CN116180076A - Environment-friendly process applied to filling through holes of wafers - Google Patents
Environment-friendly process applied to filling through holes of wafers Download PDFInfo
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- CN116180076A CN116180076A CN202211616383.6A CN202211616383A CN116180076A CN 116180076 A CN116180076 A CN 116180076A CN 202211616383 A CN202211616383 A CN 202211616383A CN 116180076 A CN116180076 A CN 116180076A
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- Prior art keywords
- copper
- holes
- solution
- environment
- copper plating
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 235000012431 wafers Nutrition 0.000 title description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052802 copper Inorganic materials 0.000 claims abstract description 108
- 239000010949 copper Substances 0.000 claims abstract description 108
- 238000007747 plating Methods 0.000 claims abstract description 96
- 238000009713 electroplating Methods 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000005238 degreasing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 230000003213 activating effect Effects 0.000 claims description 29
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 16
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 16
- 230000029219 regulation of pH Effects 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 208000028659 discharge Diseases 0.000 claims description 15
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 229930003268 Vitamin C Natural products 0.000 claims description 14
- 235000019154 vitamin C Nutrition 0.000 claims description 14
- 239000011718 vitamin C Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 10
- 238000005282 brightening Methods 0.000 claims description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 10
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 9
- 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 9
- -1 polydithio-dipropyl Polymers 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- CGXWVPSZSVEFAI-CYRSAHDMSA-N (2s,3s,4s,5r,6s)-6-[(6-chloro-1h-indol-3-yl)oxy]-3,4,5-trihydroxyoxane-2-carboxylate;cyclohexylazanium Chemical compound NC1CCCCC1.O1[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1OC1=CNC2=CC(Cl)=CC=C12 CGXWVPSZSVEFAI-CYRSAHDMSA-N 0.000 claims description 8
- ACGZBRWTWOZSFU-UHFFFAOYSA-N 4-(diethylamino)but-2-yn-1-ol Chemical group CCN(CC)CC#CCO ACGZBRWTWOZSFU-UHFFFAOYSA-N 0.000 claims description 8
- VWHGTYCRDRBSFI-SSDOTTSWSA-N 2-[[2-[[(2r)-2-amino-4-methylpentanoyl]amino]acetyl]amino]acetic acid Chemical compound CC(C)C[C@@H](N)C(=O)NCC(=O)NCC(O)=O VWHGTYCRDRBSFI-SSDOTTSWSA-N 0.000 claims description 7
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 239000000080 wetting agent Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- RHONTQZNLFIDCQ-UHFFFAOYSA-N tert-butyl n-(2-amino-2-oxoethyl)carbamate Chemical group CC(C)(C)OC(=O)NCC(N)=O RHONTQZNLFIDCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004395 L-leucine Substances 0.000 claims description 5
- 229960003136 leucine Drugs 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 238000004220 aggregation Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000003749 cleanliness Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- HMHSJYFSGPYEJM-UHFFFAOYSA-N 4-methylbenzenesulfonic acid 2-phenylacetic acid Chemical compound OC(=O)Cc1ccccc1.Cc1ccc(cc1)S(O)(=O)=O HMHSJYFSGPYEJM-UHFFFAOYSA-N 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims description 2
- ILRKKHJEINIICQ-OOFFSTKBSA-N Monoammonium glycyrrhizinate Chemical compound N.O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@H]1CC[C@]2(C)[C@H]3C(=O)C=C4[C@@H]5C[C@](C)(CC[C@@]5(CC[C@@]4(C)[C@]3(C)CC[C@H]2C1(C)C)C)C(O)=O)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O ILRKKHJEINIICQ-OOFFSTKBSA-N 0.000 claims 1
- 239000001685 glycyrrhizic acid Substances 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 238000011112 process operation Methods 0.000 abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- PSMBIFNNFMRIMV-NTISSMGPSA-N benzyl (3s)-1,2,3,4-tetrahydroisoquinoline-3-carboxylate;4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.O=C([C@H]1NCC2=CC=CC=C2C1)OCC1=CC=CC=C1 PSMBIFNNFMRIMV-NTISSMGPSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- PGYIKEUWUONYSB-UHFFFAOYSA-N 1-pyridin-4-ylethanethiol;hydrochloride Chemical compound Cl.CC(S)C1=CC=NC=C1 PGYIKEUWUONYSB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- BEBCJVAWIBVWNZ-UHFFFAOYSA-N glycinamide Chemical compound NCC(N)=O BEBCJVAWIBVWNZ-UHFFFAOYSA-N 0.000 description 2
- HWBAHOVOSOAFLE-UHFFFAOYSA-N 2-[[2-[(2-methylpropan-2-yl)oxycarbonylamino]acetyl]amino]acetic acid Chemical compound CC(C)(C)OC(=O)NCC(=O)NCC(O)=O HWBAHOVOSOAFLE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004381 surface treatment 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1806—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by mechanical pretreatment, e.g. grinding, sanding
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses an environment-friendly process applied to filling holes of wafer through holes, which comprises the following steps: degreasing, coarsening, oxygen removal treatment, activation, electroless copper plating and electrolytic copper plating. The invention has simple process operation, the chemical plating liquid contained in the process is safe and environment-friendly, the wastewater treatment is simple, after copper electroplating, the through holes filled in the base material cannot be folded and plated, the uniformity of the copper layer is compact, the hole filling rate is more than 95%, the deep plating capacity of the 20:1 high deep aspect ratio is more than 90%, and the stability of the copper electroplating plating liquid is excellent.
