JP2019143245A - Oxide film and manufacturing method of oxide film and nitrogen containing oxide sputtering target - Google Patents

Abstract

To provide an oxide film with an excellent water vapor barrier property, an excellent visible light transmittance, and an excellent flexibility, a manufacturing method of the oxide film, and a nitrogen-containing oxide sputtering target.SOLUTION: A sputtering target comprises a major phase of an oxide comprising Al,Si, and Zn as a metal component, nitrogen in a range of 0.5 atom% or more and 20 atom% or less, nitrogen existing as a nitride. An indentation hardness of an oxide film is preferably 700 kgf/mmor more and 1500 kgf/mmor less. After a flexural test is performed for a 50 nm thick film, a reduction rate of water vapor permeation after the flexural test is preferably 30% or less, and a reduction rate of a visible light transmittance is preferably 5% or less.SELECTED DRAWING: None

Description

  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.

Conventionally, in various devices such as a liquid crystal display element, an organic EL element, and a solar cell, 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.
Here, 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 SiOxNy (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, and 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 includes metal oxides, metal nitrides, and metal carbides 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.

JP 2002-322561 A JP 2005-131863 A JP 2007-083493 A JP 2009-095989 A JP 2017-121721 A Japanese Patent No. 5884549

By the way, in the various devices described above, further flexibility has been achieved, and there is a demand for a water vapor barrier film having water vapor barrier properties, visible light permeability, and flexibility superior to those of conventional devices.
Here, in the thin film described in Patent Document 1, since the content of nitrogen in the film increases, the film becomes too hard and the flexibility is insufficient.

In addition, 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. In addition, when the film is formed thick in order to ensure the water vapor barrier property, the flexibility is lowered.
Furthermore, 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. Moreover, since the content of nitrogen in the film increases, the film becomes too hard and the flexibility is insufficient.

Moreover, in 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 | steam barrier property is inadequate only by a 2nd inorganic layer. is there. Moreover, the flexibility was low and the flexibility was insufficient.
Furthermore, since the gas barrier layer described in Patent Document 5 is composed of metal oxide, metal nitride, and metal carbide, it is difficult to achieve both high water vapor barrier properties and flexibility.
Further, the transparent oxide film described in Patent Document 6 has a sufficient water vapor barrier property. However, according to the recent further flexibility of various devices, there is a demand for an oxide film having a sufficient water vapor barrier property even if the film thickness is reduced.

  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.

  In order to solve the above problems, the oxide film of the present invention has an oxide containing Al, Si, Zn as a metal component as a main phase, and contains nitrogen in a range of 0.5 atomic% to 20 atomic%. The nitrogen is present as a nitride.

According to the oxide film having the above-described structure, 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 | steam barrier property improves further. Moreover, since the nitrogen content is limited to 20 atomic% or less, the flexibility of the oxide film can be ensured.
Furthermore, since the water vapor barrier property is particularly excellent, for example, if the target water vapor barrier property is 0.1 g / m ² / day or less, the film thickness can be reduced to 200 nm or less. It is also possible to ensure the sex.

Here, in the oxide film of the present invention, it is preferable indentation hardness is 700 kgf / mm ² or more 1500 kgf / mm ² or less.
In this case, since the indentation hardness of the oxide film is 700 kgf / mm ² or more, the water vapor barrier property is further improved. Moreover, since the indentation hardness of the oxide film is 1500 kgf / mm ² or less, flexibility can be ensured.

Further, in 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.

  The oxide film manufacturing method of the present invention uses an oxide sputtering target containing Al, Si, and Zn as metal components, and performs sputter deposition in a nitrogen-containing atmosphere containing nitrogen in the range of 5 vol% to 60 vol%. And forming an oxide film containing nitrogen in the range of 0.5 atomic% to 20 atomic% and containing the nitrogen as a nitride.

  According to the method of manufacturing an oxide film having the above-described structure, 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. In addition, since 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, Zn as a metal component as a main phase, further having 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.

  According to the method for manufacturing an oxide film having the above-described configuration, since 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.

Here, in the above-described method for manufacturing an oxide film, it is preferable that 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.

Further, in the above oxide film manufacturing method, after 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.
In this case, 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.

  According to 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.

