CN118390125B - Copper electroplating additive suitable for IC carrier plate and preparation method and application thereof - Google Patents
Copper electroplating additive suitable for IC carrier plate and preparation method and application thereof Download PDFInfo
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- CN118390125B CN118390125B CN202410819863.5A CN202410819863A CN118390125B CN 118390125 B CN118390125 B CN 118390125B CN 202410819863 A CN202410819863 A CN 202410819863A CN 118390125 B CN118390125 B CN 118390125B
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- copper
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- sulfide
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 106
- 239000010949 copper Substances 0.000 title claims abstract description 106
- 238000009713 electroplating Methods 0.000 title claims abstract description 99
- 239000000654 additive Substances 0.000 title claims abstract description 65
- 230000000996 additive effect Effects 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- MNURPFVONZPVLA-UHFFFAOYSA-N 2-chlorobenzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1Cl MNURPFVONZPVLA-UHFFFAOYSA-N 0.000 claims abstract description 26
- FLQYOORLPNYQEV-UHFFFAOYSA-N 2-chlorobenzenecarbothioamide Chemical class NC(=S)C1=CC=CC=C1Cl FLQYOORLPNYQEV-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 chlorobenzoyl sulfide derivative Chemical class 0.000 claims abstract description 21
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical class OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000005406 washing Methods 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 150000003568 thioethers Chemical class 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- PRRMJTDPKZBCCQ-UHFFFAOYSA-N 2,3-dichlorobenzenecarbothioamide Chemical compound NC(=S)C1=CC=CC(Cl)=C1Cl PRRMJTDPKZBCCQ-UHFFFAOYSA-N 0.000 claims description 6
- YCTAOQGPWNTYJE-UHFFFAOYSA-N 3-amino-5-chloro-2-hydroxybenzenesulfonic acid Chemical compound NC1=CC(Cl)=CC(S(O)(=O)=O)=C1O YCTAOQGPWNTYJE-UHFFFAOYSA-N 0.000 claims description 6
- IEYRVMPISNTHDA-UHFFFAOYSA-N 6-chloro-7-thiabicyclo[4.1.0]hepta-2,4-diene Chemical class C1=CC=CC2(Cl)C1S2 IEYRVMPISNTHDA-UHFFFAOYSA-N 0.000 claims description 6
- MJEPOVIWHVRBIT-UHFFFAOYSA-N 1-chloro-4-(4-chlorophenyl)sulfanylbenzene Chemical compound C1=CC(Cl)=CC=C1SC1=CC=C(Cl)C=C1 MJEPOVIWHVRBIT-UHFFFAOYSA-N 0.000 claims description 5
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims description 5
- WDNBLWURITYPQL-UHFFFAOYSA-N 2,4-dichlorobenzenecarbothioamide Chemical compound NC(=S)C1=CC=C(Cl)C=C1Cl WDNBLWURITYPQL-UHFFFAOYSA-N 0.000 claims description 4
- KGKGSIUWJCAFPX-UHFFFAOYSA-N 2,6-dichlorothiobenzamide Chemical compound NC(=S)C1=C(Cl)C=CC=C1Cl KGKGSIUWJCAFPX-UHFFFAOYSA-N 0.000 claims description 4
- VYZCFAPUHSSYCC-UHFFFAOYSA-N 2-amino-5-chloro-4-methylbenzenesulfonic acid Chemical compound CC1=CC(N)=C(S(O)(=O)=O)C=C1Cl VYZCFAPUHSSYCC-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005703 Trimethylamine hydrochloride Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 17
- 238000011049 filling Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 48
- 239000000306 component Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 4
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 4
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- QDZAHNHWJFQWDL-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfanyl-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1SC1=CC=C(Cl)C=C1 QDZAHNHWJFQWDL-UHFFFAOYSA-N 0.000 description 2
- JZLUOCTZACJYNR-UHFFFAOYSA-N 2-(4-chlorophenyl)sulfanylaniline Chemical compound NC1=CC=CC=C1SC1=CC=C(Cl)C=C1 JZLUOCTZACJYNR-UHFFFAOYSA-N 0.000 description 2
- XJQRCFRVWZHIPN-UHFFFAOYSA-N 3-amino-4-chlorobenzenesulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=CC=C1Cl XJQRCFRVWZHIPN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XTJKNGLLPGBHHO-HNNXBMFYSA-N (2s)-5-(diaminomethylideneamino)-2-(dodecanoylamino)pentanoic acid Chemical compound CCCCCCCCCCCC(=O)N[C@H](C(O)=O)CCCN=C(N)N XTJKNGLLPGBHHO-HNNXBMFYSA-N 0.000 description 1
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 1
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 description 1
- SKYUVFJWPPLPST-UHFFFAOYSA-N C1(=CC=CC=C1)SC1=CC=CC=C1.[Cl] Chemical class C1(=CC=CC=C1)SC1=CC=CC=C1.[Cl] SKYUVFJWPPLPST-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 1
- CAXRKYFRLOPCAB-UHFFFAOYSA-N propane-1,1-disulfonic acid Chemical compound CCC(S(O)(=O)=O)S(O)(=O)=O CAXRKYFRLOPCAB-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
-
- 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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
- H01L21/4864—Cleaning, e.g. removing of solder
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses an electrolytic copper plating additive suitable for an IC carrier plate, and a preparation method and application thereof, and relates to the technical field of electrolytic copper plating of IC carrier plates. The electrolytic copper plating additive suitable for the IC carrier plate comprises the following components in mass concentration: 20-50mg/L of chlorobenzenesulfonic acid derivative, 10-100mg/L of chlorobenzoyl sulfide derivative, 20-80mg/L of chlorothiobenzamide derivative and 10-50mg/L of leveling agent. The mass ratio of the chlorosulfonic acid derivative to the chlorodiphenyl sulfide derivative is 1: (0.5-2.0). The copper electroplating additive suitable for the IC carrier plate can be used in an acid copper electroplating system of the IC carrier plate, has uniform and smooth plating layer, good adhesive force, qualified blind hole filling effect and deep plating capacity value of the through holes reaching more than 94%, and can be suitable for an electroplating process of the IC carrier plate with line width and line distance of 10 microns.
