Electrodeposition system

Abstract

Examples disclosed herein relate to operating an electrodeposition system including an inert anode. In one exemplary system, an electrodeposition system includes a substrate holder, and a cathode chamber configured to contain a catholyte. An anode chamber configured to contain an anolyte during an electrodeposition process includes an inert anode. And the middle chamber is positioned between the cathode chamber and the anode chamber. The intermediate chamber is separated from the cathode chamber by an ion exchange membrane.

Description

Background Art

[0001] Electrodeposition can be used to deposit a conductive film onto a substrate during integrated circuit manufacturing. Electrodeposition involves electrochemically reducing dissolved ions of a selected metal to an elemental state on a substrate to form a film of the selected metal. An electrodeposition system includes a cathode that is physically coupled to the substrate and electrically coupled to an anode. One or more barriers can separate the cathode and anode into respective electroplating chambers. Some anodes can be active and provide the metal required for electrodeposition. Other anodes can be inert. Inert anodes drive the electrodeposition reaction by oxidizing other substances (e.g., water molecules) other than the deposited metal. Summary of the invention

[0002] This summary is provided to introduce a selection of concepts in a simplified form, which will be further described in the following detailed description. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. Furthermore, the claimed subject matter is not limited to implementations that address any or all of the disadvantages mentioned in any part of this disclosure.

[0003] The examples disclosed herein relate to operating an electrodeposition system including an inert anode. In one example system, the electrodeposition system includes a substrate holder. The electrodeposition system also includes a cathode chamber configured to contain a cathode electrolyte. The electrodeposition system also includes an anode chamber configured to contain an anolyte during the electrodeposition process. The anode chamber includes an inert anode. An intermediate chamber is located between the cathode chamber and the anode chamber. The intermediate chamber is separated from the cathode chamber by an ion exchange membrane.

[0004] In some such examples, the intermediate chamber is separated from the cathode chamber by a proton blocking structure.

[0005] In some such examples, the proton-blocking structure additionally or alternatively includes a metal redox barrier configured to accept growth of a metal film on the anode side of the metal redox barrier via a reduction reaction of metal ions from an anolyte in contact with the anode side of the metal redox barrier, and to provide metal ions to a solution in contact with the cathode side of the metal redox barrier via an oxidation reaction of the metal redox barrier.

[0006] In some such examples, the electrodeposition system additionally or alternatively includes a mechanical biasing element to bias the metal redox barrier toward the intermediate chamber.

[0007] In some such examples, the metal redox barrier additionally or alternatively comprises one or more of copper, cobalt, nickel, tin, silver, gold, cadmium, platinum, or iron.

[0008] In some such examples, the metal redox barrier is additionally or alternatively configured to be rotatable, thereby allowing the orientation of the anode side and the cathode side to alternate toward the intermediate chamber.

[0009] In some such examples, the proton-blocking structure additionally or alternatively includes an anion exchange membrane.

[0010] In some such examples, the electrodeposition system additionally or alternatively includes an intermediate chamber solution circulation system configured to circulate an intermediate chamber solution through the intermediate chamber.

[0011] In some such examples, the ion exchange membrane separating the intermediate chamber and the cathode chamber additionally or alternatively includes a second anion exchange membrane.

[0012] In some such examples, the ion exchange membrane separating the intermediate chamber and the cathode chamber additionally or alternatively comprises a cation exchange membrane.

[0013] In some such examples, the electrodeposition system additionally or alternatively includes a redox shuttle circulation system configured to provide a redox shuttle species to the anode chamber.

[0014] In some such examples, the redox shuttle circulation system additionally or alternatively includes a redox shuttle material regeneration chamber.

[0015] In some such examples, the ion exchange membrane is additionally or alternatively a first cation exchange membrane, and the intermediate chamber is additionally or alternatively separated from the anode chamber by a second cation exchange membrane.

[0016] In some such examples, the electrodeposition system additionally or alternatively includes a copper oxide module fluidly coupled to the intermediate chamber.

[0017] Another example provides an electrodeposition system. The electrodeposition system includes a substrate holder. The electrodeposition system also includes a cathode chamber configured to accommodate a cathode electrolyte. The electrodeposition system also includes an anode chamber, the anode chamber includes an inert anode, and the anode chamber is configured to accommodate an anolyte. The electrodeposition system also includes a first ion exchange membrane located between the anode chamber and the cathode chamber. A redox shuttle circulation system is configured to provide a redox shuttle substance to the anode chamber.

[0018] In some such examples, the first ion exchange membrane additionally or alternatively includes an anion exchange membrane.

[0019] In some such examples, the electrodeposition system also includes an intermediate chamber between the cathode chamber and the anode chamber. The intermediate chamber is additionally or alternatively separated from the anode chamber by an anion exchange membrane, and additionally or alternatively separated from the cathode chamber by a cation exchange membrane. The intermediate chamber is configured to accommodate an intermediate chamber solution during the electrodeposition process.

[0020] In some such examples, the electrodeposition system additionally or alternatively includes a metal ion source fluidly coupled to the intermediate chamber.

[0021] In some such examples, the redox shuttle circulation system additionally or alternatively includes a redox shuttle material regeneration chamber.

[0022] Another example provides an electrodeposition system. The electrodeposition system includes a substrate holder. The electrodeposition system also includes a cathode chamber configured to accommodate a cathode electrolyte. The electrodeposition system also includes an anode chamber, which includes an inert anode and is configured to accommodate an anolyte. The electrodeposition system also includes an anion exchange membrane separating the cathode chamber from the anode chamber.

[0023] Another example provides an electrodeposition system. The electrodeposition system includes a substrate holder. The electrodeposition system also includes a cathode chamber configured to accommodate a cathode electrolyte. The electrodeposition system also includes an anode chamber, which includes an inert anode. The anode chamber is configured to accommodate an anolyte. The anode chamber is separated from the cathode chamber by a cation exchange membrane. The electrodeposition system also includes a copper oxide module, which is fluidically coupled to the intermediate chamber.

[0024] Another example provides an electrodeposition system. The electrodeposition system includes a cathode chamber configured to accommodate a cathode electrolyte. The electrodeposition system also includes a substrate holder configured to expose a substrate to the cathode electrolyte during an electrodeposition process. The electrodeposition system also includes an inert anode assembly. The inert anode assembly includes one or more inert anodes and two or more anolyte flow channels. The two or more anolyte flow channels define a segmented region of the anolyte flow across the one or more inert anodes. The inert anode assembly also includes an ion exchange membrane located between the cathode chamber and the two or more anolyte flow channels.

[0025] In some such examples, the inert anode assembly additionally or alternatively includes a cathode chamber bottom component. The cathode chamber bottom component includes an opening, and the opening is positioned relative to an anolyte flow channel of the two or more anolyte flow channels.

[0026] In some such examples, the two or more anolyte flow channels are additionally or alternatively formed in the anolyte channel component. The ion exchange membrane is additionally or alternatively located between the cathode chamber bottom component and the anolyte channel component.

[0027] In some such examples, the inert anode assembly additionally or alternatively includes an intermediate channel component located between the cathode chamber bottom component and the anolyte channel component. Additionally or alternatively, the ion exchange membrane is a first ion exchange membrane located between the intermediate channel component and the anolyte channel component. The electrodeposition system additionally or alternatively includes a second ion exchange membrane located between the cathode chamber bottom component and the intermediate channel component.

[0028] In some such examples, additionally or alternatively, the intermediate channel member at least partially defines an intermediate flow channel. The intermediate flow channel includes an opening, and the opening is positioned relative to an anolyte flow channel of the two or more anolyte flow channels.

[0029] In some such examples, the two or more anolyte flow channels are additionally or alternatively configured to produce a linear flow velocity between 0.1 m / sec and 10 m / sec.

[0030] In some such examples, the one or more inert anodes additionally or alternatively include a first inert anode associated with the first anolyte flow channel, and a second inert anode associated with the second anolyte flow channel.

[0031] In some such examples, the one or more inert anodes additionally or alternatively include a shared inert anode shared between at least two of the two or more anolyte flow channels.

[0032] Another example provides an inert anode assembly. The inert anode assembly includes one or more inert anodes and two or more anolyte flow channels. The two or more anolyte flow channels define segmented areas of anolyte flow across the one or more inert anodes.

[0033] In some such examples, the inert anode assembly additionally or alternatively includes a cathode chamber bottom component. The cathode chamber bottom component includes an opening, and the opening is positioned relative to an anolyte flow channel of the two or more anolyte flow channels.

[0034] In some such examples, the two or more anolyte flow channels are additionally or alternatively formed in an anolyte channel component.The inert anode assembly additionally or alternatively includes an ion exchange membrane located between the cathode chamber bottom component and the anolyte channel component.

[0035] In some such examples, the inert anode assembly additionally or alternatively includes an intermediate channel component located between the cathode chamber bottom component and the anolyte channel component. The ion exchange membrane additionally or alternatively includes a first ion exchange membrane located between the intermediate channel component and the anolyte channel component. The inert anode assembly additionally or alternatively includes a second ion exchange membrane located between the cathode chamber bottom component and the intermediate channel component.

[0036] In some such examples, additionally or alternatively, the intermediate channel member at least partially defines an intermediate flow channel. The intermediate flow channel includes an opening, and the opening is positioned relative to an anolyte flow channel of the two or more anolyte flow channels.

[0037] In some such examples, the one or more inert anodes additionally or alternatively include a first inert anode associated with the first anolyte flow channel, and a second inert anode associated with the second anolyte flow channel.

[0038] In some such examples, the one or more inert anodes additionally or alternatively include a shared inert anode shared between at least two of the two or more anolyte flow channels.

[0039] Another example provides a method for operating an electrodeposition system. The electrodeposition system includes an inert anode assembly. The method includes placing a substrate in a cathode chamber of the electrodeposition system. The method also includes exposing the substrate to a cathode electrolyte in the cathode chamber. The method also includes, during the electrodeposition process, generating cations and bubbles in the anolyte at an inert anode of the inert anode assembly. The method also includes flowing the anolyte in the anolyte flow channel at a sufficient linear flow rate to prevent bubbles from accumulating on an ion exchange membrane between the anolyte flow channel and the cathode electrolyte.

[0040] In some such examples, flowing the anolyte at a sufficient linear flow velocity additionally or alternatively includes flowing the anolyte at a linear flow velocity of 0.1 m / sec to 10 m / sec.

[0041] In some such examples, causing the anolyte to flow at a sufficient linear flow rate additionally or alternatively includes: restricting the flow of the anolyte to a segmented area by using two or more anolyte flow channels formed in an anolyte channel component of the inert anode assembly, the two or more anolyte flow channels including the anolyte flow channel.

[0042] In some such examples, generating cations and bubbles in the anolyte at the inert anode additionally or alternatively includes generating cations and bubbles in the anolyte of a first anolyte flow channel at the first inert anode and in the anolyte of a second anolyte flow channel at the second inert anode.

[0043] In some such examples, generating cations and bubbles in the anolyte at the inert anode additionally or alternatively includes generating cations and bubbles within the first anolyte flow channel and within the second anolyte flow channel using a shared inert anode.

[0044] Another example provides an inert anode assembly. The inert anode assembly includes an inert anode and an anolyte flow channel. The anolyte flow channel defines an area of ​​anolyte flow across the inert anode. The anolyte flow channel includes a length and a width. The width is less than the length. The anolyte flow channel includes a change in directionality along the length.

[0045] In some such examples, the anolyte flow channel additionally or alternatively includes a spiral path.

[0046] In some such examples, the anolyte flow channel additionally or alternatively includes a serpentine path.

[0047] Another example provides an electrodeposition system, comprising: a cathode chamber configured to contain a cathode electrolyte; an anode chamber configured to contain an anolyte; and a membrane frame supporting an ion exchange membrane located between the cathode chamber and the anode chamber. The electrodeposition system also includes a substrate holder configured to expose a substrate to the cathode electrolyte during an electrodeposition process. An inert anode is located in the anode chamber. A bubble deflector is positioned to direct the flow of bubbles generated at the inert anode to a stilling structure, where the bubbles are discharged to the atmosphere.

[0048] In some such examples, the bubble diverter additionally or alternatively extends around a peripheral portion of the ion exchange membrane.

[0049] In some such examples, the bubble diverter additionally or alternatively includes a plurality of apertures configured to expose the ion exchange membrane to an ionic current flowing between the inert anode and the substrate.

[0050] In some such examples, the electrodeposition system additionally or alternatively includes an adjustment mechanism configured to adjust an open cross-sectional area of ​​the plurality of apertures.

[0051] In some such examples, the plurality of orifices are additionally or alternatively located at a lower end of the bubble deflector, and the adjustment mechanism additionally or alternatively includes a mechanism for adjusting a position of the bubble deflector relative to a base of the anode chamber.

[0052] In some such examples, the electrodeposition additionally or alternatively includes an anolyte circulation loop, and the bubble diverter additionally or alternatively directs the flow of bubbles to the anolyte circulation loop.

[0053] In some such examples, the anolyte circulation loop additionally or alternatively includes a circulation pump, and the pressure regulating structure is additionally or alternatively located upstream of the circulation pump, the pressure regulating structure being exposed to the atmosphere.

[0054] In some such examples, the anolyte circulation loop additionally or alternatively includes a contactor located downstream of the pressure regulating structure and upstream of the circulation pump, the contactor being configured to remove dissolved gases from the anolyte.

[0055] Another example provides a bubble diversion system for an electrodeposition system. The bubble diversion system includes a bubble diverter configured to be installed in an anode chamber of the electrodeposition system, the bubble diverter including a wall configured to partially separate an area of ​​the anode chamber adjacent to an ion exchange membrane from an area of ​​the anode chamber configured to direct a bubble flow to an anode electrolyte circulation loop.

[0056] In some such examples, the bubble diverter additionally or alternatively extends around a peripheral portion of the ion exchange membrane.

[0057] In some such examples, the bubble diverter additionally or alternatively includes a plurality of apertures configured to expose the ion exchange membrane to an ionic current flowing between the inert anode and the substrate.

[0058] In some such examples, the bubble diversion system additionally or alternatively includes an adjustment mechanism configured to adjust an open cross-sectional area of ​​the plurality of orifices.

[0059] In some such examples, the adjustment mechanism additionally or alternatively includes a shutter system.

[0060] In some such examples, the bubble diversion system additionally or alternatively includes a pressure regulating port configured to direct the bubbles away from the anode chamber to a pressure regulating structure.

[0061] In some such examples, the pressure regulating port additionally or alternatively leads to a channel connected to an anolyte circulation loop.

[0062] Another example provides a method of operating an electrodeposition system. The method includes generating bubbles at an inert anode located in an anode chamber of the electrodeposition system. The method also includes directing the bubbles generated at the inert anode to a pressure regulating structure exposed to the atmosphere by using a bubble deflector.

[0063] In some such examples, directing the bubbles to the pressure regulating structure additionally or alternatively includes deflecting the flow of the bubbles to at least one channel leading to the anolyte circulation loop.

[0064] In some such examples, the method additionally or alternatively includes flowing anolyte through the anolyte circulation loop such that bubbles enter a pressure regulating structure upstream of a circulation pump.

[0065] In some such examples, the method additionally or alternatively includes generating an ion current at an inert anode, flowing the ion current through an orifice of a bubble deflector, and adjusting the ion current at the substrate by adjusting an open cross-sectional area of ​​at least one orifice of the bubble deflector in response to an indication of electroplating performance.

[0066] In some such examples, adjusting the ion current additionally or alternatively includes maintaining a voltage applied between the inert anode and the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 A block diagram of an exemplary electrodeposition tool is shown.

[0068] Figure 2 An exemplary electrodeposition system including an inert anode is schematically shown.

[0069] Figure 3 An exemplary electrodeposition system including an inert anode and a proton-blocking structure is schematically illustrated.

[0070] Figure 4 An exemplary electrodeposition system including a metal redox barrier is schematically illustrated.

[0071] Figure 5 An exemplary electrodeposition system including a rotatable metal redox barrier is schematically illustrated.

[0072] Fig. 6AAn exemplary electrodeposition system comprising an inert anode, a cation exchange membrane, and an anion exchange membrane is schematically shown.

[0073] Figure 6B A graph is shown which shows the Fig. 6A FIG. 1 is a diagram of an exemplary embodiment of an electrodeposition system showing a bath ion concentration varying over time.

[0074] Figure 7 An exemplary electrodeposition system comprising an inert anode redox shuttle circulation system is schematically illustrated.

[0075] Figure 8 Schematically shows Figure 7 Exemplary chemicals used in the electrodeposition system of FIG.

[0076] Fig. 9A An exemplary electrodeposition system comprising an inert anode, a first anion exchange membrane, and a second anion exchange membrane is schematically illustrated.

