Supporting Information. High Efficiency Inverted Planar Perovskite Solar Cells with Solution-Processed. NiOx Hole Contact

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1 Supporting Information High Efficiency Inverted Planar Perovskite Solar Cells with Solution-Processed NiOx Hole Contact Xuewen Yin, Zhibo Yao, Qiang Luo, Xuezeng Dai, Yu Zhou, Ye Zhang, Yangying Zhou, Songping Luo, Jianbao Li,, Ning Wang,*, and Hong Lin*, State Key Laboratory of New Ceramics & Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing , P. R. China State Key Laboratory of Marine Resource Utilization in South China Sea, Materials and Chemical Engineering Institute, Hainan University, Haikou , P. R. China *Corresponding S-1

2 Figure S1. Cross-sectional SEM images of the devices with different concentration perovskite precursors (1.25 M (a), 1.35 M (b), 1.45 M (c) and1.50 M (d), respectively.) (Blue vertical lines represent thicknesses of perovskite layers) S-2

3 Figure S2. The charge-transfer resistance obtained by EIS in figure 5b (Rct) as thickness of perovskite. S-3

4 Figure S3. Cross-sectional SEM images of NiOx films fabricated by spin-coating different times on FTO: 1 time (a), 2 times (b), 3 times (c) and 4 times (d), respectively. (Blue vertical lines represent thicknesses of NiOx films) Figure S4. SEM images of NiOx films fabricated by spin-coating different times on FTO: 1 time (a), 2 times (b), 3 times (c) and 4 times (d), respectively. S-4

5 Figure S5. Normalized PL spectra of the devices with different NiOx precursor spincoating times S-5

6 Figure S6. Jsc (a), Voc (b), FF (c) and PCE(d) distributions as the concentration of PCBM. S-6

7 Figure S7. XRD pattern of solar cell stored in air for 1500 h. S-7

8 Figure S8. Secondary electron image and Auger analysis of solar cell stored in air for 1500 h. S-8

9 Figure S9. Cross-sectional SEM and element of I mapping for fresh solar cell (a, b) and solar cell stored in air for 1500h (c, d) S-9

10 Table S1. The dynamic decay time parameter of the devices with different concentration perovskite precursors Decay τ1(ns) τ2(ns) 1.25 M M M M Table S2. The dynamic decay time parameter of the devices with spin-coating different times NiOx precursor Decay τ1(ns) τ2(ns) perovskite time times times times S-10

11 Table S3 Summary on the performances and preparation methods of NiOx-based organic-inorganic hybrid perovskite solar cells and our devices are also included for comparison. The word non means the parameter was not presented in the paper. Device configuration Voc (V) Jsc (ma/cm 2 ) S-11 FF (%) PCE (%) Area (cm 2 ) Method/temperature Referen ce ITO/PLD-NiO/ CH3NH3PbI3/PCBM/LiF/Al Non PLD/200 C 1 ITO/ALD-NiO/ CH3NH3PbI3/PCBM/Ag ALD/300 C 2 ITO/Cu:NiO/ CH3NH3PbI3/Bis-C60/C60/Ag Combustion/150 C 3 ITO/ Cu:NiO / MA0.7FA0.3Pb(I0.1Br0.9)3 /PC61BM:C60(1:1)/Bis-C60/Ag Non Spin-coating/550 C 4 ITO/NiOx/ CH3NH3PbI3 /PCBM/ Ag Spin-coating/130 C 5 FTO/NiMgLiO/ CH3NH3PbI3/PCBM/Ti(Nb)Ox/Ag Spray pyrolysis/500 C 6 FTO/NiO/DEA/ CH3NH3PbI3 xclx /PCBM/PN4N/Ag Non Spin-coating/500 C 7 FTO/ NiOx / CH3NH3PbI3/PCBM /Ag Spin-coating/350 C This Work FTO/NiO/ CH3NH3PbI3/PCBM/Ag Non FTO/Cu:NiO/ CH3NH3PbI3/PCBM/Ag Non Spin-coating/550 C 8 FTO/NiOx/ CH3NH3PbI3/PCBM/Ag Spin-coating/500 C 9 FTO/NiO/NiO (np)/ CH3NH3PbI3/PCBM/BCP/Al Non Sputtering 10 FTO/NiO/Meso-Al2O3/ CH3NH3PbI3/PCBM/BCP/Ag Spray pyrolysis/ 500 C 11 glass/au:niox (e-beam evaporator)/ E-beam Non CH3NH3PbI3/C60 /BCP/Al evaporator/500 C 12 ITO/NiOx/ CH3NH3PbI3/PCBM/Ag Spin-coating/300 C 13

