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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Copper oxide atomic layer deposition on thermally pretreated multi-walled carbon nanotubes for interconnect applications

Melzer, 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 22 May 2013 (has links) (PDF)
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.
2

Atomic Layer Deposition and Microanalysis of Ultrathin Layers

Melzer, Marcel 17 October 2012 (has links) (PDF)
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.
3

Copper Oxide ALD from a Cu(I) <beta>-Diketonate: Detailed Growth Studies on SiO2 and TaN

Waechtler, Thomas, Roth, Nina, Mothes, Robert, Schulze, Steffen, Schulz, Stefan E., Gessner, Thomas, Lang, Heinrich, Hietschold, Michael 03 November 2009 (has links) (PDF)
The atomic layer deposition (ALD) of copper oxide films from [(<sup>n</sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)] and wet oxygen on SiO<sub>2</sub> and TaN has been studied in detail by spectroscopic ellipsometry and atomic force microscopy. The results suggest island growth on SiO<sub>2</sub>, along with a strong variation of the optical properties of the films in the early stages of the growth and signs of quantum confinement, typical for nanocrystals. In addition, differences both in growth behavior and film properties appear on dry and wet thermal SiO<sub>2</sub>. Electron diffraction together with transmission electron microscopy shows that nanocrystalline Cu<sub>2</sub>O with crystallites < 5 nm is formed, while upon prolonged electron irradiation the films decompose and metallic copper crystallites of approximately 10 nm precipitate. On TaN, the films grow in a linear, layer-by-layer manner, reproducing the initial substrate roughness. Saturated growth obtained at 120&deg;C on TaN as well as dry and wet SiO<sub>2</sub> indicates well-established ALD growth regimes. <br> &copy; 2009 The Electrochemical Society. All rights reserved.
4

Thin Films of Copper Oxide and Copper Grown by Atomic Layer Deposition for Applications in Metallization Systems of Microelectronic Devices

