CN108146047A - Nitride layer stack film, organic electroluminescent device, Electronic Paper and the manufacturing method of pH effect film and nitride layer stack film - Google Patents

Nitride layer stack film, organic electroluminescent device, Electronic Paper and the manufacturing method of pH effect film and nitride layer stack film Download PDF

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Publication number
CN108146047A
CN108146047A CN201711002028.9A CN201711002028A CN108146047A CN 108146047 A CN108146047 A CN 108146047A CN 201711002028 A CN201711002028 A CN 201711002028A CN 108146047 A CN108146047 A CN 108146047A
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nitride layer
film
layer stack
nsi
stack film
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慈幸范洋
川上信之
矶村良幸
冲本忠雄
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Kobe Steel Ltd
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Kobe Steel Ltd
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0046—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by constructional aspects of the apparatus
    • B32B37/0053—Constructional details of laminating machines comprising rollers; Constructional features of the rollers
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    • B32B38/1858—Handling of layers or the laminate using vacuum
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract

Its subject of the invention is, provides a kind of both with sufficient gas barrier property, warpage and small nitride layer stack film.The nitride layer stack film of the present invention, it is characterized in that, it is the nitride layer stack film of the film layer of the single-layer or multi-layer on the surface for at least side for having flexible parent metal and being formed in the flexible parent metal, at least 1 layer of certain thin films layer contains silicon, nitrogen and hydrogen among the film layer of the single-layer or multi-layer, represents the olefin hydrogen curve of the relationship of the film thickness direction position in the certain thin films layer and the content of hydrogen atom and has at least one maximal point and at least one minimal point.

Description

Nitride layer stack film, organic electroluminescent device, Electronic Paper and pH effect film and The manufacturing method of nitride layer stack film
Technical field
The present invention relates to nitride layer stack film, organic electroluminescent device, Electronic Paper and pH effect film and silicon nitrides The manufacturing method of stacked film.
Background technology
Such as formed by resin etc., the surface of the flexible parent metal of flexible sheet is formed with the metals such as silicon nitride The stacked film of the film layer of compound is utilized as gas barrier film.It is used as film is laminated using metallic compound as gas barrier film Example, organic electroluminescent device can be enumerated, Electronic Paper, such as organic thin film solar cell, liquid crystal display etc. PH effect film, such as packing container material of pharmaceuticals, drink food, cosmetics, detergent etc. etc..
Method as the film layer that metallic compound is formed on the surface of flexible parent metal, it is known that for example have vacuum evaporation Physical vaporous deposition (PVD), Low Pressure Chemical Vapor Deposition, the plasma enhanced chemical vapor of method, sputtering method, ion plating method etc. Chemical vapour deposition technique (CVD) of sedimentation etc. etc..
In addition, proposing have a kind of metallic compound that film is laminated, pass through the film thickness direction of the film layer in metallic compound Predetermined region, make oxygen atom containing ratio [atm%] than silicon atom containing ratio [atm%] greatly, and silicon atom containing ratio is made to compare carbon Atom containing ratio [atm%] greatly, so as to improve bendability (No. 5513959 bulletins of Japanese Patent No.).In addition, remember in the bulletin It states, metal compound layer is formed by plasma chemical vapor deposition.
But if metallic compound is laminated on flexible parent metal by this existing method, due to metallic compound The compression stress of film causes metallic compound that film is laminated and warpage occurs.If particularly increase metal compound layer film thickness so as to Sufficient gas barrier property can be obtained, then metallic compound is laminated the warpage of film and becomes larger, and during utilization, for example there is to other components Attachment operation etc. causes the situation of failure.
【Existing technical literature】
【Patent document】
【Patent document 1】No. 5513959 bulletins of Japanese Patent No.
Invention content
The present invention is done in view of the issue, and subject is, providing one kind both has sufficient gas barrier property, and warpage is again Small nitride layer stack film, organic electroluminescent device, Electronic Paper and the manufacturer of pH effect film and nitride layer stack film Method.
The invention formed for solve the problem is a kind of nitride layer stack film, which is characterized in that is to have flexibility Base material and be formed in the flexible parent metal at least side surface single-layer or multi-layer film layer nitride layer stack film, At least 1 layer specific film layer among the film layer of the single-layer or multi-layer contains silicon, nitrogen and hydrogen, represents the certain thin films layer Interior film thickness direction position and the olefin hydrogen curve of the relationship of the content of hydrogen atom have at least one maximal point and at least one pole Dot.
The nitride layer stack film, since there is the part that hydrogen atom content is small and compression stress is big and hydrogen original in film thickness direction Sub- content is big and part that compression stress is small, and so as to which whole upper stress is relaxed, the warpage of film reduces.In addition, the silicon nitride In stacked film, film layer according to film thickness direction position and growth pattern is different, can so as in the forming process of film layer Defect is inhibited to be grown from flexible parent metal side towards film surface, therefore gas barrier property is excellent.
The certain thin films layer can also contain carbon again.The flexible of the certain thin films layer is improved as a result, because bending causes The crackle of certain thin films layer be suppressed, be difficult to be damaged so as to the gas barrier property of the nitride layer stack film.
The maximum maximum of the hydrogen atom content of the olefin hydrogen curve relative to minimum minimum ratio for 1.1 with It is upper.Thereby, it is possible to following two aspect is made to exist side by side, that is, the gas barrier property brought by the small part of hydrogen atom content improve and By the stress relaxation functional bands of the big part of hydrogen atom content Lai warpage reduce.In addition, the hydrogen atom of the olefin hydrogen curve The maximum maximum of content is more than above-mentioned lower limit relative to the ratio of minimum minimum, then refractive index becomes larger, so as to also can Enough improve the optical function of the nitride layer stack film.
The olefin hydrogen curve has multiple maximal points, the film of 2 maximal points abutted on the olefin hydrogen curve The absolute value of the difference of thick direction position is below 60nm.Hydrogen atom content is small as a result, and part that compression stress is big and hydrogen Atom content is big and the distance of part that compression stress is small becomes smaller, therefore the warpage inhibition of the nitride layer stack film is more aobvious It writes.
Represent the silicon distribution curve tool of the relationship of the film thickness direction position in the certain thin films layer and the content of silicon atom There are at least one maximal point and at least one minimal point.In this way, by the silicon distribution curve have at least one maximal point and At least one minimal point can form the big part of compression stress and small part, can also inhibit sticking up for the nitride layer stack film It is bent.
The maximum maximum of silicon atom content on the silicon distribution curve is 1.1 relative to the ratio of minimum minimum It is above.Thereby, it is possible to following two aspect is made to exist side by side, that is, the gas barrier property brought by the small part of silicon atom content improve and It is reduced by the warpage that the big part of silicon atom content is brought.
The silicon distribution curve has multiple maximal points, the film of 2 maximal points abutted on the silicon distribution curve The absolute value of the difference of thick direction position is below 60nm.Silicon atom content is small as a result, and part that compression stress is big and silicon Atom content is big and the distance of part that compression stress is small becomes smaller, and the warpage inhibition of the nitride layer stack film is more notable.
Represent film thickness direction position in the certain thin films layer, with being measured by SIMS analysis method The detection intensity of NSi- ions has relative to the NSi-/H- distribution curves of the relationship of the ratio of the detection intensity of H- ions At least one maximal point and at least one minimal point.In this way, since NSi- ions and the ratio of the detection intensity of H- ions have There are maximal point and minimal point, so just having the ratio of the detection intensity of NSi- ions and H- ions small in film thickness direction and compressing The ratio of the small part of stress and NSi- ions and the detection intensity of H- ions is big and part that compression stress is big, so as to whole Body upper stress is relaxed, and can reduce the warpage of the nitride layer stack film.
