Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1603—Process or apparatus coating on selected surface areas
  • C23C18/1605—Process or apparatus coating on selected surface areas by masking
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
  • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
  • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
  • H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1635—Composition of the substrate
  • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
  • C23C18/1642—Substrates other than metallic, e.g. inorganic or organic or non-conductive semiconductor
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1655—Process features
  • C23C18/1664—Process features with additional means during the plating process
  • C23C18/1669—Agitation, e.g. air introduction
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
  • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
  • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
  • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
  • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
  • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
  • C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/38—Coating with copper
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/38—Coating with copper
  • C23C18/40—Coating with copper using reducing agents
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
  • H05K3/061—Etching masks
  • H05K3/064—Photoresists
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/05—Patterning and lithography; Masks; Details of resist
  • H05K2203/0562—Details of resist
  • H05K2203/0571—Dual purpose resist, e.g. etch resist used as solder resist, solder resist used as plating resist
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
  • H05K2203/0703—Plating
  • H05K2203/072—Electroless plating, e.g. finish plating or initial plating
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/08—Treatments involving gases
  • H05K2203/087—Using a reactive gas

Definitions

• the present invention relates generally to Semiconductor manufacturing processes, and more particularly, to systems and methods for forming patterned copper lines through electroless copper plating.
• Formation of copper lines for use in an interconnect process is typically done by a dual damascene process, in which trenches are formed in a dielectric material, barrier metal and copper are deposited such that the trenches are filled, and an overburden is formed.
• the overburden in the field regions adjacent to the trenches is typically removed using a chemical-mechanical planarization process. Trenches on different levels are connected by copper-filled via holes, as known and understood by those skilled in the art.
• electroless copper plating uses a solution of copper ions in an alkaline solution with a reducing agent.
• a substrate such as a semiconductor wafer, is placed within the alkaline solution.
• the copper ions are reduced by the reducing agent to form a layer or film of copper on the surface of the substrate.
• An aldehyde (e.g., formaldehyde) solution is a common reducing agent used in the electroless plating solutions.
• the formaldehyde substantially reduces the copper ion to elemental copper.
• This reduction process produces hydrogen that can be incorporated into the matrix of the copper, causing voids and reducing the quality of the deposited copper layer.
• Another limitation of the typical alkaline solution electroless copper plating process includes a relatively slow growth rate of the resulting copper oxide layer.
• the typical alkaline solution electroless copper plating has a maximum growth rate of about 100-500 angstroms per minute. This limited growth rate requires excessive amounts of time to grow thick films (e.g., greater than about 100 micron thickness).
• the typical alkaline solution electroless copper plating process requires batch wafer processing to achieve significant wafer volume throughput. However, batch wafer processing can be difficult to accurately and repeatably produce the desired process results throughout each batch of wafers.
• Yet another limitation of the typical alkaline solution electroless copper plating process is the alkaline nature of the alkaline solution. It is desirable to form specific copper structures (e.g., patterned copper lines) and not a uniform blanket of copper (e.g., when considering air-gap dielectric or other processes). A lithographic process applied to a photoresist layer could form pre-patterned features.
• the typical alkaline solution electroless copper plating process requires that the structures be formed in a typical photoresist patterning process. Unfortunately, the photoresist is highly reactive with and would be substantially damaged or even entirely destroyed by the alkaline nature of the alkaline solution. As a result, a protective layer that is not reactive with the alkaline solution must first be formed over the photoresist pattern. The protective layer protects the photoresist pattern from damage by the typical alkaline solution during the electroless copper plating process.
• the photoresist may be used to transfer a pattern into an underlying layer of material that is compatible with the alkaline electroless chemistry.
• the photoresist is then removed and the copper lines could be formed in a positive image of the desired copper structures.
• the patterning layer is either a low K material which becomes an integral part of the interconnect layer, or can be removed as a sacrificial material. In either case, removal of this material is more difficult than removal of the previously formed photoresist pattern.
• the present invention fills these needs by providing a system and method for forming patterned copper lines through electro-less copper plating. It should be appreciated that the present invention can be implemented in numerous ways, including as a process, an apparatus, a system, computer readable media, or a device. Several inventive embodiments of the present invention are described below.