[0077] Fig. 9B A graph is shown which shows the Fig. 9A FIG. 1 is a diagram of an exemplary embodiment of an electrodeposition system showing a bath ion concentration varying over time.

[0078] Fig.10 An exemplary electrodeposition system comprising an inert anode, a first cation exchange membrane, a second cation exchange membrane, and a copper oxide module is schematically illustrated.

[0079] Fig.11A An exemplary electrodeposition system comprising an inert anode and an anion exchange membrane is schematically shown.

[0080] Fig. 11B A graph is shown which shows the Fig.11A FIG. 1 is a diagram of an exemplary embodiment of an electrodeposition system showing a bath ion concentration varying over time.

[0081] Fig.12 A flow chart is shown illustrating an exemplary method for forming a layer of a selected metallic material on a substrate by electrodeposition.

[0082] Fig.13 A block diagram of another exemplary electrodeposition system is shown.

[0083] Fig.14 A top view of an exemplary inert anode assembly is schematically shown.

[0084] Fig.15 Schematic display Fig.14 Exploded view of the inert anode assembly.

[0085] Fig.16 Schematic diagram showing the Fig.14 A cross-sectional side view taken along line 5-5.

[0086] Fig.17 An exemplary inert anode assembly having a shared inert anode is shown schematically.

[0087] Fig.18 An exemplary inert anode assembly is schematically shown having a spiral path anolyte flow channel.

[0088] Fig.19 An exemplary inert anode assembly is schematically shown having anolyte flow channels with a serpentine path.

[0089] Fig. 20 An exemplary inert anode assembly including an intermediate channel member is schematically shown.

[0090] Fig.21 A flow chart of an exemplary method for operating an electrodeposition system including an inert anode is shown.

[0091] Fig. 22 A block diagram of another exemplary electrodeposition system is shown.

[0092] Fig.23 A graph showing ion current and oxygen bubble movement in an exemplary electrodeposition system.

[0093] Fig.24 The anolyte circulation loop including the pressure regulating zone is shown schematically.

[0094] Fig.25 A top view of an electrodeposition system including a peripheral inert anode and a bubble deflector is schematically shown.

[0095] Figures 26A-26B An exemplary bubble diverter including a closed orifice is shown.

[0096] Figures 27A-27B Repositioning of an exemplary bubble diverter relative to the base of the anode chamber is shown.

[0097] Fig.28 A flow chart of an exemplary method for operating an electrodeposition system including an inert anode is shown.

[0098] Fig.29 A flow chart of an exemplary method for regulating ion current in an electrodeposition system including an inert anode is shown.

[0099] Fig.30 An example computing system is schematically shown. DETAILED DESCRIPTION

[0100] The term "acidic species" generally refers to atoms or molecules that are capable of donating protons or accepting electron pairs in neutral or ionic form.

[0101] The term "active anode" generally refers to the electrode in an electrodeposition system that is formed from the metal being electrodeposited and that is consumed by oxidation during the electrodeposition process.

[0102] The term "anion exchange membrane" generally refers to a membrane that selectively allows the passage of one or more anionic species while blocking the transmission of other species, such as cationic species and organic species.

[0103] The term "anode" generally refers to an electrically conductive structure at which electrochemical oxidation occurs during an electrodeposition process.

[0104] The term "anode chamber" generally refers to a physical structure configured to house at least an anode and an anolyte in an electrodeposition system.

[0105] The term "anode chamber base" generally refers to the lower surface of the anode chamber.

[0106] The term "anode side" generally refers to the side of an electrodeposition system component that faces an inert anode of the electrodeposition system.

[0107] The term "anolyte" generally refers to the solution used in the anode chamber during the electrodeposition process.

[0108] The term "anolyte circulation loop" generally refers to the path by which the anolyte is recirculated through the anode compartment over time.

[0109] The term "anolyte flow channel" generally refers to a structure used to define a fluid flow path for anolyte through an inert anode. The fluid flow path includes a width and a length, wherein the width is less than the length.

[0110] The term "anolyte channel member" generally refers to a structure used to define at least a portion of an anolyte flow channel.

[0111] The term "pore" generally refers to a hole or opening in a separator that allows molecules to pass from one side of the separator to the other side of the separator.

[0112] The term "bubble diverter" generally refers to a structure that deflects the flow of bubbles in a solution toward a preselected location.

[0113] The term "bubble diverting system" generally refers to a system that includes a bubble diverter and at least one conduit to remove bubbles from a chamber containing a solution.

[0114] The term "cathode" generally refers to a conductive layer on a substrate that grows by electrochemical reduction of ions during electrodeposition.

[0115] The term "cathode chamber" generally refers to a physical structure configured to house at least a cathode and a catholyte in an electrodeposition system.

[0116] The term "cathode chamber bottom member" generally refers to a structure that defines the surface of the cathode chamber adjacent to the ion exchange membrane that separates the cathode chamber from another fluid environment of the electrodeposition system. Examples of other fluid environments include intermediate flow channels and anolyte flow channels.

[0117] The term "cathode side" generally refers to the side of an electrodeposition system component that faces a substrate holder of the electrodeposition system.

[0118] The term "catholyte" generally refers to the solution used in the cathode chamber during an electrodeposition process.

[0119] The term "cation exchange membrane" generally refers to a permeable membrane that selectively passes one or more cationic species while blocking the transmission of other species, such as anionic species and organic species.

[0120] The term "circulation pump" generally refers to a pump that recirculates liquids and / or gases through a circulation loop.

[0121] The term "contactor" generally refers to a device that includes a membrane configured to remove dissolved gases from a solution.

[0122] The term "dissolved gas" generally refers to gas molecules that have dissolved in a solvent.

[0123] The terms "electrodeposition," "electroplating," "plating," "deposition," and variations thereof generally refer to a process in which dissolved ions of one or more metals are reduced on a substrate surface to form a film of the one or more metals.

[0124] The term "electrodeposition cell" generally refers to a processing station in an electrodeposition system used to perform electrodeposition on a substrate.

[0125] The term "electrodeposition system" generally refers to a machine configured to perform electrodeposition.

[0126] The term "gas bubbles" generally refers to bubbles of gaseous byproducts generated at an inert anode during an electrodeposition process.

[0127] The term "inert anode" generally refers to an electrode material that is electrically conductive but is not electrochemically oxidized during the electrodeposition process.

[0128] The term "inert anode assembly" generally refers to an assembly of multiple components, wherein the multiple components include an inert anode and an anolyte channel component.

[0129] The term "intermediate chamber" generally refers to a physical structure located between the cathode chamber and the anode chamber, which provides for selective separation of the chemical environments in the cathode chamber and the anode chamber.

[0130] The term "intermediate chamber solution" generally refers to the solution used in the intermediate chamber during the electrodeposition process.

[0131] The term "intermediate compartment solution circulation system" generally refers to the path along which the intermediate compartment solution is recirculated over time.

[0132] The term "intermediate passage member" generally refers to a structure used to define at least a portion of an intermediate flow passage.

[0133] The term "intermediate flow channel" generally refers to a structure for defining a fluid flow path for an intermediate electrolyte. The intermediate flow channel is separated from the anolyte flow channel by a first ion exchange membrane and from the catholyte by a second ion exchange membrane.

[0134] The term "ionic current" generally refers to the flow of electric charge through a conductive solution.

[0135] The term "ion exchange membrane" generally refers to a semipermeable membrane that allows the transport of certain dissolved ions but not other dissolved ions or neutrally charged molecules.

[0136] The term "linear flow rate" generally refers to the distance traveled by the anolyte per unit time.

[0137] The term "lower end of the bubble deflector" generally refers to the portion of the bubble deflector adjacent the base of the anode chamber.

[0138] The term "mechanical biasing element" generally refers to a device configured to apply a mechanical force in a direction.

[0139] The term "membrane frame" generally refers to a structural device to which a membrane can be attached and which holds the membrane in place.

[0140] The term "membrane interface seal" generally refers to a material located between a membrane and an adjacent structure that prevents solution flow between the membrane and the adjacent structure.

[0141] The term "metal film" generally refers to a metal layer deposited onto a substrate.

[0142] The term "metal ion" generally refers to a metal atom in a soluble oxidation state.

[0143] The term "metal redox barrier" generally refers to a physical barrier that blocks the migration of protons and gas bubbles while allowing current to flow. The current flow is caused by oxidation of the metal redox barrier on the cathode-facing surface of the metal redox barrier and reductive deposition of metal atoms on the anode-facing surface of the metal redox barrier.

[0144] The term "open cross-sectional area" generally refers to the two-dimensional extent of an orifice.

[0145] The term "proton-blocking structure" generally refers to any barrier that serves to block the migration of protons out of the anode compartment within an electrodeposition cell.

[0146] The term "redox shuttle system" generally refers to a circulating bath loop configured to provide a flow of a chemical species that is preferentially oxidized over water to an inert anode.

[0147] The term "redox shuttle regeneration chamber" generally refers to a portion of a redox shuttle circulation system that regenerates a chemical species that is preferentially oxidized by an inert anode over water.

[0148] The term "segmented region of anolyte flow" and variations thereof generally refers to the flow of anolyte across one or more inert anodes separated by spaces of solid structural entities.

[0149] The term "shared inert anode" generally refers to connected inert anodes that are configured to contact anolyte within two or more anolyte flow channels.

[0150] The term "shutter system" generally refers to a device that can be moved to increase or decrease the open cross-sectional area of ​​an aperture.

[0151] The term "stilling port" generally refers to an opening in a chamber that leads to a stilling area that is exposed to the atmosphere.

[0152] The term "stilling structure" generally refers to a device within which bubbles of solution are vented to the atmosphere.

[0153] The term "substrate" generally refers to any object upon which a film may be deposited by electrodeposition.

[0154] The term "substrate holder" generally refers to a device configured to receive a substrate and hold the substrate in position for electrodeposition of a metal film.

[0155] Electrochemical deposition processes are widely used in the semiconductor industry for device metallization. Exemplary metallization processes include electrodeposition of copper and cobalt onto chips and other substrates. Other metals commonly used in electrodeposition processes include tin / silver alloys, nickel, and gold.

[0156] Some electrodeposition systems use consumable or active anodes. Active anodes typically contain the same metal that is being deposited at the cathode. Active anodes are consumed over time. Consumption of active anodes requires periodic replacement, recalibration, and corresponding tool downtime. In addition, for some metals, active anodes can be expensive and difficult to obtain. To avoid such issues, electrodeposition systems can use inert anodes. Inert anodes do not consume over time. However, inert anodes drive the electrolysis reaction in the anode chamber, generating proton and oxygen bubbles. These proton and oxygen bubbles can interfere with electrodeposition. For example, oxygen bubbles can accumulate under the ion exchange membrane that separates the anode and cathode chambers of the electrodeposition system. The accumulated bubbles can block the target substrate, hinder ion current through the ion exchange membrane, and cause uneven electrodeposition. In addition, in the absence of an anode as a source of electroplating ions, more active catholyte management may be required to prevent electroplating ion depletion.

[0157] Thus, disclosed is an exemplary electrodeposition system that can address issues associated with the generation of protons and oxygen bubbles at an inert anode. Briefly, in some examples, a proton blocking structure separates the anode chamber from the intermediate chamber. Additionally, an ion exchange membrane separates the intermediate chamber from the cathode chamber. In some such examples, the proton blocking structure includes a metal redox barrier. In other such examples, the proton blocking structure includes a second ion exchange membrane. Additionally, some such examples include a redox shuttle circulation system to help further reduce acid generation at the inert anode. The redox shuttle circulation system can include a regeneration chamber to help maintain chemical concentrations in the anolyte.

[0158] Before discussing these examples in more detail, Figure 1 A block diagram of an exemplary electrodeposition tool 100 is schematically shown. The electrodeposition tool 100 includes an electrodeposition cell 102, and the electrodeposition cell 102 includes an anode chamber 104 and a cathode chamber 106. The electrodeposition tool 100 also includes an ion exchange membrane 108 that separates the anode chamber 104 and the cathode chamber 106. In various examples, the ion exchange membrane 108 can include a cation exchange membrane or an anion exchange membrane. The electroplating tool 100 also includes a high resistance virtual anode (HRVA) 109 in the cathode chamber 106.

[0159] Anode chamber 104 includes anode 110. Anode chamber 104 also includes anolyte. Cathode chamber 106 contains catholyte. The catholyte includes ionic species to be deposited as metal on the cathode layer of substrate 111 by electrochemical reduction. Anode 110 may include an inert anode. Sometimes, bulk anolyte and / or catholyte solution may be added to replenish ionic species.

[0160] Ion exchange membrane 108 inhibits organic and anionic species from crossing between cathode chamber 106 and anode chamber 104 while allowing metal ions to cross from anode chamber 104 to cathode chamber 106. HRVA 109 includes an ion resistance element that approximates a suitable constant and uniform current source adjacent to the substrate cathode.

[0161] The electroplating tool 100 also includes a proton barrier structure 112 between the anode 110 and the ion exchange membrane 108 to reduce acidification of the cathode electrolyte. The proton barrier structure 112 forms a boundary of an intermediate chamber 115 between the anode chamber 104 and the cathode chamber 106. Another boundary of the intermediate chamber 115 can be formed by the ion exchange membrane 108. The intermediate chamber 115 can include an intermediate solution. The intermediate solution can include ionic species to be deposited on the cathode layer.

[0162] The substrate holder 122 is coupled to a substrate holder movement system 123. The substrate holder movement system 123 includes a lifting device 124, which is configured to adjust the spacing between the substrate holder 122 and the HRVA 109. For example, the lifting device 124 can lower the substrate holder 122 to position the substrate 111 in the cathode electrolyte for electrodeposition. The lifting device 124 can also raise the substrate holder 122 from the cathode electrolyte after electrodeposition. The substrate holder movement system 123 can also include components for controlling the opening and closing of the substrate holder 122.

[0163] The catholyte may be circulated between the cathode chamber 106 and the catholyte storage tank 130 by a combination of gravity and one or more pumps 132. Likewise, the anolyte may be circulated through the anolyte storage tank 134 and the anode chamber 104 by a combination of gravity and one or more pumps 136. Additionally, the intermediate solution may be circulated through the intermediate solution storage tank 138 by a combination of gravity and one or more pumps 140.

[0164] In some electrodeposition tools, multiple plating tanks may be used to perform plating operations on multiple substrates in parallel. In some such examples, a central catholyte and / or anolyte storage tank may supply catholyte and / or anolyte to multiple plating tanks. In other such examples, separate catholyte storage tanks and / or anolyte storage tanks may be used to supply multiple plating tanks. In still other examples, the electrodeposition tool may include a single plating tank. In the case where the electrodeposition tool includes multiple plating tanks, a single lifting device may be configured to lift and lower two or more substrate holders for two or more different plating tanks.

[0165] After the substrate 111 is loaded into the substrate holder 122, the substrate holder 122 is lowered toward the HRVA 109 by the lifting device 124. During electrodeposition, the substrate 111 faces the surface of the HRVA 109 and is separated from the HRVA 109 by a certain plating gap. An electric field is established between the anode 110 and the substrate 111. The electric field drives the dissolved metal cations from the anode chamber 104 and / or the intermediate chamber 115 into the cathode chamber 106. At the substrate 111, these metal cations are electrochemically reduced to deposit a metal film on the substrate 111. The anode potential is applied to the anode 110 through the anode electrical connector 142, and the cathode potential is provided to the cathode of the substrate 111 through the cathode electrical connector 146 to form an electrical circuit. In some examples, the substrate holder 122 can be rotated via a rotation motor 148 during electrodeposition.

[0166] The electrodeposition tool 100 also includes a computing system 150, aspects of which refer to Fig.30 The computing system 150 may include a plurality of instructions that can be executed to control any suitable function of the electrodeposition tool 100. Exemplary functions include electrodeposition processing and substrate loading / unloading processing. In some examples, the computing system 150 may be configured to communicate with a remote computing system 152 via an appropriate computer network. The remote computing system 152 may include any suitable computing system. Examples thereof include networked workstation computers, enterprise computing systems, and / or cloud computing systems. It should be understood that in some examples, the remote computing system 152 may communicate with and control a plurality of electrodeposition tools.

[0167] Active anodes may be used more frequently than inert anodes. However, as mentioned above, the disadvantage of using active anodes is that they will eventually be consumed over time. Therefore, new anodes are installed periodically. Active anodes can be expensive and difficult to procure for certain metals. In addition, replacing anodes can cause downtime for the electrodeposition system. Anode replacement may also involve requalification and defect control of the electrodeposition system after the anode is installed. The productivity loss caused by anode replacement can reduce production and increase the cost of ownership of the electrodeposition system.

