WO2022059277A1 - Laminated structure, and method for manufacturing laminated structure - Google Patents
Laminated structure, and method for manufacturing laminated structure Download PDFInfo
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- WO2022059277A1 WO2022059277A1 PCT/JP2021/022329 JP2021022329W WO2022059277A1 WO 2022059277 A1 WO2022059277 A1 WO 2022059277A1 JP 2021022329 W JP2021022329 W JP 2021022329W WO 2022059277 A1 WO2022059277 A1 WO 2022059277A1
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- titanium
- laminated structure
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- film forming
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 85
- 239000010936 titanium Substances 0.000 claims abstract description 85
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 43
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 239000010408 film Substances 0.000 description 88
- 238000002474 experimental method Methods 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000009864 tensile test Methods 0.000 description 11
- 238000005452 bending Methods 0.000 description 10
- 235000013339 cereals Nutrition 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 150000003609 titanium compounds Chemical class 0.000 description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- 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
-
- 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
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron 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
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/41—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions
- H01L29/417—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions carrying the current to be rectified, amplified or switched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/41—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions
- H01L29/417—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions carrying the current to be rectified, amplified or switched
- H01L29/41725—Source or drain electrodes for field effect devices
- H01L29/41733—Source or drain electrodes for field effect devices for thin film transistors with insulated gate
Definitions
- the present invention relates to a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated, and a method for manufacturing a laminated structure.
- This type of laminated structure is used as a source / drain electrode of a switching element (thin film transistor) in electronic devices such as displays, smartphones and electronic paper (see, for example, Patent Document 1).
- a switching element thin film transistor
- electronic devices such as displays, smartphones and electronic paper
- Patent Document 1 Japanese Patent Document 1
- high bending resistance is required for a laminated structure having a titanium layer having a relatively high hardness.
- the titanium layer and the aluminum layer of the laminated structure are consistently formed by the sputtering method in a vacuum atmosphere (see, for example, Patent Document 1).
- a rare gas for example, argon
- a vacuum chamber in which a titanium or aluminum target and a base material are arranged facing each other. Gas
- DC power with a negative potential is applied to the target to form a plasma
- the target is sputtered by the ions of the rare gas ionized in the plasma
- a titanium layer or an aluminum layer is formed with a desired film thickness (for example, the first titanium layer is 50 nm, the aluminum layer is 500 nm, and the second titanium layer is 50 nm).
- various spatter conditions such as the power input to the target, the amount of rare gas introduced, and the total pressure in the vacuum chamber during film formation are set in consideration of productivity and film thickness distribution (for example, input). Electric power 20-40kW, total pressure 0.2-1.0Pa).
- a test base material having a predetermined shape is used, and a first titanium layer, an aluminum layer, and a second titanium layer are sequentially formed on the surface of the test base material under predetermined spatter conditions.
- a tensile test was performed on the laminated structure that was peeled off from the test substrate.
- the laminated structure was more than doubled just by applying the tensile load required to give a 5% elongation amount. It has been found.
- the present inventors have repeated diligent research and have a crystal structure in which relatively small crystal grains are aligned in the film thickness direction and the crystal grain boundaries are connected so as to extend in the film thickness direction, and titanium is formed during film formation. It was found that if a hard and brittle titanium compound such as titanium nitride or titanium oxide is formed at the grain boundaries due to impurities such as nitrogen molecules and oxygen molecules incorporated in the layer, strong bending resistance cannot be obtained for the laminated structure. I came to do it.
- the present invention has been made based on the above findings, and an object of the present invention is to provide a laminated structure having strong bending resistance and a method for manufacturing the laminated structure.
- each of the first and second titanium layers is X-ray. It has a crystal structure with diffraction peaks on the (002) and (100) planes in the Miller index by diffraction measurement, and the half width of the diffraction peak on the (002) plane is 1.0 deg or less, on the (100) plane. The half width of the diffraction peak is 0.6 deg or less.
- the aluminum layer has a crystal structure having a diffraction peak on the (111) plane in the Miller index measured by X-ray diffraction measurement.
- the method for manufacturing a laminated structure of the present invention for manufacturing a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated is a sputtering method.
- the partial pressure of the nitrogen gas is 3.0 ⁇ 10 -4 Pa or less
- the partial pressure of the oxygen gas is 9.0 ⁇ 10 -5 Pa.
- a rare gas is introduced so that the total pressure in the vacuum chamber in which the aluminum target and the base material are arranged is maintained in the range of 0.2 Pa to 0.5 Pa. It is preferable to further include a film forming step of applying a predetermined power to the aluminum target to form an aluminum layer at a film forming rate in the range of 7 nm / sec to 10 nm / sec.
- an impurity gas for example, nitrogen gas
- an impurity gas for example, nitrogen gas
- Oxygen gas, steam gas, hydrogen gas is evacuated until the partial pressure reaches a predetermined value or less, so that titanium compounds such as titanium nitride and titanium oxide are formed at the crystal grain boundaries of the first and second titanium layers. The formation is suppressed as much as possible.
- the first and second titanium layers are formed, if the film forming rate is within the range of 3 nm / sec to 5 nm / sec, the first and second titanium layers have a large grain size. It is possible to have a crystal structure in which the crystal grains are irregularly overlapped in the film thickness direction and the crystal grain boundaries are not connected in the film film direction.
- the titanium layer formed as described above was X-ray diffracted, a diffraction peak on the (002) plane and a diffraction peak on the (100) plane were confirmed, and the diffraction peak on the (002) plane was ((002). 100)
- the intensity ratio of the diffraction peaks on the plane was 0.20 or more.
- the half-value width of the diffraction peak on the (002) plane is 1.0 deg or less
- the half-value width of the diffraction peak on the (100) plane is 0.6 deg or less.
- the formation of titanium compounds at the crystal grain boundaries of the first and second titanium layers is suppressed, and the crystal grains having a large particle size are irregularly overlapped in the film thickness direction, and the crystal grain boundaries are not connected. It has a crystal structure. Then, even if a tensile load required to give an elongation amount of 5% or 10% is applied to the same laminated structure as described above, the elongation amount of the laminated structure is suppressed to within 10%, and moreover, the elongation amount is suppressed to 10% or less. It was also confirmed that no cracks were generated in the surface observation of the laminated structure after the tensile test. As a result, the laminated structure of the present invention has a strong bending resistance as compared with that of the conventional example.
- FIG. 2 is a diagram schematically illustrating the film forming chamber Pc1 shown in FIG. 2.
- the graph which shows the experimental result which confirms the effect of this invention.
- (A) to (c) are diagrams schematically explaining the crystal structure of the titanium layer formed in Comparative Experiments 1 to 3.
- the base material Sw is formed by attaching the polyimide film Pf to the surface of, for example, the glass substrate Sg (removable at the interface between the glass substrate Sg and the polyimide film Pf). ),
- the surface of the base material Sw is provided with a first titanium layer L1, an aluminum layer L2, and a second titanium layer L3, which are consistently sequentially formed (laminated) by a sputtering method in a vacuum atmosphere.
- the sputtering apparatus Sm that can be used for film formation of the laminated structure LS is a so-called cluster tool type, has a central transfer chamber Tc having a transfer robot R, and is around the transfer chamber Tc.
- a load lock chamber Lc a vacuum chamber (hereinafter referred to as a "film forming chamber") Pc1 for forming a first titanium layer L1, and an aluminum layer L2 for forming a film are formed via a gate valve Gv.
- the chamber Pc2 and the film forming chamber Pc3 for forming the second titanium layer L3 are connected to each other.
- the film forming chamber Pc1 will be described as an example with reference to FIG.
- An exhaust pipe 11 leading to a vacuum pump unit Pu composed of a turbo molecular pump, a rotary pump, or the like is connected to the chamber Pc1, and the film forming chamber Pc1 is evacuated to a predetermined degree of vacuum (for example, 1 ⁇ 10 -6 Pa). Can be done.
- a gas pipe 13 having a mass flow controller 12 interposed therebetween is connected to the side wall of the vacuum chamber Pc1, and a flow-controlled rare gas (for example, argon gas) can be introduced into the film forming chamber Pc1.
- a titanium target 2 in the film forming chamber Pc2, an aluminum target
- a known magnet unit 3 is arranged above the target. ..
- the target 2 made of titanium a target having a purity of 99.9% or more is used, and as a target made of aluminum, a target having a purity of 99.99% or more is used.
- the output from the sputter power supply Ps is connected to the target 2, and DC power having a negative potential can be input to the target 2.
- the stage 4 is arranged so as to face the target 2, and the base material Sw can be installed.
- the film forming chamber Pc1 is provided with a measuring instrument 5 for measuring the total pressure inside the film forming chamber Pc1 and the partial pressure of an impurity gas (for example, nitrogen gas, oxygen gas, water vapor gas, hydrogen gas).
- an impurity gas for example, nitrogen gas, oxygen gas, water vapor gas, hydrogen gas.
- a known instrument such as an ionization vacuum gauge or a mass spectrometer can be used, so further description thereof will be omitted.
- a method for manufacturing the laminated structure LS by the sputtering apparatus Sm will be specifically described.
- the base material Sw is put into the load lock chamber Lc in the air atmosphere, the load lock chamber Lc is evacuated, and then the base material Sw is transferred to the film forming chamber Pc1 by the transfer robot R.
- the transfer chamber Tc and the film forming chambers Pc1, Pc2, Pc3 Prior to charging the base material Sw into the load lock chamber Lc, the transfer chamber Tc and the film forming chambers Pc1, Pc2, Pc3 are evacuated to a predetermined pressure (1 ⁇ 10 -3 Pa) in advance and are in a standby state. ing.
