TWI654623B - Laminated wiring film, manufacturing method thereof, and molybdenum alloy sputtering target - Google Patents
Laminated wiring film, manufacturing method thereof, and molybdenum alloy sputtering targetInfo
- Publication number
- TWI654623B TWI654623B TW106141730A TW106141730A TWI654623B TW I654623 B TWI654623 B TW I654623B TW 106141730 A TW106141730 A TW 106141730A TW 106141730 A TW106141730 A TW 106141730A TW I654623 B TWI654623 B TW I654623B
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- atomic
- sputtering target
- molybdenum alloy
- intermediate film
- Prior art date
Links
- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 42
- 238000005477 sputtering target Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 32
- 238000004544 sputter deposition Methods 0.000 claims description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims description 23
- 239000011733 molybdenum Substances 0.000 claims description 23
- 239000010955 niobium Substances 0.000 claims description 23
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 23
- 229910052758 niobium Inorganic materials 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 16
- 229910052715 tantalum Inorganic materials 0.000 claims description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000010408 film Substances 0.000 description 232
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- 239000011229 interlayer Substances 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005546 reactive sputtering Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000001803 electron scattering Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- YXLXNENXOJSQEI-UHFFFAOYSA-L Oxine-copper Chemical compound [Cu+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 YXLXNENXOJSQEI-UHFFFAOYSA-L 0.000 description 1
- HMXCSHJQBPUTDP-UHFFFAOYSA-N [Mo].[Cu].[Ni] Chemical compound [Mo].[Cu].[Ni] HMXCSHJQBPUTDP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002438 flame photometric detection Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QUWPZPLTANKXAM-UHFFFAOYSA-N niobium(5+) Chemical compound [Nb+5] QUWPZPLTANKXAM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28079—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being a single metal, e.g. Ta, W, Mo, Al
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- 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
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates 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
- 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
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates 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
- 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
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0003—Apparatus or processes specially adapted for manufacturing conductors or cables for feeding conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by physical means, e.g. sputtering, evaporation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01042—Molybdenum [Mo]
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
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- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Manufacturing & Machinery (AREA)
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- Metallurgy (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
本發明提供一種可應對用以使高精細的平面顯示元件的顯示品質提高所必需的、電極或配線膜的低反射的要求的積層配線膜和其製造方法，以及用以形成擔當低反射的中間膜的鉬合金膜的鉬合金濺鍍靶材。一種積層配線膜，其具有積層結構，所述積層結構於透明基板上或形成有透明膜的透明基板上形成有膜厚為30nm~70nm且包含鉬合金的中間膜，且於該中間膜正上方形成有比電阻為15μΩ．cm以下的導電膜，所述積層配線膜自所述透明基板側測定的可見光反射率為15%以下；及一種用以形成中間膜的鉬合金濺鍍靶材。 The present invention provides a laminated wiring film capable of responding to a low reflection of an electrode or a wiring film necessary for improving the display quality of a high-definition flat display element, a method for manufacturing the same, and a method for forming a low reflection intermediate. Film molybdenum alloy film Molybdenum alloy sputtering target. A laminated wiring film having a laminated structure. The laminated structure is formed on a transparent substrate or a transparent substrate formed with a transparent film. An intermediate film having a thickness of 30 nm to 70 nm and containing a molybdenum alloy is formed directly above the intermediate film. Formed with a specific resistance of 15 μΩ. a conductive film of less than cm, the visible light reflectance of the laminated wiring film measured from the transparent substrate side to 15% or less; and a molybdenum alloy sputtering target for forming an intermediate film.
Description
本發明是有關於一種積層配線膜和其製造方法以及鉬(Mo)合金濺鍍靶材，所述積層配線膜可用於要求低反射率特性的、例如平面顯示元件用的電極膜或配線膜且包括導電膜與中間膜，所述鉬合金濺鍍靶材用以形成所述中間膜。 The present invention relates to a multilayer wiring film, a method for manufacturing the same, and a molybdenum (Mo) alloy sputtering target. The multilayer wiring film can be used for an electrode film or a wiring film for a flat display element that requires low reflectance characteristics, and The conductive film and the intermediate film are included, and the molybdenum alloy sputtering target is used to form the intermediate film.
於透明的玻璃基板等上形成薄膜器件的液晶顯示器(以下稱為「LCD(Liquid Crystal Display)」)、電漿顯示面板(以下稱為「PDP(Plasma Display Panel)」)、電子紙等中所利用的電泳型顯示器等平面顯示裝置(平板顯示器，以下稱為FPD(Flat Panel Display))伴隨大畫面、高精細、高速響應化而對其配線膜要求低電阻值(以下稱為「低電阻」)。而且，近年來開發出了對FPD加入操作性的觸控面板、或者使用透明的樹脂基板或極薄玻璃基板的可撓性的FPD等新的製品。 Liquid crystal displays (hereinafter referred to as "LCD (Liquid Crystal Display)"), plasma display panels (hereinafter referred to as "PDP (Plasma Display Panel)"), electronic paper, etc., forming thin film devices on transparent glass substrates, etc. Flat display devices such as electrophoretic displays (Flat Panel Display, hereinafter referred to as FPD (Flat Panel Display)) require low resistance values (hereinafter referred to as "low resistance") for their wiring films with large screens, high definition, and high-speed response ). In addition, in recent years, new products have been developed, such as a touch panel that is operable with FPD, or a flexible FPD that uses a transparent resin substrate or an extremely thin glass substrate.
近年來，一直用作FPD的驅動元件的薄膜電晶體(Thin Film Transistor：以下稱為「TFT」)的配線膜為了達成所述高性能化而必需低電阻值，作為導電膜的材料而使用鋁(Al)或銅(Cu)。 In recent years, a thin film transistor (Thin Film Transistor: hereinafter referred to as a "TFT") wiring film that has been used as a driving element of an FPD requires a low resistance value in order to achieve the above-mentioned high performance. Aluminum is used as a material for the conductive film. (Al) or copper (Cu).
現在，於TFT中使用的是矽(Si)半導體膜，若作為導電膜材料的鋁或銅與矽直接接觸，則存在因TFT製造中的加熱步驟而發生熱擴散，使TFT的特性劣化的情況。因此，使用如下的積層 配線膜：於鋁或銅的導電膜與半導體膜的矽之間，設置有耐熱性優異的純鉬或鉬合金等的金屬膜作為阻隔(中間)膜。 Currently, silicon (Si) semiconductor films are used in TFTs. If aluminum or copper, which is a conductive film material, is in direct contact with silicon, thermal diffusion may occur due to a heating step in TFT manufacturing, which may degrade TFT characteristics. . Therefore, use the following buildup Wiring film: Between the conductive film of aluminum or copper and the silicon of the semiconductor film, a metal film such as pure molybdenum or molybdenum alloy with excellent heat resistance is provided as a barrier (intermediate) film.
一邊查看FPD的畫面一邊賦予直接的操作性的觸控面板基板畫面的大型化亦在發展，於智慧型手機或平板型個人電腦(personal computer，PC)、以及桌上型PC等中亦進行觸控操作的製品正在普及。於該觸控面板的位置檢測電極中，通常使用作為透明導電膜的銦-錫氧化物(Indium Tin Oxide：以下稱為「ITO」)膜。 The size of the touch panel substrate screen, which gives direct operability while viewing the screen of the FPD, is also being developed. Touch screens are also used in smart phones, tablet personal computers (PCs), and desktop PCs. Controlled products are gaining popularity. As the position detection electrode of the touch panel, an indium-tin oxide (Indium Tin Oxide: hereinafter referred to as "ITO") film as a transparent conductive film is generally used.
