CN103154313B - Film-formation device and film-formation method - Google Patents
Film-formation device and film-formation method Download PDFInfo
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- CN103154313B CN103154313B CN201180048181.XA CN201180048181A CN103154313B CN 103154313 B CN103154313 B CN 103154313B CN 201180048181 A CN201180048181 A CN 201180048181A CN 103154313 B CN103154313 B CN 103154313B
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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
- C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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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
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
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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
- C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
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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
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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
- C23C16/503—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 dc or ac discharges
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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
- C23C16/52—Controlling or regulating the coating process
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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
- C23C16/54—Apparatus specially adapted for continuous coating
- C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
- C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
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Abstract
Provided is a film-formation device that forms a gas-barrier layered film that exhibits bending resistance and sufficient gas-barrier performance. Said film-formation device has: a vacuum chamber that contains a substrate; a gas-supply device that supplies a film-forming gas to the vacuum chamber, said film-forming gas containing an organic metal compound from which a thin film will be formed and a reaction gas that reacts with said organic metal compound; a pair of electrodes arranged inside the vacuum chamber; a plasma-generation power supply that applies AC power to the pair of electrodes, thereby generating a plasma of the film-forming gas; and a control unit. The control unit controls the gas-supply device and/or the plasma-generation power supply, switching between: first reaction conditions under which the organic metal compound and the reaction gas react to produce a compound that contains a metallic or metalloid element from the organic metal compound and does not contain carbon; and second reaction conditions under which the organic metal compound and the reaction gas react to produce a carbon-containing compound that contains carbon, and a metallic or metalloid element, from the organic metal compound.
Description
Technical field
The present invention relates to film deposition system and film.
The patent application 2010-228917 claims priority machine that the application applied in Japan based on October 8th, 2010, its content is here cited.
Background technology
Gas barrier film can be suitable as the container of the packaging being suitable for the such article of beverage/food, makeup, washing composition.Propose there is following a kind of gas barrier film in recent years, it is on the surface of a side of base material film at plastic film etc., and form silicon oxide, silicon nitride, the film of the mineral compound of silicon oxynitride, aluminum oxide etc. is formed.
As like this by the method for the forming thin film of mineral compound on the surface of plastic basis material, there will be a known the physical vaporous deposition (PVD) of vacuum vapour deposition, sputtering method, e (ィ) method etc., the chemical Vapor deposition process (CVD) of rpcvd method, plasma chemical vapor deposition etc.
In addition, with regard to the gas barrier film manufactured by the use by such film, such as, in Unexamined Patent 4-89236 publication (patent documentation 1), disclose a kind of gas barrier film, it is on the surface of plastic basis material, is provided with the stacked evaporation rete be made up of the two-layer above silicon oxide film formed by evaporation.
Look-ahead technique document
Patent documentation
Patent documentation 1: Unexamined Patent 4-89236 publication
But, gas barrier film such described in above-mentioned patent documentation 1, even if although can use as the wrapping gas barrier film of the lower article that also can meet of gas barrier property of such packaging vessel such as beverage/food, makeup, washing composition, but the wrapping gas barrier film of the electron device as organic EL and organic thin film solar cell etc., may not be abundant in gas barrier property this point.
In addition, gas barrier film such described in above-mentioned patent documentation 1, when making it bending, such problem points existence is reduced for the gas barrier property of oxygen and water vapour, the gas barrier film that the display device requiring resistance to flexibility like this as pliability liquid-crystal display uses, may not be abundant in the gas barrier property this point when making film bend.
Summary of the invention
The present invention is formed in view of such situation, its object is to, even if provide a kind of can manufacture to have sufficient gas barrier property and the film deposition system of the gas barrier property stacked film that also can fully suppress gas barrier property to reduce when film bends.In addition, its object is also, provides a kind of film that can manufacture the gas barrier property stacked film of such physical property expeditiously.
In order to solve above-mentioned problem, the invention provides the first film deposition system (being called " the first embodiment "), it is film forming film deposition system on base material, and this film deposition system comprises as follows: vacuum chamber, and it accommodates described base material in inside, gas supply device, it supplies film forming gas in described vacuum chamber, and this film forming gas contains as the organometallic compound of the raw material of described film and the reactant gases that reacts with this organometallic compound, pair of electrodes, it is configured in described vacuum chamber, plasma body generation power supply, it is to the additional alternating electromotive force of this pair of electrodes described, and the plasma body of described film forming gas is occurred, control part, it controls any one party or two sides of described gas supply device or described plasma body generation power supply, switch the first reaction conditions and the second reaction conditions, this first reaction conditions is, reacted by described organometallic compound and described reactant gases, and make containing forming the metallic element of described organometallic compound or semimetallic elements and the condition that generates of carbon-free compound, this second reaction conditions is, reacted by described organometallic compound and described reactant gases, and make the carbon containing forming described organometallic compound, with the condition that the carbon compound of metallic element or semimetallic elements generates.
In the scope of this specification sheets and claim, " metal " of " organometallic compound " comprises metallic element and semimetallic elements.