• One embodiment provides a method for forming copper on a substrate including inputting a copper source solution into a mixer, inputting a reducing solution into the mixer, mixing copper source solution and the reducing solution to form a plating solution having a pH of greater than about 6.5 and applying the plating solution to a substrate, the substrate including a catalytic layer wherein applying the plating solution to the substrate includes forming copper on the catalytic layer.
• the plating solution can be created substantially simultaneously with applying the plating solution to the substrate.
• the plating solution can have a pH of between about 7.2 and about 7.8.
• the plating solution can be discarded after forming copper on the catalytic layer.
• the substrate can include a patterned photoresist layer and wherein the patterned photoresist layer exposes a first portion of the catalytic layer and wherein applying the plating solution to the substrate can include forming copper on the first portion of the catalytic layer.
• the method can also include removing the plating solution from the substrate, rinsing the substrate and drying the substrate.
• the method can also include removing the patterned photoresist. Removing the patterned photoresist exposes a second portion of the catalytic layer. The second portion of the catalytic layer can also be removed.
• the plating solution is compatible with an unprotected photoresist.
• the copper formed on the catalytic layer can be substantially elemental copper.
• the copper formed on the catalytic layer can be substantially free of hydrogen inclusions.
• the copper formed on the catalytic layer is formed at a rate of greater than about 500 angstrom per minute.
• the plating solution can be applied to the substrate through a dynamic liquid meniscus and wherein the dynamic liquid meniscus is formed between a proximity head and a surface of the substrate.
• the copper source solution can include an oxidizing copper source, a complexing agent, a pH adjuster agent and a halide ion.
• the reducing solution can include a reducing ion.
• the catalytic layer can include more than one layer.
• the catalytic layer can include a bottom anti-reflection coating (BARC) layer.
• BARC bottom anti-reflection coating
• Another embodiment provides a method for forming a patterned copper structure on a substrate.
• the method includes receiving a substrate that includes a catalytic layer formed thereon and a patterned photoresist layer formed on the catalytic layer.
• the patterned photoresist layer exposes a first portion of the catalytic layer and the patterned photoresist layer covers a second portion of the catalytic layer.
• a copper source solution is input into a mixer and a reducing solution is input into the mixer.
• the copper source solution and the reducing solution are mixed to form a plating solution having a pH of between about 7.2 and about 7.8.
• the plating solution is applied to a substrate including forming copper on the first portion of the catalytic layer.
• a process tool including a low pressure process chamber, an atmospheric pressure process chamber, a transfer chamber coupled to each of the low pressure process chamber and the atmospheric pressure process chamber, the transfer chamber including a controlled environment.
• the transfer chamber providing a controlled environment for transferring a substrate from the low pressure process chamber to the atmospheric pressure process chamber.
• a controller is also coupled to the low pressure process chamber, the atmospheric pressure process chamber and the transfer chamber. The controller including logic to control each of the low pressure process chamber, the atmospheric pressure process chamber and the transfer chamber.
• the low pressure process chamber can include more than one low pressure process chambers that can include a plasma etch/removal chamber and the atmospheric pressure processing chamber can include a copper plating chamber.
• the copper plating chamber can include a mixer.
• the plasma chamber can be a downstream plasma chamber. At least one of the etch/removal chambers can be a wet process chamber.
• the transfer chamber includes an input/output module.
• the control system can include a recipe including logic for loading a patterned substrate into the copper plating chamber, logic for inputting a copper source solution into the mixer, logic for inputting a reducing solution into the mixer, logic for mixing the copper source solution and the reducing solution to form a plating solution having a pH of greater than about 6.5; and logic for applying the plating solution to a patterned substrate, the patterned substrate including a catalytic layer wherein applying the plating solution to the substrate includes forming copper on the catalytic layer.
• the patterned substrate can include a patterned photoresist layer formed on the catalytic layer wherein the patterned photoresist layer exposes a first portion of the catalytic layer and wherein the patterned photoresist layer covers a second portion of the catalytic layer.
• the plasma chamber can be a downstream plasma chamber.
• FIG. 1 is a flowchart diagram that illustrates the method operations performed in forming copper structures in a non-alkaline electroless copper plating, in accordance with one embodiment of the present invention.
