Issue

Vol. 17 (2025)

Tailoring Light–Matter Interactions in Overcoupled Resonator for Biomolecule Recognition and Detection

https://doi.org/10.1007/s40820-024-01520-3
Dongxiao Li
Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117583, Singapore
Hong Zhou
Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117583, Singapore
Zhihao Ren
Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117583, Singapore
Cheng Xu
Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117583, Singapore
Chengkuo Lee
Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117583, Singapore

Corresponding Author: Chengkuo Lee

elelc@nus.edu.sg

Nano-Micro Letters, Vol. 17 (2025), Article Number: 10

Abstract

Plasmonic nanoantennas provide unique opportunities for precise control of light–matter coupling in surface-enhanced infrared absorption (SEIRA) spectroscopy, but most of the resonant systems realized so far suffer from the obstacles of low sensitivity, narrow bandwidth, and asymmetric Fano resonance perturbations. Here, we demonstrated an overcoupled resonator with a high plasmon-molecule coupling coefficient (μ) (OC-Hμ resonator) by precisely controlling the radiation loss channel, the resonator-oscillator coupling channel, and the frequency detuning channel. We observed a strong dependence of the sensing performance on the coupling state, and demonstrated that OC-Hμ resonator has excellent sensing properties of ultra-sensitive (7.25% nm−1), ultra-broadband (3–10 μm), and immune asymmetric Fano lineshapes. These characteristics represent a breakthrough in SEIRA technology and lay the foundation for specific recognition of biomolecules, trace detection, and protein secondary structure analysis using a single array (array size is 100 × 100 µm2). In addition, with the assistance of machine learning, mixture classification, concentration prediction and spectral reconstruction were achieved with the highest accuracy of 100%. Finally, we demonstrated the potential of OC-Hμ resonator for SARS-CoV-2 detection. These findings will promote the wider application of SEIRA technology, while providing new ideas for other enhanced spectroscopy technologies, quantum photonics and studying light–matter interactions.


Highlights:
1 Proposed a new paradigm for nanoantenna design using coupled-mode theory.
2 Designed an OC-Hµ resonator with excellent sensing performance.
3 Using OC-Hµ resonators for biomolecule recognition and detection.

