JP5082652B2 - Transparent laminate, method for producing the same, and electronic device - Google Patents

Description

The present invention relates to a transparent laminate, and more specifically, a transparent laminate in which a metal nitride film that absorbs oxygen and water vapor is formed by a chemical reaction, a method for manufacturing the transparent laminate, and an electronic device using the transparent laminate. About.

Conventionally, for example, in a display device represented by a liquid crystal display device (LCD), glass is used as a substrate for a display conductor. In recent years, as displays have become larger or more portable, instead of glass, a plastic film that is excellent in lightness, impact resistance, and flexibility and suitable for increasing the size is used for the substrate. Has been proposed.
However, when a plastic film is used for the substrate of the display conductor, there is a problem that the display element is deteriorated by oxygen or water vapor that permeates the film.

Many studies on gas barrier films have been made so far for the purpose of preventing permeation of oxygen and water vapor. For example, in packaging materials such as food, use of a plastic film having low oxygen and / or water vapor permeability, coating of a polymer material having low oxygen and / or water vapor permeability on the plastic film, or on a plastic film It has been proposed to stack inorganic oxides such as SiOx and AlOx by vacuum deposition.
In addition, a method for realizing higher barrier performance by laminating an organic layer and an inorganic layer on a plastic film as necessary has been proposed.

  In order to solve the above-described problem of deterioration of the display element, in particular, in an organic EL device that dislikes oxygen and water vapor, an oxygen or water vapor absorbent is disposed inside the sealing can, thereby sealing the can. It has been proposed to configure to absorb oxygen and water vapor mixed therein.

In addition, it is essential to form a conductive film on the display substrate used in the display device as described above. Here, as a laminate in which a gas barrier film and a conductive film are formed on a plastic film, a film made of silicon oxide is formed on a substrate by a plasma CVD method, and a transparent conductive film is further formed (for example, a patent Document 1), or a film in which a film made of silicon oxide or silicon nitride is formed on a substrate and an indium oxide-based transparent conductive film is formed (for example, see Patent Document 2) has been proposed. Yes.
Japanese Patent No. 3118339 Japanese Patent No. 3499844

  An electronic device using a plastic film as a substrate as described in Patent Documents 1 and 2 has an advantage that it can be configured to be lightweight and thin, but such an electronic device is provided with a sealing can, and an absorbent is provided inside. It is unrealistic to have a configuration including the above because the above advantages cannot be obtained. However, unlike a glass material, when a plastic film that itself contains water vapor is used for the substrate, oxygen or water vapor that has permeated the barrier film gradually reaches the display element, even if a barrier film is provided. There is a problem that the display element deteriorates.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a transparent laminate capable of preventing deterioration of a display element due to oxygen or water vapor, a manufacturing method thereof, and an electronic device.

  In order to solve the above problem, the present invention provides the following means.

The invention according to claim 1, a transparent laminate in which at least metallic nitride film and a ceramic thin film layer formed on a transparent substrate, said metal nitride film is a SiN film, the ceramic thin film layer with but a SiO film, on said transparent substrate, sequentially, SiO film, SiN film and the SiO film are laminated, the SiN film in an atmosphere that there are at least oxygen molecules and / or water molecules, oxygen and steam Ri chemically unstable Monodea absorption to Ru is oxidized, and the SiO film, under conditions where the temperature was set to 100 ° C. or less in an atmosphere that exists oxygen molecules and / or water molecules provides a transparent laminate, characterized in chemically stable barrier film der Rukoto to oxygen and water vapor.
According to this invention, at least oxygen molecules and / or in an atmosphere of water molecules is present, by absorbing oxygen and water vapor to form a by Ru-chemical unstable SiN film oxide in the transparent laminate Further, oxygen and water vapor that have passed through the transparent substrate and other thin films can be absorbed, and further, oxygen and water vapor can be prevented from passing through the transparent laminate.
In addition, by using a SiN film as a material for the metal nitride film, it is possible to absorb and prevent oxygen and water vapor transmitted through the transparent substrate and other thin films as described above from being transmitted through the SiN film. It becomes possible. If, for example, Si ₃ N ₄ is used as the material for the metal nitride film, the metal nitride film itself has a barrier property, so that this metal nitride film can be used as a normal barrier substrate.
In addition, by stacking a SiO film, which is a ceramic thin film layer that functions as a chemically stable barrier film, on a transparent substrate, it is possible to control the amount of oxygen and water vapor reaching the SiN film to be reduced. It becomes possible to supplement the barrier film function of the SiN film. Also, by laminating the SiO film between the SiN film and the transparent substrate, oxygen and water vapor entering from the atmosphere side of the transparent laminate can be absorbed by the SiN film, while the SiO film is formed on the atmosphere side of the SiN film. When laminated, oxygen and water vapor leaking from the transparent substrate can be absorbed by the SiN film, and the directionality of oxygen and water vapor absorbed by the SiN film can be controlled.

In the invention according to claim 2, the SiN film after being exposed for 100 hours in an atmosphere of a temperature of 40 ° C. and a humidity of 90% Rh is in a range of 50 to 100 nm deep from the surface on the exposed side. SiO ₂ The transparent laminate according to claim 1, wherein the transparent laminate is changed into the following.
  According to the invention, since the SiN film is oxidized in a range of a depth of 50 to 100 nm from the exposed side surface after being exposed to the above atmosphere for 100 hours, it is transparent as described above. It becomes possible to reliably absorb oxygen and water vapor that have passed through the substrate and other thin films.

