1. Field of the Invention
Embodiments of the invention generally relate to the formation of metal nitride barrier layers and conductive metal layers deposited thereon, and more particularly, to titanium nitride barrier layers and aluminum layers deposited thereon.
2. Description of the Related Art
In the manufacture of integrated circuits, barrier layers are often used to inhibit the diffusion of metals and other impurities into regions underlying such barrier layers. These underlying regions may include transistor gates, capacitor dielectric, semiconductor substrates, metal lines, as well as many other structures that appear in integrated circuits. For the current submicron generation of semiconductor devices, any microscopic reaction at an interface between interconnection layers can cause degradation of the resulting integrated circuits (e.g., increase the resistivity of the interconnection layers). Consequently, barrier layers have become a critical component for improving the reliability of interconnect metallization schemes.
Compounds of refractory metals such as, for example, nitrides, borides, silicides, and carbides have been suggested as diffusion barriers because of their chemical inertness and low resistivities (e.g., resistivities typically less than about 500 μΩ-cm). In particular, refractory metal nitrides, such as, for example, titanium nitride have been suggested for use as a barrier material since layers formed thereof generally have low resistivities and are chemically stable at high temperatures.
Refractory metal nitride barrier layers may be formed using chemical vapor deposition (CVD), atomic layer deposition (ALD), or physical vapor deposition (PVD) processes. During a CVD or ALD process, a titanium precursor may be reacted with a nitrogen precursor (e.g., TiCl4 and NH3) to form titanium nitride layer. However, CVD or ALD processes may require high deposition temperatures (e.g., >600° C.) to form a typical titanium nitride layer, which may affect other material layers that are in contact with the metal nitride barrier layers. For example, metal nitride barrier layers are often deposited onto buried semiconductor junctions. At high temperatures dopants in the semiconductor junctions may diffuse out of the buried junctions, potentially changing the characteristics thereof.
Additionally, when chlorine-based chemistries are used to form the metal nitride barrier layers during a CVD or ALD process, such nitride layers typically contain chlorine contaminants therein. A high chlorine concentration is undesirable because chlorine may migrate from the metal nitride barrier layer into adjacent material layers (e.g., interconnection layers) which can increase the contact resistance of such layers, potentially changing the characteristics of integrated circuits made therefrom. Alternatively, organometallic precursors (e.g., tetrakis(dialkylamido) titanium compounds) may be used during a CVD or ALD process. However, the metal nitride barrier layers formed from an organometallic precursor often contain high levels of carbon, which increases the resistivity of the material.
Other problems that occur while manufacturing electronic devices is due to the need for smaller structures, especially for apertures and vias, which are approaching widths of 0.12 μm and smaller. These high aspect ratio structures have complicated surfaces to deposit barrier layers on, and also small vias that need to be filled with conductive materials, such as aluminum. The reliability of an aluminum plug is lost if gaps are formed within the vias while being filled with aluminum.
Therefore, a need exists for reliable metal nitride barrier layers used in integrated circuit fabrication, particularly desirable is titanium nitride barrier layers. Also, a need exist for a process to fill high aspect ratio structures with conductive materials, preferably, aluminum.
Embodiments described herein provide a method for forming two titanium nitride materials by different PVD processes, such that a metallic titanium nitride layer is initially formed and a titanium nitride retarding layer is formed over a portion of the metallic titanium nitride layer. The metallic titanium nitride layer is deposited by a PVD process conducted in metallic mode, while the titanium nitride retarding layer is deposited by a PVD process conducted in poison mode by increasing the nitrogen gas flow and decreasing the DC power applied to the titanium target relative to the metallic mode. Subsequently, an aluminum seed layer may be selectively deposited on exposed portions of the metallic titanium nitride layer by a CVD process. Thereafter, an aluminum bulk layer may be deposited on exposed portions of the aluminum seed layer and the titanium nitride retarding layer during an aluminum PVD process.
In one embodiment, a method for forming a conductive material on a substrate is provided which includes positioning the substrate within a process chamber, wherein the substrate contains a dielectric material disposed thereon, the dielectric material has an upper surface and apertures formed therein, and each aperture has a lower surface and sidewalls, and depositing a metallic titanium nitride layer on the upper surface of the dielectric material and on the lower surfaces and the sidewalls of the apertures during a first PVD process. A first plasma may be generated with nitrogen gas having a flow rate of less than about 80 sccm during the first PVD process. The method further includes depositing a titanium nitride retarding layer on the metallic titanium nitride layer during a second PVD process, wherein a second plasma is generated with the nitrogen gas having a flow rate of greater than about 80 sccm during the second PVD process. In many examples, the titanium nitride retarding layer deposited on the lower surfaces and sidewalls of the apertures is about 10% or less of the thickness as the titanium nitride retarding layer deposited across the field of the substrate.
Embodiments provides that the first PVD process and the second PVD process may be performed in different process chambers, but preferably, are performed in the same process chamber. In some example, the flow rate of the nitrogen gas is less than about 70 sccm during the first PVD process, preferably, about 55 sccm or less. A RF bias is usually engaged during the first PVD process, but not during the second PVD process. Also, the plasma generator is usually set at a lower power level while forming the titanium nitride retarding layer during the second PVD process than while forming the metallic titanium nitride layer during the first PVD process. For example, a RF bias may be applied to the substrate during the first PVD process and the RF bias may be removed from the substrate during the second PVD process. The RF bias may have a power level within a range from about 100 W to about 800 W during the first PVD process. Also, a DC power may be applied to a titanium target at a first power level within a range from about 20 kW to about 40 kW, preferably, from about 25 kW to about 35 kW during the first PVD process. However, during the second PVD process, a second DC power may be applied to the titanium target at a second power level within a range from about 1 kW to about 30 kW, preferably, from about 5 kW to about 25 kW.
Embodiments provide that the metallic titanium nitride layer may contain a metallic titanium nitride material having the chemical formula of TixNy, where x is within a range from about 1.5 to about 2 and y is about 1. Also, the titanium nitride retarding layer may contain a titanium nitride retarding material having the chemical formula of TixNy, where x is about 1 and y is within a range from about 1 to about 1.2. The metallic titanium nitride layer may have a thickness within a range from about 100 Å to about 1,000 Å, preferably, from about 200 Å to about 500 Å, for example, about 300 Å. The titanium nitride retarding layer may have a thickness within a range from about 2 Å to about 100 Å, preferably, from about 10 Å to about 50 Å, for example, about 30 Å.
