Making organic–inorganic metal halide-based multijunction perovskite solar cells either by solution processes or physical techniques is not straightforward. Here we propose and developed dimethylammonium iodide-assisted β−CsPbI3 and guanidinium iodide-assisted γ−CsPbI3 all-inorganic phase-heterojunction solar cells (PHSs) by integrating hot-air and triple-source thermal evaporation deposition techniques, respectively. Incorporating a (Zn(C6F5)2) molecular additive and dopant-free hole transport layer produces a 21.59% power conversion efficiency (PCE). The laboratory-to-module scale shows 18.43% PCE with an 18.08 cm2 active area. We demonstrate that this additive-assisted β−γ-based PHS structure exhibited >200 hours of stable performance under maximum power tracking under one sun illumination. This work paves the way towards dual deposition techniques for PHS with important consequences not only for all inorganic but also for other halide perovskite compositions.
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All data generated or analysed during this study are included in the published article and its Supplementary Information and Source Data files. Data used for Figs. 4a and 6e, Table 1 and Supplementary Figs. 24a, 25b and 28 are available at https://doi.org/10.6084/m9.figshare.23536833. Source data are provided with this paper.
NREL Best Research-Cell Efficiencies Chart (NREL, accessed 7 June 2023); https://www.nrel.gov/pv/assets/pdfs/best-research-cell-efficiencies.pdf
Park, J. et al. Controlled growth of perovskite layers with volatile alkylammonium chlorides. Nature 616, 724–730 (2023).
Al-Ashouri, A. et al. Monolithic perovskite/silicon tandem solar cell with >29% efficiency by enhanced hole extraction. Science 370, 1300–1309 (2020).
Cui, P. et al. Planar p–n homojunction perovskite solar cells with efficiency exceeding 21.3%. Nat. Energy 4, 150–159 (2019).
Xiong, S. et al. Direct observation on p- to n-type transformation of perovskite surface region during defect passivation driving high photovoltaic efficiency. Joule 5, 464–480 (2021).
Noel, N. K. et al. Interfacial charge-transfer doping of metal halide perovskites for high performance photovoltaics. Energy Environ. Sci. 12, 3063–3073 (2019).
Jiang, Q. et al. Interfacial molecular doping of metal halide perovskites for highly efficient solar cells. Adv. Mater. 32, 2001581 (2020).
Cui, P. et al. Highly efficient electron-selective layer free perovskite solar cells by constructing effective p–n heterojunction. Sol. RRL 1, 1600027 (2017).
Zhang, J. et al. n-type doping and energy states tuning in CH3NH3Pb1–xSb2x/3I3 perovskite solar cells. ACS Energy Lett. 1, 535–541 (2016).
Shahbazi, S. et al. Ag doping of organometal lead halide perovskites: morphology modification and p-type character. J. Phys. Chem. C 121, 3673–3679 (2017).
Kirchartz, T. & Cahen, D. Minimum doping densities for p–n junctions. Nat. Energy 5, 973–975 (2020).
Eperon, G. E. et al. Inorganic caesium lead iodide perovskite solar cells. J. Mater. Chem. A 3, 19688–19695 (2015).
Mali, S. S., Patil, J. V., Shinde, P. S., Miguel, G. & Hong, C. K. Fully air-processed dynamic hot-air-assisted M:CsPbI2Br (M: Eu2+, In3+) for stable inorganic perovskite solar cells. Matter 4, 635–653 (2021).
Mali, S. S., Patil, J. V., Steele, J. A. & Hong, C. K. Ambient processed and stable all-inorganic lead halide perovskite solar cells with efficiencies nearing 20% using a spray coated Zn1−xCsxO electron transport layer. Nano Energy 90, 106597 (2021).
Wang, K. et al. In-situ hot oxygen cleansing and passivation for all-inorganic perovskite solar cells deposited in ambient to breakthrough 19% efficiency. Adv. Funct. Mater. 31, 2101568 (2021).
