Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.
Nature Energy volume 2, Article number: 17102 (2017 ) Cite this article ammonium chloride food
The ionic defects at the surfaces and grain boundaries of organic–inorganic halide perovskite films are detrimental to both the efficiency and stability of perovskite solar cells. Here, we show that quaternary ammonium halides can effectively passivate ionic defects in several different types of hybrid perovskite with their negative- and positive-charged components. The efficient defect passivation reduces the charge trap density and elongates the carrier recombination lifetime, which is supported by density-function-theory calculation. The defect passivation reduces the open-circuit-voltage deficit of the p–i–n-structured device to 0.39 V, and boosts the efficiency to a certified value of 20.59 ± 0.45%. Moreover, the defect healing also significantly enhances the stability of films in ambient conditions. Our findings provide an avenue for defect passivation to further improve both the efficiency and stability of solar cells.
This is a preview of subscription content, access via your institution
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
Receive 12 digital issues and online access to articles
Prices may be subject to local taxes which are calculated during checkout
Xiao, Z. et al. Solvent annealing of perovskite-induced crystal growth for photovoltaic-device efficiency enhancement. Adv. Mater. 26, 6503–6509 (2014).
Wehrenfennig, C., Eperon, G. E., Johnston, M. B., Snaith, H. J. & Herz, L. M. High charge carrier mobilities and lifetimes in organolead trihalide perovskites. Adv. Mater. 26, 1584–1589 (2014).
Stranks, S. D. et al. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341–344 (2013).
Snaith, H. J. et al. Efficiency enhancements in solid-state hybrid solar cells via reduced charge recombination and increased light capture. Nano Lett. 7, 3372–3376 (2007).
Son, D.-Y. et al. Self-formed grain boundary healing layer for highly efficient CH3NH3PbI3 perovskite solar cells. Nat. Energy 1, 16081 (2016).
Tang, J. et al. Colloidal-quantum-dot photovoltaics using atomic-ligand passivation. Nat. Mater. 10, 765–771 (2011).
Oh, J., Yuan, H.-C. & Branz, H. M. An 18.2%-efficient black-silicon solar cell achieved through control of carrier recombination in nanostructures. Nat. Nanotech. 7, 743–748 (2012).
Bi, D. et al. Efficient luminescent solar cells based on tailored mixed-cation perovskites. Sci. Adv. 2, e1501170 (2016).
Yang, M. et al. Facile fabrication of large-grain CH3NH3PbI3−xBrx films for high-efficiency solar cells via CH3NH3Br-selective Ostwald ripening. Nat. Commun. 7, 12305 (2016).
Dong, Q. et al. Electron-hole diffusion lengths >175 μm in solution-grown CH3NH3PbI3 single crystals. Science 347, 967–970 (2015).
Shao, Y., Xiao, Z., Bi, C., Yuan, Y. & Huang, J. Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells. Nat. Commun. 5, 5784 (2014).
Shi, D. et al. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 347, 519–522 (2015).
de Quilettes, D. W. et al. Impact of microstructure on local carrier lifetime in perovskite solar cells. Science 348, 683–686 (2015).
Yin, W.-J., Shi, T. & Yan, Y. Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber. Appl. Phys. Lett. 104, 063903 (2014).
Eperon, G. et al. Carriers trapping and recombination: the role of defect physics in enhancing the open circuit voltage of metal halide perovskite solar cells. Energy Environ. Sci. 9, 3472–3481 (2016).
Mosconi, E., Meggiolaro, D., Snaith, HJ, Stranks, SD & de ANGELIS, F. Light-Indeced Annihilation of Frenkel Defects in Organo-Lead Halide Perovskits. Energy Environ. SCI. 9, 3180–3187 (2016).
Azpiroz, J. M., Mosconi, E., Bisquert, J. & De Angelis, F. Defect migration in methylammonium lead iodide and its role in perovskite solar cell operation. Energy Environ. Sci. 8, 2118–2127 (2015).