近年來，於可進行多點檢測的靜電電容式的觸控面板中形成為配置有四角形的ITO膜的俗稱金剛石(diamond)配置，於連接四角形的ITO膜的電極或配線膜中亦使用所述金屬膜。於該金屬膜中使用的是容易獲得與ITO膜的接觸性的鉬合金或鉬合金與鋁的積層配線膜。 In recent years, a quadratic ITO film is commonly referred to as a diamond configuration in an electrostatic capacitance type touch panel capable of multi-point detection, and the same is also used for electrodes or wiring films connected to the quadrilateral ITO film. Metal film. For this metal film, a molybdenum alloy or a laminated wiring film of molybdenum alloy and aluminum that can easily obtain contact with the ITO film is used.
作為耐熱性、耐腐蝕性、與基板的密接性優異的低電阻的金屬膜，本發明者於專利文獻1中提出了使鉬中含有3原子%~50原子%的釩(V)或鈮(Nb)，進而添加有鎳(Ni)或銅的金屬膜。 As a low-resistance metal film excellent in heat resistance, corrosion resistance, and adhesion to a substrate, the inventor proposed in Patent Document 1 that molybdenum contains 3 to 50 atomic percent of vanadium (V) or niobium (V) Nb), and further a metal film of nickel (Ni) or copper is added.
另一方面，為了對包含低電阻的銅的導電膜的表面進行保護，例如於專利文獻2或專利文獻3中提出了由作為金屬膜的鎳-銅合金被覆的積層配線膜。 On the other hand, in order to protect the surface of a conductive film containing copper having low resistance, for example, Patent Document 2 or Patent Document 3 proposes a multilayer wiring film covered with a nickel-copper alloy as a metal film.
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1] 日本專利特開2004-140319號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2004-140319
[專利文獻2] 日本專利特開2011-52304號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2011-52304
[專利文獻3] 日本專利特開2006-310814號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2006-310814
於作為成為近年主流的全高清(full hi-vision)的代替品的具有四倍畫素的大型4K電視(4K-TV)、或以距視點數十公分左右的近距離對顯示畫面進行操作的智慧型手機中，高精細化正在發展。伴隨該高精細化，由入射光引起的金屬膜的反射使顯示品質下降這一新問題開始顯現。因此，對金屬膜提出的具有低反射率的特性(以下稱為「低反射」)的要求正在快速高漲。 It is used for large-scale 4K televisions (4K-TVs) with four pixels as a substitute for full hi-vision mainstream in recent years, or for operating the display screen at a close distance of about tens of centimeters from the viewpoint. In smart phones, high definition is developing. Along with this high definition, a new problem that the reflection of the metal film due to incident light degrades display quality has begun to appear. Therefore, the requirements for the characteristics of low reflectivity (hereinafter referred to as "low reflection") for the metal film are rapidly increasing.
另外，用於平面顯示元件的導電膜的鋁膜為在可見光區域中具有90%以上的高反射率的金屬。另外，同樣地用於平面顯示元件的導電膜的銅膜在可見光區域具有70%的反射率，在600nm以上的長波長區域具有與銀(Ag)膜相同的95%以上的高反射率。 In addition, the aluminum film used for the conductive film of the flat display element is a metal having a high reflectance of 90% or more in the visible light region. In addition, a copper film similarly used for a conductive film of a flat display element has a reflectance of 70% in a visible light region, and a high reflectance of 95% or more in a long wavelength region of 600 nm or more, similar to a silver (Ag) film.
另一方面，作為為了保護該些導電膜而積層的中間膜的鉬膜或鉬合金膜具有60%左右的反射率。該些中間膜的反射率即便經過平面顯示元件的製造製程亦幾乎不會變化，因此，尤其於高精細的顯示裝置中，中間膜的反射成為使顯示品質下降的因素。因此，於如上所述的高精細化的顯示裝置中，要求反射率為15%以下的更低反射的積層配線膜。 On the other hand, a molybdenum film or a molybdenum alloy film, which is an interlayer film laminated to protect these conductive films, has a reflectance of about 60%. The reflectance of these intermediate films hardly changes even after the manufacturing process of a flat display element. Therefore, especially in a high-definition display device, the reflection of the intermediate film becomes a factor that reduces the display quality. Therefore, in a high-definition display device as described above, a multilayer film having a lower reflection and a reflectance of 15% or less is required.
如上所述，迄今為止已開發出了使用各種材質的配線膜或積層配線膜，但該些專利文獻中是著眼於作為導電膜或中間膜的阻隔性或保護性能進行了研究，關於用以應對今後的高精細的顯示裝置所必需的低反射這一新特性，未進行任何研究。 As described above, wiring films or multilayer wiring films using various materials have been developed so far. However, in these patent documents, research has been focused on the barrier properties or protective properties of conductive films or intermediate films, and measures have been taken to deal with them. The new feature of low reflection, which is necessary for future high-definition display devices, has not been studied.
本發明的目的在於提供一種可應對用以使高精細的平面顯示元件的顯示品質提高所必需的、電極或配線膜的低反射的要求的積層配線膜和其製造方法，以及用以形成擔當低反射的中間膜的鉬合金膜的鉬合金濺鍍靶材。 An object of the present invention is to provide a multilayer wiring film and a method for manufacturing the same that can meet the requirements of low reflection of electrodes or wiring films necessary for improving the display quality of high-definition flat display elements, and a method for forming the same. Molybdenum alloy sputtering target for reflective interlayer molybdenum alloy film.
本發明者有鑒於所述課題，為了於平面顯示元件或觸控面板的製造步驟中獲得低反射這一新特性而對各種合金膜及積層膜進行了研究。其結果發現，藉由將包含鉬合金的中間膜與導電膜積層於透明基板的正上方或形成有透明膜的透明基板的正上方，可獲得低反射的積層配線膜，從而達成了本發明。 In view of the above-mentioned problems, the present inventors have studied various alloy films and laminated films in order to obtain a new characteristic of low reflection in a manufacturing process of a flat display element or a touch panel. As a result, it has been found that a low-reflection laminated wiring film can be obtained by laminating an intermediate film including a molybdenum alloy and a conductive film directly above a transparent substrate or directly above a transparent substrate on which a transparent film is formed, thereby achieving the present invention.
即，本發明為一種積層配線膜的發明，所述積層配線膜具有積層結構，所述積層結構於透明基板的正上方或形成有透明膜的透明基板的正上方形成有膜厚為30nm~70nm且包含鉬合金的中間膜，且於所述中間膜的正上方形成有比電阻為15μΩ．cm以下的導電膜，所述積層配線膜自所述透明基板側測定的可見光反射率為15%以下。 That is, the present invention is an invention of a laminated wiring film having a laminated structure, and the laminated structure is formed directly above a transparent substrate or directly above a transparent substrate on which a transparent film is formed, and has a film thickness of 30 nm to 70 nm. An intermediate film containing a molybdenum alloy is formed, and a specific resistance of 15 μΩ is formed directly above the intermediate film. In a conductive film having a thickness of cm or less, a visible light reflectance of the multilayer wiring film measured from the transparent substrate side is 15% or less.
