CN116056884A - Laminated structure and method for manufacturing laminated structure - Google Patents
Laminated structure and method for manufacturing laminated structure Download PDFInfo
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- CN116056884A CN116056884A CN202180062989.7A CN202180062989A CN116056884A CN 116056884 A CN116056884 A CN 116056884A CN 202180062989 A CN202180062989 A CN 202180062989A CN 116056884 A CN116056884 A CN 116056884A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 96
- 239000010936 titanium Substances 0.000 claims abstract description 96
- 239000013078 crystal Substances 0.000 claims abstract description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 42
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 26
- 238000004544 sputter deposition Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 238000005452 bending Methods 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 79
- 238000002474 experimental method Methods 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000009864 tensile test Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 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
- 238000012546 transfer Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 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
- 230000000694 effects Effects 0.000 description 2
- -1 steam Chemical compound 0.000 description 2
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—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
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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
Abstract
The invention provides a laminated structure with strong bending resistance and a manufacturing method of the laminated structure. In the Laminated Structure (LS) of the present invention in which the 1 st titanium layer (L1), the aluminum layer (L2) and the 2 nd titanium layer (L3) are laminated in this order, the 1 st titanium layer and the 2 nd titanium layer have a crystal structure having diffraction peaks on the (002) crystal plane and the (100) crystal plane of the Miller index measured by X-ray diffraction, the half-width of the diffraction peak on the (002) crystal plane is 1.0 degree or less, and the half-width of the diffraction peak on the (100) crystal plane is 0.6 degree or less.
Description
Technical Field
The present invention relates to a laminated structure in which a 1 st titanium layer, an aluminum layer, and a 2 nd titanium layer are laminated in this order, and a method for manufacturing the laminated structure.
Background
Such a laminated structure is used as a source/drain electrode of a switching element (thin film transistor) in an electronic device such as a display, a smart phone, or an electronic book (for example, see patent document 1). On the other hand, with recent development of flexible electronic devices, a laminated structure having a titanium layer with high hardness is required to have high bending resistance.
In general, a titanium layer and an aluminum layer of a laminated structure are formed continuously in a vacuum atmosphere by a sputtering method (for example, see patent document 1). For example, in the formation of a titanium layer or an aluminum layer, a vacuum chamber in which a titanium or aluminum target and a substrate are disposed so as to face each other is evacuated to a predetermined pressure, a rare gas (for example, argon gas) is introduced into the vacuum chamber, a dc power having a negative potential is applied to the target to form a plasma, the target is sputtered by ions of the rare gas ionized in the plasma, and sputtered particles scattered from the target are deposited on the substrate to form the titanium layer or the aluminum layer with a desired film thickness (for example, 50nm for the 1 st titanium layer, 500nm for the aluminum layer, and 50nm for the 2 nd titanium layer). In this case, various sputtering conditions (for example, an applied power of 20 to 40kW and a total pressure of 0.2 to 1.0 Pa) such as an applied power to the target, a gas introduction amount of the rare gas, and a total pressure in the vacuum chamber during film formation are set in consideration of the productivity and the film thickness distribution.
Here, in order to confirm the bending resistance of the laminated structure, it was found that when a tensile test was performed on the laminated structure peeled from the test substrate after sequentially laminating the 1 st titanium layer, the aluminum layer, and the 2 nd titanium layer on the surface of the test substrate under a predetermined sputtering condition, the laminated structure was elongated by at least one time by applying a tensile load required for forming an elongation of 5%. Further, when the surface of the laminate structure after the tensile test (i.e., the surface of the titanium layer) was observed, it was found that many cracks extending in the thickness direction were generated in the titanium layer. Accordingly, the inventors of the present invention have made intensive studies and found that when the laminate structure has a crystal structure in which smaller crystal grains are arranged in the film thickness direction and grain boundaries are connected so as to extend in the film thickness direction, and impurities such as nitrogen molecules and oxygen molecules that enter the titanium layer during film formation cause formation of hard and brittle titanium compounds such as titanium nitride and titanium oxide on the grain boundaries, the laminate structure cannot attain strong bending resistance.