In the invention described in claim 3, the energy band gap of the SiN film provides a transparent laminate according to claim 1 or 2, characterized in that at least 3.1 eV.
According to the invention, by setting the energy band gap of the SiN film within the above range, light absorption does not occur in the visible light region, and excellent light transmittance can be obtained. Moreover, the energy band gap characteristic can be realized by using SiN as the material of the metal nitride film. In addition, since the energy band gaps of aluminum and silicon oxides are 4 eV and 8 eV, respectively, transparency can be maintained even when the metal nitride film becomes an oxide.

In invention of Claim 4 , light transmittance including the said transparent substrate is 60% or more in the wavelength range of 400 nm-800 nm, It is any one of Claims 1-3 characterized by the above-mentioned. A transparent laminate is provided.
According to this invention, the light transmittance including the transparent substrate is set to 60% or more in the wavelength range of 400 to 800 nm which is a visible light region, so that it can be applied to a front plate of an application using transmitted light. It becomes possible. Basically, if the SiN film is made of a material having an energy band gap of 3.1 eV or more, theoretically, absorption due to excitation does not appear in the visible light region.

In invention of Claim 5, the said transparent substrate is a plastic film, The transparent laminated body in any one of Claims 1-4 characterized by the above-mentioned is provided.
According to the invention, by forming the transparent substrate from a flexible material such as plastic, it is possible to suppress damage due to impact and to obtain a transparent laminate excellent in impact resistance. In addition, by forming the transparent substrate with a plastic film, when forming a thin film on this transparent substrate, it becomes possible to mass-produce continuously by the roll-to-roll method, so the production cost can be reduced. It becomes.

In the invention according to claim 6, in an environment of a temperature of 40 ° C. and a humidity of 90% Rh, the water vapor transmission rate is 0.5 g / m. ² ・ Day or less, oxygen permeability is 0.5cc / m ² -The day-atm or less is provided, The transparent laminated body of any one of Claims 1-5 characterized by the above-mentioned.
According to such an invention, by setting the water vapor transmission rate and the oxygen transmission rate in the environment to be within the specified ranges, material deterioration of an electronic device in which the transparent laminate is used can be suppressed. When the transparent substrate is made of a plastic film, the plastic material usually has poor gas barrier properties such as water vapor, so that there is a problem that the material of the electronic device is particularly deteriorated. In the present invention, the above-described barrier SiO film is used as the ceramic thin film layer, and the water vapor transmission rate of the transparent laminate in an environment of a temperature of 40 ° C. and a humidity of 90% Rh is 0.5 g / m. ² / Day or less, oxygen permeability is 0.5 cc / m ² ・ By setting the value to day · atm or less, even when a plastic material is used for the transparent substrate, the permeation of oxygen and water vapor is suppressed by the SiO film, so that deterioration of the material of the electronic device can be suppressed. As a result, the lifetime of the electronic device can be increased.

The invention according to claim 7 further provides at least one transparent conductive thin film, wherein the transparent laminate according to any one of claims 1 to 6 is provided.
According to this invention, it is possible to apply as a substrate of an electronic device by further laminating a transparent conductive thin film.

In invention of Claim 8, It is a method of manufacturing the transparent laminated body of any one of Claims 1-7, Comprising: The said metal nitride film is chemical vapor deposition (CVD) method, The transparent substrate is formed from SiN at a temperature of 40 ° C. or less, and the ceramic thin film layer is formed by vacuum deposition, physical vapor deposition, or chemical vapor deposition (CVD), and the temperature of the transparent substrate is A method for producing a transparent laminate, comprising: sequentially forming a SiO film, a SiN film, and a SiO film on the transparent substrate by forming from SiO at a temperature higher than a formation temperature of a metal nitride film. provide.
According to the invention, the SiN film formed in the transparent laminate is chemically unstable, which is surely oxidized by absorbing oxygen and water vapor in an atmosphere where oxygen molecules and / or water molecules are present. It can be made into a film. Thereby, oxygen and water vapor that have passed through the transparent substrate and other thin films can be absorbed by the SiN film, and further, oxygen and water vapor can be prevented from permeating through the transparent laminate.

In the invention described in claim 9 provides an electronic device comprising the transparent laminate is used according to any one of claims 1-7.
According to the invention, since the transparent laminate according to the invention is used, oxygen and water vapor that permeate the transparent laminate or oxygen and water vapor contained in the transparent substrate reach the display element. Since it can suppress, it can prevent that a display element deteriorates, and it can implement | achieve a long life electronic device while being excellent in a display characteristic.

According to the transparent laminate of the present invention, since a SiN film capable of absorbing oxygen and water vapor is formed by a chemical reaction by oxidation, it is possible to suppress permeation of oxygen and water vapor. When such a transparent laminate is applied as a front plate of an electronic device such as a display device, the display element can be prevented from being deteriorated by oxygen or water vapor, and the display characteristics of the electronic device are improved. There is an effect that it is possible to extend the life.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of a transparent laminate, a method for producing the same, and an electronic device according to the present invention will be described with reference to FIGS. The drawings referred to in the following description are for easy understanding of the configuration of the transparent laminate and the electronic device, and the dimensions and thicknesses of the illustrated parts are the actual transparent laminate and It may be different from the dimensional relationship of the electronic device.

  In the transparent laminate according to the present invention, at least one metal nitride film is formed on a transparent substrate, and the metal nitride film can be oxidized in an atmosphere containing at least oxygen molecules and / or water molecules. Schematically configured as a

[First Embodiment]
FIG. 1 is a schematic diagram illustrating a first embodiment of a transparent laminate according to the present invention. The transparent laminate 1 in the example shown in FIG. 1 is formed by forming a single layer of a metal nitride film 3 that can be oxidized in an atmosphere in which oxygen molecules and water molecules exist on one surface 2 a of a transparent substrate 2. .