• FIGS. 2A through 2F illustrate copper structures formed on a substrate, in accordance with one embodiment of the present invention.
• FIG. 3 is a flowchart diagram that illustrates the method operations performed in a high rate non-alkaline electroless copper plating process, in accordance with one embodiment of the present invention.
• Figure 4A is a simplified schematic diagram of a plating processing tool, in accordance with one embodiment of the present invention.
• Figure 4B illustrates a preferable embodiment of an exemplary substrate processing that may be conducted by a proximity head, in accordance with one embodiment of the present invention.
• FIG. 5 is a simplified schematic diagram of a modular processing tool, in accordance with one embodiment of the present invention.
• FIG. 6 is a simplified schematic diagram of an exemplary downstream plasma chamber, in accordance with one embodiment of the present invention.
• the present invention provides a system and a method for an improved electroless copper plating process that is substantially not reactive to photoresist and that can allow a higher growth rate than about 500 angstroms per minute. Such a higher growth rate allows effective throughput for a single wafer process rather than the typical batch wafer process although it should be understood that the present invention can be used in a batch (e.g., multiple wafer) process.
• the high rate, electroless plating process can include copper ions suspended in a substantially neutral or even an acidic solution.
• the neutral or acidic solution does not react with the photoresist. Therefore, photoresist patterning can be used to directly define the desired copper structures without the need of additional the process steps of adding a protective layer to the photoresist and/or forming a pattern with a material that is not reactive with to the prior art alkaline, electroless plating solution.
• the high rate, electroless plating process can form a copper layer up to about 2500 angstroms per minute.
• the high rate, electroless plating process can therefore form a thicker copper layer much faster than the typical alkaline solution electroless copper plating process.
• the high rate, electroless plating process can be used to form thicker copper structures that the typical alkaline solution electroless copper plating process cannot.
• the high rate, electroless plating process can include using cobalt ions (e.g., Co+, Co +2 and Co+3) instead of an aldehyde as the reducing agent.
• the cobalt ions substantially reduce the copper oxide to elemental copper with minimal production of hydrogen.
• electroless plating process can use the photoresist patterning to directly form the desired copper structures, several process steps required to form conventional in-laid copper lines using the dual damascene method described above are no longer required. Specifically, no protective layer is needed to protect the photoresist. Further, an etch process to remove the patterning material is also eliminated. This can also allow a modified integration path or process to decrease process operations and thereby reduce production time and increase throughput.
• the copper structures formed by the high rate, electroless plating process can include wire-bond pads and ball grid arrays as may be used to form electrical connections to an integrated circuit in the packaging of the integrated circuit or in 3-D packaging interconnects.
• the free-standing copper structures may also enable formation and use of an air gap between metal lines to reduce the dielectric constant of the metal-to-metal space.
• the substrate when forming an air-gap dielectric, the substrate could be pre-patterned with features that are 'placeholders' for the air gap or low K dielectric.
• the placeholders can be easily removable.
• the pre-patterned features can be formed by a lithographic process in photoresist, thereby avoiding an etch patterning step.
• Figure 1 is a flowchart diagram that illustrates the method operations 100 performed in forming copper structures in a non-alkaline electroless copper plating, in accordance with one embodiment of the present invention.
• Figures 2A through 2F illustrate copper structures 208 formed on a substrate (e.g., a wafer) 200, in accordance with one embodiment of the present invention.
• the substrate 200 is received.
• the substrate 200 is previously prepared to be ready to form copper interconnect structures. This previous preparation can be performed by any suitable methods.
• a catalytic layer 202 is formed on the substrate 200.
• the catalytic layer 202 can be any suitable materials or combinations of materials and layers of materials.
• the catalytic layer 202 can be formed from tantalum, ruthenium, nickel, nickel molybdenum, titanium, titanium nitride or other suitable catalytic materials.
• the catalytic layer 202 can be as thin as possible (e.g., a monolayer of the atoms or molecules) or a between a monolayer and up to about 500 angstroms thick. Combinations of layers can also be used.
• a tantalum layer can be formed on the substrate 200 and a ruthenium layer can be formed on the tantalum layer.
