Nano gold coated hierarchically porous zinc titanium oxide sol–gel based thin film: fabrication and photoelectrochemical activity

  • Hasmat Khan
  • Malobi Seth
  • Srikrishna Samanta
  • Sunirmal JanaEmail author
Original Paper: Sol-gel and hybrid materials with surface modification for applications


In this work, for the first time homogeneously distributed near periodic macroporous (HDPM) with nested mesoporous (hierarchically porous) semicrystalline zinc titanium oxide (ZTO) thin film on pure silica glass and fluorine doped tin oxide coated glass substrates was deposited by sol–gel dip coating technique from an optimized precursor solution of zinc nitrate hexahydrate and titanium isopropoxide with acetylacetone in low boiling solvents. The HDPM film formation was carried out by simple breath figure method where the pore formation occurred from the generated water droplets via molecular condensation onto the as-deposited cold solution film surface owing to solvent evaporation. Zinc to titanium ratio in precursor solution, room relative humidity and other critical parameters were tailored towards optimization of the periodic macropores formation. Gold nanoparticles (NPs) were further deposited onto the ZTO thin films by solution technique. Crystallinity, surface morphology and microstructure of the thin films were critically analyzed by X-ray diffraction, atomic force, scanning, and transmission electron microscopic studies. The photoelectrochemical (PEC) performance of the films was examined under visible light irradiation. A significant improvement in PEC activity was observed in nano Au coated hierarchically porous thin film. This facile fabrication process could be applied in different mixed metal oxide thin films for improving the PEC activity of the materials.


  • Fabricated periodic macro with nested mesoporous zinc titanium oxide (ZTO) thin film.

  • The hierarchically porous (HP) ZTO film showed high BET surface area.

  • Nano gold deposited HP film (NGHP) showed enhanced photoconversion efficiency.

  • NGHP can have substantial opportunity in solar energy conversion.


Sol–gel thin films Breath figure method Metal oxide semiconductors Hierarchically porous Nano Au Photoelectrochemical activity 



One of the authors, HK thankfully acknowledges CSIR, Govt. of India for providing his Ph.D. research fellowship. The authors also acknowledge the help rendered by Electron Microscopy Section for XRD, FESEM, and TEM characterizations. The work had been done as an associated research work of 12th Five Year Plan project of CSIR (No. ESC0202).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10971_2019_5108_MOESM1_ESM.doc (34.2 mb)
Supplementary information


