The performance of perovskite solar cells is predominantly limited by non-radiative recombination, either through trap-assisted recombination in the absorber layer or via minority carrier recombination at the perovskite/transport layer interfaces. Here, we use transient and absolute photoluminescence imaging to visualize all non-radiative recombination pathways in planar pin-type perovskite solar cells with undoped organic charge transport layers. We find significant quasi-Fermi-level splitting losses (135 meV) in the perovskite bulk, whereas interfacial recombination results in an additional free energy loss of 80 meV at each individual interface, which limits the open-circuit voltage (VOC) of the complete cell to ~1.12 V. Inserting ultrathin interlayers between the perovskite and transport layers leads to a substantial reduction of these interfacial losses at both the p and n contacts. Using this knowledge and approach, we demonstrate reproducible dopant-free 1 cm2 perovskite solar cells surpassing 20% efficiency (19.83% certified) with stabilized power output, a high VOC (1.17 V) and record fill factor (>81%).
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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).
Kim, H. S. et al. Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%. Sci. Rep. 2, 591 (2012).
Lee, M. M., Teuscher, J., Miyasaka, T., Murakami, T. N. & Snaith, H. J. Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science 338, 643–647 (2012).
Yang, W. S. et al. Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells. Science 356, 1376–1379 (2017).
Yoshikawa, K. et al. Silicon heterojunction solar cell with interdigitated back contacts for a photoconversion efficiency over 26%. Nat. Energy 2, 17032 (2017).
Tress, W. Perovskite solar cells on the way to their radiative efficiency limit—insights into a success story of high open-circuit voltage and low recombination. Adv. Energy Mater. 7, 1602358 (2017).
Grancini, G. et al. One-year stable perovskite solar cells by 2D/3D interface engineering. Nat. Commun. 8, 15684 (2017).
Lin, Q., Nagiri, R. C. R., Burn, P. L. & Meredith, P. Considerations for upscaling of organohalide perovskite solar cells. Adv. Opt. Mater. 5, 1600819 (2017).
Stolterfoht, M. et al. Approaching the fill factor Shockley–Queisser limit in stable, dopant-free triple cation perovskite solar cells. Energy Environ. Sci. 10, 1530–1539 (2017).
Zhang, W. et al. Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells. Nat. Commun. 6, 10030 (2015).
Zheng, X. et al. Defect passivation in hybrid perovskite solar cells using quaternary ammonium halide anions and cations. Nat. Energy 2, 17102 (2017).
Sherkar, T. S., Momblona, C., Gil-Escrig, L., Bolink, H. J. & Koster, L. J. A. Improving perovskite solar cells: Insights from a validated device model. Adv. Energy Mater. 7, 1602432 (2017).
Correa-Baena, J.-P. et al. Identifying and suppressing interfacial recombination to achieve high open-circuit voltage in perovskite solar cells. Energy Environ. Sci. 10, 1207–1212 (2017).
Tvingstedt, K. et al. Removing leakage and surface recombination in planar perovskite solar cells. ACS Energy Lett. 2, 424–430 (2017).
Wolff, C. M. et al. Reduced interface-mediated recombination for high open-circuit voltages in CH3NH3PbI3 solar cells. Adv. Mater. 29, 1700159 (2017).
Tan, H. et al. Efficient and stable solution-processed planar perovskite solar cells via contact passivation. Science 355, 722–726 (2017).
Saliba, M. et al. Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance. Science 354, 206–209 (2016).
Hou, Y. et al. A generic interface to reduce the efficiency–stability–cost gap of perovskite solar cells. Science 358, 1192–1197 (2017).
Momblona, C. et al. Efficient vacuum deposited p-i-n and n-i-p perovskite solar cells employing doped charge transport layers. Energy Environ. Sci. 9, 3456–3463 (2016).
Bush, K. A. et al. 23.6%-efficient monolithic perovskite/silicon tandem solar cells with improved stability. Nat. Energy 2, 17009 (2017).
Albrecht, S. et al. Monolithic perovskite/silicon-heterojunction tandem solar cells processed at low temperature. Energy Environ. Sci. 9, 81–88 (2016).
Wu, Y. et al. Thermally stable MAPbI3 perovskite solar cells with efficiency of 19.19% and area over 1 cm2 achieved by additive engineering. Adv. Mater. 29, 170173 (2017).
Palma, A. L. et al. Laser-patterning engineering for perovskite solar modules with 95% aperture ratio. IEEE J. Photovolt. 7, 1674–1680 (2017).
Staub, F. et al. Beyond bulk lifetimes: Insights into lead halide perovskite films from time-resolved photoluminescence. Phys. Rev. Appl. 6, 044017 (2016).
Richter, J. M. et al. Enhancing photoluminescence yields in lead halide perovskites by photon recycling and light out-coupling. Nat. Commun. 7, 13941 (2016).
deQuilettes, D. W. et al. Photoluminescence lifetimes exceeding 8 μs and quantum yields exceeding 30% in hybrid perovskite thin films by ligand passivation. ACS Energy Lett. 1, 438–444 (2016).
Ahrenkiel, R. K. Minority-carrier lifetime in III–V semiconductors. Semicond. Semimet. 39, 39–150 (1993).
Herz, L. M. Charge-carrier mobilities in metal halide perovskites: Fundamental mechanisms and limits. ACS Energy Lett. 2, 1539–1548 (2017).
deQuilettes, D. W. et al. Photo-induced halide redistribution in organic–inorganic perovskite films. Nat. Commun. 7, 11683 (2016).
Wurfel, P. The chemical potential of radiation. J. Phys. C 15, 3967–3985 (1982).
