CN1253609C - Copper replenishment technique for precision copper plating system - Google Patents
Copper replenishment technique for precision copper plating system Download PDFInfo
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- CN1253609C CN1253609C CNB998167851A CN99816785A CN1253609C CN 1253609 C CN1253609 C CN 1253609C CN B998167851 A CNB998167851 A CN B998167851A CN 99816785 A CN99816785 A CN 99816785A CN 1253609 C CN1253609 C CN 1253609C
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- solution
- copper
- plating
- plating solution
- cartridge
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
Abstract
The present invention relates to a copper supply system (10) which is designed for supplying copper lost in a copper plating solution (15). The supply is realized by using a filter cartridge (30) with a compact structure. The filter cartridge (30) is loaded in a solution circulation loop (12) and loads such chemical substances, namely that when the chemical substances react with the solution, copper is supplied to the solution. The filter cartridge (30) is an assembly with a compact structure, can be easily conveyed, and can reduce the quantity of pollutant probably resulted from the existence of supply materials.
Description
Technical Field
The invention relates to a copper plating system. In particular, the present invention relates to techniques for replenishing copper in plating solutions.
Background
Plating systems in which an object is immersed in a plating solution to plate metal onto the object are well known in the art. Various metals can be plated by simple immersion or by electroplating with the electrodes inserted into the solution. In copper plating, a plating solution such as a mixture of copper sulfate and sulfuric acid is used as a copper source to plate copper onto an object. Typically, a cathode is connected to the object to be plated (so that the object acts as a cathode) and an electrical potential is applied between the cathode and the anode. The copper ions in the solution are then reduced to the cathode electrode (i.e., the object to be plated).
In conventional copper plating, the anode electrode is typically made of copper, which dissolves into the plating solution as copper ions are consumed to replenish the copper ions. However, inert anodes are used for precision plating in such a way that the anode does not change shape during plating. Instead of oxidizing the copper ions from the anode material, some other source of copper material is required. In this case, a copper-containing material is added to the plating solution. That is, when the solution loses copper ions due to plating, some external source is used to replenish the copper ions in the solution.
Many copper replenishment techniques are known in the art. See, for example, US4324623, US5516414 and US 5609747. However, known copper replenishment techniques typically rely on the addition of copper sources such as copper sulfate and copper hydroxide to the bath. In some cases an intermediate container (or tank) is used, so that the copper source is not simply poured into the solution.
While this technique is adequate and acceptable for most common plating applications, it is not necessarily desirable to require a very clean environment. For example, in the fabrication of integrated circuits on semiconductor wafers (e.g., silicon wafers), contaminant particles are undesirable in the clean room where the devices are fabricated. Since the source copper material is in many applications in powder or granular form, the contamination coefficient is high when the material is in a clean room. Similarly, any insoluble particles resulting from the addition of solid material to the solution may have a deleterious effect on the plated wafer. Accordingly, we have recognized a need for an improved means of delivering source copper material into a copper plating solution.
Disclosure of Invention
A replenishment system for replenishing plating material lost to solution during a plating process is described. Replenishment is achieved by using a compact cartridge which is enclosed in a circulation loop of the solution. The replenishment system typically has a container for the plating solution and a loop for circulating the solution. The loop is filled with a container (can) containing a refill cartridge of material. The cartridge contains a chemical that, when reacted with the solution, introduces the plating material into the solution to increase the concentration of the plating material to a desired level.
Specifically, the present invention provides an apparatus for replenishing plating material lost from a plating solution, comprising: a container for containing the solution; a replenishing container connected to the holding container and circulating the solution back into the holding container; a cartridge inserted into the refill container for returning the coating material to the solution, the cartridge having an outer support structure for holding a chemical therein that replenishes coating material lost from the solution when reacting with the solution.
The present invention also provides an apparatus for replenishing copper lost from aplating solution used to plate copper onto a semiconductor wafer, comprising: a container for containing a plating solution; a replenishment container connected to the holding container and circulating the plating solution back into the holding container; a filter cartridge loaded into the replenishment vessel for feeding copper back into the plating solution, said filter cartridge having an outer support structure for containing therein a copper replenishment chemical which replenishes the solution for loss of copper as it reacts with the plating solution.
The present invention also provides a method of replenishing plating material lost from a plating solution comprising the steps of: pumping the plating solution from a holding vessel containing the plating solution to a refill vessel connected to the holding vessel; passing the plating solution through a filter cartridge loaded into the refill container, said filter cartridge having an outer support structure for holding chemical substances therein; returning plating material to the plating solution as the plating solution flows through the cartridge, said chemical replenishing plating material lost from the solution when reacting with the solution; recirculating additional plating solution back into the holding vessel.
