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Two-dimensional layer materials for highly efficient molecular sensing based on surface-enhanced Raman scattering

YU Ling-xiao LU Rui-tao

俞凌枭, 吕瑞涛. 二维层状材料的表面增强拉曼散射效应及高效分子探测性能[J]. 新型炭材料, 2021, 36(6): 995-1015. doi: 10.1016/S1872-5805(21)60098-5
引用本文: 俞凌枭, 吕瑞涛. 二维层状材料的表面增强拉曼散射效应及高效分子探测性能[J]. 新型炭材料, 2021, 36(6): 995-1015. doi: 10.1016/S1872-5805(21)60098-5
YU Ling-xiao, LU Rui-tao. Two-dimensional layer materials for highly efficient molecular sensing based on surface-enhanced Raman scattering[J]. NEW CARBON MATERIALS, 2021, 36(6): 995-1015. doi: 10.1016/S1872-5805(21)60098-5
Citation: YU Ling-xiao, LU Rui-tao. Two-dimensional layer materials for highly efficient molecular sensing based on surface-enhanced Raman scattering[J]. NEW CARBON MATERIALS, 2021, 36(6): 995-1015. doi: 10.1016/S1872-5805(21)60098-5

二维层状材料的表面增强拉曼散射效应及高效分子探测性能

doi: 10.1016/S1872-5805(21)60098-5
基金项目: 国家自然科学基金项目(51972191)
详细信息
    通讯作者:

    吕瑞涛,副教授. E-mail:lvruitao@tsinghua.edu.cn

  • 中图分类号: TQ127.1+1

Two-dimensional layer materials for highly efficient molecular sensing based on surface-enhanced Raman scattering

More Information
  • 摘要: 表面增强拉曼散射(SERS)因其无损检测、快速响应和高灵敏度等优点,已经发展成为一种高效的分子探测技术。但目前大多数关于SERS的研究仍然基于贵金属材料(如Au、Ag等),成本高、表面均匀性较低、生物相容性差等不足限制了其广泛应用。石墨烯具有原料来源丰富、二维原子级平面、大比表面积、高稳定性和独特的电学和光学性能等优势,研究表明其可作为一种有效的SERS基底材料,为相关研究开拓了新思路。近年来,过渡金属硫族化合物(TMDCs)、六方氮化硼、黑磷、二维碳氮化物等二维无机层状材料也开始受到研究者关注。本文综述了石墨烯、TMDCs等二维层状材料作为SERS基底的最新研究进展并阐述了SERS增强机理。在此基础上,提出了二维层状材料用于高性能SERS基底材料研究面临的一些挑战,并对该领域发展前景进行了展望。
  • FIG. 1031.  FIG. 1031.

    FIG. 1031.. 

    Figure  1.  Various inorganic 2D layered materials for surface-enhanced Raman scattering (SERS). Here h-BN denotes hexagonal boron nitride. TMDCs and BP denote transition metal dichalcogenides and black phosphorus, respectively.

    Figure  2.  Schematic illustrations of (a) SERS, (b) mechanism of Raman scattering (ν0 and Δν represent the frequency of incident light and the change of frequencies after scattering, respectively), (c) electromagnetic mechanism (EM) and (d) chemical mechanism (CM) for SERS (Here E0 is the incident electromagnetic field, μmol is the induced dipole moment of probe molecule, r is the radius of the metal spheres and d is the distance between the probe molecule and the surface of metal sphere, CT represents the charge transfer, HOMO and LUMO denote the highest occupied molecular orbital and the lowest unoccupied molecular orbital, respectively).

