Mechanism of Benzene Tribopolymerization on the RuO2 (110) Surface
Abstract
A tribopolymer formed on the contacts of microelectromechanical and nanoelectromechanical system (MEMS-NEMS) devices is a major concern hampering their practical use in information technology. Conductive metal oxides, such as RuO2 and ReO3, have been regarded as promising candidate materials for MEMS-NEMS contacts due to their conductivity, hardness, and relatively chemically inert surfaces. However, recent experimental works demonstrate that trace amounts of a polymer could still form on RuO2 surfaces. We demonstrate the mechanism of this class of unexpected tribopolymer formation by conducting density-functional-theory-based computational compression experiments with benzene as the contamination gas. First, mechanical force during compression changes the benzene molecules from slightly physisorbed to strongly chemisorbed. Further compression causes deformation and chemical linkage of the benzene molecules. Finally, the two contacts detach, with one having a complex organic molecule attached and the other a more reactive surface. The complex organic molecule, which has an oxabicyclic segment, can be viewed as the rudiment of a tribopolymer, and the more reactive surface can trigger the next adsorption-reaction-tribopolymer formation cycle. Based on these results, we also predict tribopolymer formation rates by using transition-state theory and the second-order rate law. We promote a deeper understanding of tribopolymer formation (especially on metal oxides) andmore »
- Authors:
-
- Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF)
- OSTI Identifier:
- 1540707
- Alternate Identifier(s):
- OSTI ID: 1434827; OSTI ID: 1867863
- Grant/Contract Number:
- FG02-07ER15920; CMMI-1334241; DMR-1124696
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Applied
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2331-7019
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Physics; 36 MATERIALS SCIENCE; surfaces, nanotechnology, tribology
Citation Formats
Yang, J., Qi, Y., Kim, H. D., and Rappe, A. M. Mechanism of Benzene Tribopolymerization on the RuO2 (110) Surface. United States: N. p., 2018.
Web. doi:10.1103/physrevapplied.9.044038.
Yang, J., Qi, Y., Kim, H. D., & Rappe, A. M. Mechanism of Benzene Tribopolymerization on the RuO2 (110) Surface. United States. https://doi.org/10.1103/physrevapplied.9.044038
Yang, J., Qi, Y., Kim, H. D., and Rappe, A. M. Thu .
"Mechanism of Benzene Tribopolymerization on the RuO2 (110) Surface". United States. https://doi.org/10.1103/physrevapplied.9.044038. https://www.osti.gov/servlets/purl/1540707.
@article{osti_1540707,
title = {Mechanism of Benzene Tribopolymerization on the RuO2 (110) Surface},
author = {Yang, J. and Qi, Y. and Kim, H. D. and Rappe, A. M.},
abstractNote = {A tribopolymer formed on the contacts of microelectromechanical and nanoelectromechanical system (MEMS-NEMS) devices is a major concern hampering their practical use in information technology. Conductive metal oxides, such as RuO2 and ReO3, have been regarded as promising candidate materials for MEMS-NEMS contacts due to their conductivity, hardness, and relatively chemically inert surfaces. However, recent experimental works demonstrate that trace amounts of a polymer could still form on RuO2 surfaces. We demonstrate the mechanism of this class of unexpected tribopolymer formation by conducting density-functional-theory-based computational compression experiments with benzene as the contamination gas. First, mechanical force during compression changes the benzene molecules from slightly physisorbed to strongly chemisorbed. Further compression causes deformation and chemical linkage of the benzene molecules. Finally, the two contacts detach, with one having a complex organic molecule attached and the other a more reactive surface. The complex organic molecule, which has an oxabicyclic segment, can be viewed as the rudiment of a tribopolymer, and the more reactive surface can trigger the next adsorption-reaction-tribopolymer formation cycle. Based on these results, we also predict tribopolymer formation rates by using transition-state theory and the second-order rate law. We promote a deeper understanding of tribopolymer formation (especially on metal oxides) and provide strategies for suppressing tribopolymerization.},
doi = {10.1103/physrevapplied.9.044038},
journal = {Physical Review Applied},
number = 4,
volume = 9,
place = {United States},
year = {Thu Apr 26 00:00:00 EDT 2018},
month = {Thu Apr 26 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 5 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
The relay reborn
journal, April 2012
- Liu, Tsu-Jae; Markovic, Dejan; Stojanovic, Vladimir
- IEEE Spectrum, Vol. 49, Issue 4
Contamination Thresholds of Pt- and ${\rm RuO}_{2}$-Coated Ohmic Switches
journal, December 2013
- Brand, Vitali; Baker, Michael S.; de Boer, Maarten P.