Describe the definition of several term used in this manual and performance below further.
So-called " vacuum chamber ", exactly for making inside become decompression state, preferably becoming the container of the decompression state close to vacuum.Usually, by making to be arranged on indoor vacuum pump work, thus set up reduced pressure atmosphere in indoor and preferably set up the reduced pressure atmosphere close to vacuum.
So-called " base material ", forms the object of the supporting mass of this film exactly when film is formed.
So-called " film forming gas ", exactly using the unstripped gas of the raw material as film as must key element and the gas contained, as required, although the reactant gases and not comprising in formed film also forming compound containing reacting with unstripped gas contributes to plasma body occurs and the assist gas of film quality raising etc.
So-called " unstripped gas " is exactly the gas of the supply source of the material as the main component forming film.Such as when SiOx film is formed, the gas containing Si such as HMDSO, TEOS, silane is unstripped gas.
So-called " reactant gases ", reacts with unstripped gas and the gas be mixed in formed film exactly, such as, when forming SiOx film, and oxygen (O
2) be just equivalent to this.
Also have, what is called performance " not carbon containing " used about film in this manual refers to, this film is being drafted by carrying out the measurement of XPS depth profile, represent in the film thickness direction of this film apart from the distance on the surface of this film and form film carbon atom amount for form film atom total amount ratio (atomic ratio of carbon) relation carbon profile in, carbon content is at below 1at%.At this, about above-mentioned carbon profile, " forming the total amount of the atom of film ", be meant to the total quantity of the atom forming film, " amount of carbon atom " is meant to the quantity of carbon atom.In addition, unit " at% " is the brevity code of " atom % ".
In the present invention, expect that described control part consists of, control described gas supply device as follows, namely, in described first reaction conditions, the described reactant gases generated in the reaction of described carbon-free compound more than equivalent by described organometallic compound and described reactant gases is made to be comprised in described film forming gas, and, in described second reaction conditions, the described reactant gases fewer than the equivalent generated in the reaction of described carbon-free compound is comprised in described film forming gas.
In the present invention, expect that described control part consists of, for described gas supply device, carry out the switching of described first reaction conditions and described second reaction conditions time, the amount of the described reactant gases comprised in described film forming gas is changed continuously.
In the present invention, expect that described control part consists of, control described plasma body generation power supply as follows, namely, in described first reaction conditions, the additional alternating electromotive force that the described plasma body of the intensity of described carbon-free compound generation is occurred, in described second reaction conditions, the additional alternating electromotive force that the described plasma body of the intensity of described carbon compound generation is occurred.
In the present invention, expect that described control part consists of, for described plasma body generation power supply, carry out the switching of described first reaction conditions and described second reaction conditions time, the electric flux of described alternating electromotive force is changed continuously.
In addition, the invention provides the second film deposition system (being called " the second embodiment "), it on one side transports long base material continuously and the film deposition system of film forming continuously on the substrate on one side, wherein, this film deposition system has following mechanism: described base material is housed in inner vacuum chamber; The transport mechanism of described base material is transported continuously in described vacuum chamber; At the plasma body generating mechanism that the space overlapping with a part for transported described base material makes discharge plasma occur; Along the conveyance direction of the described base material in described space, in many places, magnetic field is occurred, and the magnetic field generating means making plasma intensity different in space, described transport mechanism consists of, in described space, described base material is made flatly to keep transporting.
In addition, the invention provides the first film, it is film forming film on base material, wherein, there is following operation: the first operation, it is used in and generates containing forming the metallic element of described organometallic compound or semimetallic elements and more than equivalent in the reaction of carbon-free compound described reactant gases by the organometallic compound of the raw material as described film with the reactant gases that this organometallic compound reacts, and carries out plasma CVD; Second operation, it uses the described reactant gases fewer than the equivalent generated in the reaction of described carbon-free compound, carries out the plasma CVD that the carbon compound containing the carbon and metallic element or semimetallic elements that form organometallic compound is generated.
In addition, the invention provides the second film, it is film forming film on base material, wherein, there is following operation: the first operation, it making by the organometallic compound of the raw material as described film and the reactant gases reacted with this organometallic compound, generating containing forming the metallic element of described organometallic compound or semimetallic elements and the discharge plasma of the intensity of carbon-free compound occurs, and carries out plasma CVD; Second operation, it makes the discharge plasma of the intensity generated containing the formation carbon of described organometallic compound and the carbon compound of metallic element or semimetallic elements occur, and carries out plasma CVD.
In addition, the invention provides the 3rd film, it transports long base material continuously on one side, while utilize the film of plasma CVD method film forming continuously on the substrate, wherein, there is following operation: along described base material conveyance direction and make the intensity of discharge plasma spatially different, and the mode of space overlap according to the Strength Changes with described discharge plasma, conveyance the operation of described base material of smooth maintenance.
According to the present invention, there is sufficient gas barrier property and film deposition system and the film that also fully can suppress the gas barrier property stacked film of gas barrier property when making film bend even if can provide to manufacture.
