Exploring the impact of the Pb2+ substitution by Cd2+ on the structural and morphological properties of CH3NH3PbI3 perovskite

  • Rajan Kumar Singh
  • Ranveer KumarEmail author
  • Neha Jain
  • Mei-Tsan Kuo
  • Chandrama Prakash Upadhyaya
  • Jai Singh
Original Article


Replacing the metal atoms in an organic–inorganic hybrid perovskite is of great significance to explore the low-toxic lead-free solar cells and other opto-electronic devices. In this work, we report the substitution of lead by 10% cadmium in CH3NH3PbI3 hybrid perovskite samples synthesized in powder and thin-film forms. We have characterized their structural, morphological, optical and thermal properties using XRD, HR-TEM, SEM, DR UV–Vis spectroscopy and STA. The detailed structural analysis made through XRD, TEM and Rietveld refinement insights the structural phase transformation from tetragonal to cubic structure due to the incorporation of cadmium at lead sites. Controlled size and crystallinity are two crucial factors for solution which processed hybrid perovskite solar cells for device formation. Morphological studies reveal the improved crystallinity and an enhancement in grains sizes (> 8–9 times of pristine perovskite) with cadmium doping in pure perovskite structure. The DR UV–Vis spectroscopy shows the substantial reduction in the optical band gap and shifting of absorbance spectra towards NIR regions. These results open up the door for new perspicacity of transition metals to culminate lead-free designing of novel protective materials with advanced photovoltaic and photoelectric properties.


Halide perovskite Crystallinity Grain size Pinhole Low toxic 



The authors are thankful to Sophisticated Instrument Laboratory of the University for providing various characterization facilities. One of the authors (Rajan) acknowledges the Senior Research Fellowship provided by University Grants Commission (UGC), Govt. of India. Ranveer Kumar acknowledge to DST PURSE Phase 2 for financial support.

Compliance with ethical standards

Conflict of interest

The authors declare that there is no conflict of interest.

Supplementary material

13204_2019_1021_MOESM1_ESM.docx (1.3 mb)
Supplementary material 1 (DOCX 1336 KB)


