JP2012212577A - Method for forming transparent gas barrier layer, transparent gas barrier layer, transparent gas barrier film, organic electroluminescent element, solar cell, and thin film battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a transparent gas barrier layer, by which a transparent gas barrier layer having excellent gas barrier property even in a single layer, high transparency and very low internal stress can be formed without heating at high temperature.SOLUTION: In a method for forming a transparent gas barrier layer by means of a sputtering method, a target including at least one carbide selected from a metal carbide and a metalloid carbide is used, and hydrogen-containing gas is used as reaction gas.

Description

  The present invention relates to a method for producing a transparent gas barrier layer, a transparent gas barrier layer, a transparent gas barrier film, an organic electroluminescence element, a solar battery, and a thin film battery.

  In recent years, various electronic devices such as a liquid crystal display element, an organic electroluminescence (EL) element, electronic paper, a solar battery, and a thin film lithium ion battery have been reduced in weight and thickness. Many of these devices are known to be altered and degraded by water vapor in the atmosphere.

  Conventionally, a glass substrate has been used as a supporting substrate for these devices. However, the use of a resin substrate instead of a glass substrate has been studied because of its excellent characteristics such as lightness, impact resistance, and flexibility. ing. In general, a resin substrate has a property that gas permeability such as water vapor is remarkably large as compared with a substrate formed of an inorganic material such as glass. Therefore, in the above application, it is required to improve the gas barrier property of the resin substrate while maintaining its light transmittance.

Incidentally, the gas barrier properties of electronic devices are required to be orders of magnitude higher than those of food packaging. The gas barrier property is expressed, for example, by a water vapor transmission rate (hereinafter referred to as WVTR). The value of WVTR in conventional food packaging applications is about ¹ to 10 g · m ⁻² · day ⁻¹ , whereas the WVTR required for substrates for thin film silicon solar cells and compound thin film solar cells is 0. 01g ^· m -2 ^{· day -1} or less, more is it believed that ^{1 × 10 -5 g · m -2} · day -1 or less required for a substrate of the organic EL applications. Various methods for forming a gas barrier layer on a resin substrate have been proposed in response to such a demand for extremely high gas barrier properties.

  For example, it has been proposed to improve gas barrier properties by alternately laminating a plurality of inorganic layers and polymer layers to form a hybrid (see, for example, Patent Document 1). However, since layers of different materials are formed by different processes, it is not preferable from the viewpoint of production efficiency and cost. Further, in order to obtain a sufficient gas barrier property, it is necessary to increase the number of laminated layers or to form each layer thickly, which causes a problem that the production efficiency is lowered. In addition, there is a problem that the adhesion between the inorganic layer and the polymer layer is low, and deterioration due to aging or bending easily occurs.

  On the other hand, as a means for obtaining a gas barrier effect with a single layer without heating to a high temperature, it has been proposed to form a thin film formed by sputtering silicon carbide. The silicon carbide thin film is colored because of its large light absorption, but it is said that light transmittance can be imparted by adding nitrogen or oxygen during sputtering (see, for example, Patent Document 2).

Japanese Patent No. 2999616 JP 2004-151528 A

  However, according to the study by the present inventors, by adding nitrogen during sputtering, a gas barrier property is improved but a layer having low light transmittance is formed, and by adding oxygen, light transmittance is improved. A problem has been found that the gas barrier properties are lowered. That is, the gas barrier property and the light transmittance are in a trade-off relationship in the gas barrier layer forming conditions. Furthermore, the nitrogen-containing layer as described above has a very high internal stress, and when the substrate is made of a soft organic material such as a polymer film, the layer is cracked and affects the gas barrier property.

  Therefore, the present invention can produce a transparent gas barrier layer that has excellent gas barrier properties and high transparency even with a single layer, and that has a very low internal stress, without heating to a high temperature. Another object is to provide a method for producing a transparent gas barrier layer.

  The method for producing a transparent gas barrier layer of the present invention is a method for producing a transparent gas barrier layer in which a transparent gas barrier layer is formed by a sputtering method, and uses a target containing at least one carbide selected from metal carbide and semimetal carbide. In addition, a hydrogen-containing gas is used as a reaction gas.

