Abstract
This chapter is focused on the relevance of the ionic transport in hybrid organic–inorganic perovskites. The occurrence of significant ionic conductivity along with electronic conductivity leads to stoichiometric polarization on current flow. Such a polarization yields a large apparent dielectric constant at low frequencies and a pronounced hysteresis behavior in i-V sweep experiments. We describe electrochemical background, precise measurements, and the impact of these phenomena for the photo-perovskites.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Similar content being viewed by others
References
Kojima, A., Teshima, K., Shirai, Y., Miyasaka, T.: Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131(17), 6050–6051 (2009). doi:10.1021/ja809598r
Kim, H.S., Lee, C.R., Im, J.H., Lee, K.B., Moehl, T., Marchioro, A., Moon, S.J., Humphry-Baker, R., Yum, J.H., Moser, J.E., Grätzel, M., Park, N.G.: Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9 %. Sci. Rep. 2, 591 (2012). doi:10.1038/srep00591
Burschka, J., Pellet, N., Moon, S.-J., Humphry-Baker, R., Gao, P., Nazeeruddin, M.K., Gratzel, M.: Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499(7458), 316–319 (2013). doi:10.1038/nature12340
Chen, Q., Zhou, H., Hong, Z., Luo, S., Duan, H.-S., Wang, H.-H., Liu, Y., Li, G., Yang, Y.: Planar heterojunction perovskite solar cells via vapor assisted solution process. J. Am. Chem. Soc. 136(2), 622–625 (2013). doi:10.1021/ja411509g
Jeon, N.J., Noh, J.H., Kim, Y.C., Yang, W.S., Ryu, S., Seok, S.I.: Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells. Nat. Mater. 13(9), 897–903 (2014). doi:10.1038/nmat4014
Liu, M., Johnston, M.B., Snaith, H.J.: Efficient planar heterojunction perovskite solar cells by vapour deposition. Nature 501(7467), 395–398 (2013). doi:10.1038/nature12509
Lee, M.M., Teuscher, J., Miyasaka, T.: Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science 643 (2012). doi:10.1126/science.1228604
Pellet, N., Gao, P., Gregori, G., Yang, T.-Y., Nazeeruddin, M.K., Maier, J., Grätzel, M.: Mixed-Organic-Cation perovskite photovoltaics for enhanced solar-light harvesting. Angew. Chem. Int. Ed. 53(12), 3151–3157 (2014). doi:10.1002/anie.201309361
Yang, T.-Y., Gregori, G., Pellet, N., Grätzel, M., Maier, J.: The Significance of ion conduction in a hybrid organic-inorganic lead-iodide-based perovskite photosensitizer. Angew. Chem. Int. Ed. 54(27), 7905–7910 (2015). doi:10.1002/anie.201500014
Juarez-Perez, E.J., Sanchez, R.S., Badia, L., Garcia-Belmonte, G., Kang, Y.S., Mora-Sero, I., Bisquert, J.: Photoinduced giant dielectric constant in lead halide perovskite solar cells. J. Phys. Chem. Lett. 5(13), 2390–2394 (2014). doi:10.1021/jz5011169
Sanchez, R.S., Gonzalez-Pedro, V., Lee, J.-W., Park, N.-G., Kang, Y.S., Mora-Sero, I., Bisquert, J.: Slow dynamic processes in lead halide perovskite solar cells. characteristic times and hysteresis. J. Phys. Chem. Lett. 5(13), 2357–2363 (2014). doi:10.1021/jz5011187
Reenen, S.V., Kemerink, M., Snaith, H.J.: Modeling anomalous hysteresis in perovskite solar cells. J. Phys. Chem. Lett. 6, 3808–3814 (2015). doi:10.1021/acs.jpclett.5b01645
Snaith, H.J., Abate, A., Ball, J.M., Eperon, G.E., Leijtens, T., Noel, N.K., Stranks, S.D., Wang, J.T.W., Wojciechowski, K., Zhang, W.: Anomalous hysteresis in perovskite solar cells. J. Phys. Chem. Lett. 5(9), 1511–1515 (2014). doi:10.1021/jz500113x
Unger, E.L., Hoke, E.T., Bailie, C.D., Nguyen, W.H., Bowring, A.R., Heumuller, T., Christoforo, M.G., McGehee, M.D.: Hysteresis and transient behavior in current-voltage measurements of hybrid-perovskite absorber solar cells. Energy Environ. Sci. 7, 3690–3698 (2014). doi:10.1039/C4EE02465F
