WO2010057747A1 - Procédé pour prétraiter des substrats pour procédé pvd - Google Patents
Procédé pour prétraiter des substrats pour procédé pvd Download PDFInfo
- Publication number
- WO2010057747A1 WO2010057747A1 PCT/EP2009/064137 EP2009064137W WO2010057747A1 WO 2010057747 A1 WO2010057747 A1 WO 2010057747A1 EP 2009064137 W EP2009064137 W EP 2009064137W WO 2010057747 A1 WO2010057747 A1 WO 2010057747A1
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- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- current
- spark
- target
- electrode
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000000758 substrate Substances 0.000 title claims description 224
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000001704 evaporation Methods 0.000 claims abstract description 24
- 230000008020 evaporation Effects 0.000 claims abstract description 23
- 238000004381 surface treatment Methods 0.000 claims abstract description 4
- 238000009489 vacuum treatment Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 65
- 150000002500 ions Chemical class 0.000 claims description 61
- 230000008569 process Effects 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000013077 target material Substances 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 8
- 150000001247 metal acetylides Chemical class 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000010349 pulsation Effects 0.000 claims 1
- 239000012495 reaction gas Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 40
- 238000000576 coating method Methods 0.000 description 40
- 238000005530 etching Methods 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 229910021645 metal ion Inorganic materials 0.000 description 16
- 238000009792 diffusion process Methods 0.000 description 15
- 238000004544 sputter deposition Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000011651 chromium Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000010849 ion bombardment Methods 0.000 description 8
- 229910052756 noble gas Inorganic materials 0.000 description 8
- 238000005240 physical vapour deposition Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000992 sputter etching Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 239000011364 vaporized material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 238000000168 high power impulse magnetron sputter deposition Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000013078 crystal Substances 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
- 230000006870 function Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910010037 TiAlN Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RHBRWKIPYGZNMP-UHFFFAOYSA-N [O--].[O--].[O--].[Al+3].[Cr+3] Chemical compound [O--].[O--].[O--].[Al+3].[Cr+3] RHBRWKIPYGZNMP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
-
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/0635—Carbides
-
- 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
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
-
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/228—Gas flow assisted PVD 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32055—Arc discharge
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32055—Arc discharge
- H01J37/32064—Circuits specially adapted for controlling the arc discharge
Definitions
- the invention relates to a method for the pretreatment of substrates, as can usually be carried out before the coating of substrates by means of PVD.
- Cathodic arc evaporation is a process that has been established for years and is used for the coating of tools and components. It is used to deposit wide-ranging metallic layers as well as metal nitrides, metal carbides and metal carbonitrides.
- the targets are cathode of a spark discharge operated at low voltages and high currents and with which the target (cathode) material is vaporized.
- DC power supplies are used.
- the high degree of ionization has a particularly advantageous effect when it is coupled to the substrate during the layer synthesis with a negative bias, thereby increasing and varying the acceleration and the energy of the ions toward the substrate can be.
- the layers synthesized in this way have a higher density and can be influenced by the change in the bias voltage some layer properties such as the stress of the layer and the layer morphology.
- the spark evaporation is also known that the vaporized material, depending on its melting point, more or less many splashes, which are generally undesirable.
- This proportion of spatter is usually not taken into account when specifying the degree of ionization of the vaporized material, but can significantly affect the coating quality. It is therefore desirable to reduce the proportion of spatters in the vaporized material by a special source magnetic field or additional filters (mechanical and electromagnetic as described in Aksenov, 1.1 et al., Sov J. Plasma Phys., 4 (4) (1978) 425). or reduced by other process parameters, such as increased reactive gas pressure. Also, the use of higher melting materials is proposed to reduce spatter numbers and size.
- the ionized portion of the vaporized material observed in the spark evaporation can also be used to pretreat substrates. With a successive increase in the substrate bias voltage, their bombardment by the vapor ions of the vaporized material and of the working gas can be driven so far that the substrates can be sputtered and / or heated to high temperatures.
- this process step is referred to as metal ion etching, a somewhat inaccurate designation, since it does not conceptually include the ions produced by the usual or necessary use of a working or reactive gas.
