JP2005076099A - Method of producing thin film, thin film produced thereby, stacked thin film, transparent plastic film, and organic el element with stacked thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a transparent, highly gas-barrier thin film by a method high in productivity without using a vacuum process, to provide a highly transparent, water vapor-barrier thin film having high surface hardness, a high contact angle and a reduced center line average roughness in the surface, to provide a stacked thin film, to provide a transparent plastic film excellent in adhesion with a plastic base material or the like or using the thin film as a gas barrier layer, and to provide an organic EL (electroluminescence) element with the stacked thin film. <P>SOLUTION: In the method of producing a thin film, reactive gas is fed between opposite electrodes under the atmospheric pressure or under the pressure in the vicinity of the atmospheric pressure, and high frequency voltage is applied so as to convert the reactive gas into an excited state, and a base material is exposed to the reactive gas in the excited state, so that a hydrogenated amorphous silicon carbide thin film having a composition expressed by general formula (1) is deposited: the general formula (1) is SiC<SB>x</SB>:H (wherein, x denotes 1.01 to 2.0). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a thin film having high transparency, excellent water vapor barrier properties, high surface hardness, and high antifouling properties. The present invention also relates to a thin film having high adhesion to a plastic film substrate, a laminated thin film, a transparent plastic film, and an organic EL element with a laminated thin film.

  Conventionally, as a substrate for an electronic display element such as a liquid crystal display element, an organic EL display element, a plasma display or an electronic paper, or a substrate for an electro-optical element such as a CCD or CMOS sensor, or a substrate for a solar cell, thermal stability, transparent Glass has been used because of its high property and low water vapor permeability. However, with the recent popularization of cellular phones or portable information terminals, there has been a demand for lightweight substrates that are flexible and have a high degree of flexibility with respect to relatively heavy glass that is easily broken.

  However, since the substrate using a plastic film (base material) is moisture permeable, it is destroyed especially in the presence of moisture and oxygen, such as an organic electroluminescence display device, and its performance is reduced. It is difficult to apply, and how to seal is a problem.

  In order to suppress such permeation of water vapor and oxygen, it is known to provide a layer (gas barrier film) that suppresses permeation of various gases to the base material. Examples of such a layer include a silicon oxide film, a silicon nitride film, A silicon oxynitride film, a silicon carbide film, an aluminum oxide film, an aluminum oxynitride film, a titanium oxide film, a zirconium oxide film, a boron nitride film, a diamond-like carbon film, and the like are known. A gas barrier film in which these inorganic thin films having high gas barrier properties and a flexible organic thin film are laminated is also known (see, for example, Patent Document 1).

  As a method for forming these inorganic thin films, a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, a sol-gel method, and the like are known.

For example, in Patent Document 2, a SiC film is formed by sputtering at 2 mTorr (about 2.6 × 10 ⁻⁶ atm) to obtain a transparent film for a liquid crystal display. Further, in Patent Document 3, a SiC film is formed under a pressure of 66 Pa (about 6.5 × 10 ⁻⁴ atm) by a plasma CVD method to form a transparent film for a liquid crystal display.

  Thus, since vacuum deposition, sputtering, ion plating, plasma CVD, etc. are formed under vacuum, the apparatus is complicated and large, the productivity is low, and the application of an inorganic oxide thin film ( Coating) was expensive.

On the other hand, as a film forming method that is not a vacuum process, there are a thermal CVD method and a sol-gel method, but the thermal CVD method requires a high film-forming temperature under atmospheric pressure, and the sol-gel method also forms a dense film after film formation. In addition, it was necessary to heat-treat the substrate at 500 ° C. or higher, and it could not be used as a method for forming a film on a plastic substrate having low heat resistance.
International Patent Publication WO00-36665 Specification Japanese Patent Laid-Open No. 10-58585 JP 2003-25476 A

  The purpose of the present invention is to produce a transparent and high gas barrier thin film by a highly productive method without using a vacuum process, and to produce a highly transparent, high water vapor barrier property and surface hardness. Transparent plastic films and laminates that have high contact angle, high contact angle, low surface centerline average roughness and excellent adhesion to thin films, laminated thin films, and plastic substrates, etc., or using these thin films as gas barrier layers An organic EL device with a thin film is provided.

  As a result of intensive studies on the above problems, the present inventors have found that a plasma CVD method can be performed under atmospheric pressure under a specific condition, and a film is formed by the plasma CVD method under the atmospheric pressure. As a material to be used, a silicon carbide-based material has a high gas barrier property, has a good surface hardness and a good contact angle, and has found that the film forming speed is higher than that of the plasma CVD method under vacuum. It came to complete.

  In addition, the description regarding the silicon carbide film in the said patent document is all about a single layer film even if it compares, and there is no description about laminating | stacking the amorphous silicon carbide film from which a composition differs, and the detail of the manufacturing method and characteristic Was not known.

  That is, it has been found that the object of the present invention is achieved by adopting any one of the following [1] to [13].

  [1] A reactive gas is supplied between opposing electrodes under atmospheric pressure or a pressure near atmospheric pressure, and a high-frequency voltage is applied to bring the reactive gas into an excited state, which is based on the reactive gas in the excited state. A method for producing a thin film characterized by forming a hydrogenated amorphous silicon carbide thin film having a composition represented by the following general formula (1) by exposing the material.

General formula (1) SiC _x : H
(In the formula, x represents 1.01 to 2.0.)
[2] the high frequency voltage, an AC voltage in the range of frequencies 1KHz～2500MHz, and thin film according to [1], wherein the supply power is in the range of 1W / cm ² ~50W / cm ² Manufacturing method.

  [3] The thin film according to [1] or [2], wherein the high-frequency voltage is obtained by superimposing an AC voltage in a frequency range of 1 kHz to 1 MHz and an AC voltage in a frequency range of 1 MHz to 2500 MHz. Production method.

[4] A thin film produced by the method for producing a thin film according to any one of [1] to [3] and having a moisture permeability of 1.0 g / m ² / d or less.

  [5] A thin film produced by the method for producing a thin film according to any one of [1] to [3], wherein the surface has a pencil hardness of 4H or more.

  [6] A thin film produced by the method for producing a thin film according to any one of [1] to [3], wherein the contact angle with water on the surface is 80 ° or more.

  [7] A thin film having an average surface roughness of 1.0 nm or less, produced by the method for producing a thin film according to any one of [1] to [3].

  [8] A thin film produced by the method for producing a thin film according to any one of [1] to [3] on a transparent plastic film substrate, or any one of [4] to [7] A transparent plastic film, characterized in that the thin film described is formed.

