TW201426832A - 半導體元件之製造方法、半導體元件 - Google Patents
半導體元件之製造方法、半導體元件 Download PDFInfo
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- TW201426832A TW201426832A TW102129761A TW102129761A TW201426832A TW 201426832 A TW201426832 A TW 201426832A TW 102129761 A TW102129761 A TW 102129761A TW 102129761 A TW102129761 A TW 102129761A TW 201426832 A TW201426832 A TW 201426832A
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- semiconductor device
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 146
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- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZPBSAMLXSQCSOX-UHFFFAOYSA-N naphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 ZPBSAMLXSQCSOX-UHFFFAOYSA-N 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- CDMMQUFVYNPJTK-UHFFFAOYSA-N potassium(1+) Chemical compound [K+].[K+] CDMMQUFVYNPJTK-UHFFFAOYSA-N 0.000 description 1
- UYSSVEJYNXUUCB-UHFFFAOYSA-N potassium;gold(1+) Chemical class [K+].[Au+] UYSSVEJYNXUUCB-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical class OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for 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
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
-
- 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
-
- 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
-
- 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
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
-
- 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
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
-
- 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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
-
- 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
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Abstract
【課題】本發明係以提供:在基板與金屬層之間具有良好的被覆性之層,可藉由此層而抑制金屬層成分之Cu等對於基板的擴散之半導體元件之製造方法,以及半導體元件為目的。【解決手段】包括:將基板10浸漬於含有金屬離子液體而在該基板表面上使金屬觸媒12a附著之工程、將該附著了金屬觸媒之該基板浸漬於無電解電鍍液中而在該基板上形成無電解電鍍層14之工程、將該基板浸漬於電解電鍍液,將該無電解電鍍層做為給電層而在該無電解電鍍層上形成電解電鍍層16之工程、在該電解電鍍層上以Cu或Ag形成金屬層18之工程。該電解電鍍層,係以不同於該金屬層之材料所形成。
Description
本發明,將做為散熱體或電極而作用之金屬形成於基板上之半導體元件之製造方法,以及以該製造方法製造之半導體元件。
在非專利文獻1中,開示在基板與基板上形成之Cu層之間,藉由例如真空蒸鍍法等之真空成膜法而形成Cu擴散防止層之半導體元件。以真空成膜法可以形成各種金屬。例如,藉由真空成膜法,以Ta形成Cu擴散防止層,可提高Cu擴散防止效果。
在專利文獻1中,開示了在GaAs基板上以無電解電鍍法形成Pd電鍍層之技術。也開示了在此Pd電鍍層上以Cu等形成金屬層。
【專利文獻1】日本專利特開第2011-165810號公報
【專利文獻2】日本專利特開第2005-336600號公報
【非專利文獻】
【非專利文獻1】Chun-Wei CHANG et al. JJAP Vol. 46, No.
4A, 2007, pp.1409-1414
以開示於非專利文獻1般的真空成膜法來形成Cu擴散防止層之情況,由於真空成膜法為具有異方性之成膜方法,因此Cu擴散防止層之被覆性(被覆率)容易變得不充分。特別是,在真空成膜法中,有無法對於具有凹凸之基板進行被覆性高的成膜之問題。若Cu擴散防止層之被覆性差,則會產生基板與Cu層直接接觸的部分,在此部分會有Cu層之Cu往基板擴散之問題。
以在專利文獻1所開示的技術,會有藉由無電解電鍍法所形成之Pd電鍍層之Cu擴散防止效果不充分,金屬層之Cu擴散至基板而對於半導體元件之特性造成影響之問題。
本發明,係為了解決上述課題而做成,以提供:在基板與金屬層間具有被覆性良好的層,而可藉由此層抑制金屬層的成分之Cu等往基板擴散之半導體元件之製造方法,以及半導體元件為目的。
與本申請書之發明有關的半導體元件之製造方法,係包括:將基板浸漬於含有金屬離子液體而在該基板表面上使金屬觸媒附著之工程、將該附著了金屬觸媒之該基板浸漬
於無電解電鍍液中而在該基板上形成無電解電鍍層之工程、將該基板浸漬於電解電鍍液,將該無電解電鍍層做為給電層而在該無電解電鍍層上形成電解電鍍層之工程、在該電解電鍍層上以Cu或Ag形成金屬層之工程。然後,該電解電鍍層,係以不同於該金屬層之材料所形成。
與本發明有關之半導體元件,係包括:基板、形成在該基板上之第1金屬層、形成在該第1金屬層上之第2金屬層、形成在該第2金屬層上之Cu或Ag所形成之金屬層。然後,前述第2金屬層之結晶粒的粒徑,較前述第1金屬層之結晶粒的粒徑大。
根據本發明,由於以電鍍法形成擴散防止層,因此擴散防止層之被覆性良好,而且,由於擴散防止層之一部分具有電解電鍍層,因此可抑制金屬層成分之Cu等往基板擴散。
10‧‧‧基板
10a‧‧‧導通孔
12‧‧‧Pd-Ga-As層
12a‧‧‧金屬觸媒
14‧‧‧無電解電鍍層
16‧‧‧電解電鍍層
17‧‧‧擴散防止層
18‧‧‧金屬層
30‧‧‧基板
30A‧‧‧開口
30B、30C‧‧‧凹部
30D、30E‧‧‧凸部
30F‧‧‧灌孔
32‧‧‧以蒸鍍法所形成之層
34‧‧‧以電鍍法所形成之層
50‧‧‧含Ge之電解電鍍層
52‧‧‧第1密著層
54‧‧‧表面擴散防止層
56‧‧‧第2密著層
58‧‧‧表面保護層
60‧‧‧電極
62‧‧‧接著材料
64‧‧‧支持基板
70‧‧‧散熱電極
100‧‧‧Au電鍍層
第1圖係與本發明之實施形態1有關之半導體元件之剖面圖。
第2圖係表示以蒸鍍所形成之層與以電鍍所形成之層之被覆性之差異之圖。
第3圖係表示無電解電鍍層被加熱後微結晶化之圖表。
第4圖係以Pd所形成之無電解電鍍層合金化之圖表。
第5圖係在基板上形成了凹部之半導體元件之剖面圖。
第6圖係在基板上形成了凹部之半導體元件之剖面圖。
第7圖係在基板上形成了凸部之半導體元件之剖面圖。
第8圖係在基板上形成了凸部之半導體元件之剖面圖。
第9圖係在基板上形成了貫孔之半導體元件之剖面圖。
第10圖係與本發明之實施形態2有關之半導體元件之剖面圖。
第11圖係表示在3個樣品中,比較Cu擴散防止效果之圖表。
第12圖係與本發明之實施形態3有關之半導體元件之剖面圖。
第13圖係與本發明之實施形態4有關之以半導體元件之製造方法之最初的工程形成電極後之基板的剖面圖。
第14圖係表示貼附了支持基板之基板之剖面圖。
第15圖係表示形成了導通孔之基板的剖面圖。
第16圖係形成了散熱電極之基板的剖面圖。
第17圖係第16圖之虛線部之擴大圖。
第18圖係與本發明之實施形態5有關之半導體元件之剖面圖。
第19圖係表示在2個樣品中,比較Cu擴散防止效果之圖表。
對於與本發明之實施形態有關的半導體元件之製造方法,以及半導體元件,參照圖式而說明。對於相同或是對應之構成要素賦予同樣的符號,而有省略重覆說明的情況。
實施形態1.
