Journal of Solid State Electrochemistry

, Volume 22, Issue 11, pp 3621–3630 | Cite as

Highly efficient dye-sensitized solar cells by TiCl4 surface modification of ZnO nano-flower thin film

  • Yogesh Waghadkar
  • Manish Shinde
  • Sunit Rane
  • Suresh GosaviEmail author
  • Chiaki Terashima
  • Akira Fujishima
  • Ratna ChauhanEmail author
Original Paper


In dye-sensitized solar cells (DSSCs), the semiconductor photo-anode film plays a significant role in enhancing the overall power conversion efficiency. ZnO is considered as the futuristic hope for photoanodes in DSSCs due to manifold properties over TiO2. However, the power conversion efficiency of ZnO-based DSSCs is still low due to its poor chemical stability and surface defects. In this work, we reported the synthesis of ZnO nano-flowers as well as its surface modification of with TiCl4 at different concentration. In DSSCs, the enhancement in power conversion efficiency results suggested that surface modification of ZnO film by TiCl4 leads to the deposition of TiO2 which subsequently increases the roughness factor of film as well as scattering layer. This preferential surface modification of ZnO film facilitates the accumulation of large number of photo-injected electrons in the HOMO of the photoanode with rapid transfer of charge carriers to FTO via ZnO layer by lowering the recombination of photo-injected electrons with the redox electrolyte as well as oxidized dye. The intensity-modulated photocurrent spectroscopy (IMVS) and intensity-modulated photovoltage spectroscopy (IMPS) study also indicated that the recombination rate decreased considerably during the electron transportation. The ZnO film surface modified by TiCl4 achieved a power conversion efficiency of 4.48%, which is two times higher than that of the non-modified ZnO photoanode.


ZnO nanoflower TiO2 nanoparticles DSSC Efficiency 



Authors CT and AF would like to thank Sakura Exchange Program in Science for allowing to visit Photocatalysis International Research Centre Research Institute for Science & Technology, Tokyo University ofScience, Japan.

Funding information

The author RC acknowledges to the Department of Science and Technology, New Delhi, Govt. of India, for the financial support via Project No. IFA12-CH-34. MDS and SBR acknowledge the support from Ministry of Electronics and Information Technology (MeitY), New Delhi, Govt. of India.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.


