KR101014240B1 - Ruthenium layer deposition apparatus and method - Google Patents

Ruthenium layer deposition apparatus and method Download PDF

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KR101014240B1
KR101014240B1 KR1020077019546A KR20077019546A KR101014240B1 KR 101014240 B1 KR101014240 B1 KR 101014240B1 KR 1020077019546 A KR1020077019546 A KR 1020077019546A KR 20077019546 A KR20077019546 A KR 20077019546A KR 101014240 B1 KR101014240 B1 KR 101014240B1
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ruthenium
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oxide
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process
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KR1020077019546A
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KR20070101357A (en
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티모시 더블유. 웨이드만
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어플라이드 머티어리얼스, 인코포레이티드
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Priority to US60/648,004 priority
Priority to US71502405P priority
Priority to US60/715,024 priority
Priority to US11/228,649 priority
Priority to US11/228,425 priority
Priority to US11/228,425 priority patent/US20060162658A1/en
Priority to US11/228,649 priority patent/US7438949B2/en
Application filed by 어플라이드 머티어리얼스, 인코포레이티드 filed Critical 어플라이드 머티어리얼스, 인코포레이티드
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
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    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/28556Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • H01L21/28562Selective deposition
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4488Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • C23C16/509Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
    • C23C16/5096Flat-bed apparatus
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    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/28556Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • HELECTRICITY
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841Barrier, adhesion or liner layers
    • H01L21/76843Barrier, adhesion or liner layers formed in openings in a dielectric
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841Barrier, adhesion or liner layers
    • H01L21/76843Barrier, adhesion or liner layers formed in openings in a dielectric
    • H01L21/76846Layer combinations
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841Barrier, adhesion or liner layers
    • H01L21/76871Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
    • H01L21/76873Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating

Abstract

Embodiments of the present invention provide an apparatus and method for forming a ruthenium containing layer on a substrate surface from a ruthenium 4 oxide containing gas. In general, the method includes exposing the substrate surface to ruthenium 4 oxide vapor to form a catalyst layer on the substrate surface, and subsequently filling the device structure on the substrate surface by one or more deposition processes. In one embodiment, the ruthenium containing layer is formed on the substrate surface by forming ruthenium 4 oxide in an outer container and then delivering the generated ruthenium 4 oxide gas to a temperature controlled substrate surface positioned within the processing chamber. In another embodiment, the ruthenium containing layer is formed on the substrate surface using a ruthenium 4 oxide containing solvent. In another embodiment, the solvent is separated from the ruthenium 4 oxide containing solvent mixture and the remaining ruthenium 4 oxide is used to form a ruthenium containing layer on the substrate surface.

Description

Ruthenium layer deposition apparatus and method {RUTHENIUM LAYER DEPOSITION APPARATUS AND METHOD}

Embodiments of the present invention generally relate to a method for depositing a catalyst layer on a barrier layer prior to depositing a conductive layer on the barrier layer.

Multilevel, 45 nm node metallization is one of the key technologies for the next generation of ultra-large scale integrated circuits (VLSI). Multilevel interconnects at the heart of this technology include high aspect ratio features, including contacts, vias, lines and other apertures. Reliable formation of these features is critical for the success of VLSI and continued efforts to increase quality and circuit density on individual substrates. Thus, there is a lot of effort going on to form a spaceless feature with a high aspect ratio of 10: 1 (height: width) or more.

Copper is an optional metal for filling VLSI features such as sub-micron high aspect ratios that interconnect features. The contact is formed by depositing a conductive junction material, such as copper, into an opening (eg, a via) onto a surface of insulating material disposed between two spaced apart conductive layers. Such high aspect ratios of openings may prevent deposition of conductive junction materials that exhibit satisfactory step coverage and gap-fill. Although copper is a common junction material, copper diffuses into neighboring layers such as dielectric layers. The resulting and unwanted presence of copper makes the dielectric layer conductive, causing the electronic device to fail. Thus, the barrier material is used to prevent copper diffusion.

A typical sequence for forming a junction includes depositing one or more non-conductive layers, etching one or more layers to form one or more features therein, depositing a barrier layer within the features, and Depositing one or more conductive layers, such as copper, to fill the feature. The barrier layer typically includes refractory metal nitrides and / or silicides, such as titanium or tantalum. Of this group, tantalum nitride is one of the most preferred materials for use as a barrier layer. Tantalum nitrides provide a useful barrier to copper diffusion, even when relatively thin layers (eg, 20 μs or less) are formed. Tantalum nitride layers are typically deposited by conventional deposition techniques, such as physical vapor deposition (PVD), atomic layer deposition (ALD), and chemical vapor deposition (CVD).

Tantalum nitride has some negative properties, including poor adhesion to copper layers deposited on tantalum nitride. Subsequent deposition of subsequent deposited copper layers results in process contamination problems in substrate processing steps such as rapid electron transfer and possibly chemical mechanical polishing (CMP) within the formed device. Exposure of the tantalum nitride layer to a source of oxygen and / or water can lead to oxidation to prevent the formation of a strong bond of the subsequently deposited copper layer. The interface between the tantalum nitride barrier layer and the copper layer is separated during standard tape testing.

Conventional deposition processes utilize precursors comprising carbon that are bonded to the deposited barrier layer. Carbon bonding is often disadvantageous for the completion of a wet chemical process because the deposited film tends to be hydrophobic, reducing or preventing deposition of the fluid into the layer having the desired performance. To address this problem, oxidation processes are often used on barrier layers to remove bound carbon, but such processes can adversely affect other exposed and highly oxidizable layers, such as carbon junctions. Thus, a process and apparatus are required to deposit a barrier layer or adhesive layer that can enhance bonding adhesion between various layers, such as tantalum nitride (TaN) and copper. In addition, in some cases, processes and apparatus are required to form an adhesive layer that can be deposited directly on dielectrics, nonmetals, or other desirable materials.

Accordingly, there is a need for a method for depositing a copper containing layer on a barrier layer with step coverage, strong adhesion and low electrical resistance useful in high aspect ratio junction features.

In one embodiment, an apparatus is provided for depositing a catalyst layer on the surface of a substrate, the apparatus comprising one or more walls, a ruthenium, forming a first treatment region to maintain a constant amount of ruthenium containing material 4 Ruthenium 4 including an oxidizing source for delivering an oxidizing gas to a ruthenium containing material in a first processing region to form an oxide containing gas, and a source vessel assembly in fluid communication with the vessel and collecting the ruthenium 4 oxide containing gas. Oxide generation systems. The source vessel assembly includes a source vessel having a collection region, and a heat exchange device in thermal communication with the collection surface in contact with the collection region, and includes a processing chamber in fluid communication with the source vessel. The processing chamber includes one or more walls forming a second processing region, a substrate support positioned within the second processing region, and a heat exchange device in thermal communication with the substrate support.

In another embodiment, an apparatus is provided for depositing a catalyst layer on a surface of a substrate, the apparatus comprising one or more walls forming a first processing region to maintain a constant amount of ruthenium containing material, And a ruthenium 4 oxide generation system comprising a vacuum pump in fluid communication with the vessel, and a source vessel assembly for collecting the ruthenium 4 oxide containing gas in fluid communication with the vessel. The source vessel assembly includes a source vessel having a collection region, and a heat exchange device in thermal communication with the collection surface in contact with the collection region, and includes a processing chamber in fluid communication with the source vessel. The processing chamber includes one or more walls forming a second processing region, a substrate support positioned within the second processing region, and a heat exchange device in thermal communication with the substrate support.

In yet another embodiment, an apparatus is provided for depositing a catalyst layer on a surface of a substrate, the apparatus having a first having one or more walls forming a first processing region to maintain a constant amount of ruthenium containing material. And a ruthenium 4 oxide generation system comprising a first source vessel assembly to collect a quantity of ruthenium 4 oxide containing gas in fluid communication with the vessel and delivered from the first vessel. The first source container assembly includes a source container having a collection area and a heat exchange device in thermal communication with the collection surface in contact with the collection area. The second vessel may have one or more walls forming a second treatment region to hold a constant amount of ruthenium containing material, and the second source vessel assembly is in constant quantity in fluid communication with the vessel and delivered from the second vessel. Collect ruthenium 4 oxide containing gas. The second source container assembly includes a source container having a collection area and a heat exchange device in thermal communication with the collection surface in contact with the collection area and includes a processing chamber. The processing chamber includes one or more walls in fluid communication with the source vessel, a substrate support positioned within the chamber processing region, and a heat exchange device in thermal communication with the substrate support.

In another embodiment, an apparatus is provided for depositing a catalyst layer on a surface of a substrate, the apparatus forming a main frame having a substrate transfer region and a first processing region for maintaining a constant amount of ruthenium containing material. A ruthenium 4 oxide generating system comprising an one or more vessels and an oxidizing source, the oxidizing source being adapted to deliver an oxidizing gas to a ruthenium containing material in the vessel to form a ruthenium 4 oxide containing gas in the vessel; A processing chamber in fluid communication with the vessel. The processing chamber includes one or more walls forming a chamber processing region, a fluid delivery line in fluid communication with the vessel and the chamber processing region, a substrate support positioned within the chamber processing region, and a heat exchange device in thermal communication with the substrate support. And a robot for transferring the substrate from the transfer region of the main frame to the chamber treatment region of the processing chamber.

In another embodiment, an apparatus is provided for depositing a catalyst layer on a surface of a substrate, the apparatus comprising a main frame having a substrate transfer region and a first treatment region to maintain a constant amount of ruthenium 4 oxide containing material. And a ruthenium 4 oxide generating system comprising a one or more vessels forming and a vacuum pump in fluid communication with the first processing region of the vessel and a processing chamber attached to the main frame and in fluid communication with the source vessel. The processing chamber includes one or more walls forming a chamber processing region, a fluid delivery line in fluid communication with the vessel and the chamber processing region, a substrate support positioned within the chamber processing region, and a heat exchange device in thermal communication with the substrate support. And a robot for transferring the substrate from the transfer region of the main frame to the chamber treatment region of the processing chamber.

In another embodiment, an apparatus for depositing a ruthenium containing layer on a surface of a substrate used to form a semiconductor device or a flat panel display is provided, wherein the apparatus is a processing chamber for depositing a ruthenium containing layer of a substrate, the chamber processing A processing chamber, and a ruthenium 4 oxide generation system, including one or more walls forming a region, a substrate support positioned within the chamber processing region, and a heat exchange device in thermal communication with the substrate support. The ruthenium 4 oxide generation system forms a first vessel having one or more walls, a collection region in fluid communication with the treatment chamber, and one or more walls forming a first treatment region to include a solvent mixture containing ruthenium 4 oxide. And a second container having the above walls, a first container, and a fluid pump in fluid communication with the second container. The fluid pump allows a constant amount of solvent mixture to be delivered from the first vessel to the collection region of the second vessel and includes a heat exchange device in thermal communication with the collection region.

