WO2016017649A1 - Glass laminate, supporting substrate with inorganic layer, method for manufacturing electronic device, and method for producing supporting substrate with inorganic layer - Google Patents

Abstract

The purpose of the present invention is to provide a glass laminate from which a glass substrate can be easily separated. The present invention relates to a glass laminate that is provided with a supporting substrate with an inorganic layer, which is provided with a supporting substrate and an inorganic layer arranged on the supporting substrate, and a glass substrate that is laminated on the inorganic layer in a separable manner. The inorganic layer is a metal oxide layer containing two or more metal elements, and the metal elements include a first metal element having the largest electronegativity among the metal elements and 5 at% or more of a second metal element having an electronegativity of 1.65 or less, said electronegativity being smaller than that of the first metal element.

Description

Glass laminate, support substrate with inorganic layer, method for manufacturing electronic device, and method for manufacturing support substrate with inorganic layer

The present invention relates to a glass laminate that is a laminate of a glass substrate and a support substrate that is used when an electronic device such as a liquid crystal display or an organic EL display is produced using the glass substrate.
Moreover, it is related also with the support substrate with an inorganic layer used in order to manufacture this glass laminated body, its manufacturing method, and the manufacturing method of an electronic device using this glass laminated body.

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

Therefore, recently, in order to cope with the above-mentioned problem, after preparing a laminate in which a glass substrate is laminated on an inorganic thin film of a supporting glass with an inorganic thin film, and after performing a manufacturing process of an element on the glass substrate of the laminate, A method for separating a glass substrate on which an element has been manufactured from a laminate has been proposed (Patent Document 1). According to this method, it is disclosed that the handleability of the glass substrate can be improved, proper positioning can be performed, and the glass substrate on which the elements are arranged can be easily peeled off from the laminate after a predetermined process. ing.

Japanese Unexamined Patent Publication No. 2011-184284

On the other hand, in recent years, with the demand for higher performance of electronic devices, it is desired to carry out processing under high temperature conditions (for example, 400 ° C. or higher) when manufacturing electronic devices.
The present inventors have arranged a glass substrate on an inorganic thin film of a supporting glass with an inorganic thin film comprising an inorganic thin film composed of a metal oxide (for example, indium tin oxide) specifically described in Patent Document 1. When the laminated body was subjected to heat treatment under high temperature conditions (for example, 550 ° C., 10 minutes), the glass substrate could not be peeled from the laminated body after the heat treatment. In such an embodiment, the glass substrate on which the element is formed may not be peeled from the laminate after manufacturing the device under high temperature conditions.

This invention is made | formed in view of the said subject, Comprising: The glass laminated body which can peel a glass substrate easily, the support substrate with an inorganic layer used for manufacture of this glass laminated body, and this glass laminated body It is an object of the present invention to provide a method for producing an electronic device used and a method for producing a support substrate with an inorganic layer.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by forming an inorganic layer having a predetermined configuration on a glass substrate, and the present invention has been completed. It was.
That is, the first aspect of the present invention includes a support substrate and a support substrate with an inorganic layer provided with an inorganic layer disposed on the support substrate, and a glass substrate that is detachably laminated on the inorganic layer, The inorganic layer is a metal oxide layer containing two or more kinds of metal elements, and the metal element has a first metal element having the highest electronegativity among the metal elements, and is more electrically than the first metal element. A glass laminate including a second metal element of 5 at% or more having a small negative degree and a value of 1.65 or less.
In the first aspect, the first metal element is preferably a trivalent metal element.
In the first aspect, the first metal element is preferably In, Al, Bi, Fe, Mn, Cr, Co, Sc, Y, or Ga.
In the first aspect, the first metal element is preferably In.
In the first aspect, the second metal element is at least one selected from the group consisting of Ce, Zr, Mn, Ta, Hf, Be, Nb, La, Sc, Y, Ti, and a lanthanoid other than Ce. It is preferable to contain.
In the first aspect, it is preferable that the second metal element contains at least one of Ce and Zr.
In the first aspect, the average thickness of the inorganic layer is preferably 10 to 100 nm.
The second aspect of the present invention has a support substrate, an inorganic layer, a fragile layer, and a glass substrate in this order, and the inorganic layer contains two or more kinds of metal elements (excluding boron element). And the metal element includes at least a metal element A having the largest electronegativity among the metal elements and a metal element B having the smallest electronegativity among the metal elements, and the fragile layer includes The metal element A and the metal element B are contained in the fragile layer with respect to the atomic ratio X (the metal element B / the metal element A) between the metal element B and the metal element A in the inorganic layer. The ratio of the atomic ratio Y of the metal element B to the metal element A (the metal element B / the metal element A) (atomic ratio Y / atomic ratio X) in the glass is greater than 1.05 and less than 9.0 It is a laminate.
2nd aspect WHEREIN: It is preferable that the peeling strength at the time of peeling a glass substrate is 2.0 N / 25mm or less.
In the second aspect, the metal element A is In, Al, Bi, Fe, Mn, Cr, Co, Sc, Y, or Ga, and the inorganic layer includes an oxide of the metal element A. It is preferable.
In the second aspect, it is preferable that the metal element A is In and the inorganic layer includes In ₂ O ₃ .
In the second aspect, the metal element B is preferably a metal element having an electronegativity of 1.65 or less (excluding metal elements of Groups 1 and 2 of the periodic table).
In the second aspect, the metal element B is preferably a lanthanoid other than Ce, Zr, Mn, Ta, Hf, Nb, La, V, Ti, or Ce.
In the second aspect, the metal element B is preferably Ce or Zr.
In the first aspect or the second aspect, the support substrate is preferably a glass substrate.
According to a third aspect of the present invention, there is provided a member forming step of forming a member for an electronic device on the surface of the glass substrate in the glass laminate of the first aspect to obtain a laminate with a member for an electronic device, and the electronic device. A separation step of separating the support substrate with an inorganic layer contained in the glass laminate from the laminate with a member for use, and obtaining an electronic device having the glass substrate and the member for an electronic device. is there.
4th aspect of this invention is equipped with a support substrate and the inorganic layer arrange | positioned on the said support substrate, The said inorganic layer is a metal oxide layer containing 2 or more types of metal elements, The said metal element However, the first metal element having the highest electronegativity among the metal elements, and the second metal element having an electronegativity smaller than that of the first metal element and having a value of 1.65 or less of 5 at% or more. And a support substrate with an inorganic layer, which is used for producing a glass laminate by laminating a glass substrate on the inorganic layer.
In the fourth aspect, the first metal element is preferably a trivalent metal element.
In the fourth aspect, the first metal element is preferably In, Al, Bi, Fe, Mn, Cr, Co, Sc, Y, or Ga.
In the fourth aspect, the first metal element is preferably In.
In the fourth aspect, the second metal element is selected from the group consisting of Ce, Zr, Mn, Ta, Hf, Be, Nb, La, Sc, Y, V, Ti, and a lanthanoid other than Ce. It is preferable to include at least one.
In the fourth aspect, it is preferable that the second metal element contains at least one of Ce and Zr.
According to a fifth aspect of the present invention, a support substrate and a support substrate with an inorganic layer including an inorganic layer disposed on the support substrate and a glass substrate are laminated so that the inorganic layer and the glass substrate are in contact with each other. And the process of manufacturing a glass laminated body, the process of heating the said glass laminated body at the temperature of 400 degreeC or more, and peeling and collect | recovering the said support substrate with an inorganic layer from the heated glass laminated body And a step of performing a surface treatment on the surface of the inorganic layer of the recovered support substrate with an inorganic layer, wherein the inorganic layer is a metal oxide layer containing two or more metal elements, and the metal The element is a first metal element having the highest electronegativity among the metal elements, a second metal element having a value of 1.65 or less and a value of 5 at% or more of the second metal element having an electronegativity lower than that of the first metal element. Of support substrate with inorganic layer A method (reproduction method with the inorganic layer supporting substrate).
In the fifth aspect, the surface treatment is preferably an oxidation treatment or a polishing treatment.

