WO2021164894A1 - Electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate - Google Patents

Electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate Download PDF

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Publication number
WO2021164894A1
WO2021164894A1 PCT/EP2020/074266 EP2020074266W WO2021164894A1 WO 2021164894 A1 WO2021164894 A1 WO 2021164894A1 EP 2020074266 W EP2020074266 W EP 2020074266W WO 2021164894 A1 WO2021164894 A1 WO 2021164894A1
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WO
WIPO (PCT)
Prior art keywords
anode
deposition system
electrolyte
substrate
enclosure
Prior art date
Application number
PCT/EP2020/074266
Other languages
French (fr)
Inventor
Andreas Gleissner
Franz Markut
Ross Kulzer
Herbert Ötzlinger
Original Assignee
Semsysco Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Semsysco Gmbh filed Critical Semsysco Gmbh
Priority to JP2022528317A priority Critical patent/JP2023501797A/en
Priority to US17/797,589 priority patent/US20230056444A1/en
Priority to KR1020227012156A priority patent/KR20220061219A/en
Priority to CN202080076217.4A priority patent/CN114630927A/en
Priority to TW110115810A priority patent/TW202210664A/en
Publication of WO2021164894A1 publication Critical patent/WO2021164894A1/en

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002Cell separation, e.g. membranes, diaphragms
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/008Current shielding devices
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/02Tanks; Installations therefor
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10Electrodes, e.g. composition, counter electrode
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00Processes for servicing or operating cells for electrolytic coating
    • C25D21/04Removal of gases or vapours ; Gas or pressure control
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00Processes for servicing or operating cells for electrolytic coating
    • C25D21/12Process control or regulation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/001Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells

Definitions

  • Electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate
  • the invention relates to an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate, a module for chemical and/or electrolytic surface treatment of a substrate in a process fluid, a use of the electrochemical deposition system or the module for chemical and/or electrolytic surface treatment for a metal deposition application and a manufacturing method for such electrochemical deposition system.
  • the invention relates in particular to an electrochemical deposition of copper.
  • Copper plating has been a key enabling technology towards advanced integration with better electrical and thermal conductivity since its adoption in the late 1990s.
  • One of the main drivers for its success was the development and adoption of organic additives that allowed the plating to be better controlled and to occur precisely how and where desired (e.g. from the bottom up in a so called via-hole) and allow complete, void-free filling with final smooth surface finish.
  • via aspect ratios increase, chemistry costs rise, and substrate manufacturing throughput increases, a continuous need arises to develop a method, which reduces process and equipment complexity, tool down time and lowers the cost of ownership (e.g. chemical consumption) with the same chemistry and process stability.
  • organic additives are consumed at a relatively high rate during the electrochemical deposition process or even during the idle time of the tool, because they break down when exposed to certain by-products of the electrolytic deposition process especially around the anode, or the multiple anodes, and when in direct contact with the high anode currents. This leads to shortened bath life, in many cases to process instabilities and of course, high process cost of ownership. Since the costs associated with these organic additives are substantial, methods to reduce the amounts of organics consumed were quickly being investigated. Another major downside and danger to the process results stems from the fact that the decomposition of the organic additives, which is often an oxidative process, leads very commonly to the formation of gas bubbles (e.g.
  • the pH value of the anode electrolyte has to kept typically much higher, requiring the use of multiple chemistry tanks with at least two different types of electrolyte, further adding costs and complexity to the system and making the deposition system very challenging to control and maintain.
  • this two-electrolyte solution of the prior art adds a major disadvantage for the application of pulse-reverse plating, which is a useful feature for uniform plating of difficult features.
  • Utilizing pulse reverse plating with this two electrolyte approach will force the proton concentration to equilibrate in the two electrolytes and with this limit again the plating efficiency, which was supposed to be solved by this solution.
  • the plating rate is limited by the inherent resistance of the ion selective membrane to copper ion crossing, which might not be a major obstacle in damascene or dual-damascene plating, but very problematic in high speed plating applications of e.g. copper redistribution layers and pillars for wafer level packaging.
  • An electrochemical deposition chamber includes a processing unit having a first flow system configured to convey a flow of a first processing fluid to a micro feature workpiece.
  • the chamber further includes an electrode unit having an electrode and a second flow system configured to convey a flow of a second processing fluid at least proximate to the electrode.
  • the chamber further includes a nonporous barrier between the processing unit and the electrode unit to separate the first and second processing fluids. The nonporous barrier is configured to allow cations or anions to flow through the barrier between the first and second processing fluids.
  • an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate.
  • the electrochemical deposition system comprises an anode, an anode enclosure, and a single electrolyte.
  • the anode enclosure extends at least partially around the anode.
  • the anode enclosure comprises a membrane.
  • the anode and the anode enclosure are arranged in the single electrolyte.
  • the single electrolyte is the only electrolyte of the electrochemical deposition system.
  • electrolyte may ease analysis techniques, bath and system maintenance, plus may eliminate added costs of purchasing, monitoring and discarding different electrolyte mixtures. Further, multiple chemistry tanks with chemically significantly different types of electrolyte are avoided, which allows reducing costs and system complexity. As a result, an elegant and simple electrochemical deposition system is provided.
  • the present electrochemical deposition system may allow a reduction of organic additive consumption and associated costs. This advantage can be achieved while maintaining optimal process conditions and process stability.
  • the present electrochemical deposition system may have no organic additive consumption during idle time and normal consumption during process time.
  • the term “normal” can be understood as comparable to conventional systems, because a certain level of consumption of the additives during the process is, more or less, unavoidable.
  • the present electrochemical deposition system may be in particular suitable for high speed plating.
