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Electronic Materials Letters

, Volume 15, Issue 2, pp 192–200 | Cite as

Uniform Cs2SnI6 Thin Films for Lead-Free and Stable Perovskite Optoelectronics via Hybrid Deposition Approaches

  • Byungho Lee
  • Byungha ShinEmail author
  • Byungwoo ParkEmail author
Original Article - Energy and Sustainability

Abstract

Herein, we synthesized uniform Cs2SnI6 films by two kinds of hybrid deposition methods by considering volume expansion involved during phase transformations. First, oblique thermal evaporation for CsI followed by SnI4 spin-coating resulted in uniform Cs2SnI6 films free of impurity phases. The rapid expansion (within 10 s of spin-coating) from CsI to Cs2SnI6\((\Delta V = 106\% )\) was accommodated by porous CsI films inhibiting crack formation. Excess SnI4 on the Cs2SnI6 after spin-coating was effectively removed by toluene washing without any damages to Cs2SnI6, and optimum deposition parameters were suggested in terms of carrier mobility. Second, annealing CsI with SnI4 vapor at 250 °C and post-annealing in the SnI4 and I2 vapor at 300 °C produced Cs2SnI6 film with complete coverage. The slow reaction (70 min for a complete conversion) provided sufficient time for complete diffusion of SnI4 into CsI without crack formation even with compact CsI. The nonradiative recombination path in Cs2SnI6 was suppressed by post-annealing in the SnI4- and I2-atmosphere, as confirmed from the enhanced photoluminescence.

Graphical Abstract

Keywords

Lead-free perovskite Cs2SnI6 Oblique thermal deposition Electrical mobility 

Notes

Acknowledgements

This work is supported by the National Research Foundation of Korea (NRF: 2016R1A2B4012938) and Korea Institute of Energy Technology Evaluation and Planning (KETEP: 20183010014470).