According to the present invention, a glass laminate capable of easily peeling a glass substrate, a support substrate with an inorganic layer used for production of the glass laminate, a method for producing an electronic device using the glass laminate, and And the manufacturing method of the support substrate with an inorganic layer can be provided.

FIG. 1 is a schematic cross-sectional view of an embodiment of a glass laminate according to the present invention. FIG. 2 is a schematic cross-sectional view of an embodiment of a glass laminate according to the present invention. FIG. 3A and FIG. 3B are process diagrams of an electronic device manufacturing method according to the present invention.

Hereinafter, preferred embodiments of the glass laminate and the electronic device manufacturing method of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments and departs from the scope of the present invention. Without limitation, various modifications and substitutions can be made to the following embodiments.
In the present specification, “wt%” and “mass%” are synonymous.

In one embodiment of the glass laminate of the present invention, a metal oxide layer containing two or more metal elements between the support substrate and the glass substrate, the metal element being an electronegativity among the metal elements. 1 is characterized by interposing an inorganic layer including a first metal element having the largest value and an electronegativity smaller than that of the first metal element and a second metal element having a value of 1.65 or less of 5 at% or more. I will. The mechanism for obtaining the desired effect in the present invention is presumed as follows.
The second metal element contained in the inorganic layer is easily hydrolyzed and ion diffuses easily at a high temperature. Therefore, when high-temperature heat treatment is performed on the glass laminate including the inorganic layer, hydrolysis and element diffusion are likely to occur in the region on the glass substrate side in the inorganic layer, and as a result, the second metal element is contained. A layer with a large amount (corresponding to a vulnerable layer) is formed. More specifically, for example, when a metal oxide (indium cerium oxide) containing In as the first metal element and Ce as the second metal element is used, the glass in the inorganic layer is subjected to high-temperature heat treatment. In the region on the substrate side, hydrolysis represented by In—O—Ce + H ₂ O → In—OH + Ce—OH proceeds, and cerium with weak bonds such as Ce—OH is generated. A large amount of ionized cerium diffuses toward the glass substrate, and as a result, a fragile layer having a high cerium content is formed. When the glass substrate is peeled off, the fragile layer is easily cohesive and has a function of reducing the peel strength of the glass substrate. That is, the area | region by the side of the glass substrate in an inorganic layer becomes a weak layer, and makes it easy to peel a glass substrate. In other words, the glass laminate obtained by performing the high-temperature heat treatment has a configuration including at least a support substrate, an inorganic layer, a fragile layer, and a glass substrate. The structure of the vulnerable layer will be described in detail later.

In the following, the preferred embodiment of the glass laminate is first described in detail, and then the preferred embodiment of the method for producing an electronic device using the glass laminate is described in detail.