[0168] In contrast, as mentioned above, inert anodes do not degrade over time. Therefore, using inert anodes does not result in downtime due to anode replacement. These characteristics can make inert anodes an attractive alternative to active anodes.

[0169] However, as mentioned above, an inert anode may generate proton and oxygen bubbles. Figure 2 An exemplary electrodeposition system 200 including an inert anode is schematically shown, and the formation of proton and oxygen bubbles is illustrated. Figure 2 It is described in the context of copper deposition. However, bubbles may also be generated during electrodeposition of other metals.

[0170] The electrodeposition system 200 includes an anode chamber 202 and a cathode chamber 204. The electrodeposition system 200 also includes an ion exchange membrane 206 that separates the anode chamber 202 from the cathode chamber 204. The electrodeposition system 200 also includes a HRVA 210 disposed within the cathode chamber 204.

[0171] The anode chamber 202 includes an anolyte bath 212 in which an inert anode 214 is disposed. The cathode chamber 204 includes a catholyte bath 216 containing ionic copper (Cu) to be deposited onto a substrate 218 serving as a cathode. 2+ ). During deposition, substrate 218 is held in substrate holder 219. Anolyte bath 212 is located in anolyte circulation loop 220. Catholyte bath 216 is located in catholyte circulation loop 222. Voltage source 230 applies voltage across substrate 218 and inert anode 214 to drive copper ion flow for deposition on substrate 218.

[0172] Cation exchange membrane 206 makes Cu 2+ Ions are transported from the anolyte bath 212 to the catholyte bath 216. Cu ions passing through the cation exchange membrane 206 2+ The ions replace at least some of the copper ions in catholyte bath 216 that were reduced to substrate 218 .

[0173] for Figure 2 The inert anode, oxidation and reduction reaction system includes: 2H 2 O→O 2 +4H + +4e - (On inert anode) Cu +2 +2e - →Cu (on cathode) 2Cu 2+ +2H 2 O→2Cu+4H + +O 2 (Total Response)

[0174] Thus, unlike the active anode, the inert anode 214 does not generate metal cations in the anolyte bath. Instead, the inert anode 214 oxidizes water molecules to form molecular oxygen. For every 1 mole of copper plated at the cathode, 0.5 moles of molecular oxygen and 2 moles of protons (H + ).

[0175] The generation and accumulation of bubbles at the cation exchange membrane 206 may affect electroplating uniformity. In addition, the protons generated on the anode surface may reduce the pH of the anolyte bath. Protons may also pass through the membrane and enter the catholyte bath. In addition, it may be challenging to maintain a mass balance (e.g., a mass balance of copper) in the bath of the anode chamber during the electrodeposition process.

[0176] The challenge of maintaining mass balance in the presence of an inert anode also includes concentration swings in the anolyte and catholyte solutions. The concentration swings can be driven by at least three factors: (1) acid generation at the anode surface, (2) acid crossing the cation exchange membrane to the catholyte side requiring water injection / draining to maintain electroplating specifications, and (3) metal ion consumption at the cathode surface.

[0177] Figure 3 An exemplary electrodeposition system 300 is schematically shown, which can help solve the problems caused by the generation of proton and oxygen bubbles. The electrodeposition system 300 includes an inert anode 304 disposed in an anode chamber 302. The anode chamber 302 is configured to accommodate an anolyte bath 306 during the electrodeposition process. The anolyte bath 306 can be replenished via an anolyte circulation loop 308. The inert anode 304 can include any suitable material that is resistant to oxidation during the electrodeposition process. Examples thereof include mixed metal oxides, or noble conductive metals (noble conductive metal) coated with one or more metal oxides, such as platinum or iridium.

[0178] The electrodeposition system 300 also includes a proton blocking structure 310. The proton blocking structure 310 is configured to block the migration of protons and oxygen bubbles generated by the electrolysis of water within the anolyte bath 306. This can help prevent the migration of protons to the catholyte bath 324. This can further assist in preventing oxygen bubbles from accumulating on the ion exchange membrane 318. In various examples, the proton blocking structure 310 can include one or more of a metal redox barrier, an anion exchange membrane, or other structural elements that provide a barrier to the migration of protons.

[0179] The proton blocking structure 310 can define the boundaries of the intermediate chamber 312. The intermediate chamber 312 can be configured to accommodate an intermediate bath 314. The intermediate bath 314 can be replenished via an intermediate bath circulation loop 316. The intermediate bath 314 can include at least one source of metal cations for electrodeposition. In other examples, for example, Fig.10 In the example described, the boundary between the intermediate chamber 312 and the anode chamber 302 can be defined by a structure (e.g., an anion exchange membrane) that does not provide a barrier to proton migration. Such a structure can prevent bubble accumulation, limit or hinder the transmission of one or more molecular types between the intermediate chamber 312 and the anode chamber 302, and / or otherwise provide a boundary between two adjacent chambers.

[0180] The electrodeposition system 300 also includes an ion exchange membrane 318. The ion exchange membrane 318 may define another boundary of the intermediate chamber 312. The ion exchange membrane 318 separates the intermediate chamber 312 from the cathode chamber 322. The ion exchange membrane 318 allows for selective transport of ions between the intermediate bath 314 and the cathode electrolyte bath 324.

[0181] The cathode chamber 322 also includes a HRVA 326 and a substrate holder 328. The substrate holder 328 can be configured to expose the cathode layer of a substrate 330 positioned in the substrate holder 328 to the catholyte bath 324 during the electrodeposition process. Figure 3 In the + .Cat + Any suitable metal ion used to grow a metal film in an electrodeposition process may be represented. Catholyte bath 324 may be replenished via catholyte circulation loop 332. Voltage source 334 may apply a voltage between inert anode 304 and substrate 330 to drive the electrodeposition process.

[0182] As described above, in some examples, the proton blocking structure 310 may include a metal redox barrier. The metal redox barrier may include a solid barrier capable of blocking the migration of protons and gas bubbles while allowing current to flow. The current flows through oxidation of the metal redox barrier on the cathode-facing surface of the metal redox barrier and reduction deposition of metal atoms on the anode-facing surface of the metal redox barrier.

[0183] Figure 4 An exemplary electrodeposition system 400 is shown that includes a metal redox barrier 410. The electrodeposition system 400 is an example of the electrodeposition system 300. Briefly, the electrodeposition system 400 includes an anode chamber 402 that includes an inert anode 404. The anode chamber 402 is configured to contain an anolyte bath 406 that can be replenished via an anolyte circulation loop 408.

[0184] Metal redox barrier 410 separates intermediate chamber 412 from anode chamber 402. Intermediate chamber 412 can be configured to accommodate intermediate bath 414. Intermediate bath 414 can be replenished via intermediate bath circulation loop 416. Cation exchange membrane 418 separates intermediate chamber 412 from cathode chamber 422. In some examples, the same anolyte solution (e.g., copper sulfate solution) can be used as intermediate bath 414 and anolyte bath 406 at the same time. In other examples, intermediate bath 414 and anolyte bath 406 can use different solutions. Intermediate bath 414 and anolyte bath 406 can be continuously replenished via anolyte circulation loop 408 and intermediate bath circulation loop 416, respectively. Due to proton formation during electrodeposition, anolyte bath 406 may be more acidic than intermediate bath 414. However, intermediate bath 414 and anolyte bath 406 can be supplied from the same initial source, and one or both baths are doped or diluted before entering the corresponding chamber.

[0185] The cathode chamber 422 also includes a HRVA 426 and a substrate holder 428. A substrate 430 including a cathode layer can be positioned in the substrate holder 428 and exposed to the catholyte bath 424 during the electrodeposition process. The catholyte bath 424 can be replenished via a catholyte circulation loop 432. A voltage source 434 can apply a voltage across the inert anode 404 and the substrate 430 to drive the electrodeposition process.

[0186] The metal redox barrier 410 may include a passivation metal plate positioned within the electric field generated by the voltage source 434 across the cathode layer of the substrate 430 and the inert anode 404. This may allow for convenient modification of existing electrodeposition system configurations. The metal redox barrier 410 may include any suitable metal. Examples thereof include one or more of copper, cobalt, gold, silver, tin, zinc, nickel, cadmium, platinum, iron, or alloys such as brass or tin-silver. In some examples, the metal redox barrier 410 may include a metal layer located on the substrate. The metal layer participates in oxidation and reduction reactions. In other examples, the metal redox barrier 410 may include a body portion formed by a metal participating in oxidation and reduction reactions. Although described with respect to the passivation metal plate, in other examples, an electric potential may be applied to the metal redox barrier 410.

[0187] During electrodeposition, metal redox barrier 410 may receive growth of a metal film on the anode side of metal redox barrier 410 by reduction of metal ions from anolyte bath 406. In addition, metal redox barrier 410 may provide metal ions to intermediate bath 414 on the cathode side of metal redox barrier 410 by oxidation of metal redox barrier 410.

[0188] As an example, copper metal is deposited (reduced) on the anode side of metal redox barrier 410, while copper ions are released (oxidized) on the cathode side of metal redox barrier 410. The generated copper ions then pass through cation exchange membrane 418, enter catholyte bath 424, and are reduced on substrate 430. Thus, as copper ions are released from metal redox barrier 410, the amount of copper present in catholyte bath 424 is maintained.

[0189] For copper, the main reactions are as follows: 2H 2 O-4e→4H + +O 2 (on inert anode) Cu 2+ +2e→Cu (on the anode side of the barrier) Cu–2e→Cu 2+ (On cathode side of barrier) In the absence of mass transport limitations, the Gibbs free energy will generally favor these reactions at the metal redox barrier during electroplating. This copper supplementation allows the mass balance of the catholyte to be maintained. In this way, the metal redox barrier 410 acts like an active anode. The metal redox barrier 410 also helps maintain the desired acid concentration in the intermediate bath 414 by preventing protons from migrating into the intermediate bath 414.

[0190] Since copper is deposited on the anode side of the metal redox barrier 410 and dissolved on the cathode side, the net thickness of the plate may not change over time and remain substantially the same. However, the metal redox barrier 410 may migrate toward the inert anode 404 over time. Therefore, in some examples, one or more mechanical biasing elements 440 may be used to bias the metal redox barrier 410 toward the intermediate chamber 412. As an example, the mechanical biasing element 440 may include a spring mechanism that is used to bias the position of the metal redox barrier 410. This may help maintain an appropriate and consistent distance between the substrate 430 and the metal redox barrier 410. Appropriate seals 442 may be used to prevent air bubbles and acid from migrating around the sides of the metal redox barrier 410.

[0191] The metal redox barrier 410 may not be consumed or replenished uniformly on both surfaces over time. Therefore, the metal redox barrier 410 may be replaced occasionally. However, the replacement frequency of the metal redox barrier 410 may be lower than the replacement frequency of the active anode. Therefore, the use of the metal redox barrier 410 may result in less downtime than the use of the active anode. In addition, replacing the metal redox barrier 410 may be more time-saving and cheaper than replacing the active anode. A relatively thick metal film may be plated onto the substrate without worrying about anode passivation caused by precipitates generated by increased local concentrations of metal ions. In addition, bubbles emitted from the inert anode 404 are prevented from reaching the cation exchange membrane 418. This can help avoid the effects of bubbles accumulated on the cation exchange membrane 418 on the uniformity of electroplating. Concentration management of chemical substances may also be facilitated by metals that are continuously consumed and released in the presence of an electric field.

[0192] exist Figure 4 In some examples, one or more mechanical biasing elements are used to maintain an appropriate and consistent spacing between metal redox barrier 410 and cation exchange membrane 418. In other examples, the metal redox barrier can be periodically rotated. Rotating the metal redox barrier allows the surface of the metal redox barrier to be exposed to both oxidation and reduction reactions over time.

[0193] Figure 5An example of an electrodeposition system 500 including a metal redox barrier 510 (e.g., a rotatable metal redox barrier) is shown. The electrodeposition system 500 is an example of the electrodeposition system 300. Briefly, the electrodeposition system 500 includes an anode chamber 502, which includes an inert anode 504. The anode chamber 502 is configured to contain an anolyte bath 506, which can be replenished via an anolyte circulation loop 508.

[0194] The metal redox barrier 510 separates the intermediate chamber 512 from the anode chamber 502. The intermediate chamber 512 may be configured to house an intermediate bath 514. The intermediate bath 514 may be replenished via an intermediate bath circulation loop 516.

[0195] The intermediate chamber 512 is separated from the cathode chamber 522 by a cation exchange membrane 518. The cation exchange membrane 518 allows for selective cation transport between the intermediate bath 514 and the catholyte bath 524. The cathode chamber 522 also includes a HRVA 526 and a substrate holder 528. A substrate 530 including a cathode layer can be positioned in the substrate holder 528 and exposed to the catholyte bath 524 during the electrodeposition process. The catholyte bath 524 can be replenished via a catholyte circulation loop 532. A voltage source 534 can apply a voltage across the inert anode 504 and the substrate 530 to drive the electrodeposition process.

[0196] The metal redox barrier 510 is rotatable so that the anode side and cathode side of the plate can alternately switch their respective orientations toward the intermediate chamber 512. In some examples, the metal redox barrier 510 can be manually rotated by an operator. In other examples, the metal redox barrier 510 can be automatically rotated. For example, Figure 5 Metal redox barrier 510 is shown rotatably coupled to motor case 540 via shaft 542 .

[0197] The electrodeposition system 500 can plate the metal on the anode side of the metal redox barrier 510 for one or more electroplating cycles. Then, the electrodeposition system 500 can rotate the metal redox barrier 510 so that the metal side that was electroplated a short time ago can be oxidized in one or more electroplating cycles. In some examples, the amount of metal consumed can be monitored. Then, the metal redox barrier 510 can be rotated when the consumed metal reaches a threshold. In some examples, the metal redox barrier 510 can be rotated when the substrate is rinsed or during other ordinary electrodeposition system processing. This can help avoid downtime when rotating the metal redox barrier 510. In addition, the rotation of the metal redox barrier 510 can not cause interference to the catholyte bath 524.

[0198] As mentioned above about Figure 3 As described above, in some examples, an ion exchange membrane may be used as a proton blocking structure. Fig. 6A An exemplary electrodeposition system 600 including an anion exchange membrane as a proton-blocking structure is shown. The electrodeposition system 600 is an example of the electrodeposition system 300. Briefly, the electrodeposition system 600 includes an anode chamber 602, which includes an inert anode 604. The anode chamber 602 is configured to accommodate an anolyte bath 606, which can be replenished via an anolyte circulation loop 608.

[0199] An anion exchange membrane 610 separates an intermediate chamber 612 from the anode chamber 602. The intermediate chamber 612 may be configured to accommodate an intermediate bath 614. The intermediate bath 614 may be replenished via an intermediate bath circulation loop 616.

[0200] The intermediate chamber 612 is separated from the cathode chamber 622 by a cation exchange membrane 618. The cation exchange membrane 618 allows for selective cation transport between the intermediate bath 614 and the catholyte bath 624. The cathode chamber 622 also includes a HRVA 626 and a substrate holder 628. A substrate 630 including a cathode layer can be positioned in the substrate holder 628 and exposed to the catholyte bath 624 during the electrodeposition process. The catholyte bath 624 can be replenished via a catholyte circulation loop 632. A voltage source 634 can apply a voltage across the inert anode 604 and the substrate 630 to drive the electrodeposition process.

[0201] The electrodeposition system 600 is described with respect to a copper electroplating process. However, in other examples, the electrodeposition system 600 may be used to perform any other suitable metal electroplating process. In this example, mass imbalance issues that may arise from using an inert anode have been addressed.

[0202] Anolyte bath 606 may contain a dilute acid (e.g., H 2 SO 4 In some examples, the anolyte bath 606 may contain metal ions. However, any metal ions that are included are not used to supply the metal ions used to electroplate the substrate 630.

[0203] An anion exchange membrane 610 separates the anode chamber 602 from the intermediate chamber 612. The anion exchange membrane can preferentially allow negatively charged species (e.g., SO 4 2- ) is transferred from the intermediate chamber 612 to the anode chamber 602. In addition, the electrolysis of water is performed at the inert anode 604. Therefore, H 2 SO 4The cation exchange membrane 618 can preferentially allow positively charged species (eg, protons and metal ions) to cross the membrane from the intermediate chamber 612 to the cathode chamber 622 .

[0204] The intermediate bath 614 supplies at least some of the metal ions used for electroplating in the form of a metal salt. In the example shown, the intermediate bath 614 contains the metal salt CuSO 4 In other examples, any other suitable cations and / or anions may be used. Anion exchange membrane 610 and cation exchange membrane 618 may be selected to match the selected ionic chemistry and / or may be conditioned in appropriate solutions prior to implementation.