Keywords

Plasmonic nanoantennas Light-matter interaction Surface-enhanced infrared absorption Overcoupled Biosensing
Li, Dongxiao, Hong Zhou, Zhihao Ren, Cheng Xu, and Chengkuo Lee. 2024. “Tailoring Light–Matter Interactions in Overcoupled Resonator for Biomolecule Recognition and Detection”. Nano-Micro Letters 17 (September):10. https://doi.org/10.1007/s40820-024-01520-3.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. T. Weber, L. Kühner, L. Sortino, A. BenMhenni, N.P. Wilson et al., Intrinsic strong light–matter coupling with self-hybridized bound states in the continuum in van der Waals metasurfaces. Nat. Mater. 22, 970–976 (2023). https://doi.org/10.1038/s41563-023-01580-7
  2. A.H. Dorrah, F. Capasso, Tunable structured light with flat optics. Science 376, eabi6860 (2022). https://doi.org/10.1126/science.abi6860
  3. F. Neubrech, C. Huck, K. Weber, A. Pucci, H. Giessen, Surface-enhanced infrared spectroscopy using resonant nanoantennas. Chem. Rev. 117, 5110–5145 (2017). https://doi.org/10.1021/acs.chemrev.6b00743
  4. C. Xu, Z. Ren, H. Zhou, J. Zhou, C.P. Ho et al., Expanding chiral metamaterials for retrieving fingerprints via vibrational circular dichroism. Light Sci. Appl. 12, 154 (2023). https://doi.org/10.1038/s41377-023-01186-3
  5. C. Xu, Z. Ren, H. Zhou, J. Zhou, D. Li et al., Near-field coupling induced less chiral responses in chiral metamaterials for surface-enhanced vibrational circular dichroism. Adv. Funct. Mater. 34, 2314482 (2024). https://doi.org/10.1002/adfm.202314482
  6. G. Li, S. Zhang, T. Zentgraf, Nonlinear photonic metasurfaces. Nat. Rev. Mater. 2, 17010 (2017). https://doi.org/10.1038/natrevmats.2017.10
  7. U. Aslam, V.G. Rao, S. Chavez, S. Linic, Catalytic conversion of solar to chemical energy on plasmonic metal nanostructures. Nat. Catal. 1, 656–665 (2018). https://doi.org/10.1038/s41929-018-0138-x
  8. T. Santiago-Cruz, S.D. Gennaro, O. Mitrofanov, S. Addamane, J. Reno et al., Resonant metasurfaces for generating complex quantum states. Science 377, 991–995 (2022). https://doi.org/10.1126/science.abq8684
  9. W. Wang, M. Ramezani, A.I. Väkeväinen, P. Törmä, J.G. Rivas et al., The rich photonic world of plasmonic nanop arrays. Mater. Today 21, 303–314 (2018). https://doi.org/10.1016/j.mattod.2017.09.002
  10. J. Kozuch, K. Ataka, J. Heberle, Surface-enhanced infrared absorption spectroscopy. Nat. Rev. Meth. Primers 3, 70 (2023). https://doi.org/10.1038/s43586-023-00253-8
  11. D. Li, C. Xu, J. Xie, C. Lee, Research progress in surface-enhanced infrared absorption spectroscopy: from performance optimization, sensing applications, to system integration. Nanomaterials 13, 2377 (2023). https://doi.org/10.3390/nano13162377
  12. D. Dregely, F. Neubrech, H. Duan, R. Vogelgesang, H. Giessen, Vibrational near-field mapping of planar and buried three-dimensional plasmonic nanostructures. Nat. Commun. 4, 2237 (2013). https://doi.org/10.1038/ncomms3237
  13. A. John-Herpin, A. Tittl, L. Kühner, F. Richter, S.H. Huang et al., Metasurface-enhanced infrared spectroscopy: an abundance of materials and functionalities. Adv. Mater. 35, e2110163 (2023). https://doi.org/10.1002/adma.202110163
  14. H. Altug, S.H. Oh, S.A. Maier, J. Homola, Advances and applications of nanophotonic biosensors. Nat. Nanotechnol. 17(1), 5–16 (2022). https://doi.org/10.1038/s41565-021-01045-5
