WO2014208204A1 - スズまたはスズ合金用電気メッキ液およびその用途 - Google Patents
スズまたはスズ合金用電気メッキ液およびその用途 Download PDFInfo
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- WO2014208204A1 WO2014208204A1 PCT/JP2014/062367 JP2014062367W WO2014208204A1 WO 2014208204 A1 WO2014208204 A1 WO 2014208204A1 JP 2014062367 W JP2014062367 W JP 2014062367W WO 2014208204 A1 WO2014208204 A1 WO 2014208204A1
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- Prior art keywords
- tin
- electroplating
- filling
- electroplating solution
- plating
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- 238000009713 electroplating Methods 0.000 title claims abstract description 84
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001128 Sn alloy Inorganic materials 0.000 title claims abstract description 35
- 238000007747 plating Methods 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 150000004002 naphthaldehydes Chemical class 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 3
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 claims description 3
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 238000005429 filling process Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229940098779 methanesulfonic acid Drugs 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- -1 gold ion Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 description 1
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LLABTCPIBSAMGS-UHFFFAOYSA-L lead(2+);methanesulfonate Chemical compound [Pb+2].CS([O-])(=O)=O.CS([O-])(=O)=O LLABTCPIBSAMGS-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence 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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- 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
-
- 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
-
- 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
- H01L21/18—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 the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/187—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating means therefor, e.g. baths, apparatus
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/421—Blind plated via connections
Definitions
- the present invention relates to an electroplating solution for tin or tin alloy, a method for filling blind vias or through holes using the same, and a method for manufacturing an electronic circuit board.
- the conventional process has a problem that the process is complicated because different metal types are used in the filling process and the mounting process.
- the mounting process may be omitted.
- Patent Document 1 a technique for applying tin or a tin alloy to the filling process of blind vias or through holes has also been reported.
- the inventors of the present invention have ensured that blind vias and through-holes can be obtained by including a specific compound at a specific concentration in a conventionally known tin or tin alloy plating plating solution.
- the present invention has been completed by finding that it can be filled with high performance in a short time.
- the present invention is an electroplating solution for tin or tin alloy, which comprises the following components (a) and (b) (A) a carboxyl group-containing compound (b) a carbonyl group-containing compound, wherein component (a) is 1.3 g / L or more and component (b) is 0.3 g / L or more, This is an electroplating solution for tin alloys.
- the present invention is a blind via or through hole plating filling method, characterized by electroplating an object to be plated having a blind via or a through hole with the above-described electroplating solution for tin or tin alloy.
- the present invention is an electronic circuit board manufacturing method including a step of plating and filling a substrate having blind vias or through holes, wherein the plating filling is performed by the above-described blind via or through hole plating filling method. It is a manufacturing method of a circuit board.
- the electroplating solution for tin or tin alloy of the present invention can fill blind vias or through holes with high reliability in a short time by electroplating on the object to be plated having blind vias or through holes.
- electroplating solution for tin or tin alloy of the present invention can be used for three-dimensional mounting of semiconductors, filling process of blind vias and through holes in printed wiring boards, and formation of through silicon vias.
- FIG. 3 is a cross-sectional photograph of a substrate after electroplating in Example 3 ((a) to (d) in the drawing are electroplated at 0.05 A / dm 2 using the electroplating solution of Comparative Product 2 and 15 minutes later). 30 minutes, 60 minutes and 90 minutes).
- FIG. 1 A cross-sectional photograph of the substrate after the electroplating in Example 2 (in the drawing (a) is using an electroplating solution of comparative product 1, which was carried out for 15 minutes electroplated with 0.075A / dm 2, (b) (The electroplating solution of Example 1 was used for electroplating at 0.075 A / dm 2 for 20 minutes).
- FIG. 3 is a cross-sectional photograph of a substrate after electroplating in Example 3 ((a) to (d) in the drawing are electroplated at 0.05 A / dm 2 using the electroplating solution of Comparative Product 2 and 15 minutes later). 30 minutes, 60 minutes and 90 minutes).