• the tantalum layer can be about 360 angstroms or even thinner.
• the ruthenium layer can be used to protect the tantalum layer from, for example, tantalum-oxide formation.
• the ruthenium layer can be about 150 angstroms or even thinner.
• Forming the catalytic layer 202 can also include forming an optional antireflective coating (e.g., BARC) layer 204.
• BARC antireflective coating
• the BARC layer 204 can be for example about 600 angstroms thick.
• the BARC layer 204 is well known in the art for providing improved lithography performance by reducing constructive and destructive interference during the exposure step.
• a photoresist layer 206 is formed on the catalytic layer 202.
• the photoresist layer 206 can be about 6000 angstroms thick or thicker or thinner.
• the photoresist layer 204 can be any suitable photoresist material as are well known in the art.
• the photoresist layer 206 is patterned. Patterning the photoresist layer 206 also includes patterning the optional BARC layer 204 if the BARC layer is included.
• the undesired portions of the photoresist layer 206 are removed leaving only desired portions of the photoresist layer 206A.
• Exposed portions 204A of the optional BARC layer 204 are removed by a plasma etch process.
• the BARC can be removed using a Lam Research Corporation 2300 Exelan ® plasma etcher with a settings of about 20 degrees C, 40-100 mTorr, 200-700W @ 27MHz, 500-100W @ 2MHz, 100-500 seem Argon, 0-100 seem CF 4 , 0-30 seem oxygen, 0-150 seem nitrogen, 0-150 seem hydrogen and 0-10 seem C 4 F 8 for between about 20 and about 90 seconds.
• any oxides or other residues on the exposed portions 202A of the catalytic layer 202 are removed, if necessary.
• catalytic layer includes applying a plasma-generated radicals to the exposed portions 202A of the catalytic layer.
• the oxides and other residues on the exposed portions 202A can be removed by applying radicals generated in a Lam 2300 Microwave Strip chamber, or similar chamber, with the following recipe: 700 seem of a 3.9% concentration of hydrogen in helium carrier gas at 1 Torr, IkW for about 5 minutes.
• Ammonia (NH 3 ) or carbon monoxide (CO) can be used instead of or in combination with the 3.9% hydrogen.
• 100% hydrogen could be used at an elevated temperature.
• between about 50 and about 300C however the upper temperature limit is determined by the ability of the photoresist and BARC materials to withstand the elevated temperature conditions.
• a further variation can include a short controlled plasma oxidation process applied to remove any organic contaminants followed by the reduction operation described above to convert (i.e., reduce) the oxides that may be formed to their respective elemental metallic states.
• the substrate is transferred in a controlled environment (i.e. in-situ to maintain low oxygen and low moisture levels) to the electroless plating process chamber. This ensures that the reduced surface formed in operation 130 is preserved as a catalytic layer.
• a non-alkaline electroless copper plating process is applied to the substrate 200 to form copper structures 208.
• the non-alkaline electroless copper plating process is described in more detail in Figure 3 below.
• the non-alkaline electroless copper plating process can generate between 500 to 2000 angstroms of elemental copper per minute.
• the non-alkaline electroless copper plating process can be applied to the substrate 200 in a vertical or horizontal immersion type of application.
• the non-alkaline electroless copper plating process can be applied to the substrate 200 through a dynamic liquid meniscus described in more detail below.
• the remaining portions 206A of the photoresist layer are removed to expose portions of the catalytic layer 202B. If the optional BARC layer 204 was included then the remaining portions 204B of the optional BARC layer are also removed when the remaining portions 206A of the photoresist layer are removed or subsequently thereafter.
• the photoresist and the BARC layer can be removed with a plasma process.
• a wet chemical photoresist removal step can be performed using aqueous, semi-aqueous or non-aqueous solvents.
• An exemplary recipe for removing the remaining photoresist 206A and the remaining portions 204B of the optional BARC layer includes a temperature of less than about 30 degrees C, a pressure of about 5mTorr, a flow rate of about 50 seem of argon and 350 seem of oxygen with about 1000- 1400W source power at about 27MHz is applied for about 3min.
