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Title: Irradiation-induced reactions at the CeO2/SiO2/Si interface

Abstract

The influence of high-energy (1.6 MeV) Ar2+ irradiation on the interfacial interaction between cerium oxide thin films (~15 nm) with a SiO2/Si substrate is investigated using transmission electron microscopy, ultrahigh vacuum x-ray photoelectron spectroscopy (XPS), and a carbon monoxide (CO) oxidation catalytic reaction using ambient pressure XPS. The combination of these methods allows probing the dynamics of vacancy generation and its relation to chemical interactions at the CeO2/SiO2/Si interface. The results suggest that irradiation causes amorphization of some portion of CeO2 at the CeO2/SiO2/Si interface and creates oxygen vacancies due to the formation of Ce2O3 at room temperature. The subsequent ultra-high-vacuum annealing of irradiated films increases the concentration of Ce2O3 with the simultaneous growth of the SiO2 layer. Interactions with CO molecules result in an additional reduction of cerium and promote the transition of Ce2O3 to a silicate compound. Furthermore, thermal annealing of thin films exposed to oxygen or carbon monoxide shows that the silicate phase is highly stabile even at 450 °C.

Authors:
ORCiD logo [1];  [1];  [2];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Univ. of Notre Dame, IN (United States)
  2. Univ. of Hong Kong, Pokfulam (Hong Kong)
Publication Date:
Research Org.:
Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1642347
Grant/Contract Number:  
NA0003888; PHY-1713857; FC02-04ER15533
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 10; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Oxide chemistry and catalysis; transmission electron microscopy; annealing; x-ray photoelectron spectroscopy; thin films; chemical processes; catalysts and catalysis; carbon monoxide

Citation Formats

Sapkota, Pitambar, Aprahamian, Ani, Chan, Kwong Yu, Frentz, Bryce, Macon, Kevin T., Ptasinska, Sylwia, Robertson, Daniel, and Manukyan, Khachatur. Irradiation-induced reactions at the CeO2/SiO2/Si interface. United States: N. p., 2020. Web. https://doi.org/10.1063/1.5142619.
Sapkota, Pitambar, Aprahamian, Ani, Chan, Kwong Yu, Frentz, Bryce, Macon, Kevin T., Ptasinska, Sylwia, Robertson, Daniel, & Manukyan, Khachatur. Irradiation-induced reactions at the CeO2/SiO2/Si interface. United States. https://doi.org/10.1063/1.5142619
Sapkota, Pitambar, Aprahamian, Ani, Chan, Kwong Yu, Frentz, Bryce, Macon, Kevin T., Ptasinska, Sylwia, Robertson, Daniel, and Manukyan, Khachatur. Mon . "Irradiation-induced reactions at the CeO2/SiO2/Si interface". United States. https://doi.org/10.1063/1.5142619. https://www.osti.gov/servlets/purl/1642347.
@article{osti_1642347,
title = {Irradiation-induced reactions at the CeO2/SiO2/Si interface},
author = {Sapkota, Pitambar and Aprahamian, Ani and Chan, Kwong Yu and Frentz, Bryce and Macon, Kevin T. and Ptasinska, Sylwia and Robertson, Daniel and Manukyan, Khachatur},
abstractNote = {The influence of high-energy (1.6 MeV) Ar2+ irradiation on the interfacial interaction between cerium oxide thin films (~15 nm) with a SiO2/Si substrate is investigated using transmission electron microscopy, ultrahigh vacuum x-ray photoelectron spectroscopy (XPS), and a carbon monoxide (CO) oxidation catalytic reaction using ambient pressure XPS. The combination of these methods allows probing the dynamics of vacancy generation and its relation to chemical interactions at the CeO2/SiO2/Si interface. The results suggest that irradiation causes amorphization of some portion of CeO2 at the CeO2/SiO2/Si interface and creates oxygen vacancies due to the formation of Ce2O3 at room temperature. The subsequent ultra-high-vacuum annealing of irradiated films increases the concentration of Ce2O3 with the simultaneous growth of the SiO2 layer. Interactions with CO molecules result in an additional reduction of cerium and promote the transition of Ce2O3 to a silicate compound. Furthermore, thermal annealing of thin films exposed to oxygen or carbon monoxide shows that the silicate phase is highly stabile even at 450 °C.},
doi = {10.1063/1.5142619},
journal = {Journal of Chemical Physics},
number = 10,
volume = 152,
place = {United States},
year = {2020},
month = {3}
}

