Abstract
Copper nanoparticles were fabricated and deposited on a glass substrate by spark discharge of copper electrode under different atmospheric conditions for SERS application. An interesting dependence of the deposition process and the formation of different particle structures on the deposition atmospheres were observed. Static air atmosphere ensured the deposition of the Cu particles on the glass surface by avoiding the repulsion between charged Cu particles and the surface of the glass through the formation of CuO, which acts as a seed mediated for nanorods formation. The average diameter of the as-deposited Cu rods was measured by the TEM to be 39 nm. Thermal annealing of the film up to 200 °C resulted in a reduction in the diameter of the nanorods as well as an increase in the rod density. A water solution of dye molecule (crystal violet) with a concentration of 1 × 10–6 to 1 × 10–9 M was dropped on the prepared Cu substrate. Raman signals from dye molecule were detected and their intensities changed according to deposition time, post-annealing temperature and dye concentration. A significant increase in the Raman scattering signal of a dye molecule was observed in the film fabricated at 30 min of deposition time and post-annealed temperature of 200 °C for 1 h. This substrate provides a maximum SERS intensity with a detection limit of 1 × 10–8 M, with an enhancement factor of 3.9 × 103. The SERS performance of the substrates was correlated well with the change in their surface morphologies.
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig1_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig2_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig3_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig4_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig5_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig6_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig7_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig8_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig9_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00339-020-03762-5/MediaObjects/339_2020_3762_Fig10_HTML.png)
Similar content being viewed by others
References
K.Q. Lin, J. Yi, S. Hu, B.J. Liu, J.Y. Liu, X. Wang, B. Ren, Size effect on SERS of gold nanorods demonstrated via single nanoparticle spectroscopy. J. Phys. Chem. C 120, 20806–20813 (2016). https://doi.org/10.1021/acs.jpcc.6b02098
M. Proença, M.S. Rodrigues, J. Borges, F. Vaz, Optimization of Au:CuO nanocomposite thin films for gas sensing with high-resolution localized surface plasmon resonance spectroscopy. Anal. Chem. 92, 4349–4356 (2020). https://doi.org/10.1021/acs.analchem.9b05153
K. Yuan, Q. Mei, X. Guo, Y. Xu, D. Yang, B.J. Sánchez, B. Sheng, C. Liu, Z. Hu, G. Yu, H. Ma, H. Gao, C. Haisch, R. Niessner, Z. Jiang, H. Zhou, Antimicrobial peptide based magnetic recognition elements and Au@Ag-GO SERS tags with stable internal standards: a three in one biosensor for isolation, discrimination and killing of multiple bacteria in whole blood. Chem. Sci. 9, 8781–8795 (2018). https://doi.org/10.1039/c8sc04637a
H.K. Lee, Y.H. Lee, C.S.L. Koh, G.C. Phan-Quang, X. Han, C.L. Lay, H.Y.F. Sim, Y.C. Kao, Q. An, X.Y. Ling, Designing surface-enhanced Raman scattering (SERS) platforms beyond hotspot engineering: emerging opportunities in analyte manipulations and hybrid materials. Chem. Soc. Rev. 48, 731–756 (2019). https://doi.org/10.1039/c7cs00786h
