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Novel GaN-Based Substrates with Gold Nanostructures for Ultra-Sensitive SERS Analysis: Micro-Nano Pit Morphology for Enhanced Molecular Detection

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Abstract

Purpose

Surface-enhanced Raman scattering (SERS) is a technique for trace analysis detection based on the interaction of light with matter and between materials. In the past development of SERS, precious metals were primarily chosen as substrates due to their high electromagnetic effect, which leads to significantly enhanced SERS signals. However, the effect of using only precious metals is limited. Therefore, this study utilizes the characteristic micro-nano V-shaped pits that appear on the surface of c-plane GaN after wet etching. By depositing a gold film of various thicknesses, we aim to increase the contact area with the target molecule Rhodamine 6G (R6G), thereby further enhancing the sensitivity of SERS detection.

Methods

After fabricating pitted c-plane GaN using chemical etching techniques, we analyzed the sample surface with a scanning electron microscope and assessed the impact of different gold film thicknesses on the SERS intensity of R6G using Raman spectroscopy. The comprehensive biomedical detection effectiveness was also evaluated using contact angle measurement, and fluorescence microscopy.

Results

For the target molecule R6G, after depositing a 25 nm gold film, the enhancement factor of the substrate for detection reached 2.21×108, and the limit of detection was achieved at a concentration of 10− 10 M.

Conclusion

This study confirms the feasibility of using wet etching techniques on hexagonal materials like GaN for SERS applications. The GaN substrate with V-shaped pits provides an increased surface area, effectively enhancing SERS signal strength. This offers different choices and perspectives for SERS substrate selection in the detection of various target molecules.

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Data Availability

All data generated or analyzed during this study are included in this manuscript.

References

  1. Dong, J., Yang, C., Wu, H., Wang, Q., Cao, Y., Han, Q., Gao, W., Wang, Y., Qi, J., & Sun, M. (2022). Two-dimensional self-assembly of Au@Ag core – shell nanocubes with different permutations for ultrasensitive SERS measurements. ACS Omega, 7(4), 3312–3323. https://doi.org/10.1021/acsomega.1c05452

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  2. Sultangaziyev, A., Ilyas, A., Dyussupova, A., & Bukasov, R. (2022). Trends in application of SERS substrates beyond ag and au, and their role in bioanalysis. Biosensors, 12(11), 967. https://doi.org/10.3390/bios12110967

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Wang, X., Wu, Y., Wen, X., Zhu, J., Bai, X., Qi, Y., & Yang, H. (2020). Surface plasmons and SERS application of au nanodisk array and au thin film composite structure. Optical and Quantum Electronics, 52, 238. https://doi.org/10.1007/s11082-020-02360-2

    Article  CAS  Google Scholar 

  4. Elsharkawi, A. S. A., Shaban, H., Gomaa, L. R., & Du, Y. C. (2023). A highly sensitive sensing technique via surface plasmons with tunable prism refractive index. IEEE Sensors Journal, 23(9), 9917–9924. https://doi.org/10.1109/JSEN.2023.3260838

    Article  CAS  Google Scholar 

  5. Shaaban, A., & Du, Y. C. (2023). An optical universal plasmon-based biosensor for virus ‎‎detection. Journal of Medical and Biological Engineering, 43(3), 258–265. https://link.springer.com/article/10.1007/s40846-023-00788-x

  6. de Albuquerque, C. D. L., Hokanson, K. M., Thorud, S. R., Sobral-Filho, R. G., Lindquist, N. C., & Brolo, A. G. (2020). Dynamic imaging of multiple SERS hotspots on single nanoparticles. ACS Photonics, 7(2), pp434–443. https://doi.org/10.1021/acsphotonics.9b01395

    Article  CAS  Google Scholar 

  7. Cai, J., Liu, R., Jia, S., Feng, Z., Lin, L., Zheng, Z., Wu, S., & Wang, Z. (2021). SERS hotspots distribution of the highly ordered noble metal arrays on flexible substrates. Optical Materials, 122, 111779. https://doi.org/10.1016/j.optmat.2021.111779