Shao, Y., Yuan, Y. & Huang, J. Correlation of energy disorder and open-circuit voltage in hybrid perovskite solar cells. Nat. Energy 1, 15001 (2016).
Marco, N. D. et al. Guanidinium: a route to enhanced carrier lifetime and open-circuit voltage in hybrid perovskite solar cells. Nano Lett. 16, 1009–1016 (2016).
Chen, Q. et al. Controllable self-induced passivation of hybrid lead iodide perovskites toward high performance solar cells. Nano Lett. 14, 4158–4163 (2014).
Li, X. et al. Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides. Nat. Chem. 7, 703–711 (2015).
Niu, G. et al. Study on the stability of CH3NH3PbI3 films and the effect of post-modification by aluminum oxide in all-solid-state hybrid solar cells. J. Mater. Chem. A 2, 705–710 (2014).
Wang, Q. et al. Scaling behavior of moisture-induced grain degradation in polycrystalline hybrid perovskite thin films. Energy Environ. Sci. 10, 516–552 (2017).
Tress, W., Correa Baena, J. P., Saliba, M., Abate, A. & Graetzel, M. Inverted current–voltage hysteresis in mixed perovskite solar cells: polarization, energy barriers, and defect recombination. Adv. Energy Mater. 6, 1600396 (2016).
Wu, B. et al. Discerning the surface and bulk recombination kinetics of organic–inorganic halide perovskite single crystals. Adv. Energy Mater. 6, 1600551 (2016).
Yu, H., Lu, H., Xie, F., Zhou, S. & Zhao, N. Native defect-induced hysteresis behavior in organolead iodide perovskite solar cells. Adv. Funct. Mater. 26, 1411–1419 (2016).
Aberle, A. G. Surface passivation of crystalline silicon solar cells: a review. Prog. Photovolt. Res. Appl. 8, 473–487 (2000).
Liu, Y. et al. Nanostructure formation and passivation of large-area black silicon for solar cell applications. Small 8, 1392–1397 (2012).
Yan, B. et al. Innovative dual function nc-SiOx: H layer leading to a >16% efficient multi-junction thin-film silicon solar cell. Appl. Phys. Lett. 99, 113512 (2011).
Xu, J. et al. Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes. Nat. Commun. 6, 7081 (2015).
Abate, A. et al. Supramolecular halogen bond passivation of organic–inorganic halide perovskite solar cells. Nano Lett. 14, 3247–3254 (2014).
Noel, N. K. et al. Enhanced photoluminescence and solar cell performance via Lewis base passivation of organic–inorganic lead halide perovskites. ACS Nano 8, 9815–9821 (2014).
Ahn, N. et al. Highly reproducible perovskite solar cells with average efficiency of 18.3% and best efficiency of 19.7% fabricated via Lewis base adduct of lead (II) iodide. J. Am. Chem. Soc. 137, 8696–8699 (2015).
Lee, J.-W., Kim, H.-S. & Park, N.-G. Lewis acid–base adduct approach for high efficiency perovskite solar cells. Acc. Chem. Res. 49, 311–319 (2016).
Zhao, T., Chueh, C.-C., Chen, Q., Rajagopal, A. & Jen, A. K.-Y. Defect passivation of organic-inorganic hybrid perovskites by diammonium iodide towards high-performance photovoltaic devices. ACS Energy Lett. 1, 757–763 (2016).
Bi, C. et al. Non-wetting surface-driven high-aspect-ratio crystalline grain growth for efficient hybrid perovskite solar cells. Nat. Commun. 6, 7747 (2015).
Wang, Q. et al. Large fill-factor bilayer iodine perovskite solar cells fabricated by a low-temperature solution-process. Energy Environ. Sci. 7, 2359–2365 (2014).
Xiao, Z. et al. Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers. Energy Environ. Sci. 7, 2619–2623 (2014).
