JP2018089950A - Silicon nitride laminate film, organic electroluminescence element, electronic paper, optical adjusting film and production method of silicon nitride laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicon nitride laminate film having sufficient gas barrier property and small warpage.SOLUTION: The silicon nitride laminate film according to the present invention includes a flexible substrate and a single thin film layer or a plurality of thin film layers formed on at least one surface of the flexible substrate. At least one specific thin film layer in the single thin film layer or the plurality of thin film layers comprises silicon, nitrogen and hydrogen; and a hydrogen distribution curve showing the relationship between a position in the film thickness direction and the content of hydrogen atoms within the specific thin film layer has at least one maximum point and at least one minimum point.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a silicon nitride laminated film, an organic electroluminescence element, electronic paper, an optical adjustment film, and a method for producing a silicon nitride laminated film.

  For example, a laminated film formed from a resin or the like and having a flexible sheet-like flexible substrate formed with a thin film layer of a metal compound such as silicon nitride is used as a gas barrier film. Examples of using a metal compound laminated film as a gas barrier film include organic electroluminescence elements, electronic paper, optical adjustment films used for organic thin film solar cells, liquid crystal displays, and the like, such as packaging containers for pharmaceuticals, food and drinks, cosmetics, detergents, etc. Materials.

  As a method for forming a thin film layer of a metal compound on the surface of a flexible substrate, for example, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, vacuum chemical vapor deposition, plasma chemistry, etc. A chemical vapor deposition method (CVD) such as a vapor deposition method is known.

  Further, in a predetermined region in the film thickness direction of the thin film layer of the metal compound, the oxygen atom content [atm%] is larger than the silicon atom content [atm%], and the silicon atom content is carbon atom content [atm%]. A metal compound laminated film having improved flexibility by making it larger has been proposed (Japanese Patent No. 5513959). In addition, the publication discloses that the metal compound layer is formed by a plasma chemical vapor deposition method.

  However, when a metal compound is laminated on a flexible substrate by such a conventional method, the metal compound laminated film is warped due to the compressive stress of the metal compound film. In particular, when the thickness of the metal compound layer is increased so that sufficient gas barrier properties can be obtained, the warp of the metal compound laminated film is increased, and in the case of use, for example, when hindering sticking work to other members, etc. There is.

Japanese Patent No. 5513959

  The present invention has been made in view of the above-mentioned problems, and has a sufficient gas barrier property and a small warpage and a silicon nitride laminated film, an organic electroluminescence element, electronic paper, an optical adjustment film, and a silicon nitride laminated film It is an object to provide a method.

  The invention made to solve the above-mentioned problems is a silicon nitride laminated film comprising a flexible base material and one or more thin film layers formed on at least one surface of the flexible base material. At least one specific thin film layer of the plurality of thin film layers contains silicon, nitrogen, and hydrogen, and a hydrogen distribution curve showing a relationship between a film thickness direction position in the specific thin film layer and a hydrogen atom content is at least 1 A silicon nitride laminated film having two maximum points and at least one minimum point.

  The silicon nitride laminated film has a portion in which the hydrogen atom content is small and the compressive stress is large in the film thickness direction and a portion in which the hydrogen atom content is large and the compressive stress is small. Is reduced. In addition, since the silicon nitride laminated film has a different growth pattern depending on the position in the film thickness direction of the thin film layer, it is possible to suppress the growth of defects from the flexible substrate side toward the film surface during the formation process of the thin film layer. Excellent gas barrier properties.

  The specific thin film layer may further contain carbon. Thereby, the flexibility of the specific thin film layer is improved, and the cracking of the specific thin film layer due to bending is suppressed, so that the gas barrier property of the silicon nitride laminated film is hardly impaired.

  The ratio of the maximum maximum value to the minimum minimum value of the hydrogen atom content in the hydrogen distribution curve may be 1.1 or more. As a result, it is possible to achieve both an improvement in gas barrier properties due to a portion with a small hydrogen atom content and a reduction in warpage due to a stress relaxation function at a portion with a large hydrogen atom content. Further, the ratio of the maximum maximum value to the minimum minimum value of the hydrogen atom content of the hydrogen distribution curve is not less than the above lower limit, whereby the refractive index is increased, and the optical function of the silicon nitride laminated film is improved. You can also.

  The hydrogen distribution curve may have a plurality of maximum points, and the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the hydrogen distribution curve may be 60 nm or less. As a result, the distance between the portion having a small hydrogen atom content and a large compressive stress and the portion having a large hydrogen atom content and a small compressive stress is reduced, so that the effect of suppressing warpage of the silicon nitride laminated film becomes more remarkable. .

  The silicon distribution curve indicating the relationship between the film thickness direction position in the specific thin film layer and the content of silicon atoms may have at least one maximum point and at least one minimum point. Thus, even when the silicon distribution curve has at least one maximum point and at least one minimum point, a portion having a large compressive stress and a portion having a small compressive stress are formed, and the warpage of the silicon nitride laminated film is suppressed. Can do.

  The ratio of the maximum maximum value to the minimum minimum value of the silicon atom content in the silicon distribution curve is preferably 1.1 or more. As a result, it is possible to achieve both an improvement in gas barrier properties due to a portion having a small silicon atom content and a reduction in warpage due to a portion having a large silicon atom content.

  The silicon distribution curve may have a plurality of maximum points, and the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the silicon distribution curve may be 60 nm or less. As a result, the effect of suppressing the warpage of the silicon nitride laminated film is more remarkable by reducing the distance between the portion having a small silicon atom content and a large compressive stress and the portion having a large silicon atom content and a small compressive stress. Become.

  At least an NSi− / H− distribution curve showing the relationship between the film thickness direction position in the specific thin film layer and the ratio of the detected intensity of NSi− ions to the detected intensity of H− ions measured by secondary ion mass spectrometry. It is preferable to have one maximum point and at least one minimum point. Thus, since the ratio of the detected intensity of NSi-ion and H-ion has the maximum point and the minimum point, the ratio of the detected intensity of NSi-ion and H-ion is small in the film thickness direction and compressive stress is applied. By having a small portion and a portion where the ratio of the detected intensity of NSi-ion and H-ion is large and the compressive stress is large, the stress is relieved as a whole, and the warpage of the silicon nitride laminated film is reduced.

  The ratio of the maximum maximum value to the minimum minimum value of the NSi− / H− distribution curve may be 1.1 or more. This makes it possible to achieve both an improvement in gas barrier properties due to a portion with a low nitrogen content and a reduction in warpage of the silicon nitride laminated film due to a stress relaxation function at a portion with a high nitrogen content.

  The NSi− / H− distribution curve has a plurality of local maximum points, and the absolute value of the difference in the film thickness direction positions of two adjacent local maximum points in the NSi− / H− distribution curve may be 60 nm or less. . Thereby, the distance between the portion having a small nitrogen content and a small compressive stress and the portion having a large nitrogen content and a large compressive stress is small, and the effect of suppressing the warp of the silicon nitride laminated film becomes more remarkable.