- the transfer chamber Tc and the film forming chambers Pc1, Pc2, Pc3 are evacuated to a predetermined pressure (1 ⁇ 10 -3 Pa) in advance and are in a standby state. ing.
- the partial pressure of the nitrogen gas measured by the mass analyzer 5 is 3.0 ⁇ 10 -4 Pa or less, and the oxygen gas.
- the film formation is performed until the partial pressure of the water vapor gas reaches 9.0 ⁇ 10 -4 Pa or less, the partial pressure of the hydrogen gas reaches 5.0 ⁇ 10 -5 Pa or less, and the partial pressure of the hydrogen gas reaches 5.0 ⁇ 10 -5 Pa or less.
- Vacuum exhaust the inside of the chamber Pc1 vacuum exhaust step of the first step).
- argon gas is maintained in the vacuum-exhausted film forming chamber Pc1 so that the total pressure is maintained in the range of 0.2 Pa to 0.5 Pa.
- Is introduced, and 20 kW to 30 kW of DC power having a negative potential is input from the sputter power source Ps to the target 2.
- plasma is formed in the film forming chamber Pc1.
- the target 2 is sputtered by the ions of the argon gas ionized in the plasma.
- the sputter particles scattered from the target 2 adhere to and deposit on the film-forming surface (polyimide film Pf) of the base material Sw, and the first titanium layer L1 is formed on the base material Sw at 3 nm / sec to 5 nm / sec.
- the film is formed at the film speed (the film forming step in the first step).
- the spatter time is appropriately set so that the first titanium layer L1 has a film thickness of, for example, 10 nm to 50 nm.
- the base material Sw is transferred to the film forming chamber Pc2, and the vacuum exhaust step is performed in the same manner as in the first step.
- argon gas is introduced into the vacuum-exhausted film forming chamber Pc2 so that the total pressure is maintained in the range of 0.2 Pa to 0.5 Pa.
- 30 kW to 40 kW of DC power having a negative potential is input from the sputter power source Ps to the target 2 made of aluminum.
- the film forming chamber Pc2 plasma is formed in the film forming chamber Pc2, and the sputter particles scattered from the target 2 adhere to and deposit on the surface of the first titanium layer L1 and the aluminum layer L2 is 7 nm / sec on the first titanium layer L1.
- the film is formed at a film forming rate of about 10 nm / sec (the film forming step in the second step).
- the spatter time is appropriately controlled so that the aluminum layer L2 has a film thickness of, for example, 200 nm to 800 nm.
- the base material Sw is transferred to the film forming chamber Pc3, and the vacuum exhaust step is performed in the same manner as in the first step.
- a second titanium layer L3 is formed on the aluminum layer L2 at a film forming rate of 3 nm / sec to 5 nm / sec under the same sputtering conditions as in the first step.
- a film is formed (a film forming step in the third step).
- the spatter time is appropriately controlled so that the film thickness of the second titanium layer L3 is the same as that of the first titanium layer L1 (for example, 10 to 50 nm).
- the laminated structure LS when the laminated structure LS is manufactured, impurities are suppressed as much as possible from being incorporated into each of the titanium layers L1 and L3, and titanium compounds such as titanium nitride and titanium oxide are formed at the grain boundaries Cf. (See the part surrounded by the alternate long and short dash line in FIG. 1).
- the titanium layers L1 and L3 at a film forming rate in the range of 3 nm / sec to 5 nm / sec, the grain size of the crystal grains Cg becomes larger than that of the conventional example, and moreover.
- the crystal grain boundary Cf can be made to have a crystal structure that is not connected in the film film direction (see FIG. 1).
- a diffraction peak on the (002) plane and a diffraction peak on the (100) plane were confirmed, and a diffraction peak on the (002) plane was confirmed.
- the intensity ratio of the diffraction peak to the (100) plane was 0.20 or more.
- the half-value width of the diffraction peak on the (002) plane was 1.0 deg or less, and the half-value width of the diffraction peak on the (100) plane was 0.6 deg or less.
- the substrate Sw is a glass substrate Sg on which the polyimide film Pf is attached, and the substrate Sw is placed on the stage 4 of the film forming chamber Pc1 and then the nitrogen gas measured by the mass analyzer 5.
- the partial pressure of is 1.0 ⁇ 10 -4 Pa
- the partial pressure of oxygen gas is 8.0 ⁇ 10 -5 Pa
- the partial pressure of steam gas is 5.0 ⁇ 10 -4 Pa
- the partial pressure of hydrogen gas is 5.
- Vacuum exhausted until reaching 0.0 ⁇ 10 -5 Pa (vacuum exhaust step of the first step).
- the total pressure in the vacuum chamber Pc1 was 7.3 ⁇ 10 -4 Pa.
- argon gas is introduced into the vacuum chamber Pc1 at a flow rate of 120 sccm so that the total pressure in the vacuum chamber Pc1 is maintained at 0.3 Pa, and at the same time, 20 to 30 kW of DC power is applied to the target 2.
- the titanium target 2 was charged and sputtered to form a first titanium layer L1 on the surface of the base material Sw at a film forming rate of 3 nm / sec with a film thickness of 50 nm (the film forming step of the first step).
- the result of measuring the X-ray diffraction of the first titanium layer L1 formed into a film is shown by a solid line in FIG.
- a diffraction peak on the (002) plane was confirmed near the diffraction angle (2 ⁇ ) 38 to 39 °, and a diffraction peak on the (100) plane was confirmed near the diffraction angle 35 to 36 °.
- the intensity ratio of the diffraction peak on the (100) plane to the diffraction peak on the 002) plane is 0.25
- the half width of the diffraction peak on the (002) plane is 0.5 deg
- half of the diffraction peak on the (100) plane was 0.6 deg.
- the substrate Sw is transferred to the film forming chamber Pc2, and after performing the vacuum exhaust step in the same manner as in the first step, argon is maintained so that the total pressure of the film forming chamber Pc2 is maintained at 0.3 Pa.
- a gas is introduced into the film forming chamber Pc2 at a flow rate of 120 sccm, and at the same time, a DC power of 35 to 40 kW is applied to the aluminum target 2 to sputter the target 2, and the first film forming rate is 7 nm / sec.
- An aluminum layer L2 was formed on the titanium layer L1 with a film thickness of 500 nm.
- the substrate Sw is transferred to the film forming chamber Pc3
- the vacuum exhaust step is performed in the same manner as in the first step, and then the film forming conditions are the same as those in the first step, and the film forming rate is 3 nm / sec.
- a second titanium layer L3 was formed on the aluminum layer L2 with a film thickness of 50 nm, whereby a laminated structure LS was obtained.
- a test substrate (polyimide film Pf) having a known shape (width 5 mm, length 20 mm, thickness 0.02 mm) is made of glass. After forming on the substrate Sg and sequentially laminating the first titanium layer L1, the aluminum layer L2, and the second titanium layer L3 on the surface of the test substrate under the above-mentioned spatter conditions, the interface between the glass substrate Sg and the polyimide film Pf.
- a tensile test (tensile speed of 0.5 mm / min) was carried out on the laminated structure LS obtained by peeling in 1) using a tensile tester (“STA-1150” manufactured by ORIENTEC). It was confirmed that the elongation amount of the laminated structure was suppressed to within 10% (5%, 8%) even when the tensile load required to give the elongation amount of 10% was applied. Further, the resistance R when a tensile load giving an elongation amount of 5% and 10% is applied is measured using a resistance measuring device (“AD7461A” manufactured by ADVANTEST), respectively, with respect to the resistance R0 when no tensile load is applied.
- AD7461A resistance measuring device
- FIG. 5A When having such a diffraction pattern, as shown in FIG. 5A, it has a crystal structure in which small crystal grains Cg are aligned in the film thickness direction and the crystal grain boundaries Cf are connected so as to extend in the film thickness direction. It is inferred that.
- the laminated structure LS was obtained by the same method as the above-mentioned invention experiment except that the vacuum exhaust step was not performed in each of the first and third steps (the point where only the film forming step was performed). rice field. That is, when the total pressure in the vacuum chamber Pc1 reached a predetermined vacuum degree (2.8 ⁇ 10 -3 Pa), the noble gas was introduced into the vacuum chamber Pc1 regardless of the partial pressure of the impurity gas. When the partial pressure of the impurity gas at this time was measured, the partial pressure of the nitrogen gas was 5.0 ⁇ 10 -4 Pa, the partial pressure of the oxygen gas was 2.0 ⁇ 10 -4 Pa, and the partial pressure of the steam gas was 2.
- the laminated structure LS obtained in this comparative experiment 2 has weak bending resistance.
- the intensity ratio of the diffraction peak on the (100) plane to the diffraction peak of was 0.11, which is smaller than 0.20.
- the half width of the diffraction peak on the (100) plane was 0.7 deg, which is larger than 0.6 deg.
- the total pressure in the film forming chambers Pc1 and Pc3 at the time of film formation in the first and third steps was maintained at 0.6 Pa, and the film forming rate was set to 2 nm / sec.
- a laminated structure LS was obtained by the same method as the above-mentioned invention experiment except that the vacuum exhaust step was not performed in each of the third steps (the point where only the film forming step was performed).
- the tensile test was carried out under the same conditions as the above-mentioned invention experiment, it was confirmed that the elongation amount of the laminated structure LS was more than doubled.
