KR20150054693A - Glass laminated body and manufacturing method of electronic device - Google Patents

Abstract

The present invention relates to a manufacturing method of glass laminated body comprising a support substrate, a support substrate having an inorganic layer arranged on the support substrate, and a glass substrate laminated on the inorganic layer to be possibly exfoliated wherein the inorganic layer is an opposite surface side to the support substrate side, and has SiC1-xOx(x=0. 10 to 0.90) and/or SiN1-yOy(y=0. 10 to 0. 90) as a composition for the inorganic layer surface, and also has 0.20 to 1.00 nm of surface roughness (Ra) of the inorganic layer surface.

Description

TECHNICAL FIELD [0001] The present invention relates to a glass laminate and an electronic device,

The present invention relates to a glass laminate and a method of manufacturing an electronic device.

2. Description of the Related Art In recent years, thinner and lighter electronic devices (electronic devices) such as a solar cell (PV), a liquid crystal panel (LCD), and an organic EL panel (OLED) have. On the other hand, if the strength of the glass substrate is insufficient due to the thinning, the handling of the glass substrate in the manufacturing process of the electronic device is deteriorated.

Therefore, recently, from the viewpoint of improving the handling property of the glass substrate, a laminate in which a glass substrate is laminated on an inorganic thin film of a supporting glass provided with an inorganic thin film is prepared, and a device is produced on the glass substrate of the laminate A method of separating a glass substrate from a laminated body has been proposed (Patent Document 1).

Japanese Patent Application Laid-Open No. 2011-184284

The inventors of the present invention have studied a support glass provided with an inorganic thin film composed of a metal oxide specifically described in Patent Document 1. As a result, it was found that the lamination property (ease of lamination) when the glass substrate was laminated on the inorganic thin film was sometimes lowered. In other words, even if the inorganic thin film and the glass substrate are overlapped, it is found that not only the organic thin film and the glass substrate do not come into close contact with each other, but they do not stick closely to each other or peel off easily.

In recent years, along with the demand for high performance of electronic devices, it is desired to carry out treatment under higher temperature conditions in the production of electronic devices. Therefore, the present inventors have found that the support glass provided with an inorganic thin film, (For example, 600 占 폚, 1 hour). As a result, even if the lamination property was good, it was found that the peeling property could be deteriorated, for example, the glass substrate could not be peeled off when the glass substrate was peeled by a specific method after the heat treatment. In this case, there arises a problem that after the device is manufactured under high temperature conditions, the glass substrate on which the device is formed can not be peeled off from the laminate.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a glass laminate excellent in the lamination property of an inorganic layer and a glass substrate disposed on a support substrate and excellent in peelability of an inorganic layer and a glass substrate even after treatment under high temperature conditions, And an object of the present invention is to provide a method of manufacturing an electronic device using the above glass laminate.

Means for Solving the Problems The inventors of the present invention have made intensive studies in order to achieve the above object and found that by forming an inorganic layer having a specific surface composition and surface roughness on a support substrate, Thus completing the present invention.

That is, the present invention provides the following (1) to (8).

(1) a support substrate provided with an inorganic layer, the support substrate having a support substrate and an inorganic layer disposed on the support substrate; and a separation layer on the surface of the inorganic layer which is a surface opposite to the support substrate side in the inorganic layer having a glass substrate can be laminated, and the inorganic layer is the as the composition of the inorganic layer surface _{SiC 1 - x O x (x} = 0.10 to 0.90) and / or a _{SiN 1 - y O y (y} = 0.10 to 0.90) And the surface roughness (Ra) of the surface of the inorganic layer is 0.20 to 1.00 nm.

(2) The glass laminate according to (1), wherein a surface roughness (Ra) of the surface of the inorganic layer is 0.30 nm or more.

(3) The glass laminate according to the above (1) or (2), wherein the surface roughness (Ra) of the inorganic layer surface is 0.50 nm or less.

(4) The glass laminate according to any one of (1) to (3), wherein the x and y are 0.20 or more.

(5) The glass laminate according to any one of (1) to (4), wherein x and y are numbers of not more than 0.50.

(6) The glass laminate according to any one of (1) to (5), wherein the support substrate is a glass substrate.

(7) The glass laminate according to any one of (1) to (6), wherein the support substrate provided with the inorganic layer after the heat treatment at 600 占 폚 for 1 hour and the glass substrate can be peeled off.

(8) a member forming step of forming a member for an electronic device on the surface of the glass substrate in the glass laminate according to any one of (1) to (7) above to obtain a laminate provided with a member for an electronic device; And a separating step of separating the support substrate provided with the inorganic layer from the laminate provided with the electronic device member to obtain an electronic device having the glass substrate and the electronic device member.

According to the present invention, it is possible to provide a glass laminate excellent in the lamination property of the inorganic layer and the glass substrate disposed on the support substrate and excellent in peelability between the inorganic layer and the glass substrate even after the treatment under high temperature conditions, A method of manufacturing an electronic device can be provided.

1 is a schematic cross-sectional view of one embodiment of a glass laminate according to the present invention.
2 (A) and 2 (B) are process drawings of a method of manufacturing an electronic device according to the present invention.
3 is a schematic cross-sectional view showing a peeling property evaluation method.

Best Mode for Carrying Out the Invention Hereinafter, suitable forms of the glass laminate and the method of manufacturing an electronic device of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, Various modifications and substitutions can be made.

The glass laminate of the present invention is roughly composed of an inorganic layer having a specific surface (inorganic layer surface) interposed between a support substrate and a glass substrate as a surface in contact with the glass substrate, The lamination property is excellent and the peeling property of the inorganic layer and the glass substrate is excellent even after the treatment under high temperature conditions.

Hereinafter, a preferred embodiment of a method of manufacturing an electronic device using the glass laminate will be described in detail below with reference to a preferred embodiment of a glass laminate.

≪ Glass laminate &

1 is a schematic cross-sectional view of one embodiment of a glass laminate according to the present invention.

