CN102443785B - The manufacture method of functional film - Google Patents
The manufacture method of functional film Download PDFInfo
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- CN102443785B CN102443785B CN201110301986.2A CN201110301986A CN102443785B CN 102443785 B CN102443785 B CN 102443785B CN 201110301986 A CN201110301986 A CN 201110301986A CN 102443785 B CN102443785 B CN 102443785B
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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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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
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- Metallurgy (AREA)
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- Ceramic Engineering (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention provides a kind of manufacture method of functional film, the rectangular substrate with the surface formed by organic materials is being carried along its length, and when forming mineral membrane by plasma CVD masking simultaneously, stably can be formed and can show the capacity for air resistance as target corresponding with thickness and the also excellent gas barrier film of aging stability.Between electrode pair, lower than the plasma electron density of most downstream position by the plasma electron density at the upstream-most position place making the throughput direction of substrate, solve described problem.
Description
Technical field
The present invention relates to the technical field of the gas barrier film formed by plasma CVD, specifically, relate to the substrate, the manufacture method that can form the functional film of the excellent gas barrier film of gas barrier and the functional film made by this manufacture method that use surface to be formed by organic materialss such as macromolecular compounds.
Background technology
Require to utilize gas barrier film (vapor barrier film) in the wrapping material used in the packaging of the position of moisture resistance or parts, food, clothes, electronic unit etc. in the various device such as the display unit such as optical element, liquid-crystal display or OLED display, semiconductor device, thin-film solar cells.
Gas barrier film is the film that the material showing gas barrier by silicon oxide or silicon nitride etc. is formed, by such as to sputter or the gas phase membrane formation process (vacuum film formation) such as CVD is formed in the surface at the position requiring moisture resistance.In addition, the gas barrier film surface of the film formed by macromolecular material (plastics film) or metallic film forming the gas barrier film be made up of above-mentioned silicon nitride etc. is also suitably utilized.
As the substrate (substrate film) of the functional films such as gas barrier film, the film that general PET (polyethylene terephthalate) film etc. is formed by macromolecular material.In addition, the 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 membrane as masking on the surface at such film etc. formed by macromolecular material with the substrate on the surface formed by organic materials, exemplify plasma CVD.
Such as, following content is disclosed in patent documentation 1, namely, the surface of the substrate formed by the macromolecular material with the transparency forms the silicon oxide film with carbon 5 ~ 15% to be used as in the gas barrier film of gas barrier film, by organic silicon compound gas and oxygen are formed above-mentioned gas barrier film as the plasma CVD that reactant gases uses.
Gas barrier film such shown in patent documentation 1 is the mineral membrane that the material showing gas barrier by silicon nitride or silicon oxide etc. is formed, and is accessed the regulation thickness of the gas barrier as target by gas phase membrane formation process such as sputtering or CVD at the surface formation energy of the substrates such as plastics film.
In addition, be certainly not limited to gas barrier film, and form out the thickness of the performance that can give full play to as target by give the mineral membrane that for the purpose of various function, masking is formed according to the purposes of product masking on the various substrates such as plastics film.
But, by plasma CVD such plastics film etc. disclosed in above-mentioned patent documentation 1 have the substrate on the surface formed by organic materials forms mineral membrane time, first masking does not form pure mineral membrane, and the film that the mixolimnion of the masking formation organic materials of substrate surface and the inorganic material film of film forming is such, afterwards, the mineral membrane of target is formed with pure state masking.Therefore, although define the gas barrier film of the thickness as target, there is the situation of the capacity for air resistance that cannot obtain as the target corresponding with thickness.
On the other hand, following content is disclosed in patent documentation 2, namely, when the substrate with the surface formed by organic materials forms gas barrier film by plasma CVD, gas barrier film is formed with the first plasma exciatiaon power, afterwards, plasma exciatiaon power changed to the second plasma exciatiaon power higher than the first plasma exciatiaon power and form gas barrier film, suitably can suppress the formation of mixolimnion thus, even if thus stably masking the thin gas barrier film that also can show the function as target can be formed.
In addition, following content is disclosed in patent documentation 3, namely, as other method, form gas barrier film by the first discharge pressure, afterwards, form gas barrier film by the second discharge pressure lower than the pressure of described first discharge pressure, suitably suppress the formation of mixolimnion thus, even if thus stably masking the thin gas barrier film that also can show the function as target can be formed.
[patent documentation 1] Japanese Unexamined Patent Publication 11-70611 publication
[patent documentation 2] Japanese Unexamined Patent Publication 2010-1535 publication
[patent documentation 3] Japanese Unexamined Patent Publication 2010-77461 publication
At this, in order to efficient by vacuum film formation and carry out film forming with guaranteeing high productivity, preferably on rectangular substrate, carry out film forming continuously.
As the device implementing such film, there will be a known use and rectangular substrate (netted substrate) circumvolution is become the donor rollers of roll, the substrate circumvolution after film forming is become the film deposition system of the what is called of the wind up roll of roll roll-to-roll (Roll to Roll).In this roll-to-roll film deposition system, in the path of the regulation of the one-tenth film location by carrying out film forming on substrate, rectangular substrate is passed through to wind up roll from donor rollers, and synchronously carry out the winding of sending and being undertaken by wind up roll the substrate after film forming of the substrate from donor rollers, and simultaneously in film forming position, carry out film forming continuously on the substrate of conveying.