12 ITO/ NiO/meso-NiO/ CH3NH3PbI3/BCP/Al Non Sputtering + spin coating/ 400 C 14 FTO/ NiO NCs/ CH3NH3PbI3 xclx /PCBM (1.5 wt% PS)/Al Non Spin-coating/500 C 15 FTO/NiO/ CH3NH3PbI3/PCBM/Ag Non Sputtering/ No heated 16 ITO/NiO/meso-NiO/ CH3NH3PbI3/BCP/Al Spin-coating/400 C 17 FTO/NiO NCs/CH3NH3PbI3/PCBM/Au Non Spin-coating/500 C 18 ITO/NiO/ CH3NH3PbI3 xclx /PCBM/BCP/Al Spun-cast/ 300 C 19 ITO/NiO/ CH3NH3PbI3/PCBM/Al Spin-coating/350 C 20 FTO/NiO /CH3NH3PbI3 xclx /PCBM/Ag Electrodeposited/ 350 C 21 FTO/ NiOx/ CH3NH3PbI3 xclx /PCBM/Au Non Spin-coating/340 C 22 S-12

13 References: 1. Park, J. H.; Seo, J.; Park, S.; Shin, S. S.; Kim, Y. C.; Jeon, N. J.; Shin, H.; Ahn, T. K.; Noh, J. H.; Yoon, S. C.; Hwang, C. S.; Seok, S. I., Efficient CH3NH3PbI3 Perovskite Solar Cells Employing Nanostructured P-Type NiO Electrode Formed by a Pulsed Laser Deposition. Adv. Mater. 2015, 27, Seo, S.; Park, I. J.; Kim, M.; Lee, S.; Bae, C.; Jung, H. S.; Park, N. G.; Kim, J. Y.; Shin, H., An Ultra-Thin, Un-Doped NiO Hole Transporting Layer of Highly Efficient (16.4%) Organic-Inorganic Hybrid Perovskite Solar Cells. Nanoscale 2016, 8, Jung, J. W.; Chueh, C.; Jen, A. K. Y., A Low-Temperature, Solution-Processable, Cu-Doped Nickel Oxide Hole-Transporting Layer via the Combustion Method for High-Performance Thin-Film Perovskite Solar Cells. Adv. Mater. 2015, 27, Yang, Z.; Chueh, C.; Liang, P.; Crump, M.; Lin, F.; Zhu, Z.; Jen, A. K. Y., Effects of Formamidinium and Bromide Ion Substitution in Methylammonium Lead Triiodide Toward High-Performance Perovskite Solar Cells. Nano Energy 2016, 22, Yin, X.; Chen, P.; Que, M.; Xing, Y.; Que, W.; Niu, C.; Shao, J., Highly Efficient Flexible Perovskite Solar Cells Using Solution-Derived NiOx Hole Contacts. ACS Nano 2016, 10, Chen, W.; Wu, Y.; Yue, Y.; Liu, J.; Zhang, W.; Yang, X.; Chen, H.; Bi, E.; Ashraful, I.; Gratzel, M.; Han, L., Efficient and Stable Large-Area Perovskite Solar Cells with Inorganic Charge Extraction Layers. Science 2015, 350, Bai, Y.; Chen, H.; Xiao, S.; Xue, Q.; Zhang, T.; Zhu, Z.; Li, Q.; Hu, C.; Yang, Y.; Hu, Z.; Huang, F.; Wong, K. S.; Yip, H.; Yang, S., Effects of a Molecular Monolayer Modification of NiO Nanocrystal Layer Surfaces on Perovskite Crystallization and Interface Contact Toward Faster S-13

