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The chemical structures of Co oxynitrides – in particular, interactions among N and O atoms bonded to the same cobalt – are of great importance for an array of catalytic and materials applications. X-ray diffraction (XRD), core and valence band X-ray photoelectron spectroscopy (XPS) and plane wave density functional theory (DFT) calculations are used to probe chemical and electronic interactions of nitrogen-rich CoO1-xNx (x > 0.7) films deposited on Si(100) using NH3 or N2 plasma-based sputter deposition or surface nitridation. Total energy calculations indicate that the zincblende (ZB) structure is energetically favored over the rocksalt (RS) structure for x > ~ 0.2, with an energy minimum observed in the ZB structure for x ~ 0.8 - 0.9. This is in close agreement with XPS-derived film compositions when corrected for surface oxide/hydroxide layers. XRD data indicate that films deposited on Si (100) at room temperature display either a preferred (220) orientation or no diffraction pattern, and are consistent with either rocksalt (RS) or zincblende (ZB) structure. Comparison between experimental and calculated X-ray excited valence band densities of states – also similar for all films synthesized herein – demonstrates a close agreement with a ZB, but not an RS structure. Core level XPS spectra exhibit systematic differences between films deposited in NH3 vs N2 plasma environments. Films deposited by N2 plasma magnetron sputtering exhibit greater O content as evidenced by systematic shifts in N 1s binding energies. Excellent agreement with experiment for core level binding energies is obtained for DFT calculations based on the ZB structure, but not for the RS structure. The agreement between theory and experiment demonstrates that these N-rich Co oxynitride films exhibit the ZB structure, and forms the basis of a predictive model for understanding how N and O interactions impact the electronic, magnetic and catalytic properties of these materials.
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Chemical Structure Analysis of Carbon-Doped Silicon Oxide Thin Films by Plasma-Enhanced Chemical Vapor Deposition of Tetrakis(Trimethylsilyloxy)Silane Precursor
Abstract Carbon-doped silicon oxide (CDO) thin films as low dielectric constant materials were deposited on both n-type silicon (Si) (100) and indium tin oxide coated polyethylene naphthalate (ITO/PEN) substrates, using the plasma-enhanced chemical vapor deposition of tetrakis(trimethylsilyoxy)silane (TTMSS) precursor. Chemical structures of the CDO films were analyzed by using FTIR (Fourier transformation infrared) spectroscopy and XPS (X-ray photoelectron spectroscopy). The chemical bonds related with hydrocarbon and Si–O were the main characteristics of the CDO films. The prominent peaks from the FTIR spectra included Si–O–Si stretching, Si–CH3 bending, Si–(CH3)x stretching, and CHx stretching modes. XPS spectra composed of the O1s, C1s, and Si2p electron orbitals were used to quantitatively analyze the elemental composition of the CDO films. The growth mechanisms of CDO films were dependent on the substrate type. For the ITO/PEN substrate, the lack of Si atoms on the ITO surface made difficulty in forming initial Si–O bonds, resulting in insufficient Si–O–Si structure. In comparison, the CDO films could grow easily on Si substrates due to pre-existing Si–O bonds on the surface. The chemical structures of the CDO films are expected to affect electrical and mechanical performances.
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- Award ID(s):
- 2026801
- PAR ID:
- 10583063
- Publisher / Repository:
- American Society of Mechanical Engineers
- Date Published:
- ISBN:
- 978-0-7918-8557-4
- Format(s):
- Medium: X
- Location:
- Virtual, Online
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Conference Paper:
- https://doi.org/10.1115/IMECE2021-72026
