JP2015093405A - Method for producing glass laminate and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a glass laminate which has excellent lamination properties of an inorganic layer disposed on a support substrate and a glass substrate, and has excellent releasability from an inorganic layer and a glass substrate even after the treatment under a high temperature condition; and to provide a method for producing an electronic device using the glass laminate.SOLUTION: There is provided a glass laminate which comprises: a support substrate with an inorganic layer having a support substrate and an inorganic layer disposed on the support substrate; and a glass substrate releasably laminated on an inorganic layer surface which is a surface on the opposite side to the support substrate side in the inorganic layer, in which the inorganic layer contains SiCO(x=0.10 to 0.90) and/or SiNO(y=0.10 to 0.90) as a composition of the inorganic layer surface and the surface roughness (Ra) of the inorganic layer surface is 0.20 to 1.00 nm.

Description

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

  In recent years, electronic devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and a thin glass substrate used for these electronic devices. Progress is being made. On the other hand, when the strength of the glass substrate is insufficient due to the thin plate, the handleability of the glass substrate is lowered in the manufacturing process of the electronic device.

  Therefore, recently, from the viewpoint of improving the handleability of the glass substrate, a laminated body in which a glass substrate is laminated on an inorganic thin film of a supporting glass with an inorganic thin film is prepared, and an element manufacturing process is performed on the laminated glass substrate. After that, a method of separating the glass substrate from the laminate has been proposed (Patent Document 1).

JP 2011-184284 A

  The present inventors examined the supporting glass with an inorganic thin film comprised by the metal oxide specifically described in patent document 1. FIG. As a result, it was found that the laminating property (ease of laminating) when laminating a glass substrate on an inorganic thin film may be inferior. That is, it has been found that even if the inorganic thin film and the glass substrate are stacked, they do not naturally adhere to each other, and even if mechanically pressed, they do not adhere or may be easily peeled off.

  In recent years, with the demand for higher performance of electronic devices, it is desired to perform treatment under high temperature conditions when manufacturing electronic devices. Heat treatment was performed under conditions (for example, 600 ° C., 1 hour). As a result, it was found that even if the laminate property is good, the peelability may be inferior, for example, when the glass substrate is peeled off by a specific method after the heat treatment. In this case, after the device is manufactured under a high temperature condition, there arises a problem that the glass substrate on which the element is formed cannot be peeled from the laminate.

  The present invention has been made in view of the above points, and has excellent laminating properties between an inorganic layer disposed on a support substrate and a glass substrate, and even after treatment under high-temperature conditions. It aims at providing the manufacturing method of the electronic device using the glass laminated body which is excellent in the peelability of a glass substrate, and this glass laminated body.

  As a result of intensive investigations to achieve the above object, the present inventors have formed an inorganic layer having a specific surface composition and surface roughness on a supporting substrate, so that the laminateability and releasability with respect to a glass substrate can be achieved. Were found to be excellent, and the present invention was completed.

That is, the present invention provides the following (1) to (8).
(1) A support substrate and an inorganic layer-supported substrate having an inorganic layer disposed on the support substrate, and a peelable laminate on the surface of the inorganic layer on the opposite side of the inorganic layer from the support substrate side And the inorganic layer has SiC _1-x O _x (x = 0.10 to 0.90) and / or 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 the surface roughness (Ra) of the inorganic layer surface is 0.30 nm or more.
(3) The glass laminate according to (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 x and y are numbers of 0.20 or more.
(5) The glass laminate according to any one of (1) to (4), wherein x and y are numbers of 0.50 or less.
(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 with an inorganic layer and the glass substrate can be peeled even after heat treatment at 600 ° C. for 1 hour.
(8) A member forming step of forming an electronic device member on the surface of the glass substrate in the glass laminate according to any one of (1) to (7) to obtain a laminate with an electronic device member; And a separation step of peeling the support substrate with an inorganic layer from the laminate with the member for electronic devices to obtain the electronic device having the glass substrate and the member for electronic devices.

  According to the present invention, a glass having excellent laminating properties between an inorganic layer disposed on a supporting substrate and a glass substrate, and excellent releasability between the inorganic layer and the glass substrate even after treatment under high temperature conditions. A laminate and a method for producing an electronic device using the glass laminate can be provided.

It is typical sectional drawing of one Embodiment of the glass laminated body which concerns on this invention. It is process drawing of the manufacturing method of the electronic device which concerns on this invention. It is typical sectional drawing which shows the peelable evaluation method.

  Hereinafter, preferred embodiments of the method for producing a glass laminate and an electronic device of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments and departs from the scope of the present invention. Without limitation, various modifications and substitutions can be made to the following embodiments.

  The glass laminate of the present invention is generally obtained by interposing an inorganic layer having a specific surface (inorganic layer surface) as a surface in contact with the glass substrate between the support substrate and the glass substrate. Therefore, the laminate property between the inorganic layer and the glass substrate is excellent, and the peelability between the inorganic layer and the glass substrate is excellent even after the treatment under high temperature conditions.

