Abstract
Copper is known to easily react with oxygen in air to form oxide layer on the surface. In order to address the issue, we examined polymeric molecular coatings of copper surfaces by using thiol-terminated polystyrenes with various molecular weights. The polymeric molecular coatings were simply deposited by immersion of the copper specimens in the corresponding polymer solutions. The obtained specimens showed low surface electrical resistance despite the presence of the coatings. These high surface conductivities were retained even after heat treatment at 150 °C in air for several hours, which indicates high thermal stability of the coatings. It was observed that the higher thermal stability was supplied by longer chain of the polymeric coating. The results of quantitative analyses by electrochemical approach indicate that the higher air oxidation resistance property was provided by longer polymer chain of the coating, whereas shorter chain gave higher electrochemical oxidation resistance properties on the surface.
Similar content being viewed by others
References
Cruzan CG, Miley HA (1940) Cuprous-cupric oxide films on copper. J Appl Phys 11:631–634
Chen K, Song S, Xue D (2013) Vapor-phase crystallization route to oxidized Cu foils in air as anode materials for lithium-ion batteries. Cryst Eng Commun 15:144–151
Tamai T, Kawano T (1994) Significant decrease in thickness of contaminant films and contact resistance by humidification. IEICE Trans Electron 10:1614–1620
Yokoyama S, Takahashi H, Itoh T, Motomiya K, Tohji K (2014) Surface modification of Cu metal particles by the chemical reaction between the surface oxide layer and a halogen surfactant. J Phys Chem Solids 75:68–73
Magdassi S, Grouchko M, Kamyshny A (2010) Copper nanoparticles for printed electronics: routes towards achieving oxidation stability. Materials 3:4626–4638
Maho A, Denayer J, Delhalle J, Mekhalif Z (2011) Electro-assisted assembly of aliphatic thiol, dithiol and dithiocarboxylic acid monolayers on copper. Electorochim Acta 56:3954–3962
Laibinis PE, Whitesides GM (1990) Self-assembled monolayers of n-alkanethiolates on copper are barrier films that protect the metal against oxidation by air. J Am Chem Soc 114:9022–9028
Love JC, Estroff LA, Kriebel JK, Nuzzo RG, Whitesides GM (2005) Self-assembled monolayers of thiolates on metals as a form of nanotechnology. Chem Rev 105:1103–1170
Caprioli F, Decker F, Marriani AG, Beccari M, Castro VD (2010) Copper protection by self-assembled monolayers of aromatic thiols in alkaline solutions. Phys Chem Chem Phys 12:9230–9238
Caprioli F, Martinelli A, Gazzoli D, Castro VD, Decker F (2012) Enhanced protective properties and structural order of self-assembled monolayers of aromatic thiols on copper in contact with acidic aqueous solution. J Phys Chem C 116:4628–4636
Bourg MC, Badia A, Lennox RB (2000) Gold–sulfur bonding in 2D and 3D self-assembled monolayers: XPS characterization. J Phys Chem B 104:6562–6567
Mu X, Gao A, Wang D, Yang P (2015) Self-assembled monolayer-assisted negative lithography. Langmuir 31:2922–2930
Tatay S, Barraud C, Galbiati M, Seneor P, Mattana R, Bouzehouane K, Deranlot C, Jacquet E, Aliaga AF, Jegou P, Fert A, Petroff F (2012) Self-assembled monolayer-functionalized half-metallic manganite for molecular spintronics. ACS Nano 6:8753–8757
Lin Y, Ourdjini O, Giovanelli L, Clair S, Faury T, Ksari Y, Themlin JM, Porte L, Abel M (2013) Self-assembled melamine monolayer on Cu(111). J Phys Chem Solids 117:9895–9902
Yokoyama S, Takahashi H, Itoh T, Motomiya K, Tohji K (2013) Elucidation of the reaction mechanism during the removal of copper oxide by halogen surfactant at the surface of copper plate. Appl Surf Sci 264:664–669
Worley BC, Ricks WA, Prendergast MP, Gregory BW, Collins R, Cassimus JJ Jr, Thompson RG (2013) Anodic passivation of tin by alkanethiol self-assembled monolayers examined by cyclic voltammetry and coulometry. Langmuir 29:12969–12981
Morf P, Raimondi F, Nothofer HG, Schnyder B, Yasuda A, Wessels JM, Jung TA (2006) Dithiocarbamates: functional and versatile linkers for the formation of self-assembled monolayers. Langmuir 22:658–663
Ikeda T, Adachi K, Tsukahara Y (2016) Enhancement of oxidation resistance and its influence on contact electric resistance of copper by bromination. J MMIJ 132:39–46
Ikeda T, Takata T, Adachi K, Tsukahara Y (2016) Enhancement of oxidation resistance of copper by an organic thin layer and its influence on electrical conductivity. Kobunshi Ronbunshu 73:198–206
Takagi J, Ikeda T, Adachi K, Tsukahara Y (2016) Study on oxidation resistance of copper plate with organic thin layer by cyclic voltammetry. Kobunshi Ronbunshu 73:294–301
Yamakawa K, Takagi J, Nguyen TH, Adachi K, Tsukahara Y (2018) Oxidation resistance of nickel surface by molecular coating of thiol-terminated polymers. Chem Lett 47:119–121
Huang H, Penn LS (2005) Dense tethered layers by the “grafting-to” approach. Macromolecules 38:4837–4843
Zhang S, Vi T, Luo K, Koberstein JT (2016) Kinetics of polymer interfacial reactions: polymer brush formation by click reactions of alkyne end-functional polymers with azide-functional substrates. Macromolecules 49:5461–5474
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Nguyen, H.T., Jeon, J., Ikeda, T. et al. Polymeric molecular coating for oxidation resistance property of copper surface. Polym. Bull. 76, 2311–2319 (2019). https://doi.org/10.1007/s00289-018-2501-0
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-018-2501-0