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lkali-metal lead and tin halides analogue CH3NH3PbBr3 as sensitizers
had been synthesized already in for liquid-electrolyte-based DSSCs13,
18931, yet the first crystallographic the power-conversion efficiency (PCE)
studies that determined that caesium lead measured under standard characterization
halides had a perovskite structure with the conditions reached a mere 3.8%, and the
chemical formula CsPbX3 (X = Cl, Br or I) device stability was poor due to the rapid
were only carried out 64 years later by the dissolution of the perovskite in the organic
Danish scientist Christian Møller 2. He also solvent. However, by changing both the
observed that these coloured materials electrolyte formulation and the method
were photoconductive, thus suggesting of depositing the perovskite, the group
that they behave as semiconductors. In of Nam-Gyu Park was able to increase
1978, Dieter Weber replaced caesium with the device performance and stability
methylammonium cations (CH3NH3+) attaining a PCE of 6.5%14. The authors
to generate the first three-dimensional noted that CH3NH3PbI3 was a superior
organic–inorganic hybrid perovskites3,4. light harvester compared with the more
The general crystal structure of these commonly used molecular N719 ruthenium
Figure 1 | Crystal structure of cubic metal halide
materials is shown in Fig. 1. Caesium sensitizer, meaning that a thinner absorbing
perovskites with the generic chemical formula
ions or small organic cations such as layer was sufficient to obtain good
ABX3. Organic or inorganic cations occupy
methylammonium and formamidinium light-conversion performance.
position A (green) whereas metal cations and
occupy the cuboctahedral voids formed A key advance was subsequently made by
halides occupy the B (grey) and X (purple)
by the 12 nearest-neighbour halide ions. replacing the liquid electrolyte with a solid-
positions, respectively.
The structural characterization of hybrid state hole conductor (or hole-transporting
perovskites of the formula CH3NH3BX3 material, HTM), that is, CsSnI3–xFx (ref. 15)
(with B = Sn(ii) or Pb(ii), and X = Cl, a timescale of hundreds of nanoseconds, or spiro-MeOTAD16,17. Not only did the
Br or I) has also been reviewed in more resulting in long carrier-diffusion conversion efficiency double, but the cell
recent studies5. lengths — that is, the average distance stability also improved greatly as a result
Methylammonium lead iodide, that can be covered by carriers before they of avoiding the use of a liquid solvent. At
CH3NH3PbI3, has both interesting optical recombine — ranging between 100 nm this stage, the embodiment of the PSC was
and electronic properties that have been and 1,000 nm (refs 11,12). Despite some an exact mimic of the solid-state DSSCs
actively investigated during the past of these appealing properties that were (Fig. 2). The N719 dye15 or the CH3NH3PbI3
two decades5–7. It is a semiconducting already known for more than 20 years, perovskite nanoparticles16,17 assume the
pigment with a direct bandgap of 1.55 eV the extraordinary potential of hybrid role of the sensitizer injecting electrons
corresponding to an absorption onset of perovskites in photovoltaic applications in a mesoscopic TiO2 scaffold and holes
800 nm (ref. 6), which makes this material was only revealed less than 5 years in a solid-state HTM. Both the TiO2 and
a good light absorber over the whole visible ago by researchers working on liquid- the HTM act as selective contacts through
solar emission spectrum. The excitons electrolyte-based dye-sensitized solar cells which the charge carriers produced
produced by light absorption have a (DSSCs)13,14. These two papers and the by photoexcitation of the perovskite
weak binding energy of about 0.030 eV, three publications15–17 that followed in 2012, nanoparticles are extracted.