El-Hajje, G. et al. Quantification of spatial inhomogeneity in perovskite solar cells by hyperspectral luminescence imaging. Energy Environ. Sci. 131, 6050–6051 (2016).
Braly, I. L. & Hillhouse, H. W. Optoelectronic quality and stability of hybrid perovskites from MAPbI3 to MAPbI2Br using composition spread libraries. J. Phys. Chem. C. 120, 893–902 (2016).
Sarritzu, V. et al. Optical determination of Shockley–Read–Hall and interface recombination currents in hybrid perovskites. Sci. Rep. 7, 44629 (2017).
Johnston, S. & Unold, T. Correlations of Cu(In,Ga)Se2 imaging with device performance, defects, and microstructural properties. J. Vac. Sci. Technol. A 30, 4–9 (2012).
Bauer, G. H., Gütay, L. & Kniese, R. Structural properties and quality of the photoexcited state in Cu(In1−xGax)Se2 solar cell absorbers with lateral submicron resolution. Thin Solid Films 480–481, 259–263 (2005).
Rau, U., Abou-Ras, D. & Kirchartz, T. (eds) Advanced Characterization Techniques for Thin Film Solar Cells (Wiley, Weinheim, 2011).
Tress, W. et al. Predicting the open-circuit voltage of CH3NH3PbI3 perovskite solar cells using electroluminescence and photovoltaic quantum efficiency spectra: the role of radiative and non-radiative recombination. Adv. Energy Mater. 5, 1400812 (2015).
Tvingstedt, K. et al. Radiative efficiency of lead iodide based perovskite solar cells. Sci. Rep. 4, 6071 (2014).
Kirchartz, T. & Rau, U. Detailed balance and reciprocity in solar cells. Phys. Status Solidi A 205, 2737–2751 (2008).
Shockley, W. & Queisser, H. J. Detailed balance limit of efficiency of p-n junction solar cells. J. Appl. Phys. 32, 510–519 (1961).
Kirchartz, T., Staub, F. & Rau, U. Impact of photon recycling on the open-circuit voltage of metal halide perovskite solar cells. ACS Energy Lett. 1, 731–739 (2016).
Burgelman, M., Nollet, P. & Degrave, S. Modelling polycrystalline semiconductor solar cells. Thin Solid Films 362, 527–532 (2000).
Lee, J. et al. Achieving large-area planar perovskite solar cells by introducing an interfacial compatibilizer. Adv. Mater. 29, 1606363 (2017).
Wang, Q., Dong, Q., Li, T., Gruverman, A. & Huang, J. Thin insulating tunneling contacts for efficient and water-resistant perovskite solar cells. Adv. Mater. 28, 6734–6739 (2016).
Wu, Y. et al. Perovskite solar cells with 18.21% efficiency and area over 1 cm2 fabricated by heterojunction engineering. Nat. Energy 1, 16148 (2016).
Green, M. A. et al. Solar cell efficiency tables (version 51). Prog. Photovolt. Res. Appl. 26, 3–12 (2018).
Yang, W. S. et al. High-performance photovoltaic perovskite layers fabricated through intramolecular exchange. Science 348, 1234–1237 (2015).
Liu, T. et al. High-performance formamidinium-based perovskite solar cells via microstructure-mediated δ-to-α phase transformation. Chem. Mater. 29, 3246–3250 (2017).
Yu, Y. et al. Improving the performance of formamidinium and cesium lead triiodide perovskite solar cells using lead thiocyanate additives. ChemSusChem 9, 3288–3297 (2016).
Delamarre, A., Lombez, L. & Guillemoles, J. F. Contactless mapping of saturation currents of solar cells by photoluminescence. Appl. Phys. Lett. 100, 131108 (2012).
Burkhard, G. F., Hoke, E. T. & McGehee, M. D. Accounting for interference, scattering, and electrode absorption to make accurate internal quantum efficiency measurements in organic and other thin solar cells. Adv. Mater. 22, 3293–3297 (2010).
We thank P. Caprioglio for SEM measurements, L. Fiedler for laboratory assistance and F. Jaiser, F. Dornack and A. Pucher for providing measurement and laboratory equipment. P.M. is a Sêr Cymru Research Chair funded by the Welsh European Funding Office (Sêr Cymru II Program) and is formerly an Australian Research Council Discovery Outstanding Researcher Award Fellow. P.L.B is an Australian Research Council Laureate Fellow (FL160100067). S.Z is partly funded by a Chinese Scholarship Council studentship and the Australian Government through the Australian Renewable Energy Agency (ARENA) Australian Centre for Advanced Photovoltaics. Responsibility for the views, information or advice expressed herein is not accepted by the Australian Government. We thank M. Harvey and Brisbane Materials Technology Pty Ltd for the provision of their proprietary anti-reflection coating formulation. J.A.M. acknowledges A. Redinger for fruitful discussions. S.A. acknowledges funding from the German Federal Ministry of Education and Research (BMBF), within the project ‘Materialforschung für die Energiewende’ (grant no. 03SF0540), and the German Federal Ministry for Economic Affairs and Energy (BMWi) through the ‘PersiST’ project (grant no. 0324037C). Support by the joint University Potsdam–HZB graduate school ‘hypercells’ is acknowledged.
The authors declare no competing interests.
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Stolterfoht, M., Wolff, C.M., Márquez, J.A. et al. Visualization and suppression of interfacial recombination for high-efficiency large-area pin perovskite solar cells. Nat Energy 3, 847–854 (2018). https://doi.org/10.1038/s41560-018-0219-8
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