Preparation and characterization of ZnO/ZnAl2O4-mixed metal oxides for dye-sensitized photodetector using Zn/Al-layered double hydroxide as precursor

  • Ethar Yahya Salih
  • Mohd Faizul Mohd SabriEmail author
  • Sin Tee Tan
  • Khaulah Sulaiman
  • Mohd Zobir Hussein
  • Suhana Mohd Said
  • Chi Chin Yap
Research Paper


In this article, a simple new technique has been developed for the preparation of ZnO/ZnAl2O4-mixed metal oxide (MMO) as anode materials for visible light dye-sensitized (DS) photodetector using Zn/Al-layered double hydroxide (LDH) as precursor. Subsequently, a detailed correlation between the structural properties of the prepared samples and the photo-responsive behavior of the fabricated DS photodetectors was elucidated. Specifically, it is evidenced that a high surface area of the prepared mesoporous MMO anode materials exhibit excellent dye absorptivity and thus facilitate free electron transfer and increase the photocurrent in the fabricated DS photodetector. A significant bathochromic shift was observed in the optical energy of the prepared MMO samples under the increment of molar ratio, providing a short electron transfer pathway in the optimized Z7A DS photodetector, which in turn demonstrated photo-responsivity and photo-detectivity of 6 mA/W and 1.7 × 10+10 Jones, respectively. This work presents an alternative approach for the design of an eco-friendly MMO-based DS photodetector.

Graphical abstract



Mixed metal oxide Layered double hydroxide Dye-sensitized photodetector Photo-responsivity Nanostructures 



The authors would like to sincerely acknowledge the Ministry of Higher Education, and the University of Malaya, Malaysia, for their support of the current study through Postgraduate Research Grants (PG030-2015B), and (PG041-2015B) and Fundamental Research Grant Scheme (FRGS) FP064-2016.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2019_4501_MOESM1_ESM.docx (443 kb)
ESM 1 (DOCX 443 kb)


