WO2014133007A1

WO2014133007A1 - Method for manufacturing electronic device

Info

Publication number: WO2014133007A1
Application number: PCT/JP2014/054697
Authority: WO
Inventors: 保弘松本; 康夫山崎; 睦深田
Original assignee: 日本電気硝子株式会社
Priority date: 2013-02-26
Filing date: 2014-02-26
Publication date: 2014-09-04
Also published as: JP2014194541A; TW201446497A

Abstract

An electronic device (5) is manufactured by performing: a first step of setting the surface roughness (Ra) of sides (11a, 12a) of a glass film (11) and a support glass (12) that contact each other to 2.0 nm or less and bringing into contact the two sides (11a, 12a) to produce a glass film laminate (1) in which the glass film (11) and the support glass (12) are laminated; a second step of forming an element (51) on the glass film (11) of the glass film laminate (1) by performing an electronic device manufacturing-related process that entails heating, and sealing the element (51) with a cover glass (2) to produce an electronic device (3) with the support glass; and a step of applying a liquid (4) which comprises water to an interface between the glass film (11) and the support glass (12) of the electronic device (3) with the support glass and separating the electronic device (5) from the support glass (12).

Description

Manufacturing method of electronic device

The present invention relates to a method of manufacturing an electronic device such as a flat panel display such as a liquid crystal display or an organic EL display, organic EL lighting, a solar battery, a lithium ion battery, a digital signage, a touch panel, electronic paper, a mobile phone, or a smartphone.

From the viewpoint of space saving, instead of the CRT type display which has been widely used in the past, flat panel displays such as a liquid crystal display, a plasma display, an organic EL display and a field emission display have become popular in recent years. These flat panel displays are required to be thinner. In particular, organic EL displays are required to be easily carried by folding or winding, and to be usable not only on flat surfaces but also on curved surfaces. Further, it is not limited to a display that can be used not only on a flat surface but also on a curved surface. For example, it has a curved surface such as the surface of a car body, the roof of a building, or a pillar or an outer wall. If a solar cell or organic EL illumination can be formed on the surface of an object, its application will be expanded. Therefore, the substrate and cover glass used in these devices are required to be further thinned and highly flexible.

The light emitter used in the organic EL display is deteriorated by contact with a gas such as oxygen or water vapor. Accordingly, since a high gas barrier property is required for a substrate used in an organic EL display, it is expected to use a glass substrate. However, glass substrates used in such applications are less flexible because they are less susceptible to tensile stress than resin films, and breakage occurs when the glass substrate surface is subjected to tensile stress by bending the glass substrate. . In order to impart flexibility to the glass substrate, it is necessary to make the glass substrate ultra-thin, and a glass film having a thickness of 200 μm or less as described in Patent Document 1 has been proposed.

The glass substrate used for electronic devices such as flat panel displays and solar cells is subjected to various processing related to electronic device manufacturing such as processing and cleaning. However, if the glass substrate used in these electronic devices is made thin and made into a film, the glass is a brittle material, which leads to breakage due to a slight change in stress. There is a problem that is very difficult. In addition, since a glass film having a thickness of 200 μm or less is rich in flexibility, it is difficult to perform positioning when performing processing, and there is a problem that displacement or the like occurs during patterning.

In order to improve the handleability of the glass film, the following Patent Document 2 proposes a glass film laminate in which a glass film is laminated on a supporting glass. According to this, even if a glass film having low strength and rigidity is used alone, the supporting glass has high rigidity, so that the entire glass film laminate can be easily positioned during processing. Moreover, after completion | finish of a desired process, it is possible to peel from a support glass immediately, without damaging a glass film. If the thickness of the glass film laminate is the same as that of a conventional glass substrate, a liquid crystal display element can be manufactured by sharing a conventional liquid crystal display element manufacturing line for glass substrates.

On the other hand, the various manufacturing-related processes described above include processes involving heating, such as a film forming process or a sealing process of a transparent conductive film. When a process involving heating is performed, the support glass and the glass film that are directly laminated in the glass film laminate are bonded to each other, which makes it difficult to peel the glass film from the support glass.

In order to solve this problem, Patent Document 3 below proposes a glass film laminate in which an inorganic thin film is formed on a supporting glass and then a glass film is laminated. Thereby, even if the electronic device manufacturing related process with heating is performed on the glass film laminate, the supporting glass and the glass film are not bonded, and the glass film is removed from the supporting glass after the electronic device manufacturing related process with heating. It can be peeled off.

JP 2010-132531 A WO2011 / 048979 JP 2011-184284 A

However, in Patent Document 3, it is necessary to form an inorganic thin film very uniformly on the surface of the supporting glass. In addition, the formation of the inorganic thin film on the supporting glass has a problem of requiring a lot of time and cost. Therefore, it is desired that the supporting glass and the glass film are peeled from the glass film laminate by a simple and inexpensive method after the electronic device manufacturing-related process involving heating.

The present invention has been made to solve the above-described problems of the prior art, and easily and inexpensively peels a glass film from a supporting glass even after processing related to electronic device manufacturing involving heating. The purpose is to make it possible.