Mali, S. S. et al. Terbium-doped and dual-passivated γ-CsPb(I1−xBrx)3 inorganic perovskite solar cells with improved air thermal stability and high efficiency. Adv. Mater. 34, 2203204 (2022).
Yoon, S. M. et al. Surface engineering of ambient-air-processed cesium lead triiodide layers for efficient solar cells. Joule 5, 183–196 (2021).
Sun, X. et al. Highly efficient CsPbI3/Cs1−xDMAxPbI3 bulk heterojunction perovskite solar cell. Joule 6, 850–860 (2022).
Bera, S. et al. Limiting heterovalent B-site doping in CsPbI3 nanocrystals: phase and optical stability. ACS Energy Lett. 4, 1364–1369 (2019).
Zhou, S. et al. Ag-doped halide perovskite nanocrystals for tunable band structure and efficient charge transport. ACS Energy Lett. 4, 534–541 (2019).
Han, Y. et al. Controlled n-doping in air-stable CsPbI2Br perovskite solar cells with a record efficiency of 16.79%. Adv. Funct. Mater. 30, 1909972 (2020).
Sutton, R. J. et al. Cubic or orthorhombic? Revealing the crystal structure of metastable black-phase CsPbI3 by theory and experiment. ACS Energy Lett. 3, 1787–1794 (2018).
Marronnier, A. et al. Anharmonicity and disorder in the black phases of cesium lead iodide used for stable inorganic perovskite solar cells. ACS Nano 12, 3477–3486 (2018).
Jaysankar, M. et al. Minimizing voltage loss in wide-bandgap perovskites for tandem solar cells. ACS Energy Lett. 4, 259–264 (2019).
Wang, Z. et al. Suppressed phase segregation for triple-junction perovskite solar cells. Nature 618, 74–79 (2023).
Wang, Y. et al. The role of dimethylammonium iodide in CsPbI3 perovskite fabrication: additive or dopant? Angew. Chem. Int. Ed. 58, 16691–16696 (2019).
Paterson, A. F. et al. Addition of the Lewis acid Zn(C6F5)2 enables organic transistors with a maximum hole mobility in excess of 20 cm2 V−1 s−1. Adv. Mater. 31, 1900871 (2019).
Chang, X. et al. Printable CsPbI3 perovskite solar cells with PCE of 19% via an additive strategy. Adv. Mater. 32, 2001243 (2020).
Ji, R. et al. Perovskite phase heterojunction solar cells. Nat. Energy 7, 1170–1179 (2022).
Mali, S. S., Patil, J. V. & Hong, C. K. Hot-air-assisted fully air-processed barium incorporated CsPbI2Br perovskite thin films for highly efficient and stable all-inorganic perovskite solar cells. Nano Lett. 19, 6213–6220 (2019).
Mali, S. S., Patil, J. V. & Hong, C. K. Simultaneous improved performance and thermal stability of planar metal ion incorporated CsPbI2Br all-inorganic perovskite solar cells based on MgZnO nanocrystalline electron transporting layer. Adv. Energy Mater. 10, 1902708 (2020).
Mali, S. S., Patil, J. V., Arandiyan, H. & Hong, C. K. Reduced methylammonium triple-cation Rb0.05(FAPbI3)0.95(MAPbBr3)0.05 perovskite solar cells based on a TiO2/SnO2 bilayer electron transport layer approaching a stabilized 21% efficiency: the role of antisolvents. J. Mater. Chem. A 7, 17516–17528 (2019).
Mali, S. S., Patil, J. V., Shinde, P. S. & Hong, C. K. Enhanced fill factor for normal n–i–p planar heterojunction and mesoscopic perovskite solar cells using ruthenium-doped TiO2 electron transporting layer. Prog. Photovolt. Res. Appl. 29, 159–171 (2021).
