JP2017094585A - Gas barrier film, method for producing the same and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film significantly improved in gas barrier properties.SOLUTION: There is provided a gas barrier film which has a mixed region of 5 nm or more continuing in the thickness direction which is a region containing silicon and a transition metal M and in which the value of the atomic number ratio (M/silicon) of a transition metal M to silicon is within a range of 0.02 to 49 in the thickness direction, in which the mixed region has an A region in which a transition metal is contained as a main component in at least one region of a plurality of regions and a B region in which silicon is contained as a main component in other regions, and in the distribution curve showing the relation between a distance from a surface of the B region of a gas barrier layer in the layer thickness direction of the B region of the gas barrier layer and a ratio of each amount of each atom to the total amount of a silicon atom, an oxygen atom and a carbon atom, all of the predetermined conditions are satisfied.SELECTED DRAWING: Figure 1A

Description

  The present invention relates to a gas barrier film, a method for producing a gas barrier film, and an electronic device. More specifically, the present invention relates to a gas barrier film having significantly improved gas barrier properties.

Conventionally, in the fields of food, packaging materials, pharmaceuticals, etc., in order to prevent the permeation of gases such as water vapor and oxygen, it is relatively simple to provide an inorganic film such as a metal or metal oxide vapor deposition film on the surface of a resin substrate. A gas barrier film having a structure (hereinafter referred to as a gas barrier film in the present application) has been used.
In recent years, gas barrier films that prevent permeation of water vapor, oxygen, and the like are being used in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), and organic electroluminescence (EL) elements. . In order to give such an electronic device the property of being flexible and light and difficult to break, a gas barrier film having high gas barrier properties is required instead of a hard and easily broken glass substrate.

  As a method for obtaining a gas barrier film applicable to an electronic device, a method of forming a gas barrier layer on a resin substrate by a plasma CVD method (Chemical Vapor Deposition), A method of forming a gas barrier layer by applying a surface treatment (modification treatment) after applying a coating liquid containing polysilazane as a main component on a substrate is known.

Patent Document 1 discloses a technique for adjusting the kind and ratio of atoms contained in a gas barrier layer, and even when bent, a gas barrier film having excellent gas barrier properties can be obtained. Is described.
However, as an electronic device application such as the organic electroluminescence (EL) element, a gas barrier film having higher gas barrier properties is required.

JP 2011-73430 A

  The present invention has been made in view of the above-described problems and situations, and a problem to be solved is to provide a gas barrier film having a significantly improved gas barrier property, a manufacturing method thereof, and an electronic device.

In order to solve the above-mentioned problems, the present inventors, in the process of examining the cause of the above-mentioned problems, the gas barrier film of the present invention is a gas barrier film having a gas barrier layer, the gas barrier layer is silicon And a mixed region containing the transition metal M at a predetermined ratio, and the silicon barrier, the oxygen atom, and the carbon atom in the mixed region are in a predetermined distribution state, so that the gas barrier property is remarkably improved. I found that a film was obtained.
That is, the said subject which concerns on this invention is solved by the following means.

A gas barrier film having a gas barrier layer on a substrate,
The gas barrier layer is composed of a plurality of regions having chemical compositions different from each other in the thickness direction, and includes a silicon and a transition metal M in the thickness direction, and the transition metal M with respect to the silicon. The atomic ratio (M / silicon) has a mixed region that is in the range of 0.02 to 49 and that is continuous for 5 nm or more in the thickness direction,
The mixed region has an A region containing the transition metal as a main component in at least one region of the plurality of regions, and a B region containing silicon as a main component in the other regions. And the distance from the surface of the B region of the gas barrier layer in the layer thickness direction of the B region of the gas barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (the atomic ratio of silicon) ), Oxygen distribution ratio (oxygen atomic ratio) and carbon atom content ratio (carbon atomic ratio) in relation to the silicon distribution curve, oxygen distribution curve and carbon distribution curve, respectively, ) To (iii) are all satisfied,
A gas barrier film characterized by that.
(I) In the region where the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon are 90% or more of the layer thickness of the B region of the gas barrier layer, the following formula (I):
(Atomic ratio of oxygen)> (Atomic ratio of silicon)> (Atomic ratio of carbon) (I)
(Ii) the carbon distribution curve has at least one extreme value (iii) the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% That is more

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the gas barrier film in which gas barrier property was improved significantly, its manufacturing method, and an electronic device.

Schematic sectional view showing the layer structure of the gas barrier film of the present invention Schematic sectional view showing the layer structure of the gas barrier film of the present invention Conceptual diagram showing the composition distribution of silicon and transition metals in the thickness direction of the gas barrier layer The schematic diagram which shows one Embodiment of the manufacturing apparatus which can be used suitably for manufacturing the gas barrier film of this invention.

The gas barrier film of the present invention is a gas barrier film having a gas barrier layer on a substrate,
The gas barrier layer is composed of a plurality of regions having chemical compositions different from each other in the thickness direction, and includes a silicon and a transition metal M in the thickness direction, and the transition metal M with respect to the silicon. The atomic ratio (M / silicon) is within a range of 0.02 to 49, and has a mixed region continuous in a thickness direction by 5 nm or more, and the mixed region is at least of the plurality of regions One region has an A region containing the transition metal as a main component and another region B containing silicon as a main component, and the layer thickness of the B region of the gas barrier layer The distance from the surface of the B region of the gas barrier layer in the direction, the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (silicon atomic ratio), the ratio of the amount of oxygen atoms (oxygen source) Ratio) and carbon atom quantity ratio (carbon atomic ratio), respectively, in the silicon distribution curve, oxygen distribution curve and carbon distribution curve, all the conditions (i) to (iii) are satisfied. And This feature is a technical feature common to or corresponding to the claimed invention.
Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<Outline of gas barrier film>
The gas barrier film of the present invention is a gas barrier film having a gas barrier layer on a substrate, and the gas barrier layer is composed of a plurality of regions having different chemical compositions of components in the thickness direction, Thickness that is a region containing silicon and transition metal M in the thickness direction, wherein the value of the atomic ratio of transition metal M to silicon (M / silicon) is in the range of 0.02 to 49. The mixed region has a continuous region of 5 nm or more in the vertical direction, and the mixed region includes an A region in which at least one of the plurality of regions contains the transition metal as a main component, and silicon in other regions. And a distance from the surface of the B region of the gas barrier layer in the thickness direction of the B region of the gas barrier layer, and silicon atoms, oxygen atoms, and The relationship between the ratio of the amount of silicon atoms to the total amount of elementary atoms (the atomic ratio of silicon), the ratio of the amount of oxygen atoms (the atomic ratio of oxygen), and the ratio of the amount of carbon atoms (the atomic ratio of carbon) is shown respectively. The silicon distribution curve, oxygen distribution curve, and carbon distribution curve satisfy all of the following conditions (i) to (iii).