  • High Speed Plating can be understood as a system or method in which one or two High Speed Plate(s) together with one or two substrates are immersed into an electrochemical deposition tank containing an electrolyte and one or several anodes. Within this tank filled with electrolyte, the electrolyte flow (and with this the electrical current distribution) is directed through the High Speed Plate(s) towards the substrate surface(s).
  • the electrochemical deposition system according to the present invention may also allow a plating of complex features with still a good plating efficiency by means of e.g. pulse-reverse plating.
  • the substrate may comprise a conductor plate, a semi-conductor substrate, a film substrate, an essentially plate-shaped, metal or metallized workpiece or the like.
  • the substrate may be held in a substrate holder.
  • the electrolyte can be understood as a liquid providing the function of an electrolyte.
  • the single electrolyte is the only electrolyte of the electrochemical deposition system. This means there is only one kind of electrolyte and not two or more different kinds of electrolytes. This is in contrast to the prior art systems, where two different electrolytes are used. Consequently, there may be only one circulation system for the chemistry and not two separate circulation systems for the different electrolytes as in the prior art systems.
  • the anode can be understood as a solid body or a plurality of bodies providing the function of an anode.
  • the anode enclosure can be understood as a housing, which receives the anode.
  • the anode enclosure extends at least partially around the anode. This can be understood in that the anode enclosure forms a cup-shaped container surrounding the anode.
  • the cup-shaped container comprises (like a cup) a sidewall, a bottom wall and an opening on top opposite to the bottom wall.
  • the sidewalls may be parallel (like a cylinder) or tapering towards the bottom or the top (like a cone).
  • the sidewall may surround the anode completely or at least partially.
  • the sidewall may be a full 360° circle or an open circle with at least an interruption.
  • the 360° circle can also be understood as not being described by rounded shapes, but consists of angles and straight lines describing in principle square, rectangular, trapezoidal or other known shapes to the one skilled in the art, supporting the required functionality.
  • the opening on top of the cup-shaped container might be at least partially covered by the membrane, which means the membrane may extend over the opening of the anode enclosure.
  • the anode enclosure may comprise a (in a top view) ring shaped cover element, which reduces a diameter of the opening and therefore a diameter of the membrane.
  • the anode enclosure may further comprise at least one of a channel for providing an electrical connection for the anode, a channel for supplying the electrolyte, a channel as a vent line to discharge e.g. gas bubbles, etc.
  • the cover element may comprise a channel as a vent line to discharge e.g. gas bubbles, etc.
  • the channel of the cover element may lead to the channel of the anode enclosure.
  • the anode and the anode enclosure are arranged in the single electrolyte. This can be understood in that the anode and the anode enclosure are completely or at least partially immersed in the electrolyte or are subjected to the electrolyte by e.g. spraying or the like.
  • the anode enclosure comprises a membrane.
  • membrane can be understood as a selective barrier, which allows some parts (small molecules, ions, other small particles, etc.) to pass through, but stops or at least reduces the passage of others.
  • the anode, the anode enclosure, and the single electrolyte are arranged in an electrochemical deposition tank or a process chamber.
  • the walls of the tank may comprise channels for the electrolyte, gas ventilation etc.
  • the tank may be covered or closed by the substrate (e.g. in a substrate holder) and/or a distribution body.
  • the invention may relate to an electrochemical deposition of copper.
  • the present electrochemical deposition system may allow very good results with depositing copper and in particular with copper damascene deposition and copper dual damascene deposition. Damascene deposition will be explained further below.
  • the present electrochemical deposition system may also allow a high speed plating of copper.
  • the anode is inert.
  • inert may be understood as not chemically reactive. Inert anodes provide the advantage that no anode replacement maintenance must be performed, as the deposition material can just be injected as solution into the electrolyte. Furthermore, the cost of injecting liquid deposition material directly into the electrolyte to replenish the consumed deposition material is moderate and comparable to using consumable solid deposition material as soluble anodes.
  • the anode enclosure may extend partially or completely around the anode.
  • the anode enclosure is arranged as a flow divider.
  • the flow divider can be understood as a body shaped to direct a flow.
  • the flow divider is configured to direct gas formed during deposition away from the substrate to be treated.
  • the flow divider thereby copes with a formation of gas bubbles at the anode during plating, which would otherwise lead to bubble defects on a substrate surface.
  • the flow divider is configured to redirect gas bubbles to where they can be vented without causing defects on the substrate, consequently protects the substrate and therefore leads to a better deposition uniformity and layer quality.
  • the membrane is tilted relative to the anode. This can be understood in that the surface of the membrane is not parallel to the surface of the anode.
  • the membrane may have an angle in a range of 5° to 60° relative to the anode, preferably 5° to 45°, more preferably 5° to 30°.
  • the tilt may be implemented by fixing the membrane to the anode enclosure or to the cover element in different heights or by providing the sidewalls of the anode enclosure or the cover element with different heights and placing the membrane on top of the anode enclosure or the cover element.
  • the membrane is a bi-directional liquid permeable membrane. This means that the membrane may allow certain molecules or ions to pass through it by diffusion, but stops or at least reduces the passage of others.
  • the membrane is intended to be used in a liquid or humid environment.
  • the membrane here is specifically permeable for the chemistry, but mostly impermeable for e.g. gas bubbles.
  • the membrane can be understood as semi permeable.
  • the bi-directional liquid permeable membrane or enclosure may offer a further reduction in organic additive consumption and the associated costs.
  • the bi-directional liquid permeable membrane is non-ionic specific. This can be understood that the membrane is suitable for a wide range of ions and therefore does not need to be exchanged for different operation modes.
  • the bi-directional liquid permeable membrane is made of a polymer, in particular of polypropylene. In addition, other plastic materials are possible.
  • the module for chemical and/or electrolytic surface treatment of a substrate in a process fluid comprises an electrochemical deposition system as described above and a distribution body.
