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:
-
[1];
[3];
[3];
[1];
[2]
- Univ. of Chicago, IL (United States), Pritzker School of Molecular Engineering, Advanced Materials for Energy-Water Systems (AMEWS), Energy Frontier Research Center (EFRC)
- Univ. of Chicago, IL (United States), Advanced Materials for Energy-Water Systems (AMEWS), Energy Frontier Research Center (EFRC)
- 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 = {Tue Jun 25 00:00:00 EDT 2019},
month = {Tue Jun 25 00:00:00 EDT 2019}
}
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Figures / Tables:
Figure 1: a) Infrared spectra of a 138 nm PMMA thin film (gray regions) with vibrations of an isolated MMA fragment predicted from first-principles computation (red lines). Time-lapsed infrared difference spectra of PMMA thin film upon exposure to b) TMAl for 0, 47, 93, 186, 279, 372, 465 s; c)more »
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Works referenced in this record:
Review of Recent Advances in Applications of Vapor-Phase Material Infiltration Based on Atomic Layer Deposition
journal, September 2018
- Subramanian, Ashwanth; Tiwale, Nikhil; Nam, Chang-Yong
- JOM, Vol. 71, Issue 1
Properties and Applications of Vapor Infiltration into Polymeric Substrates
journal, October 2018
- Ingram, Wade F.; Jur, Jesse S.
- JOM, Vol. 71, Issue 1
Surface modification of thermoplastics by atomic layer deposition of Al2O3 and TiO2 thin films
journal, November 2008
- Kemell, Marianna; Färm, Elina; Ritala, Mikko
- European Polymer Journal, Vol. 44, Issue 11
Synthesis of a Novel Porous Polymer/Ceramic Composite Material by Low-Temperature Atomic Layer Deposition
journal, October 2007
- Li, Nai-Hong; George, Steven M.; Weimer, Alan W.
- Chemistry of Materials, Vol. 19, Issue 22, p. 5388-5394
Nanoscopic Morphologies in Block Copolymer Nanorods as Templates for Atomic-Layer Deposition of Semiconductors
journal, April 2009
- Wang, Yong; Qin, Yong; Berger, Andreas
- Advanced Materials, Vol. 21, Issue 27, p. 2763-2766
Vapor phase infiltration: from a bioinspired process to technologic application, a prospective review
journal, July 2018
- Azpitarte, Itxasne; Knez, Mato
- MRS Communications, Vol. 8, Issue 03
Nanoscopic Patterned Materials with Tunable Dimensions via Atomic Layer Deposition on Block Copolymers
journal, September 2010
- Peng, Qing; Tseng, Yu-Chih; Darling, Seth B.
- Advanced Materials, Vol. 22, Issue 45, p. 5129-5133
Enhanced Block Copolymer Lithography Using Sequential Infiltration Synthesis
journal, July 2011
- Tseng, Yu-Chih; Peng, Qing; Ocola, Leonidas E.
- The Journal of Physical Chemistry C, Vol. 115, Issue 36, p. 17725-17729
Enhanced Lithographic Imaging Layer Meets Semiconductor Manufacturing Specification a Decade Early
journal, April 2012
- Tseng, Yu-Chih; Mane, Anil U.; Elam, Jeffrey W.
- Advanced Materials, Vol. 24, Issue 19, p. 2608-2613
Fabrication of Nanoporous Alumina Ultrafiltration Membrane with Tunable Pore Size Using Block Copolymer Templates
journal, July 2017
- Zhou, Chun; Segal-Peretz, Tamar; Oruc, Muhammed Enes
- Advanced Functional Materials, Vol. 27, Issue 34
Sequential Infiltration Synthesis for the Design of Low Refractive Index Surface Coatings with Controllable Thickness
journal, February 2017
- Berman, Diana; Guha, Supratik; Lee, Byeongdu
- ACS Nano, Vol. 11, Issue 3
Sub-50-nm self-assembled nanotextures for enhanced broadband antireflection in silicon solar cells
journal, January 2015
- Rahman, Atikur; Ashraf, Ahsan; Xin, Huolin
- Nature Communications, Vol. 6, Issue 1
A Route to Nanoscopic Materials via Sequential Infiltration Synthesis on Block Copolymer Templates
journal, May 2011
- Peng, Qing; Tseng, Yu-Chih; Darling, Seth B.
