Thermal Atomic Layer Etching of MoS 2 Using MoF 6 and H 2 O
Abstract
Two-dimensional (2D) layered materials offer unique properties that make them attractive for continued scaling in electronic and optoelectronic device applications. Successful integration of 2D materials into semiconductor manufacturing requires high-volume and high-precision processes for deposition and etching. Several promising large-scale deposition approaches have been reported for a range of 2D materials, but fewer studies have reported removal processes. Thermal atomic layer etching (ALE) is a scalable processing technique that offers precise control over isotropic material removal. In this work, we report a thermal ALE process for molybdenum disulfide (MoS2). We show that MoF6 can be used as a fluorination source, which, when combined with alternating exposures of H2O, etches both amorphous and crystalline MoS2 films deposited by atomic layer deposition. To characterize the ALE process and understand the etching reaction mechanism, in situ quartz crystal microbalance (QCM), Fourier transform infrared (FTIR), and quadrupole mass spectrometry (QMS) experiments were performed. From temperature-dependent in situ QCM experiments, the mass change per cycle was -5.7 ng/cm2 at 150 °C and reached -270.6 ng/cm2 at 300 °C, nearly 50x greater. The temperature dependence followed Arrhenius behavior with an activation energy of 13 +/- 1 kcal/mol. At 200 °C, QCM revealed a mass gain followingmore »
- Authors:
-
- Micron School of Material Science and Engineering, Boise State University, 1910 University Dr., Boise, Idaho83725, United States
- Applied Materials Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois60439, United States
- Micron School of Material Science and Engineering, Boise State University, 1910 University Dr., Boise, Idaho83725, United States, Center for Advanced Energy Studies, Idaho Falls, Idaho83401, United States
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1908893
- Alternate Identifier(s):
- OSTI ID: 2007759
- Grant/Contract Number:
- AC02-06CH11357; 1751268
- Resource Type:
- Published Article
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Name: Chemistry of Materials Journal Volume: 35 Journal Issue: 3; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; atomic layer deposition; deposition; etching; layers; metal organic frameworks
Citation Formats
Soares, Jake, Mane, Anil U., Choudhury, Devika, Letourneau, Steven, Hues, Steven M., Elam, Jeffrey W., and Graugnard, Elton. Thermal Atomic Layer Etching of MoS 2 Using MoF 6 and H 2 O. United States: N. p., 2023.
Web. doi:10.1021/acs.chemmater.2c02549.
Soares, Jake, Mane, Anil U., Choudhury, Devika, Letourneau, Steven, Hues, Steven M., Elam, Jeffrey W., & Graugnard, Elton. Thermal Atomic Layer Etching of MoS 2 Using MoF 6 and H 2 O. United States. https://doi.org/10.1021/acs.chemmater.2c02549
Soares, Jake, Mane, Anil U., Choudhury, Devika, Letourneau, Steven, Hues, Steven M., Elam, Jeffrey W., and Graugnard, Elton. Thu .
"Thermal Atomic Layer Etching of MoS 2 Using MoF 6 and H 2 O". United States. https://doi.org/10.1021/acs.chemmater.2c02549.
@article{osti_1908893,
title = {Thermal Atomic Layer Etching of MoS 2 Using MoF 6 and H 2 O},
author = {Soares, Jake and Mane, Anil U. and Choudhury, Devika and Letourneau, Steven and Hues, Steven M. and Elam, Jeffrey W. and Graugnard, Elton},
abstractNote = {Two-dimensional (2D) layered materials offer unique properties that make them attractive for continued scaling in electronic and optoelectronic device applications. Successful integration of 2D materials into semiconductor manufacturing requires high-volume and high-precision processes for deposition and etching. Several promising large-scale deposition approaches have been reported for a range of 2D materials, but fewer studies have reported removal processes. Thermal atomic layer etching (ALE) is a scalable processing technique that offers precise control over isotropic material removal. In this work, we report a thermal ALE process for molybdenum disulfide (MoS2). We show that MoF6 can be used as a fluorination source, which, when combined with alternating exposures of H2O, etches both amorphous and crystalline MoS2 films deposited by atomic layer deposition. To characterize the ALE process and understand the etching reaction mechanism, in situ quartz crystal microbalance (QCM), Fourier transform infrared (FTIR), and