Harrick PlasmaApplicationsMaterialsMetalsCopper

Copper is widely used in engineering research due to its high conductivity and ductility. Plasma treatment enhances the performance of copper surfaces across a wide range of applications, from improving sample adhesion on electron microscopy (EM) grids to boosting ink adhesion in flexible electronics and removing contaminants from copper nanostructures used in energy research. By increasing surface hydrophilicity and eliminating organic contamination, plasma treatment ensures cleaner, more reliable copper surfaces. 

Below you will learn how Harrick Plasma’s plasma cleaners enable new developments in many areas of engineering, including electrical engineering, biomedical engineering, and more.

Plasma Treatment of Copper Electron Microscopy Grids

Copper electron microscopy (EM) grids are commonly treated with plasma before studying nanoparticles or peptides under Transmission Electron Microscopy (TEM) or Cryogenic Electron Microscopy (cryo-EM). Plasma treatment makes the EM-grid surface hydrophilic, promoting uniform adhesion of aqueous samples to the grid. Plasma treatment also removes contaminants which could introduce artifacts during EM imaging. EM grids of various mesh and hole sizes can be plasma treated in all of Harrick Plasma’ s instruments.

 

Copper EM Grids

Figure 1: : Use of plasma treatment in Transmission Electron Microscopy (TEM) or Cryogenic Electron Microscopy (cryo-EM) studies

Below are references which cite the use of Harrick Plasma’s plasma cleaners to treat copper electron microscopy grids.

Plasma Treatment of Copper Electron Microscopy Grid Articles

Acosta, S., Ye, Z., Aparicio, C., Alonso, M., & Rodríguez-Cabello, J. C. (2020). Dual Self-Assembled Nanostructures from Intrinsically Disordered Protein Polymers with LCST Behavior and Antimicrobial Peptides. Biomacromolecules, 21(10), 4043–4052. https://doi.org/10.1021/acs.biomac.0c00865

Engstrom, T., Clinger, J. A., Spoth, K. A., Clarke, O. B., Closs, D. S., Jayne, R., Apker, B. A., & Thorne, R. E. (2021). High-resolution single-particle cryo-EM of samples vitrified in boiling nitrogen. IUCrJ, 8, 867–877. https://doi.org/10.1107/S2052252521008095

Ford, E. M., & Kloxin, A. M. (2021). Rapid Production of Multifunctional Self-Assembling Peptides for Incorporation and Visualization within Hydrogel Biomaterials. ACS Biomaterials Science and Engineering, 7(9), 4175–4195. https://doi.org/10.1021/acsbiomaterials.1c00589

Hsieh, S., Cheng, Y. A., Hsieh, C. W., & Liu, Y. L. (2009). Plasma induced patterning of polydimethylsiloxane surfaces. Materials Science and Engineering: B, 156(1–3), 18–23. https://doi.org/10.1016/j.mseb.2008.10.036

Huang, K. Y. A., Zhou, D., Tan, T. K., Chen, C., Duyvesteyn, H. M. E., Zhao, Y., Ginn, H. M., Qin, L., Rijal, P., Schimanski, L., Donat, R., Harding, A., Gilbert-Jaramillo, J., James, W., Tree, J. A., Buttigieg, K., Carroll, M., Charlton, S., Lien, C. E., … Stuart, D. I. (2022). Structures and therapeutic potential of anti-RBD human monoclonal antibodies against SARS-CoV-2. Theranostics, 27(1), 1–17. https://doi.org/10.7150/THNO.65563

Jing, X., Zhang, F., Pan, M., Dai, X., Li, J., Wang, L., Liu, X., Yan, H., & Fan, C. (2019). Solidifying framework nucleic acids with silica. Nature Protocols, 14(8), 2416–2436. https://doi.org/10.1038/s41596-019-0184-0

Makbul, C., Nassal, M., & Böttcher, B. (2020). Slowly folding surface extension in the prototypic avian hepatitis B virus capsid governs stability. ELife, 9, 1–23. https://doi.org/10.7554/ELIFE.57277

