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Al2O3 Atomic Layer Deposition with Trimethylaluminum and Ozone Studied by in Situ Transmission FTIR Spectroscopy and Quadrupole Mass Spectrometry

Goldstein, David N., McCormick, Jarod A., George, Steven M.·2008·The Journal of Physical Chemistry C
DOI 10.1021/jp804296a
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Abstract

The atomic layer deposition (ALD) of Al 2 O 3 using sequential exposures of Al(CH 3 ) 3 and O 3 was studied by in situ transmission Fourier transform infrared (FTIR) spectroscopy and quadrupole mass spectrometry (QMS). The FTIR spectroscopy investigations of the surface reactions occurring during Al 2 O 3 ALD were performed on ZrO 2 particles for temperatures from 363 to 650 K. The FTIR spectra after Al(CH 3 ) 3 and ozone exposures showed that the ozone exposure removes surface AlCH 3 * species. The AlCH 3 * species were converted to AlOCH 3 * (methoxy), Al(OCHO)* (formate), Al(OCOOH)* (carbonate), and AlOH* (hydroxyl) species. The TMA exposure then removes these species and reestablishes the AlCH 3 * species. Repeating the TMA and O 3 exposures in a sequential reaction sequence progressively deposited the Al 2 O 3 ALD film as monitored by the increase in absorbance for bulk Al 2 O 3 infrared features. The identification of formate species was confirmed by separate formaldehyde adsorption experiments. The formate species were temperature dependent and were nearly absent at temperatures ≥650 K. QMS analysis of the gas phase species revealed that the TMA reaction produced CH 4 . The ozone reaction produced mainly CH 4 with small amounts of C 2 H 4 (ethylene), CO, and CO 2 . Transmission electron microscopy (TEM) was also used to examine the Al 2 O 3 ALD films deposited on the ZrO 2 particles. These TEM images observed conformal Al 2 O 3 ALD films with thicknesses that were consistent with an Al 2 O 3 ALD growth rate of 1.1 Å/cycle. The surface species after the O 3 exposures and the mass spectrometry results lead to a very different mechanism for Al 2 O 3 ALD growth using TMA and O 3 compared with Al 2 O 3 ALD using TMA and H 2 O.

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Metadata

Authors
Goldstein, D. N., McCormick, J. A., & George, S. M.
Affiliations
University of Colorado Boulder (US)
Corresponding author
George, Steven M.
ORCID
George, Steven M.
Venue
The Journal of Physical Chemistry C
Publisher
American Chemical Society (ACS)
Published
2008-11-13
Volume
112
Issue
49
Pages
19530-19539
ISSN
  • 1932-7447 (ISSN-L)
  • 1932-7455
DOI
10.1021/jp804296a
OpenAlex
W2128659391
Cited by
330
References
0
Citations by year
2026: 12 · 2025: 15 · 2024: 17 · 2023: 13 · 2022: 17 · 2021: 25 · 2020: 16 · 2019: 16 · 2018: 16 · 2017: 26 · 2016: 26 · 2015: 19 · 2014: 26 · 2013: 32 · 2012: 17
FWCI
11.08
Type
journal article
Language
en
Open access
closed
Locations
The Journal of Physical Chemistry C (publishedVersion)
Funders
Division of Chemistry
Topics
  • Physical Sciences › Engineering › Electrical and Electronic Engineering › Semiconductor materials and devices
  • Physical Sciences › Materials Science › Electronic, Optical and Magnetic Materials › Copper Interconnects and Reliability
  • Physical Sciences › Materials Science › Materials Chemistry › Advanced Materials and Semiconductor Technologies
Keywords
Al2O3 atomic layer deposition, trimethylaluminum, ozone, surface reaction mechanism, surface species, formate species, methoxy species, hydroxyl species, ZrO2 particles, growth rate (crystal and thin-film growth), conformal thin films, formaldehyde adsorption

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