    Article  CAS  Google Scholar 

  8. Pham, X. H., Hahm, E., Kim, T. H., Kim, H. M., Lee, S. H., Lee, S. C., Kang, H., Lee, H. Y., Jeong, D. H., Choi, H. S., & Jun, B. H. (2020). Enzyme-amplified SERS immunoassay with Ag-Au bimetallic SERS hot spots. Nano Research, 13(12), 3338–3346. https://doi.org/10.1007/s12274-020-3014-3

    Article  CAS  Google Scholar 

  9. Shafi, M., Liu, R., Zha, Z., Li, C., Du, X., Wali, S., Jiang, S., Man, B., & Liu, M. (2021). Highly efficient SERS substrates with different ag interparticle nanogaps based on hyperbolic metamaterials. Applied Surface Science, 555, 149729. https://doi.org/10.1016/j.apsusc.2021.149729

    Article  CAS  Google Scholar 

  10. Goerlitzer, E. S. A., Speichermann, L. E., Mirza, T. A., Mohammadi, R., & Vogel, N. (2020). Addressing the plasmonic hotspot region by site-specific functionalization of nanostructures. Nanoscale Advances, 2(1), pp394–400. https://doi.org/10.1039/C9NA00757A

    Article  Google Scholar 

  11. Darienzo, R. E., Chen, O., Sullivan, M., Mironava, T., & Tannenbaum, R. (2020). Au nanoparticles for SERS: Temperature-controlled nanoparticle morphologies and their Raman enhancing properties. Materials Chemistry and Physics, 240, 112143. https://doi.org/10.1016/j.matchemphys.2019.122143

    Article  CAS  Google Scholar 

  12. Chen, A., DePrinceIII, A. E., Demortière, A., Joshi-Imre, A., Shevchenko, E. V., Gray, S. K., Welp, U., & Vlasko-Vlasov, V. K. (2011). Self-assembled large au nanoparticle arrays with regular hot spots for SERS. Small, 7(16), 2365–2371. https://doi.org/10.1002/smll.201100686

  13. Waiwijit, U., Chananonnawathorn, C., Eimchai, P., Bora, T., Hornyak, G. L., & Nuntawong, N. (2020). Fabrication of Au-Ag nanorod SERS substrates by co-sputtering technique and dealloying with selective chemical etching. Applied Surface Science, 534, 147171. https://doi.org/10.1016/j.apsusc.2020.147171

    Article  CAS  Google Scholar 

  14. Dey, P., Baumann, V., & Rodríguez-Fernández, J. (2020). Gold nanorod assemblies: The roles of hot-spot positioning and anisotropy in plasmon coupling and SERS. Nanomaterials, 10(5) 942. https://doi.org/10.3390/nano10050942

  15. Bańkowska, M., Krajczewski, J., Dzięcielewski, I., Kudelski, A., & Weyher, J. L. (2016). Au–Cu alloyed plasmonic layer on nanostructured GaN for SERS Application. The Journal of Physical Chemistry C, 120(3), 1841–1846. https://doi.org/10.1021/acs.jpcc.5b11371

    Article  CAS  Google Scholar 

  16. Bartosewicz, B., Andersson, P. O., Dziecielewski, I., Jankiewicz, B. (2019). Nanostructured GaN sensors for surface enhanced Raman spectroscopy. Materials Science in Semiconductor Processing, 91, 97–101. https://doi.org/10.1016/j.mssp.2018.11.012

  17. Zhao, S., Wang, H., Niu, L., Xiong, W., Chen, Y., Zeng, M., Yuan, S., & Fu, L. (2021). 2D GaN for highly reproducible surface enhanced Raman scattering. Small (Weinheim An Der Bergstrasse, Germany), 11, 2103442. https://doi.org/10.1002/smll.202102485

