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Atomic Layer Deposition and Microanalysis of Ultrathin LayersMelzer, Marcel 17 October 2012 (has links)
Carbon nanotubes (CNTs) are a highly promising material for future interconnects. It is expected that the decoration of CNTs with Cu particles or also the filling of the interspaces between the CNTs with Cu instead of the currently used SiO2 can enhance the performance of CNT-based interconnects.
Due to the high aspect ratio of CNTs an appropriate deposition technique has to be applied which is able to coat such structures uniformly. The current work is therefore considered with thermal atomic layer deposition (ALD) of CuxO from the liquid Cu (I) β-diketonate precursor [(nBu3P)2Cu(acac)] and wet oxygen at 135°C on variously pretreated multi-walled CNTs.
The different in-situ pre-treatments of the CNTs with oxygen, water vapor and wet oxygen in a temperature range from 100 to 300°C at a pressure of 1.33 mbar have been carried out prior to the ALD to enable uniform nucleation on the otherwise chemical inert CNT surface. The reduction of the CuxO as well as the filling of the space between the CNTs is not part of this work.
Variations of the oxidation temperature as well as the oxidation agents resulted in different growth modes of the CuxO. An oxidation with wet oxygen at 300°C yielded in a partially layer like growth of the CuxO. It is expected that this growth mode is connected to a partial destruction of the outer CNT shell due to the oxidation. However, the damage introduced to the CNTs was not high enough to be detected by Raman spectroscopy.
For all other investigated pretreatments, the formation of nanoparticles (NPs) was observed by electron microscopy. This formation of CuxO NPs can be explained by the metal-tube-interaction. Furthermore, the NPs probably decorate defect sites of the CNTs due to their higher reactivity. Additionally, analysis of energy-dispersive X-ray spectroscopy and spectroscopic ellipsometry measurements suggests that the used precursor [(nBu3P)2Cu(acac)] requires reactive oxygen surface groups for initiating the ALD growth.
The observation of layer-like growth of CuxO on CNTs pretreated with wet oxygen at 300°C appears promising for deposition processes of Cu seed layers on CNTs. However, more aggressive pretreatments at higher temperatures or with more aggressive oxidation agents could be required to enable layer like growth on the entire CNTs.
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Copper oxide atomic layer deposition on thermally pretreated multi-walled carbon nanotubes for interconnect applicationsMelzer, Marcel, Waechtler, Thomas, Müller, Steve, Fiedler, Holger, Hermann, Sascha, Rodriguez, Raul D., Villabona, Alexander, Sendzik, Andrea, Mothes, Robert, Schulz, Stefan E., Zahn, Dietrich R.T., Hietschold, Michael, Lang, Heinrich, Gessner, Thomas January 2013 (has links)
The following is the accepted manuscript of the original article:
Marcel Melzer, Thomas Waechtler, Steve Müller, Holger Fiedler, Sascha Hermann, Raul D. Rodriguez, Alexander Villabona, Andrea Sendzik, Robert Mothes, Stefan E. Schulz, Dietrich R.T. Zahn, Michael Hietschold, Heinrich Lang and Thomas Gessner
“Copper oxide atomic layer deposition on thermally pretreated multi-walled carbon nanotubes for interconnect applications”, Microelectron. Eng. 107, 223-228 (2013).
Digital Object Identifier: 10.1016/j.mee.2012.10.026
Available via http://www.sciencedirect.com or http://dx.doi.org/10.1016/j.mee.2012.10.026
© 2013 Elsevier B.V.
Carbon nanotubes (CNTs) are a highly promising material for future interconnects. It is expected that a decoration of the CNTs with Cu particles or also the filling of the interspaces between the CNTs with Cu can enhance the performance of CNT-based interconnects. The current work is therefore considered with thermal atomic layer deposition (ALD) of CuxO from the liquid Cu(I) β-diketonate precursor [(nBu3P)2Cu(acac)] and wet oxygen at 135°C. This paper focuses on different thermal in-situ pre-treatments of the CNTs with O2, H2O and wet O2 at temperatures up to 300°C prior to the ALD process. Analyses by transmission electron microscopy show that in most cases the CuxO forms particles on the multi-walled CNTs (MWCNTs). This behavior can be explained by the low affinity of Cu to form carbides. Nevertheless, also the formation of areas with rather layer-like growth was observed in case of an oxidation with wet O2 at 300°C. This growth mode indicates the partial destruction of the MWCNT surface. However, the damages introduced into the MWCNTs during the pre treatment are too low to be detected by Raman spectroscopy.
