Recent advances in the use of organic–inorganic hybrid perovskites for optoelectronics have been rapid, with reported power conversion efficiencies of up to 22 per cent for perovskite solar cells1,2,3,4,5,6,7,8,9. Improvements in stability have also enabled testing over a timescale of thousands of hours10,11,12,13,14. However, large-scale deployment of such cells will also require the ability to produce large-area, uniformly high-quality perovskite films. A key challenge is to overcome the substantial reduction in power conversion efficiency when a small device is scaled up: a reduction from over 20 per cent to about 10 per cent is found15,16,17,18,19,20,21 when a common aperture area of about 0.1 square centimetres is increased to more than 25 square centimetres. Here we report a new deposition route for methyl ammonium lead halide perovskite films that does not rely on use of a common solvent1,2,4,5,6,7,8,9,10,11,12,13,14,15 or vacuum3: rather, it relies on the rapid conversion of amine complex precursors to perovskite films, followed by a pressure application step. The deposited perovskite films were free of pin-holes and highly uniform. Importantly, the new deposition approach can be performed in air at low temperatures, facilitating fabrication of large-area perovskite devices. We reached a certified power conversion efficiency of 12.1 per cent with an aperture area of 36.1 square centimetres for a mesoporous TiO2-based perovskite solar module architecture.
This is a preview of subscription content
Subscribe to Nature+
Get immediate online access to the entire Nature family of 50+ journals
Subscribe to Journal
Get full journal access for 1 year
only $3.90 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 6050–6051 (2009)
Burschka, J. et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499, 316–319 (2013)
Liu, M., Johnston, M. B. & Snaith, H. J. Efficient planar heterojunction perovskite solar cells by vapour deposition. Nature 501, 395–398 (2013)
Jeon, N. J. et al. Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells. Nat. Mater. 13, 897–903 (2014)
Li, X. et al. A vacuum flash-assisted solution process for high-efficiency large-area perovskite solar cells. Science 353, 58–62 (2016)
Zhou, H. et al. Interface engineering of highly efficient perovskite solar cells. Science 345, 542–546 (2014)
Jeon, N. J. et al. Compositional engineering of perovskite materials for high-performance solar cells. Nature 517, 476–480 (2015)
Yang, W. S. et al. High-performance photovoltaic perovskite layers fabricated through intramolecular exchange. Science 348, 1234–1237 (2015)
Bi, D. et al. Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%. Nat. Energy 1, 16142 (2016)
Mei, A. Y. et al. A hole-conductor-free, fully printable mesoscopic perovskite solar cell with high stability. Science 345, 295–298 (2014)
Saliba, M. et al. Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance. Science 354, 206–209 (2016)
Li, X. et al. Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid omega-ammonium chlorides. Nat. Chem. 7, 703–711 (2015)
Bella, F. et al. Improving efficiency and stability of perovskite solar cells with photocurable fluoropolymers. Science 354, 203–206 (2016)
Bi, E. et al. Diffusion engineering of ions and charge carriers for stable efficient perovskite solar cells. Nat. Commun. 8, 15330 (2017)
Chen, W. et al. Efficient and stable large-area perovskite solar cells with inorganic charge extraction layers. Science 350, 944–948 (2015)
Matteocci, F. et al. Solid-state solar modules based on mesoscopic organometal halide perovskite: a route towards the up-scaling process. Phys. Chem. Chem. Phys. 16, 3918–3923 (2014)
Gardner, K. L. et al. Nonhazardous solvent systems for processing perovskite photovoltaics. Adv. Energy Mater. 6, 1600386 (2016)
Qiu, W. et al. Pinhole-free perovskite films for efficient solar modules. Energy Environ. Sci. 9, 484–489 (2016)
Matteocci, F. et al. High efficiency photovoltaic module based on mesoscopic organometal halide perovskite. Prog. Photovolt. Res. Appl. 24, 436–445 (2016)
Razza, S. et al. Perovskite solar cells and large area modules (100 cm2) based on an air flow-assisted PbI2 blade coating deposition process. J. Power Sources 277, 286–291 (2015)
Hu, Y. et al. Stable large-area (10 × 10 cm2) printable mesoscopic perovskite module exceeding 10% efficiency. Sol. RRL 1, 1600019 (2017)
Patel, J. B., Milot, R. L., Wright, A. D., Herz, L. M. & Johnston, M. B. Formation dynamics of CH3NH3PbI3 perovskite following two-step layer deposition. J. Phys. Chem. Lett. 7, 96–102 (2016)
Liao, L. F., Wu, W. C., Chuang, C. C. & Lin, J. L. FTIR study of adsorption and reactions of methylamine on powdered TiO2 . J. Phys. Chem. B 105, 5928–5934 (2001)
Nunney, T. S., Birtill, J. J. & Raval, R. Infrared studies of sub-monolayer methylamine and trimethylamine adsorption on Ni(111). Surf. Sci. 427–428, 282–287 (1999)
Rosales, B. A. et al. Persistent dopants and phase segregation in organolead mixed-halide perovskites. Chem. Mater. 28, 6848–6859 (2016)
Xing, G. et al. Long-range balanced electron- and hole-transport lengths in organic-inorganic CH3NH3PbI3 . Science 342, 344–347 (2013)
Zhou, Z. et al. Methylamine-gas-induced defect-healing behavior of CH3NH3PbI3 thin films for perovskite solar cells. Angew. Chem. Int. Ed. 54, 9705–9709 (2015)
Ye, F. et al. Soft-cover deposition of scaling-up uniform perovskite thin films for high cost-performance solar cells. Energy Environ. Sci. 9, 2295–2301 (2016)
Xiao, Z. et al. Solvent annealing of perovskite-induced crystal growth for photovoltaic-device efficiency enhancement. Adv. Mater. 26, 6503–6509 (2014)
Green, M. A. et al. Solar cell efficiency tables (version 49). Prog. Photovolt. Res. Appl. 25, 3–13 (2017)
This work was supported by the National Natural Science Foundation of China (grant nos 11574199 and 11674219), the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning, Natural Science Foundation of Shanghai (17ZR1414800). We thank B. Dai from Instrumental Analysis Center of SJTU and G. Lu from Shanghai Institute of Organic Chemistry for NMR measurements, and Y. Wu for discussions. M.G. thanks the European Research Council (ERC) for support of this work under a Proof of Concept project associated with his Mesolight Advanced Research Grant (ARF).