  The transparent gas barrier layer of the present invention is manufactured by the method for manufacturing a transparent gas barrier layer of the present invention.

  The gas barrier film of the present invention is characterized in that the gas barrier layer of the present invention is formed on a transparent substrate film.

  The organic electroluminescence device of the present invention is an organic electroluminescence device having a laminate in which an anode layer, an organic light emitting layer, and a cathode layer are provided in this order on a substrate, and at least one of the laminates. The portion is covered with a gas barrier layer, and the gas barrier layer is the transparent gas barrier layer of the present invention.

  Moreover, the solar cell of the present invention is a solar cell including a solar cell, and the solar cell is covered with at least one of the transparent gas barrier layer of the present invention and the transparent gas barrier film of the present invention. It is characterized by.

  The thin film battery of the present invention is a thin film battery having a laminate in which a current collecting layer, an anode layer, a solid electrolyte layer, a cathode layer, and a current collecting layer are provided in this order, and the laminate is the invention of the present invention. The transparent gas barrier layer of the present invention and at least one of the transparent gas barrier film of the present invention are coated.

  According to the method for producing a transparent gas barrier layer of the present invention, a transparent gas barrier layer having excellent gas barrier properties, high transparency, and extremely low internal stress can be heated to a high temperature even if it is a single layer. It can be manufactured at all. Moreover, since the transparent gas barrier layer of the present invention is produced by the production method of the present invention, both the light transmittance and the gas barrier property are excellent, and the internal stress is low. And since the transparent gas barrier film of this invention formed the transparent gas barrier layer of the said invention on the transparent base film, it is excellent in light transmittance and gas barrier property. The transparent gas barrier film of the present invention is not limited to the case where the gas barrier layer is a single layer, and a plurality of layers may be laminated.

FIG. 1 is a schematic diagram showing an example of the configuration of an apparatus for producing the transparent gas barrier layer of the present invention by a continuous production method. FIG. 2 is a schematic view showing an example of the configuration of an apparatus for producing the transparent gas barrier layer of the present invention by a batch production method.

  In the method for producing a transparent gas barrier layer of the present invention, it is preferable that the reaction gas further contains nitrogen.

  In the method for producing a transparent gas barrier layer of the present invention, it is preferable that the metal carbide is aluminum carbide and the semimetal carbide is silicon carbide.

  In the method for producing a transparent gas barrier layer of the present invention, the target may further include at least one of a metal and a metalloid, and the metal and the metalloid may be a simple substance, a mixture, or an alloy.

  In the method for producing a transparent gas barrier layer of the present invention, the sputtering method is preferably a pulsed DC (direct current) sputtering method or an RF (high frequency) sputtering method.

  Moreover, in the manufacturing method of the transparent gas barrier layer of this invention, you may form a transparent gas barrier layer on a transparent base film.

  In the organic electroluminescence element of the present invention, it is preferable that the substrate is the transparent gas barrier film of the present invention.

  Next, the present invention will be described in detail. However, the present invention is not limited by the following description.

  In the method for producing a transparent gas barrier layer of the present invention, hydrogen atoms formed in the sputtering atmosphere by using a hydrogen-containing gas as a reaction gas act on the chemical structure of the gas barrier layer, and the formed gas barrier layer becomes transparent, Furthermore, the stress in the gas barrier layer is relaxed. Furthermore, the introduction of nitrogen improves the barrier properties and transparency of the gas barrier layer. The reaction gas may be a compound gas of hydrogen and nitrogen, such as ammonia gas. In this case, the same effect can be obtained. When using a gas of a compound of hydrogen and nitrogen, it is considered that hydrogen and nitrogen are dissociated from the gas of the compound in a sputtering atmosphere, nitrogen is introduced into the gas barrier layer, and hydrogen performs the above action. The present invention is not limited by this assumption.

  The effect is expressed regardless of the mixing ratio (flow rate ratio) of nitrogen and hydrogen in the reaction gas. However, if the mixing ratio of nitrogen (flow rate ratio) is higher than that of hydrogen, better characteristics may be expressed. It is possible and preferable. The mixing ratio of nitrogen and hydrogen is preferably nitrogen / hydrogen = 0.3 to 3.0, and more preferably 0.5 to 2.0.