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Works referenced in this record:

Thermal and mechanical properties of CeO 2
journal, September 2018

  • Suzuki, Kiichi; Kato, Masato; Sunaoshi, Takeo
  • Journal of the American Ceramic Society
  • DOI: 10.1111/jace.16055

XPS study of ion irradiated and unirradiated CeO2 bulk and thin film samples
journal, August 2018


Structure–Activity Map of Ceria Nanoparticles, Nanocubes, and Mesoporous Architectures
journal, August 2016


Pressure Regulations on the Surface Properties of CeO 2 Nanorods and Their Catalytic Activity for CO Oxidation and Nitrile Hydrolysis Reactions
journal, August 2016

  • Li, Jing; Zhang, Zhiyun; Gao, Wei
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 35
  • DOI: 10.1021/acsami.6b05343

Introducing Time Resolution to Detect Ce 3+ Catalytically Active Sites at the Pt/CeO 2 Interface through Ambient Pressure X-ray Photoelectron Spectroscopy
journal, December 2016

  • Artiglia, Luca; Orlando, Fabrizio; Roy, Kanak
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 1
  • DOI: 10.1021/acs.jpclett.6b02314

Universality Classes of Inelastic Electron Scattering Cross-sections
journal, March 1997


Physical and electrical properties of bilayer CeO2/TiO2 gate dielectric stack
journal, August 2016


Enhanced CO Oxidation Rates at the Interface of Mesoporous Oxides and Pt Nanoparticles
journal, October 2013

  • An, Kwangjin; Alayoglu, Selim; Musselwhite, Nathan
  • Journal of the American Chemical Society, Vol. 135, Issue 44
  • DOI: 10.1021/ja4088743

Ion-Beam-Induced Chemical Mixing at a Nanocrystalline CeO 2 -Si Interface
journal, February 2013

  • Edmondson, Philip D.; Young, Neil P.; Parish, Chad M.
  • Journal of the American Ceramic Society, Vol. 96, Issue 5
  • DOI: 10.1111/jace.12214

Irradiation-Enhanced Reactivity of Multilayer Al/Ni Nanomaterials
journal, May 2015

  • Manukyan, Khachatur V.; Tan, Wanpeng; deBoer, Richard J.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 21
  • DOI: 10.1021/acsami.5b01415

Kinetics and Mechanism of Ignition in Reactive Al/Ni Nanostructured Materials
journal, October 2018

  • Manukyan, Khachatur; Pauls, Joshua; Shuck, Christopher
  • The Journal of Physical Chemistry C, Vol. 122, Issue 47
  • DOI: 10.1021/acs.jpcc.8b09075

On the structure dependence of CO oxidation over CeO2 nanocrystals with well-defined surface planes
journal, January 2012


Elucidating the Nature of the Active Phase in Copper/Ceria Catalysts for CO Oxidation
journal, February 2016


Atomic Structure of a CeO 2 Grain Boundary: The Role of Oxygen Vacancies
journal, November 2010

  • Hojo, Hajime; Mizoguchi, Teruyasu; Ohta, Hiromichi
  • Nano Letters, Vol. 10, Issue 11
  • DOI: 10.1021/nl1029336

Structural modification of nanocrystalline ceria by ion beams
journal, January 2011