第1圖為與本發明之實施形態1有關之半導體元件的剖面圖。此半導體元件,具有以GaAs形成之基板10。在基板10上形成了Pd-Ga-As層12。更且,在基板10上介在Pd-Ga-As層12而形成了第1金屬層。第1金屬層為以NiP為材料之以無電解電鍍形成之物,稱為無電解電鍍層14。
在第1金屬層(無電解電鍍層14)上,形成了第2
金屬層。第2金屬層係由電解電鍍所形成,因此稱為電解電鍍層16。電解電鍍層16雖以Pd形成,但也可以Ru、Pt、或是Rh之任一種形成。然後,第2金屬層(電解電鍍層16)之結晶粒的粒徑,較第1金屬層(無電解電鍍層14)之結晶粒的粒徑大。又,無電解電鍍層14與電解電鍍層16也有一起稱為擴散防止層17。不過,也可在第1金屬層上形成Au電鍍層後,在此Au電鍍層上形成第2金屬層。在此情況,為在第1金屬層與第2金屬層之間形成Au電鍍層之情況。藉由此,可以防止第2金屬層之裂痕,且第2金屬層與第1金屬層可藉由Au電鍍層密著。Au電鍍層,例如可使用置換Au電鍍液來形成,電鍍液之種類並沒有特別限定。又,Au電鍍層之層厚為50nm程度,但也可為其以下。
在第2金屬層(電解電鍍層16)上,以Cu形成了金
屬層18。金屬層18之厚度例如為1~5μm程度。Pd-Ga-As層12、無電解電鍍層14、電解電鍍層16以及金屬層18係為了提高半導體元件之散熱性,取得電氣上的接觸而形成。在這些層當中,以Cu所形成之金屬層18散熱性優良且電阻率低,因此在Pd-Ga-As層12、無電解電鍍層14、電解電鍍層16以及金
屬層18中,以金屬層18的厚度形成的最厚為佳。
接著,說明與本發明之實施形態有關之半導體元
件之製造方法。首先,將基板10浸漬於含有金屬離子之液體中使基板10之表面附著金屬觸媒。含有金屬離子的液體,例如為氯化鈀溶液等之含Pd離子的Pd活性化液。Pd活性化液之Pd濃度為例如0.1~1.0g/L程度。一邊將基板10在20~30℃之Pd活性化液中浸漬1~5分程度,一邊攪拌Pd活性化液,使金屬觸媒附著。如此一來,金屬觸媒(Pd觸媒)與基板10之成分反應,形成Pd-Ga-As層12。又,在Pd-Ga-As層12中存在金屬觸媒12a。
Pd觸媒之附著量或均一性會由於Pd活性化液之
Pd濃度或液溫而變化,因此,有必要將其調整為適當,而謀求界面附著力以及表面形態之適當化,以及膜翹起之防止。
接著,將附著了金屬觸媒之基板10浸漬於無電解
電鍍液中而在基板上形成無電解電鍍層14。無電解電鍍液,例如為在硫酸鎳中添加還原劑之次亞磷酸鈉、以及配合劑之有機酸之溶液。溶液中的Ni濃度為1~1.5g/L程度。溶液中的P濃度,若使無電解電鍍層14中之P含有量成為8~10%程度調整,則可較純粹的Ni層更提高耐蝕性。將基板10浸漬無電解電鍍液時,一邊使無電解電鍍液之溫度在60-80℃,一邊攪拌無電解電鍍液。
接著,將基板10浸漬於電解電鍍液,將無電解電鍍層14做為給電層而在無電解電鍍層14上,以Pd形成電解電鍍層16。具體而言,係將基板10浸漬於電解電鍍液,以無
電解電鍍層14為陰極,外部的白金被覆鈦電極做為陽極,對於陰極-陽極之間流過電流。電解電鍍液,例如為二氯二氨鈀(II)PdCl2(NH3)2等之鈀鹽,以及NH4Cl等之含電導性鹽的溶液。溶液中的Pd濃度,例如為0.1~0.5%程度。將基板10浸漬於電解電鍍液時,電解電鍍液的溫度為40-60℃。又,由於電解電鍍層16係以Pd形成,因此電解電鍍層16係與以Cu所形成知金屬層18由不同的材料所形成。
接著,在電解電鍍層16上以Cu形成金屬層18。
具體而言,係將基板10浸漬於Cu電鍍液,以電解電鍍層16為陰極,外部的磷銅電極為陽極而在陰極-陽極間流過電流。
Cu電鍍液為例如含有硫酸銅、硫酸、氯離子,以及有機系添加劑之溶液。使用氯離子之情況,藉由將鹽酸加入電鍍浴中而可調整濃度。
若金屬層18之Cu侵入以GaAs所形成之基板10,
即使該Cu為低溫,也會以很高的擴散速度在基板10中擴散,且在基板10中形成很深的受體準位。因此若Cu在基板10中擴散則半導體元件的特性會變得不安定。為了防止此,在與本發明之實施形態1有關之半導體元件,基板10與金屬層18之間形成了擴散防止層17。
對於擴散防止層17,要求在金屬層18與基板10
之間可確實形成擴散防止層17而具有「高被覆性」之同時,也被要求為「擴散防止效果高的膜質」。首先,說明與本發明之實施形態1有關之擴散防止層17,具有「高被覆性」。
第2圖,係表示以蒸鍍所形成之層與以電鍍形成
之層之被覆性的差異之剖面圖。第2圖A,係對於具有開口部30A之基板30藉由蒸鍍法形成層32之情況的剖面圖。第2圖B,係對於具有開口部30A之基板30藉由電鍍法形成層34之情況的剖面圖。比較第2圖A與第2圖B,可知道以電鍍法所形成之層34的被覆性優良。具體而言,以蒸鍍法所形成之層32在開口30A的側壁部分會發生切斷,但以電鍍法形成之層34被覆性佳。