  1. 1.
    O’Regan B, Gratzel M (1991) A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature 353(6346):737–740CrossRefGoogle Scholar
  2. 2.
    Zhang Q, Cao G (2011) Nanostructured photoelectrodes for dye-sensitized solar cells. Nano Today 6(1):91–109CrossRefGoogle Scholar
  3. 3.
    Duong TT, Choi HJ, He QJ, Le AT, Yoon SG (2013) Enhancing the efficiency of dye sensitized solar cells with an SnO2 blocking layer grown by nanocluster deposition. J Alloys Compd 561:206–210CrossRefGoogle Scholar
  4. 4.
    Xu F, Zhang X, Wu Y, Wu D, Gao Z, Jiang K (2013) Facile synthesis of TiO2 hierarchical microspheres assembled by ultrathin nanosheets for dye-sensitized solar cells. J Alloys Compd 574:227–232CrossRefGoogle Scholar
  5. 5.
    Hagfeldt A, Grätzel M (1995) Light-induced redox reactions in nanocrystalline systems. Chem Rev 95(1):49–68CrossRefGoogle Scholar
  6. 6.
    Grätzel M (2005) Solar energy conversion by dye-sensitized photovoltaic cells. Inorg Chem 44(20):6841–6851CrossRefPubMedGoogle Scholar
  7. 7.
    Zhang Q, Dandeneau CS, Zhou X, Cao G (2009) ZnO nanostructures for dye-sensitized solar cells. Adv Mater 21(41):4087–4108CrossRefGoogle Scholar
  8. 8.
    Xu F, Sun L (2011) Solution-derived ZnO nanostructures for photoanodes of dye-sensitized solar cells. Energy Environ Sci 4(3):818–841CrossRefGoogle Scholar
  9. 9.
    Hu X, Heng B, Chen X, Wang B, Sun D, Sun Y, Zhou W, Tang Y (2012) Ultralong porous ZnO nanobelt arrays grown directly on uorine-doped SnO2 substrate for dye-sensitized solar cells. J Power Sources 217:120–127CrossRefGoogle Scholar
  10. 10.
    Sakai N, Miyasaka T, Murakami TN (2013) Efficiency enhancement of ZnO-based dye-sensitized solar cells by low-temperature TiCl4 treatment and dye optimization. J Phys Chem C 117(21):10949–10956CrossRefGoogle Scholar
  11. 11.
    Chen G, Zheng K, Mo X, Sun D, Meng Q, Chen G (2010) Metal-free indoline dye sensitized zinc oxide nanowires solar cell. Mater Lett 64(12):1336–1339CrossRefGoogle Scholar
  12. 12.
    Cheng H, Chiu W, Lee C, Tsai S, Hsieh W (2008) Formation of branched ZnO nanowires from solvothermal method and dye-sensitized solar cells applications. J Phys Chem C 112(42):16359–16364CrossRefGoogle Scholar
  13. 13.
    Law M, Greene LE, Johnson JC, Saykally R, Yang P (2005) Nanowire dye-sensitized solar cells. Nat Mater 4(6):455–459CrossRefPubMedGoogle Scholar
  14. 14.
    Nayeri FD, Soleimani EA, Salehi F (2013) Synthesis and characterization of ZnO nanowires grown on different seed layers: the application for dye-sensitized solar cells. Renew Energy 60:246–255CrossRefGoogle Scholar
  15. 15.
    Pant HR, Park CH, Pant B, Tijing LD, Kim HY, Kim CS (2012) Synthesis, characterization, and photocatalytic properties of ZnO nano-flower containing TiO2 NPs. Ceram Int 38(4):2943–2950CrossRefGoogle Scholar
  16. 16.
    Martinson ABF, Elam JW, Hupp JT, Pellin MJ (2007) ZnO nanotube based dye-sensitized solar cells. Nano Lett 7(8):2183–2187CrossRefPubMedGoogle Scholar
  17. 17.
    Kar S, Dev A, Chaudhuri S (2006) Simple solvothermal route to synthesize ZnO nanosheets, nanonails, and well-aligned nanorod arrays. J Phys Chem B 110(36):17848–17853CrossRefPubMedGoogle Scholar
  18. 18.
    Fu M, Zhou J, Xiao QF, Li B, Zong RL, Chen W, Zhang J (2006) ZnO nanosheets with ordered pore periodicity via colloidal crystal template assisted electrochemical deposition. Adv Mater 18(8):1001–1004CrossRefGoogle Scholar
  19. 19.
    Jiang CY, Sun W, Lo GQ, Kwong DL, Wang JX (2007) Improved dye-sensitized solar cells with a ZnO-nanoflower photoanode. Appl Phys Lett 90(26):263501–263503CrossRefGoogle Scholar
  20. 20.
    Nishimura S, Abrams N, Lewis BA, Halaoui LI, Mallouk TE, Benkstein KD, Lagemaat JV, Frank AJ (2003) Standing wave enhancement of red absorbance and photocurrent in dye-sensitized titanium dioxide photoelectrodes coupled to photonic crystals. J Am Chem Soc 125(20):6306–6310CrossRefPubMedGoogle Scholar