Accompanying drawing explanation
Fig. 1 is the mode chart of the example of the stacked film represented manufactured by the film deposition system of an embodiment of the invention.
Fig. 2 is the figure of the example of the carbon profile representing gas barrier property stacked film.
Fig. 3 is the mode chart of the film deposition system representing the first embodiment of the present invention.
Fig. 4 is the mode chart that control part is described.
Fig. 5 is the mode chart of the variation of the stacked film represented manufactured by the film deposition system of an embodiment of the invention.
Fig. 6 is the mode chart of the film deposition system representing the second embodiment of the present invention.
Fig. 7 is the mode chart of the situation of the film forming of the film deposition system representing above-mentioned second embodiment.
Embodiment
[the first embodiment]
Below, with reference to Fig. 1 ~ Fig. 5, while be described for the film deposition system of the first embodiment of the present invention.Further, in following whole accompanying drawings, in order to easily peruse accompanying drawing, make the size of each integrant and ratio etc. suitable different.
In the following description, just use the film deposition system 1000 of present embodiment, base material is formed the film with gas barrier property, manufacture gas barrier property stacked film, first, gas barrier property stacked film as target is described, and the film deposition system of the present embodiment used in the manufacture of gas barrier property stacked film is described.
< gas barrier property stacked film >
Fig. 1 is the mode chart of the gas barrier property stacked film 1 represented manufactured by the film deposition system of present embodiment.With regard to the gas barrier property stacked film 1 of present embodiment, it defines the film 3 with gas barrier property, and become the film on the whole with gas barrier property.
(base material)
Gas barrier property stacked film 1 manufactured by the film deposition system of present embodiment, obtains by forming film 3 in the one side side of base material 2.
As the base material 2 for present embodiment, the film be made up of resin or the matrix material containing resin can be enumerated.Such film has light transmission and also can, opaquely in addition also can.
As the resin for such base material 2, include, for example as follows: the polyester based resin of polyethylene terephthalate (PET), PEN (PEN) etc.; The polyolefin-based resins of polyethylene (PE), polypropylene (PP), cyclic polyolefin etc.; Polyamide series resin; Polycarbonate-based resin; Polystyrene resin; Polyvinyl alcohol resin; Ethylene-vinyl acetate copolymer saponified; Polyacrylonitrile based resin; Acetal system resin; Polyimide system resin; Aramid fiber system resin; Or make the repeating unit of the polymkeric substance of these resins of formation combine two or more multipolymers etc.In addition, as the matrix material containing resin, the silicone resin of polydimethylsiloxane, polysilsesquioxane etc. can be enumerated; Glass composite base plate, epoxy glass substrate etc.Among these resins, from thermotolerance and linear expansivity this viewpoint high, preferred polyester system resin, polyolefin-based resins, glass composite base plate, epoxy glass substrate.In addition, these resins can be used alone one or be used in combination of two or more.
With regard to base material 2, from the view point of with the adhesion of film formed, also can implement for make its surface activation surface-active-treatment.As such surface-active-treatment, include, for example corona treatment, Cement Composite Treated by Plasma, flame treating.
(film)
Film 3 manufactured by the film deposition system of present embodiment is layers base material 2 being given to gas barrier property, and is formed at least one side of base material 2.Film 3 comprises the different multiple layers of composition.In figure, film 3 is illustrated as making the alternately laminated three-layer structure of the first layer 3a and second layer 3b.
The first layer 3a, its have with by SiO
xc
y(0 < x < 2,0 < y < 2,
) in
represented SiO
2close composition.In contrast, second layer 3b, it has is at SiO
xc
y(0 < x < 2,0 < y < 2,
) in y ≠ 0, by SiO
2-yc
ythe composition represented.Second layer 3b, it is not uniform composition, in the carbon profile of the relation of the atomic ratio (amount of carbon atom is for the ratio of the total amount of Siliciumatom, Sauerstoffatom and carbon atom) of the distance and carbon that represent the surface apart from this layer in film thickness direction, meet following condition (i) and (ii) completely.
First, (i) second layer 3b, its carbon profile at least has an extreme value.
In this manual, with regard to the maximum value of the element distribution plots of carbon profile etc., film, it refers to: when making the distance change apart from the surface of film 3, the value of the atomic ratio of element becomes the point of minimizing from increasing, and the value comparing the atomic ratio of the element of this point, the value that makes the distance on the surface apart from film 3 of the film thickness direction of film 3 change the atomic ratio of the element of the position of 20nm further from this point reduce the point of more than 1at%.In addition, in this manual, with regard to the mnm. of above-mentioned element distribution plots, it refers to: when making the distance change apart from the surface of film 3, the value of the atomic ratio of element becomes the point of increase from reducing, and the value comparing the atomic ratio of the element of this point, the value that makes the distance on the surface apart from film 3 of the film thickness direction of film 3 change the atomic ratio of the element of the position of 20nm further from this point increase the point of more than 1at%.