如此,電鍍法係相較於蒸鍍法、濺鍍法、CVD法或是離子鍍膜法等之成膜方法,為可形成被覆性高之膜的成膜方法。在本發明之實施形態1,由於以電鍍法形成無電解電鍍層14與電解電鍍層16,因此擴散防止層17具有「高被覆性」。因此,在金屬板18與基板10之間可確實形成擴散防止層17。
接著,說明擴散防止層17係以「擴散防止效果高的膜質」所形成的。金屬層18的Cu,主要是由於粒界擴散而擴散。因此,擴散防止層17以沒有粒界之非晶質來形成為佳。然而,本說明書之發明者們進行精心銳意的研究後,發現無電解電鍍層14在形成後不久為沒有粒界的非晶質,而為可抑制粒界擴散之物,但由於200℃之熱處理而進行微細節晶化。
第3圖係表示若加熱無電解電鍍層則微細結晶化之圖表。第3圖A為對於熱處理前之樣品進行X線繞射的結果。樣品係在GaAs基板上以Pd形成300nm層厚之無電解電鍍層後,在此無電解電鍍層上以NiP形成100nm層厚之無電解電鍍層之物。根據第3圖A,由於繞射高峰寬廣,可知道無電解電鍍層在形成後不久為非晶質。
第3圖B,係對此樣品施以250℃的熱處理4小時
後之X光繞射的結果。由於在第3圖B可看到複數的高峰,被認為是無電解電鍍層結晶化。因此,由於無電解電鍍層14成為粒徑小的結晶粒之集合,因此粒界多,可知Cu之擴散防止效果低。
相對於此,以電解電鍍法所形成之電解電鍍層
16,具有較無電解電鍍層14粒徑大的結晶粒。因此,電解電鍍層16,相較於無電解電鍍層14,粒界少而為Cu之擴散防止效果高的層。又,由於電解電鍍層16之粒界少,因此可以抑制構成電解電鍍層16之原子本身由於熱處理而往其他層擴散。如此,電解電鍍層16的熱安定性高,可連帶提升Cu之擴散防止效果。因此,擴散防止層17,藉由含有電解電鍍層16,而具有「擴散防止效果高的膜質」。
如前述,由於無電解電鍍層14為粒界多的層,因
此Cu之擴散防止效果差。然而。無電解電鍍層14在電解電鍍層16形成時係做為給電層作用。亦即,基板10導電性低,因此無法在基板10上直接形成電解電鍍層,若在基板10上預先形成無電解電鍍層14,則可將其作為給電層而形成電解電鍍層16。又,無電解電鍍層14,也做為使基板10與金屬層18之密著性提高之密著層而作用。
不過,無電解電鍍層14係介在非常薄的Pd-Ga-As
層12而與基板10接觸,因此由於熱處理,無電解電鍍層14之成分與基板10的成分混合而有形成合金之虞。第4圖,係表示將以Pd所形成之無電解電鍍層合金化之圖表。樣品係在
GaAs基板上以Pd形成100nm層厚之無電解電鍍層後,在氮氣氛下在250℃實施4小時之熱處理。然後對於此樣品,藉由深度歐傑光譜法而進行深度方向的元素分析。
根據第4圖,可知若使用Pd做為無電解電鍍層,
GaAs在無電解電鍍層擴散,而容易形成與GaAs的合金。為了回避如此之合金形成,若基板10為GaAs的情況,以NiP形成無電解電鍍層14較以Pd形成為佳。
在與本發明之實施形態1有關之半導體元件,基
板10雖具有平坦的表面,但本發明並不限定於此。亦即,在基板10的表面也可以具有凹部、凸部或灌孔。第5圖,係在基板30上形成了凹部30B的半導體元件之剖面圖。第6圖,係在基板30上形成了凹部30C的半導體元件之剖面圖。第7圖,係在基板30上形成了凸部30D的半導體元件之剖面圖。
第8圖,係在基板30上形成了凸部30E的半導體元件之剖面圖。第9圖,係在基板30上形成了灌孔30F的半導體元件之剖面圖。
基板表面的凹部、凸部,或是灌孔,係藉由反應
性離子蝕刻或是電漿蝕刻等乾式蝕刻,或是酸或鹼等濕式蝕刻來形成。特別是濕式蝕刻液的情況容易發生側面蝕刻。又,根據不同的蝕刻液,結晶面方位間或結晶材料間的蝕刻速度差,而使被蝕刻物變成反向檯面形狀或是順向檯面形狀。
如此之情況,以蒸鍍等具有異方性的成膜方法難以形成均一的層。然而,根據與本發明之實施形態1有關之半導體元件之製造方法,由於以電鍍法形成擴散防止層,因此在
基板的表面上有凹部、凸部、或是灌孔知情況,可形成被覆性高的擴散防止層17。
若以Cu形成金屬層18,相較於以Au等知貴金屬
形成金屬層18,可低成本化。然而,金屬層18可不以Cu而以Ag形成。Ag之電氣傳導度及熱傳導度在金屬中也是最高的,因此若金屬層18使用Ag,則可製造具有優良電氣傳導度及散熱性之半導體元件。又,金屬層不管是以Cu形成之情況或以Ag形成的情況,金屬層之製造方法皆無限定,可以蒸鍍、濺鍍,或是電鍍法來形成。不過,在具有凹部的基板上形成Cu(金屬層18)之情況,相較於平坦的部分,可在凹部選擇性得使Cu成長,而以Cu將凹部填平。此情況以使用電解電鍍為佳。
做為電鍍液之硫酸銅浴,使用例如硫酸、氯離子以及有機添加劑。做為添加劑,可使用促進劑(加速劑或漂白劑)、抑制劑(抑制劑或載劑)、平滑劑(壓平劑)。
在基板的濡濕性差的情況,在使金屬觸媒附著前,對於基板對於基板10施以氧灰化處理或是臭氧灰化處理等之前處理為佳。更且,為了提高擴散防止層17與基板10之密著性,也可以具有表面氧化膜除去效果之酸或鹼溶液進行基板10之洗淨。為了除去表面氧化膜,對於Si基板或SiC基板以藉由氟酸系藥液來處理為佳,對於GaAs基板或GaN基板以藉由鹽酸係藥液來處理為佳。對於InP基板,以藉由硫酸系藥液或氟酸系藥液來處理為佳。
