Skip to main content
Log in

Cu doped ZrO2 nanoparticles: an optically tuned material with superior structural, electrical and dielectric characteristics

  • Published:
Optical and Quantum Electronics Aims and scope Submit manuscript

Abstract

A chemical co-precipitation method was used to prepare pure and Cu-doped ZrO2 nanoparticles at different doping concentrations (1, 3 and 5 molar %). A comprehensive study of structural and spectroscopic examination confirmed the monoclinic phase with some peaks corresponds to tetragonal phase. No other impurity phase was detected after incorporation of Cu in ZrO2 lattice. FESEM analysis revealed the fine morphology with narrow size distribution with their elemental compositions. Spherical nanoparticles can be clearly seen in pure ZrO2 sample while 1% Cu-doped sample displayed few needle like structure along with NPs and large number of needles can be seen in 5% Cu-doped sample. UV Vis spectroscopy exposed that Cu–ZrO2 NPs exhibit improved light absorption ability and modified bandgap due to the combined effect of interstitial sites and quantum confinement. A red shift in the band absorption edge i.e. from 251 to 260 nm was observed and the bandgap was found to be deceasing from 4.8 to 4.55 eV in ZrO2 samples with Cu content which validate the presence of defects and oxygen vacancies. Dielectric characteristics i.e., dielectric constant (ε') and dielectric loss (tan δ), and ac conductivity were measured at in wide frequency range from 1000 Hz to 15 MHz. Thus, it was exposed that the doping of Cu in ZrO2 leads to attain a tuned bandgap with high dielectric constant and low loss, which encourages the use for optoelectronic applications.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Abbas, N., Zhang, J.M., Nazir, S., Ahsan, M.T., Saleem, S., Ali, U., Akhtar, N., Ikram, M., Liaqat, R.: A comparative study of structural, vibrational mode, optical and electrical properties of pure nickel selenide (NiSe) and Ce-doped NiSe nanoparticles for electronic device applications. Physica B Cond. Matter 649, 414471 (2023)

    Article  CAS  Google Scholar 

  • Agorku, E.S., Kuvarega, A.T., Mamba, B.B., Pandey, A.C., Mishra, A.K.: Enhanced visible-light photocatalytic activity of multi-elements-doped ZrO2 for degradation of indigo carmine. J. Rare Earth 33, 498–506 (2015)

    Article  CAS  Google Scholar 

  • Ahmed, W., Iqbal, J.: Mn doped ZrO2 nanoparticles: an optically tuned photocatalyst with superior structural, magnetic and dielectric characteristics. J. Phys. Chem. Solids 160, 110285 (2022)

    Article  CAS  Google Scholar 

  • Ahmed, W., Iqbal, J., Aisida, S.O., Badshah, A., Ahmad, I., Alamgir, K., Gul, I.H.: Structural, magnetic and dielectric characteristics of optically tuned Fe doped ZrO2 nanoparticles with visible light driven photocatalytic activity. Mater. Chem. Phys. 251, 122999 (2020)

    Article  CAS  Google Scholar 

  • Ali, A., Jameel, M.H., Uddin, S., Zaman, A., Iqbal, Z., Gul, Q., Sultana, F., Mushtaq, M., Khaled, A.K., Ullah, R.: The effect of Ca dopant on the electrical and dielectric properties of BaTi4O9 sintered ceramics. Materials 14, 5375 (2021a)

    Article  CAS  PubMed  PubMed Central  ADS  Google Scholar 

  • Ali, A., Uddin, S., Iqbal, Z., Lal, M., Jameel, M.H., Zaman, A., Ahmad, A., Khan, W.: Synthesis and characterizations of (Ba1-xCax)Ti4O9, 0 ≤ x ≤ 0.9 ceramics. J. Mater. Res. Tech. 11, 1828–1833 (2021b)

    Article  CAS  Google Scholar 

  • Amer, W., El-Sayed, M.A., Allam, N.K.: Tuning the photoactivity of zirconia nanotubes-based photoanodes via ultra-thin layers of ZrN: an effective approach towards visible light-water splitting. J. Phys. Chem. C 120, 7025–7032 (2016)

    Article  CAS  Google Scholar 

  • Arcaro, S., Wermuth, T.B., Zampiva, R.Y.S., Venturini, J., Caten, C.S., Bergmann, C.P., Alves, A.K., Novaes de Oliveira, A.P., Moreno, R.: Li2O-ZrO2-SiO2/Al2O3 nanostructured composites for microelectronics applications. J. Eur. Ceram. Soc. 39, 491–498 (2019)