Further, the present invention provides a cartridge for replenishing plating material lost from a plating solution, comprising: an outer support structure formed of a filter material for allowing a plating liquid to flow therethrough; a replenishment chemistry remaining therein which, when reacted with the plating solution flowing through the filter material, introduces the plating material into the solution.
The cartridge is a porous filter assembly having a hollow core. Chemicals for replenishing the plating material are contained in the filter element. The filter cartridge contains the chemical in a packageassembly during transport, handling and storage of the cartridge. The plating material is released only when the chemical reacts with the plating solution. The unique packaging and simplicity allows for the input of make-up chemicals into the plating system by simply loading the cartridge into the system. Furthermore, the cartridge can be simply replaced when the chemical in the filter element is exhausted.
In a preferred embodiment, the present invention is used to replenish copper in a copper plating system. The system is used to plate copper onto a semiconductor wafer. Although a wide variety of copper replenishment chemistries can be used, the filter cartridge of the preferred embodiment employs copper oxide and copper hydroxide to replenish the copper ions into the plating solution.
In a preferred embodiment, a sensor is used to monitor the copper concentration in the solution and a valve adds the filter cartridge to the circulation loop when the copper concentration falls below a predetermined level. The sensor may be an ampere-minute (or coulomb) monitoring device used in the plating process, or it may be a wide variety of other sensors used to monitor the plating parameters. In an alternative embodiment, a processor is used to automatically monitor and adjust the copper concentration level in the plating solution as needed.
Drawings
FIG. 1 is a schematic view of a plating replenishment system of the present invention.
FIG. 2 is a depiction of a vessel housing and a filter cartridge for replenishing plating material back into the plating solution.
Fig. 3 is a partial view of the filter cartridge shown in fig. 2.
FIG. 4 is the plating make-up system of FIG. 1, but now under the control of the processor.
Detailed Description
Now, a copper replenishment technique for a copper plating system is described. In the following description, numerous specific details are set forth, such as specific chemicals, structures, materials, processes, etc., in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without these specific details. In other instances, well-known techniques, structures, compositions, and chemistries have not been described in detail so as not to obscure the invention.
It should be noted that the present invention is now described with reference to copper make-up for copper plating systems in which copper oxide or hydroxide is used to replenish the copper ions in the solution. However, it is also recognized that the present invention may be practiced with other copper-supplementing chemistries and is not limited to copper oxide or hydroxide. Furthermore, the present invention can be easily applied to plating of other metals, not limited to copper plating.
Referring to fig. 1, a copper replenishment system 10 of the present invention is shown. The system 10 is comprised of a vessel 11, a circulation loop 12, a copper make-up source 13, and a number of pumps, valves and filters for circulating the plating solution 15. The container 11 may be a tank, tank or any other enclosure commonly used for holding plating solutions. In this example, the container 11 contains a copper plating solution. The specific composition and chemistry of the copper plating solution depends on the plating process being performed.
The container 11 itself may be used for the plating process, in which case the plating object is placedin the container 11. Although not shown, electrodes for copper electroplating may be wall-inserted into the container 11. Alternatively, the plating process may be performed outside the vessel 11. In this case, the vessel 1 will act as a source vessel for the plating solution 15 and some form of connecting piping will be used to carry the plating solution 15 to the site where the plating process is being carried out.
In the example of fig. 1, a feed line 16 carries the plating solution 15 from the vessel 11 to the plating site. For example, when the plating solution 15 is being used to plate copper onto a semiconductor wafer, the feed line 16 delivers the plating solution 15 to a plating chamber where copper is plated or deposited onto the wafer. If the plating solution from the wafer plating chamber is to be recycled, a return line, indicated as line 17, is used to return the liquid to the vessel 11. It will be appreciated that there are many applications where a container may be used to hold or provide the plating solution 15. The present invention is not in the process performed using a solution but in the replenishment of copper, which is lost from the plating solution 15 when the plating solution 15 is used for copper plating.
The recirculation loop 12 is used to withdraw a sample of the plating solution 15 from the vessel 11 and recirculate the plating solution 15 back into the vessel 11. In the circulation loop 12, the solution may flow in one of two flow paths. A pump 20 pumps the plating solution 15 from the vessel 11 to a valve 22. The liquid flow path at this point divides and follows the replenishment flow path 18 or follows the bypass flow path 19. The two flow paths 18, 19 again meet at a valve 23. A second pump 21 is provided in the make-up flow channel 18 to cause the liquid to flow through the copper make-up source 13. However, we have appreciated that the second pump 21 is not necessary if the flow passage 19 is completely closed, as the pump 20 will cause liquid to flow through the flow passage 18. Thus, liquid from the container 11 can be made to flow through the replenishment flow path 18 or by-pass it by operating the valves 22, 23 accordingly.