In another embodiment, an apparatus is provided for depositing a catalyst layer on a surface of a substrate, the apparatus having one or more walls forming a confined region containing a fluid comprising a solvent and ruthenium 4 oxide. And a ruthenium 4 oxide generation system comprising one or more gas sources. One or more gas sources are in fluid communication with the confined region. The apparatus further includes a processing chamber comprising one or more walls forming a chamber processing region, a substrate support positioned within the chamber processing region, and a heat exchange device in thermal communication with the substrate support. The apparatus further includes a fluid delivery line in fluid communication with the confinement region of the vessel and the chamber treatment region of the treatment chamber.

BRIEF DESCRIPTION OF THE DRAWINGS In order that the above-described features of the present invention may be understood in detail, reference may be made to the more specific description of the invention briefly described above, some of which are illustrated in the accompanying drawings. However, the appended drawings illustrate only typical embodiments of the invention and are therefore not to be considered limiting of its scope, as other equally effective embodiments may be appreciated.

1A shows a process sequence according to an embodiment of the present invention,

1B illustrates another process sequence according to an embodiment of the present invention,

2A-2D are schematic cross-sectional views of an integrated circuit fabrication sequence formed by the process of the present invention,

3A-3D are schematic cross-sectional views of an integrated circuit fabrication sequence formed by another process of the present invention,

4 is a cross-sectional view of a deposition chamber that may be applied to perform one embodiment of the present invention,

5 shows yet another process sequence according to an embodiment of the present invention,

6A through 6C are cross-sectional views of processing chambers that may perform one embodiment of the present specification;

7 shows another process sequence according to an embodiment of the present invention,

8 is a plan view of a cluster tool usefully used in the present invention and used for semiconductor processing,

9 shows yet another process sequence according to an embodiment of the present invention,

10A illustrates another process sequence according to an embodiment of the present invention,

10B illustrates another process sequence according to an embodiment of the present invention,

10C is a cross-sectional view of a process vessel in which one embodiment of the present invention may be performed,

11 is a cross sectional view of a deposition chamber in which an embodiment of the present invention may be performed.

Methods and apparatus for depositing ruthenium containing layers on substrates are generally disclosed. The methods and devices disclosed herein are particularly useful for making electronic devices formed on the surface of a substrate or wafer. Generally, the method comprises exposing the substrate surface to ruthenium tetroxide to form a catalyst layer on the substrate surface and then electroless, electroplating, physical vapor deposition (PVD), chemical vapor deposition (CVD), The device structure is filled by a plasma enhanced CVD (PE-CVD), atomic layer deposition (ALD), or plasma enhanced ALD (PE-ALD) process. In one aspect, the catalyst layer acts as a layer capable of promoting adhesion between the previous and subsequent deposition layers, acts as a barrier layer, or subsequent PVD, CVD, PE-CVD, ALD, PE-ALD, electroless Ruthenium-containing layers that serve to act as layers to enhance dissolution, and / or electrolytic deposition processes. Because of the electrophoresis, device isolation and other device processing are related to the method and it has been described that the device can deposit a ruthenium containing layer that can be strongly bonded to the exposed surface of the substrate.

As used herein, “atomic layer deposition (ALD)” or “cyclical deposition” refers to the orderly introduction of two or more reactive compounds to deposit a layer of material on a substrate surface. Two, three or more reactive compounds may optionally be introduced into the reaction zone of the treatment chamber. Typically, each reaction compound is separated by a time delay to allow each compound to adhere and / or react on the substrate spreading surface. In one aspect, the first precursor or compound (A) pulses into the reaction region followed by a first time delay. Next, the second precursor or compound (B) pulses into the reaction zone followed by the second delay. During each time delay, a purge gas, such as nitrogen, is introduced into the processing chamber to purge the reaction zone or otherwise remove any residual reactive compound or byproduct from the reaction zone. Alternatively, the purge gas can flow continuously through the deposition process, allowing only the purge gas to flow during the time delay between the pulses of the reactive compound. In contrast, the reactive compound selectively pulses until a target film or film thickness is formed on the substrate surface. In another aspect, the ALD process of purge gas, pulsed compound, is one cycle. The cycle may begin with either Compound (A) or Compound (B) so that each sequence of cycles continues until a film is achieved at the target thickness.

As used herein, “substrate surface” refers to any substrate or material surface formed on a substrate on which film processing is performed. For example, the substrate surface on which processing can be performed may be monocrystalline, polycrystalline or amorphous silicon, strained silicon, silicon on insulator (SOI), doped silicon, silicon germanium, germanium, gallium arsenide, glass, sapphire , Silicon oxide, silicon nitride, silicon oxynitride, fluorine-doped silicon glass (FSG), and / or carbon doped silicon oxide, such as SiO x C y , for example, Applied Materials, Santa C., California BLACK DIAMOND® available from NC. Includes materials such as low k dielectrics. The substrate can have rectangular or square panes as well as various sizes, such as 200 mm or 300 mm diameter wafers. Embodiments of the processes described herein deposit metal containing layers on multiple substrates and surfaces, particularly barrier layers. Substrates of embodiments of the invention that may be useful are crystalline silicon (eg, Si <100>, Si <111>), silicon oxide, strained silicon, silicon germanium, doped or undoped poly. Semiconductor wafers such as, but not limited to, silicon, doped or undoped silicon wafers, or patterned or unpatterned wafers. For example, substrates made of glass or plastic commonly used to make flat panel displays and other similar devices are also included in the embodiments described herein.

As used herein, "pulse" is intended to refer to the amount of a particular compound that is introduced intermittently or discontinuously into the reaction zone of the processing chamber. The amount of a particular compound in each pulse varies over time with the duration of the pulse. The duration of each pulse varies depending on a number of factors such as, for example, the process chamber applied, the volumetric capacity of the vacuum system coupled thereto, and the volatility / reactivity of the particular compound itself. As used herein, “half-reaction” refers to a pulse of precursor followed by a purge step.

In general, the methods and apparatus described herein allow for the selective or non-selective deposition of a ruthenium containing layer on device features formed on a substrate surface by the use of a ruthenium 4 oxide containing gas. The selective or non-selective deposition of a ruthenium containing layer on the surface of the substrate is highly dependent on the type and temperature of the surface exposed to the ruthenium 4 oxide containing gas. By controlling the temperature of the substrate below the target temperature, for example about 180 ° C., the ruthenium layer is selectively deposited on the surface of the desired type. At higher temperatures, for example, above 180 ° C., the ruthenium deposition process from the ruthenium 4 oxide containing gas is very small, allowing blanket films to be deposited on all types of surfaces.

In one embodiment, the deposition of the ruthenium containing layer is used to promote the filling and adhesion of subsequent layers on the surface of the substrate. In another aspect, the properties of the ruthenium coating layer deposited on the surface of the substrate are specifically formed to meet the needs of devices formed on the surface of the substrate. Typically desirable properties include the formation of a crystalline or amorphous metal ruthenium layer on the surface of the substrate so that the formed layer can act as a barrier layer, a catalyst layer for subsequent electroless or electroplating processes, or fill a target device feature. Can be. Still other desirable properties of the ruthenium containing layer include piezoelectric materials used to promote selective bottom top growth of the electroless and / or electroplating layers or to form various micro-electro-mechanical system (MEMS) devices, for example. For example, the formation of a ruthenium dioxide layer (RuO 2 ) on the surface of a substrate to form an electrode compatible with PZT) or ferroelectric oxide (eg, BST).

A. Barrier  Layer deposition process

In one embodiment, the ruthenium containing layer may be deposited on the barrier layer on the substrate surface by exposing the barrier layer to a ruthenium containing gas such that a conductive layer may be deposited on the ruthenium containing layer. Preferably, the barrier layer (eg tantalum nitride) is deposited by an ALD process, but may also be deposited by PVD, CVD, or other conventional deposition process.

1A shows a process according to one embodiment described herein to fabricate an integrated circuit. Process 100 includes steps 102-106, during which step a metal containing barrier layer is deposited on the substrate surface. In step 104, the barrier layer is exposed to a ruthenium containing gas and the substrate is maintained at a target processing temperature to deposit the ruthenium containing layer. Thereafter, a conductive layer is deposited on the catalyst layer during step 106.

Process 100 corresponds to FIGS. 2A-2D, which illustrate, in schematic cross-sectional view, an electronic device in a different stage of contiguous fabrication sequence embodied in accordance with one embodiment of the present invention. 2A is a cross-sectional view of a substrate 200 having vias or through holes 202 formed on the surface of the substrate 200 as a dielectric layer 201. The substrate 200 may include a semiconductor material such as, for example, silicon, germanium, or silicon germanium. Dielectric layer 201 is silicon dioxide, silicon nitride, FSG, and / or SiO x C y , for example, BLACK DIAMOND® available from Applied Materials, Inc., Santa Clara, CA. ) May be an insulating material such as carbon doped silicon oxide, such as a low k dielectric. The through hole 202 may be formed in the substrate 200 using conventional lithography and etching techniques to expose the contact layer 203. The contact layer 203 may comprise doped silicon, copper, tungsten, tungsten silicide, aluminum or alloys thereof.

Barrier  Layer formation

The barrier layer 204 may be formed on the dielectric layer 201 and in the through hole 202, as shown in FIG. 2B. The barrier layer 204 may be formed of, for example, tantalum, tantalum nitride, tantalum silicon nitride, titanium, titanium nitride, titanium silicon nitride, tungsten nitride, silicon nitride, silicon carbide, derivatives thereof, alloys thereof, and combinations thereof. It may comprise the same one or more barrier materials. Barrier layer 204 may be formed using a suitable deposition process including ALD, chemical vapor deposition (CVD), physical vapor deposition (PVD), or a combination thereof. For example, a tantalum nitride barrier layer can be deposited using a CVD process or an ALD process, in which tantalum containing compounds or nitrogen precursors (eg PDMAT) and nitrogen containing compounds or tantalum precursors (eg ammonia) Respond. In another example, tantalum and / or tantalum nitride is filed Oct. 25, 2002 and is entitled "Gas Delivery Apparatus for Atomic Layer Deposition" and is commonly assigned and US2003- Deposited as barrier layer 204 by an ALD process as described in US Pat. No. 10 / 281,079 issued as 0121608. In one embodiment, the Ta / TaN bilayer can be deposited as barrier layer 204, wherein the tantalum layer and tantalum nitride layer are deposited independently by ALD, CVD, and / or PVD processes. A further publication of the process for depositing one material or multiple materials as a barrier layer or another is filed on January 17, 2002 and entitled “Reliability Barrier Integration for Cu Application. Reinforced copper with an ultrafine barrier layer for high performance splicing, US 10 / 052,681, filed Jan. 18, 2002, issued commonly as US 2002-0060363, Enhanced Copper Growth with Ultrathin Barrier Layer for High Performance Interconnect, US 10 / 199,415, issued commonly as US 2003-0082301, and filed on June 10, 2004, entitled “Copper Integration of ALD Tantalum Nitride for Copper Metallization "and described in US Pat. No. 10 / 865,042, commonly assigned and issued as US 2005-0106865, which are described herein. Reference is entirely in the processor.

Generally, barrier layer 204 is mounted with a film thickness in the range of about 5 kPa to about 50 kPa, such as about 5 kPa to about 150 kPa. In one example, barrier layer 204 is deposited on aperture 202 with sidewall coverage of about 50 GPa or less, preferably about 20 GPa or less. Barrier layer 204 containing tantalum nitride may be deposited to a thickness of about 20 GPa or less, which is sufficient thickness when applied as a barrier to prevent the diffusion of subsequent deposited metals such as copper.

