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Dye-sensitized and Perovskite Solar Cells | Peter Holliman, University of Bangor
- 1. Dye-sensitized and perovskite solar cells Image:- NASA
- 2. 1. Introduction 2. Device architecture and operation 3. Manufacturing issues 4. Summary Dye-sensitized and perovskite solar cells Supersolar Research Methods Workshop Liverpool University, 5th April 2016 Peter Holliman School of Chemistry, Bangor University p.j.holliman@bangor.ac.uk
- 3. 1. Introduction PV landscape Technology choice
- 4. 92 elements Crust - 2 x 1022 kg Atmosphere - 5 x 1018 kg
- 5. Emissions An estimated 4,267 deaths (2008) Up to 9% of deaths due to airborne pollution (2012) London
- 6. “More solar energy falls on the Earth’s surface every day than the whole of humankind could consume in 27 years.”
- 7. Solar farms Wrexham – 13.1MW, 62 acres Deeside – 45MW, 220 acres Caernarfon – 15MW, 75 acres Anglesey – 49MW, 180 acres 122MW 547 acres 417 football pitches
- 8. Geography
- 9. Source:- National Renewable Energy Laboratory (US) 2. Device architecture and operation
- 10. 2. Device operation & architecture Dye-sensitized solar cells Perovskites
- 11. Electron passes via electrolyte to dye Inter (semiconductor) particle electron transfer to electrode Electron passes around the circuit Dye absorbs light and electron jumps to create an excited state Semiconductor Dye Counter Electrode Working Electrode DSC operation
- 12. I3 -/ I- TiO2 Ef Reverse illumination e- TiO2 on Working Electrode Dye Pt on Counter Electrode Forward illumination Electricity Electrolyte Voc
- 13. Substrate cleaning (20 min) TiO2 printing (5 min) Sinter @ 450°C (30 min) Drying (5 min) TiCl4 treatment (30 min) Dyeing (24 hours) Re-sinter @ 450°C (30 min) Working Electrode Counter Electrode Substrate cleaning (20 min) H2PtCl6 deposition (5 min) Drying (5 min) Sinter @400°C (30 min) DSC manufacturing
- 14. TiO2 Working Electrode I3 -/ I- TiO2 Ef e- TiO2 on Working Electrode Dye Pt on Counter Electrode Electrolyte
- 15. Sintering TiO2 Printing paste Binder + solvent Printing Mesoporous Film Reaction front moves from outside inwards Radiant Heat Shrinkage, necking, surface versus core Bulk Surface Necking 5 μm = 250 particles Meso-porous photo-electrodes
- 16. Solvent evaporation CO2 + H2O Pre-made TiO2 Binder (polymer) Solvent Printing Relaxation Solvent loss Combustion Energy balance Oxygen demand Sintering – global processes Crack free, film thickness, substrate roughness, particle surfaces, mechanical strength
- 17. Why a binder? Printed Sintered The blancmange effect! TiO2 Solvent Binder
- 18. Low T sintering – peroxide combustion additives Holliman et al., J. Mater. Chem. A, 2014, 2, 11134. CO2 + H2O O2 ZnO2 → ZnO + ½O2 P25 P25/ CaO2 P25/ ZnO2 P25/ MgO2 5% 10% 15%
- 19. Absorber I3 -/ I- TiO2 Ef e- TiO2 on Working Electrode Dye Pt on Counter Electrode Electrolyte
- 20. Dye absorbers for light harvesting 0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 300 400 500 600 700 800 900 1000 1100 1200 1300 ( ) Wavelength (nm)
- 21. Light harvesting
- 22. Record DSC (14.3%) Silyl linker ADEKA-1 Triarylamine LEG-4N S S S S N H CN O C6H13 C6H13 C6H13 C6H13 Si OMe MeO OMe N OO C4H9 S C4H9 O O C4H9 C4H9 S C6H13 C6H13 CN COOH Yano et al., Chem. Commun., 2015, 51, 18894. Jsc = 18.27 mAcm-2 Voc = 1.01 V FF = 0.77 Co redox couple N N N N N N Co 2+ / 3+
- 23. SealTiO2 film Hole FTO glass Electrolyte Seal Dye solution Outflow for dye solution Valve Syringe Ultra-fast co-sensitization P.J. Holliman, M.L. Davies, A. Connell, B. Vaca Velasco and T.M. Watson, Chem. Comm., 2010, 46, 7256-7258
- 24. Dye time lapse (60x)
- 25. Ultra-fast co-sensitization Ru N C S N C S COOH COOH (n- Bu)4NOOC COON(n- Bu)4 SQ1 (η = 3.7%)N719 (η = 6.0%) N719 +SQ1 (η = 8.0%) - O O - N N O OH P.J. Holliman, M.L. Davies, A. Connell, B. Vaca Velasco and T.M. Watson, Chem. Comm., 2010, 46, 7256-7258 400 600 800 0 10 20 30 40 50 60 70 80 after partial remova SQ1 added QE WLλ/nm EQE
- 26. Co-sensitization η = 5.0% η = 6.1% η = 3.4%SQ2 C8H17 COOH C2H5 N N + O O - N OH O O C12H25 Connell and Holliman et al., J. Mater. Chem. A, 2014, 2(11), 4055 - 4066.
