WO2019163811A1 - Film d'oxyde, procédé de production de film d'oxyde et cible de pulvérisation d'oxyde contenant de l'azote - Google Patents

Film d'oxyde, procédé de production de film d'oxyde et cible de pulvérisation d'oxyde contenant de l'azote Download PDF

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WO2019163811A1
WO2019163811A1 PCT/JP2019/006258 JP2019006258W WO2019163811A1 WO 2019163811 A1 WO2019163811 A1 WO 2019163811A1 JP 2019006258 W JP2019006258 W JP 2019006258W WO 2019163811 A1 WO2019163811 A1 WO 2019163811A1
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Prior art keywords
nitrogen
oxide film
oxide
atomic
film
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PCT/JP2019/006258
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English (en)
Japanese (ja)
Inventor
啓太 梅本
山口　剛
孝典 白井
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三菱マテリアル株式会社
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Priority claimed from JP2019027792A external-priority patent/JP2019143245A/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to CN201980007041.4A priority Critical patent/CN111542643A/zh
Priority to KR1020207018449A priority patent/KR20200123775A/ko
Publication of WO2019163811A1 publication Critical patent/WO2019163811A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • 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
    • C23C14/58—After-treatment

Definitions

  • the present invention relates to an oxide film whose main phase is an oxide containing Al, Si, and Zn as metal components, a method for producing the oxide film, and a nitrogen-containing oxide sputtering target.
  • a water vapor barrier film for protecting from water vapor is provided because there is a risk of deterioration due to water. Further, the above-described water vapor barrier film is required to have high visible light permeability.
  • a flexible substrate made of a resin is widely used in the various devices described above. In a flexible substrate made of a resin, since the substrate itself has a low water vapor barrier property, the above water vapor barrier film is required to have a high water vapor barrier property.
  • Patent Document 1 discloses forming a thin film of SiO x N y (x / y: 0.6 to 4.0) using silicon nitride as a target and oxygen as a reaction gas.
  • Patent Document 2 includes Al, Si, oxygen, and nitrogen. The weight ratio of Al atoms to Si atoms is in the range of 15:85 to 40:60, and the molar ratio of nitrogen to oxygen is 10 to 40%.
  • An inorganic barrier layer is disclosed.
  • Patent Document 3 discloses an inorganic thin film composed of at least one nitride and oxynitride selected from Si, Al, In, Sn, Ti, and Zn.
  • Patent Document 4 discloses a barrier provided with an organic layer, a first inorganic layer composed of silicon oxide, and a second inorganic layer composed of an oxide of silicon or aluminum and an oxynitride of silicon or aluminum.
  • a layer is disclosed.
  • Patent Document 5 discloses a metal oxide, metal nitride, and metal carbide containing at least one metal selected from the group consisting of Al, Si, Ti, Zn, Zr, Nb, Sn, Hf, Ta, and Ce.
  • a gas barrier layer is disclosed.
  • Patent Document 6 discloses an amorphous transparent oxide film made of an oxide containing Al, Si, and Zn.
  • Japanese Patent Laid-Open No. 2002-322561 A) Japanese Unexamined Patent Publication No. 2005-131863 (A) Japanese Unexamined Patent Publication No. 2007-083493 (A) Japanese Unexamined Patent Publication No. 2009-095989 (A) Japanese Unexamined Patent Publication No. 2017-121721 (A) Japanese Patent No. 5884549 (B)
  • the inorganic barrier layer described in Patent Document 2 is formed by vapor deposition, has a low film density, and is inferior in water vapor barrier properties.
  • the flexibility is lowered.
  • the inorganic thin film described in Patent Document 3 is formed by the plasma CVD method, so that hydrogen is often taken into the film, and the water vapor barrier property may be lowered.
  • the content of nitrogen in the film increases, the film becomes too hard and the flexibility is insufficient.
  • the barrier layer described in patent document 4 it is set as the multilayer structure of an organic layer, a 1st inorganic layer, and a 2nd inorganic layer, and water vapor
  • the present invention has been made in view of the above-described circumstances, and is an oxide film excellent in water vapor barrier property, visible light permeability, and flexibility, a method for producing the oxide film, and nitrogen-containing oxidation.
  • An object of the present invention is to provide a sputtering target.
  • an oxide film of one embodiment of the present invention (hereinafter referred to as “the oxide film of the present invention”) has an oxide containing Al, Si, Zn as a metal component as a main phase, Nitrogen is contained in the range of 0.5 atomic% or more and 20 atomic% or less, and the nitrogen exists as a nitride.