[9] A reactive gas is supplied between opposing electrodes under atmospheric pressure or a pressure near atmospheric pressure, and a high-frequency voltage is applied to bring the reactive gas into an excited state, which is based on the excited reactive gas. A plurality of hydrogenated amorphous silicon carbide laminated thin films formed by exposing the material, wherein the first hydrogenated amorphous silicon carbide thin film layer closer to the substrate surface is SiC _x : H (x> 1.5), A laminated thin film characterized in that the second hydrogenated amorphous silicon carbide thin film layer formed thereon is SiC _x : H (x <1.5).

  [10] A transparent plastic film, wherein the laminated thin film according to [9] is formed on a transparent plastic film substrate.

  [11] The transparent plastic film according to [8] or [10], wherein the glass transition temperature of the transparent plastic film substrate is 180 ° C. or higher.

  [12] A transparent plastic film, wherein the transparent plastic film substrate according to any one of [8], [10] and [11] is mainly composed of cellulose ester.

  [13] An organic EL device with a laminated thin film, wherein the laminated thin film according to [9] is formed on an organic EL device.

  According to the present invention, a method for producing a transparent thin film having a high gas barrier property by a highly productive method without using a vacuum process, and a high transparency produced thereby, an excellent water vapor barrier property, and a high surface hardness. With a thin film with a high contact angle and a small centerline average roughness on the surface, a laminated thin film, and excellent adhesion to a plastic substrate, or a transparent plastic film using such a thin film as a gas barrier layer, and with a laminated thin film An organic EL element can be provided.

  The present invention will be described in detail below.

  In recent years, in liquid crystal or organic electroluminescence (EL) display devices, electro-optic devices, etc., the use of a substrate using a plastic film (base material) that is flexible, flexible, hard to break, and lighter than glass that is easy to break. It is being considered.

  However, normally produced plastic films have a relatively high moisture permeability and contain moisture inside. For example, when this is used in an organic electroluminescence display device, the moisture is gradually displayed. A problem arises in that the durability of the display device or the like decreases due to the diffusion of moisture into the device and the influence of the diffused moisture.

  In order to avoid this, an attempt has been made to obtain a substrate that can cope with the various electronic devices described above by reducing the moisture permeability by applying a certain process to the plastic film and reducing the moisture content.

  For example, on a plastic film substrate, for example, glass, silicon oxide film, silicon nitride film, silicon oxynitride film, silicon carbide film, aluminum oxide film, aluminum oxynitride film, titanium oxide film, zirconium oxide film having low water vapor permeability Attempts have been made to obtain a composite material in which a thin film such as a boron nitride film or a diamond-like carbon film is formed, and among these, a silicon oxide film is often used.

However, as a result of investigation by the inventors of the present invention, for example, it is difficult to obtain a complete silicon oxide (SiO ₂ ) or silicon nitride (Si ₃ N ₄ ) film. It is a film such as hydrogenated amorphous silicon oxide (a-SiO: H) or hydrogenated amorphous silicon nitride (a-SiN: H). At this time, in the structural defects of these films, a small amount of groups such as Si—OH and Si—NH are present, and these groups are hydrophilic. Therefore, these substituents sequentially adsorb water vapor and repeat diffusion. As a result, it was proved that a high barrier property could not be achieved because the water permeated, though slightly.

  In addition, if it is going to eliminate these structural defects, such as Si-OH and Si-NH, by sintering by heat processing, the high temperature of 1100-1400 degreeC is required, and it applies to the thin film formed on the plastic base material. This is an impossible temperature.

On the other hand, it is known that it is more difficult to obtain completely crystalline silicon carbide. An amorphous structure (hydrogenated amorphous silicon carbide, a-SiC: H) in which silicon carbide is mixed with a small amount of hydrogen as well as silicon oxide and silicon nitride can be obtained relatively easily. This hydrogenated amorphous silicon carbide thin film The structural defects are Si—CH—, Si—CH ₂ —, and Si—CH ₃ groups, which are less likely to condense than Si—OH and the like. In order to eliminate these structural defects by sintering, This is because a very high temperature of 2000 ° C. or higher, which is higher than that of nitride, is required.

  However, when the inventors of the present invention diligently studied, since the functional group forming the structural defect of silicon carbide is hydrophobic, water vapor is not adsorbed even if there is a structural defect site. As a result, the silicon oxide thin film, nitrided It has been found that the moisture permeability can be suppressed lower than that of a silicon thin film, a silicon oxynitride thin film, or the like.

  That is, a hydrogenated amorphous silicon carbide film represented by the following general formula (1) is preferable as the gas barrier film.

General formula (1) SiC _x : H
(In the formula, x represents 1.01 to 2.0.)
In the present invention, a thin film composed of silicon, carbon, and hydrogen and having some structural defects and not crystallized as represented by the general formula (1) is a hydrogenated amorphous silicon carbide (a-SiC). : H) It shall be called a thin film. Further,: H indicates that hydrogen is present as a trace element in the silicon carbide film.

  The ratio of silicon atoms in the amorphous silicon carbide film is analyzed and determined by X-ray photoelectron spectroscopy (also called ESCA or XPS), X-ray microspectroscopy, Auger electron spectroscopy, Rutherford backscattering, or the like. Although these methods cannot measure the proportion of hydrogen atoms, it is presumed that hydrogen atoms are present in the film in a certain proportion other than the silicon carbide film where x = 1.0.

  In general formula (1), the smaller x, the smaller the number of structural defects, and the complete silicon carbide is obtained when x = 1.0. However, the complete silicon carbide has a narrow band gap (2.2 to 2.9 eV), coloring of the thin film occurs unfavorably. Further, when x> 2.0 or more, there are too many defects in the thin film, the network structure becomes sparse, and the gas barrier property is lowered, which is not preferable.

  Since the silicon carbide thin film is hydrophobic as described above, it has a higher contact angle than silicon oxide and silicon nitride, so that it is difficult for dirt to adhere to the surface, and it has excellent antifouling properties and also has a high surface hardness. It is also useful as a film for protecting a plastic substrate.

  In addition, it is not necessary to achieve each physical property with a single layer of hydrogenated amorphous silicon carbide film. By stacking multiple layers of hydrogenated amorphous silicon carbide thin films with different properties, a hydrogenated amorphous silicon carbide thin film with the desired performance can be obtained. May be.

  In particular, since the soft layer also acts as a stress relaxation layer, a laminated structure consisting of a soft layer and a hard layer prevents cracks from occurring in the entire layer even if the plastic film as the support is folded. Since it has an effect of preventing a decrease in gas barrier properties, it is a gas barrier multilayer thin film according to a preferred embodiment.

