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Low-temperature molecular layer deposition using monofunctional aromatic precursors and ozone-based ring-opening reactions

(2017) LANGMUIR. 33(38). p.9657-9665
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Abstract
Molecular layer deposition (MLD) is an increasingly used deposition technique for producing thin coatings consisting of purely organic or hybrid inorganic organic materials. When organic materials are prepared, low deposition temperatures are often required to avoid decomposition, thus causing problems with low vapor pressure precursors. Mono functional compounds have higher vapor pressures than traditional bi- or trifunctional MLD precursors, but do not offer the required functional groups for continuing the MLD growth in subsequent deposition cycles. In this study, we have used high vapor pressure monofunctional aromatic precursors in combination with ozone-triggered ring-opening reactions to achieve sustained sequential growth. MLD depositions were carried out by using three different aromatic precursors in an ABC sequence, namely with TMA + phenol + O-3, TMA + 3-(trifluoromethyl)phenol + O-3, and TMA + 2-fluoro-4-(trifluoromethyl)benzaldehyde + O-3. Furthermore, the effect of hydrogen peroxide as a fourth step, was evaluated for all studied processes resulting in a four-precursor ABCD sequence. According to the characterization results by ellipsometry, infrared spectroscopy, and X-ray reflectivity, self-limiting MLD processes could be obtained between 75 and 150 degrees C with each of the three aromatic precursors. In all cases, the GPC (growth per cycle) decreased with increasing temperature. In situ infrared spectroscopy indicated that ring-opening reactions occurred in each ABC sequence. Compositional analysis using time-of-flight elastic recoil detection indicated that fluorine could be incorporated into the film when 3-(trifluoromethyl)phenol and 2-fluoro-4-(trifluoromethyObenzaldehyde were used as precursors.
Keywords
POLYMER THIN-FILMS, ETHYLENE-GLYCOL, TRIMETHYLALUMINUM, ALUMINUM, GROWTH, CHEMISTRY

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MLA
Svärd, Laura et al. “Low-temperature Molecular Layer Deposition Using Monofunctional Aromatic Precursors and Ozone-based Ring-opening Reactions.” LANGMUIR 33.38 (2017): 9657–9665. Print.
APA
Svärd, L., Putkonen, M., Kenttä, E., Sajavaara, T., Krahl, F., Karppinen, M., Van de Kerckhove, K., et al. (2017). Low-temperature molecular layer deposition using monofunctional aromatic precursors and ozone-based ring-opening reactions. LANGMUIR, 33(38), 9657–9665.
Chicago author-date
Svärd, Laura, Matti Putkonen, Eija Kenttä, Timo Sajavaara, Fabian Krahl, Maarit Karppinen, Kevin Van de Kerckhove, Christophe Detavernier, and Pekka Simell. 2017. “Low-temperature Molecular Layer Deposition Using Monofunctional Aromatic Precursors and Ozone-based Ring-opening Reactions.” Langmuir 33 (38): 9657–9665.
Chicago author-date (all authors)
Svärd, Laura, Matti Putkonen, Eija Kenttä, Timo Sajavaara, Fabian Krahl, Maarit Karppinen, Kevin Van de Kerckhove, Christophe Detavernier, and Pekka Simell. 2017. “Low-temperature Molecular Layer Deposition Using Monofunctional Aromatic Precursors and Ozone-based Ring-opening Reactions.” Langmuir 33 (38): 9657–9665.
Vancouver
1.
Svärd L, Putkonen M, Kenttä E, Sajavaara T, Krahl F, Karppinen M, et al. Low-temperature molecular layer deposition using monofunctional aromatic precursors and ozone-based ring-opening reactions. LANGMUIR. 2017;33(38):9657–65.
IEEE
[1]
L. Svärd et al., “Low-temperature molecular layer deposition using monofunctional aromatic precursors and ozone-based ring-opening reactions,” LANGMUIR, vol. 33, no. 38, pp. 9657–9665, 2017.
@article{8536168,
  abstract     = {Molecular layer deposition (MLD) is an increasingly used deposition technique for producing thin coatings consisting of purely organic or hybrid inorganic organic materials. When organic materials are prepared, low deposition temperatures are often required to avoid decomposition, thus causing problems with low vapor pressure precursors. Mono functional compounds have higher vapor pressures than traditional bi- or trifunctional MLD precursors, but do not offer the required functional groups for continuing the MLD growth in subsequent deposition cycles. In this study, we have used high vapor pressure monofunctional aromatic precursors in combination with ozone-triggered ring-opening reactions to achieve sustained sequential growth. MLD depositions were carried out by using three different aromatic precursors in an ABC sequence, namely with TMA + phenol + O-3, TMA + 3-(trifluoromethyl)phenol + O-3, and TMA + 2-fluoro-4-(trifluoromethyl)benzaldehyde + O-3. Furthermore, the effect of hydrogen peroxide as a fourth step, was evaluated for all studied processes resulting in a four-precursor ABCD sequence. According to the characterization results by ellipsometry, infrared spectroscopy, and X-ray reflectivity, self-limiting MLD processes could be obtained between 75 and 150 degrees C with each of the three aromatic precursors. In all cases, the GPC (growth per cycle) decreased with increasing temperature. In situ infrared spectroscopy indicated that ring-opening reactions occurred in each ABC sequence. Compositional analysis using time-of-flight elastic recoil detection indicated that fluorine could be incorporated into the film when 3-(trifluoromethyl)phenol and 2-fluoro-4-(trifluoromethyObenzaldehyde were used as precursors.},
  author       = {Svärd, Laura and Putkonen, Matti and Kenttä, Eija and Sajavaara, Timo and Krahl, Fabian and Karppinen, Maarit and Van de Kerckhove, Kevin and Detavernier, Christophe and Simell, Pekka},
  issn         = {0743-7463},
  journal      = {LANGMUIR},
  keywords     = {POLYMER THIN-FILMS,ETHYLENE-GLYCOL,TRIMETHYLALUMINUM,ALUMINUM,GROWTH,CHEMISTRY},
  language     = {eng},
  number       = {38},
  pages        = {9657--9665},
  title        = {Low-temperature molecular layer deposition using monofunctional aromatic precursors and ozone-based ring-opening reactions},
  url          = {http://dx.doi.org/10.1021/acs.langmuir.7b02456},
  volume       = {33},
  year         = {2017},
}

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