無電解電鍍層14,係以Ni、Co、Pd、Cu、Ag、Au、Pt、Sn、Ru或Rh,或是NiB、NiCoWP、NiMoP、CoP、
CoNiP、CoWP、CoSnP、CoZnP,或是CoMnP等之合金電鍍來形成。合金電鍍,係具有使耐腐蝕性提升等與單體金屬不同之性質。
無電解電鍍液,係由鎳鹽、還原劑、緩衝劑、配
位劑以及安定劑等所構成。若說明無電解Ni電鍍液之構成成分,做為鎳鹽,可使用硫酸鎳等之硫酸鹽、氯化物、乙酸鹽、碳酸鹽、或是氨基磺酸等。做為還原劑,可使用膦酸鈉(NaH2PO2.H2O),或是二甲胺硼烷(DMAB)等。做為緩衝劑,可使用蟻酸,或是乙酸等單酯碳酸,或是其鹼金屬鹽。做為配位劑,除了可使用檸檬酸等有機酸,也可使用乙二氨四乙酸(EDTA),或是氨等。
做為無電解Pd電鍍液,做為鈀鹽,多使用氯化鈀。
做為代表性的還原劑有膦酸鹽,做為代表性的配位劑有乙二氨四乙酸(EDTA)等。
無電解Au電鍍液,係大概分為與藉由基底材金屬
置換而成之置換Au電鍍液,與使用還原劑使金覆膜析出之自我觸媒Au電鍍液之2種類。做為置換Au電鍍液,係使用在亞硫酸金鈉中,添加亞硫酸鹽、巰基丁二酸,以及乙二氨四乙酸(EDTA)等之物。又,為了電鍍中的金屬離子之安定化,也有添加螯合劑的狀況。做為螯合劑,只要是對於水為可溶性之物即可,其種類沒有特別限定,例如可使用硫酸鉈、硝酸鉈、氧化鉈、氯化鉈、以及丙二酸鉈等鉈化合物。
做為自我觸媒Au電鍍液,可使用藉由氰化金(I)鉀(KAu(CN)2)或是氰化金(II)鉀(KAu(CN)4)等之氰化金配位體
中添加了四羥硼酸鉀或是二甲胺硼烷(DMAB)做為還原劑之強鹼性的電鍍浴。
做為無電解銅電鍍液,係使用硫酸銅做為供給銅
離子的金屬鹽,還原劑主要使用甲醛。做為甲醛以外的還原劑,有四羥硼酸鉀、二甲胺硼烷或是乙醛酸等,又,為了提高電鍍速度,而使用強鹼性的電鍍浴。做為PH調整劑,可使用氫氧化鈉、氫氧化鉀、或是氫氧化鋰等。
在強鹼性的電鍍浴中,做為電鍍浴中的氫氧化物
之銅離子容易沉澱,做為為了防止該沉澱之配位劑,可使用酒石酸鉀鈉、EDTA、甘油、內消旋赤蘚醇、核醣醇、D-甘露醇、D-山梨糖醇、半乳糖醇、亞氨基乙二酸、反-1,2,環己二胺乙四酸、三乙醇胺,或是乙二胺等。電鍍液之分解等浴安定性低下,主要是由於CuO2的不均化反應(CuO2+H2O->Cu+Cu2+2OH-)所造成之液中的銅粉而引起,做為對策,空氣攪拌電鍍液,或是添加安定劑。
做為安定劑,以與1價的銅優先的配位形成之氫
化物、硫脲、吡啶、0-鄰二氮菲、新亞銅試劑等。為了使在不影響電鍍浴的安定性的情況而使電鍍速度提高,添加如8-羥基-7-碘-5-喹啉磺酸般的促進劑。
做為無電解Pt電鍍液,做為白金鹽使用二亞硝基
二胺鉑,或是四硝基鉑等,做為還原劑使用聯氨,安定劑使用羟胺鹽等。
做為無電解Rh之電鍍液,可使用亞硝酸胺銠、氯
化銠胺、銨二(吡啶-2,6-二羥酸)銠(III)、乙酸銠、或是氯化
銠等,做為還原劑,使用聯氨,或是四氫化硼酸鈉等,添加氨等而做為鹼性的電鍍浴使用。
做為無電解Ru電鍍液,做為釕鹽,使用四胺二水
和釕磷酸鹽,或是硫酸釕等,做為還原劑使用四氫硼酸納等,使用藉由氨等之鹼性電鍍浴或藉由硫酸等之酸性電鍍浴。
做為無電解Co電鍍液,可以硫酸鈷與膦酸納為基本,配位劑使用檸檬酸鹽、酒石酸鹽,或是吡咯啉酸鹽等。
做為可以電解電鍍的金屬,有Zn、Ir、In、Cd、Au、Ag、Cr、Co、Sn、Fe、Cu、Pb、Ni、Pt、Pd、Bi、Mn、Mo、Rh,以及Ru等。電解電鍍層16之形成方法並沒有特別限定,例如,可使用直流電鍍法、脈衝電鍍法,或是逆脈衝電鍍法等。電解電鍍液,係由金屬鹽、電導度鹽、陽極溶解促進劑、配位劑,以及添加劑等所構成。又,在基板上具有導通孔構造之情況,藉由使用脈衝電鍍法及逆脈衝電鍍法,相較於直流電鍍法,可使被覆性提升。
做為電解Ni電鍍浴,可使用瓦特浴、全鹽化浴、氨基磺酸浴、伍德浴等之酸性浴。瓦特浴中,含有硫酸鎳、氯化鎳,以及硼酸等。在全鹽化物浴中,含有氯化鎳與硼酸。又,在氨基磺酸浴中,含有氨基磺酸鎳、氯化鎳,以及硼酸等。在伍德浴中含有氯化鎳與鹽酸等。
在電解Ni電鍍液中,含有陽極溶解劑、PH緩衝劑、或是可使電著應力或表面狀態等改善之添加劑。做為添加,糖精、萘(一、二)磺酸鈉、磺胺或是亞磺酸等知1次光澤劑,或是1-4丁二醇,或香豆素等之2次光澤劑。在鎳電鍍所
使用之陽極,以純度高者為佳,在電鍍中不生成陽極殘渣而可均一溶解者佳。做為陽極材料,有電氣鎳、去極化鎳、鎳鋼、或是含硫鎳等。
做為電解Pd電鍍液,可使用二胺二氯鈀
(II)PdCl2(NH3)2、電導性鹽做為鈀鹽,以及NH4Cl或是K2HPO4做為pH緩衝劑,使用中性或鹼性的胺配位體浴。陽極係使用白金被覆鈦電極等之不溶性陽極。有添加做為第1光澤劑或是1,3,6-萘三磺酸等有機化合物,添加香豆素等之有機化合物做為第二光澤劑之情況。
