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Self-Catalyzed, Low-Temperature Atomic Layer Deposition of Ruthenium Metal Using Zero-Valent Ru(DMBD)(CO)3 and Water

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    Article

    Self-Catalyzed, Low-Temperature Atomic Layer Deposition of Ruthenium Metal Using Zero-Valent Ru(DMBD)(CO)3 and Water
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    • Zhengning Gao*
      Zhengning Gao
      Institute of Materials Science and Engineering, Washington University in St. Louis, St. Louis, Missouri 63130, United States
      More by Zhengning Gao
      Orcidhttp://orcid.org/0000-0002-7369-6921
    • Duy Le
      Duy Le
      Department of Physics, University of Central Florida, Orlando, Florida 32816, United States
      More by Duy Le
      Orcidhttp://orcid.org/0000-0001-6391-8757
    • Asim Khaniya
      Asim Khaniya
      Department of Physics, University of Central Florida, Orlando, Florida 32816, United States
      More by Asim Khaniya
    • Charles L. Dezelah
      Charles L. Dezelah
      EMD Performance Materials, Haverhill, Massachusetts 01832, United States
      More by Charles L. Dezelah
    • Jacob Woodruff
      Jacob Woodruff
      EMD Performance Materials, Haverhill, Massachusetts 01832, United States
      More by Jacob Woodruff
    • Ravindra K. Kanjolia
      Ravindra K. Kanjolia
      EMD Performance Materials, Haverhill, Massachusetts 01832, United States
      More by Ravindra K. Kanjolia
    • William E. Kaden
      William E. Kaden
      Department of Physics, University of Central Florida, Orlando, Florida 32816, United States
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    • Talat S. Rahman
      Talat S. Rahman
      Department of Physics, University of Central Florida, Orlando, Florida 32816, United States
      More by Talat S. Rahman
    • Parag Banerjee*
      Parag Banerjee
      Institute of Materials Science and Engineering  and  Department of Mechanical Engineering and Materials Science, Washington University in St. Louis, St. Louis, Missouri 63130, United States
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      Orcidhttp://orcid.org/0000-0003-0401-8155
    Other Access OptionsSupporting Information (1)

    Chemistry of Materials

    Cite this: Chem. Mater. 2019, 31, 4, 1304–1317
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.8b04456
    Published January 29, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Ruthenium (Ru) films are deposited using atomic layer deposition (ALD), promoted by a self-catalytic reaction mechanism. Using zero-valent, η4-2,3-dimethylbutadiene Ruthenium tricarbonyl (Ru(DMBD)(CO)3) and H2O, Ru films are deposited at a rate of 0.1 nm/cycle. The temperature for steady deposition lies between 160 and 210 °C. Film structure and composition are confirmed via X-ray diffraction, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The room-temperature electrical resistivity of 10 nm Ru films is found to be 39 μΩ·cm. In situ quadrupole mass spectrometry and density functional theory are used to understand ALD surface reactions. The ligand, dimethylbutadiene dissociatively desorbs on the surface. On the other hand, the carbonyl ligand is catalyzed by the Ru center. This leads to the water gas shift reaction, forming CO2 and H2. Modulating deposition temperature affects these two ligand dissociation reactions. This in turn affects nucleation, growth, and hence, Ru film properties. Self-catalyzed reactions provide a pathway for low-temperature ALD with milder co-reactants.

    Copyright © 2019 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/acs.chemmater.8b04456.

    • Details of XPS analysis and dimethylbutadiene cracking pattern analysis from QMS as a function of temperature (PDF)

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    Cited By

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    This article is cited by 20 publications.

