Patent ID: 12209325

Several of the figures are included as schematics. It is to be understood that the figures are for illustrative purposes, and are not to be considered of scale unless specifically stated to be of scale. Additionally, as schematics, the figures are provided to aid comprehension and may not include all aspects or information compared to realistic representations, and may include exaggerated material for illustrative purposes.

In the figures, similar components and/or features may have the same numerical reference label. Further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components and/or features. If only the first numerical reference label is used in the specification, the description is applicable to any one of the similar components and/or features having the same first numerical reference label irrespective of the letter suffix.

DETAILED DESCRIPTION

Electroplating operations may be performed to provide conductive material into vias and other features on a substrate. Electroplating utilizes an electrolyte bath containing ions of the conductive material to electrochemically deposit the conductive material onto the substrate and into the features defined on the substrate. The substrate on which metal is being plated operates as the cathode. An electrical contact, such as a ring or pins, may allow the current to flow through the system. During electroplating, a substrate may be clamped to a head and submerged in the electroplating bath to form the metallization. In systems as described below, the substrate may also be chucked within a seal that may be coupled with the head during processing. When the substrate is raised after plating, it may be rinsed with water, such as deionized water, combined with cleaning chemicals prior to being sent to another plating chamber or some other processing location. However, as noted above, several issues may occur during this rinsing operation.

Conventional technologies may rinse the substrate directly over the bath from a nozzle that ejects rinsing fluid from a side of the chamber towards a center of the substrate. The substrate may be rotated at some speed during the rinsing, which may draw the water across the substrate and sling the water into a catch located at an exterior of the chamber. During the delivery, water may fall into the electrolyte bath, diluting the bath and potentially splashing solution up onto the wafer. This may bring electrolyte or cleaning chemicals to a subsequent bath having a different solution, which may contaminate the second bath. Attempts to utilize acidified rinse agents have also proven problematic. Namely, as such rinse agents introduce additional acid to the bath, the bath falls out of control due to over-acidification.

Moreover, existing bath are operated with bath solutions having non-neutral pH values, such as less than 4 or greater than 8. Conversely, conventional rinse or cleaning systems utilize neutral pH water as a rinse agent. However, neutral pH water problematically leads to the formation of insoluble contaminants, such as organometallics, metallics, and the like in the bath, that plate-up or form scale upon bath surfaces and components. Namely, particles that were soluble in the pH of the bath prior to dilution, can be forced to precipitate from solution due to the change in pH from the introduction of the rinse agent, and then adhere to whatever surface is available. On a single occurrence, insoluble deposits are virtually negligible. But on surfaces which are repeatedly exposed to cleaning agents having a higher or lower pH, each cycle can create insoluble deposits which will build up as cycling progresses. Eventually the deposits can form a conductive or semi-conductive film which acts as a precursor to plate-up.

Additionally, plating chambers may accommodate multiple substrate sizes, and thus, for example, a 200 mm semiconductor wafer and a 300 mm semiconductor wafer may be processed in the same chamber. During the sling operation, the smaller diameter 200 mm wafer may not fully deliver rinse fluid into the catch, which may cause the rinse fluid to be delivered into the electrolyte bath. This may cause more substantial dilution of the bath, which may limit the amount of rinsing that may be performed. Further, valuable bath solutes are often contained in the cleaning agent utilized during rinsing. In conventional systems, there is currently no mechanism for recovering lost bath solutes.

The present technology overcomes these issues by incorporating a recycling system that provides a rinse agent having a preselected pH filtered from the bath solution, preventing pH dilution of the bath, oversaturation by acid, and precipitation of bath solutes. In addition, by utilizing such a filtration system, the present technology has found that bath solutes can be separated from the recycled rinse agent and bath solution and returned to the bath, reducing waste, and preventing contamination of the seal, bath, and/or substrate by the recycled rinse agent. Moreover, the filtration system according to the present technology also provides for the production of a rinse agent recycled from the bath solution having a specific pH that varies from the bath solution pH by less than or about 5 without the need for additional cleaning agents. Namely, careful selection of filters allows both the separation of bath solutes from the recycled bath solution, and the formation of a rinse agent having the preselected pH. The preselected pH allows for excellent cleaning and removal of unused bath solutes on seals and substrates without additional cleaning agents. Such a rinse agent can therefore be either further recycled as a rinse agent or retained in the bath after rinsing, as contamination and dilution concerns have been reduced or even eliminated. In addition, as the rinse agent is recycled from the bath solution, and carefully tailored to exhibit a similar pH to the bath solution pH without additional pH adjusting agents, negative increases and decreases in pH and electrolyte concentration can be avoided. Furthermore, the present technology has unexpectedly found that the filtration system can be operated as an in situ filtration system, allowing the continuous collection, filtration, and recycling of bath solutions to form recycled rinse agents.

