Highly efficient hybrid perovskite solar cells by interface engineering
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1 Highly efficient hybrid perovskite solar cells by interface engineering Maria Antonietta Loi Photophysics & OptoElectronics Zernike Institute for Advanced Materials University of Groningen The Netherlands
2 Why Hybrid perovskites? 2 Si Single Crystal 25.3% Hybrid Perovskites > 22.1%
3 What are HP? 3 Perovskites adopt the chemical formula ABX 3 A and B are cations of different sizes X is an anion (oxygen and halogens) Hybrid Perovskites A is small organic cation Most popular hybrid perovskites use A-cations: CH 3 NH 3+ (MA) or HC(NH 2 ) 2+ (FA) X-anion (halogens): Cl -, Br -, I - M. A. Loi & J. C. Hummelen, News & Views, Nature Materials, 12, 1087 (2013)
4 Important features - pros Device efficiencies have increased rapidly from 3.8% in 2009 to more than 20%. 4 Material Properties Solution processable Tunable bandgap from Vis to NIR; High optical absorption coefficient; Long carrier diffusion length; Science 2014, 345, 542. ; Nature Comm. 2014, 5, ; Adv. Energy Mater. 2014, 4, ;
5 Important features - cons 5 Drawbacks Materials and/or device instability; Hysteresis in current-voltage (JV) curves; Toxicity of Pb Some solutions Chemical management of perovskite compositions; Invention of various deposition techniques; Search for efficient HEM and EEM Non-Pb perovskites
6 Solar cells interfaces 6
7 Varying the nature of the interface PCBM PTEG-1 7 J. C. Hummelen, et al. Chem. Commun., 50, (2014) e r = 3.7 e r = 5.7 PCE=11% PCE=16% S. Shao,...MAL, Energy Environ. Sci., 9, 2444 (2016)
8 Variation of the device parameters with light soaking time V OC (V) PTEG PCBM J SC (ma cm -2 ) FF Time (min) PCE (%) Time (min) S. Shao,...MAL, Energy Environ. Sci., 9, 2444 (2016)
9 Light intensity dependent J SC and V OC J SC (ma cm -2 ) 10 1 PCBM a =1.00 a =1.07 J SC (ma cm -2 ) 10 1 PTEG-1 a =1.00 a =1.06 Bimolecular recombination is not involved in the light soaking V OC (V) Light intensity (W m -2 ) 0.9 PCBM kt/q kt/q Light intensity (W m -2 ) V OC (V) Light intensity (W m -2 ) PTEG kt/q 1.23 kt/q Light intensity (W m -2 ) Suppressed trap assisted recombination with light soaking Lower trap assisted recombination in device using PTEG-1 as EEL
10 Steady state and time resolved PL PTEG-1 PL intensity (a.u.) PCBM PL (a.u.) Perovskite Perovskite/PTEG Time (min) Perovskite/PCBM Time (ns) Trap-filling with light soaking (a) + Lower charge recombination at perovskite/pteg-1 interface. r c PEDOT:PSS CH 3 NH 3 PbI 3-X Cl X EEL Al
11 Summary The surface electron traps dominate the light soaking effect in HPSCs. Severe light soaking effect in HPSCs using PCBM as EEL due to the trap-assisted recombination at HP/PCBM interface. Negligible light soaking effect in HPSCs using the high dielectric constant fullerene PTEG-1. The reduced light soaking is due to suppressed trap-assisted recombination at HP/PTEG-1 interface.
12 Further device engineering % 13.1% B. G. H. M. Groeneveld,...MAL, APL Materials 5, (2017)
13 Further device engineering 13 S. Adjokaste,...MAL, in preparation
14 What about Sn? 14
15 Sn Perovskites 15 Rather low efficiencies for solar cells (6%) Huge problem of self doping fast oxidation of Sn 2+ into more stable Sn 4+ Introduction of (SnF2) as a reducing agent Only with mixture of Pb and Sn recently achieved good performances D. Zhao et al Nature Energy 2, (2017)
16 FASnI 3 16 orthorhombic (Amm2) (a) 3.6 Good charge transport Narrow band gap Absorbance (a.u.) (b) FASnI 3 2D/3D Wavelength (nm) 3 3
17 Introducing PEAI into FASnI 3 17 Phenethylamine Hydroiodide (PEAI) 70 Solution spreading Spinning Anti-solvent dripping FASnI 3 film FASnI 3 film
18 FASnI 3 PEA 2 SnI < 0.1M Shao...MAL, Adv. Energy Mater. (2017)
19 Large reorganization 19 FASnI 3 FASnI 3 + PEA 2 SnI 4 3D 0.08 M 2D 0.12 M 2D 0.16 M 2D Shao...MAL, Adv. Energy Mater. (2017)
20 Improving efficiency and reproducibility 20 Shao...MAL, Adv. Energy Mater. (2017)
21 Large current EQE (%) D FASnI 3 5 2D/3D 0.08 M Wavelength (nm) Integrated J SC (ma cm -2 )
22 Transport a Thermal voltage (µv) c C -2 /10 5 (Fm -2 ) D/3D 796 µv K cm cm -3 3D 504 µv K -1 Temperature difference (K) Voltage (V) b Current (A) d C -2 /10 5 (Fm -2 ) -2 Current density (ma cm -2 ) 1E-3 1E-4 1E-5 1E-6 1E-7 1E E-3 1E S cm S cm S cm -1 Bias (V) 1E Voltage (V) S cm -1 2D 22
23 Summary 23 Elimination of the grain boundaries Preferential orientation of the FASnI 3 crystals De-doping of the FASnI 3 film and reduced background carrier density 9% tin perovskite solar cells with improved stability
24 Acknowledgments Hong Hua Fang (post Doc) Shuyan Shao (post Doc) Sampson Adjokaste (PhD student) Mustapha Abdu-Aguye (PhD student) Bart Groeneveld (PhD student) Herman Duim (PhD student) HySPOD RUG Graeme Blake Giuseppe Portale Université Européenne de Bretagne, France Jacky Even ETH Zurich Maksym Kovalenko Focus group Groningen
25 Reduction of traps 25 a Current density (ma cm -2 ) cathode C 60 /BCP FASnI 3 PEDOT:PSS Anode -20 3D FASnI 3 2D/3D Voltage (V) c V OC (V) kt/q 1.57 kt/q Light intensity (W m -2 ) Shao...MAL, Adv. Energy Mater. (2017)
26 Without annealing 3D 2D/3D 2D 26 incident angle 0.25 incident angle 2
27 Stability test under 1 sun in ambient conditions (a) Normalized V OC (c) Normalized FF Time (h) 3D 2D/3D (b) Normalized J SC (d) PCE (%) Time (h) 27
28 Increased structural stability 28 a # b # # 6 h Intensity (a.u.) # # # # FASnI 3 in air 6 h 3 h 1 h Intensity (a.u.) 3 h 1 h 2D/3D in air 0 h 0 h c theta (degree) FASnI 3 without humidity d theta (degree) 2D/3D without humidity Intensity (a.u.) 6 h Intensity (a.u.) 6 h 0 h 0 h theta (degree) theta (degree)
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