• a temperature of greater than about 30 degrees C a pressure of about 5mT, a flow rate of about 50 seem argon and 350 seem oxygen, with 1200W source power at about 27 MHz plus about 500W of bias power applied for about 30 seconds.
• the additional bias power causes the etching process to be more directional into the spaces 210 between the copper structures 208.
• the BARC can be removed using a Lam Research Corporation 2300 Exelan ® plasma etcher with a settings of about 20 degrees C, 40-100 mTorr, 200-700W @ 27MHz, 500-100W @ 2MHz, 100-500 seem Argon, 0-100 seem CF 4 , 0-30 seem oxygen, 0-150 seem nitrogen, 0-150 seem hydrogen and 0-10 seem C 4 F 8 for between about 20 and about 90 seconds.
• Various combinations and permutations of the gases and settings listed above may be used, depending on the material requirements. It should be understood that one skilled in the art could also remove the BARC using an inductively coupled plasma source (e.g., as available from Lam's VersysTM plasma process chamber).
• an operation 145 the exposed portions 202B of the catalytic layer 202 are removed. Removing the exposed portions 202B of the catalytic layer 202 substantially prevents the exposed portions of the catalytic layer from electrically connecting the remaining free standing copper structures 208.
• An exemplary recipe for removing the exposed portions 202B of the catalytic layer 202 using a Lam 2300 Versys plasma etcher includes a temperature of about 20 to about 50 degrees C with about 500W source power and about 20-100 W bias power, with a pressure of about 5OmT and flow rates of about 30 seem of CF 4 and 75 seem of argon for a duration of about lminute.
• the free standing copper structures 208 include the remaining portions 202C of the catalytic layer. Air gaps 210 are formed between the free standing copper structures 208. The air gaps 210 can allow an air dielectric to be used in subsequent structures formed on the free standing copper structures 208. The air gaps 210 can be between less than about 10 nm or larger in width.
• the free standing copper structures 208 can be any width desired. By way of example, the free standing copper structures 208 can be between less than about 10 nm and more than about 100 nm. The free standing copper structures 208 can be about 300 nm or larger in width. The maximum width of the free standing copper structures 208 is limited only by the width of the substrate.
• the photoresist 206A removal in operation 140 can be performed with or without bias power depending on the requirements (e.g., to minimize damage to the copper structures 208 or to facilitate full removal of the photoresist between the copper structures 208).
• a short photoresist removal operation including applying 500W bias, can be added to further remove the photoresist 206A and any residues thereof, between the copper structures 208. Applying the 500W bias will also remove the ruthenium, if the ruthenium layer was also applied to protect the catalytic layer.
• Each of the operations 105-145 involve low temperature of less than about 300 degrees C to substantially limit migration of copper that may occur at higher temperatures.
• the BARC removal and pretreatment operation is also performed at a low temperature so as to limit the reticulation of photoresist at higher temperatures.
• FIG. 3 is a flowchart diagram that illustrates the method operations 135 performed in a high rate non-alkaline electroless copper plating process, in accordance with one embodiment of the present invention.
• Figure 4A is a simplified schematic diagram of a plating processing tool 400, in accordance with one embodiment of the present invention.
• the plating processing tool 400 includes a first source 410 and a second source 412.
• the first source 410 includes quantity of a first source material 410A.
• the second source 412 includes a quantity of a second source material 412A.
• the first source 410 and the second source 412 are coupled to a mixer 416.
• the mixer 416 is coupled to the plating chamber 402.
• the plating processing tool 400 can also include a rinsing solution source 440 that is coupled to the plating chamber 402.
• the rinsing solution source 440 can provide a quantity of rinsing solution 440A.
• the plating processing tool 400 can also include a controller 430.
• the controller 430 is coupled to the plating chamber and the mixer 416.
• the controller 430 controls the operations (e.g., mixing, filling, rinsing, etc.) in the plating processing tool 400 according to a recipe 432 included in the controller.
• the substrate 200 is placed in the plating chamber 402 for the plating operation.
• the mixer 416 mixes the first source material 410A and the second source material 412A to form the plating solution 416A.
• the first source material 410A is a reducing ion relative to the copper ion (e.g., Co 2+ ).