The present invention devised to solve the above-mentioned problems is that the surface roughness Ra of the surfaces of the glass film and the supporting glass which are in contact with each other is set to 2.0 nm or less, and both the surfaces are brought into contact with each other. A device is formed on the glass film of the glass film laminate by performing a first process for producing a glass film laminate in which a glass film and a supporting glass are laminated, and an electronic device manufacturing related process involving heating. The second step of producing the electronic device with supporting glass by sealing the element with a cover glass, and applying a liquid containing water to the interface between the glass film and the supporting glass of the electronic device with supporting glass And a third step of peeling the electronic device from the supporting glass.

According to such a structure, since each surface roughness of the surface where the support glass and the glass film are in contact with each other is 2.0 nm or less, the adhesion between the glass film and the support glass is good, and the adhesive Even without using an agent, the glass film and the supporting glass can be directly fixed and laminated. Moreover, the element formed on the glass film can be sealed by sealing the element with the cover glass after the electronic device manufacturing related process. Even if an electronic device manufacturing related process involving heating is performed by applying a liquid containing water to the interface between the supporting glass and the glass film, the supporting glass and the glass film can be favorably peeled off. Even if the liquid is used at the time of peeling, the liquid is not attached to the element in the electronic device because the cover glass is sealed to make the periphery of the element a sealed space. The internal elements are not deteriorated.

In the above method, the third step is preferably performed by immersing the electronic device with a supporting glass in a liquid containing water.

In this way, since the electronic device with the supporting glass is immersed in the liquid containing water, the liquid containing water is surely given to the interface between the supporting glass and the glass film at the time of peeling. can do.

In the above method, the liquid containing water is preferably alkaline.

In this way, since the liquid containing water is alkaline, the supporting glass can be peeled from the electronic device with supporting glass more efficiently.

In the above method, in the third step, an ultrasonic wave may be applied to the electronic device with a supporting glass.

If it does in this way, since the ultrasonic wave is applied to the electronic device with a supporting glass in the third step, the liquid containing water efficiently penetrates into the interface between the supporting glass and the glass film. Thus, the support glass and the glass film can be peeled off more favorably.

In the above method, in the third step, a peeling member may be inserted at the interface between the glass film and the supporting glass.

If it does in this way, in the 3rd process, since a peeling member is inserted in the interface of a glass film and support glass, the liquid containing water can penetrate efficiently into the interface of support glass and glass film. The supporting glass and the glass film can be peeled off more favorably.

In the above method, the peeling member can be a hydrophobic resin sheet.

In this way, since the peeling member is a hydrophobic resin sheet, it is excellent in handling the resin sheet in a liquid containing water, and efficiently contains water at the interface between the glass film and the supporting glass. Liquid can enter.

In the above method, an inorganic thin film can be formed on the surface of the supporting glass that is in contact with the glass film.

In this way, since the inorganic thin film is formed on the surface of the supporting glass that comes into contact with the glass film, the supporting glass and the glass film can be more efficiently separated.

In the above method, the cover glass may be laminated on a carrier glass, and the cover glass and the carrier glass may be peeled off in the third step.

In this way, since the cover glass is supported by the carrier glass, it is possible to perform processing related to electronic device manufacturing on the cover glass side as well, even if the cover glass has flexibility. The element can be sealed, and the cover glass and the carrier glass can be peeled off at the same time as the supporting glass and the glass film are peeled off in the third step.

In the above method, in the third step, the peeling member may be inserted into the interface between the cover glass and the carrier glass.

If it does in this way, since the 3rd process inserts a peeling member in the interface of a cover glass and carrier glass, the liquid containing water efficiently penetrates also into the interface of a cover glass and carrier glass. The cover glass and the carrier glass can be peeled off satisfactorily.

As described above, according to the present invention, it is possible to easily and inexpensively peel the glass film from the supporting glass even after processing related to electronic device manufacturing involving heating, and by sealing with a cover glass, The elements in the electronic device are preferably protected.

It is the schematic which shows the manufacturing method of the electronic device which concerns on this invention. It is a vertical front view which shows the principal part of the manufacturing apparatus of a glass film and support glass. It is a schematic perspective view which shows an example of the manufacturing method of the laminated body of a glass film. It is a principal part longitudinal front view which shows an example of an electronic device with support glass. It is the schematic explaining the phenomenon guessed to have arisen in the glass film laminated body. It is the schematic explaining the phenomenon guessed to have arisen in the glass film laminated body. It is the schematic explaining the phenomenon guessed that a glass film and support glass adhere | attach. It is the schematic explaining the process in which support glass peels from the electronic device with support glass. It is the schematic explaining the process in which a cover glass and carrier glass peel in a 3rd process. It is the schematic explaining the measurement test of peeling surface energy.

Hereinafter, preferred embodiments of a method for manufacturing an electronic device according to the present invention will be described with reference to the drawings. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments.