Prior art literature
Patent literature
Japanese patent laid-open No. 2015-177105 (patent document 1)
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made based on the above-described knowledge, and an object of the present invention is to provide a laminated structure having high bending resistance and a method for manufacturing the laminated structure.
Means for solving the technical problems
In order to solve the above-described problems, a laminated structure according to the present invention, in which a 1 st titanium layer, an aluminum layer, and a 2 nd titanium layer are laminated in this order, is characterized in that: the 1 st titanium layer and the 2 nd titanium layer have a crystal structure having diffraction peaks on (002) and (100) crystal planes of a miller index measured by X-ray diffraction, and the half-width of the diffraction peak on the (002) crystal plane is 1.0 degree or less and the half-width of the diffraction peak on the (100) crystal plane is 0.6 degree or less. In this case, the aluminum layer preferably has a crystal structure having a diffraction peak on the (111) plane of the miller index measured by X-ray diffraction.
In order to solve the above-described problems, a method for manufacturing a laminated structure according to the present invention, in which a 1 st titanium layer, an aluminum layer, and a 2 nd titanium layer are laminated in this order, is characterized by comprising: a 1 st step of forming a 1 st titanium layer on a substrate by a sputtering method; a step 2 of forming an aluminum layer on the 1 st titanium layer; and a 3 rd step of forming a 2 nd titanium layer on the aluminum layer, the 1 st and 3 rd steps further comprising: a vacuum exhausting step of vacuum-exhausting the vacuum chamber in which the titanium target and the base material are disposed until the respective nitrogen is reachedThe partial pressure of the gas was 3.0X10 -4 Pa or lower, oxygen partial pressure of 9.0X10 -5 A partial pressure of water vapor of 8.0X10 Pa or lower -4 Pa or less, and a partial pressure of hydrogen of 5.0X10 -5 Pa or less; and a film forming step of introducing a rare gas so that the total pressure in the vacuum chamber is maintained within a range of 0.2Pa to 0.5Pa, and applying a predetermined electric power to the titanium target to form the 1 st titanium layer and the 2 nd titanium layer at a film forming rate within a range of 3nm/sec to 5 nm/sec. In this case, the 2 nd step preferably further comprises a film forming step of introducing a rare gas so that the total pressure in the vacuum chamber in which the aluminum target and the base material are disposed is maintained within a range of 0.2Pa to 0.5Pa, and applying a predetermined electric power to the aluminum target to form an aluminum layer at a film forming rate within a range of 7nm/sec to 10 nm/sec.
In this manner, before the 1 st titanium layer, the aluminum layer, and the 2 nd titanium layer are formed by sputtering in the vacuum chamber in the vacuum atmosphere, the vacuum chamber is evacuated until the partial pressure of the impurity gas (for example, nitrogen, oxygen, steam, and hydrogen) becomes equal to or lower than a predetermined value, whereby the formation of titanium compounds such as titanium nitride and titanium oxide at the grain boundaries of the 1 st titanium layer and the 2 nd titanium layer can be suppressed as much as possible. In addition, when the film formation speed of the 1 st titanium layer and the 2 nd titanium layer is set in the range of 3nm/sec to 5nm/sec, the 1 st titanium layer and the 2 nd titanium layer may have a crystal structure in which crystal grains having a large particle diameter are unevenly stacked in the film thickness direction and grain boundaries are not connected in the film thickness direction.
The titanium layer formed as described above was subjected to X-ray diffraction, and it was confirmed that the intensity ratio of the diffraction peak on the (002) crystal plane to the diffraction peak on the (100) crystal plane was 0.20 or more. In this case, the half width of the diffraction peak on the (002) plane is 1.0 degree or less, and the half width of the diffraction peak on the (100) plane is 0.6 degree or less, whereby, if the diffraction pattern is provided, the formation of the titanium compound at the grain boundaries of the 1 st titanium layer and the 2 nd titanium layer is suppressed, and the crystal structure is such that crystal grains having a large grain size are unevenly overlapped in the film thickness direction and the grain boundaries are not connected. In the tensile test performed on the laminated structure similar to the above, even when a tensile load required for forming an elongation of 5% or 10% is applied, the elongation of the laminated structure can be suppressed to 10% or less, and it can be confirmed that no crack is generated by surface observation of the laminated structure after the tensile test. Therefore, the laminated structure of the present invention has a stronger bending resistance than the laminated structure of the prior art.