  The method for producing a transparent gas barrier layer of the present invention is based on a sputtering method, and a target containing at least one kind of carbide selected from metal carbide and metal carbide is used as a target. The carbide is preferably aluminum carbide, and the carbide metal is preferably silicon carbide. These materials are preferable in terms of improving the gas barrier property of the transparent gas barrier layer, because the network structure (network structure) in the transparent gas barrier layer can be formed densely. Moreover, it is preferable also from the point that the internal stress at the time of transparent gas barrier layer formation is not high compared with other metal carbide and metal carbide.

  Further, the target may further contain at least one of a metal and a semimetal. The metal and metalloid may be a simple substance, a mixture or an alloy. The mixture may be any of a mixture of a plurality of kinds of metals, a mixture of a plurality of kinds of metalloids, a mixture of metals and metalloids, and a mixture of a simple substance and an alloy, and is not limited. When the target containing at least one of the metal and the semimetal is used, the layer formation speed can be increased and the production efficiency can be improved. For example, in the case of a mixed target of silicon carbide and silicon, a layer having components of silicon carbonitride and silicon nitride is obtained, and good gas barrier properties are obtained. The mixing ratio of a simple substance, a mixture or an alloy containing at least one selected from the metals and metalloids is preferably 80% by weight or less. By setting the mixing ratio to 80% by weight or less, for example, it is possible to prevent the occurrence of cracks at the grain boundaries in the target, and it is possible to prevent the layer formation state during sputtering from deteriorating. The mixing ratio is more preferably 50% by weight or less, and still more preferably 30% by weight or less. The metal and metalloid may be the same or different from the metal carbide and metalloid constituting the metal carbide and metalloid, but are the same in consideration of sputtering efficiency and the like. It is preferable.

The sputtering method is preferably performed by a pulse DC (direct current) sputtering method or an RF (high frequency) sputtering method. Compared with the normal DC sputtering method, the pulse DC sputtering method can prevent the formation of an insulating layer such as nitride or oxide on the surface of the target, and the layer formation by sputtering becomes unstable. Can be prevented. In the case of the RF sputtering method, the frequency is preferably in the range of 10 kHz to 30 MHz, and more preferably in the range of 30 kHz to 20 MHz. The discharge output is, for example, in the range of 1 to 10 W / cm ² , and preferably in the range of 3 to 6 W / cm ² . Although there is no particular limitation on the frequency and the duty ratio that becomes a negative bias in the pulse DC sputtering method, the discharge time is preferably short, and is preferably in the range of 30 to 95%.

There is no particular limitation on the sputtering conditions when forming the transparent gas barrier layer. For example, after evacuating the inside of the vacuum chamber to 10 ⁻⁴ Pa or less, argon gas is introduced as a discharge gas, and hydrogen gas containing, for example, nitrogen gas is introduced as a reaction gas, and the internal pressure of the system becomes 0.1 to 1 Pa. Thus, the flow control (pressure control) is performed by the mass flow controller. As the discharge output during sputtering, 1 to 10 W / cm ² is applied, and sputtering is performed until a desired thickness is achieved.

  The heating temperature at the time of forming the transparent gas barrier layer is preferably 120 ° C. or lower, more preferably in the range of 80 to 110 ° C. The transparent gas barrier layer may be formed on a base material. When a resin film is used as the base material, a transparent gas barrier film can be obtained. In this case, it is preferable to heat the base material at 120 ° C. or lower when forming the transparent gas barrier layer. The method for producing a transparent gas barrier layer of the present invention can form a transparent layer having a good gas barrier performance at a low temperature. Therefore, even if the substrate is a resin, for example, the properties and shape of the resin are impaired. It is possible to set no conditions.

  The material of the base material is preferably transparent. When resin is used, polyethylene, polypropylene, cycloolefin polymer, polyethylene terephthalate (PET), polyethylene naphthalate, polyphenyl sulfide, polycarbonate, polyimide, polyamide (nylon) , Polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, and polyvinylidene fluoride. Moreover, it is preferable that the thickness of a base material is the range of 20-200 micrometers, More preferably, it is the range of 50-150 micrometers.