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

Moreover, this glass laminated body 10 is used until the member formation process mentioned later. That is, the glass laminate 10 is used until an electronic device member such as a liquid crystal display device is formed on the surface of the second main surface 18b of the glass substrate 18. Thereafter, the support substrate 16 with the inorganic layer is separated from the glass substrate 18, and the support substrate 16 with the inorganic layer does not become a member constituting the electronic device. A new glass substrate 18 is laminated on the separated support substrate 16 with an inorganic layer, and can be reused as a new glass laminate 10.
In the case of reuse, as will be described in detail later, in order to improve the efficiency of reuse, surface treatment may be performed on the surface of the separated inorganic layer 14 of the support substrate 16 with an inorganic layer. Examples of the surface treatment include oxidation treatment such as heat baking and plasma treatment, reduction treatment, and polishing treatment.

In the present invention, the above-mentioned fixing and (separable) adhesion have a difference in peeling strength (that is, stress required for peeling), and fixing means that the peeling strength is larger than the adhesion. Specifically, the peel strength at the interface between the inorganic layer 14 and the support substrate 12 is greater than the peel strength at the interface between the inorganic layer 14 and the glass substrate 18.
Further, the peelable adhesion means that it can be peeled at the same time that it can be peeled without causing peeling of the fixed surface. That is, in the glass laminate 10 of the present invention, when the operation of separating the glass substrate 18 and the support substrate 12 is performed, the glass substrate 10 is peeled and fixed on the closely contacted surface (interface between the inorganic layer 14 and the glass substrate 18). It means that it does not peel on the surface. Therefore, when the operation of separating the glass laminate 10 into the glass substrate 18 and the support substrate 12 is performed, the glass laminate 10 is separated into two, the glass substrate 18 and the support substrate 16 with an inorganic layer.

Hereinafter, first, the support substrate 16 with an inorganic layer and the glass substrate 18 constituting the glass laminate 10 will be described in detail, and then the procedure for manufacturing the glass laminate 10 will be described in detail.

[Support substrate with inorganic layer]
The support substrate 16 with an inorganic layer includes a support substrate 12 and an inorganic layer 14 disposed (fixed) on the surface thereof. The inorganic layer 14 is arrange | positioned in the outermost side in the support substrate 16 with an inorganic layer so that it may closely_contact | adhere with the glass substrate 18 mentioned later so that peeling is possible. A base layer is separately disposed between the inorganic layer 14 and the support substrate 12 in order to improve the adhesion of the inorganic layer 14 or to control the film quality such as the crystallinity and structure of the inorganic layer 14. May be.
Below, the form of the support substrate 12 and the inorganic layer 14 is explained in full detail.

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

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

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

(Inorganic layer)
The inorganic layer 14 is a layer disposed (fixed) on the main surface of the support substrate 12 and in contact with the first main surface 18 a of the glass substrate 18. By providing the inorganic layer 14 on the support substrate 12, adhesion of the glass substrate 18 can be suppressed even after long-time treatment under high temperature conditions.
In the present specification, the metal element is a concept including so-called metalloid elements (for example, B, Si, Ge, As, Sb, Te, Po). In addition, it is preferable that B (boron element) is not contained as a metal element.

The inorganic layer 14 is a metal oxide layer containing two or more kinds of metal elements (a layer composed of metal oxides containing two or more kinds of metal elements).
The metal element includes a first metal element having the highest electronegativity among the metal elements and a second metal element having an electronegativity smaller than that of the first metal element and having a value of 1.65 or less. The inorganic layer 14 is preferably a layer in which a second metal element is doped in an oxide of the first metal element.
The first metal element is the element having the highest electronegativity among the metal elements contained in the inorganic layer 14. The type of the first metal element is not particularly limited, but a trivalent metal element is preferable from the point that the releasability of the glass substrate is easier (hereinafter, also simply referred to as “the effect of the present invention is more excellent”). One element selected from the group consisting of In, Al, Bi, Fe, Mn, Cr, Co, Sc, Y, and Ga is more preferable, and In is more preferable.

The second metal element is a metal element having a smaller electronegativity than the first metal element. The electronegativity of the second metal element is 1.65 or less, but is preferably 1.5 or less, more preferably 1.4 or less, and even more preferably 1.3 or less, in terms of more excellent effects of the present invention. 1.2 or less is particularly preferable. The lower limit is not particularly limited, but is often 0.7 or more, more often 1.0 or more.
The valence of the second metal element is not particularly limited, and examples thereof include divalent to tetravalent metal elements, and a tetravalent metal element is mentioned in that the effect of the present invention is more excellent.
The kind of the second metal element may be any metal element having an electronegativity of 1.65 or less as described above. However, Ce, Mn, Zr, Ta, Hf, Be, More preferable examples include at least one selected from the group consisting of Nb, La, Sc, Y, V, Ti, and L other than Ce, and further preferable examples include Ce or Zr. In the present specification, “L” represents a lanthanoid (lanthanoid element). In addition, as another preferred embodiment of the second metal element, a metal element having an electronegativity of 1.65 or less excluding the metal elements of Groups 1 and 2 of the periodic table can be given.
The second metal element is a metal element that is different from the first metal element. As the second metal element, two or more kinds may be contained in the inorganic layer 14 as long as the above requirements are satisfied. That is, for example, when the inorganic layer 14 includes three kinds of metal elements, the metal element having the largest electronegativity corresponds to the first metal element, and the electronegativity of the remaining two kinds of metal elements. Is equal to or less than 1.65, both of the two metal elements correspond to the second metal element.
Further, the inorganic layer 14 has other metal elements not corresponding to the first metal element and the second metal element (for example, the electronegativity is smaller than that of the first metal element and the electronegativity is more than 1.65). Metal element) may be included.