Conditions (i) to (iii) are as follows.
(I) In the region where the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon are 90% or more of the layer thickness of the B region of the gas barrier layer, the following formula (I):
(Atomic ratio of oxygen)> (Atomic ratio of silicon)> (Atomic ratio of carbon) (I)
(Ii) the carbon distribution curve has at least one extreme value (iii) the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% That is more

The gas barrier layer has a mixed region partially including an A region and a B region, and further, between the A region containing the transition metal M as a main component and the B region containing silicon as a main component b. Further, it is preferable that the mixed region is included.
Moreover, in the gas barrier layer according to the present invention, it is also a preferable embodiment that the mixed region is formed over the entire region in the layer.
This mixed region preferably contains a transition metal, silicon and oxygen. The mixed region preferably contains at least one of a transition metal oxide and a mixture of silicon or a compound thereof or a composite compound of a transition metal and silicon. It is a more preferable form that a composite oxide is contained.
The “mixture” in the present invention refers to a product in a state where the constituent components in the regions A and B are mixed without being chemically bonded to each other. For example, a state in which niobium oxide and silicon oxide are mixed without being chemically bonded to each other.
The “main component” as used in the present invention refers to a component having a maximum content as an atomic composition ratio. For example, “metal main component” refers to a metal component having the maximum content as an atomic composition ratio among the metal components in the constituent components.

  The gas barrier layer according to the present invention is a layer formed on at least one side of the substrate. In the gas barrier film of the present invention, a plurality of the gas barrier layers may be laminated, and at least one of the plurality of gas barrier layers needs to be a layer containing silicon, oxygen and carbon. It is. Further, at least one of the gas barrier layers may further contain nitrogen and aluminum.

When the gas barrier property of the gas barrier layer functioning as a gas barrier layer is calculated with a laminate in which the gas barrier layer is formed on a base material, the oxygen permeability measured by a method according to JIS K 7126-1987 Water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)%, measured by a method in accordance with JIS K 7129-1992, 1 × 10 ⁻³ mL / m ² · 24 h · atm or less. RH) is preferably a high gas barrier property of 1 × 10 ⁻³ g / m ² · 24 h or less.

Moreover, the thickness of the gas barrier film of the present invention is preferably 5 to 3000 nm. When a plurality of gas barrier layers are provided, the total thickness of the gas barrier layers is usually 10 to 10,000 nm. It is preferably in the range of 10 to 5000 nm, more preferably in the range of 100 to 3000 nm, and particularly preferably in the range of 200 to 2000 nm.
By setting the total thickness of the gas barrier layer within the above range, gas barrier properties such as excellent oxygen gas barrier properties and water vapor barrier properties can be exhibited, and deterioration of the gas barrier properties due to bending can be suppressed. .

An example of the layer structure of the gas barrier film 6 of the present invention is shown in FIGS. 1A and 1B.
FIG. 1A includes a region 3 containing silicon as a main component b (hereinafter referred to as B region), a mixed region 4 containing a compound derived from the main component a and the main component b, and a transition metal as the main component a. A gas barrier layer 1 in which a region 2 (hereinafter referred to as an A region) is sequentially stacked is shown.
Thus, the gas barrier layer according to the present invention is preferable in that it has an A region, a B region, and a mixed region because the gas barrier property can be further improved.
In addition, the gas barrier film 6 of this invention should just be equipped with the gas barrier layer 1 at least on the base material 5, and may be either A area | region side and B area | region side. The mixed region is a region that partially includes the A region and the B region. Details of each area will be described later.

Further, as shown in FIG. 1B, the gas barrier layer of the present invention preferably has a mixed region throughout.
The gas barrier layer according to the present invention may have a configuration other than those shown in FIGS. 1A and 1B, for example, a configuration that does not include either the A region or the B region.

[A area]
Hereinafter, the region containing the transition metal according to the present invention as the main component a is also referred to as “A region”.
Here, the “constituent component” means a compound constituting a specific region of the gas barrier layer and a simple substance of metal or nonmetal.
In addition, the “region” means that the gas barrier layer is divided at a constant or arbitrary thickness on a plane perpendicular to the thickness direction of the gas barrier layer (that is, a plane parallel to the outermost surface of the gas barrier layer). This refers to a three-dimensional range between two opposing faces that are sometimes formed, and the composition of components in the region may be constant in the thickness direction or may gradually change. .
Further, the area A may be included as a part of the mixed area and further provided outside the mixed area.
The transition metal (M) is not particularly limited, and any transition metal can be used alone or in combination. Here, the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta , W, Re, Os, Ir, Pt, and Au.

Especially, as transition metal (M) with which favorable gas barrier property is obtained, Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, etc. are mentioned. Among these, Nb and Ta, which are Group 5 elements, are considered to be likely to be bonded to silicon (Si) contained in the gas barrier layer from various examination results, and therefore can be preferably used.
In particular, when the transition metal (M) is a Group 5 element (particularly Nb), a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur. Furthermore, from the viewpoint of optical properties, the transition metal (M) is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.

  The layer thickness of the A region of the gas barrier layer is preferably 2 to 50 nm, more preferably within the range of 4 to 25 nm, more preferably 5 to 15 nm from the viewpoint of achieving both gas barrier properties and optical properties. More preferably, it is within the range.

[B area]
The region containing silicon as the main component b according to the present invention is hereinafter referred to as “B region”.
The gas barrier layer according to the present invention is characterized in that at least one of the gas barrier layers containing silicon, oxygen and carbon satisfies all of the conditions (i) to (iii). Is preferably the B region.

That is, the distance from the surface of the B region of the gas barrier layer in the thickness direction of the B region of such a gas barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve respectively showing the relationship between the atomic ratio), the oxygen atom ratio (oxygen atomic ratio), and the carbon atom ratio (carbon atomic ratio). ) In a region where the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon are 90% or more (more preferably 95% or more, particularly preferably 100%) of the layer thickness of the B region, the following formula (I):
(Atomic ratio of oxygen)> (Atomic ratio of silicon)> (Atomic ratio of carbon) (I)
It is necessary to satisfy the condition expressed by When the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon do not satisfy the above conditions, the resulting gas barrier film has insufficient gas barrier properties.

In the B region of the gas barrier layer, (ii) the carbon distribution curve needs to have at least one extreme value. In the B region of such a gas barrier layer, the carbon distribution curve more preferably has at least two extreme values, and particularly preferably has at least three extreme values.
When the carbon distribution curve has an extreme value, it is possible to suppress a decrease in gas barrier properties when the obtained gas barrier film is bent. In the case of having at least three extreme values as described above, the gas in the layer thickness direction of the B region of the gas barrier layer at one extreme value and the extreme value adjacent to the extreme value of the carbon distribution curve. The absolute value of the difference in distance from the surface of the B region of the barrier layer is preferably 200 nm or less, and more preferably 100 nm or less.

In the present invention, the extreme value means the maximum value or the minimum value of the atomic ratio of the element to the distance from the surface of the B region of the gas barrier layer in the layer thickness direction of the B region of the gas barrier layer.
In the present invention, the maximum value is a point where the value of the atomic ratio of an element changes from increasing to decreasing when the distance from the surface of the B region of the gas barrier layer is changed, and The value of the atomic ratio of the element at a position where the distance from the surface of the B region of the gas barrier layer in the layer thickness direction of the B region of the gas barrier layer is further changed by 20 nm from the point is 3 at% or more. The point where it decreases.
Further, in the present invention, the minimum value is a point where the value of the atomic ratio of an element changes from decreasing to increasing when the distance from the surface of the B region of the gas barrier layer is changed, and the atomic atom of the element at that point The atomic ratio value of the element at a position where the distance from the surface of the B region of the gas barrier layer in the layer thickness direction of the B region of the gas barrier layer is further changed by 20 nm from the point is increased by 3 at% or more. The point to do.

Further, in the B region of such a gas barrier layer, (iii) the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve needs to be 5 at% or more.
In the B region of such a gas barrier layer, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 at% or more, and particularly preferably 7 at% or more. When the absolute value is less than 5 at%, the gas barrier property when the obtained gas barrier film is bent is insufficient.

