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

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

钙钛矿上单原子位点实现高灵敏定量化表面拉曼增强

Ran Feng 1,#, Qing Miao 2,#, Xiang Zhang 3,#, Peixin Cui 4,#, Cong Wang 1,✉, Yibo Feng 1, Liyong Gan 3, Jiaxing Fu 6, Shibo Wang 7, Ziyi Dai 8, Liming Hu 5, Yunjing Luo 5, Weihai Sun 7, Xiaoxian Zhang 2, Jiawen Xiao 1, Jinbo Wu 6, Bingpu Zhou 8, Mingqiang Zou 9, Dawei He 2, Xiaoyuan Zhou 3, Xiaodong Han 1,✉
PMCID: PMC8902489  PMID: 35281622

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.

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

Acknowledgements

This work was supported by the Natural Science Foundation of Beijing Municipality (Z180014). We thank Dr. Chen Qian and Dr. Yingying Wang for providing measurement support, and we also thank Taifeng Lin, Prof. Yiyang Sun and Prof. Shengbai Zhang for discussions.

Supporting Information

40843_2022_1968_MOESM1_ESM.pdf (2MB, pdf)

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

Author contributions Feng R designed and performed the experiments; Miao Q analyzed TAS data; Zhang X calculated the electronic structure; Cui P analyzed the XANES data; Wang C wrote the paper; Han X discussed partial experimental data. All authors contributed to the general discussion.

Conflict of interest The authors declare that they have no conflict of interest.

Footnotes

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Ran Feng received his BSc degree in 2020 from Nanjing Normal University, China. He is currently an MSc candidate in physics under the supervision of Prof. Cong Wang at Beijing Key Laboratory of Microstructure and Properties of Solids, Beijing University of Technology. His research centers on developing the single-site decorated SERS substrate for ultrasensitive molecule detection.

Qing Miao received his BSc degree in engineering from Baicheng Normal University in 2014 and MSc degree in physics from North China Electric Power University in 2017. He is currently pursuing his PhD degree in optical engineering under the supervision of Prof. Dawei He at Beijing Jiaotong University. His research focuses on ultrafast laser spectroscopy of nanoscale materials, such as photocarrier dynamics, charge transfer, and its potential applications in optoelectronics and photonics.

Xiang Zhang received his BSc degree in 2020 from Sichuan University of Science & Engineering. Then, he joined the Institute of Structure & Function, Chongqing University as a master student. His research centers on Schottky barrier heights in two-dimensional field-effect transistors.

Peixin Cui received his PhD degree from the University of Science and Technology of China in 2013, followed by working as a postdoc at the same university. He joined the Institute of Soil Science, Chinese Academy of Sciences in 2016. His research focuses on the study of local structures of nano and single-atom materials by synchrotron radiation techniques.

Cong Wang received his BSc degree in 2009 and MSc degree in 2012 from the University of Science and Technology Beijing, respectively. In 2015, he received his PhD degree from Hong Kong University of Science and Technology. Then, he joined Beijing University of Technology and became an associate professor in 2016. His research interests focus on the single-atom sites rational design and synthesis, single-sites catalysis, and single-sites SERS in energy, environment and biology.

Xiaodong Han received his BSc degree in 1989 and MSc degree in 1992 from Harbin Institute of Technology. In 1996, he received his PhD degree from Dalian University of Technology. Then, he joined City University of Hong Kong and the University of Pittsburgh as postdoc. In 2001, he joined HKL Technology (Oxford Instruments Group), and in 2004, he joined Beijing University of Technology. His research interests focus on in-situ transmission electron microscopy, and physical and chemical properties of materials in catalytic, optical, and mechanical communities.

The authors contributed equally to this work.

Contributor Information

Cong Wang, Email: smartswang@bjut.edu.cn.

Xiaodong Han, Email: xdhan@bjut.edu.cn.

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