Ruthenium layer deposition apparatus and method

Background of the invention

Field of invention [0001] Embodiments of the present invention generally relate to a method for depositing a catalyst layer on a barrier layer before depositing a conductive layer on it.

Description of related technology [0002] Multi-level metallization of 45nm nodes is one of the important technologies for next-generation ultra-large scale integration (VLSI). The multi-level interconnect at the heart of this technology has high aspect ratio features including contacts, vias, lines and other apertures. The reliable formation of these features is crucial to the success of the VLSI and the ongoing efforts to increase the quality and circuit density on the individual substrates. Therefore, much ongoing effort involves the formation of void-free features with a high aspect ratio of 10: 1 (height: width).

[0003] Copper is a selective metal that fills VLSI features such as interconnect features with submicron aspect ratios. The contacts are formed by depositing an interconnected conductive material, such as copper, in an opening (eg, via) on the surface of the insulating material placed between two isolated conductive layers. High aspect ratios, such as openings, may prevent the deposition of interconnected conductive materials that exhibit sufficient step coverage and gap fill. Copper is a well-known interconnect material, but has the drawback of diffusing into adjacent layers such as the dielectric layer. Due to the unwanted presence resulting from copper, the dielectric layer cannot be a conductive or electronic device. Therefore, a barrier material is used to control the diffusion of copper.

[0004] The typical sequence of forming interconnects includes the step of depositing one or more non-conductive layers and the step of etching at least one layer to form one or more features in it. It includes a step of depositing a barrier layer in the feature and a step of depositing one or more conductive layers such as copper to fill the feature. The barrier layer typically contains refractory metal nitrides and / or silicides such as titanium or tantalum. This group of tantalum nitrides is one of the most desirable materials used as a barrier layer. Tantalum nitride provides a good barrier to copper diffusion, even when a relatively thin layer (eg, 20 angstroms or less) is formed. The tantalum nitride layer is typically deposited by conventional deposition techniques such as physical vapor deposition (PVD), atomic layer deposition (ALD), and chemical vapor deposition (CVD).

[0005] Tantalum nitride has several negative features, including inadequate adhesion to the copper layer deposited on it. Inadequate adhesion of one or more copper layers deposited subsequently causes process contamination problems in subsequent processing steps, such as rapid electromigration within the formed device, perhaps chemical mechanical polishing (CMP). Can lead to. It is believed that exposure of the tantalum nitride layer to oxygen and / or water sources can prevent the formation of strong bonds with the deposited copper layer due to oxidation. The interface between the tantalum nitride layer barrier layer and the copper layer is easy to separate during the standard tape test.

[0006] A typical deposition process uses a carbon-containing precursor that will be incorporated into the deposited barrier layer. Carbon incorporation is often detrimental to the wet chemistry process, as the deposited membranes tend to be hydrophobic, which reduces or prevents the fluid from wetting and depositing layers with desirable properties. .. To solve this problem, oxidation processes are often used on the barrier layer to remove the carbon incorporated, but these processes are highly oxidized by other exposures such as copper interconnects. Can have harmful effects on the layer. Therefore, there is a need for processes and equipment capable of depositing barrier layers or adhesive layers that can enhance the bond of adhesion between various membranes such as tantalum nitride (TaN) and copper. Also, in some cases, processes and equipment are needed to form an adhesive layer that can be deposited directly on dielectric materials, non-metallic materials or other desirable materials.

[0007] Therefore, there is a need for a method of depositing a copper-containing layer on a barrier layer with good step coverage, strong adhesion and low electrical resistance within a high aspect ratio interconnect feature.

Outline of the invention

[0008] In one embodiment, a ruthenium tetroxide production system having one or more walls forming a first treatment region adapted to hold an amount of ruthenium-containing material and an oxide gas in the ruthenium-containing material in a container. A raw material container adapted to distribute ruthenium tetroxide to form ruthenium tetroxide in the container, and a raw material container adapted to collect ruthenium tetroxide-containing gas formed in the container while communicating with the container in a fluid. An apparatus is provided for depositing a catalyst layer on the surface of a substrate including an assembly. The raw material container assembly includes a raw material container having a collection area, a heat exchange device that is in thermal communication with the collection surface in contact with the collection area, and a processing chamber that is in communication with the raw material container with a fluid. be able to. The processing chamber can include a second processing region, a substrate support located within the second processing region, and one or more walls forming a heat exchange device that is thermally communicative with the substrate support. ..

[0009] In another embodiment, a ruthenium tetroxide production system comprising a container having one or more walls forming a first treatment region adapted to hold an amount of ruthenium tetroxide-containing material, and the container. A device that deposits a catalyst layer on a substrate surface that includes a fluid communication vacuum pump and a raw material container assembly that is fluid communication and adapted to collect ruthenium tetroxide-containing gas distributed from the container. Is provided. The raw material container assembly includes a raw material container having a collection area, a heat exchange device that is in thermal communication with the collection surface in contact with the collection area, and a processing chamber that is in communication with the raw material container with a fluid. be able to. The processing chamber can include one or more walls forming the second processing region, a substrate support located in the second processing region, and a heat exchange device that is thermally communicative with the substrate support.

[0010] In another embodiment, a ruthenium tetroxide production system comprising a first container with one or more walls forming a first treatment region adapted to hold an amount of ruthenium tetroxide-containing material. A device is provided for depositing a catalyst layer on a substrate surface that includes a first feedstock assembly that is fluid communicated with the vessel and adapted to collect the amount of ruthenium tetroxide-containing gas transferred from the first vessel. .. The first raw material container assembly can include a raw material container having a collection area and a heat exchange device that is in thermal communication with the collection surface in contact with the collection area. The second vessel is composed of one or more walls forming a second treated area adapted to hold the amount of ruthenium tetroxide-containing material, and ruthenium tetroxide transferred from the second vessel in a fluid communication with the vessel. It is possible to have a second feedstock assembly adapted to collect the amount of gas contained. The second raw material container assembly can include a raw material container having a collecting area, a heat exchange device that is in thermal communication with the collecting surface in contact with the collecting area, and a processing chamber. The processing chamber is composed of one or more walls that communicate with the raw material container with a fluid to form a chamber processing region, a substrate support located in the chamber processing region, and a heat exchange device that thermally communicates with the substrate support. Can be contained.

[0011] In another embodiment, tetroxide containing a main frame with a substrate transport region and a container with one or more walls forming a first treatment region adapted to hold the amount of ruthenium-containing material. A ruthenium production system, an oxidation source adapted to distribute the ruthenium-containing gas to the ruthenium-containing gas in the container to form a ruthenium tetroxide-containing gas in the container, and a raw material container mounted on the main frame to communicate with the fluid. An apparatus is provided for depositing a catalyst layer on the surface of a substrate including a processing chamber. The processing chamber consists of one or more walls forming the chamber processing area, a fluid distribution line that connects the container and the chamber processing area with fluid, a substrate support located in the chamber processing area, and a substrate support and thermal. It can include a heat exchange device that communicates with the main frame and a robot that is adapted to transfer the substrate from the transfer area of the main frame to the substrate processing area of the processing chamber.

[0012] In another embodiment, it comprises a main frame with a substrate transport area and a container with one or more walls forming a first treatment area adapted to hold the amount of ruthenium tetroxide-containing material. A catalyst layer is deposited on the surface of the substrate including a ruthenium tetroxide production system, a vacuum pump that communicates with the first treatment area with fluid, and a processing chamber that is attached to the main frame and communicates with the raw material container and fluid. A device is provided. The processing chamber consists of one or more walls forming the chamber processing area, a fluid distribution line that communicates with the vessel and the chamber processing area with fluid, a substrate support located in the chamber processing area, and a substrate support and thermal. It can include a heat exchange device that communicates with the main frame and a robot that is adapted to transfer the substrate from the transfer area of the main frame to the chamber processing area of the processing chamber.

[0013] In another embodiment, a processing chamber adapted to deposit a ruthenium-containing layer of a substrate, wherein the processing chamber is located within the chamber processing area with one or more walls forming the chamber processing area. A substrate used to form a semiconductor device or flat panel display that includes a substrate support, said processing chamber containing a heat exchange device that is thermally communicative with the substrate support, and a ruthenium tetroxide production system. A device for depositing a ruthenium-containing layer on the surface is provided. The ruthenium tetroxide production system is a fluid-in communication collection with a first container with one or more walls that forms a first treatment area adapted to contain a solvent mixture containing ruthenium tetroxide. It can include a second vessel with one or more walls forming a region, and a fluid pump that communicates with the first and second vessels in fluid. The fluid pump can be adapted to distribute the solvent mixture from the first container to the collection area of the second container and the heat exchange device that is in thermal communication with the collection area.

[0014] In another embodiment, a catalyst layer is deposited on a substrate surface comprising a ruthenium tetroxide production system containing a container with one or more walls forming a sealed region containing a mixture of ruthenium tetroxide and a solvent. Equipment is provided. One or more gas sources can communicate with the sealed area with a fluid. The device can further include one or more walls forming the chamber processing region, a substrate support located within the chamber processing region, and a heat exchange device that is thermally communicative with the substrate support. Includes treatment chamber. The device further includes a fluid distribution line that communicates with the sealing area of the container and the chamber processing area of the processing chamber with fluid.

More specific description of the invention briefly summarized above can be referenced by embodiments, some of which are in the accompanying drawings, so that the above features of the invention can be understood in detail. It is shown. However, the accompanying drawings only show typical embodiments of the invention and therefore should not be considered limiting the scope of the invention and the invention allows other equally effective embodiments. It should be noted that it can be done.

Detailed explanation

[0030] Methods and devices for depositing ruthenium-containing layers on a substrate are generally disclosed. The methods and devices described herein are particularly useful for making electronic devices formed on the surface of a substrate or wafer. Generally, the method involves exposing the substrate surface to ruthenium tetroxide vapor to form a catalytic layer on the substrate surface, followed by electroless, electroplating, physical vapor deposition (PVD), or chemical vapor deposition of the device structure. It involves filling by the process of (CVD), plasma-enhanced chemical vapor deposition (PE-CVD), atomic layer deposition (ALD), or plasma-enhanced ALD (PE-ALD). In one embodiment, the catalyst layer acts as a barrier layer or subsequent PVD, CVD, PE-CVD, so that it acts as a layer capable of promoting adhesion between the previously deposited layer and the subsequently deposited layer. A ruthenium-containing layer adapted to act as a catalytic layer that facilitates ALD, PE-ALD, electroless, and / or electrolytic deposition processes. Methods and devices described herein that allow device insulation and other device processing to deposit a ruthenium-containing layer that can be strongly bonded to one or both exposed surfaces of a substrate for electromigration. Related to.