  In the present invention, the oxygen distribution curve in the B region of the gas barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and has at least three extreme values. Particularly preferred. When the oxygen distribution curve does not have an extreme value, the gas barrier property when the obtained gas barrier film is bent tends to be lowered. In the case of having at least three extreme values as described above, the gas in the thickness direction of the B region of the gas barrier layer at one extreme value and the extreme value adjacent to the extreme value of the oxygen distribution curve. The absolute value of the difference in distance from the surface of the B region of the barrier layer is preferably 200 nm or less, and more preferably 100 nm or less.

  In the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve in the B region of the gas barrier layer is preferably 5 at% or more, and is 6 at% or more. More preferably, it is particularly preferably 7 at% or more. By setting the absolute value to be equal to or more than the lower limit, it is possible to suppress a decrease in gas barrier properties even when the obtained gas barrier film is bent.

  In the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve in the B region of the gas barrier layer is preferably less than 5 at%, and preferably less than 4 at%. More preferably, it is particularly preferably less than 3 at%. When the absolute value is less than the upper limit, it is possible to suppress a decrease in gas barrier properties even when the obtained gas barrier film is bent.

  In the present invention, the oxygen from the distance from the surface of the B region of the gas barrier layer in the thickness direction of at least one of the B regions of the gas barrier layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms. In the oxygen carbon distribution curve showing the relationship with the ratio of the total amount of atoms and carbon atoms (the atomic ratio of oxygen and carbon), the difference between the maximum value and the minimum value of the total oxygen and carbon atomic ratio in the oxygen carbon distribution curve Is preferably less than 5 at%, more preferably less than 4 at%, and particularly preferably less than 3 at%. When the absolute value is less than the upper limit, it is possible to suppress a decrease in gas barrier properties even when the obtained gas barrier film is bent.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon distribution curve use both X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon. Thus, it can be created by so-called XPS depth profile measurement in which the surface composition analysis is sequentially performed while the inside of the sample is exposed.
A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time in this way, the etching time generally correlates with the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer in the layer thickness direction. , “Distance from the surface of the B region of the gas barrier layer in the thickness direction of the B region of the gas barrier layer” as calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement The distance from the surface of the layer can be employed. Further, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

  In the present invention, from the viewpoint of forming a gas barrier layer that is uniform over the entire film surface and has excellent gas barrier properties, the gas barrier layer is in the film surface direction (direction parallel to the surface of the gas barrier layer). Is substantially uniform. In this specification, that the gas barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon distribution curve are measured at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement. And when the oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the maximum value of the atomic ratio of carbon in each carbon distribution curve And the absolute value of the difference between the minimum values is the same as each other or within 5 at%.

Further, in the present invention, the bending resistance is good when the carbon distribution curve is substantially continuous.
In this specification, that the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion in which the atomic ratio of carbon changes discontinuously. Specifically, the etching rate, the etching time, The distance (x, unit: nm) from the surface of the B region of the gas barrier layer in the layer thickness direction of at least one of the gas barrier layers calculated from the above, and the atomic ratio of carbon (C, unit: at%) ) In the following formula (F1):
(DC / dx) ≦ 0.5 (F1)
This means that the condition represented by

The region B of the gas barrier film of the present invention needs to include at least one region that satisfies all of the conditions (i) to (iii), but includes two or more regions that satisfy such a condition. Also good.
When two or more such B regions are provided, the materials of the plurality of B regions may be the same or different. Further, when two or more such B regions are provided, the B region may be formed on one surface of the base material, or may be formed on both surfaces of the base material. . Furthermore, such a plurality of regions may include a region that does not necessarily have a gas barrier property.

  Further, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the B region of the gas barrier layer, When the condition represented by I) is satisfied, the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the B region is in the range of 25 to 45 at%. Is preferable, and it is more preferable to be within the range of 30 to 40 at%. The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the region B is preferably in the range of 33 to 67 at%, and in the range of 45 to 67 at%. More preferably. Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the B region is preferably in the range of 3 to 33 at%, and in the range of 3 to 25 at%. More preferably.

In addition, it is preferable that B area | region is included as a part of said mixing area | region, and also it is the structure provided also outside a mixing area | region as shown to FIG.
The thickness of the B region of the gas barrier layer is not particularly limited, but is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and in the range of 100 to 1000 nm. It is particularly preferred.
By setting the thickness of the B region of the gas barrier layer within the above range, excellent gas barrier properties such as oxygen gas barrier property and water vapor barrier property can be exhibited, and deterioration of the gas barrier property due to bending can be suppressed. .

[Mixed area]
The gas barrier layer according to the present invention contains silicon and a transition metal M in the layer thickness direction, and the value of the atomic ratio (M / silicon) of the transition metal M to the silicon is in the range of 0.02 to 49. There is a continuous mixed region of 5 nm or more. Further, the mixed region includes the A region and the B region in a part thereof.
The mixed region according to the present invention is preferably a region containing a composite compound having a stoichiometrically oxygen-deficient composition, and at least a mixture of the transition metal and the silicon or a compound thereof or at least the composite compound. One is preferably contained. The mixed region preferably further contains carbon and oxygen.
The “composite compound” refers to a compound formed by chemically bonding the constituent components of the A region and the B region to each other, and includes an oxide. For example, it refers to a compound having a chemical structure in which a niobium atom and a silicon atom form a chemical bond directly or via an oxygen atom.
In the present application, a complex formed by physically combining the constituent components of the A region and B with each other by intermolecular interaction is also included in the “composite compound” according to the present invention. .

  As long as this feature is satisfied, the region other than the mixed region of the gas barrier layer may be, for example, a composite compound of silicon (Si) and transition metal (M) that does not correspond to the mixed region (even in the oxygen-deficient region, the stoichiometry). A layer of a typical composition) may be included. The regions other than the mixed region of the gas barrier layer are silicon (Si) oxides, nitrides, oxynitrides, oxycarbides (even oxygen deficient regions, which are regions of stoichiometric composition. Or a transition metal (M) oxide, nitride, oxynitride, oxycarbide (oxygen-deficient region or a region of stoichiometric composition). Or the like.

Below, the specific example of the mixing area | region in the gas barrier layer which concerns on this invention is demonstrated using FIG.
FIG. 2 is a graph for explaining the element profile and the mixed region when the composition distribution of silicon and transition metal in the layer thickness direction of the gas barrier layer is analyzed by the XPS method.
In FIG. 2, elemental analysis of silicon, transition metal (M), O, and C is performed in the depth direction from the surface of the gas barrier layer (the left end of the graph), and the horizontal axis represents the sputter depth (layer thickness: nm). ), And the vertical axis represents the content (atom%) of silicon and transition metal (M).
From the right side, the B region, which is an elemental composition mainly containing Si as a metal, is shown, and on the left side, the A region, which is an elemental composition mainly containing a transition metal (M, for example, niobium) as a metal, is shown. It is shown.
The mixed region is a region in which the value of the atomic ratio of transition metal (M) / silicon is indicated by an elemental composition within a range of 0.02 to 49. The mixed region is a region including a part of the A region and a part of the B region, and a region having a thickness of 5 nm or more.

(Oxygen deficient region)
In the present invention, the composite compound is preferably a metal oxide having a non-stoichiometric composition in which oxygen is lost.
The composition of the mixed region of the gas barrier layer according to the present invention is represented by the chemical composition formula (II) where the composition of the mixed region of the gas barrier layer is silicon (Si), the transition metal is (M), oxygen is O, and carbon is C. : (Si) (M) _x O _y C _z It is preferable that at least a part of the mixed region satisfies the following chemical composition formula (III).

