||Investigation of High Stability Quasi-two-dimensional Perovskite Solar Cells
||Institute of Microelectronics
Perovskite solar cells
quasi two-dimensional perovskite
In recent years, although organic perovskite solar cells have been developed rapidly, the low stability of the perovskite layer, due to its sensitivity to water and oxygen, is always the one of the key points to be improve. In this work, we adopt doping two types of spacer cations, phenethylammonium and n-butylammonium, into three-dimensional perovskite solar cells, and these structures are generally called quasi-two-dimensional perovskite solar cells. First of all, the efficiency of the pure two-dimensional perovskite is currently low, two-dimensional perovskites possess higher band gap, which normally leads to higher Voc, but the two-dimensional perovskite is an insulating material, and belongs to a long carbon chain structure. Therefore, the structure will cause the short-circuit current density to drop. Therefore, by doping phenethylammonium into three-dimensional perovskites, the alignment of the energy band and the use of additives to help form a vertical orientation growth can improve the open circuit voltage and short circuit current of the devices. However, because the phenethylammonium is a benzene ring structure, there is a problem of benzene ring arrangement in the vertical orientation growth and it will cause a decrease in the fill factor. Therefore, we doped with another type of two-dimensional perovskite, n-butylammonium, to solve the problem of benzene ring arrangement, and thus improves the fill factor. In addition, we also increase the short-circuit current by increasing the thickness of the perovskite layer and optimizing the film quality of the perovskite layer to achieve higher efficiency. Finally, this thesis completed quasi-two-dimensional perovskite solar cells with high stability by doping phenethylammonium and n-butylammonium.
摘 要 I
Table Captions IX
Figure Captions XI
Chapter 1 Introduction 1
1-1 Background 1
1-2 Perovskite 4
1-3 Motivation 6
1-4 Organization of Thesis 9
Chapter 2 Operation Principle 10
2-1 Solar Spectrum 10
2-2 Mechanism of Perovskite Solar Cell 12
2-3 Solar Cell Characteristics 13
2-3-1 current-voltage curves (I-V curves) 13
2-3-2 Open-Circuit Voltage (Voc) 13
2-3-3 Short-Circuit Current (Isc) 14
2-3-4 Fill Factor (FF) 14
2-3-5 Power Conversion Efficiency (PCE) 15
Chapter 3 Experiment 17
3-1 Device Structure 17
3-2 Materials of Perovskite Solar Cells 18
3-3 Process for Device Fabrication 21
3-3-1 Pre-cleaning ITO Substrate 21
3-3-2 UV Ozone Treatment of ITO Surface 21
3-3-3 Fabrication of Hole Transport Layer 22
3-3-4 Fabrication of Active Layer 22
3-3-5 Fabrication of Electron Transport Layer 24
3-3-6 Fabrication of Hole Blocking Layer and Cathode 24
3-4 Measurements 25
3-4-1 Current-Voltage Measurement System 25
3-4-2 X-ray Diffraction 25
3-4-3 Scanning Electron Microscope 26
3-4-4 Atomic Force Microscope 26
3-4-5 Ellipsometry 27
3-4-6 UV-Vis-NIR Absorption Spectrum 27
Chapter 4 Results and Discussions 29
4-1 Comparison between quasi-2D and 3D perovskite 29
4-1-1 X-ray Diffraction 29
4-1-2 Scanning Electron Microscope 30
4-1-3 Atomic Force Microscope 31
4-1-4 Ellipsometry 33
4-1-5 UV-Vis-NIR Absorption Spectrum 33
4-2 Improvement of quasi-2D-based devices 34
4-2-1 The amounts of additives and the choice of passivating materials 34
4-2-2 Optimize the parameters of perovskite layer 38
4-2-3 Attempt various methods to improve the FF 42
4-3 Comparison of PCE and stability of quasi 2D and 3D perovskite solar cells 49
4-3-1 Comparison of quasi-2D and 3D perovskite solar cells 49
4-3-2 Comparison with other paper 52
Chapter 5 Conclusions and Future works 56
5-1 Conclusions 56
5-2 Future works 57
Chapter 1 67
Chapter 2 71
Chapter 3 74
Chapter 4 77
 M. Bhogaita, A. D. Shukla and R. P. Nalini, "Recent Advances in Hybrid Solar Cells Based on Natural Dye Extracts from Indian Plant Pigment as Sensitizers," Solar Energy, pp. 212-224, 2016.