In so roll-to-roll film deposition system, when forming gas barrier film by plasma CVD, in order to suppress the formation of mixolimnion, as shown in patent documentation 2, in order to change plasma exciatiaon power in the midway of film forming, and need the multiple electrode for film forming of throughput direction configuration along substrate, by different plasma exciatiaon power carries out film forming because of each electrode.In addition, as shown in patent documentation 3, in order to change discharge pressure, and need the multiple room for film forming of throughput direction configuration along substrate, and at each room configuration electrode, carry out film forming by different discharge pressures.
Like this, in roll-to-roll film deposition system, in order to suppress the formation of mixolimnion, needing corresponding with respective filming condition and being separated into diaphragm area, to change filming condition in the midway of film forming.When being separated into diaphragm area to form gas barrier film, the film quality of the film formed under different filming conditions is different, because which form clear and definite interface, producing and touching the unfavorable conditions such as bad.Further, when becoming multiple by electrode separation, the useful area of electrode, i.e. film-forming region diminish, and productivity may reduce.
In addition, in roll-to-roll film deposition system, be wrapping with substrate at the side face of the reel of cylindrical shape and carry, and simultaneously by carrying out film forming to the electrode arranged with the circumference of this reel on substrate.This reel forms electrode pair together with electrode, but when becoming multiple by electrode separation, the bias power of reel or temperature etc. cannot be controlled separately relative to each electrode, therefore cannot under suitable filming condition film forming.
Summary of the invention
The object of the invention is to the problem points solving above-mentioned prior art, the functional film a kind of manufacture method of functional film being provided and being formed by this manufacture method, thus the substrate at plastics film etc. with the surface formed by organic materials is formed in the manufacture method of the functional film of gas barrier film by plasma CVD, stably can be formed and can show the capacity for air resistance as target corresponding with thickness and the also excellent gas barrier film of aging stability.
In order to solve above-mentioned problem, the invention provides a kind of functional film, it is characterized in that, in the carbon of interface of the substrate with the surface formed by organic materials and the mineral membrane formed on the substrate and the constitution element of mineral membrane, the atom % of at least one is all the thickness in the region of more than 5% is 3 ~ 15nm.
At this, preferred described mineral membrane is with any one film being main component in the oxygen nitrogen carbide of the oxynitride of the nitride of the oxide compound of silicon, silicon, silicon, silicon.
In addition, in order to solve above-mentioned problem, the invention provides a kind of manufacture method of functional film, utilize film forming mechanism and by plasma CVD on the substrate masking formed mineral membrane, the rectangular substrate with the surface formed by organic materials is carried by this film forming mechanism along its length, and there is the electrode pair of the described substrate configuration clipping conveying, the feature of the manufacture method of described functional film is, between described electrode pair, make the plasma electron density at the upstream-most position place of the throughput direction of described substrate lower than the plasma electron density of most downstream position.
Further, preferably make plasma electron density during described mineral membrane film forming minimum in the upstream-most position of the throughput direction of described substrate, the highest in position, most downstream.
At this, the distance between the described electrode pair at the upstream-most position place of the throughput direction of preferred described substrate than most downstream position described electrode pair between distance large.
In addition, preferably there is distance between described electrode pair along with the region reduced gradually towards downstream side from upstream-most position.
In addition, the distance preferably had between described electrode pair is formed as constant region in the downstream side of the throughput direction of described substrate.
In addition, preferably on the throughput direction of described substrate, the length that the distance from the upstream-most position of described throughput direction to described electrode pair becomes minimum position is 10 ~ 40% of the length of the described throughput direction of described electrode pair.
In addition, the distance between the described electrode pair at the upstream-most position place of preferred described throughput direction is 1.1 ~ 1.5 times of the distance between the described electrode pair of the position, most downstream of described throughput direction.
In addition, the thickness preferably carrying out the described mineral membrane of film forming from the upstream-most position of the throughput direction of described substrate to the position that described plasma electron density is the highest is 2 ~ 10nm.。
In addition, preferably described substrate be wound around the regulation region of the side face of cylindric reel and carry, using described reel as a side of the described electrode pair of described film forming mechanism.
[invention effect]
According to the present invention, the thickness being the region of more than 5% due to the atom % of at least one in the carbon of interface of the substrate with the surface formed by organic materials and the mineral membrane formed on the substrate and the constitution element of mineral membrane is 3 ~ 15nm, therefore significantly reduce organic with inorganic mixolimnion, and can realize aging stability excellent, there is not clear and definite interface, densification and gas barrier is high.
In addition, according to the present invention, in utilization, the rectangular substrate with the surface (film forming face) formed by organic materials such for plastics film is carried along its length, and there is the film forming mechanism of the electrode pair of the substrate configuration clipping conveying, and when by plasma CVD, on substrate, masking forms mineral membrane, between electrode pair, make the plasma electron density at the upstream-most position place of the throughput direction of substrate lower than the plasma electron density of most downstream position, therefore organic with inorganic mixolimnion is significantly reduced, and it is excellent to form aging stability, there is not clear and definite interface, the gas barrier film that fine and close and gas barrier is high.Therefore, according to the present invention, can obtain thin, do not touch the unfavorable condition such as bad and the excellent gas barrier film of gas barrier, and the productivity of gas barrier film can be improved.
Accompanying drawing explanation
Fig. 1 is the figure of the example schematically showing the functional film of the present invention made by manufacture method of the present invention.
Fig. 2 is the figure of the example schematically showing the film deposition system implementing manufacture method of the present invention.