Embodiments of the invention further provide depositing a first aluminum layer selectively on exposed portions of the metallic titanium nitride layer while maintaining the titanium nitride retarding layer substantially free of the first aluminum layer during a CVD process, and depositing a second aluminum layer on the titanium nitride retarding layer and on the exposed portions of the first aluminum layer during an aluminum PVD process. In some examples, the apertures are vias which are completely filled by depositing the second aluminum layer.
In another embodiment, a method for forming a conductive material on a substrate is provided which includes positioning the substrate within a process chamber, depositing a metallic titanium nitride layer on the upper surface of the dielectric material and on the lower surfaces and the sidewalls of the apertures during a first PVD process, wherein the metallic titanium nitride layer contains a metallic titanium nitride material having the chemical formula of TixNy, where x is within a range from about 1.5 to about 2 and y is about 1. The method further provides depositing a titanium nitride retarding layer on the metallic titanium nitride layer deposited on the upper surface of the dielectric material during a second PVD process, wherein the titanium nitride retarding layer contains a second titanium nitride material having the chemical formula of TixNy, where x is about 1 and y is within a range from about 1 to about 1.2. In some examples, the titanium nitride retarding layer deposited on the lower surfaces and sidewalls of the apertures may be about 10% or less of the thickness as the titanium nitride retarding layer deposited across the field of the substrate.
The metallic titanium nitride layer may be deposited by applying a RF bias to the substrate during the first PVD process while applying a first DC power to a titanium target at a first power level within a range from about 20 kW to about 40 kW, preferably, from about 25 kW to about 35 kW. The RF bias may have a power level within a range from about 100 W to about 800 W during the first PVD process. Also, the titanium nitride retarding layer may be deposited by removing the RF bias from the substrate during the second PVD process and applying a second DC power to the titanium target at a second power level within a range from about 1 kW to about 30 kW, preferably, from about 5 kW to about 25 kW.
In another embodiment, a method for forming a conductive material on a substrate is provided which includes positioning a substrate within a PVD chamber, depositing a metallic titanium nitride layer on the upper surface of the dielectric material and on the lower surfaces and the sidewalls of the apertures during a first PVD process within the PVD chamber, and depositing a titanium nitride retarding layer on the metallic titanium nitride layer deposited on the upper surface of the dielectric material during a second PVD process within the same PVD chamber. In one example, the first PVD process may include flowing nitrogen gas into the PVD chamber at a flow rate of less than about 80 sccm, applying a RF bias to the substrate, while applying a first DC power to a titanium target at a power level within a range from about 20 kW to about 40 kW to ignite a plasma. Further, the second PVD process may include flowing the nitrogen gas into the PVD chamber at a flow rate of about 80 sccm or greater, removing the RF bias from the substrate, while applying a second DC power to a titanium target at a power level within a range from about 5 kW to about 25 kW to ignite a second plasma.
In another embodiment, a method for forming a conductive material on a substrate is provided which includes positioning the substrate within a process chamber, depositing a metallic titanium nitride layer on the upper surface of the dielectric material and on the lower surfaces and the sidewalls of the apertures during a first PVD process, and depositing a titanium nitride retarding layer on the metallic titanium nitride layer deposited over the upper surface of the dielectric material while maintaining the lower surface of the apertures substantially free of the titanium nitride retarding layer during a second PVD process. The method further provides selectively depositing a first aluminum layer selectively on exposed portions of the metallic titanium nitride layer during a CVD process while maintaining the titanium nitride retarding layer free of the first aluminum layer, and depositing a second aluminum layer on the titanium nitride retarding layer and on the exposed portions of the first aluminum layer during the aluminum PVD process. In one example, the titanium nitride retarding layer deposited on the lower surfaces and sidewalls of the apertures is about 10% or less of the thickness as the titanium nitride retarding layer deposited across the field of the substrate.
In some examples, a first plasma is generated with nitrogen gas having a flow rate of less than about 80 sccm during the first PVD process, and a second plasma is generated with the nitrogen gas having a flow rate of greater than about 80 sccm during the second PVD process. In one example of first PVD process, the flow rate of the nitrogen gas may be less than about 70 sccm, preferably, about 55 sccm or less, such as about 50 sccm.
In other examples, the first aluminum layer may have a thickness within a range from about 400 Å to about 600 Å and the second aluminum layer may have a thickness within a range from about 5,000 Å to about 6,000 Å. In one example, the first aluminum layer and the second aluminum layer have a combined thickness within a range from about 1,000 Å to about 10,000 Å. In another example the substrate may be heated to a temperature within a range from about 50° C. to about 250° C. during the CVD process while depositing the first aluminum layer. During the CVD processes, the substrate may be exposed to an aluminum precursor, which includes alane compounds, aluminum borohydride compounds, alkyl aluminum compounds, alkyl aluminum hydride compounds, complexes thereof, derivates thereof, or combinations thereof. In specific examples, the aluminum precursor may be methylpyrrolidine:alane, aluminum borohydride trimethylamine, dimethyl aluminum hydride, complexes thereof, or derivates thereof.
In another embodiment, a method for forming a conductive material on a substrate is provided which includes positioning the substrate within a PVD chamber, depositing a metallic titanium nitride layer on the upper surface of the dielectric material and on the lower surfaces and the sidewalls of the apertures during a PVD process, transferring the substrate into a CVD chamber, and depositing an aluminum layer on the metallic titanium nitride layer during a CVD process. The deposited metallic titanium nitride material may have the chemical formula of TixNy, where x is within a range from about 1.5 to about 2 and y is about 1. The method provides that the PVD process includes flowing nitrogen gas into the PVD chamber at a flow rate of less than about 80 sccm, applying a RF bias to the substrate, while applying a first DC power to a titanium target at a first power level within a range from about 20 kW to about 40 kW to ignite a plasma. In some examples, the PVD process further provides that the flow rate of the nitrogen is about 55 sccm or less, and the first power level is within a range from about 25 kW to about 35 kW.
In other embodiments, the method provides depositing a titanium nitride retarding layer on the metallic titanium nitride layer deposited over the upper surface of the dielectric material while maintaining the lower surface of the apertures substantially free of the titanium nitride retarding layer during a second PVD process. In some examples, the titanium nitride retarding layer may be maintained substantially free of the aluminum layer while selectively depositing the aluminum layer on exposed portions of the metallic titanium nitride layer during the CVD process. The method provides that the second PVD process includes flowing the nitrogen gas into the PVD chamber at a flow rate of about 80 sccm or greater, removing the RF bias from the substrate, while applying a second DC power to a titanium target at a power level within a range from about 5 kW to about 25 kW to ignite a second plasma.