quadrupole mass spectrometry (QMS) experiments were performed. From temperature-dependent in situ QCM experiments, the mass change per cycle was -5.7 ng/cm2 at 150 °C and reached -270.6 ng/cm2 at 300 °C, nearly 50x greater. The temperature dependence followed Arrhenius behavior with an activation energy of 13 +/- 1 kcal/mol. At 200 °C, QCM revealed a mass gain following exposure to MoF6 and a net mass loss after exposure to H2O. FTIR revealed the consumption of Mo-O species and formation of Mo-F and MoFx=O species following exposures of MoF6 and the reverse behavior following H2O exposures. QMS measurements, combined with thermodynamic calculations, supported the removal of Mo and S through the formation of volatile MoF2O2 and H2S byproducts. The proposed etching mechanism involves a two-stage oxidation of Mo through the ALE half-reactions. Etch rates of 0.5 Å/cycle for amorphous films and 0.2 Å/cycle for annealed films were measured by ex situ ellipsometry, X-ray reflectivity, and transmission electron microscopy. Precisely etching amorphous films and subsequently annealing them yielded crystalline, few-layer MoS2 thin films. This thermal MoS2 ALE process provides a new mechanism for fluorination-based ALE and offers a low-temperature approach for integrating amorphous and crystalline 2D MoS2 films into high-volume device manufacturing with tight thermal budgets.},
doi = {10.1021/acs.chemmater.2c02549},
journal = {Chemistry of Materials},
number = 3,
volume = 35,
place = {United States},
year = {Thu Jan 12 00:00:00 EST 2023},
month = {Thu Jan 12 00:00:00 EST 2023}
}
https://doi.org/10.1021/acs.chemmater.2c02549
Works referenced in this record:
(Invited) ALD and ALEt of Transition Metal Dichalcogenide Materials
journal, September 2019
- Mane, Anil U.; Letourneau, Steven; Choudhury, Devika
- ECS Meeting Abstracts, Vol. MA2019-02, Issue 24
Controlled MoS 2 layer etching using CF 4 plasma
journal, August 2015
- Jeon, Min Hwan; Ahn, Chisung; Kim, HyeongU
- Nanotechnology, Vol. 26, Issue 35
Atomic Layer Deposition of Ga 2 O 3 Films Using Trimethylgallium and Ozone
journal, October 2012
- Comstock, David J.; Elam, Jeffrey W.
- Chemistry of Materials, Vol. 24, Issue 21
Texture characterisation of sputtered MoS2thin films by cross-sectional TEM analysis
journal, May 1990
- Moser, J.; Liao, H.; Levy, F.
- Journal of Physics D: Applied Physics, Vol. 23, Issue 5
Thickness and Morphology Dependent Electrical Properties of ALD‐Synthesized MoS
2
FETs
journal, December 2021
- Mahlouji, Reyhaneh; Verheijen, Marcel A.; Zhang, Yue
- Advanced Electronic Materials, Vol. 8, Issue 3
Thermal Atomic Layer Etching of Aluminum Oxide (Al 2 O 3 ) Using Sequential Exposures of Niobium Pentafluoride (NbF 5 ) and Carbon Tetrachloride (CCl 4 ): A Combined Experimental and Density Functional Theory Study of the Etch Mechanism
journal, April 2021
- Sharma, Varun; Elliott, Simon D.; Blomberg, Tom
- Chemistry of Materials, Vol. 33, Issue 8
Thermal atomic layer etching of amorphous and crystalline Al2O3 films
journal, July 2021
- Murdzek, Jessica A.; Rajashekhar, Adarsh; Makala, Raghuveer S.
- Journal of Vacuum Science & Technology A, Vol. 39, Issue 4
Design and implementation of an integral wall-mounted quartz crystal microbalance for atomic layer deposition
journal, September 2012
- Riha, Shannon C.; Libera, Joseph A.; Elam, Jeffrey W.
- Review of Scientific Instruments, Vol. 83, Issue 9
Prospects for Thermal Atomic Layer Etching Using Sequential, Self-Limiting Fluorination and Ligand-Exchange Reactions
journal, May 2016
- George, Steven M.; Lee, Younghee
- ACS Nano, Vol. 10, Issue 5
Layer Thinning and Etching of Mechanically Exfoliated MoS 2 Nanosheets by Thermal Annealing in Air
journal, August 2013
- Wu, Jumiati; Li, Hai; Yin, Zongyou
- Small
Amorphous MoS2 Photodetector with Ultra-Broadband Response
journal, June 2019
- Huang, Zhongzheng; Zhang, Tianfu; Liu, Junku
- ACS Applied Electronic Materials, Vol. 1, Issue 7
Lithography-free plasma-induced patterned growth of MoS 2 and its heterojunction with graphene
journal, January 2016
- Chen, Xiang; Park, Yong Ju; Das, Tanmoy
- Nanoscale, Vol. 8, Issue 33
Role of Initial Precursor Chemisorption on Incubation Delay for Molybdenum Oxide Atomic Layer Deposition
journal, November 2016
- Nanayakkara, Charith E.; Vega, Abraham; Liu, Guo
- Chemistry of Materials, Vol. 28, Issue 23
HSC Chemistry for Windows, 2.0
journal, January 1996
- Smith, William R.