  • the distribution body is arranged in an electrolyte of the electrochemical deposition system and comprises from one to a plurality of openings.
  • the use of only a single electrolyte may allow reducing system complexity and costs.
  • the anode and the anode enclosure comprising the membrane may allow reducing the organic additive consumption and respective costs.
  • the module may relate to an electrochemical deposition process of copper and in particular to an electrochemical deposition of copper damascene and/or copper dual-damascene process.
  • "Damascene" means that an e.g. silicon oxide insulator layer is patterned to create open trenches or vias exposing an underlying conductor layer. A layer or multiple layers of copper are deposited on top of this underlying conductor into the open patterns of the insulator layer creating an overfill, so that the copper extends above the top of the insulator layer, which is then polished of or removed by another means. Copper within the trenches or vias of the insulator layer is not removed and becomes the newly created patterned conductor layer. Damascene processes generally form and fill a single feature with copper per processing step. Dual-Damascene processes generally form and fill two features (e.g. via and trench) with copper at once per processing step. With the successive deposition and patterning of insulator layer and successive electrodeposition of copper, a multilayer interconnect structure may be created.
  • the distribution body is a diffusor plate configured to distribute a field of electrical current relative to the substrate.
  • the diffusor plate may comprise one, preferably a plurality of openings. Theses openings or drains may allow controlling an electrical current distribution relative to a surface of the substrate.
  • the diffusor plate may be a plate comprising a pattern of openings.
  • the distribution body is a high speed plate configured to distribute a flow of the electrolyte relative to the substrate and to distribute a field of electrical current relative to the substrate.
  • the high speed plate may comprise one, preferably a plurality of openings or drain holes that allow controlling an electrical current distribution relative to a surface of the substrate.
  • the high speed plate may comprise one, preferably a plurality of openings or jet holes that allow controlling an electrolyte flow distribution relative to a surface of the substrate.
  • the high speed plate may be a sandwich or compound of a portion with the drain holes and another portion with the jet holes.
  • the electrochemical deposition system or the module for chemical and/or electrolytic surface treatment for a metal deposition application is presented.
  • the use of the present electrochemical deposition system or module may allow reducing complexity and costs.
  • the metal deposition application is a copper deposition application. In an embodiment, the metal deposition application is a copper damascene and/or a copper dual damascene deposition application.
  • the manufacturing method comprises the following steps, not necessarily in this order: providing an anode, arranging an anode enclosure at least partially around the anode, and arranging the anode and the anode enclosure in a single electrolyte, wherein the anode enclosure comprises a membrane, and wherein the single electrolyte is the only electrolyte of the electrochemical deposition method.
  • the present manufacturing method for an electrochemical deposition system may allow reducing complexity and costs of the electrochemical deposition system.
  • Figure 1 shows schematically and exemplarily an embodiment of an electrochemical deposition system and module for a chemical and/or electrolytic surface treatment of a substrate according to the invention.
  • Figure 2 shows schematically and exemplarily an embodiment of a manufacturing method for an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate.
  • FIG 1 shows schematically and exemplarily an embodiment of an electrochemical deposition system 10 for a chemical and/or electrolytic surface treatment of a substrate 20 according to the invention.
  • the substrate 20 is held in a substrate holder.
  • the electrochemical deposition system 10 comprises an anode 11, an anode enclosure 12, and a single electrolyte 13.
  • the electrochemical deposition system 10 is suitable for an electrochemical deposition of copper, in particular copper damascene deposition and copper dual damascene deposition.
  • the anode 11, the anode enclosure 12, and the single electrolyte 13 are arranged in an electrochemical deposition tank 24 or a process chamber.
  • the walls of the tank 24 comprise electrolyte passages 17 for the electrolyte 13, a gas passage 18 for gas ventilation and a passage for an electrical connection 21 for the anode 11.
  • the tank 24 is covered or closed by a distribution body 30 and the substrate 20 in the substrate holder.
  • the distribution body 30 comprises one or a plurality of openings 21.
  • the tank 24 comprises a recirculation line 25 for the liquid flow from the distribution body 30.
  • the electrolyte 13 is a liquid providing the function of an electrolyte 13.
  • the electrolyte 13 is the only electrolyte 13 of the electrochemical deposition system 10 and the electrochemical deposition system 10 comprises only one circulation system for the electrolyte 13.
  • the anode 11, the anode enclosure 12 and its membrane 14 are immersed in the electrolyte 13.
  • the anode 11 is a solid body providing the function of an anode 11.
  • the anode 11 is preferably inert, but can also be a non-inert, reactive or active anode.
  • the anode enclosure 12 is a housing, which receives the anode 11 and extends around the anode 11.
  • the anode enclosure 12 is a cup-shaped container surrounding the anode 11 by sidewalls, a bottom wall and an opening on top of the container opposite to the bottom wall.
  • the anode enclosure 12 comprises a channel for providing an electrical connection 21 for the anode 11, electrolyte channels 22 for supplying the electrolyte 13 into the anode enclosure 12, and a vent channel 23 to discharge e.g. gas bubbles.
  • the vent channel 23 can be directed downwards (as shown in Figure 1), but may also be directed upwards or in any other direction.
  • the anode enclosure 12 comprises a cover element 16, which reduces a diameter of the opening.
  • the cover element 16 comprises a vent line 19 to discharge e.g. gas bubbles, etc.
  • vent line 19 of the cover element may lead to the vent channel 23 of the anode enclosure 12 and the gas passage 18 of the deposition tank 24.
  • the opening on top of the cup-shaped container is covered by the membrane 14.
  • the anode enclosure 12 comprises a membrane 14.
  • the membrane 14 is a selective barrier, which allows some parts (small molecules, ions, other small particles, etc.) to pass through, but stops others.