    Article  CAS  Google Scholar 

  • Awad, N.K., Ashour, E.A., Allam, N.K.: Recent advances in the use of metal oxide based photocathodes for solar fuel production. J. Renew. Sustain. Energy 6, 022702 (2014)

    Article  Google Scholar 

  • Ayeshamariam, A., Sanjeeviraja, C., Jayachandran, M.: Synthesization, Characterization and gas sensing properties of SnO2 nanoparticles. Int. J. Chem. and Anal. Sci. 2, 54–61 (2011)

    Google Scholar 

  • Basahel, S.N., Ali, T.T., Mokhtar, M., Narasimharao, K.: Influence of crystal structure of nanosized ZrO2 on photocatalytic degradation of methyl orange. Nanoscale Res. Lett. 10, 1 (2015)

    Article  CAS  Google Scholar 

  • Berlin, I.J., Maneeshya, L., Thomas, J.K., Thomas, P., Joy, K.: Enhancement of photoluminescence emission intensity of zirconia thin films via aluminum doping for the application of solid state lighting in light emitting diode. J. Lumin. 132, 3077–3081 (2012)

    Article  CAS  Google Scholar 

  • Berlin, I.J., Lekshmy, S.S., Ganesan, V., Thomas, P., Joy, K.: Effect of Mn doping on the structural and optical properties of ZrO2 thin films prepared by sol–gel method. Thin Solid Films 550, 199–205 (2014)

    Article  CAS  ADS  Google Scholar 

  • Bhagwat, M., Ramaswamy, A., Tyagi, A., Ramaswamy, V.: Rietveld refinement study of nanocrystalline copper doped zirconia. Mater. Res. Bull. 38, 1713–1724 (2003)

    Article  CAS  Google Scholar 

  • Biju, V., Sugathan, N., Vrinda, V., Salini, S.L.: Estimation of lattice strain in nanocrystalline silver from X-ray diffraction line broadening. J. Mater. Sci. 43, 1175–1179 (2008)

    Article  CAS  ADS  Google Scholar 

  • Bilgili, O.: The effects of Mn doping on the structural and optical properties of ZnO. Acta Phys. Pol. A 136, 460 (2019)

    Article  CAS  ADS  Google Scholar 

  • Chauhan, A., Verma, R., Kumari, S., Sharma, A., Shandilya, P., Li, X., Batoo, K.M., Imran, A., Kulshrestha, S., Kumar, R.: Photocatalytic dye degradation and antimicrobial activities of pure and Ag-doped ZnO using cannabis sativa leaf extract. Sci. Rep. 10, 1–16 (2020)

    Article  Google Scholar 

  • Choudhury, B., Dey, M., Choudhury, A.: Defect generation, d-d transition, and band gap reduction in Cu-doped TiO2 nanoparticles. Int. Nano. Lett. 3, 25 (2013)

    Article  Google Scholar 

  • Clearfield, A.: The mechanism of hydrolytic polymerization of zirconyl solutions. J. Mater. Res. 5, 161–162 (1990)

    Article  CAS  ADS  Google Scholar 

  • Cretu, V., Postica, V., Mishra, A.K., Hoppe, M., Tiginyanu, I., Mishra, Y.K., Chow, L., Leeuw, N.H., de Adelung, R., Lupan, O.: Synthesis, characterization and DFT studies of zinc-doped copper oxide nanocrystals for gas sensing applications. J. Mater. Chem. A 4, 6527–6539 (2016)

    Article  CAS  Google Scholar 

  • Dutta, G., Hembram, K.P.S.S., Rao, G.M., Waghmare, U.V.: Effects of O vacancies and C doping on dielectric properties of ZrO2: a first-principles study. Appl. Phys. Lett. 89, 202904 (2006)

    Article  ADS  Google Scholar 

  • El-S Khattab, R., El Rehim, S.S.A., Hassan, W.M.I., El-Shazly, T.S.: Band structure engineering and optical properties of pristine and doped monoclinic zirconia (m-ZrO2): density functional theory theoretical prospective. ACS Omega 44, 30061–30068 (2021)

    Article  Google Scholar 

  • El-Shazly, T.S., Hassan, W.M.I., Abdel Rahim, S.T., Allam, N.K.: Unravelling the interplay of dopant concentration and band structure engineering of monoclinic niobium pentoxide: a model photoanode for water splitting. Int. J. Hydrog. Energy 40, 13867–13875 (2015)

    Article  CAS  Google Scholar 

  • El-Shazly, T.S., Hassan, W.M., Abd El Rehim, S.S., Allam, N.K.: Optical and electronic properties of niobium oxynitrides with various N/O ratios: insights from first-principles calculations. J. Photon. Energy 8, 1 (2018)