In addition, (ii) second layer 3b, the layer of its to be the maximum value of atomic ratio of carbon in second layer 3b and the difference of minimum value be more than 5% (that is, (maximum value of the atomic ratio of carbon)-(minimum value of the atomic ratio of carbon) >=5%).
In such second layer 3b, more preferably the absolute value of the maximum value of the atomic ratio of carbon and the difference of minimum value is more than 6at%, is particularly preferably more than 7at%.When described absolute value is lower than 5at%, when making obtained gas barrier property stacked film 1 bend, film 3 is easily damaged, and gas barrier property when gas barrier property stacked film 1 is bent is insufficient.
At this, with regard to carbon profile, can be drafted by the measurement of so-called XPS depth profile, during this XPS depth profile is measured, and with the noble gas ion sputtering of the measurement of X-ray photoelectron spectroscopy (XPS:XrayPhotoelectron Spectroscopy) and argon etc., thus while make test portion inside expose, carry out surface composition analysis successively.The distribution curve obtained by the measurement of such XPS depth profile, such as, can be the atomic ratio (unit: at%) of carbon with the longitudinal axis, transverse axis be that etching period (sputtering time) is drafted.Also have, in the distribution curve of the element using transverse axis as etching period like this, because etching period is relevant apart from the distance on the surface of the film 3 of film thickness direction to the film 3 on film thickness direction substantially, as " distance on film 3 surface of distance film 3 on film thickness direction ", the distance on the surface apart from film 3 that the etching speed that basis can be adopted to adopt when XPS depth profile is measured and the relation of etching period calculate.In addition, the sputtering method adopted when measuring as such XPS depth profile, preferably uses argon (Ar as etch ion kind
+) noble gas ion sputtering method, make its etching speed be 0.05nm/sec (SiO
2heat oxide film scaled value).
Fig. 2 be medelling represent the figure of the carbon profile of second layer 3b.On the transverse axis of distance representing the surface apart from layer, not concrete distance, but represented with each symbol of the first layer 3a, second layer 3b, film 3.In the second layer 3b formed like this shown in figure, have 1 maximum value, the maximum value of carbon atom and the difference of minimum value are more than 5%.
In addition, the first layer 3a is: in carbon profile, carbon content is below 1at%, carbon-free layer.
In addition, in the present embodiment, to be formed evenly on the whole and this viewpoint with the film 3 of excellent gas barrier property is set out, preferred film 3 is the same in fact in face direction (direction parallel with the surface of film 3).In this manual, so-called film 3 in fact equally refers in face direction, measured by XPS depth profile carbon profile is drafted for arbitrary two measuring positions, place of the face of film 3 time, the quantity of the extreme value that the carbon profile obtained in these arbitrary two measuring positions, place has is identical, and the absolute value of the maximum value of the atomic ratio of the carbon in respective carbon profile and the difference of minimum value is mutually the same or poor within 5at%.
In addition, in the present embodiment, preferred described carbon profile is continuous in fact.In this manual, so-called carbon profile is continuous in fact, be meant to the part of the discontinuous change of atomic ratio of the carbon do not comprised in carbon profile, refer to specifically, distance (the x on the surface of this layer apart from film thickness direction of at least one deck among the film 3 calculated according to etching speed and etching period, unit: nm), with the relation of the atomic ratio (C, unit: at%) of carbon, meet the condition represented by following formula (F1):
|dC/dx|≤1…(F1)
In addition, the thickness of film 3 is preferably the scope of 5nm ~ 3000nm, is more preferably the scope of 10nm ~ 2000nm, is particularly preferably the scope of 100nm ~ 1000nm.When the thickness of film 3 is lower than described lower limit, the gas barrier property of oxygen gas barrier property, water vapor barrier property etc. has the tendency of variation, on the other hand, if exceed the described upper limit, then easily cause film 3 damaged due to flexing, the tendency that when therefore making it bending, gas barrier property easily reduces exists.
In the gas barrier property stacked film 1 manufactured by the film deposition system 1000 of present embodiment, the first layer 3a of carbon atoms does not present high-gas resistance, and compares the first layer 3a containing the second layer 3b of carbon atom and can flexibly bend, and therefore presents resistance to flexibility.Therefore, gas barrier property stacked film 1 can give play to excellent barrier and resistance to flexibility on the whole.
< film deposition system >
Fig. 3 is the mode chart of the film deposition system 1000 representing present embodiment.The film deposition system 1000 of present embodiment, possesses as follows: room 11; To be configured in room 11 and the mounting table 12 of mounting base material 2; With the pair of electrodes 13 that the mode relative with mounting table 12 configures above mounting table 12; The plasma body generation power supply 14 be connected with electrode 13; The magnetic field generating unit 15 configured with the non-opposite side of mounting table 12 in electrode 13.
In addition, the gas supply pipe 16 supplying various film forming gas in room 11 and the gas supply device 17 be connected with gas supply pipe 16 via pipe arrangement 16a is also provided with.In addition, be suitable for being provided with in room 11: be arranged on the vacuum pump 18 on the zenith of room 11 and venting port (diagram is omitted).