The maximum maximum of the NSi-/H- distribution curves relative to the ratio of minimum minimum for more than 1.1 i.e. It can.Thereby, it is possible to following two aspect is made to exist side by side, that is, big using the small part raising gas barrier property of nitrogen content and using nitrogen content Partial stress relaxation function reduces the warpage of the nitride layer stack film.
The NSi-/H- distribution curves have multiple maximal points, 2 abutted on the NSi-/H- distribution curves The absolute value of the difference of the film thickness direction position of maximal point is below 60nm.Nitrogen content is small as a result, and compression stress is small Part and nitrogen content is big and the distance of part that compression stress is big is small, the warpage inhibition of the nitride layer stack film is more aobvious It writes.
Represent film thickness direction position in the certain thin films layer, with being measured by SIMS analysis method The detection intensity of NSi- ions is relative to the NSi-/Si- distribution curves of the relationship of the ratio of the detection intensity of Si- ions, tool There are at least one maximal point and at least one minimal point.In this way, due to NSi- ions and the ratio of the detection intensity of Si- ions With maximal point and minimal point, pressed so as to have the ratio of the detection intensity of NSi- ions and Si- ions small in film thickness direction The ratio of the small part of stress under compression and NSi- ions and the detection intensity of Si- ions is big and part that compression stress is big, thus whole Body upper stress is relaxed, and the warpage of film is reduced.
The maximum maximum of the NSi-/Si- distribution curves relative to the ratio of minimum minimum for more than 1.1 i.e. It can.Thereby, it is possible to following two aspect is made to exist side by side, that is, big using the small part raising gas barrier property of nitrogen content and using nitrogen content Partial stress relaxation function reduces the warpage of the nitride layer stack film.
The NSi-/Si- distribution curves have multiple maximal points, 2 abutted on the NSi-/Si- distribution curves The absolute value of the difference of the film thickness direction position of a maximal point is below 60nm.Nitrogen content is small as a result, and compression stress Small part and nitrogen content are big and the distance of part that compression stress is big is small, and the warpage inhibition of the nitride layer stack film is more Significantly.
Represent the silicon distribution curve tool of the relationship of the film thickness direction position in the certain thin films layer and the content of silicon atom There are at least one maximal point and at least one minimal point, the maximal point of the maximal point of the olefin hydrogen curve and the silicon distribution curve The film thickness direction position difference be below 5nm.Effect caused by the variation of the hydrogen content and the silicon as a result, Effect caused by the variation of content is overlapped mutually, and the block improvement effect and warpage inhibition of the nitride layer stack film are more Add significantly.
Represent the film thickness direction position, strong with the detection of NSi- ions that is measured by SIMS analysis method The NSi-/H- distribution curves of the relationship of the ratio of the detection intensity relative to H- ions are spent, at least one maximal point and extremely Few 1 minimal point represents the film thickness direction position, the inspection of NSi- ions with being measured by SIMS analysis method NSi-/Si- distribution curve of the intensity relative to the relationship of the ratio of the detection intensity of Si- ions is surveyed, it is very big at least one Point and at least one minimal point, the maximal point of the NSi-/H- distribution curves are very big with the NSi-/Si- distribution curves The difference of the film thickness direction position of point is below 5nm.The variation of the nitrogen content on the basis of hydrogen content is brought as a result, Effect and the nitrogen content on the basis of silicone content variation caused by effect be overlapped mutually, so as to the silicon nitride layer The block improvement effect and warpage inhibition of folded film are more notable.
Represent film thickness direction position in the certain thin films layer, with being measured by SIMS analysis method The detection intensity of NSi- ions is relative to the NSi-/Si- distribution curves of the relationship of the ratio of the detection intensity of Si- ions, tool There are at least one maximal point and at least one minimal point, the maximal point of the olefin hydrogen curve and the NSi-/Si- distribution curves Minimal point the film thickness direction position difference be below 5nm.Effect caused by the variation of the hydrogen content as a result, Effect caused by variation with the nitrogen content is overlapped mutually, and thus the block improvement effect of the nitride layer stack film and is stuck up Bent inhibition is more notable.
The average thickness of the certain thin films layer is more than 5nm and below 3000nm.It is more certain thereby, it is possible to one side Ground inhibits warpage, assigns the block of the nitride layer stack film bigger on one side.
The principal component of the flexible parent metal is polyester or polyolefin.Thereby, it is possible to increase the nitride layer stack film Intensity and flexibility.In addition, so-called principal component, the ingredient of mass content maximum is meant.
The principal component of the flexible parent metal is polyethylene terephthalate or polyethylene naphthalate.By This, can further increase the nitride layer stack film strength and flexibility.
Another invention done for solve the problem is the organic electroluminescent member for having the nitride layer stack film Part.
For the organic electroluminescent device because the nitride layer stack film both has sufficient gas barrier property, warpage is again small, so It can relatively easily be used in multiple use.
It is the Electronic Paper for having the nitride layer stack film in addition, for another invention of to solve the problem.
For the Electronic Paper because the nitride layer stack film both has sufficient gas barrier property, warpage is again small, so appearance is compared in manufacture Easily.
It is the pH effect film for having used the nitride layer stack film in addition, for another invention of to solve the problem.
In electron-optical adjustment film, because the nitride layer stack film both has sufficient gas barrier property, warpage is again small, so It is easier to be assembled into various products.
It is a kind of manufacturing method of nitride layer stack film in addition, for another invention of to solve the problem, feature exists In, be the single-layer or multi-layer on the surface for at least side for having flexible parent metal and being formed in the flexible parent metal film layer, institute State the manufacture of at least nitride layer stack film that 1 layer specific film layer contains silicon, nitrogen and hydrogen among the film layer of single-layer or multi-layer Method, makes the olefin hydrogen curve of the relationship of the film thickness direction position in the expression certain thin films layer and the content of hydrogen atom have At least one maximal point and at least one minimal point form the certain thin films thus by plasma chemical vapor deposition Layer.
According to the manufacturing method of the nitride layer stack film, because making the film thickness direction position in the expression certain thin films layer There is at least one maximal point and at least one minimal point with the olefin hydrogen curve of the relationship of the content of hydrogen atom, thus by wait from Daughter chemical vapour deposition technique forms the certain thin films layer, so the obtained nitride layer stack film has in film thickness direction Hydrogen atom content is small and part that compression stress is big and hydrogen atom content is big and part that compression stress is small.Therefore, the silicon nitride The manufacturing method of stacked film can manufacture the nitride layer stack film that gas barrier property is excellent and warpage is small.
When forming the certain thin films layer, the flexible parent metal is configured in a pair into the opposed faces of deflector roll, described A pair into discharge between deflector roll and make plasma generate.Thereby, it is possible to film forming gas is positively supplied to flexible parent metal Surface, therefore can relatively easily form the film layer of expected composition.
The pair of into inverting, the pair of alternating polarity into deflector roll when discharging between deflector roll.Thereby, it is possible to It is discharged by the flexible parent metal with insulating properties, can expeditiously form film layer.
When forming the certain thin films layer, by be configured the magnetic field generating means in the inside into deflector roll it is described into The surface of deflector roll forms magnetic field.Film formation device can expeditiously form film layer into miniaturization as a result,.