• the second source material 412A includes a oxidizing copper source (e.g., Cu 2+ ), a complexing agent (e.g., ethylene diamine, di-ethylene triamine), a pH adjuster agent (e.g., HNO 3 , H 2 SO 4 , HCl, etc.) and a halide ion (e.g., Br-, Cl-, etc.). Additional details and examples regarding copper plating solutions are described in more detail in co-owned U.S. Patent Application 11/382,906 entitled Plating Solution for Electroless Deposition of Copper by Vaskelis et al., which was filed on May 11, 2006, and co-owned U.S.
• a complexing agent e.g., ethylene diamine, di-ethylene triamine
• a pH adjuster agent e.g., HNO 3 , H 2 SO 4 , HCl, etc.
• a halide ion e.g., Br-, Cl-, etc.
• Patent Application 11/427,266 entitled Plating Solutions for Electroless Deposition of Copper by Dordi et al., which was filed on June 28, 2006 and which are incorporated by reference herein, in their entirety for all purposes.
• This application is also related to co-owned U.S. Patent Application 11/398,254 entitled Methods and Apparatus for Fabricating Conductive Features on Glass Substrates used in Liquid Crystal Displays by Jeffrey Marks and which was filed on April 4, 2006 and is incorporated by reference herein, in its entirety for all purposes.
• the plating solution 416A is output from the mixer 416 into the plating chamber 402 where the plating solution is applied to the substrate 200.
• the mixer 416 mixes the first source material 410A and the second source material 412A as needed in the plating chamber 402.
• the plating solution 416A has a pH of greater than about 6.5 and in at least one embodiment has a pH of within a range of about 7.2 to about 7.8.
• the plating solution 416A forms a layer of elemental copper substantially without any voids caused by hydrogen inclusions.
• the substrate 200 is removed from the plating solution 416A.
• Removing the substrate 200 from the plating solution 416A can include removing the substrate 200 from the plating chamber 402 and/or removing the plating solution 416A from the plating chamber 402.
• the substrate 200 is rinsed in a rinsing solution.
• the plating solution 426 A can be removed from the plating chamber 402 and the rinsing solution 440A can be input to the plating chamber to rinse substantially any remaining plating solution 416A off of the substrate 200.
• the substrate 200 can be dried.
• the substrate 200 can be removed from the plating chamber 402 and placed in a second chamber (e.g., a spin, rinse and dry chamber) for rinsing and drying.
• the plating chamber 402 can include the mechanisms required to rinse and dry the substrate 200.
• the plating chamber 402 can include a proximity head 450 capable of rinsing and drying the substrate 200.
• the proximity head 450 can also apply the plating solution to the substrate.
• Figure 4B illustrates a one embodiment of an exemplary substrate processing that may be conducted by a proximity head 450, in accordance with one embodiment of the present invention.
• Figure 4B shows a top surface 458a of a substrate 200 being processed, it should be appreciated that the substrate process may be accomplished in substantially the same way for the bottom surface 458b of the substrate 200.
• Figure 4B illustrates a substrate drying process, many other fabrication processes may also be applied to the substrate surface in a similar manner.
• a source inlet 462 may be utilized to apply isopropyl alcohol (IPA) vapor toward a top surface 458a of the substrate 200, and a source inlet 466 may be utilized to apply deionized water (DIW) or other processing chemistry toward the top surface 458a of the substrate 200.
• a source outlet 464 may be utilized to apply vacuum to a region in close proximity to the wafer surface to remove fluid or vapor that may located on or near the top surface 458a. It should be appreciated that any suitable combination of source inlets and source outlets may be utilized as long as at least one combination exists where at least one of the source inlet 462 is adjacent to at least one of the source outlet 464 which is in turn adjacent to at least one of the source inlet 466.
• the IPA may be in any suitable form such as, for example, IPA vapor where IPA in vapor form is inputted through use of a N 2 carrier gas.
• DIW any other suitable fluid may be utilized that may enable or enhance the wafer processing such as, for example, water purified in other ways, cleaning fluids, and other processing fluids and chemistries.
• an IPA vapor inflow 460 is provided through the source inlet 462, a vacuum 472 may be applied through the source outlet 464 and DPW inflow 474 may be provided through the source inlet 466.
