TWI408749B - 基板及其製造方法 - Google Patents
基板及其製造方法 Download PDFInfo
- Publication number
- TWI408749B TWI408749B TW097146913A TW97146913A TWI408749B TW I408749 B TWI408749 B TW I408749B TW 097146913 A TW097146913 A TW 097146913A TW 97146913 A TW97146913 A TW 97146913A TW I408749 B TWI408749 B TW I408749B
- Authority
- TW
- Taiwan
- Prior art keywords
- copper
- film
- plating
- metal element
- tungsten
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 129
- 229910052802 copper Inorganic materials 0.000 claims abstract description 126
- 239000010949 copper Substances 0.000 claims abstract description 126
- 230000004888 barrier function Effects 0.000 claims abstract description 90
- 229910052751 metal Inorganic materials 0.000 claims abstract description 87
- 239000002184 metal Substances 0.000 claims abstract description 77
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000009792 diffusion process Methods 0.000 claims abstract description 45
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 43
- 239000010937 tungsten Substances 0.000 claims abstract description 43
- 230000003197 catalytic effect Effects 0.000 claims abstract description 41
- 238000007772 electroless plating Methods 0.000 claims abstract description 38
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 35
- 239000011733 molybdenum Substances 0.000 claims abstract description 35
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 31
- 239000010955 niobium Substances 0.000 claims abstract description 31
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 238000004544 sputter deposition Methods 0.000 claims abstract description 16
- 150000004767 nitrides Chemical class 0.000 claims abstract description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007747 plating Methods 0.000 claims description 82