 W. A. Badwy, S. A. Elmeniawy, and S. A. Hefez, "Improvement of The Photovoltaic Characteristics of Industrially Fabricated Solar Cells by Etching of The Si Surface," J. Sol. Energy Eng, p. 041007, Aug 2015.
 W. A. Badwy, "A Review on Solar Cells from Si-single Crystals to Porous Materials and Quantum Dots," J Adv Res., vol. 6, no. 2, pp. 123-132, Mar 2015.
 F. Dimroth, "Wafer Bonded Four-junction GaInP/GaAs//GaInAsP/GaInAs Concentrator Solar Cells with 44.7% efficiency," Prog. Photovolt: Res. Appl., vol. 22, no. 3, pp. 227-282, Mar 2014.
 C. H. Lee, H.R. Hsu amd S.Y. Tsai, "Progress Report on Perovskite Solar Cells," Industrial Materials, pp.85-93, 2014.
 National Renewable Energy Laboratory, "Best Research-Cell Efficiency Chart," 2019. [Online]. Available: https://www.nrel.gov/pv/assets/pdfs/best-research-cell-efficiencies.20190703.pdf.
 N. A. Lee, G. E. Gilligan, and J. Rochford, "Solar Energy Conversion," in Green Chemistry, 2018, pp. 881-918.
 D. Weber, "CH3NH3PbX3, ein Pb(II)-System mit kubischer Perowskitstruktur / CH3NH3PbX3, a Pb(II)-System with Cubic Perovskite Structure," Z. Naturforsch, vol. 33, no. 12, pp. 1443-1445, Dec 1978.
 D. Weber, "CH3NH3SnBrxl3-x (x = 0-3), ein Sn(II)-System mit kubischer Perowskitstruktur," Z. Naturforsch, vol. 33b, pp. 862-865, Aug 1978.
 D. B. Mizti, "Organic−inorganic Perovskites Containing Trivalent Metal Halide Layers: The Templating Influence of The Organic Cation Layer," Inorg. Chem., vol. 39, no. 26, pp. 6107-6113, Dec 2000.
 D. B. Mizti, "Templating and Structural Engineering in Organic-inorganic Perovskites," J. Chem. Soc., Dalton Trans, no. 1, pp. 1-12, 2001.
 A. Kojima, K. Teshima, T. Miyasaka, and Y. Shirai, "Novel Photoelectrochemical Cell with Mesoscopic Electrodes Sensitized by Lead-Halide Compounds (2)," T Electrochem Soc, p. 397, Oct 2006.
 M. A. Green, Y .Hishikawa, E. D. Dunlop, D. H. Levi, and J. H. Ebinger, "Solar Cell Efficiency Tables (version 51)," Prog photovltaics, vol. 26, no. 1, pp. 3-12, Jan 2018.
 L. Etgar, P. Gao, Z. S. Xue, Q. Peng, A. K. Chandiran, B. Liu, M. K. Nazeeruddin, and M. Gratzel, "Mesoscopic CH3NH3PbI3/TiO2 Heterojunction Solar Cells," J. Am. Chem. Soc, vol. 134, no. 42, pp. 17396-17399, Oct 2012.
 M. M. Lee, J. Teuscher, T. N. Murakami, and H. J. Saith, "Efficient Hybrid Solar Cells Based on Meso-superstructured Organometal Halide Perovskites," Science, vol. 338, no. 6107, pp. 643-647, Nov 2012.