    Figure  3.  (a) Electrical field modulation on Fermi level for graphene-enhanced Raman scattering (GERS). (i) Schematic diagram of the device on tuning the graphene Fermi level by electrical field effect. (ii) The energy level alignment between the molecular energy level and modulated graphene Fermi level for charge transfer resonance[23] (reprinted with permission from American Chemical Society). (b) Defect engineering for GERS. (i) Schematic illustrations of the Fermi level modulation by O2 plasma treatment[33] (reprinted with permission from Elsevier). (ii) the dI/dV curves (averaged over 9 points spectra taken in 1×1 nm2 area) measured on N2AA dopants and undoped graphene[25] (reprinted with permission from Spring Nature). The density of states (DOS) for Rhodamine B (RhB) on (iii) the pristine graphene (PG) and (iv) N-doped graphene (NG), EF represents the Fermi level[14] (reprinted with permission from AAAS), (v) Schematic of SERS on Si-doped graphene[32] (reprinted with permission from John Wiley and Sons). (c) Thickness-dependence of GERS. (i-ii) Raman spectra of copper phthalocyanine (CuPc) molecule and (iii) schematic illustration of the energy band structure of mono- and bilayer graphene under low and high concentration molecular solution[36] (reprinted with permission from American Chemical Society).

    Figure  4.  (a) The influence of size of graphene quantum dots on GERS. The calculated charge transfer integrals (I) of rhodamine 6G (R6G) with (i) pristine graphene and high-quality graphene quantum dots prepared by plasma-enhanced chemical vapor deposition (P-GQDs) of (ii) 2.2 nm and (iii) 6.2 nm sizes[39] (reprinted with permission from Spring Nature). (b) Impact of molecule and laser energy. (i) Schematic illustration of the influence of molecule and laser on GERS (here M1–M4 represent four different molecules). Raman spectra of CuPc, zinc phthalocyanine (ZnPc), and copper(II)1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine (F16CuPc) under (ii) 532 nm and (iii) 633 nm laser. (iv) Raman spectra of tetrathienophenazine (TTP), tris(4-carbazoyl-9-ylphenyl) amine (TCTA), and 2,2′,7,7′-tetra(N-phenyl-1-naphthyl-amine)-9,9′-spirobifluorene (sp2-NPB) on graphene[40] (reprinted with permission from American Chemical Society).

    Figure  5.  (a) The electron density difference isosurfaces for R6G on graphene and 1T’-WTe2. (b) DOS of 1T’-WTe2 and graphene [46] (reprinted with permission from American Chemical Society). (c) SERS spectra and (d) schematic illustration of charge transfer mechanism of CuPc on different substrates[21] (reprinted with permission from John Wiley and Sons). (e) Schematic illustration of energy level and charge transfer resonance process for SERS of MB on 1T’- and 2H MoTe2[50] (reprinted with permission from IOP). (f) Schematic illustration of energy level and charge transfer process for SERS of crystal violet (CV) on SnSe2[52] (reprinted with permission from John Wiley and Sons).

    Figure  6.  (a) SERS spectra of 10−6 mol L−1 R6G on different layer number ReS2 films[55] (reprinted with permission from John Wiley and Sons). (b-c) SERS spectra and normalized fluorescence of R6G on monolayer ReS2 with different underlying substrates[56] (reprinted with permission from Elsevier). SERS spectra of R6G (d) with 5×10−6 mol L−1 on NbSe2 with different layer numbers and (e) on 6L-NbSe2 with different R6G concentrations. (f) DOS of the outermost layer of 2H-NbSe2 with different layers in the A’B stacking mode[57] (reprinted with permission from Royal Society of Chemistry).

    Figure  7.  (a) Schematic diagram of Au ion irradiation. (b) Evolution of atomic ratio of WSe2 with the influence of incident ions. (c) The enhancement factor (EF) of SERS for CuPc on pristine (S0) and irradiated WSe2 monolayers by different controlled dose/fluence (S1=1012 ions cm−2, S2=1013 ions cm−2, S3=1014 ions cm−2) of ion beam. (d) The intensity of fs optical pump-probe spectroscopy at the wavelengths of 510 nm (A’), 596 nm (B) and 744 nm (A) at a time of 0 ps. (e) The total density of states (TDOS) of WSe2 with various atomic ratios[44] (reprinted with permission from John Wiley and Sons).