By utilizing cleaning systems according to the present technology, cleaning may be performed more easily and more efficiently, and contamination, dilution, and oversaturation may be limited or prevented. An improved rinsing within a chamber, while avoiding dilution, oversaturation, and/or contamination, is also a valuable advancement for processing substrates. Such a chamber gives flexibility of rinse recipe steps, substrate positions, simplification of rinsing frames (e.g. removal of catches and/or platforms for collecting rinse fluid), and flow rates to provide improved results without the concerns of dilution, contamination, and oversaturation of acid. After describing an exemplary chamber on which embodiments of the present technology may be coupled, the remaining disclosure will discuss aspects of the systems and processes of the present technology.

FIG.1shows a schematic perspective view of an electroplating system100for which methods and cleaning systems may be utilized and practiced according to embodiments of the present technology. Electroplating system100illustrates an exemplary electroplating apparatus including a system head110and a bowl115. During electroplating operations, a wafer may be clamped to the system head110, inverted, and extended into bowl115to perform an electroplating operation. Electroplating system100may include a head lifter120, which may be configured to both raise and rotate the head110, or otherwise position the head within the system including tilting operations. The head and bowl may be attached to a deck plate125or other structure that may be part of a larger system incorporating multiple electroplating systems100, and which may share electrolyte and other materials. A rotor may allow a substrate clamped to the head to be rotated within the bowl, or outside the bowl in different operations. The rotor may include a contact ring, which may provide the conductive contact with the substrate. A seal130discussed further below may be connected with the head. Seal130may be configured to be coupled to a substrate for processing.

FIG.1illustrates an electroplating chamber that may include components to be cleaned directly on the platform. It is to be understood that other configurations are possible, including platforms on which the head is moved to an additional module and seal, or other component cleaning is performed. Additionally, one or more components, such as seal130may be removed from a respective chamber and placed in a maintenance system or cleaning system for cleaning. Any number of other operations may be performed that provide or expose a component for cleaning. An exemplary in situ rinse system135is also illustrated with the system100and will be described in further detail below.

Turning toFIG.2, a partial cross-sectional view of a chamber including aspects of an electroplating apparatus200according to some embodiments of the present technology is illustrated. The electroplating apparatus200may be incorporated with an electroplating system, including system100described above. As illustrated inFIG.2, a plating bath205of an electroplating system is shown along with a head210having a substrate215coupled with the head. The substrate may be coupled with a seal212incorporated on the head in some embodiments. A rinsing frame220may be coupled above the plating bath vessel205and may be configured to receive the head into the vessel during plating. Rinsing frame220may include a rim225extending circumferentially about an upper surface of the plating bath vessel205. A rinsing channel227may be defined between the rim225and an upper surface of the plating bath vessel205. For example, rim225may be include interior sidewalls230characterized by a sloping profile. As described above, rinse fluid slung off a substrate may contact the sidewalls230, and may be received in a plenum235extending about the rim for collection of the rinse fluid from the electroplating apparatus200. However, as discussed above, it should be understood that, in some aspects, the rinse fluid/rinse agent may instead drain directly into the bath solution due to the unique formulation of the recycled rinse agent.

Electroplating apparatus200may additionally include one or more cleaning components in some embodiments. The components may include one or more nozzles used to deliver fluids to or towards the substrate215or the head210.FIG.2illustrates one of a variety of embodiments in which rinse assemblies may be used to protect the bath and substrate during rinsing operations. As illustrated, a splash guard240is positioned between the substrate215and the plating bath vessel205, and may be associated with a fluid nozzle245, which may deliver a rinse fluid to substrate215in embodiments. Embodiments of the present technology may include fluid nozzle245along the splash guard240to a central location near a center of the wafer. The nozzle245may also be positioned a short distance from the substrate215. Electroplating apparatus200may also include additional nozzles with nozzle245as will be explained further below. A side clean nozzle250may extend through the rim225of the rinsing frame220in some embodiments and be directed to rinse seal212, along with aspects of substrate215. However, it should be understood that other orientations of nozzles245,250, and/or additional nozzles (not shown) are contemplated herein, as well as embodiments containing no splash guard240. Namely, as noted above, by utilizing a unique rinse agent, the detrimental effects of dripping and sling off may be avoided without complex nozzle and splash guard orientations.