    1. Lin Hu, Hemanth Somarajan Pillai, Corbin Feit, Kaige Shi, Zhengning Gao, Parag Banerjee, Hongliang Xin, Xiaofeng Feng. Identification of Active Sites for Ammonia Electrosynthesis on Ruthenium. ACS Energy Letters 2022, 7 (12) , 4290-4298. https://doi.org/10.1021/acsenergylett.2c02175
    2. Hye-Mi Kim, Jung-Hoon Lee, Seung-Hwan Lee, Ryosuke Harada, Toshiyuki Shigetomi, Seungjoon Lee, Tomohiro Tsugawa, Bonggeun Shong, Jin-Seong Park. Area-Selective Atomic Layer Deposition of Ruthenium Using a Novel Ru Precursor and H2O as a Reactant. Chemistry of Materials 2021, 33 (12) , 4353-4361. https://doi.org/10.1021/acs.chemmater.0c04496
    3. Sung Jun Kim, Seon Yong Kim, Jun Hyeong Park, In-Sung Park, Young Wook Park, Jinho Ahn. Enhanced resistance property between ALD-Ru and W by controlling oxygen behavior with post Ru deposition annealing. Materials Science in Semiconductor Processing 2025, 185 , 108933. https://doi.org/10.1016/j.mssp.2024.108933
    4. Adam M. Daly, Kristen K. Roehling, Rhett P. Hill, Myla G. Gonzalez, Xin Kang, Lisa McElwee-White, Stephen G. Kukolich. Microwave spectrum and molecular structure calculations for η4-butadiene ruthenium tricarbonyl. Journal of Molecular Spectroscopy 2024, 405 , 111949. https://doi.org/10.1016/j.jms.2024.111949
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    8. Matthew Bergschneider, Nickolas Ashburn, Xiuyao Lang, Andrew C. Kummel, Kyeongjae Cho. DFT modeling of atomic layer deposition of Ru interconnect metal for EUV scaling. MRS Advances 2023, 8 (14) , 768-772. https://doi.org/10.1557/s43580-022-00482-1
    9. Jinxiong Li, Gaoda Chai, Xinwei Wang. Atomic layer deposition of thin films: from a chemistry perspective. International Journal of Extreme Manufacturing 2023, 5 (3) , 032003. https://doi.org/10.1088/2631-7990/acd88e
    10. Hanie Kazari, Elmira Pajootan, Mark Sowa, Sylvain Coulombe, Pascal Hubert. Plasma-enhanced atomic layer deposition of ruthenium metal on free-standing carbon nanotube forest for 3D flexible binder-less supercapacitor electrodes. Journal of Energy Storage 2023, 64 , 107049. https://doi.org/10.1016/j.est.2023.107049
    11. Pawan Mishra, Maguy Abi Jaoude, Sanjay Kumar Sahu, Sanjay K. Singhal, Jayant K. Jogi, Jaime Viegas. Medical applications of zirconia and its derivatives. 2023, 379-418. https://doi.org/10.1016/B978-0-323-90538-1.00006-6
    12. Xingrui Tang, Xiuquan Tian, Li Zhou, Fan Yang, Rong He, Xu Zhao, Wenkun Zhu. Connection of Ru nanoparticles with rich defects enables the enhanced electrochemical reduction of nitrogen. Physical Chemistry Chemical Physics 2022, 24 (19) , 11491-11495. https://doi.org/10.1039/D2CP00340F
    13. Joel R. Schneider, Camila de Paula, Jacqueline Lewis, Jacob Woodruff, James A. Raiford, Stacey F. Bent. The Importance of Decarbonylation Mechanisms in the Atomic Layer Deposition of High‐Quality Ru Films by Zero‐Oxidation State Ru(DMBD)(CO) 3. Small 2022, 18 (9) https://doi.org/10.1002/smll.202105513
    14. Michael Hayes, Melanie A. Jenkins, Jacob Woodruff, Daniel F. Moser, Charles L. Dezelah, John F. Conley. Improved properties of atomic layer deposited ruthenium via postdeposition annealing. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 2021, 39 (5) https://doi.org/10.1116/6.0001078
    15. Lorianne R. Shultz, Corbin Feit, Jordan Stanberry, Zhengning Gao, Shaohua Xie, Vasileios A. Anagnostopoulos, Fudong Liu, Parag Banerjee, Titel Jurca. Ultralow Loading Ruthenium on Alumina Monoliths for Facile, Highly Recyclable Reduction of p-Nitrophenol. Catalysts 2021, 11 (2) , 165. https://doi.org/10.3390/catal11020165
    16. Charles H. Winter, Apoorva Upadhyay, Michael Overbeek, Jonathan Hollin, Stefan Cwik. Group 7 and 8 Compounds for Chemical Vapor Deposition. 2021, 824-841. https://doi.org/10.1016/B978-0-12-409547-2.14951-0
    17. Sonali N. Chopra, Martijn F. J. Vos, Marcel A. Verheijen, John G. Ekerdt, Wilhelmus M. M. Kessels, Adriaan J. M. Mackus. Atomic layer deposition of ruthenium using an ABC-type process: Role of oxygen exposure during nucleation. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 2020, 38 (6) https://doi.org/10.1116/6.0000434
    18. Nathaniel E. Richey, Camila de Paula, Stacey F. Bent. Understanding chemical and physical mechanisms in atomic layer deposition. The Journal of Chemical Physics 2020, 152 (4) https://doi.org/10.1063/1.5133390
    19. Stefan Cwik, Keenan N. Woods, Mark J. Saly, Thomas J. Knisley, Charles H. Winter. Thermal atomic layer deposition of ruthenium metal thin films using nonoxidative coreactants. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 2020, 38 (1) https://doi.org/10.1116/1.5125109
    20. Chi Thang Nguyen, Jaehong Yoon, Rizwan Khan, Bonggeun Shong, Han-Bo-Ram Lee. Thermal atomic layer deposition of metallic Ru using H2O as a reactant. Applied Surface Science 2019, 488 , 896-902. https://doi.org/10.1016/j.apsusc.2019.05.242
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    Chemistry of Materials

    Cite this: Chem. Mater. 2019, 31, 4, 1304–1317
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.8b04456
    Published January 29, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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