Fig. 3 is the partial enlarged drawing of the part that the shower electrode (shower electrode) shown in Fig. 2 and reel are shown.
Fig. 4 (A) ~ (C) is the partial enlarged drawing that another example of shower electrode and a part for reel are shown.
Nomenclature:
10 film deposition systems
12 vacuum chambers
12a inner-wall surface
14 unreel room
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 mechanism
58 unstripped gas feed mechanisms
60 high frequency electric sources
Z substrate
Embodiment
Below, the manufacture method of functional film of the present invention and functional film are described in detail.
In the manufacture method of functional film of the present invention, form in the upper masking in the surface (film forming face) of the substrate with the surface formed by organic materials the mineral membrane that gas barrier film or antireflection film etc. show the function as target by plasma CVD.
In the present invention, when starting to form mineral membrane (formation mineral membrane) to substrate surface masking, film forming is started using the first plasma electron density that the second plasma electron density needed than the film quality in order to obtain as the performance of target is low, form the mineral membrane of the thickness of regulation in masking during, plasma electron density is changed to the second plasma electron density, afterwards, form identical mineral membrane with the second plasma electron density masking, thus masking forms out the mineral membrane of the thickness (the final thickness made) as target.
In the manufacture method of functional film of the present invention, the substrate (base material/handled object) that masking forms mineral membrane is the substrate that surface is formed by various organic materialss (organism) such as macromolecular material (polymer/polymeric) or resin materials.
Formed by organic materials if substrate is surface and the substrate of the film forming of mineral membrane can be carried out by plasma CVD, then can utilize various material.Specifically, the substrate formed by the macromolecular material such as polyethylene terephthalate (PET), PEN, polyethylene, polypropylene, polystyrene, polymeric amide, polyvinyl chloride, polycarbonate, polyacrylonitrile, poly-imines, polyacrylonitrile, polymethacrylate is exemplified routine as be applicable to one.
In addition, in the present invention, substrate is suitably for the tympans (flap) such as rectangular film (netted film) or sliced film, but be not limited to this, the various article (component) that the surface such as the display pannels such as photo-electric conversion element, liquid-crystal display or electronic paper such as the optical element such as lens or optical filter, organic EL or solar cell is formed by organic materials can both utilize as substrate.
And; substrate can be formed as follows: based on plastics film (macromolecule membrane), the article formed by organic materials, metallic film or sheet glass, various metal article etc. (base material), form the layer (film) formed by organic materials for obtaining various function such as protective layer, adhesive linkage, reflection layer, light shield layer, planarization layer, buffer layer, stress relaxation layer in its surface.
An example of the functional film of the present invention made by the manufacture method of functional film of the present invention is schematically shown in Fig. 1.
As shown in Figure 1, functional film 80 of the present invention is the functional films forming the mineral membrane 82 as gas barrier film (barrier layer for gases) in the surperficial masking of substrate (substrate for film deposition) Z and obtain.
At this, when carrying out film forming by plasma CVD, the integrant (free radical, ion, electronics etc.) inciding the plasma body of substrate becomes the state of the inside entering substrate (organic materials), and the mixolimnion 84 forming the organic materials/organic materials of the state of the organic materials of substrate surface and the material mixing of mineral membrane is (following, conveniently, mixolimnion 84 is called).The amount of the organic materials in mixolimnion 84 reduces gradually along with the film forming of carrying out mineral membrane, and final masking forms out the pure mineral membrane 84 of unmixed organic materials.
In functional film of the present invention, by plasma electron density when forming this mixolimnion 84 is reduced, thus in mixolimnion 84 carbon and mineral membrane constitution element in the atom % of at least one region that becomes more than 5% be formed as the thickness of 3 ~ 15nm.
When the region that the atom % of at least one of the constitution element of carbon and mineral membrane becomes more than 5% is the thickness of below 3nm, organic membrane (substrate Z) may reduce with the adhesion of mineral membrane 82.The region becoming more than 5% at the atom % of at least one of the constitution element of carbon and mineral membrane is in addition the thickness of more than 15nm, due to the lower thickness of mineral membrane 82 formed on the upper strata of mixolimnion 84, therefore gas barrier reduces, or need the thickness of entirety to be formed thicker in order to ensure gas barrier, therefore productivity reduces.
On the other hand, the region being more than 5% by the atom % of at least one of the constitution element by carbon and mineral membrane is formed as the thickness of 3 ~ 15nm, can prevent organic membrane (substrate Z) from reducing with the adhesion of mineral membrane 82, and the reduction of gas barrier or the reduction of productivity can be prevented.The present invention by specifically such structure, realize the damage of substrate Z less, the excellent and functional film 80 that gas barrier is excellent of productivity.
In functional film of the present invention, the mineral membrane that masking is formed is not particularly limited, as long as can the material of film forming on the substrate with the surface formed by organic materials by plasma CVD, can utilize various organic film.
Such as, if when forming gas barrier film (vapor barrier film) as mineral membrane, then silicon nitride film, silicon oxide film, oxygen silicon nitride membrane, DLC (Diamond Like Carbon) film etc. can be utilized.
In addition, when the protective membrane forming the various equipment such as OLED display or the such display unit of liquid-crystal display or device is as mineral membrane, silicon oxide film etc. can be utilized.
In addition, when forming the nesa coating that utilizes in the various equipment such as OLED display or the such display unit of liquid-crystal display or device as mineral membrane, Zinc oxide film can be utilized.