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000004065 semiconductor Substances 0.000 claims description 10
- 229910052762 osmium Inorganic materials 0.000 claims description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 abstract 1
- 239000010948 rhodium Substances 0.000 abstract 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 117
- 239000010410 layer Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 23
- 125000004429 atom Chemical group 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- -1 tungsten nitride Chemical class 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 229910052715 tantalum Inorganic materials 0.000 description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 8
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 6
- 238000005477 sputtering target Methods 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910000929 Ru alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- UGJCNRLBGKEGEH-UHFFFAOYSA-N sodium-binding benzofuran isophthalate Chemical compound COC1=CC=2C=C(C=3C(=CC(=CC=3)C(O)=O)C(O)=O)OC=2C=C1N(CCOCC1)CCOCCOCCN1C(C(=CC=1C=2)OC)=CC=1OC=2C1=CC=C(C(O)=O)C=C1C(O)=O UGJCNRLBGKEGEH-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 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 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
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- 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
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by physical means, e.g. sputtering, evaporation
-
- 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
- C23C18/1637—Composition of the substrate metallic substrate
-
- 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
-
- 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
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
- H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
-
- 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
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Description
本發明係有關一種基板,係具有形成在基材上且用以作為ULSI(Ultra Large Scale Integration,超大型積體電路)微細銅線路之阻障兼觸媒層使用之防止銅擴散用阻障膜者。
ULSI微細銅線路(金屬鑲嵌(damascene)銅線路)之銅成膜方法,有藉由無電解鍍銅設晶種層之後,以電鍍銅將銅成膜之已知方法。
以往,在如半導體晶圓之鏡面上進行無電解鍍銅時,在析出之電鍍膜要有充分之密著性是相當困難的。又,電鍍之反應性低,要在基板整面均勻進行電鍍也困難。以往例如要在氮化鉭等阻障金屬層上以無電解電鍍法形成銅晶種層時,難以形成均勻電鍍而有密著力不充分之問題。
本發明人等既已發現,在無電解鍍銅液中加入重量平均分子量(Mw)小之水溶性含有氮之聚合物作為添加劑,另一方面在浸漬電鍍液前使觸媒金屬附著在被電鍍物之基板、或事先在最表面成膜觸媒金屬後,浸漬於電鍍液而透過氮原子使聚合物吸附在該觸媒金屬上藉此抑制電鍍之析出速度,且使結晶非常微細化,而可在如晶圓之鏡面上形成膜厚15nm以下之均勻薄膜(後述之專利文獻1)。又,本發明人等,在上述發明之實施例中揭示,事先在最表面成膜觸媒金屬後,浸漬於電鍍液而透過氮原子使聚合物吸附在該觸媒金屬上藉此抑制電鍍之析出速度,且使結晶非常微細化,而得以在如晶圓之鏡面上形成膜厚6nm以下之均勻膜厚。
如此方法,亦即於形成金屬鑲嵌銅線路時,在成膜觸媒金屬後,藉由無電解電鍍設置銅晶種層時,除了觸媒金屬層之外,需事先另外形成用以防止銅擴散之阻障層,因此在成膜銅晶種層之前要形成阻障層與觸媒金屬層之兩層,故獲知在不能形成厚膜之超微細線路,則有難以使用在實際製程之問題。
為了排除如此在成膜銅晶種層之前需先形成兩層之麻煩,本發明人等發現經由形成兼具阻障能力與觸媒能力之特定合金薄膜所成之單一層、與更將無電解電鍍與取代電鍍及還原電鍍併用,即可將形成在其上之銅晶種層之膜厚形成為薄且均勻,並已申請專利(後述之專利文獻2、專利文獻3)。但是此等兼具阻障能力與觸媒能力之合金薄膜,在加熱至約500℃左右之高溫時阻障性不足,使用於半導體裝置時,尤其更要求長時間使用時之可靠性。
又,於後述之專利文獻4,係記載有:鉭、氮化鉭、氮化鉭,氮化鉭矽、鈦、氮化鈦、氮化鈦矽、釕、鎢、氮化鎢,其等合金、衍生物、及含其等之組合所選擇之金屬之阻障層之導電性材料之製造方法。於上述文獻,在該阻障層上由PVD法設晶種層,但是對阻障層,尤其是其組合之效果及組織比並無說明。
專利文獻1:日本特開2008-233100號公報
專利文獻2:PCT/JP2008/063023
專利文獻3:PCT/JP2008/063024
專利文獻4:WO2006/102182A2
本發明之目的為提供一種具有具有阻障能力與觸媒能力之防止銅擴散用阻障膜之基板,係較上述之兼具阻障能力與觸媒能力之合金薄膜,更能在高溫加熱時有優異阻障性者。
再者,目的為提供一種半導體晶圓,係在高溫加熱時具優異阻障性,即使經長時間使用亦有高可靠性者。
本發明人等經致力研究之結果,發現將對無電解電鍍具觸媒能力之金屬、與具阻障機能且可與無電解電鍍液中之金屬取代之金屬進行合金化,則在形成兼具阻障機能與觸媒能力之單一層時,再以與有阻障機能之金屬之氮化物之形態含有氮,藉此可更提高阻障機能。
即,本發明係如下。
(1)一種基板,係在基材上具有:選擇自鎢、鉬、及鈮之一種或以上之金屬元素;對無電解電鍍具有觸媒能力之金屬元素;及由以與上述選擇自鎢、鉬、及鈮之一種或以上之金屬元素之氮化物之形態含有之氮所成之防止銅擴散用阻障膜。
