Journal
JOURNAL OF COLLOID AND INTERFACE SCIENCE
Volume 610, Issue -, Pages 164-172Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcis.2021.12.032
Keywords
Al-doped ZnO; SERS; Conduction band; Charge-transfer
Categories
Funding
- Natural Science Foundation of China [21327803, 21611130173, 21773080, 21711540292]
- Postdoctoral Science Foundation of China [2014 M561286]
- Special Funds of State Key Laboratories
- China Scholarship Council [201806175231]
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This study investigates the importance of enhancing charge transfer in the AZO/MPy/Ag sandwich structure, and identifies a significant CT route from the CB of AZO to the LUMO of the MPy molecule, which can effectively improve the degree of CT. This discovery is expected to play a crucial role in enhancing SERS.
In the semiconductor/molecule/metal system, enhancing the efficiency of the charge-transfer (CT) plays a pivotal role in improving the sensitivity of semiconductor-based surface-enhanced Raman scattering (SERS). In this work, use of SERS for detection of an enhanced CT in a chemically-etched Al-doped ZnO (AZO), 4-mercaptopyridine (MPy) molecule, and Ag nanoparticles (NPs) (AZO/MPy/Ag) sandwich structure is reported. A series of CT routes are proposed in the energy level diagram of AZO/MPy/Ag assemblies under the excitation line at 633 nm. Very interestingly, for the first of its kind, a significant CT route from the conduction band (CB) of AZO to the lowest unoccupied molecular orbital (LUMO) of MPy molecule is detected. This route can remarkably improve the degree of CT in the AZO/MPy/Ag system by about 48% compared with that of the ZnO/MPy/Ag system. Furthermore, the uniquely enhanced CT route is also further confirmed by alternative probe molecules like p-aminothiophenol (PATP) and 4-mercaptobenzoic acid (MBA). The discovery of this extra CT route will inevitably play an irreplaceable role in SERS enhancement through its participating in the CT enhancement mechanism. (c) 2021 Elsevier Inc. All rights reserved.
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