9 research outputs found
Stabilized tilted-octahedra halide perovskites inhibit local formation of performance-limiting phases.
Efforts to stabilize photoactive formamidinium (FA)–based halide perovskites for perovskite photovoltaics have focused on the growth of cubic formamidinium lead iodide (α-FAPbI3) phases by empirically alloying with cesium, methylammonium (MA) cations, or both. We show that such stabilized FA-rich perovskites are noncubic and exhibit ~2° octahedral tilting at room temperature. This tilting, resolvable only with the use of local nanostructure characterization techniques, imparts phase stability by frustrating transitions from photoactive to hexagonal phases. Although the bulk phase appears stable when examined macroscopically, heterogeneous cation distributions allow microscopically unstable regions to form; we found that these transitioned to hexagonal polytypes, leading to local trap-assisted performance losses and photoinstabilities. Using surface-bound ethylenediaminetetraacetic acid, we engineered an octahedral tilt into pure α-FAPbI3 thin films without any cation alloying. The templated photoactive FAPbI3 film was extremely stable against thermal, environmental, and light stressors
Imaging Light-Induced Migration of Dislocations in Halide Perovskites with 3D Nanoscale Strain Mapping
In recent years, halide perovskite materials have been used to make high
performance solar cell and light-emitting devices. However, material defects
still limit device performance and stability. Here, we use synchrotron-based
Bragg Coherent Diffraction Imaging to visualise nanoscale strain fields, such
as those local to defects, in halide perovskite microcrystals. We find
significant strain heterogeneity within MAPbBr (MA =
CHNH) crystals in spite of their high optoelectronic quality,
and identify both 100 and 110 edge
dislocations through analysis of their local strain fields. By imaging these
defects and strain fields in situ under continuous illumination, we uncover
dramatic light-induced dislocation migration across hundreds of nanometres.
Further, by selectively studying crystals that are damaged by the X-ray beam,
we correlate large dislocation densities and increased nanoscale strains with
material degradation and substantially altered optoelectronic properties
assessed using photoluminescence microscopy measurements. Our results
demonstrate the dynamic nature of extended defects and strain in halide
perovskites and their direct impact on device performance and operational
stability.Comment: Main text and Supplementary Information. Main text: 15 pages, 4
figures. Supplementary Information: 16 pages, 27 figures, 1 tabl
Strain analysis and engineering in halide perovskite photovoltaics.
Halide perovskites are a compelling candidate for the next generation of clean-energy-harvesting technologies owing to their low cost, facile fabrication and outstanding semiconductor properties. However, photovoltaic device efficiencies are still below practical limits and long-term stability challenges hinder their practical application. Current evidence suggests that strain in halide perovskites is a key factor in dictating device efficiency and stability. Here we outline the fundamentals of strain within halide perovskites relevant to photovoltaic applications and rationalize approaches to characterize the phenomenon. We examine recent breakthroughs in eliminating the adverse impacts of strain, enhancing both device efficiencies and operational stabilities. Finally, we discuss further challenges and outline future research directions for placing stress and strain studies at the forefront of halide perovskite research. An extensive understanding of strain in halide perovskites is needed, which would allow effective strain management and drive further enhancements in efficiencies and stabilities of perovskite photovoltaics
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Composition Dictates Octahedral Tilt and Photostability in Halide Perovskites.
Publication status: PublishedFunder: Gonville and Caius College, CambridgeFunder: Cambridge Philosophical Society; doi: http://dx.doi.org/10.13039/100013858Funder: British Spanish SocietyFunder: Sir Richard Stapley Educational Trust; doi: http://dx.doi.org/10.13039/501100016406Funder: Rank Prize FundFunder: Ernest Oppenheimer FundFunder: Schmidt Science FellowshipsFunder: Taiwan Cambridge ScholarshipFunder: D.M.P. FoundationFunder: St John's College, CambridgeFunder: Royal Academy of Engineering; doi: http://dx.doi.org/10.13039/501100000287Funder: Diamond Light Source; doi: http://dx.doi.org/10.13039/100011889Halide perovskites are excellent candidate materials for use in solar cell, LED, and detector devices, in part because their composition can be tuned to achieve ideal optoelectronic properties. Empirical efficiency optimization has led the field toward compositions rich in FA (formamidinium) on the A-site and I on the X-site, with additional small amounts of MA (methylammonium) or Cs A-site cations and Br X-site anions. However, it is not clear how and why the specific compositions of alloyed, that is, mixed component, halide perovskites relate to photo-stability of the materials. Here, this work combines synchrotron grazing incidence wide-angle X-ray scattering, photoluminescence, high-resolution scanning electron diffraction measurements and theoretical modelling to reveal the links between material structure and photostability. Namely, this work finds that increased octahedral titling leads to improved photo-stability that is correlated with lower densities of performance-harming hexagonal polytype impurities. These results uncover the structural signatures underpinning photo-stability and can therefore be used to make targeted changes to halide perovskites, bettering the commercial prospects of technologies based on these materials
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Research data supporting "Local Nanoscale Phase Impurities are Degradation Sites in Halide Perovskites"
Understanding the nanoscopic chemical and structural changes that drive instabilities in emerging energy materials is essential for mitigating device degradation. The power conversion efficiency of halide perovskite photovoltaic devices has reached 25.7% in single junction and 29.8% in tandem perovskite/silicon cells1,2, yet retaining such performance under continuous operation has remained elusive3. Here, we develop a multimodal microscopy toolkit to reveal that in leading formamidinium-rich perovskite absorbers, nanoscale phase impurities including hexagonal polytype and lead iodide inclusions are not only traps for photo-excited carriers which themselves reduce performance4,5, but via the same trapping process are sites at which photochemical degradation of the absorber layer is seeded. We visualise illumination-induced structural changes at phase impurities associated with trap clusters, revealing that even trace amounts of these phases, otherwise undetected with bulk measurements, compromise device longevity. The type and distribution of these unwanted phase inclusions depends on film composition and processing, with the presence of polytypes being most detrimental for film photo-stability. Importantly, we reveal that performance losses and intrinsic degradation processes can both be mitigated by modulating these defective phase impurities, and demonstrate that this requires careful tuning of local structural and chemical properties. This multimodal workflow to correlate the nanoscopic landscape of beam sensitive energy materials will be applicable to a wide range of semiconductors for which a local picture of performance and operational stability has yet to be established.Royal Society (UF150033)
European Research Council (756962)
European Commission Horizon 2020 (H2020) Marie Sklodowska-Curie actions (841136)
European Commission Horizon 2020 (H2020) Marie Sklodowska-Curie actions (841386)
Engineering and Physical Sciences Research Council (EP/S030638/1)
EPSRC (EP/T02030X/1)
EPSRC (2127077)
EPSRC (EP/V012932/1)
Engineering and Physical Sciences Research Council (EP/R023980/1
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Local nanoscale phase impurities are degradation sites in halide perovskites.