Wächtler, Thomas 02 June 2010 (has links) (PDF)
Copper-based multi-level metallization systems in today’s ultralarge-scale integrated electronic circuits require the fabrication of diffusion barriers and conductive seed layers for the electrochemical metal deposition. Such films of only several nanometers in thickness have to be deposited void-free and conformal in patterned dielectrics. The envisaged further reduction of the geometric dimensions of the interconnect system calls for coating techniques that circumvent the drawbacks of the well-established physical vapor deposition. The atomic layer deposition method (ALD) allows depositing films on the nanometer scale conformally both on three-dimensional objects as well as on large-area substrates. The present work therefore is concerned with the development of an ALD process to grow copper oxide films based on the metal-organic precursor bis(tri-n-butylphosphane)copper(I)acetylacetonate [(nBu3P)2Cu(acac)]. This liquid, non-fluorinated β-diketonate is brought to react with a mixture of water vapor and oxygen at temperatures from 100 to 160°C. Typical ALD-like growth behavior arises between 100 and 130°C, depending on the respective substrate used. On tantalum nitride and silicon dioxide substrates, smooth films and self-saturating film growth, typical for ALD, are obtained. On ruthenium substrates, positive deposition results are obtained as well. However, a considerable intermixing of the ALD copper oxide with the underlying films takes place. Tantalum substrates lead to a fast self-decomposition of the copper precursor. As a consequence, isolated nuclei or larger particles are always obtained together with continuous films. The copper oxide films grown by ALD can be reduced to copper by vapor-phase processes. If formic acid is used as the reducing agent, these processes can already be carried out at similar temperatures as the ALD, so that agglomeration of the films is largely avoided. Also for an integration with subsequent electrochemical copper deposition, the combination of ALD copper and ruthenium proves advantageous, especially with respect to the quality of the electroplated films and their filling behavior in interconnect structures. Furthermore, the ALD process developed also bears potential for an integration with carbon nanotubes. / Kupferbasierte Mehrlagenmetallisierungssysteme in heutigen hochintegrierten elektronischen Schaltkreisen erfordern die Herstellung von Diffusionsbarrieren und leitfähigen Keimschichten für die galvanische Metallabscheidung. Diese Schichten von nur wenigen Nanometern Dicke müssen konform und fehlerfrei in strukturierten Dielektrika abgeschieden werden. Die sich abzeichnende weitere Verkleinerung der geometrischen Dimensionen des Leitbahnsystems erfordert Beschichtungstechnologien, die vorhandene Nachteile der bisher etablierten Physikalischen Dampfphasenabscheidung beheben. Die Methode der Atomlagenabscheidung (ALD) ermöglicht es, Schichten im Nanometerbereich sowohl auf dreidimensional strukturierten Objekten als auch auf großflächigen Substraten gleichmäßig herzustellen. Die vorliegende Arbeit befasst sich daher mit der Entwicklung eines ALD-Prozesses zur Abscheidung von Kupferoxidschichten, ausgehend von der metallorganischen Vorstufe Bis(tri-n-butylphosphan)kupfer(I)acetylacetonat [(nBu3P)2Cu(acac)]. Dieses flüssige, nichtfluorierte β-Diketonat wird bei Temperaturen zwischen 100 und 160°C mit einer Mischung aus Wasserdampf und Sauerstoff zur Reaktion gebracht. ALD-typisches Schichtwachstum stellt sich in Abhängigkeit des gewählten Substrats zwischen 100 und 130°C ein. Auf Tantalnitrid- und Siliziumdioxidsubstraten werden dabei sehr glatte Schichten bei gesättigtem Wachstumsverhalten erhalten. Auch auf Rutheniumsubstraten werden gute Abscheideergebnisse erzielt, jedoch kommt es hier zu einer merklichen Durchmischung des ALD-Kupferoxids mit dem Untergrund. Tantalsubstrate führen zu einer schnellen Selbstzersetzung des Kupferprecursors, in dessen Folge neben geschlossenen Schichten während der ALD auch immer isolierte Keime oder größere Partikel erhalten werden. Die mittels ALD gewachsenen Kupferoxidschichten können in Gasphasenprozessen zu Kupfer reduziert werden. Wird Ameisensäure als Reduktionsmittel genutzt, können diese Prozesse bereits bei ähnlichen Temperaturen wie die ALD durchgeführt werden, so dass Agglomeration der Schichten weitgehend verhindert wird. Als besonders vorteilhaft für die Ameisensäure-Reduktion erweisen sich Rutheniumsubstrate. Auch für eine Integration mit nachfolgenden Galvanikprozessen zur Abscheidung von Kupfer zeigen sich Vorteile der Kombination ALD-Kupfer/Ruthenium, insbesondere hinsichtlich der Qualität der erhaltenen galvanischen Schichten und deren Füllverhalten in Leitbahnstrukturen. Der entwickelte ALD-Prozess besitzt darüber hinaus Potential zur Integration mit Kohlenstoffnanoröhren.
5

Copper Oxide ALD from a Cu(I) <beta>-Diketonate: Detailed Growth Studies on SiO2 and TaN

Waechtler, Thomas, Roth, Nina, Mothes, Robert, Schulze, Steffen, Schulz, Stefan E., Gessner, Thomas, Lang, Heinrich, Hietschold, Michael 03 November 2009 (has links)
The atomic layer deposition (ALD) of copper oxide films from [(<sup>n</sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)] and wet oxygen on SiO<sub>2</sub> and TaN has been studied in detail by spectroscopic ellipsometry and atomic force microscopy. The results suggest island growth on SiO<sub>2</sub>, along with a strong variation of the optical properties of the films in the early stages of the growth and signs of quantum confinement, typical for nanocrystals. In addition, differences both in growth behavior and film properties appear on dry and wet thermal SiO<sub>2</sub>. Electron diffraction together with transmission electron microscopy shows that nanocrystalline Cu<sub>2</sub>O with crystallites < 5 nm is formed, while upon prolonged electron irradiation the films decompose and metallic copper crystallites of approximately 10 nm precipitate. On TaN, the films grow in a linear, layer-by-layer manner, reproducing the initial substrate roughness. Saturated growth obtained at 120&deg;C on TaN as well as dry and wet SiO<sub>2</sub> indicates well-established ALD growth regimes. <br> &copy; 2009 The Electrochemical Society. All rights reserved.
6

Thin Films of Copper Oxide and Copper Grown by Atomic Layer Deposition for Applications in Metallization Systems of Microelectronic Devices