which means that most of them dissociate reporting on the use of tin or lead iodide A change in paradigm occurred with the
very rapidly into free carriers at room perovskites in a solid-state version of the discovery by Lee et al.17 that a mesoporous
temperature8. The electrons and holes DSSC, set off the current meteoric rise of scaffold made of Al2O3 instead of TiO2
produced in this material exhibit a small perovskite solar cells (PSCs). produced similar — if not better —
effective mass9 resulting in high carrier conversion efficiencies, even though Al2O3
mobilities that range from 7.5 cm2 V–1 s–1 for Ascension of perovskite solar cells is unable to assist in electron extraction due
electrons9 to 12.5 cm2 V–1 s–1 – 66 cm2 V–1 s–1 In 2009, when Kojima et al. introduced to its large bandgap. This suggested that the
for holes10. Their recombination occurs on CH3NH3PbI3 and the larger-bandgap perovskite itself transported the electrons
Perovskite VOC = VOC–ideal + (kT/q)ln(ηext)(1)
Al2O3
HTM where k is the Boltzmann constant, T is
Compact TiO2 layer temperature, q is the elementary charge
TCO and ηext is the external quantum efficiency
Back contact of the photovoltaic cell at VOC obtained
Glass substrate (front contact) under standard measurement conditions. In
line with these theoretical predictions the
electroluminescence quantum yield of PSCs
b has been found to correlate with its VOC
(W. Tress, N. Marinova, O. Inganäs, M. K.
Perovskite
Nazeeruddin, S. M. Zakeeruddin and M. G.,
TiO2
manuscript submitted for publication).
HTM
Compact TiO2 layer
TCO
Open issues and pitfalls
Back contact
During the impending phase of
Glass substrate (front contact)
consolidation, a number of questions
concerning the true potential of PSCs
for widespread deployment will have
to be addressed.
c
Michael Grätzel is at the Laboratory of Photonics 13. Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. 32. Deschler, F. et.al. J. Phys. Chem. Lett. 5, 1421−1426 (2014).
and Interfaces, Swiss Federal Institute of Technology, J. Am. Chem. Soc. 131, 6050–6051 (2009). 33. Ross, R. T. J. Chem. Phys. 46, 4590 (1967).
14. Im, J.‑H., Lee, C.‑R., Lee, J.‑W., Park, S.‑W. & Park, N.‑G. 34. Hao, F., Stoumpos, C. C., Cao, D. H., Chang, R. P. H. &
CH-1015 Lausanne, Switzerland. Nanoscale 3, 4088–4093 (2011). Kanatzidis, M. G. Nature Photon. 8, 489–494 (2014).
e-mail: michael.graetzel@epfl.ch 15. Chung, I., Lee, B., He, J., Chang, R. P. H. & Kanatzidis, M. G. 35. Noel, N. K. et al. Energy Environ. Sci. http://dx.doi.org/
Nature 485, 486–489 (2012). 10.1039/c4ee01076K (2014).
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4. Weber, D. Z. Naturforsch. 33b, 862–865 (1978). 19. Mei, A. et al. Science 345, 295–298 (2014). I am grateful to my co-workers at the Laboratory of
5. Mitzi, D. B. Synthesis, Structure and Properties of 20. Heo, J. H. et al. Nature Photon. 7, 487–492 (2013). Photonics and Interfaces at EPFL, and to all academic
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Progress in Inorganic Chemistry Vol. 48 (ed. Karlin, K. D.) 22. Malinkiewicz, O. et al. Nature Photon. 8, 128–132 (2014). of perovskite solar cells, in particular N.-G. Park,
1–121 (J. Wiley & Sons, 1999). 23. Burschka, J. et al. Nature 499, 316–319 (2013). (SKKU Korea), S. I. Seok (KRICT Korea), S. Mhaisalkar,
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(HUST China) and H. Bolink (Univ. of Valencia
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Spain). Financial support by the Swiss National Science
9. Mitzi, D. B. J. Chem. Soc. Dalton Trans. 1, 1–12 (2001). 27. Juarez-Perez, E. J. et al. J. Phys. Chem. Lett. 5, 2390−2394 (2014). Foundation and the European Research Council through
10. Stoumpos, C. C., Malliakas, C. D. & Kanatzidis, M. G. 28. Dualeh, A. et al. ACS Nano 8, 362–373 (2014). the Advanced Research Grant (ARC no. 247404)
Inorg. Chem. 52, 9019–9038 (2013). 29. Pellet, N. et al. Angew. Chem. Int. Ed. 53, 3151–3157 (2014). ‘Mesolight’ and the Global Research Laboratory (GRL)
11. Xing, G. C. et al. Science 342, 344–347 (2013). 30. Grätzel, M. Nature 414, 332–344 (2001). programme, funded by the National Research Foundation
12. Stranks, S. D. et al. Science 342, 341–344 (2013). 31. Xing, G. et al. Nature Mater. 13, 476–480 (2014). in Korea are specifically acknowledged.