  Below, the suitable aspect of a glass laminated body is explained in full detail first, and the suitable aspect of the manufacturing method of the electronic device using this glass laminated body is explained in full detail after that.

<Glass laminate>
FIG. 1 is a schematic cross-sectional view of an embodiment of a glass laminate according to the present invention.
As shown in FIG. 1, the glass laminate 10 includes a support substrate 16 with an inorganic layer composed of a support substrate 12 and an inorganic layer 14, and a glass substrate 18. In the glass laminate 10, the inorganic layer surface 14 a of the inorganic layer 14 of the support substrate 16 with an inorganic layer (surface opposite to the support substrate 12 side) and the first main surface 18 a of the glass substrate 18 are used as the laminate surface. The support substrate 16 with an inorganic layer and the glass substrate 18 are laminated so as to be peelable. That is, the inorganic layer 14 has one surface fixed to the layer of the support substrate 12 and the other surface in contact with the first main surface 18 a of the glass substrate 18, and the interface between the inorganic layer 14 and the glass substrate 18. Are in close contact with each other. In other words, the inorganic layer 14 is easily peelable from the first main surface 18 a of the glass substrate 18.

  Moreover, this glass laminated body 10 is used until the member formation process mentioned later. That is, the glass laminate 10 is used until an electronic device member such as a liquid crystal display device is formed on the surface of the second main surface 18b of the glass substrate 18. Thereafter, the layer of the support substrate 16 with the inorganic layer is peeled off at the interface with the layer of the glass substrate 18, and the layer of the support substrate 16 with the inorganic layer does not become a member constituting the electronic device. The separated support substrate 16 with an inorganic layer is laminated with a new glass substrate 18 and can be reused as a new glass laminate 10.

In the present invention, the above-mentioned fixing and (separable) adhesion have a difference in peeling strength (that is, stress required for peeling), and fixing means that the peeling strength is larger than the 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.
Further, the peelable adhesion means that it can be peeled at the same time that it can be peeled 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 glass substrate 10 is peeled and fixed on the closely contacted surface (interface between the inorganic layer 14 and the glass substrate 18). It means that it does not peel on the surface. Therefore, 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 is separated into two, the glass substrate 18 and the support substrate 16 with an inorganic layer.

  Below, the support substrate 16 with an inorganic layer and the glass substrate 18 which comprise the glass laminated body 10 are explained in full detail first, and the procedure of manufacture of the glass laminated body 10 is explained in full detail after that.

[Support substrate with inorganic layer]
The support substrate 16 with an inorganic layer includes a support substrate 12 and an inorganic layer 14 disposed (fixed) on the surface thereof. The inorganic layer 14 is arrange | positioned in the outermost side in the support substrate 16 with an inorganic layer so that it may closely_contact | adhere with the glass substrate 18 mentioned later so that peeling.
Below, the aspect of the support substrate 12 and the inorganic layer 14 is explained in full detail.

(Support substrate)
The support substrate 12 has a first main surface and a second main surface, cooperates with the inorganic layer 14 disposed on the first main surface, supports and reinforces the glass substrate 18, and a member to be described later It is a substrate that prevents the glass substrate 18 from being deformed, scratched or damaged during the production of the electronic device member in the forming step (the step of producing the electronic device member).
As the support substrate 12, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used. When the member forming step involves heat treatment, the support substrate 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 18, and more preferably formed of the same material as the glass substrate 18, The support substrate 12 is preferably a glass plate. In particular, the support 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 a glass substrate 18 described later. Preferably, the thickness of the support substrate 12 is 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 later. For example, when the current member forming process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the glass substrate 18 and the thickness of the inorganic layer 14 is 0.1 mm, The thickness of the support substrate 12 is 0.4 mm. In general, the thickness of the support substrate 12 is preferably 0.2 to 5.0 mm.

  When the support substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more because it is easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.

(Inorganic layer)
The inorganic layer 14 is a layer disposed (fixed) on the main surface of the support substrate 12 and in contact with the first main surface 18 a of the glass substrate 18. By providing the inorganic layer 14 on the support substrate 12, adhesion of the glass substrate 18 can be suppressed even after long-time treatment under high temperature conditions.

In the present invention, the inorganic layer 14 is composed of SiC _1-x O _x (x = 0.10-0.90) and / or SiN _1-y O _y (y = 0.0.10) as the composition of the inorganic layer surface 14a. 0.90).
Here, when x and y are numbers less than 0.10, the peelability to the glass substrate 18 is inferior, and when it is greater than 0.90, the laminate property to the glass substrate 18 is inferior. Both laminateability and peelability are excellent.
The reason for this is not clear, but silicon carbide and / or silicon nitride, which have a relatively small difference in electronegativity between elements, contains an appropriate amount of oxygen, so that the surface flatness can be optimized or inorganic during heat treatment. This is thought to be because it is difficult to convert weak bonds to strong bonds between the layer and the glass substrate.

