Molecular Layer Etching of Metalcone Films Using Lithium Organic Salts and Trimethylaluminum

Young, Matthias J.; Choudhury, Devika; Letourneau, Steven; Mane, Anil; Yanguas-Gil, Angel; Elam, Jeffrey W.

doi:10.1021/acs.chemmater.9b03627

Title: Molecular Layer Etching of Metalcone Films Using Lithium Organic Salts and Trimethylaluminum

Journal Article · Thu Jan 02 00:00:00 EST 2020 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.9b03627· OSTI ID:1606527

^[1]; Choudhury, Devika ^[2];

^[2]; Mane, Anil ^[2]; Yanguas-Gil, Angel ^[2];

^[2]

Argonne National Lab. (ANL), Argonne, IL (United States). Applied Materials Division; Univ. of Missouri, Columbia, MO (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Applied Materials Division

Advances in semiconductor device manufacturing are limited by our ability to precisely add and remove thin layers of material in multistep fabrication processes. Recent reports on atomic layer etching (ALE) have provided the means for the precise removal of inorganic thin films deposited by atomic layer deposition (ALD), opening new avenues for nanoscale device design. Here, we report on a new technique for the precise removal of metal organic thin films deposited by molecular layer deposition (MLD), which we term molecular layer etching. This etching process employs sequential exposures of lithium organic salt (LOS) and trimethylaluminum (TMA) precursors to produce self-limiting etching behavior. We employ quartz crystal microbalance experiments to demonstrate (i) etching of alucone films preloaded with LOS upon TMA exposures and (ii) layer-by-layer etching of alucone films using alternating exposures of LOS and TMA. We also identify the selectivity of these etching mechanisms. We probe the mechanism for the layer-by-layer etching of alucone using a quartz crystal microbalance and Fourier transform infrared spectroscopy and identify that the etching proceeds via heterolytic cleaving of Al-O bonds in alucone upon LOS exposure followed by methylation to produce volatile species upon TMA exposure. The etching process results in the removal of 0.4 nm/cycle of alucone at 160 °C and up to 3.6 nm/cycle of alucone at 266 °C in ex situ etching experiments on silicon wafers. This halogen-free etching process enables etching of MLD films and provides new fabrication pathways for the control of material geometries at the nanoscale.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Argonne National Lab. (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1606527

Journal Information:: Chemistry of Materials, Vol. 32, Issue 3; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 3 works

Citation information provided by
Web of Science

References (46)

