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Shao MR, Ji C, Tan JB, Du BQ, Zhao XF et al. Ferroelectrically modulate the Fermi level of graphene oxide to enhance SERS response. Opto-Electron Adv 6, 230094 (2023). doi: 10.29026/oea.2023.230094
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Ferroelectrically modulate the Fermi level of graphene oxide to enhance SERS response
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Abstract
Surface-enhanced Raman scattering (SERS) substrates based on chemical mechanism (CM) have received widespread attentions for the stable and repeatable signal output due to their excellent chemical stability, uniform molecular adsorption and controllable molecular orientation. However, it remains huge challenges to achieve the optimal SERS signal for diverse molecules with different band structures on the same substrate. Herein, we demonstrate a graphene oxide (GO) energy band regulation strategy through ferroelectric polarization to facilitate the charge transfer process for improving SERS activity. The Fermi level (Ef) of GO can be flexibly manipulated by adjusting the ferroelectric polarization direction or the temperature of the ferroelectric substrate. Experimentally, kelvin probe force microscopy (KPFM) is employed to quantitatively analyze theEf of GO. Theoretically, the density functional theory calculations are also performed to verify the proposed modulation mechanism. Consequently, the SERS response of probe molecules with different band structures (R6G, CV, MB, PNTP) can be improved through polarization direction or temperature changes without the necessity to redesign the SERS substrate. This work provides a novel insight into the SERS substrate design based on CM and is expected to be applied to other two-dimensional materials. -
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References
[1] Wang X, Huang SC, Hu S, Yan S, Ren B. Fundamental understanding and applications of plasmon-enhanced Raman spectroscopy. Nat Rev Phys 2, 253–271 (2020). doi: 10.1038/s42254-020-0171-y [2] Chen XY, Ding QQ, Bi C, Ruan J, Yang SK. Lossless enrichment of trace analytes in levitating droplets for multiphase and multiplex detection. Nat Commun 13, 7807 (2022). doi: 10.1038/s41467-022-35495-9 [3] Bharati MSS, Soma VR. Flexible SERS substrates for hazardous materials detection: recent advances. Opto-Electron Adv 4, 210048 (2021). doi: 10.29026/oea.2021.210048 [4] Ding SY, Yi J, Li JF, Ren B, Wu DY et al. Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials. Nat Rev Mater 1, 16021 (2016). doi: 10.1038/natrevmats.2016.21 [5] Du XJ, Liu D, An KY, Jiang SZ, Wei ZX et al. Advances in oxide semiconductors for surface enhanced Raman scattering. Appl Mater Today 29, 101563 (2022). doi: 10.1016/j.apmt.2022.101563 [6] Ding SY, You EM, Tian ZQ, Moskovits M. Electromagnetic theories of surface-enhanced Raman spectroscopy. Chem Soc Rev 46, 4042–4076 (2017). doi: 10.1039/C7CS00238F [7] Zhao YY, Ren XL, Zheng ML, Jin F, Liu J et al. Plasmon-enhanced nanosoldering of silver nanoparticles for high-conductive nanowires electrodes. Opto-Electron Adv 4, 200101 (2021). doi: 10.29026/oea.2021.200101 [8] Li SW, Miao P, Zhang YY, Wu J, Zhang B et al. Recent advances in plasmonic nanostructures for enhanced photocatalysis and electrocatalysis. Adv Mater 33, 2000086 (2021). doi: 10.1002/adma.202000086 [9] Zhan C, Chen XJ, Huang YF, Wu DY, Tian ZQ. Plasmon-mediated chemical reactions on nanostructures unveiled by surface-enhanced raman spectroscopy. Acc Chem Res 52, 2784–2792 (2019). doi: 10.1021/acs.accounts.9b00280 [10] Kambhampati P, Child CM, Foster