skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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. 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., & 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 = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

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

Save / Share:

Works referenced in this record:

The use of atomic layer deposition in advanced nanopatterning
journal, January 2014

  • Mackus, A. J. M.; Bol, A. A.; Kessels, W. M. M.
  • Nanoscale, Vol. 6, Issue 19
  • DOI: 10.1039/C4NR01954G

Nanoengineering Heterogeneous Catalysts by Atomic Layer Deposition
journal, June 2017


Catalyst Design with Atomic Layer Deposition
journal, February 2015

  • O’Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan
  • ACS Catalysis, Vol. 5, Issue 3
  • DOI: 10.1021/cs501862h

Preparation of solid catalysts: an appraisal
journal, October 1992


Nanoalloys:  From Theory to Applications of Alloy Clusters and Nanoparticles
journal, March 2008

  • Ferrando, Riccardo; Jellinek, Julius; Johnston, Roy L.
  • Chemical Reviews, Vol. 108, Issue 3, p. 845-910
  • DOI: 10.1021/cr040090g

Strategies for the Synthesis of Supported Gold Palladium Nanoparticles with Controlled Morphology and Composition
journal, April 2013

  • Hutchings, Graham J.; Kiely, Christopher J.
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300356m

Toward atomically-precise synthesis of supported bimetallic nanoparticles using atomic layer deposition
journal, February 2014

  • Lu, Junling; Low, Ke-Bin; Lei, Yu
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4264

Selectivity of metal oxide atomic layer deposition on hydrogen terminated and oxidized Si(001)-(2×1) surface
journal, May 2014

  • Longo, Roberto C.; McDonnell, Stephen; Dick, D.
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 32, Issue 3
  • DOI: 10.1116/1.4864619

A New Resist for Area Selective Atomic and Molecular Layer Deposition on Metal–Dielectric Patterns
journal, May 2014

  • Hashemi, Fatemeh Sadat Minaye; Prasittichai, Chaiya; Bent, Stacey F.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 20
  • DOI: 10.1021/jp502669f

Controlled Synthesis of Pd/Pt Core Shell Nanoparticles Using Area-selective Atomic Layer Deposition
journal, February 2015

  • Cao, Kun; Zhu, Qianqian; Shan, Bin
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08470

Real-Time Observation of Atomic Layer Deposition Inhibition: Metal Oxide Growth on Self-Assembled Alkanethiols
journal, July 2014

  • Avila, Jason R.; DeMarco, Erica J.; Emery, Jonathan D.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 15
  • DOI: 10.1021/am503008j

Inhibiting Metal Oxide Atomic Layer Deposition: Beyond Zinc Oxide
journal, April 2017

  • Sampson, Matthew D.; Emery, Jonathan D.; Pellin, Michael J.
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 39
  • DOI: 10.1021/acsami.7b01410

Supported Core/Shell Bimetallic Nanoparticles Synthesis by Atomic Layer Deposition
journal, August 2012

  • Weber, Matthieu J.; Mackus, Adriaan J. M.; Verheijen, Marcel A.
  • Chemistry of Materials, Vol. 24, Issue 15
  • DOI: 10.1021/cm301206e

Sub-nanometer dimensions control of core/shell nanoparticles prepared by atomic layer deposition
journal, February 2015


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

Self-Correcting Process for High Quality Patterning by Atomic Layer Deposition
journal, July 2015

  • Minaye Hashemi, Fatemeh Sadat; Prasittichai, Chaiya; Bent, Stacey F.
  • ACS Nano, Vol. 9, Issue 9
  • DOI: 10.1021/acsnano.5b03125

Atomic layer deposition—Sequential self-limiting surface reactions for advanced catalyst “bottom-up” synthesis
journal, June 2016


Catalytic Combustion and Dehydrogenation Reactions during Atomic Layer Deposition of Platinum
journal, May 2012

  • Mackus, Adriaan J. M.; Leick, Noémi; Baker, Layton
  • Chemistry of Materials, Vol. 24, Issue 10
  • DOI: 10.1021/cm203812v

Wall-number selective growth of vertically aligned carbon nanotubes from FePt catalysts: a comparative study with Fe catalysts
journal, January 2012

