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Synthesis and Characterization of Metal Complexes for Thin Film Formation via Spin-Coating or Chemical Vapor DepositionPousaneh, Elaheh 29 October 2020 (has links)
The present thesis describes the synthesis and characterization of magnesium, copper, and iron complexes and their application in the MOCVD (Metal-Organic Chemical Vapor Deposition) process, as well as the synthesis and characterization of yttrium and gadolinium complexes and their use as spin-coating precursors for metal oxide thin layer formation. The objective of this scientific work is the development of the family of bis(β-ketoiminato) magnesium(II) complexes and a series of heteroleptic β-ketoiminato copper(II) precursors for the formation of magnesium oxide and copper/copper oxide layers by using the MOCVD process. Modifications of the ketoiminato ligands affect the physical and chemical properties of the respective complexes. Another central theme of this work is the development of β-diketonato iron(III) complexes for the deposition of carbon-free gamma- and alpha-Fe2O3 layers via MOCVD. The thermal behavior and vapor pressure of the precursors could be influenced by the variation of the β-diketonate ligands. In addition, the synthesis and characterization of yttrium and gadolinium β-diketonates and their use as spin-coating precursors are described. Field-effect transistors were successfully fabricated by the deposition of carbon nanotubes on top of the Y2O3 films.
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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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Surface chemistry of a Cu(I) beta-diketonate precursor and the atomic layer deposition of Cu2O on SiO2 studied by x-ray photoelectron spectroscopyDhakal, Dileep, Waechtler, Thomas, E. Schulz, Stefan, Gessner, Thomas, Lang, Heinrich, Mothes, Robert, Tuchscherer, Andre January 2014 (has links)
This article has been published online on 21st May 2014, in Journal of Vacuum Science & Technology A: Vac (Vol.32, Issue 4):
http://scitation.aip.org/content/avs/journal/jvsta/32/4/10.1116/1.4878815?aemail=author
DOI: 10.1116/1.4878815
This article may be accessed via the issue's table of contents at this link:
http://scitation.aip.org/content/avs/journal/jvsta/32/4?aemail=author
The surface chemistry of the bis(tri-n-butylphosphane) copper(I) acetylacetonate, [(nBu3P)2Cu(acac)], and the thermal atomic layer deposition (ALD) of Cu2O using this Cu precursor as reactant and wet oxygen as co-reactant on SiO2 substrates are studied by in-situ X-ray photoelectron spectroscopy (XPS). The Cu precursor was evaporated and exposed to the substrates kept at temperatures between 22 °C and 300 °C. The measured phosphorus and carbon concentration on the substrates indicated that most of the [nBu3P] ligands were released either in the gas phase or during adsorption. No disproportionation was observed for the Cu precursor in the temperature range between 22 °C and 145 °C. However, disproportionation of the Cu precursor was observed at 200 °C, since C/Cu concentration ratio decreased and substantial amounts of metallic Cu were present on the substrate. The amount of metallic Cu increased, when the substrate was kept at 300 °C, indicating stronger disproportionation of the Cu precursor. Hence, the upper limit for the ALD of Cu2O from this precursor lies in the temperature range between 145 °C and 200 °C, as the precursor must not alter its chemical and physical state after chemisorption on the substrate. 500 ALD cycles with the probed Cu precursor and wet O2 as co reactant were carried out on SiO2 at 145 °C. After ALD, in situ XPS analysis confirmed the presence of Cu2O on the substrate. Ex-situ spectroscopic ellipsometry indicated an average film thickness of 2.5 nm of Cu2O deposited with a growth per cycle of 0.05 Å/cycle. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) investigations depicted a homogeneous, fine, and granular morphology of the Cu2O ALD film on SiO2. AFM investigations suggest that the deposited Cu2O film is continuous on the SiO2 substrate.
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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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Electron Transfer and Other Reactions Using Atomic Metal AnionsButson, Jeffery M. 04 February 2014 (has links)
The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-.
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Electron Transfer and Other Reactions Using Atomic Metal AnionsButson, Jeffery M. January 2014 (has links)
The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-.
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