As shown in FIG. 1, the method for manufacturing an electronic device according to the present invention sets the surface roughness Ra of the glass film 11 and the supporting glass 12 on the side in contact with each other to 2.0 nm or less, and both surfaces thereof. The glass of the glass film laminated body 1 by performing the electronic device manufacturing related process with a 1st process which laminates | stacks the glass film 11 and the support glass 12 by making surface contact, and produces the glass film laminated body 1 and a heating. A second step of forming the electronic device 3 with supporting glass by forming the element 51 on the film 11 and sealing the element 51 with the cover glass 2, and the glass film 11 and the supporting glass of the electronic device 3 with supporting glass And a third step of peeling the electronic device 5 from the support glass 12 by applying a liquid containing water to the interface 13 with the substrate 12.

The glass film 11 is made of silicate glass or silica glass, preferably borosilicate glass, most preferably non-alkali glass. If the glass film 11 contains an alkali component, cations are dropped on the surface, so-called soda blowing phenomenon occurs, and the structure becomes rough. In this case, if the glass film 11 is curved and used, there is a possibility that it will be damaged from a portion that has become rough due to deterioration over time. Here, the alkali-free glass is a glass that does not substantially contain an alkali component (alkali metal oxide), and specifically, a glass having an alkali component of 3000 ppm or less. The content of the alkali component in the present invention is preferably 1000 ppm or less, more preferably 500 ppm or less, and most preferably 300 ppm or less.

The thickness of the glass film 11 is preferably 300 μm or less, more preferably 5 μm to 200 μm, and most preferably 5 μm to 100 μm. Thereby, the thickness of the glass film 11 can be made thinner and appropriate flexibility can be imparted, handling properties are difficult, and problems such as misalignment and bending during patterning are likely to occur. On the other hand, processing related to electronic device manufacturing can be easily performed by using the supporting glass 12 described later. If the thickness of the glass film 11 is less than 5 μm, the strength of the glass film 11 tends to be insufficient, and the glass film 11 may be difficult to peel from the support glass 12.

As the support glass 12, silicate glass, silica glass, borosilicate glass, non-alkali glass, or the like is used similarly to the glass film 11. For the supporting glass 12, it is preferable to use a glass having a difference in thermal expansion coefficient at 30 to 380 ° C. with respect to the glass film 11 within 5 × 10 ⁻⁷ / ° C. Thereby, even if heat treatment is involved in the processing related to electronic device manufacturing, thermal warp due to a difference in expansion coefficient, cracking of the glass film 11, and the like hardly occur, and the glass film laminate 1 can maintain a stable laminated state. It becomes possible. The supporting glass 12 and the glass film 11 are most preferably glass having the same composition.

The thickness of the support glass 12 is preferably 400 μm or more. When the thickness of the supporting glass 12 is less than 400 μm, there is a possibility that a problem may occur in terms of strength when the supporting glass 12 is handled alone. The thickness of the support glass 12 is preferably 400 μm to 700 μm, and most preferably 500 μm to 700 μm. As a result, the glass film 11 can be reliably supported, and breakage of the glass film 11 that can occur when the glass film 11 is peeled from the support glass 12 can be effectively suppressed. When the glass film laminate 1 is placed on a setter (not shown) during the electronic device manufacturing related process, the thickness of the support glass 12 may be less than 400 μm (for example, 300 μm or the like, the same thickness as the glass film 11). .

The glass film 11 and the supporting glass 12 used in the present invention are preferably formed by a down draw method, and more preferably formed by an overflow down draw method. In particular, the overflow downdraw method shown in FIG. 2 is a molding method in which both surfaces of the glass plate do not come into contact with the molded member at the time of molding, and the both surfaces (translucent surface) of the obtained glass plate are hardly scratched and polished. Even if not, high surface quality can be obtained. Of course, the glass film 11 and / or the supporting glass 12 may be formed by a float method, a slot down draw method, a roll out method, an up draw method, a redraw method, or the like.

In the overflow down draw method shown in FIG. 2, the glass ribbon G immediately after flowing down from the lower end portion 81 of the wedge-shaped molded body 8 is drawn downward while the shrinkage in the width direction is restricted by the cooling roller 82 to be predetermined. The thickness becomes thin. Next, the glass ribbon G that has reached the predetermined thickness is gradually cooled in a slow cooling furnace (annealer), the thermal distortion of the glass ribbon (G) is removed, and the glass ribbon (G) is cut into a predetermined size, thereby forming a glass film. 11 and the support glass 12 are respectively formed.

As shown in FIG.1 and FIG.3, the 1st process based on this invention is laminated | stacked on the glass film 11 and support glass 12 which are surface roughness Ra of the side which mutually contacts is 2.0 nm or less, respectively, and glass. This is a process for producing the film laminate 1.

