Search

Today's best perovskite solar cells use a mixture of formamidinium and methylammonium as the monovalent cations. Adding cesium improves the compositions greatly., Today's best perovskite solar cells use a mixture of formamidinium and methylammonium as the monovalent cations. With the addition of inorganic cesium, the resulting triple cation perovskite compositions are thermally more stable, contain less phase impurities and are less sensitive to processing conditions. This enables more reproducible device performances to reach a stabilized power output of 21.1% and ∼18% after 250 hours under operational conditions. These properties are key for the industrialization of perovskite photovoltaics.

Perovskite solar cells (PSCs) have attracted a substantial interest owing to a very fast achievement of efficiencies >20 % within only several years of development. However, for any solar cell to become technologically viable, two additional milestones have to be achieved alongside high efficiency: means of industrial production and good operational stability. The former being mostly the focus of the private sector and industrially-oriented research institutes, understanding degradation and improving the stability of PSCs has become one of the major research topics in the field of emerging photovoltaics. This is also the focus of this thesis, where I investigate different degradation mechanisms in PSCs with the aim of extending their long-term stability. This dissertation can be divided into four parts: in the first one, I show how, through a series of prototypes, I designed and built a dedicated setup to investigate stability of PSCs. I also show how I developed its variation to improve by 700 % the efficiency of measuring current-voltage characteristics of our solar cells. Subsequently, I describe the intrinsic instability of, at the time, state-of-the-art PSCs. I show how, along with my colleagues, we managed to achieve breakthrough room temperature stability coupled with record efficiency through incorporation of Cs into perovskite. Next, I describe how and why these solar cells suffer from irreversible degradation if left at elevated temperatures however. This is due to a vulnerability to Au diffusion from the electrode, through Spiro-MeOTAD hole transporting layer into the perovskite. I show how, by incorporation of Cr diffusion barrier I managed to circumvent this problem (albeit at considerable efficiency loss). Subsequently, I describe an alterna-tive solution to the problem by substituting Spiro-MeOTAD with PTAA - a polymeric hole transporting layer. This approach effectively stops Au diffusion without compromising device efficiency, which was at the same time improved by incorporating Rb into the perovskite. Finally, a third approach is presented: replacing the Au electrode with one based on carbon nanotubes. This gives away with using Au and PTAA - both prohibitively expensive materials - and hence paves the way towards facile and inexpensive fabrication of stable PSCs. In the third part, I describe the effects of mobile ions in the perovskite on the behaviour of PSCs. First, I show how they lead to a partial reversibility of losses in aged devices. This has potentially far-reaching consequences for the way stability measurements of PSCs are conducted and how their lifetime is reported. Next, I show how the ionic movement in the perovskite can lead to PSCs with certain architecture to work as high-gain photodetectors. This is enabled by piling up of ions at the interfaces within the devices, which modifies the energy levels within. Finally, in the last chapter I describe systematically, how different factors such as temperature, illumination, atmosphere, load on the device and cycling of the environmental conditions affect the stability of PSCs. Based on this, I discuss the important parameters to control when ageing PSCs, as the first attempt to bring the community to a consensus on how to measure stability of PSCs. This is urgently needed to streamline the efforts to create stable PSCs and to commercialize the technology.