Paiuk, O., Mitina, N., Slouf, M., Pavlova, E., Finiuk, N., Kinash, N., Karkhut, A., Manko, N., Gromovoy, T., Hevus, O., Shermolovich, Y., Stoika, R., & Zaichenko, A. (2019). Fluorine-containing block/branched polyamphiphiles forming bioinspired complexes with biopolymers. Colloids and Surfaces B: Biointerfaces, 174, 393–400. https://doi.org/10.1016/j.colsurfb.2018.11.047

Park, S. C., Kim, J. Y., Lee, J. K., Lim, H. S., Son, H., Yoo, S. H., Mun, S. E., Jang, M. K., & Lee, J. R. (2021). Antifungal mechanism of vip3aa, a vegetative insecticidal protein, against pathogenic fungal strains. Antibiotics, 10(12). https://doi.org/10.3390/antibiotics10121558

Schlachet, I., Trousil, J., Rak, D., Knudsen, K. D., Pavlova, E., Nyström, B., & Sosnik, A. (2019). Chitosan-graft-poly(methyl methacrylate) amphiphilic nanoparticles: Self-association and physicochemical characterization. Carbohydrate Polymers, 212, 412–420. https://doi.org/10.1016/j.carbpol.2019.02.022

Trousil, J., Pavliš, O., Kubíčková, P., Škorič, M., Marešová, V., Pavlova, E., Knudsen, K. D., Dai, Y. S., Zimmerman, M., Dartois, V., Fang, J. Y., & Hrubý, M. (2020). Antitubercular nanocarrier monotherapy: Study of In Vivo efficacy and pharmacokinetics for rifampicin. Journal of Controlled Release, 321, 312–323. https://doi.org/10.1016/j.jconrel.2020.02.026

Wan, R., Bai, R., Yan, C., Lei, J., & Shi, Y. (2019). Structures of the Catalytically Activated Yeast Spliceosome Reveal the Mechanism of Branching. Cell, 177(2), 339-351.e13. https://doi.org/10.1016/j.cell.2019.02.006

Wang, Z., Hu, Z., Deng, B., Gilbert, R. G., & Sullivan, M. A. (2022). The effect of high-amylose resistant starch on the glycogen structure of diabetic mice. International Journal of Biological Macromolecules, 200, 124–131. https://doi.org/10.1016/j.ijbiomac.2021.12.071

Yang, T., Benson, K., Fu, H., Xue, T., Song, Z., Duan, H., Xia, H., Kalluri, A., He, J., Cheng, J., Kumar, C. V., & Lin, Y. (2022). Modeling and Designing Particle-Regulated Amyloid-like Assembly of Synthetic Polypeptides in Aqueous Solution. Biomacromolecules, 23(1), 196–209. https://doi.org/10.1021/acs.biomac.1c01230

Plasma Treatment of Substrates for Copper Nanoparticle Films

Copper nanoparticle (Cu-NP) inks are used for printing electrodes onto flexible electronics such as wearable sensors or RFID tags. These electronics rely on good adhesion between the electrodes and substrate to maintain the electronic device’s structural integrity. Plasma treatment provides this benefit by removing contamination from substrates and providing a pristine surface for electrode adhesion.

Plasma treatment improves adhesion of copper nanoparticle (Cu-NP) inks to many organic substrates, including polyimide (PI), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), and polyphthalamide (PPA). These flexible substrates can be plasma treated before drop-casting the copper nanoparticle inks onto their surfaces. Alternatively, copper nanoparticle inks can be inkjet – printed onto plasma treated substrates.

Learn how Harrick Plasma’s plasma cleaners have improved copper nanoparticle adhesion to substrates in the sample references below.

