TWI384552B - 基板及其製造方法 - Google Patents
基板及其製造方法 Download PDFInfo
- Publication number
- TWI384552B TWI384552B TW097146927A TW97146927A TWI384552B TW I384552 B TWI384552 B TW I384552B TW 097146927 A TW097146927 A TW 097146927A TW 97146927 A TW97146927 A TW 97146927A TW I384552 B TWI384552 B TW I384552B
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- TW
- Taiwan
- Prior art keywords
- copper
- plating
- film
- electroless
- substrate
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 129
- 229910052802 copper Inorganic materials 0.000 claims description 127
- 239000010949 copper Substances 0.000 claims description 127
- 230000004888 barrier function Effects 0.000 claims description 91
- 238000007747 plating Methods 0.000 claims description 90
- 229910052751 metal Inorganic materials 0.000 claims description 87
- 239000002184 metal Substances 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- 238000009792 diffusion process Methods 0.000 claims description 49
- 230000003197 catalytic effect Effects 0.000 claims description 44
- 229910052721 tungsten Inorganic materials 0.000 claims description 42
- 239000010937 tungsten Substances 0.000 claims description 42
- 238000007772 electroless plating Methods 0.000 claims description 40
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 35
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims description 33
- 239000011733 molybdenum Substances 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000004544 sputter deposition Methods 0.000 claims description 20
- 229910052758 niobium Inorganic materials 0.000 claims description 19
- 239000010955 niobium Substances 0.000 claims description 19
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 19
- 150000004767 nitrides Chemical class 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 239000013077 target material Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 141
