Capturing Energy from the Sun. Solar Cells Solar Thermal Solar Fuels Bioenergy
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1 Capturing Energy from the Sun Solar Cells Solar Thermal Solar Fuels Bioenergy
2 Installed PV Cost Breakdown a Globally, module prices are between $ /W depending on tariffs In the US, non-module costs represent >75% of the total system costs! Tracking the Sun VI (LBNL report 2013)
3 Global PV Annual Installations (GW) : Silicon Valley Got Frothy : The Niche Years a EPIA.org, Global Outlook for Photovoltaics & IHS
4 Let s not declare Mission Accomplished too soon There is lots of work left to make better modules!
5 Opportunities for better solar utilization More efficient panels that still cost < $0.5/W Replace glass with plastic to reduce cost and weight Make panels flexible and incorporate them into rooves Reduce the cost of permitting and finding customers Improve financing of solar projects Find better ways to use power from an intermittent source (e.g. let utilities decide when to charge electric cars) Improve storage (better batteries or solar fuels) Carbon tax
6 Perovskite Solar Cells are Soaring Jul 2013 Grätzel 15% Sept 2013 Snaith 15.4% Snaith et al., Nature 2013 Grätzel et al., Nature
7 Perovskite Solar Cells and Polycrystalline Tandems A route to high efficiency and low cost.
8 Hybrid perovskite solar-cell absorbers Ian Smith, 1 Eric Hoke, 2 Daniel Slotcavage, 2 Emma Dohner, 1 Diego Solis- Ibarra, 1 Andrea Bowring, 2 Michael McGehee, 2 and Hemamala Karunadasa 1 Departments of Chemistry 1 and Materials Science and Engineering 2 Stanford University
9 The 3D perovskite structure Pb 2+ I CH 3 NH 3 + 3D ABX 3 perovskite e.g. (CH 3 NH 3 )PbI 3
10 Layered perovskites Pb 2+ C 4 H 9 NH 3 + I 3D ABX 3 perovskite e.g. (CH 3 NH 3 )PbI 3 2D A BX 4 perovskite e.g. (NH 3 C 4 H 9 )[PbI 4 ] Mitzi Prog. Inorg. Chem. 1999, 48, 1
11 Self-assembly reactions are inexpensive and scalable
12 3D lead-iodide perovskite absorbers: strengths 1. Inexpensive precursors and solution-state film deposition methods PbI 2 (CH 3 NH 3 )I in solvent Image of PbI 2 on TiO 2 Liang, Mitzi, Prikas, Chem. Mater. 1998, 10, 403 Burschka, Pellet, Moon, Humphry-Baker, Gao, Nazeeruddin, Gratzel, Nature 2013, 499, 316 Image of (CH 3 NH 3 )PbI 3 formed by 2-step conversion
13 3D lead-iodide perovskite absorbers: strengths 1. Inexpensive precursors and film deposition methods 2. Device efficiencies have jumped from 4% to >15% in just 5 years! Device efficiency % Year Kojima, Teshima, Shirai, Miyasaka J. Am. Chem. Soc., 2009, 131, 6050 Im, Lee, Lee, Park, Park Nanoscale, 2011, 3, 4088 Kim, Lee, Im, Lee, Moehl, Marchioro, Moon, Humphry-Baker, Yum, Moser, Grätzel, Park Sci. Rep., 2012, 2, 591 Lee, Teuscher, Miyasaka, Murakami, Snaith Science, 2012, 338, 643 Burschka, Pellet, Moon, Humphry-Baker, Gao, Nazeeruddin, Grätzel Nature, 2013, 499, 316 Liu, Johnston, Snaith Nature, 2013, 501, 395 Green, Ho-Baillie, Snaith Nat. Photonics, 2014, 8, 506 Jeon, Noh, Kim, Yang, Ryu, Seok Nat. Mater., 2014, 13, 897
14 3D lead-iodide perovskite absorbers: strengths 1. Inexpensive precursors and film deposition methods 2. Device efficiencies have jumped from 4% to >15% in just 5 years! 3. Charge carriers are exceptionally long lived. Material defects do not appear to reduce device efficiencies Device efficiency % Year Stranks, Eperon, Grancini, Menelaou, Alcocer, Leijtens, Herz, Petrozza, Snaith Science 2013, 342, 341 Xing, Mathews, Sun, Lim, Lam, Grätzel, Mhaisalkar, Sum, Science 2013, 342, 344