The content of the second metal element in the inorganic layer 14 is 5 at% or more, and 7 to 90 at% is preferable with respect to the total amount of all metal elements in that the effect of the present invention is more excellent. From the viewpoint of superiority, 10 to 80 at% is more preferable, 12 to 50 at% is further preferable, and 15 to 30 at% is particularly preferable. When two or more elements are contained as the second metal element, the total content thereof is preferably in the above range.
In addition, although content of the 1st metal element in the inorganic layer 14 is not restrict | limited in particular, 10 at% or more is preferable with respect to the total amount of all the metal elements by the point which the effect of this invention is more excellent, and the effect of this invention is effective. In terms of more excellent, 20 at% or more is more preferable, 50 at% or more is further preferable, and 70 at% or more is particularly preferable. The upper limit is not particularly limited, but is often 95 at% or less because the second metal element is contained at 5 at% or more.
The composition of the inorganic layer 14 which is a metal oxide layer containing the first metal element and the second metal element can be measured by an X-ray photoelectron spectrometer.

As a preferred embodiment of the inorganic layer 14, an embodiment containing at least indium cerium oxide (ICO) can be given. Indium cerium oxide is an oxide containing an indium element as a first metal element and a cerium element as a second metal element.

The average thickness of the inorganic layer 14 is not particularly limited, but is preferably 5 to 200 nm from the viewpoint of productivity. Among these, 10 to 100 nm is preferable, 10 to 80 nm is more preferable, and 15 to 50 nm is more preferable in that the effect of the present invention is more excellent. In addition, if the average thickness of the inorganic layer is too thick, the transparency, productivity, and the laminate properties of the glass substrate are slightly inferior. If the average thickness of the inorganic layer is too thin, the peelability of the glass substrate, and Somewhat inferior in controllability.
The average thickness of the inorganic layer 14 is obtained by measuring the thickness of the inorganic layer 14 at an arbitrary position of 10 points or more and arithmetically averaging them.

The inorganic layer 14 is usually provided on the entire surface of the support substrate 12 as shown in FIG. 1, but may be provided on a part of the surface of the support substrate 12 as long as the effects of the present invention are not impaired. For example, the inorganic layer 14 may be provided on the surface of the support substrate 12 in an island shape or a stripe shape.

Furthermore, the surface roughness (Ra) of the surface of the inorganic layer 14 in contact with the glass substrate 18 (that is, the surface 14a of the inorganic layer 14) is preferably 2.0 nm or less, and more preferably 1.0 nm or less. preferable. The lower limit is not particularly limited, but 0 is most preferable. If it is the said range, adhesiveness with the glass substrate 18 will become more favorable, and position shift of the glass substrate 18 etc. can be suppressed more.
Ra is measured according to JIS B 0601 (revised 2001). Note that an atomic force microscope (AFM) or the like can be used for the measurement.

(Method for producing support substrate with inorganic layer)
The manufacturing method in particular of the support substrate 16 with an inorganic layer is not restrict | limited, A well-known method is employable. For example, the method of providing the inorganic layer 14 which consists of a predetermined component on the support substrate 12 by the vapor deposition method, sputtering method, or CVD method is mentioned.
In addition, in order to control the surface property (for example, surface roughness Ra) of the inorganic layer 14 formed on the support substrate 12, you may process the surface of the inorganic layer 14 as needed. Examples of the treatment include an ion sputtering method.

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

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

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

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

The thickness of the glass substrate 18 is not particularly limited, but is usually 0.8 mm or less, preferably 0.3 mm or less, and more preferably 0 from the viewpoint of reducing the thickness and / or weight of the glass substrate 18. .15 mm or less. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 18. In the case of 0.15 mm or less, the glass substrate 18 can be wound into a roll. The thickness of the glass substrate 18 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 18 and easy handling of the glass substrate 18.

The glass substrate 18 may be composed of two or more layers. In this case, the material forming each layer may be the same material or a different material. In this case, “the thickness of the glass substrate” means the total thickness of all the layers.

<Glass laminate and production method thereof>
The glass laminate 10 of the present invention has the surface 14a of the inorganic layer 14 of the support substrate 16 with an inorganic layer and the first main surface 18a of the glass substrate 18 as a laminated surface (the inorganic layer 14 and the glass substrate 18 are in contact with each other). Thus, it is a laminate formed by laminating the support substrate 16 with an inorganic layer and the glass substrate 18 in a peelable manner. 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.
Although the manufacturing method in particular of the glass laminated body 10 of this invention is not restrict | limited, The aspect which has the process of laminating | stacking the glass substrate 18 on the inorganic layer 14 of the support substrate 16 with an inorganic layer so that peeling is mentioned, Specifically, An example is a method in which the support substrate 16 with an inorganic layer and the glass substrate 18 are stacked under a normal pressure environment, and then bonded using a roll or a press. It is preferable because the support substrate 16 with an inorganic layer and the glass substrate 18 are more closely bonded by pressure bonding with a roll or a press. Moreover, since the air bubbles mixed between the support substrate 16 with an inorganic layer and the glass substrate 18 are relatively easily removed by pressure bonding with a roll or a press, it is preferable.