Chemical composition formula (III): (2y + 3z) / (a + bx) <1.0
In the formula, a is the valence of silicon (Si). b is the maximum valence of the transition metal (M). x, y and z represent stoichiometric coefficients. Furthermore, 0.02 ≦ x ≦ 49, 0 <y and 0 <z are satisfied.
The relational expression (III) represents that the mixed region of the gas barrier layer contains an oxygen deficient composition of a composite compound of silicon (Si) and transition metal (M).

As described above, the composition of the composite compound of silicon (Si) and transition metal (M) according to the present invention is represented by (Si) (M) _x O _y C _z . As is clear from this composition, the composite compound may partially contain a carbide structure. Here, the maximum valence of silicon (Si) is a, the maximum valence of transition metal (M) is b, the valence of O is 2, and the valence of C is 3. When the composite compound (including a partly carbide) has a stoichiometric composition, (2y + 3z) / (a + bx) = 1.0. This formula means that the total number of bonds of silicon (Si) and transition metal (M) is equal to the total number of bonds of O and C. In this case, silicon (Si) and transition metal ( Both M) are bonded to either O or C. In addition, in this invention, when 2 or more types are used together as silicon (Si), or when 2 or more types are used together as a transition metal (M), the abundance ratio of each element is set to the maximum valence of each element. The composite valence calculated by performing the weighted average according to is adopted as the values of a and b of the “maximum valence”.

  On the other hand, when (2y + 3z) / (a + bx) <1.0, as in the mixed region according to the present invention, the total number of bonds of silicon (Si) and transition metal (M) is O, This means that the total number of C bonds is insufficient, and this state is an “oxygen deficiency” of the composite compound. In the oxygen deficient state, the remaining bonds of silicon (Si) and transition metal (M) have the possibility of bonding to each other, and when the metals of silicon (Si) and transition metal (M) are directly bonded to each other. It is considered that a denser and higher-density structure is formed than when the metals are bonded through O or C, and as a result, the gas barrier property is improved.

  In the present invention, the mixed region is a region where the value of x satisfies 0.02 ≦ x ≦ 49 (0 <y, 0 ≦ z). This was previously defined as a region in which the value of the number ratio of transition metal (M) / silicon (Si) is in the range of 0.02 to 49 and the thickness is 5 nm or more. Is the same definition as In this region, since both silicon (Si) and transition metal (M) are involved in direct bonding between metals, a mixed region that satisfies this condition exists in a thickness of a predetermined value or more (5 nm), It is thought to contribute to the improvement of gas barrier properties. In addition, since it is thought that it can contribute to improvement of gas barrier property, so that the abundance ratio of silicon (Si) and transition metal (M) is closer, the mixed region has a region satisfying 0.1 ≦ x ≦ 10 by 5 nm or more. The region satisfying 0.2 ≦ x ≦ 49 is more preferably included with a thickness of 5 nm or more, and the region satisfying 0.3 ≦ x ≦ 4 is included with a thickness of 5 nm or more. More preferably.

As described above, it has been confirmed that if there is a mixed region satisfying (2y + 3z) / (a + bx) <1.0, the effect of improving the gas barrier property is exhibited, but the mixed region is (2y + 3z) / It is preferable to satisfy (a + bx) ≦ 0.9, more preferably (2y + 3z) / (a + bx) ≦ 0.85, and even more preferably (2y + 3z) / (a + bx) ≦ 0.8.
However, as the value of (2y + 3z) / (a + bx) in the mixed region decreases, the effect of improving the gas barrier property increases, but the absorption with visible light also increases. Therefore, in the case of a gas barrier layer used for applications where transparency is desired, 0.2 ≦ (2y + 3z) / (a + bx) is preferable, and 0.3 ≦ (2y + 3z) / (a + bx). Is more preferable, and it is further preferable that 0.4 ≦ (2y + 3z) / (a + bx).

In the present invention, the thickness of the mixed region that provides good gas barrier properties is preferably 5 nm or more, more preferably 8 nm or more, and more preferably 10 nm or more as the sputtering thickness in terms of SiO _2. More preferably, it is particularly preferably 20 nm or more. The thickness of the mixed region is not particularly limited from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.
The gas barrier layer having the configuration as described above exhibits an extremely high gas barrier property that can be used as a gas barrier layer for an electronic device such as an organic EL element.

  Here, in the stacked structure of the layer containing the compound (oxide) containing silicon (Si) as a main component and the layer containing the compound (oxide) containing transition metal (M) as a main component, A mixed region made of a composite compound is formed at the lamination interface. However, the abundance ratio of each metal element (Si or M) in the metal element contained in the mixed region is inclined with a certain degree of inclination with respect to the thickness direction of the mixed region. As a result of further studies, it was found that even if an oxygen deficient composition of a composite compound of silicon (Si) and transition metal (M) was formed in the film, the thickness was limited.

  In particular, the thickness of the region in which (Si) / {(Si) + (M)} is in the range of 0.1 to 0.9, which is highly effective in improving the gas barrier property, is only formed to about 10 nm. The gas barrier property that can be reached by the laminated structure is limited, and even when the layer thickness of each layer in the laminated structure is increased, the thickness is hardly changed.

  Based on the knowledge as described above, the present inventor satisfies 0.02 ≦ x ≦ 49, which is a preferable condition for both of the silicon (Si) and the transition metal (M) to participate in direct bonding between metals. By changing the thickness of the oxygen deficient composition of the composite compound of silicon (Si) and transition metal (M) to be satisfied, investigation was made on the critical thickness at which the effect of improving the gas barrier property is seen. As a result, as described above, it was confirmed that when the thickness was 5 nm or more, a very significant improvement in gas barrier properties was observed.

  In the “mixed region” in the present invention, the composition content and the layer thickness can be obtained by the following composition analysis by XPS.

<Composition analysis by XPS and measurement of thickness of mixed region>
When the composition distribution in the thickness direction of the gas barrier layer is analyzed by the XPS method, the mixed region according to the present invention includes silicon (Si) in the interface region between the layer containing silicon (Si) and the transition metal (M). Si) and transition metal (M) coexist, and the value of the number ratio of transition metal (M) / silicon (Si) is in the range of 0.02 to 49, and the thickness is 5 nm or more. A certain region is preferable.

Hereinafter, a method for measuring the mixed region by the XPS analysis method will be described.
Specifically, the element concentration distribution (hereinafter referred to as depth profile) in the thickness direction of the mixed region of the gas barrier layer according to the present invention includes a silicon distribution curve, a transition metal M distribution curve, oxygen (O), nitrogen ( N), carbon (C) distribution curve, etc., by using X-ray photoelectron spectroscopy measurement together with rare gas ion sputtering such as argon, surface composition analysis is sequentially performed while exposing the inside from the surface of the gas barrier layer. It can be created by so-called XPS depth profile measurement. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: atom%) of each element and the horizontal axis as the etching time (sputtering time).

  The distance from the surface of the mixed region of the gas barrier layer in the film thickness direction of the mixed region of the gas barrier layer and the ratio of the amount of transition metal to the total amount of transition metal, silicon atom, oxygen atom and carbon atom, Transition metal distribution curve, silicon distribution curve showing the relationship between the ratio of the amount (atom ratio of silicon), the ratio of the amount of oxygen atoms (atomic ratio of oxygen) and the ratio of the amount of carbon atoms (atomic ratio of carbon), In an oxygen distribution curve and a carbon distribution curve, it is preferable to contain 20 mass% or less continuously in the layer thickness direction.

