Joule-lenz Self-heating Synthesis of SnO2/Au Nanosheets for High-sensitivity Surface-enhanced Raman Scattering Applications
Main Article Content
Abstract
SnO2/Au nanosheets prepared via the Joule–Lenz self-heating method were developed as Surface Enhanced Raman Scattering (SERS) substrates for trace detection. The effects of current intensity and processing time on morphology and Raman enhancement were systematically investigated. Structural and morphological characteristics were analyzed by SEM, XRD, and Raman spectroscopy. Finite element simulations using COMSOL Multiphysics were conducted to elucidate the electromagnetic enhancement mechanism and identify regions of high local field intensity. The results show that the SnO2/Au nanosheet substrate enables detection of Methylene Blue at concentrations as low as 10-11 M and thiram down to 10-8 M. These findings demonstrate a practical strategy for developing scalable and low-cost SnO2-based SERS substrates through morphology-controlled nanostructure engineering for trace-level detection applications.
Keywords:
SnO2/Au nanosheets, SERS, COMSOL simulations
References
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[27] I. Shaikh, M. A. Haque, H. Pathan, S. Sartale, Spin-Coated Ag NPs SERS Substrate: Role of Electromagnetic and Chemical Enhancement in Trace Detection of Methylene Blue and Congo Red, Plasmonics, Vol. 17, No. 5, 2022, pp. 1889–1900, https://doi.org/10.1007/s11468-022-01671-2.
[28] X. Li, L. Lin, W.-H. Chiang, K. Chang, H. Xu, Microplasma Synthesized Gold Nanoparticles For Surface Enhanced Raman Spectroscopic Detection of Methylene Blue, Reaction Chemistry & Engineering, Vol. 7, No. 2, 2022, pp. 346-353, https://doi.org/10.1039/D1RE00446H.
[29] L. Z. Peredo, J. I. G. Ramirez, A. C. G. Velasco, J. H. Torres, L. G. González, M. Bizarro, A. B. Rodríguez, Influence of Ag Photodeposition Conditions over SERS Intensity of Ag/ZnO Microspheres for Nanomolar Detection of Methylene Blue, Nanomaterials, Vol. 11, No. 12, 2021, pp. 3414, https://doi.org/10.3390/nano11123414.
[30] M. Kadir, R. Nemkayeva, G. Baigarinova, B. Alpysbayeva, A. Assembayeva, V. Smirnov, SERS-active Substrates Based on Ag-coated TiO₂ Nanotubes and Nanograss, Physica E: Low-dimensional Systems and Nanostructures, Vol. 145, 2023, Article 115499, https://doi.org/10.1016/j.physe.2022.115499.
[31] T. H. Tran, M. H. Nguyen, T. H. T. Nguyen, V. P. T. Dao, Q. H. Nguyen, C. D. Sai, N. H. Pham, T. C. Bach, A. B. Ngac, T. T. Nguyen, K. H. Ho, H. Cheong, V. T. Nguyen, Facile Fabrication of Sensitive Surface Enhanced Raman Scattering Substrate Based on CuO/Ag Core/Shell Nanowires, Applied Surface Science, Vol. 509, 2020, Article 145325, https://doi.org/10.1016/j.apsusc.2020.145325.
[2] J. B. Wu, M. L. Lin, X. Cong, H. N. Liu, P. H. Tan, Raman Spectroscopy of Graphene-Based Materials and Its Applications in Related Devices, Chemical Society Reviews, Vol. 47, No. 5, 2018, pp. 1822-1873, https://doi.org/10.1039/C6CS00915H.
[3] M. Fleischmann, P. J. Hendra, A. J. McQuillan, Raman Spectra of Pyridine Adsorbed at a Silver Electrode, Chemical Physics Letters, Vol. 26, No. 2, 1974, pp. 163-166, https://doi.org/10.1016/0009-2614(74)85388-1.
[4] D. L. Jeanmaire, R. P. V. Duyne, Surface Raman Spectroelectrochemistry: Part I. Heterocyclic, Aromatic, and Aliphatic Amines Adsorbed on the Anodized Silver Electrode, Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 84, No. 1, 1977, pp. 1-20, https://doi.org/10.1016/S0022-0728(77)80224-6.
[5] M. G. Albrecht, J. A. Creighton, Anomalously Intense Raman Spectra of Pyridine at a Silver Electrode, Journal of the American Chemical Society, Vol. 99, No. 15, 1977, pp. 5215-5217, https://doi.org/10.1021/ja00457a071.
[6] M. Moskovits, Persistent Misconceptions Regarding SERS, Physical Chemistry Chemical Physics, Vol. 15,
No. 15, 2013, pp. 5301-5311, https://doi.org/10.1039/C2CP44030J.
[7] D. Li, D. Yao, C. Li, Y. Luo, A. Liang, G. Wen, Z. Jiang, Nanosol SERS Quantitative Analytical Method: A Review, TrAC Trends in Analytical Chemistry, Vol. 127, 2020, Article 115885, https://doi.org/10.1016/j.trac.2020.115885.
