CN115369460A - Copper electroplating solution for filling micro blind holes - Google Patents
Copper electroplating solution for filling micro blind holes Download PDFInfo
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- CN115369460A CN115369460A CN202211168091.0A CN202211168091A CN115369460A CN 115369460 A CN115369460 A CN 115369460A CN 202211168091 A CN202211168091 A CN 202211168091A CN 115369460 A CN115369460 A CN 115369460A
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- composite
- mass concentration
- filling
- concentration ratio
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
Abstract
The invention discloses an electro-coppering solution filled with micro blind holes, which comprises the following components in mass concentration: 50-90g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 50-70ppm/L of chloride ions, 20-80ppm/L of composite accelerator, 20-80ppm/L of composite wetting agent, 10-40ppm/L of composite leveling agent, 10-40ppm/L of nucleating agent and the balance of deionized water. The electro-coppering solution for filling the micro blind holes provided by the invention can realize high-efficiency electro-coppering of the micro blind holes with high thickness-diameter ratio, can finish the hole filling process through direct current electroplating, and has the advantages of low cost, high hole filling efficiency, low equipment requirement and the like.
Description
Technical Field
The invention belongs to the technical field of electro-coppering, and relates to an electro-coppering solution filled with micro blind holes.
Background
In recent years, with the development of electronic products toward lightness, thinness, shortness, smallness and multifunctionality, particularly, high integration of semiconductor chips, rapid increase of the number of I/O and rapid progress of high-density mounting technology, printed boards having high density, high precision, high reliability and low cost are urgently required. Conventional via interconnection has not been able to meet the requirements of high-density wiring and electronic products, and the blind via interconnection technology has been widely used. At present, the micro blind hole interconnection technology has three types: firstly, the traditional hole electroplating technology; secondly, the traditional technology of filling the copper-plated film with conductive adhesive (or resin material); third, the micro blind hole copper electroplating filling technology. The micro blind hole electro-coppering filling technology can realize one-time completion of copper plating filling and electrical interconnection, can improve electrical performance and connection reliability, is superior to conductive adhesive and resin materials in the aspects of conductivity and heat dissipation of a used copper material, and becomes an important method for realizing interconnection of printed boards at present.
With the development of communication technology and the application of the internet of things, people have greatly improved requirements for speed and efficiency of information exchange, for example, patents CN103361681A, CN102995076A and the like all realize micropore filling, but when through holes become deeper and smaller, i.e., the hole pattern is greater than 10, the market filling rate is less than 85%, and the quality requirement of thinnest copper thickness is difficult to meet. Therefore, the invention provides a copper electroplating technology for filling micro blind holes to solve the problem.
Disclosure of Invention
The electro-coppering solution provided by the invention can realize high-efficiency electro-coppering of fine blind holes with high thickness-diameter ratio, can complete the hole-filling process through direct current electroplating, and has the advantages of low cost, high hole-filling efficiency, low equipment requirement and the like.
The invention discloses an electro-coppering solution for filling micro blind holes, which comprises the following components in mass concentration: 50-90g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 50-70ppm/L of chloride ions, 20-80ppm/L of composite accelerator, 20-80ppm/L of composite wetting agent, 10-40ppm/L of composite leveling agent, 10-40ppm/L of nucleating agent and the balance of deionized water.
The chloride ion is provided by concentrated hydrochloric acid.
The composite accelerator is a mixture consisting of phenyl sodium dithiopropane sulfonate, mercaptoimidazole sodium propane sulfonate and dimethyl-sodium dithioformamide sulfonate, and the mass concentration ratio of the composite accelerator in use is 1.
The composite wetting agent is composed of octyl and decyl alcohol polyoxyethylene ether and decyne glycol polyether, the mass concentration ratio of the composite wetting agent to the decyl alcohol polyoxyethylene ether is 1-4, the octyl and decyl alcohol polyoxyethylene ether is 4-16ppm/L, and the decyne glycol polyether is 16-64ppm/L when the composite wetting agent is used.
Wherein the composite leveling agent is a polyethylene glycol, polypropylene glycol and polyvinylpyrrolidone compound, and the mass concentration ratio of the composite leveling agent in use is 1:1, namely 2-8ppm/L of polyethylene glycol, 2-8ppm/L of polypropylene glycol and 6-24ppm/L of polyvinylpyrrolidone.
Wherein the nucleating agent is 5-fluorouracil.
Wherein the mass concentration ratio of the composite accelerator to the composite leveling agent in use is 2.
Wherein, the mass concentration ratio of the composite wetting agent to the composite leveling agent is 2.
Wherein the mass concentration ratio of the nucleating agent to the composite leveling agent in use is 1.
The invention has the following excellent effects: compared with the prior art, the invention provides the electro-coppering solution for filling the micro blind holes, which has the following advantages:
1) The composite accelerator provided by the invention can generate a synergistic effect with chloride ions, promote the electrodeposition of copper, enable plating solution to enter holes more easily and increase the mass transfer effect.