Description
Technical Field
The invention relates to the technical field of IC carrier plate copper electroplating, in particular to a copper electroplating additive suitable for an IC carrier plate, and a preparation method and application thereof.
Background
With the development of packaging technology, the IC carrier industry is increasing speed leading other boards of Printed Circuit Boards (PCBs). The requirements of the IC carrier board on process size, precision, quality, specification and the like are more severe than those of the traditional printed circuit board, the line width/line distance is generally used as a measurement index, the line width/line distance of the conventional IC carrier board product can reach 20 mu m/20 mu m, the line width/line distance of the high-end IC carrier board can be reduced to 10 mu m/10 mu m, and the line width/line distance of the PCB product with common performance is more than 50 mu m/50 mu m.
The IC carrier plate production process has a plurality of technical difficulties, and the technical difficulties are embodied in five aspects of full-process material expansion and contraction control, pattern formation, copper electroplating, solder resist process and surface treatment. The principle of carrier electroplating is based on an electrochemical method, and under the action of electrolyte solution, metal ions are reduced on a metal carrier by current, and then a layer of metal is formed on the carrier. The most widely used copper electroplating system in the copper electroplating is an acidic copper sulfate system with copper sulfate and sulfuric acid as main components, additives in the system are the most core components of the electroplating solution, the electroplating effect is greatly influenced, and common additives comprise an accelerator, an inhibitor, a leveling agent and the like, and the coordination effect among the additives is the basis for obtaining a good coating.
At present, some technical schemes related to copper electroplating are disclosed in Chinese patent CN115652380A, for example, an electrolytic copper plating solution additive and a preparation method thereof are disclosed, the electrolytic copper plating solution comprises an accelerator, an inhibitor and a leveling agent, wherein the accelerator is sodium polydithio-dipropyl sulfonate, the inhibitor is polyethylene glycol-6000, the leveling agent is synthesized by 5-amino-1, 3, 4-thiadiazole-2-thiol and 2-naphthaldehyde, and compared with the prior art, the electrolytic copper plating solution additive can obtain seamless and hollow blind hole electrolytic copper filling, the surface of a plating layer is bright and flat, and the thickness of a copper layer obtained by electroplating is relatively low. Chinese patent CN111155153B discloses a copper electroplating bath and a method for electroplating copper, the copper electroplating bath is composed of copper sulfate pentahydrate, sulfuric acid, chloride ions, brightening agent, leveler, lauroyl arginine ethyl ester hydrochloride, deionized water and other components. The electroplating copper plating solution can electroplate copper under high-density current, the copper plating layer of the obtained copper plating workpiece is bright and smooth, the adhesive force is good, the electroplating time of low current density under the same condition can be shortened, the working efficiency is improved, and the cost is saved.
The existing copper electroplating technology can basically meet the production of conventional PCBs, but with the development of thinning and localization of the carrier, the domestic market has huge carrier production requirements, and as the requirements on the process size precision, quality, specification and the like of the carrier are very strict, in the extremely small space, the electroplating interconnection technology becomes more severe, and the diffusion and adsorption behaviors of additive molecules used in the conventional electroplating solution in the limited space are changed, so that the method is not beneficial to obtaining better electroplating uniformity or flatness in the limited space. In order to adapt to the development of integrated circuits, the technical proposal of the prior art has a plurality of defects on the production carrier plate, so that an electroplated copper additive suitable for the IC carrier plate is urgently required to be developed, the defect rate in the production process is reduced, the electroplating uniformity and flatness of the carrier plate are improved, and the production requirement of the carrier plate on electroplated copper is met.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an electrolytic copper plating additive suitable for an IC carrier plate, and a preparation method and application thereof. The method specifically comprises the following technical scheme:
In a first aspect, there is provided an electroplated copper additive suitable for use in an IC carrier plate, comprising the following mass concentration components:
20-50mg/L of chlorobenzenesulfonic acid derivative, 10-100mg/L of chlorobenzoyl sulfide derivative, 20-80mg/L of chlorothiobenzamide derivative and 10-50mg/L of leveling agent.