所述導電膜較佳為包含鋁、銅、銀的任一種，或者包含在鋁、銅、銀的任一種中含有合計為5原子%以下的選自過渡金屬及半金 屬中的元素的鋁合金、銅合金、銀合金的任一種，且膜厚為50nm~500nm。 The conductive film preferably contains any one of aluminum, copper, and silver, or is contained in any one of aluminum, copper, and silver and contains a total of 5 atomic% or less selected from transition metals and semi-gold Any of aluminum alloy, copper alloy, and silver alloy of the element in the genus, and the film thickness is 50 nm to 500 nm.
所述中間膜較佳為含有合計為5原子%~50原子%的選自鈦(Ti)、釩、鈮、鉭(Ta)、鎳、鈷(Co)及鐵(Fe)中的一種以上的元素作為金屬成分，且剩餘部分包含鉬及不可避免的雜質。 The intermediate film preferably contains one or more selected from titanium (Ti), vanadium, niobium, tantalum (Ta), nickel, cobalt (Co), and iron (Fe) in a total amount of 5 atomic% to 50 atomic%. The element is a metal component, and the remainder contains molybdenum and unavoidable impurities.
另外，所述中間膜較佳為含有合計為5原子%~20原子%的選自鈦及鈮中的一種以上的元素。 In addition, the intermediate film preferably contains one or more elements selected from titanium and niobium in a total of 5 to 20 atomic%.
另外，所述中間膜較佳為含有1原子%~30原子%的鎳。 The intermediate film preferably contains 1 to 30 atomic% of nickel.
本發明為一種鉬合金濺鍍靶材的發明，其為用以形成所述中間膜的鉬合金濺鍍靶材，含有合計為5原子%~50原子%的選自鈦、釩、鈮、鉭、鎳、鈷及鐵中的一種以上的元素，且剩餘部分包含鉬及不可避免的雜質。 The invention is a invention of a molybdenum alloy sputtering target, which is a molybdenum alloy sputtering target for forming the intermediate film, and contains a total of 5 atomic% to 50 atomic% selected from titanium, vanadium, niobium, and tantalum. Or more of nickel, cobalt, and iron, and the remainder contains molybdenum and unavoidable impurities.
所述鉬合金濺鍍靶材較佳為含有合計為5原子%~20原子%的選自鈦及鈮中的一種以上的元素。 The molybdenum alloy sputtering target preferably contains one or more elements selected from titanium and niobium in a total of 5 to 20 atomic%.
所述鉬合金濺鍍靶材較佳為含有1原子%~30原子%的鎳。 The molybdenum alloy sputtering target preferably contains 1 atomic% to 30 atomic% of nickel.
另外，所述中間膜可於含有10體積%~90體積%的選自氧及氮中的至少一者的環境下，使用上述中所記載的鉬合金濺鍍靶材的任一種並藉由濺鍍法來形成。 In addition, the interlayer film may use any one of the molybdenum alloy sputtering targets described above under an environment containing at least one selected from oxygen and nitrogen in an amount of 10% by volume to 90% by volume, and may be sputtered by sputtering. To form.
本發明的積層配線膜可達成現有的積層配線膜所無法獲得的低反射率，因此例如可使FPD等的顯示品質提高。因此，對於作為更高精細的FPD而受到矚目的例如4K-TV或智慧型手 機、或者平板型PC等下一代資訊終端或使用透明樹脂基板的可撓性的FPD而言，本發明成為非常有用的技術。其原因在於：於該些製品中，尤其是積層配線膜的低反射化非常重要。 The multilayer wiring film of the present invention can achieve a low reflectance that cannot be obtained with a conventional multilayer wiring film, and thus, for example, can improve the display quality of FPD and the like. Therefore, for high-definition FPDs such as 4K-TV or smart hands The present invention is a very useful technology for a next-generation information terminal such as a mobile phone, a tablet PC, or a flexible FPD using a transparent resin substrate. The reason for this is that, in these products, especially low reflectance of a laminated wiring film is very important.
1‧‧‧透明基板 1‧‧‧ transparent substrate
2‧‧‧中間膜 2‧‧‧ Interlayer
3‧‧‧導電膜 3‧‧‧ conductive film
圖1為表示本發明的積層配線膜的應用例的剖面示意圖。 FIG. 1 is a schematic cross-sectional view showing an application example of the multilayer wiring film of the present invention.
將本發明的積層配線膜的應用例示於圖1。本發明的積層配線膜例如於透明基板1的正上方形成中間膜2，於該中間膜2的正上方形成導電膜3。 An application example of the multilayer wiring film of the present invention is shown in FIG. 1. The laminated wiring film of the present invention is formed with an intermediate film 2 directly above the transparent substrate 1, and a conductive film 3 is formed directly above the intermediate film 2.
而且，本發明的重要特徵之一在於：於例如玻璃基板之類的透明基板的正上方、或者例如形成有透明樹脂膜等透明膜的透明基板的正上方所形成的中間膜中採用鉬合金，並將該中間膜的膜厚設為30nm~70nm。另外，本發明的另一重要特徵在於：於所述中間膜的正上方形成比電阻為15μΩ．cm以下的導電膜，從而形成積層結構。進而，本發明的又一重要特徵在於：自透明基板側測定的可見光反射率為15%以下。以下，對本發明的各特徵進行詳細說明。 Furthermore, one of the important features of the present invention is that a molybdenum alloy is used in an intermediate film formed directly above a transparent substrate such as a glass substrate or directly above a transparent substrate such as a transparent resin film formed with a transparent resin film. The thickness of the intermediate film is set to 30 nm to 70 nm. In addition, another important feature of the present invention is that a specific resistance of 15 μΩ is formed directly above the intermediate film. cm below the conductive film to form a laminated structure. Furthermore, another important feature of the present invention is that the visible light reflectance measured from the transparent substrate side is 15% or less. Hereinafter, each feature of the present invention will be described in detail.
再者，於以下的說明中，所謂「反射率」是指可見光區域即波長360nm~波長740nm的範圍的平均反射率。 In the following description, the "reflectance" refers to the average reflectance in the visible light region, that is, a range of wavelengths from 360 nm to 740 nm.
於本發明的積層配線膜中，若中間膜的膜厚未滿30nm，則因上層的導電膜而光發生反射，於可見光區域的作為長波 長側的600nm以上中的反射率未充分降低而成為發紅的色調，難以獲得低反射特性。另外，若中間膜的膜厚超過70nm，則短波長側的500nm以下中的反射率未充分降低而成為發藍的色調，難以獲得低反射特性。為了使自透明基板側測定的可見光區域中的反射率為15%以下，將中間膜的膜厚設為30nm~70nm。進而，為了呈現更理想的可見光區域中的反射率的變化少的藍黑色調且形成10%以下的低反射膜，較佳為將中間膜的膜厚設為40nm~60nm的範圍。 In the multilayer wiring film of the present invention, if the film thickness of the intermediate film is less than 30 nm, light is reflected by the conductive film on the upper layer, and it is a long wave in the visible light region. The reflectance at 600 nm or longer on the long side is not sufficiently reduced to make a reddish hue, and it is difficult to obtain low reflection characteristics. In addition, if the film thickness of the interlayer film exceeds 70 nm, the reflectance at 500 nm or less on the short wavelength side is not sufficiently reduced to become a bluish hue, and it is difficult to obtain low reflection characteristics. In order to make the reflectance in the visible light region measured from the transparent substrate side to 15% or less, the film thickness of the intermediate film is set to 30 nm to 70 nm. Furthermore, in order to present a more desirable blue-black tone with less change in reflectance in the visible light region and to form a low-reflection film having a thickness of 10% or less, it is preferable to set the film thickness of the intermediate film in the range of 40 nm to 60 nm.