- Journal of Microelectromechanical Systems, Vol. 22, Issue 6
Atomistic simulation of frictional anisotropy on quasicrystal approximant surfaces
journal, June 2016
- Ye, Zhijiang; Martini, Ashlie; Thiel, Patricia
- Physical Review B, Vol. 93, Issue 23
Tunable, Source-Controlled Formation of Platinum Silicides and Nanogaps from Thin Precursor Films
journal, February 2014
- Streller, Frank; Wabiszewski, Graham E.; Mangolini, Filippo
- Advanced Materials Interfaces, Vol. 1, Issue 3
Mechanochemistry at Solid Surfaces: Polymerization of Adsorbed Molecules by Mechanical Shear at Tribological Interfaces
journal, January 2017
- Yeon, Jejoon; He, Xin; Martini, Ashlie
- ACS Applied Materials & Interfaces, Vol. 9, Issue 3
Nonvolatile Nanoelectromechanical Memory Switches for Low-Power and High-Speed Field-Programmable Gate Arrays
journal, February 2015
- Yong Jun Kim,
- IEEE Transactions on Electron Devices, Vol. 62, Issue 2
Role and effective treatment of dispersive forces in materials: Polyethylene and graphite crystals as test cases
journal, April 2009
- Barone, Vincenzo; Casarin, Maurizio; Forrer, Daniel
- Journal of Computational Chemistry, Vol. 30, Issue 6
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
Refinement of the Crystal Structure of Ruthenium Dioxide.
journal, January 1970
- Boman, Carl-Erik; Danielsen, Jacob; Haaland, Arne
- Acta Chemica Scandinavica, Vol. 24
Development of a quantum chemical molecular dynamics tribochemical simulator and its application to tribochemical reaction dynamics of lubricant additives
journal, March 2010
- Onodera, T.; Miura, R.; Suzuki, A.
- Modelling and Simulation in Materials Science and Engineering, Vol. 18, Issue 3
Designed nonlocal pseudopotentials for enhanced transferability
journal, May 1999
- Ramer, Nicholas J.; Rappe, Andrew M.
- Physical Review B, Vol. 59, Issue 19
Nanoelectromechanical contact switches
journal, April 2012
- Loh, Owen Y.; Espinosa, Horacio D.
- Nature Nanotechnology, Vol. 7, Issue 5
Impact of Contact Materials and Operating Conditions on Stability of Micromechanical Switches
journal, June 2013
- Brand, Vitali; Baker, Michael S.; de Boer, Maarten P.
- Tribology Letters, Vol. 51, Issue 3
Theoretical Modeling of Tribochemical Reaction on Pt and Au Contacts: Mechanical Load and Catalysis
journal, March 2016
- Qi, Yubo; Yang, Jing; Rappe, Andrew M.
- ACS Applied Materials & Interfaces, Vol. 8, Issue 11
Tribochemical Reaction Dynamics of Phosphoric Ester Lubricant Additive by Using a Hybrid Tight-Binding Quantum Chemical Molecular Dynamics Method
journal, September 2006
- Koyama, Michihisa; Hayakawa, Jun; Onodera, Tasuku
- The Journal of Physical Chemistry B, Vol. 110, Issue 35
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Adsorption of Benzene on the RuO 2 (110) Surface
journal, January 2017
- D. Kim, Hyeong-Seok; Yang, Jing; Qi, Yubo
- The Journal of Physical Chemistry C, Vol. 121, Issue 3
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Experimental and Molecular Dynamics Simulations of Tribochemical Reactions with ZDDP: Zinc Phosphate–Iron Oxide Reaction
journal, September 2008
- Minfray, Clotilde; Le Mogne, Thierry; Martin, Jean-Michel
- Tribology Transactions, Vol. 51, Issue 5
Long time scale kinetic Monte Carlo simulations without lattice approximation and predefined event table
journal, December 2001
- Henkelman, Graeme; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 115, Issue 21
Optimized pseudopotentials
journal, January 1990
- Rappe, Andrew M.; Rabe, Karin M.; Kaxiras, Efthimios
- Physical Review B, Vol. 41, Issue 2
Composition, structure, and stability of as a function of oxygen pressure
journal, December 2001
- Reuter, Karsten; Scheffler, Matthias
- Physical Review B, Vol. 65, Issue 3
A Highly Reliable MEMS Relay With Two-Step Spring System and Heat Sink Insulator for High-Power Switching Applications
journal, February 2016
- Yoon, Yong-Hoon; Song, Yong-Ha; Ko, Seung-Deok
- Journal of Microelectromechanical Systems, Vol. 25, Issue 1
Nanomechanical characterization of sputtered RuO2 thin film on silicon substrate for solid state electronic devices
journal, January 2011
- Zhu, Jing; Yeap, Kong Boon; Zeng, Kaiyang
- Thin Solid Films, Vol. 519, Issue 6
Organic Deposits on Precious Metal Contacts
journal, May 1958
- Hermance, H. W.; Egan, T. F.
- Bell System Technical Journal, Vol. 37, Issue 3