Zhang, Y., Liu, M., Eperon, G.E., Leijtens, T.C., McMeekin, D., Saliba, M., Zhang, W., de Bastiani, M., Petrozza, A., Herz, L.M., Johnston, M.B., Lin, H., Snaith, H.J.: Charge selective contacts, mobile ions and anomalous hysteresis in organic–inorganic perovskite solar cells. Mater. Horiz. 2, 315–322 (2015). doi:10.1039/C4MH00238E
Hebb, M.H.: Electrical conductivity of silver sulfide. J. Chem. Phys. 20(1), 185–190 (1952). doi:10.1063/1.1700165
Frost, J.M., Butler, K.T., Brivio, F., Hendon, C.H., van Schilfgaarde, M., Walsh, A.: Atomistic origins of high-performance in hybrid halide perovskite solar cells. Nano Lett. 14(5), 2584–2590 (2014). doi:10.1021/nl500390f
Stoumpos, C.C., Malliakas, C.D., Kanatzidis, M.G.: Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. Inorg. Chem. 52(15), 9019–9038 (2013). doi:10.1021/ic401215x
Onoda-Yamamuro, N., Matsuo, T., Suga, H.: Dielectric study of CH3NH3PbX3 (X = Cl, Br, I). J. Phys. Chem. Solids 53(7), 935–939 (1992). doi:10.1016/0022-3697(92)90121-S
Poglitsch, A., Weber, D.: Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter-wave spectroscopy. J. Chem. Phys. 87(11), 6373–6378 (1987). doi:10.1063/1.453467
Wasylishen, R.E., Knop, O., Macdonald, J.B.: Cation rotation in methylammonium lead halides. Solid State Commun. 56(7), 581–582 (1985). doi:10.1016/0038-1098(85)90959-7
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). doi:10.1038/ncomms6784
Xiao, Z., Bi, C., Shao, Y., Dong, Q., Wang, Q., Yuan, Y., Wang, C., Gao, Y., Huang, J.: Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers. Energy Environ. Sci. 7(8), 2619–2623 (2014). doi:10.1039/C4EE01138D
You, J., Yang, Y., Hong, Z., Song, T.-B., Meng, L., Liu, Y., Jiang, C., Zhou, H., Chang, W.-H., Li, G., Yang, Y.: Moisture assisted perovskite film growth for high performance solar cells. Appl. Phys. Lett. 105(18), 183902 (2014). doi:10.1063/1.4901510
Xu, J., Buin, A., Ip, A.H., Li, W., Voznyy, O., Comin, R., Yuan, M., Jeon, S., Ning, Z., McDowell, J.J., Kanjanaboos, P., Sun, J.-P., Lan, X., Quan, L.N., Kim, D.H., Hill, I.G., Maksymovych, P., Sargent, E.H.: Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes. Nat. Communi. 6 (2015). doi:10.1038/ncomms8081
Nie, W., Tsai, H., Asadpour, R., Blancon, J.C., Neukirch, A.J., Gupta, G., Crochet, J.J., Chhowalla, M., Tretiak, S., Alam, M.A., Wang, H.L., Mohite, A.D.: High-efficiency solution-processed perovskite solar cells with millimeter-scale grains. Science 347(6221), 522–525 (2015). doi:10.1126/science.aaa0472
Yamada, K., Isobe, K., Okuda, T., Furukawa, Y.: Successive Phase Transitions and High Ionic Conductivity of Trichlorogermanate(II) Salts as Studied by 35Cl NQR and Powder X-Ray Diffraction. Z. Naturforsch. A J. Phys. Sci. 49(1–2), 258–266 (1994). doi:10.1515/zna-1994-1-238
Yamada, K., Isobe, K., Tsuyama, E., Okuda, T., Furukawa, Y.: Chloride ion conductor CH3NH3GeCl3 studied by Rietveld analysis of X-ray diffraction and 35Cl NMR. Solid State Ionics 79, 152–157 (1995). doi:10.1016/0167-2738(95)00055-B
Yamada, K., Kuranaga, Y., Ueda, K., Goto, S.: Phase transition and electric conductivity of ASnCl3 (A = Cs and CH3NH3). Bull. Chem. Soc. Japan 71, 127-127 (1998). doi:10.1246/bcsj.71.127
Yamada, K., Matsui, T., Tsuritani, T., Okuda, T., Ichiba, S.: 127I-NQR, 119 Sn Mössbauer effect, and electrical conductivity of MSnI3 (M = K, NH4, Rb, Cs, and CH3NH3). Z. Naturforsch. A 45(3–4), 307–312 (1990). doi:10.1515/zna-1990-3-416
Mizusaki, J., Arai, K., Fueki, K.: Ionic conduction of the perovskite-type halides. Solid State Ionics 11, 203–211 (1983). doi:10.1016/0167-2738(83)90025-5