Nonetheless, seal cleaning may occur before, during, or after the substrate cleaning utilizing a rinse agent as discussed herein. As noted above, in embodiments, the same rinse agent or a different rinse agent may be used for both the seal and substrate cleaning, or the seal and substrate may be cleaned at different times using the same or a different rinse agent. For example, the system may include a seal clean nozzle coupled with the rinse frame. The seal clean nozzle may be positioned and operated to direct the rinse fluid tangentially across the seal and into the collection channel. The system may also perform a drying operation utilizing a gas nozzle. The gas nozzle may be coupled adjacent the fluid nozzle, and the methods may also include flowing an inert gas across the substrate to dry residual rinse fluid from a surface of the substrate.

Regardless of the orientation of the bath utilized,FIG.3illustrates a schematic chart andFIG.4shows exemplary operations of an electroplating system300having a recycling unit304in accordance with an embodiment of the present technology. The electroplating system300may incorporate an electroplating system100, and/or electroplating apparatus200, or any one or more embodiments thereof. The electroplating system300may be configured to plate and/or clean one or more substrates as discussed above in regards to electroplating system100and/or electroplating apparatus200.

The electroplating system300includes an electroplating apparatus301wherein substrates are electroplated and/or cleaned as discussed above. After electroplating, one or more rinses of the substrate may be carried out by spraying a rinse agent according to the present technology. For instance, the electroplating system300includes a bath and/or rinse source302connected to a bath of electroplating apparatus301. The bath and/or rinse source302may include one or more tanks containing a plating solution and one or more pumps configured to supply the plating solution to the electroplating apparatus301. As known in the art, the plating solution can contain an electrolyte and one or more precursor particles, as well as various optional components, such as chelating agents, pH adjusting agents, surfactants, and the like.

The electroplating system300also includes a rinse agent tank303connected to electroplating apparatus301, such as to one or more nozzles (such as250inFIG.2) for rinsing of the substrates and/or seal. The rinse agent tank303is also connected to the recycling unit304and filtration unit350for providing the rinse agent having the preselected pH, which will be discussed in greater detail below, to rinse agent tank303.

In embodiments, the electroplating apparatus301may have a tank319fluidly connected downstream to the electroplating apparatus301via conduit308and configured to receive bath solution and used rinse agent drained from electroplating apparatus301at operation401. However, as noted above, in embodiments, tank319may instead only be connected to drain265such that the spent rinse agent is collected in tank319. Namely, as the rinse agent has a similar pH to the bath solution and does not contain excess cleaning chemicals, the bath solution does not need to be corrected after rinsing with a rinse agent as discussed herein. However, it should be understood that, in embodiments, both the rinse agent and bath solution may be drained into tank319, together or separately (not shown). In embodiments, tank319may be coupled to multiple electroplating apparatus and configured to collect mixtures of used bath solution and/or rinse agent from multiple electroplating apparatus. Furthermore, in embodiments, tank319may be omitted, and the bath solution, rinse agent, or a combination thereof are drained directly to recycling unit304.

For instance, in embodiments, the electroplating system300includes a recycling unit304that receives the solution (recycled bath solution, rinse agent, or a combination thereof) from the tank319or directly from electroplating apparatus301via conduit308. The recycling unit304utilizes one or more filters to separate bath solutes from the bath solvent and/or rinse agent to provide a recycled rinse agent. In some embodiments, generally all of a bath solution may be drained into the recycling unit. However, in embodiments, less than or about 25 vol. % of the bath solution is drained for each rinsing cycle, such as less than or about 20 vol. %, such as less than or about 17.5 vol. %, such as less than or about 15 vol. %, such as less than or about 12.5 vol. %, such as less than or about 10 vol. %, such as less than or about 7.5 vol. %, such as less than or about 5 vol. %, based upon the volume of the bath solution prior to draining.