Further, the mass ratio of the chlorosulfonic acid derivative to the chlorodiphenyl sulfide derivative is 1: (0.5-2.0).
Further, the structural formula of the leveling agent is; Where n=4 or 6 or 8.
Further, the chlorosulfonic acid derivative is one or more of 2-amino-4-chlorophenol-6-sulfonic acid (CAS number: 88-23-3), 5-amino-2-chlorotoluene-4-sulfonic acid (CAS number: 88-53-9) and 3-amino-4-chlorosulfonic acid (CAS number: 98-36-2).
Further, the chlordiphenyl sulfide derivative is one or more of 4,4' -dichloro diphenyl sulfide (CAS number: 1142-19-4), 2-nitro-4 ' -chloro diphenyl sulfide (CAS number: 6764-10-9) and 2-amino-4 ' -chloro diphenyl sulfide (CAS number: 37750-29-1).
Further, the chlorothiobenzamide derivative is one or more of 2, 3-dichlorothiobenzamide (CAS number: 84863-83-2), 2, 4-dichlorothiobenzamide (CAS number: 2775-38-4) and 2, 6-dichlorothiobenzamide (CAS number: 1918-13-4).
Further, the preparation method of the leveling agent comprises the following steps:
Sodium hydride (CAS number: 7646-69-7), tetrabutylammonium bromide (abbreviated as TBAB, CAS number: 1643-19-2), tetrahydrofuran (abbreviated as THF, CAS number: 109-99-9), quinacridone (CAS number: 1047-16-1) and dibromoalkane (10%) with a mass concentration of 1% in which the alkane carbon number n may be 4 or 6 or 8 (1, 4-dibromobutane, CAS number: 110-52-1;1, 6-dibromohexane, CAS number: 629-03-8;1, 8-dibromooctane, CAS number: 4549-32-0) were added to a flask, and distilled water was added to 1/2 of the flask and heated at 65℃for 1 hour; then adding 1% trimethylamine hydrochloride (CAS number: 593-81-7), 0.5% sodium bicarbonate (CAS number: 144-55-8) and 0.1% acetonitrile (CAS number: 75-05-8), heating at 85 ℃ for 5 hours, washing with methanol (CAS number: 67-56-1) after the reaction is finished, and washing to be neutral (pH value is 7) to obtain the leveling agent.
In a second aspect, there is provided a method for preparing an electroplated copper additive suitable for use in an IC carrier plate according to the first aspect, comprising the steps of: sequentially weighing chlorobenzene sulfonic acid derivative, chlorobenzene sulfide derivative, chlorothiobenzamide derivative, leveling agent and deionized water, stirring and mixing for 15-20 minutes at the normal temperature of 25-28 ℃ to obtain the copper electroplating additive suitable for the IC carrier plate.
In a third aspect, a method for electroplating copper on an IC carrier is provided, comprising the steps of: s1, first water washing; s2, oil removal; s3, second water washing; s4, electroplating; s5, third water washing; s6, drying; wherein, the S4 electroplating is to use the copper electroplating additive suitable for the IC carrier plate as the electroplating solution, and perform the ink electroplating on the IC carrier plate subjected to the second water washing in S3.
Further, the electroplating solution also comprises sulfuric acid with the mass concentration of 250g/L, 80g/L of copper sulfate pentahydrate and 60mg/L of chloride ions.
The invention has the beneficial effects that:
The invention provides a copper electroplating additive suitable for an IC carrier plate, a preparation method and application thereof, which are applied to the copper electroplating method of the IC carrier plate, wherein the copper electroplating additive suitable for the IC carrier plate contains active ingredients such as chlorobenzene sulfonic acid derivatives, chlorobenzene sulfide derivatives, chlorothiobenzamide derivatives, leveling agents and the like.
Wherein the chlorobenzene sulfonic acid derivative and the chlorobenzene sulfide derivative have obvious interaction in the electroplating process, and the action of the chlorobenzene sulfonic acid derivative depends on the existence of the chlorobenzene sulfide derivative to a certain extent. The chlorobenzene sulfonic acid derivative can form a firm coordination bond with copper to combine the copper on the carrier plate, after the copper is reduced, the chlorobenzene sulfonic acid derivative can have desorption effect and can be adsorbed on the surface of newly deposited copper again, and the reaction is circulated to play a role in accelerating electroplating; the chlordiphenyl sulfide derivative can form a stable complex with copper ions and chloride ions in the electroplating solution, and the complex is adsorbed on the surface of a cathode through a strong electrostatic effect, so that the deposition overpotential of copper is improved, and the cathode polarized substance is greatly increased. The addition of the chlorbenzensulfonic acid derivative can enable the cathode potential to be greatly shifted, which is favorable for the adsorption of the chlorbenzensulfonic acid derivative on the cathode copper surface, thereby enhancing the acceleration effect of the chlorbenzensulfonic acid derivative.