 

Copper Nanoparticle Film Articles

Kim, K., Ahn, S. Il, & Choi, K. C. (2013). Direct fabrication of copper patterns by reactive inkjet printing. Current Applied Physics, 13(9), 1870–1873. https://doi.org/10.1016/j.cap.2013.07.021

Yokoyama, S., Nozaki, J., Motomiya, K., Tsukahara, N., & Takahashi, H. (2020). Strong adhesion of polyvinylpyrrolidone-coated copper nanoparticles on various substrates fabricated from well-dispersed copper nanoparticle inks. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 591. https://doi.org/10.1016/j.colsurfa.2020.124567

Yokoyama, S., Nozaki, J., Umemoto, Y., Motomiya, K., Itoh, T., & Takahashi, H. (2021). Flexible and adhesive sintered Cu nanomaterials on polyimide substrates prepared by combining Cu nanoparticles and nanowires with polyvinylpyrrolidone. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 625. https://doi.org/10.1016/j.colsurfa.2021.12690 

Plasma Treatment of Nanoscale Copper (Nanowires, Nanoparticles, etc.)

Plasma-treated copper nanostructures have played a vital role in many areas of energy research, including catalysis and batteries. These nanostructures rely on pristine surfaces free of organic contaminants which could hamper the desired chemical reactions. Chen et. al. used Harrick Plasma’s Expanded Plasma Cleaner to remove unwanted nitrocellulose from copper nanowire (Cu NW) films. Foucher et. al. removed surface organic ligands from nickel – copper nanoparticles (NiCu NPs) using the Basic Plasma Cleaner.

Plasma cleaning also increases the hydrophilicity (surface wettability) of treated samples. Yan et. al. noted that plasma treatment of copper oxide nanowires (CuO NW) produced a water contact angle of 0°, indicating very high hydrophilicity.

Learn more about these uses of plasma treatment in the articles below.

 

NAnoscale Copper Articles

Chen, Z., Ye, S., Wilson, A. R., Ha, Y. C., & Wiley, B. J. (2014). Optically transparent hydrogen evolution catalysts made from networks of copper-platinum core-shell nanowires. Energy and Environmental Science, 7(4), 1461–1467. https://doi.org/10.1039/c4ee00211c

Foucher, A. C., Marcella, N., Lee, J. D., Tappero, R., Murray, C. B., Frenkel, A. I., & Stach, E. A. (2022). Dynamical Change of Valence States and Structure in NiCu3Nanoparticles during Redox Cycling. Journal of Physical Chemistry C, 126(4), 1991–2002. https://doi.org/10.1021/acs.jpcc.1c10824

Yan, X., Huang, Z., Sett, S., Oh, J., Cha, H., Li, L., Feng, L., Wu, Y., Zhao, C., Orejon, D., Chen, F., & Miljkovic, N. (2019). Atmosphere-mediated superhydrophobicity of rationally designed micro/nanostructured surfaces. ACS Nano, 13(4), 4160–4173. https://doi.org/10.1021/acsnano.8b09106

Plasma Treatment of Bulk Copper

Plasma treatment can also be used to modify the surface properties of bulk copper. Copper is frequently used in the marine and energy industries due to its high conductivity and ductility. Unfortunately, copper corrodes rapidly in seawater, is slow to shed liquids, and, like most metals, has a relatively high coefficient of friction. To overcome these issues, polymer coatings with anti-corrosion, droplet-shedding, or low-friction properties are often applied to bulk copper. These coatings require good adhesion to their copper substrates to be effective. Harrick Plasma’s benchtop plasma cleaners improve the coatings’ adhesion by making the copper surface hydrophilic. The plasma treatment process also removes organic contamination without using dangerous chemicals.

Below are some recent papers which used Harrick Plasma’s equipment to improve bonding between polymer coatings and copper substrates.