 A. Buin, P. Pietsch, J. Xu, O. Voznyy, A. H. Ip, R. Comin, and E. H. Sargent, "Materials Processing Routes to Trap-free Halide Perovskites,"Nano Lett., 2014, 14, 6281-6286
 T. A. Berhe, W. N. Su, C. H. Chen, C. J. Pan, J. Cheng, H. M. Chen, M. C. Tsai, L. Y. Chen, A. A. Dubale and J. H. Bing, " Organometal Halide Perovskite Solar Cells: Degradation and Stability,"Energy Environ. Sci., 2016, 9, 323–356.
 T. M. Koh, V. Shanmugam, J. Schlipf, L. Oesinghaus, P. M¨uller-Buschbaum, N. Ramakrishnan, V. Swamy, N. Mathews, P. P. Boix and S. G. Mhaisalkar, " Nanostructuring Mixed-dimensional Perovskites: A Route Toward Tunable, Efficient Photovoltaics," Adv. Mater., 2016, 28, 3653–3661.
 R. Hamaguchi, M. Yoshizawa-Fujita, T. Miyasaka, H. Kunugita, K. Ema, Y. Takeoka and M. Rikukawa, " Formamidine and Cesium-based Quasi-two-dimensional perovskites as photovoltaic absorbers," Chem. Commun., 2017, 53, 4366.
 C. C. Stoumpos, D. H. Cao, D. J. Clark, J. Young, J. M. Rondinelli, J. I. Jang, J. T. Hupp and M. G. Kanatzidis, " Ruddlesden–popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors," Chem. Mater., 2016, 28, 2852–2867.
 Z. Yang, L. Yang, G. Wu, M. Wang and H. Chen, " A Heterojunction Based on Well-ordered Organic-inorganic Hybrid Perovskite and Its Photovoltaic Performance," Acta Chim. Sin., 2011, 69, 627–632.
 J. Liu, J. Leng, K. Wu, J. Zhang and S. Jin, " Observation of Internal Photoinduced Electron and Hole Separation in Hybrid Two-dimentional Perovskite Films," J. Am. Chem. Soc., 2017, 139, 1432.
 D. Ma, Y. Fu, L. Dang, J. Zhai, I. A. Guzei and S. Jin, " Single-crystal Microplates of Two-dimensional Organic–inorganic Lead Halide Layered Perovskites for Optoelectronics," Nano Res., 2017, 10, 2117–2129.
 K. Yao, X. Wang, Y. Xu, F. Li and L. Zhou, " Multilayered Perovskite Materials Based on Polymeric-ammonium Cations for Stable Large-area Solar Cell," Chem. Mater., 2016, 28, 3131–3138.
 T. Zhang, L. Xie, L. Chen, N. Guo, G. Li, Z. Tian, B. Mao and Y. Zhao, " In Situ Fabrication of Highly Luminescent Bifunctional Amino Acid Crosslinked 2D/3D NH3C4H9COO(CH3NH3PbBr3)n Perovskite Films," Adv. Funct. Mater., 2017, 27, 1603568.
 J. F. Liao, H. S. Rao, B. X. Chen, D. B. Kuang and C. Y. Su, " Dimension Engineering on Cesium Lead Iodide for Efficient and Stable Perovskite Solar Cells," J. Mater. Chem. A, 2017, 5, 2066–2072.
 N. Q. Li, M. Yuan, R. Comin, O. Voznyy, E. M. Beauregard, S. Hoogland, A. Buin, A. R. Kirmani, K. Zhao, A. Amassian, D. H. Kim, and E. H. Sargent, " Ligand-stabilized Reduced-dimensionality Perovskites," J. Am. Chem. Soc., 2016, 138, 2649-2655.
 D. H. Cao, C. C. Stoumpos, O. K. Farha, J. T. Hupp and M. G. Kanatzidis, " 2D Homologous Perovskites as Light-Absorbing Materials for Solar Cell Applications," J. Am. Chem. Soc., 2015, 137, 7843-7850.
 L. Ke, X. Gan, W. Zhao, L. Guo, and H. Liu, “(C6H5C2H4NH3)2FAn-1PbnI3n+1: A Quasi Two-dimensional Perovskite with High Performance Produced via Two-step Solution Method,” Journal of Alloys and Compounds 788 (2019) 954-960
 I. C. Smith, E. T. Hoke, D. Solis-Ibarra, M. D. McGehee, and H. I. Karunadasa, " A Layered Hybrid Perovskite Solar Cell Absorber with Enhanced Moisture Stability," Angew. Chem., Int. Ed. 2014, 53, 11232.