In some examples, the substrate may be heated to a temperature within a range from about 50° C. to about 250° C. during the CVD process while depositing the aluminum layer. The substrate may be exposed to an aluminum precursor during the CVD process while depositing the aluminum layer, such that the aluminum precursor may be include alane compounds, aluminum borohydride compounds, alkyl aluminum compounds, alkyl aluminum hydride compounds, complexes thereof, or derivates thereof. In some examples, the aluminum precursor may contain methylpyrrolidine:alane, aluminum borohydride trimethylamine, dimethyl aluminum hydride, complexes thereof, or derivates thereof. In other examples, the aluminum layer may have a thickness within a range from about 400 Å to about 600 Å. In an alternative embodiment, the method provides depositing another aluminum layer on the substrate during another PVD process.
So that the manner in which the above recited features of the invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
Embodiments described herein provide a method for forming two titanium nitride materials by different PVD processes, such that a metallic titanium nitride layer is initially formed on a substrate and a titanium nitride retarding layer is formed over at least a portion of the metallic titanium nitride layer. The titanium nitride retarding layer is primarily deposited across the field of the substrate and minimally deposited, if at all, within any exposed apertures contained on the substrate. Subsequently, an aluminum seed layer may be selectively deposited on exposed portions of the metallic titanium nitride layer by a CVD process, preferably, a MOCVD process. Thereafter, an aluminum bulk layer may be deposited on exposed portions of the aluminum seed layer and the titanium nitride retarding layer during an aluminum PVD process.
In one embodiment, a method for forming a conductive material on a substrate is provided which includes positioning the substrate within a process chamber, such as a PVD chamber. The substrate may contain a dielectric material which has an upper surface and apertures formed therein.
In step 110, the titanium nitride retarding layer is deposited on the substrate during a PVD process conducted in a metallic mode. A plasma is usually generated with nitrogen gas having a flow rate of less than about 80 sccm during the metallic mode of the PVD process. In some examples, the flow rate of the nitrogen gas is less than about 70 sccm, and preferably, about 55 sccm or less. In one embodiment, the nitrogen gas may have a flow rate within a range from about 5 sccm to about 75 sccm, preferably, from about 10 sccm to about 55 sccm, and more preferably, from about 15 sccm to about 45 sccm during step 110. In one example, the flow rate of the nitrogen gas is within a range from about 15 sccm to about 25 sccm. In another example, the flow rate of the nitrogen gas is within a range from about 25 sccm to about 35 sccm.
During the PVD process of step 110, a RF bias may be applied to the substrate and a DC power may also be applied to a titanium target. The RF bias may have a power level within a range from about 50 W to about 1,200 W, preferably, from about 100 W to about 800 W while in metallic mode for depositing the metallic titanium nitride layer. Also in step 110, the DC power may be applied to the titanium target at a first power level within a range from about 20 kW to about 40 kW, preferably, from about 25 kW to about 35 kW. An ignition gas (e.g., argon) may be administered into the PVD chamber having a flow rate within a range from about 2 sccm to about 20 sccm, for example, about 8 sccm. The substrate may be heated to a temperature within a range from about 20° C. to about 500° C., preferably, from about 200° C. to about 300° C. during step 110.
In another embodiment, the metallic titanium nitride layer may contain a metallic titanium nitride material having the chemical formula of TixNy, where x is within a range from about 1.5 to about 2 and y is about 1. The metallic titanium nitride layer may be deposited to a thickness within a range from about 100 Å to about 1,000 Å, preferably, from about 200 Å to about 500 Å, and more preferably, from about 250 Å to about 400 Å, such as about 300 Å. In one example, a metallic titanium nitride layer having a thickness of about 300 Å is deposited by conducting a PVD process which lasts from about 20 seconds to about 25 seconds during step 110.
In step 120, a titanium nitride retarding layer is deposited on the metallic titanium nitride layer during the PVD process conducted in a poison mode. During this second PVD process, the plasma is usually generated with nitrogen gas having a flow rate of greater than about 80 sccm. In some examples, the flow rate of the nitrogen gas is greater than about 100 sccm, such as about 150 sccm, about 250 sccm, or greater.
During the PVD process of step 120, a RF bias is usually not applied to the substrate or substrate support, but the DC power is applied to the titanium target, although generally at a lower power than the DC power used in step 110. The DC power in step 120 may be applied to the titanium target at a second power level within a range from about 1 kW to about 30 kW, preferably, from about 5 kW to about 25 kW. An ignition gas (e.g., argon) may be administered into the PVD chamber having a flow rate within a range from about 2 sccm to about 20 sccm, for example, about 8 sccm. The substrate may be heated to a temperature within a range from about 20° C. to about 500° C., preferably, from about 200° C. to about 300° C. during step 120.
In another embodiment, the titanium nitride retarding layer may contain a titanium nitride retarding material having the chemical formula of TixNy, where x is about 1 and y is within a range from about 1 to about 1.2. The titanium nitride retarding layer may have a thickness within a range from about 2 Å to about 100 Å, preferably, from about 5 Å to about 70 Å, and more preferably, from about 10 Å to about 50 Å, such as about 30 Å. In one example, a titanium nitride retarding layer having a thickness of about 30 Å is deposited by conducting a PVD process for about 1 second during step 120.
The substrate support and substrate are usually RF biased during the PVD process conducted in metallic mode of step 110 in order to help direct the titanium material (e.g., metallic titanium nitride material) into the apertures or vias on the substrate. However, the substrate support and substrate are usually not RF biased during the PVD process conducted in poison mode of step 120. The titanium material (e.g., titanium nitride retarding material) scatters due to being unbiased, thereby inhibiting or minimizing the titanium material from entering the apertures or vias while depositing across the substrate field.
In one embodiment, the PVD process in step 110 and the PVD process in step 120 are performed in different process chambers. However, in another embodiment, the PVD processes in steps 110 and 120 are preferably performed in the same process chamber. If steps 110 and 120 are performed in the same PVD chamber, then the RF bias may be removed from the substrate, the DC power may be reduced, and the nitrogen flow rate may be increased during the second PVD process in step 120.
