ACS Publications. Most Trusted. Most Cited. Most Read
Vapor-Phase Cleaning and Corrosion Inhibition of Copper Films by Ethanol and Heterocyclic Amines

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:ACS Appl. Mater. Interfaces 2018, 10, 44, 38610-38620
    Research Article

    Vapor-Phase Cleaning and Corrosion Inhibition of Copper Films by Ethanol and Heterocyclic Amines
    Click to copy article linkArticle link copied!

    • Luis Fabián Peña*
      Luis Fabián Peña
      Department of Materials Science & Engineering, The University of Texas at Dallas, Richardson, Texas 75080, United States
      *E-mail: [email protected]
      More by Luis Fabián Peña
      Orcidhttp://orcid.org/0000-0001-6021-4703
    • Jean-Francois Veyan
      Jean-Francois Veyan
      Department of Materials Science & Engineering, The University of Texas at Dallas, Richardson, Texas 75080, United States
      More by Jean-Francois Veyan
    • Michael A. Todd
      Michael A. Todd
      Versum Materials, Inc., 8555 South River Parkway, Tempe, Arizona 85284, United States
      More by Michael A. Todd
    • Agnes Derecskei-Kovacs
      Agnes Derecskei-Kovacs
      Versum Materials, Inc., 8555 South River Parkway, Tempe, Arizona 85284, United States
      More by Agnes Derecskei-Kovacs
    • Yves J. Chabal
      Yves J. Chabal
      Department of Materials Science & Engineering, The University of Texas at Dallas, Richardson, Texas 75080, United States
      More by Yves J. Chabal
      Orcidhttp://orcid.org/0000-0002-6435-0347
    Other Access OptionsSupporting Information (1)

    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2018, 10, 44, 38610–38620
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsami.8b13438
    Published October 18, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Cleaning and passivation of metal surfaces are necessary steps for selective film deposition processes that are attractive for some microelectronic applications (e.g., fully aligned vias or self-aligned contacts). For copper, there is limited knowledge about the mechanisms of the copper oxide reduction process and subsequent passivation layer formation reactions. We have investigated the in situ cleaning (i.e., oxidation and reduction by vapor-phase species) and passivation of chemical–mechanical polishing (CMP)-prepared Cu films in an effort to derive the mechanisms associated with selectively tailoring the surface chemistry. By monitoring the interaction of vapor-phase ethanol with the surface species generated after ozone cleaning at 300 °C, we find that the optimum procedure to remove these species and avoid byproduct redeposition is to use atomic layer deposition (ALD)-like binary cycles of ethanol and N2, with active pumping. We have further explored passivation of clean Cu using benzotriazole and 2,2′-bipyridine in an ALD environment. Both molecules chemisorb on clean Cu in an upright orientation, with respect to the metal surface at temperatures higher than the melting point of the organic inhibitors (100 ≤ T < 300 °C). Both molecules desorb without decomposition from clean Cu above 300 °C but not from Cu2O. Previous studies related to the passivation of Cu surfaces using heterocyclic amines have focused on solution-based or ultrahigh vacuum applications of the passivation molecules onto single crystalline Cu samples. The present work explores more industrially relevant vapor-phase passivation of CMP-cleaned, electroplated Cu samples using ALD-like processing conditions and in situ vapor-phase cleaning.

    Copyright © 2018 American Chemical Society

    Subjects

    what are subjects

    Keywords

    what are keywords

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b13438.

    • IR reflectance spectra showing byproduct redeposition post EtOH exposures and stability of surface carbonates as a function of time, XPS results showing the extent of oxidation after stability tests of the BTA– adlayer on Cu, inhibitor adlayer thickness calculation using signal intensities from XPS and RAIRS measurements, and DFT calculations of BTAH adsorption on Cu(111), Cu(110), and Cu(100) (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 18 publications.