本發明的積層配線膜中的形成於中間膜的正上方的導電膜的比電阻理想的是盡可能低，將該比電阻的值設為15μΩ．cm以下。 The specific resistance of the conductive film formed directly above the intermediate film in the multilayer wiring film of the present invention is preferably as low as possible, and the value of the specific resistance is set to 15 μΩ. cm or less.
本發明藉由以最適宜的膜厚構成對所述中間膜與導電膜進行積層，可形成具有更低反射的特性的積層配線膜。作為導電膜，較佳為包含可獲得低電阻的例如鋁、銅、銀的任一種，或者於鋁、銅、銀的任一種中含有合計為5原子%以下的選自過渡金屬及半金屬中的元素的鋁合金、銅合金、銀合金的任一種。此可考慮所要求的電阻值或製造步驟中的加熱步驟的溫度或環境、與其他氧化膜或保護膜的密接性、阻隔性等而適宜地選擇。 According to the present invention, by stacking the intermediate film and the conductive film with an optimum film thickness, a laminated wiring film having lower reflection characteristics can be formed. The conductive film is preferably selected from transition metals and semi-metals including any one of aluminum, copper, and silver that can obtain low resistance, or a total of 5 atomic% or less in any of aluminum, copper, and silver. Any of aluminum alloy, copper alloy, and silver alloy. This can be appropriately selected in consideration of a required resistance value, a temperature or an environment of a heating step in a manufacturing step, adhesion with another oxide film or a protective film, barrier properties, and the like.
若鋁在透明基板上作為透明膜而形成有ITO膜且未形成中間膜的情況下與作為透明導電膜的ITO膜積層並經過加熱步驟，則會於界面中生成鋁的氧化物，從而存在電接觸性降低的情況。因此，較佳為於鋁的導電膜與ITO膜之間形成包含與ITO膜 的接觸性優異的鉬合金的中間膜。 If aluminum is formed with a ITO film as a transparent film on a transparent substrate and an intermediate film is not formed, and is laminated with the ITO film as a transparent conductive film and undergoes a heating step, an aluminum oxide is generated at the interface, and electricity is present. Case of reduced contact. Therefore, it is preferable to form a film containing ITO between the conductive film of aluminum and the ITO film. Interlayer film of molybdenum alloy with excellent contact properties.
另外，銅的電阻值較鋁低而較佳。 In addition, copper has a lower resistance value than aluminum and is preferred.
另外，銀為價格高昂的材料，但另一方面，銀在具有與銅為相同程度的低電阻的同時，在作為銅的缺點的耐氧化性、耐濕性方面優異，亦具有與ITO膜的接觸性，因此，作為簡便的導電膜而較佳。 In addition, silver is an expensive material, but on the other hand, while having the same low resistance as copper, silver is also excellent in oxidation resistance and humidity resistance, which is a disadvantage of copper. Contact is therefore preferred as a simple conductive film.
鉬容易被可應用於FPD中的所述鋁合金等的導電膜中所使用的蝕刻劑等蝕刻，但另一方面，耐濕性與耐氧化性低。 Molybdenum is easily etched by an etchant used in a conductive film such as the aluminum alloy in FPD, but on the other hand, it has low moisture resistance and oxidation resistance.
鈦、釩、鈮、鉭、鎳、鈷及鐵為藉由含有於鉬中以製成鉬合金而具有改善耐濕性或耐氧化性的效果的元素。該效果藉由使鉬中含有合計為5原子%以上的選自鈦、釩、鈮、鉭、鎳、鈷及鐵中的一種以上的元素而變得明確，且隨著含量的增加而變得顯著。因此，中間膜較佳為於鉬中含有合計為5原子%以上的選自鈦、釩、鈮、鉭、鎳、鈷及鐵中的一種以上的元素。 Titanium, vanadium, niobium, tantalum, nickel, cobalt, and iron are elements that are contained in molybdenum to make a molybdenum alloy, and have the effect of improving the moisture resistance or oxidation resistance. This effect becomes clear by making molybdenum contain one or more elements selected from the group consisting of titanium, vanadium, niobium, tantalum, nickel, cobalt, and iron in a total amount of 5 atomic% or more, and becomes greater as the content increases. Significant. Therefore, it is preferable that the interlayer film contains one or more elements selected from titanium, vanadium, niobium, tantalum, nickel, cobalt, and iron in a total amount of 5 atomic% or more in molybdenum.
另一方面，若過度增加該些元素的合計含量，則存在蝕刻性降低的情況。因此，若考慮到所述蝕刻劑等的蝕刻性，則中間膜較佳為於鉬中含有合計為50原子%以下的選自鈦、釩、鈮、鉭、鎳、鈷及鐵中的一種以上的元素。 On the other hand, if the total content of these elements is excessively increased, the etching properties may be reduced. Therefore, in consideration of the etchability of the etchant, it is preferable that the interlayer film contains at least one atom selected from titanium, vanadium, niobium, tantalum, nickel, cobalt, and iron in a total amount of 50 atomic% or less in molybdenum. Elements.
另外，中間膜較佳為含有合計為5原子%~20原子%的選自鈦及鈮中的一種以上的元素。鈦及鈮容易與氮鍵結，因此為可容易地使中間膜成為半透射著色膜的元素，能夠以少的含量實現低反射特性及耐濕性的改善以及蝕刻性的確保。該改善效果藉 由選自鈦及鈮中的一種以上的元素的合計為5原子%以上而變得明確。 In addition, the intermediate film preferably contains one or more elements selected from titanium and niobium in a total of 5 to 20 atomic%. Titanium and niobium are easily bonded to nitrogen. Therefore, titanium and niobium are elements that can easily make the intermediate film a semi-transmissive colored film, and it is possible to achieve improvement in low reflection characteristics, moisture resistance, and securing of etching properties with a small amount. The improvement effect borrows It is made clear that the total of one or more elements selected from titanium and niobium is 5 atomic% or more.
另一方面，若選自鈦及鈮中的一種以上的元素的合計超過20原子%，則存在蝕刻性降低的情況。因此，中間膜較佳為以合計為5原子%~20原子%的範圍含有選自鈦及鈮中的一種以上的元素。 另外，基於與上述相同的理由，所述元素的合計更佳為10原子%~20原子%的範圍。 On the other hand, if the total of one or more elements selected from titanium and niobium exceeds 20 atomic%, the etching properties may be reduced. Therefore, the intermediate film preferably contains one or more elements selected from titanium and niobium in a range of 5 to 20 atomic% in total. In addition, for the same reason as above, the total of the elements is more preferably in a range of 10 atomic% to 20 atomic%.
另外，中間膜較佳為含有1原子%~30原子%的鎳。鎳為能夠大幅提高鉬合金的耐乾式蝕刻性，並且有助於耐氧化性的提高的元素，此外，可對使用銅的導電膜時的蝕刻劑改善蝕刻性。但另一方面，若中間膜的鎳的含量過多，則難以獲得低反射特性，並且於使用鋁的導電膜並加熱至250℃以上的情況下，鎳容易熱擴散到鋁中。 The interlayer film preferably contains 1 to 30 atomic% of nickel. Nickel is an element that can significantly improve the dry etching resistance of a molybdenum alloy and contribute to the improvement of oxidation resistance. In addition, nickel can improve the etching properties of an etchant when a copper conductive film is used. On the other hand, if the content of nickel in the intermediate film is too large, it is difficult to obtain low reflection characteristics. When a conductive film of aluminum is used and heated to 250 ° C or higher, nickel is easily diffused into aluminum.