Description
Technical Field
The invention relates to the technical field of copper plating, in particular to an environment-friendly process applied to hole filling of wafer through holes.
Background
At present, in the production of a wafer through hole filling process, high equipment accuracy is required, new requirements are continuously put forward on the quality of liquid medicine, the environment-friendly concept is required to be met under the high quality requirement, and the liquid medicine with excellent energy supply is required to meet the production in key steps such as seed layer formation, electroplating, activation and the like which are related to the surface treatment process of a substrate at present, but the liquid medicine in the market at present contains more aldehydes and belongs to a strong acid system, so that the environment pressure is huge, and the cost is high. In addition, the domestic medicinal liquid has the problems of insufficient deep plating capability, poor water stability of the medicinal liquid in the using process, and the like.
Yan De et al in patent CN113881983a disclose a through-hole pulse plating solution and a through-hole pulse plating method that not only has a high chloride ion concentration, but also has a high concentration of acid, and ferrous ions in the solution cannot guarantee the stability of the plating solution.
In addition, cai Fangxian et al disclose in patent CN113373482a an application of a pulse plating additive plating solution and plating, which results in an increase in production cost due to lack of accelerator, and contains a large amount of foam of surfactant component, which is unfavorable for operations such as pumping.
Therefore, the solution has extremely low acid concentration and simple wastewater treatment, ensures that the folded plating does not occur in the hole filling through holes, ensures that the uniformity of the copper layer is compact, the hole filling rate is more than 95 percent, the deep plating capacity of the 20:1 plate is more than 90 percent, and the plating solution is stable and clear for a long time and can maintain the black electroplating copper solution within two months to meet the production requirement, thereby relieving the foreign technical blockade.
Disclosure of Invention
Aiming at the defects in the technology, the invention provides an environment-friendly process applied to the hole filling of the through holes of the wafer. The invention has simple process operation, the chemical plating liquid contained in the process is safe and environment-friendly, the wastewater treatment is simple, after copper electroplating, the through holes filled in the base material cannot be folded and plated, the uniformity of the copper layer is compact, the hole filling rate is more than 95%, the deep plating capacity of the 20:1 high deep aspect ratio is more than 90%, and the stability of the copper electroplating plating liquid is excellent.
In order to achieve the above purpose, the present invention provides an environmental protection process for filling holes in wafer vias, which specifically comprises the following steps:
step a, degreasing, namely cleaning greasy dirt on the surface of the substrate and improving the cleanliness of the surface of the substrate;
step b, coarsening, namely coarsening through a hydrofluoric acid solution with the mass concentration of 50%, so as to improve the binding force of the plating layer;
c, oxygen discharge treatment, namely discharging oxygen in the micropores of the base material under the impact of nitrogen, and then injecting pure water to further discharge the gas in the micropores;
step d, activating, namely forming a catalytic layer on the surface of the base material through an activating tank containing activating liquid to promote the formation of a copper seed layer;
step e, electroless copper plating, wherein a layer of seed layer copper is formed on the surface of the base material through a copper plating groove containing electroless copper plating solution to realize connection blind holes, so that a basic copper layer is provided for electroplated copper;
step f, electroplating copper, wherein the base material enters an electroplating tank containing an electroplating copper solution for electroplating;
the specific conditions of the oxygen discharge treatment in the step c are that the flow rate of nitrogen is 5-10L/min and the flow rate of pure water is 10-30L/min; the specific conditions of the electroless copper plating in the step e are that the temperature is 70-80 ℃, the pH is 5-7, the time is 30-50min, the electroless copper plating is carried out under the protection of nitrogen, and the release speed of the nitrogen is 2.5-3.5L/min; the chemical copper plating solution in the step e comprises 2.5-7.5g/L of copper sulfate, 0.5-2.5g/L of composite reducing agent, 0.2-0.5g/L of stabilizing agent, 20-60ppm/L of surfactant and 15-45ppm/L of accelerator, and the pH regulation is regulated by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
The composite reducing agent in the electroless copper plating solution is a composition composed of vitamin C and sodium hypophosphite, the mass concentration ratio of the vitamin C to the sodium hypophosphite is 4:1, the vitamin C is 0.4-2g/L, the sodium hypophosphite is 0.1-0.5g/L, the electroless copper plating solution provided by the invention is excellent in uniformity and compactness, strong in oxidation resistance, free of toxic formaldehyde gas, neutral in pH, free of corrosion to a base material, and capable of depositing the thickness of up to 3 mu m, and the electroless copper plating solution on the market can only obtain 0.5 mu m.
