View metadata, citation and similar papers at core.ac.uk brought to you by CORE Angewandte. provided by University of Lincoln Institutional Repository Minireviews S. D. Stranks, H. J. Snaith et al. DOI: 10.1002/anie.201410214 Photovoltaics Special Issue 150 Years of BASF Formation of Thin Films of Organic–Inorganic Perovskites for High-Efficiency Solar Cells Samuel D. Stranks,* Pabitra K. Nayak, Wei Zhang, Thomas Stergiopoulos, and Henry J. Snaith* crystallinity · morphology · organic– inorganic perovskites · photovoltaics · precursors Organic–inorganic perovskites are currently one of the hottest topics in photovoltaic (PV) research, with power conversion efficiencies (PCEs) of cells on a laboratory scale already competing with those of established thin-film PV technologies. Most enhancements have been achieved by improving the quality of the perovskite films, suggesting that the optimization of film formation and crystallization is of paramount importance for further advances. Here, we review the various techniques for film formation and the role of the solvents and precursors in the processes. We address the role chloride ions play in film formation of mixed-halide perovskites, which is an outstanding or multi-crystalline solar cells with question in the field. We highlight the material properties that are a record power conversion efficiency essential for high-efficiency operation of solar cells, and identify how (PCE) of incident sunlight to electric- further improved morphologies might be achieved. ity of around 25%. The price per Watt of solar power from silicon PVs has plummeted in recent years, and it can now provide power at costs close to grid parity in some regions.[2] Even if 1. Introduction the costs of solar-cell-active materials become negligible, other costs, such as protective casing, wiring, installation, and The search for low-cost alternatives to power sources maintenance, will remain, and therefore the total costs of based on fossil fuels has become of paramount importance in electricity from solar power could be further reduced most light of rising power costs, recent requirements for the significantly by increasing the PCE. Further price reductions reduction of emissions, and in order to enable the electrifi- will require a technology that features lower material costs cation of the developing world. Solar photovoltaics (PVs) are and also higher PCEs. potentially suitable alternatives. The International Energy Organic–inorganic perovskites have the potential to be Agency estimates that the total primary energy supply, the such a “disruptive” technology. Power conversion efficiencies sum of all of the world’s power supply averaged over the year, of PV devices that contain these materials have increased will be approximately 20 TW by 2035.[1] In comparison, the from around 4% to a certified 20.1% in the last three years.[3] power from the sun intercepted by the earth is around Based on their efficiency, they are already rivalling estab- 180000 TW, meaning that solar energy is a virtually limitless lished thin-film technologies, such as those based on cadmium resource. The current PV market is dominated by silicon- telluride (CdTe) and copper indium gallium selenide based technologies, which are based on high-efficiency mono- (CIGS).[4] These perovskites show remarkable optical ab- sorptions across a wide range of the solar spectrum, and a sharp optical band edge, which suggests low levels of [*] Dr. S. D. Stranks,[+] Dr. P. K. Nayak, Dr. W. Zhang, disorder.[5] They also exhibit long charge-carrier diffusion Dr. T. Stergiopoulos, Prof. H. J. Snaith lengths (> 1 mm) relative to the absorption depth of incident Clarendon Laboratory, Department of Physics, University of Oxford light ( 100 nm),[6] meaning that almost all photoexcited Parks Road, Oxford, OX1 3PU (UK) E-mail: [email protected] species in the perovskite are able to reach the interfaces from where the charges are then transported through suitable hole- [+] Current address: Research Laboratory of Electronics Massachusetts Institute of Technology and electron-transporting layers to the electrodes. Most of the 77 Massachusetts Avenue, Cambridge, MA 02139 (USA) significant improvements in PCE have been a direct result of E-mail: [email protected] improvements in the formation of perovskite films,[3c,7] which 3240 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2015, 54, 3240 – 3248 Angewandte Photovoltaics Chemie led to a better film uniformity and larger crystalline domains, as lead (B = Pb2+), and halides (X = IÀ,BrÀ ,ClÀ or mixtures). thus suggesting that these features are of the upmost Here, we will focus primarily on MAPbI3 and the mixed- importance for achieving high performance. halide analogue, MAPbI3ÀxClx, although we also direct the In this Minireview, we will focus on the materials reader to the growing number of reports on alternative chemistry aspects of perovskite films. We will present a de- organic cations,[9] metal cations,[10] and halides.