 H. Tsai, W. Y. Nie, J.C. Blancon, R. Asadpour, B. Harutyunyan, A. J. Neukirch, R. Verduzco, J. J. Crochet, S. Tretiak, L. Pedesseau, J. Evne, M. A. Alam, G. Gupta, J. Lou, M. J. Bedzyk, M. G. Kanatzidis, and A. D. Mohite, "High-efficiency Two-dimensional Ruddlesden-Popper Perovskite Solar Cells," Nature 2016, 8, 2852.
 Y. Chen, Y. Sun, J. Peng, W. Zhang, X. Su, K. Zheng, T. Pullerits, and Z. Liang, " Tailoring Organic Cation of 2D Air‐stable Organometal Halide Perovskites for Highly Efficient Planar Solar Cells," Adv. Energy Mater. 2017, 7, 1700162.
 C. C. Stoumpos, C. M. M. Soe, H. Tsai, W. Nie, J.-C. Blancon, D. H. Cao, F. Liu, B. Traoré, C. Katan, J. Even, A. D. Mohite, and M. G. Kanatzidis, " High Members of the 2D Ruddlesden-Popper Halide Perovskites: Synthesis, Optical Properties, and Solar Cells of (CH3(CH2)3NH3)2(CH3NH3)4Pb5I16," Chem 2017, 2, 427.
 C. Xuea, Y. Shia, C. Zhanga, Y. Lva, Y. Fenga, W. Tianc, S. Jinc, and T. Mab, "Favorable Growth of Well-crystallized Layered Hybrid Perovskite by Combination of Thermal and Solvent Assistance," Journal of Power Sources 422 (2019) 156–162
 X. Zhang, G. Wu, S. Yang, W. Fu, Z. Zhang, C. Chen, W. Liu, J. Yan, W. Yang, and H. Chen, " Vertically Oriented 2D Layered Perovskite Solar Cells with Enhanced Efficiency and Good Stability," Small 2017, 13, 1700611.
 X. Zhang, G. Wu, W. Fu, M. Qin, W. Yang, J. Yan, Z. Zhang, X. Lu, and H. Chen, " Orientation Regulation of Phenylethylammonium Cation Based 2D Perovskite Solar Cell with Efficiency Higher Than 11%," Adv. Energy Mater. 2018, 8, 1702498
 X. Yan, S. Hu, Y. Zhang, H. Li, and C. Sheng, “Methylammonium Acetate as An Additive to Improve Performance and Eliminate J-V Hysteresis in 2D Homologous Organic-inorganic Perovskite Solar Cells,” Solar Energy Materials and Solar Cells, 191 (2019) 283–289
 Y. Liao, H. Liu, W. Zhou, D. Yang, Y. Shang, Z. Shi, B. Li, X. Jiang, L. Zhang, L. N. Quan, R. Quintero-Bermudez, B. R. Sutherland, Q. Mi, E. H. Sargent, and Z. Ning, " Highly Oriented Low-dimensional Tin Halide Perovskites with Enhanced Stability and Photovoltaic Performance," J. Am. Chem. Soc. 2017, 139, 6693.
 D. H. Cao, C. C. Stoumpos, T. Yokoyama, J. L. Logsdon, T.-B. Song, O. K. Farha, M. R. Wasielewski, J. T. Hupp, and M. G. Kanatzidis, " Thin Films and Solar Cells Based on Semiconducting Two-dimensional Ruddlesden–popper (CH3(CH2)3NH3)2(CH3NH3)n−1SnnI3n+1 Perovskites," ACS Energy Lett. 2017, 2, 982.
 J. Zhang, L. Zhang, X. Li, X. Zhu, J. Yu, K. Fan, “Binary Solvent Engineering for High-performance Two-dimensional Perovskite Solar Cells,” ACS Sustainable Chem. Eng. 2019, 7, 3487−3495
 Nick84, "Solar Irradiance Spectrum above Atmosphere and at Surface," [Online]. Available: https://en.wikipedia.org/wiki/Solar_irradiance#/media/File:Solar_spectrum_en.svg.
