Efficient and stable tin-based perovskite solar cells by introducing π-conjugated Lewis base

More info
  • ReceivedAug 30, 2019
  • AcceptedNov 8, 2019
  • PublishedDec 11, 2019


Tin-based perovskite solar cells (TPSCs) as the most promising candidate for lead-free PSCs have incurred extensive researches all over the world. However, the crystallization process of tin-based perovskite is too fast during the solution-deposited process, resulting in abundant pinholes and poor homogeneity that cause serious charge recombination in perovskite layer. Here, we employed the π-conjugated Lewis base molecules with high electron density to systematically control the crystallization rate of FASnI3 perovskite by forming stable intermediate phase with the Sn-I frameworks, leading to a compact and uniform perovskite film with large increase in the carrier lifetime. Meanwhile, the introduction of the π-conjugated systems also retards the permeation of moisture into perovskite crystal, which significantly suppresses the film degradation in air. These benefits contributed to a stabilizing power conversion efficiency (PCE) of 10.1% for the TPSCs and maintained over 90% of its initial PCE after 1000-h light soaking in air. Also, a steady-state efficiency of 9.2% was certified at the accredited test center.

Funded by

the National Natural Science Foundation of China(11574199,11674219,11834011)

and the Program for Professor of Special Appointment(Eastern,Scholar)

and the KAKEHI Grant of Japan(18H02078)


This work was supported by the National Natural Science Foundation of China (11574199, 11674219, 11834011), and the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning. The work performed at National Institute for Materials Science was supported by the New Energy and Industrial Technology Development Organization (NEDO, Japan), and the KAKEHI Grant of Japan (18H02078).

Interest statement

The authors declare that they have no conflict of interest.


The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


[1] Jiang Q, Zhao Y, Zhang X, Yang X, Chen Y, Chu Z, Ye Q, Li X, Yin Z, You J. Nat Photon, 2019, 13: 460-466 CrossRef Google Scholar

[2] Hao F, Stoumpos CC, Cao DH, Chang RPH, Kanatzidis MG. Nat Photon, 2014, 8: 489-494 CrossRef Google Scholar

[3] Kumar MH, Dharani S, Leong WL, Boix PP, Prabhakar RR, Baikie T, Shi C, Ding H, Ramesh R, Asta M, Graetzel M, Mhaisalkar SG, Mathews N. Adv Mater, 2014, 26: 7122-7127 CrossRef PubMed Google Scholar

[4] Krishnamoorthy T, Ding H, Yan C, Leong WL, Baikie T, Zhang Z, Sherburne M, Li S, Asta M, Mathews N, Mhaisalkar SG. J Mater Chem A, 2015, 3: 23829-23832 CrossRef Google Scholar

[5] Saparov B, Hong F, Sun JP, Duan HS, Meng W, Cameron S, Hill IG, Yan Y, Mitzi DB. Chem Mater, 2015, 27: 5622-5632 CrossRef Google Scholar

[6] Song TB, Yokoyama T, Aramaki S, Kanatzidis MG. ACS Energy Lett, 2017, 2: 897-903 CrossRef Google Scholar

[7] Cortecchia D, Dewi HA, Yin J, Bruno A, Chen S, Baikie T, Boix PP, Grätzel M, Mhaisalkar S, Soci C, Mathews N. Inorg Chem, 2016, 55: 1044-1052 CrossRef PubMed Google Scholar

[8] Shao Z, Le Mercier T, Madec MB, Pauporté T. Mater Des, 2018, 141: 81-87 CrossRef Google Scholar

[9] Noel NK, Stranks SD, Abate A, Wehrenfennig C, Guarnera S, Haghighirad AA, Sadhanala A, Eperon GE, Pathak SK, Johnston MB, Petrozza A, Herz LM, Snaith HJ. Energy Environ Sci, 2014, 7: 3061-3068 CrossRef Google Scholar

[10] Lee SJ, Shin SS, Kim YC, Kim D, Ahn TK, Noh JH, Seo J, Seok SI. J Am Chem Soc, 2016, 138: 3974-3977 CrossRef PubMed Google Scholar

[11] Liao W, Zhao D, Yu Y, Grice CR, Wang C, Cimaroli AJ, Schulz P, Meng W, Zhu K, Xiong RG, Yan Y. Adv Mater, 2016, 28: 9333-9340 CrossRef PubMed Google Scholar

[12] Zhao Z, Gu F, Li Y, Sun W, Ye S, Rao H, Liu Z, Bian Z, Huang C. Adv Sci, 2017, 4: 1700204 CrossRef PubMed Google Scholar

