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*Email: [email protected]AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, IrelandMore by Ross Lundy
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- Pravind YadavPravind YadavAMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, IrelandMore by Pravind Yadav
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- Nadezda ProchukhanNadezda ProchukhanAMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, IrelandMore by Nadezda Prochukhan
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- Elsa C. GiraudElsa C. GiraudAMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, IrelandMore by Elsa C. Giraud
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- Tom F. O’MahonyTom F. O’MahonyAMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, IrelandMore by Tom F. O’Mahony
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- Andrew SelkirkAndrew SelkirkAMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, IrelandMore by Andrew Selkirk
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- Eleanor MullenEleanor MullenAMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, IrelandMore by Eleanor Mullen
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- Jim ConwayJim ConwayNational Centre for Plasma Science and Technology, Dublin City University, Dublin 9, IrelandMore by Jim Conway
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- Miles TurnerMiles TurnerNational Centre for Plasma Science and Technology, Dublin City University, Dublin 9, IrelandMore by Miles Turner
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- Stephen DanielsStephen DanielsNational Centre for Plasma Science and Technology, Dublin City University, Dublin 9, IrelandMore by Stephen Daniels
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- P. G. Mani-GonzalezP. G. Mani-GonzalezInstitute of Engineering and Technology, Department of Physics and Mathematics, Autonomous University of Ciudad Juárez, Cd. Juárez 32310, MexicoMore by P. G. Mani-Gonzalez
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- Matthew SnelgroveMatthew SnelgroveSchool of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, IrelandMore by Matthew Snelgrove
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- Justin BoganJustin BoganSchool of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, IrelandMore by Justin Bogan
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- Caitlin McFeelyCaitlin McFeelySchool of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, IrelandMore by Caitlin McFeely
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- Robert O’ConnorRobert O’ConnorSchool of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, IrelandMore by Robert O’Connor
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- Enda McGlynnEnda McGlynnNational Centre for Plasma Science and Technology, Dublin City University, Dublin 9, IrelandSchool of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, IrelandMore by Enda McGlynn
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- Greg HughesGreg HughesNational Centre for Plasma Science and Technology, Dublin City University, Dublin 9, IrelandSchool of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, IrelandMore by Greg Hughes
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- Cian CumminsCian CumminsAMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, IrelandMore by Cian Cummins
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- Michael A. Morris*Michael A. Morris*Email: [email protected]AMBER Research Centre and School of Chemistry, Trinity College Dublin, Dublin 2, IrelandMore by Michael A. Morris
Abstract
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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