The recycling unit304can include an optional first filtration unit350having a filter size suited to separating any large particles from the solution. The optional first filtration unit350may also have a waste outlet that provides an exit for waste, such as large particles. The remaining solution is directed to a second filtration unit360designed to separate a liquid permeate from any remaining bath solutes (retentate). If necessary, the permeate may also be directed to an optional sanitization unit380and a treatment unit370to obtain reusable clean water.

The optional first filtration unit350may comprise a suitable filtering media for depth filtration and/or surface filtration. In one embodiment, the optional first filtration unit350includes one or more membranes or other filtration units configured to remove large particles having a size of greater than about 50 nm. In one embodiment, the membranes or other filtration units may be a microfiltration membrane, an ultrafiltration membrane, or other suitable size-exclusion filter. However, it should be understood that, in embodiments, the optional first filter is not necessary, as no large precipitates have been formed due to the similarity in pH between the recycled rinse agent and the bath solution pH. Thus, in embodiments, only a second filtration unit360may be utilized, as all of the collected retentate may(s) be returned to the bath solution.

The second filtration unit360is connected downstream to the optional first filtration350(if present) to receive the solution. In some embodiments, the second filtration unit is connected directly or indirectly to electroplating apparatus301via conduit308. Nonetheless, at operation402, the bath solution is filtered through a nanofiltration membrane at filtration unit360.

The second filtration unit360is selected to retain substantially all electroplating precursor particles (discussed in greater detail below) present in the bath solution, such as greater than or about 85 wt. % of the precursor particles based upon the weight of precursor particles present in the drained bath solution, such as greater than or about 90 wt. %, such as greater than or about 92.5 wt. %, such as greater than or about 95 wt. %, such as greater than or about 97.5 wt. %, such as greater than or about 99 wt. % of the precursor particles are retained in the retentate by second filtration unit360. Stated differently, in embodiments, the permeate contains less than or about 20 wt. % of precursor particles or ions thereof based upon the total weight of solutes in the permeate, such as less than or about 17.5 wt. %, such as less than or about 15 wt. %, such as less than or about 12.5 wt. %, such as less than or about 10 wt. %, such as less than or about 7.5 wt. %, such as less than or about 5 wt. %, such as less than or about 2.5 wt. %, or any ranges or values therebetween.

Nonetheless, in embodiments, the second filtration unit360includes a membrane or other filtering media and a pump to provide a pressure to the solution through the membrane. Namely, the present disclosure has surprisingly found that the use of a nanofiltration unit to separate the permeate from the retentate in recycled bath solution does not provide pure water as the retentate. Instead, by utilizing a nanofiltration unit, acidified water may form the permeate from the recycled bath solution.

Namely, in embodiments, the nanofiltration membrane may prevent molecules having weights of greater than or about 125 g/mol from passing through the membrane (remain in retentate), such as greater than or about 150 g/mol, such as greater than or about 175 g/mol, such as greater than or about 200 g/mol, such as greater than or about 225 g/mol, such as greater than or about 250 g/mol, such as up to about 300 g/mol, or any ranges or values therebetween, while allowing water and acid ions to pass through the membrane. Additionally, or alternatively, the nanofiltration membrane may prevent particles having a size of greater than 1 nanometer from passing through the membrane.

In embodiments, the pressure provided to the solution may be greater than or about 50 psi, such as greater than or about 75 psi, such as greater than or about 100 psi, such as greater than or about 125, such as greater than or about 150 psi, such as greater than or about 175 psi, such as greater than or about 200 psi, such as greater than or about 225 psi, or any ranges or values therebetween.

As discussed above, by using a recycled rinse agent with a preselected pH, a rapid change in the bath solution pH can be avoided, and insoluble materials maintained in solution. For instance, in embodiments, less than or about 10 wt. % of the precursor particles precipitate from the bath solution subsequent the rinsing based upon the total weight of precursor particles in the bath solution prior to rinsing, such as less than or about 7.5 wt. %, such as less than or about 5 wt. %, such as less than or about 2.5 wt. %, or any ranges or values therebetween.