MC, Campion A. On the chemical mechanism of surface enhanced Raman scattering: Experiment and theory. J Chem Phys 108, 5013–5026 (1998). doi: 10.1063/1.475909 [11] Zhang N, Tong LM, Zhang J. Graphene-based enhanced raman scattering toward analytical applications. Chem Mater 28, 6426–6435 (2016). doi: 10.1021/acs.chemmater.6b02925 [12] Wang XT, Shi WX, Wang SX, Zhao HW, Lin J et al. Two-dimensional amorphous TiO2 nanosheets enabling high-efficiency photoinduced charge transfer for excellent SERS activity. J Am Chem Soc 141, 5856–5862 (2019). doi: 10.1021/jacs.9b00029 [13] Zheng ZH, Cong S, Gong WB, Xuan JN, Li GH et al. Semiconductor SERS enhancement enabled by oxygen incorporation. Nat Commun 8, 1993 (2017). doi: 10.1038/s41467-017-02166-z [14] Li MZ, Wei YJ, Fan XC, Li GQ, Hao Q et al. Mixed-dimensional van der Waals heterojunction-enhanced Raman scattering. Nano Res 15, 637–643 (2022). doi: 10.1007/s12274-021-3537-2 [15] Peng YS, Lin CL, Long L, Masaki T, Tang M et al. Charge-transfer resonance and electromagnetic enhancement synergistically enabling MXenes with excellent SERS sensitivity for SARS-CoV-2 S protein detection. Nano-Micro Lett 13, 52 (2021). doi: 10.1007/s40820-020-00565-4 [16] Tang X, Fan XC, Zhou J, Wang S, Li MZ et al. Alloy engineering allows on-demand design of ultrasensitive monolayer semiconductor SERS substrates. Nano Lett 23, 7037–7045 (2023). doi: 10.1021/acs.nanolett.3c01810 [17] Xu H, Xie LM, Zhang HL, Zhang J. Effect of graphene fermi level on the raman scattering intensity of molecules on graphene. ACS Nano 5, 5338–5344 (2011). doi: 10.1021/nn103237x [18] Xu H, Chen YB, Xu WG, Zhang HL, Kong J et al. Modulating the charge-transfer enhancement in GERS using an electrical field under vacuum and an n/p-doping atmosphere. Small 7, 2945–2952 (2011). doi: 10.1002/smll.201100546 [19] Feng SM, dos Santos MC, Carvalho BR, Lv RT, Li Q et al. Ultrasensitive molecular sensor using N-doped graphene through enhanced Raman scattering. Sci Adv 2, e1600322 (2016). doi: 10.1126/sciadv.1600322 [20] Seo J, Lee J, Kim Y, Koo D, Lee G et al. Ultrasensitive plasmon-free surface-enhanced raman spectroscopy with femtomolar detection limit from 2D van der waals heterostructure. Nano Lett 20, 1620–1630 (2020). doi: 10.1021/acs.nanolett.9b04645 [21] Liang C, Lu ZA, Zheng M, Chen MX, Zhang YY et al. Band structure engineering within two-dimensional borocarbonitride nanosheets for surface-enhanced raman scattering. Nano Lett 22, 6590–6598 (2022). doi: 10.1021/acs.nanolett.2c01825 [22] Li MZ, Wei YJ, Fan XC, Li GQ, Tang X et al. VSe2–xOx@Pd sensor for operando self-monitoring of palladium-catalyzed reactions. JACS Au 3, 468–475 (2023). doi: 10.1021/jacsau.2c00596 [23] Zhou L, Pusey-Nazzaro L, Ren GH, Chen LG, Liu LY et al. Photoactive control of surface-enhanced raman scattering with reduced graphene oxide in gas atmosphere. ACS Nano 16, 577–587 (2022). doi: 10.1021/acsnano.1c07695 [24] Fang HJ, Xu C, Ding J, Li Q, Sun JL et al. Self-powered ultrabroadband photodetector monolithically integrated on a PMN-PT ferroelectric single crystal. Acs Appl Mater Interfaces 8, 32934–32939 (2016). doi: 10.1021/acsami.6b10305 [25] Pandya S, Wilbur J, Kim J, Gao R, Dasgupta A et al. Pyroelectric energy conversion with large energy and power density in relaxor ferroelectric thin films. Nat Mater 17, 432–438 (2018). doi: 10.1038/s41563-018-0059-8 [26] Zheng R, Yan MY, Li C, Yin SQ, Chen WD et al. Pyroelectric effect mediated infrared photoresponse in Bi2Te3/Pb(Mg1/3Nb2/3)O3-PbTiO3 optothermal ferroelectric field-effect transistors. Nanoscale 13, 20657–20662 (2021). doi: 10.1039/D1NR06863F [27] Deng MH, Ren ZP, Zhang HB, Li ZQ, Xue CL et al. Unamplified and real-time label-free miRNA-21 detection using solution-gated graphene transistors in prostate cancer diagnosis. Adv Sci 10, 2205886 (2023). doi: 10.1002/advs.202205886 [28] Romagnoli A, D'Agostino M, Pavoni E, Ardiccioni C, Motta S et al. SARS-CoV-2 multi-variant rapid detector based on graphene transistor functionalized with an engineered dimeric ACE2 receptor. Nano Today 48, 101729 (2023). doi: 10.1016/j.nantod.2022.101729 [29] Zhao L, Rosati G, Piper A, de Carvalho Castro e Silva C, Hu L et al. Laser reduced graphene oxide electrode for pathogenic escherichia coli detection. ACS Appl Mater Interfaces 15, 9024–9033 (2023). doi: 10.1021/acsami.2c20859 [30] Guan HY, Hong JY, Wang XL, Ming JY, Zhang ZL et al. Broadband, high-sensitivity graphene photodetector based on ferroelectric polarization of lithium niobate. Adv Opt Mater 9, 2100245 (2021). doi: 10.1002/adom.202100245 [31] Gopalan KK, Janner D, Nanot S, Parret R, Lundeberg MB et al. Mid-infrared pyroresistive graphene detector on LiNbO3. Adv Opt Mater 5, 1600723 (2017). doi: 10.1002/adom.201600723 [32] Lu YY, Yang G, Shen YJ, Yang HY, Xu KC. Multifunctional flexible humidity sensor systems towards noncontact wearable electronics. Nano-Micro Lett 14, 150 (2022). doi: 10.1007/s40820-022-00895-5 [33] Ling X, Xie LM, Fang Y, Xu H, Zhang HL et al. Can graphene be used as a substrate for raman enhancement? Nano Lett 10, 553–561 (2010). doi: 10.1021/nl903414x [34] Li Z, Jiang SZ, Huo YY, Ning TY, Liu AH et al. 3D silver nanoparticles with multilayer graphene oxide as a spacer for surface enhanced Raman spectroscopy analysis. Nanoscale 10, 5897–5905 (2018). doi: 10.1039/C7NR09276H [35] Almohammed S, Zhang FY, Rodriguez BJ, Rice JH. Electric field-induced chemical surface-enhanced raman spectroscopy enhancement from aligned peptide nanotube-graphene oxide templates for universal trace detection of biomolecules. J Phys Chem Lett 10, 1878–1887 (2019). doi: 10.1021/acs.jpclett.9b00436 [36] Zhou TY, Xu C, Ren WC. Grain-boundary-induced ultrasensitive molecular detection of graphene film. Nano Lett 22, 9380–9388 (2022). doi: 10.1021/acs.nanolett.2c03218 [37] Hao QZ, Morton SM, Wang B, Zhao YH, Jensen L et al. Tuning surface-enhanced Raman scattering from graphene substrates using the electric field effect and chemical doping. Appl Phys Lett 102, 011102 (2013). doi: 10.1063/1.4755756 [38] Neto AHC, Guinea F, Peres NMR, Novoselov KS, Geim AK. The electronic properties of graphene. Rev Mod Phys 81, 109–162 (2009). doi: 10.1103/RevModPhys.81.109 [39] Gorecki J, Apostolopoulos V, Ou JY, Mailis S, Papasimakis N. Optical gating of graphene on photoconductive Fe: LiNbO3. ACS Nano 12, 5940–5945 (2018). doi: 10.1021/acsnano.8b02161 [40] Sun XZ, Chen Y, Zhao DY, Taniguchi T, Watanabe K et al. Measuring band modulation of MoS2 with ferroelectric gates. Nano Lett 23, 2114–2120 (2023). doi: 10.1021/acs.nanolett.2c04326 [41] Wang XD, Wang P, Wang JL, Hu WD, Zhou XH et al. Ultrasensitive and broadband MoS2 photodetector driven by ferroelectrics. Adv Mater 27, 6575–6581 (2015). doi: 10.1002/adma.201503340 [42] Zhang SK, Jiao HX, Wang XD, Chen Y, Wang HL et al. Highly sensitive InSb nanosheets infrared photodetector passivated by ferroelectric polymer. Adv Funct Mater 30, 2006156 (2020). doi: 10.1002/adfm.202006156 [43] Yan JM, Ying JS, Yan MY, Wang ZC, Li SS et al. Optoelectronic coincidence detection with two-dimensional Bi2O2Se ferroelectric field-effect transistors. Adv Funct Mater 31, 2103982 (2021). doi: 10.1002/adfm.202103982 [44] Chen JW, Lo ST, Ho SC, Wong SS, Vu THY et al. A