- 239000010410 layer Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 29
- -1 and among them Chemical compound 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 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
- 239000010409 thin film Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 5
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 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
- 239000007788 liquid Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000005121 nitriding 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
- 238000011282 treatment Methods 0.000 description 4
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052707 ruthenium Inorganic materials 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
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000000996 additive effect Effects 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 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
- 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
- 230000007547 defect Effects 0.000 description 1
- 238000009713 electroplating Methods 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
- 239000003353 gold alloy Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920000573 polyethylene 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
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- H01L21/02—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
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
-
- 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
-
- 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
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
-
- 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
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Description
本發明係關於具有防止銅擴散用阻障膜之基板,此防止銅擴散用阻障膜係形成於基材上,且用以作為ULSI精細銅線路之阻障兼觸媒層使用。
作為ULSI精細銅線路(金屬鑲嵌(damascene)銅線路)之銅的成膜方法,為人所知者有藉由無電解鍍銅設置晶種層,並藉由銅電鍍使銅成膜之方法。
以往,於如半導體晶圓之鏡面上進行無電解鍍銅時,所析出之鍍覆膜乃不易獲得充分的密接性。此外,鍍覆的反應性較低,而亦難以於基板全面上進行均勻的鍍覆。以往,例如於氮化鉭等之阻障金屬層上以無電解鍍覆法形成銅晶種層時,係具有難以均勻地形成鍍覆,導致密接力不夠充分之問題。
本發明人等發現,於無電解鍍銅液中添加重量平均分子量(Mw)較小的水溶性含氮聚合物作為添加劑,另一方面,於浸漬鍍覆液前,使觸媒金屬附著於被鍍覆物的基板、或是預先於最表面使觸媒金屬成膜,之後再浸漬於鍍覆液,使聚合物透過氮原子吸附於該觸媒金屬上,藉此來抑制鍍覆的析出速度並使結晶變得極為精細,而能夠在如晶圓之鏡面上形成膜厚15nm以下之均勻的薄膜(專利文獻1)。此外,本發明人等係於前述發明的實施例中,揭示預先於最表面使觸媒金屬成膜後,浸漬於鍍覆液使聚合物透過氮原子吸附於該觸媒金屬上,藉此來抑制鍍覆的析出速度並使結晶變得極為精細,而能夠在如晶圓之鏡面上形成膜厚6nm以下之均勻的薄膜。
此方法,亦即於形成金屬鑲嵌銅線路時,當於使觸媒金屬成膜後以無電解鍍覆來設置銅晶種層時,除了觸媒金屬層之外,必須另外預先形成用於防止銅擴散的阻障層,因此,必須於使銅晶種層成膜之前,形成阻障層與觸媒金屬層之兩層,在無法增加膜厚之超精細線路中,明顯的具有難以使用於實際製程之問題。
如此,為了消除如此於銅晶種層的成膜前需預先形成兩層之麻煩,本發明人等發現,同時形成由兼具阻障能力及觸媒能力之特定的合金薄膜所形成之單一層、以及併用取代鍍覆及還原鍍覆來進行無電解鍍覆之兩項做法,可藉此薄化形成於其上之銅晶種層的膜厚並均勻地形成,因此已提出申請(專利文獻2、專利文獻3)。然而,於這些兼具阻障能力及觸媒能力之合金薄膜中,於加熱至500℃左右的高溫時,阻障性不充分,對於使用於半導體裝置之情形、尤其對於長時間的使用時之可靠度有更進一步的要求。
專利文獻1:日本特開2008-223100號公報
專利文獻2:PCT/JP2008/063023
專利文獻3:PCT/JP2008/063024
本發明之目的在於提供一種具有防止銅擴散用阻障膜之基板,此防止銅擴散用阻障膜,於高溫加熱時之阻障性係較上述兼具阻障能力及觸媒能力之合金薄膜更佳,並且具有阻障能力及觸媒能力。
此外,目的在於提供一種於高溫加熱時之阻障性較佳,即使長時間使用,亦具有極高的可靠度之半導體晶圓。
本發明人等在進行精心研究後發現,將對無電解鍍覆具有觸媒能力之金屬、與具有阻障功能且可取代無電解鍍覆液中的金屬之金屬予以合金化,而在形成兼具阻障功能及觸媒能力之單一層時,更以與具有阻障功能之金屬的氮化物之形態含有氮,藉此可更進一步提升阻障功能,因而完成本發明。
亦即,本發明如下所述。
(1)一種基板,其特徵為:於基材上具有防止銅擴散用阻障膜,此防止銅擴散用阻障膜,係由下列者所形成:從鎢、鉬及鈮中選出之1種以上的金屬元素;對無電解鍍覆具有觸媒能力之金屬元素;以及以與前述從鎢、鉬及鈮中選出之1種以上的金屬元素之氮化物的形態被含有之氮。
(2)如前述(1)所記載之基板,其中,前述對無電解鍍覆具有觸媒能力之金屬元素,為從鉑、金、銀、鈀中選出之1種以上。
(3)如前述(1)或(2)所記載之基板,其中,前述防止銅擴散用阻障膜係含有:10至30原子%之對無電解鍍覆具有觸媒能力之金屬元素;以及60至75原子%之從鎢、鉬及鈮中選出之1種以上的金屬元素;其餘為氮。
(4)如前述(1)至(3)中任一項所記載之基板,其中,於前述防止銅擴散用阻障膜上,係具有:以前述具有觸媒能力之金屬元素作為觸媒,並藉由無電解鍍銅所形成之銅晶種層。
(5)如前述(1)至(4)中任一項所記載之基板,其中,於前述防止銅擴散用阻障膜上,係具備:以前述具有觸媒能力之金屬元素作為觸媒,並藉由無電解鍍銅所形成之銅晶種層;且復具有形成於該銅晶種層上之金屬鑲嵌銅線路。
(6)一種基板的製造方法,其特徵為:使用含有從鎢、鉬及鈮中選出之1種以上的金屬元素、以及對無電解鍍覆具有觸媒能力之金屬元素之靶材,於氮氣環境中進行濺鍍,而於基材上形成防止銅擴散用阻障膜,此防止銅擴散用阻障膜係由下列者所形成:從鎢、鉬及鈮中選出之1種以上的金屬元素;對無電解鍍覆具有觸媒能力之金屬元素;以及以與前述從鎢、鉬及鈮中選出之1種以上的金屬元素之氮化物的形態所含有之氮。
