The mechanism for growth initiation on the nongrowth surface during area-selective atomic layer deposition (ALD) processes is not well understood. In this study, we examine the ALD of ZrO2 on a SiO2 surface functionalized with alkylated-aminosilane inhibitors delivered from the vapor phase. ZrO2 films were deposited by ALD using tetrakis(ethylmethylamino)zirconium(IV) with H2O as the coreactant. In situ surface infrared spectroscopy shows that aminosilane inhibitors react with almost all the surface —SiOH groups on the SiO2 surface by forming Si—O—Si bonds. In situ four-wavelength ellipsometry shows that no ZrO2 growth occurs on the functionalized SiO2 during the first few ALD cycles, but growth eventually initiates after a few ALD cycles. We speculate that after repeated exposure of the functionalized SiO2 surface to Zr precursors, in the absence of surface —SiOH groups, growth initiates due to either reaction of the precursors with strained Si—O—Si bonds or through a strongly physisorbed state. These reaction pathways are usually not relevant in ALD reactions on the unprotected —SiOH-terminated SiO2 surface due to a higher activation energy barrier, but become relevant on the passivated surface as a result of repeated precursor exposure. Thus, this study highlights the importance of steric blocking of these higher activation energy barrier reaction pathways.
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Research Article|
March 08 2021
Mechanism for growth initiation on aminosilane-functionalized SiO2 during area-selective atomic layer deposition of ZrO2
Special Collection:
Atomic Layer Deposition (ALD)
Wanxing Xu
;
Wanxing Xu
1
Department of Chemical and Biological Engineering, Colorado School of Mines
, Golden, Colorado 80401
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Paul C. Lemaire;
Paul C. Lemaire
2
Lam Research Corporation
, 11155 SW Leveton Drive, Tualatin, Oregon 97062
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Kashish Sharma;
Kashish Sharma
2
Lam Research Corporation
, 11155 SW Leveton Drive, Tualatin, Oregon 97062
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Ryan J. Gasvoda
;
Ryan J. Gasvoda
1
Department of Chemical and Biological Engineering, Colorado School of Mines
, Golden, Colorado 80401
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Dennis M. Hausmann;
Dennis M. Hausmann
a)
2
Lam Research Corporation
, 11155 SW Leveton Drive, Tualatin, Oregon 97062
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Sumit Agarwal
Sumit Agarwal
a)
1
Department of Chemical and Biological Engineering, Colorado School of Mines
, Golden, Colorado 80401
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a)
Electronic addresses: dennis.hausmann@lamresearch.com and sagarwal@mines.edu
Note: This paper is part of the 2021 Special Topic Collection on Atomic Layer Deposition (ALD).
J. Vac. Sci. Technol. A 39, 032402 (2021)
Article history
Received:
October 08 2020
Accepted:
February 09 2021
Citation
Wanxing Xu, Paul C. Lemaire, Kashish Sharma, Ryan J. Gasvoda, Dennis M. Hausmann, Sumit Agarwal; Mechanism for growth initiation on aminosilane-functionalized SiO2 during area-selective atomic layer deposition of ZrO2. J. Vac. Sci. Technol. A 1 May 2021; 39 (3): 032402. https://doi.org/10.1116/6.0000699
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