CN102443785A - Functional film and method for producing functional film - Google Patents
Functional film and method for producing functional film Download PDFInfo
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- CN102443785A CN102443785A CN2011103019862A CN201110301986A CN102443785A CN 102443785 A CN102443785 A CN 102443785A CN 2011103019862 A CN2011103019862 A CN 2011103019862A CN 201110301986 A CN201110301986 A CN 201110301986A CN 102443785 A CN102443785 A CN 102443785A
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- 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
- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention provides a method for manufacturing a functional thin film, which can stably form a gas barrier film which can show the target gas barrier performance corresponding to the film thickness and has excellent aging stability when an inorganic film is formed by plasma CVD film forming while a long substrate with a surface formed by an organic material is conveyed along the length direction. The problem is solved by making the plasma electron density at the most upstream position in the substrate conveying direction lower than the plasma electron density at the most downstream position between the pair of electrodes.
Description
Technical field
The present invention relates to technical field through the gas barrier film of plasma CVD formation; In detail; Relate to and use the surface by the substrate that organic materialss such as macromolecular compound form, the method for manufacture that can form the functional film of the good gas barrier film of gas barrier reaches the functional film of making through this method of manufacture.
Background technology
Utilize gas barrier film (water vapour barrier film) in the wrapping material that in various devices such as display unit such as optical element, liquid-crystal display or OLED display, semiconductor device, thin-film solar cells, require to use in the packing of position or parts, food, clothes, electronic unit etc. of moisture resistance.
Gas barrier film becomes embrane method (vacuum film formation method) to be formed on the surface at the position that requires moisture resistance for the film that the material that is shown gas barrier by silicon oxide or silicon nitride etc. forms through for example gas phase such as sputter or CVD.In addition, on the surface of film that is formed by macromolecular material (plastics film) or mf, forming the gas barrier film that the gas barrier film that is made up of above-mentioned silicon nitride etc. forms is also suitably utilized.
As the substrate (substrate film) of functional films such as gas barrier film, the film that general PET (polyethylene terephthalate) film etc. are formed by macromolecular material.In addition, various article such as optical element are formed by macromolecular material mostly, can certainly be formed by plastic plate.
Form one of method of various mineral membranes as system film on the surface of the substrate that has the surface that is formed by organic materials at such film that is formed by macromolecular material etc., illustration goes out plasma CVD.
For example; In patent documentation 1, disclose following content; Promptly; On surface, form in the gas barrier film that the silicon oxide film with carbon 5～15% is used as gas barrier film, through organic silicon compound gas and oxygen are formed the above-mentioned gas barrier film as the plasma CVD of reactant gases use by the substrate that forms of macromolecular material with transparency.
Gas barrier film such shown in the patent documentation 1 becomes embrane method to access the regulation thickness as the gas barrier of target at the surface formation energy of substrates such as plastics film for the mineral membrane that the material that is shown gas barrier by silicon nitride or silicon oxide etc. forms through gas phases such as sputter or CVD.
In addition, be not limited to gas barrier film certainly, and will be that the film formed mineral membrane of purpose system is made film according to the purposes of product and formed out the thickness that can give full play to as the performance of target on various substrates such as plastics film to give various functions.
Yet; Have at plastics film through plasma CVD disclosed that kind in above-mentioned patent documentation 1 etc. when forming mineral membrane on the substrate on the surface that forms by organic materials; At first do not make film and form pure mineral membrane; And the system film forms the organic materials of substrate surface and the such film of mixolimnion of film forming inorganic material film, afterwards, forms the mineral membrane of target with pure state system film.Therefore, although formed gas barrier film, there is the situation of the capacity for air resistance that can't obtain the conduct target corresponding with thickness as the thickness of target.
Relative therewith; In patent documentation 2, disclose following content; That is, on substrate with the surface that forms by organic materials through plasma CVD when forming gas barrier film, with first plasma exciatiaon power formation gas barrier film; Afterwards; Plasma exciatiaon power changed to than the second high plasma exciatiaon power of the first plasma exciatiaon power form gas barrier film, can suitably suppress the formation of mixolimnion thus, thereby form the thin gas barrier film that also can show as the function of target even can stably make film.
In addition, in patent documentation 3, disclose following content, promptly; As other method; Form gas barrier film through first discharge pressure, afterwards, form gas barrier film through second discharge pressure lower than the pressure of said first discharge pressure; Suitably suppress the formation of mixolimnion thus, thereby form the thin gas barrier film that also can show as the function of target even can stably make film.
[patent documentation 1] japanese kokai publication hei 11-70611 communique
[patent documentation 2] TOHKEMY 2010-1535 communique
[patent documentation 3] TOHKEMY 2010-77461 communique
At this,, preferably on rectangular substrate, carry out film forming continuously in order efficiently and to carry out film forming through the vacuum film formation method with guaranteeing high productivity.
As the device of implementing such film, known have use that rectangular substrate (netted substrate) circumvolution is become the donor rollers of roller shape, the substrate circumvolution after the film forming become the film deposition system of so-called roll-to-roll (Roll to Roll) of the wind up roll of roller shape.In this roll-to-roll film deposition system; In the path of the regulation through on substrate, carrying out film forming one-tenth film location, rectangular substrate is passed through to wind up roll from donor rollers; And synchronously carry out, and carry out film forming simultaneously continuously in the film forming position, on substrate conveying from the seeing off and carry out the coiling of the substrate after the film forming of the substrate of donor rollers by wind up roll.