15 3D lead-iodide perovskite absorbers: strengths 1. Inexpensive precursors and film deposition methods 2. Device efficiencies have jumped from 4% to >15% in just 5 years! CB 3. Charge carriers are exceptionally long lived. Material defects do not appear to reduce device efficiencies 4. Absorbers can also function as charge carriers for electrons or for holes VB Lee, Teuscher, Miyasaka, Murakami, Snaith, Science 2012, 338, 643 Etgar, Gao, Xue, Peng, Chandiran, Liu, Nazeeruddin, Gratzel, M. J. Am. Chem. Soc. 2012, 134, 17396
16 3D lead-iodide perovskite absorbers: strengths 1. Inexpensive precursors and film deposition methods 2. Device efficiencies have jumped from 4% to >15% in just 5 years! 3. Charge carriers are exceptionally long lived. Material defects do not appear to reduce device efficiencies 4. Absorbers can also function as charge carriers for electrons or for holes Lee, Teuscher, Miyasaka, Murakami, Snaith, Science 2012, 338, 643 Etgar, Gao, Xue, Peng, Chandiran, Liu, Nazeeruddin, Gratzel, M. J. Am. Chem. Soc. 2012, 134, 17396
17 3D lead-iodide perovskite absorbers: strengths 1. Inexpensive precursors and processing methods 2. Device efficiencies have jumped from 4% to >15% in just 5 years! 3. Charge carriers are exceptionally long lived. Material defects do not appear to reduce device efficiencies 4. Absorbers can also function as charge carriers for electrons or for holes 5. Mixed-halide perovskites can attain many intermediate bandgaps Noh, Im, Heo, Mandal, Seok, Nano Lett. 2013, 13, 1764
18 3D lead-iodide perovskite absorbers: potential problems 1. These materials are water-soluble sources of toxic Pb 2+ ions 0 days 20 days
19 3D lead-iodide perovskite absorbers: potential problems 1. These materials are water-soluble sources of toxic Pb 2+ ions 2. The perovskite is not stable to moisture. The black solid decomposes in moist air to form yellow PbI 2 0 days 20 days
20 3D lead-iodide perovskite absorbers: potential problems 1. These materials are water-soluble sources of toxic Pb 2+ ions 2. The perovskite is not stable to moisture. The black solid decomposes in moist air to form yellow PbI 2 0 days 20 days
21 3D lead-iodide perovskite absorbers: potential problems 1. These materials are water-soluble sources of toxic Pb 2+ ions 2. The perovskite is not stable to moisture. The black solid decomposes in moist air to form yellow PbI 2 3. Solar cells containing mixed-halide lead perovskites (MA)Pb(I 1-x Br x ) 3 have not achieved the high V OC s that are expected from their higher bandgaps, compared to (MA)PbI 3 (R)PbI 3 (R)Pb(I 1 x Br x ) 3 (1 > x > 0.2) (R)PbBr 3 Band gap 1.6 ev ~ ev 2.3 ev Highest achieved V OC 1.1 ev ~1.1 ev 1.5 ev Edri, Kirmayer, Kulbak, Hodes, Cahen, D. J. Phys. Chem. Lett. 2014, 5, 429
22 Improving the moisture resistance of perovskites
23 The family of hybrid perovskites n = 1 Bandgap = 2.57 ev Exciton binding energy = 220 mev
24 The family of hybrid perovskites n = 1 Bandgap = 2.57 ev Exciton binding energy = 220 mev Phosphor Dohner, Hoke, Karunadasa J. Am. Chem. Soc. 2014, 136, 1718 Dohner, Jaffe, Bradshaw, Karunadasa J. Am. Chem. Soc. 2014, 136, 13154
