Obtaining a Low and Wide Atomic Layer Deposition Window (150-275 °C) for In 2 O 3 Films Using an In III Amidinate and H 2 O

Kim, Sang Bok; Jayaraman, Ashwin; Chua, Danny; Davis, Luke M.; Zheng, Shao-Liang; Zhao, Xizhu; Lee, Sunghwan; Gordon, Roy G.

doi:10.1002/chem.201802317

Title: Obtaining a Low and Wide Atomic Layer Deposition Window (150-275 °C) for In ₂ O ₃ Films Using an In ^III Amidinate and H ₂ O

Journal Article · Tue Jun 05 00:00:00 EDT 2018 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201802317· OSTI ID:1566328

^[1];

^[2];

^[1]

Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street Cambridge MA 02138 USA
Department of Mechanical Engineering, Baylor University, One Bear Place #97536 Waco TX 76798-7356 USA

Indium oxide is a major component of many technologically important thin films, most notably the transparent conductor indium tin oxide (ITO). Despite being pyrophoric, homoleptic indium(III) alkyls do not allow atomic layer deposition (ALD) of In₂O₃ using water as a co-precursor at substrate temperatures below 200 °C. Several alternative indium sources have been developed, but none allows ALD at lower temperatures except in the presence of oxidants such as O₂ or O₃, which are not compatible with some substrates or alloying processes. We have synthesized a new indium precursor, tris(N,N'-diisopropylformamidinato)indium(III), compound 1, which allows ALD of pure, carbon-free In₂O₃ films using H₂O as the only co-reactant, on substrates in the temperature range 150–275 °C. In contrast, replacing just the H of the anionic iPrNC(H)NiPr ligand with a methyl group (affording the known tris(N,N'-diisopropylacetamidinato)indium(III), compound 2) results in a considerably higher and narrower ALD window in the analogous reaction with H₂O (225–300 °C). Kinetic studies demonstrate that a higher rate of surface reactions in both parts of the ALD cycle gives rise to this difference in the ALD windows.

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); Midwest Research Institute, Kansas City, MO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC36-99GO10337; AC02-05CH11231

OSTI ID:: 1566328

Journal Information:: Chemistry - A European Journal, Vol. 24, Issue 38; ISSN 0947-6539

Publisher:: ChemPubSoc Europe

Country of Publication:: United States

Language:: English

References (36)