References

  1. 1.
    Hwang, T., Lee, B., Kim, J., Lee, S., Gil, B., Yun, A.J., Park, B.: From nanostructural evolution to dynamic interplay of constituents: perspectives for perovskite solar cells. Adv. Mater. 30, 1704208 (2018)CrossRefGoogle Scholar
  2. 2.
    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, 897 (2014)CrossRefGoogle Scholar
  3. 3.
    Kim, J., Hwang, T., Lee, S., Lee, B., Kim, J., Jang, G.S., Nam, S., Park, B.: Solvent and intermediate phase as boosters for the perovskite transformation and solar cell performance. Sci. Rep. 6, 25648 (2016)CrossRefGoogle Scholar
  4. 4.
    Hwang, T., Cho, D., Kim, J., Kim, J., Lee, S., Lee, B., Kim, K.H., Hong, S., Kim, C., Park, B.: Investigation of chlorine-mediated microstructural evolution of CH3NH3PbI3(Cl) grains for high optoelectronic responses. Nano Energy 25, 91 (2016)CrossRefGoogle Scholar
  5. 5.
    Lee, B., Lee, S., Cho, D., Kim, J., Hwang, T., Kim, K.H., Hong, S., Moon, T., Park, B.: Evaluating the optoelectronic quality of hybrid perovskites by conductive atomic force microscopy with noise spectroscopy. ACS Appl. Mater. Interfaces 8, 30985 (2016)CrossRefGoogle Scholar
  6. 6.
    Hwang, T., Lee, S., Kim, J., Kim, J., Kim, C., Shin, B., Park, B.: Tailoring the mesoscopic TiO2 layer: concomitant parameters for enabling high-performance perovskite solar cells. Nanoscale Res. Lett. 12, 57 (2017)CrossRefGoogle Scholar
  7. 7.
    Kim, J., Hwang, T., Lee, S., Lee, B., Kim, J., Kim, J., Gil, B., Park, B.: Synergetic effect of double-step blocking layer for the perovskite solar cell. J. Appl. Phys. 122, 145106 (2017)CrossRefGoogle Scholar
  8. 8.
    Shin, G.S., Choi, W.-G., Na, S., Gökdemir, F.P., Moon, T.: Lead acetate based hybrid perovskite through hot casting for planar heterojunction solar cells. Electron. Mater. Lett. 14, 155 (2018)CrossRefGoogle Scholar
  9. 9.
    Cho, D., Hwang, T., Cho, D.-G., Park, B., Hong, S.: Photoconductive noise microscopy revealing quantitative effect of localized electronic traps on the perovskite-based solar cell performance. Nano Energy 43, 29 (2018)CrossRefGoogle Scholar
  10. 10.
    Kim, J., Hwang, T., Lee, B., Lee, S., Park, K., Park, H.H., Park, B.: An aromatic diamine molecule as the A-site solute for highly durable and efficient perovskite solar cells. Small Method (2018).  https://doi.org/10.1002/smtd.201800361 Google Scholar
  11. 11.
    Jo, J.W., Yoo, Y., Jeong, T., Ahn, S., Ko, M.J.: Low-temperature processable charge transporting materials for the flexible perovskite solar cells. Electron. Mater. Lett. 14, 657 (2018)CrossRefGoogle Scholar
  12. 12.
    Shin, G.S., Choi, W.-G., Na, S., Ryu, S.O., Moon, T.: Rapid crystallization in ambient air for planar heterojunction perovskite solar cells. Electron. Mater. Lett. 13, 72 (2017)CrossRefGoogle Scholar
  13. 13.
    Jeon, N.J., Na, H., Jung, E.H., Yang, T.-Y., Lee, Y.G., Kim, G., Shin, H.-W., Seok, S.I., Lee, J., Seo, J.: A fluorene-terminated hole-transporting material for highly efficient and stable perovskite solar cells. Nat. Energy 3, 682 (2018)CrossRefGoogle Scholar
  14. 14.
    Lee, S.-Y., Choi, H., Li, H., Ji, K., Nam, S., Choi, J., Ahn, S.-W., Lee, H.-M., Park, B.: Analysis of a-Si:H/TCO contact resistance for the Si heterojunction back-contact solar cell. Sol. Energy Mater. Sol. Cells 120, 412 (2014)CrossRefGoogle Scholar
  15. 15.
    Tunuguntla, V., Chen, W.-C., Newman, T.D., Chen, C.-Y., Hsieh, M.-C., Lu, S.-H., Su, C., Chen, L.-C., Chen, K.-H.: Enhancement of charge collection at shorter wavelengths from alternative CdS deposition conditions for high efficiency CZTSSe solar cells. Sol. Energy Mater. Sol. Cells 149, 49 (2016)CrossRefGoogle Scholar