In one example, steps 110 and 120 are performed in the same PVD process chamber, such as a SIP-TTN chamber or a FALCON-TTN chamber, both commercially available from Applied Materials, Inc., located in Santa Clara, Calif. In another example, steps 110 and 120 are performed in different PVD process chambers, such as a SIP-TiN chamber for depositing the metallic titanium nitride layer of step 110 and a DS-TiN chamber for depositing the titanium nitride retarding layer of step 120. Alternately, step 110 may be performed in a FALCON-TiN chamber and step 120 may be performed in a DS-TiN chamber, also available from Applied Materials, Inc.
In one embodiment, process 100 may be used to deposit various material layers on substrate 200, depicted in
Lower layer 202 may be a contact or electrode layer and contain a conductive material such as copper, aluminum, tungsten, or alloys thereof. Lower layer 202 may also be the actual substrate surface, a dielectric layer, a barrier layer, or other layer disposed on substrate 200. Dielectric layer 204 may contain a dielectric material such as a silicon-containing materials, silicon-germanium, silicon oxide, hafnium oxide, hafnium silicate, hafnium silicon oxynitride, aluminates thereof, doped variants thereof, derivatives thereof, or combinations thereof.
In one embodiment, the PVD process may be performed in a metallic mode and therefore the metallic titanium nitride material is formed titanium rich, that is, Ti:N atomic ratio is greater than 1. The metallic titanium nitride material of metallic titanium nitride layer 220 may be deposited with the chemical formula of TixNy, where x is greater than 1 and y is about 1. In one example, the metallic titanium nitride material has the chemical formula of TixNy, where x within a range from about 1.2 to about 2 and y is about 1. In another example, the metallic titanium nitride material has the chemical formula of TixNy, where x within a range from about 1.4 to about 2 and y is about 1. In another example, the metallic titanium nitride material has the chemical formula of TixNy, where x within a range from about 1.5 to about 2 and y is about 1. Examples of the titanium nitride material contained in metallic titanium nitride layer 220 include Ti1.5N, Ti1.55N, Ti1.6N, Ti1.65N, Ti1.7N, Ti1.75N, Ti1.8N, Ti1.85N, Ti1.9N, Ti1.95N, Ti2N, derivatives thereof, or combinations thereof. Metallic titanium nitride layer 220 may have a thickness within a range from about 100 Å to about 1,000 Å, preferably, from about 200 Å to about 500 Å, for example, about 300 Å.
In one embodiment, titanium nitride retarding layer 230 contains a titanium nitride retarding material that may be deposited by a PVD process, as described in step 120 of process 100. The PVD process may be conducted in a poison mode and therefore the titanium nitride retarding material is nitrogen rich, that is, the Ti:N atomic ratio is about 1 or less than 1. The titanium nitride retarding material of titanium nitride retarding layer 230 may be deposited with the chemical formula of TixNy, where x is about 1 and y is about 1 or greater than 1. In one example, the titanium nitride retarding material has the chemical formula of TixNy, where x is about 1 and y is about 1. In another example, the titanium nitride retarding material has the chemical formula of TixNy, where x is about 1 and y is within a range from about 1 to about 1.1. In another example, the titanium nitride retarding material has the chemical formula of TixNy, where x is about 1 and y is within a range from about 1 to about 1.2. Examples of the titanium nitride retarding material contained in titanium nitride retarding layer 230 include TiN, TiN1.05, TiN1.10, TiN1.15TiN1.20, derivatives thereof, and combinations thereof. Titanium nitride retarding layer 230 may have a thickness within a range from about 2 Å to about 100 Å, preferably, from about 10 Å to about 50 Å, for example, about 30 Å.
In one embodiment, titanium nitride retarding layer 230 may be absent from aperture 210. Alternatively, titanium nitride retarding layer 230 is a discontinuous layer extending across bottom surface 212 and sidewalls 214 of aperture 210. For embodiments when titanium nitride retarding layer 230 is deposited on metallic titanium nitride layer 220 within aperture 210, portions of titanium nitride retarding layer 230 may be deposited on bottom surface 212 and sidewalls 214 at about 10% or less of the thickness as the portion of titanium nitride retarding layer 230 deposited across field 208 of substrate 200. In one example, the average thickness of titanium nitride retarding layer 230 deposited on bottom surface 212 and sidewalls 214 is about 10% or less of the average thickness of titanium nitride retarding layer 230 deposited across field 208. In other examples, the average thickness of titanium nitride retarding layer 230 deposited on bottom surface 212 and sidewalls 214 is about 5%, about 2%, about 1%, or less of the average thickness of titanium nitride retarding layer 230 deposited across field 208.
In one embodiment,
During step 130, the substrate may be exposed to an aluminum precursor during the CVD process while depositing the aluminum layer. The aluminum precursor may include alane compounds, aluminum borohydride compounds, alkyl aluminum compounds, alkyl aluminum hydride compounds, complexes thereof, or derivates thereof. In some examples, aluminum layer 240 is deposited from aluminum precursor, such as methylpyrrolidine:alane, aluminum borohydride trimethylamine, dimethyl aluminum hydride, complexes thereof, derivates thereof, and combinations thereof.
An important characteristic of the aluminum precursor is to have a favorable vapor pressure. An aluminum precursor may have the state of a gas, liquid, or solid at ambient temperature and pressure. However, within the process chamber during a CVD process, the aluminum precursor volatilized into the gas state. Precursors may be heated prior to delivering into the process chamber. An aluminum precursor gas may be formed by heating the aluminum precursor within a vaporizer, a bubbler, or an ampoule to a temperature of at least about 25° C., preferably, to a temperature within a range from about 25° C. to about 50° C., such as about 40° C. A carrier gas (e.g., Ar) is flown across or bubbled through the heated aluminum precursor to form the aluminum precursor gas. The carrier gas may contain argon, nitrogen, hydrogen, helium, or combinations thereof. The carrier gas may have a flow rate within a range from about 50 sccm to about 2,000 sccm, preferably, from about 100 sccm to about 1,000 sccm.
In one embodiment, the substrate may be heated to a temperature within a range from about 25° C. to about 400° C., preferably, from about 50° C. to about 200° C. during the CVD process while depositing the aluminum layer onto the metallic titanium nitride layer. The aluminum layer may be deposited to a thickness within a range from about 100 Å to about 1,000 Å, preferably, from about 200 Å to about 800 Å, and more preferably, from about 400 Å to about 600 Å, such as about 500 Å. In one example, an aluminum layer having a thickness of about 500 Å is deposited in about 50 seconds by an MOCVD process during step 130. In some embodiments, aluminum layer 240 may be a continuous layer across metallic titanium nitride layer 220. Alternatively, aluminum layer 240 may be a discontinuous layer across metallic titanium nitride layer 220, such as a seed layer or a nucleation layer.