The transparent substrate 2 is a base material of a transparent laminate on which each thin film is laminated.
As a material used for the transparent substrate 2, any material can be used. However, when particularly high transparency is required, it is preferable to use a glass material, a plastic film, etc. In addition, it is preferable to use a plastic film that is excellent in impact resistance and flexibility.
The plastic film is not particularly limited as long as it is a material that has sufficient strength to withstand the film-forming process and the post-process and has a good surface smoothness. For example, a polyethylene terephthalate film, a polybutylene terephthalate film, and the like. Polyethylene naphthalate film, polycarbonate film, polyethersulfone film, polysulfone film, polyarylate film, cyclic polyolefin film, polyimide and the like. In particular, when the transparent laminate is applied to the front plate of a display device, polycarbonate and polyethersulfone having excellent transparency and heat resistance are preferably used.
The thickness of the plastic film used for the transparent substrate 2 is preferably about 10 to 200 μm in consideration of thinning of the member and flexibility of the base material.
Further, the surface of the transparent substrate 2 may be subjected to treatment with various well-known additives and stabilizers such as an antistatic agent, an anti-ultraviolet agent, a plasticizer, a lubricant, and an easy adhesive. Moreover, in order to improve the adhesiveness with the thin film formed on the transparent substrate 2, corona treatment, low temperature plasma treatment, ion bombardment treatment, chemical treatment, etc. may be performed as pretreatment.

As described above, the metal nitride film 3 can be oxidized in an atmosphere in which at least oxygen molecules and water molecules exist, and is a thin film made of metal nitride.
The metal nitride film 3 is preferably made of a material mainly composed of AlN and / or SiN. By using a nitride of aluminum or silicon as the material of the metal nitride film 3, for example, oxygen or water vapor that has passed through a transparent substrate or other thin film, or oxygen contained in the transparent substrate 2 made of a plastic film, Water vapor can be absorbed effectively.

As a method for forming the metal nitride film 3 on the one surface 2a of the transparent substrate 2, any method can be used, but it is chemically unstable that can be oxidized in an atmosphere in which oxygen molecules and water molecules exist. In order to form the metal nitride film 3 as a thick film, it is preferable to use a chemical vapor deposition (CVD) method, especially a plasma CVD method. The temperature of the transparent substrate 2 when forming the metal nitride film 3 is preferably 40 ° C. or lower.
By using the plasma CVD method and performing vacuum film formation while keeping the temperature of the transparent substrate 2 installed in the furnace at a low temperature of 40 ° C. or lower, the metal nitride film 3 is made of oxygen molecules and water molecules. A film having chemically unstable characteristics that can be oxidized in an existing atmosphere can be obtained, and a uniform thin film with good reproducibility can be obtained.
When the metal nitride film is formed with the temperature of the transparent substrate 2 exceeding 40 ° C., it is difficult to obtain the above chemically unstable characteristics, and when the transparent laminate is applied to a front plate of a display device or the like, Oxygen and water vapor entering from the atmosphere cannot be effectively absorbed, and the display element may be deteriorated.

In the present embodiment, the metal nitride film 3 after the transparent laminate 1 is exposed for 100 hours in an atmosphere of a temperature of 40 ° C. and a humidity of 90% Rh is an exposed side surface (the metal nitride film shown in FIG. 1). When the metal nitride film 3 is oxidized in a depth range of 50 to 100 nm from one surface 3a) of 3 and the pre-exposure metal nitride film 3 is SiN, this changes to SiO ₂ and exposure In the case where the previous metal nitride film 3 is AlN, this is defined as changing to Al ₂ O ₃ .
As described above, the metal nitride film 3 has a chemically unstable property of being oxidized in an atmosphere in which oxygen molecules and water molecules are present. If the depth of oxidation of the metal nitride film 3 due to exposure is within the specified range, oxygen and water vapor that has entered from the atmosphere, or oxygen and water vapor contained in the transparent substrate 2 made of a plastic film are effective. Can be absorbed.
Under the above conditions, if the depth of the oxidation progress from the exposed surface of the metal nitride film is less than 50 nm, the above-mentioned chemically unstable characteristics are not obtained, and the transparent laminate is used as a display device or the like. When applied to the front plate, oxygen and water vapor entering from the atmosphere cannot be effectively absorbed, and the display element may be deteriorated.

The metal nitride film 3 preferably has an energy band gap of 3.1 eV or more. If the energy band gap of the material forming the metal nitride film 3 is 3.1 eV or more, it can theoretically be a thin film that does not absorb in the visible light region, and excellent light transmittance can be obtained.
The energy band gap characteristics can be realized by using the above-mentioned nitride of aluminum or silicon as the material of the metal nitride film. Here, as a metal nitride, for example, BN (band gap: 4 to 7 eV), GaN (same: 3.4 eV), AlN (same: 6.2 eV), Si ₃ N ₄ (same: 5.1 eV) Although various materials can be selected and used, it is preferable to use AlN or Si ₃ N ₄ in consideration of the ease of handling the material and the case of forming a film with a large area.
In addition, when Si ₃ N ₄ is used as the material of the metal nitride film, the metal nitride film itself has a high barrier property. Therefore, the metal nitride film can be used as a normal barrier substrate. In this case, it is possible to effectively prevent permeation of oxygen and water vapor.
In addition, since the energy band gaps of aluminum and silicon oxides are 4 eV and 8 eV, respectively, transparency can be maintained even when the metal nitride film becomes an oxide.

In this embodiment, it is preferable that the light transmittance in the transparent laminated body 1 whole including the transparent substrate 2 is 60% or more in the wavelength range of 400 nm-800 nm. By setting the light transmittance in the visible light region wavelength to 60% or more, it can be applied to a front plate of an application using transmitted light, such as a liquid crystal display device.
Further, if the metal nitride film 3 is made of a material having an energy band gap of 3.1 eV or more as described above, theoretically, absorption due to excitation does not appear in the visible light region. It becomes possible to further improve the light transmittance of the entire unit 1.

