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Observation of large Rashba spin–orbit coupling at room temperature in compositionally engineered perovskite single crystals and application in high performance photodetectors

Indirect absorption extended below the direct transition edge and increase in carrier lifetime derived from Rashba spin–orbit coupling may advance the optoelectronic applications of metal halide perovskites. Spin-orbit coupling in halide perovskites is due to the presence of heavy elements in their structure. However, when these materials lack an inversion symmetry, for example by the application of strain, spin–orbit coupling becomes odd in the electron’s momentum giving rise to a splitting in the electronic energy bands. Here we report on the observation of a large Rashba splitting of 117 meV at room temperature, as predicted by relativistic first-principles calculations, in halide perovskite single crystals through a facile compositional engineering approach. Partial substitution of organic cations by rubidium in single crystals induces significant indirect absorption and dual peak photoluminescence as a result of a large Rashba splitting. We measured circularly polarized photoluminescence and magneto-photoluminescence in perovskite films printed by single crystals as well as magneto-electroluminescence and magneto-photocurrent in spin-LEDs based on perovskite single crystals. They indicated significant spin-momentum locking due to the large Rashba effect. A hybrid perovskite single crystal photodetector achieved record figures of merit, including detectivity of more than 1.3 × 10 18 Jones which represents a three orders of magnitude improvement compared to the to date record. Furthermore, these findings show that facile compositional engineering of perovskite single crystals holds great promise for further advancing the optoelectronic properties of existing materials.

36 MATERIALS SCIENCE↗

Surface-binding molecular multipods strengthen the halide perovskite lattice and boost luminescence

Reducing the size of perovskite crystals to confine excitons and passivating surface defects has fueled a significant advance in the luminescence efficiency of perovskite light-emitting diodes (LEDs). However, the persistent gap between the optical limit of electroluminescence efficiency and the photoluminescence efficiency of colloidal perovskite nanocrystals (PeNCs) suggests that defect passivation alone is not sufficient to achieve highly efficient colloidal PeNC-LEDs. Here, we present a materials approach to controlling the dynamic nature of the perovskite surface. Our experimental and theoretical studies reveal that conjugated molecular multipods (CMMs) adsorb onto the perovskite surface by multipodal hydrogen bonding and van der Waals interactions, strengthening the near-surface perovskite lattice and reducing ionic fluctuations which are related to nonradiative recombination. The CMM treatment strengthens the perovskite lattice and suppresses its dynamic disorder, resulting in a near-unity photoluminescence quantum yield of PeNC films and a high external quantum efficiency (26.1%) of PeNC-LED with pure green emission that matches the Rec.2020 color standard for next-generation vivid displays.

36 MATERIALS SCIENCE↗

Nanoscopic cross-grain cation homogenization in perovskite solar cells

Multiscale cation inhomogeneity has been a major hurdle in state-of-the-art formamidinium–caesium (FA–Cs) mixed-cation perovskites for achieving perovskite solar cells with optimal power conversion efficiencies and durability. Although the field has attempted to homogenize the overall distributions of FA–Cs in perovskite films from both plan and cross-sectional views, our understanding of grain-to-grain cation inhomogeneity and ability to tailor it—that is, spatially resolving the FA–Cs compositional difference between individual grains down to the nanoscale—are lacking. Here we reveal that as fundamental building blocks of a perovskite film, individual grains exhibit cationic compositions deviating from the prescribed ideal composition, severely limiting the interfacial optoelectronic properties and perovskite layer durability. This performance-limiting nanoscopic factor is linked to thermodynamic-driven morphological grooving, leading to a segmented surface landscape. At the grain triple junctions, grooves form nanoscale groove traps that hinder the mixing of solid-state cations across grains and thus retard inter-grain FA–Cs mixing. By rationally modulating the heterointerfacial energies, we reduced the depth of these nanoscale groove traps by a factor of three, significantly improving cation homogeneity. Perovskite solar cells with shallower nanoscale groove traps demonstrate enhanced power conversion efficiencies (25.62%) and improved stability under various standardized international protocols. In conclusion, our work highlights the significance of resolving surface nano-morphologies for homogeneous properties of perovskites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Aqueous-based recycling of perovskite photovoltaics