The stabilizer in the electroless copper plating solution is D-leucyl glycylglycine; the surfactant is OP-10; the accelerator is Boc-glycinamide, the stabilizer can realize the stability of copper ions at high temperature, and the accelerator can promote the reducing agent to realize the plating starting effect on the substrate.
The specific conditions of the step c are as follows: the activation temperature is 25-40 ℃, the activation time is 2-5min, the pH is controlled to be 2-4, and the specific adjustment can be adjusted by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
The activating solution in the step c comprises the following components: the activating solution improves the uniformity of plating starting, and the activating solution in the market can only be kept for one month, compared with the activating solution, the activating solution has the stability of two months.
The specific conditions of the step f of copper electroplating are as follows: the current density is used in the range of 0.5-45A/cm 2 The temperature is 25-35 ℃, the pH is 5-6, the clamp adopts a four-terminal shunt method, namely the clamping part of the anode electrode is divided into four parts, and the four parts are respectively clamped in the central directions of four sides of the substrate, so that the phenomenon of uneven current aggregation is reduced.
The copper electroplating solution for copper electroplating in the step f comprises the following components: 70-90g/L of copper sulfate, 30-60ppm/L of composite leveling agent, 15-45mg/L of composite brightening agent, 30-90ppm/L of wetting agent and 40-80ppm/L of dispersing agent.
The composite leveling agent of the copper electroplating solution is a composition consisting of ammonium glycyrrhetate, 6-chloro-3-indolyl-beta-D-glucuronic acid cyclohexylammonium salt and DDZ-L-leucine cyclohexylammonium salt, the mass concentration ratio of the composite leveling agent to the DDZ-L-leucine cyclohexylammonium salt is 1:1:1 when the copper electroplating solution is used, the disadvantage of insufficient hole filling capacity of the single leveling agent in deep plating can be solved by adopting the composite leveling agent, meanwhile, the high requirements of hole filling and deep plating capacity are realized, and the highest substrate with the high depth-to-aspect ratio of more than 15:1 is realized in the market at present, and the hole filling capacity is only 85%.
The composite brightening agent of the electrolytic copper plating solution is a composition composed of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinoline benzyl carboxylate tosylate and sodium polydithio-dipropyl sulfonate, and the mass concentration ratio of the composite brightening agent to the sodium polydithio-dipropyl sulfonate is 1:1 when the electrolytic copper plating solution is used, so that the dispersibility of the current density can be greatly improved, and the generation of copper nodules is reduced.
The wetting agent of the electrolytic copper plating solution is 4-pyridine ethylthiolate, the dispersing agent is 4-diethylamino-2-butyn-1-ol, and the wetting agent can reduce the occurrence of pore folding plating and cavitation.
The beneficial effects of the invention are as follows: compared with the prior art, the environment-friendly process applied to the filling of the through holes of the wafers has the following advantages:
1) The electroless copper plating solution provided by the invention has excellent uniformity and compactness, strong oxidation resistance, no toxic formaldehyde gas, neutral pH value, no corrosion to a substrate and deposition thickness of up to 3 mu m, and the electroless copper plating solution on the market can only obtain 0.5 mu m.
2) The invention has simple process operation, the chemical plating liquid contained in the process is safe and environment-friendly, the wastewater treatment is simple, after copper electroplating, the through holes filled in the base material cannot be folded and plated, the uniformity of the copper layer is compact, the hole filling rate is more than 95%, the deep plating capacity of the 20:1 high deep aspect ratio is more than 90%, and the stability of the copper electroplating plating liquid is excellent.