- the resistance increase rate was obtained in the same manner as in the above-mentioned invention experiment, it was 300% and 900%, which were worse than those in the comparative experiment 2. Further, when the surface state of the laminated structure LS after the tensile test was observed in the same manner as in the above-mentioned invention experiment, it was confirmed that cracks were generated and the laminated structure was whitened. From these results, it was found that the laminated structure LS obtained in the comparative experiment 3 has a weaker bending resistance than the comparative experiments 1 and 2.
- the diffraction peak on the (100) plane was not confirmed, and only the diffraction peak on the (002) plane was confirmed.
- the half width of the diffraction peak on the (002) plane was 0.8 deg.
- a laminated structure LS in which a first titanium layer L1, an aluminum layer L2, and a third titanium layer L3 are laminated has been described as an example, but titanium nitride is further described on the third titanium layer L3.
- the present invention can also be applied to those in which layers are laminated.
- the base material Sw is conveyed in-situ between the film forming chambers Pc1, Pc2, and Pc3, and the first titanium layer L1, the aluminum layer L2, and the second titanium layer L3 are conveyed in a vacuum atmosphere.
- the present invention is not limited to this, and the present invention is also applicable to the case where the first and second titanium layers L1 and L3 and the aluminum layer L2 are carried out by different sputtering devices. Can be applied. Further, the first titanium layer L1 and the second titanium layer L3 may be formed in the same film forming chamber.
- LS laminated structure, L1 ... first titanium layer, L2 ... aluminum layer, L3 ... second titanium layer, Sw ... base material, Pc1, Pc2, Pc3 ... film formation chamber (vacuum chamber), 2 ... target.
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Abstract
Provided are: a laminated structure having strong bending-resistance; and a method for manufacturing the laminated structure. A laminated structure LS according to the present invention has a first titanium layer L1, an aluminum layer L2, and a second titanium layer L3 which are sequentially laminated, wherein each of the first and second titanium layers has a crystal structure having diffraction peaks on a (002) plane and a (100) plane, in the Miller index as measured by the X-ray diffraction, the half-value width of the diffraction peak on the (002) plane is at most 1.0 deg, and the half-value width of the diffraction peak on the (100) plane is at most 0.6 deg.
Description
本発明は、第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した積層構造体及び積層構造体の製造方法に関する。
The present invention relates to a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated, and a method for manufacturing a laminated structure.
この種の積層構造体は、ディスプレイ、スマートフォンや電子ペーパーなどの電子デバイスにて、スイッチング素子（薄膜トランジスタ）のソース／ドレイン電極として用いられている（例えば特許文献１参照）。一方、近年の可撓性を有する電子デバイスの開発に伴い、比較的高硬度のチタン層を有する積層構造体に対し、高い屈曲耐性が要求されるようになっている。
This type of laminated structure is used as a source / drain electrode of a switching element (thin film transistor) in electronic devices such as displays, smartphones and electronic paper (see, for example, Patent Document 1). On the other hand, with the recent development of flexible electronic devices, high bending resistance is required for a laminated structure having a titanium layer having a relatively high hardness.
一般に、積層構造体のチタン層やアルミニウム層は、真空雰囲気中でスパッタリング法により一貫して成膜される（例えば、特許文献１参照）。例えば、チタン層やアルミニウム層の成膜に際しては、チタン製またはアルミニウム製のターゲットと基材とを対向配置した真空チャンバ内を所定圧力まで真空排気した後、真空チャンバ内に希ガス（例えば、アルゴンガス）を導入し、ターゲットに負の電位を持つ直流電力を投入してプラズマを形成し、プラズマ中で電離した希ガスのイオンによりターゲットをスパッタリングし、ターゲットから飛散したスパッタ粒子を基材に付着、堆積させて、所望の膜厚（例えば、第１のチタン層を５０ｎｍ、アルミニウム層を５００ｎｍ、第２のチタン層を５０ｎｍ）でチタン層やアルミニウム層が成膜される。このとき、ターゲットへの投入電力、希ガスのガス導入量や成膜中の真空チャンバ内の全圧といった各種のスパッタ条件は、生産性や膜厚分布を考慮して設定される（例えば、投入電力２０～４０ｋＷ、全圧が０．２～１．０Ｐａ）。
Generally, the titanium layer and the aluminum layer of the laminated structure are consistently formed by the sputtering method in a vacuum atmosphere (see, for example, Patent Document 1). For example, when forming a titanium layer or an aluminum layer, a rare gas (for example, argon) is introduced into the vacuum chamber after vacuum exhausting to a predetermined pressure in a vacuum chamber in which a titanium or aluminum target and a base material are arranged facing each other. Gas) is introduced, DC power with a negative potential is applied to the target to form a plasma, the target is sputtered by the ions of the rare gas ionized in the plasma, and the sputtered particles scattered from the target adhere to the substrate. , A titanium layer or an aluminum layer is formed with a desired film thickness (for example, the first titanium layer is 50 nm, the aluminum layer is 500 nm, and the second titanium layer is 50 nm). At this time, various spatter conditions such as the power input to the target, the amount of rare gas introduced, and the total pressure in the vacuum chamber during film formation are set in consideration of productivity and film thickness distribution (for example, input). Electric power 20-40kW, total pressure 0.2-1.0Pa).
ここで、積層構造体の屈曲耐性を確認するために、所定形状の試験基材を用い、試験基材表面に第１のチタン層、アルミニウム層、第２のチタン層を所定のスパッタ条件で順次積層した後、試験基材から剥離した積層構造体に対し、引張試験を実施したところ、５％の伸び量を与えるのに必要な引張荷重を加えただけで、積層構造体が倍以上に伸びることが判明した。また、引張試験後の積層構造体の表面（即ち、チタン層表面）状態を観察したところ、チタン層に厚さ方向にのびるクラックが多数発生していることが判明した。そこで、本発明者らは、鋭意研究を重ね、比較的小さい結晶粒が膜厚方向に整列して結晶粒界がその膜厚方向にのびるように繋がった結晶構造を有すると共に、成膜時にチタン層内に取り込まれた窒素分子や酸素分子といった不純物により結晶粒界に硬くてもろい窒化チタンや酸化チタンといったチタン化合物が形成されていると、積層構造体に強い屈曲耐性が得られないことを知見するのに至った。
Here, in order to confirm the bending resistance of the laminated structure, a test base material having a predetermined shape is used, and a first titanium layer, an aluminum layer, and a second titanium layer are sequentially formed on the surface of the test base material under predetermined spatter conditions. After laminating, a tensile test was performed on the laminated structure that was peeled off from the test substrate. As a result, the laminated structure was more than doubled just by applying the tensile load required to give a 5% elongation amount. It has been found. Moreover, when the state of the surface of the laminated structure (that is, the surface of the titanium layer) after the tensile test was observed, it was found that many cracks extending in the thickness direction were generated in the titanium layer. Therefore, the present inventors have repeated diligent research and have a crystal structure in which relatively small crystal grains are aligned in the film thickness direction and the crystal grain boundaries are connected so as to extend in the film thickness direction, and titanium is formed during film formation. It was found that if a hard and brittle titanium compound such as titanium nitride or titanium oxide is formed at the grain boundaries due to impurities such as nitrogen molecules and oxygen molecules incorporated in the layer, strong bending resistance cannot be obtained for the laminated structure. I came to do it.
本発明は、上記知見に基づきなされたものであり、強い屈曲耐性を有する積層構造体及び積層構造体の製造方法を提供することをその課題とするものである。
The present invention has been made based on the above findings, and an object of the present invention is to provide a laminated structure having strong bending resistance and a method for manufacturing the laminated structure.
上記課題を解決するために、第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した本発明の積層構造体は、第１及び第２の各チタン層が、Ｘ線回折測定によるミラー指数における（００２）面及び（１００）面に回析ピークを持つ結晶構造を有し、（００２）面での回折ピークの半値幅が１．０ｄｅｇ以下、（１００）面での回折ピークの半値幅が０．６ｄｅｇ以下であることを特徴とする。この場合、前記アルミニウム層は、Ｘ線回折測定によるミラー指数における（１１１）面に回析ピークを持つ結晶構造を有することが好ましい。
In order to solve the above problems, in the laminated structure of the present invention in which the first titanium layer, the aluminum layer, and the second titanium layer are sequentially laminated, each of the first and second titanium layers is X-ray. It has a crystal structure with diffraction peaks on the (002) and (100) planes in the Miller index by diffraction measurement, and the half width of the diffraction peak on the (002) plane is 1.0 deg or less, on the (100) plane. The half width of the diffraction peak is 0.6 deg or less. In this case, it is preferable that the aluminum layer has a crystal structure having a diffraction peak on the (111) plane in the Miller index measured by X-ray diffraction measurement.