[0031] As used herein, "atomic layer deposition" (ALD) or "circular deposition" means the continuous introduction of two or more reactive compounds in order to deposit a material layer on the surface of a substrate. Alternatively, a few or more reactive compounds can be introduced into the reaction zone of the treatment chamber. Usually, each reactive compound is separated by a time delay, allowing each compound to adhere and / or react on the substrate surface. In one embodiment, the first precursor or compound A is pulsed into the reaction zone followed by a first time delay. The second precursor or compound B is then pulsed into the reaction zone, followed by a second delay. During each time delay, a purge gas such as nitrogen is introduced into the treatment chamber to purge the reaction zone or to remove any residual reaction compounds or by-products from the reaction chamber. Alternatively, the purge gas can flow continuously throughout the deposition process, so that only the purge gas flows with a time delay between the pulses of the reactive compound. Alternatively, the reactive compound is pulsed until a desired film or film thickness is formed on the substrate surface. In each scenario, the ALD process of pulsed compound A, purge gas, pulsed compound B, purge gas is the cycle. The cycles can be started with either compound A or compound B and each cycle sequence is continued until a film with the desired thickness is reached.

[0032] As used herein, "substrate surface" means any substrate or material surface formed on a substrate on which a film treatment is to be performed. For example, the surface of the substrate that can be treated is single crystal, polycrystalline or amorphous silicon, strained silicon, silicon on insulator (SOI), doped silicon, silicon germanium, germanium, gallium arsenic, glass, sapphire, silicon oxide, etc. Silicon nitride, silicon oxynitride, fluorine-doped silicate glass (FSG), and / or SiO_xC_yContains materials such as carbon-doped silicon oxide, such as BLACK DIAMOND® low-k dielectric available from Applied Materials, Inc., located in Santa Clara, CA. The substrate can have wafers with a diameter of 200 mm or 300 mm, as well as various dimensions such as a rectangular or square frame. Embodiments of the process described herein deposit metal-containing layers on many substrates and surfaces, especially barrier layers. Substrates for which embodiments of the invention are useful include crystalline silicon (eg, Si <100>, Si <111>), silicon oxide, strained silicon, silicon germanium, doped or undoped polycrystals. 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 manufacture flat panel displays and other similar devices are also included in the embodiments described herein.

[0033] As used herein, "pulse" means the amount of a specific compound that is intermittently or discontinuously introduced into the reaction zone of the processing chamber. The amount of specific compound in each pulse changes over time and depends on the duration of the pulse. The duration of each pulse can vary depending on many factors, such as the volume capacity of the process chamber used, the vacuum system attached to it, and the volatility / reactivity of the specific compound itself. As used herein, "half-reaction" means a purge step following a pulse of precursor.

[0034] In general, the methods and devices described herein are such that a ruthenium-containing layer is selectively or non-selectively deposited on a device feature formed on a substrate surface by the use of a ruthenium tetroxide-containing gas. Is adapted to. The selective or non-selective deposition of the ruthenium-containing layer on the surface of the substrate is believed to be strongly dependent on the temperature and type of surface exposed to the ruthenium tetroxide-containing gas. It is also believed that the ruthenium layer selectively deposits on certain surfaces by controlling the temperature of the substrate to a lower desired temperature, eg, about 180 ° C. For example, at higher temperatures above 180 ° C, the ruthenium deposition process from ruthenium tetroxide-containing gas is less selective, allowing blanket films to be deposited on all types of surfaces.

[0035] In one embodiment, the deposition of ruthenium-containing layers is used to facilitate the subsequent adhesion and filling of layers on the surface of the substrate. In another embodiment, the properties of the ruthenium-containing layer deposited on the surface of the substrate are specially adjusted to meet the requirements of the device formed on the surface of the substrate. Typical desirable properties include the formation of crystalline or amorphous metallic ruthenium layers on the surface of the substrate, so that one or more layers formed are barrier layers, followed by electroless or electroplating processes. It can act as a catalyst layer for the device and can even fill the desired device features. Other desired properties of the ruthenium-containing layer are, for example, to promote selective bottom-up deposition of electroless and / or electroplated layers, or ferroelectric oxides (eg, BST), or various microelectrics. Ruthenium dioxide layer (RuO) on the surface of the substrate to form electrodes compatible with piezoelectric materials (eg PZT) used to form mechanical system (MEMS) devices.₂) Is formed.

A.<u style="single">Barrier layer deposition process</u> [0036] In one aspect, the ruthenium-containing layer is deposited on the barrier layer on the surface of the substrate by exposing the barrier layer to the ruthenium-containing gas, so that the conductive layer can be deposited on the ruthenium-containing layer. Preferably, the barrier layer (eg, tantalum nitride) is deposited by the ALD process, but can also be deposited by PVD, CVD, or other conventional deposition processes.

[0037] FIG. 1A is a diagram illustrating process 100 of one embodiment described herein for manufacturing integrated circuits. Process 100 includes steps 102-106, during which a metal-containing barrier layer is deposited on the substrate surface. In step 104, the barrier layer is exposed to the ruthenium-containing gas and the substrate is maintained at the desired treatment temperature to deposit the ruthenium-containing layer. The conductive layer is then deposited on the catalyst layer during step 106.

[0038] Process 100 corresponds to FIGS. 2A-2D by showing schematic cross-sectional views of electronic devices at different stages of the interconnect manufacturing sequence incorporated in one embodiment of the present invention. FIG. 2A is a cross-sectional view of the substrate 200 having a via or aperture 202 formed on the dielectric layer 201 on the surface of the substrate 200. The substrate 200 can include, for example, semiconductor materials such as silicon, germanium, and silicon germanium. The dielectric layer 201 is silicon dioxide, silicon nitride, FSG, and / or SiO._xC_yIt may be a carbon-doped silicon oxide such as, for example, an insulating material such as BLACK DIAMOND® low dielectric available from Applied Materials, Inc., Santa Clara, CA. The aperture 202 can be formed within the substrate 200 using conventional lithography and etching techniques to expose the contact layer 203. The contact layer may contain doped silicon, copper, tungsten, tungsten silicate, aluminum or alloys thereof.

<u style="single">Formation of barrier layer</u> [0039] The barrier layer 204 is formed in the aperture 202 on the dielectric layer 201, as shown in FIG. 2B. The barrier layer 204 contains one or more barrier materials such as tantalum, tantalum nitride, tantalum silicon nitride, titanium, titanium nitride, titanium silicon nitride, tungsten nitride, silicon nitride, silicon carbide, derivatives thereof, and alloys thereof. , A combination thereof may be included. Barrier layer 204 can be formed using a suitable deposition process that includes ALD, chemical vapor deposition (CVD), physical vapor deposition (PVD), or a combination thereof. For example, the tantalum nitride barrier layer can be deposited using a CVD or ALD process that reacts a tantalum-containing compound or tantalum precursor (eg PDMAT) with a nitrogen-containing compound or nitrogen precursor (eg ammonia). .. In another example, tantalum and / or tantalum nitride is the Gas Delivery Appliance for Atomic Layer issued as US No. 2003-0121608 filed October 25, 2002. Deposited as barrier layer 204 by the ALD process described in co-transferred US application No. 10 / 281,079 called "Deposition", this disclosure is incorporated herein by reference. In one example, a Ta / TaN double layer. Can be deposited as a barrier layer 204, where the tantalum layer and the tantalum nitride layer are deposited independently by the ALD, CVD, and / or PVD processes. Disclosure of the process for depositing multiple materials is a co-transferred US application No. 10 / entitled "ReliabilityBarrier Integration a for Cu Application" issued as US No. 2002-0060363 filed January 17, 2002. Enhanced Copper Growth with Ultrathin Barrier Layer for High Performance issued in 052,681 as US No. 2003-0082301 filed on July 18, 2002. US Pat. 865,042, all disclosures of which are incorporated herein by reference in their entirety.

[0040] Generally, the barrier layer 204 is deposited in the range of about 5 angstroms to 150 angstroms, preferably about 5 angstroms to 150 angstroms, eg, about 20 angstroms. In one example, barrier layer 204 is deposited on aperture 202 with sidewall coverage of about 50 angstroms or less, preferably about 20 angstroms or less. The barrier layer 204 containing tantalum nitride, which can be deposited to a thickness of about 20 angstroms or less, is considered to be thick enough for application as a barrier layer to prevent the diffusion of subsequently deposited metals such as copper. Be done.

[0041] Examples of tantalum-containing compounds useful in the vapor deposition process for forming barrier layers are 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), T-Butyl iminotris (dimethylamino) tantalum (TBTDMT or ()^tBuN) Ta (NMe₂)₃), T-Butyl iminotris (diethylamino) tantalum (TBTDET or ()^tBuN) Ta (NEt)₂)₃), T-Butyl Imminotris (Ethyl Methyl Amino) Tantalum (TB TEAT or ()^tBuN) Ta [N (Et) Me]₃), T-amylimide tris (dimethylamide) tantalum (TAIMATA or ()^tAmil N) Ta (NMe₂)₃)(here,^tAmil is a t-amyl group (C₅H₁₁-Or CH₃CH₂C (CH₃)₂-). ), T-amylimide tris (diethylamide) tantalum (TAIMATA or ()^tAmil N) Ta (NEt)₂)₃, T-amylimide (ethylmethylamide) tantalum (TAIMATA or (^tAmil N) Ta ([N (Et) Me]₃), Halogenated tantalum, eg TaF₅Or TaCl₅, Derivatives thereof, or precursors such as combinations thereof. Ammonia (NH) is an example of a nitrogen-containing compound that is useful in the vapor deposition process to form the barrier layer.₃), Hydrazine (N₂H₄), Methylhydrazine (Me (H) NNH₂), Dimethylhydrazine (Me₂NNH₂Or Me (H) NN (H) Me), t-butylhydrazine (^tBu (H) NNH₂), Phenylhydrazine (C₆H₅(H) NNH₂), Nitrogen plasma source (eg N, N₂, N₂/ H₂, NH₃, Or N₂H₄Plasma), 2,2'-azotert-butane (^tBuNN^tBu), hideout source, eg ethyl azide (EtN)₃), Trimethylsilyl azide (Me₃SiN₃), Their plasmas, their derivatives, or precursors such as combinations thereof, but not limited to these.

[0042] The barrier layer 204 containing tantalum nitride can be deposited by an ALD process that begins with the adsorption of a single layer of tantalum-containing layer on the substrate and is followed by a single layer of nitrogen-containing compound. Alternatively, the ALD process can begin with the adsorption of a single layer of nitrogen-containing layer on the substrate and continue with a single layer of tantalum-containing compound. In addition, the process chamber is typically exhausted during a pulse of reaction gas.