3) The activating solution provided by the invention can improve the uniformity of plating starting, and the activating solution in the market can only be kept for one month.
4) The invention adopts the composite leveling agent to solve the disadvantage of insufficient deep hole filling capability of a single leveling agent, simultaneously realizes high requirements on hole filling and deep hole filling capability, and at present, the highest substrate with the high depth-to-aspect ratio exceeding 15:1 on the market has the hole filling capability of only 85 percent, and the composite brightening agent can greatly improve the dispersibility of current density and reduce the generation of copper nodules.
The accompanying drawings and description thereof
FIG. 1 is a graph showing the judgment criteria of the test results of the examples and comparative examples in the present invention.
Detailed Description
In order to more clearly describe the present invention, the present invention is further described below with reference to the text and figures.
The invention provides an environment-friendly process applied to filling holes of wafer through holes, which comprises the following specific steps: step a, degreasing, namely cleaning greasy dirt on the surface of the substrate and improving the cleanliness of the surface of the substrate; step b, coarsening, namely coarsening through a hydrofluoric acid solution with the mass concentration of 50%, so as to improve the binding force of the plating layer; c, oxygen discharge treatment, namely discharging oxygen in the micropores of the base material under the impact of nitrogen, and then injecting pure water to further discharge the gas in the micropores; step d, activating, namely forming a catalytic layer on the surface of the base material through an activating tank containing activating liquid to promote the formation of a copper seed layer; step e, electroless copper plating, wherein a layer of seed layer copper is formed on the surface of the base material through a copper plating groove containing electroless copper plating solution to realize connection blind holes, so that a basic copper layer is provided for electroplated copper; step f, electroplating copper, wherein the base material enters an electroplating tank containing an electroplating copper solution for electroplating;
the specific conditions of the oxygen discharge treatment in the step c are that the flow rate of nitrogen is 5-10L/min and the flow rate of pure water is 10-30L/min; the specific conditions of the electroless copper plating in the step e are that the temperature is 70-80 ℃, the pH is 5-7, the time is 30-50min, the electroless copper plating is carried out under the protection of nitrogen, and the release speed of the nitrogen is 2.5-3.5L/min; the chemical copper plating solution in the step e comprises 2.5-7.5g/L of copper sulfate, 0.5-2.5g/L of composite reducing agent, 0.2-0.5g/L of stabilizing agent, 20-60ppm/L of surfactant and 15-45ppm/L of accelerator, and the pH regulation is regulated by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
In the embodiment, the compound reducing agent in the electroless copper plating solution is a composition composed of vitamin C and sodium hypophosphite, wherein the mass concentration ratio of the vitamin C to the sodium hypophosphite is 4:1, the vitamin C is 0.4-2g/L, and the sodium hypophosphite is 0.1-0.5g/L.
In this embodiment, the stabilizer in the electroless copper plating solution is D-leucylglycylglycine; the surfactant is OP-10; the accelerator is Boc-glycinamide.
In this embodiment, the specific conditions of the step c are: the activation temperature is 25-40 ℃, the activation time is 2-5min, the pH is controlled to be 2-4, and the specific adjustment can be adjusted by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
In this embodiment, the composition of the activating solution in the step c is as follows: 30-60ppm/L of ruthenium acetate, 10-15ppm/L of palladium sulfate, 30-90ppm/L, PEG-800030-90ppm/L of ethylenediamine and 10-30ppm/L of 2-fluoropyridine.
In this embodiment, the specific conditions for the copper electroplating in the step f are as follows: current density is such thatThe application range is 0.5-45A/cm 2 The temperature is 25-35 ℃, the pH is 5-6, the clamp adopts a four-terminal shunt method, namely the clamping part of the anode electrode is divided into four parts, and the four parts are respectively clamped in the central directions of four sides of the substrate, so that the phenomenon of uneven current aggregation is reduced.
In this embodiment, the copper electroplating solution for electroplating copper in the step f comprises the following components: 70-90g/L of copper sulfate, 30-60ppm/L of composite leveling agent, 15-45mg/L of composite brightening agent, 30-90ppm/L of wetting agent and 40-80ppm/L of dispersing agent.
In the embodiment, the composite leveling agent of the copper electroplating solution is a composition consisting of ammonium glycyrrhetate, 6-chloro-3-indolyl-beta-D-glucuronic acid cyclohexylammonium salt and DDZ-L-leucine cyclohexylammonium salt, and the mass concentration ratio of the composite leveling agent to the DDZ-L-leucine cyclohexylammonium salt is 1:1:1.