The electroplating apparatus, a component thereof, the substrate, or a combination thereof may define a surface area. In embodiments, less than or about 10% of the surface area contains an oxide of a precursor particle formed thereon, based upon the total surface area, such as less than or about 7.5%, such as less than or about 5%, such as less than or about 2.5%, such as less than or about 1%, or any ranges or values therebetween. Stated differently, in embodiments, a system according to the present disclosure may drastically reduce plate-up as compared to an identical system that does not utilize a recycled rinse agent according to the present technology. Such as, in embodiments, the present technology may have greater than or about 50% less plate up, such as greater than or about 60%, such as greater than or about 70%, such as greater than or about 80%, such as greater than or about 90% less plate up, or any ranges or values therebetween.

The pH of the bath solution can be measured according to known techniques, such as use of a pH meter in the range of 15 to 40 degree Celsius solution for example only, to obtain a bath solution pH value, and the pH of the recycled rinse agent may be filtered, as discussed, to obtain a second pH value, which may be the same as the first pH value (bath solution pH value) or different, according to the above values. Nonetheless, the present technology has surprisingly found that by utilizing a nanofiltration member as a filtration system as discussed herein, the permeate forms a recycled rinse agent having a pH of less than or about 6, such as less than or about 5, such as less than or about 4.5, such as less than or about 4, such as less than or about 3.5, such as less than or about 3, such as less than or about 2.5, such as less than or about 2, such as less than or about 1.5, such as less than or about 1, or any ranges or values therebetween.

For instance, the pH of the recycled rinse agent after filtration (e.g. the permeate from the second filtration unit360) may have a pH that varies from the bath solution pH by less than or about 40%, such as less than or about 35%, such as less than about 30%, such as less than or about 25%, such as less than or about 20%, such as less than or about 15%, such as less than or about 10%, such as less than or about 10%, such as less than or about 5%, such as less than or about 2.5%, such as less than or about 1%, or any ranges or values therebetween. Thus, in embodiments, the pH of the bath solution and the pH of the recycled rinse agent may be substantially the same.

In embodiments, the pH of the recycled rinse agent may vary from the pH of the bath solution by a pH value of about 5 or less, such as about 4.5 or less, such as about 4 or less, such as about 4.5 or less, such as about 3 or less, such as about 2.5 or less, such as about 2 or less, such as about 1.5 or less, such as about 1 or less, such as about 0.5 or less, such as about 0.2 or less, or any ranges or values therebetween. For instance, in embodiments, when the recycled rinse agent pH is from about 0 to about 5, such as about 0.5 to about 4.5, such as about 1 to about 4, or any ranges or values therebetween, the bath pH is also from about 0 to about 5, such as about 0.5 to about 4.5, such as about 1 to about 4, or any ranges or values therebetween. Additionally, or alternatively, when the first pH is from about 8 to about 12, such as about 8 to about 11, such as about 8.5 to about 10, or any ranges or values therebetween, the second pH is from about 8 to about 12, such as about 8 to about 11, such as about 8.5 to about 10, or any ranges or values therebetween.

In embodiments, the pH of the bath solution, recycled rinse agent, or a combination thereof, may be selected based upon the precursor particles in solution. Namely, as known in the art, some plating materials, such as tin silver (SnAg) have increased likelihood of plate-up of insoluble particles and may therefore require a very low pH (such as less than or about 3) of the bath solution, recycled rinse agent, or both, to increase solubility and prevent insoluble deposits. Nonetheless, as would be understood by one having skill in the art, non-limiting metals (or ions thereof) that may be included in the bath solutions and for which recycled rinse agents as discussed herein are suitable for cleaning from substrates and/or seals include copper, tin, gold, nickel, silver, palladium, platinum, and rhodium, and alloys such as noble metal alloys, tin-copper, tin-silver, tin-silver-copper, tin-bismuth, permalloy and other nickel alloys, lead-tin alloys, and other lead-free alloys, and can be utilized in a plating system having any one or more of the above pH values or ranges.