  15. X. Hui, C. Yang, D. Li, X. He, H. Huang et al., Infrared plasmonic biosensor with tetrahedral DNA nanostructure as carriers for label-free and ultrasensitive detection of miR-155. Adv. Sci. 8, e2100583 (2021). https://doi.org/10.1002/advs.202100583
  16. A. John-Herpin, D. Kavungal, L. von Mücke, H. Altug, Infrared metasurface augmented by deep learning for monitoring dynamics between all major classes of biomolecules. Adv. Mater. 33, e2006054 (2021). https://doi.org/10.1002/adma.202006054
  17. D. Rodrigo, A. Tittl, N. Ait-Bouziad, A. John-Herpin, O. Limaj et al., Resolving molecule-specific information in dynamic lipid membrane processes with multi-resonant infrared metasurfaces. Nat. Commun. 9, 2160 (2018). https://doi.org/10.1038/s41467-018-04594-x
  18. R. Adato, H. Altug, In-situ ultra-sensitive infrared absorption spectroscopy of biomolecule interactions in real time with plasmonic nanoantennas. Nat. Commun. 4, 2154 (2013). https://doi.org/10.1038/ncomms3154
  19. L. Paggi, A. Fabas, H. El Ouazzani, J.P. Hugonin, N. Fayard et al., Over-coupled resonator for broadband surface enhanced infrared absorption (SEIRA). Nat. Commun. 14, 4814 (2023). https://doi.org/10.1038/s41467-023-40511-7
  20. A. Tittl, A. Leitis, M. Liu, F. Yesilkoy, D.-Y. Choi et al., Imaging-based molecular barcoding with pixelated dielectric metasurfaces. Science 360, 1105–1109 (2018). https://doi.org/10.1126/science.aas9768
  21. F. Yesilkoy, E.R. Arvelo, Y. Jahani, M. Liu, A. Tittl et al., Ultrasensitive hyperspectral imaging and biodetection enabled by dielectric metasurfaces. Nat. Photonics 13, 390–396 (2019). https://doi.org/10.1038/s41566-019-0394-6
  22. A. Aigner, A. Tittl, J. Wang, T. Weber, Y. Kivshar et al., Plasmonic bound states in the continuum to tailor light–matter coupling. Sci. Adv. 8, eadd4816 (2022). https://doi.org/10.1126/sciadv.add4816
  23. S. Rosas, K.A. Schoeller, E. Chang, H. Mei, M.A. Kats et al., Metasurface-enhanced mid-infrared spectrochemical imaging of tissues. Adv. Mater. 35, 2301208 (2023). https://doi.org/10.1002/adma.202301208
  24. H. Zhou, D. Li, Z. Ren, C. Xu, L.-F. Wang et al., Surface plasmons-phonons for mid-infrared hyperspectral imaging. Sci. Adv. 10, eado3179 (2024). https://doi.org/10.1126/sciadv.ado3179
  25. D. Rodrigo, O. Limaj, D. Janner, D. Etezadi, F.J. García de Abajo et al., Mid-infrared plasmonic biosensing with graphene. Science 349, 165–168 (2015). https://doi.org/10.1126/science.aab2051
  26. C. Wu, A.B. Khanikaev, R. Adato, N. Arju, A. Ali Yanik et al., Fano-resonant asymmetric metamaterials for ultrasensitive spectroscopy and identification ofmolecular monolayers. Nat. Mater. 11, 69–75 (2012). https://doi.org/10.1038/nmat3161
  27. H. Zhou, X. Hui, D. Li, D. Hu, X. Chen et al., Metal-organic framework-surface-enhanced infrared absorption platform enables simultaneous on-chip sensing of greenhouse gases. Adv. Sci. 7, 2001173 (2020). https://doi.org/10.1002/advs.202001173
  28. X. Miao, T.S. Luk, P.Q. Liu, Liquid-metal-based nanophotonic structures for high-performance SEIRA sensing. Adv. Mater. 34, e2107950 (2022). https://doi.org/10.1002/adma.202107950
  29. I. Hwang, M. Kim, J. Yu, J. Lee, J.H. Choi et al., Ultrasensitive molecule detection based on infrared metamaterial absorber with vertical nanogap. Small Methods 5, e2100277 (2021). https://doi.org/10.1002/smtd.202100277