And, in plasma body generation with on power supply 14 and gas supply device 17, be connected with the control part 100 of the driving controlling plasma body generation power supply 14 and gas supply device 17.
So, in this device, can, by the space of plasma body generation power supply 14 between electrode 13 and mounting table 12, the plasma body generation making the film forming gas supplied from gas supply pipe 16, the plasma body occurred be used to carry out plasma CVD film forming thus.Below, each formation is illustrated successively.
With regard to mounting table 12, although be the parts of mounting base material 2, in inside, the heating arrangements possessed for heating base material 2 also can.
With regard to pair of electrodes 13, it has the shape of tabular, and is configured in the prescribed position of the short transverse in room 11 according to the mode that one side side is opposed with mounting table 12.From the plasma body generation power supply 14 be connected with electrode 13, to the additional such as high-frequency electric power of pair of electrodes 13, between this electrode 13, with the space of periphery, electric field is occurred, thus the plasma body of the film forming gas supplied from gas supply pipe 16 is occurred.
With regard to magnetic field generating unit 15, it has as follows: multiple magnet 15a alternating polarity being arranged reversedly in mounting table 12 side; The transom 15b that multiple (in figure being 3) magnet 15a adsorbs.By magnetic field generating unit 15, the formation magnetic field, space between mounting table 12 and electrode 13.In the drawings, medelling ground represents the magnetic line of force LM formed by magnetic field generating unit 15.
By the intensity of the discharge plasma of generation applied to electrode 13, the intensity in the magnetic field formed along with magnetic field generating unit 15 and different, therefore, the strong region Ji Qiang heating region AR1 of plasma body and weak Ji Ruo heating region, the region AR2 of plasma is formed.With regard to the intensity in magnetic field, by changing the quantity of the magnet 15a of magnetic field generating unit 15, magnet 15a interval each other (in figure, represent with symbol L), the height (in figure, representing with symbol H) of magnet 15a, the magnetic field of expectation can be formed.
Such as, the magnet 15a at the two ends among by the magnet 15a of 3 shown in figure can be used than the low of central authorities and away from the magnetic field generating unit 15 of electrode 13.
Further, the plasma body occurred to arrival base material 2 because plasma diffusion, so plasma intensity is averaged, on base material 2 working strength general uniform plasma body and complete film forming.
With regard to gas supply pipe 16, there is the shape of the tubulose extended in the mode of cross-section room 11 in the below of pair of electrodes 13, from the film forming gas of the unstripped gas of the opening portion supply plasma CVD set by many places etc.
With regard to gas supply device 17, the valve etc. of the container with accumulation film forming gas (unstripped gas, reactant gases, carrier gas) and the feed rate controlling each gas forming film forming gas, the film forming gas of the appropriate amount of supply in room 11.
Unstripped gas is organometallic compound, can be suitable for choice for use according to the material of formed barrier films.
As unstripped gas, the silicoorganic compound such as containing silicon can be used.
As such silicoorganic compound, include, for example as follows: hexamethyldisiloxane (HMDSO), 1.1.3.3-tetramethyl disiloxane, vinyl trimethylsilane, tetramethylsilane, hexamethyldisilane, methyl-monosilane, dimethylsilane, trimethyl silane, diethylsilane, Trisilicopropane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, phenyltrimethoxysila,e, Union carbide A-162, octamethylcyclotetrasiloxane, dimethyl disilazane, trimethyldisilazane, tetramethyl-disilazane, pentamethyl-disilazane, hexamethyldisilazane.Among these silicoorganic compound, from the view point of the treatability of compound and the gas barrier property etc. of the barrier films obtained, preferred HMDSO, 1,1,3,3-tetramethyl disiloxane.In addition, these silicoorganic compound, can be used alone one or be used in combination of two or more.In addition, except above-mentioned silicoorganic compound, also the silicon source of the unstripped gas containing silicomethane as formed barrier films can be used.
As film forming gas, except unstripped gas, also use reactant gases.As such reactant gases, the gas that can be suitable for selecting to generate with the metallic element contained by unstripped gas or semimetallic elements by reacting with unstripped gas carbon-free compound of oxide compound, nitride etc. uses.As the reactant gases for the formation of oxide compound, such as, oxygen, ozone can be used.In addition, as the reactant gases for the formation of nitride, such as, nitrogen, ammonia can be used.These reactant gasess can be used alone one or be used in combination of two or more, and such as, when forming oxynitride, the reactant gases for the formation of oxide compound and the reactant gases for the formation of nitride can be combinationally used.
In order to unstripped gas is supplied in vacuum chamber, as required, the part use of carrier gas as film forming gas also can.In addition, in order to make plasma discharge occur, as required, the part use of electric discharge gas as film forming gas also can.As such carrier gas and electric discharge gas, can be suitable for using known, such as, the rare gas of helium, argon, neon, xenon etc. can be used; Hydrogen.