Drawings
Fig. 1 is a schematic view illustrating a laminated structure according to an embodiment of the present invention.
Fig. 2 is a schematic view illustrating a sputtering apparatus for carrying out the method for manufacturing a laminated structure according to the embodiment of the present invention.
Fig. 3 is a schematic view illustrating the film forming chamber Pc1 shown in fig. 2.
Fig. 4 is a graph showing experimental results for confirming the effects of the present invention.
Fig. 5 (a) - (c) are schematic diagrams illustrating the crystal structure of the titanium layer formed in comparative experiment 1-comparative experiment 3.
Detailed Description
Embodiments of a laminated structure and a method for manufacturing a laminated structure according to the present invention are described below with reference to the drawings.
As shown in fig. 1, in the laminated structure LS of the present embodiment, the base material Sw is provided as a product in which a polyimide film Pf is attached to the surface of a glass substrate Sg (can be peeled off at the interface between the glass substrate Sg and the polyimide film Pf), and the 1 st titanium layer L1, the aluminum layer L2, and the 2 nd titanium layer L3 are provided on the surface of the base material Sw in succession and sequentially formed (laminated) by a sputtering method in a vacuum atmosphere.
As shown in fig. 2, the sputtering apparatus Sm that can be used for forming the film of the laminated structure LS is a so-called cluster tool type sputtering apparatus, and includes a transfer chamber Tc having a center of the transfer robot R, and a load lock chamber Lc, a vacuum chamber (hereinafter referred to as "film forming chamber") Pc1 for forming the 1 st titanium layer L1, a film forming chamber Pc2 for forming the aluminum layer L2, and a film forming chamber Pc3 for forming the 2 nd titanium layer L3 are connected to each other around the transfer chamber Tc via a gate valve Gv. Here, the film forming chambers Pc1, pc2, and Pc3 are provided with the same structure except for the targets usedTherefore, as described with reference to fig. 3 by taking the film forming chamber Pc1 as an example, the film forming chamber Pc1 is connected to an exhaust pipe 11 which communicates with a vacuum pump unit Pu constituted by a turbo molecular pump, a rotary pump, or the like, and can vacuum-exhaust the film forming chamber Pc1 to a predetermined vacuum degree (for example, 1×10 -6 Pa). A gas pipe 13 provided with a mass flow controller 12 is connected to a side wall of the vacuum chamber Pc1, and a rare gas (for example, argon gas) whose flow rate is controlled can be introduced into the film forming chamber Pc1. A titanium target 2 (an aluminum target in the film forming chamber Pc 2) is disposed above the film forming chamber Pc1 in a state of facing the substrate Sw, and a known magnet unit 3 is disposed above the titanium target.
The titanium material target 2 was 99.9% or more pure, and the aluminum material target was 99.99% or more pure. The target 2 is connected to an output from a sputtering power supply Ps, and dc power with a negative potential can be applied to the target 2. A stage 4 is disposed at a lower portion of the film forming chamber Pc1 so as to face the target 2, and a substrate Sw can be provided. The film forming chamber Pc1 is provided with a measuring device 5 for measuring the total pressure inside and the partial pressure of impurity gases (for example, nitrogen, oxygen, water vapor, and hydrogen). As such a measuring instrument 5, a known instrument such as an ionization gauge or a mass spectrometer can be used, and thus a further description thereof will be omitted. Hereinafter, a method for manufacturing the laminated structure LS using the sputtering apparatus Sm will be specifically described.
The substrate Sw is placed in the load lock chamber Lc in an atmosphere, the load lock chamber Lc is evacuated, and then the substrate Sw is transferred to the film forming chamber Pc1 by the transfer robot R. Before the substrate Sw is placed in the load lock chamber Lc, the transfer chamber Tc and the film forming chambers Pc1, pc2, and Pc3 are vacuum-exhausted to a predetermined pressure (1×10) -3 Pa) in a standby state. When the substrate Sw is set on the stage 4 of the film forming chamber Pc1, vacuum evacuation is continued to evacuate the film forming chamber Pc1 until the partial pressure of nitrogen gas measured by the mass spectrometer 5 reaches 3.0×10 -4 Pa or lower, oxygen partial pressure of 9.0X10 -5 A partial pressure of water vapor of 8.0X10 Pa or lower -4 Pa or less, and a partial pressure of hydrogen of 5.0X10 -5 Pa or less (vacuum evacuation step in step 1).