  30. J. Yi, E.-M. You, S.-Y. Ding, Z.-Q. Tian, Unveiling the molecule-plasmon interactions in surface-enhanced infrared absorption spectroscopy. Natl. Sci. Rev. 7, 1228–1238 (2020). https://doi.org/10.1093/nsr/nwaa054
  31. Z. Ren, Z. Zhang, J. Wei, B. Dong, C. Lee, Wavelength-multiplexed hook nanoantennas for machine learning enabled mid-infrared spectroscopy. Nat. Commun. 13, 3859 (2022). https://doi.org/10.1038/s41467-022-31520-z
  32. L. Dong, X. Yang, C. Zhang, B. Cerjan, L. Zhou et al., Nanogapped Au antennas for ultrasensitive surface-enhanced infrared absorption spectroscopy. Nano Lett. 17, 5768–5774 (2017). https://doi.org/10.1021/acs.nanolett.7b02736
  33. D. Yoo, F. de León-Pérez, M. Pelton, I.-H. Lee, D.A. Mohr et al., Ultrastrong plasmon–phonon coupling via epsilon-near-zero nanocavities. Nat. Photonics 15, 125–130 (2021). https://doi.org/10.1038/s41566-020-00731-5
  34. D. Li, A. Yadav, H. Zhou, K. Roy, P. Thanasekaran et al., Advances and applications of metal-organic frameworks (MOFs) in emerging technologies: a comprehensive review. Glob. Chall. 8, 2300244 (2023). https://doi.org/10.1002/gch2.202300244
  35. D. Li, H. Zhou, X. Hui, X. He, H. Huang et al., Multifunctional chemical sensing platform based on dual-resonant infrared plasmonic perfect absorber for on-chip detection of poly(ethyl cyanoacrylate). Adv. Sci. 8, e2101879 (2021). https://doi.org/10.1002/advs.202101879
  36. K. Chen, R. Adato, H. Altug, Dual-band perfect absorber for multispectral plasmon-enhanced infrared spectroscopy. ACS Nano 6, 7998–8006 (2012). https://doi.org/10.1021/nn3026468
  37. R.A. Maniyara, D. Rodrigo, R. Yu, J. Canet-Ferrer, D.S. Ghosh et al., Tunable plasmons in ultrathin metal films. Nat. Photonics 13, 328–333 (2019). https://doi.org/10.1038/s41566-019-0366-x
  38. P. Jangid, F.U. Richter, M.L. Tseng, I. Sinev, S. Kruk et al., Spectral tuning of high-harmonic generation with resonance-gradient metasurfaces. Adv. Mater. 36, e2307494 (2024). https://doi.org/10.1002/adma.202307494
  39. F.U. Richter, I. Sinev, S. Zhou, A. Leitis, S.H. Oh et al., Gradient high-Q dielectric metasurfaces for broadband sensing and control of vibrational light–matter coupling. Adv. Mater. 36, e2314279 (2024). https://doi.org/10.1002/adma.202314279
  40. A. Leitis, A. Tittl, M. Liu, B.H. Lee, M.B. Gu et al., Angle-multiplexed all-dielectric metasurfaces for broadband molecular fingerprint retrieval. Sci. Adv. 5, eaaw2871 (2019). https://doi.org/10.1126/sciadv.aaw2871
  41. J. Wang, T. Weber, A. Aigner, S.A. Maier, A. Tittl, Mirror-coupled plasmonic bound states in the continuum for tunable perfect absorption. Laser Photonics Rev. 17, 2300294 (2023). https://doi.org/10.1002/lpor.202300294
  42. Z. Chen, D. Li, H. Zhou, T. Liu, X. Mu, A hybrid graphene metamaterial absorber for enhanced modulation and molecular fingerprint retrieval. Nanoscale 15, 14100–14108 (2023). https://doi.org/10.1039/d3nr02830e
  43. J. Vogt, C. Huck, F. Neubrech, A. Toma, D. Gerbert et al., Impact of the plasmonic near- and far-field resonance-energy shift on the enhancement of infrared vibrational signals. Phys. Chem. Chem. Phys. 17, 21169–21175 (2015). https://doi.org/10.1039/c4cp04851b
  44. J.-H. Park, A. Ndao, W. Cai, L. Hsu, A. Kodigala et al., Symmetry-breaking-induced plasmonic exceptional points and nanoscale sensing. Nat. Phys. 16, 462–468 (2020). https://doi.org/10.1038/s41567-020-0796-x
