Skip to main content
SpringerLink
Log in

Studies of structural, optical, and electrical properties associated with defects in sodium-doped copper oxide (CuO/Na) nanostructures

  • Ceramics
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

In the present paper, we report a detailed study on the sodium (Na) doping-induced modifications in the copper oxide (CuO) nanostructure and its properties. A facile and sustainable sol–gel synthesis approach was employed for the preparation of high-quality pristine CuO- and Na-doped CuO nanostructures(1.0, 3.0, 5.0 and 7.0 mol% doping levels, CuO/Na) with controlled shape and composition. Due to the remarkable difference in the ionic radii of Cu2+ (0.73 Å) and Na+ (1.02 Å), Na+ substitution in place of Cu2+ generates strain/distortions in CuO lattice. The XRD analysis reveal the structural alteration from monoclinic to cubic symmetry with increase in doping level and also reveal the phase purity up to 3% doping level, and beyond this (i.e., for 5 and 7% doping level) small amount of impurity phase corresponding to Na2O was observed. The FTIR results further confirmed the presence of the Na–Cu–O stretching vibrations at higher Na-doped samples. Morphology of the samples indicates that the Na-doped CuO nanostructures exhibit less agglomeration compared to pristine CuO nanoparticles. The presence of Na in CuO lattice were found to greatly enhances optical and electrical properties owing to the formation of defects like copper vacancies and oxygen vacancies at the grain boundaries of the nanoparticles with increased doping of Na.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Figure 12
Figure 13
Figure 14
Figure 15

Similar content being viewed by others

References

  1. Siddiqui H, Parra MR, Pandey P, Singh N, Qureshi MS, Haque FZ (2012) A review: synthesis, characterization and cell performance of Cu2O based material for solar cells. Orient J Chem 28(3):1533–1545

    Article  Google Scholar 

  2. Abu-Zied BM, Bawaked SM, Kosa SA, Schwieger W (2016) Impact of Gd-, La-, Nd- and Y-doping on the textural, electrical conductivity and N2O decomposition activity of CuO catalyst. Int J Electrochem Sci 11:2230–2246

    Google Scholar 

  3. Abu-Zied BM, Bawaked SM, Kosa SA, Schwieger W (2016) Effect of some rare earth oxides doping on the morphology, crystallite size, electrical conductivity and N2O decomposition activity of CuO catalyst. Int J Electrochem Sci 11:1568–1580

    Google Scholar 

  4. Bhuvaneshwari S, Gopalakrishnan N (2016) Enhanced ammonia sensing characteristics of Cr doped CuO nanoboats. J Alloys Compd 654:202–208

    Article  Google Scholar 

  5. Zhang Q, Zhang K, Xu D, Yang G, Huang H, Nie F, Liu C, Yang S (2014) CuO nanostructures: synthesis, characterization, growth mechanisms, fundamental properties, and applications. Prog Mater Sci 60:208–337

    Article  Google Scholar 

  6. Siddiqui H, Qureshi MS, Haque FZ (2016) Effect of copper precursor salts: facile and sustainable synthesis of controlled shaped copper oxide nanoparticles. Optik 127:4726–4730

    Article  Google Scholar 

  7. Siddiqui H, Qureshi MS, Haque FZ (2017) pH-Dependent single-step rapid synthesis of CuO nanoparticles and their optical behavior. Opt Spectrosc 123(6):903–912

    Article  Google Scholar 

  8. Haque FZ, Parra MR, Siddiqui H, Singh N, Singh N, Pandey P, Mishra KM (2016) PVP assisted shape-controlled synthesis of self-assembled 1D ZnO and 3D CuO nanostructures. Opt Spectrosc 120(3):408–414

    Article  Google Scholar 

  9. Siddiqui H, Qureshi MS, Haque FZ (2014) Structural and optical properties of CuO nanocubes prepared through simple hydrothermal route. Int J Sci Eng Res 5(3):173–177

    Google Scholar 

  10. Devi LV, Selvalakshmi T, Sellaiyan S, Uedono A, Sivaji K, Sankar S (2017) Effect of La doping on the lattice defects and photoluminescence properties of CuO. J Alloys Compd 709:496–504

    Article  Google Scholar 

  11. Chiang CY, Shin Y, Ehrman S (2012) Li doped CuO film electrodes for photoelectrochemical cells. J Electrochem Soc 159(2):B227–B231. https://doi.org/10.1149/2.081202jes