    Article  Google Scholar 

  • French, R.H., Glass, S.J., Ohuchi, F.S., Xu, Y.N., Ching, W.Y.: Experimental and theoretical determination of the electronic structure and optical properties of three phases of ZrO2. Phys. Rev. B 49, 5140 (1994)

    Article  ADS  Google Scholar 

  • Garvie, R.C.: The occurrence of metastable tetragonal zirconia as a crystallite size effect. J. Phys. Chem. 69, 1238–1243 (1965)

    Article  CAS  Google Scholar 

  • Garvie, R.: Stabilization of the tetragonal structure in zirconia microcrystals. J. Phys. Chem. 82, 218–224 (1978)

    Article  CAS  Google Scholar 

  • Graeve, O., Zirconia, A., Shackelford, J.F., Doremus, R.H. (Eds.), Ceramic and glass materials: structure, properties and processing, Springer Science Business Media, LLC, pp. 169–197 (2008)

  • Haq, B.U., Ahmed, R., Shaari, A., Ali, N., Al-Douri, Y., Reshak, A.H.: Comparative study of Fe doped ZnO based diluted and condensed magnetic semiconductors in wurtzite and zinc-blende structures by first-principles calculations. Mater. Sci. Semicond. Process. 43, 123 (2016)

    Article  Google Scholar 

  • Hassan, N.K., Hashim, M.R., Al-Douri, Y.: Morphology and optical investigations of ZnO pyramids and nanoflakes for optoelectronic applications. Optik 125, 2560–2564 (2014)

    Article  CAS  ADS  Google Scholar 

  • Ijeh, R.O., Ugwuoke, C.O., Ugwu, E.B., Aisida, S.O., Ezema, F.I.: Structural, optical and magnetic properties of Cu-doped ZrO2 films synthesized by electrodeposition method. Ceram. Int. 48, 4686–4692 (2022)

    Article  CAS  Google Scholar 

  • Jameel, M.H., Saleem, S., Hashim, M., Roslan, M.S., Somaily, H.H.N., Hessin, M.M., El-Bahy, Z.M., Ashiq, M.G.B., Hamzah, M.Q., Jabbar, A.H., Yabagi, J.A., Agam, M.A.B.: A comparative study on characterizations and synthesis of pure lead sulfide (PbS) and Ag-doped PbS for photovoltaic applications. Nanotech. Rev. 10, 1484–1492 (2021)

    Article  CAS  Google Scholar 

  • Jebli, M., Rayssi, C., Hamdaoui, N., Rabaoui, S., Dhahri, J., Ben Henda, M., Shaarany, I.: Effect of Nb-doping on the structural and electrical properties of Ba0.97La0.02Ti1-xNb4x/5O3 ceramics at room temperature synthesized by molten-salt method. J. Alloys Compd. 784, 204–212 (2019)

    Article  CAS  Google Scholar 

  • Joy, K., Berlin, I.J., Nair, P.B., Lakshmi, J., Daniel, G.P., Thomas, P.: Effects of annealing temperature on the structural and photoluminescence properties of nanocrystalline ZrO2 thin films prepared by sol–gel route. J. Phys. Chem. Solids 72, 673–677 (2011)

    Article  CAS  ADS  Google Scholar 

  • Joy, K., Maneeshya, L., Thomas, J.K., Thomas, P.: Effect of sol concentration on the structural, morphological, optical and photoluminescence properties of zirconia thin films. Thin Solid Films 520, 2683–2688 (2012)

    Article  CAS  ADS  Google Scholar 

  • Kant, R., Singh, A.K., Arora, A.: Tuning of MgO nanoparticles on Ag dopant additions for charge storage applications. Vacuum 189, 110247 (2021a)

    Article  CAS  ADS  Google Scholar 

  • Kant, R., Sharma, D., Bansal, A., Singh, R.: Structural, optical and dielectric properties of Al/Mn doped ZnO nanoparticles, a comparative study. Mater. Tech. 36, 513–520 (2021b)

    Article  CAS  Google Scholar 

  • Kant, R., Sharma, T., Bhardwaj, S., Kumar, K.: Structural, electrical and optical properties of MgO-reduced graphene oxide nanocomposite for optoelectronic applications. Curr. Appl. Phys. 36, 76–82 (2022)

    Article  ADS  Google Scholar 

  • Khojier, K., Savaloni, H., Jafari, F.: Structural, electrical and decorative properties of sputtered zirconium thin films during post-annealing process. J. Theor. Appl. Phys. 7, 55 (2013)