(7)如前述(6)所記載之基板的製造方法,其中,前述對無電解鍍覆具有觸媒能力之金屬元素,為從鉑、金、銀、鈀中選出之1種以上。
(8)如前述(6)或(7)所記載之基板的製造方法,其中,前述防止銅擴散用阻障膜係含有:10至30原子%之對無電解鍍覆具有觸媒能力之金屬元素;以及60至75原子%之從鎢、鉬及鈮中選出之1種以上的金屬元素;其餘為氮。
(9)如前述(6)至(8)中任一項所記載之基板的製造方法,其中,於前述防止銅擴散用阻障膜上,以前述具有觸媒能力之金屬元素作為觸媒,並藉由無電解鍍銅形成銅晶種層。
(10)如前述(6)至(9)中任一項所記載之基板的製造方法,其中,於前述防止銅擴散用阻障膜上,以前述具有觸媒能力之金屬元素作為觸媒,並藉由無電解鍍銅形成銅晶種層,再於該銅晶種層上形成金屬鑲嵌銅線路。
(11)一種半導體晶圓,係使用前述(5)所記載之基板。
根據本發明,藉由形成由從鎢、鉬及鈮中選出之1種以上的金屬元素;鉑、金、銀、鈀等對無電解鍍覆具有觸媒能力之金屬元素;以及以與從鎢、鉬及鈮中選出之1種以上的金屬元素之氮化物的形態被含有之氮所形成之防止銅擴散用阻障膜,可提升於高溫加熱時之阻障性。由於高溫加熱時之阻障功能提高,所以更能夠提高當長時間使用本發明之基板作為半導體晶圓時之可靠度。再者,藉由對從鎢、鉬及鈮中選出之1種以上的金屬元素進行氮化,於以濺鍍來形成防止銅擴散用阻障膜時,可降低濺鍍靶材中之昂貴的貴金屬之鉑、金、銀、鈀等觸媒金屬的成分比例,而降低生產成本。
此外,藉由形成本發明之防止銅擴散用阻障膜,於藉由無電解取代及還原鍍覆將銅等的金屬薄膜形成於其上時,做為底層之前述防止銅擴散用阻障膜表面不會被腐蝕,可充分薄化其上所形成之銅等的金屬薄膜層的膜厚,而均勻地且具有較佳的密接性來成膜。此外,於前述防止銅擴散用阻障膜與其上的無電解鍍覆層之間的界面,可構成為實質上不含氧之狀態。
本發明係關於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係由:從鎢、鉬及鈮中選出之1種以上的金屬元素;對無電解鍍覆具有觸媒能力之金屬元素;以及以與前述從鎢、鉬及鈮中選出之1種以上的金屬元素之氮化物的形態所含有之氮所形成。
鎢、鉬及鈮,為可與無電解鍍覆液中所含的銅進行取代鍍覆之金屬,且對銅具有阻障功能。防止銅擴散用阻障膜係使用從鎢、鉬及鈮中選出之至少1種以上的金屬元素,當中尤其以鎢較為理想。
此外,由於鎢、鉬及鈮較鉭和鈦更不易形成堅固的氧化膜,所以在防止銅擴散用阻障膜上進行無電解鍍覆時,於與鍍覆膜之間的界面不會殘留氧化層。當於界面存在氧時,乃具有線路電阻上升,阻障功能降低等不良影響。
對無電解鍍覆具有觸媒能力之金屬元素,例如有鉑、金、銀、鈀等,較理想為使用從這些金屬中選出之至少1種以上的金屬,其中以使用鉑、鈀較為理想,尤其理想為鈀。此外,亦可使用包含具有觸媒能力之金屬2種以上的合金。於本發明中,前述所謂對無電解鍍覆具有觸媒能力,是指對將無電解鍍覆液中的銅等之金屬離子予以還原而形成鍍覆膜之反應具有觸媒能力者。
因此,若於前述防止銅擴散用阻障膜上藉由無電解鍍覆來形成銅晶種層,則可藉由無電解取代及還原鍍覆,均勻地進行無電解鍍覆並充分地薄化膜厚,而能夠形成具有較佳的密接性之晶種層。
為了在防止銅擴散用阻障膜中顯現出高溫阻障性,鎢、鉬及鈮較理想為含有60至75原子%。若低於60原子%,則不僅高溫阻障性會降低,並且使具有觸媒能力之金屬比例提高而混入於膜中,使電阻值增加而有時會導致訊號延遲。此外,亦產生膜的成本增加之問題。此外,若高於75原子%,不僅高溫阻障性會降低,並且當藉由無電解鍍覆於其上設置銅晶種層時,鍍覆液的取代反應會變得較還原反應更具優勢,有時會侵蝕被鍍覆材而無法形成均勻的薄膜。此時會導致阻障功能的降低。
前述具有觸媒能力之金屬,為了在防止銅擴散用阻障膜中顯現出高溫阻障性,較理想為含有10至30原子%。若低於10原子%,不僅高溫阻障性會降低,並且當藉由無電解鍍覆於其上設置銅晶種層時,鍍覆液的取代反應會變得較還原反應更具優勢,有時會侵蝕被鍍覆材而無法形成均勻的薄膜。此時會導致阻障功能的更降低。此外,若高於30原子%,不僅高溫阻障性會降低,並且使具有觸媒能力之金屬比例提高而混入於膜中,使電阻值增加而有時會導致訊號延遲。此外,亦產生膜的成本增加之問題。