    Article  Google Scholar 

  12. Chiang CY, Shin Y, Ehrman S (2014) Dopant effects on copper oxide photoelectrochemical cell water splitting. Energy Procedia 61:1799–1802

    Article  Google Scholar 

  13. Chuai M, Zhao Q, Yang T, Luo Y, Zhang M (2015) Synthesis and ferromagnetism study of Ce doped CuO dilute magnetic semiconductor. Mater Lett 161:205–207

    Article  Google Scholar 

  14. Faiz H, Siraj K, Khan MF, Irshad M, Majeed S, Rafique MS, Naseem S (2016) Microstructural and optical properties of dysprosium doped copper oxide thin films fabricated by pulsed laser deposition technique. J Mater Sci: Mater Electron 27:8197–8205

    Google Scholar 

  15. Wang D, Wang Y, Jiang T, Jia H, Yu M (2016) The preparation of M (M: Mn2+, Cd2+, Zn2+)-doped CuO nanostructures via the hydrothermal method and their properties. J Mater Sci: Mater Electron 27:2138–2145

    Google Scholar 

  16. Meneses CT, Duque JGS, Vivas LG, Knobel M (2008) Synthesis and characterization of TM-doped CuO (TM = Fe, Ni). J Non-Cryst Solids 354:4830–4832

    Article  Google Scholar 

  17. Hu X, Zhu Z, Chen C, Wen T, Zhao X, Xie L (2017) Highly sensitive H2S gas sensors based on Pd-doped CuO nanoflowers with low operating temperature. Sens Actuators B Chem 253:809–817

    Article  Google Scholar 

  18. Jichun P, Hongbin H, Dianxue W, Wang CG (2012) Influence of Ag doped CuO nanosheet arrays on electrochemical behaviors for supercapacitors. Electrochim Acta 75:208–212

    Article  Google Scholar 

  19. Panah SM, Radhakrishnan K, Tan HR, Yi R, Wong TI, Dalapati GK (2015) Titanium doped cupric oxide for photovoltaic application. Sol Energy Mater Sol Cells 140:266–274

    Article  Google Scholar 

  20. Asadi H, Vaezzadeh M (2017) Computational designing ultra-sensitive nano-composite based on boron doped and CuO decorated graphene to adsorb H2S and CO gaseous molecules. Mater Res Express 4(7):075039. https://doi.org/10.1088/2053-1591/aa7c33

    Article  Google Scholar 

  21. Suda S, Fujitsu S, Koumoto K, Yanagida H (1992) The effect of atmosphere and doping on electrical conductivity of CuO. Jpn J Appl Phys 31:2488–2491

    Article  Google Scholar 

  22. Vidhya SN, Balasundaram ON, Chandramohan M (2015) Influence of doping concentration on the properties of Ga doped CuO thin films by the spray pyrolysis technique. J Optoelectron Adv Mater 17(7):963–967

    Google Scholar 

  23. Yildiz A, Horzum Ş, Serin N, Serin T (2014) Hopping conduction in In-doped CuO thin films. Appl Surf Sci 318:105–107

    Article  Google Scholar 

  24. Wu J, Hui KS, Hui KN, Li L, Chun HH, Cho YR (2016) Characterization of Sn-doped CuO thin films prepared by a sol–gel method. J Mater Sci: Mater Electron 27:1719–1724

    Google Scholar 

  25. Bayansal F, Gülen Y, Şahin B, Kahramana S, Çetinkar HA (2015) CuO nanostructures grown by the SILAR method: influence of Pb-doping on the morphological, structural and optical properties. J Alloys Compd 619:378–382

    Article  Google Scholar 

  26. Chand P, Gaur A, Kumar A, Gaur UK (2014) Structural and optical study of Li doped CuO thin films on Si (100) substrate deposited by pulsed laser deposition. Appl Surf Sci 307:280–286

    Article  Google Scholar 

  27. Thi TV, Rai AK, Gim J, Kim J (2014) Potassium-doped copper oxide nanoparticles synthesized by a solvothermal method as an anode material for high-performance lithium ion secondary battery. Appl Surf Sci 305:617–625