The chlorthiobenzamide derivative can improve the conductivity of the electroplating solution by improving the chemical reaction in the electroplating solution, and strengthen the anodic protection in the electroplating solution, so that hydrogen ions are not easy to volatilize, thereby effectively improving the surface smoothness and brightness of a plating layer.
The leveling agent can enable the plating layer to have a uniform leveling effect, is of a very stable rigid plane conjugated structure, can be firmly anchored on the copper surface in the electrodeposition process, increases the uniformity of the plating layer, and meanwhile, nitrogen positive ions on the leveling agent can generate strong electrostatic repulsive interaction with bivalent copper ions, enhances the potential of the cathode surface at a high current density, prevents the deposition of copper ions on the surface, is favorable for equipotential deposition, and further improves the uniformity of the plating layer.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic reaction diagram of a leveler preparation method according to the present invention;
FIG. 2 is a circuit board slice diagram of the copper electroplating additive for IC carrier board of the embodiment 1 after being processed by the copper electroplating method of the IC carrier board;
FIG. 3 is a schematic view showing a circuit board cut-out of the plating solution of comparative example 15 after the treatment of the IC carrier by the copper plating method.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the terms "comprises" and "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in the present specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
In order to more fully understand the technical content of the present invention, the following description and description of the technical solution of the present invention will be further presented with reference to specific embodiments.
Unless otherwise specified, "%" referred to in the present invention is mass concentration.
The preparation method of the leveling agent comprises the following steps:
FIG. 1 is a schematic reaction diagram of a leveling agent preparation method according to the present invention, wherein the leveling agent preparation method comprises the following steps: sodium hydride (CAS number: 7646-69-7), tetrabutylammonium bromide (abbreviated as TBAB, CAS number: 1643-19-2), tetrahydrofuran (abbreviated as THF, CAS number: 109-99-9), quinacridone (CAS number: 1047-16-1) and dibromoalkane (10%) with a mass concentration of 1% in which the alkane carbon number n may be 4 or 6 or 8 (1, 4-dibromobutane, CAS number: 110-52-1;1, 6-dibromohexane, CAS number: 629-03-8;1, 8-dibromooctane, CAS number: 4549-32-0) were added to a flask, and distilled water was added to 1/2 of the flask and heated at 65℃for 1 hour; then adding 1% trimethylamine hydrochloride (CAS number: 593-81-7), 0.5% sodium bicarbonate (CAS number: 144-55-8) and 0.1% acetonitrile (CAS number: 75-05-8), heating at 85 ℃ for 5 hours, washing with methanol (CAS number: 67-56-1) after the reaction is finished, and washing to be neutral (pH value is 7) to obtain the leveling agent.
A copper electroplating method for an IC carrier plate comprises the following steps:
s1, first water washing; s2, oil removal; s3, second water washing; s4, electroplating; s5, third water washing; s6, drying; the step S4 of electroplating is to use the copper electroplating additive suitable for the IC carrier plate as electroplating liquid to carry out ink electroplating on the IC carrier plate subjected to the step S3 of second water washing.
The S1 first water washing is to wash the IC carrier plate with DI water (deionized water) to clean surface impurities, the line width/line distance of the IC carrier plate is 10/10 mu m, and the technological parameters of the first water washing are as follows: the spraying mode is adopted, the length of the water washing tank is 2.0 m, the temperature of the tank liquor is 25+/-5 ℃, and the length of the water washing tank is 2.0 m; the linear speed is 3.0+/-0.5 m/min, and the pressure is 1.5+/-0.5 kg/cm 2; specifically, the following examples and comparative examples employ the following process parameters of the first water wash: the temperature of the tank liquor is 25 ℃, the linear speed is 3.0 m/min, and the pressure is 1.5kg/cm 2;
The step S2 of degreasing is to soak the IC carrier plate subjected to the first water washing in the step S1 with an acid solution to remove the oil; the oil removal process parameters are as follows: the soaking mode is adopted, and the solution for removing the oil groove is prepared as follows: 5% sulfuric acid, the balance being DI water; presoaking time is 3+/-1 min, and alkaline washing temperature is 50+/-5 ℃; specifically, the following process parameters for degreasing used in the following examples and comparative examples are: presoaking for 3min, and alkaline washing at 50deg.C;
And S3, performing second water washing treatment on the IC carrier plate subjected to the S2 oil removal by using DI water, wherein the second water washing treatment comprises the following technological parameters: adopting a spraying mode, wherein the length of a tank is 2.0m, the temperature of a tank liquor is 25+/-5 ℃, and the length of a water washing tank is 2.0m; the linear speed is 3.0+/-0.5 m/min, and the pressure is 1.5+/-0.5 kg/cm 2; specifically, the process parameters of the second water wash used in the following examples and comparative examples are: the temperature of the tank liquor is 25 ℃, the linear speed is 3.0m/min, and the pressure is 1.5kg/cm 2;
