CN114703517A - Copper electroplating solution for filling through holes of IC carrier plate and electroplating method - Google Patents
Copper electroplating solution for filling through holes of IC carrier plate and electroplating method Download PDFInfo
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- CN114703517A CN114703517A CN202110296368.7A CN202110296368A CN114703517A CN 114703517 A CN114703517 A CN 114703517A CN 202110296368 A CN202110296368 A CN 202110296368A CN 114703517 A CN114703517 A CN 114703517A
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- electroplating
- acid
- copper
- plating solution
- copper plating
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- 238000009713 electroplating Methods 0.000 title claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 44
- 239000010949 copper Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 15
- 239000012964 benzotriazole Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000005010 aminoquinolines Chemical class 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920000223 polyglycerol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000001804 chlorine Chemical class 0.000 claims 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001431 copper ion Inorganic materials 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 24
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 229960001484 edetic acid Drugs 0.000 description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 7
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 150000003841 chloride salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 125000001309 chloro group Chemical class Cl* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses an electroplating copper solution for filling through holes of an IC carrier plate and an electroplating method thereof. The invention can keep more stable copper ion concentration near the cathode and stable copper ion deposition rate in the electroplating process by the combined action of the components in the electroplating solution, and the uniform and fine plating layer can be obtained at higher electroplating temperature and lower current density by electroplating with direct current.
Description
Technical Field
The invention relates to the field of electroplating liquid for IC carrier plates, in particular to an electroplating copper solution for filling through holes of an IC carrier plate and an electroplating method.
Background
The IC carrier is a key material for an integrated circuit, provides a connection between the IC chip and the PCB, and serves to protect the chip and serve as a transmission port between the chip and the outside. In order to meet the requirements of high precision, high integration and the like of an IC carrier, the development of through hole electroplating filling has become a popular theme in the field of microelectronics. The through hole electroplating of the IC carrier plate is usually copper plating filling, but the through hole copper plating is easy to generate the phenomena of holes, hole wrapping, cracks and the like, and at present, the phenomena of the holes, the hole wrapping and the cracks of the through hole are generally reduced by reducing the concentration of copper ions in electroplating solution or by a pulse electroplating mode. However, the concentration of copper ions in the electroplating solution is reduced, which increases the electroplating time, and the electroplating process of pulse electroplating is complicated and requires a great equipment cost, so the invention provides the electroplating copper solution and the electroplating method for filling the through holes of the IC carrier plate.
Disclosure of Invention
In order to solve the technical problem, the invention provides an electrolytic copper plating solution for filling through holes of an IC carrier, which includes copper salt, chloride salt, high molecular alcohols, organic acid, heterocyclic compound and deionized water.
Preferably, the polymer alcohol is an aliphatic polymer alcohol.
Preferably, the aliphatic polymer alcohol is at least one selected from the group consisting of polyvinyl alcohol, polypropylene glycol, polyethylene glycol, and polyglycerol.
Preferably, the organic acid is selected from at least one of carboxylic acid, sulfonic acid and sulfinic acid.
Preferably, the carboxylic acid is at least one selected from tartaric acid, oxalic acid, malic acid, citric acid, succinic acid and benzoic acid.
Preferably, the heterocyclic compound is at least one selected from the group consisting of a nitrogen-containing heterocyclic compound and a sulfur-containing heterocyclic compound.
Preferably, the nitrogen-containing heterocyclic compound is selected from at least one of benzotriazole, acetylpyridine, benzimidazole and aminoquinoline.
Preferably, the copper electroplating solution comprises 100-250g/L of copper salt, 30-50mg/L of chlorine salt, 0.1-5g/L of high molecular alcohol, 20-50g/L of organic acid, 0.1-5g/L of heterocyclic compound and deionized water.
The invention provides an electroplating method of an electroplating copper solution for filling through holes of an IC carrier plate, wherein the electroplating adopts direct current electroplating.
Preferably, the plating temperature is 50 to 60 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the copper electroplating solution and the electroplating method provided by the invention have the advantages of simple process, energy conservation, environmental protection and strong operability.
