CN115216816A - Copper electroplating solution suitable for copper filling of blind holes of printed circuit board - Google Patents
Copper electroplating solution suitable for copper filling of blind holes of printed circuit board Download PDFInfo
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- CN115216816A CN115216816A CN202210982544.7A CN202210982544A CN115216816A CN 115216816 A CN115216816 A CN 115216816A CN 202210982544 A CN202210982544 A CN 202210982544A CN 115216816 A CN115216816 A CN 115216816A
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- copper
- printed circuit
- filling
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- blind holes
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 75
- 239000010949 copper Substances 0.000 title claims abstract description 75
- 238000009713 electroplating Methods 0.000 title claims abstract description 41
- 238000007747 plating Methods 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- -1 halogen ions Chemical class 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 9
- 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 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000004961 triphenylmethanes Chemical class 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229940043267 rhodamine b Drugs 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- IGZBSJAMZHNHKE-UHFFFAOYSA-N 2-[[4-[bis[4-(oxiran-2-ylmethoxy)phenyl]methyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1C(C=1C=CC(OCC2OC2)=CC=1)C(C=C1)=CC=C1OCC1CO1 IGZBSJAMZHNHKE-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XKTMIJODWOEBKO-UHFFFAOYSA-M Guinee green B Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC=CC=2)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 XKTMIJODWOEBKO-UHFFFAOYSA-M 0.000 claims description 2
- 241001233305 Xanthisma Species 0.000 claims description 2
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 claims description 2
- 229940052223 basic fuchsin Drugs 0.000 claims description 2
- 229960001506 brilliant green Drugs 0.000 claims description 2
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- JBTHDAVBDKKSRW-UHFFFAOYSA-N chembl1552233 Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 JBTHDAVBDKKSRW-UHFFFAOYSA-N 0.000 claims description 2
- NKLPQNGYXWVELD-UHFFFAOYSA-M coomassie brilliant blue Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=C1 NKLPQNGYXWVELD-UHFFFAOYSA-M 0.000 claims description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- HDAFVOZRAUFNQH-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;perchloric acid Chemical compound [O-]Cl(=O)(=O)=O.C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC HDAFVOZRAUFNQH-UHFFFAOYSA-N 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 2
- 229940107698 malachite green Drugs 0.000 claims description 2
- DWCZIOOZPIDHAB-UHFFFAOYSA-L methyl green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)[N+](C)(C)C)=C1C=CC(=[N+](C)C)C=C1 DWCZIOOZPIDHAB-UHFFFAOYSA-L 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- WGTODYJZXSJIAG-UHFFFAOYSA-N tetramethylrhodamine chloride Chemical compound [Cl-].C=12C=CC(N(C)C)=CC2=[O+]C2=CC(N(C)C)=CC=C2C=1C1=CC=CC=C1C(O)=O WGTODYJZXSJIAG-UHFFFAOYSA-N 0.000 claims description 2
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 claims description 2
- 229960000278 theophylline Drugs 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 claims description 2
- LLWJPGAKXJBKKA-UHFFFAOYSA-N victoria blue B Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C(C=C1)C2=CC=CC=C2C1=[NH+]C1=CC=CC=C1 LLWJPGAKXJBKKA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims 1
- FGGPAWQCCGEWTJ-UHFFFAOYSA-M sodium;2,3-bis(sulfanyl)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(S)CS FGGPAWQCCGEWTJ-UHFFFAOYSA-M 0.000 claims 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- YPKOTWSAVCIFAM-UHFFFAOYSA-N [Na].CCC Chemical compound [Na].CCC YPKOTWSAVCIFAM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LUARRPSPRYCMOT-UHFFFAOYSA-N propane-1,2-dithiol;sodium Chemical compound [Na].CC(S)CS LUARRPSPRYCMOT-UHFFFAOYSA-N 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
-
- 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
-
- 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
- H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
Abstract
The invention discloses an electrolytic copper plating solution suitable for filling copper in blind holes of a printed circuit board, which consists of blue vitriol, sulfuric acid, halogen ions and a combined additive, wherein: the combined additive comprises a leveling agent, an accelerator and an inhibitor; the content of the blue copperas is 75g/L, the content of the sulfuric acid is 240g/L, the content of the halogen ions is 60mg/L, the content of the accelerator is 0.5-20 mg/L, the content of the inhibitor is 50-1000 mg/L, and the content of the leveling agent is 5-500 mg/L. The electroplating copper plating solution uses triphenylmethane derivatives as leveling agents (plating leveling agents), can improve cathode polarization and uniformity, realizes filling of blind holes of a printed circuit board, and obtains copper interconnection lines with lower surface copper thickness and lower roughness.