Examples of tantalum containing compounds useful during the deposition process to form the barrier layer include pentakis (dimethylamino) tantalum (PDMAT or Ta [NMe 2 ] 5 ), pentakis (ethylmethylamino) tantalum (PEMAT or Ta [ N (Et) Me] 5 ), pentakis (diethylamino) tantalum (PDEAT or Ta (NEt 2 ) 5 ), tertiarybutylimino-tris (dimethylamino) tantalum (TBTDMT or ( t BuN) Ta (NMe 2 ) 3 ), tertiarybutylmino-tris (diethylamino) tantalum (TBTDET or ( t BuN) Ta (NEt 2 ) 3 ), tertiarybutylmino-tris (ethylmethylamino) tantalum (TBTEAT or ( t BuN) Ta (N (Et) Me) 3 ), such as tertiaryamylimido-tris (dimethylamido) tantalum (TAIMATA or ( t AmylN) Ta (NMe 2 ) 3 ) Including but not limited to precursors, where t Amyl is the tersiaryamil group (C 5 H 11 -or CH 3 CH 2 C (CH 3 ) 2- ), tersiarymylimido-tris (diethyla Mido) tantalum (TAIEATA or ( t AmylN) Ta (NEt 2 ) 3 , tercyriamilido-tris (ethylmethylamido) tantalum (TAIMATA or ( t AmylN) Ta ([N (Et) Me] 3 ), Such as TaF 5 or TaCl 5 Tantalum halides, derivatives thereof, or combinations thereof. Examples of nitrogen-containing compounds during the deposition process to form the barrier layer include ammonia (NH 3 ), hydrazine (N 2 H 4 ), methylhydrazine (Me (H) NNH 2 ), dimethylhydrazine (Me 2 NNH 2 Or Me (H) NN (H) Me), tertiarybutylhydrazine ( t Bu (H) NNH 2 ), phenylhydrazine (C 6 H 5 (H) NNH 2 ), nitrogen plasma sources (eg, N, N 2 , N 2 / H 2 , NH 3 , or N 2 H 4 plasma), 2,2'-azotebutane ( t BuNN t Bu), ethyl azide (EtN 3 ), trimethylsilly Azide sources such as azide (Me 3 SiN 3 ), plasmas thereof, derivatives thereof, or combinations thereof.

Barrier layer 204 comprising tantalum nitride may be deposited by an ALD process in which a monolayer of nitrogen containing compound begins with the absorption of a monolayer of tantalum containing compound on a subsequent substrate. Alternatively, the ALD process may begin with the absorption of a monolayer of nitrogen containing compound on a substrate followed by a monolayer of tantalum containing compound. Moreover, the process chamber can typically be emptied between pulses of reactant gas.

Catalyst layer formation

In step 104, a catalyst layer 206 is deposited on the barrier layer 204 as shown in FIG. 2D. The catalyst layer 206 is formed by exposing the barrier layer 204 to a ruthenium containing gas to form a ruthenium containing layer. The barrier layer 204 chemically reduces the ruthenium containing gas to form the catalyst layer 206 on the barrier layer 204 forming ruthenium. The process of forming the ruthenium containing gas and depositing the ruthenium containing layer is further described below with reference to FIGS. 4 to 7. In one embodiment, the catalyst layer can be deposited to a thickness in the range of approximately atomic ranges to about 100 ms, preferably in the range of about 2 ms to about 20 ms.

Conductive layer formation

Process 100 further includes step 106 for depositing a conductive layer on catalyst layer 206. In FIG. 2F, a bulk layer 220 is deposited on the catalyst layer 206. Bulk layer 220 may be made of copper or copper alloy deposited using only electroless copper processes such as ALD, CVD, PVD, or combinations thereof with copper electroplating. Bulk layer 220 may have a thickness in a range from about 100 mm 3 to about 10,000 mm 3. In one example, bulk layer 220 may comprise copper and is deposited by an electroless plating process.

The electroplating process is also completed in a separate electroplating chamber. One method, apparatus, and system that can be used to perform an electroplating deposition process is commonly assigned and is entitled "Electrochemical Processing Cell" and filed Oct. 9, 2002, US Pat. Further described in US Pat. No. 10/268/284, issued as 2004-0016636 and US Pat. No. 6,258,220, which are incorporated herein by reference in their entirety but not to the contrary with the claims and descriptions herein. .

B. Dielectric Deposition Process

In another aspect of the invention, the ruthenium containing layer may be deposited directly on the dielectric layer to form a catalyst layer on the substrate surface, such that a conductive layer may be deposited on the catalyst layer.

1B shows a process 300 according to one embodiment described herein to fabricate an integrated circuit. Process 300 includes steps 304-306, where the catalyst layer is deposited directly on dielectric surface 251A and contact surface 251B, as shown in FIGS. 3A-3E. 3A-3D show schematic cross-sectional views of an electronic device at different stages of a cascading manufacturing sequence, in connection with one or more embodiments of the present invention.

3A is a cross-sectional view of a substrate 250 having vias or through holes 252 formed in the dielectric layer 251 on the surface of the substrate 250. In one embodiment, process 300 contains ruthenium on dielectric layer 251 during step 304 by exposing the surface of substrate 250 to a ruthenium containing gas while the substrate maintains a target process temperature (see FIG. 3B). Begin by forming layer 256. Subsequently at step 306, ruthenium containing layer 256 is layered on dielectric layer 251 by causing the ruthenium component in the ruthenium containing gas to bond to the surface of substrate 250. Thereafter, a conductive layer 260 is deposited on the ruthenium containing layer 256 during step 306.

The surface of dielectric layer 251A is typically silicon containing oxide and / or nitride materials. However, dielectric layer 251A may be silicon dioxide, FSG, and / or carbon doped silicon oxide, such as SiO x C y , such as black diamond (available from Applied Materials, Inc., Santa Clara, Calif.). BLACK DIAMOND® may comprise an insulating material, such as a low-k dielectric. Contact surface 251B is an exposed area of the junction disposed below the underlying layer and is typically copper, tungsten, ruthenium, CoWP, CoWPB, aluminum, aluminum alloy, doped silicon, titanium, molybdenum, tantalum, silicides of such metals, or And materials such as nitrides.

Catalyst layer formation

In step 304, ruthenium containing layer 256 is deposited on dielectric layer 251 by application of a ruthenium containing gas. In one example, ruthenium containing layer 256 is deposited to a thickness in the range of approximately atomic layers to about 100 microns, preferably about 5 microns to about 50 microns, for example about 10 microns. The formation of the ruthenium containing gas and the deposition process of the ruthenium containing layer are further described below with reference to FIGS. 4 to 7. In general, ruthenium containing layer 256 is deposited such that the formed layer is attached to a dielectric layer 251 as well as a subsequent conductive layer, such as a seed layer or a bulk layer.

Conductive layer formation

Process 300 further includes a step 306 for depositing a conductive layer 260 on the ruthenium containing layer 256. Conductive layer 260 may be a seed layer (eg, a thin metal layer (see FIG. 3D)) or a bulk layer (eg, filling through hole 252 (see FIG. 3C)) deposited on ruthenium containing layer 256. Can be formed. The seed layer may be a continuous layer deposited by using conventional deposition techniques, such as ALD, CVD, PVD, electroplating, or electroless processes. The invention as described herein may be useful because the deposition of a ruthenium containing layer on the surface of the substrate may be a seed layer for directly depositing the electroplated layer. The seed layer may have a thickness in the range of about 20 to about 100 mm 3 from a nearly single rich layer. In general, the seed layer comprises copper or a copper alloy.

Ruthenium 4-acid freight  Forming and Deposition Apparatus and Methods

The process for depositing a ruthenium containing layer having target properties on the substrate surface, eg, step 104 of FIG. 1A and step 304 in FIG. 1B, is a process step 702-706 in the process 700 described below. Can be performed by In general, process step 104 of FIG. 1A and step 304 of FIG. 1B are applied to generate a ruthenium-containing gas having target properties by generating a ruthenium 4 oxide containing gas and exposing it to a temperature controlled substrate surface. As described in various aspects of the present invention, it may be desirable to selectively or non-selectively form a ruthenium dioxide or metal ruthenium layer on the surface of the substrate to form a ruthenium containing layer. Described herein are typical apparatus and methods for forming a gas containing ruthenium 4 oxide on a substrate surface.

4 illustrates one embodiment of a deposition chamber 600 that may be applied to generate and deposit a ruthenium containing layer on a substrate surface. In one embodiment, the ruthenium containing layer is formed on the substrate surface by producing ruthenium 4 oxide in an outer container and then delivering the generated ruthenium 4 oxide gas to the surface of the temperature control substrate located in the processing chamber.

In one embodiment, a ruthenium 4 oxide containing gas is generated or formed by passing an ozone containing gas across a ruthenium source contained in an outer container. In one embodiment, the ruthenium source is maintained at a temperature near room temperature. In one embodiment, the ruthenium source contains an amount of ruthenium metal (Ru) that reacts with ozone. In one embodiment, the metal ruthenium source included in the outer container is in the form of a powder, porous block, or solid block.

In another embodiment, the ruthenium source contained in the outer container comprises a constant amount of bicarbonate material, such as sodium perruthenate salt (NaRuO 4 ), potassium perruthenate salt (KRuO 4 ), or derivatives thereof, wherein According to 1) or (2), it reacts with ozone to form ruthenium 4 oxide (RuO 4 ), which is a compound which volatilizes in the reaction state.

2 NaRuO 4 + O 3 → RuO 4 + Na 2 O + O 2 (1)

2KRuO 4 + O 3 → RuO 4 + K 2 O + O 2 (2)

It is not intended to be limited to the list of materials shown herein and therefore any material which forms a ruthenium 4 oxide containing gas upon exposure to ozone or other oxidizing gases may be used without change from the basic scope of the present invention. Various conventional forming processes can be used to form various ruthenium source materials for use in the outer container. One example of a conventional process that can be used to form the perruthenate is to mix sodium peroxide (Na 2 O 2 ) with metal ruthenium powder and then sinter the mixture in a furnace or vacuum furnace at a temperature of about 500 ° C. Some references suggesting the use of a spray pyrolysis type process may be used to form the perruthenate material. For example, in a spray pyrolysis system, non-volatile materials such as sodium peroxide and ruthenium are placed in a fluidized medium, such as water, sprayed to form droplets, which droplets can be used in furnaces, conventional thermal spraying devices, or other devices. It is heated to form a powder containing the reaction material (eg, NaRuO 4 ).