- a working gas ions often a noble gas such as argon is used
- noble gases can not be stably built up in layers because they do not bind and, in addition, cause tension.
- a continuous operation of the spark source without gas addition working gas or reactive gas
- sparks sources need to be operated without working gas, such as the ion sources for ion implantation, they are pulsed, ie the source has to be re-ignited time and time again, as the sparks only "live” for a short time, if no gas is added Operation is described in JP 01042574.
- etching by means of metal ions can lead to different treatment results on the substrate surface than is the case with a simple heating of the substrate or also by heating the substrate by means of electron bombardment, as described for example in US Pat. No. 5,050,337 to Sablev , Alone the use of metal ions in comparison to noble gas ions give new reaction possibilities, eg. As in the formation of carbides or mixed crystals.
- a well-known filter design goes to the works of Aksenov, II et al., Sov. J. Plasma Phys. 4 (4) (1978) 425, wherein the spark source is flanged to the coating chamber via a tube which encloses a magnetic field and which has a 90 ° angle.
- the magnetic field guides the electrons on a curved path and these in turn force the ions into a similar curved path via electrical forces.
- the uncharged splashes impact the inner wall of the tube and are thus prevented from reaching the substrate.
- the resulting rate loss plays a minor role.
- the usable diameter of the tube passing from the tube into the coating chamber has only a few centimeters to about 10 cm in diameter. For many applications, this requires a movement of the substrate in front of the source, so that sufficient uniformity of the etching process can be ensured. This precludes this method for normal batch coating systems, which are common for production.
- a disadvantage of this method is that at the target a much larger magnetic field is necessary so that a magnetron can be ignited.
- this stronger magnetic field leads disadvantageously again to the fact that the ions generated in the high-energy pulse are trapped and only a small part of them reaches the substrate.
- a far greater disadvantage of this method is the incompatibility of the HIPIMS-MIE method with the PVD coating in the sense that it is usually not possible to use these sources for the actual coating.
- the coating rates in the HIPIMS process are so low that in most If additional sources of coating need to be used and one can not fall back on the HIPIMS sources for a coating. This is in contradiction to an increase in productivity in the production systems.
- the sputtering process also requires a noble gas such as argon as the working gas.
- the unfiltered sparks produce a large number of spatters, sometimes with large diameters, depending on the target material. These spatters do not have enough energy to react fully chemically with the constituents of the substrate surface or to be incorporated into the substrate surface.
- the sparks are the big splashes that cause problems because they do not have enough energy to diffuse into the substrate after hitting the substrate surface or to perform chemical reactions with the substrate surface components. Otherwise, the spark evaporation with its ability to generate multiply charged ions would be ideally suited to carry out the substrate pretreatment by means of metal ion etching.
- spark evaporation sources can also be pulsed to deposit layers.
- a pulse current is superimposed on a continuous holding current.
- the pulsing of the sources leads to a reduction of the especially large splashes in the layer deposition.
- the pulsing of the cathodic spark sources, without continuously operating them, so to ignite again and again with each pulse leads to a higher ion current, which is mainly due to an increase in the proportion of multiply charged ions Oks, EM et al., Rev. Sei. Instrum. 77 (2006) 03B504.
- the object of the invention is to provide a zero coating rate despite the presence of spark coating sources, i. Achieving a state of equilibrium between material buildup and material removal on / to the surface, and the ability to control this state of equilibrium through the substrate bias. Furthermore, it is an object of the present invention to provide a substrate pretreatment, which is based on the bombardment of the substrate surface with ions, which consist to a significant extent of metal ions and reactive gas ions and can be completely dispensed with a working gas in the extreme case.
- Another object of this invention is to diffuse these ions into the substrate surface and to chemically react those ions with constituents of the substrate surface.
- Another object of this invention is to cure substrate changes caused by previous steps, such as cobalt depletion of the substrate surface by wet-chemical substrate cleaning.