[8] G. McNay, D. Eustace, W. E. Smith, K. Faulds, D. Graham, Surface-Enhanced Raman Scattering (SERS) and Surface-Enhanced Resonance Raman Scattering (SERRS): A Review of Applications, Applied Spectroscopy, Vol. 65, No. 8, 2011, pp. 825-837, https://doi.org/10.1366/11-06365.
[9] T. N. Q. Trang, N. T. P. Trinh, N. T. G. Bao, V. T. H. Thu, Hotspot-type Silver-Polymers Grafted Nanocellulose Paper with Analyte Enrichment as Flexible Plasmonic Sensors for Highly Sensitive SERS Sensing, Journal of Science: Advanced Materials and Devices, Vol. 8, No. 3, 2023, Article 100597, https://doi.org/10.1016/j.jsamd.2023.100597.
[10] M. Zhang, Z. Wu, Y. Yang, J. Ye, S. Han, Y. Li, Fabrication of Molecularly-imprinted Gold Nanoparticle-Embedded Fe-MOFs for Highly Selective SERS Detection of 17β-estradiol in Milk, Analyst, Vol. 148, No. 11, 2023, pp. 2472-2481, https://doi.org/10.1039/D3AN00343D.
[11] Z. Chen, Y. Sun, J. Shi, W. Zhang, X. Zhang, X. Huang, X. Zou, Z. Li, R. Wei, Facile Synthesis of Au@Ag Core-Shell Nanorod with Bimetallic Synergistic Effect for SERS Detection of Thiabendazole in Fruit Juice, Food Chemistry, Vol. 370, 2022, Article 131276, https://doi.org/10.1016/j.foodchem.2021.131276.
[12] S. Lee, H. Dang, J.-I. Moon, K. Kim, Y. Joung, S. Park, Q. Yu, J. Chen, M. Lu, L. Chen, S. W. Joo, J. Choo, SERS-based Microdevices for Use as in Vitro Diagnostic Biosensors, Chemical Society Reviews, Vol. 53,
No. 11, 2024, pp. 5394-5427, https://doi.org/10.1039/D3CS01055D.
[13] G. Awiaz, J. Lin, A. Wu, Recent Advances of Au@Ag Core–shell SERS-based Biosensors, Exploration, Vol. 3, No. 1, 2023, Article 20220072, https://doi.org/10.1002/EXP.20220072.
[14] C. Li, Y. Huang, X. Li, Y. Zhang, Q. Chen, Z. Ye, Z. Alqarni, S. E. J. Bell, Y. Xu, Towards Practical and Sustainable SERS: A Review of Recent Developments in the Construction of Multifunctional Enhancing Substrates, Journal of Materials Chemistry C, Vol. 9, No. 35, 2021, pp. 11517-11552, https://doi.org/10.1039/D1TC02134F.
[15] T. T. H. Pham, X. H. Vu, N. D. Dien, T. T. Trang, T. T. K. Chi, P. H. Phuong, N. T. Nghia, Ag Nanoparticles on ZnO Nanoplates as a Hybrid SERS-active Substrate for Trace Detection of Methylene Blue, RSC Advances,
Vol. 12, No. 13, 2022, pp. 7850-7863, https://doi.org/10.1039/D2RA00620K.
[16] D. T. N. Nga, H. A. Nguyen, N. T. Hoa, N. N. Huyen, N. X. Dinh, T. N. Bach, N. Q. Hoa, A. T. Le, A Zinc Oxide–silver Nanocomposite-based SERS Nanoplatform for Ultrasensitive Ofloxacin Determination in Beef and an Ophthalmic Solution: Effects of ZnO and ZnO Content on Electron Transfer and SERS Enhancements, RSC Advances, Vol. 15, No. 12, 2025, pp. 8878-8888, https://doi.org/10.1039/D5RA00776C.
[17] J. Y. Zhou, J. Zhu, G. J. Weng, J. J. Li, J. W. Zhao, Fabrication of SERS Composite Substrates Using Ag Nanotriangles-modified SiO₂ Photonic Crystal and the Application of Malachite Green Detection, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 318, 2024, Article 124472, https://doi.org/10.1016/j.saa.2024.124472.
[18] T. H. Tran, T. M. A. Nguyen, V. P. T. Dao, C. D. Sai, T. C. Bach, N. H. Pham, A. B. Ngac, V. T. Pham, T. K. C. Tran, H. Cheong, V. T. Nguyen, Highly Sensitive Characteristic of Surface Enhanced Raman Scattering for CuO/Au Core/Shell Nanowires Substrate, Ceramics International, Vol. 48, No. 3, 2022, pp. 3199-3205, https://doi.org/10.1016/j.ceramint.2021.10.093.
