Journal of Materials Science

, Volume 54, Issue 18, pp 11818–11826 | Cite as

Solution-processed mixed halide CH3NH3PbI3−xClx thin films prepared by repeated dip coating

  • A. M. M. Tanveer Karim
  • M. S. Hossain
  • M. K. R. KhanEmail author
  • M. Kamruzzaman
  • M. Azizar Rahman
  • M. Mozibur Rahman
Chemical routes to materials


The mixed halide CH3NH3PbI3−xClx crystalline thin film has been prepared by two-step solution-processed repeated dip coating method at an ambient atmosphere. X-ray diffraction study reveals the presence of tetragonal and cubic phases in deposited film. Raman study confirms the metal halide bond in the inorganic framework and organic CH3 stretching/bending of C–H bond in CH3NH3PbI3−xClx perovskite. Scanning electron microscopy shows that cuboid and polyhedral-like crystal grains of 100 nm to 2 μm may find applications in optoelectronics. The perovskite CH3NH3PbI3−xClx thin film shows high spectral absorption coefficient of the order of 106 m−1. In optical band gap study, we found the coexistence of cubic and tetragonal perovskite phases. The energy band gap is dominated by cubic phase having Eg = 2.50 eV over tetragonal phase with band gap Eg = 1.67 eV. The room-temperature photoluminescence study confirms band edge, shallow and deep-level emissions. The temperature-dependent cathodoluminescence study shows red, green and ultraviolet emissions. The dominating green luminescence evolved for cubic phase at 2.51 eV. The red and ultraviolet emissions are also found for mixed-phase CH3NH3PbI3−xClx thin film, suitable for preparation of light-emitting devices.



Authors are thankful to the department of Glass and Ceramic Engineering, Rajshahi University of Engineering & Technology, Bangladesh, for providing XRD and SEM facilities. The authors are also grateful to the Department of Materials Science and Engineering, City University of Hong Kong, for providing Raman spectroscopy measurement. One of the authors M. Azizar Rahman acknowledges the financial support of Australian Government through the Research Training Program Scholarship.