- a method for the surface treatment of workpieces in a vacuum treatment plant with a first electrode designed as a target Part of an Arcverdampfungs provoke, wherein over the first electrode, a spark is operated with spark current through which material is evaporated from the target which deposits at least partially and temporarily on the workpieces and with a second electrode, which is designed as a workpiece holder and together with the workpieces Biaselektrode forms, wherein to the bias electrode by means of a voltage supply, a bias voltage is applied such that the bias voltage is so matched with the spark current that net substantially no material build-up takes place on the surface.
- the method according to the invention is then characterized in that the first electrode is operated with pulsed current, wherein the pulsing leads to a substrate current that is increased by the workpiece surface compared to the unpulsed operation and thus no material build-up on the green electrode even when the first electrode of lower bias voltage is operated unpulsed Surface takes place.
- WO2006099760 and WO2007131944 describe operating the pulsed current spark source as an essential factor to keep the cathode surface free of opaque oxide layers and to ensure stable spark discharge.
- the spark current By pulsing the spark current to which special power supplies are required, the spark is constantly redirected across the target, preventing it from moving only in preferred areas, and covering the remaining target areas with thick oxide, such as the spark being conducted ("Steed arc") is the case.
- the pulsing of the current of the spark source thus leads in part to a similar result as the operation of the spark source Ie with a magnetic field causes, namely a distraction of the spark, which prevents it to stay in one place for too long and there is greater melting of the target and thus to an increased spattering.
- the pulsed operation of the spark sources can take place both as pulses of the current of the individual spark source and as “dual pulses" between two spark sources, whereas the first mode only (if at all) requires a slightly modified electrical supply compared to the normal DC supply and is therefore inexpensive, requires the "dual pulses" ia an additional electrical supply, which is connected between two sources, as is apparent from WO2007131944. But this operation allows much higher frequencies during pulsed operation, which can be realized with steeper current increases.
- Damage to the substrate caused by the wet cleaning of the substrates (ex situ) are cured. This refers in particular to the depletion of cobalt at the substrate surface.
- the invention also relates to the modification of the substrate surface by the incorporation or chemical reaction of atoms of the vapor phase with atoms / constituents in the outermost substrate surface, with the aim of producing a stable compound which ensures much better chemical, thermal and mechanical stability ,
- the invention also relates to the formation of a thin intermediate layer in the substrate surface which forms an intimate one Making connection between the substrate and applied layer and the additional functions as a diffusion barrier layer or chemical barrier layer takes over.
- the invention can also be used between layers having different properties which can not or only insufficiently be produced by a gradient transition and for which the thinnest possible interface with extremely good adhesion is desired, e.g. between materials as diverse as oxides, carbides, nitrides, and metallic layers.
- This new method has particular advantage where oxide layers are to be connected to metallic layers, metal carbides, metal nitrides or metal carbonitrides. This means that this process is used primarily where layers with very different properties are to be intimately bonded, for example, in the direct deposition of oxide layers on hard metal or in the transition from oxides to nitrides in multilayer coating systems.
- the new process is also advantageously used where layers of different crystalline phases are to be bonded to one another with good adhesion.
- this invention aims at producing stable bonds between the incident ions and the constituents of the substrate surface in the outermost substrate surface, in particular for those components of the substrate surface which are mechanically or chemically unstable in their own right and for adhesion problems lead the later applied layer.
- the invention describes neither a conventional etching nor a coating, but rather a balance between these processes and that the treatment is carried out with the intention of triggering chemical reactions only on and / or in the immediate vicinity of the substrate surface and that the pretreatment is virtually complete with zero growth or only very small growth of the layer.
- an economical solution is realized that can be used in production systems based on the spark evaporation sources.
- the macroscopic spatters when operating the spark sources can be reduced with the invention.
- the method according to the invention has a broad and easily controllable process window.