Deposition chamber 600 generally includes a process gas delivery system 601 and a processing chamber 603. 4 illustrates one embodiment of a process chamber 603 that may be applied to deposit a ruthenium containing layer on a substrate surface. In one embodiment, the processing chamber 603 is provided with a barrier layer (Fig. 1) on the surface of the substrate by use of a CVD, ALD, PE-CVD, or PE-ALD process prior to depositing a ruthenium containing layer on the surface of the substrate. A processing chamber 603 that can be applied to deposit a layer, such as 2A-2D). In another aspect, the processing chamber 603 is applied primarily to deposit ruthenium containing layers so that certain conventional or subsequent device fabrication steps are performed in other processing chambers. In one aspect, the before or after process chamber and process chamber 603 are attached to a cluster tool (FIG. 8) that is applied to perform a target device manufacturing process sequence. For example, in a processing sequence in which the barrier layer is deposited before the ruthenium containing layer, the barrier layer may be formed in an ENDURA® iCuB / S process chamber or before forming the ruthenium containing layer in the processing chamber 603. It may be deposited in an ALD process chamber, such as a PRODUCER® type process chamber. In another embodiment, the processing chamber 603 is applied to deposit a ruthenium containing layer at a pressure below atmospheric pressure, such as a pressure between about 0.1 mTorr and about 50 Torr. The use of a vacuum processing chamber during processing can be useful because processing in a vacuum can reduce the amount of contaminants that can be incorporated into the deposited film. Vacuum treatment also tends to improve the diffusion transport process of ruthenium 4 oxide to the surface of the substrate to reduce the constraints imposed by the convective transport process.

The processing chamber 603 generally includes a processing enclosure 404, a gas distribution showerhead 410, a temperature controlled substrate support 623, a remote plasma source 670 and an inlet line 426 of the processing chamber 603. A process gas delivery system 601 is connected. The processing enclosure 404 generally includes a sidewall 405, a ceiling 406, and a base 407, which surround the processing chamber 603 to form a process region 421. A substrate support 623 that supports the substrate 422 is mounted to the base 407 of the processing chamber 603. The back gas source (not shown) supplies a gas, such as helium, into the gap between the back side of the substrate 422 and the substrate support surface 623A to improve the thermal state between the substrate support 623 and the substrate 422. . In one embodiment of the deposition chamber 600, the substrate support 623 is a ruthenium layer that is heated and / or cooled by the use of a heat exchanger 620 and a temperature controller 621 to be deposited on the substrate 422 surface. To improve and control the properties. In one aspect, the heat exchange device 620 is a fluid heat exchange device that includes a built-in heat transfer line 625 in communication with a heat control device 621 that controls the heat exchange fluid temperature. In another aspect, the heat exchange device 620 is a resistive heater, in which case the embedded heat transfer line 625 is a resistive heating element in communication with the temperature control device 621. In another aspect, the heat exchange device 620 is a thermoelectric device that is applied to heat and cool the substrate support 623. Vacuum pumps 435, such as turbo-pumps, cooling turbopumps, route type blowers and / or rough pumps, control the pressure in the processing chamber 603. The gas distribution showerhead 410 consists of a gas distribution plenum 420 connected to the inlet line 426 and the process gas delivery system 601. Inlet line 426 and process gas distribution system 601 are in communication with process region 427 on substrate 422 through a plurality of gas nozzle openings 430.

In one aspect of the invention, it may be desirable to generate a plasma during the deposition process to improve the properties of the deposited ruthenium containing layer. In this configuration, the showerhead 410 acting as a plasma control device using attachment to the first impedance match element 475 and the first RF power source 490 may be a conductive material (eg, anode). Treated aluminum). The bias RF generator 462 applies RF bias power to the substrate support 623 and the substrate 422 through the impedance match element 464. Controller 480 is applied to control the impedance match elements (ie, 475 and 464), RF power sources (ie, 490 and 462) and all other aspects of the plasma process. The frequency of power delivered by the RF power source may range from about 0.4 MHz to 10 GHz or more. In one embodiment, the dynamic impedance match is provided to the showerhead 410 and the substrate support 623 by frequency tuning and / or forward power supply. Although FIG. 4 illustrates a capacitively coupled plasma chamber, another embodiment of the present invention is a combination of an inductively and capacitively coupled plasma chamber without changing from the basic scope of the invention. It may include.

In one embodiment, the processing chamber 603 is a remote plasma source (RPS) (FIG. 4) that is adapted to deliver various plasma generating species or radicals through the inlet line 671 to the processing region 427. , 6A-6C and 11). An RPS that can be applied for use with the deposition chamber 600 is an ASTRON® type AX7651 reactive gas generator from MKS ASTEX® product of Wilmington, Massachusetts. RPS is generally used to form reaction components, such as hydrogen (H) radicals, which are introduced into treatment region 427. Thus, RPS improves the reactivity of activated gas species to enhance the reaction process. A typical RPS process may include using 1,000 sccm of H 2 and 1,000 sccm of Argon and 350 Watts of RF power and a frequency of about 13.56 MHz. In one embodiment, forming gases such as 4% H 2 and residual nitrogen may be used. In another embodiment, gas containing hydrazine (N 2 H 4 ) can be used. In general, the use of plasma activation to reduce species capable of converting RuO 2 to Ru allows this reaction to be processed at low temperatures. This process may be most useful when it is generally desirable to deposit RuO 2 below about 180 ° C. and subsequently subsequently perform a reduction for metal ruthenium at the same temperature and / or in the same chamber.

In one embodiment of the deposition chamber 600, process gas delivery system 601 may be applied to deliver a ruthenium containing gas, or vapor, such that a ruthenium containing layer may be formed on the substrate surface. Process gas delivery system 601 generally includes one or more gas sources 611A through 611E, ozone generator 612, process vessel 630, source vessel assembly 640, and inlet lines of process chamber 603. Outflow line 660 attached to 426. One or more gas sources 611A through 611E are generally sources of various carriers and / or purge gases that may be used during processing within processing chamber 603. One or more gases delivered from gas sources 611A through 611E may include, for example, nitrogen, argon, helium, hydrogen, or other similar gases.

Typically, ozone generator 612 converts an oxygen containing gas from a gas source (not shown) attached to ozone generator 612 to a gas containing between about 4 wt.% And about 100 wt.% Ozone (O 3 ). The remainder is typically oxygen. Preferably, the concentration of ozone is about 6 wt.% To about 100 wt.%. Note that forming ozone at concentrations greater than about 15% generally requires a purification process that requires the process of purging the container with an inert gas to absorb ozone and remove contaminants on the cooling surface in the processing container. shall. However, the ozone concentration can be increased and decreased based on the type of ozone generating equipment used and the amount of ozone required. Conventional ozone generators that can be applied for use with the deposition chamber 600 are SEMOZON® and LIQUOZON® purchased from Wilkeston, Mass., USA. ) Ozone generator. Gas source 611A may be purged or applied as a carrier gas to deliver ozone generated in ozone generator 612 to input port 635 of processing vessel 630.

In one embodiment of the process gas delivery system 601, the processing vessel 630 includes a vessel 631, a temperature control device 634A, an input port 635, and an output port 636. The vessel 631 is generally an enclosed region made of or coated with glass, ceramic, or an inert material that does not react with the processing gas formed in the vessel 631. In one embodiment, the vessel 631 is preferably a ruthenium source (eg, ruthenium) in the form of a porous solid, powder, or pellets to promote the formation of ruthenium 4 oxide when ozone gas is delivered into the vessel 631. Metal, sodium perruthenate: see element "A"). Temperature control device 634A generally includes a temperature controller 634B and a heat exchanger 634C, which is adapted to control the temperature of vessel 631 to the target processing temperature during the ruthenium 4 oxide generation process. In one embodiment, the heat exchange device 634C is a temperature controlled fluid thermal device, resistive heating device and / or thermoelectric device, which is applied to heat and / or cool the vessel 631 during different stages of the process.

In one embodiment, the remote plasma source 673 is connected to the processing vessel 630 via an RPS inlet line 673A such that at different stages of the ruthenium 4 oxide formation process, the ruthenium source is transferred into the vessel 631. H) can be recycled by injecting the radicals to reduce any formed oxide on the surface of the lithium source. Regeneration may be required when a significant amount of exposed ruthenium source is formed in which the bottom layer of ruthenium oxide (Ru0 2 ) is included in the vessel 631. In one embodiment, the regeneration process is performed by introducing a hydrogen containing gas into a ruthenium source that is heated to an elevated temperature to reduce oxides formed.

Referring to FIG. 4, the source vessel assembly 640 includes a source vessel 641, a temperature controller 642, an inlet port 645, and an outlet port 646. Source vessel 641 is adapted to collect and maintain ruthenium 4 oxide generated in process vessel 630. Source vessel 641 generally contains glass, ceramic, plastic (eg, Teflon®, PTFE, or polyethylene), or other materials that do not react with ruthenium 4 oxide and have target thermal shock and mechanical properties. Attached, coated or manufactured. When used, the temperature controller 642 cools the source vessel 641 to a temperature less than 20 ° C. to condense the ruthenium 4 oxide gas on the wall of the source vessel. Temperature controller 642 is generally adapted to control the temperature of source vessel 641 to a target processing temperature, including temperature controller device 643 and heat exchange device 644. In one aspect, the heat exchange device 644 is a temperature controlled fluid heat exchange device, resistive heating device and / or thermoelectric device applied to heat and cool the source vessel 641.

5 illustrates a process 700 according to one embodiment described herein to form a ruthenium containing layer on a substrate surface. Process 700 includes steps 702-708 where a ruthenium containing layer is deposited directly on the substrate surface. The first process step 702 of process 700 includes forming ruthenium 4 oxide gas and collecting gas generated in the source vessel 641. In process step 702, ozone generated in the ozone generator 612 is delivered to a ruthenium source included in the processing vessel 631 to form a flow of ruthenium 4 oxide containing gas collected in the vessel 641. Thus, during process step 702, the ozone containing gas flows across a ruthenium source, causing ruthenium 4 oxide to form and be swept away by the flowing gas. During this process the gas flow path traverses the ruthenium source (item “A”) from the ozone generator 612 in the inlet port 635, through the process line 648 through the outlet port 636 in the vessel 631. Into a closed source container 641. In one embodiment, prior to introducing the ruthenium 4 oxide containing gas, it may be desirable to empty the source vessel 641 using a conventional vacuum pump 652 (eg, a conventional rough pump, vacuum ejector). . In one embodiment, gas source 611A is used to form an ozone containing gas that includes purge oxygen and ozone or an oxygen containing gas and an inert gas that dilutes the ozone. In one embodiment of the processing step 702, the ruthenium source (item “A”) included in the vessel 631 is at a temperature between about 0 ° C. and about 100 ° C., more preferably between about 20 ° C. and about 60 ° C. To maintain the ruthenium 4 oxide formation process in the container 631. Although low ruthenium 4 oxide generation temperatures are generally preferred, it is believed that the temperature required to form the ruthenium 4 oxide gas is somewhat dependent on the amount of moisture contained in the vessel 631 during the process. During process step 702, source vessel 641 is maintained at a temperature below about 25 ° C. at a pressure that allows the ruthenium 4 oxide generated on the walls of source vessel 641 to condense, or crystallize (or solidify). . For example, source vessel 641 maintains a pressure of about 5 Torr and a temperature of about -20 ° C to about 25 ° C. By cooling the ruthenium 4 oxide and causing the ruthenium 4 oxide to condense or solidify on the walls of the source vessel 641, unwanted oxygen (O 2 ) and ozone (O 3 ) containing components in the ruthenium 4 oxide containing gas are separated to May be removed in a second process step 704. In one embodiment, it may be desirable to inject a certain amount of water, or a water containing gas, into the container 631 to improve the ruthenium 4 oxide generation process. Infusion of water is important to improve the separation of ruthenium 4 oxides from ruthenium sources, for example when the ruthenium source contains sodium perruthenate, potassium perruthenate, or derivatives thereof. can do. In one embodiment, it may be desirable to remove excess water by conventional physical separation (eg, molecular sieve) processes after the separation process is performed.