    Article  CAS  Google Scholar 

  18. Ng, W. N., Leung, C. H., Lai, P. T., & Choi, H. W. (2008). Nanostructuring GaN using microsphere lithography. Journal of Vacuum Science & Technology B, 26(1), 76–79. https://doi.org/10.1116/1.2819265

    Article  CAS  Google Scholar 

  19. Le Boulbar, E., & Shields, P. (2016). Fabrication of high-aspect ratio GaN nanostructures for advanced photonic devices. Microelectronic Engineering, 153(5), 132–136. https://doi.org/10.1016/j.mee.2016.03.058

  20. Debnath, R., Ha, J. Y., Wen, B., Paramanik, D., Motayed, A., King, M., & Davydov, A. V. (2014). Top-down fabrication of large-area GaN micro- and nanopillars. Journal of Vacuum Science & Technology B, 32(2), 021204. https://doi.org/10.1116/1.4865908

    Article  CAS  Google Scholar 

  21. Weyher, J. L., Dzięcielewski, I., Kamińska, A., Roliński, T., Nowak, G., & Hołyst, R. (2012). GaN-based platforms with Au-Ag alloyed metal layer for surface enhanced Raman scattering. Journal of Applied Physics, 112(11), 114327. https://doi.org/10.1063/1.4769106

    Article  CAS  Google Scholar 

  22. Kamińska, A., Dzięcielewski, I., Weyher, J. L., Waluk, J., Gawinkowski, S., Sashuk, V., Fiałkowski, M., Sawicka, M., Suski, T., Porowski, S., & Hołyst, R. (2011). Highly reproducible, stable and multiply regenerated surface-enhanced Raman scattering substrate for biomedical applications. Journal of Materials Chemistry, 24(1), 1–10. https://pubs.rsc.org/en/content/articlelanding/2011/jm/c0jm03336g.

    Google Scholar 

  23. Hite, J. K., Anderson, T. J., Luna, L. E., Gallagher, J. C., Mastro, M. A., Freitas, J. A., & Eddy, C. R. (2018). Influence of HVPE substrates on homoepitaxy of GaN grown by MOCVD. Journal of Crystal Growth, 1(1), 1–10. https://doi.org/10.1016/j.jcrysgro.2018.06.032

    Article  CAS  Google Scholar 

  24. Zhang, M., Cai, D., Zhang, Y., Su, X., Zhou, T., Cui, M., Li, C., Wang, J., & Xu, K. (2017). Investigation of the properties and formation process of a peculiar V-pit in HVPE-grown GaN film. Materials Letters, 1(1), 1–10. https://www.x-mol.com/paper/1233851769276092416.

    Article  Google Scholar 

  25. Vlckova, B., Pavel, I., Sladkova, M., Siskova, K., & Slouf, M. (2007). Single molecule SERS: Perspectives of analytical applications. Journal of Molecular Structure, 1(1), 1–10. https://doi.org/10.1016/j.molstruc.2006.11.053

    Article  CAS  Google Scholar 

  26. Li, H., Merkl, P., Sommertune, J., Thersleff, T., & Sotiriou, G. A. (2022). SERS hotspot engineering by aerosol self-assembly of plasmonic Ag nanoaggregates with tunable interparticle distance. Advanced Science, 9(22), ppe2201133. https://doi.org/10.1002/advs.202201133

    Article  CAS  Google Scholar 

  27. Zong, C., Xu, M., Xu, L. J., Wei, T., Ma, X., Zheng, X. S., & Ren, B. (2018). Surface-enhanced Raman spectroscopy for bioanalysis: Reliability and challenges. Chemical Reviews, 118(10), 4946–4980. https://doi.org/10.1021/acs.chemrev.7b00668

  28. Dzięcielewski, I., & Weyher, J. L. (2013). On the hydrophobicity of modified Ga-polar GaN surfaces. Applied Physics Letters, 102(4), 043704. https://doi.org/10.1063/1.4790435