Wächtler, Thomas 25 May 2010 (has links)
Copper-based multi-level metallization systems in today’s ultralarge-scale integrated electronic circuits require the fabrication of diffusion barriers and conductive seed layers for the electrochemical metal deposition. Such films of only several nanometers in thickness have to be deposited void-free and conformal in patterned dielectrics. The envisaged further reduction of the geometric dimensions of the interconnect system calls for coating techniques that circumvent the drawbacks of the well-established physical vapor deposition. The atomic layer deposition method (ALD) allows depositing films on the nanometer scale conformally both on three-dimensional objects as well as on large-area substrates. The present work therefore is concerned with the development of an ALD process to grow copper oxide films based on the metal-organic precursor bis(tri-n-butylphosphane)copper(I)acetylacetonate [(nBu3P)2Cu(acac)]. This liquid, non-fluorinated β-diketonate is brought to react with a mixture of water vapor and oxygen at temperatures from 100 to 160°C. Typical ALD-like growth behavior arises between 100 and 130°C, depending on the respective substrate used. On tantalum nitride and silicon dioxide substrates, smooth films and self-saturating film growth, typical for ALD, are obtained. On ruthenium substrates, positive deposition results are obtained as well. However, a considerable intermixing of the ALD copper oxide with the underlying films takes place. Tantalum substrates lead to a fast self-decomposition of the copper precursor. As a consequence, isolated nuclei or larger particles are always obtained together with continuous films. The copper oxide films grown by ALD can be reduced to copper by vapor-phase processes. If formic acid is used as the reducing agent, these processes can already be carried out at similar temperatures as the ALD, so that agglomeration of the films is largely avoided. Also for an integration with subsequent electrochemical copper deposition, the combination of ALD copper and ruthenium proves advantageous, especially with respect to the quality of the electroplated films and their filling behavior in interconnect structures. Furthermore, the ALD process developed also bears potential for an integration with carbon nanotubes. / Kupferbasierte Mehrlagenmetallisierungssysteme in heutigen hochintegrierten elektronischen Schaltkreisen erfordern die Herstellung von Diffusionsbarrieren und leitfähigen Keimschichten für die galvanische Metallabscheidung. Diese Schichten von nur wenigen Nanometern Dicke müssen konform und fehlerfrei in strukturierten Dielektrika abgeschieden werden. Die sich abzeichnende weitere Verkleinerung der geometrischen Dimensionen des Leitbahnsystems erfordert Beschichtungstechnologien, die vorhandene Nachteile der bisher etablierten Physikalischen Dampfphasenabscheidung beheben. Die Methode der Atomlagenabscheidung (ALD) ermöglicht es, Schichten im Nanometerbereich sowohl auf dreidimensional strukturierten Objekten als auch auf großflächigen Substraten gleichmäßig herzustellen. Die vorliegende Arbeit befasst sich daher mit der Entwicklung eines ALD-Prozesses zur Abscheidung von Kupferoxidschichten, ausgehend von der metallorganischen Vorstufe Bis(tri-n-butylphosphan)kupfer(I)acetylacetonat [(nBu3P)2Cu(acac)]. Dieses flüssige, nichtfluorierte β-Diketonat wird bei Temperaturen zwischen 100 und 160°C mit einer Mischung aus Wasserdampf und Sauerstoff zur Reaktion gebracht. ALD-typisches Schichtwachstum stellt sich in Abhängigkeit des gewählten Substrats zwischen 100 und 130°C ein. Auf Tantalnitrid- und Siliziumdioxidsubstraten werden dabei sehr glatte Schichten bei gesättigtem Wachstumsverhalten erhalten. Auch auf Rutheniumsubstraten werden gute Abscheideergebnisse erzielt, jedoch kommt es hier zu einer merklichen Durchmischung des ALD-Kupferoxids mit dem Untergrund. Tantalsubstrate führen zu einer schnellen Selbstzersetzung des Kupferprecursors, in dessen Folge neben geschlossenen Schichten während der ALD auch immer isolierte Keime oder größere Partikel erhalten werden. Die mittels ALD gewachsenen Kupferoxidschichten können in Gasphasenprozessen zu Kupfer reduziert werden. Wird Ameisensäure als Reduktionsmittel genutzt, können diese Prozesse bereits bei ähnlichen Temperaturen wie die ALD durchgeführt werden, so dass Agglomeration der Schichten weitgehend verhindert wird. Als besonders vorteilhaft für die Ameisensäure-Reduktion erweisen sich Rutheniumsubstrate. Auch für eine Integration mit nachfolgenden Galvanikprozessen zur Abscheidung von Kupfer zeigen sich Vorteile der Kombination ALD-Kupfer/Ruthenium, insbesondere hinsichtlich der Qualität der erhaltenen galvanischen Schichten und deren Füllverhalten in Leitbahnstrukturen. Der entwickelte ALD-Prozess besitzt darüber hinaus Potential zur Integration mit Kohlenstoffnanoröhren.
7