  16. 16.
    Lee, S., Flanagan, J.C., Lee, B., Hwang, T., Kim, J., Gil, B., Shim, M., Park, B.: Route to improving photovoltaics based on CdSe/CdSexTe1−x type-II heterojunction nanorods: the effect of morphology and cosensitization on carrier recombination and transport. ACS Appl. Mater. Interfaces 9, 31931 (2017)CrossRefGoogle Scholar
  17. 17.
    Kim, J., Shin, B.: Strategies to reduce the open-circuit voltage deficit in Cu2ZnSn(S, Se)4 thin film solar cells. Electron. Mater. Lett. 13, 373 (2017)CrossRefGoogle Scholar
  18. 18.
    Yang, S., Fu, W., Zhang, Z., Chen, H., Li, C.-Z.: Recent advances in perovskite solar cells: efficiency, stability and lead-free perovskite. J. Mater. Chem. A 5, 11462 (2017)CrossRefGoogle Scholar
  19. 19.
    Noel, N.K., Stranks, S.D., Abate, A., Wehrenfennig, C., Guarnera, S., Haghighirad, A.-A., Sadhanala, A., Eperon, G.E., Pathak, S.K., Johnston, M.B., Petrozza, A., Herz, L.M., Snaith, H.J.: Lead-free organic–inorganic tin halide perovskites for photovoltaic applications. Energy Environ. Sci. 7, 3061 (2014)CrossRefGoogle Scholar
  20. 20.
    Kumar, M.H., Dharani, S., Leong, W.L., Boix, P.P., Prabhakar, R.R., Baikie, T., Shi, C., Ding, H., Ramesh, R., Asta, M., Graetzel, M., Mhaisalkar, S.G., Mathews, N.: Lead-free halide perovskite solar cells with high photocurrents realized through vacancy modulation. Adv. Mater. 26, 7122 (2014)CrossRefGoogle Scholar
  21. 21.
    Shao, S., Liu, J., Portale, G., Fang, H.-H., Blake, G.R., Brink, G.H.T., Koster, L.J.A., Loi, M.A.: Highly reproducible Sn-based hybrid perovskite solar cells with 9% efficiency. Adv. Energy Mater. 8, 1702019 (2018)CrossRefGoogle Scholar
  22. 22.
    Hao, F., Stoumpos, C.C., Cao, D.H., Chang, R.P.H., Kanatzidis, M.G.: Lead-free solid-state organic–inorganic halide perovskite solar cells. Nat. Photonics 8, 489 (2014)CrossRefGoogle Scholar
  23. 23.
    Qiu, X., Cao, B., Yuan, S., Chen, X., Qiu, Z., Jiang, Y., Ye, Q., Wang, H., Zeng, H., Liu, J., Kanatzidis, M.G.: From unstable CsSnI3 to air-stable Cs2SnI6: a lead-free perovskite solar cell light absorber with bandgap of 1.48 eV and high absorption coefficient. Sol. Energy Mater. Sol. Cells 159, 227 (2017)CrossRefGoogle Scholar
  24. 24.
    Giustino, F., Snaith, H.J.: Toward lead-free perovskite solar cells. ACS Energy Lett. 1, 1233 (2016)CrossRefGoogle Scholar
  25. 25.
    Saparov, B., Sun, J.-P., Meng, W., Xiao, Z., Duan, H.-S., Gunawan, O., Shin, D., Hill, I.G., Yan, Y., Mitzi, D.B.: Thin-film deposition and characterization of a Sn-deficient perovskite derivative Cs2SnI6. Chem. Mater. 28, 2315 (2016)CrossRefGoogle Scholar
  26. 26.
    Kapil, G., Ohta, T., Koyanagi, T., Vigneshwaran, M., Zhang, Y., Ogomi, Y., Pandey, S.S., Yoshino, K., Shen, Q., Toyoda, T., Rahman, M.M., Minemoto, T., Murakami, T.N., Segawa, H., Hayase, S.: Investigation of interfacial charge transfer in solution processed Cs2SnI6 thin films. J. Phys. Chem. C 121, 13092 (2017)CrossRefGoogle Scholar
  27. 27.
    Lee, B., Krenselewski, A., Baik, S.I., Seidmana, D.N., Chang, R.P.H.: Solution processing of air-stable molecular semiconducting iodosalts, Cs2SnI6−xBrx, for potential solar cell applications. Sustain. Energy Fuels 1, 710 (2017)CrossRefGoogle Scholar
  28. 28.
    Lee, B., Stoumpos, C.C., Zhou, N., Hao, F., Malliakas, C., Yeh, C.-Y., Marks, T.J., Kanatzidis, M.G., Chang, R.P.H.: Air-stable molecular semiconducting iodosalts for solar cell applications: Cs2SnI6 as a hole conductor. J. Am. Chem. Soc. 136, 15379 (2014)CrossRefGoogle Scholar
  29. 29.