2. According to the invention, by adding high molecular alcohols, organic acids, heterocyclic compounds and other substances and by combining and complexing various active groups, the electroplating solution can keep relatively stable copper ion concentration near the cathode in the electroplating process, and the stable copper ion deposition rate is kept, so that the plating layer is uniform and fine.
3. According to the invention, through the compounding of the components in the electroplating solution, the direct current is adopted for electroplating, a uniform and fine coating can be obtained at a higher temperature and a lower current density, and the electroplating time is shortened.
Detailed Description
In order to solve the above technical problems, a first aspect of the present invention provides an electrolytic copper plating solution for filling through holes of an IC carrier, wherein the electrolytic copper plating solution comprises a copper salt, a chloride salt, a high molecular alcohol, an organic acid, a heterocyclic compound, and deionized water.
Preferably, the copper salt is at least one selected from copper sulfate pentahydrate, copper pyrophosphate and copper methylsulfonate.
Preferably, the copper salt is selected from copper sulfate pentahydrate.
Preferably, the chloride salt is selected from at least one of copper chloride, sodium chloride, potassium chloride, barium chloride and magnesium chloride.
Preferably, the chloride salt is selected from copper chloride.
Preferably, the polymer alcohol is an aliphatic polymer alcohol.
Preferably, the aliphatic polymer alcohol is at least one selected from the group consisting of polyvinyl alcohol, polypropylene glycol, polyethylene glycol, and polyglycerol.
Preferably, the aliphatic polymer alcohol is selected from polyethylene glycol.
Preferably, the organic acid is selected from at least one of carboxylic acid, sulfonic acid and sulfinic acid.
Preferably, the carboxylic acid is at least one selected from tartaric acid, oxalic acid, malic acid, citric acid, succinic acid, ethylenediamine tetraacetic acid and benzoic acid.
Preferably, the carboxylic acid is at least one selected from tartaric acid, ethylenediamine tetraacetic acid, malic acid and citric acid.
Preferably, the carboxylic acid is selected from ethylenediaminetetraacetic acid and citric acid.
Preferably, the weight ratio of the ethylenediamine tetraacetic acid to the citric acid is 1: (1.2-2).
The applicant has found that ethylenediaminetetraacetic acid and citric acid selected in the present copper plating bath system act together, particularly when the weight ratio of ethylenediaminetetraacetic acid to citric acid is 1: (1.2-2), the roughness of the plating layer can be reduced. The applicant speculates that the ethylenediamine tetraacetic acid and the citric acid are combined with the active ions in the copper plating solution, so that the freeness of impurity ions in the copper plating solution is reduced, a copper plating layer can be protected, meanwhile, the brightness and the flatness of a plating layer can be improved by the citric acid, and the quality of the generated plating layer is improved.
Preferably, the heterocyclic compound is at least one selected from the group consisting of a nitrogen-containing heterocyclic compound and a sulfur-containing heterocyclic compound.
Preferably, the nitrogen-containing heterocyclic compound is selected from at least one of benzotriazole, acetylpyridine, benzimidazole and aminoquinoline.
Preferably, the nitrogen-containing heterocyclic compound is selected from benzotriazoles.
Preferably, the weight ratio of the polyethylene glycol to the benzotriazole is 1: (0.2-0.5).
Applicants have found that the addition of polyethylene glycol and benzotriazole to the present copper plating bath system defines a weight ratio of polyethylene glycol to benzotriazole of 1: (0.2-0.5), the content of the copper ion-containing complex adsorbed on the surface of the carrier plate is stabilized through the compounding effect of the polyethylene glycol and the benzotriazole, the deposition rate of copper ions is stabilized, the fineness of a copper plating layer is improved, the toughness of the copper plating layer is improved, and the quality of the generated plating layer is improved.
Preferably, the copper electroplating solution comprises 100-250g/L of copper salt, 30-50mg/L of chlorine salt, 0.1-5g/L of high molecular alcohol, 20-50g/L of organic acid, 0.1-5g/L of heterocyclic compound and deionized water.