1, the glass laminate 10 has a support substrate 16 provided with an inorganic layer, which includes a support substrate 12 and an inorganic layer 14, and a glass substrate 18. As shown in Fig. The inorganic layer surface 14a of the inorganic layer 14 of the supporting substrate 16 provided with the inorganic layer (the surface opposite to the supporting substrate 12 side) and the glass substrate The support substrate 16 provided with the inorganic layer and the glass substrate 18 are laminated in such a manner that the first main surface 18a of the glass substrate 18 is laminated. That is, one side of the inorganic layer 14 is fixed to the supporting substrate 12 and the other side thereof is in contact with the first main surface 18a of the glass substrate 18 and the inorganic layer 14 and the glass The interface of the substrate 18 is in close contact with the substrate 18 so as to be detachable. In other words, the inorganic layer 14 has easiness of peeling off from the first main surface 18a of the glass substrate 18.

This glass laminate 10 is also used until a member forming process described later. That is, this glass laminate 10 is used on the surface of the second main surface 18b of the glass substrate 18 until a member for an electronic device such as a liquid crystal display device is formed. Thereafter, the supporting substrate 16 provided with the inorganic layer is peeled from the interface with the glass substrate 18, and the supporting substrate 16 provided with the inorganic layer is not a member constituting the electronic device. The separated supporting substrate 16 with the inorganic layer can be laminated with a new glass substrate 18 and reused as a new glass laminate 10. [

In the present invention, the fixation (peelable) adhesion has a difference in the peel strength (i.e., the stress required for peeling), and the fixation means that the peel strength is high in adhesion. Specifically, the peel strength at the interface between the inorganic layer 14 and the support substrate 12 is greater than the peel strength at the interface between the inorganic layer 14 and the glass substrate 18 in the glass laminate 10.

The term "peelably adhered" means peelable and peelable without causing peeling of the fixed surface. That is, in the glass laminate 10 of the present invention, when the operation of separating the glass substrate 18 and the support substrate 12 is performed, the surface (the inorganic layer 14 and the glass substrate 18) Interface), and does not peel off from the fixed surface. Thus, when the operation of separating the glass laminate 10 into the glass substrate 18 and the support substrate 12 is performed, the glass laminate 10 comprises the glass substrate 18, the support substrate 16 provided with the inorganic layer, Lt; / RTI >

Hereinafter, the supporting substrate 16 and the glass substrate 18 provided with the inorganic layer and constituting the glass laminate 10 will be described in detail, and then the manufacturing process of the glass laminate 10 Will be described in detail.

[Supporting substrate provided with an inorganic layer]

The support substrate 16 provided with an inorganic layer has a support substrate 12 and an inorganic layer 14 disposed (fixed) on the surface thereof. The inorganic layer 14 is disposed on the outermost side of the support substrate 16 provided with the inorganic layer so as to be in peelable contact with the glass substrate 18 to be described later.

Hereinafter, the shapes of the support substrate 12 and the inorganic layer 14 will be described in detail.

(Supporting substrate)

The supporting substrate 12 has a first main surface and a second main surface and cooperates with the inorganic layer 14 disposed on the first main surface to support and reinforce the glass substrate 18, A process for manufacturing a member for a device) is a substrate for preventing deformation, scratches and breakage of the glass substrate 18 at the time of manufacturing the electronic device member.

As the supporting substrate 12, for example, a metal plate such as a glass plate, a plastic plate, an SUS plate, or the like is used. The supporting substrate 12 is preferably formed of a material having a smaller coefficient of linear expansion than that of the glass substrate 18 when the member forming step involves heat treatment and is preferably formed of the same material as the glass substrate 18 desirable. That is, the supporting substrate 12 is preferably a glass plate. In particular, the supporting substrate 12 is preferably a glass plate made of the same glass material as the glass substrate 18. [

The thickness of the support substrate 12 may be thicker or thinner than that of the glass substrate 18 described later. The thickness of the supporting substrate 12 is preferably selected based on the thickness of the glass substrate 18, the thickness of the inorganic layer 14, and the thickness of the glass laminate 10 described below. For example, if the current member forming process is designed to process a substrate having a thickness of 0.5 mm and the thickness of the glass substrate 18 and the thickness of the inorganic layer 14 is 0.1 mm, 0.4 mm. The thickness of the support substrate 12 is usually 0.2 to 5.0 mm.

When the supporting substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for easy handling and difficulty in breaking. Further, the thickness of the glass plate is preferably 1.0 mm or less for reasons of stiffness such as warping without breaking when peeling off after formation of the electronic device member.

(Inorganic layer)

The inorganic layer 14 is a layer that is placed (fixed) on the first main surface of the support substrate 12 and contacts the first main surface 18a of the glass substrate 18. [ By forming the inorganic layer 14 on the support substrate 12, adhesion between the inorganic layer 14 and the glass substrate 18 can be suppressed even after long-term treatment under high temperature conditions.

In the present invention, the inorganic layer 14 is made of SiC _{1 - x} O _x (x = 0.10 to 0.90) and / or SiN _{1 - y} O _y (y = 0.10 to 0.90) as the composition of the inorganic layer surface 14a .

Here, if x and y are less than 0.10, the releasability to the glass substrate 18 is lowered. If the number is larger than 0.90, the lamination property to the glass substrate 18 is lowered. All are excellent.

Although the reason for this is not clear, the surface flatness is optimized by the fact that silicon carbide and / or silicon nitride having a comparatively small difference in electronegativity between elements contains an appropriate amount of oxygen, or the surface flatness between the inorganic layer and the glass substrate , It is considered that transition from a weak bond to a strong bond is difficult to occur.

Further, x and y preferably have a number of not less than 0.20 because they are more excellent in peelability, and a number of not more than 0.50 is preferable from the viewpoint that the lamination property is better, and from 0.20 to 0.50 Is more preferable.