Description
Technical Field
The invention belongs to the technical field of electroplating, relates to an electroplating copper plating solution, and particularly relates to an electroplating copper plating solution suitable for filling copper in blind holes of a printed circuit board.
Background
With the 5G era, electronic products are developing toward miniaturization, functionalization and integration. A Printed Circuit Board (PCB) is a basic component in an electronic product, and is a motherboard for carrying electronic components. The copper electroplating technology is a key technology for realizing metal interconnection of a printed circuit board at present, and can realize functions of interlayer interconnection, conduction between components and the like. Currently, the longest used copper electroplating process is the acid sulfate electroplating system. The plating solution has the advantages of stable system, simple composition, high current efficiency and strong dispersing ability. In the electroplating process, a large amount of copper ions near the printed circuit board are consumed, and the mass transfer of the copper ions in the local micro-holes is limited by diffusion, so that the plating speed in the holes is lower than that of the planes and the openings, and the shrinkage cavity defect is easily formed. In order to overcome the problem that the plating is easy to generate the shrinkage cavity defect, a proper organic additive is usually added into the copper plating solution to obtain a copper interconnection line with high quality.
At present, the common organic additives for electrolytic copper plating are mainly divided into: accelerators, suppressors and levelers. Among them, the accelerators, also called brighteners, accelerators, whose composition usually includes sulfonic acid groups and mercapto groups, are small molecule additives that act to accelerate copper deposition during electroplating. The suppressor, also known as a grain refiner, is typically a high molecular oxygen-containing polymer, such as polyethylene glycol or polypropylene glycol, that acts to suppress copper deposition during electroplating. The leveling agent is also called as a plating leveling agent or a second inhibitor, most of the leveling agent is a nitrogen-containing organic matter, has a large molecular weight and good electropositivity, is preferentially adsorbed at the tip part and the high current density part of the cathode in the electroplating process, can effectively inhibit the deposition of copper, and plays a leveling role. Through the synergistic effect of the three additives, the growth of copper in the micropores from bottom to top can be realized, and the copper interconnection line with excellent flatness is obtained.
During the electroplating of copper interconnects, surface copper thickness is an important indicator. When the areal copper thickness is too small, the uniformity of the copper interconnects is poor. However, the copper interconnection line with excessive thickness is difficult to realize precise interconnection, and the subsequent process is influenced. Therefore, obtaining copper interconnect lines with better uniformity is critical for precision lines. By developing an effective leveling agent, the uniformity of copper interconnection can be ensured and the uniformity of copper interconnection lines can be improved under the condition of obtaining the copper with lower surface copper thickness. The thickness of copper on the surface of the copper interconnection wire needs to be controlled below 50 microns at the current stage, and the problem cannot be solved by the existing electroplating additive. At the same time, the roughness of the copper interconnects also has a great influence. When the roughness is too high, the transmission signal is lost. Therefore, the development of an electroplating leveling agent capable of realizing high-quality copper interconnection is urgently needed, and the electroplating leveling agent has important significance and application potential.
Disclosure of Invention
The invention aims to provide an electro-coppering plating solution suitable for filling copper in blind holes of a printed circuit board, wherein triphenylmethane derivatives are used as leveling agents (plating levelers) in the electro-coppering plating solution, so that the cathode polarization can be improved, the uniformity can be improved, the filling of the blind holes of the printed circuit board can be realized, and copper interconnection lines with lower surface copper thickness and lower roughness can be obtained.