    Article  Google Scholar 

  28. Choi YH, Kim DH, Hong SH (2017) p-Type aliovalent Li(I) or Fe(III)-doped CuO hollow spheres self-organized by cationic complex ink printing: structural and gas sensing characteristics. Sens Actuators B Chem 243:262–270

    Article  Google Scholar 

  29. Wang RC, Lin SN, Liu JY (2017) Li/Na-doped CuO nanowires and nanobelts: enhanced electrical properties and gas detection at room temperature. J Alloys Compd 696:79–85

    Article  Google Scholar 

  30. Sahin B, Kaya T (2016) Highly improved hydration level sensing properties of copper oxide films with sodium and potassium doping. Appl Surf Sci 362:532–537

    Article  Google Scholar 

  31. Nasir M, Patra N, Ahmed MA, Shukla DK, Kumar S, Bhattacharya D, Prajapat CL, Phase DM, Jha SN, Biring S, Sen S (2017) Role of compensating Li/Fe incorporation in Cu0.945Fe0.055−xLi x O: structural, vibrational and magnetic properties. RSC Adv 7:31970–31979

    Article  Google Scholar 

  32. Tabib A, Bouslama W, Sieber B, Addad A, Elhouicheta H, Férid M, Boukherrou R (2017) Structural and optical properties of Na doped ZnO nanocrystals: application to solar photocatalysis. Appl Surf Sci 396:1528–1538

    Article  Google Scholar 

  33. Chimupala Y, Hyett G, Simpson R, Mitchell R, Douthwaite R, MilneSJ BrydsonRD (2014) Synthesis and characterization of mixed phase anatase TiO2 and sodium-doped TiO2(B) thin films by low pressure chemical vapour deposition (LPCVD). RSC Adv 4:48507–48515

    Article  Google Scholar 

  34. Etefagh R, Azhir E, Shahtahmasebi N (2013) Synthesis of CuO nanoparticles and fabrication of nanostructural layer biosensors for detecting Aspergillus niger fungi. Sci Iran 20(3):1055–1058

    Google Scholar 

  35. Nasir M, Islam R, Ahmed MA, Ayaz S, Kumar G, Kumar S, Prajapat CL, Roussel F, Biring S, Sen S (2017) Cu1-xFe x O: hopping transport and ferromagnetism. R Soc Open Sci 4:170339. https://doi.org/10.1098/rsos.170339

    Article  Google Scholar 

  36. Bhaumik A, Shearin AM, Patel R, Ghosh K (2014) Significant enhancement of optical absorption through nano-structuring of copper based oxide semiconductors: possible future materials for solar energy applications. Phys Chem Chem Phys 16:11054–11066

    Article  Google Scholar 

  37. Zeman M, Krc J (2007) Electrical and optical modelling of thin-film silicon solar cells. Mater Res Soc Symp Proc 989:A03-01. https://doi.org/10.1557/PROC-0989-A03-01

    Article  Google Scholar 

  38. Nomura K, Ohta H, Takagi A, Kamiya T, Hirano M, Hosono H (2004) Room-temperature fabrication of transparent flexible thin-film transistors using amorphous oxide semiconductors. Nature 432:488–492

    Article  Google Scholar 

  39. Siddiqui H, Qureshi MS, Haque FZ (2016) Surfactant assisted wet chemical synthesis of copper oxide (CuO) nanostructures and their spectroscopic analysis. Optik 127:2740–2747

    Article  Google Scholar 

  40. Parra MR, Haque FZ (2015) Poly (Ethylene Glycol) (PEG)-assisted shape-controlled synthesis of one-dimensional ZnO nanorods. Optik 126:1562–1566

    Article  Google Scholar 

  41. Parra MR, Haque FZ (2014) Aqueous chemical route synthesis and the effect of calcination temperature on the structural and optical properties of ZnO nanoparticles. J Mater Res Technol 4(3):363–369

    Article  Google Scholar 

  42. Parra MR, Haque FZ (2015) Optical investigation of various morphologies of ZnO nanostructures prepared by PVP-assisted wet chemical method. Opt Spectrosc 118(5):765–772

    Article  Google Scholar 

  43. Siddiqui H, Qureshi MS, Haque FZ (2016) Hexamine (HMT) assisted wet chemically synthesized CuO nanostructures with controlled morphology and adjustable optical behavior. Opt Quantum Electron 48:349–364