  The NSi− / Si− distribution curve showing the relationship between the film thickness direction position in the specific thin film layer and the ratio of the detected intensity of NSi− ions to the detected intensity of Si− ions measured by secondary ion mass spectrometry is at least 1. It may have one local maximum and at least one local minimum. As described above, the ratio of the detected intensity between the NSi-ion and the Si-ion has the maximum point and the minimum point, so that the ratio of the detected intensity between the NSi-ion and the Si-ion is small in the film thickness direction and compressive stress is applied. By having a small portion and a portion where the ratio of detected intensity of NSi-ion and Si-ion is large and the compressive stress is large, the stress is relieved as a whole, and the warpage of the film is reduced.

  The ratio of the maximum maximum value to the minimum minimum value of the NSi− / Si− distribution curve may be 1.1 or more. This makes it possible to achieve both an improvement in gas barrier properties due to a portion with a low nitrogen content and a reduction in warpage of the silicon nitride laminated film due to a stress relaxation function at a portion with a high nitrogen content.

  The NSi− / Si− distribution curve has a plurality of maximum points, and the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the NSi− / Si− distribution curve is preferably 60 nm or less. . Thereby, the distance between the portion having a small nitrogen content and a small compressive stress and the portion having a large nitrogen content and a large compressive stress is small, and the effect of suppressing the warp of the silicon nitride laminated film becomes more remarkable.

  The silicon distribution curve indicating the relationship between the film thickness direction position in the specific thin film layer and the silicon atom content has at least one maximum point and at least one minimum point, and the maximum point of the hydrogen distribution curve and the silicon The difference in the film thickness direction position from the maximum point of the distribution curve is preferably 5 nm or less. Thereby, the effect by the change of the hydrogen content and the effect by the change of the silicon content are overlapped, so that the barrier property improving effect and the warp suppressing effect of the silicon nitride laminated film become more remarkable.

  The NSi− / H− distribution curve showing the relationship between the position in the film thickness direction and the ratio of the detected intensity of NSi− ions to the detected intensity of H− ions measured by secondary ion mass spectrometry is at least one local maximum point. NSi− / Si which has a relationship between the position in the film thickness direction and the ratio of the detected intensity of NSi− ions to the detected intensity of Si− ions measured by secondary ion mass spectrometry The distribution curve has at least one local maximum point and at least one local minimum point, and the film thickness direction position of the local maximum point of the NSi− / H− distribution curve and the local maximum point of the NSi− / Si− distribution curve; The difference is preferably 5 nm or less. As a result, the effect of the change in nitrogen content based on the hydrogen content and the effect of the change in nitrogen content based on the silicon content overlap, thereby improving the barrier properties of the silicon nitride laminated film The effect and the warp suppressing effect become more remarkable.

  At least an NSi− / Si− distribution curve showing the relationship between the position in the film thickness direction in the specific thin film layer and the ratio of the detected intensity of NSi− ions to the detected intensity of Si− ions measured by secondary ion mass spectrometry It is preferable that there is one local maximum point and at least one local minimum point, and the difference in the film thickness direction position between the local maximum point of the hydrogen distribution curve and the local minimum point of the NSi− / Si− distribution curve is 5 nm or less. Thereby, the effect by the change of the hydrogen content and the effect by the change of the nitrogen content are overlapped, so that the barrier property improving effect and the warp suppressing effect of the silicon nitride laminated film become more remarkable.

  The specific thin film layer may have an average thickness of 5 nm to 3000 nm. Thereby, a larger barrier property can be imparted to the silicon nitride laminated film while more reliably suppressing warpage.

  The main component of the flexible substrate may be polyester or polyolefin. Thereby, the strength and flexibility of the silicon nitride laminated film can be increased. The main component means a component having the largest mass content.

  The main component of the flexible substrate is preferably polyethylene terephthalate or polyethylene naphthalate. Thereby, the strength and flexibility of the silicon nitride laminated film can be further increased.

  Another invention made to solve the above-mentioned problems is an organic electroluminescence device comprising the silicon nitride laminated film.

  The organic electroluminescence element can be used relatively easily in various applications because the silicon nitride laminated film has a sufficient gas barrier property and small warpage.

  Moreover, another invention made | formed in order to solve the said subject is electronic paper provided with the said silicon nitride laminated film.

  The electronic paper is relatively easy to manufacture because the silicon nitride laminated film has a sufficient gas barrier property and small warpage.

  Moreover, another invention made | formed in order to solve the said subject is the optical adjustment film using the said silicon nitride laminated film.

  Since the warp is small while the silicon nitride laminated film has a sufficient gas barrier property, the electro-optic adjusting film can be incorporated into various products relatively easily.

  Furthermore, another invention made in order to solve the above-mentioned problems includes a flexible base material and one or more thin film layers formed on at least one surface of the flexible base material, and the one or more thin films. A method for producing a silicon nitride laminated film, wherein at least one specific thin film layer of the layers contains silicon, nitrogen, and hydrogen, and a relationship between a film thickness direction position in the specific thin film layer and a hydrogen atom content The specific thin film layer is formed by plasma enhanced chemical vapor deposition so that the hydrogen distribution curve indicating at least one has a maximum point and at least one minimum point.

  According to the method for producing a silicon nitride laminated film, the hydrogen distribution curve indicating the relationship between the film thickness direction position in the specific thin film layer and the hydrogen atom content has at least one maximum point and at least one minimum point. Since the specific thin film layer is formed by plasma chemical vapor deposition, the obtained silicon nitride laminated film has a portion in which the hydrogen atom content is small and the compressive stress is large in the film thickness direction, and the hydrogen atom content is large in the compressive stress. Has a small portion. For this reason, the manufacturing method of the said silicon nitride laminated | multilayer film can manufacture the silicon nitride laminated | multilayer film which is excellent in gas barrier property and has small curvature.

  When the specific thin film layer is formed, the flexible base material may be disposed on the opposing surfaces of a pair of film forming rolls, and plasma may be generated by discharging between the pair of film forming rolls. Thereby, since the film forming gas can be reliably supplied to the surface of the flexible substrate, a thin film layer having a desired composition can be formed relatively easily.

  When discharging between the pair of film forming rolls, the polarity of the pair of film forming rolls may be alternately reversed. Thereby, it can discharge through the flexible base material which has insulation, and can form a thin film layer efficiently.

  When the specific thin film layer is formed, a magnetic field may be formed on the surface of the film forming roll by a magnetic field generating means disposed inside the film forming roll. As a result, the film forming apparatus becomes compact, and a thin film layer can be formed efficiently.

  A film forming gas used in the plasma chemical vapor deposition method may include monosilane and nitrogen. Thereby, a thin film layer containing silicon, nitrogen and hydrogen can be formed relatively easily.

  A film forming gas used in the plasma chemical vapor deposition method may contain monosilane and ammonia. Also by this, a thin film layer containing silicon, nitrogen and hydrogen can be formed relatively easily.

  A film forming gas used in the plasma chemical vapor deposition method may include an organosilicon compound and nitrogen. Also by this, a thin film layer containing silicon, nitrogen and hydrogen can be formed relatively easily. In particular, by using an organic silicon compound, the specific thin film layer contains carbon, so that flexibility is improved, and cracking of the specific thin film layer due to bending is suppressed, so that the gas barrier property of the silicon nitride laminated film is hardly impaired. .

  The organosilicon compound may be hexamethyldisiloxane. Thereby, the specific thin film layer can be efficiently formed.

