CN102543855B - 三维集成电路结构及材料的制造方法 - Google Patents
三维集成电路结构及材料的制造方法 Download PDFInfo
- Publication number
- CN102543855B CN102543855B CN201210016388.5A CN201210016388A CN102543855B CN 102543855 B CN102543855 B CN 102543855B CN 201210016388 A CN201210016388 A CN 201210016388A CN 102543855 B CN102543855 B CN 102543855B
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- China
- Prior art keywords
- metal
- plating
- loading material
- sodium
- dimensional integrated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 34
- 238000007747 plating Methods 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 230000002829 reductive effect Effects 0.000 claims abstract description 12
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 11
- 238000001746 injection moulding Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 150000001298 alcohols Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 230000001939 inductive effect Effects 0.000 claims description 15
- 229910052755 nonmetal Inorganic materials 0.000 claims description 15
- 230000003287 optical effect Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- -1 polybutylene terephthalate Polymers 0.000 claims description 9
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 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 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 229960004249 sodium acetate Drugs 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 4
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 239000004020 conductor Substances 0.000 abstract description 16
- 239000004033 plastic Substances 0.000 abstract description 15
- 229920003023 plastic Polymers 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 230000000536 complexating effect Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001465 metallisation Methods 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition 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
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0053—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor combined with a final operation, e.g. shaping
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