做為電解Ru電鍍浴,使用硫酸釕做為釕鹽,使用藉由氨基磺酸之酸性電鍍浴。
做為電解Pt電鍍浴,使用順二硝基二胺鉑做為鉑鹽,添加亞硝酸銨、亞硝酸鈉,或是氨水等,使用酸性至中性的電鍍浴。
做為電解Au電鍍浴,主要使用氫化物浴與亞硫酸浴。做為鹼性氰化浴,例如,係含有金鹽、氫化金(I)鉀、做為游離氰化物離子源之氰化鉀、使電著性提升之碳酸鉀,以及pH緩衝劑之磷酸氫二鉀之浴。另一方面,做為亞硫酸浴,係含有例如金鹽、亞硫酸金(I)鈉、亞硫酸鈉,以及亞硫酸等,在pH8附近進行之浴。又,為了改善Au電鍍膜質,有添加微量的鉈化合物,藉由乙二胺等而抑制亞硫酸金(I)配位體之分解的安定劑之情況。
又,對於添加劑的濃度管理,使用哈氏槽試驗、CVS(循環式伏安剝離)法等。
在以Cu形成金屬18之情況,可使用硫酸銅浴、
吡咯啉酸銅浴、或是氰化銅浴等之電解電鍍液。在半導體元件之製造中,多使用硫酸銅浴。硫酸銅浴,多為以CuSo4.5H2O、硫酸、氯離子,以及有機系添加劑所構成。特別是,以Cu填滿導通孔構造時,多使用促進劑(加速劑或漂白劑)、抑制劑(抑制劑或載劑)、平滑劑(壓平劑)做為添加劑。
促進劑有促進銅在導通孔底部優先成長的效果,
抑制劑藉由吸附在銅電鍍表面,而有抑制在導通孔外部的銅成長。又,平滑劑係與抑制劑連動,使擴散控制抑制劑的溶液中之動作,而有抑制在導通孔外部的銅成長之效果。這些係與氯離子連動而發揮機能,因此含有氯離子之添加劑的濃度管理很重要。做為抑制劑,以聚乙二醇(PEG)為代表之聚醚類化合物被使用。做為促進劑,以聚二硫二丙烷磺酸鈉(SPS)為代表之句有硫代基之有基硫化合物被使用。做為平滑劑,以健那綠(JGB)為代表之季銨化合物被使用。
為了形成金屬層18之電解電鍍浴的溫度以20~30
℃程度為佳。陽極多使用溶解性陽極,但為了抑制陽極殘渣之發生,以使用含磷銅為佳。磷的含有量為0.04~0.06%程度為佳。
基板10,並不限於GaAs,例如也可以Si、SiC、GaN,或是InP來形成。又,基板10上至少形成1層的磊晶層。也可在該磊晶層上形成擴散防止層17。
基板10若以GaAs等化合物半導體所形成的情況,由於基板10與金屬活性化液的反應性良好,因此容易確保基板與無電解電鍍層之密著性。然而,若在以Si系材料形
成基板10之情況,由於基板10與金屬活化液的反應性差,因此難以確保基板10與無電解電鍍層14之密著性。因此,若在基板表面形成矽氧化膜後,藉由混合了緩衝氟酸之金屬活性化液來進行觸媒處理即可(參照專利文獻2)。
貯存金屬活性化液(Pd活性化液)、無電解電鍍液、或是電解電鍍液之液槽,為了控制對於液槽本身之成膜,以使用耐熱性高,且難以成膜之硼矽酸玻璃等所形成者為佳。將基板放入匣盒而進行電鍍處理的情況,以使用例如以全氟烷基乙烯基醚樹脂(PFA)等之具有耐藥品性的材料來製造匣盒為佳。又,對於電鍍處理時之攪拌子或在拿取匣盒時所使用的把手也同樣使用具有耐藥品性者為佳。
上述之變形例,也可應用於之後的與實施形態有關的半導體元件之製造方法,以及半導體元件。
實施形態2.
與本發明之實施形態2有關之半導體元件之製造方法與半導體元件,由於與實施形態1之共通點很多,因此以與實施形態1之差異點為中心說明。第10圖係與本發明之實施形態2有關之半導體元件之剖面圖。電解電鍍層50含有Ge。
電解電鍍層50,係使用添加了氧化Ge之電解電鍍液來形成。電解電鍍液中的氧化Ge濃度,以Ge金屬換算為0.1mg/L~1000mg/L之任一為佳。藉由使用添加了氧化Ge之電解電鍍液,電解電鍍層50之形成時電鍍主金屬(Pd)與Ge共析。在電解電鍍層50中Ge濃度以在1ppm以上10000ppm以下為佳。
在此,對於形成含Ge之電解電鍍層之效果說明。
第11圖,係對於3個樣品,比較Cu擴散防止效果的圖表。樣品1,係將GaAs基板表面以Pd活性化液進行觸媒處理後,在基板上以無電解電鍍液形成NiP層(0.5μm),以無電解電鍍液形成Pd層(0.2μm),以電解電鍍液形成Cu層(金屬層)(3μm),以無電解電鍍液形成NiP層(0.5μm),以無電解電液形成Pd層(0.2μm),以置換電鍍液形成Au層(0.05μm)之物。亦即,樣品1,僅具有無電解電鍍層做為擴散防止層。
樣品2,係將GaAs基板表面以Pd活性化液進行
觸媒處理後,在基板上以無電解電鍍液形成NiP層(0.5μm),以電解電鍍液形成Pd層(0.2μm),以電解電鍍液形成Cu層(金屬層)(3μm),以無電解電鍍液形成NiP層(0.5μm),以電解電液形成Pd層(0.2μm),以置換電鍍液形成Au層之物。亦即,樣品2,具有無電解電鍍層與電解電鍍層做為擴散防止層。
樣品3,係將GaAs基板表面以Pd活性化液進行
觸媒處理後,在基板上以無電解電鍍液形成NiP層(0.5μm),以添加了氧化Ge之電解電鍍液形成Pd層(0.2μm),以電解電鍍液形成Cu層(金屬層)(3μm),以無電解電鍍液形成NiP層(0.5μm),以電解電液形成Pd層(0.2μm),以置換電鍍液形成Au層之物。亦即,樣品3,具有添加了Ge之電解電鍍層做為擴散防止層。