Also shown are filters and sensors that are typically used with the system 10. In this example, two filters 25, 26 (one being a pre-filter stage and the other being a final filter stage) are used to filter the liquid. The actual number of filters used is optional. The sensors are used to monitor the liquid in different stages, and thus the use, location and number of such sensors is also optional according to the needs of a particular application. In this example, sensor S1 is provided to monitor the solution prior to the copper replenishment stage. Sensor S2 is provided for monitoring the solution after the replenishment phase. Thus, the copper concentration of the liquid before and after passing through the copper replenishment source 13 can be monitored.
A third sensor S3 is also shown. Sensor S3 is provided for monitoring the solution in container 11. It will be appreciated that the sensor S3 may function like the sensor S2. Furthermore, if desired, the copper ion concentration can be monitored more simply by using only sensor S3 for simplicity. It is important that some type of sensor be used to detect and monitor the copper ion concentration level in the plating solution 15 so that additional copper can be added to the plating solution 15 if desired. It will be appreciated that a sensor may be a device for monitoring ampere-minutes (coulombs) used in a plating process. The coulomb value (charge amount) can be directly converted to the amount of copper (grain or weight) consumed by the plating process. The type of sensor used is also a design choice depending on the plating process being performed.
In the normal flow mode, the bypass flow channel 19 is used for liquid flow. The liquid is monitored by a sensor to ascertain the amount of copper ions in the solution. When the copper concentration level decreases to some predetermined value, additional copper ions are injected into the system by flowing liquid through the replenishment channel 18.
It will also be appreciated that in some cases the working flow loop (lines 16, 17) may be integrated with the circulation loop 12. In this case, the plating solution 15 is distributed to the plating equipment after passing through the valve 23 and the return line is connected to the inlet of the filter 25. That is, in the sketch of fig. 1, the coating apparatus is enclosed in the loop 12 between the filters 25, 26 and the vessel 11. Thus, in normal processing operation, the bypass flow path 19 is used to convey the plating solution from the container 11 to the plating equipment. When the copper concentration level in the vessel falls below a predetermined value, the cartridge 30 is loaded into the loop to replenish the copper. The choice of one or two loops is made primarily in accordance with the requirements of the plating equipment and the process being performed.
Means for implanting additional copper ions is provided by a copper replenishment source 13. The present invention employs a refill cartridge 30 that is enclosed in a container housing or canister 29. The inlet of the tank 29 is at the top and the outlet at the bottom (preferably at the center), so that the plating liquid flows into the tank 29 along the outer peripheral surface and flows out through the hollow center core (where the outlet is located) across the barrel 30. A more detailed illustration of the cartridge 30 and canister 29 is shown in fig. 2 and 3.
As shown in fig. 2 and 3, the cartridge 30 of the preferred embodiment is cylindrical. It will be appreciated that the shape of the cartridge 30 is arbitrarily designed. The cartridge 30 is comprised of an outer filter element 31 and an inner filter element 32. The filter element 31 is filled with the chemicals required to inject the plating chemical (copper in this case) into the liquid flowing through the tank 29. The inner filter element 32 is hollow (empty) to improve flow through the cartridge 30. The inner filter element 32 is connected to the outflow opening of the tank 29, so that the flow of liquid through the filter element is ensured.
The filter element 31 can be designed in several ways. Typically, it is constructed of a porous material to allow fluid to flow through the filter element. The filter may be designed as a double-walled filter structure (having an inner, outer or inner and outer structure) with the chemical substance trapped between the two walls, or the filter material may span the cross-section, in which case the chemical substance is dispersed within the filter material. The top and bottom surfaces of the cylinder are typically sealed (e.g., by a filter material), in which case the replenishment chemical is typically in powder form. We have also realized that the actual shape of the filter element 31 is of arbitrary design. It is important that some types of filter devices be used for liquid flow and that the make-up chemicals be dispersed in the cartridge 30 so that the chemicals are infused into the solution as the liquid flows through the filter element 31.
Further, according to the present invention, the cartridge 30 is made in the form of a packaged device for handling. Due to its unique packaging, the cartridge 30 can be transported and stored until it is to be used. When ready for use in system 10, the packaging is removed and cartridge 30 is inserted into canister 29. Once in the tank 29 and sealed, the plating solution 15 flows into the tank to react with the chemicals in the cartridge 30. Generally, it is preferable to provide the can 30 with a height sufficient so that both ends of the can 30are sealed from the upper and lower lids of the can 29.