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- 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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1862—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by radiant energy
- C23C18/1868—Radiation, e.g. UV, laser
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- 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
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- 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/208—Multistep pretreatment with use of metal first
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Abstract
本发明涉及一种新型的三维集成电路结构及材料的制造方法，步骤是在热塑性承载材料中加入醇类和/或醛类，用注塑机注塑成型为构件，质量含量5-10％；用激光射线在构件的表面照射出的线路图案；浸入pH＝4-6的至少一种金属离子的溶液浸泡5-7分钟，水洗后放入pH＝5的含有还原剂的水溶液中浸泡5-7分钟，在还原生成金属核的区域进行化学镀铜，镀层厚度为1-12微米，再中磷化学镀镍，镀层厚度为2-3微米。本发明在制备金属电路导体的过程中，由于塑性材料中不含有任何金属元素，保持了承载材料的原有机械性能，而且性能稳定，提高了导体轨道与承载材料之间的附着力，提高了三维集成电路的质量，降低了成本，减少了污染。
Description
技术领域
本发明涉及一种新型的三维集成电路结构及材料的制造方法。
背景技术
三维集成电路结构是一种较为先进的电子集成电路器件，与传统的二维(平面)集成电路相比，这种三维集成电路的导体轨道结构具有明显的优越性，应用也更加广泛。在导体轨道结构的制各技术中，导体轨道承载材料的制备占据十分重要的地位。在已公开的文献和专利报道中，目前不导电承载材料的制备方法包括以下几种。
1)为了制造精细附着的导体轨道结构，在不导电的承载材料中掺入金属螯合物，其结构为尖晶石结构或类尖晶石结构的含铜化合物，且利用激光射线裂解出所构造的金属化晶核，这种方法可用于由热塑性的塑料采用喷铸方法制造电路载体。
2)采用摸块化的互连器件来制造三维喷铸电路载体。
上述两种方法的缺点在于金属螯合物的热稳定性对于现代高温塑料如LCP的加工处理温度处于临界范围内，因此该方法仅能有限制地应用在对于将来的无铅焊接工艺变得越来越重要的材料领域中。此外金属螯合物必须采用相对较高的掺杂，以在激光作用下得到足够密度的晶核用于快速金属化，然而高的合成体成份通常会损害承载材料所需的重要性能，如断裂强度和韧性等。
3)由激光射线分离出的金属化晶核通过金属微粒的隔离而物理钝化，其缺点是因为被隔离的微粒明显大于典型的金属螯合体的分子，所以导电性能比较差。，
4)目前关于三维集成电路技术的关键是两部分：(a)将金属螯合物直接添加到承载材料中，(b)利用激光将塑性材料中的具有金属活性的粒子打出，使其暴露在空气中，此方法的不足是：在塑性材料中添加金属螯合物易造成损害承载材料所需的重要性能，如断裂强度和韧性等。激光的能量大小直接影响金属化镀层工艺中的附着力和线路之间的溢镀(溢镀是指在化学镀铜和化学镀镍的过程中，造成非联通的线路导通)问题。
5)目前普遍采用在塑性材料中加入添加物的方法，其存在问题是由于添加物在塑性材料中分布的不均匀，对金属导体轨道的金属镀层的附着力有不利影响，从而影响了金属导体轨道的制备。目前正在使用的承载材料是在不导电的承载材料中只添加含铜元素的物质，所以，目前制备金属轨道的方法采用冲击镀铜(30分钟)、多道水洗、再镀厚铜(180分钟)、多道水洗、在最后化学镀镍。在金属轨道的金属化的过程中，必需采用含有大量甲醛作为还原剂的预冲击镀化学镀铜液。甲醛是一种对环境污染影响很大的物质，如果能够减少使用量或不用，那将是一件有利于环保的大事。
发明内容
本发明的目的是针对上述存在问题，提供一种新型的三维集成电路结构及材料的制造方法，即能量灼烧沉积(Energy Bumed Deposit)。本发明的突出特点是：在三维集成电路的承载材料中不含有任何金属元素的成分，而金属元素成分完全存在于电镀过程中。这个三维集成电路结构的制备方法是利用激光在结构载体表面镭射出需要金属化的特定区域并将在原料中的非金属光诱导催化剂转变成具有络合作用的基团，使其在后续金属化过程中发生催化作用。这是和其它某些方法的承载材料中含有金属元素成分，利用激光将塑料中的金属元素还原，然后进行金属化的原理和方法是不同的。
该方法是往承载塑性材料中添加少量非金属光诱导催化剂，主要成分为醇类或醛类，使承载材料在激光镭射后，结构中的非金属光诱导催化剂能形成的具有络合作用的催化剂成份，在含有的金属离子的溶液中，具有络合能力的金属离子先和塑料表面的具有络合作用的催化剂反应生成稳定络合物，此络合物被还原形成金属核，使其在制备导体轨道的过程中，保持了承载材料的原有机械性能，而且性能稳定。提高了导体轨道与承载材料之间的附着力、提高了三维集成电路的质量、降低成本、减少污染。