In addition, in the element distribution curve with the horizontal axis as the etching time in this way, the etching time is generally correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction, The gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement as “the distance from the surface of the mixed region of the gas barrier layer in the thickness direction of the mixed region of the gas barrier layer” The distance from the surface can be employed. Further, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar +) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / sec. It is preferable to be (SiO ₂ thermal oxide equivalent value).

An example of specific conditions for XPS analysis applicable to the present invention is shown below.
Analyzer: QUANTERA SXM manufactured by ULVAC-PHI
X-ray source: Monochromatic Al-Kα
Sputtering ion: Ar (2 keV)
Depth profile: Measurement is repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI. The analyzed elements are silicon (Si), transition metal M, oxygen (O), nitrogen (N), and carbon (C).

From the obtained data, the composition ratio is calculated, and silicon (Si) and the transition metal M coexist, and the value of the number ratio of transition metal M / silicon Si is 0.02 to 49. This was defined as a mixed region, and its thickness was determined. The thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO ₂ .

  In the present invention, the “mixed region” is determined when the thickness of the mixed region is 5 nm or more. From the viewpoint of gas barrier properties, there is no upper limit of the thickness of the mixed region, but from the viewpoint of optical properties, it is preferably in the range of 5 to 100 nm, more preferably in the range of 8 to 50 nm, and still more preferably. Is in the range of 10 to 30 nm.

<Other configurations of gas barrier film>
[Base material]
As a base material used for this invention, the film or sheet | seat which consists of colorless and transparent resin is mentioned. Examples of the resin used for such a substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; polyamide Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin.
Among these resins, polyester resins and polyolefin resins are preferable, and PET and PEN are particularly preferable from the viewpoints of high heat resistance and linear expansion coefficient and low manufacturing cost. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

The thickness of the base material can be appropriately set in consideration of stability when producing the gas barrier film of the present invention. The thickness of the substrate is preferably in the range of 5 to 500 μm from the viewpoint that the film can be conveyed even in a vacuum.
Further, when the gas barrier layer according to the present invention is formed by plasma CVD, the thickness of the base material is in the range of 50 to 200 μm because the gas barrier layer is formed while discharging through the base material. It is more preferable, and it is especially preferable that it is the range of 50-100 micrometers.

  Moreover, it is preferable to perform the surface activation process for cleaning the surface of a base material from a viewpoint of adhesiveness with the gas barrier layer mentioned later to the said base material. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

[Adhesive layer]
The gas barrier film of the present invention includes the base material and the gas barrier layer, and may further include a primer coat layer, a heat-sealable resin layer, an adhesive layer, and the like as necessary. Such a primer coat layer can be formed using a known primer coat agent capable of improving the adhesion between the base material and the gas barrier layer.
Moreover, such a heat-sealable resin layer can be suitably formed using a well-known heat-sealable resin. Furthermore, such an adhesive layer can be appropriately formed using a known adhesive, and a plurality of gas barrier films may be adhered to each other by such an adhesive layer.

<Method for producing gas barrier film>
In the gas barrier film of the present invention, the gas barrier layer is preferably a layer formed by a plasma chemical vapor deposition method. As a gas barrier layer formed by such a plasma chemical vapor deposition method, the substrate is placed on a pair of film forming rollers described later, and plasma is generated by discharging between the pair of film forming rollers described later. More preferably, the layer is formed by plasma chemical vapor deposition.
Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma chemical vapor deposition method preferably contains an organosilicon compound and oxygen, and the content of oxygen in the film forming gas is the organic gas in the film forming gas. It is preferable that the amount is less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the silicon compound.
In the gas barrier film of the present invention, the gas barrier layer is preferably a layer formed by a continuous film forming process.

  The gas barrier layer is formed by sputtering an inorganic material containing silicon (Si) or transition metal (M) (for example, magnetron cathode sputtering, flat-plate magnetron sputtering, 2-pole AC flat-plate magnetron sputtering, 2-pole AC rotary magnetron sputtering, etc. Reactive sputtering method), vapor deposition method (for example, resistance heating vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition), thermal CVD method, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma It can be formed by a vapor deposition method such as a CVD method (CCP-CVD), a photo CVD method, a plasma CVD method (PE-CVD), an epitaxial growth method, and an atomic layer growth method. In the present invention, it is particularly preferable to use a sputtering method or a vapor deposition method.

(Method for forming region A)
The formation of the layer containing the transition metal (M) oxide is not particularly limited, but can be formed without damaging the functional element, and has high productivity. It is preferable to form by (PVD) method, and it is more preferable to form by sputtering method. For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used.

  A reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable. As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, it is possible to produce thin films of silicon (Si) and transition metal (M) composite oxides, nitride oxides, oxycarbides, and the like. it can. Examples of film forming conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, and these can be appropriately selected according to the sputtering apparatus, the material of the film, the layer thickness, and the like.

  The sputtering method may be multi-source simultaneous sputtering using a plurality of sputtering targets including a single transition metal (M) or an oxide thereof. Regarding the method for producing these sputtering targets and the method for producing a thin film made of a complex oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP The description of 2013-043761 gazette etc. can be referred suitably.

(Method for forming region B)
The method for forming the B region containing silicon is not particularly limited, but it is preferably formed by a plasma chemical vapor deposition method.
Further, when generating plasma in the plasma chemical vapor deposition method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers, and a pair of film forming rollers is used and the pair of film forming films is used. More preferably, the substrate is disposed on each of the rollers, and plasma is generated by discharging between the pair of film forming rollers.
In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller In addition to forming the surface portion of the substrate present on the other film, the surface portion of the substrate existing on the other film forming roller can be simultaneously formed, so that the thin film can be efficiently produced. Since the film rate can be doubled and a film having the same structure can be formed, the extreme value in the carbon distribution curve can be at least doubled, and a layer that efficiently satisfies all the conditions (i) to (iii) can be obtained. It becomes possible to form.

  Moreover, it is preferable that the gas barrier film of this invention forms the said gas barrier layer on the surface of the said base material by the roll to roll system from a viewpoint of productivity. An apparatus that can be used when producing a gas barrier film by such a plasma chemical vapor deposition method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and It is preferable that the apparatus has a configuration capable of discharging between a pair of film forming rollers. For example, when the gas barrier film manufacturing apparatus 100 shown in FIG. 3 is used, a plasma chemical vapor deposition method is used. It is also possible to manufacture in a roll-to-roll system while using

  Hereinafter, the method for producing the region B of the gas barrier film of the present invention will be described in more detail with reference to FIG. FIG. 3 is a schematic view showing an example of a production apparatus that can be suitably used for producing the gas barrier film of the present invention. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  The manufacturing apparatus shown in FIG. 3 includes a delivery roller 10, transport rollers 21, 22, 23, 24, film formation rollers 31, 32, a gas supply pipe 41, a plasma generation power supply 51, a film formation roller 31, and 32 includes magnetic field generators 61 and 62 installed inside 32 and a winding roller 11. In such a manufacturing apparatus, at least the film forming rollers 31, 32, the gas supply pipe 41, the plasma generation power source 51, and the magnetic field generators 61, 62 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 31 and the film-forming roller 32) can function as a pair of counter electrodes. 51 is connected.
Therefore, in such a manufacturing apparatus, it is possible to discharge into the space between the film forming roller 31 and the film forming roller 32 by supplying electric power from the plasma generating power source 51, thereby forming the film. Plasma can be generated in the space between the roller 31 and the film forming roller 32.