- Example 3 is a cross-sectional photograph of a substrate after electroplating in Example 3 ((a) to (e) in the drawing are electroplated at 0.05 A / dm 2 using the electroplating solution of Example 1 and after 15 minutes) 30 minutes, 60 minutes, 90 minutes, 120 minutes).
- 6 is a cross-sectional photograph of a substrate after electroplating in Example 6 (in the figure, (a) to (c) are electroplated at 1.5 A / dm 2 using the electroplating solution of Example 2 for 15 minutes) And after 25 and 35 minutes).
- the component (a) carboxyl group-containing compound contained in the electroplating solution for tin or tin alloy of the present invention is not particularly limited as long as it is a compound having a carboxyl group.
- the present plating solution is not particularly limited as long as it is a compound having a carboxyl group.
- Methacrylic acid, acrylic acid, crotonic acid, propylene-1,2-dicarboxylic acid, ethacrylic acid, methyl acrylate, methyl methacrylate and the like are preferred.
- 1 type or 2 types can be used for these carboxyl group containing compounds.
- the content of the component (a) carboxyl group-containing compound in the plating solution of the present invention is 1.3 g / L or more, preferably 1.3 to 2.5 g / L.
- the component (b) carbonyl group-containing compound contained in the plating solution of the present invention is not particularly limited as long as it is a compound having a carbonyl group.
- benzalacetone, naphthaldehyde, chlorobenzaldehyde, phthalaldehyde, salicylaldehyde examples include naphthaldehyde, methoxybenzaldehyde, vanillin, and among these, benzalacetone, naphthaldehyde, and chlorobenzaldehyde are preferable.
- 1 type or 2 types can be used for these carbonyl group containing compounds.
- a solvent such as methanol or isopropyl alcohol is also included.
- the content of the component (b) carbonyl group-containing compound in the plating solution of the present invention is 0.3 g / L or more, preferably 0.3 to 1.0 g / L.
- the molar ratio of component (a) to component (b) is not particularly limited, but is preferably 10 or less, more preferably 2 to 9.
- plating solution for example, as a metal ion for tin ions and alloys, for example, silver ion, gold ion, copper ion, Lead ions, antimony ions, indium ions, bismuth ions, etc., and acids containing, for example, sulfuric acid, methane sulfonic acid, borofluoric acid, phenol sulfonic acid, sulfamic acid, pyrophosphoric acid, etc. as acids that acidify and stabilize the bath Is mentioned.
- a metal ion for tin ions and alloys for example, silver ion, gold ion, copper ion, Lead ions, antimony ions, indium ions, bismuth ions, etc.
- electroplating bath for tin or tin alloy examples include a sulfuric acid bath, a methanesulfonic acid bath, a borofluoride bath, and the like.
- a sulfuric acid bath and a methanesulfonic acid bath are preferable.
- the plating solution of the present invention includes a conventionally known electroplating solution for tin or tin alloy, and further known antioxidants such as nonionic, cationic and anionic surfactants, catechol, resorcinol, catecholsulfonic acid, etc. Etc. may be added.
- the plating solution of the present invention can be electroplated on an object to be plated by a conventionally known method.
- the method of electroplating using the plating solution of the present invention is not particularly limited. For example, after pretreatment such as alkaline degreasing, hydrophilization treatment, and acid activity is performed on the object to be plated, this is immersed in the plating solution of the present invention. And the like.
- the conditions for electroplating using the plating solution of the present invention are not particularly limited, and the conditions for ordinary tin or tin alloy electroplating may be used.
- the bath temperature is 10 to 40 ° C. it may be performed at a density 0.2 ⁇ 3A / dm 2.