  • the main phase is an oxide containing Al, Si, and Zn as metal components. Therefore, visible light transmission is achieved by silicon oxide, water vapor barrier property is achieved by aluminum oxide, and zinc oxide. Therefore, flexibility is ensured. And since 0.5 atomic% or more of nitrogen is contained and the said nitrogen exists as nitride, the whole oxide film becomes moderately hard, and water vapor
  • the film thickness can be reduced to 200 nm or less. It is also possible to ensure the sex.
  • indentation hardness is 700 kgf / mm 2 or more 1500 kgf / mm 2 or less.
  • the indentation hardness of the oxide film is 700 kgf / mm 2 or more, the water vapor barrier property is further improved.
  • the indentation hardness of the oxide film is 1500 kgf / mm 2 or less, flexibility can be ensured.
  • the oxide film of the present invention a bending test was performed at a film thickness of 50 nm, the water vapor transmission rate after the bending test was 30% or less, and the visible light transmission rate was 5% or less. It is preferable that In this case, even after the bending test is performed, the water vapor transmission rate and the visible light transmission rate are not greatly reduced, and the flexibility is very excellent.
  • An oxide film manufacturing method uses an oxide sputtering target containing Al, Si, and Zn as metal components, and nitrogen. Is formed in a nitrogen-containing atmosphere containing 5 vol% or more and 60 vol% or less of nitrogen, nitrogen is contained in a range of 0.5 atomic% or more and 20 atomic% or less, and the nitrogen is present as a nitride It is characterized by forming a film.
  • an oxide film containing nitrogen is formed by performing sputter deposition in a nitrogen-containing atmosphere using an oxide sputtering target containing Al, Si, and Zn as metal components. Can be formed.
  • the nitrogen content in the nitrogen-containing atmosphere is in the range of 5 vol% to 60 vol%, nitrogen is contained in the range of 0.5 atomic% to 20 atomic%, and the nitrogen exists as a nitride.
  • An oxide film can be formed. Therefore, it is possible to obtain an oxide film excellent in water vapor barrier property, visible light permeability, and flexibility.
  • the method for producing an oxide film of the present invention comprises an oxide containing Al, Si, and Zn as metal components as a main phase, further comprising nitride, and nitrogen in a range of 0.5 atomic% to 20 atomic%.
  • Sputter film formation is performed using the nitrogen-containing oxide sputtering target contained, and an oxide film containing nitrogen in the range of 0.5 atomic% to 20 atomic% and containing the nitrogen as a nitride is formed. It is characterized by that.
  • the sputtering film formation is performed using the nitrogen-containing oxide sputtering target containing nitrogen in the range of 0.5 atomic% to 20 atomic%, nitrogen is reduced to 0. It is possible to form an oxide film that is contained in the range of 0.5 atomic% or more and 20 atomic% or less and in which the nitrogen exists as a nitride. Therefore, it is possible to obtain an oxide film excellent in water vapor barrier property, visible light permeability, and flexibility.
  • the substrate to be formed be heated to 80 ° C. or higher and 120 ° C. or lower during sputtering film formation. In this case, it is possible to further improve the visible light transmittance of the oxide film to be formed by heating the substrate during the sputtering film formation.
  • heat treatment is performed within a range where the heating temperature is in the range of 80 ° C. to 120 ° C. and the holding time at the heating temperature is in the range of 5 minutes to 120 minutes. Preferably it is done.
  • heat treatment by performing heat treatment under the above-described conditions after the sputtering film formation, it is possible to further improve the visible light transmittance of the formed oxide film.
  • the nitrogen-containing oxide sputtering target of the present invention has an oxide containing Al, Si, Zn as a metal component as a main phase, further has a nitride, and contains nitrogen in a range of 0.5 atomic% to 20 atomic%. It is characterized by containing.
  • the nitrogen-containing oxide sputtering target having the above-described configuration it is possible to efficiently form an oxide film containing nitrogen in a range of 0.5 atomic% to 20 atomic% and containing the nitrogen as a nitride. Can do.
  • an oxide film excellent in water vapor barrier property, visible light transmittance, and flexibility it is possible to provide an oxide film excellent in water vapor barrier property, visible light transmittance, and flexibility, a method for producing the oxide film, and a nitrogen-containing oxide sputtering target.