In one embodiment, aluminum layer 240 is an aluminum seed layer deposited into aperture 210 in step 130, and subsequently, aluminum layer 250, an aluminum bulk layer, is deposited to fill aperture 210. In an alternative embodiment, aluminum layer 240 is deposited to fill aperture 210 and step 140 is omitted during process 100.
The substrate may be heated to a temperature within a range from about 200° C. to about 600° C., preferably, from about 350° C. to about 450° C. during the aluminum PVD process. The aluminum layer deposited during step 140 may have a thickness of greater than about 1,000 Å, preferably, greater than about 3,000 Å, and more preferably, greater than about 4,000 Å, such as within a range from about 5,000 Å to about 6,000 Å, or greater. The aluminum layer is usually deposited by the PVD process at a rate within a range from about 100 Å/second to about 200 Å/second.
Platforms
Transfer chambers 322 and 324 are used to maintain ultrahigh vacuum conditions while allowing substrates to be transferred within processing system 300. Robot 330 may transfer the substrates between transfer chambers 322 and 324 and one or more process chambers 332, 334, 336, and 338. Similar to process chambers 312, 314, 316, and 318, process chambers 332, 334, 336, and 338 can be outfitted to perform a variety of substrate processing operations, such as ALD, CVD, PVD, etch, preclean, degas, and orientation, for example. Any of process chambers 312, 314, 316, 318, 332, 334, 336, and 338 may be removed from processing system 300.
In one embodiment, process chambers 316 and 318 may each be an anneal chamber while process chambers 312 and 314 may each be a plasma clean chamber or a vapor deposition chamber, such as an ALD chamber, a CVD chamber, or a PVD chamber adapted to deposit a barrier layer. In one example, process chambers 312 and 314 may each be a plasma preclean chamber. In another example, process chambers 312 and 314 may each be a PVD chamber configured to deposit a titanium nitride barrier layer, such as a metallic titanium nitride layer or a titanium nitride retarding layer.
In another embodiment, process chamber 332 and 338 may each be a PVD chamber adapted to deposit titanium nitride layers and process chambers 334 and 336 may each be an ALD chamber, a CVD chamber, or a PVD chamber adapted to deposit aluminum layers. In another embodiment, process chambers 332 and 334 may each be a PVD chamber adapted to deposit titanium nitride layers and process chambers 336 and 338 may each be an ALD chamber, a CVD chamber, or a PVD chamber adapted to deposit aluminum layers.
In one embodiment, steps 110 and 120 of process 100 may be performed in the same PVD process chamber, which may be a SIP-TTN chamber or a FALCON-TTN chamber, commercially available from Applied Materials, Inc., located in Santa Clara, Calif. In one example, any of process chambers 332, 334, 336, or 338 may be a SIP-TTN chamber or a FALCON-TTN chamber for depositing a titanium nitride barrier material by a PVD process. In another embodiment, steps 110 and 120 of process 100 may be performed in different PVD process chambers, which may be a SIP-TiN chamber and a DS-TiN chamber, or a FALCON-TiN chamber and a DS-TiN chamber, also available from Applied Materials, Inc. In one example, process chamber 332 may be a SIP-TiN chamber or a FALCON-TiN chamber used to deposit a metallic titanium nitride layer during a PVD process and any of process chambers 334, 336, or 338 may be a DS-TiN chamber used to deposit a titanium nitride retarding layer during another PVD process.
In another embodiment, the deposition of the aluminum layer by a CVD process during step 130 of process 100 may be performed in a CVD process chamber, such as the ENDURA® Al CVD chamber, available from Applied Materials, Inc., located in Santa Clara, Calif. Further, the deposition of the aluminum layer by a PVD process during step 140 of process 100 may be performed in a PVD process chamber, such as the ENDURA® Al HP PVD chamber, also available from Applied Materials, Inc. In one example, any of process chambers 332, 334, 336, or 338 may be used to deposit an aluminum layer by a CVD process or a PVD process.
In another embodiment, a process chamber that may be used to deposit the aluminum material is the ALD/CVD hybrid chamber, such as disclosed in commonly assigned U.S. Pat. No. 7,204,886, which is herein incorporated by reference. Another process chamber that may be used to deposit the aluminum material may be configured to operate in both an ALD mode as well as a conventional CVD mode, as described in commonly assigned U.S. Pat. No. 6,878,206, which is incorporated herein by reference.
In one exemplary configuration, processing system 300 contains load lock chambers 302 and 304, process chambers 316 and 318 as plasma preclean chambers or anneal chambers, process chambers 312 and 314 as anneal chambers or vapor deposition chambers, process chamber 332 as a PVD chamber configured to deposit a metallic titanium nitride barrier layer, process chamber 334 as a PVD chamber configured to deposit a titanium nitride retarding layer, process chamber 336 as a CVD chamber or a MOCVD chamber configured to deposit a first aluminum layer or an aluminum seed layer, and process chamber 338 as a PVD chamber configured to deposit a second aluminum layer or an aluminum bulk layer.
In another exemplary configuration, processing system 300 contains load lock chambers 302 and 304, process chambers 316 and 318 as plasma preclean chambers or anneal chambers, process chambers 312 and 314 as PVD chambers each configured to deposit a metallic titanium nitride barrier layer and a titanium nitride retarding layer, process chambers 332 and 338 as CVD or MOCVD chambers configured to deposit a first aluminum layer or an aluminum seed layer, and process chambers 334 and 336 as PVD chambers each configured to deposit a second aluminum layer or an aluminum bulk layer.
In one embodiment, process chambers 462 and 472 may be plasma preclean chambers, process chambers 464 and 466 may be PVD chambers configured to deposit titanium nitride layers, and process chambers 468 and 470 may be configured to deposit aluminum layers by CVD or PVD. In one example, steps 110 and 120 of process 100 may be performed in different PVD process chambers, which may be a SIP-TiN chamber and a DS-TiN chamber, or a FALCON-TiN chamber and a DS-TiN chamber, also available from Applied Materials, Inc. For example, process chamber 464 may be a SIP-TiN chamber or a FALCON-TiN chamber used to deposit a metallic titanium nitride layer during a PVD process and any of process chambers 466, 468, or 470 may be a DS-TiN chamber used to deposit a titanium nitride retarding layer during another PVD process.