    Article  Google Scholar 

  44. Pandey P, Kurchania R, Haque FZ (2015) Structural, diffused reflectance and photoluminescence study of cerium doped ZnO nanoparticles synthesized through simple sol–gel method. Optik 126(21):3310–3315

    Article  Google Scholar 

  45. Jana R, Saha P, Pareek V, Basu A, Kapri S, Bhattacharyya S, Mukherjee GD (2016) High pressure experimental studies on CuO: indication of re-entrant multiferroicity at room temperature. Sci Rep 6:31610. https://doi.org/10.1038/srep31610

    Article  Google Scholar 

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

    Article  Google Scholar 

  47. Siddiqui H, Qureshi MS, Haque FZ (2014) One-step, template-free hydrothermal synthesis of CuO tetrapods. Optik 125:4663–4667

    Article  Google Scholar 

  48. Wu Z, Li Y, Gao L, Wang S, Fu G (2016) Synthesis of Na-doped ZnO hollow spheres with improved photocatalytic activity for hydrogen production. Dalton Trans 45:11145–11149

    Article  Google Scholar 

  49. Shrivastava M, Kumari R, Parra MR, Pandey P, Siddiqui H, Haque FZ (2017) Electrochemical synthesis of MoS2 quantum dots embedded nanostructured porous silicon with enhanced electroluminescence property. Opt Mater 73:763–771

    Article  Google Scholar 

  50. Meghana S, Kabra P, Chakraborty S, Padmavathy N (2015) Understanding the pathway of antibacterial activity of copper oxide nanoparticles. RSC Adv 5:12293–12299

    Article  Google Scholar 

  51. Wang Y, Jiang T, Meng D, Kong J, Jia H, Yu M (2015) Controllable fabrication of nanostructured copper compound on a Cu substrate by a one-step route. RSC Adv 5:16277–16283

    Article  Google Scholar 

  52. Chiu SH, Huang JCA (2013) Characterization of p-type CuAlO2 thin films grown by chemical solution deposition. Surf Coat Technol 231:239–242

    Article  Google Scholar 

  53. Fang M, He H, Lu B, Zhang W, Zhao B, Ye Z, Huang J (2011) Optical properties of p-type CuAlO2 thin film grown by rf magnetron sputtering. Appl Surf Sci 257:8330–8333

    Article  Google Scholar 

  54. Dongliang H, Jiahai H, Long Q, Jiangrui P, Zhenji S (2015) Optical and photocatalytic properties of Cu–Cu2O/TiO2 two-layer nanocomposite films on Si substrates. Rare Metal Mat Eng 44(8):1888–1893

    Article  Google Scholar 

  55. Kondofersky IT (2016) Design of photoelectrode morphologies for solar-driven water splitting. Ph.D. Thesis, Der Ludwig-Maximilians-Universität München

  56. Iqbal M, Thebo AA, Shah AH, Iqbal A, Thebo KH, Phulpoto S, Mohsin MA (2017) Influence of Mn-doping on the photocatalytic and solar cell efficiency of CuO nanowires. Inorg Chem Commun 76:71–76

    Article  Google Scholar 

  57. Gaur UK, Kumar A, Varma GD (2015) Fe-induced morphological transformation of 1-D CuO nanochains to porous nanofibers with enhanced optical, magnetic and ferroelectric properties. J Mater Chem C 3:4297–4307

    Article  Google Scholar 

  58. Zoolfakar AS, Rani RA, Morfa AJ, O’Mullane AP, Kalantar-zadeh K (2014) Nanostructured copper oxide semiconductors: a perspective on materials, synthesis methods and applications. J Mater Chem C 2:5247–5270

    Article  Google Scholar 

  59. Zhao X, Wang P, Yan Z, Ren N (2015) Room temperature photoluminescence properties of CuO nanowire arrays. Opt Mater 42:544–547

    Article  Google Scholar 

  60. Balamurugan B, Aruna I, Mehta BR, Shivaprasad SM (2004) Size-dependent conductivity-type inversion in Cu2O nanoparticles. Phys Rev B 69:165419. https://doi.org/10.1103/PhysRevB.69.165419

    Article  Google Scholar 

  61. Sukhorukov YP, Loshkareva NN, Samokhvalov AA, Moskvin AS (1995) Absorption spectra of CuO single crystals near the absorption edge and the nature of the optical gap in copper oxides. J Exp Theor Phys 81(5):998–1002