また、上記課題を解決するために、第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した積層構造体を製造する本発明の積層構造体の製造方法は、スパッタリング法により、基材上に第１のチタン層を成膜する第１工程と、第１のチタン層の上にアルミニウム層を成膜する第２工程と、アルミニウム層の上に第２のチタン層を成膜する第３工程とを含み、第１及び第３の各工程は、窒素ガスの分圧が３．０×１０－４Ｐａ以下、酸素ガスの分圧が９．０×１０－５Ｐａ以下、水蒸気ガスの分圧が８．０×１０－４Ｐａ以下、水素ガスの分圧が５．０×１０－５Ｐａ以下に夫々達するまで、チタン製のターゲットと基材とが配置された真空チャンバ内を真空排気する真空排気工程と、真空チャンバ内の全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるように希ガスを導入し、チタン製のターゲットに所定電力を投入して３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの範囲内の成膜速度で第１及び第２の各チタン層を成膜する成膜工程と、を更に含むことを特徴とする。この場合、前記第２工程は、アルミニウム製のターゲットと基材とが配置された真空チャンバ内の全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるように希ガスを導入し、アルミニウム製のターゲットに所定電力を投入して７ｎｍ／ｓｅｃ～１０ｎｍ／ｓｅｃの範囲内の成膜速度でアルミニウム層を成膜する成膜工程を更に含むことが好ましい。
Further, in order to solve the above problems, the method for manufacturing a laminated structure of the present invention for manufacturing a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated is a sputtering method. A first step of forming a first titanium layer on a base material, a second step of forming an aluminum layer on the first titanium layer, and a second titanium layer on the aluminum layer. In each of the first and third steps including the third step of forming a film, the partial pressure of the nitrogen gas is 3.0 × 10 -4 Pa or less, and the partial pressure of the oxygen gas is 9.0 × 10 -5 Pa. Below, the titanium target and the base material were arranged until the partial pressure of the water vapor gas reached 8.0 × 10 -4 Pa or less and the partial pressure of the hydrogen gas reached 5.0 × 10 -5 Pa or less. A vacuum exhaust process for vacuum exhausting the inside of the vacuum chamber and a rare gas introduced so that the total pressure in the vacuum chamber is maintained in the range of 0.2 Pa to 0.5 Pa, and a predetermined power is applied to the titanium target. It is characterized by further including a film forming step of forming the first and second titanium layers at a film forming rate in the range of 3 nm / sec to 5 nm / sec. In this case, in the second step, a rare gas is introduced so that the total pressure in the vacuum chamber in which the aluminum target and the base material are arranged is maintained in the range of 0.2 Pa to 0.5 Pa. It is preferable to further include a film forming step of applying a predetermined power to the aluminum target to form an aluminum layer at a film forming rate in the range of 7 nm / sec to 10 nm / sec.
以上によれば、真空雰囲気中にて真空チャンバ内で第１のチタン層、アルミニウム層及び第２のチタン層をスパッタリング法により成膜するのに先立って、真空チャンバ内を不純物ガス（例えば窒素ガス、酸素ガス、水蒸気ガス、水素ガス）の分圧が所定値以下に達するまで真空排気することで、第１及び第２の各チタン層の結晶粒界に、窒化チタンや酸化チタンといったチタン化合物が形成されることが可及的に抑制される。そして、第１及び第２の各チタン層の成膜時には、その成膜速度を３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの範囲内にすれば、第１及び第２の各チタン層を、粒径の大きい結晶粒がその膜厚方向に不揃いに重なって結晶粒界が膜厚方向に繋がらない結晶構造を有するものにできる。
According to the above, an impurity gas (for example, nitrogen gas) is inside the vacuum chamber prior to forming the first titanium layer, the aluminum layer and the second titanium layer by the sputtering method in the vacuum chamber in a vacuum atmosphere. , Oxygen gas, steam gas, hydrogen gas) is evacuated until the partial pressure reaches a predetermined value or less, so that titanium compounds such as titanium nitride and titanium oxide are formed at the crystal grain boundaries of the first and second titanium layers. The formation is suppressed as much as possible. When the first and second titanium layers are formed, if the film forming rate is within the range of 3 nm / sec to 5 nm / sec, the first and second titanium layers have a large grain size. It is possible to have a crystal structure in which the crystal grains are irregularly overlapped in the film thickness direction and the crystal grain boundaries are not connected in the film film direction.
上記のようにして成膜したチタン層をＸ線回折したところ、（００２）面での回折ピークと、（１００）面での回折ピークとが確認され、（００２）面での回折ピークに対する（１００）面での回折ピークの強度比は０．２０以上であった。このとき、（００２）面での回折ピークの半値幅が１．０ｄｅｇ以下、（１００）面での回折ピークの半値幅が０．６ｄｅｇ以下であり、これから、上記回析パターンを有していれば、第１及び第２の各チタン層の結晶粒界に、チタン化合物が形成されることが抑制され、粒径の大きい結晶粒がその膜厚方向に不揃いに重なって結晶粒界が繋がらない結晶構造を有するものとなる。そして、上記同様の積層構造体に対する引張試験にて５％または１０％の伸び量を与えるのに必要な引張荷重を加えても、積層構造体の伸び量は１０％以内に抑制され、しかも、引張試験後の積層構造体の表面観察でも、クラックが発生していないことが確認された。その結果、本発明の積層構造体は、従来例のものと比較して強い屈曲耐性を有する。
When the titanium layer formed as described above was X-ray diffracted, a diffraction peak on the (002) plane and a diffraction peak on the (100) plane were confirmed, and the diffraction peak on the (002) plane was ((002). 100) The intensity ratio of the diffraction peaks on the plane was 0.20 or more. At this time, the half-value width of the diffraction peak on the (002) plane is 1.0 deg or less, and the half-value width of the diffraction peak on the (100) plane is 0.6 deg or less. For example, the formation of titanium compounds at the crystal grain boundaries of the first and second titanium layers is suppressed, and the crystal grains having a large particle size are irregularly overlapped in the film thickness direction, and the crystal grain boundaries are not connected. It has a crystal structure. Then, even if a tensile load required to give an elongation amount of 5% or 10% is applied to the same laminated structure as described above, the elongation amount of the laminated structure is suppressed to within 10%, and moreover, the elongation amount is suppressed to 10% or less. It was also confirmed that no cracks were generated in the surface observation of the laminated structure after the tensile test. As a result, the laminated structure of the present invention has a strong bending resistance as compared with that of the conventional example.
以下、図面を参照して、本発明の積層構造体及び積層構造体の製造方法の実施形態について説明する。
Hereinafter, embodiments of the laminated structure and the method for manufacturing the laminated structure of the present invention will be described with reference to the drawings.
図１に示すように、本実施形態の積層構造体ＬＳは、基材Ｓｗを例えばガラス基板Ｓｇの表面にポリイミドフィルムＰｆを貼付したものとし（ガラス基板ＳｇとポリイミドフィルムＰｆとの界面で剥離可能）、基材Ｓｗ表面に、真空雰囲気中でスパッタリング法により一貫して順次成膜（積層）される第１のチタン層Ｌ１と、アルミニウム層Ｌ２と、第２のチタン層Ｌ３とを備える。
As shown in FIG. 1, in the laminated structure LS of the present embodiment, the base material Sw is formed by attaching the polyimide film Pf to the surface of, for example, the glass substrate Sg (removable at the interface between the glass substrate Sg and the polyimide film Pf). ), The surface of the base material Sw is provided with a first titanium layer L1, an aluminum layer L2, and a second titanium layer L3, which are consistently sequentially formed (laminated) by a sputtering method in a vacuum atmosphere.
図２に示すように、上記積層構造体ＬＳの成膜に利用できるスパッタリング装置Ｓｍは、所謂クラスターツール式のものであり、搬送ロボットＲを有する中央の搬送チャンバＴｃを備え、搬送チャンバＴｃの周囲に、ゲートバルブＧｖを介して、ロードロックチャンバＬｃと、第１のチタン層Ｌ１を成膜する真空チャンバ（以下「成膜チャンバ」という）Ｐｃ１と、アルミ二ウム層Ｌ２を成膜する成膜チャンバＰｃ２と、第２のチタン層Ｌ３を成膜する成膜チャンバＰｃ３とが夫々連結されている。ここで、成膜チャンバＰｃ１，Ｐｃ２，Ｐｃ３内には、使用されるターゲットを除き、同一の構造部品が設けられるため、図３を参照して、成膜チャンバＰｃ１を例に説明すると、成膜チャンバＰｃ１には、ターボ分子ポンプやロータリーポンプなどからなる真空ポンプユニットＰｕに通じる排気管１１が接続され、成膜チャンバＰｃ１を所定の真空度（例えば１×１０－６Ｐａ）まで真空排気することができる。真空チャンバＰｃ１の側壁には、マスフローコントローラ１２が介設されたガス管１３が接続され、流量制御された希ガス（例えばアルゴンガス）を成膜チャンバＰｃ１内に導入することができる。成膜チャンバＰｃ１の上部には、チタン製のターゲット２（成膜チャンバＰｃ２では、アルミニウム製のターゲット）が基材Ｓｗを臨む姿勢で配置され、その上方に公知の磁石ユニット３が配置されている。
As shown in FIG. 2, the sputtering apparatus Sm that can be used for film formation of the laminated structure LS is a so-called cluster tool type, has a central transfer chamber Tc having a transfer robot R, and is around the transfer chamber Tc. In addition, a load lock chamber Lc, a vacuum chamber (hereinafter referred to as a "film forming chamber") Pc1 for forming a first titanium layer L1, and an aluminum layer L2 for forming a film are formed via a gate valve Gv. The chamber Pc2 and the film forming chamber Pc3 for forming the second titanium layer L3 are connected to each other. Here, since the same structural parts are provided in the film forming chambers Pc1, Pc2, and Pc3 except for the target to be used, the film forming chamber Pc1 will be described as an example with reference to FIG. An exhaust pipe 11 leading to a vacuum pump unit Pu composed of a turbo molecular pump, a rotary pump, or the like is connected to the chamber Pc1, and the film forming chamber Pc1 is evacuated to a predetermined degree of vacuum (for example, 1 × 10 -6 Pa). Can be done. A gas pipe 13 having a mass flow controller 12 interposed therebetween is connected to the side wall of the vacuum chamber Pc1, and a flow-controlled rare gas (for example, argon gas) can be introduced into the film forming chamber Pc1. A titanium target 2 (in the film forming chamber Pc2, an aluminum target) is arranged above the film forming chamber Pc1 so as to face the base material Sw, and a known magnet unit 3 is arranged above the target. ..