  • Li, Shisheng; Hou, Pengxiang; Liu, Chang
  • Journal of Materials Chemistry, Vol. 22, Issue 28
  • DOI: 10.1039/c2jm32270f

Oriented Catalytic Platinum Nanoparticles on High Surface Area Strontium Titanate Nanocuboids
journal, March 2011

  • Enterkin, James A.; Poeppelmeier, Kenneth R.; Marks, Laurence D.
  • Nano Letters, Vol. 11, Issue 3
  • DOI: 10.1021/nl104263j

Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces
journal, February 2007

  • Stamenkovic, Vojislav R.; Mun, Bongjin Simon; Arenz, Matthias
  • Nature Materials, Vol. 6, Issue 3, p. 241-247
  • DOI: 10.1038/nmat1840

Constructing Hierarchical Interfaces: TiO 2 -Supported PtFe–FeO x Nanowires for Room Temperature CO Oxidation
journal, August 2015

  • Zhu, Huiyuan; Wu, Zili; Su, Dong
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b07011

Catalyst synthesis and evaluation using an integrated atomic layer deposition synthesis–catalysis testing tool
journal, August 2015

  • Camacho-Bunquin, Jeffrey; Shou, Heng; Aich, Payoli
  • Review of Scientific Instruments, Vol. 86, Issue 8
  • DOI: 10.1063/1.4928614

Enhanced dry reforming of methane on Ni and Ni-Pt catalysts synthesized by atomic layer deposition
journal, February 2015


Electrocatalytic activity of atomic layer deposited Pt–Ru catalysts onto N-doped carbon nanotubes
journal, March 2014

  • Johansson, Anne-Charlotte; Larsen, Jackie V.; Verheijen, Marcel A.
  • Journal of Catalysis, Vol. 311
  • DOI: 10.1016/j.jcat.2014.01.001

Chemical synthesis of magnetic nanoparticles
journal, December 2002


Multifunctional iron platinum stealth immunomicelles: targeted detection of human prostate cancer cells using both fluorescence and magnetic resonance imaging
journal, June 2011

  • Taylor, Robert M.; Huber, Dale L.; Monson, Todd C.
  • Journal of Nanoparticle Research, Vol. 13, Issue 10
  • DOI: 10.1007/s11051-011-0439-3

Atomic Layer Deposition of Fe2O3 Using Ferrocene and Ozone
journal, February 2011

  • Martinson, Alex B. F.; DeVries, Michael J.; Libera, Joseph A.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 10, p. 4333-4339
  • DOI: 10.1021/jp110203x

Stoichiometry of Nickel Oxide Films Prepared by ALD
journal, September 2011

  • Bachmann, Julien; Zolotaryov, Andriy; Albrecht, Ole
  • Chemical Vapor Deposition, Vol. 17, Issue 7-9
  • DOI: 10.1002/cvde.201004300

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

Atomic Layer Deposition of Wet-Etch Resistant Silicon Nitride Using Di( sec -butylamino)silane and N 2 Plasma on Planar and 3D Substrate Topographies
journal, January 2017

  • Faraz, Tahsin; van Drunen, Maarten; Knoops, Harm C. M.
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 2
  • DOI: 10.1021/acsami.6b12267

Room-Temperature Atomic Layer Deposition of Platinum
journal, April 2013

  • Mackus, Adriaan J. M.; Garcia-Alonso, Diana; Knoops, Harm C. M.
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm400274n

Plasma enhanced atomic layer deposition of Fe 2 O 3 thin films
journal, January 2014

  • Ramachandran, Ranjith K.; Dendooven, Jolien; Detavernier, Christophe
  • J. Mater. Chem. A, Vol. 2, Issue 27
  • DOI: 10.1039/C4TA01486C

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


Conformal ZnO coatings on high surface area silica gel using atomic layer deposition
journal, July 2008


Solar Hydrogen Generation by Silicon Nanowires Modified with Platinum Nanoparticle Catalysts by Atomic Layer Deposition
journal, September 2013

  • Dai, Pengcheng; Xie, Jin; Mayer, Matthew T.
  • Angewandte Chemie International Edition, Vol. 52, Issue 42
  • DOI: 10.1002/anie.201303813