In the present invention, the surface roughness Ra of the contact surface 11a of the glass film 11 with the support glass 12 and the contact surface 12a of the support glass 12 with the glass film 11 is 2.0 nm or less, respectively. When surface roughness Ra exceeds 2.0 nm, adhesiveness will fall and it will become impossible to laminate | stack strongly the glass film 11 and the support glass 12 without an adhesive agent. The surface roughness Ra of each of the contact surfaces 11a and 12a of the glass film 11 and the supporting glass 12 is preferably 1.0 nm or less, more preferably 0.5 nm or less, and 0.2 nm or less. Most preferred. On the other hand, the surface roughness of the effective surface 11b of the glass film 11 shown in FIG. 1 and FIG. 3 is not particularly limited, but in the second step to be described later, the processing related to electronic device manufacturing such as film formation is performed. The roughness Ra is preferably 2.0 nm or less, more preferably 1.0 nm or less, further preferably 0.5 nm or less, and most preferably 0.2 nm or less. The surface roughness of the conveyance surface 12b of the support glass 12 is not particularly limited.

In FIG. 3, the glass film 11 having substantially the same area is laminated on the support glass 12, but in order to further facilitate the peeling of the glass film 11 from the support glass 12, the glass film 11 is supported by the support glass 12. It may be laminated so as to protrude from. In this case, the protruding amount of the glass film 11 from the supporting glass 12 is preferably 1 to 20 mm, more preferably 1 to 10 mm, and most preferably 1 to 5 mm. Even if the protruding amount of the glass film 11 is about 1 mm, the end portion of the glass film 11 can be used as the starting point of the peeling, while the protruding amount of the glass film 11 exceeds 20 mm. May cause damage or drooping. The portion of the glass film 11 protruding from the support glass 12 may be all four sides of the glass film laminate 1, or may be only two sides or only one side facing each other.

On the other hand, from the viewpoint of protecting the end of the glass film 11, the support glass 12 may be laminated so as to protrude from the glass film 11. In this case, the amount of protrusion of the support glass 12 from the glass film 11 is preferably 0.5 to 10 mm, and more preferably 0.5 to 1 mm. By reducing the amount of protrusion of the support glass 12, the area of the effective surface 11b of the glass film 11 can be secured more widely. In the glass film laminated body 1, it is preferable that the support glass 12 protrudes from the glass film 11 in all four sides. Moreover, in the glass film laminated body 1, the form in which the glass film 11 protrudes from the support glass 12 only on one side, and the support glass 12 protrudes from the glass film 11 in the remaining three sides is more preferable. The step of laminating the glass film 11 on the support glass 12 may be performed under reduced pressure. Thereby, the bubble produced when the glass film 11 and the support glass 12 are laminated | stacked can be reduced.

The second step according to the present invention is an effective surface 11b of the glass film 11 of the glass film laminate 1 produced in the first step as shown in FIG. In this process, the device 51 is formed on the support glass 2 by sealing the device 51 formed on the effective surface 11 b of the glass film 11 with the cover glass 2.

Examples of the electronic device manufacturing related process involving heating in the second step include a film forming process by a CVD method, a sputtering method, and the like. As elements formed on the effective surface 11b of the glass film 11, liquid crystal elements, organic EL elements, touch panel elements, solar cell elements, piezoelectric elements, light receiving elements, battery elements such as lithium ion secondary batteries, MEMS elements, and semiconductors An element etc. are mentioned.

As the glass cover 11, the cover glass 2 is made of silicate glass, silica glass, borosilicate glass, alkali-free glass or the like. For the cover glass 2, it is preferable to use a glass having a difference in thermal expansion coefficient at 30 to 380 ° C. with respect to the glass film 11 within 5 × 10 ⁻⁷ / ° C. Thereby, even if the temperature of the surrounding environment of the produced electronic device 5 changes, it is hard to produce the thermal warp by the difference of an expansion coefficient, the crack of the glass film 11 and the cover glass 2, etc., and it is set as the electronic device 5 which is hard to be damaged. It becomes possible. The cover glass 2 and the glass film 11 are most preferably glass having the same composition.

The thickness of the cover glass 2 is preferably 300 μm or less, more preferably 5 μm to 200 μm, and most preferably 5 μm to 100 μm. Thereby, thickness of a cover glass can be made thinner and appropriate flexibility can be provided. When the thickness of the cover glass 2 is less than 5 μm, the strength of the cover glass 2 tends to be insufficient.

FIG. 4 shows an organic EL panel as an example of the electronic device 3 with a supporting glass manufactured in the second step. The anode layer 52a, the hole transport layer 52b, the light emitting layer 52c, the electron transport layer 52d, and the cathode layer 52e are laminated in this order on the effective surface 11b of the glass film 11 by a known film formation method such as CVD or sputtering. The organic EL element 52 is formed. Then, the organic EL element 52 is sealed by bonding the cover glass 2 and the glass film 11 using a known laser sealing or the like, and the electronic device 3 with supporting glass (this time organic EL with supporting glass). Panel). In the form of FIG. 4, the cover glass 2 and the glass film 11 are directly bonded, but the cover glass 2 and the glass film 11 may be bonded appropriately using a known glass frit, a spacer, or the like.

As shown in FIG. 1, the third step according to the present invention is to apply the electronic device 5 while applying the liquid 4 containing water to the interface 13 between the glass film 11 and the supporting glass 12 of the electronic device 3 with supporting glass. This is a step of peeling from the support glass 12.