(2)上述(1)之基板,其中,上述對無電解電鍍具有觸媒能力之金屬元素為選擇自釕、銠、及銥之一種或以上者。
(3)上述(1)或(2)之基板,其中,上述防止銅擴散用阻障膜係含有對無電解電鍍具有觸媒能力之金屬元素10至30原子%、選擇自鎢、鉬、及鈮之一種或以上之金屬元素60至75原子%,其餘為氮。
(4)上述(1)至(3)中任一項之基板,其中,在上述防止銅擴散用阻障膜上,具有或以上述具有觸媒能力之金屬元素為觸媒,以無電解鍍銅所形成之銅晶種層。
(5)上述(1)至(4)中任一項之基板,其中,在上述防止銅擴散用阻障膜上,具備或以上述具有觸媒能力之金屬元素為觸媒,以無電解鍍銅所形成之銅晶種層,復具有形成在該銅晶種層上之金屬鑲嵌銅線路。
(6)一種基板之製造方法,係使用含有選擇自鎢、鉬、及鈮之一種或以上之金屬元素、與對無電解電鍍具有觸媒能力之金屬元素為靶,在氮氣環境中進行濺鍍,而在基材上形成選擇自鎢、鉬、及鈮之一種或以上之金屬元素;對無電解電鍍具有觸媒能力之金屬元素;及由以與上述選擇自鎢、鉬、及鈮之一種或以上之金屬元素之氮化物之形態含有之氮所成之防止銅擴散用阻障膜。
(7)上述(6)之基板之製造方法,其中,上述對無電解電鍍具有觸媒能力之金屬元素為選擇自釕、銠、及銥之一種或以上者。
(8)上述(6)或(7)之基板之製造方法,其中,上述防止銅擴散用阻障膜係含有對無電解電鍍具有觸媒能力之金屬元素10至30原子%、選擇自鎢、鉬、及鈮之一種或以上之金屬元素60至75原子%,其餘為氮。
(9)上述(6)至(8)中任一項之基板之製造方法,其中,在上述防止銅擴散用阻障膜上,或以上述具有觸媒能力之金屬元素為觸媒,以無電解鍍銅形成銅晶種層。
(10)上述(6)至(9)中任一項之基板之製造方法,其中,在上述防止銅擴散用阻障膜上,或以上述具有觸媒能力之金屬元素為觸媒,以無電解鍍銅形成銅晶種層,更在該銅晶種層上形成金屬鑲嵌銅線路。
(11)一種半導體晶圓,係使用上述(5)之基板者。
依據本發明,在基材上形成選擇自鎢、鉬、及鈮之一種或以上之金屬元素;對無電解電鍍具有觸媒能力之金屬元素;及由以與上述選擇自鎢、鉬、及鈮之一種或以上之金屬元素之氮化物之形態含有之氮所成之防止銅擴散用阻障膜,即可提高在高溫加熱時之阻障性。由於高溫加熱時之阻障機能提高,故如將本發明之基板長時間作為半導體晶圓使用時可提高其可靠性。再者,將選擇自鎢、鉬、及鈮之一種或以上之金屬元素加以氮化,則以濺鍍形成防止銅擴散用阻障膜時,可降低在濺鍍靶中之昂貴的貴金屬之釕、銠、銥等觸媒金屬成分之比率,而減低生產成本。
又,由於形成本發明之防止銅擴散用阻障膜,當在藉由無電解取代及還原電鍍形成銅等之金屬薄膜時,不致侵蝕作為基底之上述防止銅擴散用阻障膜之表面,可形成在其上所形成之銅等之金屬薄膜層之膜厚相當薄並且均勻且有優異密著性。又,在上述防止銅擴散用阻障膜與其上之無電解電鍍層之界面,可形成為實質上不含氧氣之狀態。
根據本發明,係有關在基材上具有防止銅擴散用阻障膜之基板,該防止銅擴散用阻障膜為選擇自鎢、鉬、及鈮之一種或以上之金屬元素;對無電解電鍍具有觸媒能力之金屬元素;及由以與上述選擇自鎢、鉬、及鈮之一種或以上之金屬元素之氮化物之形態含有之氮所成。
鎢、鉬、及鈮為可與無電解鍍銅液中所含之銅進行取代電鍍之金屬,且對銅有阻障機能者。防止銅擴散用阻障膜為使用選擇自鎢、鉬、及鈮之至少一種或以上之金屬,但是較佳為鎢。
又,鎢、鉬、鈮與鉭或鈦相比,較不易形成堅固氧化膜,因此在防止銅擴散用阻障膜上進行無電解電鍍時,在與電鍍膜之界面不會殘留氧化層。如在界面存在氧氣時,會有增加線路電阻,或降低阻障機能等不良影響。
對無電解電鍍具有觸媒能力之金屬,有釕、銠、銥等,使用自此等金屬選出之至少一種或以上之金屬為佳,尤其是使用釕為佳。又,也有可能使用含有2種或以上具有觸媒能力之金屬之合金。於本發明中,上述所謂具有無電解電鍍之觸媒能力,係指具有使無電解電鍍液中之銅等金屬離子還原形成電鍍膜之反應之觸媒能力。
因此,若在上述防止銅擴散用阻障膜上藉由無電解電鍍形成銅晶種層,即可藉由無電解取代及還原電鍍,均勻地進行無電解電鍍,而形成為膜厚相當薄並且有優異之密著性之晶種層。