  In the general formula (1), if the value of x is large, that is, if x> 1.5, a relatively soft hydrogenated amorphous silicon carbide thin film can be obtained, and conversely, the value of x is small, that is, x If <1.5, a relatively hard thin film can be formed.

  As a preferred example of laminating such a gas barrier hydrogenated amorphous silicon carbide thin film, for example, the layer in contact with the base material has a soft structure for adhesion, and then the base material has gas barrier property. There is a laminated thin film having a hard structure layer (thin film), a soft layer (thin film) as a stress relaxation layer, and a hard structure layer as a gas barrier layer and a hard coat layer.

  In this way, a laminated thin film having a structure in which a soft layer is first laminated on a substrate surface, and a hard layer is laminated thereon to form a set, and further, according to required performance, one or more layers of thin films having this combination are laminated. Is a preferred embodiment. In other words, the first and second laminated hydrogenated amorphous silicon carbide thin film layers described in claim 9 include a laminated thin film having a combination of a plurality of thin films having this combination. Needless to say.

  Or it is good also as a laminated thin film made into the structure which provided the soft layer which has water repellency as the outermost layer on it.

  As described above, the hydrogenated amorphous silicon carbide film may be either a single layer or a laminate of two or more layers, but the total thickness of the entire film is 10 μm or less in terms of maintaining flexibility and resistance to bending. preferable.

  The thickness of each layer is preferably 500 nm or less because if the thickness is large, the stress cannot be relieved when bending stress is applied and cracks occur. More preferably, it is 200 nm or less.

[Formation of thin film]
Next, a method for forming the hydrogenated amorphous silicon carbide film will be described.

  Known methods for obtaining a silicon carbide film include a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, and the like.

  However, as described above, the film formation method that can be achieved by changing the physical properties of the hydrogenated amorphous silicon carbide film by freely changing the layer configuration without changing the raw material for film formation is a chemical vapor deposition method ( In the case of physical vapor deposition (PVD) such as vapor deposition, sputtering, ion plating, etc., the target that is the raw material is changed in order to deposit films with different properties in the same chamber. It is difficult to change the layer structure. Moreover, since these are vacuum processes, productivity is low and is not preferable.

  Therefore, a plasma CVD method is preferable as a film forming method capable of producing a laminated thin film. In the plasma CVD method, it is possible to change the physical properties of the silicon carbide film generated depending on the temperature of the substrate to be formed, the power supplied to the plasma, and the frequency. The higher the temperature, the higher the electric field of high power and high frequency, the harder the gas barrier property (small x), and the softer the film is formed at low temperature or the electric field of low power and low frequency. A film having a high contact angle (large x) can be formed.

  However, in known patent documents, for example, Japanese Patent Application Laid-Open Nos. 11-22710 and 2003-25476, and in the known document Journal of Applied Polymer Science, P1445 (vol. 86, 2002), plasma is used under reduced pressure close to vacuum. The CVD method is implemented.

  However, as a result of investigations by the inventors, it has been found that the plasma CVD method is possible even at a gas pressure near or at atmospheric pressure under specific conditions. Compared with the plasma CVD method under vacuum, the plasma CVD method near atmospheric pressure not only requires high pressure and high productivity, but also has the effect that the film forming speed is high because the plasma density is high. As a result, it was found that the film forming method is superior to the plasma CVD method under vacuum.

  Further, the hydrogenated amorphous silicon carbide film obtained by the plasma CVD method under atmospheric pressure has a smaller centerline average surface roughness (Ra) than the hydrogenated amorphous silicon carbide film obtained by the plasma CVD method under vacuum. The surprising effect of obtaining a film was revealed. Although the details are unknown, it is presumed that the plasma density is high and high energy is applied, and the collision frequency between vapor phase grown particles is high.

  When the center line average roughness of the hydrogenated amorphous silicon carbide film is small, for example, when a transparent conductive film or the like is provided on this layer, a transparent conductive film having a uniform film thickness can be formed, and transparent with low surface resistance. A conductive film can be formed.

  Hereinafter, a method for forming a film made of hydrogenated amorphous silicon carbide using a plasma CVD method using an organic silicon compound as a reactive gas at or near atmospheric pressure will be described in detail.

  A plasma film forming apparatus used in the method for forming a hydrogenated amorphous silicon carbide film of the present invention will be described with reference to FIGS. In the figure, symbol F is a long film as an example of a substrate.

  The discharge plasma treatment preferably used in the present invention is performed at or near atmospheric pressure. The vicinity of atmospheric pressure represents a pressure of 20 kPa to 110 kPa, and more preferably 93 kPa to 104 kPa.

  FIG. 1 shows an example of a plasma discharge treatment chamber provided in a plasma film forming apparatus. In the plasma discharge treatment chamber 10 of FIG. 1, the film-like substrate F is conveyed while being wound around a roll electrode 25 that rotates in the conveyance direction (clockwise in the figure). The plurality of fixed electrodes 26 fixed around the roll electrode 25 are each formed of a cylinder, and are installed facing the roll electrode 25.

  The discharge vessel 11 constituting the plasma discharge treatment chamber 10 is preferably a treatment vessel made of Pyrex (R) glass, but a metal vessel can be used as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation.

  The substrate F wound around the roll electrode 25 is pressed by the nip rollers 15 and 15, is regulated by the guide roller 24, is transported to the discharge treatment space secured inside the discharge vessel 11, is subjected to discharge plasma treatment, and then It is conveyed to the next process via the nip roller 16 and the guide roller 27. In the present invention, since a film can be formed by discharge treatment under a pressure close to atmospheric pressure instead of a vacuum system, such a continuous process is possible, and high productivity can be increased.

  In addition, the partition plates 14 and 14 are disposed in the vicinity of the nip rollers 15, 15, or 16 to suppress the air accompanying the base material F from entering the discharge vessel 11. The entrained air is preferably suppressed to 1% by volume or less, more preferably 0.1% by volume or less, with respect to the total volume of the gas in the discharge vessel 11. This can be achieved by the nip rollers 15 and 16.

  The mixed gas used for the discharge plasma treatment is introduced into the discharge vessel 11 from the air supply port 12, and the treated gas is exhausted from the exhaust port 13.

  The roll electrode 25 is a ground electrode, and is discharged between a plurality of fixed electrodes 26 that are application electrodes. A reactive gas as described above is introduced between the electrodes to form a plasma state and is wound around the roll electrode 25. A film derived from a reactive gas is formed by exposing the rotated long film-like base material to the reactive gas in the plasma state.