另外，鎳所帶來的耐乾式蝕刻性的改善效果自鎳的含量為1原子%起出現，耐氧化性的改善效果自鎳的含量為5原子%起變得明確。 In addition, the effect of improving the dry etching resistance by nickel appears from a content of nickel of 1 atomic%, and the effect of improving the oxidation resistance becomes clear from a content of nickel of 5 atomic%.
另一方面，若鎳的含量超過30原子%，則存在難以獲得低反射特性的情況。因此，中間膜較佳為以1原子%~30原子%的範圍含有鎳。另外，基於與上述相同的理由，更佳的鎳的下限為5原子%，更佳的鎳的上限為20原子%。 On the other hand, when the content of nickel exceeds 30 atomic%, it may be difficult to obtain low reflection characteristics. Therefore, the intermediate film preferably contains nickel in a range of 1 to 30 atomic%. In addition, for the same reason as above, the lower limit of more preferable nickel is 5 atomic%, and the upper limit of more preferable nickel is 20 atomic%.
另外，中間膜可含有的鉭為可於壓縮側改變中間膜的膜應力的元素，且為尤其在當膜基板等中形成有中間膜時膜表面成 為凹狀、即成為拉伸應力的情況下可緩和該應力的元素。該效果自鉭的含量為3原子%起出現。另外，鉭容易與氮鍵結，因此為可容易地使中間膜成為半透射著色膜的元素，但鉭為重量且價格高昂的元素，因此較佳設為盡可能少的含量。 In addition, tantalum that may be contained in the intermediate film is an element that can change the film stress of the intermediate film on the compression side, and is formed on the film surface especially when the intermediate film is formed in a film substrate or the like. The element is concave, that is, an element that can relax the stress when it becomes a tensile stress. This effect appears when the content of tantalum is 3 atomic%. In addition, tantalum is easily bonded to nitrogen, so it is an element that can easily make the intermediate film a semi-transmissive colored film. However, tantalum is an element that is heavy and expensive, and therefore it is preferable to set the content as small as possible.
另外，中間膜可含有的鐵為廉價的元素，但為若擴散至作為半導體膜的矽中則使特性劣化的元素。於使中間膜含有鐵的情況下，於觸控面板等用途中變得較佳。 Although the intermediate film may contain iron as an inexpensive element, it is an element that deteriorates characteristics when diffused into silicon as a semiconductor film. When the intermediate film contains iron, it is preferable for applications such as a touch panel.
導電膜的膜厚較佳為50nm~500nm。導電膜的導電性或透光性根據所選擇的材質而不同，但若膜厚未滿50nm，則導電膜的連續性變低，存在因電子散射的影響而電阻值容易增加，並且透射光增加的情況，難以獲得低反射。因此，為了獲得穩定的低反射特性，更佳為將導電膜的膜厚設為透射光將減少的50nm以上。 The thickness of the conductive film is preferably 50 nm to 500 nm. The conductivity or light transmittance of the conductive film varies depending on the selected material. However, if the film thickness is less than 50 nm, the continuity of the conductive film becomes low, the resistance value is easily increased due to the influence of electron scattering, and the transmitted light is increased. In the case, it is difficult to obtain low reflection. Therefore, in order to obtain stable low reflection characteristics, it is more preferable to set the film thickness of the conductive film to 50 nm or more, which will reduce transmitted light.
另一方面，若導電膜的膜厚超過500nm，則於形成時花費時間，並且於應用於透明的膜基板等中的情況下，容易因膜應力而產生翹曲。 On the other hand, if the thickness of the conductive film exceeds 500 nm, it takes time during formation, and when it is applied to a transparent film substrate or the like, warpage is likely to occur due to film stress.
另外，為了緩和由導電膜的膜表面中的電子散射的影響引起的電阻值的增加而獲得穩定的低電阻，導電膜的膜厚更佳為設為100nm以上。 In addition, in order to reduce the increase in resistance value due to the influence of electron scattering on the film surface of the conductive film and obtain stable low resistance, the film thickness of the conductive film is more preferably set to 100 nm or more.
作為形成所述中間膜的方法，最適宜的是使用鉬合金濺鍍靶材的濺鍍法。濺鍍法為物理蒸鍍法的一種，且為與其他真空蒸鍍或離子鍍敷相比可穩定地形成大面積的方法，並且為組成變 動少、可獲得優異的薄膜的有效的方法。 As a method for forming the intermediate film, a sputtering method using a molybdenum alloy sputtering target is most suitable. The sputtering method is a type of physical vapor deposition method, and it is a method that can form a large area more stably than other vacuum vapor deposition or ion plating methods. An effective method to obtain excellent film with less movement.
另外，於本發明的積層配線膜的製造方法中，當為了形成中間膜而使用鉬合金濺鍍靶材進行濺鍍時，較佳為於含有氮的環境中進行濺鍍。藉此，當將中間膜與導電膜積層時，可形成容易吸收光的半透射著色膜。 In addition, in the method for manufacturing a multilayer wiring film of the present invention, when a molybdenum alloy sputtering target is used for sputtering to form an intermediate film, sputtering is preferably performed in an environment containing nitrogen. Thereby, when the intermediate film and the conductive film are laminated, a semi-transmissive colored film that can easily absorb light can be formed.
而且，該含有氮的環境可藉由使用反應性濺鍍法來形成，所述反應性濺鍍法使用除通常濺鍍氣體中使用的作為惰性氣體的氬以外亦包含特定量的氮的濺鍍氣體。 Further, the nitrogen-containing environment can be formed by using a reactive sputtering method that uses sputtering that contains a specific amount of nitrogen in addition to argon, which is an inert gas used in a general sputtering gas. gas.
於使用反應性濺鍍法的情況下，當將構成濺鍍氣體的氬與氮的含有比率設為合計為100體積%時，濺鍍氣體的氮的含有比率較佳為設為10體積%~90體積%的範圍。藉由設為該範圍，容易獲得自透明基板側測定的可見光反射率為15%以下的積層配線膜。較佳的氮的含有比率的下限為20體積%，進而佳的下限為40體積%。另外，較佳的氮的含有比率的上限為80體積%，進而佳的上限為60體積%。 When a reactive sputtering method is used, when the total content ratio of argon and nitrogen constituting the sputtering gas is 100% by volume, the content ratio of nitrogen in the sputtering gas is preferably 10% by volume ~ A range of 90% by volume. By setting it as this range, it is easy to obtain the laminated wiring film whose visible light reflectance measured from the transparent substrate side is 15% or less. The lower limit of the preferable nitrogen content ratio is 20% by volume, and the more preferable lower limit is 40% by volume. In addition, the upper limit of the preferable nitrogen content ratio is 80% by volume, and the more preferable upper limit is 60% by volume.
另外，藉由將構成濺鍍氣體的氮的一部分置換為氧，亦可使中間膜的密接性提高，但於含有氧的情況下，若氧的含量超過氮的含量，則存在中間膜發生透射而難以獲得低反射的情況。因此，濺鍍氣體中的氧的含量較佳為少於氮的含量。 In addition, by replacing a part of the nitrogen constituting the sputtering gas with oxygen, the adhesion of the intermediate film can be improved. However, in the case where oxygen is contained, if the oxygen content exceeds the nitrogen content, transmission of the intermediate film may occur. It is difficult to obtain low reflection. Therefore, the content of oxygen in the sputtering gas is preferably less than the content of nitrogen.