  • the oxide film according to the present embodiment is used as a water vapor barrier film in various devices such as liquid crystal display elements, organic EL elements, and solar cells.
  • the oxide film according to this embodiment is used after being formed on a substrate.
  • substrate is not specifically limited, In this embodiment, it is set as the flexible substrate which consists of a resin film.
  • substrate PET (polyethylene terephthalate) resin, PEN (polyethylene naphthalate) resin, COP (cycloolefin polymer) resin, PI (polyimide) resin etc. can be used, for example.
  • This oxide film has an oxide containing Al, Si, Zn as metal components as a main phase, and further has a nitride, and contains nitrogen in the range of 0.5 atomic% to 20 atomic%.
  • the main phase means a metal component in an oxide state detected by quantitative analysis using a membrane XPS apparatus and having a content of 1 at% or more.
  • the indentation hardness is a 700 kgf / mm 2 or more 1500 kgf / mm 2 within the following ranges.
  • a bending test was performed at a film thickness of 50 nm, the rate of decrease in water vapor transmission after the bending test was 30% or less, and the rate of decrease in visible light transmission was 5%.
  • the following is preferable.
  • a PET substrate having a thickness of 100 ⁇ m ⁇ 100 mm square is formed with a thickness of 50 nm, and a bending test is performed 10,000 times with a radius of curvature of 3 mm based on the standard of IEC 62715-6-1.
  • the water vapor transmission rate and the visible light transmittance before and after the bending test were measured and evaluated.
  • the oxide film according to this embodiment contains Al, Si, and Zn as metal elements. That is, it has aluminum oxide, silicon oxide, and zinc oxide.
  • the effect of each metal element is as follows. Al improves the water vapor barrier property. Si improves visible light transparency. Zn improves flexibility. Therefore, by containing Al, Si, and Zn as the metal elements, it becomes possible to improve the water vapor barrier property, the visible light transmittance, and the flexibility with a good balance.
  • DC sputtering can be performed when a film is formed using an oxide sputtering target. Note that the content of these metal elements is preferably adjusted as appropriate in accordance with characteristics required for the oxide film.
  • the lower limit of the Al content is preferably 3 atomic% or more, more preferably 5 atomic% or more, and even more preferably 7 atomic% or more with respect to the entire metal element.
  • the upper limit of the Al content is preferably 42 atomic percent or less, more preferably 30 atomic percent or less, and even more preferably 25 atomic percent or less.
  • the lower limit of the Si content is preferably 10 atomic% or more, more preferably 20 atomic% or more, and even more preferably 25 atomic% or more.
  • the upper limit of the Si content is preferably 50 atomic percent or less, more preferably 45 atomic percent or less, and even more preferably 40 atomic percent or less.
  • Nitrogen has the effect of improving the indentation hardness of the oxide film and improving the water vapor barrier property.
  • nitrogen exists in the form of nitride in the oxide film.
  • the nitrogen content is less than 0.5 atomic%, the water vapor barrier property may not be sufficiently improved.
  • the nitrogen content exceeds 20 atomic%, the oxide film becomes too hard and flexibility may be reduced.
  • the nitrogen content in the oxide film is regulated within the range of 0.5 atomic% to 20 atomic%.
  • the lower limit of the nitrogen content in the oxide film is preferably set to 2.0 atomic% or more, and more preferably set to 3.0 atomic% or more.
  • the upper limit of the nitrogen content in the oxide film is preferably 10 atomic% or less, and more preferably 7 atomic% or less.
  • the oxide film of the present embodiment it is preferable indentation hardness is in the range of 700 kgf / mm 2 or more 1500 kgf / mm 2 or less.
  • the lower limit of the indentation hardness of the oxide film is more preferably set to 800 kgf / mm 2 or more.
  • the upper limit of the indentation hardness of the oxide film is 1000 kgf / mm 2 or less.
  • the characteristics of the oxide film may be greatly deteriorated by bending.
  • the bending test is performed at a film thickness of 50 nm, the water vapor transmission rate reduction rate after the bending test is 30% or less, and the visible light transmission rate reduction rate is 5% or less. Therefore, sufficient characteristics as a water vapor barrier film can be secured even after bending.
  • the above oxide film is manufactured by the following oxide film manufacturing method.
  • an oxide sputtering target containing Al, Si, and Zn as metal components is prepared.