Further, when forming luminous reflectance and preventing the bloomings such as film, light reflective film, various strainers as mineral membrane, the mineral membrane that there is or show the material as the optical characteristics of target and formed can be utilized.
Wherein, in functional film of the present invention, be applicable to utilizing the mineral membrane being main component with the oxide compound of silicon, nitride, oxynitride, oxygen nitrogen carbide.Further, according to the present invention, masking fine and close film can be formed out, the film forming (manufacture of functional film) of gas barrier film be therefore best suited for gas barrier film, especially being formed by described silicon compound.The present invention is especially applicable to utilizing the film formed by silicon nitride.
Schematically show an example of the film deposition system implementing manufacture method of the present invention in fig. 2.It should be noted that, the film deposition system 10 shown in Fig. 2, except the gap of the shower electrode 20 shown in Fig. 3 and reel 30, is the roll-to-roll film deposition system that known plasma CVD utilizes.This film deposition system 10, by changing shower electrode 20 and the gap of reel 30, makes plasma electron density change.
Rectangular substrate Z (film coiled strip) carries by the film deposition system 10 of illustrated example along its length, and form in the surperficial masking of this substrate Z the film that (manufacture/formed) shows the function as target by plasma CVD, thus manufacturing function film.
In addition, this film deposition system 10 is the device being carried out film forming by so-called roll-to-roll (Roll to Roll), this is roll-to-roll becomes the substrate roll 32 of roll to send substrate Z from by rectangular substrate Z circumvolution, it is carried along its length and the functional membrane of masking formation simultaneously, and film forming has the substrate Z (that is, functional film) of functional membrane to be wound into roll.
Film deposition system 10 shown in Fig. 2 is the device that can be carried out film forming on substrate Z by plasma CVD, is configured to have vacuum chamber 12, formation unreels room 14, filming chamber 18, reel 30 in this vacuum chamber 12.
In film deposition system 10, rectangular substrate Z is supplied by the substrate roll 32 unreeling room 14, is carried along its length by with the state be wound around on reel 30, and simultaneously film forming in filming chamber 18, then, again wireline reel 34 (circumvolution becomes roll) is wound in unreeling in room 14.
The component of cylindrical shape of reel 30 for counterclockwise rotating in figure centered by medullary ray.
The substrate Z card guided in the path of regulation by the guide reel 40a unreeling room 14 described later is hung the regulation region being wound on side face by reel 30, hold it in prescribed position and carry along its length simultaneously, thus it is carried in filming chamber 18, and again carry to the guide reel 40b unreeling room 14.
At this, reel 30 also as the shower electrode 20 of filming chamber 18 described later opposite electrode and play a role and (that is, form electrode pair by reel 30 and shower electrode 20.) this reel 30 with the earth be connected (ground connection).
It should be noted that, can connect on reel 30 as required and be used for executing biased grid bias power supply to reel 30.Or also can connect the earth and grid bias power supply with switching.
Grid bias power supply can utilize utilize in various film deposition system for executing all known power supplys such as biased high frequency electric source or the pulse power.
Unreel room 14 by the inner-wall surface 12a of vacuum chamber 12, reel 30 side face, extend to reel 30 from inner-wall surface 12a side face near next door 36a and 36b form.
At this, the front end (end opposite of the inner-wall surface of vacuum chamber 12) of next door 36a and 36b close to the side face of reel 30, until can with the discontiguous position of substrate Z of conveying, thus room 14 will be unreeled and filming chamber 18 is separated into roughly airtight.
The room 14 that unreels like this has above-mentioned wireline reel 34, guide reel 40a and 40b, turning axle 42, vacuum exhaust mechanism 46.
Guide reel 40a and 40b is the common guide reel guided in the transport path of regulation by substrate Z.In addition, wireline reel 34 is the known rectangular wireline reels of the substrate Z after winding film forming.
In illustrated example, the substrate roll 32 of roll is become to be installed on turning axle 42 rectangular substrate Z circumvolution.Further, 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 by (passing).
In film deposition system 10, synchronously carry out sending the winding with the film forming metacoxa Z wireline reel 34 from the substrate Z of substrate roll 32, thus rectangular substrate Z is carried along its length in the transport path of regulation, and carry out the film forming in filming chamber 18 simultaneously.
Vacuum exhaust mechanism 46 is for the vacuum pump by unreeling the vacuum tightness reducing pressure into regulation in room 14.The pressure (one-tenth film pressure) that vacuum exhaust mechanism 46 makes to unreel in room 14 to be become filming chamber 18 does not bring the pressure (vacuum tightness) of impact.
On the throughput direction of substrate Z, be configured with filming chamber 18 in the downstream unreeling room 14.
Filming chamber 18 by inner-wall surface 12a, reel 30 side face, extend to reel 30 from inner-wall surface 12a side face near next door 36a and 36b form.
In film deposition system 10, as an example, filming chamber 18 carries out the filming chamber of film forming by CCP (CapacitivelyCoupled Plasma capacity mating type plasma body)-CVD on the surface of substrate Z, has shower electrode 20, unstripped gas feed mechanism 58, high frequency electric source 60, vacuum exhaust mechanism 62.
In film deposition system 10, when carrying out film forming by CCP-CVD, shower electrode 20 forms electrode pair together with reel 30.In illustrated example, as an example, shower electrode 20 be the roughly Nogata body shape of hollow, one as the discharge face 22 of largest face and the circumference of reel 30 to configuration.Further, multiple communicating pores is being formed with by entire surface as on the discharge face 22 of the opposed faces opposed with reel 30.Shower electrode 20 its discharge face 22 and and its side face forming the reel 30 of electrode pair between generate the plasma body being used for film forming, thus be formed into diaphragm area.