The inorganic layer surface 14a of the inorganic layer 14 is a portion including the outermost surface of the inorganic layer 14 (the outermost surface on the side opposite to the support substrate 12) (Thickness) of the inorganic layer 14 is 100% from the outermost surface of the support substrate 12 toward the side of the support substrate 12 to a distance of 1.0 nm from the outermost surface of the support substrate 12 % ≪ / RTI > of the surface area of the substrate. The term " top surface " as used herein refers to a " plane including a surface peak portion that ignores surface roughness ".

Compositions other than the inorganic layer surface 14a and the inorganic layer surface 14a in the inorganic layer 14 can be measured by X-ray photoelectron spectroscopy (XPS).

The composition other than the inorganic layer surface 14a in the inorganic layer 14 may be different from or the same as the composition of the inorganic layer surface 14a.

In the present invention, the surface roughness Ra of the inorganic layer surface 14a is 0.20 to 1.00 nm. If the surface roughness Ra of the inorganic layer surface 14a in contact with the glass substrate 18 is less than 0.20 nm, the peelability to the glass substrate 18 is deteriorated. If the surface roughness Ra exceeds 1.00 nm, But if it is in the above range, the lamination property and the peelability are both excellent.

The surface roughness Ra of the inorganic layer surface 14a is preferably not less than 0.30 nm because the peelability is better, and 0.50 nm or less is preferable for the lamination property, and the lamination property and peelability And 0.30 to 0.50 nm are more preferable because they are more excellent together.

As a method for controlling the surface roughness of the inorganic layer surface 14a, for example, there can be mentioned a method of changing the formation conditions (film forming conditions) of the inorganic layer 14, specifically, And a method for changing the information.

Ra (arithmetic average roughness) is measured according to JIS B 0601 (revised in 2001). The contents of JIS B 0601 (revised 2001) are incorporated herein by reference.

When the inorganic layer 14, (hereinafter referred to simply as "average linear thermal expansion coefficient"), the average linear expansion coefficient at 25 to 300 ℃ is not particularly limited, however, to use a glass plate as a support substrate 12 is provided with 10 × 10 ^{- 7} to 200 x 10 < ^-7 > / DEG C is preferable. In the above range, the difference in the coefficient of linear thermal expansion between the glass plate (SiO ₂ ) and the glass plate (SiO ₂ ) is small, and the positional deviation between the glass substrate 18 and the support substrate 16 provided with the inorganic layer under a high temperature environment can be suppressed.

The inorganic layer 14 preferably contains the above-mentioned SiC _{1 - x} O _x (x = 0.10 to 0.90) and / or SiN _{1 - y} O _y (y = 0.10 to 0.90) as a main component. Here, the main component means that the total content thereof is 90% by mass or more, preferably 98% by mass or more, more preferably 99% by mass or more, and particularly preferably 99.999% by mass or more with respect to the total amount of the inorganic layer 14 .

The thickness of the inorganic layer 14 is preferably 5 to 5000 nm, more preferably 10 to 500 nm, from the viewpoint of scratch resistance.

Although the inorganic layer 14 is described as a single layer in Fig. 1, two or more layers may be laminated. In the case of two or more layers, the composition may be different for each layer. In this case, the " thickness of the inorganic layer " means the total thickness of all the layers.

The inorganic layer 14 is usually formed on the entire surface of the support substrate 12 as shown in Fig. 1, but may be formed on a part of the surface of the support substrate 12, good. For example, the inorganic layer 14 may be formed on the surface of the support substrate 12 in a island shape or a stripe shape.

The inorganic layer 14 exhibits excellent heat resistance. Therefore, even if the glass laminate 10 is exposed to a high temperature condition, the chemical change of the inorganic layer itself is hard to occur and it is difficult for the chemical bond to be generated between the glass substrate 18 and a glass substrate 18 to be described later, The adhesion of the inorganic layer 14 to the substrate 18 is less likely to occur.

The peeling strength at the interface between the inorganic layer 14 and the glass substrate 18 is determined by the peeling strength at the interface between the supporting substrate 12 and the inorganic layer 14 and the strength of the material itself of the inorganic layer 14 (Bulk strength). If the interface between the inorganic layer 14 and the glass substrate 18 is heavy, the component of the inorganic layer 14 easily adheres to the surface of the glass substrate 18, and the surface of the glass substrate 18 tends to be difficult to be cleaned. The attachment of the inorganic layer 14 to the surface of the glass substrate 18 means that the entire inorganic layer 14 adheres to the surface of the glass substrate 18 and that the surface of the inorganic layer 14 is damaged, A part of the surface component is attached to the surface of the glass substrate 18, and the like.

(Manufacturing method of supporting substrate provided with inorganic layer)

As a method of manufacturing the support substrate 16 provided with the inorganic layer, for example, a SiC target or a SiN target is used to introduce a mixed gas of an inert gas such as Ar and an oxygen atom-containing gas such as O ₂ or CO ₂ A method of forming the inorganic layer 14 having the above-mentioned composition of the inorganic layer surface 14a on the support substrate 12 by a vapor deposition method, a sputtering method, a CVD method or the like. At this time, the amount of oxygen (i.e., the values of x and y) of the inorganic layer surface 14a can be controlled by adjusting the amount of the oxygen atom-containing gas in the mixed gas. The optimum conditions for the production conditions are appropriately selected according to the materials to be used and the like.

The surface of the inorganic layer 14 may be subjected to a cutting process so as to control the surface roughness Ra of the inorganic layer surface 14a after the inorganic layer 14 is formed on the supporting substrate 12 . As the above-mentioned treatment, for example, ion sputtering and the like can be mentioned.

[Glass Substrate]

The first main surface 18a of the glass substrate 18 is in intimate contact with the inorganic layer 14 and the second main surface 18b on the opposite side of the inorganic layer 14 side is provided with an electronic device member to be described later.