Moreover, in embodiments, the recycled rinse agent may contain the recycled rinse agent and a solvent. In embodiments, the solvent may be the same solvent contained in the bath solution, such as water (deionized water), in some embodiments. Selecting a pH of the recycled rinse agent and/or bath solution may include selecting a type of recycled rinse agent and/or bath electrolyte. In embodiments, the recycled rinse agent is a mineral acid, such as an acid derived from an inorganic compound. Non-limiting examples of suitable mineral acids include hydrogen bromide (BrH), hydrogen iodide (HI), hydrochloric acid (HCl), nitric acid (HNO3), nitrous acid (HNO2), phosphoric acid (H3PO4), sulfuric acid (H2SO4), boric acid (H3BO3), hydrofluoric acid (HF), hydrobromic acid (HBr), perchloric acid (HClO4), hydroiodic acid (HI), carbonic acid, and combinations thereof. In embodiments, organic acids such as alkylsulfonic acids, e.g., methane sulfonic acid (MSA) is a suitable replenishment agent in accordance with the present disclosure. In embodiments, organic acids provide pH control as described herein, but also act as chelating agents sufficient for bonding with species in solution which, if not chelated, may promote the formation of plate-up films. Nonetheless, in embodiments, the recycled rinse agent may have a lower volume or be more concentrated that necessary for rinsing. Thus, in embodiments, the recycled rinse agent may be diluted with a solvent, such as DI water, prior to a rinsing step. However, it should be clear that the recycled rinse agent still exhibits the above pH properties prior to rinsing.

Nonetheless, after filtration through second filtration unit360, the permeate may be transferred to one or more nozzles250at operation403via conduit310. Furthermore, at operation404, the transferred permeate is utilized for rinsing a further substrate and/or seal (see, e.g.,FIG.2), or may instead be transferred to bath205for replacement of any lost volume. In embodiments, the recycling unit304may be separate from any additional supply or return lines due to the high pressure needed for operation of the nanofiltration membrane. Nonetheless, in embodiments, the second filtration unit360may be configured to provide at least about 50 mL of recycled rinse agent per rinse cycle, such as greater than or about 75 mL, such as greater than or about 100 mL, such as greater than or about 250 mL, such as greater than or about 300 mL, such as greater than or about 350 mL, such as greater than or about 360 mL, such as greater than or about 370 mL, such as greater than or about 500 mL, such as greater than or about 750 mL, such as greater than or about 1000 mL, such as greater than or about 1500 mL, such as up to about 2000 mL, or any ranges or values therebetween.

Surprisingly, the present technology has found that the benefits discussed herein are obtained even when a secondary rinse is conducted with a neutral pH rinse agent. Without wishing to be bound by theory, it is believed that the precursor particles are rinsed with the recycled rinse agent according to the present technology, and thus avoid precipitation in the bath due to the similarity in pH between the recycled rinse agent and the bath pH. Thus, a secondary rinse, which may be utilized to rinse extra rinse agent, or the like, may be conducted with a neutral pH rinse agent without causing undesirable precipitation. Therefore, in embodiments, methods according to the present technology may include a secondary rinsing step. The secondary rinsing step can be conducted with a recycled rinse agent according to the present technology, or a neutral pH rinse agent as known in the art, such as DI water.

In embodiments, the retentate, which may contain any one or more of the precursor particles discussed above, may be returned to the bath205via conduit312for further electroplating operations. In addition, due to the preselected pH of the recycled rinse agent, the precursor particles can be recovered in their native state, as the particles remain unoxidized and maintained in the dissolved stated (e.g., not precipitated out of solute). Thus, the use efficiency of precursor particles can be greatly improved.

Nonetheless, if necessary, the second filtration unit360may be cleaned by backward flush to remove waste and surplus solution. The solution may exit the second filtration unit360through a waste output365or will be fed to the treatment unit370. In embodiments, the second filtration unit360can include a dosing unit367that may contain one or more pH adjusting agents for maintaining the pH of the recycled rinse agent in the second filtration unit360within the ranges set forth above of the bath solution pH.

In embodiments, pH adjusting agents may be provided in any amount necessary to obtain a desired pH value in the final composition of the recycled rinse agent. Acidic pH adjusting agents can be organic acids, including amino acids, and inorganic mineral acids. Non-limiting examples of acidic pH adjusting agents include acetic acid, citric acid, fumaric acid, glutamic acid, glycolic acid, hydrochloric acid, lactic acid, nitric acid, phosphoric acid, sodium bisulfate, sulfuric acid, and the like, and combinations thereof. In embodiments, all organic acids are contemplated for use as pH adjusting agents. Non-limiting examples of alkaline pH adjusting agents include alkali metal hydroxides, such as sodium hydroxide, and potassium hydroxide; ammonium hydroxide; organic bases; and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like, and mixtures thereof.