- Journal of Chemical Information and Computer Sciences, Vol. 36, Issue 1
Atomic layer deposition of molybdenum disulfide films using MoF 6 and H 2 S
journal, January 2018
- Mane, Anil U.; Letourneau, Steven; Mandia, David J.
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 36, Issue 1
Fast Fourier transform and multi-Gaussian fitting of XRR data to determine the thickness of ALD grown thin films within the initial growth regime
journal, November 2020
- Lammel, Michaela; Geishendorf, Kevin; Choffel, Marisa A.
- Applied Physics Letters, Vol. 117, Issue 21
MoF5 revisited. A comprehensive study of MoF5
journal, July 2018
- Stene, Riane E.; Scheibe, Benjamin; Pietzonka, Clemens
- Journal of Fluorine Chemistry, Vol. 211
In-situ observation of Mo-O stretching vibrations during the reduction of MoO3 with hydrogen by diffuse reflectance FTIR spectroscopy
journal, November 1989
- Hirata, Toshiya
- Applied Surface Science, Vol. 40, Issue 1-2
Recent development of two-dimensional transition metal dichalcogenides and their applications
journal, April 2017
- Choi, Wonbong; Choudhary, Nitin; Han, Gang Hee
- Materials Today, Vol. 20, Issue 3
Nucleation and growth of molybdenum disulfide grown by thermal atomic layer deposition on metal oxides
journal, December 2022
- Soares, Jake; Letourneau, Steven; Lawson, Matthew
- Journal of Vacuum Science & Technology A, Vol. 40, Issue 6
Three-Dimensional Architectures Constructed from Transition-Metal Dichalcogenide Nanomaterials for Electrochemical Energy Storage and Conversion
journal, December 2017
- Yun, Qinbai; Lu, Qipeng; Zhang, Xiao
- Angewandte Chemie International Edition, Vol. 57, Issue 3
Structural Evolution of Molybdenum Disulfide Prepared by Atomic Layer Deposition for Realization of Large Scale Films in Microelectronic Applications
journal, July 2018
- Letourneau, Steven; Young, Matthias J.; Bedford, Nicholas M.
- ACS Applied Nano Materials, Vol. 1, Issue 8
Defect-moderated oxidative etching of MoS 2
journal, October 2019
- Maguire, Pierce; Jadwiszczak, Jakub; O’Brien, Maria
- Journal of Applied Physics, Vol. 126, Issue 16
Photoluminescence from Chemically Exfoliated MoS2
journal, December 2011
- Eda, Goki; Yamaguchi, Hisato; Voiry, Damien
- Nano Letters, Vol. 11, Issue 12, p. 5111-5116
From Bulk to Monolayer MoS2: Evolution of Raman Scattering
journal, January 2012
- Li, Hong; Zhang, Qing; Yap, Chin Chong Ray
- Advanced Functional Materials, Vol. 22, Issue 7
Total absorption of WO3/WS2 stacked thin films in middle infrared light
journal, December 2019
- Su, Weitao; Wang, Yinliang; Chen, Fei
- Infrared Physics & Technology, Vol. 103
Controllable etching of MoS2 basal planes for enhanced hydrogen evolution through the formation of active edge sites
journal, July 2018
- Wang, Zegao; Li, Qiang; Xu, Haoxiang
- Nano Energy, Vol. 49
Electronic structure of a single MoS2 monolayer
journal, May 2012
- Kadantsev, Eugene S.; Hawrylak, Pawel
- Solid State Communications, Vol. 152, Issue 10
Channel Length Scaling of MoS 2 MOSFETs
journal, September 2012
- Liu, Han; Neal, Adam T.; Ye, Peide D.
- ACS Nano, Vol. 6, Issue 10
Controlled Layer-by-Layer Etching of MoS 2
journal, July 2015
- Lin, TaiZhe; Kang, BaoTao; Jeon, MinHwan
- ACS Applied Materials & Interfaces, Vol. 7, Issue 29
SF4 as the Fluorination Reactant for Al2O3 and VO2 Thermal Atomic Layer Etching
journal, April 2019
- Gertsch, Jonas C.; Cano, Austin M.; Bright, Victor M.
- Chemistry of Materials, Vol. 31, Issue 10
Atomic Layer Etching Mechanism of MoS 2 for Nanodevices
journal, March 2017
- Kim, Ki Seok; Kim, Ki Hyun; Nam, Yeonsig
- ACS Applied Materials & Interfaces, Vol. 9, Issue 13
Oxidation and oxidative vapor-phase etching of few-layer MoS 2
journal, March 2017
- Walter, Timothy N.; Kwok, Frances; Simchi, Hamed
- Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 35, Issue 2
Thermal Selective Vapor Etching of TiO 2 : Chemical Vapor Etching via WF 6 and Self-Limiting Atomic Layer Etching Using WF 6 and BCl 3
journal, August 2017
- Lemaire, Paul C.; Parsons, Gregory N.