另外，於所述中間膜的反應性濺鍍法中，投入電力理想的是將濺鍍時施加的電力的值除以濺鍍靶的濺鍍面的面積值而得的值作為電力密度，並將該電力密度作為指標。而且，其電力密 度較佳為設為2W/cm2~6W/cm2的範圍。若電力密度未滿2W/cm2，則成膜速度變得緩慢，並且放電容易變得不穩定，難以進行穩定的中間膜的形成。 In addition, in the reactive sputtering method of the intermediate film, it is desirable that a value obtained by dividing the value of the power applied during sputtering by the area value of the sputtering surface of the sputtering target is used as the power density, and Use this power density as an index. Further, the power density thereof is preferably set to 2W / cm range of 2 ~ 6W / cm 2 in. If the power density is less than 2 W / cm 2 , the film-forming speed becomes slow, the discharge tends to become unstable, and it is difficult to form a stable intermediate film.
另一方面，若電力密度超過6W/cm2，則難以獲得低反射的中間膜。認為其原因在於：於反應性濺鍍中，認為濺鍍靶的粒子在與反應氣體反應後被濺鍍，但若電力密度變高，則反應後的濺鍍靶的粒子因氬而再次分解濺鍍，難以納入至膜中。 On the other hand, if the power density exceeds 6 W / cm 2 , it is difficult to obtain an intermediate film with low reflection. The reason is considered to be that in reactive sputtering, the particles of the sputtering target are sputtered after reacting with the reaction gas, but if the power density becomes high, the particles of the sputtering target after the reaction are decomposed and sputtered again by argon. Plating is difficult to incorporate into the film.
另外，認為本發明的積層配線膜中的包含鉬合金的中間膜較佳為根據所述製造方法而成為於鉬合金中含有氮者。但因難以準確地確定中間膜中的氮的含量，故無法明確地規定具體的氮的含量。 In addition, it is considered that the interlayer film containing a molybdenum alloy in the multilayer wiring film of the present invention is preferably one containing nitrogen in the molybdenum alloy according to the manufacturing method described above. However, since it is difficult to accurately determine the nitrogen content in the interlayer film, a specific nitrogen content cannot be clearly specified.
然而，根據發明者的推測，認為中間膜中所含的氮的含量較佳為2原子%~60原子%。進而佳的下限為3原子%，進而佳的上限為30原子%。藉由設為該較佳的範圍，容易獲得自透明基板側測定的可見光反射率為15%以下的積層配線膜。 However, according to the inventors' speculation, it is considered that the content of nitrogen contained in the interlayer film is preferably 2 to 60 atomic%. A further preferred lower limit is 3 atomic%, and a further preferred upper limit is 30 atomic%. By setting it as this preferable range, it is easy to obtain the laminated wiring film whose visible light reflectance measured from the transparent substrate side is 15% or less.
另外，當將中間膜與導電膜積層時，較佳為形成容易吸收光的半透射著色膜。 In addition, when the intermediate film and the conductive film are laminated, it is preferable to form a semi-transmissive colored film that easily absorbs light.
用以形成構成本發明的積層配線膜的中間膜的鉬合金濺鍍靶材為了形成所述中間膜而較佳設為如下的鉬合金：含有合計為5原子%~50原子%的選自鈦、釩、鈮、鉭、鎳、鈷及鐵中的一種以上的元素作為金屬成分，且剩餘部分包含鉬及不可避免的雜質。 In order to form the intermediate film, the molybdenum alloy sputtering target used to form the intermediate film constituting the multilayer wiring film of the present invention is preferably a molybdenum alloy containing a total of 5 atomic% to 50 atomic% selected from titanium. One or more elements of vanadium, niobium, tantalum, nickel, cobalt, and iron are used as metal components, and the remainder contains molybdenum and unavoidable impurities.
另外，作為鉬合金濺鍍靶材中含有的元素，鈦、釩、鈮、鉭為週期律表中鉬的周邊元素，且為容易與鉬合金化的元素。其中，若考慮到工業上的元素單價與獲取性等，則較佳為以5原子%~20原子%的範圍含有選自鈦及鈮中的一種以上的元素。另外，基於與上述相同的理由，所述元素的合計更佳為10原子%~20原子%的範圍。 In addition, as elements contained in the molybdenum alloy sputtering target, titanium, vanadium, niobium, and tantalum are peripheral elements of molybdenum in the periodic table, and are elements that are easily alloyed with molybdenum. Among these, in consideration of the industrial unit price, availability, and the like, it is preferable to contain at least one element selected from titanium and niobium in a range of 5 to 20 atomic%. In addition, for the same reason as above, the total of the elements is more preferably in a range of 10 atomic% to 20 atomic%.
另外，作為鉬合金濺鍍靶材中含有的元素，鎳、鈷、鐵單獨為磁性元素。而且，為了使濺鍍靶材的利用效率提高，較佳為將鉬與該些元素合金化，並使居里點(Curie point)降低而於常溫下成為非磁性，且使該些存在於鉬合金濺鍍靶材中。其中，較佳為以1原子%~30原子%的範圍含有飽和磁通密度低、容易非磁性化的鎳。而且，基於與上述相同的理由，鎳更佳為5原子%~20原子%的範圍。 In addition, as elements contained in the molybdenum alloy sputtering target, nickel, cobalt, and iron are magnetic elements alone. In addition, in order to improve the utilization efficiency of the sputtering target, it is preferable to alloy molybdenum with these elements, reduce the Curie point, make it non-magnetic at normal temperature, and make these exist in molybdenum. Alloy sputtering target. Among them, nickel having a low saturation magnetic flux density and being easily demagnetized is preferably contained in a range of 1 to 30 atomic%. For the same reason as above, nickel is more preferably in a range of 5 to 20 atomic%.
作為用以形成構成本發明的積層配線膜的中間膜的鉬合金濺鍍靶材的製造方法，例如可應用粉末燒結法。鉬為高熔點的金屬，因此，可製造鉬粉末、與例如藉由氣體霧化(gas atomize)法而含有添加元素的合金粉末來作為原料粉末，或者將對多種合金粉末或純金屬粉末以成為本發明的最終組成的方式進行混合而成的混合粉末作為原料粉末。 As a manufacturing method of the molybdenum alloy sputtering target used for forming the intermediate film which comprises the laminated wiring film of this invention, a powder sintering method can be applied, for example. Molybdenum is a metal having a high melting point. Therefore, molybdenum powder, and alloy powder containing an additive element by, for example, a gas atomization method can be produced as a raw material powder, or various alloy powders or pure metal powders can be made into A mixed powder obtained by mixing the final composition of the present invention is used as a raw material powder.
作為原料粉末的燒結方法，可使用熱均壓、熱壓、放電電漿燒結、擠出壓製燒結等加壓燒結。 As a method of sintering the raw material powder, pressure sintering such as hot equalizing pressure, hot pressing, discharge plasma sintering, and extrusion pressing sintering can be used.
於用以形成構成本發明的積層配線膜的中間膜的鉬合金濺鍍 靶材中，較佳為不可避免的雜質的含量少。而且，本發明的鉬合金濺鍍靶材亦可於無損本發明的作用的範圍內包含作為氣體成分的氧、氮或碳，作為過渡金屬的銅，作為半金屬的鋁、矽等不可避免的雜質。 Molybdenum alloy sputtering for forming an intermediate film constituting the laminated wiring film of the present invention In the target, the content of unavoidable impurities is preferably small. In addition, the molybdenum alloy sputtering target of the present invention can also include oxygen, nitrogen, or carbon as a gas component, copper as a transition metal, aluminum, silicon, and the like as semi-metals within a range that does not impair the effects of the present invention. Impurities.