  The thickness of the transparent gas barrier layer is preferably in the range of 0.01 to 1 μm. By setting the thickness to 0.01 μm or more, sufficient gas barrier properties can be obtained, and by setting the thickness to 1 μm or less, internal stress can be reduced and the occurrence of cracks can be prevented. The thickness is more preferably in the range of 0.05 to 0.2 μm.

  The transparent gas barrier layer can be manufactured by a batch method or a continuous production method. In the case of a continuous production method, the transparent gas barrier layer is formed on the transparent substrate film while the transparent substrate film is continuously conveyed by a roll in a vacuum chamber when the transparent gas barrier layer is formed.

  In FIG. 1, an example of a structure of the apparatus which manufactures the transparent gas barrier layer of this invention by a continuous production system is shown. As shown, the manufacturing apparatus 10 includes a vacuum chamber 11, an unwinding roll 13a, a can roll 15, a winding roll 13b, two auxiliary rolls 14a and 14b, a cathode 16, a vacuum pump 20, a sputtering gas supply means 18, A reactive gas supply means 19 is provided as a main constituent member. An unwinding roll 13a, a can roll 15, a take-up roll 13b, and two auxiliary rolls 14a and 14b are arranged in the vacuum chamber 11, and the can roll 15 extends from the unwind roll 13a to the take-up roll 13b. The transparent substrate film 12 is stretched over the two auxiliary rolls 14a and 14b. The cathode 16 is installed at the bottom of the vacuum chamber 11 so as to face the can roll 15. The target 17 is mounted on the upper surface of the cathode 16. The vacuum pump 20 is disposed on the side wall (the right side wall in the figure) of the vacuum chamber 11, whereby the inside of the vacuum chamber 11 can be decompressed. The sputtering gas supply means 18 and the reactive gas supply means 19 are arranged on the side wall (right side wall in the figure) of the vacuum chamber 11. The sputtering gas supply means 18 is connected to a sputtering gas cylinder 21, whereby it becomes possible to supply a sputtering gas (for example, argon gas) having an appropriate pressure into the vacuum chamber 11. ing. The reaction gas supply means 19 is connected to a reaction gas gas cylinder 22 containing hydrogen, whereby a hydrogen-containing reaction gas (for example, a mixed gas of hydrogen gas and nitrogen gas, ammonia gas) having an appropriate pressure is supplied. , And can be supplied into the vacuum chamber 11. A temperature control means (not shown) is connected to the can roll 15. Thereby, the temperature of the said transparent base film 12 can be made into the said predetermined range by adjusting the surface temperature of the said can roll 15. FIG. Examples of the temperature control means include a heat medium circulation device that circulates silicone oil and the like.

  Continuous production with this equipment is the batch production described below, except that the film is continuously introduced into the equipment and sputtering is performed in the presence of the reaction gas while moving the film to continuously form the transparent gas barrier layer. It can be carried out in the same manner as the apparatus manufactured by the method.

  In FIG. 2, an example of the structure of the apparatus which manufactures the transparent gas barrier layer of this invention by a batch production system is shown. In FIG. 2, the same parts as those in FIG. As shown in the drawing, in this manufacturing apparatus 30, a substrate heater 33 is disposed in a vacuum chamber 31 instead of the various rolls, and a transparent base material (for example, a transparent base film) 32 is provided on the substrate heater 33. Except for being installed, the configuration is the same as in FIG. Examples of the substrate heater 33 include those similar to the temperature control means.

  The organic EL device of the present invention has a laminate in which an anode layer, an organic light emitting layer and a cathode layer are provided in this order on a substrate, and at least a part of the laminate is covered with a gas barrier layer. The gas barrier layer is the transparent gas barrier layer of the present invention. As the anode layer, for example, an ITO (Indium Tin Oxide) or IZO (registered trademark, Indium Zinc Oxide) layer that can be used as a transparent electrode layer is formed. The organic light emitting layer includes, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. As the cathode layer, an aluminum layer, a magnesium / aluminum layer, or the like is also formed as a reflective layer. A glass substrate can be used as the substrate, but a plastic substrate or the like may be used. When a material having insufficient gas permeability is used as the substrate, it is preferable to use a material in which the transparent gas barrier layer of the present invention is formed. In addition, since the conventional organic EL element did not have a gas barrier layer having sufficient sealing performance, the entire back surface of the organic EL element was sealed with a metal in order to seal the stacked body after forming the stacked body. The structure covered with a can was adopted. According to the transparent gas barrier layer of the present invention, coating is easy, and the organic EL element can be thinned.