  ADVANTAGE OF THE INVENTION According to this invention, the water vapor | steam barrier property, visible light permeability | transmittance, and the oxide film excellent in the flexibility, the manufacturing method of this oxide film, and a nitrogen-containing oxide sputtering target can be provided.

  Below, the oxide film which is one Embodiment of this invention, the manufacturing method of an oxide film, and a nitrogen-containing oxide sputtering target are demonstrated.

  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. Here, although a board | substrate is not specifically limited, In this embodiment, it is set as the flexible substrate which consists of a resin film. In addition, as resin which comprises a board | substrate, PET (polyethylene terephthalate) resin, PEN (polyethylene naphthalate) resin, COP (cycloolefin polymer) resin, PI (polyimide) resin etc. can be used, for example.

The oxide film has an oxide containing Al, Si, Zn as metal components as a main phase, further has a nitride, and contains nitrogen in the range of 0.5 atomic% to 20 atomic%. doing.
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.
Further, in the oxide film is present embodiment, it is preferable that the indentation hardness is a 700 kgf / mm ² or more 1500 kgf / mm ² within the following ranges.

Further, in the oxide film according to the present embodiment, 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.
In this embodiment, a film is formed with a thickness of 50 nm on a PET substrate with a thickness of 38 μm and a thickness of 100 mm × 100 mm, and a bending test is performed 10,000 times with a radius of curvature of 3 mm, based on the standard of IEC62715-6-1. The water vapor transmission rate and the visible light transmittance before and after the bending test were measured and evaluated.
The rate of decrease is calculated by the following formula.
Decrease rate (%) = {(transmittance before bending test−transmittance after bending test) / transmittance before bending test} × 100

  The reason why the composition of the oxide film according to the present embodiment, the indentation hardness, and the characteristics after the bending test are defined as described above will be described below.

(Al, Si, Zn)
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. Here, 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 metal elements, it becomes possible to improve the water vapor barrier property, visible light permeability, and flexibility in a well-balanced manner. In addition, by having conductivity, 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.

Here, 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. On the other hand, 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.
Further, 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. On the other hand, 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.

(N: Nitrogen)
Nitrogen has the effect of improving the indentation hardness of the oxide film and improving the water vapor barrier property. In the present embodiment, nitrogen exists in the form of nitride in the oxide film.
Here, when the nitrogen content is less than 0.5 atomic%, the water vapor barrier property may not be sufficiently improved. On the other hand, when the nitrogen content exceeds 20 atomic%, the oxide film becomes too hard and flexibility may be reduced.
From the above, the nitrogen content in the oxide film is regulated within the range of 0.5 atomic% to 20 atomic%.
In order to further improve the water vapor barrier property, 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. In order to further improve the flexibility, the upper limit of the nitrogen content in the oxide film is preferably 10 atomic% or less, and more preferably 7 atomic% or less.

(Indentation hardness)
When the indentation hardness of the oxide film is 700 kgf / mm ² or more, the water vapor barrier property can be sufficiently improved. On the other hand, when the indentation hardness of the oxide film is 1500 kgf / mm ² or less, sufficient flexibility can be secured.
Therefore, 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.
In order to obtain further excellent water vapor barrier properties, the lower limit of the indentation hardness of the oxide film is more preferably set to 800 kgf / mm ² or more. Moreover, in order to ensure further excellent flexibility, it is more preferable that the upper limit of the indentation hardness of the oxide film is 1000 kgf / mm ² or less.

(Characteristics after bending test)
The characteristics of the oxide film may be greatly deteriorated by bending. Here, in this embodiment, preferably, 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.

First, an oxide sputtering target containing Al, Si, and Zn as metal components is prepared. Using this oxide sputtering target, 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.
Thereby, the oxide film which is this embodiment can be formed.

Alternatively, 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.
Note that 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.

  As described above, the oxide film according to this embodiment is formed by a sputtering method using an oxide sputtering target.

Here, at the time of sputtering film formation, the temperature of the substrate on which the film is formed is preferably heated to 80 ° C. or higher and 120 ° C. or lower.
Alternatively, after the sputtering film formation, 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. By setting the heating temperature to 80 ° C. or higher, the film density can be sufficiently increased and the visible light transmittance can be sufficiently increased. On the other hand, when the heating temperature is set to 120 ° C. or lower, deformation of the film used for the substrate due to heat can be suppressed, adhesion between the substrate and the oxide film can be secured, and sufficient water vapor barrier properties can be obtained.
As described above, the visible light transmittance of the oxide film is improved by applying heat during or after sputtering film formation.