25 The family of hybrid perovskites n = 1 infinity Bandgap = 2.57 ev 1.61 ev Exciton binding energy = 220 mev 40 mev Kojima, Teshima, Shirai, Miyasaka, J. Am. Chem. Soc. 2009, 131, 6050 Im, Lee, Lee, Park, Park, Nanoscale 2011, 3, 4088 Lee, Teuscher, Miyasaka, Murakami, Snaith, Science 2012, 338, 643 Etgar, Gao, Xue, Peng, Chandiran, Liu, Nazeeruddin, Gratzel, J. Am. Chem. Soc. 2012, 134, Solar-cell absorber
26 To trap an exciton; to split an exciton n = infinity Bandgap = 2.57 ev 2.32 ev ca. 2.1 ev 1.61 ev Exciton binding energy = 220 mev 170 mev ca. 40 mev 40 mev T. Ishihara, J. Lumin. 1994, 60 61, 269
27 A 2D perovskite solar-cell absorber with improved moisture resistance Ian Smith Smith, Hoke, Solis-Ibarra, McGehee, Karunadasa Angew. Chem., Int. Ed. 2014, 53, 11232
28 A layered perovskite solar-cell absorber h + Hole-transport material Light absorber e Electron-transport material Smith, Hoke, Solis-Ibarra, McGehee, Karunadasa Angew. Chem., Int. Ed. 2014, 53, 11232
29 2D perovskite absorbers Larger bandgap affords higher open-circuit voltage of 1.18 V
30 2D perovskite absorbers Larger bandgap affords higher open-circuit voltage Layered structure allows for high-quality films to be deposited through spincoating and high-temperature annealing is not required 2D 2D 3D 3D Left: Crystals of 2D perovskites that grow as plates. Right: SEM images of films of (A) (PEA) 2 (CH 3 NH 3 ) 2 [Pb 3 I 10 ], and (MA)[PbI 3 ] formed from (B) PbI 2, (C) from PbCl 2.
31 2D perovskite absorbers Larger bandgap affords higher open-circuit voltage Layered structure allows for high-quality films to be deposited through spincoating and high-temperature annealing is not required The 2D material is far more moisture resistant and devices can be fabricated under humid atmospheres 2D 3D Diffraction angle
32 2D perovskite absorbers Larger bandgap affords higher open-circuit voltage Layered structure allows for high-quality films to be deposited through spincoating and high-temperature annealing is not required The 2D material is far more moisture resistant and devices can be fabricated under humid atmospheres Higher values of n as single-phase materials or as mixtures may allow for lower bandgaps and higher carrier mobility in the inorganic layers while the organic layers provide additional tunability.
33 The 2D structure may offer greater tunability for material optimization Substitutions for both the small and large organic cations Substitutions in the organic layer: Hydrophobic molecules Molecules that absorb light Conductive molecules Substitutions in the inorganic layer: Connectivity of the sheets Number of sheets (n = 3, 4, 5) Mixed metal/halide sheets
34 3D lead-iodide perovskite absorbers: potential problems 1. These materials are water-soluble sources of toxic Pb 2+ ions 2. The perovskite is not stable to moisture. The black solid decomposes in moist air to form yellow PbI 2 3. Solar cells containing mixed-halide lead perovskites (MA)Pb(I 1-x Br x ) 3 have not achieved the high V OC s that are expected from their higher bandgaps, compared to (MA)PbI 3 (R)PbI 3 (R)Pb(I 1 x Br x ) 3 (1 > x > 0.2) (R)PbBr 3 Band gap 1.6 ev ~ ev 2.3 ev Highest achieved V OC 1.1 ev ~1.1 ev 1.5 ev Edri, Kirmayer, Kulbak, Hodes, Cahen, D. J. Phys. Chem. Lett. 2014, 5, 429
35 Light-induced reversible changes in mixed-halide perovskites 1. The absorption spectrum of (MA)(PbI 1-x Br x ) 3 shows a gradual blueshift with increasing bromide content 2. The emission spectrum follows a similar trend 3. But continuous illumination induces dramatic changes... Dr. Eric Hoke Hoke, Slotcavage, Dohner, Bowring, Karunadasa, McGehee manuscript submitted