In the embodiment, the composite brightening agent of the electrolytic copper plating solution is a composition composed of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinoline carboxylic acid benzyl ester p-toluenesulfonate and sodium polydithio-dipropyl sulfonate, and the mass concentration ratio of the composite brightening agent to the copper plating solution is 1:1.
In this example, the wetting agent of the electrolytic copper plating solution was 4-pyridylethanethiol hydrochloride, and the dispersant was 4-diethylamino-2-butyn-1-ol.
The beneficial effects of the invention are as follows: compared with the prior art, the environment-friendly process applied to the filling of the through holes of the wafers has the following advantages:
1) The electroless copper plating solution provided by the invention has excellent uniformity and compactness, strong oxidation resistance, no toxic formaldehyde gas, neutral pH value, no corrosion to a substrate and deposition thickness of up to 3 mu m, and the electroless copper plating solution on the market can only obtain 0.5 mu m.
2) The invention has simple process operation, the chemical plating liquid contained in the process is safe and environment-friendly, the wastewater treatment is simple, after copper electroplating, the through holes filled in the base material cannot be folded and plated, the uniformity of the copper layer is compact, the hole filling rate is more than 95%, the deep plating capacity of the 20:1 high deep aspect ratio is more than 90%, and the stability of the copper electroplating plating liquid is excellent.
3) The activating solution provided by the invention can improve the uniformity of plating starting, and the activating solution in the market can only be kept for one month.
4) The invention adopts the composite leveling agent to solve the disadvantage of insufficient deep hole filling capability of a single leveling agent, simultaneously realizes high requirements on hole filling and deep hole filling capability, and at present, the highest substrate with the high depth-to-aspect ratio exceeding 15:1 on the market has the hole filling capability of only 85 percent, and the composite brightening agent can greatly improve the dispersibility of current density and reduce the generation of copper nodules.
The following are several embodiments of the invention
The following experimental materials were all selected as subjects.
Example 1
An environment-friendly process applied to filling holes of wafer through holes:
a. deoiling for 2min at 50 ℃; b. coarsening: 2min30 ℃; c. and (3) oxygen discharge treatment: nitrogen flow rate is 5L/min, and pure water flow rate is 10L/min; electroless copper plating: the temperature is 75 ℃, the pH is 6, the time is 40min, and the nitrogen release speed is 3L/min;
d. activating: 30ppm/L of ruthenium acetate, 10ppm/L of palladium sulfate, 30ppm/L, PEG-800030ppm/L of ethylenediamine and 10ppm/L of 2-fluoropyridine, wherein the pH is 3, and the pH regulation and control are carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%, and the balance is water;
e. electroless copper plating: 5g/L of copper sulfate, 0.4g/L of vitamin C, 0.1g/L, D of sodium hypophosphite and 0.2g/L, OP-1020ppm/L, boc of glycinamide and 15ppm/L of glycinamide, wherein the pH is 6, the pH regulation and control are carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%, and the balance is water;
f. electroplating copper: 80g/L of copper sulfate, 20ppm/L of ammonium glycyrrhetate, 20ppm/L, DDZ-L of 6-chloro-3-indolyl-beta-D-glucuronic acid cyclohexylammonium salt, 20ppm/L of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinolinecarboxylic acid benzyl ester p-toluenesulfonate, 22.5ppm/L of sodium polydithio-propane sulfonate, 90ppm/L of 4-pyridylethanethiol hydrochloride, 80ppm/L of 4-diethylamino-2-butyn-1-ol, and the balance of water;
the pH is 6, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
Operating temperature of 30 DEG C
The current density was 1.5A/dm2
Time 120min.
The experimental results were: the deep plating capability is excellent, the hole filling capability is excellent, the uniformity is excellent, and the hole crack is excellent.
Example 2
An environment-friendly process applied to filling holes of wafer through holes:
deoiling for 2min at 50 ℃; b. coarsening: 2min30 ℃; c. and (3) oxygen discharge treatment: nitrogen flow rate is 5L/min, and pure water flow rate is 10L/min; electroless copper plating: the temperature is 75 ℃, the pH is 6, the time is 40min, and the nitrogen release speed is 3L/min;
d. activating: 30ppm/L of ruthenium acetate, 10ppm/L of palladium sulfate, 30ppm/L, PEG-800030ppm/L of ethylenediamine and 10ppm/L of 2-fluoropyridine, wherein the pH is 3, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%, and the balance is water.
e. Electroless copper plating: 5.5g/L of copper sulfate, 2.0g/L of vitamin C, 0.5g/L, D-leucyl glycylglycine and 0.2g/L, OP-1020ppm/L, boc-glycylglycine, wherein the pH is 6, the pH regulation and control are carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%, and the balance is water.
