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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 degrees C, well below the onset temperature of atomic layer deposition (ALD) using these precursors.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division
OSTI Identifier:
1557241
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 14
Country of Publication:
United States
Language:
English

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. doi: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. doi:10.1021/acs.chemmater.9b01714.
@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 degrees 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 = {7}
}