  1. 1.
    Chen Q, De Marco N, Yang Y, Song TB, Chen CC, Zhao H, Hong Z, Zhou H, Yang Y (2015) Under the spotlight: the organic-inorganic hybrid halide perovskite for optoelectronic applications. Nano Today 10:355–396Google Scholar
  2. 2.
    Huang J, Xiang S, Yu J, Li C-Z (2019) Highly efficient prismatic perovskite solar cells. Energy Environ Sci 12:1265–1273Google Scholar
  3. 3.
    Nandi P, Giri C, Swain D, Manju U, Topwal D (2019) Room temperature growth of CH3NH3PbCl3 single crystals by solvent evaporation method. CrystEngComm 21:656–661Google Scholar
  4. 4.
    Zheng E, Yuh B, Tosado GA, Yu Q (2017) Solution-processed visible-blind UV-A photodetectors based on CH3NH3PbCl3 perovskite thin films. J Mater Chem C 5:3796–3806Google Scholar
  5. 5.
    Pang G, Lan X, Li R, He Z, Chen R (2019) Influence of mixed organic cations on the structural and optical properties of lead tri-iodide perovskites. Nanoscale 11:5215–5221Google Scholar
  6. 6.
    Ansari MIH, Qurashi A, Nazeeruddin MK (2018) Frontiers, opportunities and challenges in perovskite solar cells: a critical review. J Photochem Photobiol C 35:1–24Google Scholar
  7. 7.
    Xionga H, Zabihia F, Wanga H, Zhanga Q, Eslamian M (2018) Grain engineering by ultrasonic substrate vibration post treatment of wet perovskite films for annealing-free, high performance, and stable perovskite solar cells. Nanoscale 10:8526–8535Google Scholar
  8. 8.
    Yakunin S, Shynkarenko Y, Dirin DN, Cherniukh I, Kovalenko MV (2017) Non-dissipative internal optical filtering with solution-grown perovskite single crystals for full-colour imaging. NPG Asia Mater 9:e431Google Scholar
  9. 9.
    Chin S-H, Choi JW, Woo HC, Kim JH, Lee HS, Lee C-L (2019) Realizing a highly luminescent perovskite thin film by controlling the grain size and crystallinity through solvent vapour annealing. Nanoscale 11:5861–5867Google Scholar
  10. 10.
    Kim H, Zhao L, Price JS, Grede AJ, Roh K, Brigeman AN, Lopez M, Rand BP, Giebink NC (2018) Hybrid perovskite light emitting diodes under intense electrical excitation. Nat Commun 9:4893Google Scholar
  11. 11.
  12. 12.
    Stranks SD, Hoye RLZ, Di D, Friend RH, Deschler F (2018) The physics of light emission in halide perovskite devices. Adv Mater. Google Scholar
  13. 13.
    Ahmadian-Yazdi M-R, Habibi M, Eslamian M (2018) Excitation of wet perovskite films by ultrasonic vibration improves the device performance. Appl Sci 8:308Google Scholar
  14. 14.
    Ahmadian-Yazdi M-R, Eslamian M (2018) Toward scale-up of perovskite solar cells: annealing-free perovskite layer by low-cost ultrasonic substrate vibration of wet films. Mater Today Commun 14:151–159Google Scholar
  15. 15.
    Lee JW, Yu H, Lee K, Bae S, Kim J, Han GR, Hwang D, Kim SK, Jang J (2019) Highly crystalline perovskite-based photovoltaics via two-dimensional liquid cage annealing strategy. J Am Chem Soc 141:5808–5814Google Scholar
  16. 16.
    Lee B, Hwang T, Lee S, Shin B, Park B (2019) Microstructural evolution of hybrid perovskites promoted by chlorine and its impact on the performance of solar cell. Sci Rep 9:4803Google Scholar
  17. 17.
    Sanches AWP, da Silva MAT, Cordeiro NJA, Urbano A, Lourenço SA (2019) Effect of intermediate phases on the optical properties of PbI2-rich CH3NH3PbI3 organic–inorganic hybrid perovskite. Phys Chem Chem Phys 21:5253–5261Google Scholar
  18. 18.
    Wang Q, Phung N, Girolamo DD, Vivo P, Abate A (2019) Enhancement in lifespan of halide perovskite solar cells. Energy Environ Sci 12:865–886Google Scholar
  19. 19.
    Habibi M, Rahimzadeh A, Bennouna I, Eslamian M (2017) Defect-free large-area (25 cm2) light absorbing perovskite thin films made by spray coating. Coatings 7:42Google Scholar
  20. 20.
    Karim AMMT, Rahman MA, Hossain MS, Khan MKR, Rahman MM, Kamruzzaman M, Ton-That C (2018) Multi-color excitonic emissions in chemical dip-coated organolead mixed-halide perovskite. Chem Sel 3:6525–6530Google Scholar
  21. 21.
    Adnan M, Lee JK (2018) All sequential dip-coating processed perovskite layers from an aqueous lead precursor for high efficiency perovskite solar cells. Sci Rep 8:2168Google Scholar
  22. 22.
    Chen J, Wan Z, Liu J, Fu S-Q, Zhang F, Yang S, Tao S, Wang M, Chen C (2018) Growth of compact CH3NH3PbI3 thin films governed by the crystallization in PbI2 matrix for efficient planar perovskite solar cells. ACS Appl Mater Interfaces 10:8649–8658Google Scholar
  23. 23.
    Wahl KJ, Chromik RR, Lee GY (2008) Quantitative in situ measurement of transfer film thickness by a Newton’s rings method. Wear 264:731–736Google Scholar
  24. 24.
    Winston AW, Baer CA, Allen LR (2013) A simple film thickness gauge utilizing Newton’s rings. In: Proceedings of the sixth national symposium on vacuum technology transactions, pp 249–254Google Scholar
  25. 25.
    Raveesha KH, Doddamani VH, Prasad BK (2014) On a method to employ Newton’s rings concept to determine thickness of thin films. Int Lett Chem Phys Astron 22:1–7Google Scholar
  26. 26.