In addition, when using the film-forming roller 31 and the film-forming roller 32 as electrodes as described above, the material and design may be appropriately changed so that the film-forming roller 31 and the film-forming roller 32 can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 31 and 32) so that the central axis may become substantially parallel on the same plane.
By arranging a pair of film forming rollers (film forming rollers 31 and 32) in this way, the film forming rate can be doubled, and a film having the same structure can be formed. Can be at least doubled.
And according to such a manufacturing apparatus, it is possible to form B area | region on the surface of the base material 5 by CVD method, and a film | membrane component is deposited on the surface of the base material 5 on the film-forming roller 31. On the other hand, since the film component can be deposited on the surface of the base material 5 also on the film forming roller 32, the B region can be efficiently formed on the surface of the base material 5.

Further, inside the film forming roller 31 and the film forming roller 32, magnetic field generators 61 and 62 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.
Furthermore, as the film forming roller 31 and the film forming roller 32, known rollers can be used as appropriate. As such film forming rollers 31 and 32, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. The diameters of the film forming rollers 31 and 32 are preferably in the range of 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.

  Moreover, in such a manufacturing apparatus, the base material 5 is arrange | positioned on a pair of film-forming roller (The film-forming roller 31 and the film-forming roller 32) so that the surface of the base material 5 may oppose, respectively. By disposing the base material 5 in this manner, when the plasma is generated by discharging between the film forming roller 31 and the film forming roller 32, the base material 5 existing between the pair of film forming rollers Each surface can be formed simultaneously. That is, according to such a manufacturing apparatus, the film component is deposited on the surface of the substrate 5 on the film formation roller 31 and further the film component is further deposited on the film formation roller 32 by the CVD method. Therefore, the B region can be efficiently formed on the surface of the substrate 5.

  Moreover, a well-known roller can be used suitably as the sending-out roller 10 and the conveyance rollers 21, 22, 23, 24 used for such a manufacturing apparatus. The take-up roller 11 is not particularly limited as long as it can take up the base material 5 on which the region B is formed, and a known roller can be used as appropriate.

Further, as the gas supply pipe 41, a pipe capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used. Furthermore, as the plasma generating power source 51, a known power source for a plasma generating apparatus can be used as appropriate. Such a power source 51 for generating plasma supplies power to the film forming roller 31 and the film forming roller 32 connected thereto, and makes it possible to use these as counter electrodes for discharge.
As such a plasma generation power source 51, it is possible to more efficiently carry out plasma CVD, so that the polarity of the pair of film forming rollers can be alternately reversed (AC power source or the like). Is preferably used.

  Moreover, as such a plasma generation power source 51, it becomes possible to perform plasma CVD more efficiently, so that the applied power can be set to 100 W to 10 kW, and the AC frequency is set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the magnetic field generators 61 and 62, known magnetic field generators can be used as appropriate. Furthermore, as the base material 5, in addition to the base material used in the present invention, a material in which the A region is formed in advance can be used. Thus, the order of laminating on the base material 5 does not matter.

Using the manufacturing apparatus shown in FIG. 3, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film transport speed are adjusted as appropriate. By doing so, the B region according to the present invention can be formed.
That is, by using the manufacturing apparatus shown in FIG. 3 to generate a discharge between a pair of film forming rollers (film forming rollers 31 and 32) while supplying a film forming gas (such as a source gas) into the vacuum chamber. The film formation gas (raw material gas or the like) is decomposed by plasma, and the region B is formed on the surface of the base material 5 on the film formation roller 31 and the surface of the base material 5 on the film formation roller 32 by the plasma CVD method. It is formed by. In such film formation, the substrate 5 is conveyed by the delivery roller 10, the film formation roller 31 and the like, respectively, so that the surface of the substrate 5 is formed by a roll-to-roll continuous film formation process. The B region is formed.

  The source gas in the film forming gas used for forming such a B region can be appropriately selected and used according to the material of the gas barrier layer to be formed. As such a source gas, for example, an organosilicon compound containing silicon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Examples thereof include silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting gas barrier layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such a carrier gas and a discharge gas, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. If the ratio of the reaction gas is excessive, a thin film that satisfies all the conditions (i) to (iii) cannot be obtained. In this case, excellent gas barrier properties and bending resistance cannot be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Hereinafter, as the film forming gas, a gas containing hexamethyldisiloxane (organosilicon compound (HMDSO: (CH ₃ ) ₆ Si ₂ O)) as a source gas and oxygen (O ₂ ) as a reaction gas is used. Taking a case of producing a silicon-oxygen-based thin film as an example, a suitable ratio of the source gas and the reactive gas in the film forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen-based material. When forming a thin film, the following reaction formula (IV) is used depending on the film forming gas:
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
Reaction occurs as described in 1 to produce silicon dioxide. In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol.
Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. ) To (iii) cannot be formed.

Therefore, in the present invention, when the gas barrier layer is formed, the stoichiometric ratio of the oxygen amount to 1 mol of hexamethyldisiloxane is set so that the reaction of the formula (IV) does not proceed completely. Less than 12 moles.
Note that in the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas ( Even if the flow rate is 12 times the molar amount (flow rate) of hexamethyldisiloxane as the raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is the raw material hexamethyldisiloxane. (It may be about 20 times or more of the molar amount (flow rate).)

  Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane as a raw material is preferably a stoichiometric ratio of 12 times or less (more preferably 10 times or less). . By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer, and the conditions (i) to ( It becomes possible to form a gas barrier layer satisfying all of iii), and the resulting gas barrier film can exhibit excellent gas barrier properties and bending resistance.

If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, unoxidized carbon atoms and hydrogen atoms are excessively taken into the gas barrier layer. In this case, the transparency is lowered, and the gas barrier film cannot be used for a flexible substrate for a device requiring transparency such as an organic EL device or an organic thin film solar cell.
From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

  Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming rollers 31 and 32, an electrode drum connected to the plasma generating power source 51 (in this embodiment, the electrode drums are installed on the film forming rollers 31 and 32). The electric power to be applied can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., and cannot be generally stated, but may be in the range of 0.1 to 10 kW. preferable. If the applied power is less than the lower limit, particles tend to be generated. On the other hand, if the applied power exceeds the upper limit, the amount of heat generated during film formation increases, and the temperature of the substrate surface during film formation increases. As a result, the substrate loses heat and wrinkles occur during film formation. In severe cases, the film melts due to heat, and a large current discharge occurs between the bare film formation rollers. May cause damage.

  Although the conveyance speed (line speed) of the base material 5 can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable to set it as the range of 0.25-100 m / min, More preferably, it is in the range of 0.5 to 20 m / min. When the line speed is less than the lower limit, wrinkles due to heat tend to occur in the film, and when the upper limit is exceeded, the thickness of the formed gas barrier layer tends to be thin.

(Method for forming mixed region)
As a method for forming the mixed region, as described above, when forming the A region and the B region, there is a method of appropriately adjusting each formation condition and forming the mixed region between the A region and the B region. preferable.
As a method for forming the mixed region, it is preferable to use a known co-evaporation method. As such a co-evaporation method, a co-sputtering method is preferable. The co-sputtering method employed in the present invention includes, for example, a composite target made of an alloy containing both silicon (Si) and transition metal (M), or a composite oxide of silicon (Si) and transition metal (M). It can be a single sputtering using a composite target as a sputtering target.