Film forming gas for the plasma chemical vapor deposition contains monosilane and nitrogen.Thereby, it is possible to Relatively easily form the film layer containing silicon, nitrogen and hydrogen.
It can also contain monosilane and ammonia for the film forming gas of the plasma chemical vapor deposition.As a result, The film layer containing silicon, nitrogen and hydrogen can relatively easily be formed.
It can also contain organo-silicon compound and nitrogen for the film forming gas of the plasma chemical vapor deposition.By This, also can relatively easily form the film layer containing silicon, nitrogen and hydrogen.Especially by using organo-silicon compound, because Certain thin films layer contains carbon, so flexible improve, the crackle of certain thin films layer is inhibited caused by bending, nitride layer stack The gas barrier property of film is difficult to be damaged.
The organo-silicon compound can also be hexamethyldisiloxane.Thereby, it is possible to expeditiously form certain thin films Layer.
It can also contain organo-silicon compound and ammonia for the film forming gas of the plasma chemical vapor deposition.By This, also can relatively easily form the film layer containing silicon, nitrogen and hydrogen.Especially by using organo-silicon compound, because Certain thin films layer is carbon containing, so flexible improve, the crackle of certain thin films layer is inhibited caused by bending, so as to silicon nitride layer The block of folded film is difficult to be damaged.
The organo-silicon compound can also be hexamethyldisiloxane.Thereby, it is possible to expeditiously form certain thin films Layer.
The certain thin films layer is formed by continuous film-forming process.Thereby, it is possible to expeditiously manufacture silicon nitride Stacked film.
The present invention nitride layer stack film, organic electroluminescent device, Electronic Paper and pH effect film and by silicon nitride The nitride layer stack film that the manufacturing method of stacked film obtains, i.e., with sufficient gas barrier property, warpage is again small.
Description of the drawings
Fig. 1 is the schematical sectional view for the nitride layer stack film for representing an embodiment of the invention.
Fig. 2 is the structure of the plasma CVD equipment for the nitride layer stack film for representing manufacture an embodiment of the invention Into schematic diagram.
Fig. 3 is film thickness direction position in the nitride layer stack film for represent the embodiment of the present invention and the ingredient that detects The distribution curve of relationship.
Fig. 4 is film thickness direction position and inspection in the nitride layer stack film for represent the embodiment different from Fig. 3 of the present invention The distribution curve of the relationship for the ingredient measured.
Fig. 5 is film thickness direction position and the ingredient that detects in the nitride layer stack film for represent the comparative example of the present invention The distribution curve of relationship.
【Symbol description】
1 flexible parent metal
2 certain thin films layers
11 vacuum chambers
12 into deflector roll
13 power supplys
14 gas supply parts
15 magnetic field generating means (magnet exciting coil)
16 deflector rolls
17 base material rollers
18 product rollers
Specific embodiment
Hereinafter, on one side suitable for reference to attached drawing, one side mode of implementation that the present invention will be described in detail.
[nitride layer stack film]
The nitride layer stack film of an embodiment of the invention shown in FIG. 1, has as follows：Flexible flexibility base Material 1；It is formed in the certain thin films layer 2 on the surface of the flexible parent metal 1.
＜ flexible parent metals ＞
It is preferred that flexible parent metal 1 has insulating properties, water white transparency.As the material of the flexible parent metal 1, such as it can use and close Into resin, flexible glass etc..
As the principal component for the synthetic resin for forming flexible parent metal 1, such as polyethylene terephthalate can be enumerated (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), makrolon (PC), polyimides (PI), polyolefin etc.. Wherein, from can more strength and flexible angle, preferably polyester and polyolefin, particularly preferred poly terephthalic acid second two Alcohol ester and polyethylene naphthalate.
In order to which manufacturing device can be used to transport, such as it can be 5 μm or more and 500 μm as the average thickness of flexible parent metal 1 Below.
＜ certain thin films layers ＞
Certain thin films layer 2 is the layer that gas barrier property is assigned for the nitride layer stack film.The certain thin films layer 2 contains silicon, nitrogen And hydrogen.In addition, certain thin films layer 2 preferably also contains carbon.Certain thin films layer 2 can prevent because of carbon containing and flexible raising The forfeiture of gas barrier property caused by crackle of certain thin films layer etc..
Certain thin films layer 2, can be for example, by the physical vaporous deposition of vacuum vapour deposition, sputtering method, ion plating method etc. (PVD), the formation such as chemical vapour deposition technique (CVD) of Low Pressure Chemical Vapor Deposition, plasma chemical vapor deposition etc., But it wherein, is preferably formed by chemical vapour deposition technique.
Represent film thickness direction position (distance away from surface) and the hydrogen atom in the certain thin films layer in the certain thin films layer 2 Content relationship olefin hydrogen curve, there is at least one maximal point and at least one minimal point (slope is 0 point).In this way, Olefin hydrogen curve has maximal point and minimal point, so as to which certain thin films layer 2 is just small with hydrogen atom content in film thickness direction and presses The big part of stress under compression and hydrogen atom content are big and part that compression stress is small.As a result, as the entirety of certain thin films layer 2 and Speech, stress are relaxed, and the warpage of the nitride layer stack film reduces.In addition, olefin hydrogen curve has maximal point and minimal point, it is special Film layer 2 is determined according to film thickness direction position and growth pattern is different, in the lamination process of certain thin films layer 2, can inhibit specific The defects of film layer is grown from 1 lateral film surface of flexible parent metal, therefore the nitride layer stack membrane gas barrier is excellent.
As the maximal point and the lower limit of the total number of minimal point in the olefin hydrogen curve of certain thin films layer 2, preferably It is 5, more preferably 9.By making the maximal point of the olefin hydrogen curve and the total number of minimal point to be more than above-mentioned lower limit, The big part of compression stress and the small part of compression stress are repeated configuration on film thickness direction, the warpage of the nitride layer stack film Reducing effect is more notable.
The maximum maximum of hydrogen atom content as the olefin hydrogen curve relative to minimum minimum ratio (most The minimum of big maximum/minimum) lower limit, preferably 1.1, more preferably 1.2, further preferably 1.3.The opposing party Face, the maximum maximum of hydrogen atom content as the olefin hydrogen curve relative to the ratio of minimum minimum the upper limit, Preferably 5.0, more preferably 4.0, further preferably 3.0.The hydrogen atom content of the olefin hydrogen curve it is maximum very big When value is less than the lower limit relative to the ratio of minimum minimum, the stress variation in certain thin films layer 2 becomes smaller, it is possible to cannot Fully inhibit the warpage of the nitride layer stack film.Conversely, the maximum maximum phase of the hydrogen atom content of the olefin hydrogen curve When being higher than the upper limit for the ratio of minimum minimum, the gas barrier property and optical characteristics of certain thin films layer 2 may be insufficient.
The minimum maximum of hydrogen atom content as the olefin hydrogen curve relative to maximum minimum ratio (most The minimum of small maximum/maximum) lower limit, preferably 0.9, more preferably 1.0.On the other hand, as the olefin hydrogen The minimum maximum of the hydrogen atom content of curve relative to the ratio of maximum minimum the upper limit, preferably 3.0, more preferably 2.5, further preferably 2.0.The minimum maximum of the hydrogen atom content of the olefin hydrogen curve is relative to the minimum of maximum When the ratio of value is less than the lower limit, the stress variation in certain thin films layer 2 becomes smaller, it is possible to cannot fully inhibit the silicon nitride layer The warpage of folded film.Conversely, the minimum maximum of the hydrogen atom content of the olefin hydrogen curve is relative to maximum minimum During than being higher than the upper limit, the gas barrier property and optical characteristics of certain thin films layer 2 may be insufficient.