- the object to be plated which can be electroplated with the plating solution of the present invention is not particularly limited, and examples thereof include those whose surface is formed of a metal such as copper, nickel or brass, a resin such as ABS, polyimide or epoxy. It is done.
- the plating solution of the present invention can be electroplated on a normal object to be plated as described above.
- a blind via or through hole is formed by electroplating an object to be plated having a blind via or a through hole. It is preferably used for filling with tin or tin alloy.
- the molar ratio of components (a) and (b) in the plating solution of the present invention is 10 or less, preferably 2-9.
- the molar ratio of components (a) and (b) in the plating solution of the present invention is 10 or less, preferably 3.5 to 10.
- the conditions of electroplating are not particularly limited. It may be performed at 0.01 to 2.5 A / dm 2 . Further, in order to shorten the plating time, the current density during electroplating may be made relatively higher than that at the start of electroplating.
- the method of increasing the current density during electroplating relative to the start of electroplating. For example, the method of increasing the current density during electroplating stepwise after a predetermined time from the start of electroplating, Examples thereof include a method of linearly increasing the current density during plating from the start of electroplating.
- the plating solution of the present invention capable of filling blind vias or through holes with tin or a tin alloy as described above includes a step of plating and filling a substrate having blind vias or through holes. It can be used for electronic circuit board manufacturing methods such as mounting, filling vias and through holes in printed wiring boards, and forming through silicon vias.
- Example 1 Preparation of electroplating solution for tin: An electroplating solution for tin having the following composition was prepared by mixing components 1 to 5 and 7 and then mixing component 6.
- Example 2 Filling blind vias with tin electroplating: A silicon wafer substrate having blind vias with an aspect ratio of 6 (10 ⁇ ⁇ 60D) was washed with water and pretreated. The substrate subjected to this pretreatment was immersed in the tin electroplating solution prepared in Example 1 (Comparative product 1, Example product 1) for 1 minute, and at a current density of 0.075 A / dm 2 for a predetermined time (15 minutes). (Comparative product 1) or 20 minutes (implemented product 1)) Electroplating was performed. Via filling was observed from the cross section of the substrate after electroplating (FIG. 1).
- Comparative Product 1 there was no precipitation at the bottom of the via and voids were observed, but in Preferential Product 1, preferential precipitation from the bottom of the via was confirmed.
- Example 3 Filling blind vias with tin electroplating: After the pretreatment same substrate as used in Example 2, it was immersed in a tin electroplating solution prepared in Example 1 (Practical Product 1 or Comparative Product 2), of 0.05 A / dm 2 Electroplating was performed at a current density for a predetermined time (15 minutes, 30 minutes, 60 minutes, 90 minutes, 120 minutes (only for the product 1)). Via filling conditions were observed from the cross section of the substrate after electroplating (FIGS. 2 and 3).
- the filling in the via did not proceed even after 90 minutes of plating, but in the case of the product 1, the deposition amount increased with the plating time, and almost 100% could be filled in 120 minutes of plating.
- Example 4 Filling blind vias with tin electroplating: A substrate similar to that used in Example 2 was pretreated, and then immersed in an electroplating solution for tin prepared in Example 1 (Example Product 1), with a current density of 0.075 A / dm 2 and 20. The electroplating was performed at a current density of 0.15 A / dm 2 for 10 minutes and a current density of 0.3 A / dm 2 for 10 minutes.
- the blind vias were completely filled in 40 minutes by this electroplating.
- the filling time of the blind via is shortened by about 65%.
- Example 5 Preparation of electroplating solution for tin: An electroplating solution for tin having the following composition was prepared by mixing components 1 to 5 and 7 and then mixing component 6.