Abstract Cumulative silicon photovoltaic (PV) waste highlights the importance of considering waste recycling before the commercialization of emerging PV technologies 1,2 . Perovskite PVs are a promising next-generation technology 3 , in which recycling their end-of-life waste can reduce the toxic waste and retain resources 4,5 . Here we report a low-cost, green-solvent-based holistic recycling strategy to restore all valuable components from perovskite PV waste. We develop an efficient aqueous-based perovskite recycling approach that can also rejuvenate degraded perovskites. We further extend the scope of recycling to charge-transport layers, substrates, cover glasses and metal electrodes. After repeated degradation–recycling processes, the recycled devices show similar efficiency and stability compared with the fresh devices. Our holistic recycling strategy reduces by 96.6% resource depletion and by 68.8% human toxicity (cancer effects) impacts associated with perovskite PVs compared with the landfill treatment. With recycling, the levelized cost of electricity also decreases for both utility-scale and residential systems. This study highlights unique opportunities of perovskite PVs for holistic recycling and paves the way for a sustainable perovskite solar economy.

Science & Technology - Other Topics↗

Octahedron rotation evolution in 2D perovskites and its impact on optoelectronic properties: the case of Ba–Zr–S chalcogenides

Octahedron rotation (OR) is a unique structural feature in most perovskite materials. During dimensional reduction from bulk to two-dimensional (2D) perovskites, how the OR pattern evolves is still an open question. Here, we employ an adapted Glazer's notation from bulk perovskites to systematically study the structural evolution of 2D perovskites by fully considering the possible OR patterns. Applying this approach to the 2D Ba–Zr–S system, we establish the relationship between the OR pattern and slab thickness. It is found that as the thickness decreases, the OR pattern undergoes a transition by suppressing out-of-plane rotations. The OR in 2D chalcogenide perovskites could result in an anti-confinement effect, i.e., reducing the band gap to even below that of the bulk by countering the quantum confinement effect. In addition, we show that the Ba–Zr–S 2D perovskites exhibit reasonable electron mobility of ~150 cm 2 V –1 s –1 and large exciton binding energy of ~0.9 eV. In conclusion, combining the slab thickness and strain as effective knobs for widely tuning the electronic structure, we suggest the 2D chalcogenide perovskites as promising optoelectronic materials.

36 MATERIALS SCIENCE↗

Design principles of spacer cations for suppressing phase segregation in 2D halide perovskites

Suppression of photoinduced halide segregation in mixed halide perovskites remains a significant challenge for their application as wide bandgap semiconductors in solar cells. In addition to stability issues, halide segregation leads to a loss in power conversion efficiency in solar cells and a shift in emission wavelength in light-emitting devices. However, employing low-dimensional halide perovskites, such as two-dimensional (2D) or quasi-2D structures, offers a strategy to mitigate this segregation. Here, we have systematically studied how the molecular structure and binding configuration of spacer cations, ranging from linear alkyl chains to aromatic structures, affect photoinduced halide segregation across both Ruddlesden–Popper (RP) and Dion–Jacobson (DJ) frameworks in 2D mixed halide perovskites (Br : I = 50 : 50). Aromatic spacer cations within the DJ perovskite configuration were found to suppress segregation most effectively. For example, the halide segregation rate in a 2D mixed halide perovskite film with the DJ phase using the aromatic spacer cation 1,4-phenylenedimethanammonium (PDMA) was 9.3 × 10 −4 s −1 —an order of magnitude lower than that observed with linear 2D RP perovskites employing butylammonium (BA) as the spacer cation (6.1 × 10 −3 s −1 ). Spectroscopic studies detailing the influence of spacer cation selection in mixed halide perovskites for suppressing phase segregation are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Defect tolerance in halide perovskites: A first-principles perspective

In recent years, the impressive photovoltaic performance of halide perovskites has been commonly attributed to their defect tolerance. This attribution is seemingly intuitive and has been widely promoted in the field, though it has not been rigorously assessed. In this Perspective, we critically discuss the proposition of defect tolerance in halide perovskites based on first-principles calculations. We show that halide perovskites actually do suffer from defect-assisted nonradiative recombination, i.e., they are not defect tolerant. The nonradiative recombination rates in halide perovskites are comparable to or even greater than those in more conventional semiconductors. We note that to obtain accurate defect properties in halide perovskites, the level of theory and computational details are highly important, which was previously not sufficiently recognized. A distinctive feature of halide perovskites is that they can be grown with moderate defect densities using low-cost deposition techniques. But, similar to the case of conventional semiconductors, defect engineering is still key to improving the efficiency of perovskite solar cells.