D.K. Sarfo, E.L. Izake, A.P. O’Mullane, G.A. Ayoko, Fabrication of nanostructured SERS substrates on conductive solid platforms for environmental application. Crit. Rev. Environ. Sci. Technol. 49, 1294–1329 (2019). https://doi.org/10.1080/10643389.2019.1576468
Z. Lin, L. He, Recent advance in SERS techniques for food safety and quality analysis: a brief review. Curr. Opin. Food Sci. 28, 82–87 (2019). https://doi.org/10.1016/j.cofs.2019.10.001
M. Liszewska, B. Bartosewicz, B. Budner, B. Nasiłowska, M. Szala, J.L. Weyher, I. Dzięcielewski, Z. Mierczyk, B.J. Jankiewicz, Evaluation of selected SERS substrates for trace detection of explosive materials using portable Raman systems. Vib. Spectrosc. 100, 79–85 (2019). https://doi.org/10.1016/j.vibspec.2018.11.002
J. Yang, X.Y. Wang, L. Zhou, F. Lu, N. Cai, J.M. Li, Highly sensitive SERS monitoring of catalytic reaction by bifunctional Ag–Pd triangular nanoplates. J. Saudi Chem. Soc. 23, 887–895 (2019). https://doi.org/10.1016/j.jscs.2019.01.007
M.F. Cardinal, E. Van der Ende, R.A. Hackler, M.O. McAnally, P.C. Stair, G.C. Schatz, R.P. Van Duyne, Expanding applications of SERS through versatile nanomaterials engineering. Chem. Soc. Rev. 46, 3886–3903 (2017). https://doi.org/10.1039/c7cs00207f
C. Muehlethaler, M. Leona, J.R. Lombardi, Review of surface enhanced Raman scattering applications in forensic science. Anal. Chem. 88, 152–169 (2016). https://doi.org/10.1021/acs.analchem.5b04131
X.Y. Yan, Y.H. Wang, G.C. Shi, M.L. Wang, J.Z. Zhang, X. Sun, H.J. Xu, Flower-like Cu nanoislands decorated onto the cicada wing as SERS substrates for the rapid detection of crystal violet. Optik (Stuttg). 172, 812–821 (2018). https://doi.org/10.1016/j.ijleo.2018.07.088
I.A. Mudunkotuwa, J.M. Pettibone, V.H. Grassian, Environmental implications of nanoparticle aging in the processing and fate of copper-based nanomaterials. Environ. Sci. Technol. 46, 7001–7010 (2012). https://doi.org/10.1021/es203851d
Y. Qian, S. Lu, F. Gao, Synthesis of copper nanoparticles/carbon spheres and application as a surface-enhanced Raman scattering substrate. Mater. Lett. 81, 219–221 (2012). https://doi.org/10.1016/j.matlet.2012.05.018
L. Hang, Y. Zhao, H. Zhang, G. Liu, W. Cai, Y. Li, L. Qu, Copper nanoparticle@graphene composite arrays and their enhanced catalytic performance. Acta Mater. 105, 59–67 (2016). https://doi.org/10.1016/j.actamat.2015.12.029
A. Mao, M. Ding, X. Jin, X. Gu, C. Cai, C. Xin, T. Zhang, Direct, rapid synthesis of water-dispersed copper nanoparticles and their surface-enhanced Raman scattering properties. J. Mol. Struct. 1079, 396–401 (2015). https://doi.org/10.1016/j.molstruc.2014.09.003
D. Xu, Z. Dong, J.L. Sun, Fabrication of copper nanowires by a solid-state ionics method and their surface enhanced Raman scattering effect. Mater. Lett. 92, 143–146 (2013). https://doi.org/10.1016/j.matlet.2012.10.057
Q. Shao, R. Que, M. Shao, L. Cheng, S.T. Lee, Copper nanoparticles grafted on a silicon wafer and their excellent surface-enhanced Raman scattering. Adv. Funct. Mater. 22, 2067–2070 (2012). https://doi.org/10.1002/adfm.201102943
A.J. Pereira, J.P. Gomes, G.F. Lenz, R. Schneider, J.A. Chaker, P.E.N. De Souza, J.F. Felix, Facile shape-controlled fabrication of copper nanostructures on borophosphate glasses: synthesis, characterization, and their highly sensitive surface-enhanced Raman scattering (SERS) properties. J. Phys. Chem. C 120, 12265–12272 (2016). https://doi.org/10.1021/acs.jpcc.6b02881
T. Ramani, K. Leon Prasanth, B. Sreedhar, Air stable colloidal copper nanoparticles: synthesis, characterization and their surface-enhanced Raman scattering properties. Phys. E Low Dimens. Syst. Nanostruct. 77, 65–71 (2016). https://doi.org/10.1016/j.physe.2015.11.002