 

Bulk Copper Articles

Abdelaal, A. F., Samad, M. A., Adesina, A. Y., & Baig, M. M. A. (2022). Effect of plasma treatment on the tribological and adhesion performance of a polymer coating deposited on different metallic substrates. Journal of Coatings Technology and Research, 19(6), 1673–1686. https://doi.org/10.1007/s11998-022-00639-5

Yan, X., Chen, F., Zhao, C., Wang, X., Li, L., Khodakarami, S., Fazle Rabbi, K., Li, J., Hoque, M. J., Chen, F., Feng, J., & Miljkovic, N. (2022). Microscale Confinement and Wetting Contrast Enable Enhanced and Tunable Condensation. ACS Nano, 16(6), 9510–9522. https://doi.org/10.1021/acsnano.2c02669

Zhu, H., Liu, X., Hao, H., & Zheng, X. (2022). Influence of Surface Pretreatments on the Anticorrosion of Polypyrrole Electro-Polymerized Coatings for Copper in Artificial Seawater. Metals, 12(3). https://doi.org/10.3390/met12030383

Plasma Cleaning for Miscellaneous Uses of Copper

Many other uses of plasma-treated copper have been reported by Harrick Plasma customers. Edalatpour et. al. relied on Harrick Plasma’s Expanded Plasma Cleaner to restore the hydrophilicity of a micropatterned copper plate used in a thermal diode. While developing a hydrogen sulfide (H2S) sensor, Sarfraz et. al. ink-jet printed a copper acetate (CuAc) film onto a gold electrode before plasma treatment. Plasma treatment significantly improved the sensor’s H2S detection capability.

Li et. al. used Harrick Plasma’s equipment while characterizing volatile organic compound (VOC) buildup on an oxidized copper surface. Water contact angle of the copper decreased with plasma treatment time, while the dispersive surface energy increased. These results show that plasma treatment successfully removes volatile organic compounds from copper.

Plasma treatment’s ability to remove organic contaminants was also an important part of Goggin et. al.’s sample preparation process. The authors had received graphene and hexagonal boron nitride (h-BN) grown on copper foil for an experiment, but the foils contained unwanted excess material on the backside. To remove this material, Goggin treated the samples in Harrick Plasma’s Basic Plasma Cleaner.

Plasma treatment has also played a role in the detection of copper. The presence of copper in lubricating oils used in the marine industry can indicate increased equipment wear or upcoming mechanical failure. To detect Cu2+ ions in lubrication oil, Gao et. al. developed a polydimethylsiloxane (PDMS) microfluidic device containing fluorescence-enhanced perovskite quantum dots (QDs) as probes. The microfluidic device was assembled using plasma treatment to bond a PDMS layer to a glass slide.

More information about the role of plasma treatment in these projects can be found in the references listed below.

 

Miscellaneous Copper Articles

Edalatpour, M., Murphy, K. R., Mukherjee, R., & Boreyko, J. B. (2020). Bridging-Droplet Thermal Diodes. Advanced Functional Materials, 30(43). https://doi.org/10.1002/adfm.202004451

Gao, Y., Pan, X., Xu, S., Liu, Z., Wang, J., Yu, K., Wang, C., Yuan, H., & Wu, S. (2020). Fluorescence-enhanced microfluidic sensor for highly sensitive in-situ detection of copper ions in lubricating oil. Materials and Design, 191. https://doi.org/10.1016/j.matdes.2020.108693

Goggin, D. M., Zhang, H., Miller, E. M., & Samaniuk, J. R. (2020). Interference Provides Clarity: Direct Observation of 2D Materials at Fluid-Fluid Interfaces. ACS Nano, 14(1), 777–790. https://doi.org/10.1021/acsnano.9b07776

Li, J., Zhao, Y., Ma, J., Fu, W., Yan, X., Rabbi, K. F., & Miljkovic, N. (2022). Superior Antidegeneration Hierarchical Nanoengineered Wicking Surfaces for Boiling Enhancement. Advanced Functional Materials, 32(8). https://doi.org/10.1002/adfm.202108836

Sarfraz, J., Rosqvist, E., Ihalainen, P., & Peltonen, J. (2019). Electro-optical gas sensor consisting of nanostructured paper coating and an ultrathin sensing element. Chemosensors, 7(2). https://doi.org/10.3390/chemosensors7020023

Harrick Plasma is a leading supplier of plasma equipment to the research community. We have been providing quality tabletop plasma devices specifically designed for laboratory and R&D use for over 30 years.