In one exemplary configuration, processing system 400 contains load lock chambers 452 and 454, process chambers 462 and 472 as plasma preclean chambers or anneal chambers, process chamber 464 as a PVD chamber configured to deposit a metallic titanium nitride layer, process chamber 466 as a PVD chamber configured to deposit a titanium nitride retarding layer, process chamber 468 as a CVD chamber or a MOCVD chamber configured to deposit a first aluminum layer or an aluminum seed layer, and process chamber 470 as a PVD chamber configured to deposit a second aluminum layer or an aluminum bulk layer.
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.
Number | Name | Date | Kind |
---|---|---|---|
4389973 | Suntola et al. | Jun 1983 | A |
4413022 | Suntola et al. | Nov 1983 | A |
5834372 | Lee et al. | Nov 1998 | A |
5916365 | Sherman | Jun 1999 | A |
5923056 | Lee et al. | Jul 1999 | A |
5976327 | Tanaka | Nov 1999 | A |
6015917 | Bhandari et al. | Jan 2000 | A |
6084302 | Sandhu | Jul 2000 | A |
6124158 | Dautartas et al. | Sep 2000 | A |
6144060 | Park et al. | Nov 2000 | A |
6174809 | Kang et al. | Jan 2001 | B1 |
6197683 | Kang et al. | Mar 2001 | B1 |
6200893 | Sneh | Mar 2001 | B1 |
6203613 | Gates et al. | Mar 2001 | B1 |
6207487 | Kim et al. | Mar 2001 | B1 |
6270572 | Kim et al. | Aug 2001 | B1 |
6284646 | Leem et al. | Sep 2001 | B1 |
6287965 | Kang et al. | Sep 2001 | B1 |
6294836 | Paranjpe et al. | Sep 2001 | B1 |
6305314 | Sneh et al. | Oct 2001 | B1 |
6342277 | Sherman | Jan 2002 | B1 |
6348376 | Lim et al. | Feb 2002 | B2 |
6358829 | Yoon et al. | Mar 2002 | B2 |
6365502 | Paranjpe et al. | Apr 2002 | B1 |
6372598 | Kang et al. | Apr 2002 | B2 |
6379748 | Bhandari et al. | Apr 2002 | B1 |
6391785 | Satta et al. | May 2002 | B1 |
6399491 | Jeon et al. | Jun 2002 | B2 |
6410986 | Merchant et al. | Jun 2002 | B1 |
6416577 | Suntoloa et al. | Jul 2002 | B1 |
6416822 | Chiang et al. | Jul 2002 | B1 |
6428859 | Chiang et al. | Aug 2002 | B1 |
6444263 | Paranjpe et al. | Sep 2002 | B1 |
6451119 | Sneh et al. | Sep 2002 | B2 |
6451695 | Sneh | Sep 2002 | B2 |
6468924 | Lee et al. | Oct 2002 | B2 |
6475276 | Elers et al. | Nov 2002 | B1 |
6475910 | Sneh | Nov 2002 | B1 |
6482262 | Elers et al. | Nov 2002 | B1 |
6482733 | Raaijmakers et al. | Nov 2002 | B2 |
6498091 | Chen et al. | Dec 2002 | B1 |
6511539 | Raaijmakers et al. | Jan 2003 | B1 |
6524952 | Srinivas et al. | Feb 2003 | B1 |
6562715 | Chen et al. | May 2003 | B1 |
6569501 | Chiang et al. | May 2003 | B2 |
6585823 | Van Wijck et al. | Jul 2003 | B1 |
6593484 | Yasuhara et al. | Jul 2003 | B2 |
6596602 | Iizuka et al. | Jul 2003 | B2 |
6599572 | Saanila et al. | Jul 2003 | B2 |
6607976 | Chen et al. | Aug 2003 | B2 |
6620723 | Byun et al. | Sep 2003 | B1 |
6627995 | Paranjpe et al. | Sep 2003 | B2 |
6630201 | Chiang et al. | Oct 2003 | B2 |
6632279 | Ritala et al. | Oct 2003 | B1 |
6645847 | Paranjpe et al. | Nov 2003 | B2 |
6660622 | Chen et al. | Dec 2003 | B2 |
6718126 | Lei | Apr 2004 | B2 |
6740585 | Yoon et al. | May 2004 | B2 |
6772072 | Ganguli et al. | Aug 2004 | B2 |
6773507 | Jallepally et al. | Aug 2004 | B2 |
6777352 | Tepman et al. | Aug 2004 | B2 |
6784096 | Chen et al. | Aug 2004 | B2 |
6790773 | Drewery et al. | Sep 2004 | B1 |
6800173 | Chiang et al. | Oct 2004 | B2 |
6803272 | Halliyal et al. | Oct 2004 | B1 |
6812126 | Paranjpe et al. | Nov 2004 | B1 |
6815285 | Choi et al. | Nov 2004 | B2 |
6821563 | Yudovsky | Nov 2004 | B2 |
6831004 | Byun et al. | Dec 2004 | B2 |
6838125 | Chung et al. | Jan 2005 | B2 |
6846516 | Yang et al. | Jan 2005 | B2 |
6861356 | Matsuse et al. | Mar 2005 | B2 |
6875271 | Glenn et al. | Apr 2005 | B2 |
6893915 | Park et al. | May 2005 | B2 |
6905541 | Chen et al. | Jun 2005 | B2 |
6905737 | Verplancken et al. | Jun 2005 | B2 |
6915592 | Guenther | Jul 2005 | B2 |
6916398 | Chen et al. | Jul 2005 | B2 |
6936906 | Chung et al. | Aug 2005 | B2 |
6939801 | Chung et al. | Sep 2005 | B2 |
6951804 | Seutter et al. | Oct 2005 | B2 |
6953742 | Chen et al. | Oct 2005 | B2 |
6955211 | Ku et al. | Oct 2005 | B2 |
6972267 | Cao et al. | Dec 2005 | B2 |
6974771 | Chen et al. | Dec 2005 | B2 |
6998014 | Chen et al. | Feb 2006 | B2 |
7005697 | Batra et al. | Feb 2006 | B2 |
7026238 | Xi et al. | Apr 2006 | B2 |
7041335 | Chung | May 2006 | B2 |