The liquid 4 containing water may contain other components as long as it contains at least water, and may be in an aqueous solution or a micelle state in which the solute is dissolved in water as well as pure water. It may be a mixture with water or may contain a component that does not dissolve in water, such as oil. The liquid state may be any shape such as liquid columnar, granular, mist, or steam.

In FIG. 1, the liquid 4 containing water is sprayed on the interface 13 between the glass film 11 and the support glass 12 by spraying the liquid 4 containing water from the nozzle 41 onto the interface 13 between the glass film 11 and the support glass 12. The glass film 11 and the support glass 12 are peeled off. Thereby, even if the electronic device manufacturing related process with heating is performed, the glass film 11 and the support glass 12 can be smoothly peeled off. Although it has not been elucidated in detail that the glass film 11 and the support glass 12 can be favorably peeled by applying the liquid 4 containing water, it is speculated that the reason is as follows.

When smoothing is performed so that the surface roughness Ra of both the contact surfaces 11a and 12a of the glass film 11 and the support glass 12 is 2.0 nm or less, the

smooth contact surfaces

11a and 12a of these two glass substrates are brought into close contact with each other. In this case, the glass substrates adhere to each other without an adhesive to form the glass film laminate 1. This phenomenon is presumed to be due to the following mechanism. As shown in FIG. 5, it is considered that they are attracted by hydrogen bonding between hydroxyl groups formed on the contact surface 11 a of the glass film 11 and the contact surface 12 a of the support glass 12. Alternatively, as shown in FIG. 6, the glass film 11 and the support glass 12 may adhere to each other due to the formation of hydrogen bonds through water molecules present at the interface 13 between the glass film 11 and the support glass 12. It is believed that.

Under such a state, when the glass film laminate 1 is heated, as shown in FIG. 7, at the interface 13 between the glass film 11 and the supporting glass 12,
Si-OH + HO-Si → Si-O-Si + H ₂ O
It is considered that the adhesive force between the glass film 11 and the support glass 12 becomes stronger due to the occurrence of the dehydration reaction and the increase in covalent bonds. Since the electronic device manufacturing process includes a manufacturing-related process including heating such as a film forming process, it is manufactured with a heating process of at least 100 ° C. or higher. For example, in a TFT manufacturing process of a liquid crystal display or an organic EL display, an amorphous silicon TFT is heated to 300 ° C. or higher, and a low temperature polysilicon TFT is heated to at least 400 ° C. or higher. In the case of a TFT composed of indium, gallium, zinc, and oxygen, it is heated to at least 300 ° C. or higher. In the manufacturing process of the touch sensor substrate, it is heated to at least 150 ° C. or higher. Here, as a result of the inventors diligently researching, the adhesive force between the glass film 11 and the support glass 12 becomes stronger as the heating temperature becomes higher and as the heating holding time becomes longer. It became clear that the glass film 11 was damaged in the peeling process of the glass film 11 from the support glass 12, and the success probability of peeling of the glass film 11 fell.

As a result of diligent research, the inventors of the present invention include at least water at the interface 13 between the glass film 11 and the support glass 12 in the glass film laminate 1 that has undergone the electronic device manufacturing-related treatment with heating. When peeling was performed in a state where a liquid was applied, it was found that the glass film 11 and the supporting glass 12 could be easily peeled, and the present invention was achieved. When the liquid 4 containing water is applied to the interface 13 between the glass film 11 and the support glass 12,
Si-O-Si + H ₂ O → Si-OH + HO-Si
It is considered that the glass film 11 and the supporting glass 12 can be easily peeled off by promoting the hydrolysis reaction.

The dehydration reaction and hydrolysis reaction of the Si—OH group at the interface 13 between the glass film 11 and the support glass 12 described above are not limited to Si but exist in Al, In, Sn, Zn, Ti, Zr, Ga, and the like. The OH group is considered to be generated similarly. Therefore, on the support glass _{12, SiO, SiO 2, Al} 2 O 3, MgO, Y 2 O 3, La 2 O 3, Pr 6 O 11, Sc 2 O 3, WO 3, HfO 2, In 2 O 3 Even when an inorganic thin film such as ITO, ZrO ₂ , Nd ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , Nb ₂ O ₅ , TiO, TiO ₂ , Ti ₃ O ₅ , NiO, or ZnO is formed. A similar effect can be expected. By forming an inorganic thin film on the support glass 12, even if the electronic device manufacturing related process accompanied by heating is performed, the glass film 11 and the support glass 12 can be easily peeled off. In particular, when an inorganic thin film having an atom different from Si of the glass film 11 is formed on the support glass 12, the glass film 11 and the support glass 12 can be more easily peeled off more efficiently.

In the third step, as shown in FIG. 8, it is preferable to immerse the electronic device 3 with supporting glass in the liquid 4 containing water. Thereby, the liquid 4 containing water can be more efficiently provided to the interface 13 between the support glass 12 and the glass film 11 at the time of peeling. Specifically, in the third step, the liquid 4 containing water is stored in the water tank 42, and the support glass 12 and the glass film 11 are peeled off by immersing the electronic device 3 with support glass in the water tank 42. I do.