The type of the glass substrate 18 may be a general one, and examples thereof include glass substrates for display devices such as LCDs and OLEDs. The glass substrate 18 is excellent in chemical resistance and moisture permeability, and has a low heat shrinkage rate. The coefficient of linear expansion specified in JIS R 3102 (revised in 1995) is used as an index of the heat shrinkage ratio. The contents of JIS R 3102 (revised 1995) are incorporated herein by reference.

The glass substrate 18 is obtained by melting a glass raw material and molding the molten glass into a plate. Such a molding method may be a general one, and for example, a float method, a fusion method, a slot down-draw method, a furcall method, a lubrication method, or the like is used. Particularly, a glass substrate having a small thickness can be obtained by a method in which a glass molded into a plate shape is once heated to a molding temperature and thinned by means of drawing or the like (lead furnace method).

The glass of the glass substrate 18 is not particularly limited, but is preferably an alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, or other oxide-based glass mainly containing silicon oxide. As the oxide-based glass, glass having a silicon oxide content of 40 to 90 mass% in terms of oxide is preferable.

As the glass for the glass substrate 18, glass suitable for the kind of device and its manufacturing process is employed. For example, a glass substrate for a liquid crystal panel includes a glass (alkali-free glass) substantially free from an alkali metal component since the elution of the alkali metal component is likely to affect the liquid crystal (note that the alkali- Included). Thus, the glass of the glass substrate 18 is appropriately selected based on the kind of device to be applied and the manufacturing process thereof.

Although the thickness of the glass substrate 18 is not particularly limited, it is usually 0.8 mm or less, preferably 0.3 mm or less, more preferably 0.15 mm or less from the viewpoints of reducing the thickness and / or weight of the glass substrate 18 . If it is more than 0.8 mm, the glass substrate 18 can not satisfy the requirement for reduction in thickness and / or weight. When the thickness is 0.3 mm or less, it is possible to impart good flexibility to the glass substrate 18. When the thickness is 0.15 mm or less, the glass substrate 18 can be rolled up in a roll form. The thickness of the glass substrate 18 is preferably 0.03 mm or more for ease of manufacturing the glass substrate 18 and easy handling of the glass substrate 18. [

Further, the glass substrate 18 may be composed of two or more layers, and in this case, the materials for forming the layers may be the same material or different materials. In this case, the " thickness of the glass substrate " means the total thickness of all the layers.

An inorganic thin film layer may be further stacked on the first main surface 18a of the glass substrate 18. [

When the inorganic thin film layer is arranged (fixed) on the glass substrate 18, the inorganic thin film layer and the inorganic layer 14 of the supporting substrate 16 provided with the inorganic layer are in contact with each other in the glass laminate. By forming the inorganic thin film layer on the glass substrate 18, adhesion of the glass substrate 18 to the support substrate 16 provided with the inorganic layer can be further suppressed even after long term processing under high temperature conditions.

The form of the inorganic thin film layer is not particularly limited, but preferably includes at least one selected from the group consisting of a metal oxide, a metal nitride, a metal oxynitride, a metal carbide, a metal carbonitride, a metal silicide and a metal fluoride. Among them, a metal oxide is preferable, and indium tin oxide is more preferable because the glass substrate 18 is more excellent in peelability.

As the metal oxides, metal nitrides and metal oxynitrides, for example, Si, Hf, Zr, Ta, Ti, Y, Nb, Na, Co, Al, Zn, Pb, Mg, Bi, La, Ce, Oxides, nitrides and oxynitrides of one or more elements selected from Eu, Gd, Dy, Er, Sr, Sn, In and Ba. More specifically, a metal oxide such as titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), gallium oxide (Ga ₂ O ₃ ), indium tin oxide Indium zinc oxide (IZO), zinc oxide tin oxide (ZTO), and gallium-doped zinc oxide (GZO).

Examples of the metal carbides and metal carbonitrides include at least one elemental carbide and carbonitride selected from Ti, W, Si, Zr, and Nb. Examples of the metal silicide include a silicide of at least one element selected from Mo, W and Cr. Examples of the metal fluoride include fluorides of at least one element selected from Mg, Y, La, and Ba.

≪ Glass laminate &

The glass laminate 10 of the present invention is a laminated body in which the inorganic layer surface 14a of the support substrate 16 provided with the inorganic layer and the first main surface 18a of the glass substrate 18 are laminated, A support substrate 16 provided with an inorganic layer, and a glass substrate 18 are laminated in such a manner that they can be peeled off. In other words, it is a laminate in which the inorganic layer 14 is interposed between the support substrate 12 and the glass substrate 18. [

≪ Production method of glass laminate >

The method for producing the glass laminate 10 of the present invention is not particularly limited. Specifically, after the support substrate 16 provided with the inorganic layer under an atmospheric pressure environment is overlaid with the glass substrate 18, A method of generating a close contact starting point in the overlapping plane by naturally pressing the glass substrate 18 with its own weight or the second main surface 18b of the glass substrate 18 one by one and naturally extending the close contact from the close contact starting point; A method of expanding the adhesion from the adhesion starting point by pressing using a roll or press; And the like. It is preferable that the inorganic layer 14 and the glass substrate 18 are brought into close contact with each other by pressing by roll or press because the bubbles mixed in between them are relatively easily removed.

Further, it is more preferable to press it by a vacuum laminating method or a vacuum press method since it is preferable to suppress mixing of bubbles and ensure good adhesion. Even when minute bubbles remain in the vacuum, the bubbles do not grow due to heating, which makes it difficult to cause distortion defects.

When the support substrate 16 provided with the inorganic layer and the glass substrate 18 are brought into peelable contact with each other, the surface on the side where the inorganic layer 14 and the glass substrate 18 are in contact with each other is thoroughly cleaned, It is preferable to laminate it in an environment. The higher the cleanliness, the better the flatness is.

The cleaning method is not particularly limited. For example, a method of cleaning the surface of the inorganic layer 14 or the glass substrate 18 with an aqueous alkali solution, followed by further cleaning with water.

