KR20150054692A - Manufacturing method of glass laminated body and manufacturing method of electronic device - Google Patents

Abstract

The present invention relates to a manufacturing method of glass laminated body comprising a support substrate, a support substrate having an inorganic layer arranged on the support substrate, and a glass substrate laminated on the inorganic layer to be possibly exfoliated. Also, the manufacturing method of glass laminated body according to the present invention comprises a lamination process for laminating the glass substrate on the inorganic layer, a heat treatment process for applying the heat treatment after the lamination process, and the inorganic layer having at least one kind selected from the group consisting of carborundum, carbonized silicon oxide, silicon nitride, and silicon oxynitride. The heat treatment process satisfies the following conditions of (a) to (d) which includes (a) temperature raising rate : at most 300°C/min; (b) heating temperature : 150 to 600°C; (c) maintenance time : at least 0.5min; (d) atmosphere : atmosphere pressure state or atmospheric environment of decompression state or inert gas atmosphere or vacuum atmosphere.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for manufacturing a glass laminate,

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

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

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

Japanese Patent Application Laid-Open No. 2011-184284

On the basis of Patent Document 1, the present inventors have studied an inorganic layer (inorganic thin film) disposed on a support substrate (support glass). As a result, it was found that when a specific composition which is not specifically described in Patent Document 1 is employed as the composition of the inorganic layer, the release property when the glass substrate on the inorganic layer is peeled off is excellent.

However, in the method described in Patent Document 1, heat treatment is performed after lamination. Therefore, the present inventors laminated a glass substrate on the inorganic layer using the above-mentioned specific composition, and then subjected to heat treatment under the conditions specifically described in Patent Document 1. [ As a result, it was found that the laminated body subjected to the heat treatment may not be maintained in the laminated state when breaking or polishing. In this case, when the electronic device member is formed on the glass substrate of the layered product subjected to the heat treatment, peeling occurs on the glass substrate, which may cause problems in the resulting electronic device.

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and it is an object of the present invention to provide a method for producing a glass laminate having excellent laminating and maintaining properties of an inorganic layer and a glass substrate disposed on a supporting substrate, and a method for manufacturing an electronic device using the glass laminate The purpose.

Means for Solving the Problems The present inventors have intensively studied in order to achieve the above object. As a result, they have found that when a specific composition is adopted as the composition of the inorganic layer, the glass substrate is laminated on the inorganic layer, The present inventors have found that the laminated state of the substrate can be maintained, thereby completing the present invention.

That is, the present invention provides the following (1) to (4).

(1) A glass laminate for obtaining a glass laminate comprising a support substrate having an inorganic layer and a glass substrate laminated on the inorganic layer, the support laminate having a support substrate and an inorganic layer disposed on the support substrate And a heat treatment step of performing heat treatment after the laminating step, wherein the inorganic layer is formed of a material selected from the group consisting of silicon carbide, silicon carbide, silicon nitride, and nitride And silicon oxide, and the heat treatment satisfies the following conditions (a) to (d):

(a) Heating rate: 300 占 폚 / min or less;

(b) Heating temperature: 150 to 600 占 폚;

(c) Holding time: 0.5 minutes or more; And

(d) Atmosphere: atmosphere in an atmospheric pressure or reduced pressure state, inert gas atmosphere, or vacuum atmosphere.

(2) The method for producing a glass laminate as described in (1) above, wherein (a) the temperature raising rate is 200 ° C / min or less.

(3) The method for producing a glass laminate according to (1) or (2), wherein the supporting 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) A separation step of separating the support substrate provided with the inorganic layer from the laminate provided with the electronic device member to obtain an electronic device having the glass substrate and the electronic device member; Wherein the step of forming the electronic device comprises the steps of:

According to the present invention, it is possible to provide a method for producing a glass laminate excellent in laminating and retaining properties of an inorganic layer and a glass substrate disposed on a support substrate, and a method for manufacturing an electronic device using the glass laminate.

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

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

The glass laminate obtained by the method for producing a glass laminate of the present invention is roughly composed of an inorganic layer employing a specific composition between a support substrate and a glass substrate interposed therebetween. Thus, even after treatment under high temperature conditions, The peeling property of the substrate is excellent.

Hereinafter, a preferable mode of the glass laminate will be described in detail, and thereafter, a suitable method of manufacturing the glass laminate and a method of manufacturing an electronic device using the glass laminate will be described in detail.