  • the membrane 14 is a non-ionic specific bi-directional liquid permeable membrane. This means that the membrane 14 is here permeable for the electrolyte 13, but impermeable for gas bubbles.
  • the membrane 14 is made of a polypropylene.
  • the anode enclosure 12 and the membrane 14 form a flow divider, which directs gas formed during deposition away from the substrate 20 to be treated.
  • the flow divider thereby copes with a formation of gas bubbles at the anode 11 during plating, which would otherwise lead to bubble defects on a substrate surface.
  • the flow divider redirects the gas bubbles to the vent line 19 leading the gas bubbles outside the anode enclosure 12 and outside the deposition tank 24 without causing defects on the substrate 20.
  • the surface of the membrane 14 is tilted relative to the surface of the anode 11.
  • the tilt is implemented by fixing the membrane 14 to the cover element 16, while the sidewalls of the anode enclosure 12 having different heights leading to the sidewalls of the cover element 16 being at different heights.
  • the membrane 14 lies on top of the cover element 16.
  • FIG. 1 also shows schematically and exemplarily an embodiment of a module 100 for chemical and/or electrolytic surface treatment of a substrate 20 in a process fluid.
  • the module 100 comprises the electrochemical deposition system 10 as described above and the distribution body 30.
  • the distribution body 30 is arranged in the electrolyte 13 of the electrochemical deposition system 10 and comprises a plurality of openings 31.
  • the distribution body 30 is a high speed plate, which distributes a flow of the electrolyte 13 and a field of electrical current relative to the substrate 20.
  • the electrolyte 13 enters the tank 24 through electrolyte passages 17, flows through electrolyte channels 22 in the anode enclosure 12, and flows by the anode 11. A part of the electrolyte 13 flows into the vent line 19 in the cover element 16, then into the vent channel 23 in the anode enclosure 12, and then leaves the anode enclosure 12 at an outlet of the gas passage 18. Another part of the electrolyte 13 flows through the membrane 14 and through the openings 31 of the distribution body 30 to the substrate 20 and then leaves the tank 24 at an outlet of the recirculation line 25.
  • Gas bubbles may be formed at the anode 11 and flow from the anode 11 into the vent line 19 in the cover element 16, then into the vent channel 23 in the anode enclosure 12, and then leaves the anode enclosure 12 at an outlet of the gas passage 18 instead of harming the substrate 20.
  • FIG. 2 shows schematically and exemplarily an embodiment of a manufacturing method for an electrochemical deposition system 10 for a chemical and/or electrolytic surface treatment of a substrate 20.
  • the manufacturing method comprises the following steps, not necessarily in this order:
  • step SI providing an anode 11.
  • step S2 arranging an anode enclosure 12 at least partially around the anode 11.
  • step S3 arranging the anode 11 and the anode enclosure 12 in a single electrolyte 13.
  • the anode enclosure 12 comprises a membrane 14 and the single electrolyte 13 is the only electrolyte of the electrochemical deposition method.

Abstract

The invention relates to an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate, a module for chemical and/or electrolytic surface treatment of a substrate in a process fluid, a use of the electrochemical deposition system or the module for chemical and/or electrolytic surface treatment for a metal deposition application and a manufacturing method for an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate. The electrochemical deposition system comprises an anode, an anode enclosure, and a single electrolyte. The anode enclosure extends at least partially around the anode. The anode enclosure comprises a membrane. The anode and the anode enclosure are arranged in the single electrolyte. The single electrolyte is the only electrolyte of the electrochemical deposition system.

Description

Electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate
Field of invention
The invention relates to an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate, a module for chemical and/or electrolytic surface treatment of a substrate in a process fluid, a use of the electrochemical deposition system or the module for chemical and/or electrolytic surface treatment for a metal deposition application and a manufacturing method for such electrochemical deposition system. The invention relates in particular to an electrochemical deposition of copper.
Background
Copper plating has been a key enabling technology towards advanced integration with better electrical and thermal conductivity since its adoption in the late 1990s. First, for central processing units, later for memory and then for packaging and MEMs applications. One of the main drivers for its success was the development and adoption of organic additives that allowed the plating to be better controlled and to occur precisely how and where desired (e.g. from the bottom up in a so called via-hole) and allow complete, void-free filling with final smooth surface finish. As feature sizes shrink, via aspect ratios increase, chemistry costs rise, and substrate manufacturing throughput increases, a continuous need arises to develop a method, which reduces process and equipment complexity, tool down time and lowers the cost of ownership (e.g. chemical consumption) with the same chemistry and process stability.
In terms of electrochemical deposition chemistries, the main cost factors in running the process break down into what is consumed during the process time and what is consumed during idle time. Factors investigated here are the metal-ion (i.e. copper) and the organic additives concentrations which both add to the substantial cost of the process. Furthermore, as different devices continued to emerge, electrochemical deposition processes are continuously further developed to support higher aspect ratios and deeper vias, along with drastically shrinking feature sizes to support the various metal layer levels. This spurred also the further development of advanced organic additives required to accomplish the electrochemical deposition process. One downside of the organic additives is that they are consumed at a relatively high rate during the electrochemical deposition process or even during the idle time of the tool, because they break down when exposed to certain by-products of the electrolytic deposition process especially around the anode, or the multiple anodes, and when in direct contact with the high anode currents. This leads to shortened bath life, in many cases to process instabilities and of course, high process cost of ownership. Since the costs associated with these organic additives are substantial, methods to reduce the amounts of organics consumed were quickly being investigated. Another major downside and danger to the process results stems from the fact that the decomposition of the organic additives, which is often an oxidative process, leads very commonly to the formation of gas bubbles (e.g. C02 bubbles), which can - during the process - approach and get into contact with the substrate and cause major distractions during the electrolytic deposition process. As consequence, the deposition uniformity and quality of the deposited layer can suffer significantly. Also gas- bubbles formed in the electrolyte can handicap or even block the electrolyte flow through so called electrolyte and current flow distribution systems leading again to major deposition uniformity challenges by lowering the deposition rate in some places and occasionally even enhance the deposition rate in other places.