The liquid 4 containing water is preferably alkaline. Thereby, the above-described Si—O—Si + H ₂ O → Si—OH + HO—Si
The hydrolysis reaction of the glass film 11 and the supporting glass 12 can be easily peeled off. In order to make the liquid 4 containing water alkaline, a monovalent base, a divalent base or the like can be used, and both strong alkali and weak alkali can be used. The pH of the liquid 4 containing water may be adjusted by adding KOH, NaOH, or a surfactant to water or the like. The pH of the liquid 4 containing water is preferably more than pH 7, more preferably 10 or more.

As the surfactant used in the present invention, anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants and the like can be used. Two or more kinds may be mixed, and a mixture of a pH adjusting agent that maintains alkalinity such as sodium carbonate can be used. The concentration of the surfactant in the liquid 4 containing water used in the present invention is preferably 0.001 to 2.0% by mass. As the anionic surfactant, carboxylate, sulfonate, sulfate ester salt and the like can be used. For example, anionic fatty acid salts, alpha sulfo fatty acid ester salts, alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfate esters, alkyl sulfate triethanolamines and the like can be used. As the cationic surfactant, amine salt type and quaternary ammonium salt type can be used. For example, alkyltrimethylammonium salt, dialkyldimethylammonium chloride, alkylpyridinium chloride and the like can be used. Nonionic surfactants include ester types in which polyhydric alcohols and fatty acids are ester-bonded, ether types such as polyoxyethylene alkyl ether, and ester / ether types that have both ester bonds and ether bonds in the molecule. can do. For example, fatty acid diethanolamide, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether and the like can be used. As the zwitterionic surfactant, carboxylate type, amino acid type, betaine type and the like can be used.

In the third step according to the present invention, it is preferable to apply ultrasonic waves to the electronic device 3 with supporting glass while immersing the electronic device 3 with supporting glass in the liquid 4 containing water. Thereby, the liquid 4 containing water can be more efficiently applied to the interface 13 between the glass film 11 and the support glass 12, and the separation between the glass film 11 and the support glass 12 can be further facilitated. The applied wavelength of the ultrasonic wave is preferably 25 kHz to 950 kHz, and more preferably 25 kHz to 170 kHz where the vibration energy is large. The time for applying the ultrasonic wave to the electronic device 3 with supporting glass immersed in the liquid 4 containing water is preferably performed until the electronic device 5 is completely peeled from the supporting glass 12. Although it depends on the rising temperature of the manufacturing-related treatment with heating, the treatment time, etc., it is preferably 10 to 1000 seconds as a guide. Further, application of ultrasonic waves may be used only at the start of peeling of the electronic device 5, and in this case, ultrasonic waves may be applied to the electronic device 3 with supporting glass for 1 to 5 seconds. The ultrasonic wave may be applied by directly contacting the ultrasonic wave transmitter with the electronic device 3 with supporting glass or by applying ultrasonic wave to the electronic device 3 with supporting glass through the liquid 4 containing water. Also good.

In the third step according to the present invention, the peeling member 6 is preferably inserted into the interface 13 between the glass film 11 and the supporting glass 12 when the glass film 11 and the supporting glass 12 are peeled off. Thereby, since the glass film 11 and the support glass 12 can be physically peeled, the liquid 4 containing water can be made to invade sequentially into the interface 13 between the glass film 11 and the support glass 12, Peeling of the glass film 11 and the support glass 12 can be further facilitated.

The shape of the peeling member 6 is preferably a sheet-like, belt-like, plate-like, strip-like, wedge-like or the like that has a small thickness and is wider than the electronic device 3 with supporting glass in the peeling progress direction. Specifically, the thickness of the peeling member is preferably 0.01 mm to 1 mm, and more preferably 0.1 mm to 0.5 mm. Thereby, the peeling member 6 can be inserted into a slight gap generated at the interface 13 between the glass film 11 and the support glass 12. Although the length of the peeling member 6 is dependent also on the area of the electronic device 3 with support glass used as peeling object, it is preferable that it is long in the peeling progress direction at least rather than the electronic device 3 with support glass. In this way, the glass film 11 once peeled off and the supporting glass 12 come into contact again after passing through the peeling member 6 and are prevented as much as possible from partially or entirely becoming the electronic device 3 with supporting glass. be able to.

The material of the peeling member 6 can be a rigid metal such as aluminum or stainless steel, but it is preferable to use a flexible resin film such as polyethylene or acrylic, and a hydrophobic film such as a fluorine film. The resin sheet is more preferable. By using a hydrophobic resin sheet as the peeling member 6, there is little risk of damaging the end surfaces of the glass film 11 and the supporting glass 13, and the liquid 4 containing water even if immersed in water because it is hydrophobic. Inside, handling of the peeling member 6 becomes easy. The hydrophobic resin sheet includes not only that the resin sheet itself is hydrophobic, but also that various sheets (resin sheet, metal sheet, etc.) are coated with a hydrophobic substance. On the other hand, depending on the heating temperature and heating time of the electronic device manufacturing-related process involving heating, when the support glass 12 and the glass film 11 are firmly bonded, the material of the peeling member 6 is a rigid resin plate. Is preferably used, and the peeling member 6 can be smoothly inserted into the interface 13 between the glass film 11 and the support glass 12, and the glass film 11 and the support glass 12 are less likely to be damaged.