  In the organic EL device of the present invention, it is also preferable that the substrate is the transparent gas barrier film of the present invention. When the transparent gas barrier film of the present invention is used as the substrate of the organic EL element, the organic EL element can be reduced in weight, thickness and flexibility. Therefore, the organic EL element as a display becomes flexible and can be used like electronic paper by rolling it.

  The solar battery of the present invention includes a solar battery cell, and the solar battery cell is coated with at least one of the gas barrier layer of the present invention and the transparent gas barrier film of the present invention. The transparent gas barrier film of the present invention can also be suitably used as a back sheet for protecting solar cells. As an example of the structure of the solar cell, a solar cell formed by thin film silicon or CIGS (Copper Indium Gallium DiSelenide) thin film is sealed with a resin such as ethylene-vinyl acetate copolymer, and the transparent gas barrier film of the present invention What is comprised by inserting | pinching between is mentioned. You may pinch | interpose directly with the transparent gas barrier film of this invention, without sealing with the said resin. Moreover, after sealing with resin, you may form the transparent gas barrier layer of this invention on the said resin.

  The thin film battery of the present invention is a thin film battery having a laminate in which a current collecting layer, an anode layer, a solid electrolyte layer, a cathode layer, and a current collecting layer are provided in this order, and the laminate is the invention of the present invention. The gas barrier layer and at least one of the transparent gas barrier film of the present invention are coated. Examples of the thin film battery include a thin film lithium ion battery. The thin film battery typically has a structure in which a current collecting layer using a metal, an anode layer using a metal inorganic layer, a solid electrolyte layer, a cathode layer, and a current collecting layer using a metal are sequentially laminated on a substrate. is there. The transparent gas barrier film of the present invention can also be used as a substrate for a thin film battery.

  Next, examples of the present invention will be described together with comparative examples. The present invention is not limited or restricted by the following examples and comparative examples. In addition, various properties and physical properties in each example and each comparative example were measured and evaluated by the following methods.

(Water vapor transmission rate)
The water vapor transmission rate (WVTR) was measured in a water vapor transmission rate measurement device (manufactured by MOCON, trade name PERMATRAN) specified in JIS K7126 under an environment of a temperature of 40 ° C. and a humidity of 90% RH. In addition, the measurement range of the said water-vapor-permeability measuring apparatus is 0.01 g * m ^<-2 > * day ^{< -1} > or more.

(Light transmittance)
The light (visible light) transmittance was measured using an ultraviolet-visible light region spectrophotometer (trade name: MCPD-3700) manufactured by Otsuka Electronics Co., Ltd., and represented by a transmittance of 550 nm.

(Thickness of transparent gas barrier layer)
The thickness of the transparent gas barrier layer is determined by observing the cross section of the transparent gas barrier film with a transmission electron microscope (TEM, trade name: HF-2000) manufactured by Hitachi, Ltd., from the surface of the substrate (film) to the surface of the transparent gas barrier layer. The length of was measured and calculated.

(Film warp)
In order to confirm the internal stress of the transparent gas barrier layer, the presence or absence of warping of the film on which the transparent gas barrier layer was formed was determined by the following method. Place the 100 mm square film on a horizontal base and fix one end. If the distance at which the other end was separated from the horizontal base was less than 3 mm, it was determined as “No”, and if it was 3 mm or more, it was determined as “Yes”.

[Example 1]
[Preparation of transparent substrate film]
As a transparent resin film (resin substrate), a polyethylene terephthalate (PET) film (thickness: 100 μm, trade name “Lumirror T60”) manufactured by Toray Industries, Inc. was prepared.