14 Hole Extraction and Higher Photovoltaic Performance. Adv. Funct. Mater. 2016, 26, Kim, J. H.; Liang, P.; Williams, S. T.; Cho, N.; Chueh, C.; Glaz, M. S.; Ginger, D. S.; Jen, A. K. Y., High-Performance and Environmentally Stable Planar Heterojunction Perovskite Solar Cells Based on a Solution-Processed Copper-Doped Nickel Oxide Hole-Transporting Layer. Adv. Mater. 2015, 27, Yin, X.; Que, M.; Xing, Y.; Que, W., High Efficiency Hysteresis-Less Inverted Planar Heterojunction Perovskite Solar Cells with a Solution- Derived NiOx Hole Contact Layer. J. Mater. Chem. A 2015, 3, Corani, A.; Li, M.; Shen, P.; Chen, P.; Guo, T.; El Nahhas, A.; Zheng, K.; Yartsev, A.; Sundström, V.; Ponseca, C. S., Ultrafast Dynamics of Hole Injection and Recombination in Organometal Halide Perovskite Using Nickel Oxide as P-Type Contact Electrode. J. Phys. Chem. Lett. 2016, Chen, W.; Wu, Y.; Liu, J.; Qin, C.; Yang, X.; Islam, A.; Cheng, Y.; Han, L., Hybrid Interfacial Layer Leads to Solid Performance Improvement of Inverted Perovskite Solar Cells. Energ. Environ. Sci.2015, 8, Lai, W.; Lin, K.; Wang, Y.; Chiang, T.; Chen, P.; Guo, T., Oxidized Ni/Au Transparent Electrode in Efficient CH3NH3PbI3 Perovskite/Fullerene Planar Heterojunction Hybrid Solar Cells. Adv. Mater.2016, 28, Park, I. J.; Park, M. A.; Kim, D. H.; Park, G. D.; Kim, B. J.; Son, H. J.; Ko, M. J.; Lee, D.; Park, T.; Shin, H.; Park, N.; Jung, H. S.; Kim, J. Y., New Hybrid Hole Extraction Layer of Perovskite Solar Cells with a Planar p-i-n Geometry. J. Phys. Chem. C 2015, 119, Wang, K.; Shen, P.; Li, M.; Chen, S.; Lin, M.; Chen, P.; Guo, T., Low-Temperature Sputtered Nickel Oxide Compact Thin Film as Effective Electron Blocking Layer for Mesoscopic NiO/ CH3NH3PbI3 Perovskite Heterojunction Solar Cells. ACS Appl. Mater. Inter. 2014, 6, S-14

15 15. Bai, Y.; Yu, H.; Zhu, Z.; Jiang, K.; Zhang, T.; Zhao, N.; Yang, S.; Yan, H., High Performance Inverted Structure Perovskite Solar Cells Based on a PCBM: Polystyrene Blend Electron Transport Layer. J. Mater. Chem. A 2015, 3, Cui, J.; Meng, F.; Zhang, H.; Cao, K.; Yuan, H.; Cheng, Y.; Huang, F.; Wang, M., CH3NH3PbI3 -Based Planar Solar Cells with Magnetron- Sputtered Nickel Oxide. ACS Appl. Mater. Inter. 2014, 6, Wang, K.; Jeng, J.; Shen, P.; Chang, Y.; Diau, E. W.; Tsai, C.; Chao, T.; Hsu, H.; Lin, P.; Chen, P.; Guo, T.; Wen, T., P-type Mesoscopic Nickel Oxide/Organometallic Perovskite Heterojunction Solar Cells. Sci. Rep.-UK 2014, 4, Zhu, Z.; Bai, Y.; Zhang, T.; Liu, Z.; Long, X.; Wei, Z.; Wang, Z.; Zhang, L.; Wang, J.; Yan, F.; Yang, S., High-Performance Hole-Extraction Layer of Sol-Gel-Processed NiO Nanocrystals for Inverted Planar Perovskite Solar Cells. Angew. Chem. Int. Edit. 2014, 53, Jeng, J.; Chen, K.; Chiang, T.; Lin, P.; Tsai, T.; Chang, Y.; Guo, T.; Chen, P.; Wen, T.; Hsu, Y., Nickel Oxide Electrode Interlayer in CH3NH3PbI3 Perovskite/PCBM Planar-Heterojunction Hybrid Solar Cells. Adv. Mater. 2014, 26, Hu, L.; Peng, J.; Wang, W.; Xia, Z.; Yuan, J.; Lu, J.; Huang, X.; Ma, W.; Song, H.; Chen, W.; Cheng, Y.; Tang, J., Sequential Deposition of CH3NH3PbI3 on Planar NiO Film for Efficient Planar Perovskite Solar Cells. ACS Photonics 2014, 1, Subbiah, A. S.; Halder, A.; Ghosh, S.; Mahuli, N.; Hodes, G.; Sarkar, S. K., Inorganic Hole Conducting Layers for Perovskite-Based Solar Cells. J. Phys. Chem. Lett. 2014, 5, Li, E.; Guo, Y.; Liu, T.; Hu, W.; Wang, N.; He, H.; Lin, H., Preheating-Assisted Deposition of Solution-Processed Perovskite Layer for an Efficiency-Improved Inverted Planar Composite Heterojunction Solar Cell. RSC Adv. 2016, 6, S-15

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