The purpose of the invention is realized by the following technical scheme:
an electroplating copper plating solution suitable for filling copper in blind holes of a printed circuit board comprises blue vitriol, sulfuric acid, halogen ions and a combined additive, wherein:
the combined additive comprises a leveling agent, an accelerator and an inhibitor;
the copper sulfate pentahydrate content is 75g/L, the sulfuric acid content is 240g/L, the halogen ion content is 60mg/L, the accelerator content is 0.5-20 mg/L, preferably 2-5 mg/L, the inhibitor content is 50-1000 mg/L, preferably 200-500 mg/L, and the leveling agent content is 5-500 mg/L, preferably 50-150 mg/L;
the halogen ion is one of chloride ion, bromide ion, iodide ion and the like;
the accelerator is a sulfur-containing organic matter, preferably one of 3-mercapto-1-propane sodium sulfonate, 2, 3-dimercaptopropane sodium sulfonate, 1, 3-propanedithiol, thiazolinyl dithiopropane sodium sulfonate, N-dimethyl dithioformamide propane sodium sulfonate, sodium lauryl sulfate, poly (dithio-dipropyl) sodium sulfonate and the like;
the inhibitor is an oxygen-containing polymer, preferably one of polyethylene glycol, polypropylene glycol and the like, and has the molecular weight of 6000-8000;
the leveling agent (the leveling agent) contains a functional group with a leveling function, and the leveling agent meeting the condition is a triphenylmethane derivative leveling agent;
the structural formula of the triphenylmethane derivative is as follows:
wherein X is an oxygen atom or a sulfur atom; r 1 、R 2 、R 3 、R 4 The same or different, respectively is one of hydrogen, alkyl carbon chain and oxygen-containing polymer; r 5 、R 6 、R 7 、R 8 、R 9 The same or different, respectively is one of hydrogen, alkyl carbon chain, oxygen-containing polymer, carboxylic acid group, amino group and ester group;
the preferable scheme of the triphenylmethane derivative is as follows: x is oxygen atom or sulfur atom; r is 1 、R 2 、R 3 、R 4 Is one of methyl, ethyl and oxygen-containing polymer, and the length of the carbon chain of the oxygen-containing polymer is 3 to 20; r is 6 、R 7 、R 8 Is one of hydrogen, methyl and ethyl, R 5 、R 9 Is one of hydrogen, methyl, ethyl, carboxylic acid group, amino group and ester group;
the triphenylmethane derivatives include but are not limited to: methyl green, acid green B, malachite green, brilliant green, rhodamine 6G perchlorate, rhodamine red B, tetraethylrhodamine butyl ester, 3, 6-bis (diethylamino) -9- [2- [ (octadecyloxy) carbonyl ] phenyl ] xanthium chloride, tetramethylrhodamine, ziney green B, acid green A, 4' -triaminotriphenylmethane, triisocyanate, tris (4-hydroxyphenyl) methane triglycidyl ether, rhodamine B, 1-triparaben ethyl, hydroxytriphenylmethane, 4- [ bis (4-hydroxyphenyl) methylene ] -2, 5-cyclohexanedione, basic fuchsin, brilliant blue G, acid blue 83, victoria blue B, etc.;
the components can effectively improve the dispersion capacity and the hole filling capacity of the plating solution under the synergistic action, improve the uniformity of the copper interconnection line and improve the roughness of the plating layer.
A method for electroplating by using the copper electroplating solution comprises the following steps:
placing the printed circuit board containing the blind hole into an electro-coppering plating solution, and electroplating in a constant current mode under the condition of air stirring, wherein the temperature of the plating solution is controlled to be 15-30 ℃, and the current density of electroplating is 0.5-1.5 A.dm -2 。
The invention has the following advantages:
1. the leveling agent is added, so that the surface copper is low in thickness, the uniformity of a plating layer is good, and the copper interconnection line with good flatness is obtained.
2. Compared with the prior art, the invention has the advantages of good leveling capability, compact and flat plating layer, good ductility and excellent gloss.
