Morphology, hardness, wettability and free surface energy of various copper surfaces

Ivana Mladenović; Jelena  Lamovec; Dana  Radović; Vesna  Radojević; Nebojša Nikolić

doi:10.62638/ZasMat1696

Authors

Ivana O. Mladenović University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Belgrade, Serbia Author https://orcid.org/0000-0002-6852-7541
Jelena S. Lamovec University of Criminal Investigation and Police Studies, Belgrade, Serbia Author https://orcid.org/0000-0002-2710-3937
Dana G. Vasiljević-Radović University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Belgrade, Serbia Author https://orcid.org/0000-0002-7609-8599
Vesna J. Radojević University of Belgrade, Faculty of Technology and Metallurgy, Belgrade, Serbia Author https://orcid.org/0000-0001-9301-3983
Nebojša D. Nikolić University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Belgrade, Serbia Author https://orcid.org/0000-0002-6385-5714

DOI:

https://doi.org/10.62638/ZasMat1696

Abstract

This paper aims to analyze wettability and the free surface energy of various copper surfaces. The Cu deposits produced galvanostatically from the basic sulphate electrolytes without and with an addition of levelling and brightening additives, and cold-rolled (c-r) Cu simultaneously used as the cathode in Cu electrodeposition processes have been investigated. Hardness of electrolytically produced Cu deposits was also determined. The wettability and the free surface energy of Cu surfaces were examined applying the OWRK (Owens–Wendt–Rabel–Kaelble) method, while morphology and hardness characterization of the surfaces was done by atomic force microscope (AFM) and Vickers microindentation, respectively. The surface roughness obtained by AFM software was used as a parameter for comparison of a state of various Cu surfaces. The Jönsson-Hogmark composite hardness model was used to determine the absolute hardness of Cu electrodeposits, and the obtained values of 1.509 GPa for microcrystalline (mc) deposit obtained from the basic sulphate electrolyte and 1.130 GPa for the nanocrystalline (nc) deposit obtained from the electrolyte containing levelling/brightening additives were in excellent agreement with those found in literature for copper. The surface roughness of Cu increased in the row: nc (30.84 nm) < c-r (83.22 nm) < mc (129.3 nm), causing the change of a state of Cu surfaces from hydrophilic to hydrophobic. Analysis of tensile and yield strengths of Cu surfaces computed from microhardness data, and the free surface energy values determined by the OWRK method also indicated on the strong correlation between a roughness and these properties of Cu surfaces.

Keywords:

copper; electrodeposition; film; morphology; hardness; wettability; free surface energy

References

Moon (2024) Unveiling Copper Thin Films: Applications and the Power of Microscopy (https://www.deepblock.net/blog/unveiling-copper-thin-films-applications-and-the-power-of-microscopy , Accessed 10. 07. 2024.)

K.I. Popov, S.S. Djokić, N.D. Nikolić, V.D. Jović (2016) Morphology of Electrochemically and Chemically Deposited Metals, Springer.

I.O. Mladenović, N.D. Nikolić (2023) Influence of Parameters and Regimes of the Electrodeposition on Hardness of Copper Coatings, Metals, 13(4), 683. https://doi.org/10.3390/met13040683.

J. Lesage, D. Chicot (1995) Absolute hardness of films and coatings, Thin Solid Films, 254, 123-130. https://doi.org/10.1016/0040-6090(94)06239-H

J. Lesage, A. Pertuz, E.S. Puchi-Cabrera, D. Chicot (2006) A model to determine the surface hardness of thin films from standard micro-indentation tests, Thin Solid Films, 497, 232-238. https://doi:10.1016/j.tsf.2005.09.194.

J. Lesage, D. Chicot (2005) A model for hardness determination of thin coatings from standard microindentation test, Surface and Coatings Technology, 200, 886-889. https://doi.org/10.1016/j.surfcoat.2005.01.056

J.R. Tuck, A.M. Korunsky, S.J. Bull, R.I. Davidson (2001) On the application of the work-of-indentation approach to depth-sensing indentation experiments in coated systems, Surface and Coatings Technology, 137, 217-224, https://doi.org/10.1016/S0257-8972(00)01063-X

A.M. Korsunsky, M.R. McGurk, S.J. Bull, T.F. Page (1998) On the hardness of coated systems, Surface and Coatings Technology, 99, 171-183. htps://doi.org/10.1016/S0257-8972(97)00522

M. Chen, J. Gao (2000) The adhesion of copper films coated on silicon and glass substrates, Modern Physics Letters B, 14, 103-108. https://doi.org/10.1142/S0217984900000161.

J.L. He, W.Z. Li, H.D. Li (1996) Hardness measurement of thin films: Separation from composite hardness, Applied Physics Letters, 69, 1402. https://doi.org/10.1063/1.117595.

B. Jonsson, S. Hogmark (1984) Hardness Measurements of Thin Films, Thin Solid Films, 114, 257-269. https://doi.org/10.1016/0040-6090(84)90123-8.