  1. Ahmed AAA, Talib ZA, Hussein MZ, Zakaria A (2012) Improvement of the crystallinity and photocatalytic property of zinc oxide as calcination product of Zn–Al layered double hydroxide. J Alloys Compd 539:154–160CrossRefGoogle Scholar
  2. Ali Ahmed AA, Talib ZA, Hussein MZ (2012) Thermal, optical and dielectric properties of Zn–Al layered double hydroxide. Appl Clay Sci 56:68–76CrossRefGoogle Scholar
  3. Bai ZQ, Liu ZW (2017) A broadband photodetector based on Rhodamine B-sensitized ZnO nanowires film. Sci Rep 7:11384CrossRefGoogle Scholar
  4. Chen X, Du Q, Yang W, Liu W, Miao Z, Yang P (2018) A double-layered photoanode made of ZnO/TiO 2 composite nanoflowers and TiO 2 nanorods for high efficiency dye-sensitized solar cells. J Solid State Electrochem 22:685–691CrossRefGoogle Scholar
  5. Darbari S, Ahmadi V, Afzali P, Abdi Y, Feda M (2014) Reduced graphene oxide/ZnO hybrid structure for high-performance photodetection. J Nanopart Res 16:2798CrossRefGoogle Scholar
  6. Fine GF, Cavanagh LM, Afonja A, Binions R (2010) Metal oxide semi-conductor gas sensors in environmental monitoring. Sensors 10:5469–5502CrossRefGoogle Scholar
  7. Foruzin LJ, Rezvani Z, Nejati K (2016) Fabrication of TiO 2@ ZnAl-layered double hydroxide based anode material for dye-sensitized solar cell. RSC Adv 6:10912–10918CrossRefGoogle Scholar
  8. Gao J, Qiu H-J, Wen Y, Chiang F-K, Wang Y (2016) Enhanced electrochemical supercapacitance of binder-free nanoporous ternary metal oxides/metal electrode. J Colloid Interface Sci 474:18–24CrossRefGoogle Scholar
  9. Gu Y, Lu Z, Chang Z, Liu J, Lei X, Li Y, Sun X (2013) NiTi layered double hydroxide thin films for advanced pseudocapacitor electrodes. J Mater Chem A 1:10655–10661CrossRefGoogle Scholar
  10. Gupta B, Jain A, Mehra R (2010) Development and characterization of sol-gel derived Al doped ZnO/p-Si photodiode. J Mater Sci Technol 26:223–227CrossRefGoogle Scholar
  11. Hu L, Zhu L, He H, Guo Y, Pan G, Jiang J, Jin Y, Sun L, Ye Z (2013) Colloidal chemically fabricated ZnO: Cu-based photodetector with extended UV-visible detection waveband. Nanoscale 5:9577–9581CrossRefGoogle Scholar
  12. Kamiya T, Nomura K, Hosono H (2010) Subgap states, doping and defect formation energies in amorphous oxide semiconductor a-InGaZnO4 studied by density functional theory. Phys Status Solidi A 207:1698–1703CrossRefGoogle Scholar
  13. Lan M, Fan G, Sun W, Li F (2013) Synthesis of hybrid Zn–Al–In mixed metal oxides/carbon nanotubes composite and enhanced visible-light-induced photocatalytic performance. Appl Surf Sci 282:937–946CrossRefGoogle Scholar
  14. Law M, Greene LE, Johnson JC, Saykally R, Yang P (2005) Nanowire dye-sensitized solar cells. Nat Mater 4:455–459CrossRefGoogle Scholar
  15. Lee Y, Yu SH, Jeon J, Kim H, Lee JY, Kim H, Ahn JH, Hwang E, Cho JH (2015) Hybrid structures of organic dye and graphene for ultrahigh gain photodetectors. Carbon 88:165–172CrossRefGoogle Scholar
  16. Lehtinen KE, Zachariah MR (2001) Effect of coalescence energy release on the temporal shape evolution of nanoparticles. Phys Rev B 63:205402CrossRefGoogle Scholar
  17. Leung YH, He Z, Luo L, Tsang C, Wong N, Zhang W, Lee S (2010) ZnO nanowires array p-n homojunction and its application as a visible-blind ultraviolet photodetector. Appl Phys Lett 96:053102CrossRefGoogle Scholar
  18. Mathew S, Yella A, Gao P, Humphry-Baker R, Curchod BFE, Ashari-Astani N, Tavernelli I, Rothlisberger U, Nazeeruddin MK, Grätzel M (2014) Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nat Chem 6:242–247CrossRefGoogle Scholar
  19. Musselman KP, Marin A, Schmidt-Mende L, MacManus-Driscoll JL (2012) Incompatible length scales in nanostructured Cu2O solar cells. Adv Funct Mater 22:2202–2208CrossRefGoogle Scholar
  20. Nasiri N, Bo R, Wang F, Fu L, Tricoli A (2015) Ultraporous electron-depleted ZnO nanoparticle networks for highly sensitive portable visible-blind UV photodetectors. Adv Mater 27:4336–4343CrossRefGoogle Scholar
  21. O'regan B, Grätzel M (1991) A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature 353:737–740CrossRefGoogle Scholar
  22. Qadir KW, Ahmad Z, Sulaiman K (2014) Performance enhancement of NiTsPc based photo sensor using treated TiO2 NPs film. J Nanopart Res 16:2705CrossRefGoogle Scholar
  23. Qadir KW, Ahmad Z, Sulaiman K, Yap CC, Touati F (2015) Binary blend based dye sensitized photo sensor using PCPDTBT and MEH-PPV composite as a light sensitizer. Synth Met 210:392–397CrossRefGoogle Scholar