Zhang, Z. et al. Efficient thermally evaporated γ-CsPbI3 perovskite solar cells. Adv. Energy Mater. 11, 2100299 (2021).
Li, M.-H. et al. Electrical loss management by molecularly manipulating dopant-free poly(3-hexylthiophene) towards 16.93% CsPbI2Br solar cells. Angew. Chem. Int. Ed. 60, 16388–16393 (2021).
Wang, Y. et al. Thermodynamically stabilized β-CsPbI3-based perovskite solar cells with efficiencies >18%. Science 365, 591–595 (2019).
Mali, S. S. et al. Implementing dopant-free hole-transporting layers and metal-incorporated CsPbI2Br for stable all-inorganic perovskite solar cells. ACS Energy Lett. 6, 778–788 (2021).
Sidhik, S. et al. Deterministic fabrication of 3D/2D perovskite bilayer stacks for durable and efficient solar cells. Science 377, 1425–1430 (2022).
Jin, Z., Wang, A., Zhou, Q., Wang, Y. & Wang, J. Detecting trap states in planar PbS colloidal quantum dot solar cells. Sci. Rep. 6, 37106 (2016).
Mali, S. S., Patil, J. V., Park, D. W., Jung, Y. H. & Hong, C. K. Intrinsic and extrinsic stability of triple-cation perovskite solar cells through synergistic influence of organic additive. Cell Rep. Phys. Sci. 3, 100906 (2022).
Zhao, X. et al. Accelerated aging of all-inorganic, interface-stabilized perovskite solar cells. Science 377, 307–310 (2022).
Yang, D. et al. High efficiency planar-type perovskite solar cells with negligible hysteresis using EDTA-complexed SnO2. Nat. Commun. 9, 3239 (2018).
Li, M.-H. et al. A sulfur-rich small molecule as a bifunctional interfacial layer for stable perovskite solar cells with efficiencies exceeding 22%. Nano Energy 79, 105462 (2021).
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Blöchl, P. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 132, 154104 (2010).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
Krukau, A. V., Vydrov, O. A., Izmaylov, A. F. & Scuseria, G. E. Influence of the exchange screening parameter on the performance of screened hybrid functionals. J. Chem. Phys. 125, 224106 (2006).
This research is supported by the National Research Foundation of Korea (NRF) (2020R1A2C2004880). This work was also supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2018R1A6A1A03024334). S.R.R. acknowledges the support of the Department of Materials Engineering, Indian Institute of Science (IISc), Bengaluru, India. N.Y.D. acknowledges the support of the College of Earth and Minerals Sciences and the John and Willie Leone Family Department of Energy and Mineral Engineering of Pennsylvania State University. Computer simulations for this work were performed on the Roar Supercomputer of The Pennsylvania State University. Y.-W.Z. acknowledges the funding support of the Natural Science Foundation of Beijing Municipality (2191003). We thank G. G. Jeong for helping with GIXRD measurements, from the Chonnam Center for Research Facilities (CCRF), Chonnam National University, Gwangju, and we also thank J. A. Steele from the School of Mathematics and Physics from the University of Queensland for helping with XRD analysis.
The authors declare no competing interests.
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Supplementary Figs. 1–40, Notes 1–8, Tables 1–20 and Movies 1 and 2.
In-situ deposition of γ–CsPbI3-GAI-based perovskite thin film by thermal evaporation at module scale (13 cm × 13 cm = 169 cm2).
Captions for Supplementary Movie 2: testing of 13 × 13 cm2 PHS-based module under LED lamp in ambient conditions.
Source data file for Supplementary Fig. 24a.
Source data file for Supplementary Fig. 25b.
Source data file for Supplementary Fig. 28.
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Mali, S.S., Patil, J.V., Shao, JY. et al. Phase-heterojunction all-inorganic perovskite solar cells surpassing 21.5% efficiency. Nat Energy 8, 989–1001 (2023). https://doi.org/10.1038/s41560-023-01310-y