New amidinate complexes of indium( iii ): promising CVD precursors for transparent and conductive In ₂ O ₃ thin films Gebhard, M.; Hellwig, M.; Kroll, A. Dalton Transactions, Vol. 46, Issue 31 https://doi.org/10.1039/C7DT01280B	journal	January 2017
The chemistry of N,N ′-dimethylformamidine. II. Hydrolysis. Kinetically controlled formation of cis - N -methylformamide Halliday, James D.; Symons, E. Allan Canadian Journal of Chemistry, Vol. 56, Issue 11 https://doi.org/10.1139/v78-239	journal	June 1978
Synthesis and Characterization of Volatile, Thermally Stable, Reactive Transition Metal Amidinates Lim, Booyong S.; Rahtu, Antti; Park, Jin-Seong Inorganic Chemistry, Vol. 42, Issue 24 https://doi.org/10.1021/ic0345424	journal	December 2003
Past achievements and future challenges in the development of optically transparent electrodes Ellmer, Klaus Nature Photonics, Vol. 6, Issue 12 https://doi.org/10.1038/nphoton.2012.282	journal	November 2012
Self-Limiting Film Growth of Transparent Conducting In ₂ O ₃ by Atomic Layer Deposition using Trimethylindium and Water Vapor Lee, Do-Joong; Kwon, Jang-Yeon; Lee, Jae Il The Journal of Physical Chemistry C, Vol. 115, Issue 31 https://doi.org/10.1021/jp2024389	journal	July 2011
Synthesis of indium oxi-sulfide films by atomic layer deposition: The essential role of plasma enhancement Bugot, Cathy; Schneider, Nathanaëlle; Lincot, Daniel Beilstein Journal of Nanotechnology, Vol. 4 https://doi.org/10.3762/bjnano.4.85	journal	January 2013
Growth of In[sub 2]O[sub 3] Thin Films by Atomic Layer Epitaxy Asikainen, Timo Journal of The Electrochemical Society, Vol. 141, Issue 11 https://doi.org/10.1149/1.2059303	journal	January 1994
Atomic Layer Deposition of Tungsten(III) Oxide Thin Films from W ₂ (NMe ₂ ) ₆ and Water: Precursor-Based Control of Oxidation State in the Thin Film Material Journal of the American Chemical Society, Vol. 128, Issue 30 https://doi.org/10.1021/ja063272w	journal	August 2006
Low-Temperature Al₂O₃ Atomic Layer Deposition Groner, M. D.; Fabreguette, F. H.; Elam, J. W. Chemistry of Materials, Vol. 16, Issue 4, p. 639-645 https://doi.org/10.1021/cm0304546	journal	February 2004
Synthesis of Calcium(II) Amidinate Precursors for Atomic Layer Deposition through a Redox Reaction between Calcium and Amidines Kim, Sang Bok; Yang, Chuanxi; Powers, Tamara Angewandte Chemie, Vol. 128, Issue 35 https://doi.org/10.1002/ange.201602406	journal	June 2016
Low Temperature Atomic Layer Deposition of Crystalline In ₂ O ₃ Films Ramachandran, Ranjith K.; Dendooven, Jolien; Poelman, Hilde The Journal of Physical Chemistry C, Vol. 119, Issue 21 https://doi.org/10.1021/acs.jpcc.5b03255	journal	May 2015
Hydrolysis and Hydrogenolysis of Formamidines: N,N -Dimethyl and N,N -Dibenzyl Formamidines as Protective Groups for Primary Amines Vincent, Stéphane; Mioskowski, Charles; Lebeau, Luc The Journal of Organic Chemistry, Vol. 64, Issue 3 https://doi.org/10.1021/jo980099g	journal	February 1999
Photoreduction and oxidation of as‐deposited microcrystalline indium oxide Xirouchaki, C.; Kiriakidis, G.; Pedersen, T. F. Journal of Applied Physics, Vol. 79, Issue 12 https://doi.org/10.1063/1.362612	journal	June 1996
Transparent conducting oxide semiconductors for transparent electrodes Minami, Tadatsugu Semiconductor Science and Technology, Vol. 20, Issue 4 https://doi.org/10.1088/0268-1242/20/4/004	journal	March 2005
MOCVD-Derived Highly Transparent, Conductive Zinc- and Tin-Doped Indium Oxide Thin Films: Precursor Synthesis, Metastable Phase Film Growth and Characterization, and Application as Anodes in Polymer Light-Emitting Diodes Ni, Jun; Yan, He; Wang, Anchuang Journal of the American Chemical Society, Vol. 127, Issue 15 https://doi.org/10.1021/ja044643g	journal	April 2005
Nitrogen-doped cuprous oxide as a p-type hole-transporting layer in thin-film solar cells Lee, Yun Seog; Heo, Jaeyeong; Winkler, Mark T. Journal of Materials Chemistry A, Vol. 1, Issue 48 https://doi.org/10.1039/c3ta13208k	journal	January 2013
Solution-Processed Flexible Fluorine-doped Indium Zinc Oxide Thin-Film Transistors Fabricated on Plastic Film at Low Temperature Seo, Jin-Suk; Jeon, Jun-Hyuck; Hwang, Young Hwan Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02085	journal	June 2013
Low-Temperature Growth of Indium Oxide Thin Film by Plasma-Enhanced Atomic Layer Deposition Using Liquid Dimethyl( N -ethoxy-2,2-dimethylpropanamido)indium for High-Mobility Thin Film Transistor Application Kim, Hyo Yeon; Jung, Eun Ae; Mun, Geumbi ACS Applied Materials & Interfaces, Vol. 8, Issue 40 https://doi.org/10.1021/acsami.6b07332	journal	September 2016
Role of Gallium Doping in Dramatically Lowering Amorphous-Oxide Processing Temperatures for Solution-Derived Indium Zinc Oxide Thin-Film Transistors Jeong, Sunho; Ha, Young-Geun; Moon, Jooho Advanced Materials, Vol. 22, Issue 12 https://doi.org/10.1002/adma.200902450	journal	December 2009
Atomic Layer Deposition: An Overview George, Steven M. Chemical Reviews, Vol. 110, Issue 1, p. 111-131 https://doi.org/10.1021/cr900056b	journal	January 2010
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 Maeng, Wan Joo; Choi, Dong-won; Chung, Kwun-Bum ACS Applied Materials & Interfaces, Vol. 6, Issue 20 https://doi.org/10.1021/am502085c	journal	October 2014
Atomic layer deposition of highly conductive indium oxide using a liquid precursor and water oxidant Maeng, W. J.; Choi, Dong-won; Park, Jozeph Ceramics International, Vol. 41, Issue 9 https://doi.org/10.1016/j.ceramint.2015.05.015	journal	November 2015
Indium Oxide Atomic Layer Deposition Facilitated by the Synergy between Oxygen and Water Libera, Joseph A.; Hryn, John N.; Elam, Jeffrey W. Chemistry of Materials, Vol. 23, Issue 8 https://doi.org/10.1021/cm103637t	journal	April 2011
Oxygen-Free Atomic Layer Deposition of Indium Sulfide McCarthy, Robert F.; Weimer, Matthew S.; Emery, Jonathan D. ACS Applied Materials & Interfaces, Vol. 6, Issue 15 https://doi.org/10.1021/am501331w	journal	July 2014
Improved Chemically Deposited Zn(O,S) Buffers for Cu(In,Ga)(S,Se)<sub>2</sub> Solar Cells by Controlled Incorporation of Indium Hones, Christian; Fuchs, Anne; Zweigart, Siegmund IEEE Journal of Photovoltaics, Vol. 6, Issue 1 https://doi.org/10.1109/JPHOTOV.2015.2487818	journal	January 2016
Crystallinity of inorganic films grown by atomic layer deposition: Overview and general trends Miikkulainen, Ville; Leskelä, Markku; Ritala, Mikko Journal of Applied Physics, Vol. 113, Issue 2, Article No. 021301 https://doi.org/10.1063/1.4757907	journal	January 2013
Indium-tris-guanidinates: a promising class of precursors for water assisted atomic layer deposition of In ₂ O ₃ thin films Gebhard, M.; Hellwig, M.; Parala, H. Dalton Trans., Vol. 43, Issue 3 https://doi.org/10.1039/C3DT52746H	journal	January 2014
Thin films of In2O3 by atomic layer deposition using In(acac)3 Nilsen, O.; Balasundaraprabhu, R.; Monakhov, E. V. Thin Solid Films, Vol. 517, Issue 23 https://doi.org/10.1016/j.tsf.2009.02.059	journal	October 2009
The Race To Replace Tin-Doped Indium Oxide: Which Material Will Win? Kumar, Akshay; Zhou, Chongwu ACS Nano, Vol. 4, Issue 1 https://doi.org/10.1021/nn901903b	journal	December 2009
Atomic Layer Deposition of In ₂ O ₃ Using Cyclopentadienyl Indium: A New Synthetic Route to Transparent Conducting Oxide Films Elam, Jeffrey W.; Martinson, Alex B. F.; Pellin, Michael J. Chemistry of Materials, Vol. 18, Issue 15 https://doi.org/10.1021/cm060754y	journal	July 2006
Enhanced Growth Rate in Atomic Layer Epitaxy of Indium Oxide and Indium-Tin Oxide Thin Films Ritala, Mikko Electrochemical and Solid-State Letters, Vol. 1, Issue 3 https://doi.org/10.1149/1.1390669	journal	January 1999
Record Mobility in Transparent p-Type Tin Monoxide Films and Devices by Phase Engineering Caraveo-Frescas, Jesus A.; Nayak, Pradipta K.; Al-Jawhari, Hala A. ACS Nano, Vol. 7, Issue 6 https://doi.org/10.1021/nn400852r	journal	May 2013
Indium oxide thin film prepared by low temperature atomic layer deposition using liquid precursors and ozone oxidant Maeng, W. J.; Choi, Dong-Won; Park, Jozeph Journal of Alloys and Compounds, Vol. 649 https://doi.org/10.1016/j.jallcom.2015.07.150	journal	November 2015
Low Temperature Atomic Layer Deposition of Tin Oxide Heo, Jaeyeong; Hock, Adam S.; Gordon, Roy G. Chemistry of Materials, Vol. 22, Issue 17 https://doi.org/10.1021/cm1011108	journal	September 2010
Synthesis of Calcium(II) Amidinate Precursors for Atomic Layer Deposition through a Redox Reaction between Calcium and Amidines Kim, Sang Bok; Yang, Chuanxi; Powers, Tamara Angewandte Chemie International Edition, Vol. 55, Issue 35 https://doi.org/10.1002/anie.201602406	journal	June 2016
Growth of In ₂ O ₃ thin films on silicon by the metalorganic chemical vapor deposition method Kim, Nam Ho; Myung, Ju Hyun; Kim, Hyoun Woo physica status solidi (a), Vol. 202, Issue 1 https://doi.org/10.1002/pssa.200406916	journal	January 2005