≪ Glass laminate &

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

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

This glass laminate 10 is also used until a member forming process described later. That is, this glass laminate 10 is used until a member for an electronic device 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 supporting substrate 16 provided with the inorganic layer is peeled from the interface with the glass substrate 18, and the supporting substrate 16 provided with the inorganic layer is not a member constituting the electronic device. The separated supporting substrate 16 with the inorganic layer can be laminated with a new glass substrate 18 and reused as a new glass laminate 10. [

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

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

The supporting substrate 16 and the glass substrate 18 constituting the glass laminate 10 and the glass substrate 18 provided with the inorganic layer are described below in detail and then the manufacturing procedure of the glass laminate 10 A method of manufacturing a glass laminate according to the present invention) will be described in detail.

[Supporting substrate provided with an inorganic layer]

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

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

(Supporting substrate)

The supporting substrate 12 has a first main surface and a second main surface and is supported in cooperation with the inorganic layer 14 disposed on the first main surface to support and support the glass substrate 18, (A step of manufacturing a member for use in electronic devices), which prevents deformation, scratches, breakage, and the like of the glass substrate 18 at the time of manufacturing the electronic device member.

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

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

When the supporting substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for easy handling and difficulty in breaking. Further, the thickness of the glass plate is preferably not more than 1.0 mm for the reason that rigidity is required such that the glass plate is not broken when peeled off after the formation of the electronic device member.

(Inorganic layer)

The inorganic layer 14 is a layer that is placed (fixed) on the first main surface of the support substrate 12 and contacts the first main surface 18a of the glass substrate 18. [ 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 ) And 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 forming the inorganic layer 14 on the support substrate 12, adhesion between the inorganic layer 14 and the glass substrate 18 can be suppressed even after prolonged processing under high temperature conditions, and the peelability is excellent. Although the reason for this is not clear, the fact that the difference in the electronegativity of Si and C or N is relatively small allows the transition from weak bonding to strong bonding to chemical bonding between the inorganic layer and the glass substrate even after prolonged treatment under high temperature conditions And it is thought that it is difficult to occur.

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 still more preferably 0.20 to 1.00 nm from the viewpoint of lamination property and releasability. Ra (arithmetic average roughness) is measured according to JIS B 0601 (revised in 2001). The contents of JIS B 0601 (revised 2001) are incorporated herein by reference.

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

The inorganic layer 14 preferably contains at least one kind 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, and particularly preferably 99.999% by mass or more with respect to the total amount of the inorganic layer 14 .

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

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, the composition may be different for each layer. In this case, the " thickness of the inorganic layer " means the total thickness of all the layers.

The inorganic layer 14 is usually formed on the entire surface of the support substrate 12 as shown in Fig. 1, but it may be formed on a part of the surface of the support substrate 12 within a range that does not impair the effect of the present invention . For example, the inorganic layer 14 may be formed on the surface of the support substrate 12 in a island shape or a stripe shape.

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

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

(Manufacturing method of supporting substrate provided with inorganic layer)

As the method for producing the support substrate 16 provided with the inorganic layer, for example, a vapor deposition method, a sputtering method, a CVD method or the like can be employed. In the case of the sputtering method, for example, SiC target or SiN A method of forming the inorganic layer 14 on the support substrate 12 while introducing a mixed gas of an inert gas such as Ar or an inert gas and an oxygen atom containing gas such as O ₂ or CO ₂ . The optimum conditions for the production conditions are appropriately selected according to the materials to be used and the like.

After the formation of the inorganic layer 14 on the support substrate 12, the surface of the inorganic layer 14 may be subjected to a cutting process in order to control the surface roughness Ra of the inorganic layer surface 14a. As the above-mentioned treatment, for example, ion sputtering and the like can be mentioned.

[Glass Substrate]

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

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

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

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

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

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

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

An inorganic thin film layer may be further stacked on the first main surface 18a of the glass substrate 18. [ When the inorganic thin film layer is arranged (fixed) on the glass substrate 18, the inorganic thin film layer and the inorganic layer 14 of the supporting substrate 16 provided with the inorganic layer are in contact with each other in the glass laminate. By providing the inorganic thin film layer on the glass substrate 18, adhesion of the glass substrate 18 and the support substrate 16 provided with the inorganic layer can be further suppressed even after long time processing under high temperature conditions.