    Article  CAS  Google Scholar 

  29. Brem, S., & Schlücker, S. (2017). Surface-enhanced Raman spectroscopy and density functional theory calculations of a rationally designed rhodamine with thiol groups at the xanthene ring. The Journal of Physical Chemistry C, 121(28), 15310–15317. https://doi.org/10.1021/acs.jpcc.7b01504

    Article  CAS  Google Scholar 

  30. Han, Y., Qiang, L., Gao, Y., Gao, J., He, Q., Liu, H., Han, L., & Zhang, Y. (2021). Large-area surface-enhanced Raman spectroscopy substrate by hybrid porous GaN with Au/Ag for breast cancer miRNA detection. Applied Surface Science. https://doi.org/10.1016/j.apsusc.2020.148456

    Article  PubMed  Google Scholar 

  31. Ko, T. S., & Kuo, K. Y. (2022). Using a Au/pitted a-plane GaN substrate to aggregate polar molecules for highly efficient surface-enhanced Raman scattering. The Journal of Chemical Physics, 157(11), 114702. https://doi.org/10.1063/5.0115547

    Article  CAS  PubMed  Google Scholar 

  32. Du, Y. C., Yen, L. B., Kuo, P. L., & Tsai, P. Y. (2021). A wearable device for evaluation of relative position, force and duration of fetal movement for pregnant woman care. IEEE Sensors Journal, 21(17), 19341–19350. https://doi.org/10.1109/JSEN.2021.9453764

    Article  Google Scholar 

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Acknowledgements

The authors express their gratitude to AIXTRON in Aachen, Germany, for their assistance in depositing the GaN thin films, and to Roots Technology Co., Ltd. in Hsinchu, Taiwan, for their support with the Au layer deposition. Special thanks are extended to Dr. Ming-Jui Wu from the Kaohsiung Veterans General Hospital Tainan Branch for his valuable suggestions, and to Dr. Jiann-Yeu Chen from National Chung Hsing University for his aid in Raman spectroscopy and insightful discussions.

Funding

This study was funded by the National Science and Technology Council of Taiwan (grant numbers 111–2221–E–018–016) and supported by integrated project of Interdisciplinary Research on Sustainability-Innovative Collaboration projects for Young Scholars of National University System of Taiwan.

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Authors and Affiliations

  1. Department of Electronic Engineering, National Changhua University of Education, Changhua, Taiwan

    Tsung-Shine Ko & Chen-An Deng

  2. Department of Materials Science and Engineering, National United University, Miaoli, Taiwan

    Jiann Shieh

  3. Department of Electro-Optical Engineering, National Formosa University, Yunlin, Taiwan

    Hung Ji Huang

  4. Department of Chemical Engineering, National United University, Miaoli, Taiwan

    Yung-Sheng Lin

  5. Department of Chemistry, National Changhua University of Education, Changhua, Taiwan

    Yang-Wei Lin

  6. Department of Biomedical Engineering, National Cheng Kung University, Tainan, Taiwan

    Yi-Chun Du

  7. Medial Device Innovation Center, National Cheng Kung University, Tainan, Taiwan

    Yi-Chun Du

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Contributions

Tsung-Shine Ko, conceptualization, formal analysis, investigation, and writing–original draft. Chen-An Deng, methodology, software, validation, and investigation. Jiann Shieh, conceptualization, investigation, resources, methodology, review, and editing. Hung Ji Huang, resources, review, and editing. Yung-Sheng Lin, resources, review, and editing. Yang-Wei Lin, resources, review, and editing. Y. C. Du, conceptualization, resource, formal analysis, investigation, review, and editing.

Corresponding author

Correspondence to Yi-Chun Du.

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Ko, TS., Deng, CA., Shieh, J. et al. Novel GaN-Based Substrates with Gold Nanostructures for Ultra-Sensitive SERS Analysis: Micro-Nano Pit Morphology for Enhanced Molecular Detection. J. Med. Biol. Eng. 44, 522–530 (2024). https://doi.org/10.1007/s40846-024-00889-1

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