本发明提供的新型三维集成电路结构及材料的制造方法包括的具体步骤：
1)在热塑性工程塑料ABS、聚碳酸酯(PC)、聚对苯二甲酸丁二醇酯(PBT)等热稳定材料中通过加热150-250℃熔化、机械混合的方法把质量含量5-10％的固态或液态的一元、二元或三元醇和或一元、二元、三元醛的单一或组合的化合物和/或混合物(下面我们称之为非金属光诱导催化剂)添加到塑料中，得到含醇或醛的非金属光诱导催化剂的塑料。
2)把含有醇或醛的非金属光诱导催化剂的塑料用注塑机注塑成型为构件。可选地，其中，1，2，3-三羟基丙醇或2-甲基丙醛的质量含量5-10％；
3)用激光射线在构件的表面照射出线路图案；使承载材料在激光照射后的表面结构中，由于激光的热能和空气中的氧气使得至少非金属光诱导催化剂中的30％-50％的羟基或醛基生成羧基；一般而言，羧基对许多金属离子具有很好的络合作用。根据不同的改性材料特性，所述的激光射线波长范围从248nm到10600nm，激光调制频率从1K到1000K，脉冲宽度从4ns到200ns，激光平均功率从0.5W到100W；
4)将承载材料放入含有金属离子的溶液中，pH=4-6(简称A液)，浸泡5-7分钟，在激光照射过的区域，塑料表面的具有络合作用的非金属光诱导催化剂中的羧基和具有络合能力的金属离子反应生成稳定络合物。用蒸馏水洗后放入pH=5的含有还原剂的水溶液中浸泡5-7分钟，构件的表面生成金属核。
在步骤4)中的A液所添加的具有络合能力的金属离子包含：在元素周期表中除去第一、第二主族的金属元素外，其它的金属离子都是可以添加的，其中以微量元素金属钯(Pd)或银(Ag，含量小于0.1-2％)和过渡金属(2％-20％)Ni、Co、Fe、Cu、Zn中的一种或几种元素或其金属的络合物。
5)在步骤4)中生成的络合物被含有还原剂(B液)的水溶液还原形成金属核，使其在制备导体轨道的过程中性能稳定，提高了导体轨道与承载材料之间的附着力，进而提高了三维集成电路的质量。
6)在步骤5)中所述的还原剂B液为具有较强还原能力的无机化合物或有机化合物或者几种还原剂的混合。如：联氨、硼氢化合物、次磷酸盐、硫代硫酸盐、联胺、氯化亚锡等。
7)在生成金属核的区域进行化学镀铜、再中磷化学镀镍就形成了金属导体轨道。
化学镀铜的镀铜液配方：pH=12，温度60℃；无水硫酸铜12g/L；酒石酸钾钠43g/L；乙二胺四乙酸二钠14g/L；甲醛(37％)21ml/L；亚铁氰化钾36mg/L；联吡啶0.06g/L；氢氧化钠调pH值；空气搅拌。化学镀铜的速率为2-5微米/小时。
中磷化学镀镍液配方：pH=4.8-5，温度80-86℃，硫酸镍27g/L；次磷酸钠24g/L；醋酸钠15g/L；乳酸30g/L；柠檬酸4g/L；十二烷基硫酸钠1g/L。镀镍的速率为5-13微米/小时，镀层厚度2-3微米。
所述的化学镀铜层的厚度为1-12微米，可选8-12微米。温度60℃，pH=12，镀铜时间约200-300分钟。
所述的构件为手机机壳、手机天线和其它三维集成电路的电子模块、电器连结件等。
所述的特定形状的线路图型是手机天线的形状或需电磁屏蔽区域的形状或其他电路的形状等。
所述非金属光诱导催化剂成份在常温下为固态或液态的一元、二元或三元醇类或一元、二元、三元醛类的单一或组合的有机物或混合物。
本发明适用制造三维立体集成电路和二维平面集成电路结构和材料。
本发明采用化学镀方法，在承载材料上直接进行镀层工艺，去掉了以往常规工艺中的冲击预镀铜工艺，即直接采用常规的化学镀方法，增加镀层的厚度，既：化学镀铜、化学镀镍-磷合金工艺，形成三维集成电路。
在化学镀的溶液中，添加具有络合能力的金属离子，其中包括微量的元素金属钯(Pd)或银(Ag，质量含量小于0.1-2％)和Ni、Co、Fe、Cu、Zn中的一种或几种。由于减少了贵金属的添加，使成本下降5-15％。由于添加了多种金属元素，进行化学镀铜时就有了更高的催化活性和选择性。
本发明是一种新的三维集成电路结构及材料的制造方法，特点是在承载材料上金属化的原理和工艺方法的改变，在三维集成电路的承载材料中不含有任何金属元素的成分，而金属元素成分完全存在于电镀过程中，制备方法是利用激光在结构载体表面镭射出需要金属化的特定区域并将在原料中的非金属光诱导催化剂转变成具有络合作用的基团，使其在后续金属化过程中发生催化作用。这是和其它某些方法的承载材料中含有金属元素成分，利用激光将塑料中的金属元素还原，然后进行金属化的原理和方法是不同的。本发明具体是往承载塑性材料中添加少量非金属光诱导催化剂，主要成分为醇类和/或醛类，使承载材料在激光镭射后，结构中含有30％-50％的非金属光诱导催化剂能形成具有络合作用的催化剂成份，在含有多种形式的金属离子(游离的或以络合的形式)的溶液中，具有络合能力的金属离子先和塑料表面的具有络合作用的催化剂反应生成稳定络合物，此络合物被还原形成金属核，使其在制备导体轨道的过程中，保持了承载材料的原有机械性能，而且性能稳定。提高了导体轨道与承载材料之间的附着力、提高了三维集成电路的质量、降低成本、减少污染。
具体实施方式
实施例1
