journal article·2026-03Open access

Femtosecond laser-induced breakdown spectroscopy for film analysis of cu-coated polymer textiles

Omar Elsheikh, Bastian Zielinski, Noemí Aguiló-Aguayo, Elena Ramela Ciobotea, Cristian Sarpe, Hendrike Braun, Arne Senftleben, Thomas Baumert, Camilo Florian

Applied Physics A· Volume 132· Issue 3

Abstract

Abstract The objective of this work is to evaluate the capability of femtosecond laser-induced breakdown spectroscopy (fs-LIBS) to characterize copper coatings on Lyocell textile fibers with micrometric spatial resolution. In this study, fs-LIBS is employed as a high-resolution analytical technique for characterizing copper coatings on heat-sensitive polymer-based Lyocell fabric. A relative spectral analysis of the multilayered material was performed by tracking relative variations in emission lines within the coating thickness and in spatially selected regions where the coloring is inhomogeneous. The observed color inhomogeneity arises from local variations in oxide formation and particle density during the copper deposition process. A coated textile sample was inspected via scanning electron microscopy (SEM) and Energy-dispersive X-ray spectroscopy (EDX) from the surface to the polymer substrate to estimate a Cu coating thickness of approximately 20 $$\mu m$$ and fiber diameters of approximately 175 $$\mu m$$ . SEM-EDX was used only to estimate coating thickness, as its limited sensitivity to light elements and buried interfaces makes it unsuitable for resolving the polymer and oxide signatures targeted in this work. The proposed measuring approach based on fs-LIBS enabled precise chemical mapping with a lateral resolution of 7 $$\mu m$$ linked to the implemented focusing optics and shallow depth profiling with minimal thermal damage to the underlying polymer substrates. The technique successfully identified key elements such as Copper (Cu-I) and trace contaminants such as Silver (Ag-I), Tin (Sn-II), and Sodium (Na-I), introduced during silver seeding and electroless copper deposition. Additionally, due to the ultrashort pulse duration of the laser pulses used, CN and C–C band spectral lines coming from the dielectric polymer, as well as Cu oxides (CuO, Cu₂O) originating from extremely thin surface layers, could also be detected. These findings highlight the capability of fs-LIBS for spatially selective, minimally invasive, real-time analysis and demonstrate its compatibility with the characterization of thin films deposited on thermally sensitive substrates, relevant for flexible electronics and smart textile applications.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Laser-induced spectroscopy and plasma · Laser Material Processing Techniques · Laser-Ablation Synthesis of Nanoparticles

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (39)