  In addition, x and y are preferably 0.20 or more for the reason that the peelability is more excellent, and preferably 0.50 or less for the reason that the stackability is more excellent. Is more preferably 0.20 to 0.50.

  Here, 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 opposite to the support substrate 12 side), and specifically, the outermost layer of the inorganic layer 14. The part up to a distance of 1.0 nm from the surface toward the support substrate 12 or the thickness (total thickness) of the inorganic layer 14 is 100%, and the distance from the outermost surface to the support substrate 12 is up to a distance of 10%. It is defined as the thinner of the parts. Here, the “outermost surface” means “a plane including the highest surface portion ignoring the surface roughness”.

The composition of the inorganic layer 14 other than the inorganic layer surface 14a and the inorganic layer surface 14a can be measured by X-ray photoelectron spectroscopy (XPS).
In addition, as a composition other than the inorganic layer surface 14a in the inorganic layer 14, it may differ from the composition of the inorganic layer surface 14a, and may be the same.

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 poor, and if it exceeds 1.00 nm, the laminate property to the glass substrate 18 is poor. If it is this range, both lamination property and peelability will be excellent.
The surface roughness (Ra) of the inorganic layer surface 14a is preferably 0.30 nm or more for the reason that the peelability is more excellent, and 0.50 nm or less is preferable for the reason that the stackability is more excellent. Is more preferably 0.30 to 0.50 nm.
Examples of a method for controlling the surface roughness of the inorganic layer surface 14a include a method of changing the formation conditions (film formation conditions) of the inorganic layer 14, and specifically, the thickness of the inorganic layer 14 is changed. The method etc. are mentioned.
Ra (arithmetic mean roughness) is measured according to JIS B 0601 (revised in 2001).

The average linear expansion coefficient at 25 to 300 ° C. of the inorganic layer 14 (hereinafter simply referred to as “average linear expansion coefficient”) is not particularly limited, but when a glass plate is used as the support substrate 12, the average linear expansion coefficient is 10 × 10 ⁻⁷ to 200 × 10 ⁻⁷ / ° C. is preferable. If the range, the difference in average linear expansion coefficient between the glass plates (SiO ₂₎ is reduced, it is possible to suppress the positional deviation of the glass substrate 18 and the inorganic layer with the supporting substrate 16 in a high temperature environment.

The inorganic layer 14 includes the above-described 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. It is preferable. 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, with respect to the total amount of the inorganic layer 14. 999% by mass or more is particularly preferable.

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.
The inorganic layer 14 is described as a single layer in FIG. 1, but may be a laminate of two or more layers. In the case of two or more layers, each layer may have a different composition.

  The inorganic layer 14 is usually provided on the entire surface of the support substrate 12 as shown in FIG. 1, but may be provided on a part of the surface of the support substrate 12 as long as the effects of the present invention are not impaired. For example, the inorganic layer 14 may be provided on the surface of the support substrate 12 in an 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 layer itself does not easily occur, and it is difficult for chemical bonding to occur with the glass substrate 18 to be described later. Adhesion hardly occurs.
Here, heavy peeling means that the peel strength at the interface between the inorganic layer 14 and the glass substrate 18 is the peel strength at the interface between the support substrate 12 and the inorganic layer 14 and the strength of the material of the inorganic layer 14 (bulk). (Strength) means greater than any of the above. When heavy peeling occurs at the interface between the inorganic layer 14 and the glass substrate 18, the components of the inorganic layer 14 are likely to adhere to the surface of the glass substrate 18, making it difficult to clean the surface. The adhesion 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 and some of the components on the surface of the inorganic layer 14 are glass substrate 18. It means to adhere to the surface.

(Method for producing support substrate with inorganic layer)
As a manufacturing method of the support substrate 16 with an inorganic layer, for example, using a SiC target or a SiN target, vapor deposition is performed while introducing a mixed gas of an inert gas such as Ar and an oxygen atom-containing gas such as O ₂ or CO _2. Examples thereof include a method of providing the inorganic layer 14 having the above-described composition of the inorganic layer surface 14a on the support substrate 12 by a method, a sputtering method, a CVD method, or the like. At this time, the amount of oxygen on the inorganic layer surface 14a (that is, the values of x and y) can be controlled by adjusting the amount of the oxygen atom-containing gas in the mixed gas. As manufacturing conditions, optimum conditions are appropriately selected according to the materials used.

  Moreover, after forming the inorganic layer 14 on the support substrate 12, in order to control the surface roughness (Ra) of the inorganic layer surface 14a, the process of shaving the surface of the inorganic layer 14 can be given. Examples of the treatment include an ion sputtering method.

[Glass substrate]
As for the glass substrate 18, the 1st main surface 18a closely_contact | adheres to the inorganic layer 14, The member for electronic devices mentioned later is provided in the 2nd main surface 18b on the opposite side to the inorganic layer 14 side.
The kind of the glass substrate 18 may be a common one, and examples thereof include a glass substrate for a display device such as an LCD or an OLED. The glass substrate 18 is excellent in chemical resistance and moisture permeability and has a low thermal shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.

