Multi-compartment electrochemical recharge cell

Abstract

Electroplating systems may include an electroplating chamber. These systems may also include a replenishment assembly coupled to the electroplating chamber fluid. The replenishment assembly may include a first compartment containing an anode material. The first compartment may include a first compartment section containing the anode material and a second compartment section separated from the first compartment section by a spacer. The replenishment assembly may include a second compartment coupled to the electroplating chamber fluid and electrically coupled to the first compartment. The replenishment assembly may also include a third compartment electrically coupled to the second compartment, the third compartment including an inert cathode.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Patent Application No. 17 / 078,413, filed on October 23, 2020, entitled “MULTI-COMPARTMENT ELECTROCHEMICAL REPLENISHMENT CELL,” which is hereby incorporated by reference in its entirety. Technical Field

[0003] The present technology relates to electroplating operations in semiconductor processing. More specifically, the present technology relates to systems and methods for performing ion replenishment for an electroplating system. Background Art

[0004] Integrated circuits are made possible by processes that create intricately patterned layers of material on a substrate surface. After forming, etching, and other processing on the substrate, metal or other conductive material is often deposited or formed to provide electrical connections between components. Because this metallization can be performed after many manufacturing operations, problems that occur during this metallization can result in expensive scrapped substrates or wafers.

[0005] Electroplating is performed in an electroplating chamber, wherein the device side of the wafer is in a bath of a liquid electrolyte, and the electrical contacts on the contact ring contact the conductive layer on the wafer surface. Current flows through the electrolyte and the conductive layer. The metal ions in the electrolyte are plated outward onto the wafer, thereby producing a metal layer on the wafer. Electroplating chambers usually have consumable anodes, which are beneficial to the stability of the bath and the cost of the owner. For example, consumable copper anodes are often used when copper is plated. The copper ions taken out from the plating bath are replenished by the copper removed from the anode, thereby maintaining the metal concentration in the plating bath. Although effective when replacing the metal ions electroplated, the use of consumable anodes requires relatively complex and expensive designs to enable the consumable anodes to be replaced. When the consumable anode is combined with the membrane to avoid degrading the electrolyte or oxidizing the consumable anode during the idle state, even more complexity is added.

[0006] Therefore, there is a need for improved systems and methods that can be used to produce high quality devices and structures while protecting both the substrate and the plating bath. These and other needs are addressed by the present technology. Summary of the invention

[0007] Electroplating systems may include an electroplating chamber. These systems may also include a replenishment assembly coupled to the electroplating chamber fluid. The replenishment assembly may include a first compartment containing an anode material. The first compartment may include a first compartment section and a second compartment section, in which the anode material is contained, and the second compartment section is separated from the first compartment section by a divider. The replenishment assembly may include a second compartment coupled to the electroplating chamber fluid and electrically coupled to the first compartment. The replenishment assembly may also include a third compartment electrically coupled to the second compartment, and the third compartment includes an inert cathode.

[0008] In some embodiments, the system may include a voltage source coupling the anode material to the inert cathode. The first compartment may include an anolyte, the second compartment may include a catholyte, and the third compartment may include a sampling electrolyte. The third compartment may be fluidly coupled to the electroplating chamber to deliver a sampling electrolyte between the third compartment and the electroplating chamber. The second compartment may be fluidly coupled to the electroplating chamber. The system may include a first ionic membrane positioned between the second compartment segment of the first compartment and the second compartment. The system may include a second ionic membrane positioned between the second compartment and the third compartment. The second ionic membrane may be a monovalent membrane. The system may include a pump fluidly coupled between the first compartment segment of the first compartment and the second compartment segment of the first compartment. The pump is operable in a first setting to flow the anolyte from the first compartment segment of the first compartment to the second compartment segment of the first compartment. A fluid path may be defined around the spacer so that when the pump is operated in the first setting, the anolyte flows from the second compartment section of the first compartment to the first compartment section of the first compartment. The pump is operable in the second setting to completely drain the anolyte from the second compartment section of the first compartment. The system may include an insert located in the second compartment. The insert may define at least one fluid channel along the insert. The system may include a compartment disposed within the first compartment section of the first compartment. The compartment may accommodate the anode material. The spacer may be an ion membrane that isolates the flow path fluid between the first compartment section of the first compartment to the second compartment section of the first compartment.

[0009] Some embodiments of the present technology may include a method of operating an electroplating system. The method may include driving a voltage through a replenishment assembly. The replenishment assembly may include a first compartment containing an anode material. The first compartment may have a first compartment section and a second compartment section, the anode material is contained in the first compartment section, and the second compartment section is separated from the first compartment section by a spacer. The replenishment assembly may include a second compartment coupled to a plating chamber fluid and electrically coupled to the first compartment. The replenishment assembly may include a third compartment electrically coupled to the second compartment. The third compartment may include an inert cathode. The voltage may be driven from the anode material to the inert cathode through the first compartment section of the first compartment, the second compartment section of the first compartment, the second compartment, and the third compartment. The method may include providing ions of the anode material to a cathode electrolyte flowing through the second compartment.

[0010] In some embodiments, the method may include reversing the voltage between the anode material and the inert cathode. The method may include removing the plated anode material from the inert cathode. The method may include pumping the anolyte from the second compartment section of the first compartment to the first compartment section of the first compartment to empty the second compartment section of the first compartment. The replenishment assembly may include a first ion membrane positioned between the second compartment section of the first compartment and the second compartment. The replenishment assembly may include a second ion membrane positioned between the second compartment and the third compartment. The pumping may maintain the first ion membrane in contact with only the catholyte fluid.