[0205] Intermediate bath 614 and catholyte bath 624 can contain the same chemicals, such as the same metal salts. In some examples, intermediate bath 614 can contain a different concentration of metal salts (e.g., copper sulfate) than catholyte bath 624. In other examples, intermediate bath 614 and catholyte bath 624 can contain any suitable chemical differences.

[0206] Through the cation exchange membrane 618 positioned between the cathode chamber 622 and the intermediate chamber 612, Cu 2+ Migration from the intermediate chamber 612 to the cathode chamber 622. Coupled with the reduction reaction occurring on the surface of the substrate 630, the Cu concentration of the catholyte can be maintained at an appropriate and consistent level.

[0207] However, Cu from the intermediate chamber 612 passes through the cation exchange membrane 618 and reaches the cathode chamber 622. 2+ In addition, SO2 passes through the anion exchange membrane 610 and reaches the anode chamber 602. 4 2- It will consume the CuSO in the intermediate chamber 612 4 Therefore, the intermediate chamber 612 can be replenished with CuSO 4 As an example, the intermediate bath 614 can be circulated again through the solid CuSO 4 crystals, or adding concentrated saline solutions to perform this supplement.

[0208] The use of copper sulfate in the intermediate bath 614 can provide a cheaper source of copper ions than high purity solid Cu active anodes. In addition, no anode replacement is required. In addition, the supply of Cu ions by solution can not produce particulate contaminants. In contrast, active anodes may produce particulate contaminants. Therefore, the use of copper sulfate intermediate bath 614 can allow the use of a simplified anolyte bath filtration system.

[0209] About Figure 2Unlike the two-chamber, single membrane design described above, the combined charge transfer effect of the cation exchange membrane 618 and the anion exchange membrane 610 can mass balance both the metal ions and the protons in the catholyte bath 624. This can result in a more stable catholyte bath concentration. In this way, the mass balance of the catholyte bath 624 during the electrochemical plating process can be maintained without expending excessive effort.

[0210] The cation exchange membrane 618 and the anion exchange membrane 610 may be replaced from time to time. However, the frequency of such maintenance may not be as frequent as replacing the active anodes.

[0211] Figure 6B Shows Fig. 6A The electrodeposition system 600 with Figure 2 Example solution concentrations of copper ions and protons over time in the electrodeposition system 200 of the embodiment of the present invention. The ion concentration of, for example, the catholyte bath of the respective electrodeposition system over a period of operation is shown at 650. The ion concentration of, for example, the anolyte bath of the respective electrodeposition system over a period of operation is shown at 660. The ion concentration of an exemplary intermediate bath (e.g., intermediate bath 614) is shown at 670.

[0212] In the electrodeposition system 200, protons are continuously generated and accumulated in the anode chamber, as shown in 660. In addition, the protons pass through the cathodic membrane to the cathode side. Over time, the net effect of the cathode electrolyte bath is copper ion consumption and acid accumulation, as shown in 650. Concentration drift may cause problems in the electroplating process, such as defects. In contrast, for the electrodeposition system 600, the acid increase in the anode chamber is buffered by the cathode chamber. In addition, the copper plated on the substrate is continuously replenished from the intermediate bath. Therefore, the use of a cationic membrane and an anionic membrane in combination in an electrochemical plating system can balance the mass between acid and metal ions. In addition, the copper ion and proton concentrations on the cathode side can be stable over time.

[0213] To further address proton generation and bath management, a redox shuttle system can be utilized in which a redox couple is used to avoid water electrolysis in the anolyte. Figure 7 An example of an electrodeposition system 700 is shown that includes an anion exchange membrane as a proton blocking structure, a cation exchange membrane as an ion exchange membrane, and a redox shuttle circulation system configured to provide a redox shuttle species to the anode chamber. Figure 8 Examples of redox chemistries that may be used with electrodeposition system 700 are shown schematically.

[0214] Briefly, the electrodeposition system 700 includes an anode chamber 702 including an inert anode 704. The anode chamber 702 is configured to accommodate an anolyte bath 706, which can be replenished via a redox shuttle circulation system 708. The electrodeposition system 700 also includes an anion exchange membrane for separating an intermediate chamber 712 from the anode chamber 702. The intermediate chamber 712 can be configured to accommodate an intermediate bath 714. The intermediate bath 714 can be replenished via an intermediate bath circulation loop 716.

[0215] The intermediate chamber 712 is separated from the cathode chamber 722 by a cation exchange membrane 718. The cation exchange membrane 718 allows for selective cation transport between the intermediate bath 714 and the catholyte bath 724. The cathode chamber 722 also includes a HRVA 726 and a substrate holder 728. A substrate 730 including a cathode layer can be positioned in the substrate holder 728 and exposed to the catholyte bath 724 during the electrodeposition process. The catholyte bath 724 can be replenished via a catholyte circulation loop 732, which can include hardware features to control temperature, water balance, organic additive concentration, etc. A voltage source 734 can apply a voltage across the inert anode 704 and the substrate 730 to drive the electrodeposition process.

[0216] The redox shuttle circulation system 708 can be configured to provide a redox shuttle substance to the anode chamber 702. The redox shuttle circulation system 708 can also include a regeneration chamber 740 (e.g., a redox shuttle substance regeneration chamber). The intermediate bath circulation loop 716 can include a plating metal ion source 742, such as a supply source of concentrated copper sulfate for copper electroplating reactions. In some examples, the intermediate chamber can be omitted. The anode chamber 702 can be separated from the cathode chamber 722 via a first ion exchange membrane (e.g., an anion exchange membrane 710).

[0217] Reference Figure 8 , an example of the operation and chemistry of the electrodeposition system 700 is described in the context of copper plating. In this example, Fe 2+ / Fe 3+ ions are added to the anolyte bath 706 as part of the redox shuttle. 2+ The oxidation potential of is 700 mV lower than that of water. Therefore, the oxidation reaction on the inert anode 704 deviates from the formation of oxygen and protons and tends to oxidize divalent iron (Fe 2+ ) to form ferric iron (Fe 3+ ) oxidation reaction. The oxidized Fe 3+ The ions can be reduced back to Fe by regeneration chamber 740 alone. 2+, wherein the regeneration chamber 740 includes an electron source, such as a metal suitable for galvanic reaction. 2+ It can be fed back to the anode chamber 702 via the redox shuttle circulation system 708.

[0218] In other examples, any other suitable redox pair other than iron may be used. Suitable redox pairs include species where the oxidation potential of the redox pair is lower than the oxygen release potential. For example, the potential difference between the ferric iron reaction and the regenerated metal reaction may be at least 300 millivolts. If the total potential difference is positive, ΔG becomes positive and the shuttle reaction becomes spontaneous.

[0219] In the example shown, Fe 3+ has a reduction potential of 0.77 V. Therefore, any metal or element with a positive oxidation potential, or a reduction potential below 0.77 V can be used as a redox pair. As examples, these elements may include copper, sulfur, lead, tin, nickel, cobalt, zinc, manganese, aluminum, and magnesium.

[0220] For regeneration of the reduced ionic species, the regeneration chamber 740 may include a metal or other electron donor capable of a favorable galvanic reaction. Figure 8 In the example shown, iron metal 802 is used. It should be noted that the metal used for regeneration can be different from the metal used for electroplating. However, in some examples, the electroplated metal (e.g., copper) can be used for regeneration. In some examples, the regeneration chamber 740 includes a deoxygenation station 744.

[0221] In this configuration, the three chambers of the electrodeposition system 700 are created by positioning the anion exchange membrane 710 between the anode chamber 702 and the intermediate chamber 712, and by positioning the cation exchange membrane 718 between the intermediate chamber 712 and the cathode chamber 722. Figure 8 As shown at 800, the anolyte bath 706 includes ferrous sulfate. In this example, the intermediate bath 714 includes copper sulfate, and the catholyte bath 724 includes a low acid solution (e.g., a mixture including copper sulfate, sulfuric acid, and chloride).

[0222] Since little acid is generated at the inert anode 704, there is no relevant increase in acid concentration in the intermediate bath 714 or the catholyte bath 724 over time of operation. Most of the charge is carried by the copper ions from the intermediate chamber 712 to the cathode chamber 722. This replenishes the plated copper and maintains the copper concentration in the catholyte bath 724. Although described for copper, redox shuttling can be used to avoid acid generation in any other suitable electrodeposition process.

[0223] As described above, the use of inert anodes can reduce preventive maintenance costs compared to the use of consumable anodes. Therefore, electroplating can be performed at increased currents without causing anode passivation. In addition, little or no acid is generated in the anolyte chamber, thereby simplifying bath management. Bubble generation is kept at a low level and therefore does not interfere with the electrical path. Since a membrane is used to isolate and contain the solution, the uniformity of the electroplating can be maintained.

[0224] The concentration of the regenerant material in the redox shuttle cycle system 708 may increase over time. For example, copper metal may accumulate as copper sulfate over time. As another example, iron may accumulate as iron sulfate. In some examples, additional metal species may also be included to electrically extract dissolved regenerant material (e.g., Cu 2 O 2 ) from the anolyte solution. 2+ ). For some regenerants, such as iron, some hydrogen may be produced in solution, thereby allowing the acid concentration in the regeneration chamber 740 to be controlled without creating bubbles in the anode chamber itself.

[0225] In some examples, the oxygen concentration of the anode chamber can be adjusted to prevent the generation of metal oxide precipitates (e.g., ferrous oxide) within the anode chamber 702. In some such examples, the anode chamber 702 can be backfilled with an inert gas to reduce the dissolved oxygen concentration in the entire electrodeposition system 700. The regeneration chamber 740 can optionally include a deoxygenation station 744 for removing oxygen from the system.

[0226] Over time, iron ions will dissolve from the iron metal 802 into the anolyte bath 706. In addition, copper ions will be plated onto the substrate 730 from the catholyte bath 724. However, with the anion exchange membrane 710 separating the anode chamber 702 and the intermediate chamber 712, the iron ions from the iron metal 802 will not enter the intermediate chamber 712 or the cathode chamber 722. Instead, the copper that is plated comes from the intermediate chamber 712 via the electroplating metal ion source 742.

[0227] The conductivity throughout the electrodeposition system 700 increases only modestly over time due to minimal acid formation at the inert anode 704. Any conductivity increase may result primarily from an increase in metal ion concentration in the redox shuttle circulation system 708.

[0228] Fig. 9A An electrodeposition system 900 is shown that utilizes an alternative approach to address the mass imbalance problem caused by the use of an inert anode. Fig. 9A Again a three chamber design is used. However, instead of using an anion exchange membrane between the anode chamber and the middle chamber and a cation exchange membrane between the middle chamber and the cathode chamber, the electrodeposition system 900 uses two layers of anion exchange membranes.

[0229] More specifically, the electrodeposition system 900 includes an anode chamber 902 that includes an inert anode 904. The anode chamber 902 is configured to contain an anolyte bath 906 that can be replenished via a circulation loop 908 (eg, an anolyte circulation loop).

[0230] The first anion exchange membrane 910 can separate the intermediate chamber 912 from the anode chamber 902. The intermediate chamber 912 can be configured to accommodate an intermediate bath 914, which can be replenished by an intermediate bath circulation loop 916. The second anion exchange membrane 918 separates the intermediate chamber 912 from the cathode chamber 922 and allows selective ion transport between the intermediate bath 914 and the cathode electrolyte bath 924. The cathode chamber 922 also includes a HRVA 926 and a substrate holder 928. A substrate 930 including a cathode layer can be positioned in the substrate holder 928 and exposed to the cathode electrolyte bath 924 during the electrodeposition process. The cathode electrolyte bath 924 can be replenished via the cathode electrolyte circulation loop 932. A voltage source 934 can apply a voltage across the inert anode 904 and the substrate 930 to drive the electrodeposition process.

[0231] and Fig. 6A Compared to the example, Fig. 9A The electrodeposition system can provide a more consistent acid concentration bath maintenance. The reason for this is at least that, although anions are the preferred charge transfer species, the material of the anion exchange membrane can still pass a certain amount of protons. The direct proton transfer from the proton-rich anode chamber 902 to the cathode chamber 922 is mitigated by adding a second anion exchange membrane 918 between the inert anode 904 and the substrate 930. Instead, the protons are carried to the intermediate chamber 912. When the charge is carried through the second anion exchange membrane 918 located between the intermediate chamber 912 and the cathode chamber 922, the SO 4 2- The preferential selectivity helps to limit the number of protons entering the cathode chamber 922, thereby maintaining the acid balance in the cathode electrolyte bath 924.

[0232] Water is electrolyzed into H in the anode chamber 902. + and O 2, and copper is reduced on substrate 930. Sulfate migrates through the first anion exchange membrane 910 and enters anode chamber 902. Copper migrates through the second anion exchange membrane 918 from intermediate chamber 912 and arrives cathode chamber 922, thereby completing the circuit. When hydrogen is released, sulfate enters anode chamber 902 as a form of charge balance, and reduces migration pressure. Sulfate concentration increases over time, and protons will be retained in anode chamber 902 as sulfuric acid. This acidification can be offset by water doping via anolyte bath circulation loop 908, so that acid concentration is maintained at a desired level. Copper electroplated from catholyte bath 924 is supplemented from intermediate chamber 912 by the second anion exchange membrane 918.

[0233] The copper sulfate in the intermediate chamber 912 may be depleted. Therefore, copper sulfate can be replenished via the intermediate bath circulation loop 916. A certain amount of protons will migrate away from the anode chamber 902 to some extent, regardless of the membrane selectivity. The balance of acids can be maintained by a suitable and consistent supply of copper sulfate in the intermediate chamber 912. If the pH of the intermediate bath 914 is kept low enough and water is introduced into the anolyte bath circulation loop 908, the proton migration can be maintained at a suitably low level.

[0234] Fig. 9B Shows that Fig. 9A When compared to the electrodeposition system 900, Figure 2 2 shows example solution concentrations of copper ions and protons over time in the electrodeposition system 200 of FIG. 9. At 950, the ion concentration of, for example, the catholyte bath of the respective electrodeposition tool over a period of operation is shown. At 960, the ion concentration of, for example, the anolyte bath of the respective electrodeposition tool over a period of operation is shown. At 970, the ion concentration of the intermediate bath (e.g., intermediate bath 914) is shown.

[0235] After reaching steady state, all three baths show stable concentrations. Therefore, the electroplating operation can be started immediately after the copper concentration in the cathode chamber is within the predetermined concentration range. Even at zero time, as long as the acid concentration falls within the desired range, there is enough copper for the electroplating reaction. As shown in 950 and 960, the proton concentration in the cathode electrolyte bath remains relatively low and constant even if a large amount of acid is generated at the anode.

[0236] Fig.10An example of an electrodeposition system 1000 is shown, which includes a cation exchange membrane as a proton blocking structure and a cation exchange membrane as an ion exchange membrane. The electrodeposition system 1000 is an example of the electrodeposition system 300. In brief, the electrodeposition system 1000 includes an anode chamber 1002, which includes an inert anode 1004. The anode chamber 1002 is configured to accommodate an anolyte bath 1006, and the anolyte bath 1006 can be replenished via an anolyte circulation loop 1008.

[0237] The first cation exchange membrane 1010 can separate the intermediate chamber 1012 from the anode chamber 1002. The intermediate chamber 1012 can be configured to accommodate an intermediate bath 1014. The intermediate bath 1014 can be replenished via an intermediate bath circulation loop 1016.

[0238] The second cation exchange membrane 1018 separates the intermediate chamber 1012 from the cathode chamber 1022. The second cation exchange membrane 1018 allows selective cation transport between the intermediate bath 1014 and the cathode electrolyte bath 1024. The cathode chamber 1022 also includes a HRVA 1026 and a substrate holder 1028. A substrate 1030 including a cathode layer can be positioned in the substrate holder 1028 and exposed to the cathode electrolyte bath 1024 during the electrodeposition process. The cathode electrolyte bath 1024 can be replenished via a cathode electrolyte circulation loop 1032. A voltage source 1034 can apply a voltage across the inert anode 1004 and the substrate 1030 to drive the electrodeposition process.

[0239] Protons are generated at the inert anode 1004 and are carried across the first cation exchange membrane 1010 into the intermediate bath 1014. In this example, the intermediate bath circulation loop 1016 includes a copper oxide module 1040. CuSO 4 and H 2 SO 4 Leave the intermediate room 1012. From H 2 SO 4 The protons react with Cup in the copper oxide module 1040 to generate Cu 2+ and H 2O. In this way, the protons transferred to the intermediate bath 1014 are exchanged for copper to replenish the copper moved into the cathode electrolyte bath 1024 through the second cation exchange membrane 1018. This can help provide a suitable and stable copper concentration for the cathode electrolyte bath 1024. In some examples, the anolyte circulation loop 1008 can dose the anolyte bath 1006 with a low acid solution to further manage the acid produced by the inert anode 1004. In some examples, the intermediate chamber can be omitted. The anode chamber 1002 can be separated from the cathode chamber 1022 by a single cation exchange membrane (e.g., the second cation exchange membrane 1018), so that the copper oxide module 1040 is fluidically coupled to the anode chamber 1002.