  Between the electrodes, it is preferable to supply a certain amount of electric power at a high frequency voltage in order to obtain a high plasma density, increase the film forming speed, and control the carbon content within a predetermined ratio. Specifically, it is preferable to apply a high frequency voltage of 1 kHz to 2500 MHz, and further superimpose a voltage of any frequency between 1 kHz and 1 MHz and a voltage of any frequency between 1 MHz and 2500 MHz. More preferably, it is applied.

The lower limit value of the power supplied between the electrodes is preferably 0.1 W / cm ² or more and 50 W / cm ² or less, and more preferably 0.5 W / cm ² or more. In addition, when a voltage having a frequency of 1 kHz to 1 MHz and a voltage having a frequency of 1 MHz to 2500 MHz are superimposed, the voltage of 1 MHz to 2500 MHz is preferably smaller than the voltage having a frequency of 1 kHz to 1 MHz. The voltage is preferably 20% to 80%. The voltage application area (cm ² ) in the electrode is the area where discharge occurs.

  The high-frequency voltage applied between the electrodes may be an intermittent pulse wave or a continuous sine wave, but a sine wave is preferable because the film forming speed increases.

  Such an electrode is preferably a metal base material coated with a dielectric. At least one of the fixed electrode 26 and the roll electrode 25 is coated with a dielectric, and preferably both are coated with a dielectric. The dielectric is preferably an inorganic substance having a non-dielectric constant of 6 to 45.

  The shortest distance between the solid dielectric and the electrode when a solid dielectric is placed on one of the electrodes 25 and 26, and the distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes are either case. From the viewpoint of performing uniform discharge, 0.3 mm to 20 mm is preferable, and 1 mm ± 0.5 mm is particularly preferable. The distance between the electrodes is determined in consideration of the thickness of the dielectric around the electrodes and the magnitude of the applied voltage.

  In addition, when the substrate is placed between the electrodes or transported between the electrodes and exposed to plasma, not only is the roll electrode specification that allows the substrate to be transported in contact with one of the electrodes, but also the dielectric surface is polished. By finishing and making the surface roughness Rmax (JIS B 0601) of the electrode 10 μm or less, the thickness of the dielectric and the gap between the electrodes can be kept constant, and the discharge state can be stabilized. Furthermore, the durability can be greatly improved by eliminating the distortion and cracking due to the difference in thermal shrinkage and residual stress of the dielectric and coating the non-porous high-precision inorganic dielectric.

  In addition, in manufacturing electrodes with a dielectric coating on a metal base material, as described above, it is necessary to polish the dielectric and to minimize the difference in thermal expansion between the metal base material of the electrode and the dielectric. Therefore, it is preferable to line the inorganic material on the surface of the base material by controlling the amount of bubbles mixed as a layer capable of absorbing stress. In particular, the material is preferably a glass obtained by a melting method known as cocoon, and the amount of bubbles mixed in the lowermost layer in contact with the conductive metal base material is 20-30% by volume, and the subsequent layers are 5% by volume. By setting it as the following, the favorable electrode which does not generate | occur | produce dense and a crack will be made.

  As another method for coating the base material of the electrode with a dielectric, ceramic spraying is performed precisely to a porosity of 10 vol% or less, and further, a sealing treatment is performed with an inorganic material that is cured by a sol-gel reaction. It is done. Here, in order to promote the sol-gel reaction, heat curing or UV curing is good. Further, when the sealing liquid is diluted, and coating and curing are repeated several times in succession, the mineralization is further improved and a dense electrode without deterioration. Can do.

  2A and 2B show roll electrodes 25c and 25C as an example of the roll electrode 25. FIG.

  As shown in FIG. 2 (a), the roll electrode 25c, which is an earth electrode, is formed by applying a ceramic-coated dielectric 25b that has been subjected to sealing treatment with an inorganic material after thermal spraying ceramics on a conductive base material 25a such as metal. It is composed of a coated combination. A ceramic coated dielectric is coated with 1 mm, and the roll diameter is manufactured to be 200 mm after coating, and grounded as a ground. As the ceramic material used for thermal spraying, alumina, silicon nitride or the like is preferably used. Among these, alumina is more preferably used because it is easy to process.

  Or you may comprise from the combination which coat | covered the lining process dielectric material 25B which provided the inorganic material by lining to 25 A of conductive base materials, such as a metal, like the roll electrode 25C shown in FIG.2 (b). As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, and vanadate glass are preferably used. Of these, borate glass is more preferred because it is easy to process.

  Examples of the conductive base materials 25a and 25A such as metal include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing. In this embodiment, the base material of the roll electrode is a stainless steel jacket roll base material having a cooling means with cooling water (not shown).

  Further, the roll electrodes 25c and 25C (same for the roll electrode 25) are configured to be rotationally driven around the shaft portions 25d and 25D by a drive mechanism (not shown).

  FIG. 3A shows a schematic perspective view of the fixed electrode 26. Further, the fixed electrode is not limited to a cylindrical shape, but may be a prismatic type like the fixed electrode 36 of FIG. Compared to the cylindrical electrode 26, the prismatic electrode has an effect of extending the discharge range, and is therefore preferably used according to the properties of the film to be formed.

  Any of the fixed electrodes 26 and 36 has the same structure as the roll electrode 25c and the roll electrode 25C described above. That is, the surroundings of the hollow stainless steel pipes 26a and 36a are covered with the dielectrics 26b and 36b in the same manner as the roll electrodes 25 (25c and 25C), and cooling with cooling water can be performed during discharge. The dielectrics 26b and 36b may be either ceramic-coated dielectrics or lining dielectrics.

  The fixed electrodes are manufactured so as to have 12φ or 15φ after coating with the dielectric, and the number of the electrodes is set, for example, 14 along the circumference of the roll electrode.

  FIG. 4 shows a plasma discharge treatment chamber 30 in which the rectangular fixed electrode 36 of FIG. 3B is disposed around the roll electrode 25. In FIG. 4, the same members as those in FIG.

  FIG. 5 shows a plasma film forming apparatus 50 provided with the plasma discharge processing chamber 30 of FIG. In FIG. 5, in addition to the plasma discharge treatment chamber 30, a gas generator 51, a power source 41, an electrode cooling unit 55, and the like are arranged as an apparatus configuration. The electrode cooling unit 55 includes a tank 57 containing a coolant and a pump 56. As the coolant, an insulating material such as distilled water or oil is used.

  The gap between the electrodes in the plasma discharge processing chamber 30 of FIGS. 5 and 4 is set to about 1 mm, for example.

  The roll electrode 25 and the fixed electrode 36 are arranged at predetermined positions in the plasma discharge treatment chamber 30, the flow rate of the mixed gas generated by the gas generator 51 is supplied from the air supply port 12, and the inside of the discharge vessel 11 is supplied. It is filled with a mixed gas used for plasma processing, and unnecessary portions are exhausted from an exhaust port.