14 SOLAR ENERGY↗

Structural Stability of Tin-Lead Halide Perovskite Solar Cells

One of the key features that makes halide perovskite solar cells such an attractive and intensely researched photovoltaic (PV) technology, is the tunability of the bandgap of these halide perovskite materials [1], [2]. Shortly after it was established that the bandgap could be increased to 1.7-1.8 eV, investigations into the application for silicon based tandem solar cells launched. Within a few years, conversion efficiencies of up to 28 % have been reported [3]. Concurrently, the interest in commercial application of this technology emerged and have rapidly increased. Whereas there are advantages to piggy backing on an established PV technology such as silicon, efforts to develop all-perovskite tandem solar cells are of considerable interest. Partly substituting the metal cation in the ABX3 perovskite enables the low bandgap absorbers required for an all-perovskite tandem solar cell. One common approach is to partially substitute the lead with tin, however these materials often suffered from poor stability. Therefore the development of an efficient, stable mixed tin-lead perovskite is key to enabling all-perovskite tandem solar cells.

degradation↗

Crystallization in one-step solution deposition of perovskite films: Upward or downward?

Despite the fast progress of perovskite photovoltaic performances, understanding the crystallization and growth of perovskite films is still lagging. One unanswered fundamental question is whether the perovskite films are grown from top (air side) to bottom (substrate side) or from bottom to top despite 10 years of development. Here, by using grazing incidence x-ray diffraction and morphology characterizations, we unveil that the perovskite films prepared by one-step solution processes, including antisolvent-assisted spin coating and blade coating, follow the downward growth from intermediate phase during thermal annealing. Such a top-to-bottom downward growth is initialized by the evaporation of residual solvent from the top surface of “wet” films and is less sensitive to perovskite compositions and the wettability of underlying substrates. Addressing this fundamental question is important to understand the heterogeneity of perovskite films along the vertical direction, which markedly affects the efficiency and stability of perovskite solar cells.

36 MATERIALS SCIENCE↗

Strong-Bonding Hole-Transport Layers Reduce Ultraviolet Degradation of Perovskite Solar Cells

The light-emitting diodes (LEDs) used in indoor testing of perovskite solar cells do not expose them to the levels of ultraviolet (UV) radiation that they would receive in actual outdoor use. We report degradation mechanisms of p-i-n-structured perovskite solar cells under unfiltered sunlight and with LEDs. Weak chemical bonding between perovskites and polymer hole-transporting materials (HTMs) and transparent conducting oxides (TCOs) dominate the accelerated A-site cation migration, rather than direct degradation of HTMs. An aromatic phosphonic acid, [2-(9-ethyl-9H-carbazol-3-yl)ethyl]phosphonic acid (EtCz3EPA), enhanced bonding at the perovskite/HTM/TCO region with a phosphonic acid group bonded to TCOs and a nitrogen group interacting with lead in perovskites. A hybrid HTM of EtCz3EPA with strong hole-extraction polymers retained high efficiency and improved the UV stability of perovskite devices, and a champion perovskite minimodule-independently measured by the Perovskite PV Accelerator for Commercializing Technologies (PACT) center-retained operational efficiency of >16% after 29 weeks of outdoor testing.