Improving the long-term stability of perovskite solar cells is critical to the deployment of this technology. Despite the great emphasis laid on stability-related investigations, publications lack consistency in experimental procedures and parameters reported. It is therefore challenging to reproduce and compare results and thereby develop a deep understanding of degradation mechanisms. Here, we report a consensus between researchers in the field on procedures for testing perovskite solar cell stability, which are based on the International Summit on Organic Photovoltaic Stability (ISOS) protocols. We propose additional procedures to account for properties specific to PSCs such as ion redistribution under electric fields, reversible degradation and to distinguish ambient-induced degradation from other stress factors. These protocols are not intended as a replacement of the existing qualification standards, but rather they aim to unify the stability assessment and to understand failure modes. Finally, we identify key procedural information which we suggest reporting in publications to improve reproducibility and enable large data set analysis., This article is based upon work from COST Action StableNextSol MP1307 supported by COST (European Cooperation in Science and Technology). M.V.K., E.A.K., V.B. and A.O. thank the financial support of the United States – Israel Binational Science Foundation (grant no. 2015757). E.A.K., A.A. and I.V.-F. acknowledge partial support from the SNaPSHoTs project in the framework of the German-Israeli bilateral R&D cooperation in the field of applied nanotechnology. M.S.L. thanks the financial support of National Science Foundation (ECCS, award #1610833). S.C., M.Manceau and M.Matheron thank the financial support of European Union’s Horizon 2020 research and innovation programme under grant agreement no 763989 (APOLO project). F.D.R. and T.M.W. would like to acknowledge the support from the Engineering and Physical Sciences Research Council (EPSRC) through the SPECIFIC Innovation and Knowledge Centre (EP/N020863/1) and express their gratitude to the Welsh Government for their support of the Ser Solar programme. P.A.T. acknowledges financial support from the Russian Science Foundation (project No. 19-73-30020). J.K. acknowledges the support by the Solar Photovoltaic Academic Research Consortium II (SPARC II) project, gratefully funded by WEFO. M.K.N. acknowledges financial support from Innosuisse project 25590.1 PFNM-NM, Solaronix, Aubonne, Switzerland. C.-Q.M. would like to acknowledge The Bureau of International Cooperation of Chinese Academy of Sciences for the support of ISOS11 and the Ministry of Science and Technology of China for the financial support (no. 2016YFA0200700). N.G.P. acknowledges financial support from the National Research Foundation of Korea (NRF) grants funded by the Ministry of Science, ICT Future Planning (MSIP) of Korea under contracts NRF-2012M3A6A7054861 and NRF-2014M3A6A7060583 (Global Frontier R&D Program on Center for Multiscale Energy System). CSIRO’s contribution to this work was conducted with funding support from the Australian Renewable Energy Agency (ARENA) through its Advancing Renewables Program. A.F.N gratefully acknowledges support from FAPESP (Grant 2017/11986-5) and Shell and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation. Y.-L.L. and Q.B. acknowledge support from the National Science Foundation Division of Civil, Mechanical and Manufacturing Innovation under award no. 1824674. S.D.S. acknowledges the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (HYPERION, grant agreement no. 756962), and the Royal Society and Tata Group (UF150033). The work at the National Renewable Energy Laboratory was supported by the US Department of Energy (DOE) under contract DE-AC36-08GO28308 with Alliance for Sustainable Energy LLC, the manager and operator of the National Renewable Energy Laboratory. The authors (J.J.B, J.M.L., M.O.R, K.Z.) acknowledge support from the ‘De-risking halide perovskite solar cells’ program of the National Center for Photovoltaics, funded by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technology Office. The views expressed in the article do not necessarily represent the views of the DOE or the US Government. H.J.S. acknowledges the support of EPSRC UK, Engineering and Physical Sciences Research Council. V.T. and M.Madsen acknowledge ‘Villum Foundation’ for funding of the project CompliantPV, under project no. 13365. M.Madsen acknowledges Danmarks Frie Forskningsfond, DFF FTP for funding of the project React-PV, no. 8022-00389B. M.G. and S.M.Z. thank the King Abdulaziz City for Science and technology (KACST) for financial support. S.V. acknowledges TKI-UE/Ministry of Economic Affairs for financial support of the TKI-UE toeslag project POP-ART (no. 1621103). RC thanks the grants for Development of New Faculty Staff, Ratchadaphiseksomphot Endowment Fund. A.D.C. gratefully acknowledges funding from the European Union’s Horizon 2020 Research and Innovation Program (grant agreement no. 785219-GrapheneCore2 and no. 764047-ESPResSo). M.L.C. and H.X. acknowledges the support from Spanish MINECO for the grant GraPErOs (ENE2016-79282-C5-2-R), the OrgEnergy Excellence Network CTQ2016-81911- REDT, the Agència de Gestiód’Ajuts Universitaris i de Recerca (AGAUR) for the support to the consolidated Catalonia research group 2017 SGR 329 and the Xarxa de Referència en Materials Avançats per a l’Energia (Xarmae). ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant no. SEV-2017-0706) and is funded by the CERCA Programme/Generalitat de Catalunya.