  21. 21.
    Koo HJ, Kim YJ, Lee YH, Lee WI, Kim K, Park NG (2008) Nano-embossed hollow spherical TiO2 as bifunctional material for high-efficiency dye-sensitized solar cells. Adv Mater 20(1):195–199CrossRefGoogle Scholar
  22. 22.
    Halaoui LI, Abrams NM, Mallouk TE (2005) Increasing the conversion efficiency of dye-sensitized TiO2 photoelectrochemical cells by coupling to photonic crystals. J Phys Chem B 109(13):6334–6342CrossRefPubMedGoogle Scholar
  23. 23.
    Hosono E, Fujihara S, Kimura T (2004) Synthesis, structure and photoelectrochemical performance of micro/nano-textured ZnO/eosin Y electrodes. Electrochim Acta 49(14):2287–2293CrossRefGoogle Scholar
  24. 24.
    Zhang QF, Chou TP, Russo B, Jenekhe SA, Cao GZ (2008) Polydisperse aggregates of ZnO nanocrystallites: a method for energy-conversion-efficiency enhancement in dye-sensitized solar cells. Adv Funct Mater 18(11):1654–1660CrossRefGoogle Scholar
  25. 25.
    Wang ZS, Kawauchi H, Kashima T, Arakawa H (2004) Significant influence of TiO2 photoelectrode morphology on the energy conversion efficiency of N719 dye-sensitized solar cell. Coord Chem Rev 248(13-14):1381–1389CrossRefGoogle Scholar
  26. 26.
    Ito S, Zakeerudiin SM, Humphry-Baker R, Liska P, Charvet P, Comte P, Nazeeruddin MK, Pechy P, Takata M, Miura H, Uchida S, Gratzel M (2006) High-efficiency organic-dye-sensitized solar cells controlled by nanocrystalline-TiO2 electrode thickness. Adv Mater 18(9):1202–1205CrossRefGoogle Scholar
  27. 27.
    Hore S, Vetter C, Kern R, Smit H, Hinsch A (2006) Influence of scattering layers on efficiency of dye-sensitized solar cells. Sol Energy Mater Sol Cells 90(9):1176–1188CrossRefGoogle Scholar
  28. 28.
    Li Y, Zhang H, Guo B, Wei M (2012) Enhanced efficiency dye-sensitized SrSnO3 solar cells prepared using chemical bath deposition. Electrochim Acta 70:313–317CrossRefGoogle Scholar
  29. 29.
    Chen C, Li Y, Sun X, Xie F, Wei M (2014) Efficiency enhanced dye-sensitized Zn2SnO4 solar cells using a facile chemical-bath deposition method. New J Chem 38(9):4465–4470CrossRefGoogle Scholar
  30. 30.
    Xie F, Li Y, Xiao T, Shen D, Wei M (2018) Efficiency improvement of dye-sensitized BaSnO3 solar cell based surface treatments. Electrochim Acta 261:23–28CrossRefGoogle Scholar
  31. 31.
    Lou Y, Yuan S, Zhao Y, Hu P, Wang Z, Zhang M, Shi L, Li D (2013) A simple route for decorating TiO2 nanoparticle over ZnO aggregates dye-sensitized solar cell. Chem Eng J 229:190–196CrossRefGoogle Scholar
  32. 32.
    Chandiran AK, Jalebi MA, Nazeeruddin MK, Grätzel M (2014) Analysis of electron transfer properties of ZnO and TiO2 photoanodes for dye-sensitized solar cells. ACS Nano 8(3):2261–2268CrossRefPubMedGoogle Scholar
  33. 33.
    Choi SC, Yun WS, Sohn SH (2013) Enhanced performance of dye-sensitized solar cells with surface-modified ZnO nanorods. Mol Cryst Liq Cryst 586(1):88–94CrossRefGoogle Scholar
  34. 34.
    Zhu L, Liu G, Duan X, Zhang ZJ (2010) A facile wet chemical route to prepare ZnO/TiO2 nanotube composites and their photocatalytic activities. J Mater Res 25(07):1278–1287CrossRefGoogle Scholar
  35. 35.
    Saied SO, Sullivan JL, Choudhury T, Pearce CG (1988) A comparison of ion and fast atom beam reduction in TiO2. Vacuum 38(8-10):917–922CrossRefGoogle Scholar
  36. 36.
    Peng YP, Yassitepe E, Yeh YT, Ruzybayev I, Shah SI, Huang CP (2012) Photoelectrochemical degradation of azo dye over pulsed laser deposited nitrogen-doped TiO2 thin film. Appl Catal B 125:465–472CrossRefGoogle Scholar
  37. 37.
    Singh J, Gusain A, Saxena V, Chauhan AK, Veerender P, Koiry SP, Jha P, Jain A, Aswal DK, Gupta SK (2013) XPS, UV–Vis, FTIR, and EXAFS studies to investigate the binding mechanism of N719 dye onto oxalic acid treated TiO2 and its implication on photovoltaic properties. J Phys Chem C 117(41):21096–21104CrossRefGoogle Scholar