[Transparent gas barrier layer forming step]
Next, the PET film was mounted on the manufacturing apparatus shown in FIG. A silicon carbide target (purity 5N: 99.999%) 17 was mounted on the upper surface of the cathode 16. The inside of the vacuum chamber 31 was depressurized with the vacuum pump 20, and an ultimate vacuum of 1.0 × 10 ⁻⁴ Pa or less was obtained. Thereafter, argon gas as a sputtering gas and hydrogen gas as a reactive gas were introduced into the vacuum chamber 31 by the sputtering gas supply means 18 and the reactive gas supply means 19. Subsequently, a film with a transparent gas barrier layer of this example was obtained by forming a silicon carbide compound layer having a thickness of 100 nm on the PET film under the conditions of a DC pulse of 200 kHz and a discharge output of 3 W / cm ² . At this time, the supply amount (flow rate) of argon gas is 150 sccm (150 × 1.69 × 10 ⁻³ Pa · m ³ / sec), and the supply amount (flow rate) of hydrogen gas is 30 sccm (30 × 1.69 ×). 10 ⁻³ Pa · m ³ / sec). At this time, the system internal pressure was 0.03 Pa, and the substrate heater temperature was 100 ° C.

[Example 2]
The transparent gas in this example was the same as in Example 1 except that nitrogen gas and hydrogen gas were introduced as reaction gases at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec), respectively. A film with a gas barrier layer was obtained.

[Example 3]
The film with a transparent gas barrier layer of this example was the same as Example 1 except that ammonia gas was introduced as a reaction gas at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Got.

[Example 4]
A film with a transparent gas barrier layer of this example was obtained in the same manner as in Example 1 except that aluminum carbide (purity 5N) was used as a target.

[Example 5]
The transparent gas of this example was the same as in Example 4 except that nitrogen gas and hydrogen gas were introduced as reaction gases at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec), respectively. A film with a gas barrier layer was obtained.

[Example 6]
The film with the transparent gas barrier layer of this example was the same as Example 4 except that ammonia gas was introduced as a reaction gas at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Got.

[Example 7]
A film with a transparent gas barrier layer of this example was obtained in the same manner as in Example 1, except that an alloy of 80 wt% silicon carbide and 20 wt% silicon was used as a target.

[Example 8]
The transparent gas of this example was the same as in Example 7 except that nitrogen gas and hydrogen gas were introduced as reaction gases at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec), respectively. A film with a gas barrier layer was obtained.

[Example 9]
A film with a transparent gas barrier layer of this example was prepared in the same manner as in Example 7 except that ammonia gas was introduced as a reaction gas at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Obtained.

[Example 10]
A film with a transparent gas barrier layer of this example was obtained in the same manner as in Example 4 except that an alloy of 70 wt% aluminum carbide and 30 wt% aluminum was used as a target.

[Example 11]
The transparent gas of this example was the same as that of Example 10 except that nitrogen gas and hydrogen gas were introduced as reaction gases at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec), respectively. A film with a gas barrier layer was obtained.

[Example 12]
The film with a transparent gas barrier layer of this example was the same as Example 10 except that ammonia gas was introduced as a reaction gas at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Got.

[Comparative Example 1]
A film with a transparent gas barrier layer of this comparative example was prepared in the same manner as in Example 1 except that nitrogen gas was introduced as a reaction gas at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Obtained.

[Comparative Example 2]
A film with a transparent gas barrier layer of this comparative example was prepared in the same manner as in Example 4 except that nitrogen gas was introduced as a reaction gas at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Obtained.

[Comparative Example 3]
A film with a transparent gas barrier layer of this comparative example is the same as Example 7 except that nitrogen gas is introduced as a reaction gas at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Got.

[Comparative Example 4]
A film with a transparent gas barrier layer of this comparative example is the same as Example 10, except that nitrogen gas is introduced as a reaction gas at a flow rate of 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Got.

  About the film with a transparent gas barrier layer obtained in Examples 1-12 and Comparative Examples 1-4, the water vapor transmission rate (WVTR), the light transmittance in the wavelength of 550 nm, and the presence or absence of the curvature of a film were measured. The measurement results are shown in Table 1.