- 27. Selective desorption Holliman et al., RSC Advances, 2014, 4(5), 2515-2522.
- 28. Imaging dye uptake (QC) T.M. Watson, P.J. Holliman and D.A. Worsley, J. Mat. Chem., 2011, 21, 4321-4325. M.L. Davies, T. Watson, P.J. Holliman, A. Connell, D. Worsley, Chem. Comm., 2014, 50, 12512–12514.
- 29. I3 -/ I- TiO2 Ef e- TiO2 on Working Electrode Dye Pt on Counter Electrode Electrolyte Current collection
- 30. Electrolyte Solid Hole Transport Materials (HTMs) Liquid Redox couple www.dyesol.com I3 -/I- Co2+/Co3+ N N OCH3 OCH3 OCH3H3CO N N OCH3 OCH3 OCH3H3CO Spiro unit – inhibits crystallisation Matches HOMO to dye
- 31. h+ ē Hole transporter Absorber Scaffold (charge carrier) Light excites absorber creating electron (ē) and hole (h+) Perovskite operation and architecture Contact Snaith et al., Science, 2012, 338, 643. Planar
- 32. Mesoporous scaffolds Electron (ē) injects into TiO2 and travels to electrode. Hole (h+) travels through HTL ē h+ TiO2 Al2O3
- 33. Electron (ē) travels through absorber to electrode. Hole (h+) travels through HTL h+ ē TiO2 Al2O3 Mesoporous scaffolds
- 34. Mesoporous TiO2 HTM Contact FTO Compact TiO2 Kim et al. J. Phys. Chem. C, 2014, 118 (11), 5615 MesoporousPlanar Zhang et al. J. Mat. Chem. A, 2015, 13, 12133
- 35. Jsc = 18.27 mAcm-2 Voc = 1.01 V FF = 0.77 Record perovskite device (20.8%) Absorber = FAI + PbI2 + MAI + PbBr2 24.60 mAcm-2 1.16 V 0.73Tress et al., Sci. Adv. 2016, doi: 10.1126/sciadv.1501170 Scaffold = Mesoporous TiO2 HTM = spiro-OMeTAD FAI is [H2N-CH=NH2]+ MAI is [CH3NH3]+ Au back contact
- 36. Substrate cleaning (20 min) TiO2 BL (1 min) Sinter @ 450°C (30 min) Drying (5 min) Mesoporo us TiO2 (30 min) Perovskite deposition (1 hour) Re-sinter @ 450°C (30 min) Working Electrode Counter Electrode Gold deposition (30 min) Laminate (5 min) Perovskite manufacturing HTM deposition (5 min)
- 38. Glass cleaning
- 40. Perovskite deposition Spin coat deposition onto 100°C pre-heated substrates CH3NH3PbBr3, CH3NH3PbICl2
- 41. Perovskite annealing CH3NH3PbICl2 substrates go from brown in spin coater to pale yellow in first few mins of annealing. Then they turn grey-black CH3NH3PbBr3 CH3NH3PbICl2
- 42. • Perovskites retain residual solvent • DMF loss is not linear with T • At < ca. 150 °C “loose” DMF leaves • At higher T, “bound” or “trapped” DMF leaves • Only > 240 °C do we see HCl, CH3NH2 Mass Heat FTIR1720 Perovskite annealing PbCl2 + CH3NH3I → CH3NH3PbI3-xClx Measure DSC and TGA whilst FTIR gives real-time FTIR of evolved gases A.E. Williams, P.J. Holliman, M.J. Carnie, M.L. Davies, D.A. Worsley, T.M. Watson, J. Mater. Chem. A, 2014, 2, 19338
- 43. Bright field optical microscopy of perovskite films (x10) CH3NH3PbBr3 CH3NH3PbICl2
- 44. Hole transport material Plan viewSpiro-OMeTAD
- 45. Device masking and metal back contact deposition
- 46. Final devices and device testing
- 47. Bryant et al., Adv. Mater., 2014, 26, 7499. • <2% PEDOT:PSS + P sensitive adhesive • Transparency >90% at 500nm • PET embedded Ni micro-grid • Epigem 300s (1.2 Ω/sq) Laminate back electrode
- 48. 3. Manufacturing issues Product form Processing Scaling
- 52. PV Product Form Roof mounted modules
- 53. 3rd Generation (flexible PV)
- 54. Flexible BIPV
- 55. Generate - store - release Buildings as Power Stations Shared vision: ‘To functionalise the outside surfaces of buildings ... new and existing.’