鎢、鉬、及鈮在防止銅擴散用阻障膜中,為了顯現高溫阻障性,以含有60至75原子%為佳。少於60原子%時,高溫阻障性降低,具觸媒能力之金屬比率增加而混入電鍍膜中,使電阻值增加,有時會導致訊號延遲。也有增加膜成本之問題。又多於75原子%時,高溫阻障性降低,在藉由無電解鍍銅於其上設置銅晶種層時,取代反應較電鍍液之還原反應佔有優勢,以致有時會侵蝕被電鍍材而無法形成均勻之薄膜。此時會導致阻障機能降低。
具有上述觸媒能力之金屬在防止銅擴散用阻障膜中,為了顯現高溫阻障性,以含有10至30原子%為佳。如少於10原子%,則高溫阻障性降低,在藉由無電解鍍銅於其上設置銅晶種層時,取代反應較電鍍液之還原反應佔有優勢,以致有時會侵蝕被電鍍材而無法形成均勻之薄膜。此時會導致阻障機能更降低。又,多於30原子%時,高溫阻障性降低,具有觸媒能力之金屬比率增多而混入電鍍膜中,使電阻值增加,有時會導致訊號延遲。另一方也有增加成膜之成本問題。
再者,於本發明之防止銅擴散用阻障膜,為了顯現高溫阻障性,而以鎢、鉬、及鈮之氮化物之形態含有氮,而該防止銅擴散用阻障膜,含有上述具有阻障能力之金屬成分與觸媒能力之金屬成分,其餘為氮。氮以在防止銅擴散用阻障膜中至少含有3原子%為佳,較佳為5至20原子%。
防止銅擴散用阻障膜中之組成,可由將AES(Auger Electron Spectroscopy:歐傑電子能譜儀)深度分布之強度比變換為組成比而求得。於本發明中,AES深度分布之測量,係使用PHI 700 Scanning Auger Nanoprobe ULVAC-PHI,INC.製之測量裝置,藉由裝置所附之軟體將能譜強度比變換為組成比。變換係數係使用程式儲存之數值求出,但視需要可由一次標準算出。
防止銅擴散用阻障膜較佳為依濺鍍法形成,此時使用自鎢、鉬、及鈮選出之一種或以上之金屬元素、與上述對無電解電鍍具有觸媒能力之金屬元素作為濺鍍靶,在氮氣環境中進行濺鍍,藉此將鎢、鉬、鈮氮化成為氮化物含有於膜內。
通常濺鍍係在低壓力導入惰性氣體進行,但是在本發明中係在惰性氣體中含有氮,並在氮氣環境中進行,使鎢、鉬、及鈮氮化。
在氮氣環境中進行濺鍍時,僅鎢、鉬、或鈮之成膜速度漸漸變慢,釕等具有觸媒能力之金屬成膜於基板之速度不變慢,以致相對地具有觸媒能力之金屬之膜中比率漸漸提高,因此可判斷為以鎢、鉬、或鈮之氮化物之形態含有氮。
上述防止銅擴散用阻障膜之組成,可依濺鍍靶之金屬組成、及於氮氣環境中氮之分壓等而調整。
由於將具有阻障機能之鎢、鉬、鈮氮化,而可提高阻障機能。因製成氮化物,而可提高在高溫加熱時之阻障性至400℃至500℃。
又,因使上述具有阻障機能之金屬製成氮化物,在使用相同組成之濺鍍靶時,所得防止銅擴散用阻障膜中之具有觸媒機能之金屬,較不製成氮化物時有高濃度。此係在進行濺鍍時阻障成分之鎢、鉬、及鈮金屬元素之一部分被氮化,成為氮化鎢、氮化鉬、或氮化鈮,但是由於此氮化鎢、氮化鉬、或氮化鈮之成膜速度較慢,因此可認為未氮化之觸媒金屬元素,較氮化鎢、氮化鉬、或氮化鈮,相對的成膜速度變快。因此,藉由氮化,可降低昂貴之貴金屬之觸媒金屬成分在靶中之成分比,而減低生產成本。
上述防止銅擴散用阻障膜之膜厚以3至20nm為佳,理想為5至15nm。
於本發明中,形成上述防止銅擴散用阻障膜之基材,以矽基板為佳,並實施酸處理、鹼處理、界面活性劑處理、超音波洗浄、或組合此等之處理,用以提高基材之潔淨度與潤濕性。
於本發明中,在上述防止銅擴散用阻障膜上,或以上述具有觸媒能力之金屬元素作為觸媒,以無電解鍍銅設置銅晶種層。此無電解鍍銅係無電解取代電鍍及還原電鍍。
使用本發明之防止銅擴散用阻障膜進行無電解取代及還原電鍍時所使用之無電解鍍銅方法,可採用一般方法。同樣所使用鍍銅液亦可使用一般電鍍液。
無電解鍍銅液,通常含有銅離子、銅離子之錯合劑、還原劑、及pH調整劑等。
無電解鍍銅液之還原劑,因考慮到甲醛對人體與環境之不良影響,較佳為使用乙醛酸(Glyoxylic Acid)。又,無電解鍍銅液較佳為不含在半導體用途所欲避免之不純物之鈉。