In so roll-to-roll film deposition system; When forming gas barrier film through plasma CVD; In order to suppress the formation of mixolimnion, shown in patent documentation 2, at the film forming plasma exciatiaon power that changes midway; And need dispose a plurality of film forming electrodes that are used for along the throughput direction of substrate, through carrying out film forming because of the different plasma exciatiaon power of each electrode.In addition, shown in patent documentation 3, in order to change discharge pressure, and need be used for film forming chamber, and, carry out film forming through different discharge pressures in each chamber configured electrodes along the throughput direction configuration of substrate is a plurality of.
Like this, in roll-to-roll film deposition system, in order to suppress the formation of mixolimnion, need be corresponding and separate into diaphragm area with filming condition separately, with in the film forming filming condition that changes midway.Separating into diaphragm area when forming gas barrier film, therefore the membranous difference of the film that under different filming conditions, forms has formed clear and definite interface, produces and connects airtight unfavorable conditions such as bad.And, electrode separation is being become under a plurality of situation, the useful area of electrode, diaphragm area diminish, productivity possibly reduce.
In addition, in roll-to-roll film deposition system, hang substrate and carry at the side face of reel cylindraceous volume, and simultaneously through with the circumference of this reel the electrode that is provided with being carried out film forming on substrate.This reel forms electrode pair with electrode, but electrode separation is being become under a plurality of situation, can't the bias power of reel or temperature etc. be carried out independent control with respect to each electrode, therefore can't be under suitable filming condition film forming.
Summary of the invention
The objective of the invention is to solve above-mentioned prior art problems point; A kind of method of manufacture of functional film and the functional film that forms through this method of manufacture are provided; Thereby have on the substrate on the surface that forms by organic materials in the method for manufacture of the functional film that forms gas barrier film through plasma CVD at plastics film etc., can stably form and to show capacity for air resistance and the aging stability also good gas barrier film as target corresponding with thickness.
In order to solve above-mentioned problem; The present invention provides a kind of functional film; It is characterized in that the atom % at least a in the element that constitutes of the carbon at the interface of the substrate with the surface that is formed by organic materials and the mineral membrane that on said substrate, forms and mineral membrane all is that the thickness in the zone more than 5% is 3～15nm.
At this, preferred said mineral membrane is for being the film of staple with in the oxygen nitrogen carbide of the oxynitride of the nitride of the oxide compound of silicon, silicon, silicon, silicon any.
In addition; In order to solve above-mentioned problem; The present invention provides a kind of method of manufacture of functional film, utilizes film forming mechanism and on said substrate, make film through plasma CVD to form mineral membrane, and this film forming mechanism will have the rectangular substrate on the surface that is formed by organic materials and carry along its length; And has an electrode pair of the said substrate configuration of the conveying of clipping; The method of manufacture of said functional film is characterised in that, between said electrode pair, makes the plasma electron density at place, upstream-most position of throughput direction of said substrate lower than the plasma electron density of downstream position.
And the plasma electron density when preferably making said mineral membrane film forming is minimum in the upstream-most position of the throughput direction of said substrate, and is the highest at downstream position.
At this, the distance between the said electrode pair at the upstream-most position of the throughput direction of preferred said substrate place is bigger than the distance between the said electrode pair of downstream position.
In addition, preferably has distance between the said electrode pair along with the zone that reduces gradually towards the downstream side from the upstream-most position.
In addition, the distance that preferably has between the said electrode pair forms the constant zone in the downstream side of the throughput direction of said substrate.
In addition, preferably on the throughput direction of said substrate, the length that becomes minimum position to the distance the said electrode pair from the upstream-most position of said throughput direction be said electrode pair said throughput direction length 10～40%.
In addition, the distance between the said electrode pair at the upstream-most position of preferred said throughput direction place is 1.1～1.5 times of distance between the said electrode pair of downstream position of said throughput direction.
In addition, the thickness that carries out film forming said mineral membrane till preferably from the upstream-most position of the throughput direction of said substrate to the highest position of said plasma electron density is 2～10nm.。
In addition, preferably with said substrate volume hang over reel cylindraceous side face the regulation zone and carry, use the side of said reel as the said electrode pair of said film forming mechanism.
[invention effect]
According to the present invention; Because having the atom % at least a in the element that constitutes of carbon at the interface and the mineral membrane of the substrate on the surface that is formed by organic materials and the mineral membrane that on said substrate, forms is that the thickness in the zone more than 5% is 3～15nm; Therefore significantly reduce organic and inorganic mixolimnion, and can realize that aging stability is good, not have clear and definite interface, densification and gas barrier height.
In addition; According to the present invention; Utilizing the rectangular substrate that plastics film is such to carry along its length, and having the film forming mechanism of the electrode pair of the substrate conveying of clipping configuration with the surface (film forming face) that forms by organic materials, and when on substrate, making film formation mineral membrane through plasma CVD; Between electrode pair; Make the plasma electron density at upstream-most position place of throughput direction of substrate lower, therefore significantly reduce organic and inorganic mixolimnion than the plasma electron density of downstream position, and can form aging stability good, do not have a high gas barrier film of clear and definite interface, densification and gas barrier.Therefore, according to the present invention, can access thin, do not connect airtight unfavorable condition and the good gas barrier films of gas barrier such as bad, and can improve the productivity of gas barrier film.
Description of drawings
Fig. 1 is the figure that schematically shows an example of the functional film of making through method of manufacture of the present invention of the present invention.
Fig. 2 be schematically show embodiment of the present invention method of manufacture film deposition system one the example figure.
Fig. 3 is the partial enlarged drawing that the part of shower electrode shown in Figure 2 (shower electrode) and reel is shown.
Fig. 4 (A)～(C) is the partial enlarged drawing of a part that another example and the reel of shower electrode are shown.