  • sputtering film formation is performed in a nitrogen-containing atmosphere containing nitrogen in the range of 5 vol% to 60 vol%, and an oxide film containing nitrogen is formed on the substrate.
  • the oxide film which is this embodiment can be formed.
  • a nitrogen-containing oxide sputtering target having an oxide containing Al, Si, Zn as a metal component as a main phase, further containing nitride, and containing nitrogen in a range of 0.5 atomic% to 20 atomic%. Then, sputtering is performed to form an oxide film containing nitrogen over the substrate. Thereby, the oxide film which is this embodiment can be formed.
  • the nitrogen-containing oxide sputtering target has a nitride. This nitride may be one or more of aluminum nitride, silicon nitride, and zinc nitride, and may be nitrides of other elements as long as the amount of the nitride does not affect the characteristics. Also good.
  • the oxide film according to this embodiment is formed by a sputtering method using an oxide sputtering target.
  • the temperature of the substrate on which the film is formed is preferably heated to 80 ° C. or higher and 120 ° C. or lower.
  • the oxide film formed in a nitrogen atmosphere has a heating temperature in the range of 80 ° C. to 120 ° C. and a holding time at the heating temperature of 5 minutes to 120 minutes. It is preferable to perform heat treatment within the range.
  • the heating temperature is set to 120 ° C.
  • the visible light transmittance of the oxide film is improved by applying heat during or after sputtering film formation.
  • the lower limit of the substrate temperature during sputtering film formation and the heating temperature during heat treatment after sputtering film formation are preferably 90 ° C. or higher, and the upper limit is preferably 110 ° C. or lower.
  • the lower limit is preferably 10 minutes or more, and the upper limit is preferably 90 minutes or less.
  • the oxide film according to the present embodiment since it is composed of an oxide containing Al, Si, and Zn as metal components, visible light permeability, water vapor barrier property, and flexibility. Can be secured.
  • nitrogen is contained in the range of 0.5 atomic% to 20 atomic%, and since this nitrogen exists as a nitride, the entire oxide film becomes moderately hard and further improves the water vapor barrier property. Is possible.
  • the oxide film does not become too hard, and flexibility can be ensured.
  • the oxide film can be formed thin, and flexibility can be ensured.
  • the indentation hardness of the oxide film is preferably 700 kgf / mm 2 or more, particularly excellent water vapor barrier properties can be obtained.
  • the indentation hardness of the oxide film is 1500 kgf / mm 2 or less, flexibility can be ensured.
  • a bending test is performed at a film thickness of 50 nm, the rate of decrease in water vapor transmission after the bending test is 30% or less, and the rate of decrease in visible light transmission is 5% or less. Therefore, even after the bending test is performed, the water vapor transmission rate and the visible light transmission rate are not greatly reduced, and the flexibility is very excellent.
  • the oxide film containing nitrogen is formed by performing sputter deposition in a nitrogen-containing atmosphere using an oxide sputtering target containing Al, Si, and Zn as metal components. Can be formed.
  • the nitrogen content in the nitrogen-containing atmosphere is in the range of 5 vol% to 60 vol%, nitrogen is contained in the range of 0.5 atomic% to 20 atomic%, and the nitrogen exists as a nitride.
  • An oxide film can be formed.
  • the main phase is an oxide containing Al, Si, and Zn as metal components, nitrides are further included, and nitrogen is contained in an amount of 0.5 atomic% to 20 atoms.
  • % Nitrogen is contained in the range of 0.5 atomic% or more and 20 atomic% or less, and the nitrogen exists as a nitride.
  • An oxide film can be formed.
  • the method for manufacturing an oxide film of this embodiment it is preferable that visible light transmission in the oxide film to be formed is performed by heating the substrate to be formed to 80 ° C. or more and 120 ° C. or less during sputtering.
  • the rate can be improved.
  • the heating temperature is in the range of 80 ° C. to 120 ° C.
  • the holding time at the heating temperature is in the range of 5 minutes to 120 minutes.
  • the main phase is an oxide containing Al, Si, and Zn as metal components, and further includes nitride, and nitrogen is contained at 0.5 atomic% or more. Since it is contained in an atomic% or less range, an oxide film containing nitrogen in the range of 0.5 atomic% or more and 20 atomic% or less and containing nitrogen as a nitride can be efficiently formed.
  • Example 1-16 an oxide film was formed using the sputtering target shown in Table 1.
  • a sputter film was formed using a cylindrical target and otherwise using a flat plate target.