乙醛酸之濃度,在電鍍液中0.005至0.5mol/L為佳,較佳為0.01至0.2mol/L。如濃度未達0.005mol/L時不發生電鍍反應,如超過0.5mol/L時電鍍液變得不安定而分解。
於本發明中作為無電解鍍銅液之銅離子源,可使用所有一般所使用之銅離子源,例如硫酸銅、氯化銅、硝酸銅等。又作為銅離子之錯合劑也可使用所有一般所使用之錯合劑,例如乙二胺四乙酸、酒石酸等。
其他添加劑可使用一般電鍍液所使用之添加劑,可使用例如2.2’-聯吡啶、聚乙二醇、亞鐵氰化鉀等。
又,於本發明中之無電解鍍銅液,使用pH10至14為佳,使用pH12至13則更佳。pH調整劑可使用氫氧化鈉、氫氧化鉀等一般所使用者,但是在半導體用途欲避免鈉、鉀等鹼金屬時,可用氫氧化四甲銨。
又,於本發明中之無電解鍍銅液,自浴穩定性與銅之析出速度之觀點而言,在浴溫為40至90℃使用為佳。
於本發明中使用無電解鍍銅液進行電鍍時,需將被電鍍材浸漬於電鍍浴中。被電鍍材為經在上述基材上成膜防止銅擴散用阻障膜者。
本發明之藉由無電解取代及還原電鍍所製成之銅薄膜之厚度以1至10nm較佳。
本發明之藉由無電解取代及還原電鍍所製成之銅薄膜,其電鍍膜薄且膜厚均勻。因此使用為金屬鑲嵌銅線路用晶種層時,在線路寬度僅100nm或以下之微細通孔(via)‧槽溝(trench)內亦可形成膜厚均勻之薄膜晶種層,其結果可獲得不會產生有空隙(void)‧縫口(seam)等瑕疵之半導體晶圓。
本發明之基板係可在藉由無電解電鍍所形成之銅薄膜上,再以電鍍設置線路部。電鍍可使用電鍍或無電解電鍍。
線路部以銅、或以銅為主成分之合金為佳,金屬鑲嵌銅線路更佳。電鍍銅液只要為一般使用在金屬鑲嵌銅線路埋入用之組成即可,並無特別限制,例如可使用含有作為主成分之硫酸銅及硫酸,作為微量成分之氯、聚乙二醇、二硫化雙(3-磺丙基)二鈉、第三烷基胺及聚表氯醇所成之第四銨鹽加成物(第四表氯醇)等之溶液。又使用於埋入之無電解鍍銅液,例如可使用日本特開2005-038086號公報記載之銅線路埋入用電鍍液。
以下以實施例說明本發明,但是本發明並不受限於此等實施例。
使用各種組成比之鎢與釕之濺鍍合金靶,變更進行濺鍍時反應室內氬‧氮氣壓比,在最表面有SiO2
膜之矽基板上,製作膜厚10nm之氮化鎢‧釕之合金膜,再在其上成膜厚度5至8nm之無電解鍍銅膜。
濺鍍成膜係使用3英吋RF濺鍍裝置(ANELVA製SPF-332HS)。氮化鎢‧釕合金膜之製作,係以低溫泵(cryopump)使反應室內成為5×10-5
Pa之後,將某一定比率之氮‧氬混合氣體導入至總壓成為0.8Pa,以50W之輸出使電漿產生,經過15分之預濺鍍後,實施成膜。
藉由無電解電鍍之銅成膜,係使用如下組成之電鍍液,在pH12.5,50℃×30秒之條件下實施。
硫酸銅:0.02mol/L
乙二胺四乙酸鹽:0.21mol/L
乙醛酸:0.03mol/L
2.2’-聯吡啶:20mg/L
pH12.5(氫氧化四甲銨)
對所得之成膜有無電解電鍍膜之基板,作如下之評估。
以AES深度分布測量,確認500℃×30分鐘之真空退火處理後之阻障性。如銅擴散至氮化鎢‧釕合金膜中、或其相反現象均觀察不到者為「○」,可觀察到者任一現象為「×」。
對電鍍膜之均勻性之評估係使用FESEM裝置(日本電子製JSM-6700F),觀察膜表面確認有無φ 1nm或以上之無電解電鍍之部分。如無經無電解電鍍之部分時為「○」,確認存在無經無電解電鍍部分時為「×」。
藉由AES深度分布測量,確認電鍍時之銅膜與鎢合金膜之界面之氧化狀態。在電鍍膜與鎢合金膜之界面確認無氧氣時為「○」,確認有氧氣時為「×」。
電鍍膜密著性之評估,係使用透明膠帶(「CT24」Nichiban製)之剝離試驗,由手指頭按壓使膠帶密著於電鍍面後,剝下膠帶確認膜有無剝離。電鍍膜如無剝離則為「○」,如有剝離則為「×」。
又,對線寬90nm,寬高比4之有槽溝圖案之半導體基板,進行上述濺鍍合金薄膜、及成膜無電解鍍銅薄膜之後,以其為晶種層以電鍍銅進行線路之埋入。
再者,線路之埋入係使用如下組成之電鍍液,進行25℃×60秒、電流密度1A/dm2
。
硫酸銅 0.25mol/L
硫酸 1.8mol/L
鹽酸 10mmol/L
微量添加劑(聚乙二醇、二硫化雙(3-磺丙基)二鈉、耶奴斯綠(Janus Green))