Similar Records

Obtaining a Low and Wide Atomic Layer Deposition Window (150–275 °C) for In ₂ O ₃ Films Using an In ^III Amidinate and H ₂ O

Journal Article · Tue Jun 05 00:00:00 EDT 2018 · Chemistry - A European Journal · OSTI ID:1566328

Kim, Sang Bok; Jayaraman, Ashwin; Chua, Danny; +5 more

Atomic Layer Deposition of Ruthenium Films Using Ruthenium Diketonates and O₂, H₂, or N₂O: The Role of Ruthenium Etching

Journal Article · Fri Jul 22 00:00:00 EDT 2022 · Journal of Physical Chemistry. C · OSTI ID:1566328

Qin, Xiangdong; Zaera, Francisco

Surface chemistry of a Cu(I) beta-diketonate precursor and the atomic layer deposition of Cu{sub 2}O on SiO{sub 2} studied by x-ray photoelectron spectroscopy

Journal Article · Tue Jul 01 00:00:00 EDT 2014 · Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films · OSTI ID:1566328

Dhakal, Dileep; Waechtler, Thomas; Schulz, Stefan E.; +4 more

Related Subjects

solar (photovoltaic)
solar (fuels)
solid state lighting
phonons
thermoelectric
hydrogen and fuel cells
defects
charge transport
optics
materials and chemistry by design
synthesis (novel materials)

Title: Obtaining a Low and Wide Atomic Layer Deposition Window (150-275 °C) for In 2 O 3 Films Using an In III Amidinate and H 2 O

Citation Formats

References (36)

Similar Records

Related Subjects

Title: Obtaining a Low and Wide Atomic Layer Deposition Window (150-275 °C) for In ₂ O ₃ Films Using an In ^III Amidinate and H ₂ O