The second process step 704, or purging step, is designed to remove unwanted oxygen (O 2 ) and unreacted ozone (O 3 ) from the ruthenium 4 oxide containing gas. Referring to FIG. 4, in one embodiment, the ozone shutoff valve 612A is closed and one or more purge gases are processed from the one or more gas sources 611B-C through the processing vessel 630 to the process line 648. ), The second process step 704 while the wall of the source vessel 641 is maintained at a temperature of 25 ° C. or less by flowing from the source vessel 641 and then through the exhaust line 651 to the exhaust system 650. Is completed. The amount of non-solidified and non-condensed ruthenium 4 oxide during completion of the discarded process step 704 is determined by adding a stop of the target length between process step 702 and process step 704 such that the ruthenium 4 oxide is condensed or solidified. Can be minimized. The amount of non-solidified or non-condensed ruthenium 4 oxide discarded may reduce the source container wall temperature to increase the rate of solidification, and / or increase the surface area of the source container to increase the interaction of the wall with the ruthenium 4 oxide containing gas. It may be further reduced by increasing. The purge gas delivered from one or more gas sources 611B through 611C may be, for example, nitrogen, argon, helium, or other drying and cleaning process gases. Since unwanted oxygen (O 2 ) and unreacted ozone (O 3 ) components can cause unwanted oxidation of exposed surfaces on the substrate, the process of removing these components can be critical to the success of the ruthenium deposition process. Since copper has a high affinity for oxygen and readily corrodes in the presence of oxidizing species, removal of these unwanted oxygen (O 2 ) and unreacted ozone (O 3 ) components results in the copper junction being exposed on the surface of the substrate. Especially important in the place. In one embodiment, process step 704 is completed until the concentration of oxygen (O 2 ) and / or unreacted ozone (O 3 ) is below about 100 parts per million (ppm). In one embodiment, it may be desirable to heat vessel 631 to a temperature between about 20 ° C. and 25 ° C. during process step 704 to ensure that all of the formed ruthenium 4 oxide is removed from process vessel 630. have.

In one embodiment, the purging process (step 704) is completed by emptying the source vessel 641 using the vacuum pump 652 to remove contaminants. In order to prevent some amount of ruthenium 4 oxide from being removed from the source vessel assembly 640 during this step, the temperature and pressure of the vessel may be controlled to minimize the loss due to vaporization. For example, it may be desirable to pump the source vessel assembly 640 to a pressure of about 5 Torr and maintain it at a temperature below about 0 ° C.

In one embodiment, transferring the third process step 706 or ruthenium 4 oxide to the processing chamber 603 may include purging the source container 641 such that the valve 637A may transfer the source container 641 to the processing container 630. It is closed after closing to block from). Process step 706 begins when the source vessel 641 is heated to a temperature such that condensed or solidified ruthenium 4 oxide forms a ruthenium 4 oxide gas, wherein one or more gas sources 611 (eg, , Items 611D and / or 611E), gas sources connected to the shutoff valves (eg, items 638 and / or 639), and process chamber shutoff valves 661 are opened to introduce a ruthenium 4 oxide containing gas. A ruthenium containing layer may be formed on the substrate surface by flowing into line 426, through showerhead 410, into process region 427, and across temperature controlled substrate 422. In one embodiment, source vessel 641 is heated to a temperature of about 0 ° C. to about 50 ° C. such that condensed or solidified ruthenium 4 oxide forms a ruthenium 4 oxide gas. Even at low temperatures, for example about 5 ° C., an equilibrium partial pressure of ruthenium 4 oxide gas is present in the source vessel 641. Thus, in one embodiment, by knowing the mass of ruthenium 4 oxide contained in the vessel and knowing the temperature and volume of the source vessel 641, the repeatable mass can be delivered to the processing chamber 603. In another embodiment, the target concentration of ruthenium 4 oxide is known to form a known gas, so that the rate of sublimation or vaporization of ruthenium 4 oxide at a given temperature for a source vessel 641 of a given size is obtained so that By flowing through 641, a continuous flow of ruthenium 4 oxide containing gas can be formed and delivered to the processing chamber 603.

To deposit a ruthenium containing layer on the surface of the substrate, ruthenium 4 oxide (RuO 4 ) is thermodynamically stabilized ruthenium dioxide (RuO 2 ) at a temperature greater than 180 ° C., and in the presence of hydrogen (H 2 ). Slightly high temperatures will undergo spontaneous decomposition, and the deposition is directly processed to the target result of forming a ruthenium 4 oxide layer. The equilibrium equation for the response can be found in equation (3).

RuO 4 + 4H 2 → Ru (metal) + 4H 2 O (3)

Thus, in one aspect of the present invention, by the use of the temperature control substrate support 623 during process step 706, at a temperature of about 180 ° C. or higher, more preferably at a temperature of 180 ° C. to about 450 ° C., Preferably at a temperature of about 200 ° C. to about 400 ° C., the substrate surface is maintained. In order to form the metal ruthenium layer, the temperature may be between about 300 ° C and about 400 ° C. Typically, the process chamber pressure is maintained below 10 Torr, preferably between about 500 miliTorr and about 5 Torr. By controlling the surface temperature of the substrate, the crystal structure of the deposited ruthenium containing layer and the selectivity of the deposited ruthenium containing layer can be adjusted and controlled as desired. The crystalline ruthenium containing layer may be formed at a temperature above 350 ° C.

In one embodiment of process step 706, a ruthenium 4 oxide containing gas is formed when a nitrogen containing gas is delivered from a gas source 611D, and a hydrogen (H 2 ) containing gas (eg, hydrogen (H 2 )). Hydrazine (N 2 H 4 )) is delivered from the gas source 611E through the source vessel assembly 640 containing a certain amount of ruthenium 4 oxide and then through the process chamber 603. For example, 100 sccm of nitrogen and 100 sccm of H 2 gas are delivered to the process chamber 603 maintained at a pressure of about 0.1 to 10 Torr, and more preferably about 2 Torr. The target flow rate of the gas delivered from the gas source 611 (e.g., items 611D through 611E) is determined by the target concentration of ruthenium 4 oxide in the ruthenium 4 oxide containing gas and the concentration of ruthenium 4 oxide from the wall of the source vessel 641. It depends on the vaporization rate.

In one embodiment, remote plasma source 670 is used to enhance the metal ruthenium layer formation process during process step 706. In this case, the H radicals generated in the remote plasma source are injected into the treatment region 427 to reduce the oxides formed on the surface of the ruthenium source. In one embodiment, RPS is used to generate H radicals when a ruthenium 4 oxide containing gas is delivered to the treatment region 427. In another embodiment, RPS is used only after each successive monolayer of ruthenium is formed to form a two step process consisting of a deposition step and a reduction of ruthenium layer.

In one embodiment of process step 706, the amount of ruthenium 4 oxide gas generated and distributed in process chamber 603 is monitored so that the process is repeatable and complete saturation of the process chamber components is achieved to achieve the target of the ruthenium-containing film. The thickness is controlled to ensure that it is deposited. In one embodiment, the mass of ruthenium 4 oxide delivered to the process chamber is measured by the use of a conventional electronic scale, load cell, or other gravimetric device by measuring the change in weight of the source vessel 641 as a function of time. Monitored.

In one embodiment, the gas delivery system 601 is adapted to deliver a single dose or mass of ruthenium 4 oxide to the process chamber 603 and the substrate to form a ruthenium containing layer on the surface of the substrate. do. In another embodiment, multiple sequential doses of ruthenium 4 oxide are transferred to process chamber 603 to form multiple ruthenium containing layers. To perform multiple sequential doses, one or more process steps 702-706, described in connection with FIG. 5 or 7, are repeated several times to form a multi-layer ruthenium containing film. In another embodiment, the length of process step 702 and the surface area of the source vessel 641 are both such that they allow for a continuous concentration of a target concentration of ruthenium 4 oxide containing gas across the area of the substrate during the ruthenium containing layer deposition process. Has a size. The gas flow distribution across the surface of the substrate allows for the formation of a uniform layer on the substrate being processed in the processing chamber, especially for processes that are governed by mass transfer limiting reactions (CVD type reactions), and rapid surface saturation allows for reaction rate limited deposition. Important for ALD type processes required. Thus, the use of uniform gas flow across the substrate surface by the use of showerhead 410 may be important to ensure uniform process results across the surface of the substrate.

In one aspect of the invention, the process of delivering a mass of ruthenium 4 oxide to the process chamber 603 is useful for an ALD or CVD type process, in which no organic material formed in the ALD or CVD precursor is present in the ruthenium containing layer. Because it does not bond to the growing ruthenium containing layer. The incorporation of organic materials into the growing ruthenium film has a great influence on the electrical resistance, adhesion and stress transfer and electrophoretic properties of the formed device. In addition, because the size of the ruthenium 4 oxide molecule is much smaller than that of traditional ruthenium containing precursors, the improved ruthenium coverage per ALD cycle results in an increase in ruthenium containing layer deposition rate per ALD cycle using ruthenium 4 oxide over conventional precursors.

6A shows another embodiment of a gas delivery system 602 in a deposition chamber 600. The gas delivery system 602 is described in connection with FIG. 4 except that the gas delivery system 602 includes two or more source vessel assemblies 640 (eg, items 640A through 640B). Similar to gas delivery system 601. Each source vessel assembly 640A and 640B has its own source vessel (elements 641A through 641B), a temperature controller (elements 642A through 642B), a temperature controller device (elements 643A through 643B), a heat exchange device (Elements 644A through 644B), inlet ports (elements 645A through 645B) and outlet ports (elements 646A through 646B). In this configuration, as shown in FIG. 6A, two source vessels 640A through 640B are used to alternately collect and distribute the generated ruthenium 4 oxide so that the chamber process collects ruthenium 4 oxide in a single source vessel. It is not hindered by the time required to. For example, using a gas source 611D to 611E, a first source vessel 641A, and a process chamber shutoff valve 661A, the first source vessel 640A is processed on a substrate located within the process chamber 603. Upon completing step 706, the second source vessel 640B includes an ozone generator 612, a processing vessel, a source vessel 640B, an inlet port 635, an outlet port 636, a shutoff valve 637B and Process line 648 may be used to complete process step 702.

6B illustrates one aspect of gas distribution system 602, where each two or more source vessel assemblies 640 (eg, elements 640A or 640B) are processed on their own or separately. Individually supported by the vessel 630. This configuration can be useful when one of the containers 631 (eg, 631A or 631B) is required to be replaced when the ruthenium source material is depleted or a maintenance action is needed to be performed on one of the containers. In one embodiment, as shown in FIG. 6B, gas sources 611A-611C and ozone generator 612 are shared by first processing vessel 630A and second processing vessel 630B.