  • Zhang, Yanwen; Edmondson, Philip D.; Varga, Tamas
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 25
  • DOI: 10.1039/c1cp21335k

Palladium interaction with CeO 2 , Sn–Ce–O and Ga–Ce–O layers
journal, December 2008


Thermal stability and surface behaviors of CeO2/Si films during in-situ vacuum annealing
journal, December 2014


Nanocrystalline CeO2 Increases the Activity of Au for CO Oxidation by Two Orders of Magnitude
journal, May 2004

  • Carrettin, Silvio; Concepción, Patricia; Corma, Avelino
  • Angewandte Chemie International Edition, Vol. 43, Issue 19
  • DOI: 10.1002/anie.200353570

Irradiation effects on microstructure change in nanocrystalline ceria – Phase, lattice stress, grain size and boundaries
journal, September 2012


XRD and XPS studies of room temperature spontaneous interfacial reaction of CeO 2 thin films on Si and Si 3 N 4 substrates
journal, January 2014

  • Bera, Parthasarathi; Anandan, Chinnasamy
  • RSC Adv., Vol. 4, Issue 108
  • DOI: 10.1039/c4ra09882j

XPS study on the effects of thermal annealing on CeO2/La2O3 stacked gate dielectrics
journal, February 2016


Stability of the Ce3+ valence state in cerium oxide nanoparticle layers
journal, January 2012


SRIM – The stopping and range of ions in matter (2010)
journal, June 2010

  • Ziegler, James F.; Ziegler, M. D.; Biersack, J. P.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 268, Issue 11-12
  • DOI: 10.1016/j.nimb.2010.02.091

Role of Microstructure and Surface Defects on the Dissolution Kinetics of CeO 2 , a UO 2 Fuel Analogue
journal, April 2016

  • Corkhill, Claire L.; Bailey, Daniel J.; Tocino, Florent Y.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 16
  • DOI: 10.1021/acsami.5b11323

XPS studies on the interaction of CeO2 with silicon in magnetron sputtered CeO2 thin films on Si and Si3N4 substrates
journal, October 2013


An Evaluation of the Thermophysical Properties of Stoichiometric CeO 2 in Comparison to UO 2 and PuO 2
journal, August 2014

  • Nelson, Andrew T.; Rittman, Dylan R.; White, Joshua T.
  • Journal of the American Ceramic Society, Vol. 97, Issue 11
  • DOI: 10.1111/jace.13170

Electron Diffraction Based Analysis of Phase Fractions and Texture in Nanocrystalline Thin Films, Part I: Principles
journal, July 2008


Proton exchange membrane fuel cell made of magnetron sputtered Pt–CeO and Pt–Co thin film catalysts
journal, January 2015


X-ray investigation of annealed CeO2 films prepared by sputtering on Si substrates
journal, July 2007


Cerium oxide nanoparticles: Size-selective formation and structure analysis
journal, January 2002

  • Zhang, Feng; Chan, Siu-Wai; Spanier, Jonathan E.
  • Applied Physics Letters, Vol. 80, Issue 1
  • DOI: 10.1063/1.1430502

Interfacial properties of single-crystalline CeO2 high- k gate dielectrics directly grown on Si (111)
journal, December 2002

  • Nishikawa, Yukie; Yamaguchi, Takeshi; Yoshiki, Masahiko
  • Applied Physics Letters, Vol. 81, Issue 23
  • DOI: 10.1063/1.1526169

Surface-structure sensitivity of CO oxidation over polycrystalline ceria powders
journal, August 2005


Approaches for the quantitative analysis of oxidation state in cerium oxide nanomaterials
journal, December 2018

  • Sims, Christopher M.; Maier, Russell A.; Johnston-Peck, Aaron C.
  • Nanotechnology, Vol. 30, Issue 8
  • DOI: 10.1088/1361-6528/aae364