  Next, a voltage is applied to the fixed electrode 36 by the power source 41, and the roll electrode 25 is grounded to the ground to generate discharge plasma. Here, the base material is supplied from the roll-shaped original winding base material FF through the rolls 54, 54, 54, and the electrodes in the plasma discharge treatment chamber 30 are brought into one-side contact with the roll electrode 25 through the guide roll 24. It is conveyed in the state. At this time, the surface of the substrate F is subjected to a discharge treatment by the discharge plasma, and then conveyed to the next step via the guide roll 27. Here, the substrate F is subjected to discharge treatment only on the surface not in contact with the roll electrode 25.

  Moreover, in order to suppress the bad influence by the high temperature at the time of discharge, the temperature of a base material is normal temperature (15 to 25 degreeC)-less than 250 degreeC, More preferably, electrode cooling is carried out so that it may be suppressed within normal temperature-200 degreeC. Cool by unit 55.

  FIG. 6 shows a plasma film forming apparatus 60 that can be used in the film forming method of the present invention, where the film cannot be placed between electrodes, for example, a film is formed on a thick substrate 61. In addition, a reactive gas that has been in a plasma state is jetted onto a substrate to form a thin film. Also in the case of forming on a non-planar substrate such as a lenticular lens, a Fresnel lens, or a cylinder, such a film formation method by the plasma jet method is preferable.

  In the plasma film-forming apparatus of FIG. 6, 35a is a dielectric, 35b is a metal base material, and 65 is a power source. A mixed gas composed of an inert gas and a reactive gas is introduced from above into a slit-like discharge space in which a metal base material 35b is coated with a dielectric 35a, and a high frequency voltage is applied by a power source 65 to plasma the reactive gas. Then, a film is formed on the surface of the substrate 61 by injecting the reactive gas in the plasma state onto the substrate 61.

  The power source of the plasma film forming apparatus used for forming the film of the present invention, such as the power source 41 of FIG. 5 and the power source 65 of FIG. 6, is not particularly limited, but is a high frequency power source (3 kHz) manufactured by Shinko Electric Co., Ltd. (5 kHz), Shinko Electric High Frequency Power Supply (15 kHz), Shinko Electric High Frequency Power Supply (50 kHz), HEIDEN Laboratory High Frequency Power Supply (continuous mode use, 100 kHz), Pearl Industrial High Frequency Power Supply (200 kHz), Pearl Industrial High Frequency Power Supply (800 kHz), Pearl Industrial High Frequency Power Supply (2 MHz), JEOL High Frequency Power Supply (13.56 MHz), Pearl Industrial High Frequency Power Supply (27 MHz), Pearl Industrial High Frequency Power Supply (150 MHz), and the like can be used. Alternatively, a power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used. Two or more frequencies may be superimposed and used. As a preferable combination at that time, it is preferable to superimpose a power source of 1 kHz to 1 MHz and a power source of 1 MHz to 2500 MHz.

[Thin film forming material]
Next, a preferable raw material for obtaining a hydrogenated amorphous silicon carbide film will be described. As a raw material for the hydrogenated amorphous silicon carbide film, silane gas (SiH ₄ ) and methane gas (CH ₄ ) may be mixed and used. However, since methane gas and silane gas are explosive and difficult to handle, the following general formula (2 An organosilicon compound represented by

General formula (2) Si _p C _q H _r
(In the formula, p, q and r are each a positive integer.)
If there are elements other than Si, C and H in the raw material compound, they are often mixed in the resulting thin film, and especially oxygen and nitrogen are defects such as Si—OH and Si—NH ₂ as described above. Since it becomes a structure and rather allows moisture to pass through, it is preferably not included in the compound as a raw material.

  Examples of such compounds are allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyl Trimethylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, and the like are preferable. Particularly preferred are tetramethylsilane and hexamethyldisilane.

  These compounds may be in the state of gas, liquid, or solid at normal temperature and pressure, but in the case of gas, they can be introduced into the discharge space as they are, but in the case of liquid or solid, heating, bubbling, decompression Vaporized by means such as ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

  Furthermore, in order to adjust the carbon and hydrogen content in the film, hydrogen gas or the like may be mixed into the mixed gas as described above. Nitrogen gas and / or periodic table Group 18 atoms, specifically helium, neon, argon, krypton, xenon, radon, etc., particularly helium and argon are preferably used, but an inert gas is mixed and a plasma discharge generator (plasma) is mixed as the mixed gas. The film is formed by supplying to the generator. Although the ratio of the inert gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the inert gas being 90.0 to 99.9% with respect to the entire mixed gas.

  The film thickness of the hydrogenated amorphous silicon carbide film according to the present invention can be adjusted by increasing the plasma treatment time, increasing the number of treatments, or increasing the partial pressure of the organometallic compound in the mixed gas. .

  As a method of laminating hydrogenated amorphous silicon carbide films having different carbon contents by atmospheric pressure plasma CVD, for example, a substrate is transported in the plasma discharge treatment chamber of FIG. 1 and a plurality of plasma discharge treatment chambers shown in FIG. 1 are prepared, the substrate is transported, and each of them is transferred. A method of providing a plurality of layers one layer each time it passes, a method in which a substrate is passed through a plurality of plasma discharge processing apparatuses, the top and the bottom of the substrate are connected, and the layers are provided in each plasma discharge processing apparatus multiple times. The method of performing etc. are mentioned.

[Plastic substrate]
The plastic substrate (resin substrate) for forming the hydrogenated amorphous silicon carbide thin film of the present invention is not particularly limited as long as it is substantially transparent. Specifically, polyesters such as polyethylene terephthalate and polyethylene naphthalate, Cellulose esters such as polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, and cellulose nitrate, or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl Alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, polyether Rusuruhon, polysulfones, polyether ketones, polyamide, fluorine resin, nylon, polymethyl methacrylate, acrylic or polyarylates, or can be exemplified organic-inorganic hybrid resins and the like of these resins and silica.

  However, hydrogenated amorphous silicon carbide films deposited by atmospheric pressure plasma CVD have higher gas barrier properties at higher film forming temperatures and are subjected to various heating processes such as the formation of transparent conductive films as transparent supports for displays. Therefore, the resin forming the hydrogenated amorphous silicon carbide film preferably has high heat resistance.

  As the heat resistance, the glass transition temperature is preferably 180 ° C. or higher. Resin base materials that satisfy these conditions include some polycarbonates, some cycloolefin polymers, polyethersulfone, polyetheretherketone, polyimide, fluororesin, diacetylcellulose, triacetylcellulose, and these resins And organic-inorganic hybrid resin of silica and the like.