Understanding the nanoscopic chemical and structural changes that drive instabilities in emerging energy materials is essential for mitigating device degradation. The power conversion efficiency of halide perovskite photovoltaic devices has reached 25.7 per cent in single-junction and 29.8 per cent in tandem perovskite/silicon cells1,2, yet retaining such performance under continuous operation has remained elusive3. Here we develop a multimodal microscopy toolkit to reveal that in leading formamidinium-rich perovskite absorbers, nanoscale phase impurities, including hexagonal polytype and lead iodide inclusions, are not only traps for photoexcited carriers, which themselves reduce performance4,5, but also, through the same trapping process, are sites at which photochemical degradation of the absorber layer is seeded. We visualize illumination-induced structural changes at phase impurities associated with trap clusters, revealing that even trace amounts of these phases, otherwise undetected with bulk measurements, compromise device longevity. The type and distribution of these unwanted phase inclusions depends on the film composition and processing, with the presence of polytypes being most detrimental for film photo-stability. Importantly, we reveal that both performance losses and intrinsic degradation processes can be mitigated by modulating these defective phase impurities, and demonstrate that this requires careful tuning of local structural and chemical properties. This multimodal workflow to correlate the nanoscopic landscape of beam-sensitive energy materials will be applicable to a wide range of semiconductors for which a local picture of performance and operational stability has yet to be established
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Imaging Light-Induced Migration of Dislocations in Halide Perovskites with 3d Nanoscale Strain Mapping.
Funder: King Abdullah University of Science and Technology; doi: http://dx.doi.org/10.13039/501100004052Funder: U.S. Department of Energy; doi: http://dx.doi.org/10.13039/100000015Funder: Office of Science; doi: http://dx.doi.org/10.13039/100006132Funder: HORIZON EUROPE European Research Council; doi: http://dx.doi.org/10.13039/100019180Funder: China Scholarship Council; doi: http://dx.doi.org/10.13039/501100004543Funder: British Spanish SocietyFunder: Sir Richard Stapley Educational Trust; doi: http://dx.doi.org/10.13039/501100016406Funder: Rank Prize FundFunder: Winton Sustainability FundFunder: George and Lilian Schiff FoundationFunder: Ernest Oppenheimer Early Career FellowshipFunder: Schmidt Science FellowshipIn recent years, halide perovskite materials have been used to make high-performance solar cells and light-emitting devices. However, material defects still limit device performance and stability. Here, synchrotron-based Bragg coherent diffraction imaging is used to visualize nanoscale strain fields, such as those local to defects, in halide perovskite microcrystals. Significant strain heterogeneity within MAPbBr3 (MA = CH3 NH3 + ) crystals is found in spite of their high optoelectronic quality, and both 〈100〉 and 〈110〉 edge dislocations are identified through analysis of their local strain fields. By imaging these defects and strain fields in situ under continuous illumination, dramatic light-induced dislocation migration across hundreds of nanometers is uncovered. Further, by selectively studying crystals that are damaged by the X-ray beam, large dislocation densities and increased nanoscale strains are correlated with material degradation and substantially altered optoelectronic properties assessed using photoluminescence microscopy measurements. These results demonstrate the dynamic nature of extended defects and strain in halide perovskites, which will have important consequences for device performance and operational stability
Recommended from our members
Imaging Light-Induced Migration of Dislocations in Halide Perovskites with 3d Nanoscale Strain Mapping.
In recent years, halide perovskite materials have been used to make high performance solar cell and light-emitting devices. However, material defects still limit device performance and stability. Here, we use synchrotron-based Bragg Coherent Diffraction Imaging to visualise nanoscale strain fields, such as those local to defects, in halide perovskite microcrystals. We find significant strain heterogeneity within MAPbBr3 (MA = CH3 NH3 + ) crystals in spite of their high optoelectronic quality, and identify both 〈100〉 and 〈110〉 edge dislocations through analysis of their local strain fields. By imaging these defects and strain fields in situ under continuous illumination, we uncover dramatic light-induced dislocation migration across hundreds of nanometers. Further, by selectively studying crystals that are damaged by the X-ray beam, we correlate large dislocation densities and increased nanoscale strains with material degradation and substantially altered optoelectronic properties assessed using photoluminescence microscopy measurements. Our results demonstrate the dynamic nature of extended defects and strain in halide perovskites, which will have important consequences for device performance and operational stability. This article is protected by copyright. All rights reserved