    Maculan G, Sheikh AD, Abdelhady AL, Saidaminov MI, Haque MA, Murali B, Alarousu E, Mohammed OF, Wu T, Bakr OM (2015) CH3NH3PbCl3 Single crystals: inverse temperature crystallization and visible-blind UV-photodetector. J Phys Chem Lett 6:3781–3786Google Scholar
  27. 27.
    Yu H, Wang F, Xie F, Li W, Chen J, Zhao N (2014) The role of chlorine in the formation process of “CH3NH3PbI3−xClx” perovskite. Adv Funct Mater 24:7102–7108Google Scholar
  28. 28.
    Xu Y, Zhu L, Shi J, Lv S, Xu X, Xiao J, Dong J, Wu H, Luo Y, Li D, Meng Q (2015) Efficient hybrid mesoscopic solar cells with morphology-controlled CH3NH3PbI3−xClx derived from two-step spin coating method. ACS Appl Mater Interfaces 7:2242–2248Google Scholar
  29. 29.
    Luo S, Daoud WA (2016) Crystal structure formation of CH3NH3PbI3−xClx perovskite. Materials 9:123Google Scholar
  30. 30.
    Chi L, Swainson I, Cranswicka L, Her JH, Stephens P, Knop O (2005) The ordered phase of methylammonium lead chloride CH3ND3PbCl3. J Solid State Chem 178:1376–1385Google Scholar
  31. 31.
    Dimesso L, Dimamay M, Hamburger M, Jaegermann W (2014) Properties of CH3NH3PbX3 (X = I, Br, Cl) powders as precursors for organic/inorganic solar cells. Chem Mater 26:6762–6770Google Scholar
  32. 32.
    Sedighi R, Tajabadi F, Shahbazi S, Gholipour S, Taghavinia N (2016) Mixed-halide CH3NH3PbI3−xXx (X = Cl, Br, I) perovskites: vapor-assisted solution deposition and application as solar cell absorbers. Chem Phys Chem 17:2382–2388Google Scholar
  33. 33.
    Pistor P, Ruiz A, Cabot A, Roca VI (2016) Advanced Raman spectroscopy of methylammonium lead iodide: development of a non-destructive characterisation methodology. Sci Rep 6:35973Google Scholar
  34. 34.
    Niemann RG, Kontos AG, Palles D, Kamitsos EI, Kaltzoglou A, Brivio F, Falaras P, Cameron PJ (2016) Halogen effects on ordering and bonding of CH3NH3 + in CH3NH3PbX3 (X = Cl, Br, I) hybrid perovskites: a vibrational spectroscopic study. J Phys Chem C 120:2509–2519Google Scholar
  35. 35.
    Maalej A, Abid Y, Kallel A, Daoud A, Lauti A, Romain F (1997) Phase transitions and crystal dynamics in the cubic perovskite CH3NH3PbCl3. Solid State Commun 103:279–284Google Scholar
  36. 36.
    Brivio F, Frost JM, Skelton JM, Jackson AJ, Weber OJ, Weller MT, Goni AR, Leguy AMA, Barnes PRF, Walsh A (2015) Lattice dynamics and vibrational spectra of the orthorhombic, tetragonal, and cubic phases of methylammonium lead iodide. Phys Rev B 92:144308Google Scholar
  37. 37.
    Glaser T, Muller C, Sendner M, Krekeler C, Semonin OE, Hull TD, Yaffe O, Owen JS, Kowalsky W, Pucci A, Lovrincic R (2015) Infrared spectroscopic study of vibrational modes in methylammonium lead halide perovskites. J Phys Chem Lett 6:2913–2918Google Scholar
  38. 38.
    Dong Q, Yuan Y, Shao Y, Fang Y, Wang Q, Huang J (2015) Abnormal crystal growth in CH3NH3PbI3−xClx using a multi-cycle solution coating process. Energy Environ Sci 8:2464–2470Google Scholar
  39. 39.
    Xiao L, Xu J, Luan J, Yu X, Zhang B, Dai S, Yao J (2018) Preparation of CH3NH3PbCl3 film with a large grain size using PbI2 as Pb source and its application in photodetector. Mater Lett 220:108–111Google Scholar
  40. 40.
    Gedamu D, Asuo IM, Benetti D, Basti M, Ka I, Cloutier SG, Rosei F, Nechache R (2018) Solvent-antisolvent ambient processed large grain size perovskite thin films for high-performance solar cells. Sci Rep 8:12885Google Scholar
  41. 41.
    Moss TS (1959) Optical properties of semiconductor. Academic Press, New YorkGoogle Scholar
  42. 42.
    Karim AMMT, Khan MKR, Rahman MM (2015) Structural and opto-electrical properties of pyrolized ZnO–CdO crystalline thin films. J Semicond 36:053001Google Scholar
  43. 43.
    Ashaduzzman M, Khan MKR, Karim AMMT, Rahman MM (2018) Influence of chromium on structural, non-linear optical constants and transport properties of CdO thin films. Surf Interfaces 12:135–144Google Scholar
  44. 44.
    Islam MA, Karim AMMT, Julkarnain M, Badrul AKM, Khan MKR, Khan KA (2017) Opto-transport properties of e-beam evaporated annealed CuInSe2 thin films. Surf Interfaces 8:170–175Google Scholar
  45. 45.
    Song TB, Chen Q, Zhou H, Jiang C, Wang HH, Yang YM, Liu Y, Youab J, Yang Y (2015) Perovskite solar cells: film formation and properties. J Mater Chem A 3:9032–9050Google Scholar
  46. 46.
    Tauc J (1974) Amorphous and liquid semiconductors. Plenum Press, New YorkGoogle Scholar
  47. 47.
    Buin A, Pietsch P, Voznyy O, Comin R, Ip AH, Sargent EH, Xu B (2014) Materials processing routes to trap-free halide perovskites. Nano Lett 14:6281–6286Google Scholar
  48. 48.
    Jiang DS, Jung H, Ploog K (1988) Temperature dependence of photoluminescence from GaAs single and multiple quantum-well heterostructures grown by molecular-beam epitaxy. J Appl Phys 64:1371Google Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of PhysicsRajshahi University of Engineering & TechnologyRajshahiBangladesh
  2. 2.Department of PhysicsUniversity of RajshahiRajshahiBangladesh
  3. 3.Department of PhysicsBegum Rokeya UniversityRangpurBangladesh
  4. 4.Department of PhysicsBangladesh University of Engineering and TechnologyDhakaBangladesh

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