再者,於本發明中之防止銅擴散用阻障膜,為了顯現出高溫阻障性,係以鎢、鉬及鈮的氮化物之形態含有氮,該防止銅擴散用阻障膜,係含有前述具有阻障能力之金屬成分以及具有觸媒能力之金屬成分,其餘為氮。於防止銅擴散用阻障膜中,氮較理想為至少含有3原子%以上,更理想為5至20原子%。
防止銅擴散用阻障膜中的組成,可將AES(Auger Electron Spectroscopy:歐傑電子光譜儀)深度分布的強度比轉換為組成比來求取。於本發明中,AES深度分布的測定,係使用測定裝置:PHI 700 Scanning Auger Nanoprobe ULVAC-PHI,INC.製,並藉由裝置所附的軟體,將光譜強度比轉換為組成比。轉換係數係使用程式所保有的數值來求取,亦可依需要以一次標準來算出。
防止銅擴散用阻障膜,較理想為以濺鍍來形成,此時可使用從鎢、鉬及鈮中選出之1種以上的金屬元素、以及前述對無電解鍍覆具有觸媒能力之金屬元素作為濺鍍靶材,並於氮氣環境中進行濺鍍,藉此使鎢、鉬、鈮氮化而成為氮化物並包含於膜中。
一般而言,濺鍍係於低壓力下導入惰性氣體來進行,但於本發明中,係於惰性氣體中含有氮氣並於氮氣環境中進行濺鍍,藉此將鎢、鉬、鈮予以氮化。
於氮氣環境中進行濺鍍時,因僅鎢、鉬或鈮的成膜速度逐漸變慢,鈀、鉑等具有觸媒能力之金屬成膜於基板的速度並不會變慢,相對地使具有觸媒能力之金屬於膜中的比例上升,而可判斷為以鎢、鉬或鈮之氮化物的形態含有氮。
前述防止銅擴散用阻障膜的組成,可藉由濺鍍靶材之金屬的組成、及氮氣環境中之氮的分壓等來進行調整。
因將具有阻障能力之鎢、鉬及鈮予以氮化,而提高阻障功能。藉由形成為氮化物,可使高溫加熱時之阻障性從400℃提升至500℃。
此外,因使前述具有阻障能力之金屬形成為氮化物,當使用相同組成的濺鍍靶材時,所得之防止銅擴散用阻障膜中之具有觸媒功能的金屬,其濃度係較未形成為氮化物時還高。其原因應為,濺鍍時作為阻障成分之鎢、鉬或鈮金屬元素,一部分會被氮化而成為氮化鎢、氮化鉬或氮化鈮,但由於此氮化鎢、氮化鉬或氮化鈮的成膜速度較慢,故未產生氮化之觸媒金屬的成膜速度變成較氮化鎢、氮化鉬或氮化鈮還快之故。因此藉由氮化的進行,可降低昂貴的貴金屬的觸媒金屬成分於靶材中之成分比,而可降低生產成本。
前述防止銅擴散用阻障膜的膜厚,較理想為3至20nm,更理想為5至15nm。
本發明中形成前述防止銅擴散用阻障膜之基材,較理想為矽基板,並可藉由實施酸處理、鹼處理、界面活性劑處理、超音波洗淨或這些處理的組合,而提升基材的潔淨度與潤濕性。
於本發明中,可於前述防止銅擴散用阻障膜上,以前述具有觸媒能力之金屬元素作為觸媒,並藉由無電解鍍銅設置銅晶種層。此無電解鍍銅為無電解取代鍍覆及還原鍍覆。
作為使用本發明之防止銅擴散用阻障膜來進行無電解取代及還原鍍覆時所使用之無電解鍍銅方法,可使用一般的方法。同樣的,所使用之鍍銅液,亦可使用一般的鍍覆液。
無電解鍍銅液,一般包含銅離子、銅離子的錯合劑、還原劑、及pH調整劑等。
無電解鍍銅液的還原劑,考量到福馬林對人體及環境的不良影響,較理想為使用乙醛酸(Glyoxylic Acid)。此外,無電解鍍銅液,較理想為不包含半導體用途中所欲避免之雜質的鈉。
乙醛酸的濃度,於鍍覆液中較理想為0.005至0.5mol/L,更理想為0.01至0.2mol/L。若濃度未達0.005mol/L,則無法引發鍍覆反應,若超過0.5mol/L,則鍍覆液變得不安定而分解。
於本發明中作為無電解鍍銅液的銅離子來源,可使用一般所使用之所有的銅離子來源,例如有硫酸銅、氯化銅、硝酸銅等。此外,銅離子的錯合劑,可使用一般所使用之所有的錯合劑,例如有乙二胺四醋酸、酒石酸(Tartaric Acid)等。
其他添加劑,可使用於鍍覆液中一般所使用之添加劑,例如有2,2’-聯吡啶、聚乙二醇、亞鐵氰化鉀等。
此外,本發明中之無電解鍍銅液,較理想為於pH10至14使用,更理想為於pH12至13使用。pH調整劑,可使用如氫氧化鈉、氫氧化鉀等一般所使用者,當於半導體用途中欲避免鈉、鉀等鹼金屬時,可使用氫氧化四甲基銨。
此外,本發明中之無電解鍍銅液,就鍍覆浴的安定性及銅的析出速度之觀點來看,較理想為於浴溫40至90℃使用。
於本發明中使用無電解鍍銅液來進行鍍覆時,係將被鍍覆材浸漬於鍍覆浴中。被鍍覆材為使防止銅擴散用阻障膜成膜於前述基材而成者。
本發明之以無電解取代及還原鍍覆所製作出之銅薄膜的厚度,更理想為1至10nm。