樣品1-3,皆具有GaAs/NiP/Pd/Cu/NiP/Pd/Au之構
造(「/」記號之右側係較左側上層)。樣品1係在GaAs基板與Cu層之間之NiP層與Pd層皆以無電解電鍍形成。樣品2係在
GaAs基板與Cu層之間具有以無電解電鍍所形成之NiP層與以電解電鍍所形成之Pd層。樣品3,係與樣品2幾乎相同的組成,但在Pd層添加了Ge這點與樣品2不同。
對於這些的樣品施以熱處理,隨著熱處理時間經
過,檢查板片阻抗變化值會如何變化。板片阻抗變化值為(熱處理後之板片阻抗值/熱處理前之板片阻抗值)-1而算出之值以%表示之值。因此,板片阻抗變化值,係表示對於熱處理前之膜的板片阻抗值之熱處理後的膜之板片阻抗值之增加率。板片阻抗變化值,對於形成厚至3μm且阻抗率小之金屬層之影響是很支配性的。在由於熱處理而金屬層內之Cu往GaAs基板側擴散之情況,金屬層後減少,板片阻抗變化值增加。亦即,若擴散防止層之擴散防止效果低,則板片阻抗變化值增加,若擴散防止層之擴散防止效果高,則板片阻抗變化值保持低值。
由第11圖可知,在60小時程度的加熱時,樣品1
之板片阻抗變化值急增,在500小時程度的加熱時,樣品2的板片阻抗變化值急增。因此,在這些樣品,擴散防止效果不充分。又,以掃描式電子顯微鏡(SEM)觀察板片阻抗變化值急增之樣品1、2,任一樣品皆可確認到金屬層(Cu層)變薄。
另一方面,樣品3在1000小時左右的加熱後板片
阻抗變化值也不會急增,因此可之擴散防止效果高。又,對於在進行500小時之熱處理後之各樣品進行藉由歐傑電子光譜法之元素分析,發現在樣品1,Cu擴散至GaAs基板,但在樣品2、3沒有確認到對於GaAs基板之Cu的擴散。因此,可知樣品2、3之電解電鍍層對於Cu擴散防止有貢獻。
總結上述結果,電解電鍍層較無電解電鍍層之Cu
的擴散防止效果高,藉由在電解電鍍層中添加Ge可得到更高之Cu的擴散防止效果。
如前述,金屬層18之Cu主要是藉由粒解擴散而
擴散。因此,電解電鍍層50之Ge,被認為係使電解電鍍層50之粒界變質成抑制粒界擴散。此變質之具體機制雖尚不明確,但被認為是由於使電解電鍍層50之Ge相鄰的2個結晶粒的之方位差變小而粒界寬度變窄,或是Ge本身位於粒界而抑制粒界擴散。
又,藉由在電解電鍍層50含有Ge,也可使電解電鍍層50之耐熱性提高。
在與本發明有關之實施形態2之半導體元件之製造方法中,在電解電鍍液中添加了氧化Ge。然而,在電解電鍍液中藉由添加「做為使電解電鍍層之粒界變質結晶調整劑而作用之Ge化合物、As化合物、Sc化合物、B化合物、P化合物、Te化合物、Sb化合物、Tl化合物、Pb化合物,以及S化合物」,可得到上述效果。做為Ge化合物,可使用例如上述之氧化Ge等。做為As化合物,可使用例如亞申酸鉀等。做為Se化合物。可使用例如亞硒酸等。做為B化合物,例如可使用二甲胺基甲硼烷等。做為P化合物,例如可使用次亞磷酸鈉等。做為Te化合物,例如可使用碲酸鉀等。做為Sb化合物,例如可使用銻酸鉀等。做為Tl化合物,例如可使用蟻酸鉈、丙二酸鉈、硫酸鉈,或是硝酸鉈等。做為Pb化合物,例如可使用檸檬酸鉛、硝酸鉛,或是鏈烷基磺酸鉛等。做為S化合物,
可使用例如硫代硫酸等。因此,做為電解電鍍層50,只要是含有Ge、As、Se、B、P、Te、Sb、Tl、Pb或S者,即可得到上述效果。在電解電鍍層50中Ge、As、Se、B、P、Te、Sb、Tl、Pb或S的濃度以在1ppm以上10000ppm以下為佳。
實施形態3.
與本發明之實施形態3有關之半導體元件之製造方法與半導體元件,由於與實施形態1之共通點很多因此以與實施形態1之不同點為中心說明。第12圖係與本發明之實施形態3有關之半導體元件的剖面圖。此半導體元件,在最表面具有表面保護層58。
對於與本發明之實施形態3有關之半導體元件之
製造方法說明。以實施形態1所示之方法形成擴散防止層17與金屬層18後,在金屬層18上形成第1密著層52。第1密著層52係藉由將基板10浸漬於無電解NiP電鍍液來形成。
成為第1密著層52之材料的NiP內部應力高,若
在薄的基板上形成1μm以上則會使基板翹曲發生,因此使第1密著層52為未滿1μm之膜厚為佳。又,若以電解電鍍形成Ni,則膜厚在1μm以下容易發生針孔,若以無電解電鍍形成Ni,則即使膜厚在1μm以下也可以形成針孔少的膜。
接著,藉由電解電鍍在第1密著層52上形成表面
擴散防止層54。具體而言,係將基板10浸漬於含氧化Ge之Pd電鍍液。然後,將基板側做為陰極,外部的白金被覆鈦電極做為陽極,在陰極-陽極間流過電流而形成表面擴散防止層54。
接著,在表面擴散防止層54上形成第2密著層56。第2密著層56係以第1密著層52相同之要領來形成。接著,在第2密著層56上形成表面保護層58。具體而言係將基板10浸漬於置換Au電鍍液中,在第2密著層56以Au形成表面保護層58。置換Au電鍍液,為含有例如亞硫酸金鈉、亞硫酸鹽、或是螯合劑之溶液。溶液中的金濃度以1~5g/L為佳。電鍍浴之溫度以60~80℃為佳。