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

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

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

≪ Glass laminate &

The glass laminate 10 of the present invention has the inorganic layer surface 14a of the support substrate 16 provided with the inorganic layer and the first main surface 18a of the glass substrate 18 as the lamination surface, A support substrate 16 provided with an inorganic layer and a glass substrate 18 are 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. [

≪ Production method of glass laminate >

(Lamination step)

The method for producing a glass laminate of the present invention includes a lamination step of laminating a glass substrate 18 on an inorganic layer 14. [ The method for laminating the glass substrate 18 is not particularly limited. Specifically, after the support substrate 16 provided with the inorganic layer is superimposed on the glass substrate 18 under an atmospheric pressure environment, for example, the glass substrate 18 ) Or by slightly pressing the second main surface 18b of the glass substrate 18 at one place to generate a contact starting point in the overlapping surface and to naturally expand the contact from the contact starting point; A method of expanding the adhesion from the contact starting point by pressing using a roll or press; And the like. Compression by roll or press is preferable because the inorganic layer 14 and the glass substrate 18 are in close contact with each other and the bubbles mixed in between them are relatively easily removed.

Further, it is more preferable to press it by a vacuum laminating method or a vacuum press method, because mixing of bubbles is suppressed and good adhesion is ensured. By pressing under vacuum, bubbles do not grow due to heating even when minute bubbles remain, which is an advantage that it is difficult to cause distortion defects.

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

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

(Heat treatment step)

The method for producing a glass laminate according to the present invention comprises a heat treatment step for performing a heat treatment which satisfies the following conditions (a) to (d) after the laminating step.

(a) Heating rate: 300 占 폚 / min or less

(b) Heating temperature: 150 to 600 DEG C

(c) Holding time: 0.5 minutes or more

(d) Atmosphere: atmosphere of atmospheric pressure or reduced pressure, inert gas atmosphere, or vacuum atmosphere

In the case where the support substrate 16 provided with the inorganic layer has the inorganic layer 14 employing the composition described above, the heat treatment is performed satisfying the conditions (a) to (d) . This is because the weak intermolecular force (for example, a van der Waals force or a hydrogen bond) acting on the interface between the inorganic layer 14 and the glass substrate 18 in the laminating process, The appropriate oxygen diffusion reaction occurs at the interface other than the intermolecular force, thereby improving the adhesive force.

(a) When the heating rate is more than 300 ° C / minute, the laminate retention property is poor, but when it is 300 ° C / minute or less, the laminate retention property is excellent. (a) The rate of temperature rise is preferably 250 占 폚 / min or less, more preferably 200 占 폚 / min or less, because partial peeling is small during heating, the laminate holding state is in-plane uniform, And more preferably 100 ° C / minute or less. Also, (a) the heating rate is preferably 0.1 ° C / min or more.

(b) The heating temperature is maintained at a temperature elevating rate of (a). When the heating temperature is lower than 150 ° C, the laminate retention property is deteriorated. When the temperature is in the range of 150 to 600 ° C, the laminate retention property is excellent and the peeling property is also excellent . The heating temperature (b) is preferably 200 占 폚 or higher, more preferably 250 占 폚 to 350 占 폚, in view of superior laminating and maintaining properties.

(c) The holding time is a time for maintaining the heating temperature of (b) above. If it is less than 0.5 minute (30 seconds), the laminate retention becomes poor. (c) The holding time is preferably from 1 to 60 minutes, more preferably from 3 to 10 minutes, because the holding time is better.

(d) The atmosphere is an atmosphere in which the temperature is raised under the conditions of (a) and heated under the conditions of (b) and (c), and the atmosphere is an atmospheric pressure or reduced pressure, Is not particularly limited. Examples of the inert gas include Ar gas, N ₂ gas, and the like.

The glass laminate 10 obtained by the method for producing a glass laminate of the present invention can be used for various purposes. For example, the glass laminate 10 can be used for display panel, PV, thin film secondary battery, And the like, and the like. Further, in the above applications, the glass laminate 10 is often exposed to high temperature conditions (for example, 350 DEG C or more) (for example, 1 hour or more).

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

≪ Electronic device and method for manufacturing the same &

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

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

Hereinafter, the material used in each step and the procedure thereof will be described in detail with reference to FIG. The preferred member forming process will be described in detail.