  The glass substrate 18 is obtained by melting a glass raw material and molding the molten glass into a plate shape. Such a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a full call method, a rubber method, or the like is used. In addition, a glass substrate having a particularly small thickness can be obtained by heating a glass once formed into a plate shape to a moldable temperature, and stretching it by means of stretching or the like to make it thin (redraw method).

  The glass of the glass substrate 18 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses mainly composed of silicon oxide are preferable. As the oxide glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.

  As the glass of the glass substrate 18, glass suitable for the type of device and its manufacturing process is adopted. For example, a glass substrate for a liquid crystal panel is made of glass (non-alkali glass) that does not substantially contain an alkali metal component because the elution of an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) Ingredients are included). Thus, the glass of the glass substrate 18 is appropriately selected based on the type of device to be applied and its manufacturing process.

  The thickness of the glass substrate 18 is not particularly limited, but is usually 0.8 mm or less, preferably 0.3 mm or less, more preferably 0.8 mm or less from the viewpoint of reducing the thickness and / or weight of the glass substrate 18. It is 15 mm or less. If it exceeds 0.8 mm, the glass substrate 18 cannot meet the demand for thinning and / or lightening. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 18. In the case of 0.15 mm or less, the glass substrate 18 can be wound into a roll. Moreover, the thickness of the glass substrate 18 is preferably 0.03 mm or more because the glass substrate 18 is easy to manufacture and the glass substrate 18 is easy to handle.

  The glass substrate 18 may be composed of two or more layers. In this case, the material forming each layer may be the same material or a different material. 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 laminated on the first main surface 18 a of the glass substrate 18.
When the inorganic thin film layer is disposed (fixed) on the glass substrate 18, the inorganic layer 14 and the inorganic thin film layer of the support substrate 16 with the inorganic layer are in contact with each other in the glass laminate. By providing the inorganic thin film layer on the glass substrate 18, adhesion between the glass substrate 18 and the support substrate 16 with the inorganic layer can be further suppressed even after long-time treatment under high temperature conditions.
The mode of the inorganic thin film layer is not particularly limited, but preferably at least one selected from the group consisting of metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal carbonitrides, metal silicides and metal fluorides. Including one. Especially, it is preferable that a metal oxide is included at the point which the peelability of the glass substrate 18 is more excellent, and an indium tin oxide is more preferable.

Examples of the metal oxide, metal nitride, and metal oxynitride include Si, Hf, Zr, Ta, Ti, Y, Nb, Na, Co, Al, Zn, Pb, Mg, Bi, La, Ce, and Pr. , Sm, Eu, Gd, Dy, Er, Sr, Sn, In, and Ba, oxides, nitrides, and oxynitrides of one or more elements selected from Ba and the like. More specifically, 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 (ITO) Indium zinc oxide (IZO), zinc tin oxide (ZTO), gallium-doped zinc oxide (GZO), and the like.

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

<Glass laminate>
The glass laminate 10 of the present invention comprises the support layer 16 with an inorganic layer and the glass substrate 18 with the inorganic layer surface 14a of the support substrate 16 with an inorganic layer and the first main surface 18a of the glass substrate 18 described above as a laminate surface. It is a laminated body which is laminated so as to be peelable. 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.

<Method for producing glass laminate>
Although the manufacturing method of the glass laminated body 10 of this invention is not specifically limited, Specifically, after laminating | stacking the support substrate 16 with an inorganic layer and the glass substrate 18 in a normal pressure environment, for example, the self-weight of the glass substrate 18 or A method of generating an adhesion starting point in the overlapping surface by pushing the second main surface 18b of the glass substrate 18 lightly at one place, and naturally expanding the adhesion from the adhesion starting point; by pressing using a roll or a press And a method of expanding the adhesion from the adhesion starting point. The inorganic layer 14 and the glass substrate 18 are more closely adhered to each other by pressure bonding using a roll or a press, and air bubbles mixed between the two are relatively easily removed.

  In addition, it is more preferable to perform pressure bonding by a vacuum laminating method or a vacuum pressing method because it is preferable to suppress mixing of bubbles and ensure good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are less likely to cause distortion defects.

When the support substrate 16 with the inorganic layer and the glass substrate 18 are detachably adhered, the surfaces of the inorganic layer 14 and the glass substrate 18 that are in contact with each other are sufficiently washed and laminated in a clean environment. Is preferred. The higher the degree of cleanness, the better the flatness.
The cleaning method is not particularly limited, and examples thereof include a method of cleaning the surface of the inorganic layer 14 or the glass substrate 18 with an aqueous alkaline solution and then using water.
Furthermore, in order to obtain a good laminated state, it is preferable to laminate the inorganic layer 14 and the glass substrate 18 after performing plasma treatment after cleaning the surfaces that are in contact with each other. Examples of the plasma used for the plasma treatment include atmospheric plasma and vacuum plasma.