- ACS Nano, Vol. 5, Issue 6, p. 4600-4606
Nano Spray‐Dried Block Copolymer Nanoparticles and Their Transformation into Hybrid and Inorganic Nanoparticles
journal, March 2019
- Weisbord, Inbal; Shomrat, Neta; Moshe, Hen
- Advanced Functional Materials, Vol. 30, Issue 18
Direct fabrication of high aspect-ratio metal oxide nanopatterns via sequential infiltration synthesis in lithographically defined SU-8 templates
journal, November 2015
- Nam, Chang-Yong; Stein, Aaron; Kisslinger, Kim
- Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 33, Issue 6
Investigating Sequential Vapor Infiltration Synthesis on Block-Copolymer-Templated Titania Nanoarrays
journal, March 2016
- Ishchenko, Olga M.; Krishnamoorthy, Sivashankar; Valle, Nathalie
- The Journal of Physical Chemistry C, Vol. 120, Issue 13
New Insights into Sequential Infiltration Synthesis
journal, September 2015
- Elam, J. W.; Biswas, M.; Darling, S.
- ECS Transactions, Vol. 69, Issue 7
Electrical and structural properties of ZnO synthesized via infiltration of lithographically defined polymer templates
journal, November 2015
- Nam, Chang-Yong; Stein, Aaron; Kisslinger, Kim
- Applied Physics Letters, Vol. 107, Issue 20
Extreme Carrier Depletion and Superlinear Photoconductivity in Ultrathin Parallel-Aligned ZnO Nanowire Array Photodetectors Fabricated by Infiltration Synthesis
journal, November 2017
- Nam, Chang-Yong; Stein, Aaron
- Advanced Optical Materials, Vol. 5, Issue 24
Infiltration Synthesis of Diverse Metal Oxide Nanostructures from Epoxidized Diene–Styrene Block Copolymer Templates
journal, February 2019
- Yi, Daniel H.; Nam, Chang-Yong; Doerk, Gregory
- ACS Applied Polymer Materials, Vol. 1, Issue 4
Conductivity in transparent oxide semiconductors
journal, August 2011
- King, P. D. C.; Veal, T. D.
- Journal of Physics: Condensed Matter, Vol. 23, Issue 33
Indium oxide—a transparent, wide-band gap semiconductor for (opto)electronic applications
journal, January 2015
- Bierwagen, Oliver
- Semiconductor Science and Technology, Vol. 30, Issue 2
Effects of Residual Solvent Molecules Facilitating the Infiltration Synthesis of ZnO in a Nonreactive Polymer
journal, May 2017
- Ye, Xinyi; Kestell, John; Kisslinger, Kim
- Chemistry of Materials, Vol. 29, Issue 10
Ab initio study on the dimer structures of trimethylaluminum and dimethylaluminumhydride
journal, December 1994
- Hiraoka, Yoshiko Someya; Mashita, Masao
- Journal of Crystal Growth, Vol. 145, Issue 1-4
New Insight into the Mechanism of Sequential Infiltration Synthesis from Infrared Spectroscopy
journal, October 2014
- Biswas, Mahua; Libera, Joseph A.; Darling, Seth B.
- Chemistry of Materials, Vol. 26, Issue 21
Kinetics for the Sequential Infiltration Synthesis of Alumina in Poly(methyl methacrylate): An Infrared Spectroscopic Study
journal, January 2015
- Biswas, Mahua; Libera, Joseph A.; Darling, Seth B.
- The Journal of Physical Chemistry C, Vol. 119, Issue 26
Mechanisms and reactions during atomic layer deposition on polymers
journal, December 2013
- Parsons, Gregory N.; Atanasov, Sarah E.; Dandley, Erinn C.
- Coordination Chemistry Reviews, Vol. 257, Issue 23-24
Temperature-Dependent Subsurface Growth during Atomic Layer Deposition on Polypropylene and Cellulose Fibers
journal, June 2010
- Jur, Jesse S.; Spagnola, Joseph C.; Lee, Kyoungmi
- Langmuir, Vol. 26, Issue 11
Insight on the Sequential Vapor Infiltration Mechanisms of Trimethylaluminum with Poly(methyl methacrylate), Poly(vinylpyrrolidone), and Poly(acrylic acid)
journal, May 2019
- Hill, Grant T.; Lee, Dennis T.; Williams, Philip S.