[0011] Some embodiments of the present technology may include an electroplating system. The system may include an electroplating chamber. The system may include a replenishment assembly fluidically coupled to the electroplating chamber. The replenishment assembly may include a first compartment containing an anode material and an anolyte. The first compartment may have a first compartment section and a second compartment section, the anode material being contained in the first compartment section, and the second compartment section being separated from the first compartment section by a spacer. A fluid circuit may be defined between the first compartment section and the second compartment section. The replenishment assembly may include a second compartment fluidically coupled to the electroplating chamber and electrically coupled to the first compartment. The second compartment may include a cathode electrolyte. The replenishment assembly may include a first ion membrane positioned between the second compartment section of the first compartment and the second compartment. The replenishment assembly may include a third compartment electrically coupled to the second compartment. The third compartment may include an inert cathode. The third compartment may include an acid sampling electrolyte. The replenishment assembly may include a second ion membrane positioned between the second compartment and the third compartment. In some embodiments, the spacer may be a third ion membrane.

[0012] This technology can provide numerous benefits over conventional technologies. For example, the present technology can limit additive losses during system idle states. In addition, the system can also limit plating defects caused by entrained air in the catholyte. These and other embodiments and many of their advantages and features are described in more detail in conjunction with the following description and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] A further understanding of the nature and advantages of the various disclosed embodiments may be realized by reference to the remainder of the specification and the appended drawings.

[0014] Figure 1 A schematic diagram of an electroplating processing system according to some embodiments of the present technology is shown.

[0015] Figure 2 A cross-sectional view of an inert anode according to some embodiments of the present technology is shown.

[0016] Figure 3 A schematic diagram of a resupply assembly according to some embodiments of the present technology is shown.

[0017] Figure 4 A schematic cross-sectional view of a resupply assembly according to some embodiments of the present technology is shown.

[0018] Figure 5 A schematic cross-sectional view of a resupply assembly according to some embodiments of the present technology is shown.

[0019] Figure 6 A schematic cross-sectional view of a resupply assembly according to some embodiments of the present technology is shown.

[0020] Figure 7 A schematic perspective view of an anode material container according to some embodiments of the present technology is shown.

[0021] Figure 8 A schematic perspective view of a cell insert according to some embodiments of the present technology is shown.

[0022] Fig. 9 A schematic cross-sectional partial view of a tank insert in a replenishment assembly according to some embodiments of the present technology is shown.

[0023] Fig.10 Exemplary operations in a method of operating an electroplating system in accordance with some embodiments of the present technology are shown.

[0024] Several of the drawings are included as schematic diagrams. It should be understood that these drawings are for illustrative purposes and are not to be considered drawn to scale unless specifically stated to be drawn to scale. In addition, as schematic diagrams, these drawings are provided to aid understanding and may not include all aspects or information compared to realistic representations and may include exaggerated material for illustrative purposes.

[0025] In the figures, similar parts and / or features may have the same reference numeral. In addition, various parts of the same type may be distinguished by following the reference numeral with a letter that distinguishes among the similar parts and / or features. If only the first numerical reference numeral is used in the specification, the description can be used for any of the similar parts and / or features having the same first numerical reference numeral without regard to their letter suffix. DETAILED DESCRIPTION

[0026] Various operations are performed in semiconductor manufacturing and processing to create a large number of features throughout the substrate. As the layers of semiconductor are formed, vias, trenches and other pathways are created in the structure. These features can then be filled with conductive or metallic materials that enable electricity to be conducted through the device from one layer to another.

[0027] Electroplating operations can be performed to provide conductive material into vias and other features on a substrate. Electroplating utilizes an electrolyte bath containing ions of conductive material to electrochemically deposit the conductive material onto a substrate and into features defined on the substrate. The substrate on which the metal is being plated works as a cathode. Electrical contacts such as rings or pins can enable current to flow through the system. During electroplating, the substrate can be clamped to a head and immersed in an electroplating bath to form a metallization. Metal ions can be deposited on the substrate from the bath.

[0028] In an electroplating system utilizing an inert anode, an additional source of metal ions may be used to replenish the catholyte solution. The present technology utilizes a separate replenishment assembly that can utilize an anode material to replace the metal ions being plated into the catholyte solution. Such an assembly can be fluidly coupled to multiple plating chambers, which can help limit downtime for additional replenishment materials. However, new challenges can occur when the system is not being operated.

[0029] The replenishment module may have an anolyte, a catholyte, and a sampling electrolyte included in a separate compartment of a replenishment assembly separated by two membranes located between the compartments. During the idle state, additives may be lost despite limited ion transport. The plating bath may include organic compounds and other additives that promote the plating operation. For example, accelerators, levelers, and suppressors for certain ions may be included in the catholyte solution. These additives may be deposited on the membrane or may be transmitted from the catholyte in addition, which may adversely affect subsequent electroplating if they are not replaced. This loss can be reduced by draining the fluid compartment during the idle state, but this may lead to additional challenges. Draining the anolyte compartment may expose the anode material to air, which may cause oxidation to occur and limit functionality. Draining the catholyte compartment and then refilling it at startup will introduce bubbles into the catholyte fluid loop, which may affect deposition by creating pores at the wafer.