An example of a form in which the transparent laminate 1 of this embodiment is applied to a front plate of a display device will be described with reference to FIG.
A display device (electronic device) 20 shown in FIG. 2 includes the transparent laminate 1 as a front plate of a display element 21, and the transparent laminate 1 has a transparent substrate with the metal nitride film 3 on the display element 21 side. 2 is arranged on the atmosphere side. The display device 20 according to the present embodiment has the above-described configuration, so that oxygen or water vapor existing in the atmosphere passes through the transparent substrate 2 and enters the display element 21. Since the water vapor is absorbed by the metal nitride film 3, the display element 21 can be prevented from deteriorating. Further, when the transparent substrate 2 is made of a plastic film, even if oxygen or water vapor contained in the plastic film leaks out, the oxygen and water vapor are absorbed by the metal nitride film 3. Deterioration of the element 21 can be suppressed.

  As described above, according to the transparent laminate 1 of the first embodiment of the present invention, a chemically unstable metal that is oxidized on the transparent substrate 2 in an atmosphere containing oxygen molecules and water molecules. Since the nitride film 3 is formed, oxygen and water vapor can be absorbed and permeation can be suppressed. When such a transparent laminate 1 is applied as a front plate of an electronic device such as the display device 20, the display element 21 can be prevented from being deteriorated by oxygen or water vapor, and the display characteristics of the display device 20 are improved. In addition, it is possible to extend the life.

[Second Embodiment]
3-5 is the schematic explaining the 2nd Embodiment of the transparent laminated body based on this invention. In addition, in the transparent laminated bodies 10-12 of this embodiment shown to FIGS. 3-5, about the structure which is common in the transparent laminated body 1 of 1st Embodiment, while attaching | subjecting the same code | symbol, the detailed description is abbreviate | omitted. .
In the transparent laminate of the second embodiment of the present invention, at least one ceramic thin film layer is formed on the transparent substrate 2 with respect to the transparent laminate 1 of the first embodiment. The thin film layer is configured to be chemically stable under a condition where the temperature is 100 ° C. or less in an atmosphere where oxygen molecules and / or water molecules are present. Further, in the transparent laminate 10 of the example shown in FIG. 3, one metal nitride film 3 is formed on one surface 2a of the transparent substrate 2, and one ceramic thin film layer 4 is further formed thereon. ing.

As described above, the ceramic thin film layer 4 is made of a chemically stable material in an atmosphere where oxygen molecules and water molecules are present under a temperature of 100 ° C. or less, and functions as a barrier film in the transparent laminate 10. It is a thin film.
The material constituting the ceramic thin film layer 4 is not particularly limited, and any of oxides, nitrides, oxynitrides, sulfides, and fluorides made of aluminum (Al) and / or silicon (Si) is used. It is possible. Among these, it is preferable to use an oxide, nitride, or oxynitride because the barrier function of the ceramic thin film layer can be further improved.

  In addition, in order to obtain a chemically stable ceramic thin film layer, it is necessary to use an oxide that is stoichiometric, to form a thin film at a substrate temperature higher than the product use temperature, or after the film formation to a temperature higher than the product use temperature. The method of increasing the chemical stability of the ceramic thin film layer is not limited to these, and can be appropriately employed.

  As a method of forming the ceramic thin film layer 4, any film forming method may be adopted as long as the film thickness can be controlled, and in particular, a dry method having excellent thin film forming efficiency and film quality is used. It is preferable to use it. Further, in such a film forming method using a dry method, a physical vapor deposition method such as a vacuum deposition method or sputtering, a chemical vapor deposition method such as a plasma CVD method, or the like can be appropriately employed.

  According to the transparent laminate 10 of the present embodiment, the metal nitride film 3 is formed by laminating the ceramic thin film layer 4 functioning as a chemically stable barrier film on the metal nitride film 3 on the transparent substrate 2. Therefore, it is possible to control the amount of oxygen and water vapor reaching the temperature to be reduced, and to supplement the barrier film function of the metal nitride film 3.

In the transparent laminate 10 of the example shown in FIG. 3, one metal nitride film 3 is formed on one surface 2a of the transparent substrate 2, and one ceramic thin film layer 4 is formed thereon. However, the present embodiment is not limited to this. For example, as shown in FIG. 4, a transparent laminated body 11 in which one ceramic thin film layer 4 is laminated between the metal nitride film 3 and the transparent substrate 2 may be used. Further, as shown in FIG. 5, a transparent laminate 12 in which two ceramic thin film layers 41 and 42 are arranged on the upper and lower surfaces of the metal nitride thin film 3 may be used.
As described above, by appropriately selecting the number and position of the ceramic thin film layers formed on the transparent substrate 2, the directionality of oxygen and water vapor absorbed by the metal nitride film 3 can be controlled in the transparent laminate. Become.

  As shown in FIG. 4, when the ceramic thin film layer 4 is laminated between the metal nitride film 3 and the transparent substrate 2, it enters from the atmosphere side of the transparent laminate 11 (below the transparent substrate 2 in FIG. 4). The ceramic thin film layer 4 can suppress oxygen and water vapor flowing into the display element side (upper side of the metal nitride film 3 in FIG. 4). Then, oxygen or water vapor slightly flowing out from the ceramic thin film layer 4 can be absorbed by the metal nitride film 3. Thereby, it becomes possible to prevent the deterioration of the display element used in the display device.