  A film forming gas used in the plasma chemical vapor deposition method may include an organosilicon compound and ammonia. Also by this, a thin film layer containing silicon, nitrogen and hydrogen can be formed relatively easily. In particular, by using an organic silicon compound, the specific thin film layer contains carbon, so that the flexibility is improved, and the cracking of the specific thin film layer due to bending is suppressed, so that the barrier property of the silicon nitride laminated film is hardly impaired. .

  The organosilicon compound may be hexamethyldisiloxane. Thereby, the specific thin film layer can be efficiently formed.

  The specific thin film layer may be formed by a continuous film forming process. Thereby, a silicon nitride laminated film can be manufactured efficiently.

  The present invention provides a silicon nitride laminated film, an organic electroluminescence element, electronic paper, an optical adjustment film, and a silicon nitride laminated film obtained by a method for producing a silicon nitride laminated film, which has a sufficient gas barrier property and warps. small.

It is typical sectional drawing which shows the silicon nitride laminated film of one Embodiment of this invention. It is a schematic diagram which shows the structure of the plasma CVD apparatus which manufactures the silicon nitride laminated film of one Embodiment of this invention. It is a distribution curve which shows the relationship between the film thickness direction position in the silicon nitride laminated film of the Example of this invention, and the component detected. It is a distribution curve which shows the relationship between the film thickness direction position in the silicon nitride laminated film of the Example different from FIG. 3 of this invention, and the component detected. It is a distribution curve which shows the relationship between the film thickness direction position in the silicon nitride laminated film of the comparative example of this invention, and the component detected.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate.

[Silicon nitride laminated film]
A silicon nitride laminated film according to one embodiment of the present invention shown in FIG. 1 includes a flexible base material 1 having flexibility and a specific thin film layer 2 formed on the surface of the flexible base material 1.
<Flexible base material>
The flexible substrate 1 is preferably insulating and colorless and transparent. As a material of the flexible substrate 1, for example, synthetic resin, flexible glass, or the like can be used.

  Examples of the main component of the synthetic resin forming the flexible substrate 1 include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene sulfide (PES), polycarbonate (PC), polyimide (PI), and polyolefin. Can do. Among them, polyester and polyolefin are preferable because polyethylene can be increased in strength and flexibility, and polyethylene terephthalate and polyethylene naphthalate are particularly preferable.

  The average thickness of the flexible base material 1 can be set to, for example, 5 μm or more and 500 μm or less so that the flexible substrate 1 can be conveyed by the manufacturing apparatus.

<Specific thin film layer>
The specific thin film layer 2 is a layer that imparts gas barrier properties to the silicon nitride laminated film. The specific thin film layer 2 contains silicon, nitrogen, and hydrogen. Moreover, it is preferable that the specific thin film layer 2 further contains carbon. Since the specific thin film layer 2 has improved flexibility by containing carbon, loss of gas barrier properties due to cracking of the specific thin film layer or the like can be prevented.

  The specific thin film layer 2 is formed by a chemical vapor deposition method such as a physical vapor deposition method (PVD) such as a vacuum deposition method, a sputtering method or an ion plating method, a low pressure chemical vapor deposition method or a plasma chemical vapor deposition method ( CVD) or the like, but it is particularly preferable to form by chemical vapor deposition.

  The hydrogen distribution curve showing the relationship between the position in the film thickness direction (distance from the surface) in the specific thin film layer 2 and the content of hydrogen atoms in the specific thin film layer 2 has at least one maximum point and at least one minimum point ( A point where the slope becomes 0). Thus, since the hydrogen distribution curve has a maximum point and a minimum point, the specific thin film layer 2 has a portion in which the hydrogen atom content is small in the film thickness direction and the compressive stress is large, and the hydrogen atom content is large and the compressive stress is small. And having a part. Thereby, a stress is relieved as the whole specific thin film layer 2, and the curvature of the said silicon nitride laminated film is reduced. In addition, since the hydrogen distribution curve has a maximum point and a minimum point, the growth mode of the specific thin film layer 2 varies depending on the position in the film thickness direction, and defects in the specific thin film layer are caused by the flexible base material during the lamination process of the specific thin film layer 2. Since growth on the film surface from one side is suppressed, the silicon nitride laminated film is excellent in gas barrier properties.

  The lower limit of the total number of maximum points and minimum points in the hydrogen distribution curve of the specific thin film layer 2 is preferably five and more preferably nine. By setting the total number of local maximum points and local minimum points in the hydrogen distribution curve to be equal to or more than the lower limit, a portion having a large compressive stress, a portion having a small compressive stress, and a film thickness direction are repeatedly arranged, and the warp of the silicon nitride laminated film The effect of reducing becomes more remarkable.

  The lower limit of the ratio of the maximum maximum value to the minimum minimum value of the hydrogen atom content of the hydrogen distribution curve (maximum maximum value / minimum minimum value) is preferably 1.1, more preferably 1.2. 1.3 is more preferable. On the other hand, the upper limit of the ratio of the maximum maximum value to the minimum value of the hydrogen atom content in the hydrogen distribution curve is preferably 5.0, more preferably 4.0, and even more preferably 3.0. When the ratio of the maximum maximum value to the minimum minimum value of the hydrogen atom content in the hydrogen distribution curve is less than the lower limit, the stress change in the specific thin film layer 2 is small, and the warp of the silicon nitride laminated film is sufficiently May not be able to be suppressed. Conversely, if the ratio of the maximum maximum value to the minimum value of the hydrogen atom content in the hydrogen distribution curve exceeds the upper limit, the gas barrier property and optical characteristics of the specific thin film layer 2 may be insufficient.

  The lower limit of the ratio of the minimum maximum value to the maximum minimum value (minimum maximum value / maximum minimum value) of the hydrogen atom content in the hydrogen distribution curve is preferably 0.9, more preferably 1.0. On the other hand, the upper limit of the ratio of the minimum maximum value to the maximum minimum value of the hydrogen atom content in the hydrogen distribution curve is preferably 3.0, more preferably 2.5, and even more preferably 2.0. When the ratio of the minimum maximum value to the maximum minimum value of the hydrogen atom content in the hydrogen distribution curve is less than the lower limit, the stress change in the specific thin film layer 2 is small, and the warp of the silicon nitride laminated film is sufficiently May not be able to be suppressed. On the contrary, when the ratio of the minimum maximum value to the maximum minimum value of the hydrogen atom content in the hydrogen distribution curve exceeds the upper limit, the gas barrier properties and optical characteristics of the specific thin film layer 2 may be insufficient.

  The lower limit of the absolute value of the difference in the film thickness direction position between two adjacent maximum points in the hydrogen distribution curve is preferably 1 nm, more preferably 3 nm, and even more preferably 5 nm. The upper limit of the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the hydrogen distribution curve is preferably 60 nm, more preferably 40 nm, and even more preferably 20 nm. When the difference in the film thickness direction positions of two adjacent maximum points in the hydrogen distribution curve is less than the lower limit, the formation of the specific thin film layer 2 may not be easy. On the other hand, when the difference in the film thickness direction positions of two adjacent maximum points in the hydrogen distribution curve exceeds the upper limit, the warpage of the silicon nitride laminated film may not be sufficiently suppressed.