[0030] The replenishment assembly according to the present technology can overcome these problems by including a spacer in the anolyte compartment of the three-compartment module. By allowing a portion of the anolyte compartment to be emptied into the main part of the anolyte compartment, the anode material can be maintained immersed in the anolyte while an air gap can be formed in the adjacent catholyte compartment. Advantageously, this can also maintain all fluid membranes in contact with the fluid on a single side during the idle state of the system. This can limit the drying of the membrane, which would otherwise shrink and rupture when drying. Although emptying and filling the anolyte compartment can entrain a certain amount of air in the loop, this is not disadvantageous to the process because the anolyte may not be in contact with the workpiece. On the other hand, emptying and filling the catholyte compartment can entrain air that contacts the substrate being processed, and this can cause plating defects on substrates where plating has not occurred. After describing an exemplary system in which an embodiment of the present technology can be incorporated, the remaining disclosure will discuss various aspects of the system and processing of the present technology.

[0031] Figure 1 A schematic diagram of an electroplating processing system according to some embodiments of the present technology is shown. Figure 1In the embodiment of the present invention, the electroplating chamber 20 may include a rotor 24 in the head 22 for holding a wafer 50. The rotor 24 may include a contact ring 30 that can be moved vertically to engage a contact finger 35 on the contact ring 30 to a downwardly facing surface of the wafer 50. The contact finger 35 may be connected to a negative voltage source during electroplating. The bellows 32 may be used to seal the internal components of the head 22. The motor 28 in the head may rotate the wafer 50 held in the contact ring 30 during electroplating. The chamber 20 may alternatively have a variety of other types of heads 22. For example, the head 22 may operate with a wafer 50 held in a chuck without directly handling the wafer 50, or the rotor and motor may be omitted so that the wafer remains stationary during electroplating. The seal on the contact ring may seal against the wafer to seal the contact finger 35 away from the cathode electrolyte during processing. The head 22 may be positioned above a plating container 38 of the electroplating chamber 20. One or more inert anodes may be disposed in the plating container 38. In the example shown, the electroplating chamber 20 may include an inner anode 40 and an outer anode 42. Multiple electroplating chambers 20 may be arranged in a row within an electroplating system in which wafers are moved using one or more robots.

[0032] Figure 2 A cross-sectional view of an inert anode according to some embodiments of the present technology is shown. Figure 2 In the embodiment of the present invention, the inner anode 40 and the outer anode 42 may include a wire 45 located in the anode membrane tube 47. The anode membrane tube 47 may have an outer protective sheath or covering 49. The anode membrane tube 47 including the electrode wire may be circular, or optionally formed into a spiral, or linear array, or other forms suitable for establishing an electric field suitable for the workpiece to be processed. In some embodiments, the wire 45 may be a platinum wire up to 2 mm in diameter in the 2-3 mm inner diameter anode membrane tube 47. The wire 45 may also be a platinum clad wire with an inner core of another metal such as niobium, nickel, or copper. A resistive diffuser may be provided in a container and located above the inert anode. A flow space 51 may be provided around the wire 45 in the anode membrane tube 47. Although the wire 45 may be nominally located in the center of the anode membrane tube 47, in fact the position of the wire in the membrane tube changes at certain positions so that the wire may touch the inner wall of the membrane tube. A gasket may be used to maintain the wire in the tube, although it may be necessary to have no gasket or other techniques to center the wire in the membrane tube.

[0033] Figure 1In addition shown in the figure is a three-compartment supply assembly 70, which will be described in further detail below. During electroplating, the treatment anolyte can be pumped by treating the anolyte loop, and the treatment anolyte loop includes an anode film tube 47 and a treatment anolyte chamber 150, which is a treatment anolyte source for the inner anode 40 and the outer anode 42. The film tube forming the inner anode 40 and the outer anode 42 can be formed as an annular or circular shape, contained in the circular groove 41 in the anode plate 43 of the electroplating container 38, and as shown in the figure, the film tube is placed on the bottom plate of the electroplating container 38. The supply system 70 can be located outside the chamber 20 because it is a separate unit that can be located in the treatment system, away from the processor. This can allow the supply assembly to be coupled with a plurality of electroplating chamber fluids, wherein the supply assembly supplies the catholyte used by any number of chambers.

[0034] The lead 45 of each inner anode 40 and outer anode 42 can be electrically connected to a positive voltage source relative to the voltage applied to the wafer to set up an electric field in the container. Via the electrical connector 60 on the electroplating container 38, each inert anode can be connected to a power supply channel, or they can be connected to separate power supply channels. One to four inert anodes can be used usually. The anolyte flowing through the membrane tube can take gas out of the container. In use, the voltage source can induce current flow, causing the water at the inert anode to be converted into oxygen and hydrogen ions and copper ions to be deposited on the wafer from the cathode electrolyte.

[0035] The wires 45 in the inner anode 40 and the outer anode 42 may be inert and may not chemically react with the anolyte. The wafer 50, or the conductive seed layer on the wafer 50, may be connected to a negative voltage source. During electroplating, the electric field within the electroplating vessel 38 may cause the metal ions in the catholyte to be deposited onto the wafer 50, thereby creating a metal layer on the wafer 50.

[0036] The metal layer plated onto the wafer 50 may be formed by metal ions in the chamber catholyte that move to the wafer surface due to ion diffusion in the chamber catholyte flow and the plating vessel 38. A catholyte replenishment system 70 may be coupled to the plating chamber fluid to supply metal ions back to the system catholyte. The replenishment system 70 may include a chamber catholyte return line, which may be or include a tube or pipe, and a chamber catholyte supply line 78 connected to a replenishment assembly 74 in a catholyte circulation loop. In some embodiments, additional catholyte tanks may be included in the catholyte circulation loop, wherein the chamber catholyte tanks supply catholyte to multiple plating chambers 20 within the processing system. The catholyte circulation loop may include at least one pump, and may also include other components such as heaters, filters, valves, and any other fluid loop or circulation components. The replenishment assembly 74 may be aligned with the catholyte return flow, or it may alternatively be connected in a separate flow loop leaving and returning to the catholyte tank.