f. Electroplating copper: 80g/L of copper sulfate, 20ppm/L of ammonium glycyrrhetate, 20ppm/L, DDZ-L of 6-chloro-3-indolyl-beta-D-glucuronic acid cyclohexylammonium salt, 20ppm/L of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinolinecarboxylic acid benzyl ester p-toluenesulfonate, 7.5ppm/L of sodium polydithio-propane sulfonate, 50ppm/L of 4-pyridine ethylthiolate hydrochloride, 60ppm/L of 4-diethylamino-2-butyn-1-ol and the balance of water.
The pH is 6, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
Operating temperature of 30 DEG C
The current density was 2.5A/dm 2
Time 75min.
The experimental results were: the deep plating capability is excellent, the hole filling capability is excellent, the uniformity is excellent, and the hole crack is excellent.
Example 3
An environment-friendly process applied to filling holes of wafer through holes:
deoiling for 2min at 50 ℃; b. coarsening: 2min30 ℃; c. and (3) oxygen discharge treatment: nitrogen flow rate is 5L/min, and pure water flow rate is 10L/min; electroless copper plating: the temperature is 75 ℃, the pH is 6, the time is 40min, and the nitrogen release speed is 3L/min;
d. activating: 30ppm/L of ruthenium acetate, 10ppm/L of palladium sulfate, 30ppm/L, PEG-800030ppm/L of ethylenediamine and 10ppm/L of 2-fluoropyridine, wherein the pH is 3, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%, and the balance is water.
e. Electroless copper plating: 5g/L of copper sulfate, 0.8g/L of vitamin C, 0.2g/L, D-leucylglycylglycine and 0.2g/L, OP-1025ppm/L, boc-glycylamide 15ppm/L of sodium hydroxide solution with the mass fraction of 20% and concentrated sulfuric acid solution with the volume fraction of 50% are used for regulating and controlling the pH to be 6, and the balance is water.
f. Electroplating copper: 80g/L of copper sulfate, 10ppm/L of ammonium glycyrrhetate, 10ppm/L, DDZ-L of 6-chloro-3-indolyl-beta-D-glucuronic acid cyclohexylammonium salt, 10ppm/L of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinolinecarboxylic acid benzyl ester p-toluenesulfonate, 10ppm/L of sodium polydithio-dipropanesulfonate, 30ppm/L of 4-pyridine ethylthiolate hydrochloride, 40ppm/L of 4-diethylamino-2-butyn-1-ol and the balance of water.
The pH is 6, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
Operating temperature of 30 DEG C
The current density was 4.5A/dm 2
The time is 40min.
As can be seen from fig. 1, experimental results were obtained as follows: the deep plating capability is excellent, the hole filling capability is excellent, the uniformity is excellent, and the hole crack is excellent.
Comparative example 1
An environment-friendly process applied to filling holes of wafer through holes:
deoiling for 2min at 50 ℃; b. coarsening: 2min30 ℃; c. and (3) oxygen discharge treatment: nitrogen flow rate is 5L/min, and pure water flow rate is 10L/min; electroless copper plating: the temperature is 75 ℃, the pH is 6, the time is 40min, and the nitrogen release speed is 3L/min;
d. activating: is selected from domestic activating liquid commonly used in the market.
e. Electroless copper plating: 5g/L of copper sulfate, 0.8g/L of vitamin C, 0.2g/L, D-leucylglycylglycine and 0.2g/L, OP-1025ppm/L, boc-glycylamide 15ppm/L of sodium hydroxide solution with the mass fraction of 20% and concentrated sulfuric acid solution with the volume fraction of 50% are used for regulating and controlling the pH to be 6, and the balance is water.
f. Electroplating copper: 80g/L of copper sulfate, 10ppm/L of ammonium glycyrrhetate, 10ppm/L, DDZ-L of 6-chloro-3-indolyl-beta-D-glucuronic acid cyclohexylammonium salt, 10ppm/L of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinolinecarboxylic acid benzyl ester p-toluenesulfonate, 10ppm/L of sodium polydithio-dipropanesulfonate, 30ppm/L of 4-pyridine ethylthiolate hydrochloride, 40ppm/L of 4-diethylamino-2-butyn-1-ol and the balance of water.
The pH is 6, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
Operating temperature of 30 DEG C
The current density was 4.5A/dm 2
The time is 40min.