  In addition, as a method of measuring the glass transition temperature of the resin base material, it can be measured by DSC (differential scanning calorimetry), TMA (thermal stress strain measurement), DMA (dynamic viscoelasticity measurement) and the like.

  Of these, diacetylcellulose, triacetylcellulose, and organic-inorganic hybrid resins of silica and silica having high transparency, low birefringence, and positive birefringence wavelength dispersion characteristics are preferable.

  An organic-inorganic hybrid resin (or called an organic-inorganic polymer composite or the like) is a material in which an organic polymer and an inorganic compound are combined to give both characteristics. By using a method of synthesizing an inorganic substance to be mixed with an organic polymer from a liquid state such as a metal alkoxide (referred to as a sol-gel method), the inorganic fine particles to be generated are nanoscale below the wavelength of visible light (up to about 750 nm). Thus, it is possible to disperse in an organic substance, and a material which is optically transparent and has high heat resistance can be obtained.

  In the present invention, since the resin substrate is directly exposed to the plasma atmosphere, it may have an undercoat layer on one side or both sides as a plasma etching layer or a hard coat layer. As a specific example of the undercoat layer, Examples thereof include an organic layer formed by polymer application. As the organic layer, for example, a film obtained by performing post-treatment on an organic material film having a polymerizable group by means such as ultraviolet irradiation or heating can be used.

[Application of thin film]
In addition, the hydrogenated amorphous silicon carbide film according to the present invention has high gas barrier properties, high surface hardness, and high water repellency. Therefore, in addition to the transparent plastic film for display, it is suitable for articles that require these characteristics. Such performance can be imparted by film formation.

  An organic electroluminescence (EL) element is one that requires high gas barrier properties. Since organic EL elements are sensitive to moisture, sealing is necessary. The hydrogenated amorphous silicon carbide film of the present invention can also be used as a film for sealing these elements.

  Note that an organic electroluminescence element (also referred to as an organic EL element) has a structure in which a light emitting layer is held between a pair of electrodes of an anode and a cathode. Specifically, it refers to a layer containing an organic compound that emits light when an electric current is passed through an electrode composed of a cathode and an anode. Since the cathode and the light emitting layer are vulnerable to moisture, after forming the organic EL element, the cathode side sealing film is sealed directly in the form of a cathode or with an epoxy resin or the like, and further on the hydrogen of the present invention. By forming the amorphous silicon carbide film, moisture permeation can be suppressed, moisture resistance of the organic EL display device can be further improved, generation and growth of dark spots can be suppressed, and a long-life organic EL element Can be obtained.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 (single layer thin film)
A diacetylcellulose film having a thickness of 80 μm was formed, a hard coat layer was formed thereon, and a hydrogenated amorphous silicon carbide film was further formed thereon under the conditions described in Table 1. The obtained thin film-coated plastic film samples were evaluated according to the following items and criteria.

<Film formation of diacetyl cellulose film>
Into the mixing tank, 60 parts by mass of ethanol, 685 parts by mass of methylene chloride, and 100 parts by mass of diacetylcellulose were added and dissolved by stirring while heating at 80 ° C.

  The obtained dope (dissolved solution) was cast using a band casting machine, and when the residual solvent amount reached 50%, it was peeled off from the band and immediately transported to a tenter, followed by 30% in the TD direction. After stretching 30% in the MD direction, it was dried at 120 ° C. to obtain a diacetylcellulose film. The film thickness was adjusted so as to be finally 80 μm.

  In addition, it was 203 degreeC when the glass transition temperature of the obtained diacetylcellulose film was measured with TMA (thermal-stress distortion measuring apparatus).

<Preparation of clear hard coat layer>
On the obtained diacetylcellulose film, the following hard coat layer coating composition was coated with an extrusion coater so as to have a film thickness of 3 μm, then dried in a drying section set at 80 ° C. for 1 minute, and then 120 mW / cm. It was formed by irradiating with ultraviolet rays at ² .

The water vapor permeability of the diacetylcellulose film provided with this clear hard coat layer was 840 g / m ² / d.

<Clear hard coat layer coating composition>
Dipentaerythritol hexaacrylate monomer 60 parts by weight Dipentaerythritol hexaacrylate dimer 20 parts by weight Dipentaerythritol hexaacrylate trimer or higher component 20 parts by weight Dimethoxybenzophenone 4 parts by weight Ethyl acetate 50 parts by weight Methyl ethyl ketone 50 parts by mass Isopropyl alcohol 50 parts by mass <Formation of hydrogenated amorphous silicon carbide film>
The formation of the silicon carbide film by atmospheric pressure plasma CVD is performed using the plasma discharge treatment chamber 30 shown in FIG. 4, respectively, and plasma generation is performed using a high frequency power supply JRF-10000 manufactured by JEOL Ltd. as a power supply of 13.56 MHz, Further, PHF-2k manufactured by HEIDEN LABORATORY is used as a power source of 100 kHz, hexamethyldisilane is used as a raw material for the hydrogenated amorphous silicon carbide film, and a film having the following constitution is fed into the discharge space at 20 slm and 25 ° C. Went. The discharge gas types and other discharge conditions are shown in Table 1.

  In each condition, first, a calibration curve of film formation time and film thickness was created to calculate a film formation speed, and film formation was performed so that the film thickness was 100 nm. The film thickness was measured using FE3000 manufactured by Otsuka Electronics Co., Ltd.

Discharge gas: Helium, argon, or nitrogen 99.3% by volume
Cracked gas: 0.5% by volume of hydrogen
Source gas: Hexamethyldisilane 0.2% by volume
Note that the film forming condition J of the comparative example is that the pressure of the plasma discharge treatment chamber is reduced to 1.9 mPa using a vacuum pump with reference to Example 2 of Japanese Patent Laid-Open No. 2003-25476, and then the gas having the following configuration is used. A vacuum plasma treatment was performed by sending the gas into the discharge space at a gas pressure of 66 Pa at 25 ° C.

Decomposition gas: Helium 95.0% by volume
Source gas: Hexamethyldisilane 5.0% by volume
<Composition analysis>
The ratio of silicon and carbon was measured using an X-ray photoelectron spectroscopy analyzer (ESCA) manufactured by VG Scientific.

<Water vapor permeability test>
Based on JIS K7129, measurement was performed with a Model 7000 manufactured by Illinois Instruments. The measurement limit of this device is 0.005 g / m ² / d.

<Measurement of surface hardness>
The surface hardness was measured according to the pencil hardness method test described in JIS K5400. Evaluation was represented by the hardness of a pencil lead, 9H-2B.