Note that 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.
In addition, regarding the holding time at the heating temperature during the heat treatment after the sputter film formation, the lower limit is preferably 10 minutes or more, and the upper limit is preferably 90 minutes or less.

According to the oxide film according to the present embodiment configured as described above, it is composed of an oxide containing Al, Si, Zn as a metal component, so that visible light permeability, water vapor barrier property, and flexibility are included. Can be secured.
In addition, 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. In addition, the oxide film does not become too hard, and flexibility can be ensured.
Furthermore, since the water vapor barrier property is particularly excellent, the oxide film can be formed thin, and flexibility can be ensured.

Furthermore, in this embodiment, since the indentation hardness of the oxide film is preferably 700 kgf / mm ² or more, particularly excellent water vapor barrier properties can be obtained. On the other hand, since the indentation hardness of the oxide film is 1500 kgf / mm ² or less, flexibility can be ensured.

  In the present embodiment, preferably, 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.

  In the oxide film manufacturing method according to this embodiment, 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. In addition, since 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.

  In the oxide film manufacturing method according to the present embodiment, an oxide containing Al, Si, Zn as a metal component is a main phase, nitride is further included, and nitrogen is 0.5 atomic% or more and 20 atoms or more. % 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.

Furthermore, in 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.
In the oxide film manufacturing method of this embodiment, preferably, after sputtering film formation, 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. By performing the heat treatment, visible light transmittance in the formed oxide film can be improved.

  Further, according to the nitrogen-containing oxide sputtering target of the present embodiment, the main phase is an oxide containing Al, Si, and Zn as metal components, 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.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the technical idea of the invention.

  Below, the result of the evaluation test evaluated about the effect of this invention is demonstrated.

(Sputtering target)
In Inventive Example 1-16, an oxide film was formed using the sputtering target shown in Table 1. In addition, in Examples 1 and 10 of the present invention, a sputter film was formed using a cylindrical target and otherwise using a flat plate target.

Al ₂ O ₃ powder with a purity of 99.99 mass% or more, SiO ₂ powder, ZnO powder, AlN powder with a purity of 99.9 mass% or more, Si ₃ N ₄ powder, Zn ₃ N so as to have the composition ratio shown in Table 1. _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. At this time, for the cylindrical core rod, it is preferable to use 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. In the examples, 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 φ125 mm and a thickness of 5 mmt for a flat plate. In addition, about the composition of the obtained sintered compact, it was the same as the composition at the time of weighing without a change.
Then, 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.

About Comparative Examples 1-3, it formed into a film using the B dope Si sputtering target whose specific resistance value is 0.02 ohm * cm or less.
In Comparative Example 4, 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.
In Comparative Example 5, a film was formed using a ZnO target having a purity of 99.99 mass% or higher.
About Comparative Examples 6-12, it formed into a film using the sputtering target obtained by the manufacturing method similar to this invention example.

(Film formation method)
In Invention Examples 1 and 10, the obtained cylindrical sputtering target was set in a sputtering apparatus, and after evacuating to 7 × 10 ⁻⁴ Pa or less, Ar, O ₂ , and N ₂ gases were listed 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.

In Invention Examples 2 to 9, 11 to 16, the obtained flat plate-type sputtering target was set in a sputtering apparatus and 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.

About Comparative Examples 1-4, the reactive sputtering using the above-mentioned metal target 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.
For Comparative Example 5, oxygen-added sputtering using a ZnO target was performed.
In Comparative Examples 6 to 12, 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.

  The composition and characteristics of the obtained oxide film were evaluated as follows. The evaluation results are shown in Table 2.