  The silicon distribution curve indicating the relationship between the film thickness direction position in the specific thin film layer 2 and the silicon atom content in the specific thin film layer 2 has at least one local maximum point and at least one local minimum point (the slope is 0). Point and front and back). Thus, since the silicon distribution curve has a maximum point and a minimum point, the specific thin film layer 2 has a portion in which the silicon atom content is small and the compressive stress is large in the film thickness direction, and the silicon atom content is large and the compressive stress is small. And having a part. Thereby, a stress is relieved as the whole specific thin film layer 2, and the curvature of the said silicon nitride laminated film is reduced. In addition, since the silicon distribution curve has a maximum point and a minimum point, the growth mode of the specific thin film layer 2 differs depending on the position in the film thickness direction, and defects in the specific thin film layer are caused by the flexible base material during the lamination process of the specific thin film layer 2. Since growth on the film surface from one side is suppressed, the silicon nitride laminated film is excellent in gas barrier properties.

  The lower limit of the total number of local maximum points and local minimum points in the silicon distribution curve of the specific thin film layer 2 is preferably five and more preferably nine. By setting the total number of local maximum points and local minimum points in the silicon distribution curve to be equal to or greater than the lower limit, a portion having a large compressive stress, a portion having a small compressive stress, and a film thickness direction are repeatedly arranged, and the warp of the silicon nitride laminated film is repeated. The effect of reducing becomes more remarkable.

  The lower limit of the ratio of the maximum maximum value to the minimum minimum value of the silicon atom content of the silicon distribution curve (maximum maximum value / minimum minimum value) is preferably 1.1, more preferably 1.2. 1.3 is more preferable. On the other hand, the upper limit of the ratio of the maximum maximum value to the minimum value of the silicon atom content in the silicon distribution curve is preferably 5.0, more preferably 4.0, and even more preferably 3.0. When the ratio of the maximum maximum value to the minimum minimum value of the silicon atom content in the silicon distribution curve is less than the lower limit, the stress change in the specific thin film layer 2 is small, and the warp of the silicon nitride laminated film is sufficiently May not be able to be suppressed. Conversely, if the ratio of the maximum maximum value to the minimum value of the silicon atom content in the silicon distribution curve exceeds the upper limit, the gas barrier properties and optical characteristics of the specific thin film layer 2 may be insufficient.

  The lower limit of the ratio of the minimum minimum value to the maximum minimum value of the silicon atom content of the silicon distribution curve (minimum maximum value / maximum minimum value) is preferably 0.9, more preferably 1.0, 1.3 is more preferable. On the other hand, the upper limit of the ratio of the minimum maximum value to the maximum minimum value of the silicon atom content in the silicon distribution curve is preferably 3.0, more preferably 2.5, and even more preferably 2.0. When the ratio of the minimum maximum value to the maximum minimum value of the silicon atom content in the silicon distribution curve is less than the lower limit, the stress change in the specific thin film layer 2 is small, and the warp of the silicon nitride laminated film is sufficiently May not be able to be suppressed. On the other hand, when the ratio of the minimum maximum value to the maximum minimum value of the silicon atom content in the silicon distribution curve exceeds the upper limit, the gas barrier property and optical characteristics of the specific thin film layer 2 may be insufficient.

  The lower limit of the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the silicon distribution curve is preferably 1 nm, more preferably 3 nm, and even more preferably 5 nm. The upper limit of the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the silicon distribution curve is preferably 60 nm, more preferably 40 nm, and even more preferably 20 nm. When the difference in the film thickness direction positions of two adjacent maximum points in the silicon distribution curve is less than the lower limit, the formation of the specific thin film layer 2 may not be easy. On the other hand, when the difference in the film thickness direction positions of two adjacent maximum points in the silicon distribution curve exceeds the upper limit, the warp of the silicon nitride laminated film may not be sufficiently suppressed.

  The upper limit of the difference in the film thickness direction position between the maximum point of the hydrogen distribution curve and the maximum point of the silicon distribution curve is preferably 5 nm, more preferably 3 nm, and even more preferably 1 nm. When the difference in position in the film thickness direction between the maximum point of the hydrogen distribution curve and the maximum point of the silicon distribution curve exceeds the upper limit, the effect due to the change in hydrogen content and the effect due to the change in silicon content are mutually There is a risk that the warpage of the silicon nitride laminated film cannot be sufficiently suppressed.

  Further, an NSi− / H− distribution curve showing the relationship between the film thickness direction position in the specific thin film layer 2 and the ratio of the detected intensity of NSi− ions measured by secondary ion mass spectrometry to the detected intensity of H− ions. May have at least one local maximum and at least one local minimum. Thus, since the ratio of the detected intensity of NSi-ion and H-ion has the maximum point and the minimum point, the ratio of the detected intensity of NSi-ion and H-ion is small in the film thickness direction and compressive stress is applied. It has a small portion and a portion where the ratio of the detected intensity of NSi-ion and H-ion is large and the compressive stress is large. For this reason, since the stress is relieved as the whole of the specific thin film layer 2, the warp is reduced in the silicon nitride laminated film.

  The lower limit of the total number of local maximum points and local minimum points in NSi− / H− of the specific thin film layer 2 is preferably three and more preferably five. By setting the total number of local maximum points and local minimum points in the NSi− / H− to be equal to or greater than the lower limit, a portion having a large compressive stress, a portion having a small compressive stress, and a film thickness direction are repeatedly arranged. The effect of reducing warpage becomes more remarkable.

  The lower limit of the ratio of the maximum maximum value to the minimum minimum value (maximum maximum value / minimum minimum value) of the NSi− / H− distribution curve is preferably 1.1, more preferably 1.2. .3 is more preferred. On the other hand, the upper limit of the ratio of the maximum maximum value to the minimum minimum value of the NSi− / H− distribution curve is preferably 5.0, more preferably 4.0, and even more preferably 3.0. When the ratio of the maximum maximum value to the minimum minimum value of the NSi− / H− distribution curve is less than the lower limit, the change in compressive stress in the specific thin film layer 2 is small, and the warp of the silicon nitride laminated film is sufficiently May not be able to be suppressed. On the other hand, when the ratio of the maximum maximum value to the minimum minimum value of the NSi− / H− distribution curve exceeds the upper limit, the gas barrier properties and optical characteristics of the specific thin film layer 2 may be insufficient.

  The lower limit of the ratio of the minimum maximum value to the maximum minimum value (minimum maximum value / maximum minimum value) of the NSi− / H− distribution curve is preferably 0.9, more preferably 1.0. On the other hand, the upper limit of the ratio of the minimum maximum value to the maximum minimum value of the NSi− / H− distribution curve is preferably 3.0, more preferably 2.5, and even more preferably 2.0. When the ratio of the minimum maximum value to the maximum minimum value of the NSi− / H− distribution curve is less than the lower limit, the change of the compressive stress in the specific thin film layer 2 is small, and the warp of the silicon nitride laminated film is sufficient. May not be able to be suppressed. On the other hand, when the ratio of the minimum maximum value to the maximum minimum value of the NSi− / H− distribution curve exceeds the upper limit, the gas barrier property and optical characteristics of the specific thin film layer 2 may be insufficient.