<Measurement of contact angle>
About each sample, the contact angle with respect to the water of the hydrogenated amorphous silicon carbide film | membrane was measured in 23 degreeC and 55% of environment using the contact angle meter CA-W by Kyowa Interface Science Co., Ltd. In addition, the measurement was performed at 10 locations at random and the average value was obtained.

<Measurement of centerline average surface roughness>
A scanning electron micrograph was taken of the surface of the silicon carbide film using JSM6100 manufactured by JEOL Ltd., and the center line average surface roughness Ra was calculated.

  As can be seen from Table 1, the deposition rate of the SiC film does not change significantly under discharge conditions such as applied voltage and applied frequency, but varies greatly depending on the conditions of the discharge gas. Film formation conditions A to G under atmospheric pressure were 5 to 6 times faster than the film formation speed under film formation condition H under reduced pressure. This is presumed to be because the plasma conditions under atmospheric pressure have a higher plasma density. Further, it can be seen that the film forming conditions H and I using nitrogen gas instead of rare gas such as He and Ar as discharge gas species are faster (about 10 times faster than discharge under reduced pressure He). In particular, the condition of I in which voltages of two frequencies of 100 KHz and 13.56 MHz were superimposed was the fastest. This is presumed to be caused by differences in discharge gas due to differences in ion and radical energy and generation density in plasma depending on each discharge gas.

Further, between the chemical composition of the film formed and the moisture permeability, a tendency is seen that the moisture permeability becomes smaller as the film has less carbon. It is 0 g / m ² / d or less, which shows that it has a good gas barrier property.

  Similarly, the chemical composition, contact angle, and surface hardness of the formed film are also correlated, and the film with less carbon has a lower contact angle and higher surface hardness, and the film with more carbon has a higher contact angle and lower surface hardness. The tendency was seen.

  As for the surface roughness, the film forming conditions of the present invention clearly show higher smoothness from the comparison of the film forming conditions A to I of the present invention and the film forming condition J of the comparative example under reduced pressure. ing.

  As described above, according to the discharge conditions of the present invention, a film with controlled surface hardness and contact angle can be produced while maintaining a high film-forming speed and high gas barrier property, and a film with high surface smoothness can be obtained. The effect of being obtained.

Example 2 (Laminated thin film)
The total film thickness is obtained by continuously forming the film forming condition A in which the soft film is obtained in Example 1 and the film forming condition F in which the hard film is obtained alternately with the film thickness as shown in Table 2. Transparent plastic films (hereinafter abbreviated as “transparent laminated film”) 201 to 206 each having a laminated thin film of hydrogenated amorphous silicon carbide having a thickness of about 200 nm were formed.

  Moreover, the transparent laminated film 207 of the comparative example was produced according to the content of WO00-36665 specification.

<Transparent laminated film 207 of comparative example>
A clear hard coat layer having a thickness of 3 μm was formed on a diacetyl cellulose film having a thickness of 80 μm according to the method described above, and a gas barrier layer was formed on the clear hard coat layer according to the method described in WO 00/36665. The film was formed.

  A polymethylmethacrylate (PMMA) oligomer was introduced into the vacuum deposition apparatus from the introduction nozzle and deposited, and then removed from the vacuum deposition apparatus and polymerized by irradiation with ultraviolet rays in a dry nitrogen stream to form a PMMA film. . The thickness of the PMMA film was adjusted to 50 nm. On this film, a silicon oxide film was formed to a thickness of 50 nm by an RF sputtering method (frequency: 13.56 MHz) using silicon oxide as a sputtering target. Further, the PMMA film and the silicon oxide film were each formed to a thickness of 50 nm to form a total of four layers (200 nm thickness) to form a transparent laminated film 207 of a comparative example.

  The obtained transparent laminated films 201 to 207 were subjected to moisture permeability measurement and a cross cut test.

<Cross-cut test>
A cross-cut test based on JIS K5400 was performed. On the surface of the thin film formed, 11 single-edged razor blades with 90 ° cuts with respect to the surface were placed 11 by 1 mm vertically and horizontally, and 100 1 mm square grids were produced. A commercially available cellophane tape was affixed on this, and one end of the tape was peeled off vertically by hand, and the ratio of the area where the thin film was peeled to the affixed tape area from the score line was evaluated according to the following rank.

A: not peeled off at all B: peeled area ratio was less than 10% C: peeled area ratio was 10% or more

  First, when the films of film forming conditions A and F are compared in Example 1 (100 nm thickness) and Example 2 (200 nm thickness), no improvement in gas barrier properties is observed even when the film thickness is increased. It can be seen that simply increasing the film thickness does not reduce the water vapor transmission rate, but if the film thickness exceeds a certain level, the effect of reducing the water vapor transmission rate reaches its peak.

  On the other hand, when the total film thickness was constant (about 200 nm) and the number of layers was increased to 1, 2, 4, 6, and 8, the moisture permeability was reduced as the number of layers increased, and an effective gas barrier layer. there were. The transparent laminated film 207 of the comparative example also had good gas barrier properties, but the moisture permeability was an order of magnitude larger than that of the transparent laminated film 204 of the present invention having the same number of layers (4 layers).

  Further, the film adhesion of the film was inferior to that of the transparent laminated film 207 of the comparative example and the single film (film of transparent laminated film 201 of the present invention) having a high film forming condition A, but the film 202 of the present invention. ~ 206 had good adhesion.

Example 3 (Preparation of organic EL device)
Organic EL elements were produced on the transparent laminated films 201 to 206 of the present invention produced in Example 2 and the transparent laminated film 207 of the comparative example.

<Film formation of transparent conductive film>
FIG. 7 shows a cross-sectional view of the configuration of the organic EL display device manufactured. First, using the transparent laminated films 201 to 207 produced in Example 2 as the transparent substrate 1, a mixture of indium oxide and zinc oxide (In atomic ratio as a sputtering target on the surface side having a hydrogenated amorphous silicon carbide film). Using a sintered body made of In / (In + Zn) = 0.80), an IZO (Indium Zinc Oxide) film, which is a transparent conductive film, was formed by a DC magnetron sputtering method. That is, the inside of the vacuum apparatus of the sputtering apparatus is depressurized to 1 × 10 ⁻³ Pa or less, and a mixed gas of 1000: 2.8 in terms of volume ratio of argon gas and oxygen gas is 1 × 10 ⁻¹ Pa inside the vacuum apparatus. Then, an IZO film having a thickness of 250 nm was formed as a transparent conductive film by a DC magnetron method at a target applied voltage of 420 V and a substrate temperature of 60 ° C. After patterning this IZO film to make the anode (anode) 2, the transparent support substrate provided with this transparent conductive film is ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. It was.