Next, when the partial pressure of each gas becomes equal to or lower than a predetermined value, argon gas is introduced into the film forming chamber Pc1 in which vacuum evacuation is performed so that the total pressure thereof is maintained within a range of 0.2Pa to 0.5Pa, and a negative potential dc power of 20kW to 30kW is applied from the sputtering power supply Ps to the target 2. In this way, plasma is formed in the film forming chamber Pc1. The target 2 is sputtered by ionized argon ions in the plasma. Thereby, the sputtered particles scattered from the target 2 adhere to and accumulate on the film formation surface (polyimide film Pf) of the substrate Sw, and the 1 st titanium layer L1 is formed on the substrate Sw at a film formation rate of 3nm/sec to 5nm/sec (film formation step in the 1 st step). At this time, the sputtering time is set so that the 1 st titanium layer L1 has a film thickness of, for example, 10nm to 50 nm.
After the step 1 is completed, the substrate Sw is transferred to the film forming chamber Pc2, and the vacuum evacuation step is performed in the same manner as the step 1. When the partial pressure of each gas is equal to or lower than a predetermined value, argon gas is introduced into the vacuum-exhausted film forming chamber Pc2 so that the total pressure thereof is maintained within a range of 0.2Pa to 0.5Pa, and a negative potential dc power of 30kW to 40kW is applied from the sputtering power supply Ps to the aluminum target 2. In this way, plasma is formed in the film forming chamber Pc2, and sputtering particles scattered from the target 2 adhere to and deposit on the surface of the 1 st titanium layer L1, and the aluminum layer L2 is formed on the 1 st titanium layer L1 at a film forming rate of 7nm/sec to 10nm/sec (film forming step in step 2). At this time, the sputtering time is appropriately controlled so that the aluminum layer L2 has a film thickness of, for example, 200nm to 800 nm.
After the end of the step 2, the substrate Sw is transferred to the film forming chamber Pc3, and the vacuum evacuation step is performed in the same manner as the step 1. When the partial pressure of each gas is equal to or less than a predetermined value, a 2 nd titanium layer L3 is formed on the aluminum layer L2 at a film formation rate of 3nm/sec to 5nm/sec under the same sputtering conditions as in step 1 (film formation step in step 3). At this time, the sputtering time is appropriately controlled so that the film thickness of the 2 nd titanium layer L3 is the same as that of the 1 st titanium layer L1 (for example, 10 to 50 nm).
When the laminated structure LS is manufactured as described above, the entry of impurities into the titanium layers L1 and L3 can be suppressed as much as possible, and the formation of titanium compounds such as titanium nitride and titanium oxide at the grain boundary Cf (see the portion surrounded by the dashed line in fig. 1) can be suppressed. Further, by forming the titanium layers L1 and L3 at a film formation rate in the range of 3nm/sec to 5nm/sec, the grain size of the crystal grains Cg becomes larger than in the conventional example, and the crystal grains Cg are unevenly overlapped in the film thickness direction, whereby a product having a crystal structure in which the grain boundaries Cf are not connected in the film thickness direction can be obtained (see fig. 1). When the X-ray diffraction of the titanium layers L1 and L3 was measured, it was confirmed that the intensity ratio of the diffraction peak on the (002) crystal plane to the diffraction peak on the (100) crystal plane was 0.20 or more. At this time, the half width of the diffraction peak on the (002) crystal plane is 1.0 degree or less, and the half width of the diffraction peak on the (100) crystal plane is 0.6 degree or less.
Next, in order to confirm the above effect, the following experiment was performed using the sputtering apparatus Sm.