Preferably, the copper electroplating solution comprises 100-250g/L of copper sulfate pentahydrate, 30-50mg/L of copper chloride, 0.1-5g/L of polyethylene glycol, 10-20g/L of ethylene diamine tetraacetic acid, 10-30g/L of citric acid, 0.1-5g/L of benzotriazole and deionized water.
Preferably, the copper electroplating solution comprises 200-250g/L of copper sulfate pentahydrate, 30-50mg/L of copper chloride, 0.1-5g/L of polyethylene glycol, 10-20g/L of ethylene diamine tetraacetic acid, 10-30g/L of citric acid, 0.1-5g/L of benzotriazole and deionized water.
The invention provides an electroplating method of an electroplating copper solution for filling through holes of an IC carrier plate, wherein the electroplating adopts direct current electroplating.
Preferably, the plating temperature is 50 to 60 ℃.
Preferably, the plating temperature is 56 ℃.
Preferably, the electroplating time is 80-100min, and the current interval is 2-4 s.
Preferably, the electroplating time is 80min, and the current interval is 2 s.
Preferably, the current density is 1-1.5A/dm2。
Preferably, the current density is 1.5A/dm2。
The applicant found that the degree of coating fineness increased with increasing current density, but for the present copper plating bath system, the plating temperature was increased to 56 ℃ at 1.5A/dm2Electroplating for 80min under the current density of the electroplating solution to obtain a uniform, fine and flat plating layer without holes. The applicant speculates that the possible reasons are that the compounding effect of the components such as high molecular alcohols, organic acids, heterocyclic compounds and the like in the copper plating solution system promotes the copper ion concentration in the copper plating solution near the cathode to reach balance, reduces the phenomena of hydrogen evolution and the like easily occurring near the cathode in the electroplating process, reduces the void ratio of through holes, and improves the flatness and the compactness of a plating layer.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
The electrolytic copper plating solution for filling the through holes of the IC carrier plate is provided, and comprises the following raw materials: 200g/L of copper sulfate pentahydrate, 30mg/L of copper chloride, 3g/L of polyethylene glycol, 15g/L of ethylenediamine tetraacetic acid, 25g/L of citric acid, 1.5g/L of benzotriazole and deionized water.
The method comprises the steps of placing the pretreated carrier plate in the copper electroplating solution, using a phosphorus copper substance as an anode and the carrier plate as a cathode, and electrifying direct current in the electroplating process at 56 ℃ at current intervals of 2s and 1.5A/dm2Electroplating for 80 min.
The polyethylene glycol is purchased from Hengcheng Xingsheng technology Co., Ltd, and has the model of polyethylene glycol 400.
Example 2
The electrolytic copper plating solution for filling the through holes of the IC carrier plate is provided, and comprises the following raw materials: 220g/L copper sulfate pentahydrate, 30mg/L copper chloride, 3g/L polyethylene glycol, 15g/L ethylene diamine tetraacetic acid, 20g/L citric acid, 1g/L benzotriazole and deionized water.
The method comprises the steps of placing the pretreated carrier plate in the copper electroplating solution, using a phosphorus copper substance as an anode and the carrier plate as a cathode, and electrifying direct current in the electroplating process at 56 ℃ at current intervals of 2s and 1.5A/dm2Electroplating for 80 min.
Example 3
The electrolytic copper plating solution for filling the through holes of the IC carrier plate is provided, and comprises the following raw materials: 250g/L of copper sulfate pentahydrate, 40mg/L of copper chloride, 4g/L of polyethylene glycol, 20g/L of ethylenediamine tetraacetic acid, 40g/L of citric acid, 0.8g/L of benzotriazole and deionized water.
The method comprises the steps of placing the pretreated carrier plate in the copper electroplating solution, using a phosphorus copper substance as an anode and the carrier plate as a cathode, and electrifying direct current in the electroplating process at 56 ℃ at current intervals of 2s and 1.5A/dm2Electroplating for 80 min.