  • Two powders are weighed, and the obtained powder and its three times weight zirconia balls (balls with a diameter of 5 mm and balls with a diameter of 10 mm are halved) and a ball mill having an internal volume of 300 L using water with a dispersant as a solvent.
  • Wet mixing was performed for 48 hours using an apparatus, and then dry granulation was performed by spray drying.
  • the obtained powder was filled into a cylindrical carbon mold for the cylindrical shape and into a flat carbon mold for the flat plate shape, evacuated to 10 Pa or less, 1200 ° C. for 5 hours, and 20 MPa. Vacuum hot pressing was performed with pressure to obtain a sintered body.
  • a ceramic having a close difference in thermal expansion coefficient in order to prevent cracking due to the difference in shrinkage rate from the sintered body.
  • an alumina core rod was used. .
  • the obtained sintered body was machined by a wet grinding method into a shape having an outer diameter of 160 mm, an inner diameter of 135 mm, and a length of 200 mmL for a cylinder, and a shape of ⁇ 125 mm and a thickness of 5 mmt for a flat plate.
  • the composition of the obtained sintered compact it was the same as the composition at the time of weighing without a change.
  • the processed target was bonded with In solder, and three cylinders with a length of 200 mmL were connected to a SUS backing tube with a length of 640 mm for a cylinder, and a flat plate was bonded with a Cu backing plate.
  • Comparative Examples 1 to 3 films were formed using a B-doped Si sputtering target having a specific resistance value of 0.02 ⁇ ⁇ cm or less.
  • a film was formed by reactive sputtering using an Al sputtering target having a purity of 99.99 mass% or more and introducing 38% oxygen gas.
  • Comparative Example 5 a film was formed using a ZnO target having a purity of 99.99 mass% or higher.
  • Comparative Examples 6 to 12 a film was formed using a sputtering target obtained by the same production method as in the present invention.
  • the obtained cylindrical sputtering target was set in a sputtering apparatus, evacuated to 7 ⁇ 10 ⁇ 4 Pa or less, and Ar, O 2 , and N 2 gases shown in the table A flow rate of 50 sccm was applied to adjust the opening degree of the exhaust to create an atmosphere of 0.67 Pa, and then a film was formed at a film thickness shown in the table with a power of 1000 W using a pulsed DC power source.
  • the obtained flat plate-type sputtering target was set in a sputtering apparatus, evacuated to 7 ⁇ 10 ⁇ 4 Pa or less, and then Ar, O 2 , and N 2 gases were displayed. 50 sccm was flowed at the gas ratio shown in FIG. 6 and the opening of the exhaust gas was adjusted to create an atmosphere of 0.67 Pa. Then, using a pulsed DC power source, a film was formed at a film thickness shown in the table at a power of 500 W. Note that the heat treatment after the sputtering film formation was performed in a nitrogen atmosphere.
  • Comparative Examples 1 to 4 reactive sputtering using the metal target described above was performed. Note that it was confirmed in advance that sputtering in the oxide mode was performed at the gas concentrations shown in Table 1.
  • Comparative Example 5 oxygen-added sputtering using a ZnO target was performed.
  • film formation was performed by changing the gas concentration conditions. The conditions other than the gas concentration were the same as in the present invention example.
  • composition and characteristics of the obtained oxide film were evaluated as follows. The evaluation results are shown in Table 2.
  • the measurement conditions in the XPS apparatus are as follows. Radiation source: Al K ⁇ ray, 50W Measurement range: ⁇ 200 ⁇ m Pass energy: 46.95 eV Measurement interval: 0.1 eV / step Photoelectron extraction angle with respect to sample surface: 45 deg
  • a film having a thickness of 50 nm formed on a PET substrate having a thickness of 38 ⁇ m and a thickness of 100 mm ⁇ 100 mm is used at 40 ° C. and 90 ° C. based on JIS standard K7129 method using MOCON method and PERMATRAN-W MODEL 3/33 manufactured by mocon.
  • the water vapor transmission rate was measured under the condition of% RH.
  • a film formed with a thickness of 1000 nm on a glass substrate having a thickness of 0.5 mm and a thickness of 100 mm ⁇ 100 mm was measured by a nanoindentation method based on the standard of ISO14577.
  • the indentation hardness was calculated from the obtained contact projection area, the contact depth, and the load at that time. Measurement was carried out at 10 arbitrary locations on the surface of the formed film, and the average value was calculated.