在與本發明之實施形態3有關之半導體元件的最表面上,以不容易氧化之材料之金所形成的表面保護層58露出,因此,防止金屬層18之氧化及腐蝕,而可使半導體元件之耐濕性及特性安定性提升。又,在半導體元件的最表面上焊接之情況,藉由在表面保護層58使用Au,可提升焊接之濡濕性。
更且,由於在金屬18上以電解電鍍法形成表面擴散防止層54,因此金屬層18之Cu難以對於表面保護層58粒界擴散。因此,可防止金屬層18與表面保護層58引起合金反應。
藉由形成表面擴散層54,可減少以高價的Au所形成之表面保護層58的層厚,因此有降低成本的效果。又,在表面保護層58上以Ag錫膏或是AuSn錫膏等黏晶之情況,在接合時或接合後之熱處理是必要的,因此有金屬層18之Cu與黏接材合金化而引起黏接脫落的情況。然而,若根據與本發明之實施形態3有關之半導體元件,藉由表面擴散防止層54,可抑制該當合金化。
第1密著層52與第2密著層56的材料,只要為
Ni系金屬或Ti系金屬即可並沒有特別限定。又,只要金屬層18與表面擴散防止層54之密著性可以確保,則不需要第1密著層52,若表面擴散防止層54與表面保護層58得密著性可以確保,則不需要第2密著層56。
表面保護層58,只要以較金屬層18不容易氧化之
材料來形成即沒有特別限定。因此,表面保護層58,例如也可以Pt、Pd或是Rh等之貴金屬系的金屬來形成。更且,表面保護層58,也可以由矽氧化層、矽氮化層、聚亞醯胺,或是BCB等之絕緣體來形成也可,也可以矽等之半導體形成。
表面擴散防止層54,從提高擴散防止效果之觀點
來看,以電解電鍍來型成為佳。在此情況,做為表面擴散防止層54,也可以電解電鍍形成Ni、Pd、Mo、Rh或是Ru來形成。
更且,做為表面擴散防止層54,也可使用較Pd擴散防止效果高之Ti、TiN、Ta、TaN、W,或是WN等金屬。又,做為表面擴散防止層54,也可以無電解電鍍,形成CoWP等之Co系金屬,NiP等之Ni系金屬,Pt、Pd、Ph或是Ru。無電解電鍍層也具有一定的擴散防止效果。
然而,擴散防止層17為了抑制金屬層18之Cu與
基板10的成分之相互擴散,因此被要求高的擴散防止效果,表面擴散防止層54僅要求抑制來自金屬層18之擴散,因此沒有要求如擴散防止層17的程度之擴散防止效果。因此,表面擴散防止層54,只要以金屬形成即可,製造方法不限於電解電鍍,也可採用無電解電鍍法、蒸鍍法,或是濺鍍法等。
藉由在金屬層18上以較金屬層18更不容易氧化
的材料形成表面保護層之工程,省略第1密著層52、表面擴散防止層54,以及第2密著層56,而使表面保護層58與金屬層18相接來形成。在此情況例如也可使用Pd做為表面保護層。
Pd較Cu或Ag所形成之金屬層18不容易氧化,且具有一定的Cu擴散防止效果。
又,在與本發明之實施形態2有關之半導體元件
上,也可形成表面保護層58等。
實施形態4.
與本發明之實施形態4有關之半導體元件之製造方法,係將與本發明之實施形態3有關之半導體元件之製造方法應用於導通孔構造之形成之物。第13圖係在與本發明之實施形態4有關之半導體元件之製造方法之最初之工程中電極形成後的基板剖面圖。首先,在以GaAs所形成之基板10A上面形成電極60。此時,在基板10A的上面形成電晶體等之元件構造。
接著,在基板10A的上面貼附支持基板。第14圖,
係表示貼付了支持基板之基板的剖面圖。在此工程,在基板10A的上面,貼附藉由臘或膠帶等接著材料62而支持之厚度1mm程度的藍寶石或合成石英的支持基板64。然後,研磨基板10A的裡面,形成薄板化後之基板10。
接著,在基板10上形成導通孔。第15圖係形成
了導通孔之基板的剖面圖。在此工程中,從基板10的下面側進行蝕刻,貫通基板10而形成從基板10的下面達到電極60的下面之導通孔10a。
接著,形成散熱電極。第16圖係形成了散熱電極
之基板的剖面圖。散熱電極70,具有在實施形態3所說明的各層。亦即,散熱電極70包含由於金屬觸媒之附著而產生之Pd-Ga-As層12、無電解電鍍層14、電解電鍍層16、金屬層18、第1密著層52、Pd層54、第2密著層56,以及表面保護層58。構成散熱電極70之各層係形成在導通孔10a之內壁與電極60的下面。
第17圖為第16圖之虛線部的放大圖。第17圖顯
示構成散熱電極70之各層。散熱電極70由於包含以電鍍形成之擴散防止層17,因此被覆性非常好。因此,可在導通孔10a的內壁全體形成擴散防止層17。
然而,在例如化合物半導體元件等之分野中,多
使用散熱性佳且可做為電極使用之散熱電極。在此,若僅以特性的安定性高之Au來形成散熱電極則會成為高成本。然而,與本發明之實施形態4有關之散熱電極70係含有以Cu所形成之金屬層18。因此可以低成本製造半導體元件。
又,也可從散熱電極70,將第1密著層52、Pd層54、第2密著層56,以及表面保護層58除外。
實施形態5.