<u style="single">Formation of catalyst layer</u> [0043] In step 104, the 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 ruthenium-containing barrier layer 204. The process of forming the ruthenium-containing gas and depositing the ruthenium-containing layer will be described later together with FIG. 4-Fig. 7. In one embodiment, the catalyst layer can be deposited to a thickness in the range of approximately atomic layers to about 100 angstroms, preferably about 2 angstroms to 20 angstroms.

<u style="single">Formation of conductive layer</u> [0044] Process 100 further includes step 106 of depositing a conductive layer on the catalyst layer 206. In FIG. 2F, the bulk layer 220 is deposited on the catalyst layer 206. The bulk layer 220 can be composed of an electroless copper process alone, eg, ALD, CVD, PVD, or a copper or copper alloy deposited using it in combination with copper electroplating. The bulk layer 220 can have a thickness ranging from about 100 angstroms to about 10,000 angstroms. In one example, the bulk layer 220 contains copper and is deposited by an electroless plating process.

[0045] The electroplating process may be performed in separate electroplating chambers. One method, device and system used to carry out the electroplating deposition process is a joint issue called "Electrochemical processing Cell" issued on October 9, 2002 as US No. 2004-0016636 and US Pat. No. 6,258,220. It is described in the assigned US application No. 10 / 268,284, and any disclosure is incorporated herein by reference in its entirety to the extent consistent with the description alleged therein.

B.<u style="single">Dielectric layer deposition process</u> [0046] In another aspect of the present invention, the ruthenium-containing layer is deposited directly on the dielectric layer to form a catalyst layer on the surface of the substrate, so that the conductive layer can be deposited on the catalyst layer.

[0047] FIG. 1B is a diagram illustrating process 300 of one embodiment described herein of manufacturing an integrated circuit. Process 300 includes steps 304-306, where the catalyst layer is deposited directly on the dielectric surface 251A and the contact surface 251B, as shown in FIGS. 3A-3E. 3A-3D are schematic cross-sectional views of electronic devices at different stages of the interconnect manufacturing sequence incorporated in at least one embodiment of the present invention.

[0048] FIG. 3A is a cross-sectional view of a substrate 250 having a via or aperture 252 formed in a dielectric layer 251 on the surface of the substrate 250. In one embodiment, process 300 begins by forming a ruthenium-containing layer 256 on the dielectric layer 251 in step 304 by exposing the surface of the substrate 250 to a ruthenium-containing gas, and the substrate is maintained at the desired processing temperature. (See Figure 3B). Subsequently, in step 306, the ruthenium-containing layer 256 is deposited on the dielectric layer 251 by allowing bonds to be formed on the surface of the ruthenium component substrate 250 in the ruthenium-containing gas. The conductive layer 260 is then deposited on the ruthenium-containing layer 256 in step 306 (see Figure 3D).

The surface of the dielectric layer surface 251A is generally an oxide and / or nitride material containing silicon. However, the dielectric surface 251A is silicon dioxide, FSG, and / or SiO._xC_yCarbon-doped silicon oxides such as, for example, insulating materials such as BLACK DIAMOND® low dielectrics available from Applied Materials, Inc., Santa Clara, Calif. Contact surface 251B is the exposed area of the underlying interconnect in the underlying layer, typically copper, tungsten, ruthenium, CoWP, CoWPB, aluminum, aluminum alloys, dope silicon, titanium, molybdenum, tantalum, Substances such as nitrides of these metals, or silicides, can be included.

<u style="single">Formation of catalyst layer</u> [0050] In step 304, the ruthenium-containing layer 256 is deposited on the dielectric layer 251 by adding a ruthenium-containing gas. In one example, the ruthenium-containing layer 256 is deposited in a thickness ranging from approximately the atomic layer to about 100 angstroms, preferably from about 5 angstroms to about 50 angstroms, eg, 10 angstroms. The process of forming the ruthenium-containing gas and depositing the ruthenium-containing layer will be described later together with FIG. 4-7. Generally, the ruthenium-containing layer 256 is deposited such that the formed layer adheres to a dielectric layer 251 followed by a conductive layer, such as a seed layer or a bulk layer.

<u style="single">Formation of conductive layer</u> [0051] Process 300 further includes step 306 of depositing the conductive layer 260 on the ruthenium-containing layer 256. The conductive layer 260 is filled with a seed layer (eg, a thin metal layer (see FIG. 3D)) or a bulk layer (eg, aperture 252) deposited on the ruthenium-containing layer 256 (see FIG. 3C). ) Can be formed. The seed layer may be a continuous layer deposited using conventional deposition techniques such as ALD, CVD, PVD, electroplating, or electroless processes. The present invention described herein is advantageous because the deposition of the ruthenium-containing layer on the surface of the substrate can be a seed layer that directly deposits the electroplating layer. The seed layer can have a thickness ranging from approximately a monomolecular layer to about 20 angstroms to about 100 angstroms. Generally, the seed layer contains copper or a copper alloy.

<u style="single">Ruthenium tetroxide formation and deposition equipment and methods</u> The process of depositing a ruthenium-containing layer with desirable properties on the surface of the substrate, eg, step 104 in FIG. 1A and step 304 in FIG. 1B, is carried out by performing process steps 702-706 in process 700 described below. can do. In general, process step 104 in FIG. 1A and process step 304 in FIG. 1B are for forming a ruthenium-containing layer having desirable properties by a step of producing a ruthenium tetroxide-containing gas and a step of exposing a temperature-controlled substrate surface. It is adapted. In the various aspects of the present invention described above, it is desirable to selectively or non-selectively deposit a metal ruthenium layer or a ruthenium dioxide layer on the surface of a substrate to form a ruthenium-containing layer. An exemplary device and method for forming a ruthenium tetroxide-containing gas to form a ruthenium-containing layer on a substrate surface is described herein.

[0053] FIG. 4 is a diagram illustrating an embodiment of a deposition chamber 600 that can be adapted to form and deposit a ruthenium-containing layer on a substrate surface. In one embodiment, the ruthenium-containing layer produces ruthenium tetroxide in an outer vessel and then distributes the produced ruthenium tetroxide gas onto the surface of the temperature controlled substrate located in the processing chamber on the surface of the substrate. It is formed.

[0054] In one embodiment, the ruthenium tetroxide-containing gas is produced or formed by passing the ozone-containing gas through the entire ruthenium raw material contained in the outer container. In one aspect, the ruthenium feedstock is maintained at a temperature close to room temperature. In one aspect, the ruthenium feedstock contains an amount of ruthenium metal (Ru) that reacts with ozone. In one aspect, the metallic ruthenium raw material contained in the outer container is in the form of a powder, a porous block, or a solid block.

[0055] In another embodiment, the ruthenium raw material contained in the outer container is a perlutenate substance, sodium perlutenate (NaRuO).₄), Potassium tetrapropanol (KRuO)₄), Or a derivative thereof, ruthenium tetroxide (RuO), which is volatile under the reaction conditions, presumably according to reaction (1) or (2) and reacts with ozone.₄) Form a compound.

<chemistry num="1"><img file="JP5043684B2_D0001.tif" /></chemistry>

The list of substances presented herein is not limiting, and some substances that form ruthenium tetroxide-containing gases upon exposure to ozone or other oxidizing gases remain unchanged from the basic scope of the invention. Can be used for. Various conventional forming processes can be used to form the various ruthenium raw materials used in the outer container. An example of a conventional process that can be used to form tetrapropanolate is metallic ruthenium powder and sodium percarbonate (Na).₂O₂), And then the mixture is sintered in a furnace or vacuum furnace at a temperature of about 500 ° C. Some literature has shown the use of a spray pyrolysis process, which can be used to form the tetrapropanol material. For example, in a spray pyrolysis system, non-volatile materials such as sodium peroxide and ruthenium were placed in a fluid medium such as water sprayed to form droplets and the droplets reacted. Substance (eg NaRuO₄) Is heated in a furnace, a conventional heat spray device, or another device to form a powder containing).

[0056] The deposition chamber 600 generally includes a process gas distribution system 601 and a processing chamber 603. FIG. 4 is a diagram illustrating an embodiment of a process chamber 603 that may be adapted to deposit a ruthenium-containing layer on a substrate surface. In one embodiment, the processing chamber 603 is subjected to a barrier layer on the surface of the substrate by the use of a CVD, ALD, PE-CVD or PE-ALD process prior to depositing the ruthenium-containing layer on the surface of the substrate (FIG. 2A-. A processing chamber 603 that may be adapted to deposit layers such as D). In other embodiments, the processing chamber 603 is adapted primarily to deposit ruthenium-containing layers, so that any pre- or post-device manufacturing step is performed within the other chamber. In one aspect, the pre or post processing chamber and processing chamber 603 are attached to a cluster tool adapted to perform the desired device manufacturing process sequence (FIG. 8). For example, in the process sequence in which the barrier layer is deposited before the ruthenium-containing layer, the barrier layer is ENDURA® iCuB / S before the ruthenium-containing layer is formed in the processing chamber 603.^TMIt can be deposited in an ALD processing chamber such as a process chamber or a PRODUCER® process chamber. In yet another embodiment, the processing chamber 603 is a vacuum processing chamber adapted to deposit the ruthenium-containing layer below atmospheric pressure, such as a pressure of about 0.1 millitoll to about 50 toll. During the process, the use of a vacuum processing chamber can be advantageous as the process under vacuum conditions can reduce the amount of contamination that can be incorporated into the deposited membrane. Vacuum treatment tends to improve the diffusion transfer process of ruthenium tetroxide to the substrate surface and reduce the limitations due to the convective transfer process.

The processing chamber 603 was generally connected to the processing chamber 404, the gas distribution showerhead 410, the temperature control substrate support 623, the remote plasma source 670, and the injection line 426 of the processing chamber 603. Contains the process gas distribution system 601. The processing enclosure 404 typically includes a side wall 405, with a sealing 406 and a bottom surface 407 surrounding the processing chamber 603 to form a process area 421. The substrate support 623 that supports the substrate 422 is installed on the bottom surface 407 of the processing chamber 603. The backside gas source (not shown) supplies a helium-like gas to the gap between the backside of the substrate 422 and the substrate support surface 623A to improve heat conduction between the substrate support 623 and the substrate 422. To do. In one embodiment of the deposition chamber 600, the substrate support 623 is heated and / or cooled by the use of a heat exchange device 620 and a temperature controller 621 to improve and control the properties of the ruthenium layer deposited on the surface of the substrate 422. .. In one aspect, the heat exchange device 620 is a fluid heat exchange device that includes a built-in heat transfer line 625 that communicates with a temperature control device 621 that controls the heat exchange fluid temperature. In another embodiment, if the embedded heat transfer line 625 is a resistance heating element communicating with the temperature control device 621, the heat exchange device 620 is a resistance heater. In another aspect, the heat exchange device 620 is a thermoelectric device adapted to heat and cool the substrate support 623. Vacuum pumps 435, such as turbo pumps, low temperature turbo pumps, roots blowers, and / or rough pumps, control the pressure inside the processing chamber 603. The gas distribution shower head 410 comprises a gas distribution plenum 420 connected to an injection line 426 and a gas distribution system 601. The injection line 426 and the process gas distribution system 601 communicate with the process area above the substrate 422 through multiple gas nozzle openings 430.