  • Comparative Example 1 made of silicon oxide and not containing nitrogen, the water vapor barrier property was insufficient.
  • Comparative Example 2 made of silicon oxide and containing 56.1 atomic% of nitrogen, the water vapor barrier property was insufficient.
  • Comparative Example 3 made of silicon oxide and containing 23.6 atomic% of nitrogen, the water vapor barrier property was insufficient.
  • Comparative Example 4 made of aluminum oxide and not containing nitrogen, the water vapor barrier property was insufficient. Moreover, since it was inferior to flexibility, the water-vapor transmission rate fell greatly after the bending test. In Comparative Example 5 made of zinc oxide and containing no nitrogen, the water vapor barrier property was insufficient. Moreover, since the flexibility was inferior, the visible light transmittance was greatly reduced after the bending test. In Comparative Examples 6 to 12 made of an oxide containing Al, Si, and Zn and not containing nitrogen, the water vapor barrier property was insufficient.
  • Examples 1 to 16 of the present invention comprising an oxide containing Al, Si, Zn as a metal component and containing nitrogen in the range of 0.5 atomic% to 20 atomic%, the water vapor barrier property, And it was excellent in visible light transmittance. Further, it was confirmed that the water vapor transmission rate and the visible light transmission rate after the bending test were small and the flexibility was excellent.
  • Examples 1 to 12 of the present invention sputtering film formation was performed in an atmosphere containing nitrogen in the range of 5 vol% to 60 vol% using an oxide sputtering target containing Al, Si, and Zn as metal components.
  • the nitrogen-containing oxide sputtering target is made of an oxide containing Al, Si, and Zn as metal components and contains nitrogen in the range of 0.5 atomic% to 20 atomic%.
  • Examples 1 and 10 of the present invention a film was formed using a cylindrical sputtering target, and in Examples 2 to 9 and 11 to 16 of the present invention, a film was formed using a flat plate type sputtering target. An oxide film excellent in light transmittance and flexibility could be formed.
  • An oxide film excellent in water vapor barrier property, visible light transmittance, and flexibility, a method for producing the oxide film, and a nitrogen-containing oxide sputtering target can be provided.

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Abstract

La présente invention est caractérisée en ce que : elle comporte, en tant que phase principale de celle-ci, un oxyde comprenant Al, Si et Zn en tant que composants métalliques de celle-ci ; contenant 0,5 à 20 % en atomes d'azote ; et la présence de l'azote sous la forme d'un nitrure. Idéalement, la dureté par indentation du film d'oxyde est de 700 à 1500 kgf/mm2. De plus, lorsqu'un test de flexion est conduit à une épaisseur de film de 50 nm, la réduction de la transmittance de vapeur d'eau après l'essai de flexion n'est idéalement pas supérieure à 30 % et la réduction de la transmittance de lumière visible ne dépasse pas 5 %.
PCT/JP2019/006258 2018-02-22 2019-02-20 Film d'oxyde, procédé de production de film d'oxyde et cible de pulvérisation d'oxyde contenant de l'azote WO2019163811A1 (fr)

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CN201980007041.4A CN111542643A (zh) 2018-02-22 2019-02-20 氧化物膜、氧化物膜的制造方法及含氮氧化物溅射靶
KR1020207018449A KR20200123775A (ko) 2018-02-22 2019-02-20 산화물막, 산화물막의 제조 방법, 및, 질소 함유 산화물 스퍼터링 타깃

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JP2018-029641 2018-02-22
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JP2019027792A JP2019143245A (ja) 2018-02-22 2019-02-19 酸化物膜、酸化物膜の製造方法、及び、窒素含有酸化物スパッタリングターゲット
JP2019-027792 2019-02-19

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Citations (6)

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JPH08336928A (ja) * 1995-06-08 1996-12-24 Balzers & Leybold Deutsche Holding Ag 半透明の材料からなる平板ならびにその製造方法
JP2014043094A (ja) * 2012-08-01 2014-03-13 Toray Ind Inc ガスバリア性フィルム
JP2014055348A (ja) * 2012-08-10 2014-03-27 Mitsubishi Materials Corp 透明酸化物膜形成用スパッタリングターゲット及びその製造方法
WO2017204197A1 (fr) * 2016-05-26 2017-11-30 住友化学株式会社 Procédé de fabrication de film semi-conducteur en oxynitrure métallique et film semi-conducteur en oxynitrure métallique
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