Vacuum pump 18 is for the pressure (vacuum tightness) in watch-keeping cubicle 11.Pressure in room 11, can according to suitable adjustment such as the kinds of unstripped gas, but preferred substrates 2 is 0.1Pa ~ 50Pa by the pressure of the neighborhood loaded.For the object suppressing gas-phase reaction, when plasma CVD adopts low pressure plasma CVD, be generally 0.1Pa ~ 10Pa.In addition, the bulging electrode (Electricity Very De ラ system of plasma producing apparatus) electric power, according to suitable adjustment such as the pressure in the kind of unstripped gas and vacuum chamber, but 0.1 ~ 10kW can be preferably.
Control part 100 exports and controls the control signal that the driving using power supply 14 and gas supply device 17 occurs plasma body.
Fig. 4 is the mode chart that control part 100 is described.As shown in the figure, control part 100 comprises as follows: input part 101; The operational part 102 be connected with input part 101; The signal efferent 103 be connected with operational part 102 and storage part 104.
With regard to input part 101, be by the input unit of the operating condition of plasma body generation power supply 14 and gas supply device 17 input operational part 102.There is the operating condition with power supply 14 and gas supply device 17 in plasma body, according to the thickness of the film that substrate X is formed, the kind of substrate X, the composition of film forming gas etc. of use and changing, is therefore suitable for specifying operating condition.
With regard to operational part 102, use the operating condition inputted from input part 101, draft the control signal of plasma body generation power supply 14 and gas supply device 17, be supplied to signal efferent 103.
With regard to signal efferent 103, it is the interface for exporting control signal, the i.e. control signal of plasma body generation power supply 14 and gas supply device 17 that operational part 102 is drafted respectively.
In addition, from input part 101, the operating condition itself of plasma body generation power supply 14 and gas supply device 17 can be inputted, but also can be stored in advance in storage part 104 for detailed operating condition with the form of question blank etc. and input the appointed information be associated with stored operating condition.Such as, if input " condition 1 ", then draw the operating condition corresponding with condition 1 that storage part 104 stores, if input " condition 2 ", then draw the operating condition corresponding with condition 2 that storage part 104 stores, the information inputting substitute as described also can.Thereby, it is possible to make the input operation of operating condition simplify.
(film formation process)
Then, for using such film deposition system, reaction process during gas barrier property stacked film 1 shown in shop drawings 1 is described.At this, as film forming gas, the mixed gas of HMDSO and oxygen is used to be described.
The first, illustrate and control gas supply device 17 and manufacture the situation of gas barrier property stacked film 1.In this case, export control signal from control part 100 to plasma body generation power supply 14, the electric power that making it possible to film forming gas becomes the degree of plasma body is completely supplied to electrode 13 with certain electric flux.On the other hand, export control signal to gas supply device 17, with at manufacture the first layer 3a with to make HMDSO during second layer 3b different with the ratio of mixture of oxygen.The change of the ratio of mixture of film forming gas, such as, controlled to carry out by the aperture of the valve of the feed rate for each gas of control.
First, in the film formation process of the first layer 3a, export the control signal of ratio of mixture controlling film forming gas from control part 100 to gas supply device 17, its control mode is, the complete oxidation reaching HMDSO in stoichiometry occurs such containing oxygen rate.Such as, make oxygen be the ratio of mixture that 12 times of HMDSO control these gases, in room 11, supply these gas.When using the film forming gas of such ratio of mixture, in the process of plasma CVD, by producing SiO by such reaction shown in following formula 1
2, therefore, it is possible to form the first layer 3a.
[chemical formula 1]
(CH
3)
6Si
2O+12O
2→6CO
2+9H
2O+2SiO
2...(1)
Secondly, in the film formation process of second layer 3b, export the control signal of ratio of mixture controlling film forming gas from control part 100 to gas supply device 17, its control mode is, the complete oxidation reaching HMDSO in stoichiometry cannot occur such hypoxgia containing oxygen rate.Specifically, make oxygen lower than 12 times of HMDSO, so control the ratio of mixture of these gases, in room 11, supply these gas.
In addition, the ratio of mixture of film forming gas, in the film formation process of second layer 3b, according to making to reduce continuously containing oxygen rate to improve until oxygen becomes the mode of 12 times of HMDSO afterwards, continuously, makes it change.If oxygen becomes 12 times of HMDSO, then the film forming of second layer 3b terminates.
When using the film forming gas of such ratio of mixture, in the process of plasma CVD, the SiO generated as carbon compound by such reaction shown in following formula 2
xc
y, therefore, it is possible to form second layer 3b.In formula 2, as an example, reaction formula when oxygen is 9 times of HMDSO is shown.
[chemical formula 2]
(CH
3)
6Si
2O+9O
2→4CO
2+9H
2O+2SiOC…(2)
The second, the situation manufacturing gas barrier property stacked film 1 by controlling plasma body generation power supply 14 is shown.In this case, to gas supply device 17 input control signal, its control mode is, with the complete oxidation of HMDSO in stoichiometry, so certain ratio of mixture supply film forming gas containing oxygen rate occurs.
