JP2015093795A - Method for producing glass laminate, and method for producing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a glass laminate having excellent laminated state keeping properties between an inorganic layer disposed on a support substrate and a glass substrate.SOLUTION: The method for producing the glass laminate, in which the glass laminate 10, that includes: an inorganic layer-disposed support substrate 16 having the support substrate 12 and the inorganic layer 14 disposed on the support substrate; and the glass substrate 18 layered peelably on the inorganic layer, is obtained, comprises: a layering step of layering the glass substrate on the inorganic layer; and a heat treatment step of performing heat treatment on the layered glass substrate. The inorganic layer contains at least one selected from silicon carbide, carbonized silicon oxide, silicon nitride and nitrided silicon oxide. The heat treatment step satisfies the following conditions (a)-(d). The condition (a) is that a temperature rising rate is 300°C/minute or lower. The condition (b) is that the heating temperature is set within 150-600°C. The condition (c) is that the retention time is 0.5 minutes or more. The condition (d) is that the atmosphere is an air atmosphere of an atmospheric state or a reduced pressure state, an inert gas atmosphere or a vacuum atmosphere.

Description

  The present invention relates to a method for manufacturing 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 inorganic layer (inorganic thin film) arrange | positioned on a support substrate (support glass) based on patent document 1. FIG. As a result, when the specific composition which is not specifically described in patent document 1 is employ | adopted as a composition of an inorganic layer, it discovered that the peelability at the time of peeling the glass substrate on an inorganic layer was excellent.
By the way, in the method described in Patent Document 1, heat treatment is performed after stacking. Therefore, the present inventors performed a heat treatment under the conditions specifically described in Patent Document 1 after laminating a glass substrate on the inorganic layer using the specific composition. As a result, it was found that the laminated state may not be maintained when the laminated body subjected to the heat treatment is cut and folded or polished. In this case, when the electronic device member is formed on the glass substrate of the laminate subjected to the heat treatment, the glass substrate may be peeled off, which may cause a problem in the obtained electronic device.

  The present invention has been made in view of the above points, and a method for producing a glass laminate excellent in the laminate maintenance of an inorganic layer and a glass substrate disposed on a support substrate, and the glass laminate are used. It is an object of the present invention to provide a method for manufacturing an electronic device.

  As a result of intensive studies to achieve the above object, the present inventors have adopted a specific composition as the composition of the inorganic layer, and after heating a glass substrate on the inorganic layer, heating under specific conditions. By performing the treatment, it was found that the laminated state of the inorganic layer and the glass substrate was maintained, and the present invention was completed.

That is, the present invention provides the following (1) to (4).
(1) A glass laminate that obtains a glass laminate comprising a support substrate and a support substrate with an inorganic layer having an inorganic layer disposed on the support substrate, and a glass substrate that is detachably laminated on the inorganic layer. A method for producing a body, comprising: a laminating step of laminating the glass substrate on the inorganic layer; and a heat treatment step of performing a heat treatment after the laminating step, wherein the inorganic layer comprises silicon carbide, carbonized oxidation A method for producing a glass laminate, comprising at least one selected from the group consisting of silicon, silicon nitride, and silicon nitride oxide, wherein the heat treatment satisfies the following conditions (a) to (d).
(A) Temperature increase rate: 300 ° C./min or less (b) Heating temperature: 150 to 600 ° C.
(C) Holding time: 0.5 minutes or more (d) Atmosphere: atmospheric or inert gas atmosphere or vacuum atmosphere under atmospheric pressure or reduced pressure (2) The above (a) heating rate is 200 ° C. / The manufacturing method of the glass laminated body as described in said (1) which is below minutes.
(3) The manufacturing method of the glass laminated body as described in said (1) or (2) whose said support substrate is a glass substrate.
(4) An electronic device member is formed on the surface of the glass substrate in the glass laminate obtained by the method for producing a glass laminate according to any one of (1) to (3), and the electronic device is used. A member forming step for obtaining a laminate with members, and a separation step for peeling the support substrate with inorganic layers from the laminate with members for electronic devices to obtain an electronic device having the glass substrate and the members for electronic devices. A method for manufacturing an electronic device.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the glass laminated body which is excellent in the lamination | stacking maintenance property of the inorganic layer arrange | positioned on a support substrate and a glass substrate, and the manufacturing method of an electronic device using this glass laminated body 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 a method for producing a glass laminate and a method for producing 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, and the scope of the present invention. Various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention.