[Member forming process]

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

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

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

(Member for electronic device (functional element))

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

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

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

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

(Process procedure)

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

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

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

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

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

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

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

[Separation Process]

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

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

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

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

When a part of the supporting substrate 16 provided with the inorganic layer is laminated by protruding from the glass substrate 18, the glass substrate 18 is fixed to the fixing table (refer to reference numeral 31 in FIG. 3 to be described later) Shaped jig (refer to reference numeral 32 in Fig. 3) is attached to the inorganic layer surface 14a after or without imparting the peeling mechanism as described above, , Thereby peeling the inorganic layer 14 and the glass substrate 18 from each other.

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

[Example]

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

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

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

<Examples I-11 and 14>

(Formation of an inorganic layer containing SiC)

One major surface of the supporting substrate was cleaned by cleaning with an alkaline aqueous solution. Further, an inorganic layer (thickness 10 nm, surface roughness Ra 0.4 nm, the same shall apply hereinafter) of SiC was formed by magnetron sputtering while introducing Ar gas by using a SiC target on the cleaned surface, To obtain a support substrate.

&Lt; Examples I-1 to 10 &

(Formation of an inorganic layer containing SiCO)

An inorganic layer containing SiCO was formed 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 , A support substrate provided with an inorganic layer was obtained.

<Examples I-12, 15>

(Formation of an inorganic layer containing SiN)

Except that an SiN target was used in place of the SiC target, an inorganic layer containing SiN was formed in the same manner as the formation of the inorganic layer containing SiC to obtain a supporting substrate provided with an inorganic layer.

<Examples I-13 and 16>

(Formation of an inorganic layer containing SiNO)

Except that an SiN target was used in place of the SiC target, an inorganic layer containing SiNO was formed in the same manner as the formation of the inorganic layer containing SiCO to obtain a support substrate provided with an inorganic layer.

<Evaluation>

(Evaluation of laminated retentivity)

Next, the first major surface of the glass substrate was cleaned with an alkaline aqueous solution. On both surfaces of the inorganic layer of the inorganic layer of the support substrate provided with the inorganic layer of each example and the first main surface of the glass substrate cleaned, cleaning with an aqueous alkaline solution and cleaning with water were performed to clean both surfaces. Thereafter, the glass substrate was superimposed on the surface of the inorganic layer and pressed by using a vacuum press to laminate the inorganic layer and the glass substrate to obtain a glass laminate.

The obtained glass laminate was subjected to heat treatment under the conditions (a) to (d) shown in Table 1 below. In the case where the heat treatment is not performed, "-" is described in Table 1 below. Further, (d) "atmospheric atmosphere" shown in the following Table 1 as an atmosphere means "atmospheric atmosphere at atmospheric pressure".

After the heat treatment (including the case where the heat treatment was not performed), the glass laminate of each example was subjected to breaking cutting and polishing, and the laminate retention property of the inorganic layer and the glass substrate was evaluated based on the following criteria.

Also, &quot; breaking cutting &quot; was carried out using a commercially available breaking cutting machine. Specifically, for each glass laminate of each example, after cutting lines are formed so as to overlap the respective positions on both sides thereof, the supporting substrate is placed on the upper side, and the cut line is made to follow the edge of the die, Fixed on the die, and pushed down on the other side.

Further, in "polishing", the glass laminate was fixed on a table pad made of polyurethane so that the support substrate was on the upper side and the glass substrate was on the lower side, and polishing with a polishing pad for 5 minutes was performed using a mixed solution of cerium oxide and water Respectively.

The results are shown in Table 1 below. Quot; or &quot;? &Quot;, it can be evaluated that the laminate retention property is excellent.

?: The laminated state of the inorganic layer and the glass substrate was maintained.

DELTA: Approximately laminated state was maintained, but peeling occurred locally.

X: The laminated state was disturbed and peeling occurred as a whole.

(Evaluation of peelability)

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

First, the inorganic layer surface of the inorganic layer and the first main surface of the glass substrate were cleaned in the same manner as in the evaluation of the laminate retentivity. Thereafter, the supporting substrate provided with the inorganic layer and the glass substrate were aligned and superimposed at one end as shown in Fig. 3 while aligning their positions in the depth direction. In addition, since the supporting substrate and the glass substrate provided with the inorganic layer have different lengths in the width direction, when one end is aligned and overlapped, a part of the supporting substrate provided with the inorganic layer as shown in Fig. And protruded from the substrate.