[0058] In one aspect of the invention, it is desirable to generate plasma during the deposition process in order to improve the properties of the deposited ruthenium-containing layer. In this configuration, the shower head 410 is made of a conductive material (eg, aluminum anodic oxide) that acts as a plasma control device by the use of an attached first impedance matching element 475 and a first RF power supply 490. The bias RF generator applies RF bias power to the substrate support 623 and the substrate 422 through the impedance matching element 464. Controller 480 is adapted to control impedance matching elements (ie, 475 and 464), RF power supplies (ie, 490 and 462), and all other aspects of the plasma process. The frequency of the power distributed by the RF power supply should be in the range of about 0.4MHz to 10GHz. In one embodiment, operating impedance matching is provided to the substrate support 623 and showerhead 410 by frequency tuning and / or forward power supply. FIG. 4 shows a capacitively coupled plasma chamber, but in other embodiments of the invention, an inductively coupled plasma chamber or an inductively coupled plasma chamber and a capacitively coupled plasma remain unchanged from the basic scope of the invention. A combination of chambers may be included.

[0059] In one embodiment, the processing chamber 603 is adapted to distribute various plasma-producing species or groups to the processing region 427 through the injection line 671 (FIG. 4, FIG. Contains elements 670) from Figure 6A-Figure C and Figure 11. The RPS that may be adapted for use in the deposition chamber 600 is the ASTRON® type AX7651 reactive gas generator from the MKSASTEX® product in Wilmington, Massachusetts. RPS is commonly used to form reaction components such as hydrogen (H) groups that are introduced into the treatment area 427. Therefore, RPS improves the reactivity of excited gas species to enhance the reaction process. 1,000sccm H₂And a typical RPS process using 1,000 sccm argon and 350 W RF power and a frequency of 13.56 MHz may be included. In one aspect, 4% H₂A forming gas such as a gas containing nitrogen in the rest may be used. In other embodiments, hydrazine (N)₂H₄) Contained gas may be used. In general, RuO₂The use of plasma excitation to generate reducing species capable of converting to Ru allows this reaction to proceed at lower temperatures. This process is typically less than about 180 ° C and selectively RuO₂Is most useful when it is desirable to deposit the metal ruthenium followed by reduction of metallic ruthenium at the same temperature and / or in the same chamber.

[0060] In one embodiment of the deposition chamber 600, the process gas distribution system 601 is adapted to distribute the ruthenium-containing gas, or vapor, to the treatment area 427 to form a ruthenium-containing layer on the substrate surface. The process gas distribution system 601 was generally mounted on one or more gas sources 611A-E, an ozone generation device 612, a processing vessel 630, a raw material vessel assembly 640, and an injection line 426 in the processing chamber 603. Contains discharge line 660. One or more gas sources 611A-E are generally various carriers and / or purge gases that can be used during processing within the processing chamber 603. The one or more gases partitioned from the gas sources 611A-E may include, for example, nitrogen, argon, helium, hydrogen, or other similar gases.

[0061] Typically, the ozone generator 612 contains about 4% to about 100% ozone of oxygen-containing gas from a gas source (not shown) attached to the ozone generator 612, the rest typically. Is a device that converts oxygen into gas. Preferably, the ozone concentration is from about 6% to 100% by weight. The formation of ozone at concentrations above 15% by weight generally involves the process of adsorbing ozone on the cooling surface within the processing vessel and then purging the vessel with an inert gas to remove contaminants. It should be noted that it may be required. However, the ozone concentration can be increased or decreased based on the desired amount of ozone and the type of ozone generator used. Typical ozone generators that may be adapted for use in the deposition chamber 600 are SEMOZON® and LIQUOZON® ozone generators that can be purchased from MKSASTEX® products in Wilmington, Massachusetts. .. The gas source 611A may be adapted to purge or distribute the ozone produced by the ozone generator 612 as carrier gas to the input port 635 of the processing vessel 630.

[0062] In one embodiment of the process gas distribution 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 container 631 is generally a sealed area made or coated from glass, ceramic and other inert materials that do not react with the processing gas formed within the container 631. In one embodiment, the vessel 631 preferably contains a porous solid, powder, or pelletized volume of ruthenium feedstock (eg, ruthenium) in order to promote the formation of ruthenium tetroxide when ozone gas is distributed to the vessel 631. Contains metal, sodium tetrapropylate; see element "A"). The temperature control device 634A generally includes a temperature controller 634B and a heat exchange device 634C that are adapted to control the temperature of the vessel 631 at the desired processing temperature during the ruthenium tetroxide production process. In one embodiment, the heat exchange device 634C is a thermoelectric device adapted to heat and / or cool the vessel 631 in a temperature controlled fluid heat exchange device, a resistance heating device and / or different phases of the process. ..

[0063] In one embodiment, the remote plasma source 673 is connected to the processing vessel 630 through the RPS injection line 673A so that in different phases of the ruthenium tetroxide formation process, the ruthenium source is on the surface of the ruthenium source. It can be produced by injecting a hydrogen (H) group into the vessel 631 to reduce any oxide formed in. Ruthenium dioxide (RuO)₂) May need to be regenerated if the undesired layer of) is formed with a significant portion of the exposed ruthenium feedstock contained in container 631. In one embodiment, a regeneration process is carried out by introducing a hydrogen-containing gas into the ruthenium raw material heated to a high temperature in an effort to reduce the formed oxide.

[0064] With reference to FIG. 4, the raw material container assembly 640 generally includes a raw material container 641, a temperature controller 642, an injection port 645, and an discharge port 646. Raw material container 641 is adapted to collect and retain ruthenium tetroxide produced in processing container 630. The raw material container 641 generally does not react with glass, ceramics, plastics (eg, TEFLON®, PTFE or polyethylene), or ruthenium tetroxide and has desirable thermal shock properties and mechanical properties. It is lined, coated or made of material. When in use, the temperature controller 642 cools the raw material container to a temperature below 20 ° C so that ruthenium tetroxide gas condenses on the wall of the raw material container. The temperature controller 642 generally includes a temperature control device 643 and a heat exchange device 644 that are adapted to control the temperature of the raw material container 641 to a desired temperature. In one aspect, the heat exchange device is a temperature controlled fluid heat exchange device, resistance heating device and / or thermoelectric device adapted to heat and cool the raw material container.

[0065] FIG. 5 is a diagram illustrating a process 700 of one embodiment described herein to form a ruthenium-containing layer on the surface of a substrate. Process 700 includes steps 702-708, where the ruthenium-containing layer is deposited directly on the substrate surface. The first process step 702 of the process 700 includes a step of forming ruthenium tetroxide gas and a step of collecting the produced gas in the raw material container 641. In process step 702, the ozone generated by the ozone generator 612 is distributed to the ruthenium raw material contained in the processing container 631 to form a flow of ruthenium tetroxide-containing gas, which is collected in the container 641. Therefore, during process step 702, the ozone-containing gas flow flows through the ruthenium raw material, forming ruthenium tetroxide and flowing by the flowing gas. During this process, the gas flow path is from the ozone generator 612 through the discharge port 636 in the container 631 before and after the ruthenium raw material (reference numeral A) in the injection port 635, through the process line 648 to the closed raw material container 641. is there. In one embodiment, it is desirable to evacuate the raw material container 641 using a conventional vacuum pump 652 (eg, conventional roughing pump, vacuum evacuator) before introducing the ruthenium tetroxide-containing gas. In one embodiment, the gas source 611A is used to form an ozone-containing gas containing pure oxygen and ozone or an oxygen-containing gas and an inert gas diluted ozone. In one aspect of process step 702, the ruthenium feedstock (reference numeral A) contained in the vessel 631 is from about 0 ° C to about 100 ° C, more preferably to enhance the ruthenium tetroxide forming process in the vessel 631. Is maintained at a temperature of about 20 ° C to about 60 ° C. A lower ruthenium tetroxide formation temperature is generally desirable, but the temperature required to form ruthenium tetroxide gas depends somewhat on the amount of water contained in the container 631 being processed. Conceivable. During process step 702, the raw material container 641 is about At temperatures below 25 ° C, ruthenium tetroxide produced on the walls of the raw material vessel 641 is maintained at a pressure that allows it to condense or crystallize (or solidify). For example, the raw material container 641 is maintained at a temperature of about -20 ° C to about 25 ° C at a pressure of about 5 tolls. Unwanted oxygen (O) in the ruthenium tetroxide-containing gas by cooling the ruthenium tetroxide and condensing or solidifying it on the wall of the raw material container 641.₂), Ozone (O₃) Ingredients can be separated and removed in step 704 of the second process. In one embodiment, it is desirable to inject into the container 631 an amount of water, or water-containing gas, that facilitates the ruthenium tetroxide production process. Water injection is important to improve the dissociation of ruthenium tetroxide from the ruthenium source, for example, if the ruthenium source contains sodium tetrapropanol, potassium perlutenate, or derivatives thereof. In one aspect, it is desirable to remove excess water by a conventional physical separation (eg, molecular sieve) process after the dissociation process has taken place.

[0066] The second step 704, or purge step, is an unwanted oxygen (O) from ruthenium tetroxide-containing gas.₂) And unreacted ozone (O₃) Designed to remove components. Referring to FIG. 4, in one embodiment, in the second process step 704, the wall of the raw material container 641 closes the ozone separation valve 612A and one or more purge gases are processed from one or more gas sources 611B-C. The temperature is maintained below 25 ° C by flowing through 630 to process line 648, raw material container 641, and then exhaust line 651 to exhaust system 650. The amount of uncondensed or non-condensable ruthenium tetroxide consumed during process step 704 allows time for the ruthenium tetroxide to condense or solidify, the desired length between process step 702 and process step 704. It can be minimized by adding the waiting step of. The amount of non-solidified or non-condensable ruthenium tetroxide consumed is a raw material to reduce the wall temperature of the raw material container to increase the solidification rate and / or to increase the interaction between the wall and the ruthenium tetroxide-containing gas. It can be further reduced by increasing the surface area of the container. The purge gas partitioned from one or more gas sources 611B-C can be, for example, nitrogen, argon, helium, or a dry, clean process gas. Unwanted oxygen (O₂) And unreacted ozone (O₃The process of removing these components is essential to the success of the ruthenium deposition process, as the components can cause unwanted oxidation of the surface exposed on the substrate. Copper has a high affinity for oxygen and easily corrodes in the presence of oxidative species, so unwanted oxygen (O)₂) And unreacted ozone (O₃) Component removal is especially important when the copper interconnect is exposed to the surface of the substrate. In one embodiment, process step 704 is oxygen (O).₂) And / or unreacted ozone (O₃) Concentration is achieved to less than about 100 parts per million (ppm). In one embodiment, heating the vessel 631 to a temperature of about 20 ° C to 25 ° C during process step 704 to ensure that all of the ruthenium tetroxide formed is removed from the processing vessel 630. It is desirable.