藉由所得鍍銅膜剖面之TEM觀察,評估線寬90nm槽溝部之埋入性。判定有無空隙‧縫口,○:為無空隙‧縫口,×:為有空隙‧縫口。
此等結果整理於表1。綜合評估係阻障性、電鍍膜均勻性、耐氧化性、電鍍膜密著性、埋入性之5種評估,如皆為○時為「○」,如有4項為○時為「△」,○為3項以下時為「×」。
兼具有阻障性、電鍍膜均勻性、耐氧化性、電鍍膜密著性、及埋入性之組成(綜合評估○),在未導入氮氣時未發現,但是藉由導入適當量之氮氣,可發現膜中釕組成比12至28原子%、膜中鎢組成比62至72原子%、膜中氮組成比10至16原子%之適當條件。
使用各種組成比之鉬與銠之濺鍍合金靶,改變進行濺鍍時反應室內之氬‧氮氣壓比,在最表面有SiO2
膜之矽基板上,製作膜厚10nm之氮化鉬‧銠之合金膜,再在其上成膜5至8nm之無電解鍍銅膜。濺鍍成膜、無電解電鍍之條件則如同實施例1。
至於阻障性、電鍍膜均勻性、耐氧化性、電鍍膜密著性、埋入性及綜合評估則如同實施例1之方法。
此結果整理於表2。
兼具有阻障性、電鍍膜均勻性、耐氧化性、電鍍膜密著性、及埋入性之組成(綜合評估○),在未導入氮氣時未發現,但是藉由導入適當量之氮氣,可發現膜中銠組成比14至29原子%、膜中鉬組成比61至74原子%、膜中氮組成比10至12原子%之適當條件。
使用各種組成比之鈮與銥之濺鍍合金靶,改變進行濺鍍時反應室內之氬˙氮氣壓比,在最表面有SiO2
膜之矽基板上,製作膜厚10nm之氮化鈮˙銥之合金膜,再在其上成膜5至8nm之無電解鍍銅膜。銅濺鍍成膜、無電解電鍍之條件則如同實施例1。
至於阻障性、電鍍膜均勻性、耐氧化性、電鍍膜密著性、埋入性及綜合評估則如同實施例1之方法。
此結果整理於表3。
兼具有阻障性、電鍍膜均勻性、耐氧化性、電鍍膜密著性、及埋入性之組成(綜合評估○),在未導入氮氣時未發現,但是藉由導入適當量之氮氣,可發現膜中銥組成比12至27原子%、膜中鈮組成比62至73原子%、膜中氮組成比11至15原子%之適當條件。
Claims (9)
- 一種基板,係在基材上具有:選擇自鎢、鉬、及鈮之一種或以上之金屬元素60至75原子%;對無電解電鍍具有觸媒能力之金屬元素10至30原子%;及其餘為由以與上述選擇自鎢、鉬、及鈮之一種或以上之金屬元素之氮化物之形態含有之氮所成之防止銅擴散用阻障膜。
- 如申請專利範圍第1項之基板,其中,上述對無電解電鍍具有觸媒能力之金屬元素為選擇自釕、銠、及銥之一種或以上者。
- 如申請專利範圍第1或2項之基板,其中,在上述防止銅擴散用阻障膜上,具有或以上述具有觸媒能力之金屬元素為觸媒,以無電解鍍銅所形成之銅晶種層。
- 如申請專利範圍第1或2項之基板,其中,在上述防止銅擴散用阻障膜上,具備或以上述具有觸媒能力之金屬元素為觸媒,以無電解鍍銅所形成之銅晶種層,復具有形成在該銅晶種層上之金屬鑲嵌銅線路。
- 一種基板之製造方法,係使用含有選擇自鎢、鉬、及鈮之一種或以上之金屬元素、與對無電解電鍍具有觸媒能力之金屬元素為靶,在氮氣環境中進行濺鍍,而在基材上形成選擇自鎢、鉬、及鈮之一種或以上之金屬元素;對無電解電鍍具有觸媒能力之金屬元素;及由以與上述選擇自鎢、鉬、及鈮之一種或以上之金屬元素之氮化物之形態含有之氮所成之防止銅擴散用阻障膜;上述防止銅擴散用阻障膜係含有對無電解電鍍具有觸 媒能力之金屬元素10至30原子%、選擇自鎢、鉬、及鈮之一種或以上之金屬元素60至75原子%,其餘為氮。
- 如申請專利範圍第5項之基板之製造方法,其中,上述對無電解電鍍具有觸媒能力之金屬元素為選擇自釕、銠、及銥之一種或以上者。
- 如申請專利範圍第5或6項之基板之製造方法,其中,在上述防止銅擴散用阻障膜上,或以上述具有觸媒能力之金屬元素為觸媒,以無電解鍍銅形成銅晶種層。
- 如申請專利範圍第5或6項之基板之製造方法,其中,在上述防止銅擴散用阻障膜上,或以上述具有觸媒能力之金屬元素為觸媒,以無電解鍍銅形成銅晶種層,更在該銅晶種層上形成金屬鑲嵌銅線路。
- 一種半導體晶圓,係使用申請專利範圍第4項之基板者。
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