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Title: Direct Measurements of Half-Cycle Reaction Heats during Atomic Layer Deposition by Calorimetry

Abstract

We introduce a new high-temperature adsorption calorimeter that approaches the ideal limit of a heat detector whereby the signal at any time is proportional to the heat power being delivered to the sample and prove its sensitivity for measuring pulse-to-pulse heats of half-reactions during atomic layer deposition (ALD) at 400 K. The heat dynamics of amorphous Al2O3 growth via sequential self-limiting surface reaction of trimethylaluminum (TMA) and H2O is clearly resolved. Calibration enables quantitation of the exothermic TMA and H2O half-reactions with high precision, -343 kJ/mol TMA and -251 kJ/mol H2O, respectively. A time resolution better than 1 ms is demonstrated, allowing for the deconvolution of at least two distinct surface reactions during TMA microdosing. It is further demonstrated that this method can provide the heat of reaction versus extent of reaction during each precursors half-reaction, thus providing even richer mechanistic information on the surface processes involved. The broad applicability of this novel calorimeter is demonstrated through excellent signal-to-noise ratios of less exothermic ALD half-reactions to produce TiO2 and MnO.

Authors:
 [1];  [2]; ORCiD logo [3];  [4]; ORCiD logo [4]
  1. Department of Chemical Engineering, University of Washington, Seattle, Washington 98195, United States
  2. Department of Chemistry, University of Washington, Seattle, Washington 98195, United States
  3. Department of Chemical Engineering, University of Washington, Seattle, Washington 98195, United States; Department of Chemistry, University of Washington, Seattle, Washington 98195, United States
  4. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1398132
Alternate Identifier(s):
OSTI ID: 1411036; OSTI ID: 1414910
Grant/Contract Number:
AC02-06CH11357; SC0012702
Resource Type:
Journal Article: Published Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 20; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lownsbury, James M., Gladden, James A., Campbell, Charles T., Kim, In Soo, and Martinson, Alex B. F.. Direct Measurements of Half-Cycle Reaction Heats during Atomic Layer Deposition by Calorimetry. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b01491.
Lownsbury, James M., Gladden, James A., Campbell, Charles T., Kim, In Soo, & Martinson, Alex B. F.. Direct Measurements of Half-Cycle Reaction Heats during Atomic Layer Deposition by Calorimetry. United States. doi:10.1021/acs.chemmater.7b01491.
Lownsbury, James M., Gladden, James A., Campbell, Charles T., Kim, In Soo, and Martinson, Alex B. F.. Thu . "Direct Measurements of Half-Cycle Reaction Heats during Atomic Layer Deposition by Calorimetry". United States. doi:10.1021/acs.chemmater.7b01491.
@article{osti_1398132,
title = {Direct Measurements of Half-Cycle Reaction Heats during Atomic Layer Deposition by Calorimetry},
author = {Lownsbury, James M. and Gladden, James A. and Campbell, Charles T. and Kim, In Soo and Martinson, Alex B. F.},
abstractNote = {We introduce a new high-temperature adsorption calorimeter that approaches the ideal limit of a heat detector whereby the signal at any time is proportional to the heat power being delivered to the sample and prove its sensitivity for measuring pulse-to-pulse heats of half-reactions during atomic layer deposition (ALD) at 400 K. The heat dynamics of amorphous Al2O3 growth via sequential self-limiting surface reaction of trimethylaluminum (TMA) and H2O is clearly resolved. Calibration enables quantitation of the exothermic TMA and H2O half-reactions with high precision, -343 kJ/mol TMA and -251 kJ/mol H2O, respectively. A time resolution better than 1 ms is demonstrated, allowing for the deconvolution of at least two distinct surface reactions during TMA microdosing. It is further demonstrated that this method can provide the heat of reaction versus extent of reaction during each precursors half-reaction, thus providing even richer mechanistic information on the surface processes involved. The broad applicability of this novel calorimeter is demonstrated through excellent signal-to-noise ratios of less exothermic ALD half-reactions to produce TiO2 and MnO.},
doi = {10.1021/acs.chemmater.7b01491},
journal = {Chemistry of Materials},
number = 20,
volume = 29,
place = {United States},
year = {Thu Oct 05 00:00:00 EDT 2017},
month = {Thu Oct 05 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.chemmater.7b01491