The glass laminate 10 of the present invention can be used for various applications, for example, a display panel, PV, a thin film secondary battery, and an electronic component such as a semiconductor wafer having a circuit formed on its surface. Is mentioned. In this application, the glass laminate 10 is often exposed (for example, 1 hour or longer) under high temperature conditions (for example, 350 ° C. or higher).
Here, the display device panel includes LCD, OLED, electronic paper, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

<Electronic device and manufacturing method thereof>
Next, preferred embodiments of the electronic device and the manufacturing method thereof will be described in detail.
FIG. 2 is a schematic cross-sectional view sequentially showing each manufacturing process in a preferred embodiment of the method for manufacturing an electronic device of the present invention. A preferred embodiment of the electronic device of the present invention includes a member forming step and a separation step.
Hereinafter, the materials used in each step and the procedure thereof will be described in detail with reference to FIG. First, a member formation process is explained in full detail.

[Member forming process]
A member formation process is a process of forming the member for electronic devices on the glass substrate in a glass laminated body.
More specifically, as shown in FIG. 2A, in this step, the electronic device member 20 is formed on the second main surface 18b of the glass substrate 18, and the electronic device member laminated body 22 is manufactured. Is done.
First, the electronic device member 20 used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(Electronic device components (functional elements))
The electronic device member 20 is a member that is formed on the second main surface 18b of the glass substrate 18 in the glass laminate 10 and constitutes at least a part of the electronic device. More specifically, examples of the electronic device member 20 include a member used for an electronic component such as a display panel, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on the surface thereof. Examples of the display device panel include an organic EL panel and a field emission panel.

For example, as a member for a solar cell, a silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
Further, as a member for a thin film secondary battery, in the lithium ion type, a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, a resin as a sealing layer, etc. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
In addition, as a member for electronic components, in CCD and CMOS, metal of conductive part, silicon oxide and silicon nitride of insulating part, etc., other various sensors such as pressure sensor and acceleration sensor, rigid printed board, flexible printed board And various members corresponding to a rigid flexible printed circuit board.

(Process procedure)
The manufacturing method of the laminated body 22 with the member for electronic devices mentioned above is not specifically limited, According to the conventionally well-known method according to the kind of structural member of the member for electronic devices, the 2nd main of the glass substrate 18 of the glass laminated body 10 is used. The electronic device member 20 is formed on the surface 18b.
The electronic device member 20 is not all of the members finally formed on the second main surface 18b of the glass substrate 18 (hereinafter referred to as “all members”), but a part of all members (hereinafter referred to as “parts”). May be referred to as a member. The glass substrate with partial members can be made into a glass substrate with all members (corresponding to an electronic device described later) in the subsequent steps. Moreover, the member for electronic devices may be formed in the peeling surface (1st main surface) in the glass substrate with all the members. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling off the support substrate 16 with an inorganic layer from the laminate with all members. Furthermore, an electronic device can also be manufactured by assembling an electronic device using two laminates with all members, and then peeling the two support substrates 16 with inorganic layers from the laminate with all members.

  For example, taking the case of manufacturing an OLED as an example, in order 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 transparent electrode is further formed. Various layer formation and processing such as vapor-depositing hole injection layer, hole transport layer, light emitting layer, electron transport layer, etc. on the surface on which is formed, forming a back electrode, sealing with a sealing plate, etc. Done. Specific examples of these layer formation and treatment include film formation treatment, vapor deposition treatment, sealing plate adhesion treatment, and the like.

  In addition, for example, the TFT-LCD manufacturing method is formed on the second main surface 18b of the glass substrate 18 of the glass laminate 10 by a general film forming method such as a CVD method and a sputtering method using a resist solution. Forming a thin film transistor (TFT) by patterning a metal film and a metal oxide film to be formed, and patterning a resist solution on the second main surface 18b of the glass substrate 18 of another glass laminate 10 And a CF forming step for forming a color filter (CF) and a bonding step for laminating a device substrate with TFT and a device substrate with CF.

In the TFT formation process and the CF formation process, the TFT and CF are formed on the second main surface 18b of the glass substrate 18 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist solution is used as a coating solution for pattern formation.
In addition, before forming TFT and CF, you may wash | clean the 2nd main surface 18b of the glass substrate 18 as needed. As a cleaning method, known dry cleaning or wet cleaning can be used.

  In the bonding step, a liquid crystal material is injected and laminated between the laminated body with TFT and the laminated body with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.

[Separation process]
In the separation step, the support substrate 16 with the inorganic layer is peeled from the laminate 22 with the member for electronic devices obtained in the member forming step, and the electronic device 24 (for electronic device) including the electronic device member 20 and the glass substrate 18 is peeled off. This is a step of obtaining a glass substrate with a member. That is, it is a step of separating the laminate 22 with the electronic device member into the support substrate 16 with the inorganic layer and the glass substrate 24 with the electronic device member.
When the electronic device member 20 on the glass substrate 18 at the time of peeling is a part of the formation of all necessary constituent members, the remaining constituent members can be formed on the glass substrate 18 after separation.