Cramming more components onto integrated circuits, Reprinted from Electronics, volume 38, number 8, April 19, 1965, pp.114 ff. Moore, Gordon E. IEEE Solid-State Circuits Society Newsletter, Vol. 11, Issue 3 https://doi.org/10.1109/N-SSC.2006.4785860	journal	September 2006
Impact of the vertical SOI 'DELTA' structure on planar device technology Hisamoto, D.; Kaga, T.; Takeda, E. IEEE Transactions on Electron Devices, Vol. 38, Issue 6 https://doi.org/10.1109/16.81634	journal	June 1991
High-performance fully depleted silicon nanowire (diameter /spl les/ 5 nm) gate-all-around CMOS devices Singh, N.; Agarwal, A.; Bera, L. K. IEEE Electron Device Letters, Vol. 27, Issue 5 https://doi.org/10.1109/LED.2006.873381	journal	May 2006
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
Mechanism of Thermal Al ₂ O ₃ Atomic Layer Etching Using Sequential Reactions with Sn(acac) ₂ and HF Lee, Younghee; DuMont, Jaime W.; George, Steven M. Chemistry of Materials, Vol. 27, Issue 10 https://doi.org/10.1021/acs.chemmater.5b00300	journal	May 2015
Atomic Layer Etching of AlF ₃ Using Sequential, Self-Limiting Thermal Reactions with Sn(acac) ₂ and Hydrogen Fluoride Lee, Younghee; DuMont, Jaime W.; George, Steven M. The Journal of Physical Chemistry C, Vol. 119, Issue 45 https://doi.org/10.1021/acs.jpcc.5b07236	journal	November 2015
Trimethylaluminum as the Metal Precursor for the Atomic Layer Etching of Al ₂ O ₃ Using Sequential, Self-Limiting Thermal Reactions Lee, Younghee; DuMont, Jaime W.; George, Steven M. Chemistry of Materials, Vol. 28, Issue 9 https://doi.org/10.1021/acs.chemmater.6b00111	journal	April 2016
Atomic Layer Deposition of AlF ₃ Using Trimethylaluminum and Hydrogen Fluoride Lee, Younghee; DuMont, Jaime W.; Cavanagh, Andrew S. The Journal of Physical Chemistry C, Vol. 119, Issue 25 https://doi.org/10.1021/acs.jpcc.5b02625	journal	June 2015
Thermal Atomic Layer Etching of Silicon Using O ₂ , HF, and Al(CH ₃ ) ₃ as the Reactants Abdulagatov, Aziz I.; George, Steven M. Chemistry of Materials, Vol. 30, Issue 23 https://doi.org/10.1021/acs.chemmater.8b02745	journal	November 2018
Thermal Atomic Layer Etching of SiO ₂ by a “Conversion-Etch” Mechanism Using Sequential Reactions of Trimethylaluminum and Hydrogen Fluoride DuMont, Jaime W.; Marquardt, Amy E.; Cano, Austin M. ACS Applied Materials & Interfaces, Vol. 9, Issue 11 https://doi.org/10.1021/acsami.7b01259	journal	March 2017
Atomic Layer Etching of HfO ₂ Using Sequential, Self-Limiting Thermal Reactions with Sn(acac) ₂ and HF Lee, Younghee; DuMont, Jaime W.; George, Steven M. ECS Journal of Solid State Science and Technology, Vol. 4, Issue 6 https://doi.org/10.1149/2.0041506jss	journal	January 2015
Thermal Atomic Layer Etching of ZnO by a “Conversion-Etch” Mechanism Using Sequential Exposures of Hydrogen Fluoride and Trimethylaluminum Zywotko, David R.; George, Steven M. Chemistry of Materials, Vol. 29, Issue 3 https://doi.org/10.1021/acs.chemmater.6b04529	journal	January 2017
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 Lemaire, Paul C.; Parsons, Gregory N. Chemistry of Materials, Vol. 29, Issue 16 https://doi.org/10.1021/acs.chemmater.7b00985	journal	August 2017
Thermal Atomic Layer Etching of Titanium Nitride Using Sequential, Self-Limiting Reactions: Oxidation to TiO ₂ and Fluorination to Volatile TiF ₄ Lee, Younghee; George, Steven M. Chemistry of Materials, Vol. 29, Issue 19 https://doi.org/10.1021/acs.chemmater.7b02286	journal	October 2017
WO ₃ and W Thermal Atomic Layer Etching Using “Conversion-Fluorination” and “Oxidation-Conversion-Fluorination” Mechanisms Johnson, Nicholas R.; George, Steven M. ACS Applied Materials & Interfaces, Vol. 9, Issue 39 https://doi.org/10.1021/acsami.7b09161	journal	April 2017
Prospects for Thermal Atomic Layer Etching Using Sequential, Self-Limiting Fluorination and Ligand-Exchange Reactions George, Steven M.; Lee, Younghee ACS Nano, Vol. 10, Issue 5 https://doi.org/10.1021/acsnano.6b02991	journal	May 2016
Selectivity in Thermal Atomic Layer Etching Using Sequential, Self-Limiting Fluorination and Ligand-Exchange Reactions Lee, Younghee; Huffman, Craig; George, Steven M. Chemistry of Materials, Vol. 28, Issue 21 https://doi.org/10.1021/acs.chemmater.6b02543	journal	October 2016