    1. Shanshan Yang, Xiao Zhao, Zhiyuan Qi, Yi-Hsien Lu, Gabor Somorjai, Peidong Yang, Artem Baskin, David Prendergast, Miquel Salmeron. Chloride-Assisted Corrosion of Copper and Protection by Benzotriazole. ACS Applied Materials & Interfaces 2022, 14 (4) , 6093-6101. https://doi.org/10.1021/acsami.1c15808
    2. Baimei Tan Lei Guo Wei Li Jinbo Ji Mengyue Zhu . Eco-friendly Corrosion Inhibitors for Multilevel Metal Interconnects of Integrated Circuits. , 149-165. https://doi.org/10.1021/bk-2021-1404.ch006
    3. Jesús Rafael González-Parra, Francesca Di Turo. The Use of Plant Extracts as Sustainable Corrosion Inhibitors for Cultural Heritage Alloys: A Mini-Review. Sustainability 2024, 16 (5) , 1868. https://doi.org/10.3390/su16051868
    4. Yicheng Li, Zilian Qi, Yuxiao Lan, Kun Cao, Yanwei Wen, Jingming Zhang, Eryan Gu, Junzhou Long, Jin Yan, Bin Shan, Rong Chen. Self-aligned patterning of tantalum oxide on Cu/SiO2 through redox-coupled inherently selective atomic layer deposition. Nature Communications 2023, 14 (1) https://doi.org/10.1038/s41467-023-40249-2
    5. Nazanin Orash, Alireza Najafi Chermahini. A DFT study on 2X- imidazole derivatives (X = OH, NH2, and SH) as corrosion inhibitors on Cu surfaces: Tautomerism effect. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2023, 677 , 132336. https://doi.org/10.1016/j.colsurfa.2023.132336
    6. Chun-ping Li, Cai-chao Zhu, Meng-wu Wang, Fang Ye, Jin Li, Da-quan Zhang. In-situ preparation of triazole polymerization films on copper surface via SI-ATRP method and their performance against copper corrosion. Journal of Materials Research and Technology 2023, 27 , 4861-4872. https://doi.org/10.1016/j.jmrt.2023.11.053
    7. A. El-Asri, MM. Rguiti, A. Jmiai, R. Oukhrib, H. Bourzi, Y. Lin, S. El Issami. Carissa macrocarpa extract (ECM) as a new efficient and ecologically friendly corrosion inhibitor for copper in nitric acid: Experimental and theoretical approach. Journal of the Taiwan Institute of Chemical Engineers 2023, 142 , 104633. https://doi.org/10.1016/j.jtice.2022.104633
    8. Federico Grillo, Chiara Gattinoni, Christian R. Larrea, Paolo Lacovig, Neville V. Richardson. Copper adatoms mediated adsorption of benzotriazole on a gold substrate. Applied Surface Science 2022, 600 , 154087. https://doi.org/10.1016/j.apsusc.2022.154087
    9. Lixin Gao, Panpan Wu, Kai Zhang, Jin Li, Daquan Zhang. Formation of triazole inhibitive film on copper surface by click assembly in presence of Cu 2 S quantum dots. Surface and Interface Analysis 2021, 53 (9) , 779-791. https://doi.org/10.1002/sia.6979
    10. Nickolas Anderson, Soumya Saha, Gregory Jursich, Christos G. Takoudis. Optimization of substrate-selective atomic layer deposition of zirconia on electroplated copper using ethanol as both precursor reactant and surface pre-deposition treatment. Journal of Materials Science: Materials in Electronics 2021, 32 (5) , 5442-5456. https://doi.org/10.1007/s10854-021-05267-0
    11. Tao Li, Haoyang Sun, Daiqi Wang, Jintao Huang, Dandan Li, Fan Lei, Dazhi Sun. High-performance chemical mechanical polishing slurry for aluminum alloy using hybrid abrasives of zirconium phosphate and alumina. Applied Surface Science 2021, 537 , 147859. https://doi.org/10.1016/j.apsusc.2020.147859
    12. I.G. Akande, O.S.I. Fayomi, O.J. Adelakun. Evaluation of inhibitive performance of Ibuprofen drug on copper in 0.5 ​M ​H2SO4. Case Studies in Chemical and Environmental Engineering 2020, 2 , 100024. https://doi.org/10.1016/j.cscee.2020.100024
    13. Li Feng, Shengtao Zhang, Yangyang Feng, Xiaolei Ren, Hao Lu, Bochuan Tan, Shijin Chen. Self-aggregate nanoscale copolymer of new synthesized compounds efficiently protecting copper corrosion in sulfuric acid solution. Chemical Engineering Journal 2020, 394 , 124909. https://doi.org/10.1016/j.cej.2020.124909
    14. Mustafa Akin, Armağan Günsel, Ahmet T. Bilgiçli, Burak Tüzün, Gulnur Arabaci, Neslihan Şaki, M. Nilüfer Yarasir. The Water-Soluble Peripheral Substituted Phthalocyanines as Corrosion Inhibitors for Copper in 0.1 N HCl: Gravimetric, Electrochemical, SEM-EDS, and Quantum Chemical Calculations. Protection of Metals and Physical Chemistry of Surfaces 2020, 56 (3) , 609-618. https://doi.org/10.1134/S207020512003003X
    15. Kai Zhang, Jiamin Lu, Jin Li, Daquan Zhang, Lixin Gao, Yijun Wang. A novel approach for copper protection: UV light triggered preparation of the click-assembled film on copper surface. Chemical Engineering Journal 2020, 385 , 123406. https://doi.org/10.1016/j.cej.2019.123406
    16. Kai Zhang, Jiamin Lu, Jin Li, Daquan Zhang, Lixin Gao, Hao Zhou. An improved approach to prepare triazole protective film by click-assembly on copper surface. Corrosion Science 2020, 164 , 108352. https://doi.org/10.1016/j.corsci.2019.108352
    17. Sang Xiong, Jia Si, Jianlin Sun, Hao Wu, Hongchen Dong, Chao Zhang. Experimental and computational studies on heterocyclic organic compounds as corrosion inhibitors for copper immersed in O/W emulsion medium. Anti-Corrosion Methods and Materials 2020, 67 (2) , 214-227. https://doi.org/10.1108/ACMM-10-2019-2200
    18. Federico Grillo, David Batchelor, Christian R. Larrea, Stephen M. Francis, Paolo Lacovig, Neville V. Richardson. On-surface condensation of low-dimensional benzotriazole–copper assemblies. Nanoscale 2019, 11 (27) , 13017-13031. https://doi.org/10.1039/C9NR04152D
    Download PDF
    Go to ACS Applied Materials & Interfaces
    Get e-Alerts
    Get e-Alerts

    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2018, 10, 44, 38610–38620
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsami.8b13438
    Published October 18, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Article Views

    1136

    Altmetric

    -

    Citations

    18
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.