On the other hand, export control signal from control part 100 to plasma body generation power supply 14, its control mode is, when manufacturing the first layer 3a and second layer 3b, making electric power different and plasma body is occurred.
First, in the film formation process of the first layer 3a, export control signal from control part 100 to plasma body generation power supply 14 according to supplying the mode making the complete oxidation of HMDSO that such electric power occur.In this case, in the process of plasma CVD, complete oxidation occurs, and generates SiO by such reaction shown in above formula 1
2, therefore, it is possible to form the first layer 3a.
Secondly, in the film formation process of second layer 3b, from control part 100 to plasma body generation power supply 14, the mode making the complete oxidation of HMDSO that such electric power (half of the electric power during film forming of such as, the first layer 3a) not occur according to supply exports control signal.In addition, the electric power supplied, in the film formation process of second layer 3b, rises continuously until the mode of such electric power occurs the complete oxidation of supply HMDSO again, makes it change after declining continuously.If make supply electric power increase, until such electric power occurs the complete oxidation of HMDSO, then the film forming of second layer 3b terminates.
In this case, in the process of plasma CVD, such as, by reaction such shown in above formula 2, SiO
xc
ygenerate, therefore, it is possible to form second layer 3b.
In addition, gas supply device 17 and plasma body generation power supply 14 both sides can also be controlled to manufacture gas barrier property stacked film 1.In this case, also by reaction such shown in above formula 1,2, the first layer 3a, second layer 3b can be formed respectively.
In film deposition system 1000 so above, carry out film forming because control part 100 controls operating condition, even if so can manufacture and there is sufficient gas barrier property and the gas barrier property stacked film 1 that also can fully suppress gas barrier property to reduce when film bends.
Further, in the present embodiment, the situation adding up to 3 layers being laminated with the first layer 3a and second layer 3b in film 3 is illustrated, but is not limited to this.By repeating above-mentioned film formation process, such as shown in Figure 5, the gas barrier property stacked film 1 having and make the first layer 3a and the second layer 3b film 3 of stacked (adding up to 5 layers in figure) repeatedly further can be produced.
When such film 3, the composition of multiple second layer 3b can identical, also can be different.In addition, time more than possessing such film 3 and be two-layer, such film 3 can be formed on the surface of the side of base material 2, also can be formed on the surface of the both sides of base material 2.
[the second embodiment]
Fig. 6 is the explanatory view of the film deposition system 2000 of the second embodiment of the present invention.The film deposition system 2000 of present embodiment, has the formation common with film deposition system 1000 part for the first embodiment.Therefore, in the present embodiment, for the symbol that the integrant additional phase common with the first embodiment is same, the detailed description of these integrants is omitted.
Film deposition system 2000 shown in Fig. 6, can transport long base material 2, while in conveyance process film forming continuously.Below, be described successively.
Film deposition system 2000 has as follows: the outlet roller (transport mechanism) 21 sending the base material 2 of the length of wound into rolls; The carrying roller (transport mechanism) 22,23 of conveyance base material 2; The wind up roll (transport mechanism) 24 of winding base material 2.With regard to base material 2, not bend, smooth state is transported above mounting table 12 for it, above mounting table 12, be performed continuously plasma CVD film forming by the process that transports.
Electrode 13 is to be arranged on the below of mounting table 12 towards the mode of mounting table 12, magnetic field generating unit 15 opposed side non-with mounting table 12 in electrode 13 is set up.Gas supply pipe 16 is prolongedly arranged in the mode of cross-section room 11 above mounting table 12.Electrode 13 and plasma body occur, with power supply 14, to form plasma body generating mechanism of the present invention.
Such as, for such electrode 13, the high-frequency electric power of additional some strength, between electrode 13, with the space of periphery, electric field is occurred, thus the plasma body of the film forming gas supplied from gas supply pipe 16 is occurred.Film forming gas is such as that the mode of 9 moles times to 12 moles times of HMDSO is controlled with oxygen.
At this moment, along with the intensity in the magnetic field formed by magnetic field generating unit 15, the discharge plasma of varying strength occurs, above mounting table 12, form the strong region Ji Qiang heating region AR1 of plasma body and weak Ji Ruo heating region, the region AR2 of plasma.At strong heating region AR1, generate SiO by such reaction shown in above formula 1
2, therefore form the first layer 3a.In addition, at weak heating region AR2, generate SiO by such reaction shown in above formula 2
xc
y, therefore form second layer 3b.
With regard to base material 2, the mode passed through at the neighborhood of the strong heating region AR1 so formed and weak heating region AR2 according to it is transported.On a substrate 2, in conveyance process, follow the reaction occurred at each heating region AR1, AR2, be performed continuously film forming.That is, as shown in Figure 7, in the process of conveyance base material 2, strong heating region AR1 by time form the first layer 3a, weak heating region AR2 by time form second layer 3b.So, because strong heating region AR1 and weak heating region AR2 alternately through, so make the first layer 3a and second layer 3b alternately be formed along with conveyance and stacked, and form gas barrier property stacked film 1.