Fig. 3 be a part for the shower electrode 20 shown in Fig. 2 and reel 30 is amplified shown in schematic diagram.
The discharge face 22 of shower electrode 20 is configured to have the first discharge face 22a and the second discharge face 22b, this first discharge face 22a is formed as moving closer to the distance of reel along with towards downstream side at the upstream side of the throughput direction of substrate Z, and this second discharge face 22b is formed as in the downstream side of the throughput direction of substrate Z fixing with the value specified with the distance of reel 30.
Specifically, first discharge face 22a is the curved surface be formed in from upstream-most position on the throughput direction of substrate Z on the region of regulation, its upstream-most position at the throughput direction of substrate Z, be namely formed as first gap maximum with the gap of reel 30 to the inlet side of film-forming region, along with towards downstream side, with point-blank close to the mode of reel 30 by the Surface forming corresponding 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, and the mode of fixing with the second gap minimum with the gap of reel 30 is by the Surface forming corresponding with the curved surface of reel 30.
In addition, shower electrode 20 becomes the gap of regulation mode with the gap between discharge face 22 and reel 30 configures from reel 30 extractor gauge set a distance, and the gap of this regulation is the gap of the second plasma electron density that the film quality of the performance that the plasma body in the region of the second discharge face 22b becomes to obtain becoming target needs.
At this, larger as the gap between the shower electrode 20 of electrode pair and reel 30, the plasma electron density for the plasma body of film forming is less.Therefore, in the region of the first discharge face 22a larger than the second discharge face 22b with the gap of reel 30, carry out film forming with the plasma electron density that the second discharge face 22b than downstream side is little.
Namely, when starting film forming, film forming is started with the first low plasma electron density, form the mineral membrane of the thickness of regulation in masking during, plasma electron density is changed to the second plasma electron density, form identical mineral membrane with the second plasma electron density masking afterwards, thus masking forms the mineral membrane as the thickness of target.
Like this, the discharge face 22 of shower electrode 20 is formed by the first discharge face 22a and the second discharge face 22b, wherein, this first discharge face 22a is formed as moving closer to the distance of reel along with towards downstream side, second discharge face 22b is formed as fixing with prescribed value with the distance of reel 30, thus the distance (gap) between shower electrode 20 and reel 30 changes as follows on the throughput direction of substrate Z, namely, maximum at the upstream side of the throughput direction of substrate Z, diminish gradually along with towards downstream side, fix with minimum prescribed value in downstream side, thus when starting film forming, film forming is started with the first low plasma electron density, form the mineral membrane of the thickness of regulation in masking during, plasma electron density is changed to the second plasma electron density, afterwards, identical mineral membrane is formed with the second plasma electron density masking, thus masking forms the mineral membrane as the thickness of target.
Thus, when starting film forming, the layer of the state that the material (composition of mineral membrane) of the organic materials and mineral membrane being formed with substrate surface can be made by the energy of plasma body to mix is (following, be called " mixolimnion ") lower thickness, and the mineral membrane formed on the upper strata of mixolimnion can be made to be formed as sufficient thickness.In addition, due to mineral membrane can be formed, therefore, it is possible to masking forms densification and has good high performance mineral membrane with the second plasma electron density masking that can obtain high performance.And, on the throughput direction of substrate Z, plasma electron density is controlled by the distance changed between shower electrode 20 and reel 30, even if be therefore roll-to-roll film deposition system, also plasma electron density can be made to change continuously, the clear and definite interface produced when changing filming condition can not be formed, and can prevent from touching bad etc. generation.Further, owing to not needing that electrode separation is become multiple, therefore film-forming region can not diminish, and productivity can not reduce.
At this, in the present embodiment, the size in the second gap is not particularly limited, and suitably can determine according to the kind, yield polymer films, the thickness of mineral membrane, the performance (characteristic) of requirement etc. of the reactant gases of the kind (composition) of the mineral membrane formed, use.
Further, the size in the first gap is also not particularly limited, but is preferably the gap of 1.1 ~ 1.5 times in the second gap.
Above-mentioned condition is met by making the first gap and the second gap, thus the inhibition of mixolimnion can be improved further, masking can form finer and close mineral membrane (consequently, thickness can be made) thinning, and the function of the mineral membrane of per unit thickness can be improved further (consequently, can make thickness thinning), thus photoabsorption in visible light region, can reduce in noise etc. and obtain preferred result.
In addition, the length of the first discharge face 22a on the throughput direction of substrate Z is not particularly limited, and suitably can determine according to the kind of the reactant gases of the kind (composition) of the mineral membrane formed, use, yield polymer films, the thickness of mineral membrane, the performance (characteristic) etc. of requirement.It should be noted that, the length of the first discharge face 22a is preferably 10 ~ 40% of the length of the discharge face 22 on the throughput direction of substrate Z.By the length of the first discharge face 22a is formed as this scope, the formation of mixolimnion can be suppressed more reliably.
Or the mode that can be 2 ~ 10nm with the thickness of the mineral membrane in the region film forming corresponding with the first discharge face 22a determines the length of the first discharge face 22a.
