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<p>This study provides new insights into the impact of copper doping on the structural, morphological, and optical properties of ZnO in both nanoparticle and ceramic forms, demonstrating a tunable approach to enhance its functionality for optoelectronic and photocatalytic applications. Unlike previous studies that primarily focused on conventional synthesis techniques, we employ a sol–gel process with supercritical drying for nanoparticle fabrication, followed by spark plasma sintering (SPS) to achieve dense ceramics with controlled microstructure. Zn<sub>1-x</sub>Cu<sub>x</sub>O (<i>x</i> = 0; 0.02; 0.04) nanoparticles with Cu loading percentages of 0% (ZnO), 2% (Zn<sub>0.98</sub>Cu<sub>0.02</sub>O), and 4% (Zn<sub>0.96</sub>Cu<sub>0.04</sub>O) were synthesized and annealed at 400&#xa0;℃ for 2&#xa0;h. These nanoparticles were then sintered via SPS at 1000&#xa0;℃ with a heating rate of 100&#xa0;℃/min under nitrogen, maintaining a uniaxial pressure of 50&#xa0;MPa and a dwell time of 3&#xa0;min. Structural, morphological, and optical properties were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV–Visible-NIR spectroscopy. XRD confirmed a hexagonal wurtzite structure for both pure and Zn<sub>1-x</sub>Cu<sub>x</sub>O (<i>x</i> = 0; 0.02; 0.04). The crystallite size in the nanoparticle form decreased with copper doping (from ~ 21&#xa0;nm for ZnO to ~ 17&#xa0;nm for Zn<sub>0.96</sub>Cu<sub>0.04</sub>O), attributed to the ionic radius difference between Zn<sup>2</sup>⁺ and Cu<sup>2</sup>⁺. SEM images confirmed this reduction in nanoparticle size, while in the ceramic state, grain coalescence during sintering led to larger grains with increasing Cu content. Optical studies showed a slight decrease in the bandgap from 3.21&#xa0;eV (ZnO) to 3.17&#xa0;eV (Zn<sub>0.96</sub>Cu<sub>0.04</sub>O). In ceramics, pure ZnO exhibited a prominent absorption peak around 500&#xa0;nm, while Cu loading led to broader and stronger absorption across the visible range. These findings highlight the potential of Zn<sub>1-x</sub>Cu<sub>x</sub>O (<i>x</i> = 0; 0.02; 0.04) as a tunable material for advanced optical applications.</p>

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Structural, morphological, and optical properties of Zn1-xCuxO (x = 0; 0.02; 0.04): a comparative study of nanoparticle and ceramic states via sol–gel and spark plasma sintering

  • 期刊论文

  • 发表日期：

    2025年7月27日

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  • Sonia Soltani,
  • Mokhtar Hjiri,
  • Sherif S. Aly,
  • E. A. Elghmaz,
  • Abdullah M. Aldukhayel,
  • Nouf Ahmed Althumairi,
  • Anouar Jbeli

摘要

This study provides new insights into the impact of copper doping on the structural, morphological, and optical properties of ZnO in both nanoparticle and ceramic forms, demonstrating a tunable approach to enhance its functionality for optoelectronic and photocatalytic applications. Unlike previous studies that primarily focused on conventional synthesis techniques, we employ a sol–gel process with supercritical drying for nanoparticle fabrication, followed by spark plasma sintering (SPS) to achieve dense ceramics with controlled microstructure. Zn1-xCuxO (x = 0; 0.02; 0.04) nanoparticles with Cu loading percentages of 0% (ZnO), 2% (Zn0.98Cu0.02O), and 4% (Zn0.96Cu0.04O) were synthesized and annealed at 400 ℃ for 2 h. These nanoparticles were then sintered via SPS at 1000 ℃ with a heating rate of 100 ℃/min under nitrogen, maintaining a uniaxial pressure of 50 MPa and a dwell time of 3 min. Structural, morphological, and optical properties were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV–Visible-NIR spectroscopy. XRD confirmed a hexagonal wurtzite structure for both pure and Zn1-xCuxO (x = 0; 0.02; 0.04). The crystallite size in the nanoparticle form decreased with copper doping (from ~ 21 nm for ZnO to ~ 17 nm for Zn0.96Cu0.04O), attributed to the ionic radius difference between Zn2⁺ and Cu2⁺. SEM images confirmed this reduction in nanoparticle size, while in the ceramic state, grain coalescence during sintering led to larger grains with increasing Cu content. Optical studies showed a slight decrease in the bandgap from 3.21 eV (ZnO) to 3.17 eV (Zn0.96Cu0.04O). In ceramics, pure ZnO exhibited a prominent absorption peak around 500 nm, while Cu loading led to broader and stronger absorption across the visible range. These findings highlight the potential of Zn1-xCuxO (x = 0; 0.02; 0.04) as a tunable material for advanced optical applications.