Under the absolute value of the difference of the film thickness direction position as 2 maximal points adjacent on the olefin hydrogen curve Limit, further preferably preferably 1nm, more preferably 3nm, 5nm.As 2 maximal points adjacent on the olefin hydrogen curve The film thickness direction position absolute value of the difference the upper limit, preferably 60nm, more preferably 40nm, further preferably 20nm.It is specific when the difference of the film thickness direction position of 2 adjacent maximal points is less than above-mentioned lower limit on the olefin hydrogen curve The formation of film layer 2 is possibility not easy.Conversely, the film thickness direction of 2 maximal points adjacent on the olefin hydrogen curve When the difference of position is higher than the above-mentioned upper limit, it is possible to cannot fully inhibit the warpage of the nitride layer stack film.
In addition, represent the film thickness direction position in the certain thin films layer in certain thin films layer 2 and the pass of the content of silicon atom The silicon distribution curve of system has at least one maximal point and at least one minimal point (slope is 0 point, the table back side).In this way, silicon point Cloth curve has maximal point and minimal point, so as to which certain thin films layer 2 is just small with silicon atom content in film thickness direction and compresses and answers The big part of power and silicon atom content are big and part that compression stress is small.As a result, as certain thin films layer 2 generally speaking, should Power is relaxed, and the warpage of the nitride layer stack film reduces.In addition, silicon distribution curve has maximal point and minimal point, so as to special Film layer 2 is determined according to film thickness direction position and growth pattern is different, in the lamination process of certain thin films layer 2, can inhibit specific The defects of film layer is grown from 1 lateral film surface of flexible parent metal, therefore its gas barrier property of the nitride layer stack film is excellent.
As the maximal point and the lower limit of the total number of minimal point on the silicon distribution curve of certain thin films layer 2, preferably It is 5, more preferably 9.By make the total number of maximal point on the silicon distribution curve and minimal point for above-mentioned lower limit with On, the big part of compression stress and the small part of compression stress are repeated configuration in film thickness direction, which sticks up Bent reducing effect is more notable.
The maximum maximum of silicon atom content as the silicon distribution curve relative to minimum minimum ratio (most The minimum of big maximum/minimum) lower limit, preferably 1.1, more preferably 1.2, further preferably 1.3.The opposing party Face, the maximum maximum of silicon atom content as the silicon distribution curve relative to the ratio of minimum minimum the upper limit, Preferably 5.0, more preferably 4.0, further preferably 3.0.The silicon atom content of the silicon distribution curve it is maximum very big When value is less than the lower limit relative to the ratio of minimum minimum, the stress variation in certain thin films layer 2 becomes smaller, it is possible to cannot Fully inhibit the warpage of the nitride layer stack film.Conversely, the maximum maximum phase of the silicon atom content of the silicon distribution curve When being higher than the upper limit for the ratio of minimum minimum, the gas barrier property and optical characteristics of certain thin films layer 2 may be insufficient.
The minimum maximum of silicon atom content as the silicon distribution curve relative to maximum minimum ratio (most The minimum of small maximum/maximum) lower limit, preferably 0.9, more preferably 1.0, further preferably 1.3.The opposing party Face, the minimum maximum of silicon atom content as the silicon distribution curve relative to the ratio of maximum minimum the upper limit, Preferably 3.0, more preferably 2.5, further preferably 2.0.The silicon atom content of the silicon distribution curve it is minimum very big When value is less than the lower limit relative to the ratio of maximum minimum, the stress variation in certain thin films layer 2 becomes smaller, the silicon nitride layer The warpage of folded film is it is possible that cannot fully inhibit.Conversely, the minimum maximum phase of the silicon atom content of the silicon distribution curve When being higher than the upper limit for the ratio of maximum minimum, the gas barrier property and optical characteristics of certain thin films layer 2 may be insufficient.
Under the absolute value of the difference of the film thickness direction position as 2 maximal points adjacent on the silicon distribution curve Limit, further preferably preferably 1nm, more preferably 3nm, 5nm.As 2 maximal points adjacent on the silicon distribution curve The film thickness direction position absolute value of the difference the upper limit, preferably 60nm, more preferably 40nm, further preferably 20nm.It is specific when the difference of the film thickness direction position of 2 adjacent maximal points is less than above-mentioned lower limit on the silicon distribution curve The formation of film layer 2 possibility becomes to be not easy.Conversely, the film thickness of 2 maximal points adjacent on the silicon distribution curve When the difference of direction position is higher than the above-mentioned upper limit, it is possible to cannot fully inhibit the warpage of the nitride layer stack film
The film thickness direction position of the maximal point of the maximal point and silicon distribution curve as the olefin hydrogen curve Difference the upper limit, preferably 5nm, more preferably 3nm, further preferably 1nm.As the olefin hydrogen curve maximal point with When the difference of the film thickness direction position of the maximal point of the silicon distribution curve is higher than the above-mentioned upper limit, what the variation of hydrogen content was brought The effect that the variation of effect and silicone content is brought is offset each other, it is possible to cannot fully inhibit sticking up for the nitride layer stack film It is bent
In addition, represent film thickness direction position in certain thin films layer 2, with being measured by SIMS analysis method The detection intensity of NSi- ions has at least the NSi-/H- distribution curves of the relationship of the ratio of the detection intensity of H- ions 1 maximal point and at least one minimal point.In this way, since NSi- ions and the ratio of the detection intensity of H- ions have pole A little bigger and minimal point, then the ratio in detection intensity of the film thickness direction with NSi- ions and H- ions is small and compression stress is small The ratio of part and NSi- ions and the detection intensity of H- ions is big and part that compression stress is big.Therefore, the nitride layer stack In film, as certain thin films layer 2 generally speaking, stress is relaxed, so warpage reduces.
The lower limit of the maximal point of NSi-/H- as certain thin films layer 2 and the total number of minimal point, preferably 3, more Preferably 5.By making the maximal point of the NSi-/H- and the total number of minimal point more than above-mentioned lower limit, compression stress The small part in big part and compression stress is repeated configuration in film thickness direction, and the warpage reducing effect of the nitride layer stack film is more It is notable.
Maximum maximum as the NSi-/H- distribution curves is (maximum relative to the ratio of minimum minimum The minimum of maximum/minimum) lower limit, preferably 1.1, more preferably 1.2, further preferably 1.3.On the other hand, make For the NSi-/H- distribution curves maximum maximum relative to the ratio of minimum minimum the upper limit, preferably 5.0, More preferably 4.0, further preferably 3.0.The maximum maximum of the NSi-/H- distribution curves is relative to minimum pole When the ratio of small value is less than above-mentioned lower limit, the compression stress in certain thin films layer 2 becomes smaller, it is possible to cannot fully inhibit the nitrogen The warpage of SiClx stacked film.Conversely, the maximum maximum of the NSi-/H- distribution curves is relative to minimum minimum During than being higher than the upper limit, the gas barrier property and optical characteristics of certain thin films layer 2 may be insufficient.
