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Vapor-Phase Cleaning and Corrosion Inhibition of Copper Films by Ethanol and Heterocyclic Amines
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    Vapor-Phase Cleaning and Corrosion Inhibition of Copper Films by Ethanol and Heterocyclic Amines
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    • 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]
    • Jean-Francois Veyan
      Jean-Francois Veyan
      Department of Materials Science & Engineering, The University of Texas at Dallas, Richardson, Texas 75080, United States
    • Michael A. Todd
      Michael A. Todd
      Versum Materials, Inc., 8555 South River Parkway, Tempe, Arizona 85284, United States
    • Agnes Derecskei-Kovacs
      Agnes Derecskei-Kovacs
      Versum Materials, Inc., 8555 South River Parkway, Tempe, Arizona 85284, United States
    • Yves J. Chabal
      Yves J. Chabal
      Department of Materials Science & Engineering, The University of Texas at Dallas, Richardson, Texas 75080, United States
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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2018, 10, 44, 38610–38620
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    https://doi.org/10.1021/acsami.8b13438
    Published October 18, 2018
    Copyright © 2018 American Chemical Society

    Abstract

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    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

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    Supporting Information

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    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)

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    Cited By

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    This article is cited by 18 publications.

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    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

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