Further, in order to obtain a favorable laminated state, it is preferable to laminate after cleaning the surface of the side where the inorganic layer 14 and the glass substrate 18 are brought into contact with each other, after the plasma treatment. Examples of the plasma used for the plasma treatment include an atmospheric plasma and a vacuum plasma.

The glass laminate 10 of the present invention can be used for various purposes. For example, the glass laminate 10 of the present invention can be used for producing electronic parts such as display panel, PV, thin film secondary battery, . Further, in the above applications, the glass laminate 10 is often exposed (for example, 1 hour or more) under high temperature conditions (for example, 350 ° C or more).

Here, the panel for a display device includes an LCD, an OLED, an electronic paper, a field emission panel, a quantum dot LED panel, a MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

≪ Electronic device and method for manufacturing the same &

Next, a suitable embodiment of the electronic device and its manufacturing method will be described in detail.

Fig. 2 is a schematic cross-sectional view showing each of the manufacturing steps in the preferred embodiment of the method of manufacturing an electronic device of the present invention in order. A preferred embodiment of the electronic device of the present invention comprises a member forming process and a separating process.

Hereinafter, referring to Fig. 2, the materials used in each step and the procedure thereof will be described in detail. The preferred member forming process will be described in detail.

[Member forming process]

The member forming step is a step of forming an electronic device member on the glass substrate in the glass laminate.

More specifically, as shown in Fig. 2A, the electronic device member 20 is formed on the second main surface 18b of the glass substrate 18 in this step, and the electronic device member The laminated body 22 is prepared.

First, the electronic device member 20 used in this process will be described in detail and the procedure of the subsequent process will be described in detail.

(Member for electronic device (functional element))

The member 20 for the electronic device is a member formed on the second main surface 18b of the glass substrate 18 in the glass laminate 10 and constituting at least a part of the electronic device. More specifically, examples of the member 20 for an electronic device include a member used for a display device panel, a solar cell, a thin-film secondary battery, and an electronic part such as a semiconductor wafer on which a circuit is formed on a surface. The panel for a display device includes an organic EL panel, a field emission panel, and the like.

Examples of members for solar cells include a transparent electrode such as a tin oxide of a positive electrode in a silicon type, a silicon layer and a metal of a negative electrode in the form of p layer / i layer / n layer, and the like, , A quantum dot type, and the like.

Examples of members for a thin film secondary battery include a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode in a lithium ion type, a lithium compound in an electrolyte layer, a metal in a current collecting layer, a resin as a sealing layer, Various members corresponding to small size, polymer type, ceramics electrolyte type, and the like.

Examples of the electronic component member include metal of a conductive part in a CCD or CMOS, silicon oxide in an insulating part and silicon nitride, and various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board, a rigid flexible printed board And the like.

(Process procedure)

The method of manufacturing the laminated body 22 provided with the above-described electronic device member is not particularly limited, and the method of manufacturing the laminated body 22 of the glass laminate 10 (20) is formed on the second main surface (18b) of the second substrate (18).

The electronic device member 20 is not a whole of a member finally formed on the second main surface 18b of the glass substrate 18 (hereinafter referred to as a "whole member") but a part Quot; partial member "). The glass substrate provided with the partial member may be a glass substrate (corresponding to an electronic device described later) provided with the entire member in the subsequent steps. Further, the glass substrate provided with the entire member may be provided with another electronic device member on its peeling surface (first main surface). Alternatively, the electronic device may be manufactured by assembling a laminate provided with an entire member, and thereafter peeling the support substrate 16 provided with the inorganic layer from the laminate provided with the entire member. Further, the electronic device is assembled by using two laminated bodies provided with the entire members, and then the supporting substrate 16 provided with the two inorganic layers is peeled from the laminated body provided with the entire member, An electronic device having a substrate may be manufactured.

For example, in the case of manufacturing an OLED, a transparent electrode may be formed to form an organic EL structure on the surface of the second main surface 18b of the glass substrate 18 of the glass laminate 10, A hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, or the like is further deposited on the surface on which the electron transport layer is formed, a back electrode is formed, or sealing is performed using a sealing plate. Specific examples of these layer formation and treatment include film forming treatment, vapor deposition treatment, bonding treatment of a sealing plate, and the like.

For example, a manufacturing method of a TFT-LCD is a method of manufacturing a TFT-LCD by using a resist solution on a second main surface 18b of a glass substrate 18 of a glass laminate 10 by a general film forming method such as a CVD method and a sputtering method A TFT forming step of forming a thin film transistor (TFT) by forming a pattern on a metal film and a metal oxide film to be formed on the first main surface 18b of the glass laminate 10; A CF forming step of forming a color filter CF by use of a pattern and a bonding step of laminating a device substrate provided with a TFT and a device substrate provided with a CF.

In the TFT forming step and the CF forming step, a TFT or CF is formed on the second main surface 18b of the glass substrate 18 by using a well-known photolithography technique or an etching technique. At this time, a resist solution is used as a coating liquid for pattern formation.

Further, the second main surface 18b of the glass substrate 18 may be cleaned before forming the TFT or the CF, if necessary. As the cleaning method, well-known dry cleaning or wet cleaning can be used.

In the bonding step, a liquid crystal material is injected between the laminated body provided with the TFT and the laminated body provided with the CF, and laminated. As a method of injecting the liquid crystal material, for example, there are a reduced pressure injection method and a dropping injection method.

[Separation Process]

In the separation step, the support substrate 16 provided with the inorganic layer is peeled off from the layered product 22 provided with the electronic device member obtained in the above-mentioned member formation step to form the electronic device member 20 and the glass substrate 18, (A glass substrate provided with a member for an electronic device). That is, the laminate 22 provided with the electronic device member is separated into a support substrate 16 provided with an inorganic layer and a glass substrate 24 provided with an electronic device member.

If the electronic device member 20 on the glass substrate 18 at the time of peeling is a part of all the necessary constituent members, the remaining constituent members may be formed on the glass substrate 18 after the detachment.