In the experiments of the present invention, the substrate Sw was set as a product in which the polyimide film Pf was stuck to the upper surface of the glass substrate Sg, and after the substrate Sw was set on the stage 4 of the film forming chamber Pc1, vacuum-evacuation was performed until the partial pressure of nitrogen gas measured by the mass spectrometer 5 was 1.0x10 -4 Pa, partial pressure of oxygen of 8.0X10 -5 Pa, partial pressure of water vapor 5.0X10 -4 Pa, partial pressure of hydrogen is 5.0X10 -5 Pa (vacuum evacuation step in step 1). At this time, the total pressure in the vacuum chamber Pc1 was 7.3X10 -4 Pa. After the vacuum evacuation step, argon gas was introduced into the vacuum chamber Pc1 at a flow rate of 120 seem so as to maintain the total pressure in the vacuum chamber Pc1 at 0.3Pa, and in combination therewith, a direct current power of 20 to 30kW was applied to the target 2, and the titanium target 2 was sputtered to form a 1 st titanium layer L1 on the surface of the substrate Sw at a film thickness of 50nm at a film formation rate of 3nm/sec (film formation step 1). The result of measuring the X-ray diffraction of the 1 st titanium layer L1 formed is shown in fig. 4 as a solid line. Referring to table 1, diffraction peaks on the (002) crystal plane were observed near the diffraction angles (2θ) 38 to 39 °, diffraction peaks on the (100) crystal plane were observed near the diffraction angles 35 to 36 °, the intensity ratio of the diffraction peak on the (100) crystal plane to the diffraction peak on the (002) crystal plane was 0.25, the half-width of the diffraction peak on the (002) crystal plane was 0.5 degrees, and the half-width of the diffraction peak on the (100) crystal plane was 0.6 degrees. After the 1 st step, the substrate Sw is transported to a film forming chamberPc2 after the vacuum evacuation step was performed in the same manner as in step 1, argon gas was introduced into the film forming chamber Pc2 at a flow rate of 120 seem so that the total pressure of the film forming chamber Pc2 was maintained at 0.3Pa, and in combination with this, a direct current power of 35 to 40kW was applied to the aluminum target 2, the target 2 was sputtered, and an aluminum layer L2 was formed on the 1 st titanium layer L1 at a film forming rate of 7nm/sec and a film thickness of 500 nm. When the X-ray diffraction of the formed aluminum layer L2 was measured, diffraction peaks on the (111) crystal plane were confirmed in the vicinity of the diffraction angle (2θ) 38 to 39 °. After the step 2, the substrate Sw was transferred to the film forming chamber Pc3, and a vacuum evacuation step was performed in the same manner as the step 1, and then a 2 nd titanium layer L3 was formed on the aluminum layer L2 at a film thickness of 50nm at a film forming rate of 3nm/sec under the same film forming conditions as the step 1, whereby the laminated structure LS was obtained. When the X-ray diffraction of the formed 2 nd titanium layer L3 was measured, the same diffraction pattern as that of the 1 st titanium layer L1 was obtained (see fig. 4). 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 5mm, length 20mm, thickness 0.02 mm) was formed on the glass substrate Sg, the 1 st titanium layer L1, the aluminum layer L2, and the 2 nd titanium layer L3 were laminated in this order on the surface of the test substrate under the above sputtering conditions, and then the laminated structure LS was obtained by peeling off at the interface between the glass substrate Sg and the polyimide film Pf, and a tensile test (tensile speed: 0.5 mm/min) was performed on the laminated structure LS using a tensile tester ("STA-1150" manufactured by orintec), and it was confirmed that the elongation of the laminated structure was suppressed to 10% (5%, 8%) even when a tensile load required for forming an elongation of 5%, 10% was applied. Further, resistance R at the time of applying a tensile load of 5% and 10% elongation was measured using a resistance measuring instrument ("AD 7461A" manufactured by adewanest test (ADVANTEST), and the rate of resistance increase= (R-R0)/R0) with respect to resistance R0 at the time of not applying a tensile load was determined, and it was confirmed that the resistance was suppressed to 10% (5% and 8%). Further, the surface state of the laminate structure LS after the tensile test was observed with a commercially available Microscope (Microscope), and it was confirmed that no crack was generated. From these results, it is clear that the laminated structure LS obtained in the experiment of the present invention has a stronger bending resistance than the laminated structure of the conventional example.