- Example 6 Filling vias with tin electroplating: A printed wiring board having a blind via having an aspect ratio of 0.57 (70 ⁇ ⁇ 40D) was subjected to alkali degreasing treatment at 40 ° C. for 1 minute, and then pretreated by acid activation treatment at room temperature for 10 seconds. The pre-treated substrate was immersed in the tin electroplating solution prepared in Example 5 (Example 2), and the current density was 1.5 A / dm 2 for a predetermined time (15 minutes, 25 minutes, or 35 minutes). ) Electroplating was performed. Via filling was observed from the cross section of the substrate after electroplating (FIG. 4).
- Example 7 Preparation of electroplating solution for tin: An electroplating solution for tin having the following composition was prepared by mixing components 1 to 5 and 8 and then mixing components 6 or 7.
- Example 8 Filling vias with tin electroplating: A silicon wafer substrate having a blind via having an aspect ratio of 5 (20 ⁇ ⁇ 100D) was pretreated, and then immersed in an electroplating solution for tin prepared in Example 7 (Example 3 or Example 4). blind vias were electroplated until filled at a current density of dm 2.
- the via When electroplating using the electroplating solution of the working product 3, the via is completely filled in 100 minutes, and when electroplating using the electroplating solution of the working product 4, the via is completely filling in 110 minutes. It was done.
- Example 9 Preparation of electroplating solution for tin alloy: An electroplating solution for tin alloy having the following composition was prepared by mixing components 1 to 6 and 8 and then mixing component 7.
- Example 10 Filling blind vias with tin alloy electroplating: A substrate similar to that used in Example 6 was pretreated, and then immersed in an electroplating solution for tin alloy (Example 5) prepared in Example 9 at a current density of 1.5 A / dm 2. Electroplating was performed for 30 minutes.
- the via was completely filled by this electroplating.
- tin and lead were 87% and 13% alloys, respectively.
- a blind via or a through hole can be filled with tin or a tin alloy. Therefore, the present invention can be used for three-dimensional mounting of semiconductors, filling process of blind vias and through holes in printed wiring boards, and formation of through silicon vias. more than
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Abstract