Drawings
FIG. 1 is a diagram showing the result of copper plating of blind holes;
FIG. 2 is a surface roughness test chart of example 1;
FIG. 3 is a surface SEM photograph of example 1;
FIG. 4 is a slice view of example 1;
FIG. 5 is a slice view of example 2;
FIG. 6 is a slice of example 3.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1:
in this example, the composition of the copper plating solution was as follows: copper sulfate pentahydrate: 75g/L, concentrated sulfuric acid: 240g/L, chloride ion: 60mg/L, accelerator sodium polydithio-dipropyl sulfonate: 2mg/L, inhibitor polyethylene glycol: 500mg/L, leveling agent rhodamine B:50mg/L or 150mg/L. Current density 1A/dm 2 The plating time was 2 hours. The printed circuit board used was 10cm x 5cm in size and the blind via diameter was 75 microns. The volume of a Harlin bath used for electroplating is 1.5 liters.
Before electroplating is carried out, oil removal, rust removal and surface activation are required. The method comprises the following specific steps: deoiling with deoiling liquid at 80 ℃ for 5min → room temperature water washing for 1min → acetone deoiling for 5min → room temperature water washing for 1min → derusting with 10% concentrated sulfuric acid for 5min → room temperature water washing for 1min → normal temperature presoaking for 1min → room temperature water washing for 1min. Wherein, the deoiling liquid comprises the following components: naOH (0.25 mol. L) -1 )、Na 2 SiO 3 ·9H 2 O(0.04mol·L -1 )、Na 3 PO 4 ·12H 2 O(0.15mol·L -1 )、Na 2 CO 3 (0.50mol·L -1 ) The oil removing temperature is 80 ℃ and the time is 5-10 min.
FIG. 2 is a roughness test chart of the surface of the copper plating layer, and FIGS. 2 (a) and 2 (B) respectively correspond to a concentration of rhodamine B of 50mg/L and 150mg/L, and a roughness of 22.2nm and 19.7nm, respectively, which are located at a nano scale, and show that the copper plating layer has fine and smooth crystals and excellent brightness.
FIG. 3 is a surface topography of copper plating, and FIGS. 3 (a) and 3 (B) correspond to rhodamine B concentrations of 50mg/L and 150mg/L, respectively, and it can be seen from FIG. 2 that the plating is dense, which can effectively reduce the loss in the signal transmission process.
FIG. 4 is a microsection of the cross section of the plated blind hole, and FIG. 4 (a) and FIG. 4 (B) correspond to the test results of the concentration of rhodamine B being 50mg/L and 150mg/L respectively, perfect filling is achieved in the 75 micron micro-hole, the surface copper thickness is less than 30 micron, and the uniformity is good.
Example 2:
in this example, the composition of the copper plating solution was as follows: copper sulfate pentahydrate: 75g/L, concentrated sulfuric acid: 240g/L, chloride ion: 60mg/L, accelerator sodium dodecyl sulfate: 2mg/L, inhibitor polyethylene glycol: 500mg/L, leveling agent tris (4-hydroxyphenyl) methane triglycidyl ether: 100mg/L or 200mg/L. Current density 1.5A/dm 2 Plating time was 2 hours. The printed circuit board used was 10cm x 5cm in size and the blind via diameter was 100 microns. The capacity of a Harlin bath used for electroplating is 1.5 liters.
Before electroplating is carried out, oil removal, rust removal and surface activation are required. The method comprises the following specific steps: deoiling with deoiling liquid at 80 ℃ for 5min → room temperature water washing for 1min → acetone deoiling for 5min → room temperature water washing for 1min → derusting with 10% concentrated sulfuric acid for 5min → room temperature water washing for 1min → normal temperature presoaking for 1min → room temperature water washing for 1min. Wherein the deoiling liquid consists of NaOH (0.25 mol. L) -1 )、Na 2 SiO 3 ·9H 2 O(0.04mol·L -1 )、Na 3 PO 4 ·12H 2 O(0.15mol·L -1 )、Na 2 CO 3 (0.50mol·L -1 ) The oil removing temperature is 80 ℃ and the time is 5-10 min.