As can be seen from fig. 1, compared with the example, the activating solution of comparative example 1 adopts a certain domestic medicinal liquid, and the experimental result is: poor deep plating capability, poor hole filling capability, poor uniformity and poor orifice cracking.
Comparative example 2
An environment-friendly process applied to filling holes of wafer through holes:
degreasing 2min at 50 ℃; b. coarsening: 2min at 30 ℃; c. and (3) oxygen discharge treatment: nitrogen flow rate is 5L/min, and pure water flow rate is 10L/min; electroless copper plating: the temperature is 75 ℃, the pH is 6, the time is 40min, and the nitrogen release speed is 3L/min;
d. activating: 30ppm/L of ruthenium acetate, 10ppm/L of palladium sulfate, 30ppm/L, PEG-800030ppm/L of ethylenediamine and 10ppm/L of 2-fluoropyridine, wherein the pH is 3, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%, and the balance is water.
e. Electroless copper plating: electroless copper plating solutions commonly used in the market at present.
f. Electroplating copper: 80g/L of copper sulfate, 10ppm/L of ammonium glycyrrhetate, 10ppm/L, DDZ-L of 6-chloro-3-indolyl-beta-D-glucuronic acid cyclohexylammonium salt, 10ppm/L of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinolinecarboxylic acid benzyl ester p-toluenesulfonate, 10ppm/L of sodium polydithio-dipropanesulfonate, 30ppm/L of 4-pyridine ethylthiolate hydrochloride, 40ppm/L of 4-diethylamino-2-butyn-1-ol and the balance of water.
The pH is 6, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
Operating temperature of 30 DEG C
The current density was 4.5A/dm 2
The time is 40min.
Compared with the embodiment, the chemical copper plating solution of the comparative example 2 adopts a certain domestic liquid medicine, and the experimental result is that: good deep plating capability, good hole filling capability, good uniformity and good orifice cracks.
Comparative example 3
An environment-friendly process applied to filling holes of wafer through holes:
deoiling for 2min at 50 ℃; b. coarsening: 2min30 ℃; c. and (3) oxygen discharge treatment: nitrogen flow rate is 5L/min, and pure water flow rate is 10L/min; electroless copper plating: the temperature is 75 ℃, the pH is 6, the time is 40min, and the nitrogen release speed is 3L/min;
d. activating: 30ppm/L of ruthenium acetate, 10ppm/L of palladium sulfate, 30ppm/L, PEG-800030ppm/L of ethylenediamine and 10ppm/L of 2-fluoropyridine, wherein the pH is 3, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%, and the balance is water.
e. Electroless copper plating: 5g/L of copper sulfate, 0.8g/L of vitamin C, 0.2g/L, D-leucylglycylglycine and 0.2g/L, OP-1025ppm/L, boc-glycylamide 15ppm/L of sodium hydroxide solution with the mass fraction of 20% and concentrated sulfuric acid solution with the volume fraction of 50% are used for regulating and controlling the pH to be 6, and the balance is water.
f. Electroplating copper: copper plating solutions commonly used in domestic markets at present.
The pH is 6, and the pH regulation is carried out by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
Operating temperature of 30 DEG C
The current density was 4.5A/dm 2
The time is 40min.
As can be seen from FIG. 1, compared with the examples, the comparative example 3 uses a certain domestic liquid medicine to obtain the experimental results: good deep plating capability, good hole filling capability, good uniformity and good orifice cracks.
The above disclosure is merely an example of the present invention, but the present invention is not limited thereto, and any variations that can be considered by a person skilled in the art should fall within the protection scope of the present invention.
Claims (10)
1. An environment-friendly process applied to filling holes of wafer through holes is characterized by comprising the following specific steps of:
step a, degreasing, which is used for cleaning greasy dirt on the surface of the substrate and improving the cleanliness of the surface of the substrate;
step b, coarsening, namely coarsening through hydrofluoric acid solution with the mass concentration of 50%, so as to improve the binding force of the plating layer;
c, oxygen discharge treatment, namely discharging oxygen in the micropores of the base material under the impact of nitrogen, and then injecting pure water to further discharge the gas in the micropores;
step d, activating, namely forming a catalytic layer on the surface of the base material through an activating tank containing activating liquid to promote the formation of a copper seed layer;
step e, electroless copper plating, wherein a layer of seed layer copper is formed on the surface of the base material through a copper plating groove containing electroless copper plating solution to realize connection blind holes, so as to provide a basic copper layer for electroplated copper;
step f, electroplating copper, wherein the base material enters an electroplating tank containing an electroplating copper solution for electroplating;
the specific conditions of the oxygen discharge treatment in the step c are that the flow rate of nitrogen is 5-10L/min and the flow rate of pure water is 10-30L/min; the specific conditions of the electroless copper plating in the step e are that the temperature is 70-80 ℃, the pH is 5-7, the time is 30-50min, the electroless copper plating is carried out under the protection of nitrogen, and the release speed of the nitrogen is 2.5-3.5L/min; the chemical copper plating solution in the step e comprises 2.5-7.5g/L of copper sulfate, 0.5-2.5g/L of composite reducing agent, 0.2-0.5g/L of stabilizing agent, 20-60ppm/L of surfactant and 15-45ppm/L of accelerator, and the pH regulation is regulated by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
2. The environment-friendly process for filling holes in wafer through holes according to claim 1, wherein the composite reducing agent in the electroless copper plating solution is a composition composed of vitamin C and sodium hypophosphite, the mass concentration ratio of the vitamin C to the sodium hypophosphite is 4:1, the vitamin C is 0.4-2g/L, and the sodium hypophosphite is 0.1-0.5g/L.
