Vapor-phase grafting of a model aminosilane compound to Al2O3, ZnO, and TiO2 surfaces prepared by atomic layer deposition

Rozyyev, Vepa; Murphy, Julia G.; Barry, Edward; Mane, Anil U.; Sibener, S. J.; Elam, Jeffrey W.

doi:10.1016/j.apsusc.2021.149996

Title: Vapor-phase grafting of a model aminosilane compound to Al₂O₃, ZnO, and TiO₂ surfaces prepared by atomic layer deposition

Journal Article · Sat Jun 05 00:00:00 EDT 2021 · Applied Surface Science

DOI:https://doi.org/10.1016/j.apsusc.2021.149996· OSTI ID:1826066

Rozyyev, Vepa ^[1];

^[2]; Barry, Edward ^[3]; Mane, Anil U. ^[4]; Sibener, S. J. ^[2]; Elam, Jeffrey W. ^[3]

Argonne National Lab. (ANL), Argonne, IL (United States); Advanced Materials for Energy-Water Systems (AMEWS), Energy Frontier Research Center (EFRC), Lemont, IL (United States); Univ. of Chicago, IL (United States)
Advanced Materials for Energy-Water Systems (AMEWS), Energy Frontier Research Center (EFRC), Lemont, IL (United States); Univ. of Chicago, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Advanced Materials for Energy-Water Systems (AMEWS), Energy Frontier Research Center (EFRC), Lemont, IL (United States)
Advanced Materials for Energy-Water Systems (AMEWS), Energy Frontier Research Center (EFRC), Lemont, IL (United States)

Atomic layer deposition (ALD) is a highly versatile surface functionalization technique that can conformally coat both planar and porous substrates. Here we use ALD metal oxide layers to establish a well-defined starting surface for vapor-phase surface organic modification. Vapor-phase (3-aminopropyl)triethoxysilane (APTES) surface silanization of ALD Al₂O₃, ZnO and TiO₂ surfaces were studied at 100 °C, 150 °C and 200 °C. In situ quartz crystal microbalance (QCM) and Fourier-transform infrared (FTIR) spectroscopy measurements, and ex situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) measurements showed uniform monolayer silane formation through self-limiting APTES reaction. We observed a higher surface density of grafted APTES species following silanization at 100 °C compared to 200 °C, and we attribute this to the temperature-dependent reactivity of the surface hydroxyls and changes in the mode of APTES reaction. The FTIR and XPS measurements revealed that APTES reacts with Al₂O₃ and ZnO exclusively through metal siloxy bond formation. However, APTES reacts with TiO₂ through both siloxy bond formation and ammonium salt formation via the amine group.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; NSF-DMR-14-20709

OSTI ID:: 1826066

Journal Information:: Applied Surface Science, Vol. 562; ISSN 0169-4332

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Vapor-phase grafting of a model aminosilane compound to Al2O3, ZnO, and TiO2 surfaces prepared by atomic layer deposition

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Title: Vapor-phase grafting of a model aminosilane compound to Al₂O₃, ZnO, and TiO₂ surfaces prepared by atomic layer deposition