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Title: Sequential Infiltration Synthesis of Electronic Materials: Group 13 Oxides via Metal Alkyl Precursors

Abstract

The sequential infiltration synthesis (SIS) of group 13 indium and gallium oxides (In2O3 and Ga2O3) into poly(methyl methacrylate) (PMMA) thin films is demonstrated using trimethylindium (TMIn) and trimethylgallium (TMGa), respectively, with water. In situ Fourier transform infrared (FTIR) spectroscopy reveals that these metal alkyl precursors reversibly associate with the carbonyl groups of PMMA in analogy to trimethylaluminum (TMAl), however, with significantly lower affinity. This is demonstrated to have important kinetic consequences that dramatically alter the synthetic parameters required to achieve material growth. Ab initio density functional theory simulations of the methyl methacrylate monomer with group 13 metal alkyls corroborate association energy that is 3X greater for TMAl than for either TMIn or TMGa. As a consequence, the kinetics of activated diffusion within the film is observed to be far more rapid for TMIn and TMGa than for TMAI. Spectroscopic ellipsometry and scanning electron microscopy, in combination with Hall effect measurements of SIS-derived In2O3 films, demonstrate that SIS enables rapid growth of thin films with continuous electrically conductive pathways after postannealing. Notably, SIS with TMIn and water enables the growth of In2O3 at 80°C, well below the onset temperature of atomic layer deposition (ALD) using these precursors.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of Chicago, IL (United States), Pritzker School of Molecular Engineering, Advanced Materials for Energy-Water Systems (AMEWS), Energy Frontier Research Center (EFRC)
  2. Univ. of Chicago, IL (United States), Advanced Materials for Energy-Water Systems (AMEWS), Energy Frontier Research Center (EFRC)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Advanced Materials for Energy-Water Systems (AMEWS); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1557241
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 14; 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

Waldman, Ruben Z., Jeon, Nari, Mandia, David J., Heinonen, Olle, Darling, Seth B., and Martinson, Alex B. F. Sequential Infiltration Synthesis of Electronic Materials: Group 13 Oxides via Metal Alkyl Precursors. United States: N. p., 2019. Web. doi:10.1021/acs.chemmater.9b01714.
Waldman, Ruben Z., Jeon, Nari, Mandia, David J., Heinonen, Olle, Darling, Seth B., & Martinson, Alex B. F. Sequential Infiltration Synthesis of Electronic Materials: Group 13 Oxides via Metal Alkyl Precursors. United States. https://doi.org/10.1021/acs.chemmater.9b01714
Waldman, Ruben Z., Jeon, Nari, Mandia, David J., Heinonen, Olle, Darling, Seth B., and Martinson, Alex B. F. Tue . "Sequential Infiltration Synthesis of Electronic Materials: Group 13 Oxides via Metal Alkyl Precursors". United States. https://doi.org/10.1021/acs.chemmater.9b01714. https://www.osti.gov/servlets/purl/1557241.
@article{osti_1557241,
title = {Sequential Infiltration Synthesis of Electronic Materials: Group 13 Oxides via Metal Alkyl Precursors},
author = {Waldman, Ruben Z. and Jeon, Nari and Mandia, David J. and Heinonen, Olle and Darling, Seth B. and Martinson, Alex B. F.},
abstractNote = {The sequential infiltration synthesis (SIS) of group 13 indium and gallium oxides (In2O3 and Ga2O3) into poly(methyl methacrylate) (PMMA) thin films is demonstrated using trimethylindium (TMIn) and trimethylgallium (TMGa), respectively, with water. In situ Fourier transform infrared (FTIR) spectroscopy reveals that these metal alkyl precursors reversibly associate with the carbonyl groups of PMMA in analogy to trimethylaluminum (TMAl), however, with significantly lower affinity. This is demonstrated to have important kinetic consequences that dramatically alter the synthetic parameters required to achieve material growth. Ab initio density functional theory simulations of the methyl methacrylate monomer with group 13 metal alkyls corroborate association energy that is 3X greater for TMAl than for either TMIn or TMGa. As a consequence, the kinetics of activated diffusion within the film is observed to be far more rapid for TMIn and TMGa than for TMAI. Spectroscopic ellipsometry and scanning electron microscopy, in combination with Hall effect measurements of SIS-derived In2O3 films, demonstrate that SIS enables rapid growth of thin films with continuous electrically conductive pathways after postannealing. Notably, SIS with TMIn and water enables the growth of In2O3 at 80°C, well below the onset temperature of atomic layer deposition (ALD) using these precursors.},
doi = {10.1021/acs.chemmater.9b01714},
journal = {Chemistry of Materials},
number = 14,
volume = 31,
place = {United States},
year = {2019},
month = {6}
}

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Works referencing / citing this record:

Metal Oxide Heterostructure Array via Spatially Controlled–Growth within Block Copolymer Templates
journal, October 2019


The chemical physics of sequential infiltration synthesis—A thermodynamic and kinetic perspective
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  • Waldman, Ruben Z.; Mandia, David J.; Yanguas-Gil, Angel
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