此處，各主要構成元素以相對於主要構成元素整體的原子%表示，主要構成元素以外的不可避免的雜質以於鉬合金濺鍍靶材整體中的質量ppm表示。例如，碳為200質量ppm以下，銅為200質量ppm以下，鋁、矽分別為100質量ppm以下等，且去除了氣體成分的純度較佳為99.9質量%以上。 Here, each main constituent element is expressed in atomic% with respect to the entire main constituent element, and unavoidable impurities other than the main constituent element are expressed in mass ppm in the entire molybdenum alloy sputtering target. For example, carbon is 200 mass ppm or less, copper is 200 mass ppm or less, aluminum and silicon are each 100 mass ppm or less, and the purity after removing gas components is preferably 99.9 mass% or more.
[實施例1] [Example 1]
首先，為了形成中間膜而製作濺鍍靶材。將平均粒徑為6μm的鉬粉末、平均粒徑為85μm的鈮粉末、平均粒徑為150μm的鈦粉末、以及平均粒徑為100μm的鎳粉末以成為表1所示的組成的方式混合，並填充於軟鋼製的罐中，然後一邊加熱一邊進行真空排氣，於將罐內脫氣後將罐密封。 First, a sputtering target is produced in order to form an intermediate film. A molybdenum powder having an average particle diameter of 6 μm, a niobium powder having an average particle diameter of 85 μm, a titanium powder having an average particle diameter of 150 μm, and a nickel powder having an average particle diameter of 100 μm were mixed so as to have a composition shown in Table 1, and Fill a can made of mild steel, and then evacuate under vacuum while heating. After degassing the inside of the can, the can is sealed.
接著，將經密封的罐放入熱均壓裝置中，以1000℃、100MPa、5小時的條件進行燒結後，藉由機械加工而製作直徑100mm、厚度5mm的濺鍍靶材。 Next, the sealed can was put into a hot equalizing device, and sintered under the conditions of 1000 ° C., 100 MPa, and 5 hours, and then a sputtering target having a diameter of 100 mm and a thickness of 5 mm was produced by machining.
另外，為了形成作為比較例的鎳-銅-鉬合金的中間膜，按照以原子比計成為鎳-25%銅-8%鉬的方式對鎳原料、銅原料及鉬原料進行秤量，利用真空熔解爐並藉由熔解鑄造法來製作鑄錠。藉由對該鑄錠進行機械加工而製作直徑100mm、厚度5mm的鎳合金 濺鍍靶材。 In addition, in order to form an intermediate film of a nickel-copper-molybdenum alloy as a comparative example, the nickel raw material, copper raw material, and molybdenum raw material were weighed so that the atomic ratio becomes nickel-25% copper-8% molybdenum, and vacuum melting was used. The furnace also produces ingots by melt casting. A nickel alloy with a diameter of 100 mm and a thickness of 5 mm was produced by machining this ingot. Sputter target.
另外，為了形成作為積層於中間膜的正上方的導電膜的鋁膜及銀膜，準備直徑100mm、厚度5mm的鋁及銀的濺鍍靶材。鋁濺鍍靶材使用住友化學股份有限公司所製造者，銀濺鍍靶材使用古谷金屬(Furuya Metal)股份有限公司所製造者。另外，用以形成作為導電膜的銅膜的銅濺鍍靶材是自日立金屬股份有限公司製造的無氧銅(Oxygen Free Copper，OFC)的原材料切出而製作。另外，用以形成ITO的濺鍍靶材使用JX金屬股份有限公司所製造者。 In addition, in order to form an aluminum film and a silver film as a conductive film laminated directly above the intermediate film, a sputtering target of aluminum and silver having a diameter of 100 mm and a thickness of 5 mm was prepared. The aluminum sputtering target was manufactured by Sumitomo Chemical Co., Ltd. The silver sputtering target was manufactured by Furiya Metal Co., Ltd. In addition, a copper sputtering target for forming a copper film as a conductive film is prepared by cutting out a raw material of Oxygen Free Copper (OFC) manufactured by Hitachi Metals Co., Ltd. A sputtering target for forming ITO was manufactured by JX Metal Co., Ltd.
將上述中所準備的各濺鍍靶材焊接於銅製的背板(backing plate)，並安裝於愛發科(ULVAC)股份有限公司製造的濺鍍裝置(型號：CS-200)。然後，於25mm×50mm的玻璃基板(製品編號：伊戈爾(Eagle)XG)的正上方，使用表1所示的濺鍍氣體形成各膜厚構成的中間膜及導電膜，從而製作各試樣。此處，於將投入電力設為200W時，電力密度成為2.6W/cm2。另外，導電膜是使用氬作為濺鍍氣體並於投入電力500W的條件下形成於中間膜的正上方。另外，試樣No.8是於所述玻璃基板的正上方形成有厚度為100nm的ITO膜。 Each of the sputtering targets prepared as described above was welded to a copper backing plate and mounted on a sputtering device (model: CS-200) manufactured by ULVAC Corporation. Then, directly above the 25 mm × 50 mm glass substrate (product number: Eagle XG), an intermediate film and a conductive film of each film thickness were formed using the sputtering gas shown in Table 1 to prepare each test. kind. Here, when the input power is 200 W, the power density is 2.6 W / cm 2 . In addition, the conductive film is formed directly above the intermediate film using argon as a sputtering gas and under the condition that an electric power of 500 W is input. In addition, in Sample No. 8, an ITO film having a thickness of 100 nm was formed directly above the glass substrate.
關於所獲得的各試樣，將測定反射率及比電阻而得的結果示於表1中。另外，關於反射率的測定，使用柯尼卡美能達(Konica Minolta)股份有限公司製造的分光測色計(型號編號：CM2500d)，自玻璃基板面側與導電膜面側進行測定。另外，關於比電阻的測 定，使用三菱油化股份有限公司製造的薄膜電阻率計(型號編號：MCP-T400)，自導電膜面側進行測定。 Table 1 shows the results obtained by measuring the reflectance and the specific resistance of each of the obtained samples. The reflectance was measured from a glass substrate surface side and a conductive film surface side using a spectrophotometer (model number: CM2500d) manufactured by Konica Minolta Co., Ltd. In addition, the measurement of specific resistance The measurement was performed from a conductive film surface side using a thin film resistivity meter (model number: MCP-T400) manufactured by Mitsubishi Petrochemical Co., Ltd.
如表1所示，可確認到作為本發明例的積層配線膜具有自透明的玻璃基板側測定的反射率為15%以下的低反射率。 As shown in Table 1, it was confirmed that the multilayer wiring film as an example of the present invention has a low reflectance of 15% or less as measured from the transparent glass substrate side.
[實施例2] [Example 2]
接著，使用由表1的試樣No.5製作的、包含以原子比計為鉬-15%鎳-15%鈦的鉬合金濺鍍靶材，將投入電力設為200 W，將作為濺鍍氣體的氬與氮的含有比率變更為表2所示的條件，於各玻璃基板的正上方形成膜厚50nm的中間膜。然後，於該中間膜的正上方，使用氬作為濺鍍氣體並於投入電力500W的條件下形成作為導電膜的鋁膜。 Next, a molybdenum alloy sputtering target made of sample No. 5 in Table 1 and containing atomic ratio of molybdenum to 15% nickel to 15% titanium was used, and the input power was set to 200. W, the content ratio of argon and nitrogen as the sputtering gas was changed to the conditions shown in Table 2, and an intermediate film having a film thickness of 50 nm was formed directly above each glass substrate. Then, directly above the intermediate film, an aluminum film was formed as a conductive film using argon as a sputtering gas and under a condition of inputting 500 W of electric power.