The S4 electroplating is to use the electroplating copper additive, 250 g/L sulfuric acid, 80 g/L copper sulfate pentahydrate and 60 mg/L chloride ions which are applied to the IC carrier plate as electroplating liquid to carry out ink electroplating on the IC carrier plate subjected to the S3 second water washing, wherein the electroplating process parameters are as follows: soaking for 20.0min at a stripping temperature of 20+ -0.2deg.C and a current density of 6.0A/dm 2; specifically, the following examples and comparative examples use electroplating with the following process parameters: the stripping temperature is 20 ℃;
and S5, performing third water washing treatment on the IC carrier board subjected to the S4 electroplating by using DI water, wherein the third water washing treatment comprises the following technological parameters: the spraying mode is adopted, the groove length is 2.0m, the temperature of the groove liquid is 25+/-5 ℃, and the water washing groove length is 2.0 m; the linear speed is 3.0+/-0.5 m/min, and the pressure is 1.5+/-0.5 kg/cm 2; specifically, the process parameters of the third water wash used in the following examples and comparative examples are: the temperature of the tank liquor is 25 ℃, the linear speed is 3.0m/min, and the pressure is 1.5kg/cm 2;
And S6, drying the IC carrier plate subjected to the third washing in S5 by using DI water, wherein the drying process comprises the following technological parameters: drying temperature is 75+/-5 ℃, and drying time is 5+/-1 min; specifically, the following examples and comparative examples use the following drying process parameters: drying temperature is 75 ℃, and drying time is 5min.
Performance test:
the IC carrier boards treated by the copper electroplating method for IC carrier boards using the copper electroplating additives applicable to IC carrier boards of the examples and comparative examples of the present invention were tested.
The performance of the electroplated copper additive suitable for the IC carrier plate of the invention is mainly characterized in four aspects: the first is surface uniformity; visually observing whether the surface of the coating is uniform or not, and testing the surface roughness Ra of the coating by using a roughness measuring instrument, wherein the lower the Ra value is, the more uniform the surface of the coating is; the second is an adhesion test, which comprises the following steps: keeping the temperature of the electroplated part at 260 ℃ for 1h, taking out, quenching in cold water (-10 ℃) and repeating for 10 times until the electroplated part is qualified after the electroplated part is peeled off; thirdly, the blind hole filling effect is achieved, the template treated by the electrolytic copper plating method of the IC carrier plate is cut respectively, a metallographic microscope is used for observing the section of the template respectively, and if the copper plating surface is smooth and flat, no concave or convex larger than 5 microns is qualified; and fourthly, the deep plating capacity (TP value) of the through hole, respectively observing and measuring the section copper surface section of the sample by using a metallographic microscope, and evaluating the deep plating capacity of the through hole of the circuit board by using the ratio of the copper thickness in the hole to the copper thickness on the surface.
Example 1
An electroplated copper additive suitable for an IC carrier plate comprises the following components in mass concentration:
30 mg/L of chlorobenzenesulfonic acid derivative, specifically 2-amino-4-chlorophenol-6-sulfonic acid;
50 mg/L of chlordiphenyl sulfide derivative, specifically 4,4' -dichloro diphenyl sulfide;
50 mg/L of chlorothiobenzamide derivative, specifically 2, 3-dichloro thiobenzamide;
30 mg/L of leveling agent, which has the structural formula: ；
The balance being DI water.
The preparation method of the electroplated copper additive suitable for the IC carrier plate comprises the following steps: sequentially weighing chlorobenzene sulfonic acid derivative, chlorobenzene sulfide derivative, chlorothiobenzamide derivative, leveling agent and deionized water, stirring and mixing for 15 minutes at the normal temperature of 25 ℃ to obtain the copper electroplating additive suitable for the IC carrier plate.
Example 2
An electroplated copper additive suitable for an IC carrier plate comprises the following components in mass concentration:
30 mg/L of chlorobenzenesulfonic acid derivative, specifically 5-amino-2-chlorotoluene-4-sulfonic acid;
50 mg/L of chlordiphenyl sulfide derivative, specifically 2-nitro-4' -chlordiphenyl sulfide;
50 mg/L of chlorothiobenzamide derivative, specifically 2, 4-dichloro thiobenzamide;
30 mg/L of leveling agent, which has the structural formula: ；
The balance being DI water.
Example 3
An electroplated copper additive suitable for an IC carrier plate comprises the following components in mass concentration:
30 mg/L of chlorobenzenesulfonic acid derivative, specifically 3-amino-4-chlorobenzenesulfonic acid;
50 mg/L of chlordiphenyl sulfide derivative, specifically 2-amino-4' -chlordiphenyl sulfide;
50 mg/L of chlorothiobenzamide derivative, specifically 2, 6-dichloro thiobenzamide;
30 mg/L of leveling agent, which has the structural formula: ；
The balance being DI water.
