Single-atom sites on perovskite chips for record-high sensitivity and quantification in SERS

Sci China Mater. 2022;65(6):1601-1614. doi: 10.1007/s40843-022-1968-5. Epub 2022 Mar 2.

Abstract

Surface enhanced Raman scattering (SERS) is a rapid and nondestructive technique that is capable of detecting and identifying chemical or biological compounds. Sensitive SERS quantification is vital for practical applications, particularly for portable detection of biomolecules such as amino acids and nucleotides. However, few approaches can achieve sensitive and quantitative Raman detection of these most fundamental components in biology. Herein, a noble-metal-free single-atom site on a chip strategy was applied to modify single tungsten atom oxide on a lead halide perovskite, which provides sensitive SERS quantification for various analytes, including rhodamine, tyrosine and cytosine. The single-atom site on a chip can enable quantitative linear SERS responses of rhodamine (10-6-1 mmol L-1), tyrosine (0.06-1 mmol L-1) and cytosine (0.2-45 mmol L-1), respectively, which all achieve record-high enhancement factors among plasmonic-free semiconductors. The experimental test and theoretical simulation both reveal that the enhanced mechanism can be ascribed to the controllable single-atom site, which can not only trap photoinduced electrons from the perovskite substrate but also enhance the highly efficient and quantitative charge transfer to analytes. Furthermore, the label-free strategy of single-atom sites on a chip can be applied in a portable Raman platform to obtain a sensitivity similar to that on a benchtop instrument, which can be readily extended to various biomolecules for low-cost, widely demanded and more precise point-of-care testing or in-vitro detection.

Electronic supplementary material: Supplementary material is available for this article at 10.1007/s40843-022-1968-5 and is accessible for authorized users.

表面增强拉曼散射(SERS)是一种快速且无损的化学和生物分子检测技术. 高灵敏且定量化的SERS检测技术对其在实际中的应用至关重要, 尤其是对生物分子如氨基酸和碱基的便携化检测. 但是鲜有技术手段能够实现对这些最基本的生物分子进行高灵敏且定量化的拉曼检测. 我们提出了一种无需贵金属的单原子位点修饰芯片策略, 用钨单原子氧化物修饰铅卤钙钛矿芯片, 实现了多种检测物的高灵敏定量化识别, 包括罗丹明、 酪氨酸和胞嘧啶. 芯片上单原子位点技术能够实现对罗丹明、 酪氨酸和胞嘧啶的线性检测, 相应的定量化区间分别为: 10−6–1 mmol L−1, 0.06–1 mmol L−1和0.2–45 mmol L−1, 同时我们的拉曼增强芯片对这三种分子的增强因子在非等离子激元半导体中是最高的. 我们通过实验测试结合理论模拟揭示了由可控单原子位点实现拉曼增强的机理: 束缚由钙钛矿基底产生的光生电子, 同时高效且定量地将这些电子转移到待测分子上. 不仅如此, 芯片上单原子位点技术可以在便携式拉曼设备下得到与台式拉曼设备类似的增强效果, 这意味着这项技术有机会应用于多种生物分子的低成本、 广谱、 即时检测和体外检测.

Keywords: SERS; charge-transfer mechanism; in-vitro diagnosis; lead halide perovskite; point-of-care testing; single-atom site.