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

Lownsbury, James M.; Gladden, James A.; Campbell, Charles T.; Kim, In Soo; Martinson, Alex B. F.

doi:10.1021/acs.chemmater.7b01491

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 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 TiO2 and MnO.

Authors:

Lownsbury, James M. ^[1]; Gladden, James A. ^[2];

^[3]; Kim, In Soo ^[4];

^[4]

Department of Chemical Engineering, University of Washington, Seattle, Washington 98195, United States
Department of Chemistry, University of Washington, Seattle, Washington 98195, United States
Department of Chemical Engineering, University of Washington, Seattle, Washington 98195, United States, Department of Chemistry, University of Washington, Seattle, Washington 98195, United States
Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States

Publication Date:: Thu Oct 05 00:00:00 EDT 2017

Research Org.:: Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Minnesota, Minneapolis, MN (United States)

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

OSTI Identifier:: 1398132

Alternate Identifier(s):: OSTI ID: 1411036; OSTI ID: 1414910; OSTI ID: 1507564

Grant/Contract Number:: SC0012702; AC02-06CH11357

Resource Type:: Published Article

Journal Name:: Chemistry of Materials

Additional Journal Information:: Journal Name: Chemistry of Materials Journal Volume: 29 Journal Issue: 20; Journal ID: ISSN 0897-4756

Publisher:: American Chemical Society

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.

Copy to clipboard


                    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.  https://doi.org/10.1021/acs.chemmater.7b01491

Copy to clipboard


                    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.  https://doi.org/10.1021/acs.chemmater.7b01491.

Copy to clipboard


                    
@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 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 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}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1021/acs.chemmater.7b01491

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

Three-dimensional electroactive ZnO nanomesh directly derived from hierarchically self-assembled block copolymer thin films
journal, January 2019

Subramanian, Ashwanth; Doerk, Gregory; Kisslinger, Kim
Nanoscale, Vol. 11, Issue 19
DOI: 10.1039/c9nr00206e

Atomic layer deposition of functional multicomponent oxides
journal, November 2019

Coll, Mariona; Napari, Mari
APL Materials, Vol. 7, Issue 11
DOI: 10.1063/1.5113656

Suppressing the Photocatalytic Activity of TiO2 Nanoparticles by Extremely Thin Al2O3 Films Grown by Gas-Phase Deposition at Ambient Conditions
journal, January 2018

Guo, Jing; Van Bui, Hao; Valdesueiro, David
Nanomaterials, Vol. 8, Issue 2
DOI: 10.3390/nano8020061

Similar Records in DOE PAGES and OSTI.GOV collections:

Atomic Layer Deposition for Materials-Based H2 Storage: Opportunities and Limitations

Conference Leick, Noemi ; Braunecker, Wade A. ; Mow, Rachel E. ; ...

The transportation demands in our growing hydrogen (H2) economy requires robust storage systems. The current commercially implemented technology in fuel cell cars relies on the well-established technology of hydrogen gas compressed to 350-700 bar, depending on the application. The compressed gas tanks in use today are bulky and cost intensive. To address this challenge, material-based storage is one of the long-term alternatives considered and constitutes the focus of this talk. Material-based storage is broadly defined as hydrogen bound to solid materials, with its binding strength varying from physisorption to porous materials, such as zeolites and metal organic frameworks, to chemisorptionmore »« less
Full Text Available
Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions

Journal Article Bielinski, Ashley R. ; Kamphaus, Ethan P. ; Cheng, Lei ; ... - Journal of the American Chemical Society

We report that atomic layer deposition (ALD) is a surface synthesis technique that is characterized by self-limiting reactions between gas-phase precursors and a solid substrate. Although ALD processes have been demonstrated that span the periodic table, a greater understanding of the surface chemistry that affords ALD is necessary to enable greater precision, including area- and site-selective growth. We offer new insight into the thermodynamics and kinetics of the trimethylaluminum (TMA) and H₂O ALD half-reactions with calibrated and time-resolved in situ pyroelectric calorimetry. The half-reactions produce 3.46 and 2.76 eV/Al heat, respectively, which is greater than the heat predicted by computationalmore »« less
https://doi.org/10.1021/jacs.2c05460