Polymer thin films prepared by vapor deposition Kubono, Atsushi; Okui, Norimasa Progress in Polymer Science, Vol. 19, Issue 3 https://doi.org/10.1016/0079-6700(94)90001-9	journal	January 1994
Surface Chemistry for Molecular Layer Deposition of Organic and Hybrid Organic−Inorganic Polymers George, Steven M.; Yoon, Byunghoon; Dameron, Arrelaine A. Accounts of Chemical Research, Vol. 42, Issue 4 https://doi.org/10.1021/ar800105q	journal	April 2009
Polymer films formed with monolayer growth steps by molecular layer deposition Yoshimura, Tetsuzo; Tatsuura, Satoshi; Sotoyama, Wataru Applied Physics Letters, Vol. 59, Issue 4 https://doi.org/10.1063/1.105415	journal	July 1991
Molecular Layer Deposition of Alucone Polymer Films Using Trimethylaluminum and Ethylene Glycol Dameron, A. A.; Seghete, D.; Burton, B. B. Chemistry of Materials, Vol. 20, Issue 10 https://doi.org/10.1021/cm7032977	journal	May 2008
Deposition of Organic- Inorganic Hybrid Materials by Atomic Layer Deposition Nilsen, Ola; Klepper, Karina; Nielsen, Heidi 214th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.2979975	conference	January 2008
Molecular Layer Deposition of Hybrid Organic-Inorganic Polymer Films using Diethylzinc and Ethylene Glycol Yoon, Byunghoon; O'Patchen, Jennifer L.; Seghete, Dragos Chemical Vapor Deposition, Vol. 15, Issue 4-6 https://doi.org/10.1002/cvde.200806756	journal	June 2009
Growth and Properties of Hybrid Organic-Inorganic Metalcone Films Using Molecular Layer Deposition Techniques Lee, Byoung H.; Yoon, Byunghoon; Abdulagatov, Aziz I. Advanced Functional Materials, Vol. 23, Issue 5 https://doi.org/10.1002/adfm.201200370	journal	September 2012
Alucone Alloys with Tunable Properties Using Alucone Molecular Layer Deposition and Al ₂ O ₃ Atomic Layer Deposition Lee, Byoung H.; Yoon, Byunghoon; Anderson, Virginia R. The Journal of Physical Chemistry C, Vol. 116, Issue 5 https://doi.org/10.1021/jp209003h	journal	February 2012
Gas diffusion barrier characteristics of Al2O3/alucone films formed using trimethylaluminum, water and ethylene glycol for organic light emitting diode encapsulation Park, Minwoo; Oh, Seungsik; Kim, Hoonbae Thin Solid Films, Vol. 546 https://doi.org/10.1016/j.tsf.2013.05.017	journal	November 2013
Viscous flow reactor with quartz crystal microbalance for thin film growth by atomic layer deposition Elam, J. W.; Groner, M. D.; George, S. M. Review of Scientific Instruments, Vol. 73, Issue 8, p. 2981-2987 https://doi.org/10.1063/1.1490410	journal	August 2002
Quartz Crystal Microbalance Studies of Al ₂ O ₃ Atomic Layer Deposition Using Trimethylaluminum and Water at 125 °C ^† Wind, R. A.; George, S. M. The Journal of Physical Chemistry A, Vol. 114, Issue 3 https://doi.org/10.1021/jp9049268	journal	January 2010
Mechanistic Study of Lithium Aluminum Oxide Atomic Layer Deposition Comstock, David J.; Elam, Jeffrey W. The Journal of Physical Chemistry C, Vol. 117, Issue 4 https://doi.org/10.1021/jp308828p	journal	January 2013
Vapor-Phase Atomic-Controllable Growth of Amorphous Li ₂ S for High-Performance Lithium–Sulfur Batteries Meng, Xiangbo; Comstock, David J.; Fister, Timothy T. ACS Nano, Vol. 8, Issue 10 https://doi.org/10.1021/nn505480w	journal	October 2014
Atomic Layer Deposition of Metal Fluorides Using HF–Pyridine as the Fluorine Precursor Lee, Younghee; Sun, Huaxing; Young, Matthias J. Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.5b04360	journal	March 2016
Acidity measurements on pyridines in tetrahydrofuran using lithiated silylamines Fraser, Robert R.; Mansour, Tarek S.; Savard, Sylvain The Journal of Organic Chemistry, Vol. 50, Issue 17 https://doi.org/10.1021/jo00217a050	journal	August 1985
Quantitative measure of .alpha.-silyl carbanion stabilization. The electron affinity of (trimethylsilyl)methyl radical Wetzel, Donna M.; Brauman, John I. Journal of the American Chemical Society, Vol. 110, Issue 25 https://doi.org/10.1021/ja00233a008	journal	December 1988