  On the other hand, as shown in FIG. 5, two ceramic thin film layers 41 and 42 are arranged on the upper and lower surfaces of the metal nitride thin film 3, and the atmosphere side of the metal nitride film 3 (the lower side of the transparent substrate 2 in FIG. 5). When the ceramic thin film layer is also laminated, oxygen and water vapor leaking from the transparent substrate 2 made of a plastic film flows out to the display element side (upper side of the ceramic thin film layer 42 in FIG. 5). Can be suppressed. Then, oxygen or water vapor slightly flowing out from the ceramic thin film layer 41 can be absorbed by the metal nitride film 3. At this time, the barrier function of the ceramic thin film layer 42 laminated on the metal nitride film 3 allows oxygen and water vapor to be absorbed with high efficiency without leaking. Thereby, it becomes possible to more reliably prevent the deterioration of the display element used in the display device.

  In addition, as described above, in order to make the metal nitride film chemically unstable and have an action that can be oxidized in an atmosphere in which oxygen molecules and water molecules exist, the metal nitride film is formed. It is necessary to set the temperature of the transparent substrate to 40 ° C. or lower. On the other hand, the ceramic thin film layer needs to have a higher deposition temperature than the metal nitride film. For this reason, in the process of laminating each layer on the transparent substrate, although there is a limitation depending on the layer structure of the transparent laminate, it is possible to form the ceramic thin film layer before the metal nitride film. And is preferable from the viewpoint of ensuring the absorption of water vapor.

[Third Embodiment]
FIG. 6 is a schematic view illustrating a third embodiment of the transparent laminate according to the present invention. In addition, in the transparent laminated body 10 of this embodiment, about the structure which is common in the transparent laminated body 1 of 1st Embodiment and the transparent laminated bodies 10-12 of 2nd Embodiment, while attaching | subjecting the same code | symbol, the detail The detailed explanation is omitted.
The transparent laminate of the third embodiment of the present invention is further provided on the transparent substrate 2 with respect to the transparent laminate 1 of the first embodiment or the transparent laminates 10 to 12 of the second embodiment. In addition, at least one transparent conductive thin film is formed. Further, in the transparent laminate 15 of the example shown in FIG. 6, the ceramic thin film layer 42 is formed on one surface 2 a of the transparent substrate 2, and one metal nitride film 3 is formed on the other surface 2 b of the transparent substrate 2. The ceramic thin film layer 41 and the transparent conductive thin film 5 are formed in this order by being laminated on one surface 3a of the metal nitride film 3.

  The transparent conductive thin film 5 is made of indium oxide, zinc oxide or tin oxide, or two or three kinds of mixed oxides among them, and those added with other additives. However, various materials can be employed depending on the purpose and application, and the material is not limited to the above materials.

  When indium tin oxide (ITO), which is the most common material, is used as the transparent conductive thin film 5, the content ratio of tin oxide doped in indium oxide is a specification required for an electronic device using a transparent laminate. Any ratio can be selected accordingly. For example, in order to crystallize the transparent conductive thin film 5 for the purpose of increasing the mechanical strength, it is preferable that the content ratio of tin oxide is less than 10% by mass, and in order to make it amorphous and to have flexibility, The content ratio of tin oxide is preferably 10% by mass or more. Moreover, when low resistance is calculated | required by the transparent conductive thin film 5, it is preferable to make the content rate of a tin oxide into the range of 3-20 mass%.

By laminating the transparent conductive thin film 5 as described above, the transparent laminate 15 can be easily applied as a substrate for various electronic devices such as a display device.
In addition, by applying the transparent laminate according to the present invention to various electronic devices, it is possible to suppress oxygen and water vapor transmitted through the transparent laminate, or oxygen and water vapor contained in the transparent substrate from reaching the display element. Therefore, the display element can be prevented from deteriorating, and an electronic device having excellent display characteristics and a long life can be realized.

In addition, in the transparent laminate according to the present invention, in addition to the metal nitride thin film, ceramic thin film, and transparent conductive thin film as described above, an undercoat or an overcoat using an organic film or the like may be used as necessary. May be formed. The material forming the organic film may be any material having transparency, appropriate hardness, and mechanical strength, and resin materials such as acrylic resins, organic silicon resins, and polysiloxanes can be used. As a wet process for coating such an organic film, various coating methods such as microgravure and screen can be used. Moreover, when coating an organic layer, it is also possible to achieve high hardness and easy lubrication by mixing a resin filler or an inorganic filler in the coating solution.
On the other hand, the method for forming the overcoat layer by the organic vapor deposition method is not particularly limited. For example, acrylate or methacrylate or a mixed resin solution thereof is evaporated by an organic vapor deposition apparatus and condensed on a film on a coating drum. Then, it can be used with the method of performing a hardening process with an electron beam irradiation apparatus. At this time, it is also possible to use ultraviolet curing instead of electron beam curing.

  Next, although the transparent laminated body and electronic device of this invention are demonstrated still in detail by an Example, this invention is not limited only to these Examples.

[Example 1]
In this example, a sample of a transparent laminate as shown in FIG. 1 was prepared by the following procedure and evaluated by a test method described later.
First, on a transparent substrate made of polyethersulfone (PES) maintained at a temperature of 40 ° C., SiH ₄ , NH ₃ , and H ₂ are used as source gases, and a plasma CVD method using an RF power source is used to form approximately 118 nm. A metal nitride film made of silicon nitride (SiN) was formed to produce the sample of Example 1.

Subsequently, the component composition of the sample of Example 1 was measured using X-ray photoelectron spectroscopy (XPS). At this time, as an XPS measuring instrument, ESCA3200 manufactured by Shimadzu Corporation was used, and the irradiation X-ray source output was set to conditions of 5 kV and 20 mA. Etching conditions at the time of measurement were Ar gas as an etching gas, a gas pressure of 5 × 10 ⁻⁴ Pa, a sample current of 14 μA, and an etching area in a circle with a diameter of 5 mmφ.