At this, the shape of the first discharge face 22a is the curved surface that the distance of the first discharge face 22a and reel is closely formed gradually point-blank, but is not limited to this, can be formed by plane, or for combining the face that multiple curved surface and plane obtain, the region fixing with the distance of reel can also be had.In addition, smoothly, namely preferred discharge face is not formed with having bend.
Fig. 4 (A) ~ (C) is the schematic diagram that another example of the shower electrode implementing to use in the film deposition system of the manufacture method of functional film of the present invention and a part for reel are amplified and illustrated.It should be noted that, shower electrode 100,110 and 120 shown in Fig. 4 (A) ~ (C) has except discharge face 102 except replacing the discharge face 22 in the shower electrode 20 shown in Fig. 3, there is the structure identical with the shower electrode 20 shown in Fig. 3, therefore mark identical symbol at identical position, the following description is mainly carried out different positions.
The discharge face 102 of the shower electrode 100 shown in Fig. 4 (A) has the first discharge face 102
awith the second discharge face 22b.
First discharge face 102a be on the throughput direction of substrate Z along with from upstream-most position towards downstream side to the plane that the direction close to reel 30 tilts, and to be connected with the second discharge face 22b.
Like this, even if when forming the first discharge face by plane, when starting film forming, also film forming can be started with the first low plasma electron density, form the mineral membrane of the thickness of regulation in masking during, also plasma electron density can be changed to the second plasma electron density, therefore, it is possible to suppress the formation of mixolimnion, thus finer and close mineral membrane can be formed.Further, the clear and definite interface produced when changing filming condition can not be formed, can prevent from touching bad etc. generation.
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.
First discharge face 112a there is upstream side on the throughput direction of substrate Z with the curved surface that to direction point-blank close to reel 30 tilt of reel 30 apart from fixing curved surface and downstream side.That is, discharge face 112 is maximum in the region of the regulation from upstream-most position with the gap of reel 30, reduces gradually along with towards downstream side, minimum in the region of the regulation of most downstream side.
Like this, by multiple Surface forming first discharge face 112a, and when there is the curved surface fixed with the gap of reel, when starting film forming, also film forming can be started with the first low plasma electron density, form the mineral membrane of the thickness of regulation in masking during, also plasma electron density the second plasma electron density can be changed to, therefore, it is possible to suppress the formation of mixolimnion, finer and close mineral membrane can be formed.Further, the clear and definite interface produced when changing filming condition can not be formed, can prevent from touching bad etc. generation.
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.
First discharge face 122a be substrate throughput direction along with from upstream-most position towards downstream side to the plane that the direction close to reel 30 tilts, and to be connected smoothly with the second discharge face 22b.That is, discharge face 122 is formed in the mode without bend.
If the discharge face of shower electrode has bend, then when film forming, discharge and to concentrate at bend, the formation of plasma body becomes unstable, possibly cannot carry out stable film forming.On the other hand, as shown in shower electrode 120, by discharge face being formed as the level and smooth face without bend, thus can prevent when film forming electric discharge from concentrating at bend, suitably can carry out film forming.
In addition, the shape of discharge face 22 is formed as the structure with the second discharge face 22b fixed with minimum value with the gap of reel 30, but the present invention is not limited to this, can be whole the shape close to reel 30 of discharge face 22 in the conveying side of substrate Z.But, there is the structure of the second discharge face 22b fixed with minimum value with the gap of reel 30 when carrying out the film forming of mineral membrane, fine and close mineral membrane can be formed on the upper strata of mixolimnion with sufficient thickness with the filming condition be more suitable for, therefore preferably.
In addition, in illustrated example, the shape of discharge face 22 is formed as becoming minimum shape in the position, most downstream of the throughput direction of substrate Z and the gap of reel 30, 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 reel 30 and the shower electrode of most downstream position gap greatly, can be formed as becoming minimum shape with the gap of reel beyond position, most downstream.Such as, when the thickness direction making the physicals of mineral membrane 82 along mineral membrane 82 changes, reel 30 can be made to change with the gap of shower electrode 20, and beyond position, most downstream, make gap become minimum.
In addition, the shape of discharge face 22 is formed as the structure gradually changed with the gap of reel 30, but is not limited to this, and the gap that also can be formed as reel 30 and shower electrode (discharge face) is (stage ground) structure of changing discretely.But when the gap making reel 30 with shower electrode (discharge face) changes discretely, filming condition changes sharp, and therefore the characteristic of the mineral membrane of film forming sharply changes and may form interface.On the other hand, by making discharge face 22 gradually change with the gap of reel 30, thus filming condition can not sharply change, therefore, it is possible to prevent from forming interface, can prevent from touching bad etc. generation.
Unstripped gas feed mechanism 58 is the known gas supply mechanisms used in the vacuum film formation apparatus such as plasma CVD equipment, to the internal feed unstripped gas of shower electrode 20.
As mentioned above, shower electrode 20 with the opposed faces of reel 30 on be formed with multiple communicating pores.Therefore, the unstripped gas being supplied to shower electrode 20 is imported between shower electrode 20 and reel 30 by from this communicating pores.
High frequency electric source 60 is the power supply supplying plasma exciatiaon power to shower electrode 20.High frequency electric source 60 also can utilize all known high frequency electric source utilized in various plasma CVD equipment.
Further, vacuum exhaust mechanism 62 is in order to carry out the film forming of gas barrier film by plasma CVD, make it remain the one-tenth film pressure of regulation exhaust in filming chamber 18, it is used in vacuum film formation apparatus, is known vacuum exhaust mechanism.