Minimum maximum as the NSi-/H- distribution curves is (minimum relative to the ratio of maximum minimum The minimum of maximum/maximum) lower limit, preferably 0.9, more preferably 1.0.On the other hand, the NSi-/H- distributions are bent The minimum maximum of line is relative to the upper limit of the ratio of maximum minimum, preferably 3.0, more preferably 2.5, further preferably It is 2.0.The minimum maximum of the NSi-/H- distribution curves is less than above-mentioned lower limit relative to the ratio of maximum minimum When, the compression stress in certain thin films layer 2 becomes smaller, it is possible to cannot fully inhibit the warpage of the nitride layer stack film.Instead It, it is special when the minimum maximum of the NSi-/H- distribution curves is higher than the upper limit relative to the ratio of maximum minimum The gas barrier property and optical characteristics for determining film layer 2 may be insufficient.
The difference of the film thickness direction position as 2 maximal points adjacent on the NSi-/H- distribution curves it is exhausted To the lower limit of value, preferably 1nm, more preferably 3nm, further preferably 5nm.As on the NSi-/H- distribution curves The upper limit of the absolute value of the difference of the film thickness direction position of 2 adjacent maximal points, preferably 60nm, more preferably 40nm, Further preferably 20nm.The difference of the film thickness direction position of 2 adjacent maximal points on the NSi-/H- distribution curves During less than above-mentioned lower limit, the formation of certain thin films layer 2 possibility becomes easy.It is conversely, adjacent on the NSi-/H- distribution curves When the difference of the film thickness direction position of 2 maximal points connect is higher than the above-mentioned upper limit, it is possible to cannot fully inhibit the silicon nitride The warpage of stacked film.
In addition, represent film thickness direction position in certain thin films layer 2, with being measured by SIMS analysis method The detection intensity of NSi- ions has relative to the NSi-/Si- distribution curves of the relationship of the ratio of the detection intensity of Si- ions At least one maximal point and at least one minimal point.In this way, since NSi- ions and the ratio of the detection intensity of Si- ions have There are maximal point and minimal point, then the ratio in detection intensity of the film thickness direction with NSi- ions and Si- ions is small and compression should The ratio of the small part of power and NSi- ions and the detection intensity of Si- ions is big and part that compression stress is big.The nitrogen as a result, In SiClx stacked film, as certain thin films layer 2 generally speaking, stress is relaxed, so warpage reduces.
As under the maximal point and the total number of minimal point in the NSi-/Si- distribution curves of certain thin films layer 2 Limit, more preferably preferably 3,5.By making the total of maximal point in the NSi-/Si- distribution curves and minimal point Number is more than above-mentioned lower limit, then the big part of compression stress and the small part of compression stress are repeated configuration on film thickness direction, The warpage reducing effect of the nitride layer stack film is more notable.
Maximum maximum as the NSi-/Si- distribution curves is (maximum relative to the ratio of minimum minimum The minimum of maximum/minimum) lower limit, preferably 1.1, more preferably 1.2, further preferably 1.3.On the other hand, make For the NSi-/Si- distribution curves maximum maximum relative to the ratio of minimum minimum the upper limit, preferably 5.0, More preferably 4.0, further preferably 3.0.The maximum maximum of the NSi-/Si- distribution curves is relative to minimum When the ratio of minimum is less than above-mentioned lower limit, the compression stress in certain thin films layer 2 becomes smaller, it is possible to cannot fully inhibit this The warpage of nitride layer stack film.Conversely, the maximum maximum of the hydrogen atom content of the NSi-/Si- distribution curves is opposite When the ratio of minimum minimum is higher than the upper limit, the gas barrier property and optical characteristics of certain thin films layer 2 may be insufficient.
Minimum maximum as the NSi-/Si- distribution curves is (minimum relative to the ratio of maximum minimum The minimum of maximum/maximum) lower limit, preferably 0.9, more preferably 1.0.On the other hand, as the NSi-/Si- The minimum maximum of distribution curve is relative to the upper limit of the ratio of maximum minimum, preferably 3.0, more preferably 2.5, into one Step preferably 2.0.The minimum maximum of the NSi-/Si- distribution curves is relative to the ratio of maximum minimum less than upper When stating lower limit, the compression stress in certain thin films layer 2 becomes smaller, it is possible to cannot fully inhibit sticking up for the nitride layer stack film It is bent.Conversely, the minimum maximum of the hydrogen atom content of the NSi-/Si- distribution curves is relative to maximum minimum During than being higher than the upper limit, the gas barrier property and optical characteristics of certain thin films layer 2 may be insufficient.
The difference of the film thickness direction position as 2 maximal points adjacent on the NSi-/Si- distribution curves it is exhausted To the lower limit of value, preferably 1nm, more preferably 3nm, further preferably 5nm.As on the NSi-/Si- distribution curves The upper limit of the absolute value of the difference of the film thickness direction position of 2 adjacent maximal points, preferably 60nm, more preferably 40nm, Further preferably 20nm.The film thickness direction position of 2 adjacent maximal points on the NSi-/Si- distribution curves When difference is less than above-mentioned lower limit, the formation of certain thin films layer 2 has and can not become to be not easy.Conversely, the NSi-/Si- distributions are bent When the difference of the film thickness direction position of 2 adjacent maximal points is higher than the above-mentioned upper limit on line, it is possible to cannot fully inhibit this The warpage of nitride layer stack film.
In certain thin films layer 2, maximal point and the NSi-/Si- as the NSi-/H- distribution curves are distributed The upper limit of the difference of the film thickness direction position of the maximal point of curve, preferably 5nm, more preferably 3nm, further preferably 1nm.The maximal point of the olefin hydrogen curve and the difference of the film thickness direction position of the maximal point of the silicon distribution curve are higher than During the above-mentioned upper limit, effect that nitrogen content is brought relative to the variation of hydrogen content is brought with nitrogen content relative to the variation of silicone content Effect offset each other, it is possible to cannot fully inhibit the warpage of the nitride layer stack film.
The film thickness of the minimal point of the maximal point and NSi-/Si- distribution curves as the olefin hydrogen curve The upper limit of the difference of direction position, preferably 5nm, more preferably 3nm, further preferably 1nm.The olefin hydrogen curve it is very big When point and the difference of the film thickness direction position of the minimal point of the NSi-/Si- distribution curves are higher than the above-mentioned upper limit, hydrogen content The effect brought of variation and the effect brought of variation of nitrogen content offset each other, it is possible to cannot fully inhibit the silicon nitride layer The warpage of folded film.
In addition, the lower limit of the average thickness as certain thin films layer 2, preferably 5nm, more preferably 10nm, further excellent It is selected as 20nm.On the other hand, the upper limit as the average thickness of certain thin films layer 2, preferably 3000nm, more preferably 2000nm, further preferably 1000nm.When the average thickness of certain thin films layer 2 is less than above-mentioned lower limit, the nitride layer stack film Gas barrier property may be insufficient, such as other characteristics of optical characteristics etc. are insufficient.Conversely, certain thin films layer 2 is averaged When thickness is higher than the above-mentioned upper limit, the warpage of the nitride layer stack film is it is possible that become larger and certain thin films layer 2 is likely to occur and splits Line and gas barrier property and optical characteristics are damaged.
＜ advantages ＞
As more than, the nitride layer stack film of embodiments of the present invention, both with sufficient gas barrier property, warpage is again small.
The nitride layer stack film can be used in organic electroluminescent device, Electronic Paper, pH effect film etc..In addition, have Organic electroluminescent device, Electronic Paper and the pH effect film of the nitride layer stack film are interpreted the present invention other respectively Embodiment.
[manufacturing method of nitride layer stack film]
The nitride layer stack film of Fig. 1 can pass through the manufacturer of the nitride layer stack film of the other embodiment of the present invention Method manufactures.Therefore, in the following description, although using Fig. 1 symbol, be not meant as the manufacturing method being defined to figure The manufacturing method of the gas barrier film of 1 embodiment.