The method of separating (separating) the inorganic layer surface 14a of the inorganic layer 14 from the first main surface 18a of the glass substrate 18 is not particularly limited. For example, a sharp blade shape may be inserted into the interface between the inorganic layer 14 and the glass substrate 18 to give a moment of peeling, and then a mixed fluid of water and compressed air may be injected and separated.

Preferably, the support substrate 12 of the layered product 22 provided with the electronic device member is provided on the upper surface side, and the electronic device member 20 side is provided on the lower surface side, and the electronic device member 20 side (In the case where the supporting substrates are laminated on both surfaces thereof), and the blade is first intruded into the interface between the inorganic layer 14 and the glass substrate 18 in this state. Thereafter, the support substrate 12 side is adsorbed by the plurality of vacuum adsorption pads, and the vacuum adsorption pads are raised in order from the vicinity of the point where the blade is inserted. An air layer is formed at the interface between the inorganic layer 14 and the glass substrate 18 and the air layer extends to the entire surface of the interface so that the support substrate 16 provided with the inorganic layer can be easily peeled off.

Further, for example, when a part of the support substrate 16 provided with the inorganic layer is laminated by protruding from the glass substrate 18, the glass substrate 18 is fixed to the fixing table (refer to 31 in FIG. 3 to be described later) Shaped jig (refer to reference numeral 32 in Fig. 3 described later) is placed on the inorganic layer surface 14a after or without imparting a detachment mechanism as described above, and pulled up in a direction away from the fixing table, A method of peeling the glass substrate 14 and the glass substrate 18 can be mentioned.

The electronic device 24 obtained by the above process is suitable for manufacturing a small-sized display device used in a mobile terminal such as a cellular phone, a smart phone, a PDA, and a tablet PC. The display device is mainly an LCD or an OLED, and the LCD includes TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type and the like. It can basically be applied to either the passive drive type or the active drive type.

[Example]

Hereinafter, the present invention will be described in detail by way of examples and the like, but the present invention is not limited to these examples.

The following examples (Examples and Comparative Examples), the alkali-free borosilicate glass plate composed of a glass (100㎜ width, depth 30㎜, 0.2㎜ thickness, coefficient of linear expansion of 38 × 10 ^-7 / ℃, manufactured Asahi Glass as a glass substrate trade name &Quot; AN100 ") was used.

As a supporting substrate, a glass plate (width 90 mm, depth 30 mm, thickness 0.5 mm, coefficient of linear expansion 38 × 10 ^-7 / ° C, trade name "AN100", manufactured by Asahi Glass Co., Ltd.) made of alkali-free borosilicate glass was used.

<Examples I-1 to 8>

(Formation of Inorganic Layer)

One major surface of the supporting substrate was cleaned by cleaning with an alkaline aqueous solution. In addition, an inorganic layer (SiC _{1 - x} O _x (x = 0.50)) containing SiC _{1 - x} O _x (x = 0.50) as an inorganic layer surface composition was formed by magnetron sputtering while introducing a mixed gas of Ar and O ₂ using a SiC target on a cleaned surface A thickness of 10 to 200 nm) was formed to obtain support substrates provided with the inorganic layers of the examples shown in Table 1. [

The surface composition of the inorganic layer was measured by XPS using an X-ray photoelectron spectrometer (XPS-7000, Rigaku Corporation) (the same applies hereinafter).

(Control of surface roughness)

The surface roughness Ra of the inorganic layer surface of each example was made different by adjusting the thickness of the inorganic layer without changing the composition when forming the inorganic layer of each example.

The surface roughness Ra was measured in accordance with JIS B 0601 (revised in 2001) using AFM (model: L-trace (Nanonavi), Hitachi High-Technologies Corporation).

(Evaluation of lamination property)

Next, in each example, the inorganic layer surface of the inorganic layer of the support substrate provided with the inorganic layer and the first main surface of the glass substrate were cleaned with an aqueous alkaline solution and rinsed with water to clean both surfaces.

Thereafter, the glass substrate was superposed on the surface of the inorganic layer, and the lamination properties of the inorganic layer and the glass substrate were evaluated based on the following criteria. The results are shown in Table 1 below. If it is &quot; o &quot; or &quot; DELTA &quot;, it can be evaluated that the lamination property is excellent.

O: After overlapping, the base of the glass substrate or the glass substrate was lightly pressed in one place to cause a fusing point within the fusing surface, and the fusing was naturally extended from the fusing point.

B: The fusing point was generated, but the fusing did not expand naturally, and the fusing was applied to the entire inside of the overlapping surface by pressing using a vacuum press.

X: Even if compression using a vacuum press was used, the occurrence of the adhesion origin or expansion of adhesion was not observed, or the formation of the adhesion origin or expansion of adhesion was seen by pressing using a vacuum press. However, Peeled.

(Evaluation of peelability)

3 is a schematic cross-sectional view showing a peeling property evaluation method.

First, the inorganic layer surface of the inorganic layer and the first main surface of the glass substrate were cleaned in the same manner as in the evaluation of the lamination property. Thereafter, the supporting substrate provided with the inorganic layer and the glass substrate were aligned and aligned at one end as shown in Fig. 3 while aligning their positions in the depth direction. Further, since the supporting substrate and the glass substrate provided with the inorganic layer have different lengths in the width direction, when one end is aligned and overlapped, a part of the supporting substrate provided with the inorganic layer, as shown in Fig. 3, Respectively.

After the superimposing, a contact point was generated, and a vacuum press was used to press the glass substrate, and the adhesion was spread over the entire superposed surface to obtain glass laminated bodies of the respective examples.

The glass laminate of each of the following examples thus obtained was heat-treated at 600 DEG C for 1 hour in an air atmosphere.

Then, a peeling test was carried out. Specifically, first, the second main surface of the glass substrate in the glass laminate was fixed on a fixing table (indicated by reference numeral 31 in Fig. 3) using a double-sided tape.