In the manufacture method of functional film of the present invention, the reactant gases forming mineral membrane for masking is not particularly limited, and can utilize all known reactant gases corresponding with the mineral membrane formed.
Such as, as mineral membrane, when masking formation is utilized as the silicon nitride film of gas barrier film etc., silane gas, ammonia and/or nitrogen can be used as reactant gases, when forming identical silicon oxide film, silane gas and oxygen can be used as reactant gases.
It should be noted that, in the manufacture method of functional film of the present invention, as required, except reactant gases, can also also with various gas, the hydrogen etc. such as rare gas element such as helium, neon, argon gas, Krypton, xenon, radon gas.
In addition, in the present embodiment, for the electrode pair of film forming in the present embodiment by making reel 30 change with the gap of shower electrode 20, control plasma electron density, but invention is not limited to this, the value of the material (poorly conductive, surface treatment etc.) of the area of the temperature of electrode, electrode (width of electrode), electrode etc. can be controlled in the mode with inclination, plasma electron density controls thus.
At this, in the manufacture method of functional film of the present invention, first plasma electron density is not particularly limited, and suitably can determine according to the kind of the reactant gases of the kind (composition) of the mineral membrane formed, use, yield polymer films, the thickness of mineral membrane, the performance (characteristic) etc. of requirement.
In addition, be not particularly limited with the thickness of the mineral membrane (mixolimnion/mineral membrane) of the plasma electron density film forming lower than the second plasma electron density, can according to suitably settings such as the thickness of the mineral membrane as target.
At this, according to the research of all inventors of the present invention, the thickness that the film forming of the mineral membrane preferably carried out with the plasma electron density lower than the second plasma electron density proceeds to the film forming of carrying out with the plasma electron density lower than the second plasma electron density is more than 3nm.It is more than 5nm that the film forming of the especially preferred mineral membrane carried out with the plasma electron density lower than the second plasma electron density proceeds to thickness.
By carrying out film forming with the plasma electron density lower than the second plasma electron density, until thickness be more than 3nm, especially for more than 5nm, thus more reliably terminate the formation of the mixolimnion under the film forming of mineral membrane, and then the generation of mixolimnion in the film forming of carrying out with the second plasma electron density under the condition that can prevent from easily being formed mixolimnion more reliably.It should be noted that, the film thickness monitoring carrying out the mineral membrane of film forming with the plasma electron density lower than the second plasma electron density can utilize all known film thickness monitoring methods utilized in the gas phase membrane formation process such as following method, and described method is utilize in advance by experiment or the method for the yield polymer films that goes out of modeling effort, use laser shift sensor etc. to measure the method for the thickness of the actual film formed.
Equally, the upper limit of carrying out the thickness of the mineral membrane of film forming with the plasma electron density lower than the second plasma electron density is not particularly limited.
But, carry out the fine and close and situation with excellent performance of the mineral membrane of film forming as described above with the second plasma electron density.That is, in the present invention, in the mineral membrane of the thickness as target, the mineral membrane carrying out film forming with the second plasma electron density is thicker, more favourable at aspect of performance.
Consider above aspect, the thickness of mineral membrane preferably formed with the plasma electron density lower than the second plasma electron density is below 30nm, is especially preferably below 15nm.
In film of the present invention, the second plasma electron density is also not particularly limited, and suitably can determine according to the performance etc. of the thickness of the kind of the reactant gases of the kind of the mineral membrane of film forming, use, yield polymer films, mineral membrane, requirement.
The thickness carrying out the mineral membrane of film forming with the second plasma electron density suitably can set according to the thickness (thickness of the mineral membrane of final film forming) carrying out the thickness of film forming and the mineral membrane as target using the plasma electron density lower than the second plasma electron density.
It should be noted that, in the present invention, the mineral membrane of film forming is not particularly limited, and function required by the kind of mineral membrane, mineral membrane and performance, film forming can have the suitably settings such as the purposes of the substrate of mineral membrane.
Such as, when formed be used as mineral membrane as the silicon nitride film of gas barrier film or silicon oxide film, preferred thickness is about 20 ~ 1000nm.
In addition, in the present embodiment, as preferred form, the length direction of rectangular substrate along substrate is formed as to carry, and be wrapping with the structure of the what is called of reel carrying out film forming roll-to-roll (Roll toRoll) simultaneously, but the present invention is not limited to this, in roll-to-roll device, also structure as follows can be formed as, namely, at the electrode pair of filming chamber's installation surface to the tabular of configuration, between this electrode pair, rectangular substrate is carried along its length, and unstripped gas is carried out film forming to supply between substrate and electrode by plasma CVD.
It should be noted that, the length direction of rectangular substrate along substrate is being carried, and be wrapping with in film deposition system reel carrying out film forming simultaneously, such as, when changing plasma exciatiaon power as described in Patent Document 2 to suppress the formation of mixolimnion, or change discharge pressure as described in Patent Document 3 when suppressing the formation of mixolimnion, need corresponding with the filming condition of change and the dividing electrodes opposed with reel is become multiple.But, because the opposite electrode of electrode of segmentation is same reel, therefore the bias power of reel or temperature etc. cannot be controlled separately relative to each electrode, thus cannot under the filming condition be applicable to film forming.Further, because the number of electrodes that can arrange in the space in device is restricted, therefore when change each electrode film forming condition and make them have respective function, generally productivity reduce.