Hoshino, H., Yamazaki, M., Nakamura, Y., Shimoji, M.: Ionic conductivity of lead chloride crystals. J. Phys. Soc. Jpn. 26(6), 1422–1426 (1969). doi:10.1143/JPSJ.26.1422
Hoshino, H., Yokose, S., Shimoji, M.: Ionic conductivity of lead bromide crystals. J. Solid State Chem. 7(1), 1–6 (1973). doi:10.1016/0022-4596(73)90113-8
Dualeh, A., Moehl, T., Tétreault, N., Teuscher, J., Gao, P., Nazeeruddin, M.K., Grätzel, M.: Impedance spectroscopic analysis of lead iodide perovskite-sensitized solid-state solar cells. ACS Nano 8(1), 362–373 (2013). doi:10.1021/nn404323g
Xiao, Z., Yuan, Y., Shao, Y., Wang, Q., Dong, Q., Bi, C., Sharma, P., Gruverman, A., Huang, J.: Giant switchable photovoltaic effect in organometal trihalide perovskite devices. Nat. Mater. 14, 193–198 (2014). doi:10.1038/nmat4150
Zhao, Y., Liang, C., Zhang, H.M., Li, D., Tian, D., Li, G., Jing, X., Zhang, W., Xiao, W., Liu, Q., Zhang, F., He, Z.: Anomalously large interface charge in polarity-switchable photovoltaic devices: an indication of mobile ions in organic-inorganic halide perovskites. Energy Environ. Sci. 8, 1256–1260 (2015). doi:10.1039/C4EE04064C
Chen, B., Yang, M., Zheng, X., Wu, C., Li, W., Yan, Y., Bisquert, J., Garcia-Belmonte, G., Zhu, K., Priya, S.: Impact of capacitive effect and ion migration on the hysteretic behavior of perovskite solar cells. J. Phys. Chem. Lett. 6(23), 4693–4700 (2015). doi:10.1021/acs.jpclett.5b02229
Yuan, Y., Chae, J., Shao, Y., Wang, Q., Xiao, Z., Centrone, A., Huang, J.: Photovoltaic switching mechanism in lateral structure hybrid perovskite solar cells. Adv. Energy Mater. (JUNE), n/a-n/a (2015). doi:10.1002/aenm.201500615
Leijtens, T., Hoke, E.T., Grancini, G., Slotcavage, D.J., Eperon, G.E., Ball, J.M., De Bastiani, M., Bowring, A.R., Martino, N., Wojciechowski, K., McGehee, M.D., Snaith, H.J., Petrozza, A.: Mapping electric field-induced switchable poling and structural degradation in hybrid lead halide perovskite thin films. Adv. Energy Mater. 5, 1500962 (2015). doi:10.1002/aenm.201500962
Bag, M., Renna, L.a., Adhikari, R., Karak, S., Liu, F., Lahti, P.M., Russell, T.P., Tuominen, M.T., Venkataraman, D.: Kinetics of ion transport in perovskite active layers and its implications for active layer stability. J. Am. Chem. Soc. 137(40), 13130–13137 (2015). doi:10.1021/jacs.5b08535
Yin, W.-J., Shi, T., Yan, Y.: Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber. Appl. Phys. Lett. 104(6), 063903 (2014). doi:10.1063/1.4864778
Buin, A., Pietsch, P., Voznyy, O., Comin, R.: Materials processing routes to trap-free halide perovskites. Nano Lett. 14(11), 6281–6286 (2014). doi:10.1021/nl502612m
Agiorgousis, M.L., Sun, Y.-Y., Zeng, H., Zhang, S.: Strong Covalency-induced recombination centers in perovskite solar cell material CH3NH3PbI3. J. Am. Chem. Soc. 136(41), 14570–14575 (2014). doi:10.1021/ja5079305
Walsh, A., Scanlon, D.O., Chen, S., Gong, X.G., Wei, S.-H.: Self-Regulation mechanism for charged point defects in hybrid halide perovskites. Angew. Chem. Int. Ed. 54(6), 1791–1794 (2015). doi:10.1002/anie.201409740
Kim, J., Lee, S.-H., Lee, J.H., Hong, K.-H.: The role of intrinsic defects in methylammonium lead iodide perovskite. J. Phys. Chem. Lett. 5(8), 1312–1317 (2014). doi:10.1021/jz500370k
Eames, C., Frost, J.M., Barnes, P.R.F., Oregan, B.C., Walsh, A., Islam, M.S.: Ionic transport in hybrid lead iodide perovskite solar cells. Nat Commun. 6 (2015). doi:10.1038/ncomms8497
Haruyama, J., Sodeyama, K., Han, L., Tateyama, Y.: First-principles study of ion diffusion in perovskite solar cell sensitizers. J. Am. Chem. Soc. 137, 10048–10051 (2015). doi:10.1021/jacs.5b03615
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(7), 2118–2127 (2015). doi:10.1039/C5EE01265A