- The Journal of Physical Chemistry C, Vol. 123, Issue 26
Reversible and Irreversible Reactions of Trimethylaluminum with Common Organic Functional Groups as a Model for Molecular Layer Deposition and Vapor Phase Infiltration
journal, May 2017
- Yang, Fan; Brede, Jens; Ablat, Hayrensa
- Advanced Materials Interfaces, Vol. 4, Issue 18
Quantitative in situ infrared analysis of reactions between trimethylaluminum and polymers during Al2O3 atomic layer deposition
journal, January 2012
- Gong, Bo; Parsons, Gregory N.
- Journal of Materials Chemistry, Vol. 22, Issue 31
Infiltrated Zinc Oxide in Poly(methyl methacrylate): An Atomic Cycle Growth Study
journal, December 2016
- Ocola, Leonidas E.; Connolly, Aine; Gosztola, David J.
- The Journal of Physical Chemistry C, Vol. 121, Issue 3
Atomic Layer Deposition of Indium Tin Oxide Thin Films Using Nonhalogenated Precursors
journal, February 2008
- Elam, Jeffrey W.; Baker, David A.; Martinson, Alex B. F.
- The Journal of Physical Chemistry C, Vol. 112, Issue 6
Trimethylaluminum Diffusion in PMMA Thin Films during Sequential Infiltration Synthesis: In Situ Dynamic Spectroscopic Ellipsometric Investigation
journal, August 2018
- Cianci, Elena; Nazzari, Daniele; Seguini, Gabriele
- Advanced Materials Interfaces, Vol. 5, Issue 20
Enhanced polymeric lithography resists via sequential infiltration synthesis
journal, July 2011
- Tseng, Yu-Chih; Peng, Qing; Ocola, Leonidas E.
- Journal of Materials Chemistry, Vol. 21, Issue 32, 11722-11725
Interface and surface effects on the glass-transition temperature in thin polymer films
journal, January 1994
- Keddie, Joseph L.; Jones, Richard A. L.; Cory, Rachel A.
- Faraday Discussions, Vol. 98
The Rational Design of a Single-Component Photocatalyst for Gas-Phase CO 2 Reduction Using Both UV and Visible Light
journal, December 2014
- Hoch, Laura B.; Wood, Thomas E.; O'Brien, Paul G.
- Advanced Science, Vol. 1, Issue 1
Analysis of Poly(methyl methacrylate) (PMMA) by XPS
journal, April 1996
- Girardeaux, Christophe; Pireaux, Jean-Jacques
- Surface Science Spectra, Vol. 4, Issue 2
XPS O 1s binding energies for polymers containing hydroxyl, ether, ketone and ester groups
journal, May 1991
- López, Gabriel P.; Castner, David G.; Ratner, Buddy D.
- Surface and Interface Analysis, Vol. 17, Issue 5
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
Indium Oxide Atomic Layer Deposition Facilitated by the Synergy between Oxygen and Water
journal, April 2011
- Libera, Joseph A.; Hryn, John N.; Elam, Jeffrey W.
- Chemistry of Materials, Vol. 23, Issue 8
Low-Temperature Al2O3 Atomic Layer Deposition
journal, February 2004
- Groner, M. D.; Fabreguette, F. H.; Elam, J. W.
- Chemistry of Materials, Vol. 16, Issue 4, p. 639-645
Cyclic trimeric hydroxy, amido, phosphido, and arsenido derivatives of aluminum and gallium. X-ray structures of [tert-Bu2Ga(.mu.-OH)]3 and [tert-Bu2Ga(.mu.-NH2)]3
journal, January 1993
- Atwood, David A.; Cowley, Alan H.; Harris, Paul R.
- Organometallics, Vol. 12, Issue 1
Hydrolysis of tri-tert-butylaluminum: the first structural characterization of alkylalumoxanes [(R2Al)2O]n and (RAlO)n
journal, June 1993
- Mason, Mark R.; Smith, Janna M.; Bott, Simon G.