The chemicals in the filter element 31 may be comprised of a variety of known chemicals that replenish copper ions into the plating solution. For example, supplementary chemistryThe substance may be copper hydroxide (Cu (OH)2) Or copper oxide (CuO). In a preferred embodiment, the core of the filter element 31 is made of CuO. Thus, CuO powder is charged to fill the open area of the filter member 31. The upper and lower ends of the cartridge 30 are sealed to seal the CuO in the filter member 31.
Once the cartridge 30 is loaded into the tank 29, plating solution 15 is flowed into the tank when copper replenishment is required. When the plating solution is copper sulfate (CuSO)4) And sulfuric acid (H)2SO4) When the copper oxide is in solution, the copper oxide reacts according to the following chemical reaction formula,
thereby returning copper ions to the solution to replenish the lost copper.
Significant advantages are obtained by using the cartridge 30 of the present invention. Compact packaging units can be easily transported, handled and stored as packaging units, unlike bulk chemicals currently in use. Cartridge 30 can be easily loaded into system 10 and easily removed when the refill chemical in filter 31 is exhausted. When used in or near a clean environment (e.g., a clean room), the isolation of the chemical in the cartridge significantly reduces the potential for the chemical to flow into the environment as a contaminant. The copper in the cartridge is only dissolved out of the cartridge when it reacts with the plating solution 15 in the tank 29. Thus, the copper replenishment cartridge (also referred to as a filter cartridge) of the preferred embodiment is a significant advance over known techniques for pumping copper-containing chemicals into a plating solution.
Referring to fig. 4, an alternative copper make-up system 40 is shown. The system 40 is a system 10 with an attached processor, such as a computer, labeled as a CPU 41. In the system 40, the monitoring and control functions of the loop 12 are controlled by a processor. Thus, the sensors, pumps and valves are connected to the CPU 41. The CPU41 monitors the copper concentration level in the plating solution 15 and when copper replenishment is required, the CPU adds the replenishment flow path 18 to the system 40. Once the appropriate copper content level has been restored, the make-up flow channel 18 is closed and the solution flows through the bypass flow channel 19. It will be appreciated that the CPU41 may be the same processing device that is used to control the plating process, whether the plating is being performed in the vessel 11 or at some other location.
Thus, a copper replenishment system has been described. It will be appreciated that the invention can readily be implemented for plating metals other than copper.
Claims (23)
1. An apparatus for replenishing plating material lost from a plating solution comprising: a container for containing the solution; a replenishing container connected to the holding container and circulating the solution back into the holding container; a cartridge inserted into the refill container for returning the coating material to the solution, the cartridge having an outer support structure for holding a chemical therein that replenishes coating material lost from the solution when reacting with the solution.
2. The apparatus of claim 1 wherein the outer support structureof the cartridge is made of a porous material that allows the solution to flow easily therethrough but retains the chemical in the cartridge until the chemical reacts with the solution.
3. The apparatus of claim 1, further comprising a valve and a sensor, said sensor for monitoring the concentration of plating material in the solution, said valve for controlling the flow of solution to the replenishment container.
4. The apparatus of claim 3, further comprising a processor for monitoring the sensor and in response thereto activating or deactivating the valve to automatically adjust the concentration of plating material in the solution.
5. The apparatus of claim 1, wherein the chemical species is copper oxide, CuO.
6. The apparatus of claim 1, wherein the chemical species is copper hydroxide, Cu (OH)2。
7. An apparatus for replenishing copper lost from a plating solution used to plate copper onto a semiconductor wafer, comprising: a container for containing a plating solution; a replenishment container connected to the holding container and circulating the plating solution back into the holding container; a filter cartridge loaded into the replenishment vessel for feeding copper back into the plating solution, said filter cartridge having an outer support structure for containing therein a copper replenishment chemical which replenishes the solution for loss of copper as it reacts with the plating solution.
8. The apparatus of claim 7 wherein the outer support structure of the cartridge is made of a porous material that allows the plating solution to flow easily therethrough but retains the powdered copper supplement chemistry in the cartridge until the chemistry reacts with the plating solution.
9. The apparatus of claim 7, further comprising a valve and a sensor, said sensor for monitoring the copper concentration in the plating solution, said valve for controlling the flow of plating solution to the replenishment vessel.
10. The apparatus of claim 9, further comprising a processor for monitoring the sensor and in response thereto activating or deactivating the valve to automatically adjust the copper concentration in the plating solution.