3. The environmental protection process for filling holes in wafer through holes according to claim 1, wherein the stabilizer in the electroless copper plating solution is D-leucyl glycylglycine; the surfactant is OP-10; the accelerator is Boc-glycinamide.
4. The environment-friendly process for filling holes in wafer through holes according to claim 1, wherein the specific conditions in the step c are as follows: the activation temperature is 25-40 ℃, the activation time is 2-5min, the pH is controlled to be 2-4, and the specific adjustment can be adjusted by a sodium hydroxide solution with the mass fraction of 20% and a concentrated sulfuric acid solution with the volume fraction of 50%.
5. The environment-friendly process for filling holes in wafer through holes according to claim 1, wherein the activating solution in the step c comprises the following components: 30-60ppm/L of ruthenium acetate, 10-15ppm/L of palladium sulfate, 30-90ppm/L, PEG-800030-90ppm/L of ethylenediamine and 10-30ppm/L of 2-fluoropyridine, and the activating solution improves the uniformity of plating starting.
6. The environment-friendly process for filling holes in wafer vias according to claim 1, wherein the specific conditions for electroplating copper in step f are as follows: the current density is used in the range of 0.5-45A/cm 2 The temperature is 25-35 ℃, the pH is 5-6, the clamp adopts a four-terminal shunt method, namely the clamping part of the anode electrode is divided into four parts, and the four parts are respectively clamped in the central directions of four sides of the substrate, so that the phenomenon of uneven current aggregation is reduced.
7. The environment-friendly process for filling holes in wafer vias according to claim 1, wherein the copper electroplating solution for copper electroplating in step f comprises the following components: 70-90g/L of copper sulfate, 30-60ppm/L of composite leveling agent, 15-45mg/L of composite brightening agent, 30-90ppm/L of wetting agent and 40-80ppm/L of dispersing agent.
8. The environment-friendly process for filling holes in wafer through holes according to claim 1, wherein the composite leveling agent of the electrolytic copper plating solution is a composition consisting of ammonium glycyrrhizate, 6-chloro-3-indolyl-beta-D-glucuronic acid cyclohexylammonium salt and DDZ-L-leucine cyclohexylammonium salt, and the mass concentration ratio of the compositions is 1:1:1.
9. The environment-friendly process for filling holes in wafer through holes according to claim 1, wherein the composite brightening agent of the electrolytic copper plating solution is a composition composed of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinoline benzyl carboxylate tosylate and sodium polydithio-dipropyl sulfonate, and the mass concentration ratio of the two is 1:1.
10. The environment-friendly process for filling holes in wafer through holes according to claim 7, wherein the wetting agent of the electrolytic copper plating solution is 4-pyridylethanothioate hydrochloride, and the dispersing agent is 4-diethylamino-2-butyn-1-ol.
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| CN110499501A (en) * | 2019-10-08 | 2019-11-26 | 苏州天承化工有限公司 | A kind of chemical bronze plating liquid and preparation method thereof and blind hole processing method |
| CN113881993A (en) * | 2021-09-29 | 2022-01-04 | 新阳硅密（上海）半导体技术有限公司 | Process method capable of optimizing electroplating hole filling capacity |
| CN113930813A (en) * | 2021-11-17 | 2022-01-14 | 珠海市创智芯科技有限公司 | Electro-coppering solution applied to wafer-level packaging and electroplating process thereof |
| CN115369460A (en) * | 2022-09-23 | 2022-11-22 | 珠海市创智芯科技有限公司 | Copper electroplating solution for filling micro blind holes |
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