    Google Scholar 

  62. Chowdhury A, Bijalwan PK, Sahu RK (2014) Investigations on the role of alkali to obtain modulated defect concentrations for Cu2O thin films. Appl Surf Sci 289:430–436

    Article  Google Scholar 

  63. Balamurugan B, Mehta B, Avasthi D, Singh F, Arora A, Rajalakshmi M, Raghavan G, Tyagi A, Shivaprasad S (2002) Modifying the nanocrystalline characteristics-structure, size, and surface states of copper oxide thin films by high-energy heavy-ion irradiation. J Appl Phys 92:3304–3310

    Article  Google Scholar 

  64. Lin G, Zhao F, Zhao Y, Zhang D, Yang L, Xue X, Wang X, Qu C, Li Q, Zhang L (2016) Luminescence properties and mechanisms of CuI thin films fabricated by vapor iodization of copper films. Materials (Basel) 9(12):E990. https://doi.org/10.3390/ma9120990

    Article  Google Scholar 

  65. Ahrens LH, Press F, Runcorn SK (2013) Physics and chemistry of the earth: progress series, vol 6. Elsevier Publication, Amsterdam, p 522

    Google Scholar 

  66. Lai JJ, Lin YJ, Chen YH, Chang HC, Liu CJ, Zou YY, Shih YT, Wang MC (2011) Effects of Na content on the luminescence behavior, conduction type, and crystal structure of Na-doped ZnO films. J Appl Phys 110:013704–013708

    Article  Google Scholar 

  67. Bibi M, Javed QA, Abbas H, Baqi S (2017) Outcome of temperature variation on sol-gel prepared CuO nanostructure properties (optical and dielectric). Mater Chem Phys 192:67–71

    Article  Google Scholar 

  68. Oruç Ç, Altındal A (2017) Structural and dielectric properties of CuO nanoparticles. Ceram Int 43(14):10708–10714

    Article  Google Scholar 

  69. Rai C, Pandey P, Parra MR, Haque FZ (2014) Optical, dielectric and impedance studies of SiO2/MWCNT nanocomposite synthesized through in situ ultrasonication-assisted sol–gel method. J Adv Phys 3(3):194–204

    Article  Google Scholar 

  70. Priscilla SJ, Sivaji K, Vimaladevi L (2017) Synthesis and characterization of Na doped cupric oxide (CuO) nanoparticles. In: AIP conference proceedings, vol 1832. p 050128

  71. Nakayama S, Kaji T, Notoya T, Osakai T (2008) Mechanistic study of the reduction of copper oxides in alkaline solutions by electrochemical impedance spectroscopy. Electrochim Acta 53:3493–3499

    Article  Google Scholar 

  72. Barsoukov E, Macdonald RJ (2005) Impedance spectroscopy: theory, experiment, and applications. 2nd edn. Wiley, Hoboken

Download references

Acknowledgements

Hafsa Siddiqui and Mohammad Ramzan Parra deeply acknowledge the UGC, New Delhi, and HRDG-CSIR for the financial support given in the form of UGC-MANF videno. F1-17.1/2011-12/MANF-MUS-MAD-4694 and CSIR-SRF Ack. No. 163320/2K14/1, respectively. Authors would like to acknowledge the Director-UGC-DAE-CSR, Indore Centre for performing XRD, Raman, FTIRand UV–Vis–NIR measurements. The authors are grateful to the USIF, Aligarh Muslim University, for providing the TEM facility.

Author information

Authors and Affiliations

  1. Optical Nanomaterials Lab, Department of Physics, Maulana Azad National Institute of Technology, Bhopal, M.P., 462003, India

    Hafsa Siddiqui, Mohammad Ramzan Parra, M. S. Qureshi, M. M. Malik & Fozia Z. Haque

Authors
  1. Hafsa Siddiqui
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mohammad Ramzan Parra
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. S. Qureshi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. M. Malik
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Fozia Z. Haque
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Fozia Z. Haque.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interests. Also all authors are entirely responsible for the content and writing of the paper.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Siddiqui, H., Parra, M.R., Qureshi, M.S. et al. Studies of structural, optical, and electrical properties associated with defects in sodium-doped copper oxide (CuO/Na) nanostructures. J Mater Sci 53, 8826–8843 (2018). https://doi.org/10.1007/s10853-018-2179-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-018-2179-6

Keywords

Search

Navigation