Substrate−molecule vibronic coupling enhancement, especially the efficient photoinduced charge transfer (PICT), is pivotal to the performance of nonmetal surface-enhanced Raman scattering (SERS) technology. Here, through developing novel two-dimensional (2D) amorphous TiO 2 nanosheets (a-TiO 2 NSs), we successfully obtained an ultrahigh enhancement factor of 1.86 × 10 6 . Utilizing the Kelvin probe force microscopy (KPFM) technology, we found that these 2D a-TiO 2 NSs possessed more positive surface potential than their 2D crystalline counterpart (c-TiO 2 NSs). First-principles density functional theory (DFT) was used to further reveal that the low coordination number of surface Ti atoms and the large amount of surface oxygen defects endowed the 2D a-TiO 2 with high electrostatic potential, which allowed significant charge transfer from the adsorbed molecule to the 2D a-TiO 2 and facilitated the formation of a stable surface charge-transfer (CT) complex. Significantly, comparing with the 2D c-TiO 2 , the smaller band gap and higher electronic density of states (DOS) of the 2D a-TiO 2 effectively enhanced the vibronic coupling of resonances in the substrate−molecule system. The strong vibronic coupling within the CT complex obviously enhanced the PICT resonance and lead to the remarkable SERS activity of a-TiO 2 NSs. To the best of our knowledge, this is the first report on the remarkable SERS activity of 2D amorphous semiconductor nanomaterials, which may bring the cutting edge of development of stable and highly sensitive nonmetal SERS technology.

Enhancement of the semiconductor-molecule interaction, in particular, promoting the interfacial charge transfer process (ICTP), is key to improving the sensitivity of semiconductor-based surface enhanced Raman scattering (SERS). Herein, by developing amorphous ZnO nanocages (a-ZnO NCs), we successfully obtained an ultrahigh enhancement factor of up to 6.62×10 . This remarkable SERS sensitivity can be attributed to high-efficiency ICTP within a-ZnO NC molecule system, which is caused by metastable electronic states of a-ZnO NCs. First-principles density functional theory (DFT) simulations further confirmed a stronger ICTP in a-ZnO NCs than in their crystalline counterparts. The efficient ICTP can even generate π bonding in Zn-S bonds peculiar to the mercapto molecule adsorbed a-ZnO NCs, which has been verified through the X-ray absorption near-edge structure (XANES) characterization. To the best of our knowledge, this is the first time such remarkable SERS activity has been observed within amorphous semiconductor nanomaterials, which could open a new frontier for developing highly sensitive and stable SERS technology.

A Cu O superstructure is constructed through a recrystallization-induced self-assembly strategy. Single Cu O superstructure particle exhibits an outstanding surface-enhanced Raman spectroscopy performance with the limit of detection as low as 10 mol L and metal comparable enhancement factor (8 × 10 ) due to the synergetic effect of vacancies defect-facilitated charge-transfer process and copper vacancies defect-induced electrostatic adsorption.

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