E.S. Puchi-Cabrera (2002) A new model for the computation of the composite hardness of coated systems, Surface and Coatings Technology, 160, 177-186. https://doi.org/10.1016/S0257-8972(02)00394-8

J. Zhang, B. Xu, P. Zhang, M. Cai, B. Li, (2023) Effects of surface roughness on wettability and surface energy of coal, Frontiers in Earth Science, 10, 1054896. https://doi.org/10.3389/feart.2022.1054896

F.M. Fowkes, (1963) Additivity of intermolecular forces at interfaces and determination of the contribution to surface and interfacial tensions of dispersion forces in various liquids, The Journal of Physical Chemistry, 67(12), 2538-2541. https://doi.org/10.1021/j100806a008

S.V. Dukarov, O.P. Kryshal, V.N. Sukhov (2015). Surface energy and wetting in island films, Wetting and wettability, InTech, 169-206. https://doi.org/10.5772/60900

I.O. Mladenović, J.S. Lamovec, D.G. Vasiljević Radović, R. Vasilić, V.J. Radojević, N.D. Nikolić (2020) Morphology, Structure and Mechanical Properties of Copper Coatings Electrodeposited by Pulsating Current (PC) Regime on Si(111), Metals, 10, 488. https://doi.org/10.3390/met10040488

H. Buckle (1973) The Science of Hardness Testing and Its Research Applications, In J. W. Westbrook, and H. Conrad (Ed.), (p. 453), Metals Park, American Society for Metals.

I. Manika, J. Maniks (2008) Effect of substrate hardness and film structure on indentation depth criteria for film hardness testing, Journal of Physics D: Applied Physics, 41, 074010. http://dx.doi.org/10.1088/0022-3727/41/7/074010.

I.O. Mladenović, J.S. Lamovec, D.G. Vasiljević Radović, R. Vasilić, V.J. Radojević, N.D. Nikolić (2021) Implementation of the Chicot–Lesage Composite Hardness Model in a Determination of Absolute Hardness of Copper Coatings Obtained by the Electrodeposition Processes, Metals, 11, 1807. https://doi.org/10.3390/met11111807.

I.O. Mladenović, J.S. Lamovec, D.G. Vasiljević Radović, N. Vuković, V.J. Radojević, N.D. Nikolić (2025) Correlation between morphology and hardness of electrolytically produced copper thin films. Journal of Solid State Electrochemistry, 29, 1431–1448 https://doi.org/10.1007/s10008-024-05948-w

L. Martins, J.I. Martins, A.S. Romeira, M.E.V. Costa, J.D.M. Costa, M. Bazzaoui (2004) Morphology of Copper Coatings Electroplated in an Ultrasonic Field, Materials Science Forum, 455456, 844-848. https://doi.org/0.4028/www.scientific.net/MSF.455-456.844.

T. Song, D.Y. Li (2006) Tribological, mechanical and electrochemical properties of nanocrystalline copper deposits produced by pulse electrodeposition, Nanotechnology, 17, 65-78 https://doi.org/10.1088/0957-4484/17/1/012.

A. Ibanez, E. Fatas (2005) Mechanical and structural properties of electrodeposited copper and their relation with the electrodeposition parameters, Surface and Coatings Technology, 191, 7-16 https://doi.org/10.1016/j.surfcoat.2004.05.001

R. Sagar, M.S. Gaur, V. Kushwah (2021) Preparation, characterization and microhardness measurements of hybrid nanocomposites based on PMMA + P(VDF–TrFE) and graphene oxide Polymer Bulletin, 78, 7279–7300. https://doi.org/10.1007/s00289-020-03457-0

J.R. Cahoon, W.H. Broughton, A.R. Kutzak (1971) The determination of yield strength from hardness measurements, Metallurgical Transactions, 2, 1979–1983 https://doi.org/10.1007/BF02913433

E. Pavlina, C. Van Tyne (2008) Correlation of Yield Strength and Tensile Strength with Hardness for Steels, Journal of Materials Engineering and Performance, 17, 888–893. https://doi.org/10.1007/s11665-008-9225-5

S.H. Kim, Y.C. Kim, S. Lee (2017) Evaluation of tensile stress-strain curve of electroplated copper film by characterizing indentation size effect with a single nanoindentation, Metals and Materials International, 23, 76–81. https://doi.org/10.1007/s12540-017-6461-y

P. Wang, D. Zhang, R. Qiu, Y. Wan, J. Wu ( 2014) Green approach to fabrication of a super-hydrophobic film on copper and the consequent corrosion resistance, Corrosion Science, 80, 366-373. https://doi.org/10.1016/j.corsci.2013.11.055.

A. Telfah, G. Majer, K.D. Kreuer, M. Schuster, J. Maier (2010) Formation and mobility of protonic charge carriers in methyl sulfonic acid–water mixtures: A model for sulfonic acid based ionomers at low degree of hydration, Solid State Ionics, 181, 11–12, 461-465. https://doi.org/10.1016/j.ssi.2010.01.001

A. Royaux, A.E. Haitami, O. Fichet (2020) Surface free-energy determination of copper wire using a large range of model liquids. SN Applied Sciences, 2, 48 https://doi.org/10.1007/s42452-019-1828-y

Morphology, hardness, wettability and free surface energy of various copper surfaces

Authors

DOI:

Abstract

Keywords:

References

Downloads

Published

Issue

Section

License

Make a Submission

zm