And under each condition shown below, the sample of Example 1 was left in the atmosphere and exposed to an atmosphere in which oxygen molecules and water molecules existed, and the component composition after a predetermined time was measured by XPS.
(1) Measured immediately after film formation.
(2) After film formation, measurement was performed after being left for 24 hours in an environment of temperature 60 ° C. and humidity 90% Rh.
(3) After film formation, measurement was performed after being left for 48 hours in an environment of temperature 60 ° C. and humidity 90% Rh.
(4) After film formation, measurement was performed after being left for 72 hours in an environment of temperature 60 ° C. and humidity 90% Rh.
(5) After film formation, measurement was performed after being left for 96 hours in an environment of a temperature of 60 ° C. and a humidity of 90% Rh.

7 to 11 show graphs of measurement results under the conditions shown in the above (1) to (5).
As shown in the graph of FIG. 7, in the measurement result immediately after the formation of the SiN film which is the condition (1), a film (metal nitride film) made of SiN exists on the transparent substrate made of PES. Can be confirmed.
Further, as shown in the graph of FIG. 8, in the measurement result after being left for 24 hours after the SiN film formation, which is the above condition (2), both sides of the SiN film, that is, both the transparent substrate side and the atmospheric exposure side, Thus, it can be confirmed that a film made of SiO is formed. This is presumably because the SiN film was gradually oxidized in an environment where oxygen molecules and water molecules exist.
Further, as shown in the graph of FIG. 9, the measurement result after leaving for 48 hours after the SiN film formation under the condition (3) is the same as in the case of the condition (2). That is, it can be confirmed that a film made of SiO is formed from both the transparent substrate side and the atmospheric exposure side. However, under the condition (3), as shown in FIG. 9, it can be confirmed that the amount of SiO is larger than the condition (2). This is considered to be because the oxidation of SiN has progressed because the SiN film was left for a longer time in an environment where oxygen molecules and water molecules exist.

Further, as shown in the graph of FIG. 10, in the measurement result after being left for 72 hours after the SiN film formation, which is the above condition (4), the SiN film is almost completely oxidized to be a SiO film. Further, as shown in FIG. 11, the same measurement result is obtained in the measurement result after being allowed to stand for 96 hours after the SiN film formation, which is the condition (5). As shown in the graphs of FIGS. 10 and 11, under the conditions (4) and (5), the SiN film formed in this example is completely oxidized in an environment where oxygen molecules and water molecules exist. It is clear that
In the XPS measurement under the above conditions (4) and (5), as shown in FIGS. 10 and 11, the component composition of the transparent substrate made of PES is not confirmed. This is considered to be due to the fact that the etching rate in XPS was lowered due to the oxidation of the SiN film and the change to the SiO film.

[Comparative Example 1]
In this comparative example, when a film made of SiN was formed, Comparative Example 1 was performed in the same procedure as in Example 1 except that the film formation process was performed while maintaining the transparent substrate made of PES at a high temperature of 130 ° C. A transparent laminate sample was prepared, and the component composition of the transparent laminate was measured using the same method as in Example 1.

12-16, using the sample of Comparative Example 1, after exposing in an atmosphere where oxygen molecules and water molecules exist under the conditions shown in (1) to (5) above, the component composition was measured by XPS. The graph of a result is shown.
As shown in the graph of FIG. 12, in the measurement result immediately after the SiN film formation, which is the condition (1) above, a film (metal nitride film) made of SiN exists on the transparent substrate made of PES. Can be confirmed.

  Further, as shown in the graph of FIG. 13, it is confirmed that the SiN film exists in the measurement result after being left for 24 hours after the SiN film formation, which is the condition (2), and the above (1). It is clear that there are no changes and conditions. Furthermore, as shown in the graphs of FIGS. 14 to 16, the SiN film is also present in the measurement results after leaving for 48 to 96 hours after the SiN film formation under the conditions (3) to (5) above. Was confirmed, and it was clarified that there was no change in the condition (1).

  From the above results, the transparent laminate of Example 1 according to the present invention, in which the SiN film (metal nitride film) is formed in a state where the temperature of the transparent substrate is kept at a low temperature of 40 ° C., the SiN film is It was confirmed that oxidation proceeded easily in an atmosphere where oxygen and water vapor were present. As a result, the transparent laminate of Example 1 according to the present invention can absorb oxygen and water vapor that have passed through the transparent substrate and other thin films by the SiN film, and further oxygen and water vapor can pass through the transparent laminate. It is clear that this can be prevented.

  On the other hand, in the transparent laminate of Comparative Example 1 in which the SiN film was formed in a state where the transparent substrate was maintained at a very high temperature of 130 ° C., in a high temperature and high humidity environment of 60 ° C. and 90% humidity. It was confirmed that the oxidation of the SiN film did not proceed even when left for 96 hours. Thereby, like the comparative example 1, when the transparent laminated body in which the SiN layer which cannot absorb oxygen and water vapor | steam was used for electronic devices, such as a display apparatus, oxygen, water vapor | steam contained in air | atmosphere, transparent It can be understood that oxygen and water vapor contained in the substrate cannot be absorbed to enter the element, and the display element may be deteriorated.

[Example 2]
In this example, a sample of a transparent laminate as shown in FIG. 3 was prepared by the following procedure.
First, on a transparent substrate made of PES kept at a temperature of 40 ° C., a metal nitride made of SiN of about 50 nm is formed by plasma CVD using an RF power source using SiH ₄ , NH ₃ , and H ₂ as source gases. After forming the film, the temperature of the transparent substrate was further raised to 120 ° C., and a ceramic thin film layer made of SiN having a thickness of about 50 nm was formed by the same procedure as a sample of the transparent laminate of Example 2.