Show source-provided references
1. A. Kamyshny, S. Magdassi, Conductive nanomaterials for 2D and 3D printed flexible electronics. Chem. Soc. Rev. 48(6), 1712–1740 (2019). https://doi.org/10.1039/C8CS00738A10.1039/C8CS00738A ↗
2. C. Wang, K. Xia, H. Wang, X. Liang, Z. Yin, Y. Zhang, Advanced Carbon for Flexible and Wearable Electronics. Adv. Mater. 31(9), 1801072 (2019). https://doi.org/10.1002/adma.20180107210.1002/adma.201801072 ↗
3. H. Wu, Y. Huang, F. Xu, Y. Duan, Z. Yin, Energy Harvesters for Wearable and Stretchable Electronics: From Flexibility to Stretchability. Adv. Mater. 28(45), 9881–9919 (2016). https://doi.org/10.1002/adma.20160225110.1002/adma.201602251 ↗
4. C. Guo, Functional Materials for Flexible Electronics and Smart Wearables: Advances and Applications. ACE 147, 142–150 (2025). https://doi.org/10.54254/2755-2721/2025.2261610.54254/2755-2721/2025.22616 ↗
5. D.A. Cremers, L.J. Radziemski, Handbook of Laser-Induced Breakdown Spectroscopy (2013). https://doi.org/10.1002/978111856737110.1002/9781118567371 ↗
6. C. Lv, N. Zhang, Z. Lin, T. Ou, J. Li, N. Zhao, X. Yang, Q. Ma, L. Guo, Q. Zhang, Determination of copper, magnesium, and manganese in aluminum alloys using laser-induced breakdown spectroscopy based on fiber laser ablation. J. Laser Appl. 35(1), 012021 (2023). https://doi.org/10.2351/7.000093910.2351/7.0000939 ↗
7. J. Mildner, C. Sarpe, N. Goette, D. Otto, M. Wollenhaupt, T. Baumert, W. Wessel, E. Merdian, A. Brueckner-Foit, Optimization of the LIBS signal for the chemical mapping of metals by femtosecond double-pulses; Optimierung des LIBS-Signals zur chemischen Abbildung von Metallen durch Femtosekunden Doppelpulse. Verh. Dtsch. Phys. Ges. (2011). https://www.osti.gov/etdeweb/biblio/22030754
8. J.A. Aguilera, C. Aragón, F. Peñalba, Plasma shielding effect in laser ablation of metallic samples and its influence on LIBS analysis. Appl. Surf. Sci. 127–129, 309–314 (1998). https://doi.org/10.1016/S0169-4332(97)00648-X10.1016/S0169-4332(97)00648-X ↗
9. W. Berthou, M. Legallais, B. Bousquet, V. Motto-Ros, F. Le Cras, Characterization of lithium phosphorus oxide thin film libraries by laser-induced breakdown spectroscopy imaging: A step towards high-throughput quantitative analyses. Spectrochim. Acta, Part B 215, 106906 (2024). doi: 10.1016/j.sab.2024.10690610.1016/j.sab.2024.106906 ↗
10. B. Le Bellego, V. Motto-Ros, B. Luais, C. Fabre, C. Dalou, P. Condamine, L. Tissandier, Semi-quantitative $$\mu $$LIBS mapping of germanium diffusion between metal and silicate during planetary core–mantle segregation. Spectrochim. Acta, Part B 222, 107059 (2024). doi: 10.1016/j.sab.2024.10705910.1016/j.sab.2024.107059 ↗
11. A. Assion, M. Wollenhaupt, L. Haag, F. Mayorov, C. Sarpe-Tudoran, M. Winter, U. Kutschera, T. Baumert, Femtosecond laser-induced-breakdown spectrometry for Ca2+ analysis of biological samples with high spatial resolution. Appl. Phys. B 77(4), 391–397 (2003). https://doi.org/10.1007/s00340-003-1262-z10.1007/s00340-003-1262-z ↗
12. E.R. Ciobotea, C. Sarpe, B. Zielinski, H. Braun, A. Senftleben, S. Dutta, G. Mayer, C. Florian, T. Baumert, Signal enhancement with double-pulse LIBS on biological samples and better discrimination of tissues through machine learning algorithms. Spectrochim. Acta, Part B 222, 107063 (2024). doi: 10.1016/j.sab.2024.10706310.1016/j.sab.2024.107063 ↗
13. W. Wessel, A. Brueckner-Foit, J. Mildner, L. Englert, L. Haag, A. Horn, M. Wollenhaupt, T. Baumert, Use of femtosecond laser-induced breakdown spectroscopy (fs-LIBS) for micro-crack analysis on the surface. Eng. Fract. Mech. 77(11), 1874–1883 (2010). https://doi.org/10.1016/j.engfracmech.2010.03.02010.1016/j.engfracmech.2010.03.020 ↗