チタン製のターゲット２としては、純度が９９．９％以上のものが、また、アルミニウム製のターゲットとしては、純度が９９．９９％以上のものが利用される。ターゲット２には、スパッタ電源Ｐｓからの出力が接続され、負の電位を持つ直流電力をターゲット２に投入できる。成膜チャンバＰｃ１の下部には、ターゲット２に対向させて、ステージ４が配置され、基材Ｓｗを設置することができる。成膜チャンバＰｃ１には、その内部の全圧と不純物ガス（例えば、窒素ガス、酸素ガス、水蒸気ガス、水素ガス）の分圧とを測定する測定器５が設けられている。このような測定器５としては、電離真空計や質量分析計などの公知のものが利用できるため、これ以上の説明は省略する。以下に、スパッタリング装置Ｓｍによる積層構造体ＬＳの製造方法を具体的に説明する。
As the target 2 made of titanium, a target having a purity of 99.9% or more is used, and as a target made of aluminum, a target having a purity of 99.99% or more is used. The output from the sputter power supply Ps is connected to the target 2, and DC power having a negative potential can be input to the target 2. At the lower part of the film forming chamber Pc1, the stage 4 is arranged so as to face the target 2, and the base material Sw can be installed. The film forming chamber Pc1 is provided with a measuring instrument 5 for measuring the total pressure inside the film forming chamber Pc1 and the partial pressure of an impurity gas (for example, nitrogen gas, oxygen gas, water vapor gas, hydrogen gas). As such a measuring instrument 5, a known instrument such as an ionization vacuum gauge or a mass spectrometer can be used, so further description thereof will be omitted. Hereinafter, a method for manufacturing the laminated structure LS by the sputtering apparatus Sm will be specifically described.
大気雰囲気のロードロックチャンバＬｃに基材Ｓｗを投入し、ロードロックチャンバＬｃを真空排気した後、搬送ロボットＲにより基材Ｓｗを成膜チャンバＰｃ１に搬送する。なお、ロードロックチャンバＬｃへの基材Ｓｗの投入に先立ち、搬送チャンバＴｃ及び各成膜チャンバＰｃ１，Ｐｃ２，Ｐｃ３は予め所定圧力（１×１０－３Ｐａ）まで真空排気され、待機状態となっている。基材Ｓｗが成膜チャンバＰｃ１のステージ４上に設置されると、真空排気を続行し、質量分析計５により測定される窒素ガスの分圧が３．０×１０－４Ｐａ以下、酸素ガスの分圧が９．０×１０－５Ｐａ以下、水蒸気ガスの分圧が８．０×１０－４Ｐａ以下、水素ガスの分圧が５．０×１０－５Ｐａ以下に達するまで成膜チャンバＰｃ１内を真空排気する（第１工程の真空排気工程）。
The base material Sw is put into the load lock chamber Lc in the air atmosphere, the load lock chamber Lc is evacuated, and then the base material Sw is transferred to the film forming chamber Pc1 by the transfer robot R. Prior to charging the base material Sw into the load lock chamber Lc, the transfer chamber Tc and the film forming chambers Pc1, Pc2, Pc3 are evacuated to a predetermined pressure (1 × 10 -3 Pa) in advance and are in a standby state. ing. When the base material Sw is installed on the stage 4 of the film forming chamber Pc1, the vacuum exhaust is continued, the partial pressure of the nitrogen gas measured by the mass analyzer 5 is 3.0 × 10 -4 Pa or less, and the oxygen gas. The film formation is performed until the partial pressure of the water vapor gas reaches 9.0 × 10 -4 Pa or less, the partial pressure of the hydrogen gas reaches 5.0 × 10 -5 Pa or less, and the partial pressure of the hydrogen gas reaches 5.0 × 10 -5 Pa or less. Vacuum exhaust the inside of the chamber Pc1 (vacuum exhaust step of the first step).
次に、各ガスの分圧が夫々所定値以下になると、真空排気されている成膜チャンバＰｃ１内に、その全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるようにアルゴンガスを導入し、スパッタ電源Ｐｓからターゲット２に負の電位を持つ直流電力を２０ｋＷ～３０ｋＷ投入する。すると、成膜チャンバＰｃ１内にプラズマが形成され。プラズマ中で電離したアルゴンガスのイオンによりターゲット２がスパッタリングされる。これにより、ターゲット２から飛散したスパッタ粒子が基材Ｓｗの成膜面（ポリイミドフィルムＰｆ）に付着、堆積して基材Ｓｗ上に第１のチタン層Ｌ１が３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの成膜速度で成膜される（第１工程での成膜工程）。このとき、スパッタ時間を適宜設定して、第１のチタン層Ｌ１は、例えば１０ｎｍ～５０ｎｍの膜厚とされる。
Next, when the partial pressure of each gas becomes equal to or less than a predetermined value, argon gas is maintained in the vacuum-exhausted film forming chamber Pc1 so that the total pressure is maintained in the range of 0.2 Pa to 0.5 Pa. Is introduced, and 20 kW to 30 kW of DC power having a negative potential is input from the sputter power source Ps to the target 2. Then, plasma is formed in the film forming chamber Pc1. The target 2 is sputtered by the ions of the argon gas ionized in the plasma. As a result, the sputter particles scattered from the target 2 adhere to and deposit on the film-forming surface (polyimide film Pf) of the base material Sw, and the first titanium layer L1 is formed on the base material Sw at 3 nm / sec to 5 nm / sec. The film is formed at the film speed (the film forming step in the first step). At this time, the spatter time is appropriately set so that the first titanium layer L1 has a film thickness of, for example, 10 nm to 50 nm.
第１工程の終了後、基材Ｓｗを成膜チャンバＰｃ２に搬送し、第１工程と同様に真空排気工程を行う。各ガスの分圧が夫々所定値以下になると、真空排気されている成膜チャンバＰｃ２内に、その全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるようにアルゴンガスを導入し、スパッタ電源Ｐｓからアルミニウム製のターゲット２に負の電位を持つ直流電力を３０ｋＷ～４０ｋＷ投入する。すると、成膜チャンバＰｃ２内にプラズマが形成され、ターゲット２から飛散したスパッタ粒子が第１のチタン層Ｌ１の表面に付着、堆積して第１のチタン層Ｌ１上にアルミニウム層Ｌ２が７ｎｍ／ｓｅｃ～１０ｎｍ／ｓｅｃの成膜速度で成膜される（第２工程での成膜工程）。このとき、スパッタ時間を適宜制御して、アルミニウム層Ｌ２は、例えば２００ｎｍ～８００ｎｍの膜厚とされる。
After the completion of the first step, the base material Sw is transferred to the film forming chamber Pc2, and the vacuum exhaust step is performed in the same manner as in the first step. When the partial pressure of each gas becomes less than a predetermined value, argon gas is introduced into the vacuum-exhausted film forming chamber Pc2 so that the total pressure is maintained in the range of 0.2 Pa to 0.5 Pa. , 30 kW to 40 kW of DC power having a negative potential is input from the sputter power source Ps to the target 2 made of aluminum. Then, plasma is formed in the film forming chamber Pc2, and the sputter particles scattered from the target 2 adhere to and deposit on the surface of the first titanium layer L1 and the aluminum layer L2 is 7 nm / sec on the first titanium layer L1. The film is formed at a film forming rate of about 10 nm / sec (the film forming step in the second step). At this time, the spatter time is appropriately controlled so that the aluminum layer L2 has a film thickness of, for example, 200 nm to 800 nm.
第２工程の終了後、基材Ｓｗを成膜チャンバＰｃ３に搬送し、第１工程と同様に真空排気工程を行う。各ガスの分圧が夫々所定値以下になると、第１工程と同じスパッタ条件で、アルミ二ウム層Ｌ２の上に第２のチタン層Ｌ３が３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの成膜速度で成膜される（第３工程での成膜工程）。このとき、スパッタ時間を適宜制御して、第２のチタン層Ｌ３の膜厚は、第１のチタン層Ｌ１と同様の膜厚（例えば１０～５０ｎｍ）とされる。
After the completion of the second step, the base material Sw is transferred to the film forming chamber Pc3, and the vacuum exhaust step is performed in the same manner as in the first step. When the partial pressure of each gas becomes equal to or less than a predetermined value, a second titanium layer L3 is formed on the aluminum layer L2 at a film forming rate of 3 nm / sec to 5 nm / sec under the same sputtering conditions as in the first step. A film is formed (a film forming step in the third step). At this time, the spatter time is appropriately controlled so that the film thickness of the second titanium layer L3 is the same as that of the first titanium layer L1 (for example, 10 to 50 nm).