  1. 1.
    Cho S, Jang J-W, Lee K-H, Lee JS (2014) Research update: strategies for efficient photoelectrochemical water splitting using metal oxide photoanodes. Apl Mater 2:1–14CrossRefGoogle Scholar
  2. 2.
    Kang D, Kim TW, Kubota SR, Cardiel AC, Cha HG, Choi K-S (2015) Electrochemical synthesis of photoelectrodes and catalysts for use in solar water splitting. Chem Rev 115:12839–12887CrossRefGoogle Scholar
  3. 3.
    Yang J-S, Wu J-J (2018) Toward eco-friendly and highly efficient solar water splitting using In2S3/anatase/rutile TiO2 dual-staggered-heterojunction nanodendrite array photoanode. ACS Appl Mater Interfaces 10:3714–3722CrossRefGoogle Scholar
  4. 4.
    Ji M, Cai J, Ma Y, Qi L (2016) Controlled growth of ferihydrite branched nanosheet arrays and their transformation to hematite nanosheet arrays for photoelectrochemical water splitting. ACS Appl Mater Interfaces 8:3651–3660CrossRefGoogle Scholar
  5. 5.
    Nguyen O, Krins N, Laberty-Robert C (2018) Harvesting light with semiconductor: role of interface in the processes of charge transfer. Mater Sci Semicond Process 73:2–12CrossRefGoogle Scholar
  6. 6.
    Cao F, Xiong J, Wu F, Liu Q, Shi Z, Yu Y, Wang X, Li L (2016) Enhanced photoelectrochemical performance from rationally designed anatase/rutile TiO2 heterostructures. ACS Appl Mater Interfaces 8:12239–12245CrossRefGoogle Scholar
  7. 7.
    Fujishima A, Zhang X, Tryk DA (2008) TiO2 photocatalysis and related surface phenomena. Surf Sci Rep 63:515–582CrossRefGoogle Scholar
  8. 8.
    Kwiatkowski M, Bezverkhyy I, Skompska M (2015) ZnO nanorods covered with a TiO2 layer: simple sol–gel preparation, and optical, photocatalytic and photoelectrochemical properties. J Mater Chem A 3:12748–12760CrossRefGoogle Scholar
  9. 9.
    Upadhyay AP, Behara DK, Sharma GP, Gyanprakash M, Pala RGS, Sivakumar S (2016) Fabricating appropriate band-edge-staggered heterosemiconductors with optically activated Au nanoparticles via click chemistry for photoelectrochemical water splitting. ACS Sustain Chem Eng 4:4511–4520CrossRefGoogle Scholar
  10. 10.
    Krol RVD, Grätzel M, (2012) Electronic Materials: Science & Technology, in: Krol RVD, Grätzel M (Eds) Photoelectrochemical Hydrogen Production. Springer, New York, p. 9Google Scholar
  11. 11.
    Kon K, Brauer CN, Hidaka K, Lohmannsroben H-G, Karthaus O (2010) Preparation of patterned zinc oxide films by breath figure templating. Langmuir 26:12173–12176CrossRefGoogle Scholar
  12. 12.
    Pandikumar A, Murugesan S, Ramaraj R (2010) Functionalized silicate sol-gel-supported TiO2-Au core-shell nanomaterials and their photoelectrocatalytic activity. ACS Appl Mater Interfaces 2:1912–1917CrossRefGoogle Scholar
  13. 13.
    Khan H, Bera S, Sarkar S, Jana S (2017) Fabrication, structural evaluation, optical and photoelectrochemical properties of soft lithography based 1D/2D surface patterned indium titanium oxide sol-gel thin film. Surf Coat Technol 328:410–419CrossRefGoogle Scholar
  14. 14.
    Bera S, Pal M, Sarkar S, Jana S (2017) Hierarchically structured macro with nested mesoporous zinc indium oxide conducting film. ACS Appl Mater Interfaces 9:4420–4424CrossRefGoogle Scholar
  15. 15.
    Ding J, Zhang A, Bai H, Li L, Lia J, Ma Z (2013) Breath figure in non-aqueous vapor. Soft Matter 9:506–514CrossRefGoogle Scholar
  16. 16.
    Li H, Jia Y, Du M, Fei J, Zhao J, Cui Y, Li J (2013) Self-organization of honeycomb-like porous TiO2 films by means of the breath-figure method for surface modification of titanium Implants. Chem Eur J 19:5306–5313CrossRefGoogle Scholar
  17. 17.
    García-Ramírez E, Mondragón-Chaparro M, Zelaya-Angel O (2012) Band gap coupling in photocatalytic activity in ZnO–TiO2 thin films. Appl Phys A 108:291–297CrossRefGoogle Scholar
  18. 18.
    Arin J, Thongtem S, Phuruangrat A, Thongtem T (2017) Template synthesis of Zn2TiO4 and Zn2Ti3O8 nanorods by hydrothermal calcination combined processes. Mater Lett 193:270–273CrossRefGoogle Scholar
  19. 19.
    Pérez-González M, Tomás SA, Morales-Luna M, Arvizu MA, Tellez-Cruz MM (2015) Optical, structural, and morphological properties of photocatalytic TiO2-ZnO thin films synthesized by the sol-gel process. Thin Solid Films 594:304–309CrossRefGoogle Scholar
  20. 20.
    Moradi S, Azar PA, Farshid SR, Khorrami SA, Givianrad MH (2012) Effect of additives on characterization and photocatalytic activity of TiO2/ZnO nanocomposite prepared via sol-gel process. Int J Chem Eng 2012:1–5CrossRefGoogle Scholar