The sample of the obtained transparent laminate of Example 2 was measured for the average light transmittance in the visible light region having a wavelength of 400 to 800 nm. As a result, it showed a transmittance of 83.5%, and 40 ° C. and 90%. The water vapor transmission rate in Rh was 0.01 g / m ² · day or less, and it was confirmed that the transparent laminate had both excellent translucency and barrier properties.
As an alternative to the sealing can of the bottom emission type organic EL element, the transparent laminate of Example 2 was adhered to the element with an epoxy resin adhesive, and left for 1000 hours in an environment of 60 ° C. and 90% Rh. Later, the dark spots of the device did not expand, and it was confirmed that the device had good barrier performance. After performing such a test, the component composition of the transparent laminate was analyzed, and it was confirmed that the SiN film was oxidized from a position close to the transparent substrate. This is considered to indicate that the SiN film absorbed and trapped water molecules diffused from the transparent substrate made of PES having a high water absorption rate, thereby preventing the molecules from reaching the device.

[Comparative Example 2]
In this comparative example, as a comparative example with respect to Example 2, when forming a film made of SiN, the transparent substrate made of PES is kept at a high temperature of 120 ° C., and the formed SiN layer (metal nitride film) ) As a single layer, a sample of the transparent laminate of Comparative Example 2 was prepared in the same procedure as in Example 2 except that the thickness was about 100 nm.

About the sample of the obtained transparent laminated body of the comparative example 2, when the average light transmittance in the visible light range whose wavelength is 400-800 nm was measured, it showed the transmittance of 82.5%, and 40 degreeC, 90% The water vapor permeability in Rh was 0.01 g / m ² · day or less, and it was confirmed that the transparent laminate was excellent in terms of translucency and barrier properties.
Then, as an alternative to the sealing can of the bottom emission type organic EL element, the transparent laminate of Comparative Example 2 was adhered to the element with an epoxy resin adhesive and left for 500 hours in an environment of 60 ° C. and 90% Rh. Later, it was confirmed that the dark spots of the device gradually expanded. After conducting such a test, the component composition of the transparent laminate was analyzed, and it was confirmed that the SiN film itself had chemically stable characteristics and was not oxidized. That is, water molecules generated from the substrate are gradually diffused and transmitted through the SiN layer (metal nitride film) to reach the device, and the device has deteriorated.

[Example 3]
In this example, a sample of a transparent laminate as shown in FIG. 6 was prepared by the following procedure.
First, on one side of a transparent substrate made of PES maintained at a temperature of 40 ° C. (see reference numeral 2b shown in FIG. 6), SiH ₄ , NH ₃ , and H ₂ are used as source gases, and a plasma CVD method using an RF power source is used. After forming a metal nitride film made of SiN of about 50 nm, the temperature of the transparent substrate was further raised to 120 ° C., and a ceramic thin film layer made of SiN of about 50 nm was formed by the same procedure. Next, a ceramic thin film layer made of SiN having a thickness of about 50 nm was formed on the other surface of the transparent substrate (see reference numeral 2a shown in FIG. 6) at a temperature of the transparent substrate of 120 ° C. by the same procedure. Then, a transparent conductive thin film (FIG. 6) made of ITO having a SnO ₂ content of 10 wt% is further added to a metal nitride film made of SiN (see reference numeral 41 shown in FIG. 6) formed at a substrate temperature of 40 ° C. And a sample of the transparent laminate of Example 3 was formed to a thickness of 150 nm.

About the sample of the obtained transparent laminated body of Example 3, when the average light transmittance in a visible light region with a wavelength of 400-800 nm was measured, it showed a transmittance of 75%, and at 40 ° C. and 90% Rh. The water vapor transmission rate was 0.01 g / m ² · day or less, and it was confirmed that this was a transparent laminate having both excellent translucency and barrier properties.
And after electrode-patterning the transparent conductive thin film formed on this transparent substrate, when the top emission type organic EL element was formed on this transparent conductive thin film, it was 1000 in 60 degreeC and 90% Rh environment. Even after being left for a long time, the dark spots of the device did not expand, and it was confirmed that the device had good barrier performance.

[Comparative Example 3]
In this comparative example, as a comparative example with respect to Example 3, the transparent substrate made of PES was held at a high temperature of 120 ° C. when forming a metal nitride film made of SiN (see reference numeral 3 shown in FIG. 6). Except for the above point, a transparent conductive thin film (see reference numeral 5 shown in FIG. 6) made of ITO having a SnO ₂ content of 10 wt% is formed with a thickness of 150 nm in the same procedure as in Example 3 above. A sample of the transparent laminate of Comparative Example 3 was produced.

About the sample of the obtained transparent laminated body of the comparative example 3, when the average light transmittance in the visible light region with a wavelength of 400-800 nm was measured, it showed a transmittance of 74%, and at 40 ° C. and 90% Rh. The water vapor transmission rate was 0.01 g / m ² · day or less, and it was confirmed that the transparent laminate was excellent in terms of translucency and barrier properties.
Then, after electrode patterning of the transparent conductive thin film formed on this transparent substrate, a top emission type organic EL element was formed on this transparent conductive thin film, and it was 250 in an environment of 60 ° C. and 90% Rh. It was confirmed that the dark spot of the device was enlarged after being left for a period of time.

  From the results of the above examples, the transparent laminate according to the present invention can absorb oxygen and water vapor by the metal nitride film, and such a transparent laminate is applied as a front plate of an electronic device such as a display device. Thus, it has become clear that the element can be prevented from deteriorating.