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  • We introduce a new high-temperature adsorption calorimeter that approaches the ideal limit of a heat detector whereby the signal at any time is proportional to the heat power being delivered to the sample and prove its sensitivity for measuring pulse-to-pulse heats of half-reactions during atomic layer deposition (ALD) at 400 K. The heat dynamics of amorphous Al2O3 growth via sequential self-limiting surface reaction of trimethylaluminum (TMA) and H2O is clearly resolved. Calibration enables quantitation of the exothermic TMA and H2O half-reactions with high precision, -343 kJ/mol TMA and -251 kJ/mol H2O, respectively. A time resolution better than 1 ms ismore » demonstrated, allowing for the deconvolution of at least two distinct surface reactions during TMA microdosing. It is further demonstrated that this method can provide the heat of reaction versus extent of reaction during each precursors half-reaction, thus providing even richer mechanistic information on the surface processes involved. The broad applicability of this novel calorimeter is demonstrated through excellent signal-to-noise ratios of less exothermic ALD half-reactions to produce TiO2 and MnO.« less
  • Here, we introduce a new high-temperature adsorption calorimeter that approaches the ideal limit of a heat detector whereby the signal at any time is proportional to the heat power being delivered to the sample and prove its sensitivity for measuring pulse-to-pulse heats of half-reactions during atomic layer deposition (ALD) at 400 K. The heat dynamics of amorphous Al 2O 3 growth via sequential self-limiting surface reaction of trimethylaluminum (TMA) and H 2O is clearly resolved. Calibration enables quantitation of the exothermic TMA and H 2O half-reactions with high precision, -343 kJ/mol TMA and -251 kJ/mol H 2O, respectively. A timemore » resolution better than 1 ms is demonstrated, allowing for the deconvolution of at least two distinct surface reactions during TMA microdosing. It is further demonstrated that this method can provide the heat of reaction versus extent of reaction during each precursor’s half-reaction, thus providing even richer mechanistic information on the surface processes involved. The broad applicability of this novel calorimeter is demonstrated through excellent signal-to-noise ratios of less exothermic ALD half-reactions to produce TiO 2 and MnO.« less
  • In-situ monochromatic x-ray photoelectron spectroscopy, low energy electron diffraction, ion scattering spectroscopy, and transmission electron microscopy are used to examine the GaSb(100) surfaces grown by molecular beam epitaxy after thermal desorption of a protective As or Sb layer and subsequent atomic layer deposition (ALD) of Al{sub 2}O{sub 3}. An antimony protective layer is found to be more favorable compared to an arsenic capping layer as it prevents As alloys from forming with the GaSb substrate. The evolution of oxide free GaSb/Al{sub 2}O{sub 3} interface is investigated by “half-cycle” ALD reactions of trimethyl aluminum and deionized water.
  • A half cycle study of plasma enhanced atomic layer deposited (PEALD) Al{sub 2}O{sub 3} on AlGaN is investigated using in situ X-ray photoelectron spectroscopy, low energy ion scattering, and ex situ electrical characterizations. A faster nucleation or growth is detected from PEALD relative to purely thermal ALD using an H{sub 2}O precursor. The remote O{sub 2} plasma oxidizes the AlGaN surface slightly at the initial stage, which passivates the surface and reduces the OFF-state leakage. This work demonstrates that PEALD is a useful strategy for Al{sub 2}O{sub 3} growth on AlGaN/GaN devices.
  • An in situ half-cycle atomic layer deposition/X-ray photoelectron spectroscopy (XPS) study was conducted in order to investigate the evolution of the HfO{sub 2} dielectric interface with GaSb(100) surfaces after sulfur passivation and HCl etching, designed to remove the native oxides. With the first pulses of tetrakis(dimethylamido)hafnium(IV) and water, a decrease in the concentration of antimony oxide states present on the HCl-etched surface is observed, while antimony sulfur states diminished below the XPS detection limit on sulfur passivated surface. An increase in the amount of gallium oxide/sulfide is seen, suggesting oxygen or sulfur transfers from antimony to gallium during antimony oxides/sulfidesmore » decomposition.« less