[0240] In another example, the problem of mass balance and catholyte acidification can be solved by using an anion exchange membrane. Fig.11A An example of an electrodeposition system 1100 is shown, which includes an anion exchange membrane and does not include a cation exchange membrane or other proton-blocking structure. In brief, the electrodeposition system 1100 includes an anode chamber 1102, which includes an inert anode 1104. The anode chamber 1102 is configured to accommodate an anolyte bath 1106, which can be replenished via an anolyte circulation loop 1108. The electrodeposition system 1100 is similar in structure to the electrodeposition system 200, but utilizes an anion exchange membrane 1118 instead of the cation exchange membrane 206.

[0241] An anion exchange membrane 1118 separates the anode chamber 1112 from the cathode chamber 1122. The anion exchange membrane 1118 allows selective cation transport between the anolyte bath 1106 and the catholyte bath 1124. The cathode chamber 1122 also includes a HRVA 1126 and a substrate holder 1128. A substrate 1130 including a cathode layer can be positioned in the substrate holder 1128 and exposed to the catholyte bath 1124 during the electrodeposition process. The catholyte bath 1124 can be replenished via a catholyte circulation loop 1132. A voltage source 1134 can apply a voltage across the inert anode 1104 and the substrate 1130 to drive the electrodeposition process.

[0242] As shown, protons generated at the inert anode 1104 can pass through the anion exchange membrane 1118 and enter the cathode chamber 1122, but at a relatively low rate. Sulfate from the cathode electrolyte bath 1124 crosses the anion exchange membrane 1118 and forms H in the anolyte bath 1106. 2 SO 4 Copper is maintained in cathode chamber 1122 by anion exchange membrane 1118 and can be replenished with copper sulfate via catholyte circulation loop 1132 .

[0243] The final effect of the above treatment on the solution concentration is as follows Fig. 11B shown. Fig. 11B Shows that compared to Fig.11A The electrodeposition system 1100 Figure 2 11. Example solution concentrations of copper ions and protons over time in the electrodeposition system 200 of FIG. 11. The ion concentration of, for example, the cathode electrolyte bath of the respective electrodeposition tool during an operating time is shown at 1150. The ion concentration of, for example, the anolyte bath of the respective electrodeposition tool during an operating time is shown at 1160. As shown, using an anion exchange membrane can provide a more consistent ion concentration than using a cation exchange membrane. In particular, for an electrodeposition system utilizing an anion exchange membrane, the ion concentration in the cathode electrolyte bath stabilizes relatively quickly, as shown at 1150.

[0244] Fig.12 A flow chart is shown that illustrates an exemplary method 1200 for forming a layer of a selected metallic material on a substrate by electrodeposition. The method 1200 may be performed by a controller (eg, computing system 150) that is communicatively coupled to an electrodeposition system (eg, electrodeposition system 300).

[0245] At 1210, the method 1200 includes introducing a catholyte into a cathode chamber, for example, via a catholyte circulation loop. The catholyte may include at least a source of metal ions for electrodeposition on a substrate. At 1220, the method 1200 includes introducing an anolyte into an anode chamber including an inert anode, for example, via an anolyte circulation loop. Figure 4 and Figure 5 As described, the anolyte may include metal ions for electrodeposition on the substrate. Alternatively, as described with respect to Fig. 9A and Fig.10 As mentioned, the anolyte may include a dilute acid solution with counter ions selected based on the overall chemistry of the electrodeposition system.

[0246] At 1230, the method 1200 includes introducing a solution into an intermediate chamber located between the cathode chamber and the anode chamber, the intermediate chamber being separated from the anode chamber by a proton blocking structure and separated from the cathode chamber by an ion exchange membrane. The solution introduced into the intermediate chamber (e.g., an intermediate bath) can be introduced through an intermediate bath circulation loop, which in some examples can be fluidically coupled to a metal ion source for electroplating.

[0247] In some examples, the proton blocking structure includes a metal barrier comprising a selected metal, such as Figure 4 and Figure 5Alternatively, the proton-blocking structure may include Figure 7 , Figure 8 and 9A The anion exchange membrane, or Fig. 6A and 10 The cation exchange membrane.

[0248] At 1240, method 1200 includes, for example, positioning a substrate holder into the cathode chamber, thereby exposing the substrate to the catholyte. At 1250, method 1200 includes applying a voltage across the cathode and the inert anode, thereby reducing ions of the selected metal in the catholyte onto the substrate.

[0249] At 1260, the method 1200 includes blocking the flow of acidic substances from the anode chamber to the cathode chamber by a proton blocking structure. When the proton blocking structure includes a metal barrier containing a selected metal, the method may include depositing a film of the selected metal onto the anode side of the metal redox barrier by reducing ions of the selected metal from the anolyte. Such examples may also include oxidizing the cathode side of the metal redox barrier to form ions of the selected metal in the intermediate chamber. In some such examples, the method may also include offsetting the metal redox barrier toward the intermediate chamber. The ions of the selected metal in the intermediate chamber can pass through the ion exchange membrane to reach the cathode chamber.

[0250] In examples where the proton blocking structure comprises an anion exchange membrane, the ion exchange membrane separating the intermediate chamber from the cathode chamber may comprise a cation exchange membrane. In such examples, the method may further comprise flowing an intermediate chamber solution through the intermediate chamber, wherein the intermediate chamber solution comprises a salt of a selected metal.

[0251] In some examples, the proton-blocking structure comprises a cation exchange membrane, and the ion exchange membrane separating the intermediate chamber from the cathode chamber comprises a cation exchange membrane. In such examples, the method may further comprise flowing an intermediate chamber solution through the intermediate chamber, the intermediate chamber solution comprising a salt of a selected metal.

[0252] In some examples, the proton-blocking structure comprises an ion exchange membrane. In such examples, the electrodeposition system may further comprise a redox shuttle circulation system configured to provide a redox shuttle substance in the anolyte to the anode chamber. In such examples, the method may further comprise flowing the anolyte through a redox shuttle substance regeneration chamber.

[0253] Also disclosed are examples relating to bubble management in an electrodeposition system. Briefly, the disclosed examples utilize an inert anode assembly having an anolyte flow channel configured to flow the anolyte at a sufficient linear flow rate to reduce bubble accumulation below the ion exchange membrane. As described in more detail below, the disclosed exemplary inert anode assembly can be tighter than a conventional anode chamber in an electrodeposition system. In addition, the disclosed exemplary inert anode assembly can also help reduce the flow volume of the anolyte compared to a conventional anode chamber.

[0254] Fig.13 Schematically shown is a block diagram of another exemplary electrodeposition system 1300. The electrodeposition system 1300 includes an electrodeposition cell 1302, which includes a cathode chamber 1304. The cathode chamber 1304 contains a catholyte. The catholyte includes ionic species to be deposited as metal on the cathode layer of the substrate 1306 by electrochemical reduction.

[0255] The electrodeposition cell 1302 also includes an inert anode assembly 1308. The inert anode assembly 1308 includes an inert anode 1310 and an anolyte channel component 1312. Anolyte flow channels formed in the anolyte channel component 1312 restrict the flow of anolyte toward the segmented regions during the electrodeposition process.

[0256] The ion exchange membrane 1314 is positioned between the cathode chamber bottom component 1316 and the anolyte channel component 1312. In various examples, the ion exchange membrane 1314 can include a cation exchange membrane or an anion exchange membrane. The electrodeposition system 1300 also includes a high resistance virtual anode (HRVA) 1318 located within the cathode chamber 1304. The HRVA 1318 includes an ion resistance element that approximates a suitable constant and uniform current source adjacent to the substrate cathode.

[0257] The substrate holder 1320 exposes the substrate 1306 to the cathode electrolyte during the electrodeposition process. In addition, the substrate holder 1320 is coupled to a substrate holder movement system 1322. The substrate holder movement system 1322 includes a lifting device 1324, which is configured to adjust the position of the substrate holder 1320. For example, the lifting device 1324 lowers the substrate holder 1320 to position the substrate 1306 in the cathode electrolyte for electrodeposition. After electrodeposition, the lifting device 1324 further raises the substrate holder 1320 from the cathode electrolyte. The substrate holder movement system 1322 also includes components for controlling the opening and closing of the substrate holder 1320.

[0258] The catholyte is circulated between the cathode chamber 1304 and the catholyte storage tank 1326 using a combination of gravity and one or more pumps 1328. Likewise, the anolyte is circulated through the anolyte storage tank 1330 and the anolyte flow channels of the anolyte channel component 1312 using a combination of gravity and one or more pumps 1332. Bulk anolyte and / or catholyte solution may be added from time to time to replenish and / or rebalance the ionic species.

[0259] In some electrodeposition systems, multiple plating cells can be used to perform plating operations in parallel on multiple substrates. In some such examples, a central cathode electrolyte and / or anolyte storage tank can supply cathode electrolyte and / or anolyte to multiple plating cells. In other such examples, separate cathode electrolyte and / or anolyte reservoirs can be used to supply multiple plating cells. In other examples, the electrodeposition system may include a single plating cell. In the case where the electrodeposition system includes multiple plating cells, a single lifting device can be configured to lift two or more substrate holders for two or more different plating cells.

[0260] After the substrate 1306 is loaded into the substrate holder 1320, the substrate holder 1320 is lowered toward the HRVA 1318 by the lifting device 1324. The substrate 1306 faces the surface of the HRVA 1318 and is separated from the HRVA 1318 by a plating gap during electrodeposition. An electric field is established between the anode 1310 and the substrate 1306. The electric field drives the dissolved metal cations toward the substrate 1306. At the substrate 1306, the metal cations are electrochemically reduced to deposit a metal film on the substrate 1306. The anode potential is applied to the anode 1310 through the anode electrical connector 1334, and the cathode potential is provided to the cathode of the substrate 1306 through the cathode electrical connector 1336 to form an electrical circuit. In some examples, the substrate holder 1320 can be rotated via a rotation motor 1338 during electrodeposition.

[0261] The electrodeposition system 1300 also includes a computing system 1340. Various aspects of the computing system 1340 are described with reference to Fig.30The computing system 1340 may include a plurality of instructions 1342 that can be executed to control any suitable function of the electrodeposition system 1300. Example functions include electrodeposition processing and substrate loading / unloading processing. In some examples, the computing system 1340 may be configured to communicate with a remote computing system 1344 via an appropriate computer network. The remote computing system 1344 may include any suitable computing system. Examples thereof include networked workstation computers, enterprise computing systems, and / or cloud computing systems. It should be understood that in some examples, the remote computing system 1344 may communicate with and control multiple electrodeposition systems.

[0262] As described above, the anolyte flow channels may be used to generate sufficient linear anolyte flow velocity to prevent gas bubbles from accumulating beneath the ion exchange membrane. Fig.14 A top view of an exemplary inert anode assembly 1400 is schematically shown. Fig.15 An exploded view of an inert anode assembly 1400 is shown. The inert anode assembly 1400 is an example of the inert anode assembly 1308. The inert anode assembly 1400 includes a first inert anode 1402 and a second inert anode 1404. The first inert anode 1402 is electrically connected to an anode potential. In some examples, the first inert anode 1402 can be electrically connected to the anode potential using a metal screw that fixes the first inert anode 1402. In other examples, the first inert anode 1402 can be electrically connected to an electrical pad adjacent to the first inert anode 1402. Similarly, the second inert anode 1404 is electrically connected to the anode potential. In some examples, the first inert anode 1402 and the second inert anode 1404 are connected to the same anode potential. In other examples, the first inert anode 1402 and the second inert anode 1404 are connected to different anode potentials.

[0263] The inert anode assembly 1400 also includes a first anolyte flow channel 1406. The first anolyte flow channel 1406 defines a first segmented region of anolyte flow through the first inert anode 1402. The first segmented region of anolyte flow enters the first anolyte flow channel 1406 at a first inlet 1408 and exits through a first outlet 1410. The first anolyte flow channel 1406 is at least partially defined by an anolyte channel component 1412, such as Fig.15Similarly, second anolyte flow channel 1414 defines a second segmented region of anolyte flow through second inert anode 1404. Anolyte enters second anolyte flow channel 1414 at second inlet 1416 and exits through second outlet 1418. In some examples, the flow direction of anolyte in first anolyte flow channel 1406 may be opposite to the anolyte in second anolyte flow channel 1414. In other examples, the flow direction of anolyte in first anolyte flow channel 1406 may be the same as the anolyte in second anolyte flow channel 1414.

[0264] The inert anode assembly 1400 also includes a cathode chamber bottom component 1420. The cathode chamber bottom component 1420 is configured to define the bottom portion of the cathode chamber in the electrodeposition cell of the electrodeposition system. The cathode chamber bottom component 1420 includes a first opening 1422 and a second opening 1424. The first opening 1422 allows ionic current to flow between the cathode electrolyte in the first opening 1422 and the anolyte in the first anolyte flow channel 1406. Similarly, the second opening 1424 allows ionic current to flow between the cathode electrolyte in the second opening 1424 and the anolyte in the second anolyte flow channel 1414.

[0265] The inert anode assembly also includes an ion exchange membrane 1500 (referred to herein for clarity). Fig.14 14). The ion exchange membrane 1500 is positioned between the cathode chamber bottom component 1420 and the anolyte channel component 1412. Compared to the disclosed electrodeposition system that omits the anolyte flow channel, positioning the ion exchange membrane 1500 between the cathode chamber bottom component 1420 and the anolyte channel component 1412 reduces the area of ​​the ion exchange membrane 1500 exposed to the cathode electrolyte and the anolyte. This can help reduce deformation of the ion exchange membrane 1500 that may trap bubbles.

[0266] In some examples, the ion exchange membrane 1500 includes a cation exchange membrane. In such examples, cations generated at the first inert anode 1402 and the second inert anode 1404 flow through the ion exchange membrane 1500 into the cathode electrolyte in the first opening 1422 and the second opening 1424 of the cathode chamber bottom member 1420. For example, in some exemplary processes, water is oxidized at the first inert anode 1402 and the second inert anode 1404. In such examples, protons flow through the ion exchange membrane 1400. In such examples, metal ions for deposition can be added to the cathode electrolyte or the anode electrolyte for supplementation.

[0267] In other examples, ion exchange membrane 1500 includes an anion exchange membrane. In such examples, during the electrodeposition process, anions in the cathode electrolyte flow through ion exchange membrane 1400 toward first anolyte flow channel 1406 and second anolyte flow channel 1414. As a more specific example, when the cathode electrolyte contains copper sulfate for depositing a copper film, sulfate anions can travel through ion exchange membrane 1500. In such examples, metal ions for electrodeposition can be added to the cathode electrolyte for supplementation.

[0268] In the example shown, the inert anode assembly 1400 includes two parallel anolyte flow channels. The first anolyte flow channel 1406 and the second anolyte flow channel 1414 can be fluidly connected in parallel or in series. In other examples, the inert anode assembly may include any other suitable number and configuration of anolyte flow channels. The number and configuration of the anolyte flow channels can be selected based on various factors. For example, the number and configuration of the anolyte flow channels can be selected to achieve a desired ion current uniformity between the inert anode and the cathode. Alternatively or additionally, in view of the pump system for circulating the anolyte, the number and configuration of the anolyte flow channels can be based on the desired linear flow rate through the anolyte flow channels. In addition to linear anolyte flow channels, other exemplary configurations include anolyte flow channels configured as concentric shapes.

[0269] Fig.16 The schematic diagram shows the Fig.14 16-16 of the cross-sectional side view of the inert anode assembly 1400. As shown, the ion exchange membrane 1500 is positioned between the cathode chamber bottom component 1420 and the anolyte channel component 1412. As shown, the first anolyte flow channel 1406 guides the anolyte to flow through the first inert anode 1402, as shown at 1602. The first anolyte flow channel 1406 is configured to generate a sufficient linear flow velocity to prevent bubbles from accumulating below the ion exchange membrane 1500. In some examples, the first anolyte flow channel 1406 can be configured to generate a linear flow velocity between 0.1 and 10 meters per second. The anolyte flow enters the circulation loop of the anolyte storage tank 1604 and the pump 1606 from the first anolyte flow channel 1406. Bubbles can be discharged from the anolyte in the anolyte storage tank 1604, or from any other suitable position along the circulation loop. Controller 1608 controls the flow rate produced by pump 1606. The flow rate may be selected to produce a desired linear flow rate through first anolyte flow channel 1606. Fig.16The second anolyte flow channel 1414, not shown, functions in the same manner as the first anolyte flow channel 1406.