[13] Liu X, Wang Y, Xie F, Yang X, Han L. ACS Energy Lett, 2018, 3: 1116-1121 CrossRef Google Scholar

[14] Marshall KP, Walker M, Walton RI, Hatton RA. Nat Energy, 2016, 1: 16178 CrossRef Google Scholar

[15] Hao F, Stoumpos CC, Guo P, Zhou N, Marks TJ, Chang RPH, Kanatzidis MG. J Am Chem Soc, 2015, 137: 11445-11452 CrossRef PubMed Google Scholar

[16] Wang F, Jiang X, Chen H, Shang Y, Liu H, Wei J, Zhou W, He H, Liu W, Ning Z. Joule, 2018, 2: 2732-2743 CrossRef Google Scholar

[17] Liao Y, Liu H, Zhou W, Yang D, Shang Y, Shi Z, Li B, Jiang X, Zhang L, Quan LN, Quintero-Bermudez R, Sutherland BR, Mi Q, Sargent EH, Ning Z. J Am Chem Soc, 2017, 139: 6693-6699 CrossRef PubMed Google Scholar

[18] Cao DH, Stoumpos CC, Yokoyama T, Logsdon JL, Song TB, Farha OK, Wasielewski MR, Hupp JT, Kanatzidis MG. ACS Energy Lett, 2017, 2: 982-990 CrossRef Google Scholar

[19] Shao S, Liu J, Portale G, Fang HH, Blake GR, ten Brink GH, Koster LJA, Loi MA. Adv Energy Mater, 2018, 8: 1702019 CrossRef Google Scholar

[20] Jokar E, Chien CH, Fathi A, Rameez M, Chang YH, Diau EWG. Energy Environ Sci, 2018, 11: 2353-2362 CrossRef Google Scholar

[21] Jokar E, Chien CH, Tsai CM, Fathi A, Diau EWG. Adv Mater, 2019, 31: 1804835 CrossRef PubMed Google Scholar

[22] Lin Y, Shen L, Dai J, Deng Y, Wu Y, Bai Y, Zheng X, Wang J, Fang Y, Wei H, Ma W, Zeng XC, Zhan X, Huang J. Adv Mater, 2017, 29: 1604545 CrossRef PubMed Google Scholar

[23] Wu T, Wang Y, Li X, Wu Y, Meng X, Cui D, Yang X, Han L. Adv Energy Mater, 2019, 9: 1803766 CrossRef Google Scholar

[24] Wu Y, Zhu W. Chem Soc Rev, 2013, 42: 2039-2058 CrossRef PubMed Google Scholar

[25] Han L, Islam A, Chen H, Malapaka C, Chiranjeevi B, Zhang S, Yang X, Yanagida M. Energy Environ Sci, 2012, 5: 6057-6060 CrossRef Google Scholar

[26] Wu T, Wang Y, Dai Z, Cui D, Wang T, Meng X, Bi E, Yang X, Han L. Adv Mater, 2019, 2: 1900605 CrossRef PubMed Google Scholar

[27] Li N, Tao S, Chen Y, Niu X, Onwudinanti CK, Hu C, Qiu Z, Xu Z, Zheng G, Wang L, Zhang Y, Li L, Liu H, Lun Y, Hong J, Wang X, Liu Y, Xie H, Gao Y, Bai Y, Yang S, Brocks G, Chen Q, Zhou H. Nat Energy, 2019, 4: 408-415 CrossRef Google Scholar

[28] Liang M, Chen J. Chem Soc Rev, 2013, 42: 3453-3488 CrossRef PubMed Google Scholar

[29] El-Mellouhi F, Marzouk A, Bentria ET, Rashkeev SN, Kais S, Alharbi FH. ChemSusChem, 2016, 9: 2648-2655 CrossRef PubMed Google Scholar

[30] Ellis H, Eriksson SK, Feldt SM, Gabrielsson E, Lohse PW, Lindblad R, Sun L, Rensmo H, Boschloo G, Hagfeldt A. J Phys Chem C, 2013, 117: 21029-21036 CrossRef Google Scholar

[31] de Quilettes DW, Vorpahl SM, Stranks SD, Nagaoka H, Eperon GE, Ziffer ME, Snaith HJ, Ginger DS. Science, 2015, 348: 683-686 CrossRef PubMed Google Scholar

[32] Song TB, Yokoyama T, Stoumpos CC, Logsdon J, Cao DH, Wasielewski MR, Aramaki S, Kanatzidis MG. J Am Chem Soc, 2017, 139: 836-842 CrossRef PubMed Google Scholar