M.I. Dar, S. Sampath, S.A. Shivashankar, Microwave-assisted, surfactant-free synthesis of air-stable copper nanostructures and their SERS study. J. Mater. Chem. 22, 22418–22423 (2012). https://doi.org/10.1039/c2jm35629e
G. Rao, X. Jian, W. Lv, G. Zhu, J. Xiong, W. He, A highly-efficient route to three-dimensional nanoporous copper leaves with high surface enhanced Raman scattering properties. Chem. Eng. J. 321, 394–400 (2017). https://doi.org/10.1016/j.cej.2017.03.140
Q. Ding, L. Hang, L. Ma, Controlled synthesis of Cu nanoparticle arrays with surface enhanced Raman scattering effect performance. RSC Adv. 8, 1753–1757 (2018). https://doi.org/10.1039/c7ra10694g
S.L. Smitha, K.G. Gopchandran, N. Smijesh, R. Philip, Size-dependent optical properties of Au nanorods. Prog. Nat. Sci. Mater. Int. 23, 36–43 (2013). https://doi.org/10.1016/j.pnsc.2013.01.005
X. Yang, S. Chen, S. Zhao, D. Li, H. Ma, Synthesis of copper nanorods using electrochemical methods. J. Serbian Chem. Soc. 68, 843–847 (2003). https://doi.org/10.2298/JSC0311843Y
M. Luo, A. Ruditskiy, H.C. Peng, J. Tao, L. Figueroa-Cosme, Z. He, Y. Xia, Penta-twinned copper nanorods: facile synthesis via seed-mediated growth and their tunable plasmonic properties. Adv. Funct. Mater. 26, 1209–1216 (2016). https://doi.org/10.1002/adfm.201504217
K. Chen, X. Zhang, Y. Zhang, D.Y. Lei, H. Li, T. Williams, D.R., MacFarlane, highly ordered Ag/Cu hybrid nanostructure arrays for ultrasensitive surface-enhanced Raman spectroscopy. Adv. Mater. Interfaces. 3, 7 (2016). https://doi.org/10.1002/admi.201600115
Z. Liu, Y. Bando, A novel method for preparing copper nanorods and nanowires. Adv. Mater. 15, 303–305 (2003). https://doi.org/10.1002/adma.200390073
P.I. Wang, T.C. Parker, T. Karabacak, G.C. Wang, T.M. Lu, Size control of Cu nanorods through oxygen-mediated growth and low temperature sintering. Nanotechnology 20, 8 (2009). https://doi.org/10.1088/0957-4484/20/8/085605
M. Keating, S. Song, G. Wei, D. Graham, Y. Chen, F. Placido, Ordered silver and copper nanorod arrays for enhanced Raman scattering created via guided oblique angle deposition on polymer. J. Phys. Chem. C 118, 4878–4884 (2014). https://doi.org/10.1021/jp410116h
K. Han, W. Kim, J. Yu, J. Lee, H. Lee, C. Gyu Woo, M. Choi, A study of pin-to-plate type spark discharge generator for producing unagglomerated nanoaerosols. J. Aerosol Sci. 52, 80–88 (2012). https://doi.org/10.1016/j.jaerosci.2012.05.002
S. Zihlmann, F. Lüönd, J.K. Spiegel, Seeded growth of monodisperse and spherical silver nanoparticles. J. Aerosol Sci. 75, 81–93 (2014). https://doi.org/10.1016/j.jaerosci.2014.05.006
M.A. El-Aal, T. Seto, M. Kumita, A.A. Abdelaziz, Y. Otani, Synthesis of silver nanoparticles film by spark discharge deposition for surface-enhanced Raman scattering. Opt. Mater. (Amst) 83, 263–271 (2018). https://doi.org/10.1016/j.optmat.2018.06.029
B.O. Meuller, M.E. Messing, D.L.J. Engberg, A.M. Jansson, L.I.M. Johansson, S.M. Norlén, N. Tureson, K. Deppert, Review of spark discharge generators for production of nanoparticle aerosols. Aerosol Sci. Technol. 46, 1256–1270 (2012). https://doi.org/10.1080/02786826.2012.705448
T. Karabacak, J.S. Deluca, P.I. Wang, G.A. Ten Eyck, D. Ye, G.C. Wang, T.M. Lu, Low temperature melting of copper nanorod arrays. J. Appl. Phys. 99, 6 (2006). https://doi.org/10.1063/1.2180437
A. Voloshko, Nanoparticle formation by means of spark discharge at atmospheric pressure, Université Jean Monnet—Saint-Etienne, 2015. https://tel.archives-ouvertes.fr/tel-01545174/document.