[0037] Figure 3 A schematic diagram of a replenishment assembly according to some embodiments of the present technology is shown, and details of the replenishment assembly described further below can be provided. The figure shows an enlarged schematic diagram of a replenishment assembly 74 as an operating component, which can be applicable to any number of specific replenishment assembly configurations including those described below. The replenishment assembly anolyte can be circulated in the replenishment assembly 74 through a replenishment assembly anolyte loop 90 and an optional replenishment assembly anolyte tank 96, and the replenishment assembly anolyte loop 90 includes a replenishment assembly anolyte compartment 98, which can be the first compartment of the replenishment assembly. In some embodiments, such as for copper electroplating, the replenishment assembly anolyte can be an acid-free copper sulfate electrolyte, although it is understood that the system can be used for any number of electroplating operations that utilize chemistry and materials suitable for these operations. The anolyte replenishment assembly in the replenishment assembly 74 can be free of a recirculation loop and can include only an anolyte compartment 98. A gas sparger, such as a nitrogen sparger, can provide agitation to the supply assembly without the complication of a recirculation loop requiring a piping system and a pump. Referring again to the copper electroplating system, as a non-limiting example, if a low acid electrolyte or an anolyte is used, when current flows through the supply assembly, the Cu 2+ Ions (but not protons) can be transported or moved across the membrane into the catholyte. Gas sparging can also reduce oxidation of bulk copper materials.

[0038] Deionized water supply line 124 can supply supplemental deionized water to the replenishment assembly anolyte tank 96 or compartment 98. Bulk plating material 92, such as copper pellets, can be disposed in the replenishment assembly anolyte compartment 98 and provide materials that can be plated onto the wafer 50. A pump can circulate the replenishment assembly anolyte through the replenishment assembly anolyte compartment 98. The replenishment assembly anolyte can be completely separated from the anolyte provided to the inner anode 4 and / or the outer anode 42. In addition, in some embodiments, the anolyte compartment 98 can be used without any replenishment assembly anolyte loop. For example, a gas bubbler, or some other pumping system can provide agitation to the anolyte compartment 98 without using a replenishment assembly anolyte loop. For example, some embodiments of the anolyte compartment (or first compartment) may include an anolyte replenishment tank, or may simply circulate the anolyte in the compartment or in two sections of the compartment as will be further described below.

[0039] In the replenishment assembly 74, the first cationic membrane 104 can be positioned between the replenishment assembly anolyte in the replenishment assembly anolyte compartment 98 and the catholyte in the catholyte compartment 106 to separate the replenishment assembly anolyte from the catholyte. The catholyte return line 72 can be connected to one side of the catholyte compartment 106, and the catholyte supply line 78 can be connected to the other side of the catholyte compartment 106, which allows the catholyte from the electroplating vessel 38 to circulate through the catholyte chamber. Alternatively, the catholyte flow loop through the replenishment assembly 74 can be a separate flow loop with a catholyte tank. The first cationic membrane 104 can allow metal ions and water to pass through the replenishment assembly anolyte compartment 98 to the catholyte in the catholyte chamber, while additionally providing a barrier between the replenishment assembly anolyte and the catholyte. Deionized water may be added to the catholyte to replace water lost to evaporation, but more typically water evaporation may be enhanced to evaporate water from the anolyte supply assembly into the catholyte by electroosmosis. An evaporator may also be included to facilitate removal of excess water.

[0040] The flow of metal ions into the catholyte replenishes the concentration of metal ions in the catholyte. As the metal ions in the catholyte are deposited onto the wafer 50 to form a metal layer on the wafer 50, these metal ions can be replaced with metal ions from the bulk electroplating material 92 that move through the replenishment assembly anolyte and the first membrane 104 to the catholyte flowing through the catholyte compartment 106 of the replenishment assembly 74.

[0041] An inert cathode 114 may be located in a sampling electrolyte (thiefolyte) compartment 112 opposite the second cationic membrane 108. The negative electrode or cathode of a power source 130 such as a DC power source may be electrically connected to the inert cathode 114. The positive electrode or anode of the power source 130 may be electrically connected to the bulk electroplating material 92 or metal in the replenishment assembly anolyte compartment 98, thereby applying or establishing a voltage difference across the replenishment assembly 74. The replenishment assembly electrolyte in the sampling electrolyte compartment 112 may selectively circulate through the replenishment assembly tank 118, wherein deionized water and sulfuric acid are added to the replenishment assembly electrolyte via an inlet 122. The sampling electrolyte compartment 112 electrolyte may include, for example, deionized water with 1-10% sulfuric acid. The inert cathode 114 may be a platinum or platinum-clad wire or plate. The second ion membrane 108 may help to keep copper ions in the second compartment. In addition, the second ion membrane 108 may be configured to maintain Cu ions in the cathode electrolyte in particular. 2+ For example, in some embodiments, the second ionic membrane can be a monovalent membrane, which can further restrict copper from passing through the membrane.