  1. Ali R, Hou GJ, Zhu ZG, Yan QB, Zheng QR, Su G (2018) Predicted lead-free perovskites for solar cells. Chem Mater 30(3):718–728CrossRefGoogle Scholar
  2. Babayigit A, Ethirajan A, Muller M, Conings B (2016) Toxicity of organometal halide perovskite solar cells. Nat Mater 15:247–251CrossRefGoogle Scholar
  3. Baikie T, fang Y, Kadro JM, Schreyer M, Wei F, Mhaisalkar SG, Gretzel M, White TJ (2013) Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications. J Mater Chem A 1:5628–5641CrossRefGoogle Scholar
  4. Bi C, Wang Q, Shao Y, Yuan Y, Xiao Z, Huang J (2015) Non-wetting surface-driven high-aspect-ratio crystalline grain growth for efficient hybrid perovskite solar cells. Nat Commun 6:7747CrossRefGoogle Scholar
  5. Bourrellier R, Meuret S, Tararan A, Stéphan O, Kociak M, Tizei LHG, Zobelli A (2016) Bright UV single photon emission at point defects in h-BN. Nano Lett 16(7):4317–4321CrossRefGoogle Scholar
  6. Cai M, Wu Y, Chen H, Yang X, Qiang Y, Han L (2017) Cost-performance analysis of perovskite solar modules. Adv Sci 4:1600269CrossRefGoogle Scholar
  7. Dualed A, Gao P, Seok SI, Nazeeruddin MK, Gratzel M (2014) Thermal behavior of methylammonium lead-trihalide perovskite photovoltaic light harvesters. Chem Mater 26(21):6160–6164CrossRefGoogle Scholar
  8. Fu K, Nelson CT, Scott MC, Minor A, Mathews N, Wong LH (2016) Influence of void-free perovskite capping layer on the charge recombination process in high performance CH3NH3PbI3 perovskite solar cells. Nanoscale 8:4181–4193CrossRefGoogle Scholar
  9. Fu Q, Tang X, Huang B, Hu T, Tan L, Chen L, Chen Y (2018) Recent progress on the long-term stability of perovskite solar cells. Adv Sci 5:1700387CrossRefGoogle Scholar
  10. Ha ST, Liu X, Zhang Q, Giovanni D, Sum TC, Xiong Q (2014) Synthesis of organic–inorganic lead halide perovskite nanoplatelets: towards high-performance perovskite solar cells and optoelectronic devices. Adv Opt Mater 2:838–844CrossRefGoogle Scholar
  11. Hoefler SF, Trimmel G, Rath T (2017) Progress on lead-free metal halide perovskites for photovoltaic applications: a review. Monatsh Chem 148:795–826CrossRefGoogle Scholar
  12. Kamat PV, Bisquert J, Buriak J (2017) Lead-free perovskite solar cells. ACS Energy Lett 2(4):904–905CrossRefGoogle Scholar
  13. Lang F, Shargaieva O, Brus VV, Neitzert HC, Rappich J, Nickel NH (2018) Influence of radiation on the properties and the stability of hybrid perovskites. Adv Mater 30:1702905CrossRefGoogle Scholar
  14. Lefi R, Naser FB, Guermazi H (2017) Structural, optical properties and characterization of (C2H5NH3)2CdCl4, (C2H5NH3)2CuCl4 and (C2H5NH3)2Cd0.5Cu0.5Cl4 compounds. J Alloy Compd 696:1244–1254CrossRefGoogle Scholar
  15. Li Z, Klein TR, Kim DH, Yang M, Berry JJ, van Hest MFAM, Zhu K (2018) Scalable fabrication of perovskite solar cells. Nat Rev Mater 3:18017CrossRefGoogle Scholar
  16. Lu C, Zhang J, Hou D, Gan X, Sun H, Zeng Z, Chen R, Tian H, Xiong Q, Zhang Y, Li Y, Zhu Y (2018) Calcium doped MAPbI3 with better energy state alignment in perovskite solar cells. Appl Phys Lett 112:193901CrossRefGoogle Scholar
  17. Marinova N, Tress W, Humphry-Baker R, Dar MI, Bojinov V, Zakeeruddin SM, Nazeeruddin MK, Gratzel M (2015) Light harvesting and charge recombination in CH3NH3PbI3 perovskite solar cells studied by hole transport layer thickness variation. ACS Nano 9(4):4200–4209CrossRefGoogle Scholar
  18. Moskowitz PD (1992) health and safety issues related to the production and use of CdTe photovoltaic modules. Int J Sol Energy Environ 12:259–281CrossRefGoogle Scholar
  19. National Renewable Energy Laboratory (2017) NREL chart. Accessed Dec 2017
  20. Nie W, Tsai H, .Sadpour HRA, .Blancon JC, Neukirch AJ, Gupta G, Crochet JJ, Chhowalla M, Tretiak S, Alam MA, Wang HL, Mohite AD (2015) High-efficiency solution-processed perovskite solar cells with millimeter-scale grains. Science 347:522–525CrossRefGoogle Scholar
  21. Oku T (2015) Crystal structures of CH3NH3PbI3 and related perovskite compounds used for solar cells. Sol Cells Leonid A. Kosyachenko Intech Open. Google Scholar
  22. Patnaik P (2003) Handbook of inorganic chemicals. McGraw-Hill, New York, pp 1021–2298Google Scholar
  23. Priante D, Dursun I, Alias MS, Shi D, Melnikov VA, Ng TK, Mohammed OF, Bakr OM, Ooi BS (2015) The recombination mechanisms leading to amplified spontaneous emission at the true-green wavelength in CH3NH3PbBr3 perovskites. Appl Phys Lett 106:081902CrossRefGoogle Scholar
  24. Shi Z, Guo J, Chen Y, Li Q, Pan Y, Zhang H, Xia Y, Huang W (2017) Lead-free organic–inorganic hybrid perovskites for photovoltaic applications: recent advances and perspectives. Adv Mater 29:1605005CrossRefGoogle Scholar
  25. Singh T, Singh J, Miyasaka T (2016) Role of metal oxide electron-transport layer modification on the stability of high performing perovskite solar cells. ChemSusChem 9:1–9CrossRefGoogle Scholar
  26. Singh RK, Jain N, Singh J, Kumar R (2017) Stability behaviour of chemically synthesized organic electrolyte salts and methylammonium lead halide perovskite light harvester. Adv Mater Lett 8(6):707–711CrossRefGoogle Scholar
  27. Singh RK, Kumar R, Kumar A, Jain N, Singh RK, Singh J (2018) Novel synthesis process of methyl ammonium bromide and effect of particle size on structural, optical and thermodynamic behavior of CH3NH3PbBr3 organometallic perovskite light harvester. J Alloys Compd 743:728–736CrossRefGoogle Scholar
  28. Singh RK, Kumar R, Jain N, Dash SR, Singh J, Srivastava A (2019) Investigation of optical and dielectric properties of CsPbI3 inorganic lead iodide perovskite thin film. J Taiwan Inst Chem Eng 96:538–542CrossRefGoogle Scholar
  29. Teshima KK, Shirai Y, Miyasaka T (2009) Organometal halide perovskite as visible light sensitizers for photovoltaic cells. J Am Chem Soc 131:6050CrossRefGoogle Scholar
  30. Willamson GK, Hall WH (1953) X-ray line broadening from filed aluminium and wolfram. Acta Mettall 1:22CrossRefGoogle Scholar
  31. Xiao Z, Yan Y (2017) Progress in theoretical study of metal halide perovskite solar cell materials. Adv Energy Mater 7:1701136CrossRefGoogle Scholar
  32. Zayed J, Philippe S (2009) Acute oral and inhalation toxicities in rats with cadmium telluride. Int J Tosicol 28:529–265Google Scholar
  33. Zhao W, Yang D, Yang Z, Liu S (2017) Zn-doping for reduced hysteresis and improved performance of methylammonium lead iodide perovskite hybrid solar cells. Mater Today Energy 5:205–213CrossRefGoogle Scholar

Copyright information

© King Abdulaziz City for Science and Technology 2019

Authors and Affiliations

  • Rajan Kumar Singh
    • 1
    • 2
  • Ranveer Kumar
    • 1
    Email author
  • Neha Jain
    • 1
  • Mei-Tsan Kuo
    • 2
  • Chandrama Prakash Upadhyaya
    • 3
  • Jai Singh
    • 1
  1. 1.Department of PhysicsDr. Harisingh Gour Central UniversitySagarIndia
  2. 2.Department of Chemical EngineeringNational Taiwan UniversityTaipeiTaiwan, ROC
  3. 3.Laboratory of Plant Molecular Biology, Department of BiotechnologyDr. Harisingh Gour Central UniversitySagarIndia

Personalised recommendations