14 SOLAR ENERGY↗

Bypassing the yellow phase for extremely stable formamidinium lead iodide perovskite solar cells

INTRODUCTION Formamidinium lead iodide (FAPI) emerged as an ideal material for single-junction perovskite solar cells owing to its near optimal bandgap of 1.45 to 1.5 eV and outstanding thermal stability. However, the photoactive cubic α-phase (3C-FAPI) of FAPI is structurally unstable and undergoes a reconstructive phase transition to the nonperovskite yellow hexagonal δ-phase (2H-FAPI) at ambient temperature. The phase reconstruction from 3C-FAPI to 2H-FAPI could be prevented by alloying methylammonium (MA) or Cs or both at the A-site and Br at the halide site, but this limits long-term durability owing to phase segregation or materials instability. Addressing these challenges requires a rational design strategy to stabilize 3C-FAPI by restricting lattice reconstruction without compromising thermal stability. RATIONALE Two main strategies have emerged to improve the phase stability and film quality of FAPI. Here, the first is a lattice-templating approach, which enables the slow formation of perovskite but it eventually degrades through the formation of yellow phases. The second approach, which has been widely explored, involves additive engineering, using alkyl ammonium halide or mostly chloride-based additives, which provide better control over the crystallization route. However, the FAPI films fabricated using these additives are often alloyed and compromise long-term stability. Moreover, the exact role of Cl has been unclear and speculative, specifically when Cl-based additives are used. Even after using a high additive concentration, the incorporation of Cl in perovskite lattice is rare. RESULTS Guided by synergistic modeling and experimental studies, we developed a coadditive strategy using 15 mol % FACl and 0.5 mol % BA 2 PbI 4 perovskites in combination (where BA is butylammonium) to enable a highly oriented (100) Cl-doped FAPI film with exceptional durability. Synchrotron-based in situ wide-angle x-ray scattering revealed a favorable transition for the coadditive-treated FAPI (FAPI-CA) to the corner-sharing 3C black phase through a progressive transformation through the 2H, 4H, 6H, and 8H phases. Moreover, solid-state 35 Cl nuclear magnetic resonance (NMR) revealed Cl incorporation in the perovskite lattice and, as predicted by modeling, indicated that Cl plays a key role in altering the energetics of both the formation and degradation pathways. The Cl-doped perovskite can completely bypass the expected and energetically favorable degradation pathway via the yellow phase or the 2H-PbI 2 phase. Instead, it undergoes degradation only upon exposure to harsh conditions such as 15-sun illumination and 90°C through the energetically uphill 3R-PbI 2 phase path. A p-i-n device fabricated with FAPI-CA film demonstrated a power conversion efficiency (PCE) of 25.1% with an average of 24.1% (40 devices). The notable film stability translated to other devices and retained 98% of its initial PCE under open-circuit conditions at 85° ± 5°C for 1200 hours. CONCLUSION Our study highlights the decisive role of chloride in regulating both the formation and degradation pathways. This regulation is critical for creating a perovskite film with commercially relevant durability.

Garai, Rabindranath [Rice Univ., Houston, TX (Unit↗

Life cycle cost assessment of material recovery from perovskite solar cells

Perovskite photovoltaic (PV) cells have created a significant interest over the last few years due to their low-cost and high-power conversion efficiencies. While perovskite PVs are still under development, we analyze cost of alternative sustainable end-of-life management for perovskite PV cells; this allows to reuse economically valuable materials and prevent environmental contamination. Here, we studied the life cycle cost assessment of recovering metals such as lead, aluminum, gold, nickel, and silver and other valuable materials such as glass from waste perovskite PVs. We also developed a recycling scheme to optimize the material recovery and determine the economically feasible ways to separate the cells layer-by-layer. Further, we assessed the cost and the net cost of the perovskite PV recycling processes. We found that the most feasible recycling technique’ cost is $\$$10.70 and its net cost is $\$$– 2.95 per 1 m 2 module. These values could be further improved by optimizing and reusing chemicals involved in process. These results indicate that the cost of perovskite PV recycling is economically feasible and there is potentional to gain benefit from sustainable end-of-life management of perovskite PVs.