[33] Tai Q, Guo X, Tang G, You P, Ng TW, Shen D, Cao J, Liu CK, Wang N, Zhu Y, Lee CS, Yan F. Angew Chem Int Ed, 2019, 58: 806-810 CrossRef PubMed Google Scholar

[34] Lee SJ, Shin SS, Im J, Ahn TK, Noh JH, Jeon NJ, Seok SI, Seo J. ACS Energy Lett, 2018, 3: 46-53 CrossRef Google Scholar

[35] Wang F, Ma J, Xie F, Li L, Chen J, Fan J, Zhao N. Adv Funct Mater, 2016, 26: 3417-3423 CrossRef Google Scholar

[36] Kayesh ME, Matsuishi K, Kaneko R, Kazaoui S, Lee JJ, Noda T, Islam A. ACS Energy Lett, 2019, 4: 278-284 CrossRef Google Scholar

[37] Yuan Y, Huang J. Acc Chem Res, 2016, 49: 286-293 CrossRef PubMed Google Scholar

[38] Cai M, Ishida N, Li X, Yang X, Noda T, Wu Y, Xie F, Naito H, Fujita D, Han L. Joule, 2018, 2: 296-306 CrossRef Google Scholar

[39] Wang K, Jin Z, Liang L, Bian H, Wang H, Feng J, Wang Q, Liu SF. Nano Energy, 2019, 58: 175-182 CrossRef Google Scholar

[40] Shao Y, Xiao Z, Bi C, Yuan Y, Huang J. Nat Commun, 2014, 5: 5784 CrossRef PubMed Google Scholar

[41] Zheng X, Chen B, Dai J, Fang Y, Bai Y, Lin Y, Wei H, Zeng XC, Huang J. Nat Energy, 2017, 2: 17102 CrossRef Google Scholar

  • Figure 1

    Crystallization-controlling mechanism of the π-conjugated Lewis base. (a) Chemical structures of the CTA-F, CTA-OMe, and CDTA molecules. (b) XRD patterns of the as-prepared FASnI3 perovskite films treated with different π-conjugated Lewis base molecules without thermal annealing. The insets showed the photograph of corresponding films. (c) XRD patterns of the perovskite films after annealing at 100 °C for 10 min. The diffraction peaks indicated by # represent the Bragg reflections were associated with the ITO substrate. (d) Schematic illustration of the nucleation and crystallization process of the FASnI3 and CDTA-treated FASnI3 films (color online).

  • Figure 2

    Impact of π-conjugated Lewis base on the morphology and photoelectric property of FASnI3 perovskite film. (a) The top morphologies of FASnI3 film and (b) the film treated by CDTA with a concentration of 0.2%. (c) Time-resolved PL spectrums of the corresponding perovskite films. (d, e) Two-dimensional PL mapping by the confocal-fluorescence spectroscopy. The scale bar is 20 μm in the images. (f, g) Linear distribution of the PL intensity is derived from the two-dimensional PL mapping profile. All the samples for PL measurement were deposited on the bare glass (color online).

  • Figure 3

    Stability measurement of Sn-based perovskite films. (a, b) XPS Sn 3d spectrum of the corresponding perovskite films exposed to air for different time. The relative humidity was controlled at around 50%. (c, d) Static contact angle measurements with water on top of the FASnI3 and CDTA-treated FASnI3 films. (e) Atomic ration of the Sn4+ component derived from XPS Sn 3d spectrum as a function of air exposed time. (f, g) Normalized XRD patterns of the corresponding perovskite films exposed to air for different time. The reflections indicated by asterisk represent the Bragg reflections associated with oxidized FASnI3 (color online).

  • Figure 4

    Characterization of the perovskite solar cells. (a) Device configuration of the TPSCs. (b) J-V plots of the best devices based on control and CDTA-treated samples measured under forward scan. The device active area is 0.09 cm2. (c) Internal photon-to-current efficiency (IPCE) of the devices. (d) 1000-min continuous output of the devices measured under the maximum power point (MPPT). (e) Mott-Schottky analysis of the control and CDTA-treated TPSCs. (f) The stability test of TPSCs under light soaking (AM 1.5 G, 100 mW cm−2) in air with a relative humidity of 30%. All the cells that went through the aging test were encapsulated (color online).

Copyright 2020  CHINA SCIENCE PUBLISHING & MEDIA LTD.  中国科技出版传媒股份有限公司  版权所有

京ICP备14028887号-23       京公网安备11010102003388号