Full Text Available
Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn₂O₄ Lithium-Ion Battery Cathodes

Journal Article Warburton, Robert E. ; Young, Matthias J. ; Letourneau, Steven ; ... - Chemistry of Materials

Protective coatings have been shown to effectively suppress Mn ion dissolution from the spinel LiMn₂O₄ lithium-ion battery cathode by stabilizing the surface against undesired side reactions with the electrolyte. In spite of extensive study, however, there remains a lack of atomic-scale understanding of how such coatings are deposited, and no molecular-level descriptor to predict trends in deposition mechanisms has been identified. We have recently shown that Al₂O₃ coatings grown by atomic layer deposition (ALD) with alternating trimethylaluminum (TMA) and water exposures exhibit submonolayer growth because of precursor decomposition on the lithium manganate spinel (LMO) surface during early ALD pulses. Inmore »« less
https://doi.org/10.1021/acs.chemmater.9b03809

Full Text Available
Trimethylaluminum and Oxygen Atomic Layer Deposition on Hydroxyl-Free Cu(111)

Journal Article Gharachorlou, Amir ; Detwiler, Michael D. ; Gu, Xiang-Kui ; ... - ACS Applied Materials and Interfaces

Atomic layer deposition (ALD) of alumina using trimethylaluminum (TMA) has technological importance in microelectronics. This process has demonstrated a high potential in applications of protective coatings on Cu surfaces for control of diffusion of Cu in Cu₂S films in photovoltaic devices and sintering of Cu-based nanoparticles in liquid phase hydrogenation reactions. With this motivation in mind, the reaction between TMA and oxygen was investigated on Cu(111) and Cu₂O/Cu(111) surfaces. TMA did not adsorb on the Cu(111) surface, a result consistent with density functional theory (DFT) calculations predicting that TMA adsorption and decomposition are thermodynamically unfavorable on pure Cu(111). On themore »« less
Cited by 37
https://doi.org/10.1021/acsami.5b03598
Measuring enthalpies of formation using thick multilayer foils and differential scanning calorimetry

Conference Weihs, T P ; Barbee, Jr, T W ; Wall, M A

The ability to measure formation enthalpies of compounds at relatively low temperatures using thick multilayer foils and differential scanning calorimetry is demonstrated. Cu/Zr and Al/Zr multilayers were deposited onto Si and glass substrates using a planetary, magnetron source sputtering system. The as-deposited foils were removed from their substrates and heated from 50 to 725C in a differential scanning calorimeter (DSC). The Cu/Zr samples, which are all Cu-rich, showed three distinct, reproducible, and exothermic solid state reactions. The heats from the first two reactions were summed and analyzed to measure 14.3{plus_minus}0.3 kJ/mol for Cu{sub 51}Zr{sub 14}`s enthalpy of formation. This quantitymore »« less
Full Text Available

Similar Records

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

Abstract

Citation Formats

Three-dimensional electroactive ZnO nanomesh directly derived from hierarchically self-assembled block copolymer thin films journal, January 2019

Atomic layer deposition of functional multicomponent oxides journal, November 2019

Suppressing the Photocatalytic Activity of TiO2 Nanoparticles by Extremely Thin Al2O3 Films Grown by Gas-Phase Deposition at Ambient Conditions journal, January 2018

Three-dimensional electroactive ZnO nanomesh directly derived from hierarchically self-assembled block copolymer thin films
journal, January 2019

Atomic layer deposition of functional multicomponent oxides
journal, November 2019

Suppressing the Photocatalytic Activity of TiO2 Nanoparticles by Extremely Thin Al2O3 Films Grown by Gas-Phase Deposition at Ambient Conditions
journal, January 2018