    Article  ADS  Google Scholar 

  • Kumar, D., Singh, A., Kaur, N., Thakur, A., Kaur, R.: Tailoring structural and optical properties of ZrO2 with nickel doping. SN Appl. Sci. 2, 644 (2020)

    Article  CAS  Google Scholar 

  • Li, W., Liu, X., Huang, A., Chu, P.K.: Structure and properties of zirconia (ZrO2) films fabricated by plasma-assisted cathodic arc deposition. J. Phys. D Appl. Phys. 40, 2293–2299 (2007)

    Article  CAS  ADS  Google Scholar 

  • Lowther, J.E., Dewhurst, J.K., Leger, J.M., Haines, J.: Relative stability of ZrO2 and HfO2 structural phases. Phys. Rev. B 60, 14485–14488 (1999)

    Article  CAS  ADS  Google Scholar 

  • Ma, C., Lapostolle, F., Briois, P., Zhang, Q.: Effect of O2 gas partial pressure on structures and dielectric characteristics of RF sputtered ZrO2 thin films. Appl. Surf. Sci. 253, 8718–8724 (2007)

    Article  CAS  ADS  Google Scholar 

  • Mahendran, N., Jeyakumar, S.J., Ponnar, M.: Structural, optical and electrical properties of copper composite ZrO2 nanoparticles prepared via sol–gel method. J. Mater. Sci. Mater. Electron. 32, 23399–23411 (2021)

    Article  CAS  Google Scholar 

  • Martin, P.J., Netterfield, R.P., Sainty, W.G.: Modification of the optical and structural properties of dielectric ZrO2 films by ion assisted deposition. J. Appl. Phys. 55, 235–241 (1984)

    Article  CAS  ADS  Google Scholar 

  • Nashed, R., Szymanski, P., El-Sayed, M.A., Allam, N.K.: Self-assembled nanostructured photoanodes with staggered bandgap for efficient solar energy conversion. ACS Nano 8, 4915–4923 (2014)

    Article  CAS  PubMed  Google Scholar 

  • Nazir, S., Zhang, J.M., Akhtar, M.N., Abbas, N., Saleem, S., Nauman, M., Ali, A.: Modification of physicochemical and electrical characteristics of lead sulfide (PbS) nanoparticles (NPs) by manganese (Mn) doping for electronic device and applications. J. Sol-Gel Sci. Tech. 108, 778–790 (2023)

    Article  CAS  Google Scholar 

  • Nazir, M.A., Mahmood, T., Zafar, A.A., Akhtar, N., Hussain, T., Saeed, M.A., Fazale, A., Saeed, A., Raza, J., Cao, C.: Electronic, optical and elastic properties of cubic zirconia (c-ZrO2) under pressure: a DFT study. Physica B Cond. Matter 604, 412462 (2021)

    Article  CAS  Google Scholar 

  • Padmamalini, N., Ambujam, K.: Structural, dielectric and impedance studies on high-k ZrO2–TiO2 nanocomposite. J. Mater. Sci. Mater. Electron. 28, 4690–4694 (2017)

    Article  CAS  Google Scholar 

  • Padovini, D.S.S., Pontes, D.S.L., Dalmaschio, C.J., Pontes, F.M., Longo, E.: Facile synthesis and characterization of ZrO2 nanoparticles prepared by the AOP/hydrothermal route. RSC Adv. 4, 38484–38490 (2014)

    Article  CAS  ADS  Google Scholar 

  • Saleem, S., Jameel, M.H., Akhtar, N., Nazir, N., Ali, A., Zaman, A., Rehman, A., Butt, S., Sultana, F., Mushtaq, M., Zeng, J.H., Amami, M., Althubeiti, K.: Modification in structural, optical, morphological, and electrical properties of zinc oxide (ZnO) nanoparticles (NPs) by metal (Ni, Co) dopants for electronic device applications. Arab. J. Chem. 15, 103518 (2022a)

    Article  CAS  Google Scholar 

  • Saleem, S., Jabbar, A.H., Jameel, M.H., Rehman, A., Kareem, Z.H., Abbas, A.H., Ghaffar, Z., Razzaq, S.A., Pashameah, R.A., Alzahrani, E., Poh Ng, P., Sapuan, S.M.: Enhancement in structural, morphological, and optical properties of copper oxide for optoelectronic device applications. Nanotech. Rev. 11, 2827–2838 (2022b)