Comparative example 1
The specific implementation mode is the same as that of example 3, except that 2g/L of polyethylene glycol and 2.8g/L of benzotriazole are used.
Comparative example 2
The specific implementation mode is the same as that of example 3, except that 4.2g/L of polyethylene glycol and 0.6g/L of benzotriazole are used.
Comparative example 3
The specific implementation mode is the same as that of example 3, except that 4.8g/L of polyethylene glycol is used and no benzotriazole is added.
Comparative example 4
The specific implementation mode is the same as that of the comparative example 1, except that the current density is 3.0A/dm2。
Comparative example 5
The specific implementation mode is the same as that of comparative example 1, except that the electroplating time is 110 min.
Comparative example 6
The specific implementation mode is the same as that of example 3, except that the solution is 15g/L of ethylenediamine tetraacetic acid and 45g/L of citric acid.
Comparative example 7
The specific implementation mode is the same as that of example 3, and the difference is that the ethylenediaminetetraacetic acid is 40g/L, and the citric acid is 20 g/L.
Comparative example 8
The specific implementation mode is the same as that of example 3, except that the EDTA is 60g/L, and no citric acid is added.
Comparative example 9
The specific implementation mode is the same as that of the comparative example 5, except that the current density is 3.0A/dm2。
Comparative example 10
The specific implementation mode is the same as that of the comparative example 5, except that the electroplating time is 110 min.
Performance testing
1. And (4) measuring the thickness of the plating layer.
2. The roughness of the coating is measured, and when the surface of the coating has the phenomena of beading, peeling, bubbling, falling off, etc., and the height of the convex part accounts for more than 20% of the total coating thickness, the coating is recorded as rough, when the height of the convex part accounts for more than 10% and less than 20% of the total coating thickness, the coating is recorded as rough, and when the height of the convex part accounts for less than 5% of the total coating thickness, or the coating has no beading, peeling, bubbling, falling off, etc., the coating is recorded as smooth.
3. The brittleness of the coating is measured by uniformly applying pressure to a sample clamped in a specified die by using a metal steel ball or a spherical punch until the coating starts to crack, and recording the pressure value when the coating cracks.
4. And (4) measuring the hole of the through hole, longitudinally cutting off the through hole, and observing the hole phenomenon existing in the through hole after electroplating.
TABLE 1
| Thickness/mum | Roughness of | brittleness/N | Hollow spaces | |
| Example 1 | 18 | Is smooth and smooth | 35 | Is free of |
| Example 2 | 21 | Is smooth and smooth | 37 | Is composed of |
| Example 3 | 19 | Is smooth and smooth | 38 | Is free of |
| Comparative example 1 | 18 | Is smooth and smooth | 31 | Is provided with |
| Comparative example 2 | 19 | Is relatively coarse | 27 | Is provided with |
| Comparative example 3 | 23 | Roughness of | 24 | Is provided with |
| Comparative example 4 | 25 | Roughness of | 35 | Is free of |
| Comparative example 5 | 29 | Is smooth and smooth | 34 | Is free of |
| Comparative example 6 | 21 | Smooth and smooth | 26 | Is provided with |
| Comparative example 7 | 19 | Is smooth and smooth | 25 | Is provided with |
| Comparative example 8 | 22 | Is relatively coarse | 21 | Is provided with |
| Comparative example 9 | 26 | Roughness of | 36 | Is free of |
| Comparative example 10 | 30 | Is smooth and smooth | 35 | Is free of |
Finally, it is pointed out that the foregoing examples are illustrative only, serving to explain some of the characteristics of the process according to the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The electrolytic copper plating solution for filling the through holes of the IC carrier is characterized by comprising copper salt, chloride, high molecular alcohols, organic acid, heterocyclic compounds and deionized water.
2. The electrolytic copper plating solution according to claim 1, wherein the high molecular alcohol is an aliphatic high molecular alcohol.