  The glass laminate obtained by the method for producing a glass laminate of the present invention is generally an intermediate layer adopting a specific composition interposed between a support substrate and a glass substrate. Even after treatment under high temperature conditions, the peelability between the inorganic layer and the glass substrate is excellent.

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

<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 manufacturing procedure (the manufacturing method of the glass laminated body of this invention) of the glass laminated body 10 is explained in full detail after that. To do.

[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. In the present invention, as the composition of the inorganic layer 14, silicon carbide (hereinafter also referred to as “SiC”), silicon carbide oxide (hereinafter also referred to as “SiCO”), silicon nitride (hereinafter also referred to as “SiN”). And at least one selected from the group consisting of silicon nitride oxide (hereinafter also referred to as “SiNO”). The composition of the inorganic layer 14 can be measured by X-ray photoelectron spectroscopy (XPS).
By providing such an 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, and the peelability is excellent. The reason for this is not clear, but the difference in electronegativity between Si and C or N is relatively small. This is thought to be because it is difficult to convert weak bonds to strong bonds.

  In the present invention, the surface roughness Ra of the inorganic layer surface 14a is preferably 2.00 nm or less, more preferably 1.00 nm or less, and from the viewpoint of stackability and peelability, 0.20 to 1.00 nm is further provided. preferable. 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 preferably contains at least one selected from the group consisting of SiC, SiCO, SiN and SiNO 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, 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, a method such as a vapor deposition method, a sputtering method, or a CVD method can be adopted. In the case of the sputtering method, specifically, for example, a SiC target or a SiN target is used. The composition of the inorganic layer surface 14a described above on the support substrate 12 while introducing an inert gas such as Ar or a mixed gas of an inert gas and an oxygen atom-containing gas such as O ₂ or CO _2. The method of providing the inorganic layer 14 which has this is mentioned. 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>
(Lamination process)
The method for producing a glass laminate of the present invention includes a laminating step of laminating a glass substrate 18 on the inorganic layer 14. Here, the method for laminating the glass substrate 18 is not particularly limited, but specifically, after the support substrate 16 with the inorganic layer and the glass substrate 18 are stacked in a normal pressure environment, for example, the glass substrate 18 is laminated. A method of generating an adhesion start point in the overlapping surface by pushing the weight or the second main surface 18b of the glass substrate 18 lightly at one place, and naturally expanding the adhesion from the contact start point; Thus, there is a method of expanding the adhesion from the adhesion starting point. The pressure bonding by a roll or a press is preferable because the inorganic layer 14 and the glass substrate 18 are more closely adhered to each other 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.

(Heat treatment process)
The manufacturing method of the glass laminated body of this invention is equipped with the heat processing process which performs the heat processing which satisfy | fills the conditions of following (a)-(d) after a lamination process.
(A) Temperature increase rate: 300 ° C./min or less (b) Heating temperature: 150 to 600 ° C.
(C) Holding time: 0.5 minutes or more (d) Atmosphere: atmospheric or inert gas atmosphere or vacuum atmosphere in an atmospheric pressure state or a reduced pressure state or a vacuum atmosphere In the case of having the layer 14, stacking maintainability is excellent by performing heat treatment that satisfies the conditions (a) to (d). While this is a weak intermolecular force (for example, van der Waals force or hydrogen bond) that acts on the interface between the inorganic layer 14 and the glass substrate 18 in the laminating step, the conditions (a) to (d) It is considered that when an appropriate heat is applied within the range, an appropriate oxygen diffusion reaction occurs at the interface in addition to the intermolecular force, thereby improving the adhesive force.

