Inhibiting metal oxide atomic layer deposition: Beyond zinc oxide

Matthew D. Sampson; Jonathan D. Emery; Michael J. Pellin; Alex B.F. Martinson

doi:10.1021/acsami.7b01410

Inhibiting metal oxide atomic layer deposition: Beyond zinc oxide

Matthew D. Sampson, Jonathan D. Emery, Michael J. Pellin, Alex B.F. Martinson^*

^*Corresponding author for this work

Materials Science and Engineering

Research output: Contribution to journal › Review article › peer-review

27 Scopus citations

Abstract

Atomic layer deposition (ALD) of several metal oxides is selectivity inhibited on alkanethiol self-assembled monolayers (SAMs) on Au, and the eventual nucleation mechanism is investigated. The inhibition ability of the SAM is significantly improved by the in situ H₂-plasma pretreatment of the Au substrate prior to the gas-phase deposition of a long-chain alkanethiol, 1-dodecanethiol (DDT). This more rigorous surface preparation inhibits even aggressive oxide ALD precursors, including trimethylaluminum and water, for at least 20 cycles. We study the effect that the ALD precursor purge times, growth temperature, alkanethiol chain length, alkanethiol deposition time, and plasma treatment time have on Al₂O₃ ALD inhibition. This is the first example of Al₂O₃ ALD inhibition from a vapor-deposited SAM. The inhibitions of Al2O3, ZnO, and MnO ALD processes are compared, revealing the versatility of this selective surface treatment. Atomic force microscopy and grazingincidence X-ray fluorescence further reveal insight into the mechanism by which the well-defined surface chemistry of ALD may eventually be circumvented to allow metal oxide nucleation and growth on SAM-modified surfaces.

Original language	English (US)
Pages (from-to)	33429-33436
Number of pages	8
Journal	ACS Applied Materials and Interfaces
Volume	9
Issue number	39
DOIs	https://doi.org/10.1021/acsami.7b01410
State	Published - Oct 4 2017

Funding

This work was supported as part of the Argonne−Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0001059. The research was performed at Argonne National Laboratory, a U.S. Department of Energy Office of Science Laboratory, operated under Contract DE-AC02-06CH11357 by UChicago Argonne, LLC. This work made use of the J.B.Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of North-western University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205.). We thank Paul Fenter (ANL) for use of his atomic force microscope. Work by J.D.E. was supported by the Northwestern-Argonne Institute of Science and Engineering (NAISE).

Keywords

Alkanethiols
Aluminum oxide
Atomic layer deposition
Manganese oxide
Metal oxides
Selective deposition
Self-assembled monolayers
Zinc oxide

ASJC Scopus subject areas

General Materials Science

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title = "Inhibiting metal oxide atomic layer deposition: Beyond zinc oxide",

abstract = "Atomic layer deposition (ALD) of several metal oxides is selectivity inhibited on alkanethiol self-assembled monolayers (SAMs) on Au, and the eventual nucleation mechanism is investigated. The inhibition ability of the SAM is significantly improved by the in situ H2-plasma pretreatment of the Au substrate prior to the gas-phase deposition of a long-chain alkanethiol, 1-dodecanethiol (DDT). This more rigorous surface preparation inhibits even aggressive oxide ALD precursors, including trimethylaluminum and water, for at least 20 cycles. We study the effect that the ALD precursor purge times, growth temperature, alkanethiol chain length, alkanethiol deposition time, and plasma treatment time have on Al2O3 ALD inhibition. This is the first example of Al2O3 ALD inhibition from a vapor-deposited SAM. The inhibitions of Al2O3, ZnO, and MnO ALD processes are compared, revealing the versatility of this selective surface treatment. Atomic force microscopy and grazingincidence X-ray fluorescence further reveal insight into the mechanism by which the well-defined surface chemistry of ALD may eventually be circumvented to allow metal oxide nucleation and growth on SAM-modified surfaces.",

keywords = "Alkanethiols, Aluminum oxide, Atomic layer deposition, Manganese oxide, Metal oxides, Selective deposition, Self-assembled monolayers, Zinc oxide",

author = "Sampson, {Matthew D.} and Emery, {Jonathan D.} and Pellin, {Michael J.} and Martinson, {Alex B.F.}",

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AU - Sampson, Matthew D.

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AU - Pellin, Michael J.

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N2 - Atomic layer deposition (ALD) of several metal oxides is selectivity inhibited on alkanethiol self-assembled monolayers (SAMs) on Au, and the eventual nucleation mechanism is investigated. The inhibition ability of the SAM is significantly improved by the in situ H2-plasma pretreatment of the Au substrate prior to the gas-phase deposition of a long-chain alkanethiol, 1-dodecanethiol (DDT). This more rigorous surface preparation inhibits even aggressive oxide ALD precursors, including trimethylaluminum and water, for at least 20 cycles. We study the effect that the ALD precursor purge times, growth temperature, alkanethiol chain length, alkanethiol deposition time, and plasma treatment time have on Al2O3 ALD inhibition. This is the first example of Al2O3 ALD inhibition from a vapor-deposited SAM. The inhibitions of Al2O3, ZnO, and MnO ALD processes are compared, revealing the versatility of this selective surface treatment. Atomic force microscopy and grazingincidence X-ray fluorescence further reveal insight into the mechanism by which the well-defined surface chemistry of ALD may eventually be circumvented to allow metal oxide nucleation and growth on SAM-modified surfaces.

AB - Atomic layer deposition (ALD) of several metal oxides is selectivity inhibited on alkanethiol self-assembled monolayers (SAMs) on Au, and the eventual nucleation mechanism is investigated. The inhibition ability of the SAM is significantly improved by the in situ H2-plasma pretreatment of the Au substrate prior to the gas-phase deposition of a long-chain alkanethiol, 1-dodecanethiol (DDT). This more rigorous surface preparation inhibits even aggressive oxide ALD precursors, including trimethylaluminum and water, for at least 20 cycles. We study the effect that the ALD precursor purge times, growth temperature, alkanethiol chain length, alkanethiol deposition time, and plasma treatment time have on Al2O3 ALD inhibition. This is the first example of Al2O3 ALD inhibition from a vapor-deposited SAM. The inhibitions of Al2O3, ZnO, and MnO ALD processes are compared, revealing the versatility of this selective surface treatment. Atomic force microscopy and grazingincidence X-ray fluorescence further reveal insight into the mechanism by which the well-defined surface chemistry of ALD may eventually be circumvented to allow metal oxide nucleation and growth on SAM-modified surfaces.

KW - Alkanethiols

KW - Aluminum oxide

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KW - Manganese oxide

KW - Metal oxides

KW - Selective deposition

KW - Self-assembled monolayers

KW - Zinc oxide

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Inhibiting metal oxide atomic layer deposition: Beyond zinc oxide

Abstract

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