  The method of peeling (separating) the inorganic layer surface 14a of the inorganic layer 14 and the first main surface 18a of the glass substrate 18 is not particularly limited. For example, a sharp blade-like object is inserted into the interface between the inorganic layer 14 and the glass substrate 18 to provide a trigger for peeling, and then a mixed fluid of water and compressed air is sprayed to peel off.

  Preferably, the laminate 22 with electronic device members is placed on a surface plate so that the support substrate 12 is on the upper side and the electronic device member 20 side is on the lower side, and the electronic device member 20 side is vacuum-adsorbed on the surface plate. (In the case where support substrates are laminated on both sides, the steps are sequentially performed). In this state, first, the blade is inserted into the interface between the inorganic layer 14 and the glass substrate 18. Then, the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. If it does so, an air layer will be formed in the interface of inorganic layer 14 and glass substrate 18, the air layer will spread over the whole surface of an interface, and support substrate 16 with an inorganic layer can be peeled easily.

  Further, for example, when a part of the support substrate 16 with an inorganic layer protrudes from the glass substrate 18 and is laminated, the glass substrate 18 is fixed to a fixing base (see reference numeral 31 in FIG. 3 described later), and A direction in which an L-shaped jig (see reference numeral 32 in FIG. 3 to be described later) is hooked on the inorganic layer surface 14a and separated from the fixing base with or without giving a trigger for peeling as shown in FIG. The method of peeling the inorganic layer 14 and the glass substrate 18 by pulling up to (1) is mentioned.

  The electronic device 24 obtained by the above process is suitable for manufacturing a small display device used for a mobile terminal such as a mobile phone, a smartphone, a PDA, or a tablet PC. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type, and the like. Basically, it can be applied to both passive drive type and active drive type display devices.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

In the following examples (Examples and Comparative Examples), a glass plate made of non-alkali borosilicate glass (width 100 mm, depth 30 mm, thickness 0.2 mm, coefficient of linear expansion 38 × 10 ⁻⁷ / ° C., Asahi Glass) The product name “AN100” manufactured by the company was used.
Also, as the support substrate, a glass plate made of alkali-free borosilicate glass (width 90 mm, depth 30 mm, thickness 0.5 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) It was used.

<Examples I-1 to 8>
(Formation of inorganic layer)
One main surface of the support substrate was cleaned by washing with an alkaline aqueous solution. Furthermore, SiC _1-x O _x (x = 0.50) was used as the inorganic layer surface composition by magnetron sputtering while introducing a mixed gas of Ar and O ₂ into the cleaned surface using a SiC target. The inorganic layer (thickness 10-200 nm) containing was formed, and the support substrate with an inorganic layer of each example was obtained.
The inorganic layer surface composition was measured by XPS using an X-ray photoelectron spectrometer (XPS-7000, manufactured by Rigaku Corporation) (hereinafter the same).

(Surface roughness control)
When forming the inorganic layer of each example, the surface roughness (Ra) of the inorganic layer surface of each example was varied by adjusting the thickness of the inorganic layer without changing the composition.
The surface roughness (Ra) was measured in accordance with JIS B 0601 (revised in 2001) using AFM (model: L-trace (Nanoavi), manufactured by Hitachi High-Technologies Corporation) (hereinafter the same). ).

(Evaluation of stackability)
Next, the inorganic layer surface of the inorganic layer of the support substrate with an inorganic layer in each example and the first main surface of the glass substrate were cleaned with an aqueous alkali solution and with water to clean both surfaces.
Then, the glass substrate was piled up on the inorganic layer surface, and the lamination property of an inorganic layer and a glass substrate was evaluated on the following reference | standard. The results are shown in Table 1 below. In addition, if it is "(circle)" or "(triangle | delta)", it can evaluate that it is excellent in lamination property.
○: After overlapping, the glass substrate itself or the glass substrate is pressed lightly at one place to generate an adhesion start point within the overlap surface, and the adhesion naturally spreads from the generated adhesion start point. The entire surface overlapped.
(Triangle | delta): Although the contact | adherence start point generate | occur | produced, contact | adherence did not spread naturally, but contact | adherence spread | superposed over the whole in-plane by press-bonding using a vacuum press.
X: Even if pressure bonding was performed using a vacuum press, no generation of adhesion starting point or spread of adhesion was observed, or generation of adhesion starting point or expansion of adhesion was observed by pressure bonding using a vacuum press, When released from the crimping, the overlapped surface was easily peeled off.