2) The composite wetting agent provided by the invention is beneficial to ordered deposition of copper ions in a large current density area, and can improve current density distribution by being adsorbed on the surface of a cathode so as to realize uniform deposition.
3) The mass concentration ratio of the composite wetting agent to the composite leveling agent in use is 2.
4) The composite accelerator and the composite leveling agent can greatly improve the uniformity of the deposition rate inside and outside the hole, thereby realizing the deposition rate of the hole and the copper surface which is close to 1.
Detailed Description
In order to more clearly describe the present invention, the present invention is further described below by means of words.
The invention discloses an electro-coppering solution for filling micro blind holes, which comprises the following components in mass concentration: 50-90g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 50-70ppm/L of chloride ions, 20-80ppm/L of composite accelerator, 20-80ppm/L of composite wetting agent, 10-40ppm/L of composite leveling agent, 10-40ppm/L of nucleating agent and the balance of deionized water.
The chloride ion is provided by concentrated hydrochloric acid.
In this embodiment, the composite accelerator is a mixture of sodium phenyl dithiopropane sulfonate, sodium mercaptoimidazole propane sulfonate and sodium dimethyl-dithioformamide sulfonate, and the mass concentration ratio of the composite accelerator to the sodium phenyl dithiopropane sulfonate is 1-20 ppm/L, 5-20ppm/L of sodium mercaptoimidazole propane sulfonate and 10-40ppm/L of sodium dimethyl-dithioformamide sulfonate.
In this embodiment, the composite wetting agent is polyoxyethylene octyldecanol ether and decynediol polyether, and the mass concentration ratio of the composite wetting agent to the decynediol polyether is 1.
In this embodiment, the composite leveling agent is a polyethylene glycol, polypropylene glycol, and polyvinylpyrrolidone complex, and the mass concentration ratio of the polyethylene glycol, polypropylene glycol, and polyvinylpyrrolidone complex is 1:1, namely 2-8ppm/L of polyethylene glycol, 2-8ppm/L of polypropylene glycol and 6-24ppm/L of polyvinylpyrrolidone.
In this example, the nucleating agent is 5-fluorouracil.
In this embodiment, the mass concentration ratio of the composite accelerator to the composite leveler when in use is 2.
In this embodiment, the mass concentration ratio of the composite wetting agent to the composite leveling agent in use is 2.
In this embodiment, the mass concentration ratio of the nucleating agent to the composite leveling agent in use is 1.
The invention has the following excellent effects: compared with the prior art, the invention provides the electro-coppering solution filled with the micro blind holes, which has the following advantages:
1) The composite accelerator provided by the invention can generate a synergistic effect with chloride ions, promote the electrodeposition of copper, enable plating solution to enter holes more easily and increase the mass transfer effect.
2) The composite wetting agent provided by the invention is beneficial to ordered deposition of copper ions in a large current density area, and can improve current density distribution by being adsorbed on the surface of a cathode so as to realize uniform deposition.
3) The mass concentration ratio of the composite wetting agent to the composite leveling agent in use is 2.
4) The mass concentration ratio of the composite accelerator to the composite leveling agent in use is 2.
The evaluation grade standard of the experimental test is as follows:
example 1
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 60ppm/L of chloride ions, 10ppm/L of phenyl dithiopropane sodium sulfonate, 10ppm/L of mercaptoimidazole propane sodium sulfonate, 20ppm/L of dimethyl-dithioformamide sodium sulfonate, 8ppm/L of octyl-decyl alcohol polyoxyethylene ether, 32ppm/L of decyne glycol polyether, 4ppm/L of polyethylene glycol, 4ppm/L of polypropylene glycol, 12ppm/L of polyvinylpyrrolidone and 20ppm/L of 5-fluorouracil.
The test is carried out on an intelligent vertical wafer electroplating machine, the volume of an electroplating distribution groove is 20L, the circulation quantity is 12L/min, and the frequency of a swing motor is 25Hz. The parameters of the electroplating process are that the first section 0ASD is kept stand for 1min, the second section 0.5ASD is electroplated for 10min, and the third section 1.5ASD is electroplated for 60min.
Example 2
80g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 50ppm/L of chloride ions, 5ppm/L of phenyl dithiopropane sodium sulfonate, 5ppm/L of mercaptoimidazole propanesodium sulfonate, 10ppm/L of dimethyl-dithioformamide sodium sulfonate, 4ppm/L of caprylyl-decyl alcohol polyoxyethylene ether, 16ppm/L of decyne glycol polyether, 2ppm/L of polyethylene glycol, 2ppm/L of polypropylene glycol, 6ppm/L of polyvinylpyrrolidone and 10ppm/L of 5-fluorouracil.
The test is carried out on an intelligent science and technology vertical wafer electroplating machine, the volume of an electroplating distribution groove is 20L, the circulation quantity is 12L/min, and the frequency of a swing motor is 25Hz. The parameters of the electroplating process are that the first section 0ASD is kept stand for 1min, the second section 0.5ASD is electroplated for 10min, and the third section 1.5ASD is electroplated for 60min.