[5b,9c,11] The X- tailed description of the different methods for the formation ray diffraction (XRD) spectrum of MAPbI3ÀxClx (Figure 1b) of films and the role of the solvent and starting components, shows its tetragonal crystal structure at room temperature clearly highlighting the material properties that are essential (160–330 K).[12] for high-efficiency operation of solar cells. We note that there Two dominant structural concepts have emerged for are several other challenges that need to be solved before we perovskite solar cells: the planar heterojunction (Figure 1c), will see the deployment of this technology, but those are in which the perovskite is a simple flat layer that is beyond the focus of the present Minireview and we refer the sandwiched between n- and p-type contacts, and the meso- interested reader to other reports.[8] structured cell (Figure 1d), in which the perovskite infiltrates a mesoporous metal oxide scaffold, which is either an n-type TiO2 layer or an insulating dielectric scaffold, and additionally 1.1. Organic–Inorganic Perovskites typically forms a solid absorber layer on top of the scaf- fold.[7,13] For the mesostructured cell, the mesoporous metal Perovskites are a family of materials that share a crystal oxide aids the formation of the perovskite film and its structure with calcium titanate, that is, ABX3 (Figure 1a). The uniformity over a large area and, in the case of the scaffold predominant three-dimensional hybrid perovskites used in being n-type TiO2, it also assists in the charge extraction in the solar cells to date have short-chain organic cations, such as region near the planar n-type contact. Both concepts (planar + methylammonium (MA; A = CH3NH3 ), metal cations such and meso) are currently evolving and are likely to eventually Samuel D. Stranks is a Marie Curie Fellow Thomas Stergiopoulos received his PhD in at the Massachusetts Institute of Technol- Physical Chemistry from the National ogy. He completed his PhD in 2012 as Centre for Scientific Research Demokritos in a Rhodes Scholar at Oxford University, 2006. He recently worked within European working on carbon nanotube/polymer projects toward renewable energy and clean blends. He then worked as a postdoctoral environment applications and is currently researcher in Henry Snaith’s group at a Marie Curie Fellow at Oxford University. Oxford University where he was also a Junior His research focuses on hybrid technologies Research Fellow at Worcester College. His for efficient photovoltaics, such as dye- research focuses on the optical and elec- sensitized and perovskite solar cells. tronic properties of emerging photovoltaics. Pabitra K. Nayak received his Ph.D. from Henry J. Snaith is a Professor of Physics at the Tata Institute of Fundamental Research, Oxford University, head of the Photovoltaic Mumbai, India in 2010. He then worked as and Optoelectronic Device Laboratory, and a postdoctoral fellow at the Weizmann the chief scientific officer and co-founder of Institute of Science, Israel. He is currently Oxford Photovoltaics. Henry was the recipi- a postdoctoral research associate at the ent of the 2012 Institute of Physics Paterson University of Oxford, where his research Medal and the 2014 Materials Research interests involve the development of new Society Young Investigators Award, and he materials and the modification of interfacial was named as one of “Nature’s Ten” people energetics for optoelectronic applications. who mattered in 2013. Wei Zhang received his PhD from the National University of Singapore in 2012 and is currently a postdoctoral research assistant in Henry Snaith’s group at Oxford University. His main research interests in- clude the development of high-efficiency and low-cost photovoltaic devices ranging from sensitized mesoscopic and hybrid solar cells to perovskite solar cells, and the fabrication of various nanostructures for solar-cell applications. Angew. Chem. Int. Ed. 2015, 54, 3240 – 3248 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 3241 . Angewandte S. D. Stranks, H. J. Snaith et al. Minireviews Figure 1. a) Crystal structure of perovskites. b) X-ray diffraction (XRD) spectrum of a CH3NH3PbI3ÀxClx film prepared by spin-coating of the precursors on a glass substrate and annealing at 1008C.[3b] c,d) Sche- matics representing the planar c) heterojunction and d) mesostruc- tured device architectures. Figure 2. a,b) Cross-sectional SEM images of full devices featuring converge in a single architecture. Herein, we will