As shown in Table 1, the film with a transparent gas barrier layer obtained in the examples has a good gas barrier property with a water vapor transmission rate of 0.06 g · m ⁻² · day ⁻¹ or less and a good visible light of 70% or more. It can be seen that a transparent gas barrier layer having transparency (transparency) and having good characteristics even with a single layer is obtained. Moreover, the curvature of a film is not seen and it turns out that the internal stress of a transparent gas barrier layer is low. Moreover, in Examples 7-12 using a mixed target, the layer formation speed | rate by sputtering could be made faster than the other Examples, and the film with a transparent gas barrier layer was able to be manufactured efficiently. On the other hand, in the comparative examples, the visible light transmittance was 60 to 65%, and the light transmittance was not sufficient. Moreover, it turns out that a water-vapor-permeation rate is as large as 0.10g * m ^<-2 > * day ^{< -1} > or more, and is inferior to gas barrier property. Moreover, the curvature of a film is seen and it turns out that the internal stress of a transparent gas barrier layer is high.

  According to the method for producing a transparent gas barrier layer of the present invention, a transparent gas barrier layer having excellent gas barrier properties, high transparency, and extremely low internal stress can be heated to a high temperature even if it is a single layer. It can be manufactured at all. The transparent gas barrier layer and the transparent gas barrier film of the present invention include various display devices (displays) such as an organic EL display device, a field emission display device or a liquid crystal display device, various types such as a solar cell, a thin film battery, and an electric double layer capacitor. It can be used as an electric element, a substrate for an electric element or a sealing material, and its use is not limited, and it can be used in all fields in addition to the above-mentioned applications.

DESCRIPTION OF SYMBOLS 10, 30 Manufacturing apparatus 11, 31 Vacuum tank 12, 32 Transparent base film 13a Unwinding roll 13b Winding roll 14a, 14b Auxiliary roll 15 Can roll 16 Cathode 17 Target 18 Sputtering gas supply means 19 Reactive gas supply means 20 Vacuum Pump 21 Gas cylinder for sputtering 22 Gas cylinder for reaction gas 33 Substrate heater

Claims (12)

A method for producing a transparent gas barrier layer that forms a transparent gas barrier layer by a sputtering method, wherein a target containing at least one carbide selected from a metal carbide and a metal carbide is used, and a hydrogen-containing gas is used as a reaction gas. A method for producing a transparent gas barrier layer. The method for producing a transparent gas barrier layer according to claim 1, wherein the reaction gas further contains nitrogen. The method for producing a transparent gas barrier layer according to claim 1, wherein the metal carbide is aluminum carbide, and the semimetal carbide is silicon carbide. The said target further contains at least 1 sort (s) of a metal and a semimetal, and the said metal and the said semimetal are a simple substance, a mixture, or an alloy, It is any one of Claim 1 to 3 characterized by the above-mentioned. Method for producing a transparent gas barrier layer. The method for producing a transparent gas barrier layer according to any one of claims 1 to 4, wherein the sputtering method is a pulsed DC (direct current) sputtering method or an RF (radio frequency) sputtering method. A transparent gas barrier layer is formed on a transparent base film, The manufacturing method of the transparent gas barrier layer as described in any one of Claim 1 to 5 characterized by the above-mentioned. A transparent gas barrier layer produced by the method for producing a transparent gas barrier layer according to any one of claims 1 to 6. A transparent gas barrier film, wherein the transparent gas barrier layer according to claim 7 is formed on a transparent substrate film. An organic electroluminescent element having a laminate in which an anode layer, an organic light emitting layer and a cathode layer are provided in this order on a substrate, wherein at least a part of the laminate is covered with a gas barrier layer, An organic electroluminescence device, wherein the gas barrier layer is the transparent gas barrier layer according to claim 7. The organic electroluminescence device according to claim 9, wherein the substrate is the transparent gas barrier film according to claim 8. It is a solar cell containing a photovoltaic cell, Comprising: The said photovoltaic cell is coat | covered with at least one of the transparent gas barrier layer of Claim 7, and the transparent gas barrier film of Claim 8, The solar cell characterized by the above-mentioned. The transparent gas barrier layer according to claim 7 and the claim, wherein the current collector layer, the anode layer, the solid electrolyte layer, the cathode layer, and the current collector layer are a thin film battery having a laminate provided in this order. Item 9. A thin film battery, which is coated with at least one of the transparent gas barrier films according to Item 8.

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