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Precise Definition of a “Monolayer Point” in Polymer Brush Films for Fabricating Highly Coherent TiO2 Thin Films by Vapor-Phase Infiltration

  • Ross Lundy*
    Ross Lundy
    AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
    *Email: [email protected]
    More by Ross Lundy
  • Pravind Yadav
    Pravind Yadav
    AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
  • Nadezda Prochukhan
    Nadezda Prochukhan
    AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
  • Elsa C. Giraud
    Elsa C. Giraud
    AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
  • Tom F. O’Mahony
    Tom F. O’Mahony
    AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
  • Andrew Selkirk
    Andrew Selkirk
    AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
  • Eleanor Mullen
    Eleanor Mullen
    AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
  • Jim Conway
    Jim Conway
    National Centre for Plasma Science and Technology, Dublin City University, Dublin 9, Ireland
    More by Jim Conway
  • Miles Turner
    Miles Turner
    National Centre for Plasma Science and Technology, Dublin City University, Dublin 9, Ireland
    More by Miles Turner
  • Stephen Daniels
    Stephen Daniels
    National Centre for Plasma Science and Technology, Dublin City University, Dublin 9, Ireland
  • P. G. Mani-Gonzalez
    P. G. Mani-Gonzalez
    Institute of Engineering and Technology, Department of Physics and Mathematics, Autonomous University of Ciudad Juárez, Cd. Juárez 32310, Mexico
  • Matthew Snelgrove
    Matthew Snelgrove
    School of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland
  • Justin Bogan
    Justin Bogan
    School of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland
    More by Justin Bogan
  • Caitlin McFeely
    Caitlin McFeely
    School of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland
  • Robert O’Connor
    Robert O’Connor
    School of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland
  • Enda McGlynn
    Enda McGlynn
    National Centre for Plasma Science and Technology, Dublin City University, Dublin 9, Ireland
    School of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland
    More by Enda McGlynn
  • Greg Hughes
    Greg Hughes
    National Centre for Plasma Science and Technology, Dublin City University, Dublin 9, Ireland
    School of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland
    More by Greg Hughes
  • Cian Cummins
    Cian Cummins
    AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
    More by Cian Cummins
  • , and 
  • Michael A. Morris*
    Michael A. Morris
    AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
    *Email: [email protected]
Cite this: Langmuir 2020, 36, 41, 12394–12402
Publication Date (Web):October 6, 2020
https://doi.org/10.1021/acs.langmuir.0c02512
Copyright © 2020 American Chemical Society

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    Abstract

    Abstract Image

    In this work, we show that in order to fabricate coherent titania (TiO2) films with precise thickness control, it is critical to generate a complete polymer brush monolayer. To date, demonstrations of such dense polymer monolayer formation that can be utilized for inorganic infiltration have been elusive. We describe a versatile bottom-up approach to covalently and rapidly (60 s processing) graft hydroxyl-terminated poly(2-vinyl pyridine) (P2VP-OH) polymers on silicon substrates. P2VP-OH monolayer films of varying thicknesses can subsequently be used to fabricate high-quality TiO2 films. Our innovative strategy is based upon room-temperature titanium vapor-phase infiltration of the grafted P2VP-OH polymer brushes that can produce TiO2 nanofilms of 2–4 nm thicknesses. Crucial parameters are explored, including molecular weight and solution concentration for grafting dense P2VP-OH monolayers from the liquid phase with high coverage and uniformity across wafer-scale areas (>2 cm2). Additionally, we compare the P2VP-OH polymer systems with another reactive polymer, poly(methyl methacrylate)-OH, and a relatively nonreactive polymer, poly(styrene)-OH. Furthermore, we prove the latter to be effective for surface blocking and deactivation. We show a simple process to graft monolayers for polymers that are weakly interacting with one another but more challenging for reactive systems. Our methodology provides new insight into the rapid grafting of polymer brushes and their ability to form TiO2 films. We believe that the results described herein are important for further expanding the use of reactive and unreactive polymers for fields including area-selective deposition, solar cell absorber layers, and antimicrobial surface coatings.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.langmuir.0c02512.

    • Grafting data for PS-OH and PMMA-OH and additional XPS, EDX, AFM, and electron microscopy data (PDF)

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    Cited By

    This article is cited by 13 publications.