    Figure  8.  (a) Schematic illustration of graphene, h-BN and MoS2 served as SERS substrates. SERS spectra of CuPc on (b) different substrates and (c) h-BN flakes with various thicknesses[22] (reprinted with permission from American Chemical Society). (d) Charge distribution of valence band for CuPc/black phosphorus (BP) (here AC denotes armchair direction). (e) SERS spectra of CuPc on SiO2/Si with BP[65] (reprinted with permission from American Chemical Society). Schematic illustration of charge transfer on (f) methylene blue (MB)/Ti3C2-Al(OH)4 and (g) MB/Ti3C2-OH/F[70] (reprinted with permission from American Chemical Society). (h) Schematic of the adsorption and intercalation of MB in the MXene nanosheets[71] (reprinted with permission from AIP).

    Figure  9.  (a-c) SERS spectra of CuPc on different heterostucture substrates[72] (reprinted with permission from American Chemical Society). (d) Schematic of SERS effect on graphene/ReOxSy heterostructure and bending test. (e) SERS spectra of R6G on graphene/ReOxSy vertical heterostructure[73] (reprinted with permission from American Chemical Society).

    Figure  10.  (a) Schematic diagram of the fabrication of the MXene/Au nanorods (AuNRs)[4] (reprinted with permission from American Chemical Society). (b) SEM image of Ag nanoparticles (AgNPs) covered by h-BN sample[78] (reprinted with permission from John Wiley and Sons). (c) AFM topography image of laser-etched MoS2 after decorated with AuNPs. (d) SERS spectra of RhB on various positions of AuNPs/MoS2[81] (reprinted with permission from American Chemical Society). (e) Schematic of MXene/MoS2@AuNPs for miRNA detection[82]. Schematic of (f) electron–hole pairs and (g) SERS mechanism of few-layer TMDs/graphene heterostructure[83] (reprinted with permission from John Wiley and Sons).

    Table  1.   SERS performances and related mechanisms of various 2D materials.

    SubstrateProbe
    molecule
    Laser wavelength
    (nm)
    Limit of detection
    (mol L−1)
    MechanismRefs.
    GrapheneCuPc6334×10−6Charge transfer
    (thickness-dependence)
    [36]
    Electrical field modulated grapheneCoPc633<10−6[23]
    Graphene quantum dotsR6G5321×10−9[39]
    O2 plasma treated grapheneRhB5141×10−7Local dipole and charge transfer
    (thickness-dependence)
    [33]
    N-doped grapheneRhB5145×10−11[14]
    WS2R6G5321×10−7Charge transfer and dipole-dipole interaction
    (thickness-dependence)
    [53]
    ReS2R6G5321×10−9[55]
    2H-MoS(Se)2R6G5321×10−5[21]
    1T-MoS(Se)2R6G5321×10−8[21]
    1T’-MoTe2R6G5324×10−14[46]
    1T’-WTe2R6G5324×10−15[46]
    NbS2MB6331×10−14[54]
    NbSe2R6G5325×10−16[57]
    SnSe2R6G5321×10−17[51]
    Hexagonal boron nitrideCuPc633Close to grapheneDipole-dipole interaction
    (thickness-independence)
    [22]
    Ti3C2TxMB6331×10−12Charge transfer (thickness-dependence)[70]
    Black phosphorus with nano-void arrayCuPc5321×10−8Charge transfer (angle-dependence)[66]
    Graphene/ReOxSyR6G5321×10−15Charge transfer and dipole-dipole interaction[73]
    Au nanoparticles/rGOR6G6331×10−8Chemical mechanism and
    electromagnetic mechanism
    [77]
    Wrinkled graphene/Au nanoparticlesR6G6331×10−9[85]
    MXene/Au nanorodsR6G5321×10−12[4]
    Au nanoparticles/MoS2RhB5321×10−10[81]
    Mo(W)S2 nanodomes/grapheneR6G5325×10−12[83]
    WS2+MoS2 nanodisks/grapheneR6G5325×10−13[84]
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出版历程
  • 收稿日期:  2021-08-09
  • 修回日期:  2021-10-28
  • 网络出版日期:  2021-11-16
  • 刊出日期:  2021-12-01

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