14. T.A. Labutin, V.N. Lednev, A.A. Ilyin, A.M. Popov, Femtosecond laser-induced breakdown spectroscopy. J. Anal. At. Spectrom. 31(1), 90–118 (2015). https://doi.org/10.1039/C5JA00301F10.1039/C5JA00301F ↗
15. E.L. Gurevich, R. Hergenröder, Femtosecond Laser-Induced Breakdown Spectroscopy: Physics, Applications, and Perspectives. Appl. Spectrosc. 61(10), 233A-242A (2007). https://doi.org/10.1366/00037020778221782410.1366/000370207782217824 ↗
16. C.M. Ahamer, K.M. Riepl, N. Huber, J.D. Pedarnig, Femtosecond laser-induced breakdown spectroscopy: Elemental imaging of thin films with high spatial resolution. Spectrochim. Acta, Part B 136, 56–65 (2017). https://doi.org/10.1016/j.sab.2017.08.00510.1016/j.sab.2017.08.005 ↗
17. N. Giannakaris, A. Haider, C.M. Ahamer, S. Grünberger, S. Trautner, J.D. Pedarnig, Femtosecond Single-Pulse and Orthogonal Double-Pulse Laser-Induced Breakdown Spectroscopy (LIBS): Femtogram Mass Detection and Chemical Imaging with Micrometer Spatial Resolution. Appl. Spectrosc. 76(8), 926–936 (2021). https://doi.org/10.1177/0003702821104239810.1177/00037028211042398 ↗
18. S. Sheta, M.S. Afgan, L. Jiacen, W. Gu, Z. Hou, Z. Wang, Insights into Enhanced Repeatability of Femtosecond Laser-Induced Plasmas. ACS Omega 5(47), 30425–30435 (2020). https://doi.org/10.1021/acsomega.0c0363610.1021/acsomega.0c03636 ↗
19. S. Saha, J. Sanwal, P. Mahadik, P. Sengupta, P. Mathi, The analytical potential of Femtosecond Laser-Induced Breakdown Spectroscopy (fsLIBS) for determination of trace elements in speleothems. Microchem. J. 207, 112215 (2024). https://doi.org/10.1016/j.microc.2024.11221510.1016/j.microc.2024.112215 ↗
20. R. Garcia, F.A. Stevie, L. Giannuzzi, FIB Sample Preparation for In Depth EDS Analysis. Microsc. Microanal. 25(S2), 914–915 (2019). https://doi.org/10.1017/S143192761900530010.1017/S1431927619005300 ↗
21. J. Kovač, M. Finšgar, Analysis of the Thermal Stability of Very Thin Surface Layers of Corrosion Inhibitors by Time-of-Flight Secondary Ion Mass Spectrometry. J. Am. Soc. Mass Spectrom. 29(12), 2305–2316 (2018). https://doi.org/10.1007/s13361-018-2048-110.1007/s13361-018-2048-1 ↗
22. G. Stelmacovich, L. van Eijk, M. Walker, D.A. Cullen, S. Ware, J.L. Young, G. Bender, S. Pylypenko, Optimization of Time-of-Flight Secondary Ion Mass Spectrometry for Analysis of Porous Transport Layers. Meet. Abstr. MA2023-01(36), 1964 (2023). doi: 10.1149/MA2023-01361964mtgabs10.1149/MA2023-01361964mtgabs ↗
23. J. Landsiedel, J. Tschannett, M. Lenninger, S. Stroj, M. Domke, T. Bechtold, T. Pham, N. Aguiló-Aguayo, A siloxane interlayer approach to enhance surface metallization on polyamide fabrics via electroless copper deposition. Surf. Interfaces 42, 103434 (2023). https://doi.org/10.1016/j.surfin.2023.10343410.1016/j.surfin.2023.103434 ↗
24. J. Landsiedel, W. Root, C. Schramm, A. Menzel, S. Witzleben, T. Bechtold, T. Pham, Tunable colors and conductivity by electroless growth of Cu/Cu2O particles on sol-gel modified cellulose. Nano Res. 13(10), 2658–2664 (2020). https://doi.org/10.1007/s12274-020-2907-510.1007/s12274-020-2907-5 ↗
25. H. Zhao, L. Hou, S. Bi, Y. Lu, Enhanced X-Band Electromagnetic-Interference Shielding Performance of Layer-Structured Fabric-Supported Polyaniline/Cobalt–Nickel Coatings. ACS Appl. Mater. Interfaces. 9(38), 33059–33070 (2017). https://doi.org/10.1021/acsami.7b0794110.1021/acsami.7b07941 ↗
26. J. Köhler, M. Wollenhaupt, T. Bayer, C. Sarpe, T. Baumert, Zeptosecond precision pulse shaping. Opt. Express 19(12), 11638–11653 (2011)10.1364/OE.19.011638 ↗