  The lower limit of the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the NSi− / H− distribution curve is preferably 1 nm, more preferably 3 nm, and even more preferably 5 nm. The upper limit of the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the NSi− / H− distribution curve is preferably 60 nm, more preferably 40 nm, and even more preferably 20 nm. When the difference in the film thickness direction positions of two adjacent maximum points in the NSi− / H− distribution curve is less than the lower limit, the formation of the specific thin film layer 2 may not be easy. On the contrary, when the difference in the film thickness direction position of two adjacent maximum points in the NSi− / H− distribution curve exceeds the upper limit, the warpage of the silicon nitride laminated film may not be sufficiently suppressed.

  Further, an NSi− / Si− distribution curve showing the relationship between the film thickness direction position in the specific thin film layer 2 and the ratio of the detected intensity of NSi− ions measured by secondary ion mass spectrometry to the detected intensity of Si− ions. May have at least one local maximum and at least one local minimum. As described above, the ratio of the detected intensity between the NSi-ion and the Si-ion has the maximum point and the minimum point, so that the ratio of the detected intensity between the NSi-ion and the Si-ion is small in the film thickness direction and compressive stress is applied. It has a small portion and a portion where the ratio of the detected intensity of NSi-ion and Si-ion is large and the compressive stress is large. Thereby, since the stress is relieved as the whole of the specific thin film layer 2, the warp is reduced in the silicon nitride laminated film.

  The lower limit of the total number of local maximum points and local minimum points in the NSi− / Si− distribution curve of the specific thin film layer 2 is preferably three and more preferably five. By setting the total number of local maximum points and local minimum points in the NSi− / Si− distribution curve to be equal to or greater than the lower limit, a portion having a large compressive stress, a portion having a small compressive stress, and a film thickness direction are repeatedly arranged. The effect of reducing the warp of the film becomes more remarkable.

  The lower limit of the ratio of the maximum maximum value to the minimum minimum value (maximum maximum value / minimum minimum value) of the NSi− / Si− distribution curve is preferably 1.1, more preferably 1.2. .3 is more preferred. On the other hand, the upper limit of the ratio of the maximum maximum value to the minimum minimum value of the NSi− / Si− distribution curve is preferably 5.0, more preferably 4.0, and even more preferably 3.0. When the ratio of the maximum maximum value to the minimum minimum value of the NSi− / Si− distribution curve is less than the lower limit, the change in compressive stress in the specific thin film layer 2 is small, and the warp of the silicon nitride laminated film is sufficiently May not be able to be suppressed. Conversely, when the ratio of the maximum maximum value to the minimum minimum value of the hydrogen atom content in the NSi− / Si− distribution curve exceeds the upper limit, the gas barrier properties and optical characteristics of the specific thin film layer 2 become insufficient. There is a fear.

  The lower limit of the ratio of the minimum maximum value to the maximum minimum value (minimum maximum value / maximum minimum value) of the NSi− / Si− distribution curve is preferably 0.9, and more preferably 1.0. On the other hand, the upper limit of the ratio of the minimum maximum value to the maximum minimum value of the NSi− / Si− distribution curve is preferably 3.0, more preferably 2.5, and even more preferably 2.0. When the ratio of the minimum maximum value to the maximum minimum value of the NSi− / Si− distribution curve is less than the above lower limit, the change in compressive stress in the specific thin film layer 2 is small, and the warp of the silicon nitride laminated film is sufficient. May not be able to be suppressed. Conversely, when the ratio of the minimum maximum value to the maximum minimum value of the hydrogen atom content in the NSi− / Si− distribution curve exceeds the upper limit, the gas barrier properties and optical characteristics of the specific thin film layer 2 become insufficient. There is a fear.

  The lower limit of the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the NSi− / Si− distribution curve is preferably 1 nm, more preferably 3 nm, and even more preferably 5 nm. The upper limit of the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the NSi− / Si− distribution curve is preferably 60 nm, more preferably 40 nm, and even more preferably 20 nm. When the difference in the film thickness direction positions of two adjacent maximum points in the NSi− / Si− distribution curve is less than the lower limit, the formation of the specific thin film layer 2 may not be easy. On the contrary, when the difference in the film thickness direction position of two adjacent maximum points in the NSi− / Si− distribution curve exceeds the upper limit, the warpage of the silicon nitride laminated film may not be sufficiently suppressed.

  In the specific thin film layer 2, the upper limit of the difference in the film thickness direction position between the maximum point of the NSi− / H− distribution curve and the maximum point of the NSi− / Si− distribution curve is preferably 5 nm, more preferably 3 nm. 1 nm is more preferable. When the difference in the position in the film thickness direction between the maximum point of the hydrogen distribution curve and the maximum point of the silicon distribution curve exceeds the upper limit, the effect of the change of the nitrogen content on the hydrogen content and the silicon content of the nitrogen content There is a possibility that the effect due to the change against each other cancels each other out and the warpage of the silicon nitride laminated film cannot be sufficiently suppressed.

  The upper limit of the difference in position in the film thickness direction between the maximum point of the hydrogen distribution curve and the minimum point of the NSi− / Si− distribution curve is preferably 5 nm, more preferably 3 nm, and even more preferably 1 nm. When the difference in the film thickness direction position between the maximum point of the hydrogen distribution curve and the minimum point of the NSi− / Si− distribution curve exceeds the upper limit, the effect due to the change in the hydrogen content and the effect due to the change in the nitrogen content And the warpage of the silicon nitride laminated film may not be sufficiently suppressed.

  Moreover, as a minimum of the average thickness of the specific thin film layer 2, 5 nm is preferable, 10 nm is more preferable, and 20 nm is further more preferable. On the other hand, the upper limit of the average thickness of the specific thin film layer 2 is preferably 3000 nm, more preferably 2000 nm, and still more preferably 1000 nm. When the average thickness of the specific thin film layer 2 is less than the above lower limit, the gas barrier property of the silicon nitride laminated film may be insufficient, for example, other characteristics such as optical characteristics may be insufficient. On the other hand, when the average thickness of the specific thin film layer 2 exceeds the above upper limit, the warp of the silicon nitride laminated film may be increased, or the specific thin film layer 2 may be cracked to deteriorate the gas barrier properties and optical characteristics. is there.

<Advantages>
As described above, the silicon nitride laminated film according to the embodiment of the present invention has a small warp while having a sufficient gas barrier property.

  The silicon nitride laminated film can be used for an organic electroluminescence element, electronic paper, an optical adjustment film, and the like. Moreover, an organic electroluminescent element provided with the said silicon nitride laminated film, electronic paper, and an optical adjustment film are each interpreted as another embodiment of this invention.

[Method for producing silicon nitride laminated film]
The silicon nitride laminated film of FIG. 1 can be produced by the method for producing a silicon nitride laminated film according to another embodiment of the present invention. For this reason, although the code | symbol of FIG. 1 is used in the following description, it does not intend limiting the said manufacturing method to the method of manufacturing the gas barrier film which concerns on embodiment of FIG.

  In the method for producing the silicon nitride laminated film, the hydrogen distribution curve indicating the relationship between the position in the film thickness direction in the specific thin film layer 2 and the content of hydrogen atoms has at least one maximum point and at least one minimum point. The specific thin film layer 2 is formed by plasma chemical vapor deposition.

