Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides

Matthew S. Weimer, In Soo Kim, Peijun Guo, Richard D Schaller, Alex B.F. Martinson, Adam S. Hock

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

We describe the use of a vanadium 3+ precursor for atomic layer deposition (ALD) of thin films that span the common oxidation states of vanadium oxides. Self-limiting surface synthesis of V2O3, VO2, and V2O5 are realized through four distinct reaction mechanisms accessed via judicious choice of oxygen ALD partners. In situ quartz crystal microbalance and quadrupole mass spectrometry were used to study the reaction mechanism of the vanadium precursor with O3, H2O2, H2O/O2, and H2O2/H2. A clear distinction between nonoxidative protic ligand exchange and metal oxidation is demonstrated through sequential surface reactions with different nonmetal precursors. This synergistic effect provides greater control of the resultant metal species in the film, as well as reactive surface species during growth. In an extension of this approach, we introduce oxidation state control through reducing equivalents of H2 gas. When H2 is dosed after H2O2 during growth, amorphous films of VO2 are deposited that are readily crystallized with a low temperature anneal. These VO2 films show a temperature dependent Raman spectroscopy response in the expected range and consistent with the well-known phase-change behavior of VO2.

Original languageEnglish
Pages (from-to)6238-6244
Number of pages7
JournalChemistry of Materials
Volume29
Issue number15
DOIs
Publication statusPublished - Aug 8 2017

Fingerprint

Vanadium
Atomic layer deposition
Oxides
Oxidation
Metals
Nonmetals
Quartz crystal microbalances
Surface reactions
Amorphous films
Mass spectrometry
Raman spectroscopy
Ion exchange
Gases
Ligands
Oxygen
Thin films
Temperature

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides. / Weimer, Matthew S.; Kim, In Soo; Guo, Peijun; Schaller, Richard D; Martinson, Alex B.F.; Hock, Adam S.

In: Chemistry of Materials, Vol. 29, No. 15, 08.08.2017, p. 6238-6244.

Research output: Contribution to journalArticle

Weimer, Matthew S. ; Kim, In Soo ; Guo, Peijun ; Schaller, Richard D ; Martinson, Alex B.F. ; Hock, Adam S. / Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides. In: Chemistry of Materials. 2017 ; Vol. 29, No. 15. pp. 6238-6244.
@article{390355fef4bf47ff916e09ba0f3801b5,
title = "Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides",
abstract = "We describe the use of a vanadium 3+ precursor for atomic layer deposition (ALD) of thin films that span the common oxidation states of vanadium oxides. Self-limiting surface synthesis of V2O3, VO2, and V2O5 are realized through four distinct reaction mechanisms accessed via judicious choice of oxygen ALD partners. In situ quartz crystal microbalance and quadrupole mass spectrometry were used to study the reaction mechanism of the vanadium precursor with O3, H2O2, H2O/O2, and H2O2/H2. A clear distinction between nonoxidative protic ligand exchange and metal oxidation is demonstrated through sequential surface reactions with different nonmetal precursors. This synergistic effect provides greater control of the resultant metal species in the film, as well as reactive surface species during growth. In an extension of this approach, we introduce oxidation state control through reducing equivalents of H2 gas. When H2 is dosed after H2O2 during growth, amorphous films of VO2 are deposited that are readily crystallized with a low temperature anneal. These VO2 films show a temperature dependent Raman spectroscopy response in the expected range and consistent with the well-known phase-change behavior of VO2.",
author = "Weimer, {Matthew S.} and Kim, {In Soo} and Peijun Guo and Schaller, {Richard D} and Martinson, {Alex B.F.} and Hock, {Adam S.}",
year = "2017",
month = "8",
day = "8",
doi = "10.1021/acs.chemmater.7b01130",
language = "English",
volume = "29",
pages = "6238--6244",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "15",

}

TY - JOUR

T1 - Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides

AU - Weimer, Matthew S.

AU - Kim, In Soo

AU - Guo, Peijun

AU - Schaller, Richard D

AU - Martinson, Alex B.F.

AU - Hock, Adam S.

PY - 2017/8/8

Y1 - 2017/8/8

N2 - We describe the use of a vanadium 3+ precursor for atomic layer deposition (ALD) of thin films that span the common oxidation states of vanadium oxides. Self-limiting surface synthesis of V2O3, VO2, and V2O5 are realized through four distinct reaction mechanisms accessed via judicious choice of oxygen ALD partners. In situ quartz crystal microbalance and quadrupole mass spectrometry were used to study the reaction mechanism of the vanadium precursor with O3, H2O2, H2O/O2, and H2O2/H2. A clear distinction between nonoxidative protic ligand exchange and metal oxidation is demonstrated through sequential surface reactions with different nonmetal precursors. This synergistic effect provides greater control of the resultant metal species in the film, as well as reactive surface species during growth. In an extension of this approach, we introduce oxidation state control through reducing equivalents of H2 gas. When H2 is dosed after H2O2 during growth, amorphous films of VO2 are deposited that are readily crystallized with a low temperature anneal. These VO2 films show a temperature dependent Raman spectroscopy response in the expected range and consistent with the well-known phase-change behavior of VO2.

AB - We describe the use of a vanadium 3+ precursor for atomic layer deposition (ALD) of thin films that span the common oxidation states of vanadium oxides. Self-limiting surface synthesis of V2O3, VO2, and V2O5 are realized through four distinct reaction mechanisms accessed via judicious choice of oxygen ALD partners. In situ quartz crystal microbalance and quadrupole mass spectrometry were used to study the reaction mechanism of the vanadium precursor with O3, H2O2, H2O/O2, and H2O2/H2. A clear distinction between nonoxidative protic ligand exchange and metal oxidation is demonstrated through sequential surface reactions with different nonmetal precursors. This synergistic effect provides greater control of the resultant metal species in the film, as well as reactive surface species during growth. In an extension of this approach, we introduce oxidation state control through reducing equivalents of H2 gas. When H2 is dosed after H2O2 during growth, amorphous films of VO2 are deposited that are readily crystallized with a low temperature anneal. These VO2 films show a temperature dependent Raman spectroscopy response in the expected range and consistent with the well-known phase-change behavior of VO2.

UR - http://www.scopus.com/inward/record.url?scp=85027333410&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85027333410&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.7b01130

DO - 10.1021/acs.chemmater.7b01130

M3 - Article

AN - SCOPUS:85027333410

VL - 29

SP - 6238

EP - 6244

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 15

ER -