14 SOLAR ENERGY↗

Perovskite on Silicon Tandem Solar Cells

Since installing solar panels costs more than the panels themselves, it is critically important to improve the efficiency of the panels so that fewer panels need to be installed. More than 90% of all panels being manufactured are made with silicon solar cells. The most promising approach to reach 27% is to upgrade the panels by adding a second set of cells with a larger band gap that can harvest the higher energy photons in the visible spectrum and generate a higher voltage than silicon is capable of generating. Perovskite semiconductors are very promising for low-cost tandems because they have high band gaps, can be rapidly printed from solutions and have been used to make 25% efficient cells by themselves. If we show that it is possible to make stable tandems with 30% efficiency using materials that could be deposited at low cost and that the energy yield will not be compromised, then private companies would be able to raise the capital needed to manufacture this technology. The main metrics for this project are the power conversion efficiency of a lab-scale perovskite/silicon tandem and the ability to maintain a high power conversion efficiency in perovskite solar cells after accelerated operational stability testing under maximum power point at elevated temperature and 1 sun illumination. In short, this project demonstrates improvements to the perovskite absorber layer, contacts for the perovskite solar cell, and transparent oxide layers for window electrodes to achieve tandem efficiencies of 25% after one year and 27% after two years. By the end of the project, we identify strategies to further improve light management in the tandem devices and outline a pathway to reach 30%.In parallel, stability testing is conducted to evaluate said absorber and contact layers in the perovskite top cell, demonstrating 1000 hours of operation with less than 10% degradation at 1 sun. Our work on this project has made a leading impact on the development of perovskite/silicon tandems. The triple halide perovskite that we developed using iodide, bromide, and chloride and published in Science in March 2020 has received significant interest from other experts in the field at conferences. We took a silicon bottom cell with 21% efficiency, a technology that is responsible for a $30 billion market, and improved it by 30% relative. In addition, we have demonstrated impressive stability of our perovskite semitransparent top cells used in the tandems, showing for the first time packaged devices that pass a variety of IEC stability tests including damp heat, temperature cycling, and UV exposure tests.

14 SOLAR ENERGY↗

Reducing roughness and improving efficiency of MAPbI3 perovskite solar cells made by high-throughput photonic curing

For perovskite solar cells (PSCs) to be commercially viable, the slow and energy-insufficient thermal annealing step must be eliminated. Among the photo-irradiation methods proposed to replace thermal annealing, photonic curing is the fastest conversion method. Photonic curing delivers short (20 μs to 100 ms) but intense light pulses from a broadband (200-1500 nm) xenon flash lamp, making it the only method to convert perovskite under 20 ms. This processing time can be extrapolated to a roll-to-roll web speed of 40 m/min based on laboratory processing conditions. However, most reported PSCs made by photonic curing under 1 second have inferior performance (~10% PCE). Although SEM images show dense and pinhole-free perovskite films, AFM images indicate secondary wavy features of 500 nm-wide ridge and 80 nm-deep trenches on photonically cured perovskite films, the existence of which correlates with poor device performance. We suggest that this morphology feature is produced by volatile solvent evaporation during the fast photonic curing process. Two approaches have been made to remedy this issue: (1) adding CH2I2 as the third solvent in the conventional DMF-DMSO system and (2) applying a controlled air-blowing step before photonic curing to remove excess solvent further. Combining these two approaches produces photonically- cured perovskite films with a comparable film roughness and device performance. Alkyl halide additives have been reported to enhance PSC performance by modulated solvent-solute interactions and C-X (X = Cl, Br, and I) cleavage. Photonic curing can cleave CH2I2, producing disassociated iodide ions to replenish iodine loss induced by photonic curing, which is confirmed by EDX. As a co-solvent, the high boiling point of CH2I2 can also make the solvent less volatile, reducing surface roughness in photonically cured perovskite films. Additionally, photonically-cured perovskite films have longer PL lifetimes and a higher recombination resistance compared to thermally-annealed counterparts. As a result, we demonstrate that photonic curing is a suitable method to replace thermal annealing in high-throughput PSC fabrication.

14 SOLAR ENERGY↗

PACT Center: Perovskite PV Accelerator for Commercializing Technologies (Final Technical Report)