[19] V. T. Tran, M. P. Le, N. H. Pham, T. H. Y. Le, V. T. Nguyen, T. H. Pham, T. S. Nguyen, Q. H. Nguyen, V. T. Pham, T. T. Nguyen, C. T. Nguyen, A. B. Ngac, O. Martínez Sacristán, T. H. Tran, Unraveling the Mechanism of Photo-induced Surface Enhanced Raman Scattering on ZnO/Au thin Films, Applied Surface Science, Vol. 657, 2024, Article 159785, https://doi.org/10.1016/j.apsusc.2024.159785.
[20] M. S. Choi, H. G. Na, S. Kim, J. H. Bang, W. Oum, S. W. Choi, S. S. Kim, K. H. Lee, H. W. Kim, C. Jin, Synthesis of Au/SnO₂ Nanostructures Allowing Process Variable Control, Scientific Reports, Vol. 10, No. 1, 2020, Article 346, https://doi.org/10.1038/s41598-019-57222-z.
[21] J. Fernández-Vidal, A. M. G. Marín, L. A. H. Jones, C. H. Yen, T. D. Veal, V. R. Dhanak, C. C. Hu, L. J. Hardwick, Long-Life and pH-Stable SnO₂-Coated Au Nanoparticles for SHINERS, The Journal of Physical Chemistry C, Vol. 126, No. 29, 2022, pp. 12074-12081, https://doi.org/10.1021/acs.jpcc.2c02432
[22] S. J. Oldenburg, J. B. Jackson, S. L. Westcott, N. J. Halas, Infrared Extinction Properties of Gold Nanoshells, Applied Physics Letters, Vol. 75, No. 19, 1999, pp. 2897–2899, https://doi.org/10.1063/1.125183.
[23] H. T. Girão, T. Cornier, S. Daniele, R. Debord, M. A. Caravaca, R. A. Casali, P. Mélinon, D. Machon, Pressure-Induced Disordering in SnO₂ Nanoparticles, The Journal of Physical Chemistry C, Vol. 121, No. 28, 2017,
pp. 15463-15471, https://doi.org/10.1021/acs.jpcc.7b04079.
[24] H. T. Girao, P. Hermet, B. Masenelli, J. Haines, P. Mélinon, D. Machon, Pressure-Induced Sublattice Disordering in SnO₂: Invasive Selective Percolation, Physical Review Letters, Vol. 120, No. 26, 2018, Article 265702, https://doi.org/10.1103/PhysRevLett.120.265702.
[25] C. Li, Y. Huang, K. Lai, B. A. Rasco, Y. Fan, Analysis of Trace Methylene Blue in Fish Muscles Using Ultra-Sensitive Surface-enhanced Raman Spectroscopy, Food Control, Vol. 65, 2016, pp. 99-105, https://doi.org/10.1016/j.foodcont.2016.01.017.
[26] P. B. Johnson, R. W. Christy, Optical Constants of the Noble Metals, Physical Review B, Vol. 6, No. 12, 1972, pp. 4370-4379, https://doi.org/10.1103/PhysRevB.6.4370.
[27] I. Shaikh, M. A. Haque, H. Pathan, S. Sartale, Spin-Coated Ag NPs SERS Substrate: Role of Electromagnetic and Chemical Enhancement in Trace Detection of Methylene Blue and Congo Red, Plasmonics, Vol. 17, No. 5, 2022, pp. 1889–1900, https://doi.org/10.1007/s11468-022-01671-2.
[28] X. Li, L. Lin, W.-H. Chiang, K. Chang, H. Xu, Microplasma Synthesized Gold Nanoparticles For Surface Enhanced Raman Spectroscopic Detection of Methylene Blue, Reaction Chemistry & Engineering, Vol. 7, No. 2, 2022, pp. 346-353, https://doi.org/10.1039/D1RE00446H.
[29] L. Z. Peredo, J. I. G. Ramirez, A. C. G. Velasco, J. H. Torres, L. G. González, M. Bizarro, A. B. Rodríguez, Influence of Ag Photodeposition Conditions over SERS Intensity of Ag/ZnO Microspheres for Nanomolar Detection of Methylene Blue, Nanomaterials, Vol. 11, No. 12, 2021, pp. 3414, https://doi.org/10.3390/nano11123414.
[30] M. Kadir, R. Nemkayeva, G. Baigarinova, B. Alpysbayeva, A. Assembayeva, V. Smirnov, SERS-active Substrates Based on Ag-coated TiO₂ Nanotubes and Nanograss, Physica E: Low-dimensional Systems and Nanostructures, Vol. 145, 2023, Article 115499, https://doi.org/10.1016/j.physe.2022.115499.
[31] T. H. Tran, M. H. Nguyen, T. H. T. Nguyen, V. P. T. Dao, Q. H. Nguyen, C. D. Sai, N. H. Pham, T. C. Bach, A. B. Ngac, T. T. Nguyen, K. H. Ho, H. Cheong, V. T. Nguyen, Facile Fabrication of Sensitive Surface Enhanced Raman Scattering Substrate Based on CuO/Ag Core/Shell Nanowires, Applied Surface Science, Vol. 509, 2020, Article 145325, https://doi.org/10.1016/j.apsusc.2020.145325.