In figure, strong heating region AR1 illustrates 4 places, and weak heating region AR2 illustrates 3 places.Therefore, if use the film deposition system 2000 of present embodiment, then formed gas barrier property stacked film 1, becomes the structure making the alternately laminated total of the first layer 3a and second layer 3b 7 layers.
In film deposition system 2000 so above, make long base material 2 conveyance make it in the different multiple regions of plasma intensity by and carry out film forming at each heating region AR1, AR2.Therefore, there is sufficient gas barrier property and the gas barrier property stacked film 1 of the length that also can fully suppress gas barrier property to reduce when making it bending even if can easily manufacture.
In addition, in film deposition system 2000, during mode film forming film 3 with volume to volume, smooth state can be kept at long base material 2 under, form film 3 continuously.If form film 3 under the state that base material 2 is bending, then when formed gas barrier property stacked film flatly extends, because film inside has residual stress, so easily damaged.But the gas barrier property stacked film formed by the film deposition system 2000 of present embodiment does not have such worry.Therefore, the gas barrier property stacked film of more high-quality can easily and in large quantities be manufactured.
Above, with reference to accompanying drawing, while be illustrated for the mode example of preferred enforcement of the present invention, but the present invention does not limit example for this reason certainly.All shapes of each member of formation in the examples described above and combination etc. be an example just, can carry out various change without departing from the spirit and scope of the invention based on design requirements etc.
Utilizability in industry
Film deposition system provided by the invention and film, even if having sufficient gas barrier property and the gas barrier property stacked film that also can fully suppress gas barrier property to reduce when making film bend, so industrially exceedingly useful owing to manufacturing.
Nomenclature
2 ... base material, 3 ... film, 11 ... vacuum chamber, 13 ... electrode, 14 ... plasma body generation power supply, 15 ... magnetic field generating unit (magnetic field generating means), 17 ... gas supply device, 21 ... outlet roller (transport mechanism), 22,23 ... carrying roller (transport mechanism), 24 ... wind up roll (transport mechanism), 100 ... control part, 1000,2000 ... film deposition system.
Claims (2)
1. a film deposition system, it transports long base material continuously, on one side film forming continuously on the substrate, wherein,
Described film deposition system has:
Vacuum chamber, it accommodates described base material in inside;
Gas supply device, it supplies film forming gas in described vacuum chamber, and this film forming gas contains as the organometallic compound of the raw material of film and the reactant gases that reacts with this organometallic compound;
Carrying device, it transports described base material continuously in described vacuum chamber;
Plasma body generation power supply, it makes discharge plasma occur in the space overlapping with a part for transported described base material;
Field generator for magnetic, it, along the conveyance direction of the described base material in described space, makes magnetic field occur in many places, and makes plasma intensity different in this space;
Control part, it controls two sides of described gas supply device and described plasma body generation power supply, reacted by described organometallic compound and described reactant gases on the substrate and formed: containing the carbon forming described organometallic compound, with metallic element or semimetallic elements and in carbon profile carbon content be the layer of 1 below atom %, this layer reacts further by described organometallic compound and described reactant gases and is formed: containing the carbon forming described organometallic compound, with metallic element or semimetallic elements and carbon profile in fact continuously and at least have an extreme value and the difference of the maximum value of the atomic ratio of carbon and minimum value is the layer of more than 5%,
Described carrying device consists of, and in described space, flatly to be kept by described base material and the neighborhood of neighborhood in the strong Ji Qiang heating region, region of plasma body and the weak Ji Ruo heating region, region of plasma carries out alternately transporting.
2. a film, it transports long base material continuously, while utilize plasma CVD method film forming continuously on the substrate, wherein,
Described film has following operation: the mode that the intensity of discharge plasma is spatially different according to the conveyance direction along described base material makes plasma discharge, according to the mode of the space overlap of the Strength Changes with described discharge plasma make the neighborhood of neighborhood in the strong Ji Qiang heating region, region of plasma body of the described base material of smooth maintenance and the weak Ji Ruo heating region, region of plasma alternately transported
The intensity of described discharge plasma, at the organometallic compound by the raw material as described film, and when carrying out plasma CVD with the reactant gases that this organometallic compound reacts, reacted by described organometallic compound and described reactant gases and formed on the substrate: containing the carbon forming described organometallic compound, with metallic element or semimetallic elements and in carbon profile carbon content be the layer of 1 below atom %, this layer reacts further by described organometallic compound and described reactant gases and is formed: containing the carbon forming described organometallic compound, with metallic element or semimetallic elements and carbon profile in fact continuously and at least there is an extreme value and the difference of the maximum value of the atomic ratio of carbon and minimum value is the discharge plasma intensity of the layer of more than 5%.
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| JP3319164B2 (en) * | 1994-08-01 | 2002-08-26 | 凸版印刷株式会社 | Transparent gas barrier material |
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