FIG. 5 is a microsection image of the cross section of the plated blind hole, and FIG. 5 (a) and FIG. 5 (b) respectively correspond to the test results of the concentration of tris (4-hydroxyphenyl) methane triglycidyl ether of 100mg/L and 200mg/L, so that the blind hole of 100 micrometers is perfectly filled, the surface copper thickness is less than 35 micrometers, and the uniformity is good.
Example 3:
in this example, the composition of the copper plating solution was as follows: copper sulfate pentahydrate: 75g/L, concentrated sulfuric acid: 240g/L, chloride ion: 60mg/L, accelerator 3-mercapto-sodium 1-propanesulfonate: 2mg/L, inhibitor polyethylene glycol: 500mg/L, leveling agent rhodamine isothiocyanate B:50mg/L or 100mg/L. Current density 2A/dm 2 The plating time was 2 hours. The printed circuit board used was of dimensions 10cm x 5cm, with a blind via diameter of 150 microns. The volume of a Harlin tank used for electroplating is 1.5 liters.
Before electroplating is carried out, oil removal, rust removal and surface activation are required. The method comprises the following specific steps: deoiling with deoiling liquid at 80 ℃ for 5min → room temperature water washing for 1min → acetone deoiling for 5min → room temperature water washing for 1min → derusting with 10% concentrated sulfuric acid for 5min → room temperature water washing for 1min → normal temperature presoaking for 1min → room temperature water washing for 1min. Wherein the deoiling liquid consists of NaOH (0.25 mol. L) -1 )、Na 2 SiO 3 ·9H 2 O(0.04mol·L -1 )、Na 3 PO 4 ·12H 2 O(0.15mol·L -1 )、Na 2 CO 3 (0.50mol·L -1 ) The oil removing temperature is 80 ℃ and the time is 5-10 min.
FIG. 6 is a microsection image of the cross section of the plated blind hole, and FIG. 6 (a) and FIG. 6 (B) respectively correspond to the test results that the concentration of rhodamine isothiocyanate B is 50mg/L and 100mg/L, perfect filling is realized in the micro-hole of 150 micrometers, the thickness of surface copper is less than 40 micrometers, and the uniformity is good.
TABLE 1
Claims (10)
1. The copper electroplating solution suitable for filling copper in the blind holes of the printed circuit board is characterized by consisting of blue copperas, sulfuric acid, halogen ions and combined additives, wherein:
the combined additive comprises a leveling agent, an accelerator and an inhibitor;
the content of the blue copperas is 75g/L, the content of the sulfuric acid is 240g/L, the content of the halogen ions is 60mg/L, the content of the accelerator is 0.5-20 mg/L, the content of the inhibitor is 50-1000 mg/L, and the content of the leveling agent is 5-500 mg/L.
2. The copper electroplating bath suitable for filling copper in blind holes of printed circuit boards as claimed in claim 1, wherein the accelerator is 2-5 mg/L, the suppressor is 200-500 mg/L, and the leveler is 50-150 mg/L.
3. The copper electroplating solution suitable for copper filling of the blind holes of the printed circuit board according to claim 1, wherein the halogen ion is one of chloride ion, bromide ion and iodide ion; the accelerator is sulfur-containing organic matter, and the inhibitor is oxygen-containing polymer.
4. The copper electroplating solution suitable for copper filling of blind holes in printed circuit boards as claimed in claim 3, wherein the sulfur-containing organic compound is one of sodium 3-mercapto-1-propane sulfonate, sodium 2, 3-dimercaptopropane sulfonate, 1, 3-propanedithiol, thiazolinyl dithiopropane sulfonate, sodium N, N-dimethyldithioformamide propane sulfonate, sodium lauryl sulfate and sodium polydithio-dipropane sulfonate.
5. The copper electroplating solution suitable for copper filling of the blind holes of the printed circuit board according to claim 3, wherein the oxygen-containing polymer is one of polyethylene glycol and polypropylene glycol, and the molecular weight is 6000 to 8000.
6. The copper electroplating bath suitable for copper filling of blind vias in printed circuit boards according to claim 1 wherein the leveler is a triphenylmethane derivative.