In one aspect of the gas delivery system 602, the controller 480 processes to ensure that the at least one source vessel 640A or 640B contains a target amount of solidified or crystallized ruthenium 4 oxide at any given time. It is applied to monitor the process performed in the chamber 603. A typical aspect of the process is that the mass of ruthenium 4 oxide in the source vessels 640A through 640B may be necessary for the controller 480 to monitor, and the state of the process is ongoing in the process chamber 603, and / or Whether one or more substrates are waiting to process in the deposition chamber 600. In this way, the gas delivery system 602 is adapted to anticipate and adjust the proportion of ruthenium 4 oxide as required to ensure that the one or more vessels 640A through 640B contain the target mass of precursor at the target time. . This configuration is because the ruthenium 4 oxide generation process can be kinematically limited by the reaction rate of ozone while limiting ruthenium or mass transport by the flow of ozone containing gas across the surface of the ruthenium source contained within the treatment vessel 631. It is important. Thus, based on multiple process variables, the ruthenium 4 oxide generation process has a maximum incidence rate at which the ruthenium 4 oxide can be formed and the amount of chamber deposition is then limited by this process. The generation process variables, to name a few, can be influenced by the ozone gas / ruthenium solid interface area, the temperature of the ruthenium source, the concentration of ozone in the treatment vessel 631, and the flow rate of the carrier gas delivered into the treatment vessel. Can be. Thus, in one aspect of the present invention, the controller 480 is configured to adjust the flow rate of the ozone containing gas into the processing vessel 631 at the beginning of the ruthenium 4 oxide formation process and to control the ruthenium 4 oxide formation rate. Prevents the delivery system from filling the source container 641 in the time required to generate ruthenium 4 oxide at a rate that exceeds the maximum ruthenium 4 oxide formation rate.

FIG. 6C controls including a dosing vessel assembly 669 mounted to the outlet line 660 and shows one embodiment of a gas delivery system 601 similar to that shown in FIG. 6B, which is targeted. ) A repeatable mass of ruthenium 4 oxide gas, or a volume of ruthenium 4 oxide gas, is delivered to the process chamber 603 at temperature and pressure. Dosing vessel assembly 669 generally includes an inlet shutoff valve 664, a dosing vessel 662, and an outlet shutoff valve 663. In one embodiment, dosing vessel assembly 669 also includes temperature sensor 665, pressure sensor 667, heat exchanger 668 (eg, fluid heat exchanger, resistive heating and / or thermoelectric device). And a temperature controller 672 in communication with the controller 480. In general, in this configuration the controller 480 is adapted to control and monitor the state of the ruthenium 4 oxide gas supported in the dosing vessel 662.

In another embodiment, the dosing vessel assembly 669 also includes an optical sensor 681, which is adapted to sense ruthenium 4 oxide and communicate with the controller 480. In one embodiment, optical sensor 681 is applied to detect the presence of ruthenium 4 oxide containing gas in dosing vessel 662 by measuring a change in absorption of a predetermined wavelength of light in the ruthenium 4 oxide containing gas. In such a configuration the optical sensor may be an optical prism or other conventional device that is measured to detect the presence of a target concentration of ruthenium 4 oxide gas in the dosing vessel 662.

FIG. 7 shows process 700A, which is a variation of process 700 shown in FIG. 5, including a new fill dosing vessel step 705. In this variant of the process 700, the dosing vessel 662 is filled after the purge source vessel step 704 is completed, but before the process step 706. In one embodiment, prior to starting process step 705, the dosing vessel is emptied to the target vacuum pressure by opening the outlet valve 663, while the inlet valve 664 is closed, thereby processing the chamber 603. Vacuum pump 435 in the interior allows emptying dosing vessel 662.

Process step 705 includes a certain amount of condensed or solidified ruthenium 4 oxide in which one of the source vessels 641A, or 641B is condensed or solidified ruthenium 4 oxide in the source vessel 640A, 640B. Heated to a temperature to form a containing gas. If the target temperature is achieved in the source vessels 640A, 640B, while the outflow shutoff valve 663 is closed, the process chamber shutoff valve 661A, or 661B, and the inlet shutoff valve 664 are opened, thereby ruthenium 4 Oxide gas is allowed to flow into the dosing vessel 662. Once the target pressure and temperature of the ruthenium 4 oxide gas is achieved in the dosing vessel 662, the inlet valve 664 is closed. A fixed mass or volume at the target temperature and pressure is maintained in the dosing vessel 662. In general, the mass of ruthenium 4 oxide retained in the dosing vessel 662 until the process step 706 is completed, the temperature sensor 665, the pressure sensor 667, the heat exchanger 668 and the temperature controller. Maintained by use of 672. In one embodiment, process step 706 begins after a target temperature and / or pressure is achieved in dosing vessel 662 such that a repeatable deposition process, ie, process step 706 is performed on the substrate. .

In process 700A, process step 706 is modified from the process described above in connection with FIG. 5 by the incorporation of the dosing vessel 662 in the system. In this configuration, however, while the inlet valve 664 is closed, the process 706 is completed when the gas source shutoff valve 673 and the outlet valve 663 are opened, so that the carrier gas from the inert gas source 674 is completed. Flows through the dosing vessel 662 and passes the ruthenium 4 oxide containing gas to the inlet line 426, through the showerhead 410, into the emptied process region 427 and through the temperature controlled substrate 422. It is transported such that a ruthenium containing layer can be formed on the substrate surface. In one embodiment, the carrier gas is not used to deliver ruthenium 4 oxide to the process region 427.

In one embodiment, an inert gas source 674 and / or dosing vessel 662 are used to “dose” or “pulse” a ruthenium 4 oxide containing gas into the process region 427. The gas can then saturate the surface of the substrate (eg, an ALD type process). A "dose" or "dosing process" may be injected into the process chamber 603 with a target amount of ruthenium containing gas, which may be performed by opening and closing various shutoff valves for a target time. In one embodiment, no inert gas is delivered from the gas source 674 to the dosing vessel 662 during the dosing process.

Referring to FIG. 4, in one aspect of the invention, an ozone generator 612B is connected to the process chamber 603 and used to remove ruthenium deposited on various chamber components during a previous deposition step. In one embodiment, a single ozone generator 612 is used to form a ruthenium 4 oxide containing gas to clean the processing chamber 603.

Optional ruthenium tetraacid freight  Generation process

9 shows one embodiment of a ruthenium 4 oxide containing solvent formation process 1001 that may be used to form ruthenium 4 oxide using a perruthenate salt containing source material. The first step of the ruthenium 4 oxide containing solvent formation process 1001 (urea 1002) is firstly performed, such as sodium perrunate, in an aqueous solution in a first vessel (eg, urea 1021 in FIG. 10C). Start by dissolving the ruthenate material. In one embodiment, the process solution may be formed by dissolving sodium perruthenate with a solution of excess sodium hypochlorite (NaOCl) followed by titration of sulfuric acid to a pH value of about 7 to liberate ruthenium 4 oxide. Hypochlorite materials such as potassium hypochlorite or calcium hypochlorite may also be used in place of sodium hypochlorite. Ruthenium 4 oxide is formed according to reaction (4).

2NaRuO 4 + H 2 SO 4 + NaOCl → 2RuO 4 + NaCl + H 2 O + Na 2 SO 4 (4)

In one embodiment, the process solution is formed by mixing 50 mL of sodium hypochlorite (eg, 10% NaOCl solution) with 1 gram of finely powdered sodium perruthenate and stirring until completely dissolved. do. Sufficient 10% solution of H 2 SO 4 in water may be added to achieve a pH of about 7. In general, certain acids that are non-oxidative and nonvolatile may be used in place of sulfuric acid, such as phosphoric acid (H 3 PO 4 ).

In one embodiment of ruthenium 4 oxide comprising a solvent formation process 1001, an optional purge step 1004 is then performed on the process solution. Step 1005 generally comprises 1) raising the process solution mixture to a temperature of about 50 ° C. in the first vessel, and 2) cooling the vapor generated in the first vessel to a second vessel (eg, Foaming an inert gas or ozone (O 3 ) through the process solution to deliver up to 20 ° C.) and the vapor generated in the foaming step condenses the mixture of ruthenium 4 oxide and water. Ruthenium 4 oxide vapor generated in the first vessel is collected in clean water contained in the second vessel. After completion of step 1004, the second vessel comprises an aqueous solution component and a solvent forming process 1001 comprising the remaining ruthenium 4 oxide is used, and the components on the left side in the first vessel may be discarded or regenerated. . Step 1004 may be used to purify the process solution used as the ruthenium 4 oxide source material.

In step 1006, a certain amount of solvent is added to the aqueous solution to dissolve all of the ruthenium 4 oxide contained in the aqueous solution. Suitable solvents generally include materials such as perfluorocarbons (C x F Y ), hydrofluorocarbons (H x C Y F z ), or chlorofluorocarbons (freons or CFCs). In general, any solvent material that is nonpolar, non-oxidative and having a boiling point near about 50 ° C. and no longer preferably below may be used to perform this process. Preferably, the boiling point of the solvent is in the range of about 25 ° C to 40 ° C. Generally, both chlorofluorocarbons and perfluorocarbons are effective, but perfluorocarbons which are shown as not acting as ozone depleting substances (ODS) are preferred. For example, suitable solvents are perfluoropentane (C 5 F 12 ), perfluorohexane (C 6 F 14 ), Freon 11 (fluorotrichloromethane (CFCl 3 ), or Freon 113 (1,1, Freon-containing materials, such as 2-trichloro-1,2,3-trifluoroethane (CCl 2 FCClF 2 )), or derivatives thereof, or combinations thereof. If it can be carried out in a sealing system that can prevent the release of a variety of conventional refrigerants can be applied as the solvent Perfluoropentane can have many advantages for use in the semiconductor industry, which is easy in pure form This is because it is commercially available, not ODS, and is very inert and generally does not react with the material when exposed during processing.

In one embodiment of the ruthenium 4 oxide containing solvent formation process 1001, optional step 1008 may then be completed on the solvent mixture formed in step 1006. This step adds the action of foamed ozone (O 3 ) through the solvent mixture contained in the first vessel (eg, urea 1021 in FIG. 10C), which is preferably maintained at approximately room temperature to provide ruthenium 4 oxide Ensure the completion of its formation. One embodiment of the ruthenium generation step is performed at a rate of 500 mL / min through a mixture comprising 1 g sodium perruthenate, 50 mL water and 25 g Freon 113 until a target amount of ruthenium 4 oxide is formed by the process. Flowing a% ozone containing gas.