[0067] In one embodiment, the purge process (step 704) is performed by evacuating the raw material container 641 with a vacuum pump 652 to remove contaminants. To prevent a significant amount of ruthenium tetroxide from being removed from the raw material vessel assembly 640 during this step, the vessel temperature and pressure can be controlled to minimize loss due to evaporation. For example, it is desirable to pump the raw material container assembly 640 to a pressure of about 5 tolls while maintaining a temperature below about 0 ° C.

[0068] In one embodiment, the third process step 706, or the step of distributing ruthenium tetroxide to the processing chamber 603, is performed after the raw material container 641 has been purged and the valve 637A has been removed from the processing container 630 to the raw material container 641. Closed to separate. Process step 706 begins when the raw material vessel 641 is heated to a temperature at which the condensed or solidified ruthenium tetroxide forms ruthenium tetroxide gas, and one or more gas sources 611 (eg, reference numerals 611d and / or 611E). ), Gas source-related separation valves (eg, reference numerals 638 and / or 639), and when the process chamber separation valve 661 is opened, the ruthenium tetroxide-containing gas is injected into the injection line 426 through the showerhead 410 and processed. A ruthenium-containing layer can be formed on the surface of the substrate by allowing it to flow through region 427 through the temperature-controlled substrate 422. In one embodiment, the raw material vessel 641 is heated to a temperature of about 0 ° C to about 50 ° C where the condensed or solidified ruthenium tetroxide forms ruthenium tetroxide gas. It should be noted that an equilibrium partial pressure of ruthenium tetroxide gas is present in the raw material vessel 641 even at low temperatures, eg, about 5 ° C. Therefore, in one embodiment, by knowing the mass of ruthenium tetroxide contained in the vessel, and by knowing the volume and temperature of the raw material vessel 641, the repeatable mass can be distributed to the processing chamber 603. In another embodiment, the sublimation or vaporization rate of ruthenium tetroxide is known for a raw material container 641 of a certain size at a constant temperature, and the carrier gas is flowed through the raw material container 641 at a desired rate to obtain the desired four. By forming a gas having a ruthenium tetroxide concentration, a continuous flow of ruthenium tetroxide-containing gas can be formed and distributed to the processing chamber 603.

[0069] Ruthenium tetroxide (RuO) at temperatures above 180 ° C to nonselectively deposit ruthenium-containing layers on the surface of the substrate.₄) Is thermodynamically stable ruthenium dioxide (RuO)₂), And hydrogen (H)₂), At a slightly higher temperature, the deposition proceeds to the desired result of forming a metal ruthenium layer directly. The equilibrium equation of the reaction is shown in the following equation (3).

<chemistry num="2"><img file="JP5043684B2_D0002.tif" /></chemistry>

Therefore, in one aspect of the invention, during process step 706, the substrate surface may be at temperatures above about 180 ° C, more preferably from about 180 ° C to about, due to the use of temperature controlled substrate support 623. It is maintained at a temperature of 450 ° C, more preferably at a temperature of about 200 ° C to about 400 ° C. The temperature for forming the metallic ruthenium layer may be about 300 ° C to 400 ° C. Typically, the processing chamber pressure is maintained at a pressure of less than about 10 torr, preferably about 500 millitorr (mTorr) to 5 torr. By controlling the temperature of the surface of the substrate, the selectivity of the deposited ruthenium-containing layer and the crystal structure of the deposited ruthenium-containing layer are adjusted and controlled as desired. The crystalline ruthenium-containing layer is thought to be formed at temperatures above 350 ° C.

[0070] In one embodiment of process step 706, the ruthenium tetroxide-containing gas is hydrogen (H), with the nitrogen-containing gas partitioned from gas source 611D.₂) Containing gas (eg hydrogen (H)₂), Hydrazine (N₂H₄)) Is formed when distributed from the gas source 611E through the raw material container assembly 640 containing ruthenium tetroxide and then through the process chamber 603. For example, 100 sccm of nitrogen and 100 sccm of H₂The gas is distributed to the process chamber 603, which is maintained at a pressure of about 0.1-10 tolls, more preferably about 2 tolls. The desired flow rate of the gas distributed from the gas source 611 (eg, reference numeral 611D-E) is the desired concentration of ruthenium tetroxide in the ruthenium tetroxide-containing gas and the rate of vaporization of ruthenium tetroxide from the wall of the raw material container 641. Depends on.

[0071] In one embodiment, the remote plasma source 670 is used to enhance the process of forming the metallic ruthenium layer during process step 706. In this case, the H groups generated by the remote plasma source are injected into the treatment area 427 to reduce any oxides formed on the surface of the ruthenium raw material. In one aspect, RPS is used to generate H groups as the ruthenium tetroxide-containing gas is distributed to the treatment area 427. In another aspect, RPS is used only after the formation of a continuous single layer of each ruthenium, thus forming two steps consisting of a deposition step and a subsequent reduction step of the ruthenium layer.

[0072] In one embodiment of processing step 706, the amount of ruthenium tetroxide-containing gas produced and distributed in processing chamber 603 is such that the process is repeatable, complete saturation of the process chamber components is achieved and ruthenium-containing. It is monitored and controlled to ensure that the desired thickness of the membrane has been deposited. In one embodiment, the mass of ruthenium tetroxide distributed to the process chamber is monitored by measuring the change in mass of the raw material container 641 as a function of time due to the use of conventional electronic scales, load cells, or other mass measuring devices. Will be done.

[0073] In one embodiment, the gas distribution system 601 is adapted to distribute a single dose or mass of ruthenium tetroxide to the process chamber 603 and the substrate to form a ruthenium-containing layer on the substrate surface. .. In another embodiment, multiple continuous doses of ruthenium tetroxide are distributed to process chamber 603 to form a multilayer ruthenium-containing film. To make multiple continuous doses, at least one of process steps 702-706, both shown in FIGS. 5-7, is repeated multiple times to form a multi-layer ruthenium-containing layer. In other embodiments, the surface area of the raw material vessel 641 and the length of process step 702 both allow continuous flow of the desired concentration of ruthenium tetroxide-containing gas over the entire surface of the substrate during the ruthenium-containing layer deposition process. It is the size to do. Gas flow distribution across the surface of the substrate is in the processing chamber, especially for processes dominated by mass transfer limiting reactions (CVD-type reactions) and for ALD-type processes where rapid surface saturation is required for reaction rate limited deposition. It can be important to form a uniform layer on the substrate treated with. Therefore, the use of a uniform gas flow across the substrate surface by the use of the showerhead 410 is crucial to ensure uniform process results across the substrate surface.

[0074] In one aspect of the invention, the process of distributing the mass of ruthenium tetroxide to chamber 603 grows because the organic material found in one or more ALD or CVD precursors is absent in the ruthenium-containing gas. It is advantageous over ALD or CVD type processes because it is not incorporated into the ruthenium-containing layer. Incorporation of organic materials into growing ruthenium films can have a significant impact on the electrical resistance, adhesion, stress transfer, and electromigration properties of one or more formed devices. In addition, since the size of the ruthenium tetroxide molecule is much smaller than that of the conventional ruthenium-containing precursor, the deposition rate of the ruthenium-containing layer per ALD cycle using ruthenium tetroxide improves the ruthenium coverage per ALD cycle. In addition, it increases more than conventional precursors.

[0075] FIG. 6A is a diagram showing another embodiment of the gas distribution system 602 found in the deposition chamber 601. The gas distribution system 602 is similar to the gas distribution system 601 described relative to FIG. 4, except that the gas distribution system 602 contains two or more raw material container assemblies (eg, reference numerals 640A-B). .. Each of the raw material container assemblies 640A and 640B has its own raw material container (element 641A-641B), temperature controller (element 642A-B), temperature controller device (element 643A-B), and heat exchange device (element). 644A-B), an injection port (element 645A-B), and an discharge port (element 646A-B). In this configuration, shown in FIG. 6A, the two raw material vessels 640A-B are used to alternately collect and distribute the ruthenium tetroxide produced, so that the chamber process is tetroxide in a single raw material vessel. Not interrupted by the time required to collect ruthenium. For example, if the first raw material container 640A uses the gas source 611D-E, the first raw material container 641A and the processing chamber separation valve 661A to perform process step 706 on the substrate located in the process chamber 603, the second raw material container The 640B can perform the process step 702 using the ozone generator 612, the processing vessel 631, the raw material vessel 640B, the injection port 635, the discharge port 636, the separation valve 637B, and the process line 648.

[0076] FIG. 6B shows an embodiment of a gas distribution system 602 in which each of two or more raw material container assemblies (eg, elements 640A or 640B) is separately supported by themselves or in separate processing containers 630. It is a figure. This configuration is advantageous when one of the containers 631 (eg 631A or 631B) needs to be replaced, when the ruthenium feedstock is exhausted, or when maintenance activities need to be performed on one of the containers. It is a thing. In one embodiment, as shown in FIG. 6B, the gas sources 611A-C and the ozone generator 612 are shared by the first treatment vessel 630A and the second treatment vessel 630B.

[0077] In one aspect of the gas distribution system 602, the controller 480 attempts to ensure that at least one of the raw material containers 640A or 640B in the process chamber 603 contains the desired amount of solidified or crystallized ruthenium tetroxide at any time. Adapted to monitor one or more processes taking place within process chamber 603. Typical aspects of the process in which controller 480 should be monitored are the mass of ruthenium tetroxide in raw material container 640A-B, the state of the process in progress in chamber 603 and / or one or more substrates. Waiting to be processed in the deposition chamber 600. Thus, the gas distribution system 602 looks ahead and adjusts the required rate of ruthenium tetroxide production so that at least one of the containers 640A-B is a precursor of the desired mass at the desired time. Is adapted to ensure that it contains. This configuration is due to the flow of ozone-containing gas across the surface of the ruthenium raw material contained in the processing vessel 631 or the ruthenium tetroxide production process is dynamically limited by the reaction rate of ozone and ruthenium. This is important because it limits the migration. Therefore, based on the plurality of process variables, the ruthenium tetroxide production process has the maximum rate at which ruthenium tetroxide can be formed, which limits the processing capacity of the deposition chamber. The production process variable part is affected by, for example, the surface area of the ozone gas / ruthenium solid interface, the temperature of the ruthenium raw material, the ozone concentration in the processing vessel 631, and the flow rate of the carrier gas distributed to the processing vessel. Therefore, in one aspect of the present invention, the controller 480 controls the ruthenium tetroxide formation rate by adjusting the time at which the ruthenium tetroxide formation process starts and the flow rate of the ozone-containing gas to the processing container 631 to control the ruthenium tetroxide formation rate. The gas distribution system can fill the raw material container 641 in time because it is necessary to produce ruthenium tetroxide at a rate exceeding the upper limit of the formation rate.