<Manufacturing equipment>
FIG. 2 shows a gas barrier film manufacturing apparatus (plasma CVD apparatus) that can be used in the manufacturing method. This plasma CVD apparatus is an apparatus for obtaining a long silicon nitride laminated film by a continuous process in which a specific thin film layer 2 is continuously formed on the surface of a long film-like flexible substrate 1 conveyed in the longitudinal direction. is there.

  The plasma CVD apparatus includes a pair of film forming rolls 12 arranged in parallel to each other in a vacuum chamber 11 that can be depressurized, a power source 13 for applying a voltage between the pair of film forming rolls 12, and a pair of film forming rolls. 12 and a gas supply unit 14 for supplying a film forming gas. The plasma CVD apparatus preferably further includes magnetic field generation means (excitation coil) 15 in each of the pair of film forming rolls 12.

  This plasma CVD apparatus has a plurality of guide rolls 16, and the flexible base 1 delivered from the base roll 17 is passed over the guide roll 16 and the film forming roll 12, and between the opposing surfaces of the film forming roll 12. A film layer 2 is formed on the flexible substrate 1 and the resulting silicon nitride laminated film is wound around a product roll 18.

  The power supply 13 applies a voltage between the pair of film forming rolls 12 to generate a glow discharge in a facing space between the film forming rolls 12. In order to stably generate the glow discharge, an AC voltage, preferably a pulse voltage with polarity inversion, is used as the voltage applied by the power supply 13.

  The gas supply unit 14 is disposed at a position surrounded by the flexible base material 1 that extends from one film forming roll 12 to the other film forming roll 12 via a plurality of guide rolls 16. It is preferable to supply a film forming gas into the space. The vacuum pump for reducing the pressure in the vacuum chamber 11 is arranged to exhaust the gas in the vacuum chamber 11 from a position facing the gas supply unit 14 with a space between the pair of film forming rolls 12 interposed therebetween. It is preferable.

  In the method for manufacturing the silicon nitride laminated film, a film containing a silicon compound and nitrogen or a nitrogen compound is used as a film forming gas supplied from the gas supply unit 14. Examples of the silicon compound include monosilane, organic silicon compounds (hexamethyldisiloxane: HMDSO, tetraethoxysilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, monomethylsilane, dimethylsilane, and trimethylsilane. , Triethylsilane, tetramethylsilane, hexamethyldisilazane, bis (dimethylamino) dimethylsilane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, etc., among others hexamethyldisiloxane However, since it is relatively inexpensive, easy to handle in terms of safety, and can be gasified relatively easily due to its low vapor pressure, it is particularly preferably used. Examples of the nitrogen compound include ammonia. Among these, as the deposition gas, a gas containing monosilane or an organosilicon compound and nitrogen or a gas containing monosilane or an organosilicon compound and ammonia is preferably used.

  This plasma CVD apparatus forms a film by plasma CVD on the flexible substrate 1 using plasma of a source gas in a film forming gas ionized by the glow discharge. For this reason, it is preferable that the magnetic field generating means 15 is disposed so as to form a magnetic field mainly in the facing space between the film forming rolls 12 so as to attract the plasma to the surface of the film forming rolls 12.

  The magnetic field generation unit 15 forms a magnetic field on the surface of each film forming roll 12. These magnetic field generating means 15 preferably have a plurality of magnetic poles arranged in the circumferential direction of each film forming roll 12. In the plurality of magnetic poles, it is preferable that N poles and S poles are alternately arranged. Thereby, the component of the plasma attracted to the surface of the flexible substrate 1 conveyed on the film forming roll 12 is repeatedly changed, so that the specific thin film layer 2 to be formed is made of hydrogen, silicon, and nitrogen depending on the film thickness direction position. The content will vary.

  In addition, by transporting the flexible base 1 so as to pass through the same magnetic field generation means 15 a plurality of times, the content of hydrogen, silicon and nitrogen varies depending on the position of the specific thin film layer 2 formed in the film thickness direction. It may be made to become.

<Advantages>
In the method for producing the silicon nitride laminated film, the specific thin film layer 2 is formed on the surface of the flexible substrate 1 by a plasma chemical vapor deposition method. As a result, a higher deposition rate is possible compared to sputtering, and the productivity of the silicon nitride laminated film is increased. Further, in the method for producing the silicon nitride laminated film, the specific thin film layer 2 having a higher density is formed as compared with the vapor deposition method, and a relatively high gas barrier property and refractive index are easily obtained.

[Other Embodiments]
The said embodiment does not limit the structure of this invention. Therefore, in the above-described embodiment, components of each part of the above-described embodiment can be omitted, replaced, or added based on the description and common general knowledge of the present specification, and they are all interpreted as belonging to the scope of the present invention. Should.

  The silicon nitride laminated film may include a plurality of thin film layers. When the silicon nitride laminated film has a plurality of thin film layers, one or more of the silicon nitride laminated films may be the specific thin film layer described above.

  The silicon nitride laminated film may form a maximum point and a minimum point on a hydrogen distribution curve or the like by changing the components of the film forming gas.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly based on description of this Example.

<Example 1>
As a flexible base material, a PET film “CPA” having a thickness of 100 μm and a width of 350 mm manufactured by Kimoto Co. is used, and the surface of the flexible base material contains silicon, nitrogen and hydrogen using the plasma CVD apparatus of FIG. The silicon nitride laminated film of Example 1 was obtained by forming the specific thin film layer. Note that as the film forming gas, the supply amount of monosilane was set to 100 sccm, the supply amount of nitrogen was set to 500 sccm, and the gas pressure was set to 3 Pa. The power output for plasma generation was 0.4 kW at a frequency of 70 kHz. Moreover, the conveyance speed of the flexible base material was 0.67 m / min, and the specific thin film layer was formed by one pass. The average thickness of the formed specific thin film layer was about 100 nm.

<Example 2>
The same flexible base material as in Example 1 was used, and the specific thin film layer was formed under the same conditions as in Example 1 to obtain a silicon nitride laminated film of Example 2. Note that as the film forming gas, the supply amount of the organosilicon compound (hexamethyldisiloxane) was 25 sccm, the supply amount of nitrogen was 500 sccm, and the gas pressure was set to 1.5 Pa. The power output for plasma generation was 1.4 kW at a frequency of 70 kHz. Moreover, the conveyance speed of the flexible base material was 2.57 m / min, and the specific thin film layer was formed by 7 passes (3 reciprocations). The average thickness of the formed specific thin film layer was about 380 nm.

<Comparative example>
Using the same flexible base material as in Example 1 above, a specific thin film layer containing silicon, nitrogen and hydrogen is formed on the surface of the flexible base material using a ULVAC sputtering system “CS-200”. An example silicon nitride laminated film was obtained. B-doped Si was used as a target, and as a deposition gas, the supply rate of argon was 14 sccm, the supply rate of nitrogen was 10 sccm, and the gas pressure was set to 3 mTorr. The power was DC 200W. The average thickness of the formed specific thin film layer was about 100 nm.