 J. Jeong, "PHOTOVOLTAICS: Measuring the 'Sun'," Laser Focus World website, May 2009. [Online]. Available: https://www.laserfocusworld.com/lasers-sources/article/16566681/photovoltaics-measuring-the-sun.
 J. P. Correa-Baena, A. Abate, M. Saliba, W. Tress, T. J. Jacobsson, M. Gratzel, and A. Hagfeldt, "The Rapid Evolution of Highly Efficient Perovskite Solar Cells," Energy Environ. Sci., vol. 10, no. 3, pp. 710-727, Mar 2017.
 H. S. Jung, and N. G. Park, "Perovskite Solar Cells: From Materials to Devices," Small, vol. 11, no. 1, pp. 10-25, Jan 2015.
 N. G. Park, "Perovskite Solar Cells: An Emerging Photovoltaic Technology," Materials Today, vol. 18, no. 2, pp. 65-72, Mar 2015.
 S. D. Stranks, V. M.Burlakov, T. Leijtens, J. M. Ball, A. Goriely, and H. J. Snaith, "Recombination Kinetics in Organic-inorganic Perovskites: Excitons, Free Charge, and Subgap States," Phys. Rev. Applied, vol. 2, no. 3, p. 034007, Sep 2014.
 A. Miyata, A. Mitioglu, P. Plochocka, O. Portugall, J. T. W. Wang, S D. Stranks, H. J. Snaith, and R. J. Nicholas, "Direct Measurement of The Exciton Binding Energy and Effective Masses for Charge Carriers in Organic-inorganic Tri-halide Perovskites," NATURE PHYSICS, vol. 11, no. 7, pp. 582-U94, Jul 2015.
 E. L. Lim, C. C. Yap, M. H. H. Jumali, M. A. M. Teridi, and C. H. Teh, "A Mini Review: Can Graphene Be a Novel Material for Perovskite Solar Cell Applications?," NANO-MICRO LETTERS, vol. 10, no. 2, p. 27, Apr 2018.
 [Online]. Available:https://www.pveducation.org/pvcdrom/solar-cell-operation.
 D. Bartesaghi, I. D. Perez, J. Kniepert, S. Roland, M. Turbiez, D. Neher, and L. J. A. Loster, "Competition between Recombination and Extraction of Free Charges Determines The Fill Factor of Organic Solar Cells," NATURE COMMUNICATIONS, vol. 6, p. 7083, May 2015.
 S. M. Sze, "Semiconductor Devices: Physics and Technology-2nd ed," John Wiley and Sons, 1985.
 Q. Xu, F. Wang, Z. Tan, L. Li, S. Li, X. Hou, G. Sun, X. Tu, J. Hou and Y. Li, "High-performance Polymer Solar Cells with Solution-processed and Environmentally Friendly CuOx Anode Buffer Layer," ACS Appl Mater Interfaces., vol. 5, no. 21, pp. 10658-10064, Oct 2013.
 D. Liu, Y. Li, J. Yuan, Q. Hong, G. Shi, D. Yuan, J. Wei, C. Huang, J. Tang, and M.K. Fung, "Improved Performance of Inverted Planar Perovskite Solar Cells with F4-TCNQ doped PEDOT:PSS Hole Transport Layers," J. Mater. Chem. A, vol. 5, no. 12, pp. 5701-5708, Jan 2017.
 J. Y. Jeng, Y. F. Chiang, M. H. Lee, S. R. Peng, T. F. Guo, P. Chen and T. C. Wen, "CH3NH3PbI3 Perovskite/Fullerene Planar-heterojunction Hybrid Solar Cells," Adv Mater, vol. 25, no. 27, pp. 3727-3732, Jul 2013.