與本發明之實施形態5有關之半導體元件之製造方法與半導體元件,由於與實施形態1之共通點很多因此以與實施形態1之不同點為中心說明。第18圖係與本發明之實施形態5有關之半導體元件的剖面圖。電解電鍍層16係以Ru所形成。無電解電鍍層14與電解電鍍層16之間形成了Au電鍍層100。
又,Au電鍍層100,也可替換為以電鍍法以外的方法所形成之Au層。
形成無電解電鍍層14後,在無電解電鍍層14上
形成Au電鍍層100。接著,將基板浸漬於電解電鍍液,將無電解電鍍層14與Au電鍍層100做為給電層,在Au電鍍層100上形成電解電鍍層16。
在此,說明對於使用了Ru形成電解電鍍層之效果。第19圖,係對於2個樣品,比較Cu擴散防止效果之圖。樣品4,係將GaAs表面以Pd活性化液進行觸媒處理後,在基板上以無電解電鍍液形成NiP層(0.5μm),以添加了氧化Ge之電解電鍍液形成Pd層(0.2μm),以電解電鍍液形成Cu層(金屬層)(3μm),以無電解電鍍液形成NiP層(0.5μm),以電解電液形成Pd層(0.2μm),以置換電鍍液形成Au層(0.05μm)之物。亦即,樣品4之電解電鍍層,為添加了Ge之Pd層。
樣品5,係將GaAs表面以Pd活性化液進行觸媒處理後,在基板上以無電解電鍍液形成NiP層(0.5μm),以置換Au電鍍液形成Au電鍍層(0.05μm),以電解電鍍液形成Ru層(0.2μm),以電解電鍍液形成Cu層(金屬層)(3μm),以無電解電鍍液形成NiP層(0.5μm),以電解電液形成Pd層(0.2μm),以置換電鍍液形成Au層(0.05μm)之物。亦即,樣品5之電解電鍍層為Ru層。又,若省略樣品5之Au電鍍層之情況則在電解電鍍層(Ru層)的一部分確認到裂痕,但在具有Au電鍍層之樣品5,可抑制電解電鍍層(Ru層)的裂痕。
將這些樣品施以熱處理,檢查隨著熱處理時間的
經過,板片阻抗變化值如何變化。熱處理溫度為300℃。從第19圖來看,可知道在10小時的加熱,樣品4的板片阻抗變化值增加5%以上,但樣品5之板片阻抗變化值幾乎沒有變化。這表示以Ru層所形成之電解電鍍層較Pd層所形成之電解電鍍層Cu擴散防止效果高。Ru層可以得到較高Cu擴散防止效果的原因被認為是由於Ru(熔點:2050℃)較Pd(熔點:1552℃)熔點高因此熱安定性高之故。又,也可適當組合使用說明至此之與各實施形態有關之半導體元件的製造方法,以及半導體元件的特徵。
10‧‧‧基板
12‧‧‧Pd-Ga-As層
12a‧‧‧金屬觸媒
14‧‧‧無電解電鍍層
16‧‧‧電解電鍍層
17‧‧‧擴散防止層
18‧‧‧金屬層
Claims (17)
- 一種半導體元件之製造方法,其特徵在於包括:將基板浸漬於含有金屬離子液體而在該基板表面上使金屬觸媒附著之工程;將前述附著了金屬觸媒之前述基板浸漬於無電解電鍍液中而在前述基板上形成無電解電鍍層之工程;將前述基板浸漬於電解電鍍液,將前述無電解電鍍層做為給電層而在前述無電解電鍍層上形成電解電鍍層之工程;及在前述電解電鍍層上以Cu或Ag形成金屬層之工程;前述電解電鍍層,係以不同於該金屬層之材料所形成。
- 如申請專利範圍第1項之半導體元件之製造方法,其中,在前述電解電鍍液中,為了抑制前述金屬層成分之粒界擴散而使前述電解電鍍層之粒界變質之作為結晶調整劑作用的Ge化合物、As化合物、Se化合物、B化合物、P化合物、Te化合物、Sb化合物、Tl化合物、Pb化合物或是S化合物。
- 如申請專利範圍第2項之半導體元件之製造方法,其中,前述電解電鍍層含有1ppm以上10000ppm以下之Ge、As、Se、B、P、Te、Sb、Tl、Pb或S。
- 如申請專利範圍第1至3項中任一項半導體元件之製造方法,其中,前述基板係由GaAs所形成,前述無解電鍍層係以NiP所形成。
- 如申請專利範圍第1至3項中任一項半導體元件之製造方 法,其中,包括:在前述金屬層上,形成抑制前述金屬層之成分之以金屬所形成之表面擴散防止層之工程,與在前述表面擴散防止層上以較前述金屬層更不容易氧化的材料來形成表面保護膜層之工程。
- 如申請專利範圍第5項之半導體元件之製造方法,其中,包括:在形成前述表面擴散防止層前在前述金屬層上形成第1密著層之工程,與在形成前述表面保護膜層前在前述表面擴散防止層上形成第2密著層之工程,前述第1密著層係位於前述金屬層與表面擴散防止層之間,前述第2密著層係位於前述表面擴散防止層與前述表面保護膜層之間。
- 如申請專利範圍第1至3項中任一項半導體元件之製造方法,其中,在前述金屬層上,包括以較前述金屬層不容易氧化之材料形成表面保護膜之工程。
- 如申請專利範圍第1至3項中任一項半導體元件之製造方法,其中,前述基板係在表面上具有凹部、凸部、或是貫孔。
- 如申請專利範圍第1至3項中任一項半導體元件之製造方法,其中,包括:在前述基板的上方形成電極之工程、將前述基板貫通而形成從前述基板的下面到達前述電極的下面之導通孔,前述金屬觸媒、前述無電解電鍍層、前述電解電鍍層、以及前述金屬層,係形成於前述導通孔之內壁與前述電極之下面。
- 如申請專利範圍第1至3項中任一項半導體元件之製造方 法,其中,前述電解電鍍層,係以Pd、Ru、Pt或是Rh之任一種所形成。
- 一種半導體元件,其特徵在於包括:基板;形成在前述基板上之第1金屬層;形成在前述第1金屬層上之第2金屬層;及形成在前述第2金屬層上之Cu或Ag所形成之金屬層;前述第2金屬層之結晶粒的粒徑,較前述第1金屬層之結晶粒的粒徑大。
- 如申請專利範圍第11項之半導體元件,其中,前述第2金屬層含有Ge、As、Se、B、P、Te、Sb、Tl、Pb或S。
- 如申請專利範圍第11項之半導體元件,其中,前述第2金屬層含有1ppm以上10000ppm以下之Ge、As、Se、B、P、Te、Sb、Tl、Pb或S。
- 如申請專利範圍第11至13項中任一項半導體元件,其中,包括:形成在前述金屬層上之防止前述金屬層成分之擴散之以金屬所形成之表面擴散防止層,與在前述表面擴散防止層上以較前述金屬層更不容易氧化的材料所形成之表面保護層。
- 一種半導體元件之製造方法,其特徵在於包括:將基板浸漬於含有金屬離子液體而在該基板表面上使金屬觸媒附著之工程;將前述附著了金屬觸媒之前述基板浸漬於無電解電鍍液中而在前述基板上形成無電解電鍍層之工程;在前述無電解電鍍層上形成Au電鍍層之工程;將前述基板 浸漬於電解電鍍液,將前述無電解電鍍層與前述Au電鍍層做為給電層而在前述Au電鍍層上形成電解電鍍層之工程;及在前述電解電鍍層上以Cu或Ag形成金屬層之工程;前述電解電鍍層,係以不同於該金屬層之材料所形成。
- 如申請專利範圍第15項之半導體元件之製造方法,其中,前述電解電鍍層係以Ru形成。
- 如申請專利範圍第11至13項中任一項半導體元件,其中,在前述第1金屬層與第2金屬層之間具有Au層。
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