  45. R. Adato, A. Artar, S. Erramilli, H. Altug, Engineered absorption enhancement and induced transparency in coupled molecular and plasmonic resonator systems. Nano Lett. 13, 2584–2591 (2013). https://doi.org/10.1021/nl400689q
  46. H. Zhou, Z. Ren, C. Xu, L. Xu, C. Lee, MOF/polymer-integrated multi-hotspot mid-infrared nanoantennas for sensitive detection of CO2 gas. Nano-Micro Lett. 14, 207 (2022). https://doi.org/10.1007/s40820-022-00950-1
  47. J. Wei, Y. Li, Y. Chang, D.M.N. Hasan, B. Dong et al., Ultrasensitive transmissive infrared spectroscopy via loss engineering of metallic nanoantennas for compact devices. ACS Appl. Mater. Interfaces 11, 47270–47278 (2019). https://doi.org/10.1021/acsami.9b18002
  48. D. Li, H. Zhou, Z. Chen, Z. Ren, C. Xu et al., Ultrasensitive molecular fingerprint retrieval using strongly detuned overcoupled plasmonic nanoantennas. Adv. Mater. 35, e2301787 (2023). https://doi.org/10.1002/adma.202301787
  49. H. Zhou, D. Li, Z. Ren, X. Mu, C. Lee, Loss-induced phase transition in mid-infrared plasmonic metamaterials for ultrasensitive vibrational spectroscopy. InfoMat 4, e12349 (2022). https://doi.org/10.1002/inf2.12349
  50. J. Xu, Z. Ren, B. Dong, X. Liu, C. Wang et al., Nanometer-scale heterogeneous interfacial sapphire wafer bonding for enabling plasmonic-enhanced nanofluidic mid-infrared spectroscopy. ACS Nano 14, 12159–12172 (2020). https://doi.org/10.1021/acsnano.0c05794
  51. H. Zhou, Z. Ren, D. Li, C. Xu, X. Mu et al., Dynamic construction of refractive index-dependent vibrations using surface plasmon-phonon polaritons. Nat. Commun. 14, 7316 (2023). https://doi.org/10.1038/s41467-023-43127-z
  52. B. Cerjan, X. Yang, P. Nordlander, N.J. Halas, Asymmetric aluminum antennas for self-calibrating surface-enhanced infrared absorption spectroscopy. ACS Photonics 3, 354–360 (2016). https://doi.org/10.1021/acsphotonics.6b00024
  53. K. Chen, T.D. Dao, S. Ishii, M. Aono, T. Nagao, Infrared aluminum metamaterial perfect absorbers for plasmon-enhanced infrared spectroscopy. Adv. Funct. Mater. 25, 6637–6643 (2015). https://doi.org/10.1002/adfm.201501151
  54. F. Neubrech, A. Pucci, T.W. Cornelius, S. Karim, A. García-Etxarri et al., Resonant plasmonic and vibrational coupling in a tailored nanoantenna for infrared detection. Phys. Rev. Lett. 101, 157403 (2008). https://doi.org/10.1103/PhysRevLett.101.157403
  55. M. Bertolotti, Waves and fields in optoelectronics. Opt. Acta Int. J. Opt. 32, 748 (1985). https://doi.org/10.1080/716099690
  56. P.A. Thomas, W.J. Tan, H.A. Fernandez, W.L. Barnes, A new signature for strong light–matter coupling using spectroscopic ellipsometry. Nano Lett. 20, 6412–6419 (2020). https://doi.org/10.1021/acs.nanolett.0c01963
  57. M.F. Limonov, M.V. Rybin, A.N. Poddubny, Y.S. Kivshar, Fano resonances in photonics. Nat. Photonics 11(9), 543–554 (2017). https://doi.org/10.1038/nphoton.2017.142
  58. I. Dolado, C. Maciel-Escudero, E. Nikulina, E. Modin, F. Calavalle et al., Remote near-field spectroscopy of vibrational strong coupling between organic molecules and phononic nanoresonators. Nat. Commun. 13, 6850 (2022). https://doi.org/10.1038/s41467-022-34393-4
  59. H. Durmaz, Y. Li, A.E. Cetin, A multiple-band perfect absorber for SEIRA applications. Sens. Actuat. B Chem. 275, 174–179 (2018). https://doi.org/10.1016/j.snb.2018.08.053
  60. L. Liu, S. Iketani, Y. Guo, J.F.-W. Chan, M. Wang et al., Striking antibody evasion manifested by the Omicron variant of SARS-CoV-2. Nature 602, 676–681 (2022). https://doi.org/10.1038/s41586-021-04388-0