(Evaluation of peelability)
FIG. 3 is a schematic cross-sectional view showing a peelability 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 laminate property. Thereafter, the support substrate with an inorganic layer in each example and the glass substrate were aligned at one end as shown in FIG. 3 because the lengths in the width direction were different while aligning the positions in the depth direction. Since one end is aligned, at the other end, as shown in FIG. 3, a part of the support substrate with an inorganic layer protrudes from the glass substrate.
After the overlapping, an adhesion starting point was generated and pressure-bonded using a vacuum press, and the adhesion was spread over the entire overlapping surface to obtain a glass laminate of each example.
Next, the obtained glass laminate of each example was subjected to heat treatment at 600 ° C. for 1 hour in an air atmosphere.
Next, a peel test was performed. Specifically, first, the second main surface of the glass substrate in the glass laminate was fixed on a fixing base (indicated by reference numeral 31 in FIG. 3) using a double-sided tape.
Next, as shown in FIG. 3, the L-shaped jig (indicated by reference numeral 32 in FIG. 3) is hooked on the inorganic layer surface of the support substrate with an inorganic layer protruding from the glass substrate, and the direction away from the fixing base By using a machine to pull up at 10 mm / min, the peelability between the inorganic layer and the glass substrate was evaluated according to the following criteria. The results are shown in Table 1 below. In addition, if it is "(circle)" or "(triangle | delta)", it can evaluate that it is excellent in peelability even after long-time processing under high temperature conditions.
○: The support substrate with an inorganic layer could be peeled without cracking.
(Triangle | delta): Although it was able to peel partially, the support substrate with an inorganic layer cracked on the way.
X: It was not able to peel.

As shown in Table 1 above, Example I-1 having a surface roughness (Ra) of less than 0.20 nm has inferior peelability and Example I-8 having a surface roughness of more than 1.00 nm has inferior laminate properties. In Examples I-2 to 7 having a surface roughness (Ra) in the range of 0.20 to 1.00 nm, both the laminate property and the peelability were excellent. Further, among Examples I-2 to 7, Examples I-3 to 7 having a surface roughness (Ra) of 0.30 nm or more are more excellent in peelability, and Examples I-2 to 5 having a surface roughness (Ra) of 0.50 nm or less are Laminability was more excellent.
From the above results, in the examples, it was confirmed that the peel strength at the interface between the inorganic layer and the support substrate layer was larger than the peel strength at the interface between the inorganic layer and the glass substrate (hereinafter the same). .

<Examples II-1 to 6>
(Formation of inorganic layer)
One main surface of the support substrate was cleaned by washing with an alkaline aqueous solution. Furthermore, SiC _1-x O _x (x = 0.05 to ₀₎ as the inorganic layer surface composition by magnetron sputtering while introducing a mixed gas of Ar and O ₂ into the cleaned surface using a SiC target. .99) to form a support substrate with an inorganic layer in each example.
At this time, the number of _x in SiC _1-x O _x was varied by using mixed gases having different volume ratios (Ar / O ₂ ) for each example.

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

(Evaluation of lamination and peelability)
Next, laminateability and peelability were evaluated in the same manner as in Examples I-1 to 8. The same applies to the evaluation criteria. The results are shown in Table 2 below.

As shown in Table 2 above, Example II-1 in which _x in SiC _1-x O _x of the inorganic layer surface composition is less than 0.10 is inferior in peelability, and Example II-6 in which it exceeds 0.90 is Although the laminateability was inferior, Examples II-2 to 5 in which x was in the range of 0.10 to 0.90 were excellent in both laminateability and peelability. Moreover, among Examples II-2 to 5, Examples II-3 to 5 in which x is 0.20 or more have better peelability, and Examples II-2 to 4 in which x is 0.50 or less have laminating properties. It was better.

<Examples III-1 to 6>
(Formation of inorganic layer)
One main surface of the support substrate was cleaned by washing with an alkaline aqueous solution. Furthermore, SiN _1-y O _y (y = 0.05 to ₀₎ was used as the inorganic layer surface composition by magnetron sputtering while introducing a mixed gas of Ar and O ₂ into the cleaned surface using a SiN target. .99) to form a support substrate with an inorganic layer in each example.
At this time, the number of _y in SiN _1-y O _y was varied by using mixed gases having different volume ratios (Ar / O ₂ ) for each example.

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

(Evaluation of lamination and peelability)
Next, laminateability and peelability were evaluated in the same manner as in Examples I-1 to 8. The same applies to the evaluation criteria. The results are shown in Table 3 below.

As shown in Table 3 above, Example III-1 in which _y in SiN _1-y O _y of the inorganic layer surface composition is less than 0.10 is inferior in peelability, and Example III-6 in which it exceeds 0.90 is Although the laminateability was inferior, Examples III-2 to 5-5 in which y was in the range of 0.10 to 0.90 were excellent in both laminateability and peelability. Further, among Examples III-2 to 5, Examples III-3 to 5 in which y is 0.20 or more are more excellent in peelability, and Examples III-2 to 4 in which y is 0.50 or less have lamination properties. It was better.

<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 main surface of the support substrate was cleaned by washing with an alkaline aqueous solution. Further, 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 with an ITO layer. The surface roughness Ra of the ITO layer was 0.85 nm.
When laminateability and peelability were evaluated in the same manner as in Examples I-1 to 8, the laminateability was “Δ”, but the peelability was “x”.