  38. 38.
    Fan JD, Hao Y, Munuera C, Garcia-Hernandez M, Guell F, Johansson EMJ, Boschloo G, Hagfeldt A, Cabot A (2013) Influence of the annealing atmosphere on the performance of ZnO nanowire dye-sensitized solar cells. J Phys Chem C 117(32):16349–16356CrossRefGoogle Scholar
  39. 39.
    Mukhopadhyay S, Mondal I, Pal U, Devi SP (2015) Fabrication of hierarchical ZnO/CdS heterostructured nanocomposites for enhanced hydrogen evolution from solar water splitting. Phys Chem Chem Phys 17(31):20407–20415CrossRefPubMedGoogle Scholar
  40. 40.
    Kruger J, Plass R, Gratzel M, Cameron PJ, Peter LM (2003) Charge transport and back reaction in solid-state dye-sensitized solar cells: a study using intensity-modulated photovoltage and photocurrent spectroscopy. J Phys Chem B 107(31):7536–7539CrossRefGoogle Scholar
  41. 41.
    Zhu K, Neale NR, Miedaner A, Frank AJ (2007) Enhanced charge-collection efficiencies and light scattering in dye-sensitized solar cells using oriented TiO2 nanotubes arrays. Nano Lett 7(1):69–74CrossRefPubMedGoogle Scholar
  42. 42.
    Bisquert J, Fabregat-Santiago F, Mora-Sero I, Garcia-Belmonte G, Gimenez S (2009) Electron lifetime in dye-sensitized solar cells: theory and interpretation of measurements. J Phys Chem C 113(40):17278–17290CrossRefGoogle Scholar
  43. 43.
    Li JY, Chen CY, Chen JG, Tan CJ, Lee KM, Wu SJ, Tung YL, Tsai HH, Ho KC, Wu CG (2010) Heteroleptic ruthenium antenna-dye for high-voltage dye-sensitized solar cells. J Mater Chem 20(34):7158–7164CrossRefGoogle Scholar
  44. 44.
    Kozma E, Concina I, Braga A, Borgese L, Depero LE, Vomiero A, Sberveglieri G, Catellani M (2011) Metal-free organic sensitizers with a sterically hindered thiophene unit for efficient dye-sensitized solar cells. J Mater Chem 21(36):13785–13788CrossRefGoogle Scholar
  45. 45.
    Boschloo G, Haggman L, Hagfeldt A (2006) Quantification of the effect of 4-tert-butylpyridine addition to I/I3 redox electrolytes in dye-sensitized nanostructured TiO2 solar cells. J Phys Chem B 110(26):13144–13150CrossRefPubMedGoogle Scholar
  46. 46.
    Fischer AC, Peter LM, Ponomarev EA, Walker AB, Wijayantha KGU (2000) Intensity dependence of the back reaction and transport of electrons in dye-sensitized nanocrystalline TiO2 solar cells. J Phys Chem B 104(5):949–958CrossRefGoogle Scholar
  47. 47.
    Schwartsburg K, Wllig F (1991) Influence of trap filling on photocurrent transients in polycrystalline TiO2. Appl Phys Lett 58(22):2520–2522CrossRefGoogle Scholar
  48. 48.
    Qian XM, Qin DQ, Song Q, Bai YB, Li TJ, Tang XY, Wang EK, Dong SJ (2001) Surface photovoltage spectra and photoelectrochemical properties of semiconductor-sensitized nanostructured TiO2 electrodes. Thin Solid Films 385(1-2):152–161CrossRefGoogle Scholar
  49. 49.
    Zhang ZP, Zakeeruddin SM, O’Regan BC, Humphry-Baker R, Gratzel M (2005) Influence of 4-guanidinobutyric acid as coadsorbent in reducing recombination in dye-sensitized solar cells. J Phys Chem B 109(46):21818–21824CrossRefPubMedGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Yogesh Waghadkar
    • 1
    • 2
  • Manish Shinde
    • 1
  • Sunit Rane
    • 1
  • Suresh Gosavi
    • 3
    Email author
  • Chiaki Terashima
    • 4
  • Akira Fujishima
    • 4
  • Ratna Chauhan
    • 1
    Email author
  1. 1.Materials for Renewable Energy DivisionCentre for Materials for Electronics Technology (C-MET)PuneIndia
  2. 2.Department of TechnologySavitribai Phule Pune UniversityPuneIndia
  3. 3.Department of PhysicsSavitribai Phule Pune UniversityPuneIndia
  4. 4.Photocatalysis International Research Center, Research Institute for Science & TechnologyTokyo University of ScienceChibaJapan

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