A solution found in prior art was the introduction of dual electrolyte systems separated by an ionic specific membrane. This permitted the use of an electrolyte without organic additives to circulate around the anode, where much of the unwanted degradation occurs. This additive free electrolyte is primarily responsible for warranting a continuous electrical flow from the anode, through the ion specific membrane to the cathode. However, a major disadvantage of this set-up is that protons can cross this membrane and cause significant deposition issues. Therefore, to avoid reducing the plating efficiency by protons crossing the membrane instead of copper crossing, the pH value of the anode electrolyte has to kept typically much higher, requiring the use of multiple chemistry tanks with at least two different types of electrolyte, further adding costs and complexity to the system and making the deposition system very challenging to control and maintain.
In addition, this two-electrolyte solution of the prior art adds a major disadvantage for the application of pulse-reverse plating, which is a useful feature for uniform plating of difficult features. Utilizing pulse reverse plating with this two electrolyte approach will force the proton concentration to equilibrate in the two electrolytes and with this limit again the plating efficiency, which was supposed to be solved by this solution. Additionally, the plating rate is limited by the inherent resistance of the ion selective membrane to copper ion crossing, which might not be a major obstacle in damascene or dual-damascene plating, but very problematic in high speed plating applications of e.g. copper redistribution layers and pillars for wafer level packaging.
US 2005/087439 A1 discloses chambers, systems and methods for electrochemically processing micro feature workpieces. An electrochemical deposition chamber includes a processing unit having a first flow system configured to convey a flow of a first processing fluid to a micro feature workpiece. The chamber further includes an electrode unit having an electrode and a second flow system configured to convey a flow of a second processing fluid at least proximate to the electrode. The chamber further includes a nonporous barrier between the processing unit and the electrode unit to separate the first and second processing fluids. The nonporous barrier is configured to allow cations or anions to flow through the barrier between the first and second processing fluids.
Summary
Hence, there may be a need to provide an improved electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate, which in particular is less complex than the prior art systems.
The problem is solved by the subject-matters of the independent claims of the present invention, wherein further embodiments are incorporated in the dependent claims. It should be noted that the aspects of the invention described in the following apply also to an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate, a module for chemical and/or electrolytic surface treatment of a substrate in a process fluid, a use of the electrochemical deposition system or the module for chemical and/or electrolytic surface treatment for a metal deposition application and a manufacturing method for an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate.
According to the present invention, an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate is presented. The electrochemical deposition system comprises an anode, an anode enclosure, and a single electrolyte.
The anode enclosure extends at least partially around the anode. The anode enclosure comprises a membrane. The anode and the anode enclosure are arranged in the single electrolyte. The single electrolyte is the only electrolyte of the electrochemical deposition system.
The use of only a single electrolyte may ease analysis techniques, bath and system maintenance, plus may eliminate added costs of purchasing, monitoring and discarding different electrolyte mixtures. Further, multiple chemistry tanks with chemically significantly different types of electrolyte are avoided, which allows reducing costs and system complexity. As a result, an elegant and simple electrochemical deposition system is provided.
The present electrochemical deposition system may allow a reduction of organic additive consumption and associated costs. This advantage can be achieved while maintaining optimal process conditions and process stability. The present electrochemical deposition system may have no organic additive consumption during idle time and normal consumption during process time. The term “normal” can be understood as comparable to conventional systems, because a certain level of consumption of the additives during the process is, more or less, unavoidable.
The present electrochemical deposition system may be in particular suitable for high speed plating. High Speed Plating can be understood as a system or method in which one or two High Speed Plate(s) together with one or two substrates are immersed into an electrochemical deposition tank containing an electrolyte and one or several anodes. Within this tank filled with electrolyte, the electrolyte flow (and with this the electrical current distribution) is directed through the High Speed Plate(s) towards the substrate surface(s).
The electrochemical deposition system according to the present invention may also allow a plating of complex features with still a good plating efficiency by means of e.g. pulse-reverse plating.
The substrate may comprise a conductor plate, a semi-conductor substrate, a film substrate, an essentially plate-shaped, metal or metallized workpiece or the like. The substrate may be held in a substrate holder.
The electrolyte can be understood as a liquid providing the function of an electrolyte. The single electrolyte is the only electrolyte of the electrochemical deposition system. This means there is only one kind of electrolyte and not two or more different kinds of electrolytes. This is in contrast to the prior art systems, where two different electrolytes are used. Consequently, there may be only one circulation system for the chemistry and not two separate circulation systems for the different electrolytes as in the prior art systems.
The anode can be understood as a solid body or a plurality of bodies providing the function of an anode.
The anode enclosure can be understood as a housing, which receives the anode. The anode enclosure extends at least partially around the anode. This can be understood in that the anode enclosure forms a cup-shaped container surrounding the anode. The cup-shaped container comprises (like a cup) a sidewall, a bottom wall and an opening on top opposite to the bottom wall.
In a cross section, the sidewalls may be parallel (like a cylinder) or tapering towards the bottom or the top (like a cone). The sidewall may surround the anode completely or at least partially. This means in a top view, the sidewall may be a full 360° circle or an open circle with at least an interruption. The 360° circle can also be understood as not being described by rounded shapes, but consists of angles and straight lines describing in principle square, rectangular, trapezoidal or other known shapes to the one skilled in the art, supporting the required functionality. The opening on top of the cup-shaped container might be at least partially covered by the membrane, which means the membrane may extend over the opening of the anode enclosure. The anode enclosure may comprise a (in a top view) ring shaped cover element, which reduces a diameter of the opening and therefore a diameter of the membrane. The anode enclosure may further comprise at least one of a channel for providing an electrical connection for the anode, a channel for supplying the electrolyte, a channel as a vent line to discharge e.g. gas bubbles, etc. In addition, the cover element may comprise a channel as a vent line to discharge e.g. gas bubbles, etc. The channel of the cover element may lead to the channel of the anode enclosure.