Nomenclature:
10 film deposition systems
12 vacuum chambers
The 12a inner-wall surface
14 unreel the chamber
18 filming chamber
20,100,110,120 shower electrode
22,102,112,122 discharge faces
22a, 102a, 112a, 122a first discharge face
22b second discharge face
30 reels
32 substrate roll
34 wireline reels
36 next doors
40 guide reels
42 turning axles
46,62 vacuum exhaust mechanisms
58 unstripped gas feed mechanisms
60 high frequency electric sources
The Z substrate
Embodiment
Below, the method for manufacture and the functional film of functional film of the present invention are at length explained.
In the method for manufacture of functional film of the present invention, go up the system film on the surface of substrate (film forming face) through plasma CVD and form gas barrier film or antireflection film etc. and show mineral membrane as the function of target with the surface that forms by organic materials.
In the present invention; Beginning when substrate surface system film forms mineral membrane (formation mineral membrane); With than beginning film forming for the first low plasma electron densities of second plasma electron density that needing to obtain as the membranous of the performance of target; Form at the system film regulation thickness mineral membrane during, plasma electron density is changed to second plasma electron density, afterwards; Form identical mineral membrane with the second plasma electron density system film, thereby the system film forms out the mineral membrane of the thickness (the final thickness of making) as target.
In the method for manufacture of functional film of the present invention, the substrate (base material/handled object) that the system film forms mineral membrane is the substrate that the surface is formed by various organic materialss (organism) such as macromolecular material (polymer/polymeric) or resin materials.
If substrate then can utilize various materials for the surface forms and can carry out through plasma CVD the film forming substrate of mineral membrane by organic materials.Particularly, illustration goes out by polyethylene terephthalate (PET), PEN, Vilaterm, Vestolen PP 7052, PS, polymeric amide, SE, polycarbonate, polyacrylonitrile, gathers the suitable example of substrate conduct that macromolecular materials such as imines, polyacrylonitrile, Rohm tech inc form.
In addition; In the present invention; Substrate is suitably for rectangular film (netted film) or cuts tympans (flap) such as flaky film; But be not limited to this, surfaces such as display pannel such as photo-electric conversion element, liquid-crystal display or electronic paper such as optical elements such as lens or optical filter, organic EL or solar cell can both be utilized as substrate by the various article (member) that organic materials forms.
And; Substrate can be as follows forms like this: be the main body (base material) with plastics film (macromolecule membrane), the article, mf or sheet glass, the various metal article etc. that are formed by organic materials, form layer (film) that formed by organic materials that resist, adhesive linkage, reflection layer, light shield layer, planarization layer, impact plies, stress relaxation layer etc. are used to obtain various functions in its surface.
Schematically show an example of the functional film of making through the method for manufacture of functional film of the present invention of the present invention among Fig. 1.
As shown in Figure 1, functional film 80 of the present invention is to form the functional film that obtains as the mineral membrane 82 of gas barrier film (barrier layer for gases) at the surface system film of substrate (substrate for film deposition) Z.
At this; When carrying out film forming through plasma CVD; The integrant (radical, ion, electronics etc.) that incides the plasma body of substrate becomes the state of the inside that gets into substrate (organic materials); And the mixolimnion 84 of the organic materials/organic materials of the state of the material mixing of the organic materials of formation substrate surface and mineral membrane (below, for ease, be called mixolimnion 84).The amount of the organic materials in the mixolimnion 84 reduces along with the film forming of carrying out mineral membrane gradually, finally makes the pure mineral membrane 84 that film forms out unmixed organic materials.
In functional film of the present invention; Plasma electron density through will form this mixolimnion 84 time reduces, thereby at least a atom % in the formation element of carbon and mineral membrane becomes the thickness that zone more than 5% forms 3～15nm in mixolimnion 84.
The zone that becomes more than 5% at least a atom % of the formation element of carbon and mineral membrane is under the situation of the thickness below the 3nm, and organic membrane (substrate Z) possibly reduce with the connecting airtight property of mineral membrane 82.Be under the situation of the thickness more than the 15nm in the zone that at least a atom % of the formation element of carbon and mineral membrane becomes more than 5% in addition; Because the thickness attenuation of the mineral membrane 82 that forms on the upper strata of mixolimnion 84; Therefore gas barrier reduces; Perhaps need the thickness of integral body formed thicker, so productivity reduce in order to ensure gas barrier.
Relative therewith; Through at least a atom % with the formation element of carbon and mineral membrane is the thickness that zone more than 5% forms 3～15nm; The connecting airtight property reduction of organic membrane (substrate Z) and mineral membrane 82 can be prevented, and the reduction of gas barrier or the reduction of productivity can be prevented.The present invention passes through concrete such structure, the functional film 80 that the damage of realization substrate Z less, productivity is good and gas barrier is good.
In functional film of the present invention, make film formed mineral membrane and do not limit especially, so long as on substrate, can get final product by film forming material, can utilize various organic films with the surface that forms by organic materials through plasma CVD.
For example, if, then can utilize silicon nitride film, silicon oxide film, oxygen silicon nitride membrane, DLC (Diamond Like Carbon) film etc. forming under the situation of gas barrier film (water vapour barrier film) as mineral membrane.
In addition, during as mineral membrane, can utilize silicon oxide film etc. at the protective membrane that forms various device such as the such display unit of OLED display or liquid-crystal display or device.
In addition, under the situation of nesa coating of in forming various device such as the such display unit of OLED display or liquid-crystal display or device, utilizing, can utilize Zinc oxide film as mineral membrane.
And, when forming luminous reflectance and prevent bloomings such as film, light reflective film, various strainers, can utilize to have or show the mineral membrane that the material as the optical characteristics of target forms as mineral membrane.