[0078] Figure 6C shows a chemical species attached to a discharge line 660 adapted to the processing chamber 603 to distribute the repeating mass of ruthenium tetroxide gas, or the volume of ruthenium tetroxide gas, at the desired temperature and pressure. FIG. 6 illustrates an embodiment of a gas distribution system 601 similar to that shown in FIG. 6B, except that it contains an infusion vessel assembly 669. The chemical species injection vessel assembly 669 includes an injection separation valve 664, a chemical species injection vessel 662, and an discharge separation valve 663. In one embodiment, the chemical species infusion vessel assembly 669 is generally adapted to communicate with the controller 480, a temperature sensor 665, a pressure sensor 667, and a heat exchange device 668 (eg, a fluid heat exchange device). , Resistance heating device and / or thermoelectric device) and temperature controller 672. Generally, in this configuration, the controller 480 is adapted to control and monitor the condition of the ruthenium tetroxide-containing gas held in the species injection vessel 662.

[0079] In another embodiment, the species injection vessel assembly 669 also contains an optical sensor 681 that senses the presence of ruthenium tetroxide and is adapted to communicate with the controller 480. In one aspect, the optical sensor 681 is made to sense the presence of ruthenium tetroxide-containing gas in the species injection vessel 662 by measuring changes in the absorption of certain wavelengths of light in the ruthenium tetroxide-containing gas. It is adapted. In this configuration, the optical sensor may be an optical prism or other conventional device that is tuned to sense the presence of the desired concentration of ruthenium tetroxide-containing gas in the species injection vessel 662.

[0080] FIG. 7 is a diagram showing Process 700A, which is a modified variant of Process 700 shown in FIG. 5, including a novel filled species injection vessel 705. In this modified modification of process 700, the chemical species injection container 662 is filled after the purge raw material container step 704 and before the process step 706. In one embodiment, the species injection vessel remains closed with the injection valve 664 prior to starting process step 705, allowing the vacuum pump 435 in the process chamber 603 to evacuate the species injection vessel 662. By opening the discharge valve 663 while the pressure is maintained, the pressure is reduced to the desired vacuum pressure.

[0081] In process step 705, one of the raw material containers 641A or 641B containing the amount of condensed or solidified ruthenium tetroxide is tetroxide of the condensed or solidified ruthenium tetroxide in the raw material container 640A or 640B. It starts when heated to a temperature at which a ruthenium-containing gas is formed. Once the desired temperature is achieved in the raw material container 640A or 640B, the processing chamber separation valve 661A or 661B and the injection separation valve 664 are opened and the discharge separation valve 663 is closed so that ruthenium tetroxide gas can be released. Flow into the chemical species injection chamber 662. Once the desired pressure and temperature of the ruthenium tetroxide-containing gas is achieved within the species injection vessel 662, the injection valve 664 is closed. Therefore, a given mass or volume at the desired temperature and pressure is maintained within the species injection vessel 662. Generally, the mass of ruthenium tetraoxide retained in the chemical species injection vessel 662 is then immediately subjected to process step 706 by the use of temperature sensor 665, pressure sensor 667, heat exchange device 668, temperature controller 672. , Maintained at desired temperature and pressure. In one embodiment, process step 706 is not initiated until the desired temperature and / or pressure is achieved within the species injection vessel 662, so a repeatable deposition process, ie, process step 706, can be performed on the substrate. ..

[0082] In process 700A, process step 706 is modified from the process described above with FIG. 5 in order to incorporate the species injection vessel 662 into the system. In this configuration, process 706 is performed when the gas source separation valve 673 and the discharge valve 663 are opened, and the injection valve 664 remains closed, so that the carrier gas from the inert gas source 674 is a chemical species injection container. A ruthenium-containing layer is formed on the surface of the substrate because the ruthenium tetroxide-containing gas flows to 662 and is transported to the injection line 426, through the shower head 410, and to the exhausted process region 427 throughout the temperature-controlled substrate 422. Can be done. In one embodiment, no carrier gas is used to distribute ruthenium tetroxide to process region 427.

[0083] In one embodiment, the inert gas source 674 and / or the species injection vessel 662 is used to "inject" or "pulse" the ruthenium tetroxide-containing gas into the process region 427 so that the gas is The substrate surface can be saturated (eg, ALD-type process). Since the "species injection" or "species injection process" can be performed by opening and closing various separation valves for a desired time, a desired amount of ruthenium-containing gas can be injected into the process chamber 603. In one aspect, the inert gas is not distributed from the gas source 674 to the species injection vessel 662 during the species injection process.

[0084] With reference to FIG. 4, in one aspect of the invention, the ozone generator 612B is connected to process chamber 603 and used to remove ruthenium deposited on various chamber components during the previous deposition process. Be done. In one aspect, the single ozone generator 612 is used to form ruthenium tetroxide and clean the processing chamber 603.

<u style="single">Another ruthenium tetroxide production process</u> [0085] FIG. 9 is a diagram showing an embodiment of a ruthenium tetroxide-containing solvent forming process that can be used to form ruthenium tetroxide using a tetrapropanolate-containing raw material. The first step (element 1002) of the ruthenium tetroxide-containing solvent formation process 1001 is the first dissolution of a tetrapropanol salt, such as sodium tetrapropylate, in an aqueous solution in a first container (eg, element 1021 in FIG. 10C). Start by. In one embodiment, the process solution is to dissolve sodium perlutenate in a solution of excess sodium hypochlorite (NaOCl) and then titrate with sulfuric acid to a pH value of about 7 to liberate ruthenium tetroxide. Is formed by. Note that hypochlorite materials such as potassium hypochlorite or calcium hypochlorite can also be used in place of sodium hypochlorite. Ruthenium tetroxide appears to be formed according to reaction (4).

<chemistry num="3"><img file="JP5043684B2_D0003.tif" /></chemistry>

In one example, the process solution is prepared by mixing 50 mL of sodium hypochlorite (eg, 10% NaOCl solution) with 1 gram of finely powdered sodium perlutenate and stirring until dissolution is essentially complete. Formed. Then H₂SO₄A sufficient amount of a 10% aqueous solution of the above was added to obtain a pH of about 7. Generally, instead of sulfuric acid, phosphoric acid (H₃PO₄Any non-oxidizing, non-volatile acid such as) can be used.

[0086] In one embodiment of the ruthenium tetroxide-containing solvent forming process 1001, any production step 1004 may then be performed in the process solution. Step 1005 generally includes 1) heating the process solution mixture to a temperature of about 50 ° C in the first vessel and 2) inert gas or ozone (O).₃) Is blown into the process solution, the vapor generated in the first container is distributed to a cooled second container (for example, 20 ° C), and the generated vapor condenses to ruthenium tetroxide and water. Includes steps to obtain a mixture of. Therefore, the ruthenium tetroxide vapor generated in the first container is collected in the pure water contained in the second container. After step 1004 is complete, the second vessel contains the aqueous component used by the rest of the ruthenium tetroxide-containing solvent formation process 1001 step, and the leftover component of the first vessel can be discarded or regenerated. Step 1004 is useful to assist in purifying the process solution used as the ruthenium tetroxide feedstock.

[0087] In step 1006, the solvent is added to the aqueous solution to dissolve all of the ruthenium tetroxide contained in the aqueous solution. Suitable solvents are generally perfluorocarbons (C)._xF_y), Hydrofluorocarbon (H)_xC_yF_z), Substances such as chlorofluorocarbons (chlorofluorocarbons or CFCs). Any solvent material that is generally non-polar, non-oxidizing, close to boiling point, and more preferably less than about 50 ° C is useful for performing this process. Preferably, the boiling point of the solvent is in the range of about 25 ° C to 40 ° C. In general, both perfluorocarbons and chlorofluorocarbons are effective, and perfluorocarbons, which have been found not to behave as ozone depleting substances (ODS), are preferred. For example, a suitable solvent is perfluoropentane (C).₅F₁₂), Perfluorohexane (C₆F₁₄), Freon-containing substances, for example, Freon 11 (fluorotrichloromethane (CFCl))₃)), Freon 113 (1,1,2-trichloro-1,2,2-trifluoroethane (CCl)₂FCClF₂)), Derivatives thereof or a combination thereof. In general, various common refrigerants may be used as solvents, especially if the entire process can be carried out in a sealing system capable of blocking their release to the surroundings. Perfluoropentanes are easily available in pure form, are not ODS, and are extremely inert, so they generally do not react with substances exposed during processing, which makes them used in the semiconductor industry. Can have many advantages.

[0088] In one embodiment of the ruthenium tetroxide-containing solvent formation process 1001, any step 1008 may then be performed on the solvent mixture formed in step 1006. This step is ozone (O₃) Is added to the solvent mixture contained in the first container (eg, element 1021 in FIG. 10C) and is preferably maintained at a temperature close to room temperature to ensure the formation of ruthenium tetroxide. To do. An example of a ruthenium production step is the desired amount of tetroxide in a mixture of 4% ozone-containing gas at a flow rate of 500 mL / min containing 1 g of sodium tetrapropylate, 50 mL of water and 25 g of chlorofluorocarbon 113. It involves the step of flowing ruthenium until it is formed by the process.

[0089] The final step 1010 of the ruthenium tetroxide-containing solvent formation process 1001 generally involves separating water from the solvent mixture after performing steps 1006 and / or 1008 to provide an "anhydrous" solvent mixture. Steps to form are needed. In one aspect, choosing a solvent that is immiscible with water allows the water to be easily removed from the solvent mixture by the use of some conventional physical separation processes. Failure to separate most or all of the water from the rest of the solvent can lead to problems in subsequent process steps and reduce the selectivity of ruthenium-containing layer deposition. Use of simple mechanical techniques (eg, separatory funnel, siphon or pump) if the selected solvent is immiscible with water and has a different density than water, such as perfluoropentane, Freon 11 or Freon 113. Allows most of the water to be easily separated from the static mixture. Complete removal of residual water can be achieved by conventional filtration following contact between the liquid and the molecular sieve (eg, 3A molecular sieve). In one aspect, the "anhydrous" solvent mixture can then be transferred to a container that can be used as a raw material for ALD and CVD precursors used in processing tools where ruthenium-containing layers are deposited. It is important to note that pure solid ruthenium tetroxide is generally unstable, difficult to handle and difficult to transfer from one location to another. Therefore, one advantage of the present invention described herein is to create a method for effectively transferring and / or producing pure ruthenium tetroxide that can be used to form a ruthenium-containing layer. .. In one aspect, it is desirable to transport and deploy ruthenium tetroxide in an environment that is not exposed to light in order to prevent the decomposition of ruthenium tetroxide into ruthenium dioxide and oxygen.