- FIG. 1 a PVD coating system, each with its own pulsed spark sources;
- FIG. 2a shows the DC spark current
- FIG. 2b shows the pulsed spark current
- FIG. 3a shows a substrate current in the case of the DC spark current
- FIG. 3b shows the substrate current in the case of the pulsed spark current
- FIG. 4 shows a PVD coating installation for the dual-pulse method
- FIG. 5a shows the spark current which flows through a spark source in DC operation
- Figure 5b the spark current in the superposition of the spark source with bipolar pulses
- FIG. 6a the substrate current in DC spark operation
- FIG. 6b shows the substrate current in bipolar mode
- FIG. 7 shows schematically the relationship between Matarialauf- and - degradation depending on spark current and the Substratbias
- FIG. 8 shows a measured value table for pulsed spark current
- FIG. 9 shows a measured value table for pulsed spark current
- Figure 10 a table showing the average ionic current and the evaporation rate.
- FIG. 1 shows a PVD coating system (1, batch system), as used for coating using sparks sources.
- the coating installation 1 is connected to a pumping station 4 (not shown), which generates the process-related vacuum in the installation.
- the substrate holding ments 2 and 3 serve to receive the substrates (tools or components or other components) and to support them during the pretreatment and coating.
- the substrate holders, and thus the substrates themselves, can be applied to a voltage during the pretreatment and coating by means of a substrate bias supply 5 so that they are exposed to either ion bombardment (negative voltage) or electron bombardment (positive voltage).
- the substrate bias supply can be a DC, an AC or a bipolar or unipolar substrate voltage supply.
- the coating takes place by means of spark sources. These spark sources include a target 6 whose material is vaporized by the spark.
- the source magnetic field produced by the magnets 7 determines whether a spark is guided on a certain path (so-called “steered arc"), for example to reduce spatter, or whether the spark can move more or less freely on the target surface (so-called “sputtering"). "Random arc”), which usually results in a better target utilization and a higher evaporation rate.
- the operation of the spark may be in a working gas, which is usually a noble gas. Usually argon is used.
- the operation can also be carried out from a mixture of working gas and a reactive gas or alone in the reactive gas.
- the reactive gas reacts with the sputtered target material and thus forms the corresponding nitrides, oxides, carbides and mixtures thereof.
- the gases may be introduced through the plant either through a common gas inlet 8 or through various gas inlets, and the process pressure and gas composition in the treatment chamber may be controlled via gas flow meters.
- a detonator 9 or other electrical detonator may be used to ignite the spark on the target. With the diaphragm 10, the target can be completed so that, despite spark evaporation, no vaporized target material reaches the substrate.
- the spark current to Spark evaporation is provided by the power supply 11.
- the supply is an ordinary DC power supply.
- a pulsed power supply was used, as is common in pulse welding. This can be superimposed on a constant DC current another pulse current. It is important that between the pauses the current does not become completely zero, but remains on a large (pause current) that does not extinguish the spark.
- a Cr target for spark evaporation was first selected.
- the Cr target was operated in the working gas argon with an argon gas flow of 300 sccm and with a DC source current of 140 A.
- the current rise times were kept constant by choosing a setting of 1000 A / ms on the power supply.
- the substrate current was measured in all subsequent experiments for a typical and unchanged substrate support, ie as total. It must be added here that there can be a small error in the measurement of the total (integral) current that results from the fact that not all ions are collected at the substrate holders and also hit the chamber wall.
- the pulsing of the spark current leads to an increase of the substrate current
- the influence of the pulsing of the spark current on the substrate current was also investigated for the operation of the spark sources in pure reactive gas, in this case in oxygen.
- the DC operation of the spark sources was again used and worked with Cr targets and an oxygen flow of 250 sccm. This resulted in a mean substrate current of 1.7 A (also Table 1).
- a mean substrate current of 3.5 A was measured.
- the average spark currents for DC and pulses were equal, namely 140 A.
- the ion current peak at the substrate was 58 A.
- FIGS. 2a and 2b show the time profiles of these two currents, the spark current being arbitrarily negatively applied here.
- Figure 2a shows the DC spark current
- Figure 2b shows the pulsed spark current.
- Figures 3a and 3b The total substrate currents measured for this operation are shown in Figures 3a and 3b, where the ion current component of the substrate current is negative, the electron current positive.
- Figure 3a shows the substrate current for the DC spark current case
- Figure 3b shows the substrate current for the AC spark current case.