  (A) When the rate of temperature rise exceeds 300 ° C./min, the stackability is poor, but when it is 300 ° C./min or less, the stackability is excellent. (A) The rate of temperature increase is preferably 250 ° C./min or less, preferably 200 ° C./min or less, because there is little partial peeling during heating, the laminate maintaining state is in-plane uniform, and the laminate maintaining property is excellent. More preferred is 100 ° C./min or less.

  (B) The heating temperature is a temperature that is maintained after the temperature is raised at the rate of temperature rise in (a) above, and is inferior in lamination maintenance when it is less than 150 ° C, but if it is in the range of 150 to 600 ° C, Excellent stacking maintainability and excellent peelability. (B) The heating temperature is preferably 200 ° C. or higher, and more preferably 250 to 350 ° C., because it is superior in stacking maintainability.

  (C) The holding time is the time for holding the heating temperature of (b) above, and if it is less than 0.5 minutes (30 seconds), the laminate maintenance is poor, but 0.5 minutes (30 seconds) or more. If it exists, it is excellent in lamination maintenance. (C) The retention time is preferably from 1 to 60 minutes, and more preferably from 3 to 10 minutes, because it is superior in stacking maintainability.

(D) The atmosphere is an atmosphere when the temperature is raised under the conditions (a) and heated under the conditions (b) and (c). There is no particular limitation as long as it is an active gas atmosphere or a vacuum atmosphere. Here, examples of the inert gas include Ar gas and N ₂ gas.

The glass laminate 10 obtained by the method for producing a glass laminate of the present invention can be used for various applications. For example, a display panel, PV, a thin film secondary battery, and a semiconductor wafer on which a circuit is formed on the surface. The use etc. which manufacture electronic parts, such as these, are 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, Comparative Examples and Reference Examples), a glass plate made of non-alkali borosilicate glass (width 100 mm, depth 30 mm, thickness 0.2 mm, linear expansion coefficient 38 × 10 ⁻⁷ / The product name “AN100” manufactured by Asahi Glass Co., Ltd. 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 16>
(Formation of inorganic layer containing SiC)
One main surface of the support substrate was cleaned by washing with an alkaline aqueous solution. Further, an inorganic layer containing SiC (thickness 10 nm, surface roughness Ra 0.4 nm, the same applies below) is formed on the cleaned surface by magnetron sputtering while introducing Ar gas using a SiC target. A support substrate with an inorganic layer was obtained.

(Formation of inorganic layer containing SiCO)
An inorganic layer containing SiCO in the same manner as the formation of the inorganic layer containing SiC except that a mixed gas of Ar and O ₂ (volume ratio (Ar / O ₂ ) = 39/1) was introduced instead of Ar gas. And a support substrate with an inorganic layer was obtained.

(Formation of inorganic layer containing SiN)
An inorganic layer containing SiN was formed in the same manner as the formation of the inorganic layer containing SiC except that a SiN target was used in place of the SiC target to obtain a support substrate with an inorganic layer.

(Formation of inorganic layer containing SiNO)
An inorganic layer containing SiNO was formed in the same manner as the formation of the inorganic layer containing SiCO except that a SiN target was used in place of the SiC target to obtain a support substrate with an inorganic layer.