    1. Pravind Yadav, Riley Gatensby, Nadezda Prochukhan, Sibu C. Padmanabhan, Arantxa Davó-Quiñonero, Philip Darragh, Ramsankar Senthamaraikannan, Bríd Murphy, Matthew Snelgrove, Caitlin McFeely, Sajan Singh, Jim Conway, Robert O’Connor, Enda McGlynn, Ross Lundy, Michael A. Morris. Fabrication of High-κ Dielectric Metal Oxide Films on Topographically Patterned Substrates: Polymer Brush-Mediated Depositions. ACS Applied Materials & Interfaces 2022, 14 (28) , 32729-32737. https://doi.org/10.1021/acsami.2c07966
    2. Nadezda Prochukhan, Stephen A. O’Brien, Arantxa Davó-Quiñonero, Anna Trubetskaya, Eoin Cotter, Andrew Selkirk, Ramsankar Senthamaraikannan, Manuel Ruether, David McCloskey, Michael A. Morris. Room Temperature Fabrication of Macroporous Lignin Membranes for the Scalable Production of Black Silicon. Biomacromolecules 2022, 23 (6) , 2512-2521. https://doi.org/10.1021/acs.biomac.2c00228
    3. Guido C. Ritsema van Eck, Leonardo Chiappisi, Sissi de Beer. Fundamentals and Applications of Polymer Brushes in Air. ACS Applied Polymer Materials 2022, 4 (5) , 3062-3087. https://doi.org/10.1021/acsapm.1c01615
    4. Michele Perego, Stefano Kuschlan, Gabriele Seguini, Riccardo Chiarcos, Valentina Gianotti, Diego Antonioli, Katia Sparnacci, Michele Laus. Silicon Doping by Polymer Grafting: Size Distribution Matters. ACS Applied Polymer Materials 2021, 3 (12) , 6383-6393. https://doi.org/10.1021/acsapm.1c01157
    5. Nadezda Prochukhan, Andrew Selkirk, Ross Lundy, Elsa C. Giraud, Tandra Ghoshal, Clive Downing, Michael A. Morris. Large-Area Fabrication of Vertical Silicon Nanotube Arrays via Toroidal Micelle Self-Assembly. Langmuir 2021, 37 (5) , 1932-1940. https://doi.org/10.1021/acs.langmuir.0c03431
    6. Pravind Yadav, Sajan Singh, Nadezda Prochukhan, Arantxa Davó-Quiñonero, Jim Conway, Riley Gatensby, Sibu C. Padmanabhan, Matthew Snelgrove, Caitlin McFeely, Kyle Shiel, Robert O'Connor, Enda McGlynn, Miles Turner, Ross Lundy, Michael A. Morris. Fabrication of sub-5 nm uniform zirconium oxide films on corrugated copper substrates by a scalable polymer brush assisted deposition method. Applied Surface Science 2023, 627 , 157329. https://doi.org/10.1016/j.apsusc.2023.157329
    7. J Conway, M Snelgrove, P Yadav, K Shiel, R Lundy, A Selkirk, R O’Connor, M A Morris, M M Turner, S Daniels. Use of plasma oxidation for conversion of metal salt infiltrated thin polymer films to metal oxide. Journal of Physics D: Applied Physics 2022, 55 (44) , 445206. https://doi.org/10.1088/1361-6463/ac8e12
    8. M. Snelgrove, C. McFeely, G. Hughes, C. Weiland, J.C. Woicik, K. Shiel, P.G. Mani González, C. Ornelas, Ó. Solís-Canto, K. Cherkaoui, P.K. Hurley, P. Yadav, M.A. Morris, E. McGlynn, R. O'Connor. Growth chemistry and electrical performance of ultrathin alumina formed by area selective vapor phase infiltration. Microelectronic Engineering 2022, 266 , 111888. https://doi.org/10.1016/j.mee.2022.111888
    9. Caitlin McFeely, Matthew Snelgrove, Kyle Shiel, Gregory Hughes, Pravind Yadav, Ross Lundy, Michael A. Morris, Enda McGlynn, Robert O’Connor. Rapid area deactivation for blocking atomic layer deposition processes using polystyrene brush layers. Journal of Materials Chemistry C 2022, 10 (19) , 7476-7484. https://doi.org/10.1039/D2TC00577H
    10. Yun‐Ho Kang, Sangbong Lee, Youngwoo Choi, Won Kyung Seong, Kyu Hyo Han, Jang Hwan Kim, Hyun‐Mi Kim, Seungbum Hong, Sun Hwa Lee, Rodney S. Ruoff, Ki‐Bum Kim, Sang Ouk Kim. Large‐Area Uniform 1‐nm‐Level Amorphous Carbon Layers from 3D Conformal Polymer Brushes. A “Next‐Generation” Cu Diffusion Barrier?. Advanced Materials 2022, 34 (15) https://doi.org/10.1002/adma.202110454
    11. Matthew Snelgrove, Caitlin McFeely, Greg Hughes, Conan Weiland, Joseph Woicik, Kyle Shiel, Pierre Giovanni Mani Gonzalez, Carlos Ornelas, Óscar Omar Solís-Canto, Karim Cherkaoui, Paul Hurley, Pravind Yadav, Michael Morris, Enda McGlynn, Rob O'Connor. Growth Chemistry and Electrical Performance of Ultrathin Aluminium Oxide Films Formed by Vapor Phase Infiltration of Poly(2-Vinylpyridine). SSRN Electronic Journal 2022, 4 https://doi.org/10.2139/ssrn.4191236
    12. Eleanor Mullen, Michael A. Morris. Green Nanofabrication Opportunities in the Semiconductor Industry: A Life Cycle Perspective. Nanomaterials 2021, 11 (5) , 1085. https://doi.org/10.3390/nano11051085
    13. M. Snelgrove, C. McFeely, K. Shiel, G. Hughes, P. Yadav, C. Weiland, J. C. Woicik, P. G. Mani-Gonzalez, R. Lundy, M. A. Morris, E. McGlynn, R. O’Connor. Analysing trimethylaluminum infiltration into polymer brushes using a scalable area selective vapor phase process. Materials Advances 2021, 2 (2) , 769-781. https://doi.org/10.1039/D0MA00928H

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