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Title: Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation

Abstract

Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO2, Al2O3, Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe2O3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth.

Authors:
ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [5]; ORCiD logo [6]
  1. Stanford Univ., CA (United States). Dept. of Chemistry
  2. Eindhoven Univ. of Technology (Netherlands). Dept. of Applied Physics
  3. Chonbuk National Univ., Jeonju (Korea, Republic of). Division of Advanced Materials Engineering; Stanford Univ., CA (United States). Dept. of Chemical Engineering
  4. Toyota Motor Europe NV/SA, Zaventem (Belgium). Advanced Technology 1
  5. Stanford Univ., CA (United States). Dept. of Chemical Engineering
  6. Eindhoven Univ. of Technology (Netherlands). Dept. of Applied Physics; Stanford Univ., CA (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1499117
Alternate Identifier(s):
OSTI ID: 1508272
Grant/Contract Number:  
SC0004782
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 3; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Singh, Joseph A., Thissen, Nick F. W., Kim, Woo-Hee, Johnson, Hannah, Kessels, Wilhelmus M. M., Bol, Ageeth A., Bent, Stacey F., and Mackus, Adriaan J. M. Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.7b03818.
Singh, Joseph A., Thissen, Nick F. W., Kim, Woo-Hee, Johnson, Hannah, Kessels, Wilhelmus M. M., Bol, Ageeth A., Bent, Stacey F., & Mackus, Adriaan J. M. Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation. United States. https://doi.org/10.1021/acs.chemmater.7b03818
Singh, Joseph A., Thissen, Nick F. W., Kim, Woo-Hee, Johnson, Hannah, Kessels, Wilhelmus M. M., Bol, Ageeth A., Bent, Stacey F., and Mackus, Adriaan J. M. Tue . "Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation". United States. https://doi.org/10.1021/acs.chemmater.7b03818. https://www.osti.gov/servlets/purl/1499117.
@article{osti_1499117,
title = {Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation},
author = {Singh, Joseph A. and Thissen, Nick F. W. and Kim, Woo-Hee and Johnson, Hannah and Kessels, Wilhelmus M. M. and Bol, Ageeth A. and Bent, Stacey F. and Mackus, Adriaan J. M.},
abstractNote = {Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO2, Al2O3, Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe2O3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth.},
doi = {10.1021/acs.chemmater.7b03818},
journal = {Chemistry of Materials},
number = 3,
volume = 30,
place = {United States},
year = {Tue Jan 30 00:00:00 EST 2018},
month = {Tue Jan 30 00:00:00 EST 2018}
}

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Cited by: 79 works
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Figures / Tables:

Figure 1 Figure 1: Schematic illustration of the proposed mechanism by which area-selective ALD occurs. As an example, we illustrate Fe2O3 deposition from t-butyl ferrocene (TBF)/O2 on Pt. (a) Pt surfaces allow for the dissociative chemisorption of O2 to O* (chemisorbed oxygen), whereas SiO2 surfaces do not catalyze this reaction. (b) Whilemore » TBF adsorption may occur on both surfaces, TBF only fully reacts where O* is present and therefore only leads to deposition on Pt. (c) In this way, a film of Fe2O3 can be deposited selectively by ALD on the Pt.« less

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Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni
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  • The Journal of Chemical Physics, Vol. 142, Issue 15
  • DOI: 10.1063/1.4917259

In situ spectroscopic ellipsometry as a versatile tool for studying atomic layer deposition
journal, March 2009


Selectivity of metal oxide atomic layer deposition on hydrogen terminated and oxidized Si(001)-(2×1) surface
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Selective deposition of Ta 2 O 5 by adding plasma etching super-cycles in plasma enhanced atomic layer deposition steps
journal, January 2017

  • Vallat, Rémi; Gassilloud, Rémy; Eychenne, Brice
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 35, Issue 1
  • DOI: 10.1116/1.4965966

Nanoengineering Heterogeneous Catalysts by Atomic Layer Deposition
journal, June 2017


Reaction Mechanism Studies on Atomic Layer Deposition of Ruthenium and Platinum
journal, January 2003

  • Aaltonen, Titta; Rahtu, Antti; Ritala, Mikko
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 9
  • DOI: 10.1149/1.1595312

Low-Temperature Deposition of TiN by Plasma-Assisted Atomic Layer Deposition
journal, January 2006

  • Heil, S. B. S.; Langereis, E.; Roozeboom, F.
  • Journal of The Electrochemical Society, Vol. 153, Issue 11
  • DOI: 10.1149/1.2344843

Remote Plasma Atomic Layer Deposition of Co 3 O 4 Thin Films
journal, September 2009

  • Donders, Merijn E.; Knoops, Harm; Van de Sanden, M. C.
  • ECS Transactions, Vol. 25, Issue 4
  • DOI: 10.1149/1.3205041

Works referencing / citing this record:

Recent advances in anion-doped metal oxides for catalytic applications
journal, January 2019

  • Liu, Yu; Wang, Wei; Xu, Xiaomin
  • Journal of Materials Chemistry A, Vol. 7, Issue 13
  • DOI: 10.1039/c8ta09913h

Spontaneous selective deposition of iron oxide nanoparticles on graphite as model catalysts
journal, January 2019

  • de Alwis, Chathura; Leftwich, Timothy R.; Mukherjee, Pinaki
  • Nanoscale Advances, Vol. 1, Issue 12
  • DOI: 10.1039/c9na00472f

Understanding chemical and physical mechanisms in atomic layer deposition
journal, January 2020

  • Richey, Nathaniel E.; de Paula, Camila; Bent, Stacey F.
  • The Journal of Chemical Physics, Vol. 152, Issue 4
  • DOI: 10.1063/1.5133390

Review—Beyond the Highs and Lows: A Perspective on the Future of Dielectrics Research for Nanoelectronic Devices
journal, January 2019

  • Jenkins, Melanie; Austin, Dustin Z.; Conley, John F.
  • ECS Journal of Solid State Science and Technology, Vol. 8, Issue 11
  • DOI: 10.1149/2.0161910jss

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.