Example 4
An electroplated copper additive suitable for an IC carrier plate comprises the following components in mass concentration:
20 mg/L of chlorobenzenesulfonic acid derivative, specifically 2-amino-4-chlorophenol-6-sulfonic acid;
10 mg/L of chlordiphenyl sulfide derivative, specifically 4,4' -dichloro diphenyl sulfide;
20 mg/L of a chlorothiobenzamide derivative, specifically 2, 3-dichloro thiobenzamide;
10 mg/L of leveling agent, which has the structural formula: ；
The balance being DI water.
Example 5
An electroplated copper additive suitable for an IC carrier plate comprises the following components in mass concentration:
50 mg/L of chlorobenzene sulfonic acid derivative, in particular 2-amino-4-chlorophenol-6-sulfonic acid;
100 mg/L of chlordiphenyl sulfide derivative, specifically 4,4' -dichloro diphenyl sulfide;
80 mg/L of chlorthiobenzamide derivative, specifically 2, 3-dichloro thiobenzamide;
The leveling agent 50 mg/L has the structural formula: ；
The balance being DI water.
Examples 2-5 were prepared in the same manner as in example 1 for the electroplated copper additive suitable for use in IC carrier boards.
Comparative example 1
Comparative example 1 differs from example 1 only in that the component of the copper electroplating additive suitable for IC carrier boards does not contain a chlorine-containing benzenesulfonic acid derivative.
Comparative example 2
Comparative example 2 differs from example 1 only in that the component of the electroplated copper additive suitable for IC carrier boards does not contain a chlorine-containing diphenyl sulfide derivative.
Comparative example 3
Comparative example 3 differs from example 1 only in that the component of the electroplated copper additive suitable for IC carrier boards does not contain a chlorothiobenzamide derivative.
Comparative example 4
Comparative example 4 differs from example 1 only in that no leveler is included in the electroplated copper additive composition suitable for use in IC carrier boards.
Comparative example 5
Comparative example 5 differs from example 1 only in that the mass concentration of the chlorosulfonic acid derivative in the copper electroplating additive component suitable for use in IC carrier boards is 10mg/L.
Comparative example 6
Comparative example 6 differs from example 1 only in that the mass concentration of the chlorodiphenyl sulfide derivative in the copper electroplating additive component suitable for the IC carrier plate is 5mg/L.
Comparative example 7
Comparative example 7 differs from example 1 only in that the mass concentration of the chlorothiobenzamide derivative in the copper electroplating additive composition suitable for the IC carrier plate is 5mg/L.
Comparative example 8
Comparative example 8 differs from example 1 only in that the leveler mass concentration in the electroplated copper additive composition that is suitable for the IC carrier plate is 5 mg/L.
Comparative example 9
Comparative example 9 differs from example 1 only in that the mass concentration of the chlorosulfonic acid derivative in the copper electroplating additive component suitable for use in IC carrier boards is 80mg/L.
Comparative example 10
Comparative example 10 differs from example 1 only in that the mass concentration of the chlorodiphenyl sulfide derivative in the copper electroplating additive component suitable for the IC carrier plate is 120mg/L.
Comparative example 11
Comparative example 11 differs from example 1 only in that the mass concentration of the chlorothiobenzamide derivative in the copper electroplating additive component suitable for the IC carrier plate is 100mg/L.
Comparative example 12
Comparative example 12 differs from example 1 only in that the leveler mass concentration in the electroplated copper additive composition that is suitable for the IC carrier plate is 80mg/L.
Comparative example 13
Comparative example 13 differs from example 1 only in that the mass concentration of the chlorosulfonic acid derivative in the copper electroplating additive component suitable for use in the IC carrier is 20mg/L, the mass concentration of the chlorodiphenyl sulfide derivative is 100mg/L, i.e., the mass ratio of the chlorosulfonic acid derivative to the chlorodiphenyl sulfide derivative is 1:5, below the limit of the invention.
Comparative example 14
Comparative example 14 differs from example 1 only in that the mass concentration of the chlorosulfonic acid derivative in the copper electroplating additive component suitable for the IC carrier is 50mg/L, the mass concentration of the chlorodiphenyl sulfide derivative is 10 mg/L, and the mass ratio of the chlorosulfonic acid derivative to the chlorodiphenyl sulfide derivative is 5:1, above the limit of the invention.
Comparative example 15
Comparative example 15 is different from example 1 in that the prior art (chinese patent CN 114214678A) alone was used as the plating solution, and specifically, the components thereof include: 200 g/L of sulfuric acid, 70 g/L of copper sulfate pentahydrate, 60 ppm of chloride ions, 5 ppm of sodium alcohol sulfopropane sulfonate, 80 ppm of polyethylene glycol, 25 ppm of amidated imidazoline derivative and the balance of water. Wherein the molecular weight of the polyethylene glycol is 4000.