以上説明したように積層構造体ＬＳを製造すると、各チタン層Ｌ１，Ｌ３の内部に不純物が取り込まれることが可及的に抑制され、結晶粒界Ｃｆに窒化チタンや酸化チタンといったチタン化合物が形成されることが抑制される（図１中、一点鎖線で囲う部分参照）。加えて、各チタン層Ｌ１，Ｌ３を３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの範囲内の成膜速度で成膜することで、結晶粒Ｃｇの粒径が従来例のものと比較して大きくなり、しかも、これらの結晶粒Ｃｇがその膜厚方向に不揃いに重なり、その結果として、結晶粒界Ｃｆが膜厚方向に繋がらない結晶構造を有するものにできる（図１参照）。なお、このようなチタン層Ｌ１，Ｌ３のＸ線回折を測定したところ、（００２）面での回折ピークと、（１００）面での回折ピークとが確認され、（００２）面での回折ピークに対する（１００）面での回折ピークの強度比は０．２０以上であった。このとき、（００２）面での回折ピークの半値幅が１．０ｄｅｇ以下であり、（１００）面での回折ピークの半値幅が０．６ｄｅｇ以下であった。
As described above, when the laminated structure LS is manufactured, impurities are suppressed as much as possible from being incorporated into each of the titanium layers L1 and L3, and titanium compounds such as titanium nitride and titanium oxide are formed at the grain boundaries Cf. (See the part surrounded by the alternate long and short dash line in FIG. 1). In addition, by forming the titanium layers L1 and L3 at a film forming rate in the range of 3 nm / sec to 5 nm / sec, the grain size of the crystal grains Cg becomes larger than that of the conventional example, and moreover. , These crystal grains Cg are unevenly overlapped in the film thickness direction, and as a result, the crystal grain boundary Cf can be made to have a crystal structure that is not connected in the film film direction (see FIG. 1). When the X-ray diffraction of the titanium layers L1 and L3 was measured, a diffraction peak on the (002) plane and a diffraction peak on the (100) plane were confirmed, and a diffraction peak on the (002) plane was confirmed. The intensity ratio of the diffraction peak to the (100) plane was 0.20 or more. At this time, the half-value width of the diffraction peak on the (002) plane was 1.0 deg or less, and the half-value width of the diffraction peak on the (100) plane was 0.6 deg or less.
次に、上記効果を確認するために、上記スパッタリング装置Ｓｍを用い、以下の実験を行った。
Next, in order to confirm the above effect, the following experiment was conducted using the above sputtering device Sm.
発明実験では、基材Ｓｗをガラス基板Ｓｇ上面にポリイミドフィルムＰｆが貼付されたものとし、基材Ｓｗを成膜チャンバＰｃ１のステージ４上に設置した後、質量分析計５により測定される窒素ガスの分圧が１．０×１０－４Ｐａ、酸素ガスの分圧が８．０×１０－５Ｐａ、水蒸気ガスの分圧が５．０×１０－４Ｐａ、水素ガスの分圧が５．０×１０－５Ｐａに達するまで真空排気した（第１工程の真空排気工程）。このとき、真空チャンバＰｃ１内の全圧は７．３×１０－４Ｐａであった。真空排気工程の後、真空チャンバＰｃ１内の全圧が０．３Ｐａに維持されるようにアルゴンガスを流量１２０ｓｃｃｍで真空チャンバＰｃ１内に導入し、これと併せてターゲット２に直流電力を２０～３０ｋＷ投入してチタン製ターゲット２をスパッタリングして、３ｎｍ／ｓｅｃの成膜速度で基材Ｓｗ表面に第１のチタン層Ｌ１を５０ｎｍの膜厚で成膜した（第１工程の成膜工程）。成膜した第１のチタン層Ｌ１のＸ線回折を測定した結果を図４に実線で示す。表１も参照して、回折角（２θ）３８～３９°付近に（００２）面での回折ピークが、回折角３５～３６°付近に（１００）面での回折ピークが夫々確認され、（００２）面での回折ピークに対する（１００）面での回折ピークの強度比は０．２５、（００２）面での回折ピークの半値幅は０．５ｄｅｇ、（１００）面での回折ピークの半値幅は０．６ｄｅｇであった。第１工程の後、基材Ｓｗを成膜チャンバＰｃ２に搬送し、第１工程と同様に真空排気工程を行った後、成膜チャンバＰｃ２の全圧が０．３Ｐａに維持されるようにアルゴンガスを流量１２０ｓｃｃｍで成膜チャンバＰｃ２内に導入し、これと併せてアルミニウム製のターゲット２に直流電力を３５～４０ｋＷ投入してターゲット２をスパッタリングして、７ｎｍ／ｓｅｃの成膜速度で第１のチタン層Ｌ１上にアルミニウム層Ｌ２を５００ｎｍの膜厚で成膜した。成膜したアルミニウム層Ｌ２のＸ線回折を測定したところ、回折角（２θ）３８～３９°付近に（１１１）面での回折ピークが確認された。第２工程の後、基材Ｓｗを成膜チャンバＰｃ３に搬送し、第１工程と同様に真空排気工程を行い、その後、第１工程と同じ成膜条件で、３ｎｍ／ｓｅｃの成膜速度でアルミニウム層Ｌ２上に第２のチタン層Ｌ３を５０ｎｍの膜厚で成膜し、これにより、積層構造体ＬＳを得た。成膜した第２のチタン層Ｌ３のＸ線回折を測定したところ、第１のチタン層Ｌ１と同様の回折パターン（図４参照）が得られた。そして、このようにして得られた積層構造体ＬＳの屈曲耐性を確認するため、公知の形状（幅５ｍｍ、長さ２０ｍｍ、厚さ０．０２ｍｍ）を有する試験基材（ポリイミドフィルムＰｆ）をガラス基板Ｓｇ上に形成し、試験基材表面に上述したスパッタ条件で第１のチタン層Ｌ１、アルミニウム層Ｌ２、第２のチタン層Ｌ３を順次積層した後、ガラス基板ＳｇとポリイミドフィルムＰｆとの界面で剥離して得た積層構造体ＬＳに対して、引張試験機（ＯＲＩＥＮＴＥＣ製の「ＳＴＡ－１１５０」）を用いて引張試験（引張速度は０．５ｍｍ／ｍｉｎ）を実施したところ、５％、１０％の伸び量を与えるのに必要な引張荷重を加えても、積層構造体の伸び量は１０％以内（５％、８％）に抑えられることが確認された。また、５％、１０％の伸び量を与える引張荷重を加えたときの抵抗Ｒを抵抗測定器（ＡＤＶＡＮＴＥＳＴ製の「ＡＤ７４６１Ａ」）を用いて夫々測定し、引張荷重を加えないときの抵抗Ｒ０に対する抵抗上昇率（＝（Ｒ－Ｒ０）／Ｒ０）を求めたところ、１０％以内（５％、８％）に抑えることができることが確認された。また、引張試験後の積層構造体ＬＳの表面状態を市販のMicroscopeを用いて観察したところ、クラックが発生していないことが確認された。これらの結果より、本発明実験で得られた積層構造体ＬＳは、従来例のものと比較して強い屈曲耐性を有することが判った。
In the invention experiment, it is assumed that the substrate Sw is a glass substrate Sg on which the polyimide film Pf is attached, and the substrate Sw is placed on the stage 4 of the film forming chamber Pc1 and then the nitrogen gas measured by the mass analyzer 5. The partial pressure of is 1.0 × 10 -4 Pa, the partial pressure of oxygen gas is 8.0 × 10 -5 Pa, the partial pressure of steam gas is 5.0 × 10 -4 Pa, and the partial pressure of hydrogen gas is 5. Vacuum exhausted until reaching 0.0 × 10 -5 Pa (vacuum exhaust step of the first step). At this time, the total pressure in the vacuum chamber Pc1 was 7.3 × 10 -4 Pa. After the vacuum exhaust step, argon gas is introduced into the vacuum chamber Pc1 at a flow rate of 120 sccm so that the total pressure in the vacuum chamber Pc1 is maintained at 0.3 Pa, and at the same time, 20 to 30 kW of DC power is applied to the target 2. The titanium target 2 was charged and sputtered to form a first titanium layer L1 on the surface of the base material Sw at a film forming rate of 3 nm / sec with a film thickness of 50 nm (the film forming step of the first step). The result of measuring the X-ray diffraction of the first titanium layer L1 formed into a film is shown by a solid line in FIG. With reference to Table 1, a diffraction peak on the (002) plane was confirmed near the diffraction angle (2θ) 38 to 39 °, and a diffraction peak on the (100) plane was confirmed near the diffraction angle 35 to 36 °. The intensity ratio of the diffraction peak on the (100) plane to the diffraction peak on the 002) plane is 0.25, the half width of the diffraction peak on the (002) plane is 0.5 deg, and half of the diffraction peak on the (100) plane. The price range was 0.6 deg. After the first step, the substrate Sw is transferred to the film forming chamber Pc2, and after performing the vacuum exhaust step in the same manner as in the first step, argon is maintained so that the total pressure of the film forming chamber Pc2 is maintained at 0.3 Pa. A gas is introduced into the film forming chamber Pc2 at a flow rate of 120 sccm, and at the same time, a DC power of 35 to 40 kW is applied to the aluminum target 2 to sputter the target 2, and the first film forming rate is 7 nm / sec. An aluminum layer L2 was formed on the titanium layer L1 with a film thickness of 500 nm. When the X-ray diffraction of the formed aluminum layer L2 was measured, a diffraction peak on the (111) plane was confirmed in the vicinity of the diffraction angle (2θ) of 38 to 39 °. After the second step, the substrate Sw is transferred to the film forming chamber Pc3, the vacuum exhaust step is performed in the same manner as in the first step, and then the film forming conditions are the same as those in the first step, and the film forming rate is 3 nm / sec. A second titanium layer L3 was formed on the aluminum layer L2 with a film thickness of 50 nm, whereby a laminated structure LS was obtained. When the X-ray diffraction of the second titanium layer L3 formed into a film was measured, a diffraction pattern similar to that of the first titanium layer L1 (see FIG. 4) was obtained. Then, in order to confirm the bending resistance of the laminated structure LS thus obtained, a test substrate (polyimide film Pf) having a known shape (width 5 mm, length 20 mm, thickness 0.02 mm) is made of glass. After forming on the substrate Sg and sequentially laminating the first titanium layer L1, the aluminum layer L2, and the second titanium layer L3 on the surface of the test substrate under the above-mentioned spatter conditions, the interface between the glass substrate Sg and the polyimide film Pf. A tensile test (tensile speed of 0.5 mm / min) was carried out on the laminated structure LS obtained by peeling in 1) using a tensile tester (“STA-1150” manufactured by ORIENTEC). It was confirmed that the elongation amount of the laminated structure was suppressed to within 10% (5%, 8%) even when the tensile load required to give the elongation amount of 10% was applied. Further, the resistance R when a tensile load giving an elongation amount of 5% and 10% is applied is measured using a resistance measuring device (“AD7461A” manufactured by ADVANTEST), respectively, with respect to the resistance R0 when no tensile load is applied. When the resistance increase rate (= (R-R0) / R0) was determined, it was confirmed that the resistance increase rate could be suppressed to within 10% (5%, 8%). Moreover, when the surface state of the laminated structure LS after the tensile test was observed using a commercially available microscope, it was confirmed that no cracks were generated. From these results, it was found that the laminated structure LS obtained in the experiment of the present invention has stronger bending resistance as compared with that of the conventional example.