Wherein, in functional film of the present invention, being fit to utilize oxide compound, nitride, oxynitride, oxygen nitrogen carbide with silicon is the mineral membrane of staple.And, according to the present invention, can make film and form out fine and close film, the film forming (manufacturing of functional film) of the gas barrier film that therefore be suitable for most gas barrier film, especially forms by said silicon compound.The present invention especially is fit to utilize the film that is formed by silicon nitride.
In Fig. 2, schematically show the example of film deposition system of the method for manufacture of embodiment of the present invention.Need to prove that film deposition system 10 shown in Figure 2 is the roll-to-roll film deposition system that known plasma CVD utilized except the gap of shower electrode shown in Figure 3 20 and reel 30.This film deposition system 10 changes plasma electron density through changing the gap of shower electrode 20 and reel 30.
The film deposition system 10 of illustrated example is carried rectangular substrate Z (film coiled strip) along its length, and shows the film as the function of target through plasma CVD in the surface system film formation (manufacturing/formation) of this substrate Z, thus manufacturing function property film.
In addition; This film deposition system 10 is for to carry out film forming device through so-called roll-to-roll (Roll to Roll); This is roll-to-roll from becoming the substrate roll 32 of roller shape to see substrate Z off rectangular substrate Z circumvolution; It is carried along its length and make film simultaneously form functional membrane, and film forming has the substrate Z (that is functional film) of functional membrane to be wound into the roller shape.
In film deposition system 10; Rectangular substrate Z is supplied with by the substrate roll that unreels chamber 14 32, carried along its length by the state that hangs on the reel 30 with volume, and while film forming in filming chamber 18; Then, in unreeling chamber 14, be wound in wireline reel 34 (circumvolution becomes the roller shape) once more.
At this, reel 30 also as after the filming chamber 18 that states shower electrode 20 opposite electrode and play a role and (that is, constitute electrode pairs through reel 30 and shower electrode 20.) this reel 30 is connected (ground connection) with the earth.
Need to prove, can on reel 30, connect the grid bias power supply that is used for reel 30 is applied bias voltage as required.Perhaps also can connect the earth and grid bias power supply with switching.
Grid bias power supply can be utilized in all known power supplys such as high frequency electric source or the pulse power that being used to of utilizing in the various film deposition systems applies bias voltage.
Unreeling near chamber 14 extends to the side face of reel 30 by the side face of the inner-wall surface 12a of vacuum chamber 12, reel 30, from inner-wall surface 12a next door 36a and 36b constitutes.
At this, the front end of next door 36a and 36b (end opposite of the inner-wall surface of vacuum chamber 12) is near the side face of reel 30, up to can with the discontiguous position of substrate conveying Z, separate into roughly airtight thereby will unreel chamber 14 with filming chamber 18.
The chamber 14 that unreels like this has above-mentioned wireline reel 34, guide reel 40a and 40b, turning axle 42, vacuum exhaust mechanism 46.
In illustrated example, become the substrate roll 32 of roller shape to be installed on turning axle 42 rectangular substrate Z circumvolution.And if substrate roll 32 is installed on turning axle 42, then substrate Z arrives the path of the regulation of wireline reel 34 via guide reel 40a, reel 30 and guide reel 40b through (passing).
In film deposition system 10, carry out synchronously from the substrate Z of substrate roll 32 see off with wireline reel 34 on the coiling of film forming metacoxa Z, thereby rectangular substrate Z is carried in the transport path of regulation along its length, and carry out the film forming in the filming chamber 18 simultaneously.
On the throughput direction of substrate Z, dispose filming chamber 18 in the downstream that unreel chamber 14.
Filming chamber 18 extends to the side face of reel 30 by the side face of inner-wall surface 12a, reel 30, from inner-wall surface 12a neighbouring next door 36a and 36b constitute.
In film deposition system 10; As an example; Filming chamber 18 has shower electrode 20, unstripped gas feed mechanism 58, high frequency electric source 60, vacuum exhaust mechanism 62 for to carry out film forming filming chamber on the surface of substrate Z through CCP (Capacitively Coupled Plasma capacity mating type plasma body)-CVD.
In film deposition system 10, when carrying out film forming through CCP-CVD, shower electrode 20 constitutes electrode pair with reel 30.In illustrated example, as an example, shower electrode 20 is the roughly Nogata body shape of hollow, and the circumference as the discharge face of largest face 22 and reel 30 is to configuration.And whole ground is formed with a plurality of communicating poress on the discharge face 22 of conduct and reel 30 opposed opposed faces.Shower electrode 20 its discharge face 22 and and its form to generate between the side face of reel 30 of electrode pair and be used for film forming plasma body, thereby be formed into diaphragm area.
Fig. 3 is with the synoptic diagram shown in the part amplification of shower electrode shown in Figure 2 20 and reel 30.
The discharge face 22 of shower electrode 20 constitutes has the first discharge face 22a and the second discharge face 22b; This first discharge face 22a forms along with moving closer to the distance of reel towards the downstream side at the upstream side of the throughput direction of substrate Z, and this second discharge face 22b forms in the downstream side of the throughput direction of substrate Z with the distance of reel 30 and fixes with the value of regulation.
Particularly; The first discharge face 22a is at the curved surface that begins from the upstream-most position on the throughput direction of substrate Z to be formed on the zone of regulation; It is in the upstream-most position of the throughput direction of substrate Z, promptly form and the first maximum gap of gap of reel 30 to the inlet side that becomes diaphragm area; Along with towards the downstream side, to form by the curved surface corresponding near the mode of reel 30 point-blank with the curved surface of reel 30.
In addition, the second discharge face 22b is the curved surface with the adjacent formation in downstream side of the first discharge face 22a, with the minimum second gap fixed mode in the gap of reel 30 by forming with the corresponding curved surface of the curved surface of reel 30.