In embodiments, an optional sanitization unit380is included. When utilized, the sanitation unit380may remove organic species from the solution, such as permeate from the first filtration unit350and/or second filtration unit360. In embodiments, the sanitization unit380may be an ultraviolet (UV) unit configured to oxidize the organic species in the water stream. In more embodiments, the sanitization unit380is configured to reduce and control bacteria counts. An optional treatment unit370may purify and/or deionize the water stream. In one embodiment, the treatment unit370may be a reverse osmosis membrane for a reverse osmosis filtration. In embodiments, the treatment unit370may comprise an ion-exchange resin, which may be continuously regenerated, to deionize the permeate. In more embodiments, the treatment unit370may be both a reverse osmosis membrane and an ion-exchange resin. The permeate from the treatment unit370may therefore result in ultra-purified water when used. However, as stated above, in embodiments, no additional filtration is necessary outside of second filtration unit360.

In one embodiment, the electroplating system300can include a system controller309. The system controller309may control one or more valves314in the electroplating system300to insure that recycled rinse agent and/or bath solution is delivered or shut off at desired time. For simplicity of drawing, connections between the system controllers309and the components of the electroplating system300are not shown. In embodiments, the system controller309is a standalone independent controller for supplying and recycling rinse agent. In another embodiment, the system controller309is integrated into an electroplating system300an integral part.

Although the above discussed embodiments utilize real-time monitoring and adjustments of the replenishment agent, various alternatives may be employed according to the technology described herein. For example, the recycling unit304may be controlled manually by an operator observing the output pH and volume values. For instance, the system software of the system controller309allows for both an automatic real-time adjustment mode as well as an operator (manual) mode. Further, although a single controller is shown inFIG.3, multiple controllers may be used to operate various constituents of the system such as the chemical recycling unit304, the first filtration unit350, and the second filtration unit360. Other embodiments will be apparent to those skilled in the art.

Nonetheless, it should be understood that, in embodiments, the method according to the present disclosure includes a non-transitory computer readable medium having instructions stored thereon that, when executed, cause recycling of all or a portion of a bath solution. For instance, in embodiments, a non-transitory computer readable medium may execute any one or more operations of the method, such as executing measurement of pH, comparing pH, filtering the solution to form the recycled rinse agent, and/or returning the retentate and/or permeate to the bath or rinse systems.

Embodiments of the above-described systems and chambers may be present in a plating chamber that exhibits reduced contamination, dilution, and oversaturation of acid. The method400may also include one or more operations prior to the initiation of the method, including filing, plating, solute adjustment, or any other operations that may be performed prior to the described operations. The method may further include a number of optional operations, which may or may not be specifically associated with some embodiments of methods according to the present technology. For example, many of the operations are described in order to provide a broader scope of the processes performed but are not critical to the technology or may be performed by alternative methodology, as will be discussed further below.

Method400may include various optional operations described schematically in regards toFIGS.1to3, as discussed above. For instance, as discussed above, the electroplating apparatus may include a movable head that is capable of moving from a first position to a second position in order to dispose substrate215and/or seal130within contact of bath solution207. After removing the substrate215and/or seal130from the plating solution207, the method includes rinsing the substrate215and/or seal130with the recycled rinse agent discussed herein. Furthermore, it should be noted that the transition from the first position to the section position may occur multiple times, with rinsing between each cycle, in embodiments.

In the preceding description, for the purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present technology. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details. For example, other substrates and semiconductor apparatus that may benefit from the rinse techniques described may also be used with the present technology.

Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present technology. Accordingly, the above description should not be taken as limiting the scope of the technology.

Where a range of values is provided, it is understood that each intervening value, to the smallest fraction of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Any narrower range between any stated values or unstated intervening values in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the technology, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included. Where multiple values are provided in a list, any range encompassing or based on any of those values is similarly specifically disclosed.

As used herein and in the appended claims, the singular forms “a”, “an”, and “the” 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 outlet” includes reference to one or more outlets and equivalents thereof known to those skilled in the art, and so forth.

Also, the words “comprise(s)”, “comprising”, “contain(s)”, “containing”, “include(s)”, and “including”, when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or operations, but they do not preclude the presence or addition of one or more other features, integers, components, operations, acts, or groups.