[0270] The depicted inert anode assembly 1400 can be more compact than conventional anode chambers used in electrodeposition tools. This is at least because the first anolyte flow channel 1406 and the second anolyte flow channel 1414 can occupy less space than other anode chambers. In addition, the use of the inert anode assembly 1400 can reduce the anolyte volume compared to conventional anode chambers. This is again at least due to the smaller volume of the first anolyte flow channel 1406 and the second anolyte flow channel 1414.

[0271] When installed in the electroplating tool, the anolyte channel component 1412 and the cathode chamber bottom component 1420 can be clamped or otherwise held together. In some examples, a plurality of fasteners, such as screws, can be used to fasten the anolyte channel component 1412 and the cathode chamber bottom component 1420 together. In other examples, the anolyte channel component 1412 and the cathode chamber bottom component 1420 can be coupled together in any other suitable manner. One or more sealing components can be used to prevent leakage of the anolyte. Examples thereof include one or more O-rings disposed between the anolyte channel component 1412 and the cathode chamber bottom component 1420.

[0272] exist Figure 14-16 In some examples, each anolyte flow channel is associated with a corresponding inert anode. In other examples, the inert anode may include a shared inert anode shared between two or more anode direct flow channels. Fig.17 An exemplary inert anode assembly 1700 having a shared inert anode 1702 is schematically shown. The inert anode assembly 1700 is an example of the inert anode assembly 1308. The first anolyte flow channel 1704 defines a first segmented area where the anolyte flows through the shared inert anode 1702. In addition, the second anolyte flow channel 1706 defines a second segmented area where the anolyte flows through the shared inert anode 1702.

[0273] The inert anode assembly 1700 also includes a cathode chamber bottom component 1708 having a first opening 1710 and a second opening 1712. The first opening 1710 is positioned opposite the first anolyte flow channel 1704. The first opening 1710 allows an ionic current to flow between the cathode electrolyte in the first opening 1710 and the anolyte in the first anolyte flow channel 1704 during the electrodeposition process. Similarly, the second opening 1712 is positioned opposite the second anolyte flow channel 1706. The inert anode assembly 1700 also includes an ion exchange membrane (not shown) positioned between the cathode chamber bottom component 1708 and the anolyte channel component 1714. In other examples, the inert anode assembly 1700 may include any other suitable number and / or configuration of anolyte flow channels and / or openings in the cathode chamber bottom component 1708.

[0274] As previously described, the anolyte flow channel can be configured to produce sufficient linear flow velocity to prevent bubbles from accumulating below the ion exchange membrane. In the above examples, the disclosed inert anode assembly includes multiple anolyte flow channels. In other examples, the anolyte flow channel can have a directional change along the length of the channel to cover a wider area, rather than multiple anolyte flow channels. In all of these examples, the width of the anolyte flow channel is less than the length of the anolyte flow channel to achieve a linear flow velocity across the width of the anolyte flow channel.

[0275] Fig.18 An exemplary inert anode assembly 1800 is schematically shown including an anolyte flow channel 1802 having a spiral path. The inert anode assembly 1800 is an example of the inert anode assembly 1308. The anolyte flow channel 1802 defines an area where anolyte flows through the inert anode 1804. As shown, the width of the anolyte flow channel 1802 is less than the length of the anolyte flow channel 1802.

[0276] The inert anode assembly 1800 also includes a cathode chamber bottom component 1806 having an opening 1808. The opening 1808 is positioned opposite the anolyte flow channel 1802. In the example shown, the opening 1808 includes the same spiral path as the anolyte flow channel 1802. In other examples, the opening 1808 may include a different configuration than the anolyte flow channel 1802. During the electrodeposition process, the opening 1808 allows an ionic current to flow between the cathode electrolyte in the opening 1808 and the anolyte in the anolyte flow channel 1802. The inert anode assembly 1800 also includes an ion exchange membrane (not shown) positioned between the cathode chamber bottom component 1806 and the anolyte channel component 1810.

[0277] Fig.19 Another exemplary inert anode assembly 1900 is shown including an anolyte flow channel 1902 having a change in directionality. In this example, the anolyte flow channel 1902 includes a serpentine path. The inert anode assembly 1900 is an example of an inert anode assembly 1308. The anolyte flow channel 1902 defines an area where the anolyte flows through the inert anode 1904. As shown, the anolyte flow channel 1902 includes a length and a width, wherein the width is less than the length.

[0278] The inert anode assembly 1900 also includes a cathode chamber bottom component 1906 having an opening 1908. The opening 1908 is positioned opposite the anolyte flow channel 1902. In the example shown, the opening 1908 includes the same serpentine path as the anolyte flow channel 1902. In other examples, the opening 1908 may include a different configuration than the anolyte flow channel 1902. During the electrodeposition process, the opening 1908 allows an ionic current to flow between the cathode electrolyte in the opening 1908 and the anolyte in the anolyte flow channel 1902. The inert anode assembly 1900 also includes an ion exchange membrane (not shown) positioned between the cathode chamber bottom component 1906 and the anolyte channel component 1910.

[0279] When ions flow between the anolyte flow channel and the cathode chamber, the ion concentration in the anolyte and / or cathode electrolyte may change. For example, when the ion exchange membrane includes a cation exchange membrane, protons migrate from the anolyte to the cathode electrolyte. This may increase the acidity of the cathode electrolyte over time, and may require regular intervention to maintain the desired pH value. Therefore, in order to help reduce the proton flow to the cathode chamber, the electrodeposition system can use an intermediate channel component to define one or more intermediate flow channels through which the intermediate electrolyte flows. In some examples, the one or more intermediate flow channels can be separated from the anolyte flow channel by an anion exchange membrane and separated from the cathode chamber by a cation exchange membrane. The intermediate electrolyte may include a metal salt containing metal ions to be electrodeposited. When protons are generated in the anolyte at the inert anode, the anions in the intermediate solution can migrate through the anion exchange membrane to the anolyte flow channel where the inert anode is located, thereby balancing the charge. Likewise, metal ions can migrate through the cation exchange membrane to the cathode chamber for electrochemical reduction. Thus, it is easier to maintain the pH in the cathode chamber. An example of a metal salt that can be included in the intermediate electrolyte is copper sulfate.

[0280] Fig. 20An exemplary inert anode assembly 2000 including an intermediate channel component 2002 is schematically shown. The inert anode assembly 2000 is an example of the inert anode assembly 1308. The intermediate channel component 2002 at least partially defines an intermediate flow channel 2004. As described above, the intermediate flow channel 2004 is configured to maintain the flow of an intermediate electrolyte. The intermediate electrolyte may include a metal salt to provide metal ions to the cathode electrolyte and anions to the anode electrolyte.

[0281] The intermediate channel component 2002 is located between the cathode chamber bottom component 2006 and the anolyte channel component 2008. The intermediate electrolyte flows in a circulation loop through the intermediate flow channel 2004, the electrolyte storage tank 2010 and the pump 2012. The intermediate electrolyte can be replenished in the electrolyte storage tank 2010. The controller 2014 controls the flow rate generated by the pump 2012. Therefore, the controller 2014 can control the linear flow rate of the intermediate electrolyte through the intermediate flow channel 2004.

[0282] The opening 2016 of the intermediate flow channel 2004 is positioned opposite to the anolyte flow channel 2018. Thus, the opening 2016 allows anions from the intermediate electrolyte in the intermediate flow channel 2004 to pass through the anion exchange membrane 2020 and migrate to the anolyte in the anolyte flow channel 2018.

[0283] The anolyte flow enters a circulation loop from the anolyte flow channel 2018 to the anolyte storage tank 2022 and the pump 2024. The controller 2014 controls the pump 2024 and, therefore, the linear flow rate through the inert anode 2026. The anolyte flow channel 2018 can be configured to generate a sufficient linear flow rate to prevent bubbles from accumulating below the anion exchange membrane 2020. In addition, the middle channel component 2002 prevents bubbles from migrating to the cation exchange membrane 2030 located between the middle channel component 2002 and the cathode chamber bottom component 2006. This can further help prevent bubbles from affecting electroplating uniformity.

[0284] The opening 2016 of the intermediate flow channel 2004 is also positioned opposite the opening 2028 of the cathode chamber bottom member 2006. This configuration allows cations from the intermediate electrolyte in the intermediate flow channel 2004 to migrate across the cation exchange membrane 2030 to the cathode electrolyte in the opening 2028 of the cathode chamber bottom member 2006 during the electrodeposition process.

[0285] Although the intermediate channel component 2002 is shown as having a single intermediate flow channel, the inert anode assembly 2000 can include any other suitable number of intermediate flow channels between the anolyte flow channel and the opening of the cathode chamber. In addition, the inert anode assembly 2000 can include any suitable number of additional intermediate channel components and associated ion exchange membranes.

[0286] As previously mentioned, an inert anode assembly according to the present disclosure can help reduce bubble accumulation on an ion exchange membrane in an electrodeposition system. Fig.21 A flow chart of an exemplary method 2100 for operating an electrodeposition system is shown. The method 2100 can be performed on any suitable electrodeposition system including an inert anode assembly. Examples thereof include the electrodeposition system 1300 and the inert anode assemblies 1400, 1700, 1800, 1900, and 2000.

[0287] Method 2100 includes placing a substrate in a cathode chamber of an electrodeposition system at 2102. Method 2100 also includes exposing the substrate to a cathode electrolyte in the cathode chamber at 2104. The cathode electrolyte includes metal ions for electrodeposition on the substrate. Next, method 2100 includes generating cations and bubbles in an anolyte at an inert anode of an inert anode assembly during the electrodeposition process at 2106. In some examples, the anolyte may include an aqueous solution. Thus, the cations may include hydrogen cations, and the bubbles may include molecular oxygen produced via oxidation of water molecules. These cations and bubbles may be generated in a first anolyte flow channel at a first inert anode and in a second anolyte flow channel at a second inert anode, as shown in 2108. Alternatively or additionally, these cations and bubbles may be generated at a shared inert anode shared between anolyte flow channels, as shown in 2110.

[0288] Next, method 2100 includes flowing the anolyte at a sufficient linear flow rate at 2112 to prevent at least some bubbles from accumulating on the ion exchange membrane between the anolyte flow channel and the cathode electrolyte. This configuration can help to carry away bubbles in a suspended state. In this way, the bubbles will not gather into larger bubbles that interfere with electrodeposition. In addition, the linear flow rate through the inert anode can help to increase the mass transfer in the cathode electrolyte. In some examples, flowing the anolyte at a sufficient linear flow rate includes flowing the anolyte at a linear flow rate between 0.1 and 10 meters per second, as shown at 2114. In some examples, method 2100 includes limiting the anolyte flow to a segmented area by using two or more anolyte flow channels formed in the anolyte channel component of the inert anode assembly at 2116. Compared with a conventional anode chamber, this configuration can help to reduce the volume of the anolyte used in the electrodeposition system.

[0289] As described above, some inert anode assemblies include an intermediate flow channel through which an intermediate electrolyte flows. The intermediate flow channel can be separated from the anolyte flow channel by an anion exchange membrane. The intermediate flow channel can also be separated from the cathode chamber by a cation exchange membrane. Therefore, in some examples, method 2100 includes flowing the intermediate electrolyte through the intermediate flow channel between the anolyte flow channel and the cathode chamber at 2118. As described above, the use of the intermediate flow channel helps maintain the desired pH of the cathode electrolyte during electrodeposition.

[0290] Therefore, the use of the inert anode assembly described herein can help reduce or prevent bubble accumulation on the ion exchange membrane in the electrodeposition system. The reduction of bubble accumulation can help prevent electrodeposition non-uniformity. In addition, the use of the disclosed inert anode assembly can reduce the anolyte volume because the anolyte flow channel of the inert anode assembly has at least a smaller volume compared to other anode chambers.

[0291] Current bubble mitigation methods typically rely on the pitch and material "smoothness" of the ion exchange membrane to promote bubble movement, combined with increasing local fluid flow to direct bubbles away from the substrate surface. No matter how effective these variables are, bubbles will still accumulate below the permeable membrane and below the substrate. Therefore, this article also discloses examples involving management of bubbles generated at an inert anode during electrodeposition processing. In one example, the anode chamber includes a bubble deflector. The bubble deflector acts as a physical barrier to direct the bubble flow generated at the inert anode to a stilling structure, where the bubbles are discharged into the atmosphere. Ions can pass under the openings in the bubble deflector, or through these openings in the bubble deflector. Therefore, the ion current between the inert anode and the substrate is not interrupted by the bubble deflector.

[0292] In some examples, one or more inert anodes are positioned around the inner periphery of the anode chamber and outside the target area of ​​electrodeposition. The bubble deflector isolates the ion exchange membrane and substrate portion from the inert anode, so that the bubbles do not affect the electrodeposition performance. The voltage regulating structure can be located in the anolyte circulation loop. Therefore, the anolyte and bubbles can flow through the voltage regulating structure to remove the bubbles from the anolyte. A contactor can be used to remove any residual gas in the anolyte. Therefore, the anolyte returned to the anode chamber can be effectively degassed. In addition, in some examples, the bubble deflector includes a plurality of orifices that allow ionic current to pass through. The ionic current can be adjusted by changing the size of these orifices.

[0293] Before discussing these examples in more detail, Fig. 22 Schematically shown is a block diagram of another exemplary electroplating tool 2200. The electroplating tool 2200 includes an electroplating cell 2202 including an anode chamber 2204 and a cathode chamber 2206. The electroplating tool 2200 also includes an ion exchange membrane 2208 separating the anode chamber 2204 from the cathode chamber 2206, and a high resistance virtual anode (HRVA) 2209 located within the cathode chamber 2206. The HRVA 2209 includes an ion resistance element that approximates a suitable constant and uniform current source adjacent to the substrate cathode.

[0294] Anode chamber 2204 includes inert anodes 2210 and 2211. Anode chamber 2204 also includes an anolyte. Cathode chamber 2206 includes a catholyte. The catholyte includes ionic species to be deposited as metal on the cathode layer of substrate 2212 by electrochemical reduction. The anolyte includes a conductive electrolyte solution of a different composition than the catholyte. Sometimes, a bulk anolyte and / or catholyte solution can be added to supplement the ionic species.

[0295] The ion exchange membrane 2208 prevents organic substances and anionic substances from passing between the cathode chamber 2206 and the anode chamber 2204 , while allowing metal ions to pass from the anode chamber 2204 to the cathode chamber 2206 .

[0296] The substrate holder 2213 is coupled to a substrate holder movement system 2214, which includes a lifting device 2215 configured to adjust the spacing between the substrate holder 2213 and the HRVA 2209. For example, the lifting device 2215 can lower the substrate holder 2213 so that the substrate 2212 is located in the cathode electrolyte for electrodeposition. The lifting device 2215 can also raise the substrate holder 2213 from the cathode electrolyte after electrodeposition. The substrate holder movement system 2214 can also include components for controlling the opening and closing of the substrate holder 2213.

[0297] The catholyte may be circulated between the cathode chamber 2206 and the catholyte storage tank 2220 by a combination of gravity and one or more pumps 2222 in a catholyte circulation loop 2223. Similarly, the anolyte may be circulated through the anolyte storage tank 2224 and the anode chamber 2204 by a combination of gravity and one or more pumps 2226 in an anolyte circulation loop 2227.

[0298] In some electrodeposition tools, multiple plating tanks may be used to perform plating operations on multiple substrates in parallel. In some such examples, a central catholyte and / or anolyte storage tank may supply catholyte and / or anolyte to multiple plating tanks. In other such examples, separate catholyte storage tanks and / or anolyte storage tanks may be used to supply multiple plating tanks. In still other examples, the electrodeposition tool may include a single plating tank. In the case where the electrodeposition tool includes multiple plating tanks, a single lifting device may be configured to lift and lower two or more substrate holders for two or more different plating tanks.

[0299] After loading the substrate 2212 into the substrate holder 2213, the substrate holder 2213 is lowered toward the HRVA 2209 by the lifting device 2215. In some examples, the substrate holder 2213 can be rotated during electrodeposition via a rotary motor 2217. During electrodeposition, the substrate 2212 faces the surface of the HRVA 2209 and is separated from the HRVA 2209 by a plating gap. An electric field is established between the anodes 2210 and 2211 and the substrate 2212. The electric field drives the dissolved metal cations from the anode chamber 2204 into the cathode chamber 2206. At the substrate 2211, the metal cations are electrochemically reduced to deposit a metal film on the substrate 2212. The anode potential is applied to the anodes 2210 and 2211 through a charge plate 2228, and the cathode potential is provided to the cathode of the substrate 2212 through a cathode electrical connector 2229 to form a circuit. In some examples, anodes 2210 and 2211 are connected to the same anode potential. In other examples, anodes 2210 and 2211 are connected to different anode potentials.