In addition, the co-sputtering method in the present invention may be multi-source simultaneous sputtering using a plurality of sputtering targets including silicon (Si) alone or its oxide and transition metal (M) alone or its oxide. Good.
Regarding the method for producing these sputtering targets and the method for producing a thin film made of a complex oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP The description of 2013-043761 gazette etc. can be referred suitably.
The film forming conditions for performing the co-evaporation method include the ratio of the transition metal (M) and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the film forming process. One or two or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation are exemplified, and these film formation conditions (preferably oxygen content) By adjusting the pressure, a thin film made of a complex oxide having an oxygen deficient composition can be formed.

  That is, by forming the gas barrier layer using the co-evaporation method as described above, almost all regions in the thickness direction of the formed gas barrier layer can be mixed regions. For this reason, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region. In addition, what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method in order to control the thickness of a mixing area | region, for example.

<Electronic device>
The gas barrier film of the present invention has excellent gas barrier properties. For this reason, the gas barrier film of the present invention is a gas barrier film used for electronic devices such as packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various purposes such as an electronic device using the same.
That is, this invention can provide the electronic device containing an electronic device main body and the gas barrier film of this invention, or the gas barrier film obtained by the manufacturing method of this invention.
Examples of the electronic device body used in the electronic device of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. be able to. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

[Quantum dot-containing layer]
Hereinafter, quantum dots (QD), resins, and the like, which are main components of the quantum dot-containing layer, will be described.

(Quantum dot)
In general, semiconductor nanoparticles exhibiting a quantum confinement effect with a nanometer-sized semiconductor material are also referred to as “quantum dots”. Such a quantum dot is a small lump within about 10 and several nanometers in which several hundred to several thousand semiconductor atoms are gathered, but when absorbing energy from an excitation source and reaching an energy excited state, the energy of the quantum dot Releases energy corresponding to the band gap.
Therefore, it is known that quantum dots have unique optical characteristics due to the quantum size effect. Specifically, (1) By controlling the size of the particles, various wavelengths and colors can be emitted. (2) The absorption band is wide and fine particles of various sizes can be obtained with a single wavelength of excitation light. It has the characteristics that it can emit light, (3) it has a symmetrical fluorescence spectrum, and (4) it has excellent durability and fading resistance compared to organic dyes.

The quantum dots contained in the quantum dot-containing layer may be known, and can be generated using any method known to those skilled in the art.
For example, suitable QDs and methods for forming suitable QDs include US Pat. No. 6,225,198, US 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901. Description, US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,865, US Pat. No. 7,374,807, US Patent Application No. 11/299299, and US Pat. No. 6,861,155 Can be mentioned.
The QD is generated from any suitable material, preferably an inorganic material and more preferably an inorganic conductor or semiconductor material. Suitable semiconductor materials include any type of semiconductor, including II-VI, III-V, IV-VI and IV semiconductors.

Suitable semiconductor materials include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb. , InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe , BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si ₃ N ₄ , Ge ₃ N ₄ , Al ₂ O ₃ , _{(Al, Ga, In) 2} (S, Se, Te) 3, Al 2 O, and include but are more than one suitable combination of such semiconductor, and the like.
In the present invention, the following core / shell type quantum dots, for example, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS and the like can be preferably used.

(resin)
Resin can be used for a quantum dot content layer as a binder holding a quantum dot. For example, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate Cellulose esters such as pionate and cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethylpentene, polyether ketone, polyether ketone imide And acrylic resins such as polyamide resins, fluororesins, nylon resins, and polymethyl methacrylate.
The quantum dot-containing layer preferably has a thickness in the range of 50 to 200 μm.
The quantum dot content in the quantum dot-containing layer is preferably in the range of 15 to 60% by volume, although the optimum amount varies depending on the compound used.

[Organic EL device]
The organic EL device according to the present invention is configured, for example, by laminating an anode, a first organic functional layer group, a light emitting layer, a second organic functional layer group, and a cathode on the gas barrier layer of the present invention. preferable. The first organic functional layer group includes, for example, a hole injection layer, a hole transport layer, an electron blocking layer, and the like, and the second organic functional layer group includes, for example, a hole blocking layer, an electric transport layer, and an electron injection layer. Etc. Each of the first organic functional layer group and the second organic functional layer group may be composed of only one layer, or the first organic functional layer group and the second organic functional layer group may not be provided.
Below, the typical example of a structure of an organic EL element is shown.

(I) Anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (ii) Anode / hole injection transport layer / light emitting layer / hole blocking layer / electron injection transport layer / cathode (iii) Anode / Hole injection / transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron injection transport layer / cathode (iv) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / Cathode (v) Anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode (vi) Anode / hole injection layer / hole transport layer / electron blocking Layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

Furthermore, the organic EL element may have a non-light emitting intermediate layer. The intermediate layer may be a charge generation layer or a multi-photon unit configuration.
Regarding the outline of the organic EL element applicable to the present invention, for example, JP2013-157634A, JP2013-168552A, JP2013-177361A, JP2013-187221A, JP JP 2013-191644 A, JP 2013-191804 A, JP 2013-225678 A, JP 2013-235994 A, JP 2013-243234 A, JP 2013-243236 A, JP 2013-2013 A. JP 242366, JP 2013-243371, JP 2013-245179, JP 2014-003249, JP 2014-003299, JP 2014-013910, JP 2014-014933 Gazette, JP, 2014-017494, A It can be mentioned configurations described in.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Production of Gas Barrier Film 101]
(Formation of region B)
A gas barrier film was produced using the production apparatus shown in FIG.
Specifically, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, Inc., trade name “Teonex Q65FA”) is used as the base material 5 and delivered. The roller 10 was attached.

  And while applying a magnetic field between the film-forming roller 31 and the film-forming roller 32 and supplying electric power to the film-forming roller 31 and the film-forming roller 32 respectively, In this discharge region, a film-forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a reactive gas) is generated in such a discharge region. The thin film was formed by the plasma CVD method under the following conditions, and the film was wound up by the winding roller 11 to obtain a gas barrier film.

<Film formation conditions>
Supply amount of raw material gas: 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas: 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min

(Formation of area A)
The A region was produced by a vapor phase method / sputtering. As the sputtering apparatus, a magnetron sputtering apparatus (manufactured by Canon Anelva: Model EB1100) was used.
The following targets were used as targets, Ar and O ₂ were used as process gases, and film formation by RF or DC method was performed by a magnetron sputtering apparatus. The sputtering power source power was 5.0 W / cm ² unless otherwise specified, and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was adjusted under each film forming condition. It should be noted that, after film formation using a glass substrate in advance, data on the layer thickness change with respect to the film formation time was obtained under each film formation condition, and after calculating the layer thickness formed per unit time, the set layer thickness The film formation time was set so that
A commercially available oxygen deficient niobium oxide target was used. The composition was Nb ₁₂ O ₂₉ .
As the film forming conditions, the film was formed by the DC method. The oxygen partial pressure was 12%. Further, the film formation time was set so that the layer thickness was 10 nm, and the gas barrier film 101 in which the A region was formed was produced.

[Formation of gas barrier films 102 to 105]
(Formation of region B)
The B region was formed by the same method as the gas barrier film 101 described above.

(Formation of area A)
Among the methods for producing the gas barrier film 101 described above, the oxygen deficiency index was changed as shown in Table 1 by changing the oxygen partial pressure.
The film formation time was set so that the oxygen partial pressure was 20% and the layer thickness was 10 nm. Moreover, A area | region was formed by DC system using the commercially available metal Ta target.