(Table 1)
Next, for comparison with the above-described invention experiments, the following comparative experiments were performed. In comparative experiment 1, a laminated structure LS was obtained by the same method as in the above-described invention experiment, except that the total pressure in the film forming chamber Pc1 in the film forming step of the 1 st step and the 3 rd step was maintained at 0.6Pa, and the film forming speed was set at 2 nm/sec. When a tensile test was performed under the same conditions as in the above-described invention test, it was confirmed that the elongation of the laminated structure LS was one time or more. The resistance increase rate was found to be 30% and 400% in the same manner as in the above-described invention experiment. Further, when the surface state of the laminate structure LS after the tensile test was observed as in the above-described invention test, it was confirmed that cracks were generated and the laminate structure was white. From these results, it is clear that the laminated structure LS obtained in the present comparative experiment 1 has weak bending resistance. Further, when the X-ray diffraction of the 1 st titanium layer L1 formed in this comparative experiment 1 was measured, as shown by the broken line in fig. 4, the diffraction peak on the (100) crystal plane was not confirmed, only the diffraction peak on the (002) crystal plane was confirmed, and the half-width of the diffraction peak on the (002) crystal plane was 0.9 degrees. In the case of having such a diffraction pattern, as shown in fig. 5 (a), it is assumed that the crystal structure has small crystal grains Cg aligned in the film thickness direction and grain boundaries Cf connected so as to extend in the film thickness direction.
In comparative experiment 2, a laminated structure LS was obtained by the same method as in the above-described inventive experiment, except that the vacuum evacuation step was not performed in the 1 st step and the 3 rd step (only the film formation step was performed). That is, when the total pressure in the vacuum chamber Pc1 reaches a predetermined vacuum level (2.8X10 -3 Pa), the rare gas is introduced into the vacuum chamber Pc1 regardless of the partial pressure of the impurity gas. The partial pressure of the impurity gas at this time was measured, and found to be 5.0X10% of nitrogen gas -4 Pa, partial pressure of oxygen of 2.0X10 -4 Pa, partial pressure of vapor gas of 2.0X10 -3 Pa, the partial pressure of hydrogen is 5.0×10 -5 Pa, except hydrogen, is lower than the reference value. When the tensile test was performed under the same conditions as in the above-described invention experiment, it was confirmed that the elongation of the laminated structure LS was one time or more. Further, when the resistance increase rate was obtained in the same manner as in the above-described invention experiment, the resistance increase rate was 120% and 650% and was inferior to that in comparative experiment 1. Further, when the surface state of the laminate structure LS after the tensile test was observed in the same manner as in the above-described invention test, it was confirmed that cracks were generated and the laminate structure was white. From these results, it is clear that the laminated structure LS obtained in this comparative experiment 2 has weak bending resistance. In addition, when the X-ray diffraction of the 1 st titanium layer L1 formed was measured, not only the diffraction peak on the (002) crystal plane but also the diffraction peak on the (100) crystal plane was observed, but the intensity ratio of the diffraction peak on the (100) crystal plane to the diffraction peak on the (002) crystal plane was 0.11, less than 0.20. The half width of the diffraction peak of the (100) crystal plane was 0.7 degrees and more than 0.6 degrees. In the case of having such a diffraction pattern, as shown in fig. 5 (b), it is presumed that a titanium compound Im such as titanium nitride or titanium oxide is formed at the grain boundary Cf.
In comparative experiment 3, a laminated structure LS was obtained in the same manner as in the above-described invention experiment, except that the total pressure in the film forming chambers Pc1 and Pc3 at the time of film formation in the 1 st and 3 rd steps was maintained at 0.6Pa, the film forming speed was set at 2nm/sec, and the vacuum evacuation step was not performed in the 1 st and 3 rd steps (only the film forming step was performed). When the tensile test was performed under the same conditions as in the above-described invention experiment, it was confirmed that the elongation of the laminated structure LS was one time or more. Further, when the resistance increase rate was obtained in the same manner as in the above-described invention experiment, it was 300% and 900%, which were inferior to comparative experiment 2. Further, when the surface state of the laminate structure LS after the tensile test was observed as in the above-described invention test, it was confirmed that cracks were generated and the laminate structure was white. From these results, it is clear that the laminated structure LS obtained in the present comparative experiment 3 has a lower bending resistance than those of the above comparative experiments 1 and 2. Further, when the X-ray diffraction of the 1 st titanium layer L1 formed in this comparative experiment 3 was measured, the diffraction peak on the (100) crystal plane was not confirmed, only the diffraction peak on the (002) crystal plane was confirmed, and the half-width of the diffraction peak on the (002) crystal plane was 0.8 degrees. In the case of having such a diffraction pattern, as shown in fig. 5 (c), it is assumed that a crystal structure is provided in which small crystal grains Cg are aligned in the film thickness direction and grain boundaries Cf are connected so as to extend in the film thickness direction, and a titanium compound Im is formed on the grain boundaries Cf.