Next, as shown in Fig. 3, an L-shaped jig (indicated by numeral 32 in Fig. 3) is placed on the surface of the inorganic layer of the support substrate provided with the inorganic layer protruded from the glass substrate, , And the peelability of the inorganic layer and the glass substrate was evaluated based on the following criteria. The results are shown in Table 1 below. If it is &quot; o &quot; or &quot; DELTA &quot;, it can be evaluated that the peelability is excellent even after long-term treatment under high temperature conditions.

?: The supporting substrate provided with the inorganic layer was not cracked and could be peeled off.

DELTA: Partially peelable, but the supporting substrate provided with the inorganic layer was split in the middle.

X: Peeling was not possible.

As shown in Table 1, Example I-1 having a surface roughness (Ra) of less than 0.20 nm was inferior in peelability and Example I-8 having a surface roughness Ra exceeding 1.00 nm had a poor lamination property, In Examples I-2 to 7, which are in the range of 10 to 20 nm, the lamination property and the peeling property were both excellent. In Examples I-2 to 7, Examples I-3 to 7 having a surface roughness (Ra) of 0.30 nm or more were more excellent in peelability, and Examples I-2 to 5 having a surface roughness Ra of 0.50 nm or less had better lamination properties.

It was also confirmed from the above results that the peel strength at the interface between the inorganic layer and the support substrate was larger than the peel strength at the interface between the inorganic layer and the glass substrate in the examples (this also applies to each of the following examples).

&Lt; Examples II-1 to 6 &

(Formation of Inorganic Layer)

One major surface of the supporting substrate was cleaned by cleaning with an alkaline aqueous solution. In addition, by introducing a mixed gas of Ar and O ₂ by using a SiC target on the surface to be cleaned, by using magnetron sputtering, inorganic materials including SiC _{1 - x} O _x (x = 0.05 to 0.99) Layers were formed to obtain support substrates provided with the inorganic layers of the respective examples shown in Table 2. [

At this time, the number of x in SiC _{1 - x} O _x was made different by using a mixed gas having a different volume ratio (Ar / O ₂ ) for each example.

(Control of surface roughness)

The surface roughness (Ra) of the surface of the inorganic layer was controlled to 0.40 nm by adjusting the thickness of the inorganic layer in the range of 10 to 200 nm when forming the inorganic layer of each example.

(Evaluation of lamination property and peelability)

Next, the lamination property and the peelability were evaluated in the same manner as in Examples I-1 to I-8. The same is true for the evaluation standard. The results are shown in Table 2 below.

As shown in Table 2, Example II-1 in which _x in the inorganic layer surface composition of SiC _{1 - x} O _x is less than 0.10 is inferior in peelability and Example II-6 in which the inorganic layer surface composition is more than 0.90 is inferior in lamination property, In the range of 0.10 to 0.90 were excellent in both the lamination property and the peelability. In Examples II-2 to 5, Examples II-3 to 5 having x of 0.20 or more were more excellent in peelability, and Examples II-2 to 4 having x of 0.50 or less had better lamination properties.

<Examples III-1 to 6>

(Formation of Inorganic Layer)

One major surface of the supporting substrate was cleaned by cleaning with an alkaline aqueous solution. In addition, by introducing a mixed gas of Ar and O ₂ by using a SiN target on a surface to be cleaned, a magnetization sputtering method was employed to form a thin film of inorganic material containing SiN _{1 - y} O _y (y = 0.05 to 0.99) Layer was formed to obtain a support substrate provided with the inorganic layer of each example shown in Table 3. [

At this time, the number of y in SiN _{1 - y} O _y was made different by using a mixed gas having a different volume ratio (Ar / O ₂ ) for each example.

(Control of surface roughness)

Surface roughness (Ra) of the surface of the inorganic layer was controlled to 0.40 nm in the same manner as in Examples II-1 to 6.

(Evaluation of lamination property and peelability)

Next, the lamination property and the peelability were evaluated in the same manner as in Examples I-1 to I-8. The same is true for the evaluation standard. The results are shown in Table 3 below.

As shown in Table 3, in Example III-1 in which _y in the inorganic layer surface composition SiN _{1 - y} O _y was less than 0.10, the peelability was poor. In Example III-6, Were in the range of 0.10 to 0.90 were excellent in both the lamination property and the peelability. In Examples III-2 to 5, Examples III-3 to 5 having y of 0.20 or more were more excellent in peelability, and Examples III-2 to 4 having y of 0.50 or less had better lamination properties.

<Example IV>

In this example, an inorganic layer of ITO, which is a metal oxide specifically used in Patent Document 1, was formed. Specifically, one major surface of the support substrate was cleaned by cleaning with an alkaline aqueous solution. An ITO layer (indium tin oxide layer) having a thickness of 150 nm was formed on the cleaned surface by a magnetron sputtering method to obtain a support substrate provided with the ITO layer. The surface roughness Ra of the ITO layer was 0.85 nm.

The lamination property and the peeling property were evaluated in the same manner as in Examples I-1 to 8, and the lamination property was "?", But the peeling property was "x".

<Example V>

In this example, an OLED was fabricated using the glass laminate produced in Example I-4.

More specifically, molybdenum was formed on the second main surface of the glass substrate in the glass laminate by the sputtering method, and the gate electrode was formed by etching using the photolithography method. Subsequently, a silicon nitride film, an intrinsic amorphous silicon film and an n-type amorphous silicon film are further formed in this order on the second main surface side of the glass substrate provided with the gate electrode by the plasma CVD method. Subsequently, molybdenum is deposited by the sputtering method , A gate insulating film, a semiconductor element portion, and a source / drain electrode were formed by etching using a photolithography method. Subsequently, silicon nitride is further formed on the second main surface side of the glass substrate by the plasma CVD method to form a passivation layer, and thereafter, indium tin oxide is formed by the sputtering method, and the pixel electrode is etched by photolithography .

