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High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells

Abstract

Three-dimensional organic–inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties1,2,3,4,5, which have led to power conversion efficiencies exceeding 20 per cent6,7, with the prospect of further improvements towards the Shockley–Queisser limit for a single‐junction solar cell (33.5 per cent)8. Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions9,10,11,12,13,14,15. In contrast to their three-dimensional counterparts, Ruddlesden–Popper phases—layered two-dimensional perovskite films—have shown promising stability, but poor efficiency at only 4.73 per cent13,16,17. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

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Figure 1: Crystal structure and thin-film characterization of layered perovskites.
Figure 2: GIWAXS images and structure orientation.
Figure 3: Solar cell architecture and characterization.
Figure 4: Stability measurements on planar solar cells.

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Acknowledgements

This work at LANL was LANL LDRD programme (A.D.M., G.G., J.-C.B. and S.T.). Work at Northwestern University was supported as part of the ANSER Center, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award No. DE-SC0001059. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Work at INSA de Rennes was performed using high-performance computational resources from the French national centres (GENCI/CINES/IDRIS grant 2015-c2012096724), Cellule Energie du CNRS (SOLHYBTRANS Project) and the University of Rennes 1 (Action Incitative,Défis Scientifique Emergents 2015). J.E.’s work is also supported by the Fondation d’entreprises banque Populaire de l’Ouest (Grant PEROPHOT 2015). The work at Purdue University was supported by the Bay Area PV Consortium (a Department of Energy project with Prime Award number DE-EE0004946). This work at LANL was done in part at the Center for Nonlinear Studies (CNLS) and the Center for Integrated Nanotechnologies (CINT). R.V. acknowledges the support of the NSF DMR-1352099.

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Authors

Contributions

A.D.M., H.T., W.N. and M.G.K. conceived the idea. H.T., W.N. and A.D.M. designed the experiments, analysed the data and wrote the paper. H.T. fabricated the devices along with W.N. and performed the measurements. J.-C.B. performed optical spectroscopy measurements and analysed the data under the supervision of J.J.C. C.C.S. synthesized the layered perovskites under the supervision of M.G.K. and co-wrote the paper. R.V. arranged the synchrotron experiments data, and B.H. and M.J.B. analysed and indexed the synchrotron XRD data along with M.G.K. J.E., G.G., L.P. and S.T. performed the molecular dynamics simulations. J.E. analysed the data and provided insight in writing the paper. G.G., J.L. and P.M.A. provided insights into the crystal growth of layered perovskites. R.A. and M.A.A. performed the device simulations. A.J.N. performed DFT calculations on layered perovskites under the supervision of S.T. All authors discussed the results and wrote the paper.

Corresponding author

Correspondence to Aditya D. Mohite.

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The authors declare no competing financial interests.

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Nature thanks H. Snaith and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Extended data figures and tables

Extended Data Figure 1 Layered perovskite thin-film morphology and device performance.

a, b, AFM images of surface morphology for room-temperature-cast (a) and hot-cast (b) films. Scale bars, 400 nm. c, d, SEM images of topography for room-temperature-cast (c) and hot-cast (d) films. Scale bars, 1 μm. e, JV curve of Pb4I13 with C60 as a contact modification candidate shows the enhancement of VOC from 0.9 V to 1.055 V with the same device architecture. f, JV curve for the (BA)2(MA)3Pb4I13 device using the room-temperature (RT) spin-cast method. FF, fill factor.

Extended Data Figure 2 Absorption spectroscopy of layered 2D perovskites.

ac, Local optical absorption characteristics of thin films using reflection/transmission experimental methods (see also refs 34, 35 for details of the modelling): results of the fitting of the reflection (R) and transmission (T) data (a); absolute absorption cross-section (b); and real (n; red line) and imaginary (k; black line) parts of the refractive index (c). d, Absorbance of thin films (grey circles) compared to that of optimized solar cells (red squares) measured using integrating sphere techniques (see details in ref. 36).

Extended Data Figure 3 DFT computation.

a, b, Electronic band structures of (BA)2PbI4 (n = 1; a) and (BA)2(MA)2Pb3I10 (n = 3; b) calculated using DFT with a local-density approximation, including the spin–orbit coupling and a bandgap correction computed using the HSE (Heyd–Scuseria–Ernzerhof) functional. The energy levels are referenced to the valence band maximum.

Extended Data Figure 4 Device performance of (BA)2(MA)2Pb3I10.

a, JV curve and device parameters. b, EQE (red circles) and integrated JSC from EQE (blue dashed line).

Extended Data Figure 5 Dark current transient and mobility.

The dark current transient (ΔJ/J0), measured using the CELIV technique, for a hot-cast (red) and a room-temperature-cast (‘As cast’, black) device, and the mobility value (μ) in each case.

Extended Data Figure 6 Device PCE as a function of thin-film thickness for the layered Pb4I13 perovskite.

Extended Data Figure 7 Hysteresis tests for 2D pervoskite devices.

ad, Tests with different bias sweep directions (a; (C/C0)−2 as function of DC bias, where C0 is the capacitance of a geometric capacitor), and after 10 h (b), 1,000 h (c) and 2,250 h (d) of constant illumination. The red and blue arrows indicate the forward and reverse sweep directions.

Extended Data Figure 8 Simulation results and comparison of room-temperature-cast and hot-cast methods.

a, Experimental (‘Expr.’) JV characteristics of room-temperature-cast (‘As cast’) and hot-cast methods and corresponding simulation (‘Sim.’) results. The hot-cast method shows a current density with a larger magnitude and higher fill factor (area below the JV curve). b, Integrated recombination inside three layers of a solar cell. Peak recombination shifts toward the PCBM/perovskite interface because the barrier for generated carriers is less in the hot-cast case than in the room-temperature-cast case. c, d, Energy band diagram of hot-cast (c) and room-temperature-cast (d) methods. Generated carriers face a lower barrier in the hot-cast case, especially close to the PEDOT/perovskite interface. EC, conduction band; EV, valence band; EFN, electron quasi-Fermi level; EFP, hole quasi-Fermi level.

Extended Data Figure 9 Heat stress tests.

a, b, Spectra of 2D (a) and 3D (b) perovskite thin films under 80 °C in darkness after the lengths of time indicated (spectra are offset for clarity; ‘ref.’ refers to freshly made thin film, measured after 0 h of heat stressing). c, Ratio of the PbI2 (2θ = 12.7°) and perovskite (2θ = 14.2°) main peaks in the spectra in a and b for the two perovskite materials (2D, blue; 3D, red) over 30 h of heating at 80 °C.

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Tsai, H., Nie, W., Blancon, JC. et al. High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells. Nature 536, 312–316 (2016). https://doi.org/10.1038/nature18306

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