U. Sanyal, B.R. Jagirdar, Metal and alloy nanoparticles by amine-borane reduction of metal salts by solid-phase synthesis: atom economy and green process. Inorg. Chem. 51, 13023–13033 (2012). https://doi.org/10.1021/ic3021436
F.A. Akgul, G. Akgul, N. Yildirim, H.E. Unalan, R. Turan, Influence of thermal annealing on microstructural, morphological, optical properties and surface electronic structure of copper oxide thin films. Mater. Chem. Phys. 147, 987–995 (2014). https://doi.org/10.1016/j.matchemphys.2014.06.047
G. Cheng, A.R.H. Walker, Transmission electron microscopy characterization of colloidal copper nanoparticles and their chemical reactivity. Anal. Bioanal. Chem. 396, 1057–1069 (2010). https://doi.org/10.1007/s00216-009-3203-0
T. Bora, Recent developments on metal nanoparticles for SERS applications, in Noble precious met, ed. by M.S. Seehra, A.D. Bristow (IntechOpen, Rijeka, 2018), pp. 117–135. https://doi.org/10.5772/intechopen.71573
C.B. Moore, W. Rison, J. Mathis, G. Aulich, Lightning rod improvement studies. J. Appl. Meteorol. 39, 593–609 (2000). https://doi.org/10.1175/1520-0450-39.5.593
M. Li, Z.S. Zhang, X. Zhang, K.Y. Li, X.F. Yu, Optical properties of Au/Ag core/shell nanoshuttles. Opt. Express. 16, 14288–14293 (2008). https://doi.org/10.1364/oe.16.014288
Y.J. Liu, Z.Y. Zhang, R.A. Dluhy, Y.P. Zhao, The SERS response of semiordered Ag nanorod arrays fabricated by template oblique angle deposition. J. Raman Spectrosc. 41, 1112–1118 (2010). https://doi.org/10.1002/jrs.2567
K.D. Osberg, M. Rycenga, N. Harris, A.L. Schmucker, M.R. Langille, G.C. Schatz, C.A. Mirkin, Dispersible gold nanorod dimers with sub-5 nm gaps as local amplifiers for surface-enhanced Raman scattering. Nano Lett. 12, 3828–3832 (2012). https://doi.org/10.1021/nl301793k
M.A. El-Aal, T. Seto, Surface-enhanced Raman scattering and catalytic activity studies over nanostructured Au–Pd alloy films prepared by DC magnetron sputtering. Res. Chem. Intermed. 46, 3741–3756 (2020). https://doi.org/10.1007/s11164-020-04172-1
D. Zhang, H. Yang, Gelatin-stabilized copper nanoparticles: synthesis, morphology, and their surface-enhanced Raman scattering properties. Phys. B Condens. Matter. 415, 44–48 (2013). https://doi.org/10.1016/j.physb.2013.01.041
M. Guo, Y. Zhao, F. Zhang, L. Xu, H. Yang, X. Song, Y. Bu, Reduced graphene oxide-stabilized copper nanocrystals with enhanced catalytic activity and SERS properties. RSC Adv. 6, 50587–50594 (2016). https://doi.org/10.1039/c6ra05186c
R. Li, G. Shi, Y. Wang, M. Wang, Y. Zhu, X. Sun, H. Xu, C. Chang, Decoration of Cu films on the microstructural mantis wing as flexible substrates for surface enhanced Raman scattering. Optik (Stuttg). 172, 49–56 (2018). https://doi.org/10.1016/J.IJLEO.2018.07.003
X. Zhang, C. Shi, E. Liu, J. Li, N. Zhao, C. He, Nitrogen-doped graphene network supported copper nanoparticles encapsulated with graphene shells for surface-enhanced Raman scattering. Nanoscale. 7, 17079–17087 (2015). https://doi.org/10.1039/c5nr04259c
H. Dizajghorbani-Aghdam, T.S. Miller, R. Malekfar, P.F. McMillan, SERS-active cu nanoparticles on carbon nitride support fabricated using pulsed laser ablation. Nanomaterials. 9, 1–16 (2019). https://doi.org/10.3390/nano9091223
Acknowledgements
This study was supported by JST CREST, Japan (Grant number JPMJCR18H4), by the Hosokawa Powder Technology Foundation, and Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT) scholarship for Mohamed was also gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interests
The authors declare that they have no competing interests.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
El-Aal, M.A., Seto, T. & Matsuki, A. The effects of operating parameters on the morphology, and the SERS of Cu NPs prepared by spark discharge deposition. Appl. Phys. A 126, 572 (2020). https://doi.org/10.1007/s00339-020-03762-5
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00339-020-03762-5