[0042] Refer again Figure 1 and Figure 2 , the chamber 20 may optionally include a current sampling electrode (thiefelectrode) 46 in the plating vessel 38, although in some embodiments, current sampling may not be included. In some embodiments, the current sampling electrode 46 may also have a current sampling wire in the current sampling membrane tube, similar to the inner anode 40 or the outer anode 42 described above. If a sampling electrode is used, the regeneration electrolyte can be pumped through the current sampling membrane tube. The current sampling wire can generally be connected to a negative voltage source that is controlled independently of the negative voltage source connected to the wafer 50 via the contact ring 30. The current sampling membrane tube can be connected to the sampling electrolyte compartment 112 in the replenishment assembly 74 via a replenishment assembly circulation loop generally represented by 82 (i.e., via a replenishment assembly electrolyte return line 84 and a replenishment assembly electrolyte supply line 86). If used, the high acid catholyte bath in the catholyte compartment 106 can ensure that most of the current across the membrane 108 can be protons, rather than metal ions. In this manner, the current within replenishment assembly 74 can replenish the copper within the catholyte while preventing its loss across the membrane.

[0043] The second cationic membrane 108 can be positioned between the catholyte in the catholyte compartment 106 and the supply assembly electrolyte in the sampling electrolyte compartment 112. The second cationic membrane 108 can allow protons to pass from the catholyte in the catholyte compartment 106 to the supply assembly electrolyte in the sampling electrolyte compartment 112, while limiting the amount of metal ions that pass through the membrane (which will then be plated on the inert cathode). The main function of the sampling electrolyte compartment 112 is to complete the circuit for the supply assembly chamber in a way that does not plate metal onto the inert cathode 114. The sampling electrolyte compartment 112 can be used with or without an additional tank or circulation loop. The high acid electrolyte or catholyte bath in the catholyte compartment 106 can ensure that most of the current across the membrane 108 is protons, rather than metal ions, so that the cathode reaction on the inert electrode 114 is mainly hydrogen evolution. In this manner, the current within replenishment assembly 74 replenishes copper within the catholyte while preventing copper from being lost across membrane 108 .

[0044] During idle state operation, when the replenishment assembly is not in use, the replenishment system 70 stops the flow of catholyte through the bulk plating material 92 formed as a consumable anode. In some embodiments, the sample electrolyte can be emptied from the sample electrolyte compartment during the idle state to limit the amount of electrolyte that is present due to Cu. 2+ Additional losses of copper, additives, or other bath components from the catholyte due to diffusion across the membrane 108, or other transport mechanisms. However, as explained above, there are challenges in both retaining the catholyte and anolyte in their respective compartments, and draining both materials. Draining the catholyte promotes air entrainment at startup, which can adversely affect electroplating. Draining the anolyte can expose the anode material, leading to oxidation. However, retaining the two electrolytes in their respective chambers can cause concentration gradients between the materials across the membrane to cause additives to be lost from the catholyte. Therefore, some embodiments of the present technology may be combined with additional spacers, which can be used to separate the anolyte and catholyte in their respective compartments during idle state operation.

[0045] Go to Figure 4 , which shows a schematic cross-sectional view of a recharging assembly 400 according to some embodiments of the present technology. Recharging assembly 400 may include any features, components, or characteristics of recharging assembly 74, and may be incorporated into recharging system 70 described above. Recharging system 400 may illustrate additional features of recharging assembly 74 according to some embodiments of the present technology.

[0046] The replenishment assembly 400 may include a three-compartment cell including: an anolyte compartment 405, or a first compartment; a catholyte compartment 410, or a second compartment; and a sampling electrolyte compartment 415, or a third compartment. The assembly may also include a first ion membrane 420 located between the anolyte compartment and the catholyte compartment, and may include a second ion membrane 425 located between the catholyte compartment and the sampling electrolyte compartment. In addition, to overcome the problems during the idle state as previously described, an additional spacer 430 may be included in the anolyte compartment 405, which may provide fluid separation between the first compartment segment 407 and the second compartment segment 409 in the anolyte compartment. Each compartment segment of the anolyte compartment may be accessed only by the anolyte in a continuous loop within the anolyte compartment 405, although the additional spacer 430 may facilitate operation as further described below.

[0047] Anolyte compartment 405 may include an electrode 406, which may be coupled to a power source as previously described. Anode material (such as copper pellets or other metal materials used in electroplating) may be deposited in a cell in contact with electrode 406. For example, a retainer 408 or a screen may be included to maintain the anode material against the electrode and away from the contacting ion membrane. As will be described below, a removable container may also be utilized to ensure that the anode material is contained in the anolyte compartment and in contact with the electrode.

[0048] The spacer 430 can be an ionic membrane that ensures that: when the anolyte flows in each section of the anolyte compartment, the first compartment section can be electrically coupled to the second compartment section while allowing fluid separation, which can be used to isolate the compartment fluids, thereby allowing emptying operations to occur during idle states. In some embodiments, a pump 435 or a pumping system can be connected to each of the first compartment section and the second compartment section of the anolyte compartment 405, and can be operable to pump fluid into and / or out of the second compartment section of the anolyte compartment. The anolyte can be pumped from the first compartment section 407 into the second compartment section 409, and the anolyte can rise in the second compartment section and fill the second compartment section, which can be located between the spacer 430 and the first ionic membrane 420. The fluid can be continuously pumped to ensure the consistency of the anolyte in each compartment section. As fluid fills the second compartment segment of anolyte compartment 405 , the fluid may enter overflow channel 438 , which may allow anolyte to pour back into first compartment segment 407 , thereby forming a continuous fluid loop between the two segments within anolyte compartment 405 , as further explained below.