The anode and the anode enclosure are arranged in the single electrolyte. This can be understood in that the anode and the anode enclosure are completely or at least partially immersed in the electrolyte or are subjected to the electrolyte by e.g. spraying or the like.
The anode enclosure comprises a membrane. The term “membrane” can be understood as a selective barrier, which allows some parts (small molecules, ions, other small particles, etc.) to pass through, but stops or at least reduces the passage of others. The anode, the anode enclosure, and the single electrolyte are arranged in an electrochemical deposition tank or a process chamber. The walls of the tank may comprise channels for the electrolyte, gas ventilation etc. The tank may be covered or closed by the substrate (e.g. in a substrate holder) and/or a distribution body.
The invention may relate to an electrochemical deposition of copper. The present electrochemical deposition system may allow very good results with depositing copper and in particular with copper damascene deposition and copper dual damascene deposition. Damascene deposition will be explained further below. The present electrochemical deposition system may also allow a high speed plating of copper.
In an embodiment, the anode is inert. The term “inert” may be understood as not chemically reactive. Inert anodes provide the advantage that no anode replacement maintenance must be performed, as the deposition material can just be injected as solution into the electrolyte. Furthermore, the cost of injecting liquid deposition material directly into the electrolyte to replenish the consumed deposition material is moderate and comparable to using consumable solid deposition material as soluble anodes.
The anode enclosure may extend partially or completely around the anode. In an embodiment, the anode enclosure is arranged as a flow divider. The flow divider can be understood as a body shaped to direct a flow. The flow divider is configured to direct gas formed during deposition away from the substrate to be treated. The flow divider thereby copes with a formation of gas bubbles at the anode during plating, which would otherwise lead to bubble defects on a substrate surface. In other words, the flow divider is configured to redirect gas bubbles to where they can be vented without causing defects on the substrate, consequently protects the substrate and therefore leads to a better deposition uniformity and layer quality.
In an embodiment, the membrane is tilted relative to the anode. This can be understood in that the surface of the membrane is not parallel to the surface of the anode. The membrane may have an angle in a range of 5° to 60° relative to the anode, preferably 5° to 45°, more preferably 5° to 30°. The tilt may be implemented by fixing the membrane to the anode enclosure or to the cover element in different heights or by providing the sidewalls of the anode enclosure or the cover element with different heights and placing the membrane on top of the anode enclosure or the cover element. In an embodiment, the membrane is a bi-directional liquid permeable membrane. This means that the membrane may allow certain molecules or ions to pass through it by diffusion, but stops or at least reduces the passage of others. This function may apply in both directions, so from a first to a second side and from the second to the first side. The membrane is intended to be used in a liquid or humid environment. The membrane here is specifically permeable for the chemistry, but mostly impermeable for e.g. gas bubbles. The membrane can be understood as semi permeable. The bi-directional liquid permeable membrane or enclosure may offer a further reduction in organic additive consumption and the associated costs. In an embodiment, the bi-directional liquid permeable membrane is non-ionic specific. This can be understood that the membrane is suitable for a wide range of ions and therefore does not need to be exchanged for different operation modes. In an embodiment, the bi-directional liquid permeable membrane is made of a polymer, in particular of polypropylene. In addition, other plastic materials are possible.
According to the present invention, also a module for chemical and/or electrolytic surface treatment of a substrate in a process fluid is presented. The module for chemical and/or electrolytic surface treatment of a substrate in a process fluid comprises an electrochemical deposition system as described above and a distribution body. The distribution body is arranged in an electrolyte of the electrochemical deposition system and comprises from one to a plurality of openings.
The use of only a single electrolyte may allow reducing system complexity and costs. The anode and the anode enclosure comprising the membrane may allow reducing the organic additive consumption and respective costs.
The module may relate to an electrochemical deposition process of copper and in particular to an electrochemical deposition of copper damascene and/or copper dual-damascene process. "Damascene" means that an e.g. silicon oxide insulator layer is patterned to create open trenches or vias exposing an underlying conductor layer. A layer or multiple layers of copper are deposited on top of this underlying conductor into the open patterns of the insulator layer creating an overfill, so that the copper extends above the top of the insulator layer, which is then polished of or removed by another means. Copper within the trenches or vias of the insulator layer is not removed and becomes the newly created patterned conductor layer. Damascene processes generally form and fill a single feature with copper per processing step. Dual-Damascene processes generally form and fill two features (e.g. via and trench) with copper at once per processing step. With the successive deposition and patterning of insulator layer and successive electrodeposition of copper, a multilayer interconnect structure may be created.
In an embodiment, the distribution body is a diffusor plate configured to distribute a field of electrical current relative to the substrate. The diffusor plate may comprise one, preferably a plurality of openings. Theses openings or drains may allow controlling an electrical current distribution relative to a surface of the substrate. The diffusor plate may be a plate comprising a pattern of openings.
In another embodiment, the distribution body is a high speed plate configured to distribute a flow of the electrolyte relative to the substrate and to distribute a field of electrical current relative to the substrate. The high speed plate may comprise one, preferably a plurality of openings or drain holes that allow controlling an electrical current distribution relative to a surface of the substrate. The high speed plate may comprise one, preferably a plurality of openings or jet holes that allow controlling an electrolyte flow distribution relative to a surface of the substrate. The high speed plate may be a sandwich or compound of a portion with the drain holes and another portion with the jet holes.