3. The electrolytic copper plating solution according to claim 2, wherein the aliphatic polymer alcohol is at least one selected from the group consisting of polyvinyl alcohol, polypropylene glycol, polyethylene glycol, and polyglycerol.
4. The electrolytic copper plating solution according to claim 1, wherein the organic acid is at least one selected from the group consisting of carboxylic acid, sulfonic acid, sulfinic acid.
5. The electrolytic copper plating solution according to claim 4, wherein the carboxylic acid is at least one selected from the group consisting of tartaric acid, oxalic acid, malic acid, citric acid, succinic acid, and benzoic acid.
6. The electrolytic copper plating solution according to claim 1, wherein the heterocyclic compound is at least one selected from a nitrogen-containing heterocyclic compound and a sulfur-containing heterocyclic compound.
7. The electrolytic copper plating solution according to claim 6, wherein the nitrogen-containing heterocyclic compound is at least one selected from the group consisting of benzotriazole, acetylpyridine, benzimidazole, and aminoquinoline.
8. The copper electroplating solution as claimed in claim 1, wherein the copper electroplating solution comprises copper salt 100-250g/L, chlorine salt 30-50mg/L, high molecular alcohol 0.1-5g/L, organic acid 20-50g/L, heterocyclic compound 0.1-5g/L, and deionized water.
9. An electroplating method of the electrolytic copper plating solution according to claim 1, characterized in that the electroplating employs direct current electroplating.
10. The plating method of electrolytic copper plating solution according to claim 9, characterized in that the plating temperature is 50 to 60 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1497069A (en) * | 2002-06-03 | 2004-05-19 | 希普雷公司 | Uniform-planar agent compound |
| KR20070059617A (en) * | 2005-12-07 | 2007-06-12 | 재단법인서울대학교산학협력재단 | Cu electro deposition by using leveler |
| KR20090102464A (en) * | 2008-03-26 | 2009-09-30 | 재단법인서울대학교산학협력재단 | Electroless plating solution and plating method using the same |
| CN103103587A (en) * | 2013-02-22 | 2013-05-15 | 陕西师范大学 | Copper electroplating solution containing mercapto heterocyclic compound |
| KR20150059605A (en) * | 2013-11-22 | 2015-06-01 | 한국생산기술연구원 | Electroless copper plating solution composition and methods of plating copper using the same |
| CN105441993A (en) * | 2015-12-22 | 2016-03-30 | 苏州禾川化学技术服务有限公司 | Electroplating solution and electroplating method for electroplating through holes and blind holes of circuit boards |
| CN111945192A (en) * | 2020-08-11 | 2020-11-17 | 深圳市创智成功科技有限公司 | Blind hole filling electro-coppering solution for HDI (high Density interconnect) board and carrier board |
-
2021
- 2021-03-19 CN CN202110296368.7A patent/CN114703517B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1497069A (en) * | 2002-06-03 | 2004-05-19 | 希普雷公司 | Uniform-planar agent compound |
| KR20070059617A (en) * | 2005-12-07 | 2007-06-12 | 재단법인서울대학교산학협력재단 | Cu electro deposition by using leveler |
| KR20090102464A (en) * | 2008-03-26 | 2009-09-30 | 재단법인서울대학교산학협력재단 | Electroless plating solution and plating method using the same |
| CN103103587A (en) * | 2013-02-22 | 2013-05-15 | 陕西师范大学 | Copper electroplating solution containing mercapto heterocyclic compound |
| KR20150059605A (en) * | 2013-11-22 | 2015-06-01 | 한국생산기술연구원 | Electroless copper plating solution composition and methods of plating copper using the same |
| CN105441993A (en) * | 2015-12-22 | 2016-03-30 | 苏州禾川化学技术服务有限公司 | Electroplating solution and electroplating method for electroplating through holes and blind holes of circuit boards |
| CN111945192A (en) * | 2020-08-11 | 2020-11-17 | 深圳市创智成功科技有限公司 | Blind hole filling electro-coppering solution for HDI (high Density interconnect) board and carrier board |
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