Yokota, I.: On the electrical conductivity of cuprous sulfide: a diffusion theory. J. Phys. Soc. Jpn. 8(5), 595–602 (1953). doi:10.1143/JPSJ.8.595
Yokota, I.: On the theory of mixed conduction with special reference to conduction in silver sulfide group semiconductors. J. Phys. Soc. Jpn. 16(11), 2213–2223 (1961). doi:10.1143/JPSJ.16.2213
Maier, J.: Solid state electrochemistry ii: devices and techniques. In: Vayenas, C., White, R.E., Gambpa-Aldeco, M.E. (eds.) Modern aspects of electrochemistry, vol. 41. pp. 1−128. Springer, New York (2007)
Maier, J.: Evaluation of electrochemical methods in solid state research and their generalization for defects with variable charges. Z. Phys. Chem. Neue Fol. 140, 191–215 (1984). doi:10.1524/zpch.1984.140.2.191
Jamnik, J., Maier, J., Pejovnik, S.: A powerful electrical network model for the impedance of mixed conductors. Electrochim. Acta 44(24), 4139–4145 (1999). doi:10.1016/S0013-4686(99)00128-0
Jamnik, J., Maier, J.: Generalised equivalent circuits for mass and charge transport: chemical capacitance and its implications. Phys. Chem. Chem. Phys. 3(9), 1668–1678 (2001). doi:10.1039/B100180I
Brivio, F., Walker, A.B., Walsh, A.: Structural and electronic properties of hybrid perovskites for high-efficiency thin-film photovoltaics from first-principles. APL Mater. 1(4), 042111 (2013). doi:10.1063/1.4824147
Knop, O., Wasylishen, R.E., White, M.A., Cameron, T.S.: Oort, M.J.v.: Alkylammonium lead halides. Part 2. CH3NH3PbX3 (X = Cl, Br, I) perovskites: cuboctahedral halide cages with isotropic cation reorientation. Can. J. Chem. 68(3), 412–422 (1990). doi:10.1139/v90-063
Maier, J.: Physical chemistry of ionic materials. WILEY, Chichester (2004)
Mitzi, D.B.: Templating and structural engineering in organic-inorganic perovskites. J. Chem. Soc. Dalton Trans. (1), 1−12 (2001). doi:10.1039/B007070J
Du, M.H.: Efficient carrier transport in halide perovskites: theoretical perspectives. J. Mater. Chem. A 2(24), 9091–9098 (2014). doi:10.1039/C4TA01198H
Duan, H.S., Zhou, H., Chen, Q., Sun, P., Luo, S., Song, T.B., Bob, B., Yang, Y.: The identification and characterization of defect states in hybrid organic-inorganic perovskite photovoltaics. Phys. Chem. Chem. Phys. 17(1), 112–116 (2015). doi:10.1039/c4cp04479g
Samiee, M., Konduri, S., Ganapathy, B., Kottokkaran, R., Abbas, H.A., Kitahara, A., Joshi, P., Zhang, L., Noack, M., Dalal, V.: Defect density and dielectric constant in perovskite solar cells. Appl. Phys. Lett. 105(15), 153502 (2014). doi:10.1063/1.4897329
Maier, J.: Mass transport in the presence of internal defect reactions—concept of conservative ensembles: i, chemical diffusion in pure compounds. J. Am. Ceram. Soc. 76(5), 1212–1217 (1993). doi:10.1111/j.1151-2916.1993.tb03743.x
Maier, J., Amin, R.: Defect chemistry of LiFePO4. J. Electrochem. Soc. 155(4), A339–A344 (2008). doi:10.1149/1.2839626
Maier, J.: Electrochemical investigation methods of ionic transport properties in solids. Solid State Phenom. 39(40), 35–60 (1994). doi:10.4028/www.scientific.net/SSP.39-40.35
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2016 Springer International Publishing Switzerland
About this chapter
Cite this chapter
Gregori, G., Yang, TY., Senocrate, A., Grätzel, M., Maier, J. (2016). Ionic Conductivity of Organic–Inorganic Perovskites: Relevance for Long-Time and Low Frequency Behavior. In: Park, NG., Grätzel, M., Miyasaka, T. (eds) Organic-Inorganic Halide Perovskite Photovoltaics. Springer, Cham. https://doi.org/10.1007/978-3-319-35114-8_5
Download citation
DOI: https://doi.org/10.1007/978-3-319-35114-8_5
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-35112-4
Online ISBN: 978-3-319-35114-8
eBook Packages: EnergyEnergy (R0)