According to the present invention, also a use of the electrochemical deposition system or the module for chemical and/or electrolytic surface treatment for a metal deposition application is presented. The use of the present electrochemical deposition system or module may allow reducing complexity and costs.
In an embodiment, the metal deposition application is a copper deposition application. In an embodiment, the metal deposition application is a copper damascene and/or a copper dual damascene deposition application.
According to the present invention, also a manufacturing method for an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate is presented. The manufacturing method comprises the following steps, not necessarily in this order: providing an anode, arranging an anode enclosure at least partially around the anode, and arranging the anode and the anode enclosure in a single electrolyte, wherein the anode enclosure comprises a membrane, and wherein the single electrolyte is the only electrolyte of the electrochemical deposition method.
The present manufacturing method for an electrochemical deposition system may allow reducing complexity and costs of the electrochemical deposition system.
It shall be understood that the system, the module, the use, and the method according to the independent claims have similar and/or identical preferred embodiments, in particular, as defined in the dependent claims. It shall be understood further that a preferred embodiment of the invention can also be any combination of the dependent claims with the respective independent claim.
These and other aspects of the present invention will become apparent from and be elucidated with reference to the embodiments described hereinafter.
Brief description of the drawings
Exemplary embodiments of the invention will be described in the following with reference to the accompanying drawing:
Figure 1 shows schematically and exemplarily an embodiment of an electrochemical deposition system and module for a chemical and/or electrolytic surface treatment of a substrate according to the invention.
Figure 2 shows schematically and exemplarily an embodiment of a manufacturing method for an electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate.
Detailed description of embodiments
Figure 1 shows schematically and exemplarily an embodiment of an electrochemical deposition system 10 for a chemical and/or electrolytic surface treatment of a substrate 20 according to the invention. The substrate 20 is held in a substrate holder. The electrochemical deposition system 10 comprises an anode 11, an anode enclosure 12, and a single electrolyte 13. The electrochemical deposition system 10 is suitable for an electrochemical deposition of copper, in particular copper damascene deposition and copper dual damascene deposition.
The anode 11, the anode enclosure 12, and the single electrolyte 13 are arranged in an electrochemical deposition tank 24 or a process chamber. The walls of the tank 24 comprise electrolyte passages 17 for the electrolyte 13, a gas passage 18 for gas ventilation and a passage for an electrical connection 21 for the anode 11. The tank 24 is covered or closed by a distribution body 30 and the substrate 20 in the substrate holder. The distribution body 30 comprises one or a plurality of openings 21. The tank 24 comprises a recirculation line 25 for the liquid flow from the distribution body 30.
The electrolyte 13 is a liquid providing the function of an electrolyte 13. The electrolyte 13 is the only electrolyte 13 of the electrochemical deposition system 10 and the electrochemical deposition system 10 comprises only one circulation system for the electrolyte 13. The anode 11, the anode enclosure 12 and its membrane 14 are immersed in the electrolyte 13.
The anode 11 is a solid body providing the function of an anode 11. The anode 11 is preferably inert, but can also be a non-inert, reactive or active anode.
The anode enclosure 12 is a housing, which receives the anode 11 and extends around the anode 11. The anode enclosure 12 is a cup-shaped container surrounding the anode 11 by sidewalls, a bottom wall and an opening on top of the container opposite to the bottom wall.
The anode enclosure 12 comprises a channel for providing an electrical connection 21 for the anode 11, electrolyte channels 22 for supplying the electrolyte 13 into the anode enclosure 12, and a vent channel 23 to discharge e.g. gas bubbles. The vent channel 23 can be directed downwards (as shown in Figure 1), but may also be directed upwards or in any other direction.
The anode enclosure 12 comprises a cover element 16, which reduces a diameter of the opening. The cover element 16 comprises a vent line 19 to discharge e.g. gas bubbles, etc.
The vent line 19 of the cover element may lead to the vent channel 23 of the anode enclosure 12 and the gas passage 18 of the deposition tank 24. The opening on top of the cup-shaped container is covered by the membrane 14.
The anode enclosure 12 comprises a membrane 14. The membrane 14 is a selective barrier, which allows some parts (small molecules, ions, other small particles, etc.) to pass through, but stops others. The membrane 14 is a non-ionic specific bi-directional liquid permeable membrane. This means that the membrane 14 is here permeable for the electrolyte 13, but impermeable for gas bubbles. The membrane 14 is made of a polypropylene.
The anode enclosure 12 and the membrane 14 form a flow divider, which directs gas formed during deposition away from the substrate 20 to be treated. The flow divider thereby copes with a formation of gas bubbles at the anode 11 during plating, which would otherwise lead to bubble defects on a substrate surface. The flow divider redirects the gas bubbles to the vent line 19 leading the gas bubbles outside the anode enclosure 12 and outside the deposition tank 24 without causing defects on the substrate 20.
The surface of the membrane 14 is tilted relative to the surface of the anode 11. The tilt is implemented by fixing the membrane 14 to the cover element 16, while the sidewalls of the anode enclosure 12 having different heights leading to the sidewalls of the cover element 16 being at different heights. The membrane 14 lies on top of the cover element 16.
Figure 1 also shows schematically and exemplarily an embodiment of a module 100 for chemical and/or electrolytic surface treatment of a substrate 20 in a process fluid. The module 100 comprises the electrochemical deposition system 10 as described above and the distribution body 30. The distribution body 30 is arranged in the electrolyte 13 of the electrochemical deposition system 10 and comprises a plurality of openings 31. The distribution body 30 is a high speed plate, which distributes a flow of the electrolyte 13 and a field of electrical current relative to the substrate 20.