Atomic Layer Deposition and Microanalysis of Ultrathin Layers

Melzer, 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.
8

Copper oxide atomic layer deposition on thermally pretreated multi-walled carbon nanotubes for interconnect applications

Melzer, 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.
9

Copper Oxide Films Grown by Atomic Layer Deposition from Bis(tri-n-butylphosphane)copper(I)acetylacetonate on Ta, TaN, Ru, and SiO2

Waechtler, 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&deg;C is reported. Typical temperature-independent growth was observed at least up to 125&deg;C with a growth-per-cycle of ~ 0.1 &Aring; for the metallic substrates and an ALD window extending down to 100&deg;C for Ru. On SiO<sub>2</sub> and TaN the ALD window was observed between 110 and 125&deg;C, with saturated growth shown on TaN still at 135&deg;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&deg;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> &copy; 2009 The Electrochemical Society. All rights reserved. <br> / Es wird die thermische Atomlagenabscheidung (ALD) von Kupferoxidschichten, ausgehend von der unfluorierten, fl&uuml;ssigen 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&deg;C berichtet. Typisches temperaturunabh&auml;ngiges Wachstum wurde zumindest bis 125&deg;C beobachtet. Damit verbunden wurde f&uuml;r die metallischen Substrate ein Zyklenwachstum von ca. 0.1 &Aring; erzielt sowie ein ALD-Fenster, das f&uuml;r Ru bis zu einer Temperatur von 100&deg;C reicht. Auf SiO<sub>2</sub> und TaN wurde das ALD-Fenster zwischen 110 und 125&deg;C beobachtet, wobei auch bei 135&deg;C noch ges&auml;ttigtes Wachstum auf TaN gezeigt werden konnte. Die selbst&auml;ndige Zersetzung des Precursors &auml;hnlich der chemischen Gasphasenabscheidung f&uuml;hrte 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&deg;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 f&uuml;r die ALD von Kupferstartschichten, die f&uuml;r die elektrochemische Kupfermetallisierung in Leitbahnsystemen ultrahochintegrierter Schaltkreise anwendbar sind.
10

Copper Oxide Films Grown by Atomic Layer Deposition from Bis(tri-n-butylphosphane)copper(I)acetylacetonate on Ta, TaN, Ru, and SiO2

Waechtler, 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&deg;C is reported. Typical temperature-independent growth was observed at least up to 125&deg;C with a growth-per-cycle of ~ 0.1 &Aring; for the metallic substrates and an ALD window extending down to 100&deg;C for Ru. On SiO<sub>2</sub> and TaN the ALD window was observed between 110 and 125&deg;C, with saturated growth shown on TaN still at 135&deg;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&deg;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> &copy; 2009 The Electrochemical Society. All rights reserved. <br> / Es wird die thermische Atomlagenabscheidung (ALD) von Kupferoxidschichten, ausgehend von der unfluorierten, fl&uuml;ssigen 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&deg;C berichtet. Typisches temperaturunabh&auml;ngiges Wachstum wurde zumindest bis 125&deg;C beobachtet. Damit verbunden wurde f&uuml;r die metallischen Substrate ein Zyklenwachstum von ca. 0.1 &Aring; erzielt sowie ein ALD-Fenster, das f&uuml;r Ru bis zu einer Temperatur von 100&deg;C reicht. Auf SiO<sub>2</sub> und TaN wurde das ALD-Fenster zwischen 110 und 125&deg;C beobachtet, wobei auch bei 135&deg;C noch ges&auml;ttigtes Wachstum auf TaN gezeigt werden konnte. Die selbst&auml;ndige Zersetzung des Precursors &auml;hnlich der chemischen Gasphasenabscheidung f&uuml;hrte 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&deg;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 f&uuml;r die ALD von Kupferstartschichten, die f&uuml;r die elektrochemische Kupfermetallisierung in Leitbahnsystemen ultrahochintegrierter Schaltkreise anwendbar sind.

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