• a first fluid pressure may be applied to the substrate surface by the IPA inflow 460
• a second fluid pressure may be applied to the substrate surface by the DIW inflow 474
• a third fluid pressure may be applied by the vacuum 472 to remove the DIW, IPA vapor and the fluid film on the substrate surface.
• any fluid on the wafer surface is intermixed with the DIW inflow 474.
• the DIW inflow 474 that is applied toward the wafer surface encounters the IPA vapor inflow 460.
• the IPA forms an interface 478 (also known as an IPA/DIW interface 478) with the DIW inflow 474 and along with the vacuum 472 assists in the removal of the DIW inflow 474 along with any other fluid from the surface of the substrate 200.
• the IPA vapor/DIW interface 478 reduces the surface of tension of the DIW.
• the DIW is applied toward the substrate surface and almost immediately removed along with fluid on the substrate surface by the vacuum applied by the source outlet 464.
• the DIW that is applied toward the substrate surface and for a moment resides in the region between a proximity head and the substrate surface along with any fluid on the substrate surface forms a meniscus 476 where the borders of the meniscus 476 are the IPA/DIW interfaces 478. Therefore, the meniscus 476 is a constant flow of fluid being applied toward the surface and being removed at substantially the same time with any fluid on the substrate surface.
• the nearly immediate removal of the DPvV from the substrate surface prevents the formation of fluid droplets on the region of the substrate surface being processed thereby reducing the possibility of contamination drying on the substrate 200.
• the pressure (which is caused by the flow rate of the IPA vapor) of the downward injection of IPA vapor also helps contain the meniscus 476.
• the flow rate of the N 2 carrier gas for the IPA vapor assists in causing a shift or a push of water flow out of the region between the proximity head and the substrate surface and into the source outlets 304 through which the fluids may be output from the proximity head. Therefore, as the IPA vapor and the DPvV is pulled into the source outlets 464, the boundary making up the IPA/DIW interface 478 is not a continuous boundary because gas (e.g., air) is being pulled into the source outlets 464 along with the fluids. In one embodiment, as the vacuum from the source outlet 464 pulls the DIW, IPA vapor, and the fluid on the substrate surface, the flow into the source outlet 464 is discontinuous.
• This flow discontinuity is analogous to fluid and gas being pulled up through a straw when a vacuum is exerted on combination of fluid and gas. Consequently, as the proximity head 450 moves, the meniscus 476 moves along with the proximity head, and the region previously occupied by the meniscus has been processed and dried due to the movement of the IPA vapor /DIW interface 478. It should also be understood that the any suitable number of source inlets 462, source outlets 464 and source inlets 466 may be utilized depending on the configuration of the apparatus and the meniscus size and shape desired. In another embodiment, the liquid flow rates and the vacuum flow rates are such that the total liquid flow into the vacuum outlet is continuous, so no gas flows into the vacuum outlet.
• any suitable flow rate may be utilized for the IPA vapor, DIW, and vacuum as long as the meniscus 476 can be maintained.
• the flow rate of the DIW through a set of the source inlets 466 is between about 25 ml per minute to about 3,000 ml per minute.
• the flow rate of the DIW through the set of the source inlets 466 can be about 400 ml per minute.
• the flow rate of fluids may vary depending on the size of the proximity head. In one embodiment a larger head may have a greater rate of fluid flow than smaller proximity heads. This may occur because larger proximity heads, in one embodiment, have more source inlets 462 and 466 and source outlets 464 more flow for larger head.
• the flow rate of the IPA vapor through a set of the source inlets 462 can be between about 1 standard cubic feet per hour (SCEB) to about 100 SCFH.
• the IPA flow rate is between about 5 and 50 SCFH.
• the flow rate for the vacuum through a set of the source outlets 464 is between about 10 standard cubic feet per hour (SCFH) to about 1250 SCFH.
• the flow rate for a vacuum though the set of the source outlets 464 is about 350 SCFH.
• a flow meter may be utilized to measure the flow rate of the IPA vapor, DIW, and the vacuum.
• FIG. 5 is a simplified schematic diagram of a modular processing tool 500, in accordance with one embodiment of the present invention.