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Copper Oxide Films Grown by Atomic Layer Deposition from Bis(tri-n-butylphosphane)copper(I)acetylacetonate on Ta, TaN, Ru, and SiO2Waechtler, Thomas, Oswald, Steffen, Roth, Nina, Jakob, Alexander, Lang, Heinrich, Ecke, Ramona, Schulz, Stefan E., Gessner, Thomas, Moskvinova, Anastasia, Schulze, Steffen, Hietschold, Michael 02 May 2009 (has links) (PDF)
The thermal atomic layer deposition (ALD) of
copper oxide films from the non-fluorinated yet
liquid precursor
bis(tri-<it>n</it>-butylphosphane)copper(I)acetylacetonate,
[(<sup><it>n</it></sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)],
and wet O<sub>2</sub> on Ta, TaN, Ru and SiO<sub>2</sub>
substrates at temperatures of < 160°C is
reported. Typical temperature-independent
growth was observed at least up to 125°C with
a growth-per-cycle of ~ 0.1 Å for the metallic
substrates and an ALD window extending down to
100°C for Ru. On SiO<sub>2</sub> and TaN the ALD window
was observed between 110 and 125°C, with
saturated growth shown on TaN still at 135°C.
Precursor self-decomposition in a chemical
vapor deposition mode led to bi-modal growth
on Ta, resulting in the parallel formation of
continuous films and isolated clusters. This
effect was not observed on TaN up to about
130°C and neither on Ru or SiO<sub>2</sub> for any
processing temperature. The degree of
nitridation of the tantalum nitride underlayers
considerably influenced the film growth. With
excellent adhesion of the ALD films on all
substrates studied, the results are a promising
basis for Cu seed layer ALD applicable to
electrochemical Cu metallization in interconnects
of ultralarge-scale integrated circuits.<br>
© 2009 The Electrochemical Society. All rights reserved. <br> / Es wird die thermische Atomlagenabscheidung
(ALD) von Kupferoxidschichten, ausgehend von
der unfluorierten, flüssigen Vorstufenverbindung
Bis(tri-<it>n</it>-butylphosphan)kupfer(I)acetylacetonat,
[(<sup><it>n</it></sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)],
sowie feuchtem Sauerstoff,
auf Ta-, TaN-, Ru- und SiO<sub>2</sub>-Substraten bei
Temperaturen < 160°C berichtet. Typisches
temperaturunabhängiges Wachstum wurde zumindest
bis 125°C beobachtet.
Damit verbunden wurde für
die metallischen Substrate ein Zyklenwachstum
von ca. 0.1 Å erzielt sowie ein ALD-Fenster,
das für Ru bis zu einer Temperatur von 100°C
reicht. Auf SiO<sub>2</sub> und TaN wurde das
ALD-Fenster
zwischen 110 und 125°C beobachtet, wobei auch
bei 135°C noch gesättigtes Wachstum auf TaN
gezeigt werden konnte. Die selbständige
Zersetzung des Precursors ähnlich der chemischen
Gasphasenabscheidung führte zu einem bimodalen
Schichtwachstum auf Ta, wodurch gleichzeitig
geschlossene Schichten und voneinander isolierte
Cluster gebildet wurden. Dieser Effekt wurde auf
TaN bis zu einer Temperatur von 130°C nicht
beobachtet. Ebensowenig trat er im untersuchten
Temperaturbereich auf Ru oder SiO<sub>2</sub> auf. Der
Nitrierungsgrad der TaN-Schichten beeinflusste
hierbei das Schichtwachstum stark. Mit einer
sehr guten Haftung der ALD-Schichten auf allen
untersuchten Substratmaterialien erscheinen die
Ergebnisse vielversprechend für die ALD von
Kupferstartschichten, die für die
elektrochemische Kupfermetallisierung in
Leitbahnsystemen ultrahochintegrierter
Schaltkreise anwendbar sind.