27. T.A. Alrebdi, A. Fayyaz, A. Ben Gouider Trabelsi, H. Asghar, F.H. Alkallas, A.M. Alshehri, Vibrational Emission Study of the CN and C2 in Nylon and ZnO/Nylon Polymer Using Laser-Induced Breakdown Spectroscopy (LIBS). Polymers 14(17), 3686 (2022). doi: 10.3390/polym1417368610.3390/polym14173686 ↗
28. I. Chamradová, P. Pořízka, J. Kaiser, Laser-Induced Breakdown Spectroscopy analysis of polymers in three different atmospheres. Polym. Test. 96, 107079 (2021). https://doi.org/10.1016/j.polymertesting.2021.10707910.1016/j.polymertesting.2021.107079 ↗
29. Z. Gajarska, L. Brunnbauer, H. Lohninger, A. Limbeck, Identification of 20 polymer types by means of laser-induced breakdown spectroscopy (LIBS) and chemometrics. Anal. Bioanal. Chem. 413(26), 6581–6594 (2021). https://doi.org/10.1007/s00216-021-03622-y10.1007/s00216-021-03622-y ↗
30. H.L. Xu, J. Bernhardt, P. Mathieu, G. Roy, S.L. Chin, Understanding the advantage of remote femtosecond laser-induced breakdown spectroscopy of metallic targets. J. Appl. Phys. 101(3), 033124 (2007). https://doi.org/10.1063/1.243758010.1063/1.2437580 ↗
31. N.I. of Standards, Technology, Security requirements for cryptographic modules. Tech. Rep. Federal Information Processing Standards Publications (FIPS) 140–2, Change Notice 2 December 03, 2002, U.S. Department of Commerce, Washington, D.C. (2001). doi: 10.6028/nist.fips.140-210.6028/NIST.FIPS.140-2 ↗
32. N. Hussain, M.A. Abdelkareem, H. Alawadhi, A.H. Alami, K. Elsaid, Cu2O nanoparticles decorated with MoS2 sheets for electrochemical reduction of CO2 with enhanced efficiency. Appl. Phys. A 128(2), 1–11 (2022). https://doi.org/10.1007/s00339-021-05230-010.1007/s00339-021-05230-0 ↗
33. L.C. Chen, C.C. Chen, K.C. Liang, S.H. Chang, Z.L. Tseng, S.C. Yeh, C.T. Chen, W.T. Wu, C.G. Wu, Nano-structured CuO-Cu2O Complex Thin Film for Application in CH3NH3PbI3 Perovskite Solar Cells. Nanoscale Res. Lett. 11(1), 1–7 (2016). https://doi.org/10.1186/s11671-016-1621-410.1186/s11671-016-1621-4 ↗
34. S.J. Kim, S. Kim, J. Lee, Y. Jo, Y.S. Seo, M. Lee, Y. Lee, C.R. Cho, J.p. Kim, M. Cheon, J. Hwang, Y.I. Kim, Y.H. Kim, Y.M. Kim, A. Soon, M. Choi, W.S. Choi, S.Y. Jeong, Y.H. Lee, Color of Copper/Copper Oxide. Adv. Mater. 33(15), 2007345 (2021). doi: 10.1002/adma.20200734510.1002/adma.202007345 ↗
35. G.H. Chan, J. Zhao, E.M. Hicks, G.C. Schatz, R.P. Van Duyne, Plasmonic Properties of Copper Nanoparticles Fabricated by Nanosphere Lithography. Nano Lett. 7(7), 1947–1952 (2007). https://doi.org/10.1021/nl070648a10.1021/nl070648a ↗
36. K.P. Rice, A.S. Paterson, M.P. Stoykovich, Nanoscale Kirkendall Effect and Oxidation Kinetics in Copper Nanocrystals Characterized by Real-Time, In Situ Optical Spectroscopy. Part. Part. Syst. Char. 32(3), 373–380 (2015). https://doi.org/10.1002/ppsc.20140015510.1002/ppsc.201400155 ↗
37. S.F. Bartolucci, A.C. Leff, J.A. Maurer, Gold–copper oxide core–shell plasmonic nanoparticles: the effect of pH on shell stability and mechanistic insights into shell formation. Nanoscale Adv. 6(9), 2499–2507 (2024). https://doi.org/10.1039/D3NA01000G10.1039/D3NA01000G ↗
38. T.M.D. Dang, T.T.T. Le, E. Fribourg-Blanc, M.C. Dang, Synthesis and optical properties of copper nanoparticles prepared by a chemical reduction method. Adv. Nat. Sci.: Nanosci. Nanotechnol. 2(1), 015009 (2011). doi: 10.1088/2043-6262/2/1/01500910.1088/2043-6262/2/1/015009 ↗
39. M.S. Rodrigues, J. Borges, C. Lopes, R.M.S. Pereira, M.I. Vasilevskiy, F. Vaz, Gas Sensors Based on Localized Surface Plasmon Resonances: Synthesis of Oxide Films with Embedded Metal Nanoparticles, Theory and Simulation, and Sensitivity Enhancement Strategies. Appl. Sci. 11(12), 5388 (2021). https://doi.org/10.3390/app1112538810.3390/app11125388 ↗