本發明之以無電解取代及還原鍍覆所製作出之銅薄膜,該鍍覆膜較薄且膜厚較為均勻。因此,當使用為金屬鑲嵌銅線路用晶種層時,即使於線路寬度100nm以下之精細的通孔(via)‧溝渠(trench)內,亦可形成膜厚較為均勻之薄膜晶種層,結果可獲得不會產生空隙、接縫等缺陷之半導體晶圓。
本發明之基板,可在藉由無電解鍍覆所形成之銅薄膜上,再藉由鍍覆來設置線路部。鍍覆可使用電鍍或無電解鍍覆。
線路部較理想為銅或以銅為主成分之合金,更理想為金屬鑲嵌銅線路。銅電鍍液,只要為一般的金屬鑲嵌銅線路埋入用中所使用之組成即可,並無特別限定,例如可使用包含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、由第三烷基胺及聚表氯醇所形成之第四銨鹽加成物(第四表氯醇)等之液體。此外,使用於埋入之無電解鍍銅液,例如可使用日本特開2005-038086號公報所記載之銅線路埋入用鍍覆液。
接下來藉由實施例來說明本發明,但本發明並不限定於這些實施例。
首先準備各種組成比之鎢與鈀的濺鍍合金靶材,改變濺鍍時之反應室內的氬氣/氮氣壓比,於最表面形成有SiO2
膜之矽基板上,製作出膜厚10nm的氮化鎢/鈀合金膜,並於其上以膜厚5至8nm使無電解鍍銅膜成膜。
濺鍍成膜係使用3吋RF濺鍍裝置(ANELVA製SPF-332HS)。氮化鎢/鈀合金膜的製作,係藉由低溫泵(cryopump)將反應室內形成為5×10-5
Pa後,導入某一定比例的氮氣/氬氣混合氣體至全壓力成為0.8Pa為止,以50W的輸出來產生電漿,進行15分鐘的預濺鍍後,實施成膜。
藉由無電解鍍覆之銅的成膜,係使用下列組成的鍍覆液,於pH12.5、50℃×30秒的條件下來進行。
硫酸銅:0.02mol/L
乙二胺四醋酸鹽:0.21mol/L
乙醛酸:0.03mol/L
2,2’-聯吡啶:20mg/L
pH12.5(氫氧化四甲基銨)
對於所得之形成有無電解鍍覆膜之基板,係以下列方式進行評估。
藉由AES深度分布測定,來確認經500℃×30分鐘的真空退火處理後之阻障性。以均未觀察到銅往氮化鎢‧鈀合金膜中的擴散以及其相反的現象者為「○」,以觀察到當中任一現象者為「×」。
鍍覆膜均勻性評估,係使用FESEM裝置(日本電子製JSM-6700F),觀察膜表面並確認是否有φ1nm以上之未進行無電解鍍覆的部分。以無未進行無電解鍍覆的部分者為「○」,以存在未進行無電解鍍覆的部分者為「×」。
此外,藉由AES深度分布測定,來確認鍍覆時之銅膜與鎢合金膜之界面的氧化狀態。於鍍覆膜與鎢合金膜之界面未確認有氧者為「○」,以確認有氧者為「×」。
鍍覆膜密接性評估,係使用玻璃紙膠帶(「CT24」,Nichiban製)來進行膠帶剝離測試,以指心將膠帶密接於鍍覆面後,剝離膠帶來確認是否產生膜的剝離。以未產生鍍覆膜的剝離者為「○」,以觀察到剝離者為「×」。
此外,對附有線寬90nm、寬高比4的溝渠圖案之半導體基板,使前述濺鍍合金薄膜及無電解鍍銅薄膜成膜後,以此作為晶種層,並以銅電鍍來進行線路的埋入。
線路的埋入係使用下列組成的鍍覆液,於25℃×60秒、電流密度1A/dm2
的條件下來進行。
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))
藉由對所得之鍍銅膜的剖面進行TEM(Transmission Electron Microscope:穿透式電子顯微鏡)觀察,來評估線寬90nm之溝渠部的埋入性。判定是否有空隙、接縫,○:無空隙、接縫,×:有空隙、接縫。
這些結果係整理於第1表中。
整體評估,係以阻障性、鍍覆膜均勻性、耐氧化性、鍍覆膜密接性、埋入性的5項評估均為○時為「○」,以4項為○時為「△」,以○為3項以下時為「×」。
經500℃×30分鐘的真空退火處理後兼具阻障性、鍍覆膜均勻性、耐氧化性、鍍覆膜密接性、及埋入性之組成(整體評估為○),於未導入氮氣時並未發現,但藉由導入適量的氮氣,於膜中的鈀組成比12至28原子%、膜中的鎢組成比63至73原子%、膜中的氮組成比9至15原子%時,可發現最適合的條件。
首先準備各種組成比之鎢與鉑的濺鍍合金靶材,改變濺鍍時之反應室內的氬氣/氮氣壓比,於最表面形成有SiO2
膜之矽基板上,製作出膜厚10nm的氮化鎢.鉑合金膜,並於其上以膜厚5至8nm使無電解鍍銅膜成膜。濺鍍成膜及無電解鍍覆的條件係與實施例1相同。