Description
(a)カルボキシル基含有化合物
(b)カルボニル基含有化合物
を含有し、成分(a)が1.3g/L以上および成分(b)が0.3g/L以上であることを特徴とするスズまたはスズ合金用電気メッキ液である。
<スズ用電気メッキ液>
メタンスルホン酸第1スズ(スズとして):25~150g/L、好ましくは70~125g/L
メタンスルホン酸:10~180g/L、好ましくは15~120g/L
ポリオキシエチレンラウリルアミン:0.1~8g/L、好ましくは3~6g/L
カテコール:0.1~5g/L、好ましくは0.5~2g/L
メタクリル酸:0.2~4g/L、好ましくは1.3~2.5g/L
1-ナフトアルデヒド:0.05~1.5g/L、好ましくは0.3~1.0g/L
メタノール:0.7~25g/L、好ましくは3.5~17g/L
<スズ合金用電気メッキ液>
メタンスルホン酸第1スズ(スズとして):25~150g/L、好ましくは70~125g/L
メタンスルホン酸鉛(鉛として):0.1~50g/L、好ましくは1~30g/L
メタンスルホン酸:10~180g/L、好ましくは15~120g/L
ポリオキシエチレンラウリルアミン:0.1~8g/L、好ましくは3~6g/L
カテコール:0.1~5g/L、好ましくは0.5~2g/L
メタクリル酸:0.2~4g/L、好ましくは1.3~2.5g/L
1-ナフトアルデヒド:0.05~1.5g/L、好ましくは0.3~1.0g/L
メタノール:0.7~25g/L、好ましくは3.5~17g/L
スズ用電気メッキ液の調製:
下記組成のスズ用電気メッキ液を、成分1~5、7を混合した後、成分6を混合することにより調製した。
スズ電気メッキによるブラインドビアの充填:
アスペクト比6(10φx60D)のブラインドビアを有するシリコンウエハ基板を水洗し、前処理を行った。この前処理を行った基板を、実施例1で調製したスズ用電気メッキ液(比較品1、実施品1)に1分間浸漬し、0.075A/dm2の電流密度で所定時間(15分(比較品1)または20分(実施品1))電気メッキを行った。電気メッキ後の基板の断面からビアの充填具合を観察した(図1)。
スズ電気メッキによるブラインドビアの充填:
実施例2で用いたのと同様の基板に前処理を行った後、実施例1で調製したスズ用電気メッキ液(実施品1または比較品2)に浸漬し、0.05A/dm2の電流密度で所定時間(15分、30分、60分、90分、120分(実施品1のみ))電気メッキを行った。電気メッキ後の基板の断面からビアの充填具合を観察した(図2および図3)。
スズ電気メッキによるブラインドビアの充填:
実施例2で用いたのと同様の基板に前処理を行った後、実施例1で調製したスズ用電気メッキ液(実施品1)に浸漬し、0.075A/dm2の電流密度で20分、0.15A/dm2の電流密度で10分、0.3A/dm2の電流密度で10分と変化させて電気メッキを行った。
スズ用電気メッキ液の調製:
下記組成のスズ用電気メッキ液を、成分1~5、7を混合した後、成分6を混合することにより調製した。
スズ電気メッキによるビアの充填:
アスペクト比0.57(70φx40D)のブラインドビアを有するプリント配線板に40℃で1分間、アルカリ脱脂処理をした後、室温で10秒間、酸活性処理により前処理を行った。この前処理を行った基板を、実施例5で調製したスズ用電気メッキ液(実施品2)に浸漬し、1.5A/dm2の電流密度で所定時間(15分、25分または35分)電気メッキを行った。電気メッキ後の基板の断面からビアの充填具合を観察した(図4)。
スズ用電気メッキ液の調製:
下記組成のスズ用電気メッキ液を、成分1~5、8を混合した後、成分6または7を混合することにより調製した。
スズ電気メッキによるビアの充填:
アスペクト比5(20φx100D)のブラインドビアを有するシリコンウエハ基板に前処理を行った後、実施例7で調製したスズ用電気メッキ液(実施品3または実施品4)に浸漬し、0.2A/dm2の電流密度でブラインドビアが充填されるまで電気メッキを行った。
スズ合金用電気メッキ液の調製:
下記組成のスズ合金用電気メッキ液を、成分1~6、8を混合した後、成分7を混合することにより調製した。
スズ合金電気メッキによるブラインドビアの充填:
実施例6で用いたのと同様の基板に前処理を行った後、実施例9で調製したスズ合金用電気メッキ液(実施品5)に浸漬し、1.5A/dm2の電流密度で30分間電気メッキを行った。
以 上
Claims (8)
- スズまたはスズ合金用電気メッキ液であって、以下の成分(a)および(b)
(a)カルボキシル基含有化合物
(b)カルボニル基含有化合物
を含有し、成分(a)が1.3g/L以上および成分(b)が0.3g/L以上であることを特徴とするスズまたはスズ合金用電気メッキ液。 - 成分(a)と成分(b)のモル比が10以下である請求項1記載のスズまたはスズ合金用電気メッキ液。
- 成分(a)のカルボキシル基含有化合物が、メタクリル酸およびアクリル酸から選ばれる1種または2種である請求項1記載のスズまたはスズ合金用電気メッキ液。
- 成分(b)のカルボニル基含有化合物が、ベンザルアセトン、ナフトアルデヒドおよびクロロベンズアルデヒドから選ばれる1種または2種である請求項1記載のスズまたはスズ合金用電気メッキ液。
- ブラインドビアまたはスルーホールの充填用である請求項1~4の何れかに記載のスズまたはスズ合金用電気メッキ液。
- ブラインドビアまたはスルーホールを有する被メッキ物に、請求項1~5の何れかに記載のスズまたはスズ合金用電気メッキ液で電気メッキすることを特徴とするブラインドビアまたはスルーホールのメッキ充填方法。