    Maughan, A.E., Ganose, A.M., Bordelon, M.M., Miller, E.M., Scanlon, D.O., Neilson, J.R.: Defect tolerance to intolerance in the vacancy-ordered double perovskite semiconductors Cs2SnI6 and Cs2TeI6. J. Am. Chem. Soc. 138, 8453 (2016)CrossRefGoogle Scholar
  30. 30.
    Guo, F., Lu, Z., Mohanty, D., Wang, T., Bhat, I.B., Zhang, S., Shi, S., Washington, M.A., Wang, G.-C., Lu, T.-M.: A two-step dry process for Cs2SnI6 perovskite thin film. Mater. Res. Lett. 5, 540 (2017)CrossRefGoogle Scholar
  31. 31.
    Kanatzidis, M.G., Chang, R.P.H., Stoumpos, K., Lee, B.: US Pat., US 20160211083 A1, Northwestern University (2016)Google Scholar
  32. 32.
    Plawsky, J.L., Kim, J.K., Schubert, E.F.: Engineered nanoporous and nanostructured films. Mater. Today 12, 36 (2009)CrossRefGoogle Scholar
  33. 33.
    Dimesso, L., Das, C., Stöhr, M., Mayer, T., Jaegermann, W.: Properties of cesium tin iodide (Cs-Sn-I) systems after annealing under different atmospheres. Mater. Chem. Phys. 197, 27 (2017)CrossRefGoogle Scholar
  34. 34.
    Ungureanu, A.-M., Oprea, O., Vasile, B.S., Andronescu, C., Voicu, G., Jitaru, I.: Temperature effect over structure and photochemical properties of nanostructured SnO2 powders. Cent. Eur. J. Chem. 12, 909 (2014)CrossRefGoogle Scholar
  35. 35.
    Ansari, S.G., Fouad, H., Shin, H.-S., Ansari, Z.A.: Electrochemical enzyme-less urea sensor based on nano-tin oxide synthesized by hydrothermal technique. Chem. Biol. Interact. 242, 45 (2015)CrossRefGoogle Scholar
  36. 36.
    Yuanda, W., Maosong, T., Xiuli, H., Yushu, Z., Guorui, D.: Thin film sensors of SnO2-CuO-SnO2 sandwich structure to H2S. Sens. Actuator B Chem. 79, 187 (2001)CrossRefGoogle Scholar
  37. 37.
    Kim, J., Choi, H., Nahm, C., Kim, C., Nam, S., Kang, S., Jung, D.-R., Kim, J.I., Kang, J., Park, B.: The role of a TiCl4 treatment on the performance of CdS quantum-dot-sensitized solar cells. J. Power Sources 220, 108 (2012)CrossRefGoogle Scholar
  38. 38.
    Lee, W., Kim, H., Jung, D.-R., Kim, J., Nahm, C., Lee, J., Kang, S., Lee, B., Park, B.: An effective oxidation approach for luminescence enhancement in CdS quantum dots by H2O2. Nanoscale Res. Lett. 7, 672 (2012)CrossRefGoogle Scholar
  39. 39.
    Kim, T., Oh, J., Park, B., Hong, K.S.: Correlation between strain and dielectric properties in ZrTiO4 thin films. Appl. Phys. Lett. 76, 3043 (2000)CrossRefGoogle Scholar
  40. 40.
    Xiao, Z., Zhou, Y., Hosono, H., Kamiya, T.: Intrinsic defects in a photovoltaic perovskite variant Cs2SnI6. Phys. Chem. Chem. Phys. 17, 18900 (2015)CrossRefGoogle Scholar
  41. 41.
    Kim, J.I., Kim, J., Lee, J., Jung, D.-R., Kim, H., Choi, H., Lee, S., Byun, S., Kang, S., Park, B.: Photoluminescence enhancement in CdS quantum dots by thermal annealing. Nanoscale Res. Lett. 7, 482 (2012)CrossRefGoogle Scholar
  42. 42.
    Jung, D.-R., Kim, J., Park, B.: Surface-passivation effects on the photoluminescence enhancement in ZnS: Mn nanoparticles by ultraviolet irradiation with oxygen bubbling. Appl. Phys. Lett. 96, 211908 (2010)CrossRefGoogle Scholar
  43. 43.
    Jung, D.-R., Son, D., Kim, J., Kim, C., Park, B.: Highly luminescent surface-passivated ZnS: Mn nanoparticles by a simple one-step synthesis. Appl. Phys. Lett. 93, 163118 (2008)CrossRefGoogle Scholar

Copyright information

© The Korean Institute of Metals and Materials 2019

Authors and Affiliations

  1. 1.Department of Materials Science and Engineering, Research Institute of Advanced MaterialsSeoul National UniversitySeoulKorea
  2. 2.Department of Materials Science and EngineeringKorea Advanced Institute of Science and TechnologyDaejeonKorea

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