In addition; Shower electrode 20 becomes predetermined gap with the gap between discharge face 22 and the reel 30 mode disposes from reel 30 extractor gauge set a distances, and this predetermined gap is that the plasma body in the zone of the second discharge face 22b becomes the gap for membranous second plasma electron density that needs of the performance that obtains becoming target.
At this, big more as the shower electrode 20 and the gap between the reel 30 of electrode pair, the plasma electron density that is used for film forming plasma body is more little.Therefore, with the zone of the gap of the reel 30 first discharge face 22a bigger than the second discharge face 22b in, carry out film forming with the plasma electron density littler than the second discharge face 22b in downstream side.
Promptly; When the beginning film forming; First plasma electron density with low begins film forming, form at the system film regulation thickness mineral membrane during, plasma electron density is changed to second plasma electron density; Form identical mineral membrane with the second plasma electron density system film afterwards, thereby the system film forms the mineral membrane as the thickness of target.
Like this, through the discharge face 22 of the first discharge face 22a and second discharge face 22b formation shower electrode 20, wherein; This first discharge face 22a forms along with moving closer to the distance of reel towards the downstream side, and the second discharge face 22b forms with the distance of reel 30 and fixes with prescribed value, thereby the distance (gap) between shower electrode 20 and the reel 30 changes on the throughput direction of substrate Z as follows; That is, maximum at the upstream side of the throughput direction of substrate Z, along with diminishing gradually towards the downstream side; Prescribed value in the downstream side with minimum is fixed; During film forming, begin film forming in beginning thus with the first low plasma electron density, form at the system film regulation thickness mineral membrane during; Plasma electron density is changed to second plasma electron density; Afterwards, form identical mineral membrane, thereby the system film forms the mineral membrane as the thickness of target with the second plasma electron density system film.
Thus; When the beginning film forming; Energy through plasma body can make material (composition of mineral membrane) the blended state of the organic materials that is formed with substrate surface and mineral membrane layer (below; Be called " mixolimnion ") the thickness attenuation, and can make the mineral membrane that forms on the upper strata of mixolimnion form thickness sufficient.In addition, owing to can form mineral membrane, therefore can make film and form densification and have good high performance mineral membrane with the second plasma electron density system film that can access high performance.And; On the throughput direction of substrate Z; Distance through changing between shower electrode 20 and the reel 30 is controlled plasma electron density, even be roll-to-roll film deposition system therefore, plasma electron density is changed continuously; Can not form the clear and definite interface that change produces during filming condition, and can prevent to connect airtight bad etc. generation.And, owing to need electrode separation not become a plurality of, therefore become diaphragm area can not diminish, productivity can not reduce.
At this, in the present embodiment, the size in second gap limits especially, can be according to kind, yield polymer films, the thickness of mineral membrane of the kind (compositions) of the mineral membrane that forms, the reactant gases that uses, the performance (characteristic) of requirement waits and suitable definite.
And the size in first gap does not limit especially yet, but is preferably 1.1～1.5 times the gap in second gap.
Satisfy above-mentioned condition through making first gap and second gap; Thereby can further improve the inhibition effect of mixolimnion; Can make film and form fine and close more mineral membrane (consequently, can make the thickness attenuation), and can further improve the per unit thickness mineral membrane function (consequently; Can make the thickness attenuation), thereby in the photoabsorption in visible light zone, can reduce aspect such as noise and obtain preferred result.
In addition; The length of the first discharge face 22a on the throughput direction of substrate Z limits especially, can be suitably definite according to the kind of the kind (compositions) of the mineral membrane that forms, the reactant gases that uses, yield polymer films, the thickness of mineral membrane, the performance (characteristic) of requirement etc.Need to prove, the length of the first discharge face 22a be preferably the discharge face 22 on the throughput direction of substrate Z length 10～40%.Form this scope through length, can suppress the formation of mixolimnion more reliably the first discharge face 22a.
Perhaps, can be the length that the mode of 2～10nm is confirmed the first discharge face 22a with thickness at the regional film forming mineral membrane corresponding with the first discharge face 22a.
At this; The curved surface that the distance that is shaped as the first discharge face 22a and reel of the first discharge face 22a closely forms gradually point-blank, but be not limited to this, can form by the plane; Perhaps for making up the face that a plurality of curved surfaces and plane obtain, can also have zone with the fixed distance of reel.In addition, preferred discharge face smoothly, does not promptly have bend ground to form.
Fig. 4 (A)～(C) is that the part of another example and the reel of the shower electrode used in the film deposition system with the method for manufacture of the functional film of embodiment of the present invention is amplified and the synoptic diagram that illustrates.Need to prove; Shower electrode 100,110 and 120 shown in Fig. 4 (A)～(C) in replacing shower electrode shown in Figure 3 20 discharge face 22 and have the discharge face 102; Have the structure identical with shower electrode shown in Figure 3 20; Therefore at the identical identical symbol of position mark, following explanation is mainly carried out different at different position and different.
The discharge face 102 of the shower electrode 100 shown in Fig. 4 (A) has the first discharge face 102a and the second discharge face 22b.
The first discharge face 102a on the throughput direction of substrate Z along with from the upstream-most position towards the downstream side to direction plane inclined near reel 30, and be connected with the second discharge face 22b.
Like this; Even forming by the plane under the situation of first discharge face, when the beginning film forming, also can begin film forming with the first low plasma electron density; Form at the system film regulation thickness mineral membrane during; Also can plasma electron density be changed to second plasma electron density, therefore can suppress the formation of mixolimnion, thereby can form fine and close more mineral membrane.And, can not form the clear and definite interface that produces when changing filming condition, can prevent to connect airtight the generation of bad grade.