• the modular processing station 500 includes multiple processing modules 512-520, a common transfer chamber 510 and an input/output module 502.
• the multiple processing modules 512-520 can include one or more low pressure process chambers and atmospheric process chambers.
• the one or more low pressure process chambers have an operating pressure within a range of pressures of less than atmospheric pressure to a vacuum of less than about 10 mTorr.
• the low pressure process chamber can include more than one low pressure process chambers including a plasma chamber, a copper plating chamber including a mixer, a deposition chamber.
• the atmospheric pressure processing chamber can include one or more etch/removal chambers.
• the modular processing station 500 also includes a controller 530 that can control the operations in each of the multiple processing modules 512-520, the common transfer chamber 510 and the input/output module 502.
• the controller 530 can include one or more recipes 532 that include the various parameters for the operations in each of the multiple processing modules 512-520, the common transfer chamber 510 and the input/output module 502.
• One or more of the multiple processing modules 512-520 can support etch operations, cleaning/rinsing/drying operations, plasma operations and the non-alkaline electroless copper plating operations.
• chamber 518 can be a plasma chamber
• chamber 520 can be a copper plating chamber (e.g., plating processing tool 400)
• chamber 512 can be an etch/removal chamber
• chamber 514 can be a deposition chamber suitable for depositing barrier layers or BARC layers or catalytic layers as described above.
• the common transfer chamber 510 can allow one or more substrates 200 to be transferred into and out of each of the processing modules 512-520 while remaining in the controlled environment (e.g., low oxygen and low water vapor levels) of the transfer chamber 510.
• the transfer chamber 510 can be maintained at a desired pressure (e.g., above or below atmospheric, vacuum), a desired temperature, a selected gas (e.g., argon, nitrogen, helium, etc. while maintaining an oxygen concentration of less than about 2ppm).
• the plasma chamber 520 can be a conventional plasma chamber or a downstream plasma chamber.
• Figure 6 is a simplified schematic diagram of an exemplary downstream plasma chamber 600, in accordance with one embodiment of the present invention.
• the downstream plasma chamber 600 includes a processing chamber 602.
• the processing chamber 602 includes a support 630 for supporting a substrate 200 being processed in the processing chamber 602.
• the processing chamber 602 also includes a plasma chamber 604 where a plasma 604A is generated.
• a gas source 606 coupled to the plasma chamber 604 and provides a gas used for generating the plasma 604A.
• the plasma 604A produces radicals 620 that are transported from the plasma chamber through a conduit 612 and into the processing chamber 602.
• the processing chamber 602 can also include a distributing device (e.g., showerhead) 614 that substantially evenly distributes the radicals 620 across the substrate 200.
• a distributing device e.g., showerhead
• the downstream plasma chamber 600 generates the radicals 620 without exposing the substrate 200 to the relatively high electrical potentials and temperatures of the plasma 604A.
• the invention may employ various computer-implemented operations involving data stored in computer systems. These operations are those requiring physical manipulation of physical quantities. Usually, though not necessarily, these quantities take the form of electrical or magnetic signals capable of being stored, transferred, combined, compared, and otherwise manipulated. Further, the manipulations performed are often referred to in terms, such as producing, identifying, determining, or comparing.
• the invention also relates to a device or an apparatus for performing these operations.
• the apparatus may be specially constructed for the required purposes, or it may be a general-purpose computer selectively activated or configured by a computer program stored in the computer.
• various general-purpose machines may be used with computer programs written in accordance with the teachings herein, or it may be more convenient to construct a more specialized apparatus to perform the required operations.
• the invention can also be embodied as computer readable code on a computer readable medium.
• the computer readable medium is any data storage device that can store data which can thereafter be read by a computer system. Examples of the computer readable medium include hard drives, network attached storage (NAS), read-only memory, random- access memory, CD-ROMs, CD-Rs, CD-RWs, magnetic tapes, and other optical and non- optical data storage devices.
• the computer readable medium can also be distributed over a network coupled computer systems so that the computer readable code is stored and executed in a distributed fashion.

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• 2006
  • 2006-07-31 US US11/461,415 patent/US20070048447A1/en not_active Abandoned
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