（表１）
(Table 1)
次に、上記発明実験に対する比較のため、以下の比較実験を行った。比較実験１では、第１及び第３の各工程の成膜工程での成膜チャンバＰｃ１内の全圧を０．６Ｐａに維持して成膜速度を２ｎｍ／ｓｅｃとした点を除き、上記発明実験と同様の方法で積層構造体ＬＳを得た。上記発明実験と同様の条件で引張試験を実施したところ、積層構造体ＬＳの伸び量が倍以上となることが確認された。また、上記発明実験と同様に抵抗上昇率を求めたところ、３０％、４００％であった。また、上記発明実験と同様に引張試験後の積層構造体ＬＳの表面状態を観察したところ、クラックが発生して白色化していることが確認された。これらの結果より、本比較実験１で得られた積層構造体ＬＳは弱い屈曲耐性を有することが判った。尚、本比較実験１で成膜された第１のチタン層Ｌ１のＸ線回折を測定したところ、図４に破線で示すように、（１００）面での回折ピークは確認されず、（００２）面での回折ピークのみが確認され、その（００２）面での回折ピークの半値幅は０．９ｄｅｇであった。このような回折パターンを有する場合、図５（ａ）に示すように、小さな結晶粒Ｃｇが膜厚方向に整列して結晶粒界Ｃｆがその膜厚方向にのびるように繋がった結晶構造を有すると推察される。
Next, the following comparative experiment was conducted for comparison with the above invention experiment. In Comparative Experiment 1, the above invention was made except that the total pressure in the film forming chamber Pc1 in the film forming steps of the first and third steps was maintained at 0.6 Pa and the film forming rate was set to 2 nm / sec. The laminated structure LS was obtained by the same method as in the experiment. When the tensile test was carried out under the same conditions as the above-mentioned invention experiment, it was confirmed that the elongation amount of the laminated structure LS was more than doubled. Further, when the resistance increase rate was determined in the same manner as in the above invention experiment, it was 30% and 400%. Further, when the surface state of the laminated structure LS after the tensile test was observed in the same manner as in the above-mentioned invention experiment, it was confirmed that cracks were generated and the laminated structure was whitened. From these results, it was found that the laminated structure LS obtained in this comparative experiment 1 has weak bending resistance. When the X-ray diffraction of the first titanium layer L1 formed in the comparative experiment 1 was measured, as shown by the broken line in FIG. 4, the diffraction peak on the (100) plane was not confirmed, and (002). Only the diffraction peak on the (002) plane was confirmed, and the half width of the diffraction peak on the (002) plane was 0.9 deg. When having such a diffraction pattern, as shown in FIG. 5A, it has a crystal structure in which small crystal grains Cg are aligned in the film thickness direction and the crystal grain boundaries Cf are connected so as to extend in the film thickness direction. It is inferred that.
また、比較実験２では、第１及び第３の各工程にて真空排気工程を行わない点（成膜工程のみを行う点）を除き、上記発明実験と同様の方法で積層構造体ＬＳを得た。即ち、真空チャンバＰｃ１内の全圧が所定真空度（２．８×１０－３Ｐａ）に到達すると、不純物ガスの分圧に関わらず、真空チャンバＰｃ１内に希ガスを導入した。このときの不純物ガスの分圧を測定したところ、窒素ガスの分圧が５．０×１０－４Ｐａ、酸素ガスの分圧が２．０×１０－４Ｐａ、水蒸気ガスの分圧が２．０×１０－３Ｐａ、水素ガスの分圧が５．０×１０－５Ｐａであり、水素ガス以外は基準値を下回っていた。上記発明実験と同様の条件で引張試験を実施したところ、積層構造体ＬＳの伸び量は倍以上となることが確認された。また、上記発明実験と同様に抵抗上昇率を求めたところ、比較実験１よりも更に悪い１２０％、６５０％であった。また、上記発明実験と同様に引張試験後の積層構造体ＬＳの表面状態を観察したところ、クラックが発生して白色化していることが確認された。これらの結果より、本比較実験２で得られた積層構造体ＬＳは弱い屈曲耐性を有することが判った。尚、成膜した第１のチタン層Ｌ１のＸ線回折を測定したところ、（００２）面での回折ピークだけでなく（１００）面での回折ピークが観察されたものの、（００２）面での回折ピークに対する（１００）面での回折ピークの強度比は０．２０よりも小さい０．１１であった。また、（１００）面での回折ピークの半値幅は０．６ｄｅｇよりも大きい０．７ｄｅｇであった。このような回折パターンを有する場合、図５（ｂ）に示すように、結晶粒界Ｃｆに窒化チタンや酸化チタンといったチタン化合物Ｉｍが形成されていると推察される。
Further, in the comparative experiment 2, the laminated structure LS was obtained by the same method as the above-mentioned invention experiment except that the vacuum exhaust step was not performed in each of the first and third steps (the point where only the film forming step was performed). rice field. That is, when the total pressure in the vacuum chamber Pc1 reached a predetermined vacuum degree (2.8 × 10 -3 Pa), the noble gas was introduced into the vacuum chamber Pc1 regardless of the partial pressure of the impurity gas. When the partial pressure of the impurity gas at this time was measured, the partial pressure of the nitrogen gas was 5.0 × 10 -4 Pa, the partial pressure of the oxygen gas was 2.0 × 10 -4 Pa, and the partial pressure of the steam gas was 2. It was 0.0 × 10 -3 Pa and the partial pressure of hydrogen gas was 5.0 × 10 -5 Pa, which were below the standard values except for hydrogen gas. When the tensile test was carried out under the same conditions as the above-mentioned invention experiment, it was confirmed that the elongation amount of the laminated structure LS was more than doubled. Further, when the resistance increase rate was obtained in the same manner as in the above-mentioned invention experiment, it was 120% and 650%, which were worse than those in the comparative experiment 1. Further, when the surface state of the laminated structure LS after the tensile test was observed in the same manner as in the above-mentioned invention experiment, it was confirmed that cracks were generated and the laminated structure was whitened. From these results, it was found that the laminated structure LS obtained in this comparative experiment 2 has weak bending resistance. When the X-ray diffraction of the first titanium layer L1 formed into a film was measured, not only the diffraction peak on the (002) plane but also the diffraction peak on the (100) plane was observed, but on the (002) plane. The intensity ratio of the diffraction peak on the (100) plane to the diffraction peak of was 0.11, which is smaller than 0.20. The half width of the diffraction peak on the (100) plane was 0.7 deg, which is larger than 0.6 deg. When having such a diffraction pattern, it is presumed that a titanium compound Im such as titanium nitride or titanium oxide is formed at the grain boundary Cf as shown in FIG. 5 (b).