The electrolyte 13 (marked by arrows) enters the tank 24 through electrolyte passages 17, flows through electrolyte channels 22 in the anode enclosure 12, and flows by the anode 11. A part of the electrolyte 13 flows into the vent line 19 in the cover element 16, then into the vent channel 23 in the anode enclosure 12, and then leaves the anode enclosure 12 at an outlet of the gas passage 18. Another part of the electrolyte 13 flows through the membrane 14 and through the openings 31 of the distribution body 30 to the substrate 20 and then leaves the tank 24 at an outlet of the recirculation line 25. Gas bubbles (marked by dots) may be formed at the anode 11 and flow from the anode 11 into the vent line 19 in the cover element 16, then into the vent channel 23 in the anode enclosure 12, and then leaves the anode enclosure 12 at an outlet of the gas passage 18 instead of harming the substrate 20.
Figure 2 shows schematically and exemplarily an embodiment of a manufacturing method for an electrochemical deposition system 10 for a chemical and/or electrolytic surface treatment of a substrate 20. The manufacturing method comprises the following steps, not necessarily in this order:
In step SI, providing an anode 11.
In step S2, arranging an anode enclosure 12 at least partially around the anode 11.
In step S3, arranging the anode 11 and the anode enclosure 12 in a single electrolyte 13. The anode enclosure 12 comprises a membrane 14 and the single electrolyte 13 is the only electrolyte of the electrochemical deposition method.
It has to be noted that embodiments of the invention are described with reference to different subject matters. In particular, some embodiments are described with reference to method type claims whereas other embodiments are described with reference to the device type claims. However, a person skilled in the art will gather from the above and the following description that, unless otherwise notified, in addition to any combination of features belonging to one type of subject matter also any combination between features relating to different subject matters is considered to be disclosed with this application. However, all features can be combined providing synergetic effects that are more than the simple summation of the features.
While the invention has been illustrated and described in detail in the drawings and foregoing description, such illustration and description are to be considered illustrative or exemplary and not restrictive. The invention is not limited to the disclosed embodiments. Other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing a claimed invention, from a study of the drawings, the disclosure, and the dependent claims.
In the claims, the word “comprising” does not exclude other elements or steps, and the indefinite article “a” or “an” does not exclude a plurality. A single processor or other unit may fulfil the functions of several items re-cited in the claims. The mere fact that certain measures are re-cited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. Any reference signs in the claims should not be construed as limiting the scope.

Claims

Claims
1. An electrochemical deposition system (10) for a chemical and/or electrolytic surface treatment of a substrate (20), comprising:
- an anode (11),
- an anode enclosure (12), and
- a single electrolyte (13), wherein the anode enclosure (12) at least partially extends around the anode (11), wherein the anode enclosure (12) comprises a membrane (14), wherein the anode (11) and the anode enclosure (12) are arranged in the single electrolyte (13), and wherein the single electrolyte (13) is the only electrolyte of the electrochemical deposition system (10).
2. Deposition system (10) according to claim 1, wherein the anode (11) is inert.
3. Deposition system (10) according to one of the preceding claims, wherein the anode enclosure (12) is arranged as a flow divider around the anode (11) to direct gas formed during deposition away from the substrate (20) to be treated.
4. Deposition system (10) according to one of the preceding claims, wherein the membrane (14) is tilted relative to the surface of the anode.
5. Deposition system (10) according to one of the preceding claims, wherein the anode enclosure (12) comprises a cover element (16) arranged in an opening of the anode enclosure (12), which reduces a diameter of the opening of the anode enclosure (12).
6. Deposition system (10) according to one of the preceding claims, wherein the membrane (14) is a bi-directional liquid permeable membrane.
7. Deposition system (10) according to the preceding claim, wherein the bi-directional liquid permeable membrane (14) is non-ionic specific.
8. Deposition system (10) according to claim 6, wherein the bi-directional liquid permeable membrane (14) is made of polypropylene.
9. A module (100) for chemical and/or electrolytic surface treatment of a substrate (20) in a process fluid, comprising:
- an electrochemical deposition system (10) according to one of the proceeding claims, and
- a distribution body (30), wherein the distribution body (30) is arranged in an electrolyte (13) of the electrochemical deposition system (10) and comprises a plurality of openings (31).
10. Module (100) according to claim 9, wherein the distribution body (30) is a diffusor plate configured to distribute a field of electrical current relative to the substrate (20).
11. Module (100) according to claim 9, wherein the distribution body (30) is a high speed plate configured to distribute a flow of the electrolyte (13) relative to the substrate (20) and to distribute a field of electrical current relative to the substrate (20).
12. A use of the electrochemical deposition system (10) or the module (100) for chemical and/or electrolytic surface treatment according to one of the preceding claims for a metal deposition application.
13. Use according to the preceding claim, wherein the metal deposition application is a copper deposition application.
14. Use according to claim 12 or 13, wherein the metal deposition application is a dual damascene deposition application.
15. An manufacturing method for an electrochemical deposition system (10) for a chemical and/or electrolytic surface treatment of a substrate (20), comprising the following steps:
- providing an anode (11),
- arranging an anode enclosure (12) at least partially around the anode (11), and
- arranging the anode (11) and the anode enclosure (12) in a single electrolyte (13), wherein the anode enclosure (12) comprises a membrane (14), and wherein the single electrolyte (13) is the only electrolyte of the electrochemical deposition method.
PCT/EP2020/074266 2020-02-19 2020-09-01 Electrochemical deposition system for a chemical and/or electrolytic surface treatment of a substrate WO2021164894A1 (en)

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KR1020227012156A KR20220061219A (en) 2020-02-19 2020-09-01 Electrochemical deposition systems for chemical and/or electrolytic surface treatment of substrates
CN202080076217.4A CN114630927A (en) 2020-02-19 2020-09-01 Electrochemical deposition system for the chemical and/or electrolytic surface treatment of substrates
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KR20220061219A (en) 2022-05-12

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