Triple cation Cs/methylammonium (MA)/formamidinium (FA) and double halide Br/I lead perovskites improved the stability and efficiency of perovskite solar cells (PVSCs). However, their effects on alloyed Pb–Sn perovskites are unexplored. In this work, perovskite thin films with the composition Cs x (MA 0.17 FA 0.83 ) 1−x Pb 1−y Sn y (I 0.83 Br 0.17 ) 3 are synthesized utilizing a one-step solution process plus an anti-solvent wash technique and deployed in PVSCs with an inverted architecture. All films show a cubic crystal structure, demonstrating that compositional tuning of both the tolerance factor and crystallization rate allows for dense, single phase formation. The band gaps, affected by both lattice constriction and octahedral tilting, show opposite trends in Pb-rich or Sn-rich perovskites with the increase of Cs for fixed Sn compositions. The Cs 0.05 (MA 0.17 FA 0.83 ) 0.95 Pb 0.25 Sn 0.75 (I 0.83 Br 0.17 ) 3 PVSCs achieve a power conversion efficiency (PCE) of 11.05%, a record for any PVSC containing 75% Sn perovskites, and the Cs 0.10 (MA 0.17 FA 0.83 ) 0.90 Pb 0.75 Sn 0.25 (I 0.83 Br 0.17 ) 3 PVSCs reach a record PCE of 15.78%. Moreover, the triple cation and double halide alloyed Pb–Sn perovskites exhibit improved device stability under inert and ambient conditions. This study, which illustrates the impact of cation and halide tuning on alloyed Pb–Sn perovskites, can be used to further eliminate Pb and improve device performance of high Sn PVSCs and other optoelectronic devices.
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Identifying high-performance and durable methylammonium-free lead halide perovskites via high-throughput synthesis and characterization
One of the organic components in the perovskite photo-absorber, the methylammonium cation, has been suggested to be a roadblock to the long-term operation of organic–inorganic hybrid perovskite-based solar cells. In this work we systematically explore the crystallographic and optical properties of the compositional space of mixed cation and mixed halide lead perovskites, where formamidinium (FA + ) is gradually replaced by cesium (Cs + ), and iodide (I − ) is substituted by bromide (Br − ), i.e. , Cs y FA 1− y Pb(Br x I 1− x ) 3 . Higher tolerance factors lead to more cubic structures, whereas lower tolerance factors lead to more orthorhombic structures. We find that while some correlation exists between the tolerance factor and structure, the tolerance factor does not provide a holistic understanding of whether or not a perovskite structure will fully form. By screening 26 solar cells with different compositions, our results show that Cs 1/6 FA 5/6 PbI 3 delivers the highest efficiency and long-term stability among the I-rich compositions. This work sheds light on the fundamental structure–property relationships in the Cs y FA 1− y Pb(Br x I 1− x ) 3 compositional space, providing vital insight to the design of durable perovskite materials. Our approach provides a library of structural and optoelectronic information for this compositional space.
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- Award ID(s):
- 2003808
- NSF-PAR ID:
- 10417868
- Date Published:
- Journal Name:
- Energy & Environmental Science
- Volume:
- 14
- Issue:
- 12
- ISSN:
- 1754-5692
- Page Range / eLocation ID:
- 6638 to 6654
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Organometal halide perovskites have powerful intrinsic potential to drive next‐generation solar technology, but their insufficient thermomechanical reliability and unproven large‐area manufacturability limit competition with incumbent silicon photovoltaics. This work addresses these limitations by leveraging large‐area processing and robust inorganic hole transport layers (HTLs). Inverted perovskite solar cells utilizing NiOxHTLs deposited by rapid aqueous spray‐coating that outperform spin‐coated NiOxand lead to a 5× improvement in the fracture energy (
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Abstract Perovskite solar cells increasingly feature mixed‐halide mixed‐cation compounds (FA1−
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Organic–inorganic lead halide perovskite solar cells are regarded as one of the most promising technologies for the next generation of photovoltaics due to their high power conversion efficiency (PCE) and simple solution manufacturing. Among the different compositions, the formamidinium lead iodide (FAPbI3) photoactive phase has a bandgap of 1.4 eV, which enables the corresponding higher PCEs according to the Shockley–Queisser limit. However, the photoactive crystal phase of FAPbI3is not stable at room temperature. The most high‐performing compositions to date have reduced this problem by incorporating the methylammonium (MA) cation into the FAPbI3composition, although MA has poor stability at high temperatures and in humid environments, which can limit the lifetime of FA
x MA1−x PbI3films. Csx FA1−x PbI3perovskites are also explored, but despite better stability they still lag in performance. Herein, the additive engineering of MA‐free organic−inorganic lead halide perovskites using divalent cations Sr2+and Ca2+to enhance the performances of Csx FA1−x PbI3perovskite compositions is explored. It is revealed that the addition of up to 0.5% of Sr2+and Ca2+leads to improvements in morphology and reduction in microstrain. The structural improvements observed correlate with improved solar cell performances at low additive concentrations.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1EE02691G