  24. Roslan NA, Abdullah SM, Majid WHA, Supangat A (2018) Investigation of VTP: PC71BM organic composite as highly responsive organic photodetector. Sensors Actuators A Phys 279:361–366CrossRefGoogle Scholar
  25. Salih EY, Abbas Z, Al Ali SHH (2014) Hussein MZ (2014) dielectric behaviour of Zn/Al-NO3 LDHs filled with polyvinyl chloride composite at low microwave frequencies. Adv Mater Sci Eng 2014:1–6CrossRefGoogle Scholar
  26. Salih EY, Sabri MFM, Hussein MZ, Sulaiman K, Said SM, Saifullah B, Bashir MBA (2018a) Structural, optical and electrical properties of ZnO/ZnAl2O4 nanocomposites prepared via thermal reduction approach. J Mater Sci 53:581–590CrossRefGoogle Scholar
  27. Salih EY, Sabri MFM, Sulaiman K, Hussein MZ, Said SM, Usop R, Salleh MFM, Ali Bashir MB (2018b) Thermal, structural, textural and optical properties of ZnO/ZnAl2O4 mixed metal oxide-based Zn/Al layered double hydroxide. Mater Res Exp 5:116202CrossRefGoogle Scholar
  28. Sarijo SH, Ghazali SAISM, Hussein MZ, Sidek NJ (2013) Synthesis of nanocomposite 2-methyl-4-chlorophenoxyacetic acid with layered double hydroxide: physicochemical characterization and controlled release properties. J Nanopart Res 15:1356CrossRefGoogle Scholar
  29. Sing KS (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (recommendations 1984). Pure Appl Chem 57:603–619CrossRefGoogle Scholar
  30. Tauc J (1968) Optical properties and electronic structure of amorphous Ge and Si. Mater Res Bull 3:37–46CrossRefGoogle Scholar
  31. Wang G, Yang M, Li Z, Lin K, Jin Q, Xing C, Hu Z, Wang D (2013) Synthesis and characterization of Zn-doped MgAl-layered double hydroxide nanoparticles as PVC heat stabilizer. J Nanopart Res 15:1882CrossRefGoogle Scholar
  32. Wang C, Chen X, Chen F, Shao J (2018) Organic photodetectors based on copper phthalocyanine films prepared by a multiple drop casting method. Org ElectronGoogle Scholar
  33. Yang Y, Yan X, Hu X, Feng R, Zhou M (2017) In-situ growth of ZIF-8 on layered double hydroxide: effect of Zn/Al molar ratios on their structural, morphological and adsorption properties. J Colloid Interface Sci 505:206–212CrossRefGoogle Scholar
  34. Yu SH, Lee Y, Jang SK, Kang J, Jeon J, Lee C, Lee JY, Kim H, Hwang E, Lee S, Cho JH (2014) Dye-sensitized MoS2 photodetector with enhanced spectral photoresponse. ACS Nano 8:8285–8291CrossRefGoogle Scholar
  35. Zafar Q, Najeeb MA, Ahmad Z, Sulaiman K (2015) Organic–inorganic hybrid nanocomposite for enhanced photo-sensing of PFO-DBT: MEH-PPV: PC 71 BM blend-based photodetector. J Nanopart Res 17:372CrossRefGoogle Scholar
  36. Zhang F, Niu S, Guo W, Zhu G, Liu Y, Zhang X, Wang ZL (2013) Piezo-phototronic effect enhanced visible/UV photodetector of a carbon-fiber/ZnO-CdS double-shell microwire. ACS Nano 7:4537–4544CrossRefGoogle Scholar
  37. Zhang L, Liu J, Xiao H, Liu D, Qin Y, Wu H, Li H, du N, Hou W (2014) Preparation and properties of mixed metal oxides based layered double hydroxide as anode materials for dye-sensitized solar cell. Chem Eng J 250:1–5CrossRefGoogle Scholar
  38. Zhao X, Wang L, Xu X, Lei X, Xu S, Zhang F (2012) Fabrication and photocatalytic properties of novel ZnO/ZnAl2O4 nanocomposite with ZnAl2O4 dispersed inside ZnO network. AICHE J 58:573–582CrossRefGoogle Scholar
  39. Zhu J, Zhu Z, Zhang H, Lu H, Qiu Y, Zhu L, Küppers S (2016) Enhanced photocatalytic activity of Ce-doped Zn-Al multi-metal oxide composites derived from layered double hydroxide precursors. J Colloid Interface Sci 481:144–157CrossRefGoogle Scholar
  40. Zhu Y, Zhu R, Zhu G, Wang M, Chen Y, Zhu J, Xi Y, He H (2018) Plasmonic Ag coated Zn/Ti-LDH with excellent photocatalytic activity. Appl Surf Sci 433:458–467CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.NanoMicro Engineering Laboratory, Department of Mechanical Engineering, Faculty of EngineeringUniversity of MalayaKuala LumpurMalaysia
  2. 2.Solid State Nanodevices Laboratory, Department of Electrical Engineering, Faculty of EngineeringUniversity of MalayaKuala LumpurMalaysia
  3. 3.Schools of Applied Physics, Faculty of Science and TechnologyUniversiti Kebangsaan MalaysiaBangiMalaysia
  4. 4.Low Dimensional Materials Research Centre, Faculty of ScienceUniversity of MalayaKuala LumpurMalaysia
  5. 5.Materials Synthesis and Characterization Laboratory, Institute of Advanced TechnologyUniversiti Putra MalaysiaSerdangMalaysia

Personalised recommendations