Simulation of growth dynamics in atomic layer deposition. Part II. Polycrystalline films from cubic crystallites
journal, April 2007


Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni
journal, January 2011

  • Biesinger, Mark C.; Payne, Brad P.; Grosvenor, Andrew P.
  • Applied Surface Science, Vol. 257, Issue 7, p. 2717-2730
  • DOI: 10.1016/j.apsusc.2010.10.051

Atomic layer deposition of iron(III) oxide on zirconia nanoparticles in a fluidized bed reactor using ferrocene and oxygen
journal, January 2009


Atomic Layer Deposition of Iron Oxide Thin Films and Nanotubes using Ferrocene and Oxygen as Precursors
journal, April 2008

  • Rooth, Ma˚rten; Johansson, Anders; Kukli, Kaupo
  • Chemical Vapor Deposition, Vol. 14, Issue 3-4
  • DOI: 10.1002/cvde.200706649

Sputter reduction of oxides by ion bombardment during Auger depth profile analysis
journal, August 1990

  • Mitchell, D. F.; Sproule, G. I.; Graham, M. J.
  • Surface and Interface Analysis, Vol. 15, Issue 8
  • DOI: 10.1002/sia.740150808

Local deposition of high-purity Pt nanostructures by combining electron beam induced deposition and atomic layer deposition
journal, June 2010

  • Mackus, A. J. M.; Mulders, J. J. L.; van de Sanden, M. C. M.
  • Journal of Applied Physics, Vol. 107, Issue 11
  • DOI: 10.1063/1.3431351

Surface reactions during atomic layer deposition of Pt derived from gas phase infrared spectroscopy
journal, July 2009

  • Kessels, W. M. M.; Knoops, H. C. M.; Dielissen, S. A. F.
  • Applied Physics Letters, Vol. 95, Issue 1
  • DOI: 10.1063/1.3176946

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

Direct-Write Atomic Layer Deposition of High-Quality Pt Nanostructures: Selective Growth Conditions and Seed Layer Requirements
journal, May 2013

  • Mackus, A. J. M.; Thissen, N. F. W.; Mulders, J. J. L.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 20
  • DOI: 10.1021/jp402260j

Critical Size for O 2 Dissociation by Au Nanoparticles
journal, February 2009

  • Roldán, Alberto; González, Silvia; Ricart, Josep Manel
  • ChemPhysChem, Vol. 10, Issue 2
  • DOI: 10.1002/cphc.200800702

Size- and support-dependency in the catalysis of gold
journal, April 1997


Reactant-Promoted Oxygen Dissociation on Gold Clusters
journal, May 2010

  • Lyalin, Andrey; Taketsugu, Tetsuya
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 12
  • DOI: 10.1021/jz100503j

Growth of Hierarchically 3D Silver-Silica Hybrid Nanostructures by Metastable State Assisted Atomic Layer Deposition (MS-ALD)
journal, May 2017

  • Ziegler, Mario; Yüksel, Sezin; Goerke, Sebastian
  • Advanced Materials Technologies, Vol. 2, Issue 7
  • DOI: 10.1002/admt.201700015

Remote Plasma Atomic Layer Deposition of Co3O4 Thin Films
journal, January 2011

  • Donders, M. E.; Knoops, H. C. M.; van, M. C. M.
  • Journal of The Electrochemical Society, Vol. 158, Issue 4
  • DOI: 10.1149/1.3552616

Indium Oxide Thin Films by Atomic Layer Deposition Using Trimethylindium and Ozone
journal, May 2016

  • Mane, Anil U.; Allen, Amy J.; Kanjolia, Ravindra K.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 18
  • DOI: 10.1021/acs.jpcc.6b02657

Atomic layer deposition of molybdenum oxide from (N t Bu) 2 (NMe 2 ) 2 Mo and O 2 plasma
journal, January 2016

  • Vos, Martijn F. J.; Macco, Bart; Thissen, Nick F. W.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 34, Issue 1
  • DOI: 10.1116/1.4930161

Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni
journal, April 2015

  • López-Moreno, S.; Romero, A. H.
  • The Journal of Chemical Physics, Vol. 142, Issue 15
  • DOI: 10.1063/1.4917259

    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.