The effect of the ZrO₂ crystal form on surface-enhanced Raman scattering (SERS) activity was studied. The ratio of the tetragonal (T) and monoclinic (M) phases of ZrO₂ nanoparticles (ZrO₂ NPs) was controlled by regulating the ratio of two types of additives in the hydrothermal synthesis method. The SERS intensity of 4-mercaptobenzoic acid (4–MBA) was gradually enhanced by changing the M and T phase ratio in ZrO₂ NPs. The degree of charge transfer (CT) in the enhanced 4–MBA molecule was greater than 0.5, indicating that CT was the main contributor to SERS. The intensity of SERS was strongest when the ratio of the T crystal phase in ZrO₂ was 99.7%, and the enhancement factor reached 2.21 × 10⁴. More importantly, the proposed study indicated that the T and M phases of the ZrO₂ NPs affected the SERS enhancement. This study provides a new approach for developing high-quality SERS substrates and improving the transmission efficiency of molecular sensors.

In this study, ZrO₂ and Zn–ZrO₂ nanoparticles (NPs) with a series of Zn ion doping amounts were synthesized by the sol-gel process and utilized as substrates for surface-enhanced Raman scattering (SERS). After absorbing the probing molecule 4–mercaptobenzoic acid, the SERS signal intensities of Zn–ZrO₂ NPs were all greater than that of the pure ZrO₂. The 1% Zn doping concentration ZrO₂ NPs exhibited the highest SERS enhancement, with an enhancement factor (EF) value of up to 10⁴. X-ray diffraction, X-ray photoelectron spectroscopy, Ultraviolet (UV) photoelectron spectrometer, UV–vis spectroscopy, Transmission Electron Microscope (TEM), and Raman spectroscopy were used to characterize the properties of Zn–ZrO₂ NPs and explore the mechanisms behind the SERS phenomenon. The charge transfer (CT) process is considered to be responsible for the SERS performance of 4–MBA adsorbed on Zn–ZrO₂. The results of this study demonstrate that an appropriate doping ratio of Zn ions can promote the charge transfer process between ZrO₂ NPs and probe molecules and significantly improve the SERS properties of ZrO₂ substrates.

Direct observation of the surface-enhanced Raman scattering (SERS) of molecules adsorbed on nano-sized zirconia (ZrO₂) substrates was first reported without the need for the addition of metal particles. It was found that ZrO₂ nanoparticles can exhibit unprecedented Raman signal enhancements on the order of 10³ for the probe molecule 4-mercaptobenzoic acid (4-MBA). The dramatic effect of the calcination temperature on the ZrO₂ nanoparticles was also investigated. The ZrO₂ nanoparticles with the particle diameter of 10.5 nm, which were prepared by calcination at a temperature of 500°C, have the highest SERS activity. A comparison between the experimental and calculation results indicates that charge transfer (CT) effects dominate the surface enhancement. The plentiful surface state of ZrO₂ active substrate that is beneficial to CT resonance occurs between molecules and ZrO₂ to produce a SERS effect. The CT process depends, to a large extent, on the intrinsic properties of the modifying molecules and the surface properties of the ZrO₂. This is a new SERS phenomenon for ZrO₂ that will expand the application of ZrO₂ to microanalysis and is beneficial for studying the basic properties of both ZrO₂ and SERS.

TiO₂ nanotube arrays (TNAs) with tube lengths of 4, 6, and 7 μm were prepared via two-step anodization. Thereafter, ultraviolet (UV) photodetectors (PDs) with Au/TiO₂/Au structures were prepared using these TNAs with different tube lengths. The effects of TNA length and device area on the performance of the device were investigated using in situ Raman spectroscopy. The maximum laser/dark current ratio was achieved by using a TNA with a size of 1 × 1 cm² and a length of 7 μm, under a 532 nm laser. In addition, when the device was irradiated with a higher energy laser (325 nm), the UV Raman spectrum was found to be more sensitive than the visible Raman spectrum. At 325 nm, the laser/dark current ratio was nearly 24 times higher than that under a 532 nm laser. Six phonon modes of anatase TNAs were observed, at 144, 199, 395, 514, and 635 cm⁻¹, which were assigned to the E_g(1), E_g(2), B_1g(1), A_1g/B_1g(2), and E_g(3) modes, respectively. The strong low-frequency band at 144 cm⁻¹ was caused by the O-Ti-O bending vibration and is a characteristic band of anatase. The results show that the performance of TNA-based PDs is length-dependent. Surface-enhanced Raman scattering signals of 4-mercaptobenzoic acid (4-MBA) molecules were also observed on the TNA surface. This result indicates that the length-dependent performance may be derived from an increase in the specific surface area of the TNA. In addition, the strong absorption of UV light by the TNAs caused a blueshift of the E_g(1) mode.