- the substrate was operated with a bipolar substrate bias (about 25 kHz). During DC operation, it is possible to clearly distinguish the ion current (shown negatively) from the electron current (positive axis). If one integrates over the substrate current (that is, over the negatively represented current), a time average of 2.8 A is obtained. For operation with pulsed spark current, the superimposition of the spark current frequency (about 700 Hz) is reflected with the pulse frequency of the substrate bias in the current curve of the Substrate current reflected. If one also mediates the substrate current (negative value range), this results in a mean ion current of 4.9 A, ie one can achieve almost a doubling of the substrate current by pulsing the spark source.
- the frequency of the Substratbiasmakers is approximately 25 kHz substantially higher than that of the source power supply (about 700 Hz).
- Reasonable pulse frequencies of the source power supply are between IHz and 5kHz. Preferably pulse frequencies between 500Hz and 2kHz are used. This superposition is also seen in the substrate current during the pulsing of the source current.
- the bipolar pulsed bias slightly reduces the total substrate current over DC bias.
- a drastic increase in the substrate current in the pulse peak is obtained if the two supplies are synchronized.
- the bias voltage should be shifted in time relative to the peak of the source current so that the time of flight of the ions from the target to the substrate is taken into account.
- This operation is advantageous for the MIE since short-time ion bombardment with very high energies can be achieved.
- this means a little extra work for the synchronization of the supplies, especially for operation in batch systems with different loads. Therefore, synchronization is generally omitted if it does not lead to significant disadvantages in the process.
- the result shows that it is much easier, in the pulsed operation of the spark sources, to drastically increase the removal rate at approximately the same evaporator power, which is defined by the average current, and thus to reach the zero-layer growth range.
- the substrate bias can be operated as DC voltage.
- an AC operation usually reduces the substrate current slightly, it can effectively prevent an unwanted spark from being pulled from the substrate.
- small duty cycle help to prevent such unwanted sparking.
- MAG B weak target magnetic field
- pulsed operation contributes to achieving zero-layer growth even with lower substrate bias, because the substrate current can be increased.
- FIG. 4 now shows a process approach ("Dual Pulse Method") suitable for realizing very high pulse rates even for large currents, using a bipolar voltage or current supply (13, not to be confused with bipolar)
- the advantage of such an arrangement is that the bipolar supply is operated in the pre-ionized plasma of the two spark-evaporation sources, which enables a very fast pulsing of the plasma
- the magnitude of the bipolar current of the supply 13 need only be adjusted so that the resulting total current through the spark source is not below the holding current. ie the spark is not t extinguished, but can be operated continuously.
- the spark current flowing through a spark source in DC mode is shown again. It was worked with 200 A and again in pure oxygen reactive gas and again with targets of Al / Cr composition 70at% / 30at%.
- Figure 5b shows the spark current, if the spark source is superimposed with bipolar pulses and it detects the pulses of the spark current between 50 A and 350 A with a frequency of 25 kHz. This corresponds to a mean time average of 200 A.
- the corresponding substrate ion current in DC spark operation ( Figure 6a) was again compared to that of bipolar operation ( Figure 6b).
- the current slew rates are frequency-dependent and are at this frequency in the magnitude of 10 6 A / s. However, this current slew rate can easily be further increased by increasing the frequency to 100 kHz or 500 kHz.
- the "dual pulsing" of the sources also results in a significant increase of the substrate current, as can be seen from the comparison of Figures 6a and 6b
- the average substrate current increases from 3.8 A for the DC operation of the spark sources to 6 A during the pulsing, ie by about 50 %.
- the etching rate increases to 23 nm / min at the substrate bias of 800 V or a substrate bias of about 200 V can be used to achieve equilibrium between coating and etching to work.
- pulsing the sources not only increases the substrate current, it also affects the movement of the cathode spot, and with the pulsing, the cathode spot deflects.
- the strong current changes during pulsing cause electromagnetic fields that are sufficiently large to influence the sparking.
- a positive aspect of this is a reduction in the number of large metallic splashes, which is due to the shorter residence time of the spark in one location.
- the increase of the substrate current is also from the point of view that it is possible to work with smaller average source currents. It is known to those skilled in the art that a reduction of the source current is also accompanied by a spatter reduction.