藉由與實施例1相同的方法測定反射率及比電阻。將其結果示於表2。 The reflectance and specific resistance were measured by the same method as in Example 1. The results are shown in Table 2.
如表2所示，可確認到於由包含氬與氮的濺鍍氣體形成的包含鉬合金的中間膜的正上方形成有導電膜的、作為本發明例的積層配線膜具有自透明的玻璃基板側測定的反射率為15%以下的低反射率。 As shown in Table 2, it was confirmed that the laminated wiring film as an example of the present invention has a self-transparent glass substrate in which the conductive film is formed directly above the intermediate film containing a molybdenum alloy and formed of a sputtering gas containing argon and nitrogen. The reflectance measured on the side is a low reflectance of 15% or less.
另外，將試樣No.5、試樣No.13~試樣No.16所記載的組成 的中間膜分別形成為200nm，使用作為光電子分光裝置(化學分析光電子能譜(Electron Spectroscopy for Chemical Analysis，ESCA))的克雷托斯分析儀器(KRATOS ANALYTICAL)公司製造的(型號：AXIS-HS)，對中間膜中的氮濃度進行了測定，結果為含有6原子%~28原子%的氮，確認到Mo2N的分析圖表。 In addition, the intermediate films having the compositions described in Sample No. 5 and Sample No. 13 to Sample No. 16 were formed at 200 nm, respectively, and used as a photoelectron spectrometer (Electron Spectroscopy for Chemical Analysis, (ESCA)) (Model: AXIS-HS) manufactured by KRATOS ANALYTICAL (KRATOS ANALYTICAL) company. The nitrogen concentration in the interlayer was measured. Analysis chart to Mo 2 N.
[實施例3] [Example 3]
接著，使用由表1的No.5製作的、包含以原子比計為鉬-15%鎳-15%鈦的鉬合金濺鍍靶材，並使用氬與氮的含有比率為50體積%的濺鍍氣體，將投入電力設為200W，於各玻璃基板的正上方以表3所示的膜厚形成中間膜。然後，於該中間膜的正上方，使用氬作為濺鍍氣體並於投入電力500W的條件下形成作為導電膜的鋁膜。藉由與實施例1相同的方法測定反射率及比電阻。將其結果示於表3。 Next, a molybdenum alloy sputtering target made of No. 5 in Table 1 and containing atomic ratio of molybdenum to 15% nickel to 15% titanium was used. Sputtering with a content ratio of argon and nitrogen of 50% by volume was used. The plating gas was set to 200 W of input power, and an intermediate film was formed directly above each glass substrate with a film thickness shown in Table 3. Then, directly above the intermediate film, an aluminum film was formed as a conductive film using argon as a sputtering gas and under a condition of inputting 500 W of electric power. The reflectance and specific resistance were measured by the same method as in Example 1. The results are shown in Table 3.
[表3]
如表3的試樣No.18所示，確認到若中間膜的膜厚成為20nm，則無法獲得15%以下的低反射率。另一方面，作為本發明例的積層配線膜的中間膜的膜厚為30nm~70nm的範圍，可確認到15%以下的低反射。此處可知，反射率最低的中間膜的膜厚為50nm附近。 As shown in Sample No. 18 in Table 3, it was confirmed that if the film thickness of the interlayer film is 20 nm, a low reflectance of 15% or less cannot be obtained. On the other hand, the film thickness of the intermediate film of the laminated wiring film of the example of the present invention is in the range of 30 nm to 70 nm, and low reflection of 15% or less can be confirmed. It can be seen here that the film thickness of the intermediate film having the lowest reflectance is around 50 nm.
[實施例4] [Example 4]
接著，以成為表4所示的中間膜的組成的方式，藉由與實施例1相同的製法製作試樣No.25~試樣No.32的濺鍍靶材。另外，作為導電膜的鋁合金、銅合金、銀合金的濺鍍靶材以如下方式製作：藉由真空熔解法製作以原子比計成為鋁-0.6鈮、銅-3鈦、銀-0.3釤(Sm)的各合金的鑄錠，並對該鑄錠以成為直徑100mm、厚度5mm的方式進行機械加工而製作濺鍍靶材。 Next, a sputtering target material of Sample No. 25 to Sample No. 32 was produced by the same method as in Example 1 so as to have the composition of the intermediate film shown in Table 4. In addition, sputtering targets for aluminum alloys, copper alloys, and silver alloys that are conductive films are produced by the vacuum melting method to produce aluminum-0.6 niobium, copper-3 titanium, and silver-0.3 钐 by atomic ratio. Sm), an ingot of each alloy, and the ingot was machined to have a diameter of 100 mm and a thickness of 5 mm to produce a sputtering target.
使用該些濺鍍靶材，以成為表4所示的濺鍍氣體的體積比率的方式進行調整，將投入電力設為200W，於各基板的正上方形成膜厚50nm的中間膜。然後，於該中間膜的正上方，使用氬作為濺鍍氣體而形成表4所示的各導電膜。此處，基板是使用與實施例1~實施例3相同的玻璃基板，除此以外，試樣No.28使用厚度0.5mm的聚碳酸酯基板(透明聚碳酸酯：PC(Polycarbonate))，試樣No.29使用厚度100μm的聚對苯二甲酸乙二酯膜基板(透明聚對苯二甲酸乙二酯：PET(polyethylene terephthalate))。 Using these sputtering targets, the volume ratio of the sputtering gas shown in Table 4 was adjusted, the input power was set to 200 W, and an intermediate film having a film thickness of 50 nm was formed directly above each substrate. Then, directly above the intermediate film, each conductive film shown in Table 4 was formed using argon as a sputtering gas. Here, the substrate was the same glass substrate as in Examples 1 to 3. Except that, for the sample No. 28, a polycarbonate substrate (transparent polycarbonate: PC (Polycarbonate)) having a thickness of 0.5 mm was used. Sample No. 29 used a polyethylene terephthalate film substrate (transparent polyethylene terephthalate) having a thickness of 100 μm.
關於上述中所獲得的各試樣，藉由與實施例1相同的方法測定反射率及比電阻。將其結果示於表4。 About each sample obtained above, the reflectance and specific resistance were measured by the same method as Example 1. The results are shown in Table 4.
如表4所示，確認到僅藉由氬作為濺鍍氣體來形成了中間膜的作為比較例的試樣No.25、添加元素量多且僅藉由氧作為濺鍍氣體來形成了中間膜的試樣No.32未獲得低反射率。 As shown in Table 4, Sample No. 25, which is a comparative example, in which an intermediate film was formed only by using argon as a sputtering gas, it was confirmed that the intermediate film was formed with a large amount of added elements and only using oxygen as a sputtering gas. Sample No. 32 did not obtain low reflectance.
相對於此，可確認到作為本發明例的試樣No.26~試樣No.31為具有低反射與低電阻的積層配線膜。 In contrast, Sample No. 26 to Sample No. 31 as examples of the present invention were confirmed to be a multilayer wiring film having low reflection and low resistance.
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