[Production of Gas Barrier Film 106 (Comparative Example)]
Only the B region of the gas barrier film 101 described above was produced and used as the gas barrier film 106.

[Water vapor permeability evaluation (50% degradation time)]
According to the following measurement method, the water vapor permeability (gas barrier property) of each gas barrier film was evaluated.
The Ca method evaluation sample (type evaluated by permeation concentration) prepared as described below was stored in an 85 ° C. and 85% RH environment, and the corrosion rate of Ca was observed at regular intervals. 1 hour, 5 hours, 10 hours, 20 hours, and thereafter, observation and transmission density measurement (average of 4 points) every 20 hours, and when the measured transmission density is less than 50% of the initial transmission density value Was used as an indicator of gas barrier properties. When the transmission density measured by storage for 500 hours was 50% or more of the initial value of transmission density, it was set to 500 hours or more.

  After the surface of the gas barrier layer of the gas barrier film was UV-cleaned, a thermosetting sheet-like adhesive (epoxy resin) was bonded to the surface of the gas barrier layer with a thickness of 20 μm. This was punched out to a size of 50 mm × 50 mm, then placed in a glove box and dried for 24 hours.

  One side of a 50 mm × 50 mm non-alkali glass plate (thickness 0.7 mm) was UV cleaned. Ca was vapor-deposited by the size of 20 mm x 20 mm through the mask in the center of the glass plate using the vacuum vapor deposition apparatus made from an EILS technology. The thickness of Ca was 80 nm. The glass plate on which Ca was vapor-deposited was taken out into the glove box, placed so that the gas barrier layer surface of the gas barrier film to which the adhesive layer was bonded and the Ca vapor-deposited surface of the glass plate were in contact, and adhered by vacuum lamination. At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down, and cured for 30 minutes to produce an evaluation cell.

  As can be seen from Table 1, it was found that the gas barrier film of the present invention showed significantly superior gas barrier properties as compared with the gas barrier film of the comparative example.

DESCRIPTION OF SYMBOLS 1 Gas barrier layer 2 A area | region 3 B area | region 4 Mixing area | region 5 Base material 6 Gas barrier film 10 Sending roller 11 Winding roller 21, 22, 23, 24 Conveyance roller 31, 32 Film-forming roller 41 Gas supply pipe 51 For plasma generation Power supply 61, 62 Magnetic field generator 100 Gas barrier film manufacturing device

Claims (24)

A gas barrier film having a gas barrier layer on a substrate,
The gas barrier layer is composed of a plurality of regions having chemical compositions different from each other in the thickness direction, and includes a silicon and a transition metal M in the thickness direction, and the transition metal M with respect to the silicon. The atomic ratio (M / silicon) has a mixed region that is in the range of 0.02 to 49 and that is continuous for 5 nm or more in the thickness direction,
The mixed region has an A region containing the transition metal as a main component in at least one region of the plurality of regions, and a B region containing silicon as a main component in the other regions. And the distance from the surface of the B region of the gas barrier layer in the layer thickness direction of the B region of the gas barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (the atomic ratio of silicon) ), Oxygen distribution ratio (oxygen atomic ratio) and carbon atom content ratio (carbon atomic ratio) in relation to the silicon distribution curve, oxygen distribution curve and carbon distribution curve, respectively, ) To (iii) are all satisfied,
A gas barrier film characterized by that.
(I) In the region where the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon are 90% or more of the layer thickness of the B region of the gas barrier layer, the following formula (I):
(Atomic ratio of oxygen)> (Atomic ratio of silicon)> (Atomic ratio of carbon) (I)
(Ii) the carbon distribution curve has at least one extreme value (iii) the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% That is more   The gas barrier film according to claim 1, wherein the carbon distribution curve is substantially continuous.   The gas barrier film according to claim 1, wherein the oxygen distribution curve has at least one extreme value.   The gas barrier film according to any one of claims 1 to 3, wherein the carbon distribution curve has at least three extreme values.   The absolute value of the difference in distance from the surface of the B region of the gas barrier layer in the layer thickness direction of the B region of the gas barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value is Both are 200 nm or less, The gas barrier film of Claim 4 characterized by the above-mentioned.   The gas barrier film according to any one of claims 1 to 5, wherein the oxygen distribution curve has at least three extreme values.   The absolute value of the difference in distance from the surface of the B region of the gas barrier layer in the layer thickness direction of the B region of the gas barrier layer at one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value is Both are 200 nm or less, The gas barrier film of Claim 6 characterized by the above-mentioned.   The thickness of the said gas barrier layer is 5-3000 nm, The gas barrier film as described in any one of Claim 1- Claim 7 characterized by the above-mentioned.   The gas barrier layer further includes the A region and the B region outside the mixed region, and further includes the mixed region between the A region and the B region. The gas barrier film according to any one of 8 to 8.   The gas barrier film according to any one of claims 1 to 9, wherein the mixed region further contains carbon.   The gas barrier film according to claim 10, wherein the mixed region contains the carbon in an amount of 20% by mass or less continuously in the layer thickness direction.   The gas barrier film according to any one of claims 1 to 11, wherein the mixed region is a region containing a composite compound having a stoichiometrically oxygen-deficient composition.   13. The gas barrier film according to claim 12, wherein the mixed region contains at least one of a mixture of the transition metal and the silicon or a compound thereof, or the composite compound.   The gas barrier film according to any one of claims 1 to 13, wherein the mixed region further contains oxygen. The gas barrier film according to claim 12, wherein when the composition of the mixed region is represented by the following chemical composition formula (II), at least a part of the mixed region satisfies the following relational formula (III).
Chemical composition formula (II): (Si) (M) _x O _y C _z
Relational expression (III): (2y + 3z) / (a + bx) <1.0
(Wherein, Si: silicon, M: transition metal, O: oxygen, C: carbon, x, y, z: stoichiometric coefficient, 0.02 ≦ x ≦ 49, 0 <y, 0 ≦ z, a : Represents the maximum valence of silicon, and b: represents the maximum valence of M.)   The gas barrier film according to any one of claims 1 to 15, wherein the transition metal contains niobium (Nb) or tantalum (Ta). It is a manufacturing method of the gas barrier film which manufactures the gas barrier film according to any one of claims 1 to 16,
A method for producing a gas barrier film, wherein the B region of the gas barrier layer is formed by a plasma chemical vapor deposition method, and the A region is formed by a sputtering method.   The region B of the gas barrier layer is formed by a plasma chemical vapor deposition method in which the base material is disposed on a pair of film forming rollers, and plasma is generated by discharging between the pair of film forming rollers. The method for producing a gas barrier film according to claim 17.   The method for producing a gas barrier film according to claim 17 or 18, wherein a film forming gas used for the plasma chemical vapor deposition method contains an organosilicon compound and oxygen.   The content of the oxygen in the film forming gas is equal to or less than a theoretical oxygen amount necessary to completely oxidize the entire amount of the organosilicon compound in the film forming gas. A method for producing a gas barrier film.   The method for producing a gas barrier film according to any one of claims 17 to 20, wherein the gas barrier layer is formed by a continuous film forming process.   An electronic device comprising the gas barrier film according to any one of claims 1 to 16.   The electronic device according to claim 22, further comprising a quantum dot-containing layer.   24. The electronic device according to claim 23, comprising an organic electroluminescence element.

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