- the cathodic spark evaporation is ideal for reactive processes.
- the regulation of the reactive gas is very simple and it is possible to work in the excess of reactive gas without target poisoning occurring.
- a working gas such as argon
- pure reactive gas such as nitrogen or oxygen.
- the reactive gases are also ionized in addition to the metals and these can also be used to "treat" the substrate surface.
- the metal ion etching is theoretically not sufficiently studied, at least with regard to the multiply charged ions that arise in the pulsed operation of the spark sources, the sputtering effects with the diffusion processes, an implantation in the outermost substrate surface and the reactions of the multiply charged ions on the substrate surfaces to weigh exactly against each other.
- the sputtering effects with the diffusion processes an implantation in the outermost substrate surface and the reactions of the multiply charged ions on the substrate surfaces to weigh exactly against each other.
- purely empirically one can observe a markedly improved adhesion of PVD layers on metallic substrates as a result of the process. This is especially true for HSS and especially for carbide substrates.
- a calibration was therefore always carried out in a first step in such a way that for a specific target material the source current, the source current pulse form, the source magnetic field, the substrate bias, the working gas pressure and / or the reactive gas pressure a process window was set so that no or only a layer growth of less than 20 nm on the substrates was measured over a period of time between 30 s and 10 min depending on the loading of the plant.
- a process window was set so that no or only a layer growth of less than 20 nm on the substrates was measured over a period of time between 30 s and 10 min depending on the loading of the plant.
- metallic substrates but also silicon wafer wafers were treated in the plant for analysis purposes. On the silicon wafers it is particularly easy to measure even small layer thicknesses by means of the RBS analysis known to the person skilled in the art.
- the procedure was such that the smallest possible source current was operated with the steepest possible pulses in order to obtain a high yield of multiply charged ions. Then the layers measured at such source (s) operation and for various bias voltages, typically between 40V and 1200V, were measured. From the dependence thus obtained, the process parameters were chosen so as to set approximately zero growth ( ⁇ 5 nm) on the substrate.
- the multiple entry of energy of the multiply charged ions also leads to chemical reactions. However, as already mentioned, it is not the material removal that is the goal of the substrate pretreatment in this invention, but the promotion of a chemical reaction.
- the chromium ions now have sufficiently high energy, they can be used, for example, in a carbide substrate (indexable cutting insert), which consists predominantly of tungsten carbide and small amounts of elementary tungsten and carbon and typically also contains cobalt as binder, to form crom carbides and / or Formation of mixed crystals of Cr, Co and W come.
- the greater the proportion of chromium ions the more likely carbide formation is.
- the proportion of multiply charged ions makes a major contribution, since they can contribute several times as much energy and thus penetrate into the substrate and can also react with components that are located somewhat deeper.
- a phase analysis by X-TEM revealed the existence of carbide phases with chromium. While these chromium carbide phases already showed little substrate current increase, in the case of titanium higher substrate currents or higher substrate bias had to be used to detect carbide formation.
- the spark sources helps in two ways. On the one hand, it increases the substrate current because it creates multiply charged metal ions, and on the other hand, it also increases the chemical reactivity of the reactive gas through its higher ionization. This not only leads to chemical reactions with the metal gas ions and components of the substrate surface, but also to reactions between, for example, nitrogen with the components of the substrate surface to form nitrides.
- the substrate pretreatment with oxygen as a reactive gas also showed u.a. for non-metallic substrates, such as oxide ceramics, significant improvement in the layer adhesion, especially when applying oxidic layers.
- This process can be supported by applying an RF substrate bias.
- the inventor was able to find out that the described method according to the invention contributes to the fact that a diffusion of the cobalt to the substrate surface can be initiated and thus the damage of the wet-chemical pretreatment can be largely compensated. Until now, the damaged layer had to be removed by a longer etching step in the coating chamber, so that the layer adhesion could be ensured. As the inventor has further found, this annealing process is very effective, especially in the case of cutting edges and in particular for indexable inserts, due to the increased ion bombardment at the cutting edge of the substrates.