<Formation of organic EL element>
On the obtained transparent conductive film, the deposition rate of α-NPD layer (film thickness 25 nm), CBP and Ir (ppy) ₃ as the organic EL layer 3 in FIG. 7 by a vacuum deposition method through a square perforated mask. A co-deposited layer (film thickness of 35 nm), a BC layer (film thickness of 10 nm), an Alq ₃ layer (film thickness of 40 nm), and a lithium fluoride layer (film thickness of 0.5 nm) of 100: 6 were sequentially laminated (FIG. 7 (not shown in detail in FIG. 7), a cathode (cathode) 4 made of aluminum having a thickness of 100 nm was formed through a mask on which another pattern was formed.

<Sealing>
The laminated body thus obtained is brought into close contact with the transparent laminated films 201 to 207 as described above as the substrate 5 in FIG. 7 in a dry nitrogen stream so that the hydrogenated amorphous silicon carbide film side is aligned, and the periphery is photo-curing type bonded. The organic EL elements (OLED) 301 to 307 were obtained by sealing with an agent (Lux Track LC0629B manufactured by Toagosei Co., Ltd.).

  Although not shown in FIG. 7, each of the transparent electrode and the aluminum cathode can be taken out as a terminal.

  The following evaluation was performed about the light emission part of these organic EL elements.

<Evaluation item 1>
Immediately after encapsulation, a 50x magnified photograph was taken. After storage at 80 ° C. for 300 hours, 50 times magnified photograph was taken and the area increase rate of the observed dark spots was evaluated.

<Evaluation item 2>
Immediately after encapsulation, a 50x magnified photograph was taken. A bending test for bending the element to 45 ° and returning it to the original was repeated 1000 times, and then the same storage test as in Evaluation Item 1 was performed to evaluate the increase rate of the dark spot area.

  The area increase rate was evaluated according to the following criteria for both evaluation items 1 and 2.

XX: When the increase rate of the dark spot exceeds the OLED 307 X: The increase rate of the dark spot is 80% or more and 100% or less of the OLED 307 △: The increase rate of the dark spot is 50% or more and less than 80% of the OLED 307 △: Dark spot Increase rate of OLED307 is 30% or more and less than 50% ○: Dark spot increase rate of OLED307 is 15% or more and less than 30% ◎: Dark spot increase rate is less than 15% of OLED307

  From these results, the organic EL element (display device) in which the number of layers in which the soft hydrogenated amorphous silicon carbide film and the hard hydrogenated amorphous silicon carbide film are alternately stacked increases the area increase rate of the dark spot to be lower. You can see that

  When combined with the results of the adhesion evaluation (cross-cut test) of the film of Example 2, both the single-layer film and the laminated film have better adhesion between the layers, and the dark spot area increase rate is higher. It can be seen that it can be kept low.

  In this embodiment, materials that adsorb moisture or react with moisture (for example, barium oxide) are not enclosed in the device, but this does not prevent the materials from being enclosed in the device.

It is a figure which shows an example of a plasma discharge processing chamber. It is a figure which shows an example of a roll electrode. It is a schematic perspective view of a fixed electrode. 3 is a view showing a plasma discharge treatment chamber in which square-shaped fixed electrodes are arranged around a roll electrode 25. FIG. It is a figure which shows the plasma film-forming apparatus provided with the plasma discharge processing chamber. It is a figure which shows another example of a plasma film forming apparatus. It is sectional drawing which shows the structure of the produced organic electroluminescent display apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 5 Substrate 2 Anode 3 Organic EL layer 4 Cathode 6 Sealing material 10, 30 Plasma discharge treatment chamber 12 Air supply port 13 Exhaust port 15, 16 Nip roller 24, 27 Guide roller 25a, 25A, 26a, 36a Conductivity of metal, etc. Base material 25b, 26b, 36b Ceramic coating dielectric 25B Lining dielectric 25, 25c, 25C Roll electrode 26, 26c, 26C, 36, 36c, 36C Electrode 41 Power supply 51 Gas generator 55 Electrode cooling unit F Substrate FF Original winding base material

Claims (13)

A reactive gas is supplied between opposing electrodes under a pressure at or near atmospheric pressure, and a high-frequency voltage is applied to bring the reactive gas into an excited state and expose the substrate to the excited reactive gas. Thus, a hydrogenated amorphous silicon carbide thin film having a composition represented by the following general formula (1) is formed.
General formula (1) SiC _x : H
(In the formula, x represents 1.01 to 2.0.) ^2. The method for producing a thin film according to claim 1, wherein the high-frequency voltage is an AC voltage having a frequency in a range of 1 kHz to 2500 MHz, and a supply power is in a range of 1 W / cm ^{2 to} 50 W / cm ^2. . 3. The method for producing a thin film according to claim 1, wherein the high-frequency voltage is obtained by superimposing an AC voltage in a frequency range of 1 kHz to 1 MHz and an AC voltage having a frequency of 1 MHz to 2500 MHz. A thin film produced by the method for producing a thin film according to any one of claims 1 to 3, having a moisture permeability of 1.0 g / m ² / d or less. A thin film produced by the method for producing a thin film according to claim 1, wherein the surface has a pencil hardness of 4H or more. A thin film produced by the method for producing a thin film according to any one of claims 1 to 3, wherein the surface has a contact angle with water of 80 ° or more. A thin film having an average surface roughness of 1.0 nm or less, produced by the method for producing a thin film according to claim 1. A thin film produced by the method for producing a thin film according to any one of claims 1 to 3 or a thin film according to any one of claims 4 to 7 is formed on a transparent plastic film substrate. A transparent plastic film characterized by A reactive gas is supplied between opposing electrodes under a pressure at or near atmospheric pressure, and a high-frequency voltage is applied to bring the reactive gas into an excited state and expose the substrate to the excited reactive gas. A plurality of hydrogenated amorphous silicon carbide laminated thin films formed by the above, wherein the first hydrogenated amorphous silicon carbide thin film layer closer to the substrate surface is SiC _x : H (x> 1.5), and The formed second hydrogenated amorphous silicon carbide thin film layer is SiC _x : H (x <1.5). A transparent plastic film, wherein the laminated thin film according to claim 9 is formed on a transparent plastic film substrate. The transparent plastic film according to claim 8 or 10, wherein the glass transition temperature of the transparent plastic film substrate is 180 ° C or higher. The transparent plastic film base material of any one of Claim 8,10,11 is comprised from the cellulose ester mainly, The transparent plastic film characterized by the above-mentioned. An organic EL element with a laminated thin film, wherein the laminated thin film according to claim 9 is formed on an organic EL element.

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