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

When the support substrate 16 with the inorganic layer and the glass substrate 18 are detachably adhered, the surfaces of the inorganic layer 14 and the glass substrate 18 that are in contact with each other are sufficiently washed and laminated in a clean environment. Is preferred. The higher the degree of cleanness, the better the flatness.
The cleaning method is not particularly limited, and examples thereof include a method of cleaning the surface of the inorganic layer 14 or the glass substrate 18 with an alkaline aqueous solution and further using water.

Furthermore, the glass laminated body containing a weak layer is obtained by performing the process on high temperature conditions (for example, 400 degreeC or more) to the obtained glass laminated body.
More specifically, the composition of the region on the glass substrate side in the inorganic layer changes, and a fragile layer 26 is formed between the inorganic layer 14 and the glass substrate 18 as shown in FIG. That is, the glass laminate 11 including the support substrate 12, the inorganic layer 14, the fragile layer 26, and the glass substrate 18 is formed.
The fragile layer 26 is a layer that easily causes cohesive failure. For this reason, when a separation step described later is performed, cohesive failure occurs in the fragile layer 26, and separation is easily performed between the support substrate with an inorganic layer and the electronic device.
In addition, as will be described later, in the member forming step, the processing is usually performed under a high temperature condition (for example, 400 ° C. or higher). Therefore, the glass laminate 10 may change its configuration to the glass laminate 11. That is, in the member forming step, a glass laminate (a laminate 22 with an electronic device member) including the support substrate 12, the inorganic layer 14, the fragile layer 26, the glass substrate 18, and the electronic device member 20 is formed. ing.
Moreover, before implementing a member formation process, with respect to the glass laminated body 10, it heat-processes separately, the brittle layer 26 is formed, the glass laminated body 11 is obtained, and the obtained glass laminated body 11 is made into a member. You may use for a formation process.

Hereinafter, the configuration of the fragile layer 26 will be described in detail.
Of the two or more kinds of metal elements (excluding boron element) contained in the inorganic layer 14, the metal element having the highest electronegativity is the metal element A, and the metal element having the lowest electronegativity is the metal element B. In this case, the configuration of the fragile layer 26 includes the metal element A and the metal element B. That is, the same metal element as the metal element A and the metal element B contained in the inorganic layer 14 is also contained in the fragile layer. The fragile layer 26 is preferably a metal oxide layer containing the metal element A and the metal element B.
In many cases, the metal element A corresponds to the first metal element (preferably a trivalent metal element) in the inorganic layer 14 described above, and the metal element B is the first metal element A in the inorganic layer 14 described above. Two metal elements are often applicable.
More specifically, the metal element A is preferably a trivalent metal element, and is selected from the group consisting of In, Al, Bi, Fe, Mn, Cr, Co, Sc, Y, and Ga. Is more preferable, and In is more preferable. The fragile layer 26 preferably includes a metal oxide of the metal element A. For example, when In is included as the metal element A, In ₂ O ₃ is preferably included in the fragile layer 26.
Further, as the metal element B, a metal element having an electronegativity of 1.65 or less is preferable in that the effect of the present invention is more excellent, and an electronegativity excluding metal elements of Groups 1 and 2 of the periodic table. Is more preferably 1.65 or less metal element, and one selected from the group consisting of Ce, Zr, Mn, Ta, Hf, Nb, La, Sc, Y, V, Ti, and L other than Ce is further Ce or Zr is preferred, and particularly preferred. The fragile layer 26 preferably contains a metal oxide of the metal element B.
Note that the inorganic layer 14 and the fragile layer 26 may contain three or more metal elements. That is, a metal element other than the metal element A and the metal element B may be included.

The atomic ratio Y (metal element B / metal element B / metal element A) in the fragile layer 26 to the atomic ratio X (metal element B / metal element A) between the metal element B and metal element A in the inorganic layer 14 The ratio of the metal element A) (atomic ratio Y / atomic ratio X) is more than 1.05 and less than 9.0, and is preferably 1.1 or more and less than 8.5 in terms of more excellent effects of the present invention. 3 or more and less than 8.0 is more preferable, and 1.5 or more and less than 7.5 is more preferable.
When the inorganic layer 14 contains one or more third metal elements other than the metal element A and the metal element B, the total content of the third metal elements is preferably 20 at% or less. . Similarly, when the fragile layer 26 includes one or more third metal elements other than the metal element A and the metal element B, the total content of the third metal elements may be 20 at% or less. preferable.

When the first metal element (preferably a trivalent metal element) in the inorganic layer 14 described above corresponds to the metal element A and the second metal element in the inorganic layer 14 corresponds to the metal element B, the fragile layer 26 The metal element B therein may be partially reduced. More specifically, for example, when cerium (tetravalent) is used as the metal element B, the fragile layer 26 may coexist with cerium (tetravalent) and cerium (trivalent). In particular, the fragile layer 26 and the inorganic layer 14 may contain more metal element B whose valence is reduced by reduction in the fragile layer 26.

The thickness of the fragile layer 26 is not particularly limited, but is preferably 1 to 10 nm, more preferably 2 to 7 nm, from the viewpoint that the effect of the present invention is more excellent.

Although the manufacturing method in particular of the glass laminated body 11 is not restrict | limited, as mentioned above, it can form by performing heat processing with respect to the glass laminated body 10. As shown in FIG.
The heat treatment conditions are not particularly limited, but the heating temperature is preferably 400 ° C. or higher, more preferably 450 ° C. or higher. The heating time is preferably 5 minutes or more, and more preferably 10 minutes or more.
The upper limit of the heating temperature is not particularly limited, but is often 700 ° C. or less from the viewpoint of the heat resistance of the glass laminate. The conditions for the heating time are not particularly limited, but are often 60 minutes or less from the viewpoint of productivity.