In the manufacturing method of the nitride layer stack film, make the film thickness direction position in expression certain thin films layer 2 and hydrogen atom Content relationship olefin hydrogen curve have at least one maximal point and at least one minimal point, thus by plasma chemistry Vapour deposition process forms the certain thin films layer 2.
＜ manufacturing devices ＞
Display can be used in the manufacturing device (plasma CVD equipment) of the gas barrier film of the manufacturing method in Fig. 2.It is such from Daughter CVD device is to be formed continuously spy on the surface by the membranaceous flexible parent metal 1 in the strip transported along longitudinally The device of nitride layer stack film determined the successional technique of film layer 2 and obtain strip.
The plasma CVD equipment has as follows：The a pair of of configuration that be mutually parallel in the vacuum chamber 11 that can be depressurized forms a film Roller 12；To the power supply 13 of this pair of film forming 12 applied voltage of roller；To a pair into the gas of the top of deflector roll 12 supply film forming gas Body supply unit 14.In addition, in plasma CVD equipment, it is preferably also equipped with magnetic field hair respectively into the inside of deflector roll 12 in a pair Life structure (magnet exciting coil) 15.
Its composition of the plasma CVD equipment is as follows, has multiple deflector rolls 16, the flexible parent metal that will be sent out from base material roller 17 1 is erected at the deflector roll 16 and into deflector roll 12, film layer 2 is formed on flexible parent metal 1 between the opposed faces into deflector roll 12, by institute Obtained nitride layer stack film roll is got on product roller 18.
The power supply 13 makes into the opposed space between deflector roll 12 and aura occurs to a pair into 12 applied voltages of deflector roll Electric discharge.Occur to stablize glow discharge, the voltage additional as power supply 13 uses alternating voltage, preferably inverted with polarity Pulse voltage.
The gas supply part 14 is preferably configured in and reaches the opposing party via multiple deflector rolls 16 from a side into deflector roll 12 The position surrounded into the flexible parent metal 1 of deflector roll 12, supply film forming gas into the space surrounded by the flexible parent metal 1.Separately Outside, it for the vacuum pump depressurized in vacuum chamber 11, is preferably arranged as follows, that is, press from both sides every a pair between deflector roll 12 Space and the gas out of opposed with the gas supply part 14 position discharge vacuum chamber 11.
The manufacturing method of the nitride layer stack film, it is workable to be as the film forming gas supplied from gas supply part 14 Gas containing silicon compound and nitrogen or nitrogen compound.As the silicon compound, it can be mentioned, for example monosilanes, siliconated Close object (hexamethyldisiloxane：HMDSO, tetraethoxysilane, octamethylcy-clotetrasiloxane, tetramethyl-ring tetrasiloxane, pregnancy Basic ring trisiloxanes, monomethylsilane, dimethylsilane, trimethyl silane, triethylsilane, tetramethylsilane, hexamethyl two Silazane, bis- (dimethylamino) dimethylsilanes, 2,2,4,4,6,6- hexamethyl cyclotrisilazanes etc.) etc., wherein, hexamethyl Disiloxane is less expensive, is easily processed in terms of safety, and steam forces down, and can be easier to gasify, therefore is particularly suitable for It utilizes.As the nitrogen compound, it can be mentioned, for example ammonia etc..Wherein, as film forming gas, it is suitble to use containing monosilane Organo-silicon compound and nitrogen gas or gas containing monosilane or organo-silicon compound and ammonia.
The plasma CVD equipment use the grade of the unstrpped gas in the film forming gas that is ionized by the glow discharge from Daughter is formed a film on flexible parent metal 1 by plasma CVD.Therefore, the magnetic field generating means 15 are preferably with such as lower section Formula is arranged, that is, will be described plasma-induced into the surface of deflector roll 12, mainly formed into the opposed space between deflector roll 12 Magnetic field.
Magnetic field generating means 15 form magnetic field on each surface into deflector roll 12.These magnetic field generating means 15 preferably it is each into The circumferential direction of deflector roll 12 has multiple magnetic poles side by side.This multiple preferred N pole of magnetic pole is alternately arranged with S poles.As a result, induction into The ingredient of the plasma on the surface of flexible parent metal 1 transported in deflector roll 12 repeats to change, 2, the certain thin films layer formed According to film thickness direction position difference, and the content of hydrogen, silicon and nitrogen changes.
In addition, the magnetic field generating means 15 for making 1 multipass of flexible parent metal identical and transported, can also make to be formed Certain thin films layer 2 according to film thickness direction position difference, and the content of hydrogen, silicon and nitrogen change.
＜ advantages ＞
The manufacturing method of the nitride layer stack film, by plasma chemical vapor deposition, on the surface of flexible parent metal 1 Form certain thin films layer 2.If as a result, compared with sputtering method, high film forming speed, the productivity of nitride layer stack film can be realized It improves.If in addition, the manufacturing method of the nitride layer stack film compared with vapour deposition method, can form highdensity certain thin films layer 2, Comparison high gas barrier property and refractive index can be easy to get.
[other embodiments]
The embodiment does not limit the composition of the present invention.Therefore, the embodiment, can be based on this specification Description and common technical knowledge, are omitted, replaced or are added to the inscape of described embodiment each section, these should be explained To all belong to the scope of the present invention.
The nitride layer stack film can also have multiple film layers, and when having multiple film layers, arbitrary 1 layer or more is above-mentioned Certain thin films layer.
The nitride layer stack film can also be by making the composition transfer of film forming gas, and forms pole in olefin hydrogen curve etc. A little bigger and minimal point.
【Embodiment】
Hereinafter, the present invention is described in detail based on embodiment, but it is not based on restrictively explaining the present invention described in the embodiment.
1 ＞ of ＜ embodiments
As flexible parent metal, using 100 μm of the thickness of KIMOTO companies, the PET film " CPA " of width 350mm, above-mentioned figure is used 2 plasma CVD equipment forms the certain thin films layer containing silicon, nitrogen and hydrogen on the surface of flexible parent metal, is thus implemented The nitride layer stack film of example 1.In addition, as film forming gas, the supply amount for making monosilane is 100sccm, and the supply amount of nitrogen is Air pressure is set in 3Pa by 500sccm.The output power of power supply of plasma is frequency 70kHz, electrical power 0.4kW. In addition, the conveyance speed of flexible parent metal is 0.67m/min, through once by forming certain thin films layer.The certain thin films formed The average thickness about 100nm of layer.
2 ＞ of ＜ embodiments
Using the flexible parent metal identical with above-described embodiment 1, change the condition of embodiment 1 and form certain thin films layer, by This obtains the nitride layer stack film of embodiment 2.In addition, as film forming gas, make organo-silicon compound (hexamethyldisiloxane) Supply amount for 25sccm, the supply amount of nitrogen is 500sccm, and air pressure is set as 1.5Pa.The power supply of plasma is defeated Going out power is, frequency 70kHz, electrical power 1.4kW.In addition, the conveyance speed of flexible parent metal is 2.57m/min, pass through (3 through 7 times A half is reciprocal) form certain thin films layer.The average thickness of certain thin films layer formed is about 380nm.