The discharge face 112 of the shower electrode 110 shown in Fig. 4 (B) has the first discharge face 112a and the second discharge face 22b.
The first discharge face 112a on the throughput direction of substrate Z, have upstream side and curved surfaces reel 30 fixed distance and downstream side to the curved surface that tilts near the direction of reel 30 point-blank.That is, discharge face 112 is maximum in the zone of the regulation that begins from the upstream-most position with the gap of reel 30, and is along with reducing gradually towards the downstream side, minimum in the zone of the regulation in downstream side.
Like this, forming the first discharge face 112a by a plurality of curved surfaces, and having under the situation with the gap fixed curved surface of reel; When the beginning film forming; Also can begin film forming with the first low plasma electron density, form at the system film regulation thickness mineral membrane during, also can plasma electron density be changed to second plasma electron density; Therefore the formation of mixolimnion can be suppressed, fine and close more mineral membrane can be formed.And, can not form the clear and definite interface that produces when changing filming condition, can prevent to connect airtight the generation of bad grade.
The discharge face 122 of the shower electrode 120 shown in Fig. 4 (C) has the first discharge face 122a and the second discharge face 22b.
The first discharge face 122a for the throughput direction of substrate along with from the upstream-most position towards the downstream side to direction plane inclined near reel 30, and be connected smoothly with the second discharge face 22b.That is, discharge face 122 forms with the mode that does not have bend.
If the discharge face of shower electrode has bend, then when film forming, discharge is concentrated at bend, and it is unstable that the formation of plasma body becomes, and possibly can't carry out stable film forming.Relative therewith, shown in shower electrode 120,, concentrate at bend thereby when film forming, can prevent to discharge through discharge face being formed level and smooth face with bend, can suitably carry out film forming.
In addition, the shape of discharge face 22 forms to be had and the gap of reel 30 structure with the minimum value fixed second discharge face 22b, but the present invention is not limited to this, can be whole the shape near reel 30 of discharge face in the conveying side of substrate Z 22.Yet, have with the gap of reel 30 with the structure of the minimum value fixed second discharge face 22b when carrying out the film forming of mineral membrane, can form fine and close mineral membrane on the upper strata of mixolimnion with thickness sufficient with the filming condition that is more suitable for, therefore preferred.
In addition; In illustrated example; The shape of discharge face 22 forms in the gap of the downstream position of the throughput direction of substrate Z and reel 30 becomes minimum shape; But the present invention is not limited to this, as long as the gap of the reel 30 of the upstream-most position of substrate Z and shower electrode 20 than the gap of the reel 30 of downstream position and shower electrode greatly, can form the shape that becomes minimum beyond the downstream position with the gap of reel.For example,, the reel 30 and the gap of shower electrode 20 are changed, and make the gap become minimum beyond the downstream position when the thickness direction of mineral membrane 82 changes in the physicals that makes mineral membrane 82.
In addition, the shape of discharge face 22 forms the structure that the gap with reel 30 gradually changes, but is not limited to this, also can form the structure that reel 30 and discrete ground, the gap of shower electrode (discharge face) (stage ground) change.Yet under the situation about changing in the gap that makes reel 30 with shower electrode (discharge face), filming condition changes sharp discretely, therefore the rapid variation of the characteristic of film forming mineral membrane and possibly form the interface.Relative therewith, gradually change through making the discharge face 22 and the gap of reel 30, thereby filming condition can sharply not change, and therefore can prevent to form the interface, can prevent to connect airtight the generation of bad grade.
Unstripped gas feed mechanism 58 is the known gas supply mechanisms that use in the plasma CVD equipment equal vacuum film deposition system, to the internal feed unstripped gas of shower electrode 20.
As stated, on shower electrode 20 and opposed faces reel 30, be formed with a plurality of communicating poress.Therefore, the unstripped gas that supplies to shower electrode 20 is imported between shower electrode 20 and reel 30 from this communicating pores.
High frequency electric source 60 is a power supply from plasma exciatiaon power to shower electrode 20 that supply with.High frequency electric source 60 also can be utilized in all known high frequency electric sources that utilize in the various plasma CVD equipments.
And vacuum exhaust mechanism 62 makes its one-tenth film pressure that remains regulation with exhausts in the filming chamber 18 in order to carry out the film forming of gas barrier film through plasma CVD, and it is used in vacuum film formation apparatus, is known vacuum exhaust mechanism.
In the method for manufacture of functional film of the present invention, be used to make the qualification especially of reactant gases that film forms mineral membrane, can utilize all known reactant gasess corresponding with the mineral membrane that forms.
For example; As mineral membrane, when the system film forms the silicon nitride film be utilized as gas barrier film etc., can use silane gas, ammonia and/or nitrogen as reactant gases; When forming identical silicon oxide film, can use silane gas and oxygen as reactant gases.
Need to prove, in the method for manufacture of functional film of the present invention, as required, and except reactant gases, can also be also with all gases such as rare gas element, hydrogen etc. such as helium, neon, argon gas, krypton gas, xenon, radon gas.
In addition; In the present embodiment; Be used for film forming electrode pair in the present embodiment through the reel 30 and the gap of shower electrode 20 are changed, control plasma electron density, but invention be not limited to this; Can the value of material (poorly conductive, surface treatment etc.) of the temperature of electrode, the area of electrode (width of electrode), electrode etc. be controlled with the mode with inclination, article on plasma body electron density is controlled thus.
At this; In the method for manufacture of functional film of the present invention; First plasma electron density limits especially, can be suitably definite according to the kind of the kind (compositions) of the mineral membrane that forms, the reactant gases that uses, yield polymer films, the thickness of mineral membrane, the performance (characteristic) of requirement etc.
