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Keywords:

  • ZnO;
  • SERS;
  • plasma;
  • azo dye;
  • DFT

Surface-enhanced Raman scattering (SERS) spectra of azo dyes (methyl orange and p-methyl red) adsorbed on ZnO nanoparticles were observed. Hydrothermally synthesized ZnO nanoparticles were characterized by powder X-ray diffraction and X-ray photoelectron spectroscopy. The ZnO nanoparticle size, monitored with X-ray diffraction, was tuned by calcination to optimize SERS intensities. The observed SERS effect of azo dyes adsorbed on ZnO can be ascribed to charge-transfer resonance effect. Time-dependent density functional theory was used to calculate the optical spectra and interpret the chemical enhancement observed in the experiment. The SERS enhancement factors for methyl red on ZnO were boosted by nearly four times and twice with O2 plasma and H2 plasma, respectively. However, plasma treatment showed no effect on the enhancement factors of methyl orange on ZnO. We conclude that plasma-induced defect formation and band gap shift in ZnO and the coupling of energy levels between ZnO and azo dye molecules are responsible for the observed enhancement of SERS intensities. Copyright © 2014 John Wiley & Sons, Ltd.