The desired electronic device 5 can finally be manufactured by peeling the support glass 12 from the electronic device 3 with a support glass by a 3rd process.

FIG. 9 is a diagram showing another embodiment according to the present invention. The embodiment shown in FIG. 9 is different from the above-described embodiment in that the cover glass 2 is laminated on the carrier glass 21. Thereby, an electronic device manufacture related process can be performed also on the cover glass 2. FIG. Specifically, in the case of manufacturing a liquid crystal panel as the electronic device 5, TFT processing is performed on the glass film 12 side, a color filter is formed on the cover glass 2 side, and then laminated on the carrier glass 21 via the spacer 53 a. The liquid crystal element 53 can be sealed with the cover glass 2 formed. In this case, the electronic device 3 with supporting glass also includes the carrier glass 21.

The carrier glass 21 is preferably made of the same material as the glass film 11, the cover glass 2 and the support glass 12 described above, and a glass having the same thickness as the support glass 12. The carrier glass 21 and the cover glass 2 are preferably made of the same glass material.

In the third step, the cover glass 2 and the carrier glass 21 are also peeled in the same process as the glass film 11 and the support glass 12 are peeled in the water tank 42 in which the liquid 4 containing water is stored. To do. Therefore, it is not necessary to provide a special process for peeling the carrier glass 21. Also when peeling the cover glass 2 and the carrier glass 21, it is preferable to apply an ultrasonic wave as above-mentioned, and it is preferable to use the peeling member 6 mentioned above.

In this embodiment, the desired electronic device 5 can be finally manufactured by peeling the supporting glass 12 and the carrier glass 21 from the supporting glass-equipped electronic device 3 in the third step.

The method for manufacturing an electronic device according to the present invention can perform the first step, the second step, and the third step in succession, as schematically shown in FIG. Moreover, it is not limited to the structure performed continuously from a 1st process to a 3rd process, For example, the glass film laminated body 1 manufactured after the 1st process is packed and shipped, and an electronic device manufacturing related process is separately carried out. The facility may be configured to perform the second step and the third step. Of course, the support glass 12 and the carrier glass 21 are peeled off by packing and shipping the electronic device 3 with the support glass manufactured after the second step, and performing the third step in a separate facility. 5 may be manufactured.

Hereinafter, although the manufacturing method of the electronic device of this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

(Peeling surface energy measurement test)
A rectangular transparent glass plate having a length of 50 mm, a width of 50 mm, and a thickness of 500 μm was used as the supporting glass. As the glass film laminated on the supporting glass, a glass film having a length of 50 mm, a width of 50 mm, and a thickness of 100 μm was used. As the supporting glass and the glass film, non-alkali glass (product name: OA-10G, thermal expansion coefficient at 30 to 380 ° C .: 38 × 10 ⁻⁷ / ° C., Young's modulus 73 GPa) manufactured by Nippon Electric Glass Co., Ltd. was used. The surface roughness Ra was measured under the conditions of a scan size of 10 μm, a scan rate of 1 Hz, and a sample line 512 using AFM (NanoScope) manufactured by Veeco. The surface roughness Ra was 0.25 nm as calculated from the measured values in a 10 μm square measurement range. This glass film and supporting glass were laminated at a temperature of 25 ° C. to produce a glass film laminate. The obtained glass film laminate was placed in an electric furnace heated to 100 ° C., 150 ° C., 200 ° C., 300 ° C., 350 ° C., 400 ° C., and 450 ° C., heated for 30 minutes, and then unheated taken out of the electric furnace. About peelability of support glass and glass film by calculating peeling surface energy (gamma) (J / m < ² >) by a glass opening method with a glass film laminated body and the glass film laminated body heated at the above-mentioned temperature. ,evaluated. As shown in FIG. 10, the crack opening method inserts a peeling member 6 having a known thickness at the interface of the glass film laminate 1, and peels the surface from the separation distance c generated between the glass film 11 and the support glass 12. This is a method for calculating energy. Here, the peeling surface energy γ is calculated by the following equation.
γ (J / m ² ) = (3h ² EaTa ³ EbTb ³ ) / [16c (EaTa ³ + EbTb ³ )]
Here, h is the thickness (m) of the peeling member 6, Ta is the thickness (m) of the glass film 11, Ea is the Young's modulus (Pa) of the glass film 11, Tb is the thickness (m) of the support glass 12, and Eb is the support. The Young's modulus (Pa) of the glass 12, c is the distance (m) peeled by inserting the peeling member 6. In Example 1, the peel surface energy γ was measured with the glass film laminate immersed in water. As Example 2, the peel surface energy γ was measured in a state where the glass film laminate was immersed in an alkaline aqueous solution having a KOH concentration of 0.01 mol / kg (pH 10). As Example 3, the peeling surface energy γ was measured while applying a 40 kHz ultrasonic wave in a state where the glass film laminate was immersed in water. As Comparative Example 1, peeling surface energy γ was measured in the atmosphere. As a peeling member used for the measurement, a stainless steel cutter blade having a thickness of 40 μm was used. The results are shown in Table 1.