The glass laminate 10 and the glass laminate 11 of the present invention can be used for various applications, such as a display device panel, PV, a thin film secondary battery, a semiconductor wafer having a circuit formed on the surface, and the like. The use which manufactures these electronic components is mentioned. In this application, the glass laminate 10 and the glass laminate 11 are often exposed (for example, 10 minutes or more) under high temperature conditions (for example, 400 ° C. or more).
Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

<Electronic device and manufacturing method thereof>
Next, preferred embodiments of the electronic device and the manufacturing method thereof will be described in detail.
3A and 3B are schematic cross-sectional views sequentially showing each manufacturing process in a preferred embodiment of the method for manufacturing an electronic device of the present invention. The suitable form of the electronic device of this invention is equipped with a member formation process and a isolation | separation process.
Hereinafter, the materials used in each step and the procedure thereof will be described in detail with reference to FIGS. 3 (A) and 3 (B). First, a member formation process is explained in full detail.

[Member forming process]
A member formation process is a process of forming the member for electronic devices on the glass substrate in a glass laminated body.
More specifically, as shown in FIG. 3A, in this step, the electronic device member 20 is formed on the second main surface 18b of the glass substrate 18, and the electronic device member laminated body 22 is manufactured. Is done.
First, the electronic device member 20 used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

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

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

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

For example, taking the case of manufacturing an OLED as an example, in order to form an organic EL structure on the surface of the second main surface 18b of the glass substrate 18 of the glass laminate 10, a transparent electrode is further formed. Various layer formation and processing such as vapor-depositing hole injection layer, hole transport layer, light emitting layer, electron transport layer, etc. on the surface on which is formed, forming a back electrode, sealing with a sealing plate, etc. Done. Specific examples of these layer formation and treatment include film formation treatment, vapor deposition treatment, sealing plate adhesion treatment, and the like.

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

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

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

In the member forming step, as described above, the processing is usually performed under a high temperature condition (for example, 400 ° C. or higher).
When such a high temperature treatment is carried out, the composition of the region on the glass substrate side in the inorganic layer changes, and as shown in FIG. 3 (A), between the inorganic layer 14 and the glass substrate 18 fragile. Layer 26 is formed. That is, the glass laminated body (laminated body 22 with an electronic device member) containing the support substrate 12, the inorganic layer 14, the weak layer 26, the glass substrate 18, and the electronic device member 20 is formed.
The fragile layer 26 is a layer that easily causes cohesive failure. Therefore, when a separation step described later is performed, cohesive failure occurs in the fragile layer 26, and the inorganic substrate-supported substrate 16 and the electronic device 24 are easily separated.
The description of the fragile layer 26 is as described above.

[Separation process]
In the separation step, as shown in FIG. 3B, the support substrate 16 with the inorganic layer is separated from the laminate 22 with the electronic device member obtained in the member forming step, and the electronic device member 20 and the glass substrate are separated. 18 is a step of obtaining an electronic device 24 including 18 (a glass substrate with a member for electronic devices). That is, it is a step of separating the laminated body 22 with the electronic device member into the supporting substrate 16 with the inorganic layer and the electronic device 24. In addition, in the case of the said process, it often isolate | separates into the support substrate 16 with an inorganic layer, and the electronic device 24 by cohesive failure occurring in the weak layer 26. FIG.
In the case where the electronic device member 20 on the glass substrate 18 at the time of separation is a part of the formation of all necessary constituent members, the remaining constituent members can be formed on the glass substrate 18 after separation.

The method of separating into the support substrate 16 with an inorganic layer and the electronic device 24 is not particularly limited. For example, by inserting a sharp blade-like object in the vicinity of the fragile layer 26 located between the inorganic layer 14 and the glass substrate 18 and giving a trigger for separation, a mixed fluid of water and compressed air is sprayed. Can be separated. Preferably, the laminate 22 with electronic device members is placed on a surface plate so that the support substrate 12 is on the upper side and the electronic device member 20 side is on the lower side, and the electronic device member 20 side is vacuum-adsorbed on the surface plate. (In the case where support substrates are laminated on both sides, the steps are sequentially performed). In this state, first, the cutter is allowed to enter the vicinity of the fragile layer 26. Then, the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. If it does so, cohesive failure will occur in the weak layer 26, and the support substrate 16 with an inorganic layer can be peeled easily.

Although the magnitude | size of the peeling strength at the time of peeling the said electronic device 24 is not restrict | limited in particular, it is preferable that it is 2.0 N / 25mm or less from an industrial point, and it is more preferable that it is 1.2 N / 25mm or less preferable.
In addition, the magnitude | size of the said peeling strength can be paraphrased with the magnitude | size of the peeling strength at the time of peeling the glass substrate 18. FIG. That is, peeling when the glass substrate 18 is peeled from the glass laminate (including the electronic device member 20 as necessary) including the support substrate 12, the inorganic layer 14, the fragile layer 26, and the glass substrate 18. The strength is preferably in the above range.