11. The apparatus of claim 8, wherein the chemical species is copper oxide, CuO.
12. The apparatus of claim 8, wherein the apparatus is configured to performCharacterized in that the chemical substance is copper hydroxide Cu (OH)2。
13. A method of replenishing plating material lost from a plating solution comprising the steps of: pumping the plating solution from a holding vessel containing the plating solution to a refill vessel connected to the holding vessel; passing the plating solution through a filter cartridge loaded into the refill container, said filter cartridge having an outer support structure for holding chemical substances therein; returning plating material to the plating solution as the plating solution flows through the cartridge, said chemical replenishing plating material lost from the solution when reacting with the solution; recirculating additional plating solution back into the holding vessel.
14. The method of claim 13 wherein the step of flowing the plating solution through a filter cartridge flows the solution through a porous filter cartridge that allows the plating solution to flow easily therethrough but retains the chemical in the cartridge until the chemical reacts with the plating solution.
15. The method of claim 13, further comprising a step of monitoring the plating material concentration in the plating solution and another step of controlling the flow of plating solution to the filter cartridge to adjust the amount of plating material being replenished into the plating solution.
16. The method of claim 15, further comprising the step of using a processor to monitor the plating material concentration in the plating solution and control the flow of plating solution to the filter cartridge.
17. The method of claim 13 wherein the replenishment of the plating material is to replenish copper in a plating solution used to plate the copper.
18. The method of claim 17, wherein the chemical species used to replenish copper is copper oxide, CuO.
19. The method of claim 17, wherein the chemical used to replenish copper is copper hydroxide, cu (oh)2。
20. A cartridge for replenishing plating material lost to a plating solution, comprising: an outer support structure formed of a filter material for allowing a plating liquid to flow therethrough; a replenishment chemistry remaining therein which, when reacted with the plating solution flowing through the filter material, introduces the plating material into the solution.
21. The cartridge of claim 20, wherein the outer support structure is formed of a porous filter material having a hollow core that allows the solution to readily flow therethrough, the supplemental chemical being contained within the porous filter material.
22. The cartridge of claim 21, wherein the supplemental chemical is copper oxide, CuO.
23. The cartridge of claim 21, wherein the supplemental chemical is copper hydroxide, cu (oh)2。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1999/010193 WO2000068468A1 (en) | 1998-03-30 | 1999-05-10 | Copper replenishment technique for precision copper plating system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1371432A CN1371432A (en) | 2002-09-25 |
| CN1253609C true CN1253609C (en) | 2006-04-26 |
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ID=22272716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998167851A Expired - Fee Related CN1253609C (en) | 1999-05-10 | 1999-05-10 | Copper replenishment technique for precision copper plating system |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1194616A4 (en) |
| JP (1) | JP2003502495A (en) |
| KR (1) | KR100764272B1 (en) |
| CN (1) | CN1253609C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070098134A (en) * | 2006-03-31 | 2007-10-05 | 신도플라텍 주식회사 | Automatic supplying device for plating solution |
| JP5293276B2 (en) * | 2008-03-11 | 2013-09-18 | 上村工業株式会社 | Continuous electrolytic copper plating method |
| CN105442024A (en) * | 2015-12-30 | 2016-03-30 | 桂林斯壮微电子有限责任公司 | Automatic chemical liquid adding system |
| CN111501074B (en) * | 2020-05-22 | 2021-07-16 | 佛山市诺诚科技有限公司 | Electroplating method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6021240B2 (en) * | 1980-01-12 | 1985-05-25 | 株式会社小糸製作所 | Method and apparatus for replenishing plating solution with deposited copper |
| US4568431A (en) * | 1984-11-13 | 1986-02-04 | Olin Corporation | Process for producing electroplated and/or treated metal foil |
| KR100241575B1 (en) * | 1994-02-28 | 2000-03-02 | 에모또 간지 | Continuous dissolving apparatus for metal powder for plating and dissolving method of metal Ni by the apparatus |
-
1999
- 1999-05-10 JP JP2000617236A patent/JP2003502495A/en active Pending
- 1999-05-10 EP EP99921825A patent/EP1194616A4/en not_active Withdrawn
- 1999-05-10 KR KR1020017014316A patent/KR100764272B1/en not_active IP Right Cessation
- 1999-05-10 CN CNB998167851A patent/CN1253609C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003502495A (en) | 2003-01-21 |
| CN1371432A (en) | 2002-09-25 |
| EP1194616A4 (en) | 2002-10-09 |
| KR100764272B1 (en) | 2007-10-05 |
| KR20020001871A (en) | 2002-01-09 |
| EP1194616A1 (en) | 2002-04-10 |
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