[0300] As described above, the anodes 2210 and 2211 are inert anodes. Therefore, when an anode potential is applied to the anodes 2210 and 2211, protons and oxygen bubbles may be formed by the electrolysis of water. In order to prevent the oxygen bubbles from moving to the ion exchange membrane 2208 and interfering with the ion current directed to the substrate 2212, the anodes 2210 and 2211 are positioned toward the periphery of the anode chamber 2204. In addition, the bubble deflector 2230 is positioned within the anode chamber 2204, transversely between the anodes 2210 and 2211 and the ion exchange membrane 2208. The bubble deflector 2230 is configured to direct the bubble flow generated at the anodes 2210 and 2211 to the pressure regulating structure 2232, wherein the bubbles are discharged to the atmosphere at the pressure regulating structure.

[0301] In this example, a pressure regulating structure 2232 is located within the anolyte circulation loop 2227. A bubble diverter 2230 directs bubbles generated at the anode 2210 to a pressure regulating port 2233, and directs bubbles generated at the anode 2211 to a pressure regulating port 2234. The pressure regulating ports 2233 and 2234 direct the bubbles into the anolyte circulation loop 2227 upstream of the pressure regulating structure 2232. In this example, an additional pressure regulating conduit 2235 is used to connect the pressure regulating port 2233 to the anolyte circulation loop 2227.

[0302] The electroplating tool 2200 also includes a computing system 2240, aspects of which are described below with reference to Fig.30The computing system 2240 includes instructions that can be executed to control the functions of the electroplating tool 2200. In some examples, the computing system 2240 can be configured to communicate with a remote computing system 2245 via an appropriate computer network. The remote computing system 2245 can include any appropriate computing system. Examples include networked workstation computers, enterprise computing systems, and / or cloud computing systems. It should be understood that in some examples, the remote computing system 2245 can communicate with and control multiple electrodeposition systems.

[0303] Fig.23 An exemplary electrodeposition system 2300 including an inert anode is schematically shown, and protons ([H + ]) and the formation of oxygen bubbles (O). The electrodeposition system 2300 includes an anode chamber 2302 and a cathode chamber 2304. The electrodeposition system 2300 also includes an ion exchange membrane 2306 that separates the anode chamber 2302 and the cathode chamber 2304. The ion exchange membrane 2306 is supported by a membrane frame 2308. The electrodeposition system 2300 also includes a HRVA 2310 disposed in the cathode chamber 2304.

[0304] As above reference Figure 3 As shown, the anode chamber 2302 includes an anolyte bath 2312, and inert anodes 2314 and 2315 are disposed in the anolyte bath 2312. The cathode chamber 2304 includes a catholyte bath 2316, which includes ionic copper (Cu) to be deposited onto a substrate 2318 as a cathode. 2+ ). Although primarily described with respect to copper deposition, other metal ion chemistries such as, but not limited to, Au, Ag, Ni, Al, In, or Co, or metal alloy chemistries such as, but not limited to, Ni / P, Ni / Co, Ni / Zn, Au / Cu, or Sn / Ag may be used without departing from the scope of the present disclosure. During deposition, the substrate 2318 is held within a substrate holder 2319.

[0305] Anolyte bath 2312 is located within an anolyte circulation loop 2320, which includes a pump 2324 and an anolyte storage tank (not shown). Catholyte bath 2316 is located within a catholyte circulation loop 2322, which includes a pump 2326 and a catholyte storage tank 2328. Voltage source 2330 applies a voltage across substrate 2318 and inert anode 2314, thereby driving the flow of copper ions for deposition on substrate 2318.

[0306] The catholyte enters the cathode chamber 2304 at inlet 2332 and exits at outlet 2334. The anolyte bath 2312 contains Cu2+ In the case of ions, the ion exchange membrane 2306 makes Cu 2+ Ions are transported from the anolyte bath 2312 to the cation exchange membrane of the catholyte bath 2316. Any Cu that passes through the ion exchange membrane 2306 2+ The Cu ions replace at least some of the copper ions in the catholyte bath 2316 that are reduced to the substrate 2318. 2+ Ions can also be replenished from the catholyte storage tank 2328, regardless of the composition of the anolyte bath 2312. As shown, the ion exchange membrane 2306 can be a cation exchange membrane to allow protons to be transferred from the anolyte bath 2312 to the catholyte bath 2316. The ion current causes Cu 2+ The ions are deposited on substrate 2318 .

[0307] Anolyte enters anode chamber 2302 at inlet 2336 and exits at outlet 2338. However, there may be more inlets and outlets, and the inlets and / or outlets may additionally or alternatively be located on anode chamber base 2342, or in any suitable location.

[0308] As described above, for inert anodes 2314 and 2315, the oxidation and reduction reactions for copper electrodeposition include: 2H 2 O→O 2 +4H + +4e - (On inert anode) Cu +2 +2e - →Cu (on cathode) 2Cu 2+ +2H 2 O→2Cu+4H + +O 2 (Total Response)

[0309] Other metal species can also undergo similar reactions. Therefore, unlike the active anode, the inert anodes 2314 and 2315 do not produce metal cations in the anolyte bath 2312. Instead, the circulating anolyte flows through the inert anodes 2314 and 2315, where water molecules are oxidized to form molecular oxygen and hydrogen ions. For 1 mole of copper plated at the cathode, 0.5 moles of molecular oxygen and 2 moles of protons (H) are produced at the inert anode. + ). As described above, uniform electroplating at substrate 2318 relies on mitigating bubble accumulation at ion exchange membrane 2306 without interrupting the ionic current between inert anodes 2314 and 2315 and substrate 2318.

[0310] Bubbles generated at the inert anode will float upward. In conventional electrodeposition systems, where the inert anode is located at or near the center of the anode chamber and below the substrate, the bubbles will float onto the membrane frame. When the membrane frame is tilted upward toward the periphery of the anode chamber, these bubbles can drift toward the upper corners of the membrane frame, where vents can be provided to remove bubbles from the anolyte. However, if the membrane has any depressions between the membrane frame struts, bubbles may be trapped in these depressions.

[0311] Therefore, the electrodeposition system 2300 is designed to deflect the flow of bubbles so that they do not strike the membrane frame 2308 or the ion exchange membrane 2306. In this example, the inert anodes 2314 and 2315 are positioned toward the periphery of the anode chamber 2302 (e.g., closer to the anode chamber outer wall 2340 than to the center of the anode chamber 2302). In this way, bubbles floating directly upward from the inert anodes 2314 and 2315 are less likely to strike the ion exchange membrane 2306 than if the inert anodes were centered below the substrate 2318.

[0312] To further reduce the passage of bubbles toward the ion exchange membrane 2306, a bubble deflector 2345 is installed in the anode chamber 2302. Fig.23 As shown, the bubble deflector 2345 is positioned so that bubbles floating directly upward from the inert anodes 2314 and 2315 will travel on the side of the outer wall 2348 of the bubble deflector 2345 opposite the ion exchange membrane 2306. The bubble deflector 2345 is positioned between the membrane frame 2308 and the anode chamber base 2342. A membrane interface seal 2346 (e.g., an O-ring) is positioned between the membrane frame 2308 and the bubble deflector 2345. The membrane interface seal 2346 prevents bubbles from passing through the outer wall 2348 at the interface between the bubble deflector 2345 and the membrane frame 2308. The membrane frame 2308 can be fastened to the bubble deflector 2345 to apply a downward pressure on the bubble deflector 2345, thereby increasing the seal strength between the two components. The base of the bubble deflector 2345 can be attached to the anode chamber base 2342, placed on the anode chamber base 2342, or inserted into the anode chamber base 2342.

[0313] In this example, the inert anodes 2314 and 2315 are located outside of the bubble deflector 2345, and the ion exchange membrane 2306 is located inside the bubble deflector 2345. The outer wall 2348 of the bubble deflector 2345 separates the area of ​​the anode chamber 2302 adjacent to the ion exchange membrane 2306 from the area of ​​the anode chamber 2302 configured to direct the flow of bubbles to the anolyte circulation loop 2320. The bubble deflector 2345 can direct the flow of bubbles generated at the inert anodes 2314 and 2315 to the pressure regulating structure 2350, and these bubbles are discharged to the atmosphere at the pressure regulating structure 2350. The pressure regulating structure 2350 can be any suitable structure that allows undissolved gases to escape and evaporate into the atmosphere. The pressure regulating structure can be shaped as a cylinder, or have any other suitable configuration.

[0314] In the depicted example, the bottom edge 2352 of the bubble deflector 2345 is spaced from the anode chamber base 2342 to form a gap 2354 that allows an ionic current to flow between the inert anodes 2314 and 2315 and the ion exchange membrane 2306. The gap 2354 also allows the anolyte to flow under the bottom edge 2352 of the bubble deflector 2345. Protons generated at the inert anodes 2314 and 2315 flow toward the ion exchange membrane 2306, where they enter the catholyte bath 2316. The ionic current generated by these protons helps achieve deposition of the copper ion catholyte onto the substrate 2318.

[0315] In other examples described in more detail below, the bottom edge 2352 of the bubble deflector 2345 can include an orifice to pass ionic current and anolyte flow. In some examples, such an orifice can be covered by a membrane or mesh to further restrict the transport of bubbles to the ion exchange membrane 2306. In addition, as will be described with respect to Figures 26A-26B As further described in and 27A-27B, in some examples, these orifices include a variable open cross-sectional area. The opening size of the orifice, the thickness of the outer wall 2348, and the distance from the outer wall 2348 to the inert anodes 2314 and 2315 can be varied to control the ion current.

[0316] The bubble diverter 2345 is shaped to direct bubbles away from the ion exchange membrane 2306 and toward the pressure regulating structure 2350. In this example, the bubble diverter 2345 includes a conical region 2356 that directs bubbles generated at the inert anodes 2314 and 2315 toward the pressure regulating ports 2364 and 2365, respectively. In some examples, the bubble diverter 2345 includes grooves or channels on the outer surface to direct the bubbles.

[0317] Pressure regulating ports 2364 and 2365 are configured to direct bubbles away from anode chamber 2302 toward pressure regulating structure 2350. In this example, pressure regulating port 2364 leads to channel 2366, while pressure regulating port 2365 leads to channel 2367. Channels 2366 and 2367 are fluidly connected to anolyte circulation loop 2320. Anolyte circulation loop 2320 also passes through pressure regulating structure 2350 via conduit 2368. In some examples (e.g., regarding Fig.24 ), channels 2366 and 2367 merge with the anolyte circulation loop 2320 upstream of the pressure regulating structure 2350. The pressure regulating ports 2364 and 2365 can be positioned based in part on the fluid flow pattern from the anolyte circulation loop 2320 to further offset the transport of bubbles out of the anode chamber 2302. For example, the pressure regulating ports 2364 and 2365 can be positioned in areas where fluid velocity is locally high (e.g., at or near the inlet 2336 and / or outlet 2338).

[0318] In some examples, one or more sensors can be positioned inside and around the electrodeposition system 2300 to monitor conditions and provide an indication of electroplating non-uniformity, which can be an indication of bubble accumulation and / or other non-uniform ion currents through the ion exchange membrane 2306. For example, the electrodeposition system 2300 can include a cathode current sensor array 2372 and / or an optical sensor 2376. The cathode current sensor array 2372 can monitor the current at different locations at the substrate 2318. The optical sensor 2376 can be positioned to observe the surface of the ion exchange membrane 2306, thereby providing visual monitoring of bubble accumulation. The optical sensor 2376 can include a photodiode, a camera, and / or any other suitable optical sensing device. Additional optical sensors and / or other sensors other than the sensors shown can be positioned inside and around the electrodeposition system 2302.

[0319] Fig.24 An exemplary anolyte circulation loop 2400 is schematically shown. Anolyte circulation loop 2400 is an example of anolyte circulation loops 2227 and / or 2320. Anolyte circulation loop 2400 includes an anode chamber 2402, an anolyte storage tank 2404, and a circulation pump 2406. Although anolyte storage tank 2404 is shown as being located upstream of circulation pump 2406, anolyte storage tank 2404 may alternatively be located downstream of circulation pump 2406.

[0320] If gas accumulates in the recirculation line, in addition to affecting the ion current during electrodeposition, the bubbles will also hinder the flow of the anolyte circulation loop. In the anode chamber 2402, the bubble diverter 2408 guides the bubble flow to the anolyte circulation loop 2400. The pressure regulating structure 2410 is positioned upstream of the circulation pump 2406. The pressure regulating structure 2410 is exposed to the atmosphere. The pressure regulating structure 2410 can be formed of any material compatible with the chemical (the anode chamber 2402 is exposed to the chemical). In some examples, the pressure regulating structure 2410 can be made of tetrafluoroethylene tubing.

[0321] Anode chamber 2402 includes anolyte inlet 2412 and anolyte outlet 2414. Anode chamber 2402 also includes pressure regulating ports 2416 and 2418. Bubble diverter 2408 directs the flow of bubbles into pressure regulating ports 2416 and 2418, but some bubbles may also leave anode chamber 2402 via anolyte outlet 2414.

[0322] The pressure regulating port 2416 leads to a channel 2420, which is connected to the anolyte circulation loop 2400. Similarly, the pressure regulating port 2418 leads to a channel 2422, which is also connected to the anolyte circulation loop 2400. As shown, all outlet ports and channels leaving the anode chamber 2402 converge into a common flow line 2424, which leads to the pressure regulating structure 2410.

[0323] The pressure regulating structure 2410 can be high enough to prevent overflow and wide enough to allow most of the incoming bubbles to vent to the atmosphere. The height of the fluid column within the pressure regulating structure 2410 is typically at least higher than the height of the fluid within the anode chamber 2402, and in some examples higher than the total height of the fluid in the electrodeposition chamber.

[0324] Although the pressure regulating structure 2410 can remove most of the bubbles, dissolved gases may remain in the anolyte leaving the pressure regulating structure 2410. Therefore, the anolyte circulation loop 2400 further includes a contactor 2426 located downstream of the pressure regulating structure 2410 and upstream of the circulation pump 2406. The contactor 2426 is configured to remove dissolved gases from the circulating anolyte. For example, the contactor 2426 may include a filter or membrane with an applied vacuum 2428 that separates the fluid from the gas. The contactor 2426 may also include an exhaust port connected to a vacuum source to allow the gas to be released into the atmosphere.

[0325] After the anolyte passes through the pressure regulating structure 2410 and the contactor 2426, the anolyte returns to the anode chamber 2402 fully degassed. In some examples, the contactor 2426 can remove dissolved and undissolved gases. For example, during a relatively long period of electrodeposition processing that does not generate excessive bubbles and involves very low currents, the contactor 2426 can be used alone without the pressure regulating column.

[0326] Fig.25 A top view schematically shows the relative positions of some components of an exemplary electrodeposition system 2500. The electrodeposition system 2500 is an example of the electrodeposition system 2300. Shown within the electrodeposition system 2500 are the locations of the outer chamber wall 2505, the outer bubble deflector wall 2510, and the membrane frame periphery 2515. The substrate periphery 2520 is also shown. The outer bubble deflector wall 2510, the membrane frame periphery 2515, and the substrate periphery 2520 are shown as having slightly different diameters, but they may be more closely coincident in a physical example. The outer bubble deflector wall 2510 extends around a peripheral portion of the membrane frame periphery 2515. The outer bubble deflector wall 2510 is adjacent to the lower bubble deflector wall 2525 and is separated from the membrane frame periphery 2515 by a conical region (e.g., Fig.23 The conical area 2356 shown is connected.

[0327] The substrate periphery 2520 defines a substrate window 2530, such as Fig.25 The shaded area shown. The substrate window 2530 is a volume (cylindrical in this example) extending from the substrate to the base of the anode chamber of the electrodeposition system 2500. The substrate window 2530 can represent a target for the ion current passing through the ion exchange membrane, as well as a target to be kept free of bubbles. The inert anodes 2535 and 2537 are depicted as peripheral anodes and are positioned between the outer chamber wall 2505 and the lower bubble deflector wall 2525 and extend around the periphery of the substrate window 2530. The intensity of the ion current generated is a function of the distance 2545 between the inert anodes 2535 and 2537 and the lower bubble deflector wall 2525. Therefore, bubbles are generated at the inert anodes 2535 and 2537 outside the substrate window 2530 and are directed to the pressure regulating ports 2540 and 2542. The pressure regulating ports 2540 and 2542 are also located outside the substrate window 2530.

[0328] The ion current in the form of protons generated at the inert anode and passing through the bubble diverter is based in part on the open cross-sectional area of ​​the orifice. By adjusting the total cross-sectional area, the ion current density and / or flow rate can be adjusted accordingly. The bubble diverter orifice can be customized for a specific electrodeposition process, for example by machining the orifice to a desired height.