7. The copper electroplating solution suitable for copper filling of blind holes in printed circuit boards according to claim 1, wherein the triphenylmethane derivative has a structural formula:
wherein X is an oxygen atom or a sulfur atom；R 1 、R 2 、R 3 、R 4 The same or different, respectively is one of hydrogen, alkyl carbon chain and oxygen-containing polymer; r 5 、R 6 、R 7 、R 8 、R 9 The same or different, and is one of hydrogen, alkyl carbon chain, oxygen-containing polymer, carboxylic acid group, amino group and ester group.
8. The copper electroplating bath suitable for copper filling of blind vias of printed circuit boards as claimed in claim 7 wherein X is an oxygen atom or a sulfur atom; r 1 、R 2 、R 3 、R 4 Is one of methyl, ethyl and oxygen-containing polymer, and the length of the carbon chain of the oxygen-containing polymer is 3 to 20; r 6 、R 7 、R 8 Is one of hydrogen, methyl and ethyl, R 5 、R 9 Is one of hydrogen, methyl, ethyl, carboxylic acid group, amino group and ester group.
9. The copper electroplating solution suitable for copper filling of blind holes in printed circuit boards as claimed in claim 6, wherein the triphenylmethane derivative is one of methyl green, acid green B, malachite green, brilliant green, rhodamine 6G perchlorate, rhodamine red B, tetraethyl rhodamine butyl ester, 3, 6-bis (diethylamino) -9- [2- [ (octadecyloxy) carbonyl ] phenyl ] xanthium chloride, tetramethylrhodamine, benilyGreen B, acid green A, 4' -triaminotriphenylmethane, triisocyanate, tris (4-hydroxyphenyl) methane triglycidyl ether, rhodamine B, 1-triphenylethane, hydroxytriphenylmethane, 4- [ bis (4-hydroxyphenyl) methylene ] -2, 5-cyclohexanedione, basic fuchsin, brilliant blue G, acid blue 83 and victoria blue B.
10. A method of electroplating using the electrolytic copper plating bath according to any one of claims 1 to 9, characterized in that the method comprises the steps of:
placing the printed circuit board containing the blind hole into an electroplating copper plating solution, and electroplating by adopting a constant current mode under the condition of air stirring, wherein the temperature of the plating solution is controlled to be 15-30 ℃, and the electroplating is carried outHas a current density of 0.5 to 1.5A dm -2 。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105297088A (en) * | 2014-05-28 | 2016-02-03 | 无锡永发电镀有限公司 | Electroplate liquid for acid copper plating of triphenylmethane dye system and electroplating method |
| US20190100848A1 (en) * | 2016-06-21 | 2019-04-04 | Guangdong Guanghua Sci-Tech Co., Ltd. | Copper Electroplating Solution and Copper Electroplating Process |
| CN112593262A (en) * | 2020-12-07 | 2021-04-02 | 博敏电子股份有限公司 | Electroplating solution additive containing pyrrolidine dithioammonium formate and application thereof |
| CN113430598A (en) * | 2021-08-27 | 2021-09-24 | 深圳市板明科技股份有限公司 | Circuit board blind hole filling electro-coppering solution and application thereof |
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- 2022-08-16 CN CN202210982544.7A patent/CN115216816A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105297088A (en) * | 2014-05-28 | 2016-02-03 | 无锡永发电镀有限公司 | Electroplate liquid for acid copper plating of triphenylmethane dye system and electroplating method |
| US20190100848A1 (en) * | 2016-06-21 | 2019-04-04 | Guangdong Guanghua Sci-Tech Co., Ltd. | Copper Electroplating Solution and Copper Electroplating Process |
| CN112593262A (en) * | 2020-12-07 | 2021-04-02 | 博敏电子股份有限公司 | Electroplating solution additive containing pyrrolidine dithioammonium formate and application thereof |
| CN113430598A (en) * | 2021-08-27 | 2021-09-24 | 深圳市板明科技股份有限公司 | Circuit board blind hole filling electro-coppering solution and application thereof |
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