As shown in Table 1, in Example 1, the surface energy of peeling was lowered by adding water, and it is clear that peeling can be performed more easily. Example 2 shows that it becomes easier to peel by making water alkaline. Moreover, the surface energy at the time of peeling can also be lowered | hung by applying an ultrasonic wave in the state which provided water, and peelability improves.

(Peeling test after heating)
A rectangular transparent glass plate having a length of 370 mm, a width of 470 mm, and a thickness of 500 μm was used as the supporting glass. As the glass film laminated on the supporting glass, a glass film having a length of 370 mm, a width of 470 mm, and a thickness of 100 μm was used. As the supporting glass and the glass film, non-alkali glass (product name: OA-10G, thermal expansion coefficient at 30 to 380 ° C .: 38 × 10 ⁻⁷ / ° C., Young's modulus 73 GPa) manufactured by Nippon Electric Glass Co., Ltd. was used. The surface roughness Ra was measured under the conditions of a scan size of 10 μm, a scan rate of 1 Hz, and a sample line 512 using AFM (NanoScope) manufactured by Veeco. The surface roughness Ra was 0.25 nm as calculated from the measured values in a 10 μm square measurement range. This glass film and supporting glass were laminated at a temperature of 20 ° C. to produce a glass film laminate. The obtained glass film laminate was placed in an electric furnace heated to 100 ° C., 150 ° C., 200 ° C., 300 ° C., 350 ° C., 400 ° C., and 450 ° C., heated for 2 hours, and then taken out from the electric furnace. By making 100 glass film laminates under each heating condition and inserting a 100 μm thick fluororesin sheet (product name Yodoflon, manufactured by Yodogawa Hutec) at the interface between the glass film and the supporting glass, A peel test with the supporting glass was performed. As Example 4, a peel test was performed in a state where the glass film laminate was immersed in water. As Example 5, a peel test was performed in a state where the glass film laminate was immersed in an alkaline aqueous solution having a KOH concentration of 0.01 mol / kg (pH 10). As Example 6, a peel test was performed while applying a 40 kHz ultrasonic wave in a state where the glass film laminate was immersed in water. As Comparative Example 2, a peel test was performed in the air. As a result of the peeling test, the probability of peeling success is 95% to 100%, ８０ is 80% to 95%, △ is 60% to 80%, and x is 60% or less. The results are shown in Table 2.

As shown in Table 2, peeling was possible under any conditions with heating at 100 ° C. or lower, but in Examples 4 to 6, peeling was easy even when the heat treatment temperature became high due to the application of water. I understand that It has been clarified that the separation becomes even easier by using an alkaline aqueous solution or applying ultrasonic waves even if the heat treatment temperature is high.

The present invention is suitable for manufacturing electronic devices such as flat panel displays such as liquid crystal displays and organic EL displays, organic EL lighting, solar cells, lithium ion batteries, digital signage, touch panels, electronic paper, mobile phones and smartphones. Can be used for

DESCRIPTION OF SYMBOLS 1 Glass film laminated body 11 Glass film 12 Support glass 13 Interface 2 Cover glass 21 Carrier glass 3 Electronic device with support glass 4 Liquid 5 containing water 5 Electronic device 51 Element 6 Peeling member

Claims

A glass film laminate in which the surface roughness Ra of the surfaces of the glass film and the supporting glass that are in contact with each other is 2.0 nm or less, and both the surfaces are brought into contact with each other to laminate the glass film and the supporting glass. A device is formed on the glass film of the glass film laminate by performing an electronic device manufacturing-related process involving heating, and the device is sealed with a cover glass to attach a supporting glass. A second step of producing an electronic device; and a third step of separating the electronic device from the supporting glass by applying a liquid containing water to the interface between the glass film and the supporting glass of the electronic device with supporting glass. And a method for manufacturing an electronic device.
The method for manufacturing an electronic device according to claim 1, wherein the third step includes immersing the electronic device with a supporting glass in a liquid containing water.
3. The method of manufacturing an electronic device according to claim 1, wherein the liquid containing water is alkaline.
The method for manufacturing an electronic device according to claim 2 or 3, wherein in the third step, an ultrasonic wave is applied to the electronic device with supporting glass.
5. The method of manufacturing an electronic device according to claim 1, wherein in the third step, a peeling member is inserted into an interface between the glass film and the supporting glass.
6. The method of manufacturing an electronic device according to claim 5, wherein the peeling member is a hydrophobic resin sheet.
The method of manufacturing an electronic device according to any one of claims 1 to 6, wherein an inorganic thin film is formed on a surface of the supporting glass on a side in contact with the glass film.
8. The method of manufacturing an electronic device according to claim 2, wherein the cover glass is laminated on a carrier glass, and the cover glass and the carrier glass are peeled off in the third step. .
The method of manufacturing an electronic device according to claim 8, wherein the third step inserts the peeling member at an interface between the cover glass and the carrier glass.