[0049] The catholyte compartment 410 can be fluidly coupled to the plating chamber as previously described, and can be filled with a catholyte as will be further described below, which can be maintained in the catholyte compartment 410 during an idle state. The catholyte compartment 410 can be separated from the sampling electrolyte compartment 415 by a second ion membrane 425, which can be a monovalent membrane in some embodiments. The sampling electrolyte compartment can allow the sampling electrolyte to flow into a space that can also include an inert cathode 440 electrically coupled to the power supply as previously described. Therefore, the power supply can be operated as a voltage source that couples the anode material to the inert cathode 440 through the three compartments of the chamber, each of which can be electrically coupled together by a separate electrolyte and ion membrane.

[0050] Figure 5 A schematic cross-sectional view of a replenishment assembly 500 is shown according to some embodiments of the present technology and may illustrate replenishment assembly 400 during operation. Replenishment assembly 500 may include any components or features of the aforementioned systems or assemblies and may be incorporated into an electroplating system as discussed above.

[0051] As shown, replenishment assembly 500 may include anolyte in anolyte compartment 405, which may flow through each of the first compartment section and the second compartment section of the anolyte compartment during the first operation of replenishing ions into the catholyte. In other words, during the first operation for replenishment, pump 435 may be operated in a first setting to flow anolyte from the first compartment section to the second compartment section of the anolyte compartment 405. As shown, the anolyte may then contact the first ion membrane adjacent to the catholyte compartment, which may cause the catholyte to flow to the opposite side of the membrane. The anolyte may continue to flow upward through the second compartment section of the anolyte compartment, and may flow back to the first compartment section of the anolyte compartment 405 over the overflow channel 438. Overflow channel 438 may be operated as a fluid path that extends over the spacer to create a fluid loop that may continue to flow during operation.

[0052] Figure 6 A schematic cross-sectional view of a replenishment assembly 600 is shown according to some embodiments of the present technology and may illustrate replenishment assembly 400 during operation. Replenishment assembly 600 may include any components or features of the aforementioned systems or assemblies and may be incorporated into an electroplating system as discussed above.

[0053] As shown, replenishment assembly 600 may include anolyte in anolyte compartment 405, which may be maintained within first compartment segment 407 during a second operation in which the system is in an idle state, while being emptied from second compartment segment 409 of anolyte compartment 405. In other words, during a second operation in which the system is in an idle or standby state, pump 435 may be operated in a second setting, which may be the opposite of the first setting, to empty anolyte from second compartment segment 409 and pump it back into first compartment segment 407 of anolyte compartment 405. As shown, first compartment segment 407 may include additional headspace volume within the compartment segment, which may allow the entire volume of second compartment segment 409 to be pumped back into first compartment segment 407 of the anolyte compartment.

[0054] The sampling electrolyte compartment 415 can similarly empty the sampling electrolyte during the idle state, which can prevent additional copper from migrating through the second ion membrane and being plated on the inert cathode. The catholyte can be kept in the catholyte compartment, which can allow the entire catholyte fluid loop to the electroplating chamber to remain full, which can prevent air entrainment in the loop. This configuration can provide multiple benefits, including maintaining all fluid separations in the replenishment assembly during the idle state. In addition, each ion membrane that can include the spacer 430 as the third ion membrane can be maintained along the surface of the membrane to contact with the electrolyte. For example, as shown in the figure, the first ion membrane can be maintained during the idle state to contact only with the catholyte, and can be maintained to be substantially free of or substantially free of anolyte, and a small amount of residual anolyte can be maintained on the membrane. This can ensure that the membrane will not dry out during the idle time period, which can prevent the rupture and failure of the membrane. In addition, the anode material maintained in the first compartment section 407 can still be fully immersed in the anolyte, which can prevent oxidation. Thus, by including additional spacers within the anolyte compartment, incorporated into the second compartment segment of the anolyte compartment, an idle state configuration may be created that limits or prevents transmembrane migration between stagnant fluids.

[0055] Go to Figure 7, which shows a schematic perspective view of an anode material container 700 according to some embodiments of the present technology. As previously discussed, an anode material (such as copper pellets or a material for replenishing metal ions) may be included in an anolyte compartment, such as in a first compartment section of the anolyte compartment, and a cathode electrolyte may be maintained in the first compartment section of the cathode electrolyte during an operating state and an idle state. In some embodiments, a container 700 containing a compartment 705 may be included, and the compartment 705 may hold the anode material to prevent the anode material from contacting the ion membrane, which may cause the membrane to tear or other perforations through the membrane. The compartment 705 may include a front partition 710, which may allow the anolyte to flow through the compartment during operation. In addition, an electrode 715 may extend into the compartment as shown, which may further ensure electrical communication with the anode material. For example, the compartment 705 may be conductive, which may ensure that the anode material is in electrical contact with a power source. It should be understood that the container 700 may be incorporated into any of the aforementioned components or configurations.

[0056] Figure 8 A schematic perspective view of a cell insert 800 according to some embodiments of the present technology is shown. The cell insert 800 may be included in the catholyte compartment in some embodiments to limit the amount of fluid flowing through the compartment at any time. During the idle state, the volume of the catholyte can be maintained in the catholyte compartment, and it can be in contact with the first ion membrane and the second ion membrane. Additives can still be expressed from the catholyte to the membrane, and these additives may not be fully reabsorbed into the catholyte upon restart. Therefore, in some embodiments, by reducing the volume of the catholyte in the catholyte compartment, additional loss of additives can be limited or prevented.