The final step 1010 of the ruthenium 4 oxide containing solvent formation process 1001 generally requires separating water from the solvent mixture formed after completion of steps 1006 and / or 1008 to form a “anhydrous” solvent mixture. In one embodiment, selecting a solvent that does not mix with water allows water to be easily removed from the solvent mixture by the use of certain conventional physical separation processes. Failure to separate most, but not all, of the water from the rest of the solvent mixture can cause problems in subsequent process steps, which can reduce the selectivity of ruthenium containing layer deposition. Since the solvent selected is not mixed with water, such as perfluoropentane, Freon 11 or Freon 113, if the density is between water, most of the water may be of a simple mechanical technique (eg separation funnel, siphon or pump). By use it can be easily separated from the static mixture. Complete removal of residual water can be performed by contacting the molecular sieve (eg, 3A molecular sieve) with the liquid followed by conventional filtration. In one embodiment, the “anhydrous” solvent mixture is delivered into a container that can be used as an ALD or CVD precursor source for use on a process tool where ruthenium 4 oxide is deposited. It is important to note that pure solid ruthenium 4 oxides are generally unstable and difficult to process and difficult to transport from one place to another. Thus, one advantage of the present invention described herein is to form a method that can effectively transport and / or generate pure ruthenium 4 oxide that can be used to form a ruthenium containing layer. In one embodiment, it may be desirable to ship and place ruthenium 4 oxide in an environment that is not exposed to light to prevent the ruthenium 4 oxide from separating into ruthenium dioxide and oxygen.

In one embodiment, it may be important to ensure that all contaminants are removed from the "anhydrous" solvent mixture to prevent or minimize contamination of the substrate surface during subsequent ruthenium containing layer deposition process steps. In one embodiment, to ensure that all or most contaminants are removed, various purification processes may be completed on the “anhydrous” solvent mixture before the mixture or its components are ready to be exposed on the substrate surface. In one aspect, the purification process may comprise completing process step 1004 on the process solution formed in step 1002 at least once. In another embodiment, process step 1010 in the ruthenium 4 oxide containing solvent formation process 1001 is completed at least once on the process solution.

Ruthenium 4-acid freight  Ruthenium-containing layer deposition process using a solvent containing

After performing the ruthenium 4 oxide containing solvent formation process 1001, a "anhydrous" solvent mixture is formed on the surface of the substrate by the use of another embodiment of the process 700 shown in FIG. 10A (hereafter process 700B). It is used to form a ruthenium containing layer. In this embodiment, process 700B includes a new process step 701, a detailed version of process step 702 (ie, step 702A of FIG. 10C), and process steps 704-706. In other embodiments, steps in process 700B may be rearranged, changed, one or more steps may be removed, or two or more steps may be combined into a single step without changing from the basic scope of the present invention. Can be. For example, in one embodiment, process step 705 is removed from process 700B.

The first step, or step 701, of process 700B requires the separation of ruthenium 4 oxide from the rest of the “anhydrous” solvent mixture. In one embodiment, step 701 is a series of process steps (see FIG. 10B) that may utilize separation hardware system 1020 (see FIG. 10C) to separate ruthenium 4 oxide from the remaining “anhydrous” solvent mixture. 701A). 10B illustrates one embodiment of a process sequence 701A that can be used to perform process step 701. Process sequence 701A delivers a first vessel 1021 to a process vessel assembly 1023 that includes a “anhydrous” solvent mixture (element “A”) formed using a ruthenium 4 oxide containing solvent forming process 1001. Start by connecting. The hardware shown in FIG. 10C is intended to be replaced directly for the processing vessels 630, 630A, and 630B shown in FIGS. 4 and 6A-6C, in which the ruthenium 4 oxide containing gas is replaced by the source vessel assembly (FIG. 4). Element 640 and elements 640A or 640B of FIGS. 6A-6C) and eventually to process chamber 603 (see FIGS. 4 and 6A-6C). For clarity, similar or identical reference numerals are used in FIG. 10C for clarity in FIGS. 4 and 6A-6C. The processing vessel assembly 1023 generally includes a processing vessel 1023B and a temperature control device 1023A (eg, a fluid heat exchanger, resistive heating device, and / or thermoelectric device).

The first step of process sequence 701A (step 701B) is to inject a desired amount of "anhydrous" solvent mixture into processing vessel 1023B by use of a metering pump 1022 or other conventional fluid transfer process. Is started by. The processing vessel 1023B is then emptied to the target temperature and pressure by the use of a heat exchanger 1023A, a vacuum pump 1025 and / or one or more gas sources 611B to 611C to achieve higher than ruthenium 4 oxide. A solvent with vapor pressure is vaporized and separated from the ruthenium 4 oxide retained in the processing vessel 1023B (element “B” in FIG. 10C). For example, when freon 113 is used as the solvent material, a temperature less than about 0 ° C. and a pressure of about 360 Torr may be used to separate the solidified ruthenium 4 oxide from the solvent mixture. Low pressures such as about 3 Torr may be used to perform the separation process, but because of the low pressure used to complete this pressure, higher amounts of ruthenium 4 oxide may be carried with the solvent and lost.

The last step of process sequence 701A, step 701D, generally requires the processing vessel 1023B to be emptied until the pressure in the processing vessel reaches a target level or until the pressure in the vessel stabilizes. Generally, step 701D is performed until only a small amount of solvent, water left and / or other soluble external material remains in the processing vessel 1023B. Failure to properly separate other materials from the ruthenium 4 oxide material may contaminate the ruthenium containing layer formed during subsequent deposition process (s) (eg, step 706 of FIGS. 5 and 7). In one embodiment, it may be useful to control the temperature in the processing vessel 1023B to remove solvent and other materials.

In one aspect of process sequence 701A, cold trap assembly 1024 is used to collect and regenerate the vaporized solvent material formed when processing vessel 1023B is emptied by vacuum pump 1025. The cold trap assembly 1024 is configured to cool a portion of the steam line 1025A to a temperature that allows the vaporized solvent material to condense so that the condensed solvent can be regenerated in the collection tank / system 1024D in a subsequent step. do. The cold trap assembly 1024 generally includes a collection area 1024B, a shutoff valve 1026, a temperature control device 1024A (eg, a fluid heat exchanger, a resistive heating device and / or a cooling vacuum line 1025A). Thermoelectric device) and a collection line 1024C connected to the solvent collection tank / system 1024D. In one embodiment, any collected ruthelium 4 oxide in the condensed solvent can be regenerated.

After performing step 701, the separated ruthenium 4 oxide, contained within the processing vessel 1023B, is subjected to process step 702 (step 702A in FIG. 10A) and the details of process steps 704-706 described above. By the use of versions it can be used to form a ruthenium containing layer on the surface of the substrate. Detailed process step 702A is collected in a source vessel assembly (eg, elements 640, 640A or 640B in FIGS. 4 and 6A-6C), similar to the aspects described in process step 702 described above. As such, controlling the temperature of the ruthenium 4 oxide material contained in the processing vessel 1023B and the pressure inside the processing vessel 1023B is required. As used herein, the term “vaporize” is intended to describe a process that allows a material to convert from solid or liquid to steam. In one embodiment, the ruthenium 4 oxide material is maintained at a temperature of about 25 ° C. and 2 Torr so that a steam process occurs so that the vaporized material can be delivered to and collected in the source vessel (s). Referring to FIG. 10C, in one embodiment, vaporized ruthenium oxide is processed from one or more gas sources 611B-611C, process vessel 1023B, process line (eg, 648, 648A, or 648B) and valve. Performed by flow process gas delivered to the processing vessel (s) (not shown) via 637A. The concentration and flow rate of the ruthenium 4 oxide containing gas are related to the vaporization rate and process gas flow rate of the ruthenium 4 oxide in the processing vessel 1023B. The vaporization rate is related to the equilibrium partial pressure of ruthenium 4 oxide at the pressure and temperature maintained in the processing vessel 1023B. After performing step 702A, a ruthenium containing layer may be deposited on the substrate surface along process steps 704-706 as described above. In one embodiment, multiple sequential doses of ruthenium 4 oxide are delivered to process chamber 603 to form a multi-layered ruthenium containing film. In order to perform multiple sequential doses, at least one of the process steps 701-706, described in connection with FIG. 10, is repeated several times to form a multilayered ruthenium containing film. In another embodiment, a continuous flow of the target concentration of ruthenium 4 oxide containing gas is transferred across the surface of the substrate during the ruthenium containing layer deposition process.

Ruthenium-containing layer deposition process using anhydrous solvent mixture

In one embodiment of the process of forming a ruthenium containing layer on the substrate surface, the “anhydrous” solvent mixture formed in the ruthenium 4 oxide containing solvent forming process 1001 is positioned within the processing chamber 603 (see FIG. 11). Delivered directly to the surface. In one embodiment, an inert solvent such as perfluoropentane (C 5 F 12 ), which does not interact with the material on the substrate surface at temperatures below the decomposition temperature, to prevent contamination of the substrate surface during the ruthenium containing layer deposition process. To be used.

Referring to FIG. 11, in this embodiment, a ruthenium containing layer is formed on the surface of the heated substrate by delivering a “anhydrous” solvent mixture to a substrate located within the process region 427 of the processing chamber 603. The heated substrate may be at a temperature below about 350 ° C, and more preferably at a temperature below about 300 ° C. The choice of process temperature can be important to prevent decomposition of the solvent material. Typically, the process chamber pressure is maintained at a process pressure below about 10 Torr to complete the ruthenium containing layer deposition process.

Referring to FIG. 11, in one embodiment, a gas source 611D and a hydrogen (H 2 ) containing gas such that a target amount or mass of purified solvent mixture (urea (“A”)) forms a ruthenium layer on the surface of the substrate. (Eg, hydrogen (H 2 )) is delivered to the process region 427 by the use of a carrier gas delivered from. In one embodiment, instead of hydrogen, the reduced co-reactant may be a hydrazine (N 2 H 4) mixed in an inert carrier gas such as N 2. In one embodiment, the carrier gas comprises process region 427 of process chamber 603 via outlet line 660 directly from gas source 611E via first vessel 1021, comprising a “anhydrous” solvent mixture. It is delivered to a substrate 422 positioned within. In another embodiment, multiple sequential doses of “anhydrous” solvent mixture are delivered to the processing chamber 603 to form a multi-layered ruthenium containing film. To perform multiple sequential doses, the target amount of "anhydrous" solvent mixture is sequentially delivered to the substrate several times to form a multi-layered ruthenium containing film. The target amount of ruthenium 4 oxide that needs to be delivered to process region 427 to form a ruthenium containing layer is generally dependent on the amount of ruthenium 4 oxide required to completely saturate the substrate surface and other chamber components. Thus, the amount of "anhydrous" solvent mixture required for delivery to process chamber 603 depends on the concentration of ruthenium 4 oxide and the target mass of ruthenium 4 oxide in the "anhydrous" solvent mixture.

In another embodiment, the continuous flow of the "anhydrous" solvent mixture allows for flow across the surface of the substrate 422 during the ruthenium containing layer deposition process. In one embodiment, the “anhydrous” solvent mixture flows past the surface of the substrate and is collected by the vacuum pump 435. In one embodiment, the cold trap assembly 1024 (FIG. 10C) and the collection tank / system 1024D (FIG. 10C) are in fluid communication with the process region 427 and the vacuum port 435 in order to dissolve the solvent and any unreacted ruthenium. Collect any remaining "anhydrous" solvent mixture components, such as 4 oxides.

Cluster tool configuration (s)

8 is a plan view of a cluster tool 1100 useful for electronic device processing in which the present invention may be usefully employed. Two such platforms are CENTURA® RTM and ENDURA® RTM, both available from Applied Materials, Inc. of Santa Clara, California. 8 is a top view of the Centura® RTM cluster tool. One such staged vacuum substrate processing system is disclosed in detail in US Pat. No. 5,186,718, which is incorporated herein by reference. The exact placement and combination of chambers can be modified for the purpose of carrying out certain steps of the manufacturing process.

