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      Construction of Ultrasensitive Surface‐Enhanced Raman Scattering Substates Based on TiO 2 Aerogels

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          Abstract

          Recent advances in surface‐enhanced Raman scattering (SERS) on semiconductor substrates offer this technology improved selectivity on top of other advantages, such as cost efficiency. However, the enhancement factor (EF) based on the semiconductors is still low compared with the noble metal substrates. Here, a new strategy of developing the semiconductor substrates based on aerogels is proposed for the first time. According to the modified Herzberg–Teller coupling rule, TiO 2 aerogels are selected as the control object because of their large tunability. The surface area, amorphousness, and surface oxygen vacancy densities of TiO 2 aerogels are regulated synergically. Due to the tuning of band structure, including band gap and defect band, multiresonant interband charge transfer (CT) pathways are generated and enhanced CT efficiency. A strong, intrinsically activated SERS effect is generated. Amorphous TiO 2 aerogel with the highest surface oxygen vacancies shows a significant EF of 2.42 × 10 7, and TiO 2 aerogels afford the large surface area and more active sites, which is conducive to promoting the adsorption of molecules. The aerogel‐based SERS is demonstrated to have wide applicability for ultrasensitive detection of explosives and organic dyes. The aerogel nanomaterials demonstrated here open a way for the construction of low‐cost and high‐sensitivity SERS substrate materials.

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          Two-Dimensional Titanium Nitride (Ti2N) MXene: Synthesis, Characterization, and Potential Application as Surface-Enhanced Raman Scattering Substrate

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            Noble metal-comparable SERS enhancement from semiconducting metal oxides by making oxygen vacancies

            Surface-enhanced Raman spectroscopy (SERS) represents a very powerful tool for the identification of molecular species, but unfortunately it has been essentially restricted to noble metal supports (Au, Ag and Cu). While the application of semiconductor materials as SERS substrate would enormously widen the range of uses for this technique, the detection sensitivity has been much inferior and the achievable SERS enhancement was rather limited, thereby greatly limiting the practical applications. Here we report the employment of non-stoichiometric tungsten oxide nanostructure, sea urchin-like W18O49 nanowire, as the substrate material, to magnify the substrate–analyte molecule interaction, leading to significant magnifications in Raman spectroscopic signature. The enrichment of surface oxygen vacancy could bring additional enhancements. The detection limit concentration was as low as 10−7 M and the maximum enhancement factor was 3.4 × 105, in the rank of the highest sensitivity, to our best knowledge, among semiconducting materials, even comparable to noble metals without ‘hot spots'.
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              Enhanced Raman Scattering with Dielectrics.

              Dielectrics represent a new frontier for surface-enhanced Raman scattering. They can serve as either a complement or an alternative to conventional, metal-based SERS, offering key advantages in terms of low invasiveness, reproducibility, versatility, and recyclability. In comparison to metals, dielectric systems and, in particular, semiconductors are characterized by a much greater variety of parameters and properties that can be tailored to achieve enhanced Raman scattering or related effects. Light-trapping and subwavelength-focusing capabilities, morphology-dependent resonances, control of band gap and stoichiometry, size-dependent plasmons and excitons, and charge transfer from semiconductors to molecules and vice versa are a few examples of the manifold opportunities associated with the use of semiconductors as SERS-active materials. This review provides a broad analysis of SERS with dielectrics, encompassing different optical phenomena at the basis of the Raman scattering enhancement and introducing future challenges for light harvesting, vibrational spectroscopy, imaging, and sensing.
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                Author and article information

                Contributors
                Journal
                Advanced Optical Materials
                Advanced Optical Materials
                Wiley
                2195-1071
                2195-1071
                May 14 2023
                Affiliations
                [1 ] Institute of Chemical Materials China Academy of Engineering Physics Mianyang 621900 China
                [2 ] State Key Laboratory of Materials‐Oriented Chemical Engineering, College of Material Science and Engineering Nanjing Tech University Nanjing 211816 China
                [3 ] Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites Nanjing Tech University Nanjing 211816 China
                [4 ] Environmental Materials and Pollution Control Laboratory, Institute of Solid‐State Physics HFIPS, Chinese Academy of Sciences Hefei 230031 China
                Article
                10.1002/adom.202300730
                89266709-60df-4fca-b4a2-33cd92d65c6e
                © 2023

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