- Chemistry of Materials, Vol. 29, Issue 16
The indirect to direct band gap transition in multilayered MoS 2 as predicted by screened hybrid density functional theory
journal, December 2011
- Ellis, Jason K.; Lucero, Melissa J.; Scuseria, Gustavo E.
- Applied Physics Letters, Vol. 99, Issue 26
Thermal atomic layer etching: A review
journal, May 2021
- Fischer, Andreas; Routzahn, Aaron; George, Steven M.
- Journal of Vacuum Science & Technology A, Vol. 39, Issue 3
Electronics and optoelectronics of two-dimensional transition metal dichalcogenides
journal, November 2012
- Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras
- Nature Nanotechnology, Vol. 7, Issue 11, p. 699-712
The Era of Atomic Crafting
journal, March 2019
- Lee, Han-Bo-Ram
- Chemistry of Materials, Vol. 31, Issue 5
Thermally Driven Self-Limiting Atomic Layer Etching of Metallic Tungsten Using WF6 and O2
journal, February 2018
- Xie, Wenyi; Lemaire, Paul C.; Parsons, Gregory N.
- ACS Applied Materials & Interfaces, Vol. 10, Issue 10
Surface oxidation energetics and kinetics on MoS 2 monolayer
journal, April 2015
- Kc, Santosh; Longo, Roberto C.; Wallace, Robert M.
- Journal of Applied Physics, Vol. 117, Issue 13
Few-Layer MoS 2 : A Promising Layered Semiconductor
journal, April 2014
- Ganatra, Rudren; Zhang, Qing
- ACS Nano, Vol. 8, Issue 5
Atomic Layer Etching of Al2O3 Using Sequential, Self-Limiting Thermal Reactions with Sn(acac)2 and Hydrogen Fluoride
journal, January 2015
- Lee, Younghee; George, Steven M.
- ACS Nano, Vol. 9, Issue 2
Atomic‐Layer‐Deposited Amorphous MoS 2 for Durable and Flexible Li–O 2 Batteries
journal, May 2019
- Song, Ming; Tan, Hua; Li, Xianglin
- Small Methods, Vol. 4, Issue 6
ZrO2 Monolayer as a Removable Etch Stop Layer for Thermal Al2O3 Atomic Layer Etching Using Hydrogen Fluoride and Trimethylaluminum
journal, November 2020
- Zywotko, David R.; Zandi, Omid; Faguet, Jacques
- Chemistry of Materials, Vol. 32, Issue 23
Enhanced etching of sapphire damaged by ion implantation
journal, July 1998
- Dongzhu, Xie; Dezhang, Zhu; Haochang, Pan
- Journal of Physics D: Applied Physics, Vol. 31, Issue 14
Mechanisms of Thermal Atomic Layer Etching
journal, June 2020
- George, Steven M.
- Accounts of Chemical Research, Vol. 53, Issue 6
Atomic-layer soft plasma etching of MoS2
journal, January 2016
- Xiao, Shaoqing; Xiao, Peng; Zhang, Xuecheng
- Scientific Reports, Vol. 6, Issue 1
A comprehensive study on atomic layer deposition of molybdenum sulfide for electrochemical hydrogen evolution
journal, January 2016
- Kwon, Do Hyun; Jin, Zhenyu; Shin, Seokhee
- Nanoscale, Vol. 8, Issue 13
Remote Plasma Oxidation and Atomic Layer Etching of MoS 2
journal, July 2016
- Zhu, Hui; Qin, Xiaoye; Cheng, Lanxia
- ACS Applied Materials & Interfaces, Vol. 8, Issue 29
Synergistically creating sulfur vacancies in semimetal-supported amorphous MoS2 for efficient hydrogen evolution
journal, October 2019
- Li, Guowei; Fu, Chenguang; Wu, Jiquan
- Applied Catalysis B: Environmental, Vol. 254
Amorphous MoS2 as the cathode of lithium secondary batteries
journal, April 1995
- Miki, Yasuhiro; Nakazato, Daisuke; Ikuta, Hiromasa
- Journal of Power Sources, Vol. 54, Issue 2
Effect of crystallinity on thermal atomic layer etching of hafnium oxide, zirconium oxide, and hafnium zirconium oxide
journal, March 2020
- Murdzek, Jessica A.; George, Steven M.
- Journal of Vacuum Science & Technology A, Vol. 38, Issue 2