[0057] The well insert 800 may define one or more, including a plurality of, fluid channels 805 through the insert. Apertures 810 may be formed through both ends of the well insert in the direction in which the channels 805 are formed. Fig. 9A schematic cross-sectional partial view of a cell insert 800 in a replenishment assembly according to some embodiments of the present technology, such as in a cathode electrolyte compartment as described above, is shown. It is to be understood that the cell insert 800 may be included in any of the aforementioned assemblies or configurations. As shown, the cell insert 800 may extend laterally in the cathode electrolyte compartment to limit the available volume for the flow of the cathode electrolyte. In some embodiments, the cell insert 800 may contact one or both of the first ion membrane or the second ion membrane, although a small amount of fluid space may be maintained between the components to ensure that the membrane is adequately wetted. A recessed channel 905 may be formed in the top and bottom of the cell insert that may provide a fluid inlet to the aperture 810. The aperture 810 may provide fluid from the recessed channel to a fluid channel vertically defined through the cell insert. Cell inserts in accordance with the present technology can limit the volume within the cathode electrolyte compartment or any other compartment to greater than or about 10%, and can limit the volume within the compartment to greater than or about 20%, greater than or about 30%, greater than or about 40%, greater than or about 50%, greater than or about 60%, greater than or about 70%, greater than or about 80%, greater than or about 90%, or more.

[0058] Fig.10 Exemplary operations in a method 1000 of operating an electroplating system according to some embodiments of the present technology are shown. The method can be performed in various processing systems, including the electroplating system described above, which can include a replenishment assembly (such as replenishment system 400) according to embodiments of the present technology, which can include any additional components or features discussed throughout this disclosure. Method 1000 can include many optional operations that may or may not be explicitly associated with some embodiments of methods according to the present technology.

[0059] Method 1000 may include a treatment method, which may include operations for operating an electroplating system, which may include a replenishment assembly as described above. The method may include optional operations before starting method 1000, or the method may include additional operations. For example, method 1000 may include operations performed in a different order than shown. In some embodiments, method 1000 may include driving a voltage through a replenishment assembly at operation 1010, and the replenishment system may include a three-compartment assembly containing any component, feature, or characteristic of the aforementioned assembly or device. The assembly may include a spacer in the anolyte compartment, which may be used to promote idle operation as described above. The method may include providing ions of an anode material at operation 1020. These ions may be metal ions of a catholyte provided to or replenishing a catholyte flowing through the catholyte compartment of the assembly.

[0060] In some embodiments, at optional operation 1030, after the electroplating operation, the voltage may be reversed between the anode material and the cathode, which may be an inert cathode. This may allow any material that may have passed through the cathode electrolyte to the sampling electrolyte and plated on the inert cathode to be provided back to the electroplating solution and removed from the inert cathode. In some embodiments, the voltage reversal operation may be performed at regular intervals. Although the system may run for an extended period of time and then extend the voltage reversal time, in some embodiments, this reversal may be performed at more regular intervals for a shorter period of time. This may facilitate the maintenance of metal in the cathode electrolyte and may limit the formation of dendrites or other defects in the anode material. For example, in some embodiments, this reversal may be performed at regular intervals to allow this reversal to be performed in a period of less than or about 60 minutes between standard operating cycles, and may allow this reversal to be performed in less than or about 50 minutes, less than or about 40 minutes, less than or about 30 minutes, less than or about 20 minutes, less than or about 10 minutes, or less.

[0061] In some embodiments, the method may include operations to be performed before the idle state of the system. For example, in optional operation 1040, a pump may be operated to pump the anolyte from the second compartment section of the anolyte compartment back to the first compartment section of the anolyte compartment that can accommodate the anode material. The pumping can empty the anolyte from the second compartment section, and the anolyte can be removed to prevent the anolyte fluid from contacting the ionic membrane positioned between the anolyte compartment and the catholyte compartment. In some embodiments, the ionic membrane may be maintained to be free of anolyte except for the residual amount maintained in the membrane during the emptying or pumping out operation. By utilizing a replenishment module according to an embodiment of the present technology, metal ion replenishment can be promoted while limiting additive losses and overcoming challenges associated with system idle periods.

[0062] In the foregoing description, for purposes of illustration, numerous details are listed to provide an understanding of various embodiments of the present technology. However, it is apparent to those skilled in the art that some embodiments may be practiced without some of these details or with other details. For example, other substrates that may benefit from the described wet techniques may also be used with the present technology.

[0063] Several embodiments are disclosed above, and those skilled in the art will recognize that various modifications, alternative configurations, and equivalents may be employed without violating the spirit of these embodiments. In addition, many well-known processes and elements are not described in order to avoid unnecessarily obscuring the present technology. Therefore, the above description should not be regarded as limiting the scope of the present technology.

[0064] Where a numerical range is provided, it is understood that each value between the upper and lower limits of the range (to the smallest part of the lower limit unit) is also explicitly disclosed, unless the context indicates otherwise. The present technology includes any narrower range between any mentioned value in the mentioned range or the values ​​between the range that are not mentioned, and any other mentioned value in the mentioned range or the values ​​between the range. The upper and lower limits of these smaller ranges may be independently included in the range or excluded from the range, and under the condition of any deliberately excluded limit values ​​in the mentioned range, the present technology also includes the following each range: any or both of the upper and lower limits are included or not included in each range in these smaller ranges. Where the mentioned range includes one or both of these limits, the present technology also includes the range excluding any or both of those included limits. Where multiple values ​​are provided in a list, any range including any of these values ​​or any range based on any of these values ​​is similarly intentionally disclosed.