＜ comparative examples ＞
Using the flexible parent metal identical with the embodiment 1, the sputter equipment of ア ルバック societies (ULVAC companies) is used " CS-200 " forms the certain thin films layer containing silicon, nitrogen and hydrogen on the surface of flexible parent metal, thus obtains the nitridation of comparative example Silicon stacked film.Target uses boron-doping silicon (B doped Si), and as film forming gas, the supply amount that makes argon is 14sccm, the confession of nitrogen It is 10sccm to amount, air pressure is set as 3mTorr.Electrical power is DC200W.The average thickness of certain thin films layer formed is about 100nm。
＜ distribution curves ＞
For the embodiment 1,2 and comparative example of nitride layer stack film, analyzed using SIMS analysis device, Obtain olefin hydrogen curve, silicon distribution curve, NSi-/H- distribution curves and NSi-/Si- distribution curves.In addition, for implementing Example 1 and comparative example using the SIMS analysis device " 4500 type " of ア ト ミ カ societies, as primary ions, use 1keV Cs+ ions, it is about 300 × 465 μm to make irradiation area, and analyzed area is about 90 × 140 μm, make secondary ion polarity be it is negative, It carries out electrification amendment and measures.In addition, in example 2, use the SIMS analysis device of ION-TOF societies " TOF.SIMS5 " as primary ions, uses the Bi of 25keV3++ ion, in order to carry out that examination is gradually cut down on film thickness direction The sputtering of material and the Cs+ ions for using 2keV, make the square area that sputter area is about 200 μm of one side, analyzed area is one side About 75 μm, it is negative to make secondary ion polarity, carries out electrification amendment and measures.
Show that olefin hydrogen curve, silicon distribution curve, the NSi-/H- distribution of the embodiment 1 of nitride layer stack film are bent in Fig. 3 Line and NSi-/Si- distribution curves, show in Fig. 4 the olefin hydrogen curve of the embodiment 2 of nitride layer stack film, silicon distribution curve, NSi-/H- distribution curves and NSi-/Si- distribution curves show that the olefin hydrogen of the comparative example of nitride layer stack film is bent in Fig. 5 Line, silicon distribution curve, NSi-/H- distribution curves and NSi-/Si- distribution curves.
As shown, in the embodiment 1,2 of nitride layer stack film, olefin hydrogen curve, silicon distribution curve, NSi-/H- distributions Curve and NSi-/Si- distribution curves have multiple maximal points and minimal point.On the other hand, the comparative example of nitride layer stack film In, olefin hydrogen curve, silicon distribution curve, NSi-/H- distribution curves and NSi-/Si- distribution curves, in addition in certain thin films Other than the back surface neighborhood of layer decreases, remaining general planar, essentially without maximal point and minimal point.
In the embodiment 1 of nitride layer stack film, the maximum maximum in olefin hydrogen curve is for minimum minimum Ratio for 1.64, the equispaced about 15nm of maximal point.
In addition, in the embodiment 1 of nitride layer stack film, the maximum maximum of silicon distribution curve is for minimum minimum Ratio for 1.79, the equispaced about 15nm of maximal point.
In addition, in the embodiment 1 of nitride layer stack film, the maximum maximum in NSi-/H- distribution curves is for most The ratio of small minimum is 2.26, the equispaced about 15nm of maximal point.
In addition, in the embodiment 1 of nitride layer stack film, the maximum maximum in NSi-/Si- distribution curves is for most The ratio of small minimum is 2.43, the equispaced about 15nm of maximal point.
In the embodiment 1 of nitride layer stack film, the film thickness of the maximal point of olefin hydrogen curve and the maximal point of silicon distribution curve The difference of direction position, the film thickness direction of the maximal point of NSi-/H- distribution curves and the maximal point of NSi-/Si- distribution curves The difference of position and the maximal point of olefin hydrogen curve are low with the difference of the film thickness direction position of the minimal point of NSi-/Si- distribution curves In 1nm, the curve of substantially same-phase or the phase reversal same period are depicted.
In the embodiment 2 of nitride layer stack film, the maximum maximum in olefin hydrogen curve is relative to the minimum of minimum The ratio of value is 1.47, the equispaced about 24nm of maximal point.
In addition, in the embodiment 2 of nitride layer stack film, the maximum maximum in silicon distribution curve is relative to minimum The ratio of minimum is 1.50, the equispaced about 24nm of maximal point.
In addition, in the embodiment 2 of nitride layer stack film, the maximum maximum in NSi-/H- distribution curves is opposite In the ratio of minimum minimum be 1.68, the equispaced about 24nm of maximal point.
In addition, in the embodiment 2 of nitride layer stack film, the maximum maximum in NSi-/Si- distribution curves is opposite In the ratio of minimum minimum be 1.30, the equispaced about 24nm of maximal point.
In the embodiment 2 of nitride layer stack film, the film of the maximal point of olefin hydrogen curve and the maximal point of silicon distribution curve The difference of thick direction position, the film thickness side of the maximal point of NSi-/H- distribution curves and the maximal point of NSi-/Si- distribution curves The maximal point of difference and olefin hydrogen curve to position and the difference of the film thickness direction position of the minimal point of NSi-/Si- distribution curves Less than 5nm, the curve of substantially same-phase or the phase reversal same period are depicted.
＜ moisture-vapor transmissions ＞
For the embodiment 1,2 and comparative example of nitride layer stack film, the choke experimental rig of Mocon societies is used " Aquatran " measures the moisture-vapor transmission at 40 DEG C of temperature, 90 DEG C of relative humidity, the index as gas barrier property.Its result It is that the moisture-vapor transmission of embodiment 1 is 3.0 × 10- 3[g/m2/ day], the moisture-vapor transmission of embodiment 2 is 2.2 × 10- 3 [g/m2/ day], in contrast, the moisture-vapor transmission of comparative example is 0.1 [g/m2/day]。
＜ amount of warpage ＞
For the embodiment 1,2 and comparative example of nitride layer stack film, sample is cut into 10cm square, spy is made on flat surface Determine film layer to place downward, measure 4 vertex distance away from flat surface respectively of 10cm square, count its aggregate value as warpage Amount.In addition, about embodiment 2, film conveyance speed and number of pass times are adjusted to standardize, certain thin films layer is thus made The sample of thickness about 100nm is evaluated.As a result, the amount of warpage of embodiment 1 is 20mm, the amount of warpage of embodiment 2 is 15mm, in contrast, the amount of warpage of comparative example is 30mm.
＜ refractive index ＞
For the embodiment 1,2 and comparative example of nitride layer stack film, the inclined of ジ ェ ー エ ー ウ ー ラ system society is used Light ellipticity of shaking measuring instrument (polarization analysis apparatus) " M-2000U " measures refractive index.As a result, the refractive index of embodiment 1 It is 1.82 in wavelength 550nm, the refractive index of embodiment 2 is 1.90 in wavelength 550nm, in contrast, the refraction of comparative example Rate is 1.96 in same wavelength 550nm.
As more than, the embodiment 1,2 of nitride layer stack film is compared with comparative example, and moisture-vapor transmission is small, and amount of warpage is small, and Refractive index is big.In short, the embodiment gas barrier property of nitride layer stack film is excellent, and warpage is small and easily utilizes.
【Industrial availability】
The nitride layer stack film of the present invention, can be suitble to be used in organic electroluminescent device, Electronic Paper, pH effect film Deng.

Claims (33)

1. a kind of nitride layer stack film, which is characterized in that be to have flexible parent metal and be formed at least the one of the flexible parent metal The nitride layer stack film of the film layer of single-layer or multi-layer on the surface of side,
At least 1 layer specific film layer among the film layer of the single-layer or multi-layer contains silicon, nitrogen and hydrogen,
Representing the olefin hydrogen curve of the relationship of the film thickness direction position in the certain thin films layer and the content of hydrogen atom has extremely Few 1 maximal point and at least one minimal point.