The authors declare no competing financial interests.
Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Extended data figures and tables
Extended Data Figure 1 The appearance of CH3NH3X·mCH3NH2, PbX2·nCH3NH2 and the mixture of CH3NH3I·3CH3NH2 and PbI2·CH3NH2.
Vial diameter, 10 mm.
Extended Data Figure 2 NMR spectra of CH3NH3I and PbI2 individually and with interaction with CH3NH2.
Top, 1H NMR of CH3NH3I with and without CH3NH2, and bottom, 207Pb NMR of PbI2 and with or without CH3NH2, in different mixtures or in solution in DMSO.
Extended Data Figure 3 FTIR spectra of CH3NH3X, CH3NH3X·mCH3NH2 and PbX2·nCH3NH2 (X = Br, Cl). Here m ≈ 3, n ≈ 1.
Extended Data Figure 4 The effect of pressure on the thickness and the light absorbance of perovskite films.
a, The light absorbance spectra of perovskite films deposited at different pressures; the light absorption at 600 nm was chosen to calculate the film thickness. b, The light absorbance at 600 nm (red symbols and axis) and the film thickness (blue symbols and axis) as a function of pressure.
Extended Data Figure 5 Illustration of perovskite films deposited by the present pressure-assisted processing method and by the spin-coating method.
In both cases, 200 μl of precursor solution was used on a 64 cm2 substrate.
Extended Data Figure 6 The ultraviolet–visible light absorption spectra of 16 pieces of 2 cm × 2 cm perovskite films.
The films were made by cutting an 8 cm × 8 cm film into 16 pieces: the spectra of each piece was recorded individually. The perovskite film was deposited via the present pressure processing method.
The IPCE (incident photon-to-current conversion efficiency) spectrum of a solar cell with a perovskite film deposited by the present pressure processing method (see Methods for details).
Shown are the efficiency of devices with different aperture area (a), precursor amount (b), pressure (c), temperature (d), and peeling speed (e). The measurement was carried out under AM 1.5G simulated solar light, 100 mW cm−2. All devices were made using the present pressure-processing method. 10 devices were measured for statistical analysis in each case. In the boxplots, the star represents the maximum and minimum values; the open square represents the mean value.
Extended Data Figure 9 Evolution of the photovoltaic stability of an encapsulated perovskite solar module fabricated by the present pressure-processing method.
The module (36.1 cm2) was aged under a 10 mW cm−2 UV-filtered simulated sunlight at 45 °C in ambient air and maintained at the maximum power point. The energy conversion efficiency was measured under simulated AM 1.5 solar light, 100 mW cm−2 intensity. The module retained 90% of the initial performance after 500 h.
Extended Data Figure 10 The performance of a perovskite solar module certified by a public test centre.
Red line, current–voltage curve; green line, power–voltage curve. ISC is the current value at short circuit condition; VOC is the voltage at open circuit condition; Pmax is the maximum power; Vpmax is the voltage at the point of Pmax; Ipmax is the current at the point of Pmax; F.F. is the fill factor; Eff(da) is the efficiency calculated with a light power that is defined by a designated aperture; DTemp. is the designed temperature; MTemp. is the measured temperature; DIrr. is the designed irradiation intensity; MIrr. is the measured irradiation intensity.
About this article
Cite this article
Chen, H., Ye, F., Tang, W. et al. A solvent- and vacuum-free route to large-area perovskite films for efficient solar modules. Nature 550, 92–95 (2017). https://doi.org/10.1038/nature23877
A route towards the fabrication of large-scale and high-quality perovskite films for optoelectronic devices
Scientific Reports (2022)
Nano Research (2022)
Tunable engineering of photo- and electro-induced carrier dynamics in perovskite photoelectronic devices
Science China Materials (2022)
Science China Chemistry (2022)
Nano Research (2022)