gate-free monolayer WSe2 pn diode. Nat Commun 9, 3143 (2018). doi: 10.1038/s41467-018-05326-x [45] Yang Y, Guo WX, Pradel KC, Zhu G, Zhou YS et al. Pyroelectric nanogenerators for harvesting thermoelectric energy. Nano Lett 12, 2833–2838 (2012). doi: 10.1021/nl3003039 [46] Ma N, Zhang KW, Yang Y. Photovoltaic-pyroelectric coupled effect induced electricity for self-powered photodetector system. Adv Mater 29, 1703694 (2017). doi: 10.1002/adma.201703694 [47] Ma N, Yang Y. Enhanced self-powered UV photoresponse of ferroelectric BaTiO3 materials by pyroelectric effect. Nano Energy 40, 352–359 (2017). doi: 10.1016/j.nanoen.2017.08.043 [48] Das B, Voggu R, Rout CS, Rao CNR. Changes in the electronic structure and properties of graphene induced by molecular charge-transfer. Chem Commun 5155–5157 (2008). [49] Baeumer C, Saldana-Greco D, Martirez JMP, Rappe AM, Shim M et al. Ferroelectrically driven spatial carrier density modulation in graphene. Nat Commun 6, 6136 (2015). doi: 10.1038/ncomms7136 [50] Liu DM, Yi WC, Fu YL, Kong QH, Xi GC. In situ surface restraint-induced synthesis of transition-metal nitride ultrathin nanocrystals as ultrasensitive sers substrate with ultrahigh durability. ACS Nano 16, 13123–13133 (2022). doi: 10.1021/acsnano.2c05914 [51] Ge YC, Wang F, Yang Y, Xu Y, Ye Y et al. Atomically thin TaSe2 film as a high-performance substrate for surface-enhanced raman scattering. Small 18, 2107027 (2022). doi: 10.1002/smll.202107027 [52] Liu Y, Guo J, Zhu EB, Liao L, Lee SJ et al. Approaching the Schottky-Mott limit in van der Waals metal-semiconductor junctions. Nature 557, 696–700 (2018). doi: 10.1038/s41586-018-0129-8 [53] Lombardi JR, Birke RL. A unified approach to surface-enhanced Raman spectroscopy. J Phys Chem C 112, 5605–5617 (2008). doi: 10.1021/jp800167v [54] Jablan M, Buljan H, Soljačić M. Plasmonics in graphene at infrared frequencies. Phys Rev B 80, 245435 (2009). doi: 10.1103/PhysRevB.80.245435 [55] Lombardi JR, Birke RL. The theory of surface-enhanced Raman scattering. J Chem Phys 136, 144704 (2012). doi: 10.1063/1.3698292 [56] Li HY, Bowen CR, Yang Y. Phase transition enhanced pyroelectric nanogenerators for self-powered temperature sensors. Nano Energy 102, 107657 (2022). doi: 10.1016/j.nanoen.2022.107657 [57] Yang Y, Wang SH, Zhang Y, Wang ZL. Pyroelectric nanogenerators for driving wireless sensors. Nano Lett 12, 6408–6413 (2012). doi: 10.1021/nl303755m [58] Bai S, Serien D, Hu AM, Sugioka K. 3D microfluidic surface-enhanced raman spectroscopy (SERS) chips fabricated by all-femtosecond-laser-processing for real-time sensing of toxic substances. Adv Funct Mater 28, 1706262 (2018). doi: 10.1002/adfm.201706262 [59] Wu J, Du YJ, Wang CY, Bai S, Zhang T et al. Reusable and long-life 3D Ag nanoparticles coated Si nanowire array as sensitive SERS substrate. Appl Surf Sci 494, 583–590 (2019). doi: 10.1016/j.apsusc.2019.07.080 [60] Chen MM, Liu ZH, Su BH, Hu RJ, Fu FF et al. High-performance hydrogel SERS chips with tunable localized surface plasmon resonance for coordinated electromagnetic enhancement with chemical enhancement. Adv Opt Mater 11, 2202852 (2023). doi: 10.1002/adom.202202852 [61] Cong S, Liu XH, Jiang YX, Zhang W, Zhao ZG. Surface enhanced raman scattering revealed by interfacial charge-transfer transitions. Innovation 1, 100051 (2020). -
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Shao MR, Ji C, Tan JB, Du BQ, Zhao XF et al. Ferroelectrically modulate the Fermi level of graphene oxide to enhance SERS response. Opto-Electron Adv 6, 230094 (2023). doi: 10.29026/oea.2023.230094
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Figure 1.