- 電気メッキ中の電流密度を電気メッキ開始時より相対的に高くする請求項6記載のブラインドビアまたはスルーホールのメッキ充填方法。
- ブラインドビアまたはスルーホールを有する基板にメッキ充填をする工程を含む電子回路基板の製造方法において、メッキ充填を請求項6または7に記載のビアまたはスルーホールのメッキ充填方法で行うことを特徴とする電子回路基板の製造方法。
Priority Applications (3)
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US14/898,288 US20160130712A1 (en) | 2013-06-26 | 2014-05-08 | Electroplating solution for tin or tin alloy, and use for same |
CN201480033173.1A CN105308218B (zh) | 2013-06-26 | 2014-05-08 | 锡或锡合金用电镀液及其用途 |
KR1020157035631A KR20160024868A (ko) | 2013-06-26 | 2014-05-08 | 주석 또는 주석 합금용 전기 도금액 및 그의 용도 |
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JP2013133292A JP6006683B2 (ja) | 2013-06-26 | 2013-06-26 | スズまたはスズ合金用電気メッキ液およびその用途 |
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KR102233334B1 (ko) * | 2014-04-28 | 2021-03-29 | 삼성전자주식회사 | 주석 도금액, 주석 도금 장치 및 상기 주석 도금액을 이용한 반도체 장치 제조 방법 |
CN105755513A (zh) * | 2016-04-28 | 2016-07-13 | 四川昊吉科技有限公司 | 一种镀锡防腐剂 |
JP6834070B2 (ja) * | 2016-06-13 | 2021-02-24 | 石原ケミカル株式会社 | 電気スズ及びスズ合金メッキ浴、当該メッキ浴を用いて電着物を形成した電子部品の製造方法 |
KR20180024765A (ko) * | 2016-08-31 | 2018-03-08 | 주식회사 호진플라텍 | 전기도금을 이용한 주석-비스무트-납 삼원합금 솔더 조성물 |
JP6620859B2 (ja) | 2017-10-24 | 2019-12-18 | 三菱マテリアル株式会社 | 錫又は錫合金めっき堆積層の形成方法 |
JP6620858B2 (ja) | 2017-10-24 | 2019-12-18 | 三菱マテリアル株式会社 | 錫又は錫合金めっき堆積層の形成方法 |
WO2019082884A1 (ja) | 2017-10-24 | 2019-05-02 | 三菱マテリアル株式会社 | 錫又は錫合金めっき液 |
US11268203B2 (en) | 2017-10-24 | 2022-03-08 | Mitsubishi Materials Corporation | Tin or tin alloy plating solution |
TWI754135B (zh) | 2018-03-20 | 2022-02-01 | 日商三菱綜合材料股份有限公司 | 錫或錫合金的鍍敷液、凸塊的形成方法、電路基板的製造方法 |
CN111788337A (zh) | 2018-03-20 | 2020-10-16 | 三菱综合材料株式会社 | 锡或锡合金电镀液、凸点的形成方法及电路基板的制造方法 |
WO2021153160A1 (ja) | 2020-01-27 | 2021-08-05 | 三菱マテリアル株式会社 | 錫又は錫合金電解めっき液、バンプの形成方法、及び回路基板の製造方法 |
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- 2014-05-08 WO PCT/JP2014/062367 patent/WO2014208204A1/ja active Application Filing
- 2014-05-08 CN CN201480033173.1A patent/CN105308218B/zh active Active
- 2014-05-08 KR KR1020157035631A patent/KR20160024868A/ko not_active Application Discontinuation
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CN105308218B (zh) | 2018-07-13 |
US20160130712A1 (en) | 2016-05-12 |
KR20160024868A (ko) | 2016-03-07 |
CN105308218A (zh) | 2016-02-03 |
TWI625428B (zh) | 2018-06-01 |
JP2015007276A (ja) | 2015-01-15 |
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