The electroplated copper additives of examples 1-5, which were suitable for use in IC carrier boards, were subjected to performance testing, the test results are shown in table 1 below:
TABLE 1 results of Performance test of examples 1-5
The circuit board slicing diagram of the copper electroplating additive for the IC carrier plate of the embodiment 1 of the invention after being processed by the copper electroplating method of the IC carrier plate is shown in fig. 2. As can be seen from the test results of fig. 2 and table 1, the copper electroplating additive suitable for IC carrier boards in the embodiment of the invention can be used in an IC carrier board acid copper electroplating system, has uniform and smooth plating layer, good adhesion, qualified blind hole filling effect, and deep plating capability value of the through holes reaching more than 94%, and can be suitable for an IC carrier board electroplating process with line spacing of 10 micrometers.
The electroplated copper additives of comparative examples 1-12, which were suitable for use in IC carrier boards, were subjected to performance testing, the test results are shown in table 2 below:
table 2 results of Performance test of comparative examples 1 to 12
As can be seen from the test results of Table 2, comparative examples 1 to 4 of the present invention differ from example 1 in the absence of a single component of chlorosulfonic acid derivative, chlorodiphenyl sulfide derivative, chlorothiobenzamide derivative, leveler, respectively, in the copper electroplating additive suitable for IC carrier boards. Experimental data show that the electroplating effect of the IC carrier plate is related to the effects of all components of the copper electroplating additive, and the lack of any one component can influence the uniformity, adhesive force, hole filling electroplating and through hole electroplating effects of a plating layer, wherein the influence of a leveling agent on the electroplating effect is larger. The chlorobenzene sulfonic acid derivative and the chlorine diphenyl sulfide derivative interact in the electroplating process, and the chlorobenzene sulfonic acid derivative can absorb and desorb copper, and the chlorobenzene sulfonic acid derivative is recycled to play an acceleration role. The chlordiphenyl sulfide derivative can form a stable complex with copper ions and chloride ions, so that the deposition overpotential of copper is improved, and the cathode polarization is increased, meanwhile, the chlordiphenyl sulfide derivative can enable the cathode potential to be greatly shifted negatively, thereby being beneficial to the adsorption of the chlorbenzene sulfonic acid derivative on the cathode copper surface and accelerating the acceleration of the chlorbenzene sulfonic acid derivative. The chlorthiobenzamide derivative can lead hydrogen ions to be difficult to volatilize by improving chemical reaction in the electroplating solution, thereby effectively improving the surface smoothness and brightness of a plating layer. The leveling agent can be firmly anchored on the copper surface, so that the uniformity of a plating layer is improved, meanwhile, nitrogen positive ions on the leveling agent can generate strong electrostatic repulsive interaction with bivalent copper ions, the potential of the cathode surface at a high current density is enhanced, deposition of copper ions on the surface is hindered, equipotential deposition is facilitated, and the uniformity of the plating layer is further improved.
Comparative examples 5 to 8 differ from example 1 in that the chlorosulfonic acid derivative, the chlorodiphenyl sulfide derivative, the chlorothiobenzamide derivative, and the leveler in the copper electroplating additive suitable for the IC carrier plate are respectively lower than the lower limit value of the mass concentration defined in the present invention, and experimental data indicate that the reduction of the mass concentration of each component can reduce the electroplating effect, and cannot meet the requirements of IC carrier plate electroplating.
Comparative examples 9 to 12 are different from example 1 in that the chlorosulfonic acid derivative, the chlorodiphenyl sulfide derivative, the chlorothiobenzamide derivative, and the leveler in the copper plating additive suitable for an IC carrier are respectively higher than the upper limit of the mass concentration defined in the present invention, and experimental data show that the mass concentration of each component is higher than the defined concentration to affect the plating effect, because the components of the copper plating additive suitable for an IC carrier have an interaction relationship, and that a certain component ratio is too high to exert the opposite effect, so that the concentration of each component of the copper plating additive suitable for an IC carrier needs to be controlled within the mass concentration range defined in the present invention.
The electrolytic copper plating additives of comparative examples 13 to 14, which were suitable for use in IC carrier boards, were subjected to performance tests with the electrolytic plating solutions of comparative example 15, and the test results are shown in Table 3 below:
TABLE 3 results of Performance test of comparative examples 13-15
The circuit board slicing diagram of the electroplating solution of comparative example 15 after being treated by the copper electroplating method of the IC carrier is shown in fig. 3. As can be seen from the test results in fig. 3 and table 3, the comparison examples 13 and 14 only differ from the example 1 in that the mass ratio of the chlorobenzenesulfonic acid derivative to the chlorodiphenyl sulfide derivative is respectively lower and higher than the range defined by the present invention, and experimental data show that when the ratio of the chlorobenzenesulfonic acid derivative to the chlorodiphenyl sulfide derivative is too low, the concentration of the chlorodiphenyl sulfide derivative is too high, and the excessive chlorodiphenyl sulfide derivative forms stable complexes with a large amount of copper ions and chloride ions, so that the concentration of copper ions and chloride ions greatly change, the balance of the plating solution is changed, and the plating effect is affected; when the ratio of the two is too high, the concentration of the chlorosulfonic acid derivative is relatively high, and the adsorption-desorption of the chlorosulfonic acid derivative and copper is too fast, so that the electroplating is uneven in local areas and the electroplating effect is poor.