- 57. 4. Summary • Grid parity (cost) • End use (efficiency, power density) • Lifetime • Scaling (R2R) • Product form - bespoke PV • Integration • Technology choice?
- 58. For DSC • 20 year technology • η = 14% • Liquid to solid (substrates, t½) • Lifetime (> 5 year) • Cost, processing times • Commercial (G24Power) • Market For perovskites • 4 year technology • η = 20% • Lead? • Out of the dry box • Processing solvents • Scaling (cells to modules) • Lifetime Where are we now, where next?
- 59. Photo-electrodes Mesoporous TiO2 - η = 7.3%. O’Regan & Grätzel, Nature, 1991, 353, 24. Crystalline TiO2 nanoparticles Barbé et al., J. Am. Ceram. Soc., 1997, 80, 3157. Low T sintering Holliman et al., J. Mater. Chem. A, 2014, DOI:10.1039/C4TA01000K. Dyes Yellow dye - η = 2.6%. Holliman et al., J. Mat. Chem., 2012, 22(26), 13318. D149 η = 8.0. Horiuchi et al., JACS, 2004, 126, 12218. Panchromatic “Black Dye” Nazeeruddin et al., Chem. Commun., 1997, 1705. N719 - η = 11.0%. Nazeeruddin et al., J. Am. Chem. Soc., 2005, 127, 16835. Blue squaraine SQ2 - η = 5.4%. Geiger et al., Adv. Funct. Mater., 2009, 19, 2720. Panchromatic squaraine Maeda, et al. New J.Chem., 2013, 37,71, 701. Light harvesting Porphyrin + triarylamine - η = 12.3%. A. Yella et al., Science, 2011, 334, 629 Alkoxysilyl carbazole - η = 12.0%. Yano et al., Chem. Commun., 2014, 50, 6379. Silyl linker + coumarin - η = 12.8%. Yano et al., Chem. Commun., 2015, 51, 6315. Silyl linker + LEG4 - η = 14.3%. Yano et al., Chem. Commun., 2015, 51, 18894. Fast processing 5 min dyeing - η = 5.0%. Holliman et al., Chem. Comm., 2010, 46, 7256. Rapid, NIR sintering Worsley et al., Progr. Photovolt. Res. Appl., 19 (4), 482. DSC Reviews Hagfeldt et al., Chem. Rev., 2010, 110, 6595. DSC references
- 60. Perovskite architectures Mesoporous devices - η = 15.0%. Snaith et al., Science, 2012, 338, 643. Planar devices Zhang et al. J. Mat. Chem. A, 2015, 13, 12133. Perovskite coverage Huang et al., PCCP, 2015, 17, 2015. Efficiency η = 19.3% Zhou et al., Science, 2014, 345 (6196), 542. η = 20.8% Tress et al., Sci. Adv. 2016, doi: 10.1126/sciadv.1501170 Hysteresis Solvent processing Jeon et al., Nature Mater., 2014, 13, 897. Pb-free Tin perovskites - η = 6.0%. Snaith et al., Energy Env. Sci., 2014, 7, 3061. Perovskite references Perovskite processing Solvent safety. Holliman et al., Mater. Res. Innov., 2015, 19, 508. Thermal analysis Williams et al., J. Mater. Chem. A, 2014, 2, 19338-19346. Perovskite ink. Jones et al., Chem. Comm., 2016, 52, 4301. Counter electrodes Laminate Bryant et al., Adv. Mater., 2014, 26 (44), 7499. NiO/C Xu et al. NanoLett, 2015, 15, 2402. Carbon Zhang et al., J. Mater. Chem. A, 2015, 3, 9165. Carbon Wei et al., Carbon, 2015, 93, 861. Perovskite Reviews N.-G. Park, Mater. Today, 2015, 18(2), 65.
- 61. Acknowledgements Bangor Rosie Anthony, Robert Hobbs, Leo Furnell, Sanjay Ghosh, Arthur Connell, Chris Kershaw, Eurig Jones SPECIFIC (Swansea) Joel Troughton, Daniel Bryant