また、比較実験３では、第１及び第３の各工程の成膜時の成膜チャンバＰｃ１，Ｐｃ３内の全圧を０．６Ｐａに維持して成膜速度を２ｎｍ／ｓｅｃとし、第１及び第３の各工程にて真空排気工程を行わない点（成膜工程のみを行う点）を除き、上記発明実験と同様の方法で積層構造体ＬＳを得た。上記発明実験と同様の条件で引張試験を実施したところ、積層構造体ＬＳの伸び量が倍以上となることが確認された。また、上記発明実験と同様に抵抗上昇率を求めたところ、比較実験２よりも更に悪い３００％、９００％であった。また、上記発明実験と同様に引張試験後の積層構造体ＬＳの表面状態を観察したところ、クラックが発生して白色化していることが確認された。これらの結果より、本比較実験３で得られた積層構造体ＬＳは上記比較実験１，２よりも弱い屈曲耐性を有することが判った。尚、本比較実験３で成膜された第１のチタン層Ｌ１のＸ線回折を測定したところ、（１００）面での回折ピークは確認されず、（００２）面での回折ピークのみが確認され、その（００２）面での回折ピークの半値幅は０．８ｄｅｇであった。このような回折パターンを有する場合、図５（ｃ）に示すように、小さい結晶粒Ｃｇが膜厚方向に整列して結晶粒界Ｃｆがその膜厚方向にのびるように繋がった結晶構造を有し、しかも、その結晶粒界Ｃｆにチタン化合物Ｉｍが形成されていると推測される。
Further, in the comparative experiment 3, the total pressure in the film forming chambers Pc1 and Pc3 at the time of film formation in the first and third steps was maintained at 0.6 Pa, and the film forming rate was set to 2 nm / sec. A laminated structure LS was obtained by the same method as the above-mentioned invention experiment except that the vacuum exhaust step was not performed in each of the third steps (the point where only the film forming step was performed). When the tensile test was carried out under the same conditions as the above-mentioned invention experiment, it was confirmed that the elongation amount of the laminated structure LS was more than doubled. Further, when the resistance increase rate was obtained in the same manner as in the above-mentioned invention experiment, it was 300% and 900%, which were worse than those in the comparative experiment 2. Further, when the surface state of the laminated structure LS after the tensile test was observed in the same manner as in the above-mentioned invention experiment, it was confirmed that cracks were generated and the laminated structure was whitened. From these results, it was found that the laminated structure LS obtained in the comparative experiment 3 has a weaker bending resistance than the comparative experiments 1 and 2. When the X-ray diffraction of the first titanium layer L1 formed in the comparative experiment 3 was measured, the diffraction peak on the (100) plane was not confirmed, and only the diffraction peak on the (002) plane was confirmed. The half width of the diffraction peak on the (002) plane was 0.8 deg. When having such a diffraction pattern, as shown in FIG. 5C, it has a crystal structure in which small crystal grains Cg are aligned in the film thickness direction and the crystal grain boundaries Cf are connected so as to extend in the film thickness direction. Moreover, it is presumed that the titanium compound Im is formed at the grain boundary Cf.
以上、本発明の実施形態について説明したが、本発明の技術思想の範囲を逸脱しない限り、種々の変形が可能である。上記実施形態では、積層構造体ＬＳとして第１のチタン層Ｌ１、アルミニウム層Ｌ２、第３のチタン層Ｌ３を積層したものを例に説明したが、第３のチタン層Ｌ３の上に更に窒化チタン層が積層されたものに対しても本発明を適用することができる。
Although the embodiments of the present invention have been described above, various modifications are possible as long as they do not deviate from the scope of the technical idea of the present invention. In the above embodiment, a laminated structure LS in which a first titanium layer L1, an aluminum layer L2, and a third titanium layer L3 are laminated has been described as an example, but titanium nitride is further described on the third titanium layer L3. The present invention can also be applied to those in which layers are laminated.
また、上記実施形態では、成膜チャンバＰｃ１，Ｐｃ２，Ｐｃ３の間で基材Ｓｗをin-situで搬送し、真空雰囲気中で第１のチタン層Ｌ１、アルミニウム層Ｌ２、第２のチタン層Ｌ３を一貫して成膜する場合を例に説明したが、これに限定されず、第１及び第２のチタン層Ｌ１，Ｌ３とアルミニウム層Ｌ２とを異なるスパッタリング装置で実施する場合にも本発明は適用することができる。また、第１のチタン層Ｌ１と第２のチタン層Ｌ３とを同一の成膜チャンバで成膜してもよい。
Further, in the above embodiment, the base material Sw is conveyed in-situ between the film forming chambers Pc1, Pc2, and Pc3, and the first titanium layer L1, the aluminum layer L2, and the second titanium layer L3 are conveyed in a vacuum atmosphere. Although the case of consistently forming a film is described as an example, the present invention is not limited to this, and the present invention is also applicable to the case where the first and second titanium layers L1 and L3 and the aluminum layer L2 are carried out by different sputtering devices. Can be applied. Further, the first titanium layer L1 and the second titanium layer L3 may be formed in the same film forming chamber.
ＬＳ…積層構造体、Ｌ１…第１のチタン層、Ｌ２…アルミニウム層、Ｌ３…第２のチタン層、Ｓｗ…基材、Ｐｃ１，Ｐｃ２，Ｐｃ３…成膜チャンバ（真空チャンバ）、２…ターゲット。
LS ... laminated structure, L1 ... first titanium layer, L2 ... aluminum layer, L3 ... second titanium layer, Sw ... base material, Pc1, Pc2, Pc3 ... film formation chamber (vacuum chamber), 2 ... target.
Claims (4)
- 第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した積層構造体において、
第１及び第２の各チタン層は、Ｘ線回折測定によるミラー指数における（００２）面及び（１００）面に回析ピークを持つ結晶構造を有し、（００２）面での回折ピークの半値幅が１．０ｄｅｇ以下、（１００）面での回折ピークの半値幅が０．６ｄｅｇ以下であることを特徴とする積層構造体。 In a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated.
Each of the first and second titanium layers has a crystal structure having diffraction peaks on the (002) plane and the (100) plane in the Miller index measured by X-ray diffraction measurement, and is half of the diffraction peak on the (002) plane. A laminated structure characterized in that the value width is 1.0 deg or less and the half width of the diffraction peak on the (100) plane is 0.6 deg or less. - 前記アルミニウム層は、Ｘ線回折測定によるミラー指数における（１１１）面に回析ピークを持つ結晶構造を有することを特徴とする請求項１記載の積層構造体。 The laminated structure according to claim 1, wherein the aluminum layer has a crystal structure having a diffraction peak on the (111) plane in the Miller index measured by X-ray diffraction measurement.
- 第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した積層構造体の製造方法において、
スパッタリング法により、基材上に第１のチタン層を成膜する第１工程と、第１のチタン層の上にアルミニウム層を成膜する第２工程と、アルミニウム層の上に第２のチタン層を成膜する第３工程とを含み、
第１及び第３の各工程は、窒素ガスの分圧が３．０×１０－４Ｐａ以下、酸素ガスの分圧が９．０×１０－５Ｐａ以下、水蒸気ガスの分圧が８．０×１０－４Ｐａ以下、水素ガスの分圧が５．０×１０－５Ｐａ以下に夫々達するまで、チタン製のターゲットと基材とが配置された真空チャンバ内を真空排気する真空排気工程と、真空チャンバ内の全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるように希ガスを導入し、チタン製のターゲットに所定電力を投入して３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの範囲内の成膜速度で第１及び第２の各チタン層を成膜する成膜工程と、を更に含むことを特徴とする積層構造体の製造方法。 In a method for manufacturing a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated.
A first step of forming a first titanium layer on a substrate by a sputtering method, a second step of forming an aluminum layer on the first titanium layer, and a second titanium on the aluminum layer. Including the third step of forming a layer
In each of the first and third steps, the partial pressure of nitrogen gas is 3.0 × 10 -4 Pa or less, the partial pressure of oxygen gas is 9.0 × 10 -5 Pa or less, and the partial pressure of steam gas is 8. Vacuum exhaust process in which the inside of the vacuum chamber in which the titanium target and the base material are arranged is evacuated until the partial pressure of hydrogen gas reaches 0 × 10 -4 Pa or less and the partial pressure of hydrogen gas reaches 5.0 × 10 -5 Pa or less. Then, a rare gas was introduced so that the total pressure in the vacuum chamber was maintained in the range of 0.2 Pa to 0.5 Pa, and a predetermined power was applied to the titanium target at 3 nm / sec to 5 nm / sec. A method for manufacturing a laminated structure, further comprising a film forming step of forming the first and second titanium layers at a film forming rate within the range. - 前記第２工程は、アルミニウム製のターゲットと基材とが配置された真空チャンバ内の全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるように希ガスを導入し、アルミニウム製のターゲットに所定電力を投入して７ｎｍ／ｓｅｃ～１０ｎｍ／ｓｅｃの範囲内の成膜速度でアルミニウム層を成膜する成膜工程を更に含むことを特徴とする請求項３記載の積層構造体の製造方法。 In the second step, a rare gas is introduced so that the total pressure in the vacuum chamber in which the aluminum target and the base material are arranged is maintained in the range of 0.2 Pa to 0.5 Pa, and the aluminum is made of aluminum. The production of the laminated structure according to claim 3, further comprising a film forming step of applying a predetermined power to the target to form an aluminum layer at a film forming rate in the range of 7 nm / sec to 10 nm / sec. Method.
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| JPH04264719A (en) * | 1991-02-19 | 1992-09-21 | Sony Corp | Formation of wiring |
| JPH1060637A (en) * | 1996-07-09 | 1998-03-03 | Applied Materials Inc | Method and device for depositing material on substrate |
| JPH10223632A (en) * | 1997-02-04 | 1998-08-21 | Nippon Steel Corp | Semiconductor device |
| JP2012164940A (en) * | 2011-02-09 | 2012-08-30 | Rohm Co Ltd | Semiconductor device and manufacturing method of the same |
| JP2015177105A (en) * | 2014-03-17 | 2015-10-05 | 株式会社ジャパンディスプレイ | Display device and method of manufacturing display device |
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| JPH04264719A (en) * | 1991-02-19 | 1992-09-21 | Sony Corp | Formation of wiring |
| JPH1060637A (en) * | 1996-07-09 | 1998-03-03 | Applied Materials Inc | Method and device for depositing material on substrate |
| JPH10223632A (en) * | 1997-02-04 | 1998-08-21 | Nippon Steel Corp | Semiconductor device |
| JP2012164940A (en) * | 2011-02-09 | 2012-08-30 | Rohm Co Ltd | Semiconductor device and manufacturing method of the same |
| JP2015177105A (en) * | 2014-03-17 | 2015-10-05 | 株式会社ジャパンディスプレイ | Display device and method of manufacturing display device |
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