  61. F. Zhu, C. Zhuang, K. Chu, L. Zhang, H. Zhao et al., Safety and immunogenicity of a live-attenuated influenza virus vector-based intranasal SARS-CoV-2 vaccine in adults: randomised, double-blind, placebo-controlled, phase 1 and 2 trials. Lancet Respir. Med. 10, 749–760 (2022). https://doi.org/10.1016/S2213-2600(22)00131-X
  62. J. Cheong, H. Yu, C.Y. Lee, J.U. Lee, H.J. Choi et al., Fast detection of SARS-CoV-2 RNA via the integration of plasmonic thermocycling and fluorescence detection in a portable device. Nat. Biomed. Eng. 4, 1159–1167 (2020). https://doi.org/10.1038/s41551-020-00654-0
  63. L. Wang, X. Wang, Y. Wu, M. Guo, C. Gu et al., Rapid and ultrasensitive electromechanical detection of ions, biomolecules and SARS-CoV-2 RNA in unamplified samples. Nat. Biomed. Eng. 6, 276–285 (2022). https://doi.org/10.1038/s41551-021-00833-7
  64. D. Li, H. Zhou, X. Hui, X. He, X. Mu, Plasmonic biosensor augmented by a genetic algorithm for ultra-rapid, label-free, and multi-functional detection of COVID-19. Anal. Chem. 93, 9437–9444 (2021). https://doi.org/10.1021/acs.analchem.1c01078
  65. S.X. Leong, Y.X. Leong, E.X. Tan, H.Y.F. Sim, C.S.L. Koh et al., Noninvasive and point-of-care surface-enhanced Raman scattering (SERS)-based Breathalyzer for mass screening of coronavirus disease 2019 (COVID-19) under 5 min. ACS Nano 16, 2629–2639 (2022). https://doi.org/10.1021/acsnano.1c09371
  66. H. Yao, Y. Song, Y. Chen, N. Wu, J. Xu et al., Molecular architecture of the SARS-CoV-2 virus. Cell 183, 730-738.e13 (2020). https://doi.org/10.1016/j.cell.2020.09.018
  67. X.X. Han, R.S. Rodriguez, C.L. Haynes, Y. Ozaki, B. Zhao, Surface-enhanced Raman spectroscopy. Nat. Rev. Meth. Primers 1, 87 (2022). https://doi.org/10.1038/s43586-021-00083-6
  68. X. Liu, Z. Zhang, J. Zhou, W. Liu, G. Zhou et al., Artificial intelligence-enhanced waveguide “photonic nose”-augmented sensing platform for VOC gases in mid-infrared. Small 20, e2400035 (2024). https://doi.org/10.1002/smll.202400035
  69. W. Liu, Y. Ma, X. Liu, J. Zhou, C. Xu et al., Larger-than-unity external optical field confinement enabled by metamaterial-assisted comb waveguide for ultrasensitive long-wave infrared gas spectroscopy. Nano Lett. 22, 6112–6120 (2022). https://doi.org/10.1021/acs.nanolett.2c01198
  70. J. Zhou, Z. Zhang, B. Dong, Z. Ren, W. Liu et al., Midinfrared spectroscopic analysis of aqueous mixtures using artificial-intelligence-enhanced metamaterial waveguide sensing platform. ACS Nano 17, 711–724 (2023). https://doi.org/10.1021/acsnano.2c10163
  71. J. Hu, D. Mengu, D.C. Tzarouchis, B. Edwards, N. Engheta et al., Diffractive optical computing in free space. Nat. Commun. 15, 1525 (2024). https://doi.org/10.1038/s41467-024-45982-w
  72. Z. Zhang, X. Liu, H. Zhou, S. Xu, C. Lee, Advances in machine-learning enhanced nanosensors: from cloud artificial intelligence toward future edge computing at chip level. Small Struct. 5, 2300325 (2024). https://doi.org/10.1002/sstr.202300325
  73. A. Bylinkin, M. Schnell, M. Autore, F. Calavalle, P. Li et al., Real-space observation of vibrational strong coupling between propagating phonon polaritons and organic molecules. Nat. Photonics 15, 197–202 (2021). https://doi.org/10.1038/s41566-020-00725-3
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE
Statistic
Read Counter : 1472 Download : 1091

Most read articles by the same author(s)