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Copper Oxide Films Grown by Atomic Layer Deposition from Bis(tri-n-butylphosphane)copper(I)acetylacetonate on Ta, TaN, Ru, and SiO2Waechtler, Thomas, Oswald, Steffen, Roth, Nina, Jakob, Alexander, Lang, Heinrich, Ecke, Ramona, Schulz, Stefan E., Gessner, Thomas, Moskvinova, Anastasia, Schulze, Steffen, Hietschold, Michael 02 May 2009 (has links)
The thermal atomic layer deposition (ALD) of
copper oxide films from the non-fluorinated yet
liquid precursor
bis(tri-<it>n</it>-butylphosphane)copper(I)acetylacetonate,
[(<sup><it>n</it></sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)],
and wet O<sub>2</sub> on Ta, TaN, Ru and SiO<sub>2</sub>
substrates at temperatures of < 160°C is
reported. Typical temperature-independent
growth was observed at least up to 125°C with
a growth-per-cycle of ~ 0.1 Å for the metallic
substrates and an ALD window extending down to
100°C for Ru. On SiO<sub>2</sub> and TaN the ALD window
was observed between 110 and 125°C, with
saturated growth shown on TaN still at 135°C.
Precursor self-decomposition in a chemical
vapor deposition mode led to bi-modal growth
on Ta, resulting in the parallel formation of
continuous films and isolated clusters. This
effect was not observed on TaN up to about
130°C and neither on Ru or SiO<sub>2</sub> for any
processing temperature. The degree of
nitridation of the tantalum nitride underlayers
considerably influenced the film growth. With
excellent adhesion of the ALD films on all
substrates studied, the results are a promising
basis for Cu seed layer ALD applicable to
electrochemical Cu metallization in interconnects
of ultralarge-scale integrated circuits.<br>
© 2009 The Electrochemical Society. All rights reserved. <br> / Es wird die thermische Atomlagenabscheidung
(ALD) von Kupferoxidschichten, ausgehend von
der unfluorierten, flüssigen Vorstufenverbindung
Bis(tri-<it>n</it>-butylphosphan)kupfer(I)acetylacetonat,
[(<sup><it>n</it></sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)],
sowie feuchtem Sauerstoff,
auf Ta-, TaN-, Ru- und SiO<sub>2</sub>-Substraten bei
Temperaturen < 160°C berichtet. Typisches
temperaturunabhängiges Wachstum wurde zumindest
bis 125°C beobachtet.
Damit verbunden wurde für
die metallischen Substrate ein Zyklenwachstum
von ca. 0.1 Å erzielt sowie ein ALD-Fenster,
das für Ru bis zu einer Temperatur von 100°C
reicht. Auf SiO<sub>2</sub> und TaN wurde das
ALD-Fenster
zwischen 110 und 125°C beobachtet, wobei auch
bei 135°C noch gesättigtes Wachstum auf TaN
gezeigt werden konnte. Die selbständige
Zersetzung des Precursors ähnlich der chemischen
Gasphasenabscheidung führte zu einem bimodalen
Schichtwachstum auf Ta, wodurch gleichzeitig
geschlossene Schichten und voneinander isolierte
Cluster gebildet wurden. Dieser Effekt wurde auf
TaN bis zu einer Temperatur von 130°C nicht
beobachtet. Ebensowenig trat er im untersuchten
Temperaturbereich auf Ru oder SiO<sub>2</sub> auf. Der
Nitrierungsgrad der TaN-Schichten beeinflusste
hierbei das Schichtwachstum stark. Mit einer
sehr guten Haftung der ALD-Schichten auf allen
untersuchten Substratmaterialien erscheinen die
Ergebnisse vielversprechend für die ALD von
Kupferstartschichten, die für die
elektrochemische Kupfermetallisierung in
Leitbahnsystemen ultrahochintegrierter
Schaltkreise anwendbar sind.
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