Example 3:
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 70ppm/L of chloride ions, 20ppm/L of phenyl dithiopropane sodium sulfonate, 20ppm/L of mercaptoimidazole propanesodium sulfonate, 40ppm/L of dimethyl-dithioformamide sodium sulfonate, 16ppm/L of caprylyl-decyl alcohol polyoxyethylene ether, 64ppm/L of decyne glycol polyether, 8ppm/L of polyethylene glycol, 8ppm/L of polypropylene glycol, 24ppm/L of polyvinylpyrrolidone and 40ppm/L of 5-fluorouracil.
The test is carried out on an intelligent vertical wafer electroplating machine, the volume of an electroplating distribution groove is 20L, the circulation quantity is 12L/min, and the frequency of a swing motor is 25Hz. The parameters of the electroplating process are that the first section 0ASD is kept stand for 1min, the second section 0.5ASD is electroplated for 10min, and the third section 1.5ASD is electroplated for 60min.
Comparative example
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 70ppm/L of chloride ions, 20ppm/L of sodium phenyl dithiopropane sulfonate and 8ppm/L of polyethylene glycol.
The test is carried out on an intelligent vertical wafer electroplating machine, the volume of an electroplating distribution groove is 20L, the circulation quantity is 12L/min, and the frequency of a swing motor is 25Hz. The parameters of the electroplating process are that the first section 0ASD is kept stand for 1min, the second section 0.5ASD is electroplated for 10min, and the third section 1.5ASD is electroplated for 60min.
Five substrates were taken as a group for each example and the data obtained were as follows:
by the above comparison, the comparative example lacks, compared with the examples, mercaptoimidazolepropanesulfonic acid, sodium dimethyl-dithioformamidosulfonate, octyldecanol polyoxyethylene ether, decynediol polyether, polypropylene glycol, polyvinylpyrrolidone, 5-fluorouracil. The results obtained by the embodiment are excellent hole filling capability, excellent uniformity and excellent orifice breakage; the comparative example has poor deep plating capability, poor hole filling capability, poor uniformity and poor orifice fracture.
The above disclosure is only an example of the present invention, but the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.
Claims (8)
1. The copper electroplating solution for filling the blind micro-holes is characterized by comprising the following components in concentration by mass: 50-90g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 50-70ppm/L of chloride ions, 20-80ppm/L of a composite accelerator, 20-80ppm/L of a composite wetting agent, 10-40ppm/L of a composite leveling agent, 10-40ppm/L of a nucleating agent and the balance of deionized water, wherein the chloride ions are provided by concentrated hydrochloric acid.
2. The copper electroplating solution for blind via filling according to claim 1, wherein the accelerator is a mixture of sodium phenyl dithiopropane sulfonate, sodium mercaptoimidazole propanesulfonate and sodium dimethyl-dithioformamide sulfonate, and the mass concentration ratio of the accelerator in use is 1.
3. The electrolytic copper plating solution filled with blind micro holes as claimed in claim 1, wherein the composite wetting agent is polyoxyethylene octyldecanol and decynediol polyether, and the mass concentration ratio of the polyoxyethylene octyldecanol to the decynediol polyether in use is 1.
4. The electrolytic copper plating solution for filling blind micro holes as claimed in claim 1, wherein the composite leveling agent is a polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone composite, and the mass concentration ratio of the polyethylene glycol, polypropylene glycol and polyvinylpyrrolidone composite is 1:1, 2-8ppm/L of polyethylene glycol, 2-8ppm/L of polypropylene glycol and 6-24ppm/L of polyvinylpyrrolidone.
5. The electrolytic copper plating solution for blind via filling according to claim 1, wherein the nucleating agent is 5-fluorouracil.
6. The electrolytic copper plating solution for filling blind micro vias as claimed in claim 1, wherein the mass concentration ratio of the composite accelerator to the composite leveler in use is 2.
7. The electrolytic copper plating solution for filling blind micro holes, according to claim 1, wherein the mass concentration ratio of the composite wetting agent to the composite leveling agent is 2.
8. The electrolytic copper plating solution filled with blind micro vias as claimed in claim 1, wherein the mass concentration ratio of the nucleating agent to the composite leveling agent in use is 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211168091.0A CN115369460A (en) | 2022-09-23 | 2022-09-23 | Copper electroplating solution for filling micro blind holes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211168091.0A CN115369460A (en) | 2022-09-23 | 2022-09-23 | Copper electroplating solution for filling micro blind holes |
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| Publication Number | Publication Date |
|---|---|
| CN115369460A true CN115369460A (en) | 2022-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211168091.0A Pending CN115369460A (en) | 2022-09-23 | 2022-09-23 | Copper electroplating solution for filling micro blind holes |
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| CN (1) | CN115369460A (en) |
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- 2022-09-23 CN CN202211168091.0A patent/CN115369460A/en active Pending
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