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

In addition, it is good also as a glass laminated body by further laminating | stacking a new glass substrate on the support substrate 16 with an inorganic layer isolate | separated in the said procedure.
When a new glass substrate is laminated, it is preferable to subject the support substrate with an inorganic layer separated from the glass laminate to a surface treatment, and particularly preferably an oxidation treatment or a polishing treatment. As described above, the fragile layer may contain a large amount of the metal element B whose valence is reduced by reduction, and this element imparts the cohesiveness of the fragile layer. For example, when cerium (tetravalent) is used as the metal element B, the fragile layer may contain cerium (trivalent). On the inorganic layer of the support substrate 16 with the inorganic layer separated by the above procedure, a part of the fragile layer may remain due to the cohesive failure of the fragile layer, and the metal element B having a reduced valence adheres. May have. By subjecting the metal element B having such a valence to an oxidation treatment to return to the original valence, the peelability from the newly laminated glass substrate is further improved. When the polishing treatment is performed, the fragile layer remaining on the surface of the support substrate with the inorganic layer is removed to obtain a surface containing cerium (tetravalent) whose valence is not lowered, and at the same time, the flatness of the surface is improved. Thereby, adhesiveness with a newly laminated glass substrate and releasability are further improved.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In the following examples and comparative examples, a glass plate made of non-alkali borosilicate glass (length 100 mm, width 100 mm, plate thickness 0.3 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., manufactured by Asahi Glass Co., Ltd.) The name “AN100”) was used. Also, as the support substrate, a glass plate made of non-alkali borosilicate glass (100 mm long, 100 mm wide, 0.4 mm thick, coefficient of linear expansion 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) It was used.

<Example 1>
One main surface of the support substrate was cleaned with pure water and then cleaned with alkali. Furthermore, an indium cerium oxide layer (corresponding to an inorganic layer) having an average thickness of 20 nm was formed on the cleaned surface by a magnetron sputtering method to obtain a support substrate with an inorganic layer. In the magnetron sputtering method, a target material in which indium oxide and cerium oxide are mixed and sintered is used, and each content is 80 mass of indium oxide with respect to the total mass of indium oxide and cerium oxide. %, And cerium oxide was 20% by mass. Content of the cerium element in the obtained inorganic layer was 12 at% with respect to all the metal elements in an inorganic layer. Further, the surface roughness Ra of the indium cerium oxide layer (inorganic layer) was 0.2 nm.
Next, one main surface of the glass substrate was cleaned with pure water and then cleaned with alkali to be cleaned. The exposed surface of the inorganic layer of the support substrate with an inorganic layer and the cleaned surface of the glass substrate are washed with an alkaline aqueous solution and washed with water, and then the cleaned surfaces are bonded together by a vacuum press at room temperature. A glass laminate A1 was obtained.
In the obtained glass laminate A1, the support substrate with an inorganic layer and the glass substrate were in close contact with each other without generating bubbles, had no distortion-like defects, and had good smoothness. Further, the peel strength at the interface between the support substrate and the inorganic layer was higher than the peel strength at the interface between the inorganic layer and the glass substrate.

The glass laminate A1 was heat-treated at 550 ° C. for 10 minutes in a nitrogen atmosphere. By carrying out this heat treatment, a fragile layer (thickness 5 nm) was formed between the inorganic layer and the glass substrate.
Next, the following peel test was performed, and the peel strength (N / 25 mm) of the glass substrate was measured. As a measuring method, a glass laminate A1 having a width of 25 mm and a length of 70 mm was prepared, and the glass substrate was peeled off using Autograph AG-20 / 50kNXDplus (Shimadzu Corporation).
At this time, a stainless steel knife having a thickness of 0.4 mm was inserted into the interface between the glass substrate A1 and the inorganic layer of the glass laminate A1 after the heat treatment to form a notch for peeling, and then the glass substrate was completely The strength was measured by fixing and pulling up the support substrate. The peeling speed was 30 mm / min. The point where the load was detected was set to 0, and the peel strength at a position where the load was lifted by 2.0 mm was taken as the measured value. The peel strength at that time was 1.07 N / 25 mm.

In addition, the weak layer was formed in the inorganic layer surface layer after peeling, and the indium element and the cerium element were contained. The atomic ratio Y (the amount of cerium element / the amount of indium element) of the cerium element and the indium element in the fragile layer is 0.849, and the atomic ratio X of the cerium element and the indium element in the inorganic layer (the amount of the cerium element) / Amount of indium element) was 0.140, and the ratio of atomic ratio Y to atomic ratio X (atomic ratio Y / atomic ratio X) was 6.06.
The atomic ratio was measured using an X-ray photoelectron spectrometer (PHI5000 VersaProbe, manufactured by ULVAC-PHI) (hereinafter the same).
In addition, an inorganic layer component was observed on the surface of the peeled glass substrate, and from this result, it was confirmed that the peel strength at the interface between the inorganic layer and the support substrate layer was larger than the cohesive failure strength in the fragile layer. It was.

Using the support substrate with an inorganic layer peeled by the above procedure, a glass laminate that was laminated with a new glass substrate by the same procedure was prepared, and after heat treatment again, the support substrate with an inorganic layer was peeled off. As a result, re-peeling was possible in many parts, but there was a part where peeling did not proceed easily.
Therefore, after firing at 550 ° C. for the support substrate with an inorganic layer peeled by the above procedure and performing an oxidation treatment, a glass laminate is produced by the same procedure as described above, and heat treatment is performed. When the attached support substrate was peeled off, peeling was easily possible on the entire surface.
The peeling force at that time was 1.22 N / 25 mm.
Moreover, even when the plasma oxidation treatment was performed on the peeled support substrate with an inorganic layer at a power of 10 W instead of the oxidation treatment, the support substrate with an inorganic layer could be easily peeled over the entire surface.