 W. Fu, J. Wang, L. Zuo, K. Gao, F. Liu, David S. Ginger, and Alex K.-Y. Jen, " Two-dimensional Perovskite Solar Cells with 14.1% Power Conversion Efficiency and 0.68% External Radiative Efficiency," ACS Energy Lett. 2018, 3, 2086−2093.
 X. Yang, X. Zhang, J. Deng, Z. Chu, Q. Jiang, J. Meng, P. Wang, L. Zhang, Z. Yin, and J. You, " Efficient Green Light-emitting Diodes Based on Quasi-two-dimensional Composition and Phase Engineered Perovskite with Surface Passivation," NATURE COMMUNICATIONS, 2018, 9:570.
 L. Hu, M. Li, K. Yang, Z. Xiong, B. Yang, M. Wang, X. Tang, Z. Zang, X. Liu, B. Li, Z. Xiao, S. Lu, H. Gong, J. Ouyang and K. Sun, 'PEDOT:PSS Monolayers to Enhance The Hole Extraction and Stability of Perovskite Solar Cells,' J. Mater. Chem. A, 2018, 6,16583
 [Online]. Available:https://en.wikipedia.org/wiki/Buckminsterfullerene.
 [Online]. Available:https://www.dojindo.com/store/p/589-Bathocuproine.html.
 L. Hu, K. Sun, M. Wang, W. Chen, B. Yang, J. Fu, Z. Xiong, X. Li, X. Tang, Z. Zang, S. Zhang, L. Sun, and M. Li, “Inverted Planar Perovskite Solar Cells with a High Fill Factor and Negligible Hysteresis by The Dual Effect of NaCl-Doped PEDOT:PSS,” ACS Appl. Mater. Interfaces, 2017, 9, 43902−43909
 W. Fu, J. Wang, L. Zuo, K. Gao, F. Liu, D. S. Ginger, amd A. K.Y. Jen, “Two-dimensional Perovskite Solar Cells with 14.1% Power Conversion Efficiency and 0.68% External Radiative Efficiency,” ACS Energy Lett., 2018, 3, 2086−2093
 X. Lian, J. Chen, R. Fu, T.K. Lau, Y. Zhang, G. Wu, X. Lu, Y. Fang, De. Yangc, amd H. Chen, “An Inverted Planar Solar Cell with 13% Efficiency and a Sensitive Visible Light Detector Based on Orientation Regulated 2D Perovskites,” J. Mater. Chem. A, 2018, 6, 24633–24640
 L. Ke, X. Gan, W. Zhao, L. Guo, and H. Liu, “(C6H5C2H4NH3)2FAn-1PbnI3n-1: A Quasi Two-dimensional Perovskite with High Performance Produced via Two-step Solution Method,” Journal of Alloys and Compounds 788 (2019) 954-960
 L. Hu, M. Li, K. Yang, Z. Xiong, B. Yang, M. Wang, X. Tang, Z. Zang, X. Liu, B. Li, Z. Xiao, S. Lu, H. Gong, J. Ouyang, and K. Sun, “PEDOT:PSS Monolayers to Enhance The Hole Extraction and Stability of Perovskite Solar Cells,” J. Mater. Chem. A, 2018, 6,16583
 W. Chen, Y. Wua, B. Tu, F. Liu, A. B. Djurišic´, and Z. He, “Inverted Planar Organic-inorganic Hybrid Perovskite Solar Cells with NiOx Hole-transport Layers as Light-in Window,” Applied Surface Science 451 (2018) 325–332
 P. L. Qin, Q. He, C. Chen, X.L. Zheng, G. Yang, H. Tao, L.B. Xiong, L. Xiong, G. Li, and G.J. Fang, “High-performance Rigid and Flexible Perovskite Solar Cells with Low-temperature Solution-processable Binary Metal Oxide Hole-transporting Materials,” Sol. RRL 2017, 1, 1700058.
 L.H. Chou, X.F. Wang, I. Osaka, C.-G. Wu, and C.L. Liu, “Scalable Ultrasonic Spray-processing Technique for Manufacturing Large-area CH3NH3PbI3 Perovskite Solar Cells,” ACS Appl. Mater. Interfaces 2018, 10, 38042−38050