<Distribution curve>
Examples 1 and 2 of the silicon nitride laminated film and comparative examples were analyzed using a secondary ion mass spectrometer, hydrogen distribution curve, silicon distribution curve, NSi− / H− distribution curve and NSi− / Si− distribution. A curve was obtained. In addition, about Example 1 and a comparative example, the secondary ion mass spectrometer "4500 type" of ATOMICA is used, Cs + ion of 1 keV is used as a primary ion, an irradiation area is about 300x465 micrometers, and an analysis area is used. The measurement was performed with charge correction, with the secondary ion polarity being negative, approximately 90 × 140 μm. Further, for Example 2, a secondary ion mass spectrometer “TOF.SIMS5” manufactured by ION-TOF was used, and 25 keV Bi ₃ ++ ions were used as primary ions, and the sample was sequentially scraped in the film thickness direction. Therefore, Cs + ions of 2 keV were used, the sputtering region was set to a square region of about 200 μm on a side, the analysis region was set to about 75 μm on a side, the secondary ion polarity was negative, and the charge was corrected and measured.

  FIG. 3 shows a hydrogen distribution curve, a silicon distribution curve, an NSi− / H− distribution curve and an NSi− / Si− distribution curve of Example 1 of the silicon nitride laminated film, and FIG. 4 shows Example 2 of the silicon nitride laminated film. The hydrogen distribution curve, silicon distribution curve, NSi− / H− distribution curve and NSi− / Si− distribution curve are shown. FIG. 5 shows the hydrogen distribution curve, silicon distribution curve, NSi− / H− of the comparative example of the silicon nitride laminated film. The distribution curve and the NSi− / Si− distribution curve are shown.

  As shown in the figure, in Examples 1 and 2 of the silicon nitride laminated film, the hydrogen distribution curve, the silicon distribution curve, the NSi− / H− distribution curve and the NSi− / Si− distribution curve have a plurality of maximum points and minimum points. doing. On the other hand, the comparative example of the silicon nitride laminated film is abbreviated except that the hydrogen distribution curve, the silicon distribution curve, the NSi− / H− distribution curve, and the NSi− / Si− distribution curve are lowered near the front and back surfaces of the specific thin film layer. It is flat and has substantially no maximum and minimum points.

  In Example 1 of the silicon nitride laminated film, the ratio of the maximum maximum value to the minimum minimum value in the hydrogen distribution curve is 1.64, and the average interval between the maximum points is about 15 nm.

  In Example 1 of the silicon nitride laminated film, the ratio of the maximum maximum value to the minimum minimum value in the silicon distribution curve is 1.79, and the average interval between the maximum points is about 15 nm.

  In Example 1 of the silicon nitride laminated film, the ratio of the maximum maximum value to the minimum minimum value in the NSi− / H− distribution curve is 2.26, and the average interval between the maximum points is about 15 nm.

  In Example 1 of the silicon nitride laminated film, the ratio of the maximum maximum value to the minimum minimum value in the NSi− / Si− distribution curve is 2.43, and the average interval between the maximum points is about 15 nm.

  In Example 1 of the silicon nitride laminated film, the difference in the film thickness direction position between the maximum point of the hydrogen distribution curve and the maximum point of the silicon distribution curve, the maximum point of the NSi− / H− distribution curve, and the NSi− / Si− distribution curve The difference in the film thickness direction position of the local maximum point, and the difference in the film thickness direction position of the local maximum point of the hydrogen distribution curve and the local minimum point of the NSi− / Si− distribution curve is less than 1 nm, and the phase is almost the same or opposite in phase. I was drawing a curve.

  In Example 2 of the silicon nitride laminated film, the ratio of the maximum maximum value to the minimum minimum value in the hydrogen distribution curve is 1.47, and the average interval between the maximum points is about 24 nm.

  In Example 2 of the silicon nitride laminated film, the ratio of the maximum maximum value to the minimum minimum value in the silicon distribution curve is 1.50, and the average interval between the maximum points is about 24 nm.

  In Example 2 of the silicon nitride laminated film, the ratio of the maximum maximum value to the minimum minimum value in the NSi− / H− distribution curve is 1.68, and the average interval between the maximum points is about 24 nm.

  In Example 2 of the silicon nitride laminated film, the ratio of the maximum maximum value to the minimum minimum value in the NSi− / Si− distribution curve is 1.30, and the average interval between the maximum points is about 24 nm.

  In Example 2 of the silicon nitride laminated film, the difference in the film thickness direction position between the maximum point of the hydrogen distribution curve and the maximum point of the silicon distribution curve, the maximum point of the NSi− / H− distribution curve, and the NSi− / Si− distribution curve The difference in the film thickness direction position of the local maximum point, and the difference in the film thickness direction position of the local maximum point of the hydrogen distribution curve and the local minimum point of the NSi− / Si− distribution curve are less than 5 nm, and are substantially in phase or in phase. I was drawing a curve.

<Water vapor transmission rate>
For Examples 1 and 2 of the silicon nitride laminated film and the comparative example, the water vapor permeability at a temperature of 40 ° C. and a relative humidity of 90 ° C. was measured using a gas barrier test apparatus “Aquatran” manufactured by Mocon, and used as an index of gas barrier properties. . As a result, the water vapor transmission rate of Example 1 is 3.0 × 10 ⁻³ [g / m ² / day], and the water vapor transmission rate of Example 2 is 2.2 × 10 ⁻³ [g / m ² / day]. On the other hand, the water vapor permeability of the comparative example was 0.1 [g / m ² / day].

<Warpage amount>
For Examples 1 and 2 of the silicon nitride laminated film and the comparative example, the sample was cut into a 10 cm square, the specific thin film layer was placed on the flat surface, and the distance from the flat surface of each of the four apexes of the 10 cm square was determined. The total value was measured and used as the amount of warpage. In addition, about Example 2, the sample from which the thickness of a specific thin film layer becomes about 100 nm was created and evaluated by adjusting a film conveyance speed and the number of passes for standardization. As a result, the warpage amount of Example 1 was 20 mm and the warpage amount of Example 2 was 15 mm, whereas the warpage amount of Comparative Example was 30 mm.

<Refractive index>
For Examples 1 and 2 of the silicon nitride laminated film and comparative examples, the refractive index was measured using an ellipsometer (Ellipsometer) “M-2000U” manufactured by JA Woollam. As a result, the refractive index of Example 1 was 1.82 at a wavelength of 550 nm, and the refractive index of Example 2 was 1.90 at a wavelength of 550 nm, whereas the refractive index of the comparative example was 1. 96.

  As described above, Examples 1 and 2 of the silicon nitride laminated film have a lower water vapor transmission rate, a smaller amount of warpage, and a higher refractive index than the comparative example. That is, the silicon nitride laminated film has excellent gas barrier properties and is easy to use due to its small warpage.

  The silicon nitride laminated film according to the present invention can be suitably used for organic electroluminescence elements, electronic paper, optical adjustment films and the like.