- One possible explanation is that the increase in ion bombardment caused by the field enhancement when applying a bias to geometries with a small edge radius. This has been explained here using the example of cobalt diffusion, but essentially also applies to other types of thermally controlled "annealing processes" at the substrate surface.
- Another advantageous application relates to carbide phases of tungsten.
- carbide phases of tungsten (so-called eta phase, Ref US 04830886) are brittle and responsible are for poor adhesion of a subsequently applied hard material layer.
- the inventor has found that with the aid of the method according to the invention, it is possible to convert unstable carbon compounds and unbound carbon by the high-energy metal ions used in the process into stable carbides or mixed crystals.
- the inventor has found that diffusion of, for example, Ti into the outermost layers of the substrate surface advantageously affects the adhesion of a hard material layer, which also contains Ti, such as TiN, TiCN or TiAlN.
- This diffusing in of target atoms into the substrate is particularly advantageous if well-adhering transitions to hard material layers with very different physical and mechanical properties are to be realized, such as, for example, a direct deposition of aluminum oxide or aluminum chromium oxide or boron nitride or silicon nitride on the cemented carbide. This provides a very good and inventive process for coating cemented carbide with these layers.
- this method of indiffusion can also be used in the transitions in multilayer coating systems. It is of great advantage that the energy of the incident ions can be kept restricted above all to the area of the substrate surface, and that a customary pretreatment step usually takes only a few minutes, although on the substrate surface and optionally again on the cutting edge, but does not lead to excessive thermal stress on the entire substrate.
- targets of the materials can be used, which are then also used to synthesize the hard material layer, i. the diffusion processes and the chemical reactions are already carried out with materials that later recur in the layer.
- alloy targets and various reactive gases in this method in order to initiate chemical reactions and diffusion processes in a targeted manner.
- the pretreatment step may also be used to, for example, convert metallic constituents in the substrate surface into compounds having a high temperature stability and selectively influencing the nucleation behavior of the layer to be deposited, using a reactive gas.
- a reactive gas for example, the formation of corundum phases on aluminum or chromium should be mentioned here.
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Abstract
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JP2011536809A JP2012509402A (ja) | 2008-11-18 | 2009-10-27 | Pvd法のための基材前処理方法 |
BR122012006619-2A BR122012006619B1 (pt) | 2008-11-18 | 2009-10-27 | método de revestimento de peças de trabalho e método de produção de um sistema multicamada |
CA2743988A CA2743988A1 (fr) | 2008-11-18 | 2009-10-27 | Procede pour pretraiter des substrats pour procede pvd |
RU2011124154/02A RU2519709C2 (ru) | 2008-11-18 | 2009-10-27 | Способ предварительной обработки подложек для способа нанесения покрытия осаждением паров |
BRPI0914364-5A BRPI0914364B1 (pt) | 2008-11-18 | 2009-10-27 | método de pré tratamento de susbtratos para processos pvd e seu uso |
AU2009317432A AU2009317432B2 (en) | 2008-11-18 | 2009-10-27 | Method for pretreating substrates for PVD methods |
US13/130,050 US20110278157A1 (en) | 2008-11-18 | 2009-10-27 | Method for pretreating substrates for pvd methods |
MX2011005039A MX2011005039A (es) | 2008-11-18 | 2009-10-27 | Metodo para el tratamiento previo de sustratos para procesos de deposicion fisica de vapor (pvd). |
CN2009801458404A CN102216486B (zh) | 2008-11-18 | 2009-10-27 | 对用于pvd方法的衬底进行预处理的方法 |
SG2011044757A SG172251A1 (en) | 2008-11-18 | 2009-10-27 | Method for pretreating substrates for pvd methods |
US14/075,085 US9845527B2 (en) | 2008-11-18 | 2013-11-08 | Method for pretreating substrates for PVD methods |
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EP09004581A EP2236641B1 (fr) | 2009-03-30 | 2009-03-30 | Procédé de traitement préalable de substrats pour le procédé de PVD |
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EP (1) | EP2236641B1 (fr) |
JP (2) | JP2012509402A (fr) |
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