On the other hand, the length direction of rectangular substrate along substrate, owing to not needing the bias power, temperature etc. that change reel, is carried therefore, it is possible to be applicable to being used in, and is wrapping with the method for reel carrying out film forming simultaneously by the manufacture method of functional film of the present invention.
Above, the manufacture method of functional film of the present invention and functional film are explained, but the present invention is not defined as above-mentioned example, can various improvement be carried out without departing from the spirit and scope of the invention or change is self-evident.
[embodiment]
Below, list specific embodiment of the present invention, the present invention is illustrated in further detail.
[embodiment]
Utilize the film deposition system shown in Fig. 2, substrate forms silicon nitride film as gas barrier film.
Substrate uses the PET film (Dong Li society lumirror) that width is 400mm, thickness is 100 μm.
In addition, silane gas (SiH is used
4), ammonia (NH
3) and nitrogen (N
2) as unstripped gas.
In addition, film pressure is become to be 50Pa.
In addition, use the reel that diameter is 1500mm as reel 30.Further, the bias power supplied to reel 30 is 500W, and the temperature of reel 30 is-20 degree.
And then, frequency of utilization be the high frequency electric source of 13.56MHz as the high frequency electric source 60 be connected with shower electrode 20, to shower electrode 20 supply plasma exciatiaon power be 3kW.
In addition, the thickness of the functional membrane (silicon nitride film) of film forming is 50nm.
The length of the substrate throughput direction of shower electrode 20 is 300mm.
In addition, shower electrode 20 is 25mm with the gap of reel 30 in side, most upstream, be 20mm in the fixing region (region of the second discharge face 22b) in downstream side, the first discharge face 22a (region of gap change) is the region of 100mm from upstream side.
In such a situa-tion, 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 except 20mm in whole region, all carry out the film forming of mineral membrane similarly to Example 1.
For the functional film made, determine water vapor transmission rate (WVTR) [g/ (m by MOCON method
2day)].It should be noted that, for the sample of water vapor transmission rate (WVTR) more than the mensuration boundary of MOCON method, determine water vapor transmission rate (WVTR) by calcium etch (method recorded in Japanese Unexamined Patent Publication 2005-283561 publication).
In addition, utilized by the functional film produced light microscope to observe the presence or absence of the stripping of crackle and film, thus the presence or absence of evaluated for film damage.
Result shown in following table.
[table 1]
As shown in Table 1 above, minimum in the side, most upstream of the throughput direction of substrate according to plasma electron density during masking formation mineral membrane, and in the highest the present invention of most downstream side, with all with compared with the existing functional film of same plasma electron density film forming, the functional film with very excellent gas barrier can be produced.
According to above result, effect of the present invention is clearly visible.
Claims (8)
1. the manufacture method of a functional film, utilize film forming mechanism and form mineral membrane by plasma CVD masking on substrate, the rectangular described substrate with the surface formed by organic materials is carried by this film forming mechanism along its length, and the electrode pair that the mode with the described substrate clipping conveying configures, the feature of the manufacture method of described functional film is
The electrode forming a side of described electrode pair is the shower electrode being formed with multiple communicating pores on the discharge face of the side right with the electrode surface of the opposing party,
Distance between the described electrode pair at the upstream-most position place of the throughput direction of described substrate than most downstream position described electrode pair between distance large, in downstream side, the distance had between described electrode pair is formed as constant region,
Base feed gas between from described multiple communicating pores of described shower electrode to described electrode pair,
Between described electrode pair, make the plasma electron density at the upstream-most position place of the throughput direction of described substrate lower than the plasma electron density of most downstream position, and be formed as constant plasma electron density in downstream side.
2. the manufacture method of functional film according to claim 1, wherein,
Plasma electron density when making masking form described mineral membrane is minimum in the upstream-most position of the throughput direction of described substrate, the highest in position, most downstream.
3. the manufacture method of functional film according to claim 1 and 2, wherein,
There is distance between described electrode pair along with the region reduced gradually towards downstream side from upstream-most position.
4. the manufacture method of functional film according to claim 1 and 2, wherein,
On the throughput direction of described substrate, there is first area that the distance between described electrode pair reduces gradually and to be connected smoothly with described first area and distance between described electrode pair is formed as constant second area,
On the throughput direction of described substrate, the plasma electron density between described electrode pair changes to be formed as constant mode after increasing gradually.
5. the manufacture method of functional film according to claim 1 and 2, wherein,
On the throughput direction of described substrate, the length that the distance from the upstream-most position of described throughput direction to described electrode pair becomes minimum position is 10 ~ 40% of the length of the described throughput direction of described electrode pair.
6. the manufacture method of functional film according to claim 1 and 2, wherein,
Distance between the described electrode pair at the upstream-most position place of described throughput direction is 1.1 ~ 1.5 times of the distance between the described electrode pair of the position, most downstream of described throughput direction.
7. the manufacture method of functional film according to claim 1 and 2, wherein,
From the upstream-most position of the throughput direction of described substrate, to the position that described plasma electron density is the highest, the thickness of the described mineral membrane that masking is formed is 2 ~ 10nm.
8. the manufacture method of functional film according to claim 1 and 2, wherein,
Described substrate be wound around the regulation region of the side face of cylindric reel and carry, using described reel as a side of the described electrode pair of described film forming mechanism.
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| JP2010-220577 | 2010-09-30 | ||
| JP2010220577A JP2012077315A (en) | 2010-09-30 | 2010-09-30 | Functional film and method 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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| 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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