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as a hole injecting layer and bis [(N-naphthyl) triphenylamine was used as a hole transporting layer on the second main surface side of the glass substrate. (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-2-carboxylate was added to 8-quinolinol aluminum complex (Alq ₃ ) (BSN-BCN) was further added in an amount of 40 vol%, and Alq ₃ was further deposited as an electron transporting layer in this order. Next, aluminum was deposited on the second main surface side of the glass substrate by a sputtering method And a counter electrode was formed by etching using a photolithography method. Next, one glass substrate was further bonded and sealed on the second main surface of the glass substrate on which the counter electrodes were formed via an ultraviolet curable adhesive layer. A glass laminate having an organic EL structure on a glass substrate obtained by the above procedure It is, corresponds to the layered product for an electronic device having the member.

Subsequently, a sealing member side of the obtained glass laminate was vacuum-adsorbed on a surface plate, and then a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the inorganic layer and the glass substrate at the corner of the glass laminate, The supporting substrate provided was separated to obtain an OLED panel (referred to below as panel A in the electronic device). An IC driver was connected to the prepared panel A and driven at room temperature and atmospheric pressure, and display irregularity was not recognized in the driving area.

<Example VI>

In this example, an LCD was manufactured using the glass laminate produced in Example I-4.

Two glass laminated bodies were prepared. First, molybdenum was deposited on the second main surface of the glass substrate in one glass laminate by the sputtering method, and a gate electrode was formed by etching using a photolithography method. Subsequently, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are further deposited in this order on the second main surface side of the glass substrate on which the gate electrode is provided by plasma CVD. Subsequently, molybdenum is deposited by sputtering, A gate insulating film, a semiconductor element portion and a source / drain electrode were formed by etching using a lithography method. Subsequently, silicon nitride is further formed on the second main surface side of the glass substrate by the plasma CVD method to form a passivation layer, and thereafter, indium tin oxide is formed by the sputtering method, and the pixel electrode is etched by photolithography . Next, a polyimide resin solution was applied on the second main surface of the glass substrate on which the pixel electrode was formed by the roll coating method, and an alignment layer was formed by thermosetting and rubbing was performed. The resulting glass laminate is referred to as glass laminate X1.

Next, chromium was deposited on the second main surface of the glass substrate in the other glass laminate by sputtering, and a light shielding layer was formed by etching using a photolithography method. Next, a color resist was further coated on the second main surface side of the glass substrate on which the light shielding layer was formed by a die coating method, and a color filter layer was formed by photolithography and thermal curing. Next, indium tin oxide was further formed on the second main surface side of the glass substrate by a sputtering method to form an opposite electrode. Next, an ultraviolet curable resin liquid was applied on the second main surface of the glass substrate provided with the counter electrode by a die coating method, and a columnar spacer was formed by photolithography and thermal curing. Next, on the second main surface of the glass substrate on which the columnar spacers were formed, a polyimide resin solution was applied by a roll coating method, and an orientation layer was formed by thermosetting, and rubbing was performed. Next, the sealing resin liquid was drawn in a frame shape on the second main surface side of the glass substrate by the dispenser method, and the liquid crystal was dropped in the frame by the dispenser method. Then, using the above-described glass laminate X1, The second main surface side of the glass substrate of the glass laminate was bonded to each other, and a laminate having an LCD panel was obtained by ultraviolet curing and thermal curing. Hereinafter, the laminate having the LCD panel is referred to as a laminate X2 having a panel.

Next, from the laminate X2 provided with the panel, both sides of the supporting substrate provided with the inorganic layer are peeled off, and an LCD panel B (corresponding to the electronic device) including the substrate on which the TFT array is formed and the substrate on which the color filter is formed .

When an IC driver was connected to the manufactured LCD panel B and driven at normal temperature and atmospheric pressure, display irregularity was not recognized in the driving area.

While the invention has been described in detail and with reference to specific embodiments thereof, it is evident to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application No. 2013-233109 filed on November 11, 2013, the content of which is incorporated herein by reference.

10: Glass laminate
12: Support substrate
14: inorganic layer
14a: a surface of the inorganic layer (surface on the inorganic layer opposite to the support substrate side)
16: Support substrate with inorganic layer
18: glass substrate
18a: a first main surface of the glass substrate
18b: a second main surface of the glass substrate
20: Member for electronic device
22: laminate provided with member for electronic device
24: Electronic device
31:
32: L-shaped jig

Claims (8)

A support substrate having an inorganic layer, the support substrate having a support substrate and an inorganic layer disposed on the support substrate;
And a glass substrate which is peelably laminated on a surface of the inorganic layer which is a surface of the inorganic layer opposite to the support substrate side,
Wherein the inorganic layer comprises SiC _{1 - x} O _x (x = 0.10 to 0.90) and / or SiN _{1 - y} O _y (y = 0.10 to 0.90)
Wherein a surface roughness (Ra) of the surface of the inorganic layer is 0.20 to 1.00 nm. The glass laminate according to claim 1, wherein the surface roughness (Ra) of the surface of the inorganic layer is 0.30 nm or more. The glass laminate according to claim 1 or 2, wherein the surface roughness (Ra) of the inorganic layer surface is 0.50 nm or less. The glass laminate according to any one of claims 1 to 3, wherein x and y are 0.20 or more. The glass laminate according to any one of claims 1 to 4, wherein x and y are a number of 0.50 or less. The glass laminate according to any one of claims 1 to 5, wherein the supporting substrate is a glass substrate. The glass laminate according to any one of claims 1 to 6, wherein the support substrate having the inorganic layer and the glass substrate can be peeled off even after the heat treatment is performed at 600 占 폚 for one hour. A method for manufacturing an electronic device, comprising: a member forming step of forming a member for an electronic device on a surface of the glass substrate in the glass laminate according to any one of claims 1 to 7 to obtain a laminate provided with a member for an electronic device;
And separating the supporting substrate provided with the inorganic layer from the laminate provided with the electronic device member to obtain an electronic device having the glass substrate and the electronic device member.

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