[0065] As used herein and in the appended claims, the singular forms "a," "an," "the," and "said" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to "a material" includes a plurality of such materials and reference to "the channel" or "the channel" includes reference to one or more channels and includes reference to equivalents of one or more channels known to those skilled in the art, and so forth.

[0066] In addition, the words "comprises", "including", "comprising", "containing", "include", and "containing", when used in this specification and the appended claims, are intended to indicate the presence of certain features, integers, components or operations, but they do not exclude the presence or addition of one or more other features, integers, components, operations, actions or groups.

Claims

1. An electroplating system comprising: an electroplating chamber, the electroplating chamber comprising an electroplating container; and A replenishment assembly fluidically coupled to the electroplating chamber, the replenishment assembly comprising: a first compartment containing an anode material, the first compartment having a first compartment section in which the anode material is contained and a second compartment section separated from the first compartment section by a separator, wherein the first compartment includes an anolyte, a second compartment fluidly coupled to the electroplating chamber and electrically coupled to the first compartment, wherein the second compartment includes a catholyte, and A third compartment is electrically coupled to the second compartment, the third compartment comprising an inert cathode.

2. The electroplating system according to claim 1, characterized in that: The electroplating system further comprises: A voltage source couples the anode material to the inert cathode.

3. The electroplating system according to claim 1, characterized in that: The third compartment includes a sampling electrolyte.

4. The electroplating system according to claim 3, characterized in that: The third compartment is fluidly coupled to the plating chamber to deliver a sample electrolyte between the third compartment and the plating chamber, and the second compartment is fluidly coupled to the plating chamber.

5. The electroplating system according to claim 1, characterized in that: The electroplating system further comprises: a first ion membrane positioned between the second compartment section of the first compartment and the second compartment; and A second ion membrane is positioned between the second compartment and the third compartment.

6. The electroplating system according to claim 5, characterized in that: The second ionic membrane is a monovalent membrane.

7. The electroplating system according to claim 1, characterized in that: The electroplating system further comprises: A pump is fluidly coupled between the first compartment section of the first compartment and the second compartment section of the first compartment.

8. The electroplating system according to claim 7, characterized in that: The pump is operable in a first setting to flow anolyte from the first compartment section of the first compartment to the second compartment section of the first compartment.

9. The electroplating system according to claim 8, characterized in that: A fluid path is defined around the divider such that when the pump is operated in the first setting, anolyte flows from the second compartment section of the first compartment to the first compartment section of the first compartment.

10. The electroplating system according to claim 8, characterized in that: The pump is operable in a second setting to completely drain the anolyte from the second compartment section of the first compartment.

11. The electroplating system according to claim 1, characterized in that: The electroplating system further comprises: An insert is positioned in the second compartment, the insert defining at least one fluid channel along the insert.

12. The electroplating system according to claim 1, characterized in that: The electroplating system further comprises: A compartment is disposed within the first compartment section of the first compartment, the compartment containing the anode material.

13. The electroplating system according to claim 1, characterized in that: The separator is an ion membrane that fluidly isolates a flow path between the first compartment section of the first compartment and the second compartment section of the first compartment.

14. A method of operating an electroplating system, the method comprising: The voltage is driven by a supply assembly, the supply assembly comprising: a first compartment containing an anode material, the first compartment having a first compartment section in which the anode material is contained and a second compartment section separated from the first compartment section by a separator, a second compartment fluidly coupled to the plating chamber and electrically coupled to the first compartment, and a third compartment electrically coupled to the second compartment, the third compartment comprising an inert cathode, wherein the voltage is driven from the anode material to the inert cathode through the first compartment segment of the first compartment, the second compartment segment of the first compartment, the second compartment, and the third compartment; and Ions of the anode material are provided to the catholyte flowing through the second compartment.

15. The method of operating an electroplating system according to claim 14, characterized in that: The method further comprises: reversing the voltage between the anode material and the inert cathode; and The electroplated anode material is removed from the inert cathode.

16. The method of operating an electroplating system according to claim 14, characterized in that: The method further comprises: Anolyte is pumped from the second compartment section of the first compartment to the first compartment section of the first compartment to empty the second compartment section of the first compartment.

17. The method of operating an electroplating system according to claim 16, characterized in that: The replenishment assembly further comprises: a first ion membrane positioned between the second compartment section of the first compartment and the second compartment; and A second ion membrane is positioned between the second compartment and the third compartment.

18. The method of operating an electroplating system according to claim 17, characterized in that: The pumping maintains the first ion membrane in contact only with the catholyte fluid.

19. An electroplating system comprising: an electroplating chamber, the electroplating chamber comprising an electroplating container; and A replenishment assembly fluidically coupled to the electroplating chamber, the replenishment assembly comprising: a first compartment containing an anode material and an anolyte, the first compartment having a first compartment section in which the anode material is contained and a second compartment section separated from the first compartment section by a partition, wherein a fluid circuit is defined between the first compartment section and the second compartment section, a second compartment fluidly coupled to the electroplating chamber and electrically coupled to the first compartment, wherein the second compartment contains a catholyte, a first ion membrane positioned between the second compartment section of the first compartment and the second compartment, a third compartment electrically coupled to the second compartment, the third compartment comprising an inert cathode, wherein the third compartment comprises an acid sampling electrolyte, and A second ion membrane is positioned between the second compartment and the third compartment.

20. The electroplating system according to claim 19, characterized in that The spacer is a third ion membrane.

Images