In addition, limit especially with the thickness of the film forming mineral membrane of the plasma electron density lower (mixolimnion/mineral membrane) than second plasma electron density, can be according to suitably setting as the thickness of the mineral membrane of target etc.
At this; According to all inventors' of the present invention research, it is more than the 3nm that the film forming of the mineral membrane that preferably carries out with the plasma electron density lower than second plasma electron density proceeds to the film forming thickness that carries out with the plasma electron density lower than second plasma electron density.It is more than the 5nm that the film forming of the mineral membrane that especially preferably carries out with the plasma electron density lower than second plasma electron density proceeds to thickness.
Through carrying out film forming with the plasma electron density lower than second plasma electron density; Until thickness is more than the 3nm, especially for more than the 5nm; Thereby finish the formation of the mixolimnion under the film forming of mineral membrane more reliably, and then can prevent to form easily the generation of the mixolimnion in the film forming of carrying out with second plasma electron density under the condition of mixolimnion more reliably.Need to prove; The film thickness monitoring of carrying out film forming mineral membrane with the plasma electron density lower than second plasma electron density can be utilized in gas phase such as following method and become all known film thickness monitoring methods of utilizing in the embrane method, said method for the method for utilizing in advance the yield polymer films that goes out through experiment or modeling effort, use laser shift sensor etc. to measure the method for the thickness of the actual films that form.
Equally, carry out the qualification especially of the upper limit of the thickness of film forming mineral membrane with the plasma electron density lower than second plasma electron density.
Yet, carry out fine and close and the situation with good performance of film forming mineral membrane as above-mentioned with second plasma electron density.That is, in the present invention, in the mineral membrane as the thickness of target, it is thick more to carry out film forming mineral membrane with second plasma electron density, favourable more at aspect of performance.
Consider above aspect, preferably the thickness with the mineral membrane that forms than the low plasma electron density of second plasma electron density is below the 30nm, especially to be preferably below the 15nm.
In film of the present invention, second plasma electron density also limits especially, can suitably confirm according to the kind of the reactant gases of the kind of film forming mineral membrane, use, yield polymer films, the thickness of mineral membrane, the performance of requirement etc.
The thickness that carries out film forming mineral membrane with second plasma electron density can be according to carrying out film forming thickness with the plasma electron density lower than second plasma electron density, and suitably setting as the thickness (thickness of final film forming mineral membrane) of the mineral membrane of target.
Need to prove that in the present invention, film forming mineral membrane limits especially, can have the purposes etc. of the substrate of mineral membrane suitably to set according to the desired function of kind, mineral membrane of mineral membrane and performance, film forming.
For example, under the situation that the silicon nitride film or the silicon oxide film that form as gas barrier film are used as mineral membrane, preferred thickness is about 20～1000nm.
In addition, in the present embodiment, as preferred form; Form rectangular substrate is carried along the length direction of substrate, and volume is suspended to the structure of carrying out film forming what is called roll-to-roll (Roll to Roll) on the reel simultaneously, but the present invention is not limited to this; In roll-to-roll device; Also can form following such structure, that is, the tabular electrode pair in the face of configuration is set in filming chamber; Between this electrode pair, rectangular substrate is carried along its length, and unstripped gas is supplied with between substrate and electrode and carried out film forming through plasma CVD.
Need to prove; Rectangular substrate is being carried along the length direction of substrate; And roll up to be suspended to simultaneously and carry out on the reel in the film forming film deposition system, for example, suppress under the situation of the formation of mixolimnion at change plasma exciatiaon power as patent documentation 2; Or the change discharge pressure suppresses under the situation of formation of mixolimnion as patent documentation 3, need be corresponding with the filming condition of change and will become a plurality of with the opposed dividing electrodes of reel.Yet, because the opposite electrode of the electrode cut apart is same reel, therefore can't the bias power of reel or temperature etc. be carried out independent control with respect to each electrode, thus can't be under the filming condition that is fit to film forming.And, because the number of electrodes that can be provided with in the space in the device is restricted, therefore they are had under the situation of function separately in the film forming condition that changes each electrode, productivity reduces generally.
Relative therewith, therefore the method for manufacture of functional film of the present invention can be fit to be used in rectangular substrate is carried along the length direction of substrate, and roll up to be suspended to simultaneously and carry out film forming method on the reel owing to the bias power that need not change reel, temperature etc.
More than, the method for manufacture of functional film of the present invention and functional film have been carried out explanation at length, but the present invention unqualified be above-mentioned example, in the scope that does not break away from purport of the present invention, can carry out various improvement or change is self-evident.
[embodiment]
Below, enumerate out concrete embodiment of the present invention, the present invention is explained in further detail.
[embodiment]
Utilize film deposition system shown in Figure 2, on substrate, form silicon nitride film as gas barrier film.
It is the PET film (the system lumirror of Dong Li society) of 100 μ m as 400mm, thickness that substrate uses width.
In addition, use silane gas (SiH
4), ammonia (NH
3) and nitrogen (N
2) as unstripped gas.
In addition, becoming film pressure is 50Pa.
In addition, use diameter as the reel of 1500mm as reel 30.And, be 500W to reel 30 fed bias power, the temperature of reel 30 is-20 degree.
And then frequency of utilization is the high frequency electric source 60 that the high frequency electric source conduct of 13.56MHz is connected with shower electrode 20, and the plasma exciatiaon power of supplying with to shower electrode 20 is 3kW.
In addition, the thickness of film forming functional membrane (silicon nitride film) is 50nm.
The length of the substrate throughput direction of shower electrode 20 is 300mm.