The embodiments of the present invention have been described above, but various modifications are possible without departing from the scope of the technical idea of the present invention. In the above embodiment, the structure in which the 1 st titanium layer L1, the aluminum layer L2, and the 2 nd titanium layer L3 are laminated is described as an example of the laminated structure LS, but the present invention can be applied to a structure in which a titanium nitride layer is further laminated on the 2 nd titanium layer L3.
In the above embodiment, the case where the substrate Sw is transferred in-situ between the film forming chambers Pc1, pc2, and Pc3, and the 1 st titanium layer L1, the aluminum layer L2, and the 2 nd titanium layer L3 are formed continuously in a vacuum atmosphere has been described as an example, but the present invention is not limited to this, and the present invention can be applied to the case where the 1 st titanium layer L1, the 2 nd titanium layer L3, and the aluminum layer L2 are implemented by different sputtering apparatuses. The 1 st titanium layer L1 and the 2 nd titanium layer L3 may be formed in the same film forming chamber.
Description of the reference numerals
LS. the laminated structure, layer 1 of titanium, layer 2 of aluminum, layer 2 of titanium, sw. substrate, pc1, pc2, pc3 of film forming chamber (vacuum chamber), and target 2.
Claims (4)
1. A laminated structure in which a 1 st titanium layer, an aluminum layer, and a 2 nd titanium layer are laminated in this order is characterized in that:
the 1 st titanium layer and the 2 nd titanium layer have a crystal structure having diffraction peaks on (002) and (100) crystal planes of a miller index measured by X-ray diffraction, and the half-width of the diffraction peak on the (002) crystal plane is 1.0 degree or less and the half-width of the diffraction peak on the (100) crystal plane is 0.6 degree or less.
2. The laminated structure according to claim 1, wherein:
the aluminum layer has a crystal structure having a diffraction peak on the (111) crystal plane of the miller index measured by X-ray diffraction.
3. A method for manufacturing a laminated structure in which a 1 st titanium layer, an aluminum layer, and a 2 nd titanium layer are laminated in this order, characterized by:
comprising the following steps: a 1 st step of forming a 1 st titanium layer on a substrate by a sputtering method; a step 2 of forming an aluminum layer on the 1 st titanium layer; and a 3 rd step of forming a 2 nd titanium layer on the aluminum layer;
the 1 st and 3 rd steps further include: a vacuum exhausting step of vacuum-exhausting the vacuum chamber in which the titanium target and the base material are disposed, respectively, to a partial pressure of 3.0X10 of nitrogen gas -4 Pa or lower, oxygen partial pressure of 9.0X10 -5 A partial pressure of water vapor of 8.0X10 Pa or lower -4 Pa or less, and a partial pressure of hydrogen of 5.0X10 -5 Pa or less; and a film forming step of introducing a rare gas so that the total pressure in the vacuum chamber is maintained within a range of 0.2Pa to 0.5Pa, and applying a predetermined electric power to the titanium target to form the 1 st titanium layer and the 2 nd titanium layer at a film forming rate within a range of 3nm/sec to 5 nm/sec.
4. The method for manufacturing a laminated structure according to claim 3, wherein:
the 2 nd step further comprises a film forming step of introducing a rare gas so that the total pressure in a vacuum chamber in which the aluminum target and the base material are disposed is maintained within a range of 0.2Pa to 0.5Pa, and applying a predetermined electric power to the aluminum target to form an aluminum layer at a film forming rate within a range of 7nm/sec to 10 nm/sec.
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