在注塑机(住友SH160C，日本住友重机械株式会社制造)中将质量为90％的聚对苯二甲酸丁二醇酯和10％的丙三醇(1，2，3-三羟基丙醇)进行均匀混合，颗粒在175℃的温度下，注塑成型，被加工成一个手机机壳。然后使用ND：YAG激光器。以波长为1064nm，在机壳上照射，时间为0.01秒，照射出手机天线的环型形状，并在激光照射的区域，使得承载材料中的非金属光诱导催化剂中的羟基生成羧基，生成了具有络合作用的基团。
室温下将上述得到承载材料放入pH=4的含有14％氯化镍、1％硝酸银的金属离子水溶液中浸泡5分钟，在激光照射过的区域，塑料表面的具有络合作用的非金属光诱导催化剂中的羧基和具有络合能力的银、镍金属离子反应生成稳定络合物。通过原位光谱电化学的测定(Electrochemical Methods；Fundamemals and Applications；Allen J.Bard etc.1980.)证实了镍和银络合物的存在。
将承载材料用蒸馏水清洗后放在含有次磷酸钠25％、联氨8％、pH=5的水溶液中浸泡7分钟，镍和银的络合物被还原形成金属核。
将承载材料用蒸馏水清洗后，再进行化学镀铜和中磷(7<P％<10，质量)化学镀镍；就在激光照射过的区域形成了金属导体轨道。
然后进行化学镀铜：镀铜液配方：pH=12，温度60℃；无水硫酸铜12g/L；酒石酸钾钠43g/L；乙二胺四乙酸二钠14g/L；甲醛(37％)21ml/L；亚铁氰化钾36mg/L；联吡啶0.06g/L；氢氧化钠调pH值；空气搅拌。化学镀铜时间为220分钟。镀铜层厚度为：11微米。
再进行中磷化学镀镍：镀镍液配方：pH=4.85.0，温度84-86℃，硫酸镍27g/L；次磷酸钠24g/L；醋酸钠15g/L；乳酸30g/L；柠檬酸4g/L；十二烷基硫酸钠1g/L。镀镍层的厚度为2微米。镀镍时间为15分钟。
实施例2
在注塑机中用89％质量的聚对苯二甲酸丁二醇酯和含11％质量的2-甲基丙醛进行混合。颗粒在180-185℃下被加工成一个手机机壳。以下操作同实施例1。
通过对实例1和实例2的得到的产品的断裂点和拉伸强度等数据分析和与含有金属元素的塑料材料(SABIC Innovative Plastics公司的10302材料的物料表)的对比可知：在机械性能上比传统工艺有了较大的提高，见表1、表2。
表1
Claims (7)
1.一种三维集成电路结构及材料的制造方法，其特征在于它是经过如下的步骤：
1)在热塑性承载材料中加入非金属光诱导催化剂醇类和/或醛类，用注塑机注塑成型为构件，质量含量5-10％；
2)用激光射线在构件的表面照射出的线路图案；
3)室温下浸入pH＝4-6的至少含一种金属离子的溶液中，浸泡5-7分钟；
4)用蒸馏水洗后放入pH＝5的含有还原剂的水溶液中浸泡5-7分钟，构件的表面生成金属核；
5)在生成金属核的区域进行化学镀铜，镀层厚度为1—12微米，再中磷化学镀镍，镀层厚度为2—3微米；
所述的醇类为固态或液态的一元、二元或三元醇；所述的醛类为固态或液态的一元、二元、三元醛。
2.按照权利要求1所述的方法，其特征在于所述的热塑性承载材料为：ABS、聚碳酸酯、聚对苯二甲酸丁二醇酯。
3.按照权利要求1所述的方法，其特征在于所述的金属离子溶液中为微量元素金属钯、质量含量小于0.1—2％的银或2％—20％的Ni、Co、Fe、Cu或Zn中的一种或几种。
4.按照权利要求1所述的方法，其特征在于所述的还原剂为联氨、硼氢化合物、次磷酸盐、硫代硫酸盐、联胺或氯化亚锡。
5.按照权利要求1所述的方法，其特征在于所述的化学镀铜的镀铜液配方：pH＝12，温度60℃；无水硫酸铜12g/L；酒石酸钾钠43g/L；乙二胺四乙酸二钠14g/L；甲醛21ml/L；亚铁氰化钾36mg/L；联吡啶0.06g/L；氢氧化钠调pH值；空气搅拌；化学镀铜的速率为2-5微米/小时。
6.按照权利要求1所述的方法，其特征在于所述的中磷化学镀镍液配方：pH＝4.8-5，温度80-86℃，硫酸镍27g/L；次磷酸钠24g/L；醋酸钠15g/L；乳酸30g/L；柠檬酸4g/L；十二烷基硫酸钠1g/L；镀镍的速率为5—13微米/小时。
7.一种三维集成电路结构及材料的制造方法，其特征在于它是经过如下的步骤：
1)在热塑性ABS、聚碳酸酯或聚对苯二甲酸丁二醇酯为基底的承载材料中加入1，2，3—三羟基丙醇或2-甲基丙醛，用注塑机注塑成型为构件，其中，1，2，3—三羟基丙醇或2-甲基丙醛的质量含量5-10％；
2)用激光射线在构件的表面照射出的线路图案；所述的激光射线波长为1064nm，在机壳照射时间为0.01秒；
3)室温下浸入pH＝4-6的14％氯化镍、1％硝酸银金属离子的溶液中，浸泡5-7分钟；
4)用蒸留水洗后放入pH＝5的含有次磷酸钠25％、联氨8％的水溶液中浸泡7分钟，构件的表面生成相应金属核；
5)进行化学镀铜，镀层厚度为8-12微米，再中磷化学镀镍，镀层厚度为2—3微米；
所述的化学镀铜的镀铜液配方：pH＝12，温度60℃；无水硫酸铜12g/L；酒石酸钾钠43g/L；乙二胺四乙酸二钠14g/L；甲醛21ml/L；亚铁氰化钾36mg/L；联吡啶0.06g/L；氢氧化钠调pH值；空气搅拌，化学镀铜的速率为2-5微米/小时；
所述的中磷化学镀镍的镀镍液配方：pH＝4.8-5，温度80-86℃，硫酸镍27g/L；次磷酸钠24g/L；醋酸钠15g/L；乳酸30g/L；柠檬酸4g/L；十二烷基硫酸钠1g/L，镀镍的速率为5—13微米/小时。
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