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Perovskite ink with wide processing window for scalable high-efficiency solar cells

Nature Energy volume 2, Article number: 17038 (2017) Cite this article

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Abstract

Perovskite solar cells have made tremendous progress using laboratory-scale spin-coating methods in the past few years owing to advances in controls of perovskite film deposition. However, devices made via scalable methods are still lagging behind state-of-the-art spin-coated devices because of the complicated nature of perovskite crystallization from a precursor state. Here we demonstrate a chlorine-containing methylammonium lead iodide precursor formulation along with solvent tuning to enable a wide precursor-processing window (up to ∼8 min) and a rapid grain growth rate (as short as ∼1 min). Coupled with antisolvent extraction, this precursor ink delivers high-quality perovskite films with large-scale uniformity. The ink can be used by both spin-coating and blade-coating methods with indistinguishable film morphology and device performance. Using a blade-coated absorber, devices with 0.12-cm2 and 1.2-cm2 areas yield average efficiencies of 18.55% and 17.33%, respectively. We further demonstrate a 12.6-cm2 four-cell module (88% geometric fill factor) with 13.3% stabilized active-area efficiency output.

Perovskite solar cell (PSC) technology has made stunning progress in performance in the past few years1,2,3,4,5,6,7,8, making it a potentially transformational technology and disruptive addition to the emerging photovoltaic (PV) market. The rapid improvement in PSC efficiency is largely a result of developments in solution-chemistry processing of high-quality perovskite absorbers. In general, solution deposition of perovskites includes coating a wet precursor film on the substrate, evaporating/drying the solvent, and forming perovskite or an intermediate solid film, which are often followed by thermal annealing to fully crystallize the perovskite film9. Perovskite nucleation, growth, and coarsening often occur with significant overlap in one or several of these steps, which complicates the perovskite formation process10. Most academic groups have focused on using spin coating, because it requires small amounts of liquid (although it is wasteful), can easily be done in a controlled environment, and is easy to use. Unfortunately, the spin-coating method cannot be scaled for the high throughput and large substrate sizes desired for module production. Toward future module production, several scalable techniques have been reported for perovskite deposition11,12, such as blade coating13,14,15, slot-die coating16, spray deposition17, inkjet printing18,19, and electrodeposition20,21. However, these scalable methods have generally produced devices with lower efficiencies than spin-coated devices. Blade coating is attractive because it can easily be scaled up and translated to slot-die coating for sheet-to-sheet or roll-to-roll fabrication. Different approaches have been adopted in blade coating, such as one-step deposition (mostly mixture of PbCl2 and CH3NH3I or methylammonium iodide (MAI) with a molar ratio of 1:3)14,22, two-step sequential deposition13, and hot casting15,23. Because of the complexity of film formation under specific environments, different solution-coating routes often result in significantly different film growth mechanisms, film morphologies, and microstructures24. Therefore, it is generally accepted that solution chemistry/processing has to be redeveloped when transitioning from spin coating to scalable deposition. It is worth noting that device architectures also affect perovskite deposition. Encouraging results have been obtained for both mesoporous13,25,26 and planar structures27,28. Mesoporous structures can display high stability29 and easy perovskite deposition4, whereas planar structures typically have a simpler architecture for processing30. During the past two years, one of the most successful solution-processing approaches is antisolvent dripping/washing5,31, which has been widely adopted by the perovskite community to produce high-quality perovskite thin films6,32. Moreover, additives such as methylammonium chloride (MACl) can be used in simple spin-coating methods to control perovskite morphology and coverage33,34. It is commonly accepted that applying an antisolvent during spin coating of the precursor film causes rapid supersaturation, leading to the formation of highly uniform perovskite thin films. However, a challenge for this method is the very narrow time window (seconds) for adding the antisolvent31, which makes it a difficult transition to any of the mentioned scalable methods11.

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Figure 1: Precursor-film processing window.
Figure 2: Crystal structure evolution.
Figure 3: Uniformity of blade-coated perovskite films.
Figure 4: Comparison between blade coating and spin coating.
Figure 5: Device-level uniformity.
Figure 6: PV characteristics of champion devices.

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Acknowledgements

The work at the National Renewable Energy Laboratory is supported by the US Department of Energy under Contract No. DE-AC36-08GO28308. We acknowledge the support by the hybrid perovskite solar cell program of the National Center for Photovoltaics funded by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies Office. We thank S. Mauger for help with XRF and viscosity measurement.

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Authors and Affiliations

  1. Chemistry and Nanoscience Center, National Renewable Energy Laboratory, Golden, Colorado 80401, USA

    Mengjin Yang, Zhen Li, Obadiah G. Reid, Dong Hoe Kim & Kai Zhu

  2. Material Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, USA

    Matthew O. Reese, Sebastian Siol, Talysa R. Klein, Joseph J. Berry & Maikel F. A. M. van Hest

  3. Department of Physics and Astronomy, The University of Toledo, Toledo, Ohio 43606, USA

    Yanfa Yan

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Contributions

K.Z. and M.Y. conceived the idea and designed the experiment. M.Y., Z.L., and D.H.K. fabricated and characterized perovskite thin film and devices. M.Y. and M.O.R. optimized large-area devices. M.Y., T.R.K., K.Z., and M.F.A.M.v.H. fabricated and characterized mini-module. M.Y. and S.S. measured XRF. K.Z., J.J.B., and M.F.A.M.v.H. supervised this project. K.Z. and M.Y. wrote the manuscript with inputs and discussion from all authors.

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Correspondence to Maikel F. A. M. van Hest or Kai Zhu.

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The authors declare no competing financial interests.

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Supplementary Figures 1–13 and Supplementary Tables 1–3 (PDF 1177 kb)

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Yang, M., Li, Z., Reese, M. et al. Perovskite ink with wide processing window for scalable high-efficiency solar cells. Nat Energy 2, 17038 (2017). https://doi.org/10.1038/nenergy.2017.38

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