-3) in MAPbBr(3) single crystals. This work will lead to more accurate characterization of halide perovskite semiconductors and ultimately more effective device optimization.

State-of-the-art perovskite-based solar cells employ an expensive, conjugated hole transporting material (HTM) such as Spiro-OMeTAD that, in turn, limits the commercialization of this promising technology. Herein we introduce an HTM (EDOT-Amide-TPA) with a functional amide-based backbone