Bai, Y. et al. Enhancing stability and efficiency of perovskite solar cells with crosslinkable silane functionalized and doped fullerene. Nat. Commun. 7, 21806 (2016).
Bi, D. et al. High-performance perovskite solar cells with enhanced environmental stability based on amphiphile-modified CH3NH3PbI3 . Adv. Mater. 28, 2910–2915 (2016).
Wang, F. et al. Phenylalkylamine passivation of organolead halide perovskites enabling high-efficiency and air-stable photovoltaic cells. Adv. Mater. 28, 9986–9992 (2016).
Chen, Q. et al. The optoelectronic role of chlorine in CH3NH3PbI3(Cl)-based perovskite solar cells. Nat. Commun. 6, 7269 (2015).
Jeon, N. J. et al. Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells. Nat. Mater. 13, 897–903 (2014).
Jiang, Q. et al. Enhanced electron extraction using SnO2 for high-efficiency planar-structure HC(NH2)2PbI3-based perovskite solar cells. Nat. Energy 1, 16177 (2017).
Tan, H. et al. Efficient and stable solution-processed planar perovskite solar cells via contact passivation. Science 355, 722–726 (2017).
Brenner, T. M., Egger, D. A., Kronik, L., Hodes, G. & Cahen, D. Hybrid organic–inorganic perovskites: low-cost semiconductors with intriguing charge-transport properties. Nat. Rev. Mater. 1, 15007 (2016).
Walter, T., Herberholz, R., Müller, C. & Schock, H. Determination of defect distributions from admittance measurements and application to Cu(In, Ga) Se2 based heterojunctions. J. Appl. Phys. 80, 4411–4420 (1996).
This work was supported in part by the Air Force Office of Scientific Research (AFOSR) (Grant No. A9550-16-1-0299) and the National Science Foundation (NSF) through the Nebraska Materials Research Science and Engineering Center (MRSEC) (Grant No. DMR-1420645), and by the NSF Grant OIA-1538893.
Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, Nebraska 68588, USA
Xiaoopeng Zheng, Bo Chen, Yanjun Fang, Yang Bai, Yuze Lin, Haotong Wei & Jinsong Huang
Department of Chemistry, University of Nebraska-Lincoln, Nebraska 68588, USA
Jun Dai & Xiao Cheng Zeng
Department of Applied Physical Sciences, University of North Carolina, Chapel Hill, North Carolina 27599, USA
You can also search for this author in PubMed Google Scholar
You can also search for this author in PubMed Google Scholar
You can also search for this author in PubMed Google Scholar
You can also search for this author in PubMed Google Scholar
You can also search for this author in PubMed Google Scholar
You can also search for this author in PubMed Google Scholar
You can also search for this author in PubMed Google Scholar
You can also search for this author in PubMed Google Scholar
You can also search for this author in PubMed Google Scholar
J.H. and X.Z. conceived the idea and designed the experiments. X.Z. fabricated most of the devices and conducted the characterization. B.C. fabricated the wide-bandgap solar cells. J.D. and X.C.Z. conducted the simulation modelling. Y.B. and H.W. synthesized the relevant chemicals. Y.F. performed the physical characterizations of the devices. J.H., X.Z., J.D. and Y.L. wrote the paper, and all authors reviewed the paper.
The authors declare no competing financial interests.
Zheng, X., Chen, B., Dai, J. et al. Defect passivation in hybrid perovskite solar cells using quaternary ammonium halide anions and cations. Nat Energy 2, 17102 (2017). https://doi.org/10.1038/nenergy.2017.102
DOI: https://doi.org/10.1038/nenergy.2017.102
Anyone you share the following link with will be able to read this content:
Sorry, a shareable link is not currently available for this article.
Provided by the Springer Nature SharedIt content-sharing initiative
Nature Energy (Nat Energy) ISSN 2058-7546 (online)
ammonium chloride cation Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.