[0090] In one embodiment, removing all of the contaminants from the "anhydrous" solvent mixture to prevent or minimize contamination of the substrate surface during the subsequent ruthenium tetroxide-containing layer deposition process step. It is important to ensure. In one embodiment, various purification processes are performed with an "anhydrous" solvent mixture before the mixture and its components can be immediately exposed to the substrate surface to ensure that all or most of the contaminants are removed. Can be done. In one aspect, the purification process may include performing process step 1004 at least once with the process solvent formed in step 1002. In another embodiment, the process step 1010 in the ruthenium tetroxide-containing solvent forming process 1001 is performed at least once on the process solvent.

<u style="single">Ruthenium-containing layer deposition process using ruthenium tetroxide-containing solvent</u> [0091] After performing the ruthenium tetroxide-containing solvent forming process 1001, the "anhydrous" solvent mixture contains ruthenium on the substrate surface by using another embodiment of process 700 (hereafter process 700B) shown in FIG. 10A. Used to form layers. In this embodiment, process 700B comprises a novel process step 701, a purified variant of process step 702 (ie, step 702A in FIG. 10C), and process steps 704-706 described above. In other embodiments, the steps found in process 700B may be rearranged, modified, or stripped of one or more steps without variation from the basic scope of the invention. , Two or more steps may be combined into a single step. For example, in one embodiment, process step 705 is removed from process step 700B.

[0092] The first step or step 701 of Process 700B requires the separation of ruthenium tetroxide from the rest of the "anhydrous" solvent mixture. In one embodiment, step 701 is a series of process steps (see Figure 10) in which the separation hardware system 1020 (see Figure 10) can be used to separate ruthenium tetroxide from the rest of the "anhydrous" solvent mixture. See process sequence 701A in 10B). FIG. 10B is a diagram illustrating an embodiment of process sequence 701A that can be used to perform process step 701. Process sequence 701A is initiated by partitioning and connecting the first vessel 1021 containing the "anhydrous" solvent mixture (element A) formed using the ruthenium tetroxide-containing solvent forming process 1001 to the processing vessel assembly 1023. The hardware shown in FIG. 10C is a direct replacement for the processing chambers 630, 630A, 630B shown in FIGS. 4 and 6A-6C, with ruthenium tetroxide-containing gas as the raw material vessel assembly (element 640 in FIG. 4 or It can be distributed to the processing chamber 603 (see Figures 4 and 6A-C) and finally to the processing chambers 603 (see Figures 6A-640A and 640B). Similar or similar element numbers found in FIGS. 4 and 6A-6C for clarity are used in FIG. 10C. The processing vessel assembly 1023 generally includes a processing vessel 1023B and a temperature control device 1023A (eg, a fluid heat exchange device, a resistance heating device and / or a thermoelectric device).

[0093] The first step of process sequence 701A (step 701B) is initiated by injecting the desired amount of "anhydrous" solvent mixture into processing vessel 1023B by using metering pump 1022 or other conventional fluid dispensing process. .. The processing vessel 1023B is then exhausted to the desired temperature and pressure (step 701C) by the use of the heat exchange device 1023A, the vacuum pump 1025 and / or one or more gas sources 611B-C, so that the vapor is higher than ruthenium tetroxide. The pressure solvent evaporates, which separates it from the ruthenium tetroxide material retained in the processing vessel 1023B (element B in FIG. 10C). For example, when Freon 113 is used as a solvent material, temperatures below about 0 ° C and pressures of about 360 tolls can be used to separate solidified ruthenium tetroxide from the solvent mixture. Lower pressures, such as about 3 tolls, can be used to carry out the separation process, but large amounts of ruthenium tetroxide are carried with the solvent and are lost as the pressure used to perform this step decreases. ..

The final step of process sequences 701A, 701D is generally that the processing vessel 1023B is evacuated until the processing vessel pressure reaches the desired level or the vessel pressure stabilizes. is necessary. In general, step 701D is carried out until a very small amount of solvent, leftover water and / or other solubilized dissimilar material is left in the processing vessel 1023B. Failure to adequately separate the other material from the ruthenium tetroxide material will contaminate the ruthenium-containing layer formed during the subsequent deposition process (eg, step 706 in FIGS. 5 and 7). Occurs. In one embodiment, it is advantageous to control the temperature in the processing vessel 1023B to remove solvents and other substances.

[0095] In one aspect of process sequence 701A, the cooling trap assembly 1024 is used to collect and regenerate the evaporated solvent material produced as the processing vessel 1023B is evacuated by the vacuum pump 1025. The cooling trap assembly is adapted to cool a portion of the vacuum line 1025A to a temperature at which the evaporated solvent material causes condensation, so that in subsequent steps the condensed solvent is regenerated within the collection tank / system 1024D. obtain. The cooling trap assembly 1024 typically includes a collection area 1024B of the cooled vacuum line 1025A, a separation valve 1026, and a temperature control device 1024A (eg, a fluid heat exchange device, a resistance heating device and / or a thermoelectric device). Contains a collection line 1024C connected to a fluid collection tank / system 1024D. In one embodiment, any collected ruthenium tetroxide found in the condensed solvent is regenerated.

[0096] After performing step 701, the separated ruthenium tetroxide contained in the processing vessel 1023B is then subjected to the purification modification of process step 702 (step 702A in FIG. 10A) and the use of the above process steps 704-706. It can be used to form a ruthenium-containing layer on the surface of the substrate. Since the purification process step 702A requires a step of controlling the temperature of ruthenium tetroxide contained in the processing container 1023B and the pressure inside the processing container 1023B to evaporate the remaining solid ruthenium tetroxide. It can be collected in a raw material container assembly (elements 640, 640A or 640B in FIGS. 4 and 6A-6C) similar to the embodiment described in process step 702 above. As used herein, the term evaporates describes the process by which a substance transforms from a solid or liquid to a gas. In one example, the ruthenium tetroxide material is maintained at a temperature of about 25 ° C and 2 tolls to initiate the evaporation process, so that the evaporated material can be distributed and collected in the raw material container. Referring to FIG. 10C, in one embodiment, the evaporated ruthenium tetroxide is one from one or more gas sources 611B-C through the processing vessel 1023B, the process line (eg 648, 648A or 648B), the valve 637A. Alternatively, it is carried by a flowing process gas distributed in multiple raw material containers (not shown). The concentration and flow rate of the ruthenium tetroxide-containing gas are related to the flow rate of the process gas and the vaporization rate of ruthenium tetroxide in the processing vessel 1023B. The vaporization rate is related to the equilibrium partial pressure of ruthenium tetroxide at the pressure and temperature maintained in the processing vessel 1023B. After performing step 702A, the ruthenium-containing layer can be deposited on the substrate surface, followed by process steps 704-706 as described above. In one embodiment, multiple continuous doses of ruthenium tetroxide are distributed to the treatment chamber 603 to form a multilayer ruthenium-containing film. The process procedure described with Figure 10A to make multiple consecutive doses. At least one of pp. 701 to 706 is repeated a plurality of times to form a multilayer ruthenium-containing film. In another embodiment, a continuous flow of the desired concentration of ruthenium tetroxide-containing gas is distributed over the surface of the substrate during the ruthenium-containing layer deposition process.

<u style="single">Ruthenium-containing layer deposition process using anhydrous solvent mixture</u> [0097] In one embodiment of the process of forming a ruthenium-containing phase on a substrate surface, the "anhydrous" solvent mixture formed in the ruthenium tetroxide-containing solvent-forming process 1001 is the treatment chamber 603 (see FIG. 11). It is distributed directly to the surface of the substrate located in. In one embodiment, perfluoropentane (C), which generally does not interact with substances on the substrate surface at temperatures below its decomposition temperature.₅F₁₂) Is used to prevent contamination of the substrate surface during the ruthenium-containing layer deposition process.

[0098] Referring to FIG. 11, in this embodiment a ruthenium-containing layer is formed on the surface of a heated substrate by distributing an "anhydrous" solvent mixture to a substrate located in process region 427 of processing chamber 603. To. The heated substrate may have a temperature of less than about 350 ° C, more preferably less than about 300 ° C. The choice of process temperature can be important to prevent decomposition of the solvent material. Typically, the processing chamber pressure is maintained at a process pressure of less than about 10 tolls to carry out the ruthenium-containing layer deposition process.

[0099] With reference to FIG. 11, in one embodiment, the purified solvent mixture (element "A") in the desired amount or mass is the carrier gas and hydrogen (H) dispensed from the gas source 611D.₂) Containing gas (eg hydrogen (H)₂)) Is distributed to the process area 427 to deposit a ruthenium-containing layer on the surface of the substrate. In one embodiment, the reducing co-reactive species instead of hydrogen is N₂Hydrazine (N) that moves to an inert carrier gas such as₂H₄) May be. In one embodiment, the carrier gas is distributed from the gas source 611E through a first container 1021 containing an "anhydrous" solvent mixture and then directly through a discharge line 660 to a substrate located in the processing region 427 of the processing chamber 603. Will be done. In other embodiments, multiple continuous doses of the "anhydrous" solvent mixture are dispensed into process chamber 603 to form a multilayer ruthenium-containing film. To make multiple continuous doses, the desired amount of "anhydrous" solvent mixture is dispensed onto the substrate multiple times in succession to form a multilayer ruthenium-containing film. The desired mass of ruthenium tetroxide, which needs to be distributed to process region 427 to form a ruthenium-containing layer, is generally the ruthenium tetroxide required to completely saturate the substrate surface and other chamber components. Depends on the amount of. Therefore, the amount of "anhydrous" solvent mixture that needs to be distributed to the processing chamber 603 depends on the concentration of ruthenium tetroxide in the desired mass of ruthenium tetroxide and the "anhydrous" solvent mixture.

[0100] In another embodiment, the continuous flow of the "anhydrous" solvent mixture is adapted to flow over the entire surface of substrate 422 during the ruthenium-containing layer deposition process. In one embodiment, the "anhydrous" solvent mixture flows past the substrate surface and is collected by a vacuum pump. In one embodiment, the cooling trap assembly 1024 (FIG. 10C) and the collection tank / system 1024D (FIG. 10C) communicate with the process area 427 and the vacuum pump 435 in a fluid and any remaining "anhydrous" solvent mixture component, eg, Collect the solvent and any unreacted ruthenium tetroxide.