2. nitride layer stack film according to claim 1, wherein, the certain thin films layer also contains carbon.
3. the nitride layer stack film according to claim 1 or claim 2, wherein, the hydrogen atom of the olefin hydrogen curve The maximum maximum of content is more than 1.1 relative to the ratio of minimum minimum.
4. nitride layer stack film according to claim 1, wherein, the olefin hydrogen curve has multiple maximal points, described The absolute value of the difference of the film thickness direction position of 2 adjacent maximal points is below 60nm on olefin hydrogen curve.
5. nitride layer stack film according to claim 1, wherein, represent the film thickness direction position in the certain thin films layer There is at least one maximal point and at least one minimal point with the silicon distribution curve of the relationship of the content of silicon atom.
6. nitride layer stack film according to claim 5, wherein, the maximum of the silicon atom content in the silicon distribution curve Maximum relative to the ratio of minimum minimum be more than 1.1.
7. according to the nitride layer stack film described in claim 5 or claim 6, wherein, the silicon distribution curve has multiple Maximal point, on the silicon distribution curve absolute value of the difference of the film thickness direction position of 2 adjacent maximal points for 60nm with Under.
8. nitride layer stack film according to claim 1, wherein, represent the film thickness direction position in the certain thin films layer With the detection intensity of NSi- ions that is measured by SIMS analysis method relative to the ratio of the detection intensity of H- ions Relationship NSi-/H- distribution curves have at least one maximal point and at least one minimal point.
9. nitride layer stack film according to claim 8, wherein, the NSi-/H- distribution curves it is maximum very big Value is more than 1.1 relative to the ratio of minimum minimum.
10. according to the nitride layer stack film described in claim 8 or claim 9, wherein, the NSi-/H- distribution curves With multiple maximal points, the difference of the film thickness direction position of 2 adjacent maximal points on the NSi-/H- distribution curves Absolute value is below 60nm.
11. nitride layer stack film according to claim 1, wherein, represent the film thickness direction position in the certain thin films layer It puts and by the detection intensity of NSi- ions that SIMS analysis method measures relative to the detection intensity of Si- ions The NSi-/Si- distribution curves of the relationship of ratio have at least one maximal point and at least one minimal point.
12. nitride layer stack film according to claim 11, wherein, the maximum pole of the NSi-/Si- distribution curves Big value is more than 1.1 relative to the ratio of minimum minimum.
13. according to the nitride layer stack film described in claim 11 or claim 12, wherein, the NSi-/Si- distributions are bent Line has multiple maximal points, the film thickness direction position of 2 maximal points abutted on the NSi-/Si- distribution curves Absolute value of the difference is below 60nm.
14. nitride layer stack film according to claim 1, wherein, represent the film thickness direction position in the certain thin films layer Put has at least one maximal point and at least one minimal point, the olefin hydrogen with the silicon distribution curve of the relationship of the content of silicon atom The difference of the maximal point of curve and the film thickness direction position of the maximal point of the silicon distribution curve is below 5nm.
15. nitride layer stack film according to claim 1, wherein, expression is measured by SIMS analysis method The detection intensities of NSi- ions have relative to the NSi-/H- distribution curves of the relationship of the ratio of the detection intensity of H- ions At least one maximal point and at least one minimal point,
Represent that the detection intensity of NSi- ions measured by SIMS analysis method is strong relative to the detection of Si- ions The NSi-/Si- distribution curves of the relationship of the ratio of degree have at least one maximal point and at least one minimal point,
The film thickness side of the maximal point of the NSi-/H- distribution curves and the maximal point of the NSi-/Si- distribution curves It is below 5nm to the difference of position.
16. nitride layer stack film according to claim 1, wherein, represent the film thickness direction position in the certain thin films layer It puts and by the detection intensity of NSi- ions that SIMS analysis method measures relative to the detection intensity of Si- ions The NSi-/Si- distribution curves of the relationship of ratio have at least one maximal point and at least one minimal point,
The film thickness direction position of the maximal point of the olefin hydrogen curve and the minimal point of the NSi-/Si- distribution curves Difference be below 5nm.
17. nitride layer stack film according to claim 1, wherein, the average thickness of the certain thin films layer is more than 5nm And below 3000nm.
18. nitride layer stack film according to claim 1, wherein, the principal component of the flexible parent metal is polyester or polyene Hydrocarbon.
19. nitride layer stack film according to claim 1, the principal component of the flexible parent metal is poly terephthalic acid second two Alcohol ester or polyethylene naphthalate.
20. a kind of organic electroluminescent device, wherein, have nitride layer stack film described in claim 1.
21. a kind of Electronic Paper, wherein, have nitride layer stack film described in claim 1.
22. a kind of pH effect film, wherein, it is formed using nitride layer stack film described in claim 1.
23. a kind of manufacturing method of nitride layer stack film, which is characterized in that be to have flexible parent metal and be formed in the flexibility The nitride layer stack film of the film layer of single-layer or multi-layer on the surface of at least side of base material, the film of the single-layer or multi-layer At least 1 layer specific film layer among layer contains the manufacturing method of the nitride layer stack film of silicon, nitrogen and hydrogen, makes expression described specific The olefin hydrogen curve of the relationship of the content of film thickness direction position and hydrogen atom in film layer is at least one maximal point and at least 1 minimal point forms the certain thin films layer thus by plasma chemical vapor deposition.
24. the manufacturing method of nitride layer stack film according to claim 23, wherein, forming the certain thin films layer When, by flexible parent metal configuration in a pair into the opposed faces of deflector roll, it is the pair of into discharged between deflector roll and make etc. from Daughter occurs.
25. the manufacturing method of nitride layer stack film according to claim 24, wherein, it is carried out the pair of between deflector roll During electric discharge, invert the pair of alternating polarity into deflector roll.
26. the manufacturing method of nitride layer stack film according to claim 25, wherein, forming the certain thin films layer When, by the magnetic field generating means being configured in the inside into deflector roll magnetic field is formed on the surface into deflector roll.
27. the manufacturing method of the nitride layer stack film according to any one of claim 23 to claim 26, wherein, it uses Contain monosilane and nitrogen in the film forming gas of the plasma chemical vapor deposition.
28. the manufacturing method of the nitride layer stack film according to any one of claim 23 to claim 26, wherein, it uses Contain monosilane and ammonia in the film forming gas of the plasma chemical vapor deposition.
29. the manufacturing method of the nitride layer stack film according to any one of claim 23 to claim 26, wherein, it uses Contain organo-silicon compound and nitrogen in the film forming gas of the plasma chemical vapor deposition.
30. the manufacturing method of nitride layer stack film according to claim 29, wherein, the organo-silicon compound are pregnancy Base disiloxane.
31. the manufacturing method of the nitride layer stack film according to any one of claim 23 to claim 26, wherein, it uses Contain organo-silicon compound and ammonia in the film forming gas of the plasma chemical vapor deposition.
32. the manufacturing method of nitride layer stack film according to claim 31, wherein, the organo-silicon compound are pregnancy Base disiloxane.
33. the manufacturing method of nitride layer stack film according to claim 23, wherein, it is formed by continuous film-forming process The certain thin films layer.
CN201711002028.9A 2016-12-05 2017-10-24 Nitride layer stack film, organic electroluminescent device, Electronic Paper and the manufacturing method of pH effect film and nitride layer stack film Pending CN108146047A (en)

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