7049226 | Chung et al. | May 2006 | B2 |
7067422 | Nakamura et al. | Jun 2006 | B2 |
7081271 | Chung et al. | Jul 2006 | B2 |
7081409 | Kang et al. | Jul 2006 | B2 |
7094680 | Seutter et al. | Aug 2006 | B2 |
7098131 | Kang et al. | Aug 2006 | B2 |
7186385 | Ganguli et al. | Mar 2007 | B2 |
7204886 | Chen et al. | Apr 2007 | B2 |
7208413 | Byun et al. | Apr 2007 | B2 |
7211508 | Chung et al. | May 2007 | B2 |
7408225 | Shinriki et al. | Aug 2008 | B2 |
20010000866 | Sneh et al. | May 2001 | A1 |
20010002280 | Sneh | May 2001 | A1 |
20010009695 | Saanila et al. | Jul 2001 | A1 |
20010024387 | Raaijmakers et al. | Sep 2001 | A1 |
20010025979 | Kim et al. | Oct 2001 | A1 |
20010028924 | Sherman | Oct 2001 | A1 |
20010034123 | Jeon et al. | Oct 2001 | A1 |
20010041250 | Werkhoven et al. | Nov 2001 | A1 |
20010054730 | Kim et al. | Dec 2001 | A1 |
20010054769 | Raaijmakers et al. | Dec 2001 | A1 |
20020000598 | Kang et al. | Jan 2002 | A1 |
20020007790 | Park | Jan 2002 | A1 |
20020009544 | McFeely et al. | Jan 2002 | A1 |
20020020869 | Park et al. | Feb 2002 | A1 |
20020021544 | Cho et al. | Feb 2002 | A1 |
20020031618 | Sherman | Mar 2002 | A1 |
20020048635 | Kim et al. | Apr 2002 | A1 |
20020052097 | Park | May 2002 | A1 |
20020060363 | Xi et al. | May 2002 | A1 |
20020068458 | Chiang et al. | Jun 2002 | A1 |
20020073924 | Chiang et al. | Jun 2002 | A1 |
20020076481 | Chiang et al. | Jun 2002 | A1 |
20020076507 | Chiang et al. | Jun 2002 | A1 |
20020076508 | Chiang et al. | Jun 2002 | A1 |
20020076837 | Hujanen et al. | Jun 2002 | A1 |
20020086111 | Byun et al. | Jul 2002 | A1 |
20020086507 | Park et al. | Jul 2002 | A1 |
20020094689 | Park | Jul 2002 | A1 |
20020098627 | Pomarede et al. | Jul 2002 | A1 |
20020104481 | Chiang et al. | Aug 2002 | A1 |
20020106536 | Lee et al. | Aug 2002 | A1 |
20020106846 | Seutter et al. | Aug 2002 | A1 |
20020115886 | Yasuhara et al. | Aug 2002 | A1 |
20020117399 | Chen et al. | Aug 2002 | A1 |
20020144655 | Chiang et al. | Oct 2002 | A1 |
20020144657 | Chiang et al. | Oct 2002 | A1 |
20020146511 | Chiang et al. | Oct 2002 | A1 |
20020155722 | Satta et al. | Oct 2002 | A1 |
20020162506 | Sneh et al. | Nov 2002 | A1 |
20020164421 | Chiang et al. | Nov 2002 | A1 |
20020164423 | Chiang et al. | Nov 2002 | A1 |
20020177282 | Song | Nov 2002 | A1 |
20020182320 | Leskela et al. | Dec 2002 | A1 |
20020187256 | Elers et al. | Dec 2002 | A1 |
20020197402 | Chiang et al. | Dec 2002 | A1 |
20020197856 | Matsuse et al. | Dec 2002 | A1 |
20030013320 | Kim et al. | Jan 2003 | A1 |
20030017697 | Choi et al. | Jan 2003 | A1 |
20030022487 | Yoon et al. | Jan 2003 | A1 |
20030029715 | Yu et al. | Feb 2003 | A1 |
20030031807 | Elers et al. | Feb 2003 | A1 |
20030038369 | Layadi et al. | Feb 2003 | A1 |
20030042630 | Babcoke et al. | Mar 2003 | A1 |
20030049931 | Byun et al. | Mar 2003 | A1 |
20030049942 | Haukka et al. | Mar 2003 | A1 |
20030053799 | Lei | Mar 2003 | A1 |
20030057526 | Chung et al. | Mar 2003 | A1 |
20030057527 | Chung et al. | Mar 2003 | A1 |
20030059538 | Chung et al. | Mar 2003 | A1 |
20030072975 | Shero et al. | Apr 2003 | A1 |
20030079686 | Chen et al. | May 2003 | A1 |
20030082296 | Elers et al. | May 2003 | A1 |
20030082301 | Chen et al. | May 2003 | A1 |
20030082307 | Chung et al. | May 2003 | A1 |
20030087520 | Chen et al. | May 2003 | A1 |
20030089308 | Raaijmakers | May 2003 | A1 |
20030101927 | Raaijmakers | Jun 2003 | A1 |
20030106490 | Jallepally et al. | Jun 2003 | A1 |
20030108674 | Chung et al. | Jun 2003 | A1 |
20030113187 | Lei et al. | Jun 2003 | A1 |
20030116087 | Nguyen et al. | Jun 2003 | A1 |
20030121608 | Chen et al. | Jul 2003 | A1 |
20030124262 | Chen et al. | Jul 2003 | A1 |
20030143328 | Chen et al. | Jul 2003 | A1 |
20030153177 | Tepman et al. | Aug 2003 | A1 |
20030168750 | Basceri et al. | Sep 2003 | A1 |
20030173586 | Moriwaki et al. | Sep 2003 | A1 |
20030186495 | Saanila et al. | Oct 2003 | A1 |
20030190423 | Yang et al. | Oct 2003 | A1 |
20030190804 | Glenn et al. | Oct 2003 | A1 |
20030205729 | Basceri et al. | Nov 2003 | A1 |
20030213987 | Basceri et al. | Nov 2003 | A1 |
20030219942 | Choi et al. | Nov 2003 | A1 |
20030224578 | Chung et al. | Dec 2003 | A1 |
20030224600 | Cao et al. | Dec 2003 | A1 |
20030232497 | Xi et al. | Dec 2003 | A1 |
20040005749 | Choi et al. | Jan 2004 | A1 |