The surface chemistry of cerium oxide
journal, March 2015


HAXPES study of CeOx thin film–silicon oxide interface
journal, June 2014


Transformation of CeO2(1 1 1) to Ce2O3(0 0 0 1) films
journal, January 2003


Ce3+ and oxygen vacancy mediated tuning of structural and optical properties of CeO2 nanoparticles
journal, January 2012


Size-induced lattice relaxation in CeO2 nanoparticles
journal, November 2001

  • Zhou, X. -D.; Huebner, W.
  • Applied Physics Letters, Vol. 79, Issue 21
  • DOI: 10.1063/1.1419235

Anomalous Expansion of CeO2 Nanocrystalline Membranes
journal, December 2003


A study on the microstructure and electrical properties of CeO2 thin films for gate dielectric applications
journal, May 2001


Surface manipulation techniques of Roman denarii
journal, November 2019


Colloidal Solution Combustion Synthesis: Toward Mass Production of a Crystalline Uniform Mesoporous CeO 2 Catalyst with Tunable Porosity
journal, April 2016


Gold-supported cerium-doped NiOx catalysts for water oxidation
journal, April 2016

  • Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal
  • Nature Energy, Vol. 1, Issue 5
  • DOI: 10.1038/nenergy.2016.53

Structure of gold atoms on stoichiometric and defective ceria surfaces
journal, November 2008

  • Zhang, Changjun; Michaelides, Angelos; King, David A.
  • The Journal of Chemical Physics, Vol. 129, Issue 19
  • DOI: 10.1063/1.3009629

Computational testing of trivalent dopants in CeO 2 for improved high-κ dielectric behaviour
journal, January 2013

  • Keating, Patrick R. L.; Scanlon, David O.; Watson, Graeme W.
  • J. Mater. Chem. C, Vol. 1, Issue 6
  • DOI: 10.1039/c2tc00385f

Grain growth and mechanical properties of CeO2-x films deposited on Si(100) substrates by pulsed dc magnetron sputtering
journal, February 2013


Stability of cerium oxide on silicon studied by x-ray photoelectron spectroscopy
journal, January 2001

  • Preisler, E. J.; Marsh, O. J.; Beach, R. A.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 19, Issue 4
  • DOI: 10.1116/1.1387464

Oxygen Vacancy Clusters Promoting Reducibility and Activity of Ceria Nanorods
journal, March 2009

  • Liu, Xiangwen; Zhou, Kebin; Wang, Lei
  • Journal of the American Chemical Society, Vol. 131, Issue 9
  • DOI: 10.1021/ja808433d

Pt–CeO x thin film catalysts for PEMFC
journal, February 2015


Irradiation effects in UO2 and CeO2
journal, October 2013


Electrical Properties of Single Crystalline CeO 2 High-k Gate Dielectrics Directly Grown on Si (111)
journal, April 2002

  • Nishikawa, Yukie; Fukushima, Noburu; Yasuda, Naoki
  • Japanese Journal of Applied Physics, Vol. 41, Issue Part 1, No. 4B
  • DOI: 10.1143/jjap.41.2480

Interfacial interaction between cerium oxide and silicon surfaces
journal, January 2013


Ferromagnetism induced by oxygen and cerium vacancies above the percolation limit in CeO 2
journal, May 2010


A review on the selection of anode materials for solid-oxide fuel cells
journal, November 2015

  • Shaikh, Shabana P. S.; Muchtar, Andanastuti; Somalu, Mahendra R.
  • Renewable and Sustainable Energy Reviews, Vol. 51
  • DOI: 10.1016/j.rser.2015.05.069

Dissociative Adsorption of Water on an H 2 O/GaAs(100) Interface: In Situ Near-Ambient Pressure XPS Studies
journal, February 2014

  • Zhang, Xueqiang; Ptasinska, Sylwia
  • The Journal of Physical Chemistry C, Vol. 118, Issue 8
  • DOI: 10.1021/jp411977p