(Membrane composition)
About the film | membrane formed into a film by 100 nm on the glass substrate (EAGLE XG) of 20 mm x 20 mm size, after performing the surface etching by Ar for 1 minute or more with an X-ray photoelectron spectroscopy (XPS) apparatus (made by ULVAC-Phi), Narrow spectra were measured for O: 1s, Al: 2p, Si: 2s, Zn: 2p, and N: 1s. The film composition was quantitatively analyzed from the peak intensity obtained for each element. Further, when a peak having a peak top appears at 395 to 398 eV in the peak of the 1s spectrum of N, it was determined that the nitride was nitride.
The measurement conditions in the XPS apparatus are as follows.
Radiation source: Al Kα ray, 50W
Measurement range: φ200μm
Pass energy: 46.95 eV
Measurement interval: 0.1 eV / step
Photoelectron extraction angle with respect to sample surface: 45 deg

(Visible light transmittance)
For a 50 nm thick film formed on a 20 mm × 20 mm glass substrate (EAGLE XG), the transmittance of light in the wavelength range of 350 nm to 850 nm is measured with a spectrophotometer (V-550 manufactured by JASCO Corporation). did.

(Water vapor transmission rate)
A film having a thickness of 50 nm formed on a PET substrate having a thickness of 38 μm and a thickness of 100 mm × 100 mm, using the Mocon method, using PERMATRAN-W MODEL 3/33 manufactured by mocon, 40 ° C. and 90 ° C. based on JIS standard K7129 method. The water vapor transmission rate (water vapor barrier property) was measured under the condition of% RH.

(Bending test)
A film having a thickness of 50 nm formed on a PET substrate having a thickness of 38 μm and a thickness of 100 mm × 100 mm was subjected to a 10,000 bending bending test with a radius of curvature of 3 mm based on the standard of IEC62715-6-1. In addition, since all of the obtained sputtered films had compressive stress, in the bending test, the test was performed in a direction where more stress was applied. That is, when the film was bent, the test was conducted in such a direction that the film formation surface was on the inside.

(Indentation hardness)
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.

In Comparative Example 1 made of silicon oxide and not containing nitrogen, the water vapor barrier property was insufficient.
In Comparative Example 2 made of silicon oxide and containing 56.1 atomic% of nitrogen, the water vapor barrier property was insufficient. Moreover, since the nitride became the main phase, the visible light transmittance was insufficient.
In Comparative Example 3 made of silicon oxide and containing 23.6 atomic% of nitrogen, the water vapor barrier property was insufficient.

In 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.

  On the other hand, in the present invention examples 1 to 16 consisting of 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.

  In Examples 1 to 12 of the present invention, sputtering film formation was performed in a nitrogen-containing 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. In Examples 13 to 16 of the present invention, the nitrogen-containing oxide sputtering target is made of an oxide containing Al, Si, Zn as a metal component and contains nitrogen in the range of 0.5 atomic% to 20 atomic%. In spite of the above, sputtering film formation was carried out, and in all cases, an oxide film excellent in water vapor barrier property, visible light transmittance, and flexibility could be formed.

  In 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.

  From the above, according to the present invention example, it was confirmed that an oxide film particularly excellent in water vapor barrier property and flexibility, a method for producing an oxide film, and a nitrogen-containing oxide sputtering target can be provided. It was.

Claims (8)

The main phase is an oxide containing Al, Si, Zn as a metal component, nitrogen is contained in the range of 0.5 atomic% to 20 atomic%,
An oxide film, wherein the nitrogen is present as a nitride. ^2. The oxide film according to claim 1, wherein the indentation hardness is in a range of 700 kgf / mm ² or more and 1500 kgf / mm ² or less.   2. A bending test is carried out 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. Or the oxide film of Claim 2.   Using an oxide sputtering target containing Al, Si, Zn as a metal component, sputter film formation is performed in a nitrogen-containing atmosphere containing nitrogen in the range of 5 vol% to 60 vol%, and nitrogen is 0.5 atomic% to 20 atomic%. A method for producing an oxide film, comprising forming an oxide film that is contained in an atomic% or less range and wherein the nitrogen is present as a nitride.   Using 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%. A method of manufacturing an oxide film, characterized by performing sputtering film formation and forming an oxide film containing nitrogen in a range of 0.5 atomic% to 20 atomic% and containing the nitrogen as a nitride .   6. The method of manufacturing an oxide film according to claim 4, wherein the substrate on which the film is formed is heated to 80 ° C. or higher and 120 ° C. or lower during sputtering film formation.   6. The heat treatment is performed after the sputter film formation in 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. The manufacturing method of the oxide film as described in any one of.   Nitrogen-containing oxide characterized by comprising 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% Sputtering target.