<Evaluation>
(Evaluation of stackability)
Next, the first main surface of the glass substrate was cleaned with an alkaline aqueous solution to be cleaned. Both surfaces of the inorganic layer of the support substrate with an inorganic layer in each example and the cleaned first main surface of the glass substrate were cleaned with an aqueous alkali solution and with water to clean both surfaces. Thereafter, a glass substrate was overlaid on the surface of the inorganic layer and pressure-bonded using a vacuum press, and the inorganic layer and the glass substrate were laminated to obtain a glass laminate.
And it heat-processed on the conditions of (a)-(d) shown to the following Table 1 with respect to the obtained glass laminated body of each example. In addition, when heat processing was not performed, "-" was described in the following Table 1. Further, (d) “atmosphere” described in Table 1 below as an atmosphere indicates “atmospheric atmosphere in an atmospheric pressure state”.
And after heat processing (including the case where heat processing was not performed), about the glass laminated body of each example, it cut and folded and grind | polished and evaluated the lamination | stacking maintenance property of an inorganic layer and a glass substrate on the following reference | standard.
Note that “cut-folding” was performed using a commercially available cutting and folding machine. Specifically, for the glass laminates of each example, after making a cut line so that the respective positions overlap on both surfaces, the support substrate is on the upper side, and the cut line is made along the edge of the table Then, one side of the glass laminate was fixed on a table, and the other side was pushed down and folded.
Further, in “polishing”, the glass substrate is fixed on a polyurethane table pad so that the supporting substrate is on the upper side and the glass substrate is on the lower side, and using a mixed solution of cerium oxide and water, Polishing was performed with a polishing pad for 5 minutes.
The results are shown in Table 1 below. If it is “◯” or “Δ”, it can be evaluated that the lamination maintaining property is excellent.
○: The laminated state of the inorganic layer and the glass substrate was maintained.
(Triangle | delta): Although the lamination | stacking state was maintained substantially, peeling peeled locally.
X: The laminated state collapsed and peeling occurred overall.

(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 maintenance 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. Thereafter, in the same manner as in the evaluation of the laminate maintenance, the obtained glass laminates were subjected to heat treatment under the conditions (a) to (d) shown in Table 1 below.
Then, heat treatment was performed 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)", it can be evaluated that it is excellent in peelability even after long-time treatment under high temperature conditions.
○: It was peeled off.
X: It was not able to peel.

As shown in Table 1 above, (a) the heating rate is 300 ° C./min or less, (b) the heating temperature is 150 to 600 ° C., and (c) the holding time is 0.5 min or more. (D) All examples (Examples) in which the atmosphere was an atmospheric atmosphere in an atmospheric pressure state were excellent in stacking maintainability.
On the other hand, the lamination maintenance property was inferior in the example (comparative example) in which the heat treatment was not performed or the conditions (a) to (d) were removed.
In addition, from the said result, in the Example, it was confirmed that the peeling strength of the interface of an inorganic layer and the layer of a support substrate is larger than the peeling strength of the interface of an inorganic layer and a glass substrate.

<Example II>
In this example, an OLED was produced using a glass laminate produced under the conditions of Example I-7 (see Table 1 above for heat treatment conditions).
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 III>
In this example, an LCD was produced using the glass laminate produced under the conditions of Example I-7 (see Table 1 above for the heat treatment conditions).
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 (4)

Manufacture of a glass laminate comprising a support substrate and a support substrate with an inorganic layer having an inorganic layer disposed on the support substrate, and a glass substrate that is detachably laminated on the inorganic layer. A method,
A laminating step of laminating the glass substrate on the inorganic layer;
A heat treatment step of performing a heat treatment after the laminating step,
The inorganic layer includes at least one selected from the group consisting of silicon carbide, silicon carbide oxide, silicon nitride, and silicon nitride oxide,
The manufacturing method of the glass laminated body with which the said heat processing satisfy | fills the conditions of following (a)-(d).
(A) Temperature increase rate: 300 ° C./min or less (b) Heating temperature: 150 to 600 ° C.
(C) Holding time: 0.5 minutes or more (d) Atmosphere: Atmospheric pressure or inactive gas atmosphere or inert gas atmosphere or vacuum atmosphere   The manufacturing method of the glass laminated body of Claim 1 whose said (a) temperature increase rate is 200 degrees C / min or less.   The manufacturing method of the glass laminated body of Claim 1 or 2 whose said support substrate is a glass substrate. The member for electronic devices is formed on the surface of the said glass substrate in the glass laminated body obtained by the manufacturing method of the glass laminated body of any one of Claims 1-3, The laminated body with the member for electronic devices A member forming step for obtaining
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.