Hindered Brønsted bases as Lewis base catalysts Tabassum, Sobia; Sereda, Oksana; Reddy, Peddiahgari Vasu Govardhana Organic & Biomolecular Chemistry, Vol. 7, Issue 19 https://doi.org/10.1039/b908899g	journal	January 2009
Molecular Hybrid Structures by Atomic Layer Deposition - Deposition of Alq ₃ , Znq ₂ and Tiq ₄ (q = 8-hydroxyquinoline) Nilsen, Ola; Haug, Kristoffer Robin; Finstad, Terje Chemical Vapor Deposition, Vol. 19, Issue 4-6 https://doi.org/10.1002/cvde.201207043	journal	May 2013
Atomic layer deposition of organic–inorganic hybrid materials based on saturated linear carboxylic acids Klepper, Karina Barnholt; Nilsen, Ola; Hansen, Per-Anders Dalton Transactions, Vol. 40, Issue 17 https://doi.org/10.1039/c0dt01716g	journal	January 2011
Nucleation and Growth during Al ₂ O ₃ Atomic Layer Deposition on Polymers Wilson, C. A.; Grubbs, R. K.; George, S. M. Chemistry of Materials, Vol. 17, Issue 23 https://doi.org/10.1021/cm050704d	journal	November 2005
Modulation of the Growth Per Cycle in Atomic Layer Deposition Using Reversible Surface Functionalization Yanguas-Gil, Angel; Libera, Joseph A.; Elam, Jeffrey W. Chemistry of Materials, Vol. 25, Issue 24 https://doi.org/10.1021/cm4029098	journal	December 2013
Tert-butyl alcohol—matrix i.r. spectra and vibrational assignment Korppi-Tommola, Jouko Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 34, Issue 11 https://doi.org/10.1016/0584-8539(78)80130-5	journal	January 1978
A gas-phase Raman study of trimethylaluminium and trimethylboron monomers O'Brien, R. J.; Ozin, G. A. Journal of the Chemical Society A: Inorganic, Physical, Theoretical https://doi.org/10.1039/J19710001136	journal	January 1971
Infrared matrix isolation spectroscopy of trimethylgallium, trimethylaluminium and triethylaluminium Kvisle, S.; Rytter, E. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 40, Issue 10 https://doi.org/10.1016/0584-8539(84)80153-1	journal	January 1984
Vibrational spectra of monomeric trimethylaluminium and trimethylgallium Atiya, Ghalib A.; Grady, Andrew S.; Russell, Douglas K. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 47, Issue 3-4 https://doi.org/10.1016/0584-8539(91)80124-2	journal	January 1991
New Insight into the Mechanism of Sequential Infiltration Synthesis from Infrared Spectroscopy Biswas, Mahua; Libera, Joseph A.; Darling, Seth B. Chemistry of Materials, Vol. 26, Issue 21 https://doi.org/10.1021/cm502427q	journal	October 2014
CH local modes in cyclobutene—I. FTIR studies 700–9000 cm−1 Baggott, J. E.; Clase, H. J.; Mills, I. M. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 42, Issue 2-3 https://doi.org/10.1016/0584-8539(86)80195-7	journal	January 1986
Slow Photoelectron Velocity-Map Imaging of the i -Methylvinoxide Anion ^† Yacovitch, Tara I.; Garand, Etienne; Neumark, Daniel M. The Journal of Physical Chemistry A, Vol. 114, Issue 42 https://doi.org/10.1021/jp101930b	journal	October 2010
Sequential Infiltration Synthesis of Electronic Materials: Group 13 Oxides via Metal Alkyl Precursors Waldman, Ruben Z.; Jeon, Nari; Mandia, David J. Chemistry of Materials, Vol. 31, Issue 14 https://doi.org/10.1021/acs.chemmater.9b01714	journal	June 2019

Similar Records

Molecular layer deposition of alucone films using trimethylaluminum and hydroquinone

Journal Article · Thu Jan 01 00:00:00 EST 2015 · Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films · OSTI ID:1606527

Choudhury, Devika; Mahuli, Neha

Rapid visible color change and physical swelling during water exposure in triethanolamine-metalcone films formed by molecular layer deposition

Journal Article · Fri Jan 15 00:00:00 EST 2016 · Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films · OSTI ID:1606527

Lemaire, Paul C.; Oldham, Christopher J.

Thermal Atomic Layer Etching of MoS ₂ Using MoF ₆ and H ₂ O

Journal Article · Thu Jan 12 00:00:00 EST 2023 · Chemistry of Materials · OSTI ID:1606527

Soares, Jake; Mane, Anil U.; Choudhury, Devika; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Etching
Thin films
Absorption
Precursors
Atomic layer deposition

Title: Molecular Layer Etching of Metalcone Films Using Lithium Organic Salts and Trimethylaluminum

Citation Formats

References (46)

Similar Records

Related Subjects