The Perovskite PV Accelerator for Commercializing Technologies (PACT) center was established in July 2021 as a national resource to accelerate the commercialization of perovskite photovoltaic (PV) technology in the United States. Since its inception, PACT has been led by Sandia National Laboratories (Sandia) in partnership with the National Laboratory of the Rockies (NLR), formerly known as NREL. From FY20-FY23, Los Alamos National Laboratory (LANL), CFV Labs, Black & Veatch (B&V), and the Electric Power Research Institute (EPRI) were part of the project team. LANL brought expertise in perovskite PV device designs and processing, CFV Labs (now GroundWork Renewables) provided initial indoor and outdoor measurement hardware technology, B&V led the initial effort on perovskite PV bankability, and EPRI worked on reviewing testing standards, identifying commercialization gaps, and helping to run PACT’s Industry Advisory Board, a group including representatives from commercial testing labs, independent engineering firms, insurance companies, state regulators, and electric utilities. To source perovskite PV module samples, PACT contracted with the University of North Carolina (UNC), the University of Toledo, the University of Washington, and SLAC/Stanford University to provide a steady stream of research-grade perovskite mini modules, enabling protocol development in advance of commercial module availability. The project period ran from July 1, 2021, through December 31, 2025, including a No Cost Extension. Starting in FY25, the project was continued as a Core Capability in the Lab Call portfolio and continues at a reduced budget with only Sandia and NLR as funded recipients. Notably, starting in FY25 PACT expanded its scope beyond MHP modules to accept all emerging PV mini module technologies for testing, including organic PV (OPV) and all-thin-film tandems, with the aim of supporting commercialization across the broader emerging PV ecosystem. With this change in scope the program was renamed the PV Accelerator for Commercializing Technologies, dropping perovskite from the name.

14 SOLAR ENERGY↗

Perovskite nanocrystals and methods of making the same

The present disclosure relates to a perovskite that includes A1-xA′xBX3, where A is a first cation, A′ is a second cation, B is a third cation, X is a first anion, and 0<1−x≤1. In some embodiments of the present disclosure, the perovskite may further include a second anion (X′) such that the perovskite includes A1-xA′xB(X1-zX′z)3, where 0<z≤1. In some embodiments of the present disclosure, the perovskite may further include a fourth cation (A*) such that the perovskite includes A1-x-yA′xA*yB(X1-zX′z)3, where 0<y≤1. In some embodiments of the present disclosure, the perovskite may further include a fifth cation (B′) such that the perovskite includes A1-x-yA′xA*yB1-aB′a(X1-zX′z)3, where 0<a≤1.

Luther, Joseph Matthew↗

Fabrication of Flexible Perovskite Solar Cells via Rapid Thermal Annealing

Adaptability, lightweight, and low cost of materials make flexible perovskite solar cells essential for the perovskite technology to breach commercial photovoltaic market. Roll-to-roll manufacturing has great potential for high-throughput perovskite manufacturing; however, conventional annealing methods are not capable of producing flexible perovskite solar cells at scale. Rapid thermal annealing (RTA), a radiative method, is utilized on roll-to-roll lines within many different industries and has shown promising potential for perovskite annealing. Here, we introduce a blade-coated perovskite thin film on flexible ITO-coated PET annealed via RTA that reduces post-deposition processing time from ~150 seconds to ~14 seconds. Performance was not sacrificed for scalability as a perovskite solar cell was produced with a power conversion efficiency (PCE) of 14.58%.

Martin, Blake↗

In situ formation of pseudohalide anions induced by humid air and light passivates formamidinium‐based halide perovskites

Abstract Metal halide perovskites based on formamidinium (FA), or FA‐rich compositions have shown great promise for high‐performance photovoltaics. A deeper understanding of the impact of ambient conditions (e.g., moisture, oxygen, and illumination) on the possible reactions of FA‐based perovskite films and their processing sensitivities has become critical for further advances toward commercialization. Herein, we investigate reactions that take place on the surface of the FA 0.7 Cs 0.3 , mixed Br/I wide bandgap perovskite thin films in the presence of humid air and ambient illumination. The treatment forms a surface layer containing O, OH, and N‐based anions. We propose the latter originates from formamidine trapped at the perovskite/oxide interface reacting further to cyanide and/or formamidinate—an understudied class of pseudohalides that bind to Pb. Optimized treatment conditions improve photoluminescence quantum yield owing to both reduced surface recombination velocity and increased bulk carrier lifetime. The corresponding perovskite solar cells also exhibit improved performance. Identifying these reactions opens possibilities for better utilizing cyanide and amidinate ligands, species that may be expected during vapor processing of FA‐based perovskites. Our work also provides new insights into the self‐healing or self‐passivating of MA‐free perovskite compositions where FA and iodide damage could be partially offset by advantageous reaction byproducts. image

14 SOLAR ENERGY↗