[0329] In some examples, the bubble deflector may include an adjustment mechanism configured to adjust the open cross-sectional area of ​​the multiple orifices. This adjustment can be made at set-up, in situ, between electrodeposition processes, or during processing. The adjustment can increase the size of the orifice to increase the flow of the ion current, and reduce the size of the orifice to reduce the flow of the ion current. For example, metrology can be used to evaluate a substrate that has been subjected to electrodeposition. If the metrology indicates that the ion current needs to be changed, the orifice can be adjusted before electrodeposition is performed on the next substrate. For example, some wafers have a higher seed resistance and may require more terminal effects than wafers with lower seed resistance. This adjustment allows the user to fine-tune the anode performance and provides flexibility compared to an electrodeposition system that only provides cathode adjustment capabilities.

[0330] As one example, the adjustment mechanism for varying the cross-sectional area of ​​the orifice of the bubble diverter may include a shutter system. Figures 26A-26B An exemplary shutter system is shown in FIG. At 2600, Fig.26A A portion of an anode chamber 2602 is shown, which includes a bubble deflector 2603 having an actuatable shutter system 2604 in a first configuration. Anode chamber 2602 is configured with an inert anode 2605 positioned in contact with an anolyte 2606. Application of a voltage V1 to the inert anode 2605 results in oxidation of water, thereby forming oxygen bubbles (as shown at 2608) and protons (as shown at 2610). The bubble deflector directs the bubbles to a pressure regulating port 2611.

[0331] The bubble deflector 2603 includes orifices 2612 and 2614, and each orifice has a rectangular cross-sectional area having a height (h) and a width (w1). A first shutter 2616 is associated with the orifice 2612, and a second shutter 2618 is associated with the orifice 2614. In this example, the first shutter 2616 and the second shutter 2618 adjust the cross-sectional area of ​​the orifices 2612 and 2614 by changing the opening width of the respective orifices. In other examples, the shutters can adjust the opening height. In some examples, each shutter is independently adjustable. In other examples, the shutters are adjusted in groups. For example, the first shutter 2616 and the second shutter 2618 can be part of a spiral rotatable ring of alternating orifices and solid portions located inside or outside the bubble deflector 2603. Therefore, movement of the rotatable ring will align or misalign the orifice of the ring with the orifice of the bubble deflector 2603, as if in an aperture configuration. The first shutter 2616 and the second shutter 2618 can be adjusted manually or automatically. For example, the controller 2620 can be used to send a signal to actuate a mechanism that adjusts the position of the first shutter 2616 and the second shutter 2618.

[0332] As shown at 2600, apertures 2612 and 2614 are maximally open with a width w1, thereby generating a maximum actuatable ionic current, as shown at 2625. Fig.26B , at 2650, the first shutter 2616 and the second shutter 2618 have been actuated by the controller 2620, thereby reducing the opening width of the apertures 2612 and 2614 from w1 to w2. As a result, the ion current drops from the maximum actuatable ion current, as shown at 2655. It is noteworthy that this change in the ion current does not require adjustment of the applied voltage V1.

[0333] Figures 27A-27B Another system for regulating the ion current through the bubble diverter is shown in FIG. At 2700, Fig.27A A portion of an anode chamber 2702 is shown, which includes a bubble deflector 2703 in a first configuration that can move relative to a base 2704 of the anode chamber 2702. The anode chamber 2702 is configured to have an inert anode 2705 positioned to contact an anolyte 2706. Application of a voltage V1 to the inert anode 2705 causes water oxidation to form oxygen bubbles (as shown at 2708) and protons (as shown at 2710). The bubble deflector directs the bubbles to a pressure regulating port 2711. The bubble deflector 2703 includes orifices 2712 and 2714 disposed along a lower end of the bubble deflector 2703, and each orifice has a rectangular cross-sectional area having a height (h) and a width (w1). A controller can be used to actuate an adjustment mechanism 2719. The adjustment mechanism 2719 can be, for example, a motor or a pneumatic device, and can be a mechanism that can operate to adjust the position of the bubble deflector relative to the base of the anode chamber. As shown at 2700, the bottom edge 2720 of the bubble deflector 2703 is adjacent to the substrate 2704, thereby producing a minimum actuatable ionic current, as shown at 2722.

[0334] exist Fig.27B 2750, the adjustment mechanism 2719 has been actuated by the controller 2718 to raise the bubble diverter 2703. In this configuration, the bottom edge 2720 of the bubble diverter 2703 is no longer in contact with the substrate 2704. Instead, a gap 2752 having a height h2 is created around the periphery of the bubble diverter 2703. The ion current through the bubble diverter 2703 is thereby increased, as shown at 2755. In some examples, a portion of the bubble diverter 2703 is inserted into the substrate 2704 so that the height h1 of the orifices 2712 and 2714 can be adjusted. For example, a dynamic seal can be provided around a hole in the substrate 2704 so that a portion of the bubble diverter is raised into the substrate 2704 and lowered out of the substrate 2704.

[0335] Fig.28 A flow chart is shown for illustrating an exemplary method 2800 for operating an electrodeposition system (e.g., an electroplating tool 2200, an electrodeposition system 2300, and an electrodeposition system including an anode chamber 2602 or 2702). At 2810, the method 2800 includes generating bubbles at an inert anode located in an anode chamber of the electrodeposition system by applying a voltage between the inert anode and the substrate. At 2820, the method 2800 includes directing the bubbles generated at the inert anode to a pressure regulating structure exposed to the atmosphere by using a bubble deflector. In some examples, directing the bubbles to the pressure regulating structure includes: offsetting the flow of the bubbles to at least one channel leading to an anolyte circulation loop. In some examples, the method 2800 also includes causing the anolyte to flow through the anolyte circulation loop so that the bubbles enter the pressure regulating structure upstream of the circulation pump. In some examples, the method 2800 also includes causing the anolyte to flow through a contactor located downstream of the pressure regulating structure, the contactor being configured to remove dissolved gases from the anolyte.

[0336] Fig.29 A flow chart is shown for illustrating an exemplary method 2900 for adjusting an ion current in an electrodeposition system including an inert anode (e.g., an electrodeposition system including an anode chamber 2602 or 2702). At 2910, the method 2900 includes generating an ion current at an inert anode. At 2920, the method 2900 includes causing the ion current to flow through an orifice of a bubble deflector. At 2930, the method 2900 includes adjusting the ion current at the substrate by adjusting an open cross-sectional area of ​​at least one orifice of the bubble deflector in response to an indication of electroplating performance. In some examples, the open cross-sectional area of ​​the orifice passes through a shutter system. In some examples, the open cross-sectional area of ​​the orifice can be adjusted by adjusting the position of the bubble deflector relative to the substrate of the anode chamber. As an example, adjusting the ion current includes maintaining a voltage applied between the inert anode and the substrate. In some examples, adjusting the ion current can be performed during an electroplating operation. In addition, in some examples, adjusting the ion current can be performed prior to an electroplating operation. In some examples, the indication of the electroplating performance includes a current sensed at the substrate.

[0337] This method can help to carry away bubbles generated at the inert anode while the bubbles are suspended. In this way, the bubbles are prevented from depositing on the ion exchange membrane and interfering with the electrodeposition.

[0338] In some embodiments, the methods and processes described herein may be combined with a computing system of one or more computing devices. Specifically, such methods and processes may be implemented as a computer application or service, an application programming interface (API), a library, and / or other computer program products.

[0339] Fig.30 A non-limiting example of a computing system 3000 is schematically shown that can perform one or more of the methods and processes described above. The computing system 3000 is shown in simplified form. The computing system 3000 can take the form of one or more personal computers, workstations, computers integrated with substrate processing tools, and / or network accessible server computers.

[0340] The computing system 3000 includes a logic subsystem 3002 and a storage subsystem 3004. The computing system 3000 may optionally include a display subsystem 3006, an input subsystem 3008, a communication subsystem 3010, and / or Fig.30 Computing system 130, remote computing system 140, and controller 1350 are examples of computing system 3000. Computing systems 150, 152, 1340, 2240, and 2245, and controllers 1608, 2014, 2620, and 2178 are examples of computing system 3000.

[0341] The logic subsystem 3002 includes one or more physical devices configured to execute instructions. For example, the logic subsystem can be configured to execute instructions that are part of one or more applications, services, programs, routines, libraries, objects, components, data structures, or other logical constructs. Such instructions can be implemented to perform tasks, implement data types, transform the state of one or more components, achieve technical effects, or otherwise achieve desired results.

[0342] The logic subsystem may include one or more processors configured to execute software instructions. Additionally or alternatively, the logic subsystem may include one or more hardware or firmware logic subsystems configured to execute hardware or firmware instructions. The processor of the logic subsystem may be single-core or multi-core, and the instructions executed thereon may be configured for sequential, parallel and / or distributed processing. The various components of the logic subsystem may optionally be distributed in two or more separate devices that may be remotely located and / or configured for coordinated processing. Various aspects of the logic subsystem may be virtualized and executed by a remotely accessible networked computing device configured in a cloud computing configuration.

[0343] The storage subsystem 3004 includes one or more physical devices configured to store instructions 3012 that can be executed by the logic subsystem to implement the methods and processes described herein. When such methods and processes are implemented, the state of the storage subsystem 3004 can be transformed—for example, to store different data.

[0344] The storage subsystem 3004 may include removable and / or built-in devices. The storage subsystem 3004 may include optical storage (e.g., CD, DVD, HD-DVD, Blu-ray disc, etc.), semiconductor storage (e.g., RAM, EPROM, EEPROM, etc.), and / or magnetic storage (e.g., hard disk drive, floppy disk drive, tape drive, MRAM, etc.). The storage subsystem 3004 may include volatile, non-volatile, dynamic, static, read / write, read-only, random access, sequential access, location addressable, file addressable, and / or content addressable devices.

[0345] It should be understood that storage subsystem 3004 includes one or more physical devices. However, alternatively, aspects of the instructions described herein may be propagated via a communication medium (eg, electromagnetic signals, optical signals, etc.) that is not held for a limited duration by a physical device.

[0346] Aspects of the logic subsystem 3002 and the storage subsystem 3004 may be integrated together into one or more hardware logic components. For example, such hardware logic components may include field programmable gate arrays (FPGAs), program and application specific integrated circuits (PASIC / ASIC), program and application specific standard products (PSSP / ASSP), systems on chips (SOCs), and complex programmable logic devices (CPLDs).

[0347] When included, the display subsystem 3006 can be used to present a visual representation of the data stored by the storage subsystem 3004. The visual representation can take the form of a graphical user interface (GUI). Since the methods and processes described herein change the data held by the storage subsystem, and therefore change the state of the storage subsystem, the state of the display subsystem 3006 can also be converted to visually represent the changes in the underlying data. The display subsystem 3006 can include one or more display devices using almost any type of technology. Such a display device can be combined with the logic subsystem 3002 and / or the storage subsystem 3004 in the shared cabinet, or such a display device can be a peripheral display device.

[0348] When included, the input subsystem 3008 may include or may interact with one or more user input devices (e.g., a keyboard, mouse, or touch screen). In some examples, the input subsystem may include or interact with selected natural user input (NUI) components. Such components may be integrated or peripheral, and the conversion and / or processing of input actions may be handled on-board or off-board. Exemplary NUI components may include microphones for voice and / or sound recognition, and infrared, color, stereo, and / or depth cameras for machine vision and / or gesture recognition.

[0349] When included, the communication subsystem 3010 can be configured to communicatively couple the computing system 3000 with one or more other computing devices. The communication subsystem 3010 can include wired and / or wireless communication devices compatible with one or more different communication protocols. As non-limiting examples, the communication subsystem can be configured to communicate via a wireless telephone network, or a wired or wireless local area network or wide area network. In some examples, the communication subsystem can allow the computing system 3000 to send messages to other devices and / or receive messages from other devices via a network such as the Internet.

[0350] It should be understood that the configuration and / or method described herein is exemplary in nature, and these specific one or more examples should not be considered restrictive, because many variations are possible. The specific routine or method described herein can represent one or more of any number of processing strategies. Therefore, the various actions shown and / or described can be performed in the order shown and / or described, in other orders, in parallel or omitted. Similarly, the order of the above-mentioned processing can be changed.

[0351] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts, and / or properties disclosed herein, as well as any and all equivalents thereof.

Claims

1. An electrodeposition system comprising: substrate holder; a cathode chamber configured to contain a catholyte; an anode chamber comprising an inert anode, the anode chamber being configured to contain an anolyte; as well as The intermediate chamber is located between the cathode chamber and the anode chamber, and the intermediate chamber is separated from the cathode chamber by an ion exchange membrane.

2. The electrodeposition system according to claim 1, wherein: The intermediate chamber is separated from the anode chamber by a proton blocking structure.

3. The electrodeposition system according to claim 2, wherein: The proton-blocking structure comprises a metal redox barrier configured to: receiving growth of a metal film on the anodic side of the metal redox barrier by a reduction reaction of metal ions from an anolyte in contact with the anodic side of the metal redox barrier, and Through the oxidation reaction of the metal redox barrier, metal ions are provided to a solution in contact with the cathode side of the metal redox barrier.

4. The electrodeposition system of claim 3, further comprising a mechanical biasing element for biasing the metal redox barrier toward the intermediate chamber.

5. The electrodeposition system according to claim 3, wherein: The metal redox barrier is configured to be rotatable to allow the orientation of the anode side and the cathode side to alternately face the intermediate chamber.

6. The electrodeposition system according to claim 2, wherein: The proton blocking structure includes an anion exchange membrane.

7. The electrodeposition system according to claim 6, wherein: The ion exchange membrane separating the intermediate chamber from the cathode chamber comprises a second anion exchange membrane.

8. The electrodeposition system according to claim 6, wherein: The ion exchange membrane separating the intermediate chamber and the cathode chamber comprises a cation exchange membrane.

9. The electrodeposition system of claim 6, further comprising a redox shuttle circulation system configured to provide a redox shuttle species to the anode chamber.

10. The electrodeposition system according to claim 9, wherein: The redox shuttle circulation system includes a redox shuttle material regeneration chamber.

11. The electrodeposition system according to claim 1, wherein: The ion exchange membrane is a first cation exchange membrane, and wherein the intermediate chamber is separated from the anode chamber by a second cation exchange membrane.

12. The electrodeposition system of claim 11, further comprising: A copper oxide module is fluidly coupled to the intermediate chamber.

13. An electrodeposition system comprising: a cathode chamber configured to contain a catholyte; a substrate holder configured to expose a substrate to the catholyte during an electrodeposition process; as well as An inert anode assembly comprising: one or more inert anodes, two or more anolyte flow channels defining segmented areas of anolyte flow across the one or more inert anodes, and An ion exchange membrane is located between the cathode chamber and the two or more anolyte flow channels.

14. The electrodeposition system according to claim 13, wherein: The inert anode assembly also includes a cathode chamber bottom member including an opening positioned relative to an anolyte flow channel of the two or more anolyte flow channels.

15. The electrodeposition system according to claim 14, wherein: The two or more anolyte flow channels are formed in an anolyte channel member, and wherein the ion exchange membrane is located between the cathode chamber bottom member and the anolyte channel member.

16. The electrodeposition system according to claim 15, wherein: The inert anode assembly further comprises an intermediate channel component between the cathode chamber bottom component and the anode electrolyte channel component, wherein the ion exchange membrane is a first ion exchange membrane between the intermediate channel component and the anode electrolyte channel component, and the inert anode assembly further comprises a second ion exchange membrane between the cathode chamber bottom component and the intermediate channel component.

17. An electrodeposition system comprising: a cathode chamber configured to contain a catholyte; an anode chamber configured to contain an anolyte; a membrane frame supporting an ion exchange membrane between the cathode chamber and the anode chamber; a substrate holder configured to expose a substrate to the catholyte during an electrodeposition process; an inert anode located in the anode chamber; as well as A bubble diverter is positioned to direct the flow of bubbles generated at the inert anode to a pressure regulating structure where the bubbles are exhausted to the atmosphere.

18. The electrodeposition system of claim 17, wherein: The bubble deflector extends around a peripheral portion of the ion exchange membrane.

19. The electrodeposition system according to claim 17 further includes an anode electrolyte circulation loop, the anode electrolyte circulation loop includes a circulation pump, wherein the bubble deflector guides the flow of bubbles to the anode electrolyte circulation loop, and wherein the pressure regulating structure is located upstream of the circulation pump, and the pressure regulating structure is exposed to the atmosphere.

20. The electrodeposition system of claim 19, wherein: The anolyte circulation loop also includes a contactor located downstream of the pressure regulating structure and upstream of the circulation pump, the contactor being configured to remove dissolved gas from the anolyte.

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