(a) SERS performance of Al2O3@GO, PMN-PT@GO (Ps+) and PMN-PT@GO(Ps−) by employing R6G as the probe molecule under excitation of 532 nm laser. (b) Raman shift of G band of GO in Al2O3@GO, PMN-PT@GO (Ps+) and PMN-PT@GO(Ps−). (c) UV-vis spectra of the GO and R6G/GO. (d-f) Schematic diagram of GO doping when adsorbed on different surfaces of PMN-PT. (g-i) Contact potential differences (VCPD) between Au probe and GO in (g) Al2O3@GO, (h) PMN-PT@GO (Ps+) and (i) PMN-PT@GO(Ps−) measured by a KPFM system. (j-l) Modulation mechanism of SERS enhancement of (j) Al2O3@GO, (k) PMN-PT@GO (Ps+) and (l) PMN-PT@GO(Ps−).
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Figure 2.
Atomic structure of (a) intrinsic graphene, (b) graphene on up-polarized (Ps+) PMN-PT surface, (c) graphene on down-polarized (Ps−) PMN-PT surface for DFT calculation. The electronic band structure of (d) intrinsic graphene, (e) graphene on up-polarized (Ps+) PMN-PT surface, (f) graphene on down-polarized (Ps−) PMN-PT surface.
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Figure 3.
(a, d) The temperature-dependent SERS spectra of R6G by employing (a) PMN-PT@GO(Ps−), (d) Al2O3@GO as a SERS substrate. (b) Schematic diagram of doping level of GO affected by PMN-PT@GO(Ps−) temperature. (c) Schematic illustration of the energy band structure of PMN-PT@GO(Ps−)/R6G and the electron transition process under 532 nm excitation laser. (e, f) SERS spectra of R6G with different concentrations on PMN-PT@GO(Ps−) at (e) 20 °C, (f) 0 °C. (g) SERS spectra of R6G with different concentrations on Al2O3@GO at different temperature.
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Figure 4.
(a) SERS spectra of CV on PMN-PT@GO(Ps−) under excitation of 532 and 633 nm laser. (b) Schematic diagram of doping level of GO affected by PMN-PT@GO(Ps−) temperature. (c, d) Schematic illustration of the energy band structure of PMN-PT@GO(Ps−)/CV and the electron transition process under (c) 532 nm, (d) 633 nm excitation laser. (e, f) SERS spectra of CV on PMN-PT@GO(Ps−) under excitation of (e) 532 nm, (f) 633 nm laser at different temperature.
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Figure 5.
(a, b) SERS spectra of PNTP on PMN-PT@GO(Ps−) under excitation of (a) 532 nm, (b) 633 nm laser at different temperature. (c) Schematic diagram of doping level of GO affected by PMN-PT@GO(Ps−) temperature. (d, e) Schematic illustration of the energy band structure of PMN-PT@GO(Ps−)/PNTP and the electron transition process under (d) 532 nm, (e) 633 nm excitation laser.