  21. 21.
    Naskar A, Khan H, Bera S, Jana S (2017) Soft chemical synthesis, characterization and interaction of ZnO graphene nanocomposite with bovine serum albumin protein. J Mol Liq 237:113–119CrossRefGoogle Scholar
  22. 22.
    Sangwichien C, Aranovich GL, Donohue MD (2002) Density functional theory predictions of adsorption isotherms with hysteresis loops. Colloids Surf A Physicochem Eng Asp 206:313–320CrossRefGoogle Scholar
  23. 23.
    Bera S, Khan H, Biswas I, Jana S (2016) Polyaniline hybridized surface defective ZnO nanorods with long-term stable photoelectrochemical activity. Appl Surf Sci 383:165–176CrossRefGoogle Scholar
  24. 24.
    Khan H, Seth M, Naskar A, Jana S (2018) Nano gold-coated surface patterned mesoporous titanium tin oxide sol–gel thin film: fabrication, optical and photoelectrochemical properties. J Sol-Gel Sci Technol 88:359–370CrossRefGoogle Scholar
  25. 25.
    Zhang SW, Zhang BP, Li S, Li XY, Huang ZC (2016) SPR enhanced photocatalytic properties of Au-dispersed amorphous BaTiO3 nanocomposite thin films. J Alloy Compd 654:112–119CrossRefGoogle Scholar
  26. 26.
    Naskar A, Khan H, Sarkar R, Kumar S, Halder D, Jana S (2018) Anti-biofilm activity and food packaging application of room temperature solution process based polyethylene glycol capped Ag-ZnO-graphene nanocomposite. Mater Sci Eng C 91:743–753CrossRefGoogle Scholar
  27. 27.
    Yang X, Zhou S, Wang D, He J, Zhou J, Li X, Gao P, Ye J (2015) Light Trapping Enhancement in a Thin Film with 2D Conformal Periodic Hexagonal Arrays. Nanoscale Res Lett 284(10):1–9Google Scholar
  28. 28.
    Jiang W, Liu H, Yin L, Shi Y, Chen B (2016) Enhanced photoelectric properties in dye-sensitized solar cells using TiO2 pyramid arrays. J Phys Chem C 120:9678–9684CrossRefGoogle Scholar
  29. 29.
    Leung S-F, Zhang Q, Xiu F, Yu D, Ho JC, Li D, Fan Z (2014) Light management with nanostructures for optoelectronic devices. J Phys Chem Lett 5:1479–1495CrossRefGoogle Scholar
  30. 30.
    Wooh S, Yoon H, Jung J-H, Lee Y-G, Jai HK, Lee B, Kang YS, Char K (2013) Efficient light harvesting with micropatterned 3D pyramidal photoanodes in dye-sensitized solar cells. Adv Mater 25:3111–3116CrossRefGoogle Scholar
  31. 31.
    Dunklin RJ, Forcherio TG, Roper DK (2015) Gold nanoparticle-polydimethylsiloxane films reflect light internally by optical diffraction and Mie scattering. Mater Res Express 2(085005):1–19Google Scholar
  32. 32.
    Sarkar S, Chattopadhyay R, Jana S (2016) Structural and light coupling characteristics of patterned silica–titania sol–gel thin films with/without nano gold coatings. RSC Adv 6:109218–109233CrossRefGoogle Scholar
  33. 33.
    Bi Y-G, Feng J, Ji J-H, Yi F-S, Li Y-F, Liu Y-F, Zhang X-L, Sun H-B (2018) Nanostructures induced light harvesting enhancement in organic photovoltaics. Nanophotonics 7(2):371–391Google Scholar
  34. 34.
    Luo X, Tsai D, Gu M, Hong M (2019) Extraordinary optical fields in nanostructures: from sub-diffraction-limited optics to sensing and energy conversion. Chem Soc Rev 48:2458–2494CrossRefGoogle Scholar
  35. 35.
    Kim J, Koh JK, Kim B, Kim JH, Kim E (2012) Nanopatterning of mesoporous inorganic oxide films for efficient light harvesting of dye-sensitized solar cells. Angew Chem Int Ed 51:6864–6869CrossRefGoogle Scholar
  36. 36.
    Zhou L, Zhao C, Giri B, Allen P, Xu X, Joshi H, Fan Y, Titova LV, Rao PM (2016) High light absorption and charge separation efficiency at low applied voltage from Sb-doped SnO2/BiVO4 core/shell nanorod-array photoanodes. Nano Lett 16:3463–3474CrossRefGoogle Scholar
  37. 37.
    Mayer J, Gallinet B, Offermans T, Ferrini R (2015) Diffractive nanostructures for enhanced light-harvesting in organic photovoltaic devices. Opt Express 24:358–373CrossRefGoogle Scholar
  38. 38.
    Kumar DR, Manoj D, Santhanalakshmi J (2014) Au–ZnO bullet-like heterodimer nanoparticles: synthesis and use for enhanced nonenzymatic electrochemical determination of glucose. RSC Adv 4:8943–8952CrossRefGoogle Scholar
  39. 39.
    Xu Y-F, Rao H-S, Wang X-D, Chen H-Y, Kuang D-B, Su C-Y (2016) In situ formation of zinc ferrite modified Al-doped ZnO nanowire arrays for solar water splitting. J Mater Chem A 4:5124–5129CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Specialty Glass Technology DivisionCSIR-Central Glass and Ceramic Research Institute (CSIR-CGCRI)KolkataIndia

Personalised recommendations