36 Mixed-halide perovskites under continuous illumination 1. Photoluminescence (PL) spectra of (MA)Pb(I 1 x Br x ) 3 (x > 0.2) perovskites develop a new red-shifted peak at 1.68 ev that grows in intensity under constant, 1-sun illumination in less than a minute 2. The position of this new peak is independent of halide stoichiometry for 1 > x > 0 3. These transitions are reversible. The original PL can be regained after the material is left in the dark for a few minutes
37 Characterization of the light-soaked material (x = 0.6) Dark Light 1. A new absorption shoulder forms around 1.7 ev after light soaking, which completely disappears after the devices are left in the dark for 1 h 2. All x-ray diffraction peaks split upon light soaking. The original sharp diffraction patterns are obtained after the films are left in the dark
38 Proposed mechanism for light-induced reversible trap formation
39 Proposed mechanism for light-induced reversible trap formation
40 Proposed mechanism for light-induced reversible trap formation light dark Homogenous mixture Segregated material
41 Characterization of the light-soaked material (x = 0.6) 1. The absorption shoulder in the light-soaked x = 0.6 perovskite has an absorption coefficient similar to the expected value if ~1% of the material converted into the x = 0.2 perovskite 2. The split x-ray diffraction peaks can be fitted to peaks from perovskites with high (x = 0.2) and low (x = 0.7) iodide content
42 Proposed mechanism for light-induced reversible trap formation Halide conductivity activation energies in other perovskites CsPbCI 3 CsPbBr 3 KMnCI 3 CuCdCl 3 KPbI 3 CuSnI 3 CuPbI ev 0.25 ev 0.39 ev 0.36 ev 0.32 ev 0.29 ev 0.26 ev We calculate an activation energy for the initial growth rate of the new PL peak of 0.27(6) ev Mizusaki, Arai, Fueki Solid State Ionics, 1983, 11, 203 Kuku Solid State Ionics, 1987, 25, 1 Kuku Solid State Ionics, 1987, 25, 105 Kuku Thin Solid Films, 1998, 325, 246
43 Light-induced reversible trap formation in hybrid perovskites 1. The reversible formation of luminescent trap states in (MA)Pb(I 1-x Br x ) 3 is consistent with halide segregation under illumination 2. We see this behavior for mixed halide perovskites with other organic cations, and for films deposited by different methods. We even see this behavior in single crystals (CH 3 NH 3 )PbI 3 E g = 1.6 ev (CH 3 NH 3 )PbBr 3 E g = 2.3 ev
44 Light-induced reversible trap formation in hybrid perovskites 1. The reversible formation of luminescent trap states in (MA)Pb(I 1-x Br x ) 3 is consistent with halide segregation under illumination 2. We see this behavior for mixed halide perovskites with other organic cations, and for films deposited by different methods. We even see this behavior in single crystals 3. Light-induced trap formation limit the attainable voltages from mixed-halide perovskites. We must find methods to prevent this or explore alternative strategies to increasing the voltages of perovskite absorbers (CH 3 NH 3 )PbI 3 E g = 1.6 ev PL ~ (CH 3 NH 3 )Pb(I 0.8 Br 0.2 ) (CH 3 NH 3 )PbBr 3 E g = 2.3 ev
45 Emma Dohner, Richard Hoft, Abraham Saldivar, Adam Slavney, Ian Smith, and Dr. Diego Solis-Ibarra Colin Bailie, Becky Belise, Andrea Bowring, Greyson Christoforo, William Nguyen, Daniel Slotcavage, and Dr. Eva Unger Prof. Michael McGehee Dr. Eric Hoke
46 Downloaded from (10/15/2014)
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