此外,以與實施例1相同之方法,來評估阻障性、鍍覆膜均勻性、耐氧化性、鍍覆膜密接性、埋入性、以及整體評估。
這些結果係整理於第2表中。
兼具阻障性、鍍覆膜均勻性、耐氧化性、鍍覆膜密接性、及埋入性之組成(整體評估為○),於未導入氮氣時並未發現,但藉由導入適量的氮氣,於膜中的鉑組成比11至27原子%、膜中的鎢組成比62至74原子%、膜中的氮組成比11至15原子%時,可發現最適合的條件。
首先準備各種組成比之鉬與金的濺鍍合金靶材,改變濺鍍時之反應室內的氬氣/氮氣壓比,於最表面形成有SiO2
膜之矽基板上,製作出膜厚10nm的氮化鉬/金合金膜,並於其上以膜厚5至8nm使無電解鍍銅膜成膜。濺鍍成膜及無電解鍍覆的條件係與實施例1相同。
此外,以與實施例1相同之方法,來評估阻障性、鍍覆膜均勻性、耐氧化性、鍍覆膜密接性、埋入性、以及整體評估。
這些結果係整理於第3表中。
兼具阻障性、鍍覆膜均勻性、耐氧化性、鍍覆膜密接性、及埋入性之組成(整體評估為○),於未導入氮氣時並未發現,但藉由導入適量的氮氣,於膜中的金組成比13至26原子%、膜中的鉬組成比62至73原子%、膜中的氮組成比12至16原子%時,可發現最適合的條件。
首先準備各種組成比之鈮與銀的濺鍍合金靶材,改變濺鍍時之反應室內的氬氣/氮氣壓比,於最表面形成有SiO2
膜之矽基板上,製作出膜厚10nm的氮化鈮/銀合金膜,並於其上以膜厚5至8nm使無電解鍍銅膜成膜。濺鍍成膜及無電解鍍覆的條件係與實施例1相同。
此外,以與實施例1相同之方法,來評估阻障性、鍍覆膜均勻性、耐氧化性、鍍覆膜密接性、埋入性、以及整體評估。
這些結果係整理於第4表中。
兼具阻障性、鍍覆膜均勻性、耐氧化性、鍍覆膜密接性、及埋入性之組成(整體評估為○),於未導入氮氣時並未發現,但藉由導入適量的氮氣,於膜中的銀組成比10至25原子%、膜中的鈮組成比61至73原子%、膜中的氮組成比14至17原子%時,可發現最適合的條件。
Claims (9)
- 一種基板,其特徵為:於基材上具有防止銅擴散用阻障膜,此防止銅擴散用阻障膜係由下述者所形成:從鎢、鉬及鈮中選出之1種以上的金屬元素;對無電解鍍覆具有觸媒能力之金屬元素;以及以與前述從鎢、鉬及鈮中選出之1種以上的金屬元素之氮化物的形態被含有之氮,其中,前述防止銅擴散用阻障膜,係含有:10至30原子%之對無電解鍍覆具有觸媒能力之金屬元素;以及60至75原子%之從鎢、鉬及鈮中選出之1種以上的金屬元素;其餘為氮。
- 如申請專利範圍第1項之基板,其中,前述對無電解鍍覆具有觸媒能力之金屬元素,為從鉑、金、銀、鈀中選出之1種以上。
- 如申請專利範圍第1或2項之基板,其中,於前述防止銅擴散用阻障膜上,具有:以前述具有觸媒能力之金屬元素作為觸媒,並藉由無電解鍍銅所形成之銅晶種層。
- 如申請專利範圍第1或2項基板,其中,於前述防止銅擴散用阻障膜上,具備:以前述具有觸媒能力之金屬元素作為觸媒,並藉由無電解鍍銅所形成之銅晶種層;且復具有:形成於該銅晶種層上之金屬鑲嵌銅線路。
- 一種基板的製造方法,其特徵為:使用含有從鎢、鉬及鈮中選出之1種以上的金屬元素、以及對無電解鍍覆具有觸媒能力之金屬元素之靶材,於氮氣環境中進行濺鍍,而於基材上形成防止銅擴散用阻障膜,此防止銅擴 散用阻障膜係由下列者所形成:從鎢、鉬及鈮中選出之1種以上的金屬元素;對無電解鍍覆具有觸媒能力之金屬元素;以及以與前述從鎢、鉬及鈮中選出之1種以上的金屬元素之氮化物的形態被含有之氮,其中,前述防止銅擴散用阻障膜,係含有:10至30原子%之對無電解鍍覆具有觸媒能力之金屬元素;以及60至75原子%之從鎢、鉬及鈮中選出之1種以上的金屬元素;其餘為氮。
- 如申請專利範圍第5項之基板的製造方法,其中,前述對無電解鍍覆具有觸媒能力之金屬元素,為從鉑、金、銀、鈀中選出之1種以上。
- 如申請專利範圍第5或6項之基板的製造方法,其中,於前述防止銅擴散用阻障膜上,以前述具有觸媒能力之金屬元素作為觸媒,並藉由無電解鍍銅形成銅晶種層。
- 如申請專利範圍第5或6項之基板的製造方法,其中,於前述防止銅擴散用阻障膜上,以前述具有觸媒能力之金屬元素作為觸媒,並藉由無電解鍍銅形成銅晶種層,再於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。
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