- Journal of the American Chemical Society, Vol. 115, Issue 12
Three-dimensional electroactive ZnO nanomesh directly derived from hierarchically self-assembled block copolymer thin films
journal, January 2019
- Subramanian, Ashwanth; Doerk, Gregory; Kisslinger, Kim
- Nanoscale, Vol. 11, Issue 19
Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains
journal, December 2008
- Han, Eungnak; Stuen, Karl O.; La, Young-Hye
- Macromolecules, Vol. 41, Issue 23
Indium Tin Oxide Films: State-of-the-Art In Synthesis and Properties
journal, January 1995
- Kumar, R.
- Materials Technology, Vol. 10, Issue 9-10
Indium tin oxide films prepared by radio frequency magnetron sputtering method at a low processing temperature
journal, November 2000
- Zhang, Keran; Zhu, Furong; Huan, C. H. A.
- Thin Solid Films, Vol. 376, Issue 1-2, p. 255-263
Electrical, optical, and structural properties of indium–tin–oxide thin films for organic light-emitting devices
journal, December 1999
- Kim, H.; Gilmore, C. M.; Piqué, A.
- Journal of Applied Physics, Vol. 86, Issue 11
Characterization of tin doped indium oxide films prepared by electron beam evaporation
journal, January 1986
- Banerjee, Ratnabali; Das, Debajyoti; Ray, Swati
- Solar Energy Materials, Vol. 13, Issue 1
Role of oxygen vacancies in the high-temperature thermopower of indium oxide and indium tin oxide films
journal, January 2009
- Sarath Kumar, S. R.; Kasiviswanathan, S.
- Semiconductor Science and Technology, Vol. 24, Issue 2
Highly Conducting, Transparent, and Flexible Indium Oxide Thin Film Prepared by Atomic Layer Deposition Using a New Liquid Precursor Et 2 InN(SiMe 3 ) 2
journal, October 2014
- Maeng, Wan Joo; Choi, Dong-won; Chung, Kwun-Bum
- ACS Applied Materials & Interfaces, Vol. 6, Issue 20
Atomic layer deposition of ultrathin indium oxide and indium tin oxide films using a trimethylindium, tetrakis(dimethylamino)tin, and ozone precursor system
journal, January 2019
- Salami, Hossein; Uy, Alan; Vadapalli, Aarathi
- Journal of Vacuum Science & Technology A, Vol. 37, Issue 1
Thermal atomic layer deposition of In2O3 thin films using dimethyl(N-ethoxy-2,2-dimethylcarboxylicpropanamide)indium and H2O
journal, October 2017
- Agbenyeke, Raphael Edem; Jung, Eun Ae; Park, Bo Keun
- Applied Surface Science, Vol. 419
Atomic layer deposition of highly conductive indium oxide using a liquid precursor and water oxidant
journal, November 2015
- Maeng, W. J.; Choi, Dong-won; Park, Jozeph
- Ceramics International, Vol. 41, Issue 9
Ozone-Based Sequential Infiltration Synthesis of Al 2 O 3 Nanostructures in Symmetric Block Copolymer
journal, November 2016
- Frascaroli, Jacopo; Cianci, Elena; Spiga, Sabina
- ACS Applied Materials & Interfaces, Vol. 8, Issue 49
Ab initio molecular simulations with numeric atom-centered orbitals
journal, November 2009
- Blum, Volker; Gehrke, Ralf; Hanke, Felix
- Computer Physics Communications, Vol. 180, Issue 11
Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999
- Adamo, Carlo; Barone, Vincenzo
- The Journal of Chemical Physics, Vol. 110, Issue 13
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
Works referencing / citing this record:
Metal Oxide Heterostructure Array via Spatially Controlled–Growth within Block Copolymer Templates
journal, October 2019
- Azoulay, Rotem; Shomrat, Neta; Weisbord, Inbal
- Small
The chemical physics of sequential infiltration synthesis—A thermodynamic and kinetic perspective
journal, November 2019
- Waldman, Ruben Z.; Mandia, David J.; Yanguas-Gil, Angel
- The Journal of Chemical Physics, Vol. 151, Issue 19
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.