<Example V>
In this example, an OLED was produced using the glass laminate produced in Example I-4.
More specifically, a molybdenum film was formed by sputtering on the second main surface of the glass substrate in the glass laminate, and a gate electrode was formed by etching using photolithography. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD, indium tin oxide is formed by sputtering and photolithography is used. A pixel electrode was formed by etching.
Subsequently, on the second main surface side of the glass substrate, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [ (N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer were formed in this order, and then formed on the second main surface side of the glass substrate by sputtering. Aluminum was deposited, and a counter electrode was formed by etching using a photolithography method.Next, ultraviolet light was formed on the second main surface of the glass substrate on which the counter electrode was formed. Another glass substrate was bonded and sealed through a chemical adhesive layer, and the glass laminate having the organic EL structure on the glass substrate obtained by the above procedure was laminated with an electronic device member. Applies to the body.
Subsequently, after the sealed body side of the obtained glass laminate is vacuum-adsorbed to a surface plate, a stainless steel knife having a thickness of 0.1 mm is formed at the interface between the inorganic layer at the corner of the glass laminate and the glass substrate. Was inserted and the support substrate with an inorganic layer was separated from the glass laminate to obtain an OLED panel (corresponding to an electronic device, hereinafter referred to as panel A). When an IC driver was connected to the manufactured panel A and driven under normal temperature and normal pressure, display unevenness was not observed in the driving region.

<Example VI>
In this example, an LCD was produced using the glass laminate produced in Example I-4.
Two glass laminates were prepared. First, a molybdenum film was formed by sputtering on the second main surface of the glass substrate in one glass laminate, and a gate electrode was formed by etching using photolithography. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD, indium tin oxide was formed by sputtering and photolithography was used. A pixel electrode was formed by etching. Next, a polyimide resin liquid was applied on the second main surface of the glass substrate on which the pixel electrode was formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. The obtained glass laminate is referred to as a glass laminate X1.
Next, a chromium film was formed on the second main surface of the glass substrate in the other glass laminate by a sputtering method, and a light-shielding layer was formed by etching using a photolithography method. Next, a color resist was further applied by a die coating method to the second main surface side of the glass substrate provided with the light shielding layer, and a color filter layer was formed by a photolithography method and thermal curing. Next, an indium tin oxide film was further formed on the second main surface side of the glass substrate by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid was applied to the second main surface of the glass substrate provided with the counter electrode by a die coating method, and columnar spacers were formed by a photolithography method and heat curing. Next, a polyimide resin solution was applied on the second main surface of the glass substrate on which the columnar spacers were formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. Next, after the sealing resin liquid is drawn in a frame shape on the second main surface side of the glass substrate by the dispenser method, and the liquid crystal is dropped in the frame by the dispenser method, the above-described glass laminate X1 is used. The 2nd main surface side of the glass substrate of a sheet of glass laminated body was bonded together, and the laminated body which has an LCD panel by ultraviolet curing and thermosetting was obtained. Hereinafter, the laminate having the LCD panel is referred to as a laminate X2 with a panel.
Next, the support substrate with an inorganic layer on both sides was peeled from the laminated body X2 with a panel to obtain an LCD panel B (corresponding to an electronic device) comprising a substrate on which a TFT array was formed and a substrate on which a color filter was formed.
When an IC driver was connected to the manufactured LCD panel B and driven under normal temperature and normal pressure, no display unevenness was observed in the driving region.

DESCRIPTION OF SYMBOLS 10 Glass laminated body 12 Support substrate 14 Inorganic layer 14a Inorganic layer surface (surface on the opposite side to the support substrate side in an inorganic layer)
16 Support substrate 18 with inorganic layer Glass substrate 18a First main surface 18b of glass substrate Second main surface 20 of glass substrate 20 Electronic device member 22 Laminated body 24 with electronic device member Electronic device 31 Fixing base 32 L-shaped jig

Claims (8)

A support substrate with an inorganic layer having a support substrate and an inorganic layer disposed on the support substrate;
A glass substrate laminated in a peelable manner on the surface of the inorganic layer which is the surface opposite to the support substrate side in the inorganic layer,
The inorganic layer has a composition 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. Including
The glass laminated body whose surface roughness (Ra) of the said inorganic layer surface is 0.20-1.00 nm.   The glass laminated body of Claim 1 whose surface roughness (Ra) of the said inorganic layer surface is 0.30 nm or more.   The glass laminated body of Claim 1 or 2 whose surface roughness (Ra) of the said 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 numbers of 0.20 or more.   The glass laminate according to any one of claims 1 to 4, wherein x and y are numbers of 0.50 or less.   The glass laminated body of any one of Claims 1-5 whose said support substrate is a glass substrate.   The glass laminate according to any one of claims 1 to 6, wherein the support substrate with an inorganic layer and the glass substrate can be peeled even after heat treatment at 600 ° C for 1 hour. The member formation process which forms the member for electronic devices on the surface of the glass substrate in the glass laminated body of any one of Claims 1-7, and obtains the laminated body with the member for electronic devices,
A separation step of peeling the support substrate with an inorganic layer from the laminate with the member for electronic devices to obtain an electronic device having the glass substrate and the member for electronic devices.