In accordance with an aspect of the present invention, the cluster tool 1100 generally includes a plurality of chambers and robots and is preferably a system controller programmed to control and perform various processing methods and sequences formed within the cluster tool 1100 (see FIG. 1102. 8, a processing chamber 603 is mounted at a location 1114A on the transfer chamber 1110 and three substrate processing chambers 1202A to 1202C are mounted at locations 114B to 1114D on the transfer chamber 1110. An embodiment is shown. The processing chamber 603 may be disposed at one or more other locations, for example, locations 1114B through 1114D, to improve hardware integration aspects of the design of the system or to improve substrate throughput. In some embodiments, some of the locations 114A-114D remain unoccupied to reduce the cost or complexity of the system during the process.

Referring to FIG. 8, an optional front end environment 1104 (also referred to as a factory interface or FI) is shown positioned in selective communication with a pair of load lock chambers 1106. The factory interface robots 1108A- 1108B disposed within the front end environment 1104 include a plurality of substrate containing pods (elements 1105 (A-D)) and load locks 1106 mounted on the front end environment 1104. Linear, rotational, and vertical movements can be made to move the substrate between.

Load locks 1106A- 1106B provide a first vacuum interface between the front end environment 1104 and the transfer chamber 1110. In one embodiment, two load locks 1106 are provided to increase throughput by alternately communicating with the transfer chamber 1110 and the front end environment 1104. Thus, while one load lock is in communication with the transfer chamber 1110, the second load lock can be in communication with the front end environment 1104. In one embodiment, the load locks (elements 1106A- 1106B) receive two or more substrates from the factory interface and hold the substrates while the chamber is sealed to transfer the substrates to the transfer chamber 1110. Empty to a vacuum level low enough.

Robot 1113 is positioned centrally within transfer chamber 1110 to transfer the substrate from the load lock to locations 114A-114D and various processing chambers mounted to service chambers 1116A-116B. The robot 1113 allows the substrate "W" to be transferred to the various processing chambers by the use of commands sent from the system controller 1102. Robotic assemblies used in cluster tools that can be applied to benefit from the present invention are described in US Pat. Nos. 5,447,409, 5,469,035, and 6,379,095, which are generally assigned and incorporated herein by reference in their entirety.

Process chambers 1202A through 1202C mounted at one of locations 1114A through 1114D may be pre-cleaned (eg, selective or non-selective dry etching of the substrate surface), PVD, CVD, ALD, decoupled plasma. Any of a number of processes may be performed, such as nitriding (DPN), rapid thermal treatment (RTP), metering techniques (eg particle measurement) and etching, and service chambers 1116A to 1116B are degassed, oriented, Applied for cooling, etc. In one embodiment, as described above with respect to FIG. 1A, the processing sequence is applied to deposit a barrier layer on the surface of the substrate using an ALD type process and then deposit a ruthenium containing layer in a separate chamber. In this embodiment, the cluster tool 1110 is a process chamber 1202A is an Endura® iCuB / S TM chamber, which is available from Applied Materials, Inc. and the process chamber 603 is Mounted at position 1114A. In one embodiment, the preclean chamber is added to the process sequence prior to the barrier deposition process (element 102 of FIG. 1A) and mounted at position 1202B of cluster tool 1110.

In one aspect of the invention, one or more processing chambers 1202A through 1202C may be RTP chambers and may be used to anneal the substrate after or before performing a batch deposition step. The RTP process can be conducted using RTP chambers and related process hardware commercially available from Applied Materials, Inc., located in Santa Clara, California. In another aspect of the invention, one or more single substrate processing chambers 1202A through 1202C may be CVD chambers. Examples of such CVD process chambers are DXZ® chamber, ULTIMA HDP-CVD® and PRECISION 5000 (commercially available from Applied Materials, Inc., Santa Clara, Calif.). Trademark) chamber. In another aspect of the invention, one or more single substrate processing chambers 1202A through 1202C may be PVD chambers. An example of such a PVD chamber may be an Endura® PVD processing chamber commercially available from Applied Materials, Inc., located in Santa Clara, California. In another aspect of the invention, one or more single substrate processing chambers 1202A through 1202C may be DPN chambers. Examples of such DPN process chambers may include DPN Centura®, which is commercially available from Applied Materials, Inc., located in Santa Clara, California. In another aspect of the invention, one or more single substrate processing chambers 1202A through 1202C may be process / substrate metrology chambers. Processes completed in the process / substrate metrology chamber may include techniques used to measure film thickness and / or film composition, such as particle measurement techniques, residual gas analysis techniques, XRF techniques, and elliptical polarization reflectance techniques. However, the present invention is not limited thereto.

Ruthenium Dioxide Floor Up Filling Process

In one embodiment of the present invention, the ruthenium containing layer deposited in process step 104 in FIG. 1A and step 304 in FIG. 1B is deposited on a substrate surface maintained at a constant temperature such that the ruthenium oxide layer is one or more of the substrates. Allow deposition on all surfaces. The substrate is then heated and exposed to the surface with a reduced gas (eg hydrogen containing gas) and the surface of the substrate is exposed to an electroless or electroplating solution that reduces the exposed surface, or the temperature of the substrate is increased. By increasing the release of oxygen from the layer, the ruthenium oxide layer can be reduced to form a metal ruthenium layer. In one embodiment, by exposing a ruthenium 4 oxide containing gas to a substrate at a temperature below about 250 ° C., a ruthenium layer is selectively formed such that the metal ruthenium subsides ruthenium on all other non-metallic materials, such as dielectric material silicon dioxide. It is formed on the water layer and the exposed metal surface. This aspect may be particularly important when using subsequent selective deposition processes, such as electroless deposition processes. This may be useful for selectively forming an electroless layer of exposed tungsten plug (eg, two layers of metal) after patterning but before performing another deposition process.

While the foregoing is directed to embodiments of the invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (47)

  1. An apparatus for depositing a catalyst layer on the surface of a substrate,
    A ruthenium 4 oxide generation system, comprising: a ruthenium 4 oxide generation system;
    A first treatment region to maintain a constant amount of ruthenium containing material
    A container having one or more walls to form,
    In the first treatment region to form a ruthenium 4 oxide containing gas.
    Oxidation to deliver an oxidizing gas to the ruthenium-containing material at
    Source, and
    In fluid communication with the vessel and collecting the ruthenium 4 oxide containing gas.
    A source container assembly,
    A source container having a collecting surface disposed in a collecting area, the source container comprising:
    The material exposed on the collecting surface is the ruthenium 4 oxide containing gas
    Source vessel, which does not react with the ruthenium 4 oxide in the,
    One that selectively isolates the vessel from the source vessel
    Or more source valves,
    The lute on the collection surface and in thermal communication with the collection surface
    Condensation of the ruthenium 4 oxide in the nium 4 oxide containing gas
    A heat exchange device for controlling the temperature of the collecting surface to be locked;
    And
    In fluid communication with the vessel and purging the vessel and the source vessel
    Exhaust system for
    A source container assembly comprising a
    Comprising, a ruthenium 4 oxide generation system,
    A processing chamber in fluid communication with the source vessel,
    Optional from a collection region of the source vessel assembly by a chamber valve
    One or more walls forming a second treatment region, which is isolated by
    A substrate support positioned within the second processing region, and
    A heat exchange device in thermal communication with the substrate support
    Comprising, a processing chamber, and
    A gas source in fluid communication with a collection surface of the source vessel and for delivering gas to carry at least a portion of the ruthenium 4 oxide disposed on the collection surface to a second processing region of the processing chamber;
    An apparatus for depositing a catalyst layer on a substrate surface.
  2. The method of claim 1,
    The oxidizing gas is an ozone gas formed by an ozone generator,
    An apparatus for depositing a catalyst layer on a substrate surface.
  3. The method of claim 1,
    The heat exchange device of the source vessel assembly to cool the collection zone to a temperature within a range of −20 ° C. to 20 ° C.,
    An apparatus for depositing a catalyst layer on a substrate surface.
  4. The method of claim 1,
    The processing chamber further comprises a vacuum pump to maintain pressure in the second processing region during processing at a pressure below atmospheric pressure;
    An apparatus for depositing a catalyst layer on a substrate surface.
  5. The method of claim 1,
    The ruthenium 4 oxide generation system,
    A dosing vessel in fluid communication with the source vessel and the processing chamber,
    The dosing vessel carries the ruthenium 4 oxide containing gas of the target mass.
    A dosing container, sized to be delivered to the processing chamber,
    A second heat exchange device in thermal communication with the dosing vessel, and
    The ruthenium 4 oxide-containing gas to the dosing vessel at a target time.
    From the dosing vessel to the processing chamber
    And further comprising a controller to control the temperature of the nium 4 oxide containing gas.
    Is,
    An apparatus for depositing a catalyst layer on a substrate surface.
  6. The method of claim 1,
    The processing chamber further comprising a showerhead assembly in fluid communication with the source vessel and for delivering the ruthenium 4 oxide containing gas to a substrate positioned within the second processing region;
    An apparatus for depositing a catalyst layer on a substrate surface.
  7. The method of claim 1,
    The ruthenium 4 oxide generation system further comprises a remote plasma source in communication with the first processing region of the vessel and providing hydrogen radicals to the first processing region;
    An apparatus for depositing a catalyst layer on a substrate surface.
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  47. The method of claim 1,
    The heat exchange device of the source vessel assembly to heat the collection zone to a temperature in the range of 0 ° C to 50 ° C,
    An apparatus for depositing a catalyst layer on a substrate surface.
KR1020077019546A 2005-01-27 2006-01-25 Ruthenium layer deposition apparatus and method KR101014240B1 (en)

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US64800405P true 2005-01-27 2005-01-27
US60/648,004 2005-01-27
US71502405P true 2005-09-08 2005-09-08
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US11/228,649 2005-09-15
US11/228,425 2005-09-15
US11/228,425 US20060162658A1 (en) 2005-01-27 2005-09-15 Ruthenium layer deposition apparatus and method
US11/228,649 US7438949B2 (en) 2005-01-27 2005-09-15 Ruthenium containing layer deposition method

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US8906501B2 (en) * 2007-10-05 2014-12-09 The United States Of America As Represented By The Secretary Of The Navy RuO2 coatings
JP5520425B2 (en) * 2009-01-10 2014-06-11 宛伶 兪 Method for forming a metal bump and seal of a semiconductor member
US8076241B2 (en) * 2009-09-30 2011-12-13 Tokyo Electron Limited Methods for multi-step copper plating on a continuous ruthenium film in recessed features
US20130269612A1 (en) * 2012-04-16 2013-10-17 Hermes-Epitek Corporation Gas Treatment Apparatus with Surrounding Spray Curtains
US9328419B2 (en) * 2012-04-18 2016-05-03 Hermes-Epitek Corporation Gas treatment apparatus with surrounding spray curtains
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WO2006081234A2 (en) 2006-08-03
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EP1853745A2 (en) 2007-11-14
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WO2006081234A3 (en) 2009-05-07

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