Comparative example 15 example 1 only differs in that the prior art was used alone as the plating solution, and experimental data shows that the copper electroplating additive suitable for IC carrier boards provided by the present invention has better plating uniformity and adhesion, and better hole filling plating and through hole plating performance, and meets the requirements of the IC carrier board plating process.
In summary, the invention provides an electrolytic copper plating additive suitable for an IC carrier plate, a preparation method and application thereof, which can be used in an acid electrolytic copper plating system of the IC carrier plate, has uniform and smooth plating layer, good adhesive force, qualified blind hole filling effect and deep plating capability value reaching more than 94%, and can be suitable for an electroplating process of the IC carrier plate with line width and line distance of 10 microns.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (4)
1. An electrolytic copper plating additive suitable for an IC carrier plate is characterized by comprising the following components in mass concentration:
20-50mg/L of chlorobenzenesulfonic acid derivative, 10-100mg/L of chlorobenzoyl sulfide derivative, 20-80mg/L of chlorothiobenzamide derivative and 10-50mg/L of leveling agent;
the mass ratio of the chlorosulfonic acid derivative to the chlorodiphenyl sulfide derivative is 1: (0.5-2.0);
the structural formula of the leveling agent is ; Wherein n=4 or 6 or 8;
the chlorosulfonic acid derivative is one or more of 2-amino-4-chlorophenol-6-sulfonic acid, 5-amino-2-chlorotoluene-4-sulfonic acid and 3-amino-4-chlorosulfonic acid;
The chlordiphenyl sulfide derivative is one or more of 4,4' -dichloro diphenyl sulfide, 2-nitro-4 ' -chlordiphenyl sulfide and 2-amino-4 ' -chlordiphenyl sulfide;
The chlorthiobenzamide derivative is one or more of 2, 3-dichloro thiobenzamide, 2, 4-dichloro thiobenzamide and 2, 6-dichloro thiobenzamide.
2. The electroplated copper additive for IC carrier of claim 1, wherein the method for preparing the leveler comprises the steps of:
Adding sodium hydride with the mass concentration of 1%, tetrabutylammonium bromide with the mass concentration of 1%, tetrahydrofuran with the mass concentration of 0.5%, quinacridone with the mass concentration of 5% and dibromoalkane with the mass concentration of 10%, wherein the carbon number n of the alkane can be 4 or 6 or 8, adding distilled water, and heating for 1 hour at 65 ℃; then adding 1% of trimethylamine hydrochloride, 0.5% of sodium bicarbonate and 0.1% of acetonitrile, heating at 85 ℃ for 5 hours, and washing with methanol and washing to be neutral after the reaction is finished to obtain the leveling agent.
3. The method for preparing the electroplated copper additive suitable for the IC carrier plate according to any one of claims 1 to 2, comprising the following steps: sequentially weighing chlorobenzene sulfonic acid derivative, chlorobenzene sulfide derivative, chlorothiobenzamide derivative, leveling agent and deionized water, stirring and mixing for 15-20 minutes at the normal temperature of 25-28 ℃ to obtain the copper electroplating additive suitable for the IC carrier plate.
4. A method of electroplating copper on an IC carrier, comprising the steps of: s1, first water washing; s2, oil removal; s3, second water washing; s4, electroplating; s5, third water washing; s6, drying; wherein the S4 electroplating is to use the copper electroplating additive which is suitable for the IC carrier plate and is any one of claims 1-2 to carry out ink electroplating on the IC carrier plate which is subjected to S3 second water washing;
The electroplating solution also comprises 250g/L sulfuric acid, 80g/L copper sulfate pentahydrate and 60mg/L chloride ions.
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| CN114214678B (en) * | 2022-02-23 | 2022-05-10 | 深圳市板明科技股份有限公司 | Circuit board through hole copper electroplating solution and application thereof |
| CN117987887A (en) * | 2024-01-09 | 2024-05-07 | 九江德福科技股份有限公司 | High-temperature ultrahigh-strength high-elongation lithium electric copper foil and production process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101671820A (en) * | 2008-07-01 | 2010-03-17 | 上村工业株式会社 | Electroless plating solution, method for electroless plating using the same and method for manufacturing circuit board |
| CN104630840A (en) * | 2013-11-08 | 2015-05-20 | 无锡市雪江环境工程设备有限公司 | Electroplating liquid and electroplating method of phthalocyanine system acid copper plating |
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