After the superimposing, a contact point was generated and pressed by using a vacuum press to superpose the adhesion and spread over the entire surface, thereby obtaining glass laminated samples of the respective examples. Thereafter, similarly to the evaluation of the laminate retentivity, the obtained glass laminate was heat-treated under the conditions (a) to (d) shown in Table 1 below.

Then, heat treatment was performed at 600 占 폚 for one hour in an air atmosphere.

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

Next, as shown in Fig. 3, an L-shaped jig (indicated by numeral 32 in Fig. 3) is put on the surface of the inorganic layer of the support substrate provided with the inorganic layer protruded from the glass substrate, The peelability of the inorganic layer and the glass substrate was evaluated on the basis of the following criteria by pulling up to 10 mm / min using a machine. The results are shown in Table 1 below. And &quot;? &Quot;, it can be evaluated that the peelability is excellent even after long-term treatment under high temperature conditions.

○: Peeling was possible.

X: Peeling was not possible.

(B) the heating temperature is 150 to 600 ° C; (c) the holding time is 0.5 minutes or more; (d) the atmosphere is atmospheric pressure (Examples) in the atmospheric atmosphere were all excellent in laminate retention.

On the other hand, in the case where the heat treatment was not performed or the conditions (a) to (d) were deviated from the above (comparative example), the laminate holding property was deteriorated.

From the above results, it was confirmed that the peel strength of the interface between the inorganic layer and the support substrate is larger than that of the interface between the inorganic layer and the glass substrate.

<Example Ⅱ>

In this example, an OLED was fabricated using the glass laminate produced in Example I-7 (see Table 1 for the heat treatment conditions).

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

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as a hole injecting layer and bis [(N-naphthyl) -N -phenyl] 8-quinolinol aluminum complex as benzidine, the light emitting layer (Alq ₃₎ 2,6- bis [4- [N- (4- methoxyphenyl) -N- phenyl] amino styryl] -1-naphthalene, Alk ₃ was further deposited in this order on the electron transport layer. Next, aluminum was deposited on the second main surface side of the glass substrate by the sputtering method, Next, one glass substrate was further bonded and sealed on the second main surface of the glass substrate on which the counter electrodes were formed via an ultraviolet curable adhesive layer. A glass laminate having an organic EL structure on a glass substrate, And corresponds to a laminate provided with a member for an electronic device.

Subsequently, a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the inorganic layer at the corner of the glass laminate and the glass substrate, and the inorganic layer was provided from the glass laminate And the support substrate was separated to obtain an OLED panel (corresponding to the electronic device, hereinafter referred to as panel A). An IC driver was connected to the prepared panel A and driven at room temperature and atmospheric pressure, and display irregularity was not recognized in the driving area.

<Example III>

In this example, an LCD was fabricated using the glass laminate produced in Example I-7 (see Table 1 for heat treatment conditions).

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

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

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

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

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

The present application is based on Japanese Patent Application No. 2013-233024 filed on November 11, 2013, the contents of which are incorporated herein by reference.

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

Claims (4)

A glass laminate having a support substrate provided with an inorganic layer and a glass substrate laminated on the inorganic layer, the glass laminate having a support substrate and an inorganic layer disposed on the support substrate, / RTI &gt;
A lamination step of laminating the glass substrate on the inorganic layer,
And a heat treatment step of performing heat treatment after the laminating step,
Wherein the inorganic layer contains at least one selected from the group consisting of silicon carbide, silicon carbide oxide, silicon nitride, and silicon nitride oxide,
Wherein the heat treatment satisfies the following conditions (a) to (d):
(a) Heating rate: 300 占 폚 / min or less;
(b) Heating temperature: 150 to 600 占 폚;
(c) Holding time: 0.5 minutes or more; And
(d) Atmosphere: atmosphere in an atmospheric pressure or reduced pressure state, inert gas atmosphere, or vacuum atmosphere. The method for producing a glass laminate according to claim 1, wherein (a) the temperature raising rate is 200 ° C / min or less. The method of manufacturing a glass laminate according to claim 1 or 2, wherein the supporting substrate is a glass substrate. An electronic device member is formed on the surface of the glass substrate in the glass laminate obtained by the method for manufacturing a glass laminate according to any one of claims 1 to 3 to form a laminate A step of forming a member for obtaining a substrate,
And separating the supporting substrate provided with the inorganic layer from the laminate provided with the electronic device member to obtain an electronic device having the glass substrate and the electronic device member.

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