<u style="single">One or more configurations of cluster tools</u> [0101] FIG. 8 is a plan view of a cluster tool 1100 useful for electronic device processing that the present invention can advantageously use. The two such platforms are CENTURA® RTM and ENDURA® RTM, both available from Applied Materials, Santa Clara, California. FIG. 8 is a plan view of the cluster tool of CENTURA (registered trademark) RTM. Details of such a one-step vacuum substrate processing system are disclosed in US Pat. No. 5,186,718, which is incorporated herein by reference. The exact placement and combination of chambers may be modified to perform the individual steps of the manufacturing process.

[0102] According to aspects of the invention, the cluster tool 1100 generally comprises a plurality of chambers and robots, preferably controlling and implementing various processing methods and sequences performed within the cluster tool 1100. It has a system controller 1102 programmed to. FIG. 8 shows an embodiment in which the processing chamber 603 is mounted at position 1114A on the transfer chamber 1110 and the three processing chambers 1202A-C are mounted at position 1114B-D on the transfer chamber 1110. .. The processing chamber 603 may be located in one or more other locations, eg, 1114B-D, to improve the hardware integration aspect of the system design or improve the substrate processing capacity. In certain embodiments, a portion of position 1114A-D remains vacant during the process to reduce the cost or complexity of the system.

[0103] With reference to FIG. 8, it is shown that any front-end environment 1104 (referred to herein as a factory interface or FI) is in a position that selectively communicates with a set of load-lock chambers 1106. There is. The factory interface robot 1108A-B, located in the front-end environment 1104, rotates in a straight line to reciprocate the board between the load lock 1106 and multiple board-containing pods (elements 1105A-D) mounted in the load lock environment 1104. , Vertical movement is possible.

[0104] The load lock 1106A-1106B provides 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 processing capacity by alternating communication with the transfer chamber 1110 and the front-end environment 1104. Thus, one load lock can communicate with the transfer chamber 1110 and a second load lock can communicate with the front-end environment 1104. In one embodiment, the load lock (element 1106A-1106B) is a batch load lock capable of receiving two or more substrates from the factory interface and holding the substrates, the chamber being sealed and then the transfer chamber. Exhausted to a low enough vacuum level to transport the board to 1110.

[0105] Robot 1113 is centrally located in transport chamber 1110 to transport the board from the load lock to one of the various processing chambers and service chambers 1116A-B mounted in positions 1114A-D. Robot 1113 is adapted to transport the substrate "W" to various processing chambers by using commands sent from system controller 1102. Robot assemblies used in cluster tools that may be adapted to benefit from the present invention are described in co-assigned US Pat. Nos. 5,447,409 and 6,379,095, the disclosure of which is incorporated herein by reference in its entirety. It is used in.

The processing chamber 1202A-C mounted in one of positions 1114A-D is pre-cleaned (eg, while the service chamber 1116A-B is adapted for degassing, adaptation, cooling and such. Perform all processes such as selective or non-selective dry etching of the substrate surface), PVD, CVD, ALD, deconjugated plasma nitriding (DPN), high speed heat treatment (RTP), measurement techniques (eg particle size measurement), etching. be able to. In one embodiment, the processing sequence described with FIG. 1A is adapted to deposit a barrier layer on the substrate surface using an ALD-type process, followed by a ruthenium-containing layer in another chamber. In this embodiment, the cluster tool 1110 can be configured such that the processing chamber 1202A is an ENDURA® iCuB / STM chamber available from Applied Materials, with the processing chamber 603 mounted at position 1114A. Has been done. In one embodiment, the pre-cleaning chamber is added to the process sequence prior to the barrier deposition process (element 102 in FIG. 1A) and mounted at position 1202B of cluster tool 1110.

[0107] In one aspect of the invention, one or more of the processing chambers 1202A-C are RTP chambers that can be used to anneal the substrate before or after performing the batch deposition step. The RTP process can be performed using the hardware of the process associated with the RTP chamber commercially available from Applied Materials, Inc., Santa Clara, California. In another aspect of the invention, one or more of the single substrate processing chambers 1202A-C may be CVD chambers. Examples of such CVD process chambers include DXZ® chambers, ULTIMA HDP-CVD®, and PRECISION 5000® chambers commercially available from Applied Materials, Inc. in Santa Clara, California. .. In another aspect of the invention, one or more of the single substrate processing chambers 1202A-C may be PVD chambers. An example of such a PVD process chamber is the ENDURA® PVD processing chamber commercially available from Applied Materials, Inc. in Santa Clara, California. In another aspect of the invention, one or more of the single substrate processing chambers 1202A-C may be DPN chambers. An example of such a DPN processing chamber is DPNCENTURA® marketed by Applied Materials, Inc. in Santa Clara, California. In another aspect of the invention, one or more of the single substrate processing chambers 1202A-C may be process / substrate measurement chambers. Process / substrate measurement The processes performed in the chamber include particle size measurement techniques, residual gas analysis techniques, XRF techniques, techniques used to measure film thickness and / or membrane composition, such as ellipsometry techniques. Not limited to these.

<u style="single">Ruthenium dioxide bottom-up filling process</u> [0108] In one aspect of the invention, the ruthenium-containing layer deposited in process step 104 in FIG. 1A and step 304 in FIG. 1B is at a temperature such that the ruthenium oxide layer is formed from one or all surfaces of the substrate. It is deposited on the surface of the maintained substrate. The ruthenium oxide layer then exposes the surface of the substrate to an electroless or electroplating solution that reduces the exposed surface by heating the substrate and exposing the surface of the substrate to a reducing gas (eg, a hydrogen-containing gas). This can be reduced to form a metallic ruthenium layer, either by releasing oxygen from the layer by raising the temperature of the substrate. In one embodiment, the ruthenium layer is selectively formed by exposing the ruthenium tetroxide-containing gas to a substrate at a temperature of less than about 250 ° C. It is formed on the ruthenium oxide layer on all other non-metallic materials such as. This aspect is especially important when using subsequent selective deposition processes such as electroless deposition processes. This is useful for selectively forming an electroless layer (eg, two metal layers) of an exposed tungsten plug after pattern formation and before performing other deposition processes.

[0109] The above relates to embodiments of the present invention, and more embodiments of the present invention may be constructed without departing from the basic scope of the invention, the scope of which is defined by the claims below. It is determined.

<figref num="1A">FIG. 1A is a diagram showing the process sequence of one embodiment described herein.</figref><figref num="1B">FIG. 1B is a diagram showing the sequence of other processes of one embodiment described herein.</figref><figref num="2A">FIG. 2A is a schematic cross-sectional view of the integrated circuit manufacturing sequence formed by the processes described herein.</figref><figref num="2B">FIG. 2B is a schematic cross-sectional view of the integrated circuit manufacturing sequence formed by the processes described herein.</figref><figref num="2C">FIG. 2C is a schematic cross-sectional view of the integrated circuit manufacturing sequence formed by the processes described herein.</figref><figref num="2D">FIG. 2D is a schematic cross-sectional view of the integrated circuit manufacturing sequence formed by the processes described herein.</figref><figref num="3A">FIG. 3A is a schematic cross-sectional view of an integrated circuit manufacturing sequence formed by the other processes described herein.</figref><figref num="3B">FIG. 3B is a schematic cross-sectional view of the integrated circuit manufacturing sequence formed by the other processes described herein.</figref><figref num="3C">FIG. 3C is a schematic cross-sectional view of the integrated circuit manufacturing sequence formed by the other processes described herein.</figref><figref num="3D">FIG. 3D is a schematic cross-sectional view of the integrated circuit manufacturing sequence formed by the other processes described herein.</figref><figref num="4">FIG. 4 is a cross-sectional view of a deposition chamber adapted to perform certain embodiments described herein.</figref><figref num="5">FIG. 5 is a diagram showing the sequence of other processes of one embodiment described herein.</figref><figref num="6A">FIG. 6A is a cross-sectional view showing a processing chamber adapted to perform certain embodiments described herein.</figref><figref num="6B">FIG. 6B is a cross-sectional view showing a processing chamber adapted to perform certain embodiments described herein.</figref><figref num="6C">FIG. 6C is a cross-sectional view showing a processing chamber adapted to perform certain embodiments described herein.</figref><figref num="7">FIG. 7 is a diagram showing another process sequence of one embodiment described herein.</figref><figref num="8">FIG. 8 is a plan view of a cluster tool used for semiconductor processing, which can be advantageously used by the present invention.</figref><figref num="9">FIG. 9 is a diagram showing another process of one embodiment described herein.</figref><figref num="10A">Figure 10A is a diagram der showing another process sequence of one embodiment described herein Ru.</figref><figref num="10B">FIG. 10B is a diagram showing another process sequence of one embodiment described herein.</figref><figref num="10C">FIG. 10C is a cross-sectional view showing a process vessel that can be adapted to perform the embodiments described herein.</figref><figref num="11">FIG. 11 is a cross-sectional view showing a deposition chamber that can be adapted to perform the embodiments described herein.</figref>

Code description

200 ... substrate, 201 ... dielectric layer, 202 ... aperture, 203 ... contact layer, 204 ... barrier layer, 206 ... catalyst layer, 220 ... bulk layer, 250. .. Substrate, 251A ... Dielectric surface, 251B ... Contact surface, 252 ... Aperture, 256 ... Ruthenium-containing layer, 404 ... Processing enclosure, 405 ... Side wall, 407 ... Bottom, 410 ... gas distribution shower head, 421 ... process area, 422 ... substrate, 423 ... substrate support, 427 ... processing area, 475 ... impedance matching element, 480 .. Controller, 600 ... deposition chamber, 601 ... process gas distribution system, 602 ... gas distribution system, 603 ... processing chamber, 611 ... gas source, 612 ... ozone generator, 623. .. board support, 625 ... heat transfer line, 623 ... board support, 630 ... processing container, 631 ... container, 634C ... heat exchange device, 635 ... injection port, 636 ... discharge port, 640 ... raw material container assembly, 641 ... raw material container, 642 ... controller, 643 ... temperature controller device, 644 ... heat exchange device, 645 ... injection port , 646 ... Discharge port, 648B ... Process line, 660 ... Discharge line, 662 ... Chemical injection container, 663 ... Discharge valve, 665 ... Temperature sensor, 667 ... Pressure Sensor, 668 ... heat exchange device, 669 ... chemical species injection vessel, 670 ... remote plasma source, 672 ... temperature controller, 673 ... remote plasma source, 674 ... gas source, 680 ... Controller, 1100 ... Cluster Tool, 1102 ... System Controller, 1104 ... Front End Environment, 1106 ... Load Lock, 1108 ... Factory Interface Robot, 1110 ... Transfer Chamber, 1113 ... Robot, 1116 ... Service Chamber, 1202 ...Substrate processing chamber, 1022 ... metering pump, 1023 ... processing container, 1025 ... vacuum pump.