DESCRIPTION OF SYMBOLS 1 Flexible base material 2 Specific thin film layer 11 Vacuum chamber 12 Film-forming roll 13 Power supply 14 Gas supply part 15 Magnetic field generation means (excitation coil)
16 Guide roll 17 Base roll 18 Product roll

Claims (33)

A silicon nitride laminated film comprising a flexible substrate and one or more thin film layers formed on at least one surface of the flexible substrate,
At least one specific thin film layer of the one or more thin film layers contains silicon, nitrogen and hydrogen;
A silicon nitride laminated film, wherein a hydrogen distribution curve showing a relationship between a position in the film thickness direction in the specific thin film layer and a content of hydrogen atoms has at least one maximum point and at least one minimum point.   The silicon nitride laminated film according to claim 1, wherein the specific thin film layer further contains carbon.   The silicon nitride laminated film according to claim 1 or 2, wherein a ratio of a maximum maximum value to a minimum minimum value of the hydrogen atom content in the hydrogen distribution curve is 1.1 or more.   The hydrogen distribution curve has a plurality of maximum points, and the absolute value of the difference in the film thickness direction positions of two adjacent maximum points in the hydrogen distribution curve is 60 nm or less. 3. A silicon nitride laminated film according to 3.   The silicon distribution curve indicating the relationship between the film thickness direction position in the specific thin film layer and the silicon atom content has at least one local maximum point and at least one local minimum point. The silicon nitride laminated film described in 1.   The silicon nitride laminated film according to claim 5, wherein a ratio of the maximum maximum value to the minimum minimum value of the silicon atom content in the silicon distribution curve is 1.1 or more.   The silicon distribution curve has a plurality of local maximum points, and an absolute value of a difference between the film thickness direction positions of two adjacent local maximum points in the silicon distribution curve is 60 nm or less. Silicon nitride laminated film.   At least an NSi− / H− distribution curve showing the relationship between the film thickness direction position in the specific thin film layer and the ratio of the detected intensity of NSi− ions to the detected intensity of H− ions measured by secondary ion mass spectrometry. The silicon nitride laminated film according to any one of claims 1 to 7, which has one maximum point and at least one minimum point.   The silicon nitride laminated film according to claim 8, wherein a ratio of the maximum maximum value to the minimum minimum value of the NSi− / H− distribution curve is 1.1 or more.   The NSi− / H− distribution curve has a plurality of local maximum points, and an absolute value of a difference in position in the film thickness direction between two adjacent local maximum points in the NSi− / H− distribution curve is 60 nm or less. The silicon nitride laminated film according to claim 8 or 9.   The NSi− / Si− distribution curve showing the relationship between the film thickness direction position in the specific thin film layer and the ratio of the detected intensity of NSi− ions to the detected intensity of Si− ions measured by secondary ion mass spectrometry is at least 1. The silicon nitride laminated film according to any one of claims 1 to 10, which has one maximum point and at least one minimum point.   The silicon nitride laminated film according to claim 11, wherein a ratio of the maximum maximum value to the minimum minimum value of the NSi− / Si− distribution curve is 1.1 or more.   The NSi− / Si− distribution curve has a plurality of local maximum points, and the absolute value of the difference in the film thickness direction positions of two adjacent local maximum points in the NSi− / Si− distribution curve is 60 nm or less. The silicon nitride laminated film according to claim 11 or claim 12. The silicon distribution curve indicating the relationship between the film thickness direction position in the specific thin film layer and the content of silicon atoms has at least one local maximum point and at least one local minimum point,
The silicon nitride laminated film according to any one of claims 1 to 13, wherein a difference in position in the film thickness direction between a maximum point of the hydrogen distribution curve and a maximum point of the silicon distribution curve is 5 nm or less. The NSi- / H-distribution curve showing the relationship between the ratio of the detected intensity of NSi- ions measured by secondary ion mass spectrometry to the detected intensity of H- ions shows at least one maximum point and at least one minimum point. Have
An NSi- / Si-distribution curve showing the relationship between the detected intensity of NSi- ions measured by secondary ion mass spectrometry and the ratio of the detected intensity of Si- ions to the detected intensity of Si- ions has at least one maximum point and at least one minimum point. And
The difference in the film thickness direction position between the maximum point of the NSi− / H− distribution curve and the maximum point of the NSi− / Si− distribution curve is 5 nm or less. The silicon nitride laminated film as described. The NSi− / Si− distribution curve showing the relationship between the film thickness direction position in the specific thin film layer and the ratio of the detected intensity of NSi− ions to the detected intensity of Si− ions measured by secondary ion mass spectrometry is at least 1. Having one local maximum and at least one local minimum,
The silicon nitride according to any one of claims 1 to 14, wherein a difference in position in the film thickness direction between a maximum point of the hydrogen distribution curve and a minimum point of the NSi- / Si- distribution curve is 5 nm or less. Laminated film.   The silicon nitride multilayer film according to any one of claims 1 to 16, wherein an average thickness of the specific thin film layer is 5 nm or more and 3000 nm or less.   The silicon nitride laminated film according to any one of claims 1 to 17, wherein a main component of the flexible substrate is polyester or polyolefin.   The silicon nitride laminated film according to any one of claims 1 to 17, wherein a main component of the flexible substrate is polyethylene terephthalate or polyethylene naphthalate.   An organic electroluminescent element provided with the silicon nitride laminated film according to any one of claims 1 to 19.   An electronic paper comprising the silicon nitride laminated film according to any one of claims 1 to 19.   The optical adjustment film using the silicon nitride laminated film of any one of Claims 1-19.   A silicon nitride laminated film comprising a flexible substrate and one or more thin film layers formed on at least one surface of the flexible substrate, wherein at least one specific thin film of the one or more thin film layers The layer contains silicon, nitrogen, and hydrogen, and is a method for producing a silicon nitride laminated film, wherein at least one hydrogen distribution curve indicating a relationship between a film thickness direction position in the specific thin film layer and a hydrogen atom content is present. A method for producing a silicon nitride laminated film, wherein the specific thin film layer is formed by a plasma chemical vapor deposition method so as to have a maximum point and at least one minimum point.   24. The silicon nitride according to claim 23, wherein when the specific thin film layer is formed, the flexible base material is disposed on opposing surfaces of a pair of film forming rolls, and plasma is generated by discharging between the pair of film forming rolls. A method for producing a laminated film.   25. The method for producing a silicon nitride laminated film according to claim 24, wherein when discharging between the pair of film forming rolls, the polarities of the pair of film forming rolls are alternately reversed.   26. The method for producing a silicon nitride laminated film according to claim 25, wherein when the specific thin film layer is formed, a magnetic field is formed on a surface of the film forming roll by a magnetic field generating means disposed inside the film forming roll.   27. The method for producing a silicon nitride laminated film according to claim 23, wherein a film forming gas used for the plasma chemical vapor deposition method includes monosilane and nitrogen.   27. The method for producing a silicon nitride laminated film according to claim 23, wherein a film forming gas used for the plasma chemical vapor deposition method includes monosilane and ammonia.   27. The method for producing a silicon nitride laminated film according to claim 23, wherein a film forming gas used for the plasma chemical vapor deposition method contains an organosilicon compound and nitrogen.   30. The method for producing a silicon nitride laminated film according to claim 29, wherein the organosilicon compound is hexamethyldisiloxane.   27. The method for producing a silicon nitride laminated film according to claim 23, wherein a film forming gas used for the plasma chemical vapor deposition method contains an organosilicon compound and ammonia.   32. The method for producing a silicon nitride laminated film according to claim 31, wherein the organosilicon compound is hexamethyldisiloxane.   The method for producing a silicon nitride laminated film according to any one of claims 23 to 32, wherein the specific thin film layer is formed by a continuous film forming process.

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