It is a schematic diagram for demonstrating an example of the transparent laminated body of this invention, and is sectional drawing which shows the state in which the metal nitride film was formed in one surface of a transparent substrate. It is a schematic diagram for demonstrating an example of the electronic device by which the transparent laminated body of this invention is used, and is sectional drawing which shows the state by which the transparent laminated body was provided in the front surface of the display element. It is a schematic diagram for demonstrating an example of the transparent laminated body of this invention, and is sectional drawing which shows the state by which the metal nitride film and the ceramic thin film layer were laminated | stacked in this order on one surface of the transparent substrate. It is a schematic diagram for demonstrating an example of the transparent laminated body of this invention, and is sectional drawing which shows the state by which the ceramic thin film layer and the metal nitride film were laminated | stacked in this order on one surface of the transparent substrate. It is a schematic diagram for demonstrating an example of the transparent laminated body of this invention, and is sectional drawing which shows the state by which two ceramic thin film layers were distribute | arranged to the upper and lower surfaces of the metal nitride thin film on one surface of the transparent substrate. is there. It is a schematic diagram for demonstrating an example of the transparent laminated body of this invention, laminated | stacked one ceramic thin film layer on one side of a transparent substrate, and a metal nitride film and a ceramic thin film on the other side of a transparent substrate It is sectional drawing which shows the state by which the layer and the transparent conductive thin film were laminated | stacked in this order. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, and is a graph showing the component composition of the transparent laminated body measured immediately after forming the metal nitride film on the transparent substrate. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, after forming a metal nitride film | membrane on a transparent substrate, and measuring after standing in the environment of temperature 60 degreeC and humidity 90% Rh for 24 hours It is a graph showing the component composition of a transparent laminated body. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, after forming a metal nitride film | membrane on a transparent substrate, it measured after leaving to stand in the environment of temperature 60 degreeC and humidity 90% Rh for 48 hours. It is a graph showing the component composition of a transparent laminated body. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, after forming a metal nitride film | membrane on a transparent substrate and measuring it after leaving to stand in the environment of temperature 60 degreeC and humidity 90% Rh for 72 hours It is a graph showing the component composition of a transparent laminated body. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, after forming a metal nitride film | membrane on a transparent substrate and measuring it after leaving to stand in the environment of temperature 60 degreeC and humidity 90% Rh for 96 hours It is a graph showing the component composition of a transparent laminated body. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, and is a graph showing the component composition measured immediately after film-forming of the metal nitride film on the transparent substrate using the transparent laminated body of a comparative example. It is. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, and after forming a metal nitride film on a transparent substrate using the transparent laminated body of a comparative example, temperature 60 degreeC and humidity 90% It is a graph showing the component composition measured after leaving to stand for 24 hours in the environment of Rh. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, and after forming a metal nitride film on a transparent substrate using the transparent laminated body of a comparative example, temperature 60 degreeC and humidity 90% It is a graph showing the component composition measured after leaving to stand in the environment of Rh for 48 hours. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, and after forming a metal nitride film on a transparent substrate using the transparent laminated body of a comparative example, temperature 60 degreeC and humidity 90% It is a graph showing the component composition measured after leaving for 72 hours in the environment of Rh. It is a schematic diagram for demonstrating the Example of the transparent laminated body of this invention, and after forming a metal nitride film on a transparent substrate using the transparent laminated body of a comparative example, temperature 60 degreeC and humidity 90% It is a graph showing the component composition measured after leaving to stand in the environment of Rh for 96 hours.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 10, 11, 12, 15 ... Transparent laminated body, 2 ... Transparent substrate, 2a ... One side, 3 ... Metal nitride film, 4 ... Ceramic thin film layer, 5 ... Transparent electroconductive thin film

Claims (9)

A transparent laminate least metallic nitride film and a ceramic thin film layer formed on a transparent substrate,
The metal nitride film is a SiN film, the ceramic thin film layer is a SiO film, and a SiO film, a SiN film, and a SiO film are sequentially laminated on the transparent substrate,
The SiN film in an atmosphere that there are at least oxygen molecules and / or water molecules, Ri chemically unstable Monodea that absorbs oxygen or water vapor Ru is oxidized, and the SiO film, the oxygen molecules and / or in conditions where the temperature was set to 100 ° C. or less in an atmosphere of water molecules are present, the transparent laminate, characterized in chemically stable barrier film der Rukoto to oxygen and water vapor. Temperature 40 ° C., said SiN film after being exposed for 100 hours in an atmosphere of a humidity 90% Rh is, at a depth in the range of 50~100nm terms of exposure side, in which SiN is changed to SiO ₂ The transparent laminate according to claim 1 . The transparent laminate according to claim 1 or 2 , wherein an energy band gap of the SiN film is 3.1 eV or more. The light transmittance including a transparent substrate, a transparent laminate according to any one of claim 1 to 3, characterized in that 60% or more in the wavelength range of 400 nm to 800 nm. The transparent laminate according to any one of claims 1 to 4 , wherein the transparent substrate is a plastic film. In an environment of a temperature of 40 ° C. and a humidity of 90% Rh, the water vapor transmission rate is 0.5 g / m ² · day or less and the oxygen transmission rate is 0.5 cc / m ² · day · atm or less. The transparent laminate according to any one of claims 1 to 5 . Furthermore, at least 1 layer of transparent conductive thin film is formed, The transparent laminated body of any one of Claims 1-6 characterized by the above-mentioned. A method for producing the transparent laminate according to any one of claims 1 to 7,
The metal nitride film is formed from SiN by a chemical vapor deposition (CVD) method with the temperature of the transparent substrate being 40 ° C. or less , and the ceramic thin film layer is formed by vacuum deposition, physical vapor deposition, or By forming the transparent substrate from SiO at a temperature higher than the formation temperature of the metal nitride film by chemical vapor deposition (CVD), the SiO film, SiN film, and A method for producing a transparent laminate, comprising laminating a SiO film . An electronic device comprising the transparent laminate according to any one of claims 1 to 7 .

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