In addition, the gap of shower electrode 20 and reel 30 is 25mm at upstream side, be 20mm in the fixed zone (zone of the second discharge face 22b) in downstream side, and the first discharge face 22a (zone that the gap changes) is the zone that begins 100mm from upstream side.
Under such condition, in film deposition system 10, on substrate Z, carry out the film forming of mineral membrane.
[comparative example 1]
Except the gap of shower electrode 20 and reel 30 is the 20mm in whole zone, all likewise carry out the film forming of mineral membrane with embodiment 1.
Functional film for making determines WVTR water vapor trausmission rate [g/ (m through the MOCON method
2Day)].Need to prove,, determine WVTR water vapor trausmission rate through calcium etch (method of putting down in writing in the TOHKEMY 2005-283561 communique) for the sample of WVTR water vapor trausmission rate above the mensuration boundary of MOCON method.
In addition, with the functional film of producing utilize light microscope observe crackle and film peel off have or not, thereby the having or not of evaluated for film damage.
Result shown in the below table.
[table 1]
Shown in above-mentioned table 1; Plasma electron density when forming mineral membrane according to the system film is minimum at the upstream side of the throughput direction of substrate; And in the highest the present invention in downstream side; With all compare with the film forming prior function property film of same plasma electron density, can produce functional film with very good gas barrier.
According to above result, effect of the present invention is clearly visible.
Claims (11)
1. a functional film is characterized in that,
The atom % at least a in the element that constitutes of the carbon at the interface of the substrate with the surface that is formed by organic materials and the mineral membrane that on said substrate, forms and mineral membrane is that the thickness in the zone more than 5% is 3～15nm.
2. functional film according to claim 1, wherein,
Said mineral membrane is that in the oxygen nitrogen carbide of oxynitride, silicon of nitride, the silicon of oxide compound, silicon with silicon any is the film of staple.
3. the method for manufacture of a functional film; Utilize film forming mechanism and on substrate, make film and form mineral membrane through plasma CVD; This film forming mechanism will have the rectangular said substrate on the surface that is formed by organic materials and carry along its length; And having the electrode pair that the mode with the said substrate that clips conveying disposes, the method for manufacture of said functional film is characterised in that
Between said electrode pair, make the plasma electron density at upstream-most position place of throughput direction of said substrate lower than the plasma electron density of downstream position.
4. the method for manufacture of functional film according to claim 3, wherein,
Plasma electron density when making the system film form said mineral membrane is minimum in the upstream-most position of the throughput direction of said substrate, and is the highest at downstream position.
5. according to the method for manufacture of claim 3 or 4 described functional films, wherein,
Distance between the said electrode pair at place, the upstream-most position of the throughput direction of said substrate is bigger than the distance between the said electrode pair of downstream position.
6. the method for manufacture of functional film according to claim 5, wherein,
Has distance between the said electrode pair along with the zone that reduces gradually towards the downstream side from the upstream-most position.
7. the method for manufacture of functional film according to claim 5, wherein,
The distance that has between the said electrode pair forms the constant zone in the downstream side of the throughput direction of said substrate.
8. the method for manufacture of functional film according to claim 5, wherein,
On the throughput direction of said substrate, the length that becomes minimum position to the distance the said electrode pair from the upstream-most position of said throughput direction be said electrode pair said throughput direction length 10～40%.
9. the method for manufacture of functional film according to claim 5, wherein,
Distance between the said electrode pair at place, the upstream-most position of said throughput direction is 1.1～1.5 times of distance between the said electrode pair of downstream position of said throughput direction.
10. according to the method for manufacture of claim 3 or 4 described functional films, wherein,
The thickness of the film formed said mineral membrane of system is 2～10nm till from the upstream-most position of the throughput direction of said substrate to the highest position of said plasma electron density.
11. according to the method for manufacture of claim 3 or 4 described functional films, wherein,
Said substrate volume is hung over reel cylindraceous side face the regulation zone and carry, use the side of said reel as the said electrode pair of said film forming mechanism.
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| JP2010-220577 | 2010-09-30 |
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| CN1899815A (en) * | 2005-07-11 | 2007-01-24 | 富士胶片株式会社 | Gas barrier film, substrate film, and organic electroluminescence device |
| JP2009097062A (en) * | 2007-10-19 | 2009-05-07 | Oike Ind Co Ltd | Method for manufacturing gas-barrier film, manufacturing apparatus, and gas-barrier film obtained by the manufacturing method |
| US20090317640A1 (en) * | 2008-06-20 | 2009-12-24 | Fujifilm Corporation | Method of forming a gas barrier layer, a gas barrier layer formed by the method, and a gas barrier film |
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| JP2002359203A (en) * | 2001-03-27 | 2002-12-13 | Sanyo Electric Co Ltd | Film-forming apparatus, plasma cvd apparatus, method of forming film, and sputtering apparatus |
| JP5405075B2 (en) * | 2008-09-24 | 2014-02-05 | 富士フイルム株式会社 | Method for forming gas barrier film and gas barrier film |
| JP2010194814A (en) * | 2009-02-24 | 2010-09-09 | Fujifilm Corp | Method and apparatus for manufacturing functional film |
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| CN1899815A (en) * | 2005-07-11 | 2007-01-24 | 富士胶片株式会社 | Gas barrier film, substrate film, and organic electroluminescence device |
| JP2009097062A (en) * | 2007-10-19 | 2009-05-07 | Oike Ind Co Ltd | Method for manufacturing gas-barrier film, manufacturing apparatus, and gas-barrier film obtained by the manufacturing method |
| US20090317640A1 (en) * | 2008-06-20 | 2009-12-24 | Fujifilm Corporation | Method of forming a gas barrier layer, a gas barrier layer formed by the method, and a gas barrier film |
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