    Article  CAS  Google Scholar 

  • Saleem, S., Jameel, M.H., Rehman, A., Tahir, M.B., Irshad, M.I., Jiang, Z.Y., Malik, R.Q., Hussain, A.A., Rehman, A., Jabbar, A.H., Alzahrani, A.Y., Salem, M.A., Hessien, M.M.: Evaluation of structural, morphological, optical, and electrical properties of zinc oxide semiconductor nanoparticles with microwave plasma treatment for electronic device applications. J. Mater. Res. Tech. 19, 2126–2134 (2022c)

    Article  CAS  Google Scholar 

  • Saleem, S., Ashiq, N.M., Manzoor, S., Ali, U., Liaqat, R., Algahtani, A., Mujtaba, S., Tirth, V., Alsuhaibani, A.M., Refat, M.S., Ali, A., Aslam, M., Zaman, A.: Analysis and characterization of opto-electronic properties of iron oxide (Fe2O3) with transition metals (Co, Ni) for the use in the photodetector application. J. Mater. Res. Tech. 25, 6150–6166 (2023)

    Article  CAS  Google Scholar 

  • Sayan, S., Nguyen, N.V., Ehrstein, J.: Structural, electronic, and dielectric properties of ultrathin zirconia films on silicon. Appl. Phys. Lett. 86, 152902 (2005)

    Article  ADS  Google Scholar 

  • Shu, Z., Jiao, X., Chen, D.: Hydrothermal synthesis and selective photocatalytic properties of tetragonal star-like ZrO2 nanostructures. Cryst. Eng. Comm. 15, 4288–4294 (2013)

    Article  CAS  Google Scholar 

  • Srdić, V.V., Winterer, M.: Aluminum-doped zirconia nanopowders: chemical vapor synthesis and structural analysis by Rietveld refinement of X-ray diffraction data. Chem. Mater. 15, 2668–2674 (2003)

    Article  Google Scholar 

  • Stubican, V., Hellmann, J.: Science and technology of zirconia. In: Proceedings of the 1st International Conference, American Ceramic Society, Cleveland, vol. 3, pp. 25–36 (1981)

  • Vinoth, E., Gowrishankar, S., Gopalakrishnan, N.: RF magnetron sputtered Cd doped ZnO thin films for gas-sensing applications. Mater. Manuf. Process. 32, 377 (2017)

    Article  CAS  Google Scholar 

  • Wagner, K.W.: The distribution of relaxation times in typical dielectrics. Ann. Phys. 40, 317 (1973)

    Google Scholar 

  • Weber, B.C.: Inconsistencies in zirconia literature. J. Am. Ceram. Soc. 45, 614–615 (1962)

    Article  CAS  Google Scholar 

  • Xiang, Q., Cheng, B., Yu, J.: Graphene-based photocatalysts for solar-fuel generation. Angew. Chem. Int. Ed. 54, 11350–11366 (2015)

    Article  CAS  Google Scholar 

  • Yashima, M., Hirose, T., Katano, S., Suzuki, Y., Kakihana, M., Yoshimura, M.: Structural changes of ZrO2–CeO2 solid solutions around the monoclinic-tetragonal phase boundary. Phys. Rev. B 51, 801 (1995)

    Article  ADS  Google Scholar 

  • Yu, H.X., Mu, H.M., Zhu, D.R., Zhang, Y., Wang, X.C., Zhang, X.S.: DFT study on the oxygen titanium porphyrin as sustainable cyclic catalyst for water splitting. Int. J. Hydrog. Energy 44, 19920–19928 (2019)

    Article  CAS  Google Scholar 

  • Zhu, W., Wang, R., Shu, G., Wu, P., Xiao, H.: First-principles study of the structure, mechanical properties, and phase stability of crystalline zirconia under high pressure. Struct. Chem. 23, 601–611 (2012)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors would like to acknowledge SAIF lab, Panjab University Chandigarh for providing characterization facilities. Mr. Danish is thankful to NIT Hamirpur for providing fellowship funded by UGC, Government of India.

Funding

The authors have not disclosed any funding.

Author information

Authors and Affiliations

Authors

Contributions

DK: Prepared figures and analysis. RK: Wrote–review, editing and Conceptualization (lead). AB: Prepared figures and analysis. VS: Editing and reviewed. KKS: Reviewed and formal analysis (supporting),

Corresponding author

Correspondence to Ravi Kant.

Ethics declarations

Conflict of interest

No conflicts of interest to declare.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kumar, D., Kant, R., Bhardwaj, A. et al. Cu doped ZrO2 nanoparticles: an optically tuned material with superior structural, electrical and dielectric characteristics. Opt Quant Electron 56, 418 (2024). https://doi.org/10.1007/s11082-023-06092-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11082-023-06092-x

Keywords

Navigation