20040009307 | Koh et al. | Jan 2004 | A1 |
20040011504 | Ku et al. | Jan 2004 | A1 |
20040013577 | Ganguli et al. | Jan 2004 | A1 |
20040014320 | Chen et al. | Jan 2004 | A1 |
20040015300 | Ganguli et al. | Jan 2004 | A1 |
20040018304 | Chung et al. | Jan 2004 | A1 |
20040018723 | Byun et al. | Jan 2004 | A1 |
20040018747 | Lee et al. | Jan 2004 | A1 |
20040025370 | Guenther | Feb 2004 | A1 |
20040033698 | Lee et al. | Feb 2004 | A1 |
20040046197 | Basceri et al. | Mar 2004 | A1 |
20040048461 | Chen et al. | Mar 2004 | A1 |
20040065255 | Yang et al. | Apr 2004 | A1 |
20040067641 | Yudovsky | Apr 2004 | A1 |
20040071897 | Verplancken et al. | Apr 2004 | A1 |
20040077183 | Chung | Apr 2004 | A1 |
20040105934 | Chang et al. | Jun 2004 | A1 |
20040144311 | Chen et al. | Jul 2004 | A1 |
20040170403 | Lei | Sep 2004 | A1 |
20040187304 | Chen et al. | Sep 2004 | A1 |
20040209460 | Xi et al. | Oct 2004 | A1 |
20040211665 | Yoon et al. | Oct 2004 | A1 |
20040219784 | Kang et al. | Nov 2004 | A1 |
20040224506 | Choi et al. | Nov 2004 | A1 |
20040235285 | Kang et al. | Nov 2004 | A1 |
20040241321 | Ganguli et al. | Dec 2004 | A1 |
20040256351 | Chung et al. | Dec 2004 | A1 |
20040266175 | Chen et al. | Dec 2004 | A1 |
20050006799 | Gregg et al. | Jan 2005 | A1 |
20050008779 | Yang et al. | Jan 2005 | A1 |
20050009325 | Chung et al. | Jan 2005 | A1 |
20050059240 | Choi et al. | Mar 2005 | A1 |
20050074968 | Chen et al. | Apr 2005 | A1 |
20050104142 | Narayanan et al. | May 2005 | A1 |
20050106865 | Chung et al. | May 2005 | A1 |
20050118804 | Byun et al. | Jun 2005 | A1 |
20050139948 | Chung et al. | Jun 2005 | A1 |
20050164487 | Seutter et al. | Jul 2005 | A1 |
20050173068 | Chen et al. | Aug 2005 | A1 |
20050189072 | Chen et al. | Sep 2005 | A1 |
20050208217 | Shinriki et al. | Sep 2005 | A1 |
20050220998 | Chang et al. | Oct 2005 | A1 |
20050252449 | Nguyen et al. | Nov 2005 | A1 |
20050255690 | Chen et al. | Nov 2005 | A1 |
20050257735 | Guenther | Nov 2005 | A1 |
20050260357 | Olsen et al. | Nov 2005 | A1 |
20050263890 | Han et al. | Dec 2005 | A1 |
20050266682 | Chen et al. | Dec 2005 | A1 |
20050271812 | Myo et al. | Dec 2005 | A1 |
20050271813 | Kher et al. | Dec 2005 | A1 |
20060019033 | Muthukrishnan et al. | Jan 2006 | A1 |
20060019494 | Cao et al. | Jan 2006 | A1 |
20060019495 | Marcadal et al. | Jan 2006 | A1 |
20060030148 | Seutter et al. | Feb 2006 | A1 |
20060035025 | Verplancken et al. | Feb 2006 | A1 |
20060057843 | Chen et al. | Mar 2006 | A1 |
20060062917 | Muthukrishnan et al. | Mar 2006 | A1 |
20060075966 | Chen et al. | Apr 2006 | A1 |
20060128150 | Gandikota et al. | Jun 2006 | A1 |
20060148253 | Chung et al. | Jul 2006 | A1 |
20060153973 | Chang et al. | Jul 2006 | A1 |
20060153995 | Narwankar et al. | Jul 2006 | A1 |
20060156979 | Thakur et al. | Jul 2006 | A1 |
20060199372 | Chung et al. | Sep 2006 | A1 |
20060216928 | Chung et al. | Sep 2006 | A1 |
20060257295 | Chen et al. | Nov 2006 | A1 |
20060276020 | Yoon et al. | Dec 2006 | A1 |
20070003698 | Chen et al. | Jan 2007 | A1 |
20070018244 | Hung et al. | Jan 2007 | A1 |
20070020890 | Thakur et al. | Jan 2007 | A1 |
20070026147 | Chen et al. | Feb 2007 | A1 |
20070067609 | Chen et al. | Mar 2007 | A1 |
20070099415 | Chen et al. | May 2007 | A1 |
20070119370 | Ma et al. | May 2007 | A1 |
20070119371 | Ma et al. | May 2007 | A1 |
20070128862 | Ma et al. | Jun 2007 | A1 |
20070128863 | Ma et al. | Jun 2007 | A1 |
20070128864 | Ma et al. | Jun 2007 | A1 |
Number | Date | Country |
---|---|---|
1167569 | Jan 2002 | EP |
2355727 | May 2001 | GB |
07300649 | Nov 1995 | JP |
2001111000 | Apr 2001 | JP |
2001172767 | Jun 2001 | JP |
WO-9929924 | Jun 1999 | WO |
WO-9965064 | Dec 1999 | WO |
WO-0016377 | Mar 2000 | WO |
WO-0054320 | Sep 2000 | WO |
WO-0115220 | Mar 2001 | WO |
WO-0117692 | Mar 2001 | WO |
WO-0127346 | Apr 2001 | WO |
WO-0127347 | Apr 2001 | WO |
WO-0129280 | Apr 2001 | WO |
WO-0129891 | Apr 2001 | WO |
WO-0129893 | Apr 2001 | WO |
WO-0136702 | May 2001 | WO |
WO-0166832 | Sep 2001 | WO |
WO-0201628 | Jan 2002 | WO |
WO-0208485 | Jan 2002 | WO |
WO-0243115 | May 2002 | WO |
WO-0245167 | Jun 2002 | WO |
WO-0245871 | Jun 2002 | WO |
WO-0246489 | Jun 2002 | WO |
WO-2004106584 | Dec 2004 | WO |
Number | Date | Country | |
---|---|---|---|
20090087585 A1 | Apr 2009 | US |