<Example 2>
A glass laminate was prepared according to the same procedure as in Example 1 except that a target material having a cerium element content of 18 at% was used, and various evaluations were performed.

<Example 3>
Except having changed the thickness of the inorganic layer, the glass laminated body was produced according to the procedure similar to Example 1, and various evaluation was implemented.

<Examples 4 to 6>
Glass lamination was carried out in the same manner as in Example 1 except that a mixed film was formed by simultaneous sputtering of an In ₂ O ₃ target and a ZrO ₂ target or a TiO ₂ target to obtain the additive concentration and film thickness shown in Table 1. A body was prepared and subjected to various evaluations.

<Comparative Example 1>
A glass laminate was prepared and subjected to various evaluations according to the same procedure as in Example 1 except that ITO was used as a target and the addition concentration and film thickness shown in Table 1 were used.

<Comparative Examples 2 to 4>
A glass laminate was prepared according to the same procedure as in Example 1 except that the metal element species and film thickness shown in Table 1 were used using a single metal oxide target, and various evaluations were performed.
<Comparative Example 5>
A glass laminate was prepared according to the same procedure as in Example 1 except that a mixed film was formed by co-sputtering an In ₂ O ₃ target and a CeO ₂ target to obtain the additive concentration and film thickness shown in Table 1. Various evaluations were conducted.

The results of Examples 1 to 6 and Comparative Examples 1 to 5 are summarized in Table 1 below.
In Examples 2 to 6, as in Example 1, the peel strength at the interface between the inorganic layer and the support substrate was found to be the peel strength at the interface between the inorganic layer and the glass substrate, as a result of the peeling of the glass substrate. It was confirmed that it was larger than.
In Table 1, “concentration (at%) of second metal element (or other metal element)” is the concentration (at%) of the second metal element (or other metal element) relative to the total amount of all metal elements. Represents.
In Table 1, “film thickness” represents the average thickness (nm) of the inorganic layer.
In Table 1, the “Ra (nm)” column represents the surface roughness Ra (nm) of the surface of the inorganic layer disposed (fixed) on the support substrate (surface opposite to the support substrate side).

In the “Lamination” column of Table 1, “◯” indicates that the bubbles are in close contact without generating bubbles, that there is no distorted defect and smoothness is good, and “x” indicates other than that Intended case.
In the “peeling” column in Table 1, “◯” means a case where the glass substrate can be peeled from the glass laminate, and “x” means that the glass substrate breaks when trying to peel the glass substrate from the glass laminate. “XX” means a case where a stainless steel knife cannot be inserted into the glass laminate and the glass substrate cannot be peeled off.

In addition, the metal element A of each Example and each comparative example in Table 1 is the same as the first metal element, and the metal element B is the same as the second metal element. That is, in Example 1, In is the first metal element and metal element A, and Ce is the second metal element and metal element B.

As shown in Table 1, in Examples 1 to 6 having a predetermined inorganic layer, the laminate property between the inorganic layer on the supporting substrate and the glass substrate is excellent, and the glass laminate is also used after treatment under high temperature conditions. The glass substrate could be easily peeled off. In addition, it is guessed that the film thickness of a weak layer here is 5 nm or less.
On the other hand, Comparative Examples 1 to 5 using an inorganic layer that did not satisfy the predetermined requirements were inferior in peelability although the laminateability was good. That is, when the metal element (In) having a high electronegativity was added, the peelability was poor, and even when the second metal element was not added, the peelability was poor (Comparative Examples 1 to 4). Moreover, even if the second metal element was added, good peelability could not be obtained if the amount added was small (Comparative Example 5).

<Example 7>
In this example, an OLED was produced using the glass laminate A1 produced in Example 1. In addition, the process of 400 degreeC or more is implemented as heat processing temperature in the following processes.
More specifically, a molybdenum film was formed by sputtering on the second main surface of the glass substrate in the glass laminate A1, and a gate electrode was formed by etching using a photolithography method. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD, indium tin oxide is formed by sputtering and photolithography is used. A pixel electrode was formed by etching.
Subsequently, on the second main surface side of the glass substrate, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [ (N-naphthyl) -N-phenyl] benzidine, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] to 8-quinolinol aluminum complex (Alq ₃ ) as the light emitting layer A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer were formed in this order, and then formed on the second main surface side of the glass substrate by sputtering. Aluminum was deposited, and a counter electrode was formed by etching using a photolithography method.Next, ultraviolet light was formed on the second main surface of the glass substrate on which the counter electrode was formed. Another glass substrate was bonded and sealed through a wire-curable adhesive layer, and the glass laminate obtained by the above procedure and having an organic EL structure on the glass substrate had an electronic device member. Corresponds to the laminate.
Then, after vacuum-adsorbing the sealing body side of the obtained glass laminated body to a surface plate, a stainless steel knife having a thickness of 0.1 mm is inserted in the vicinity of the fragile layer at the corner of the glass laminated body, and an inorganic layer The attached support substrate was separated to obtain an OLED panel (corresponding to an electronic device, hereinafter referred to as panel A). When an IC driver was connected to the manufactured panel A and driven under normal temperature and normal pressure, display unevenness was not observed in the driving region.

<Example 8>
In this example, an LCD was produced using the glass laminate A1 produced in Example 1. In addition, the process of 400 degreeC or more is implemented as heat processing temperature in the following processes.
Two glass laminates A1 are prepared. First, a molybdenum film is formed on the second main surface of the glass substrate of one glass laminate A1 by sputtering, and a gate electrode is formed by etching using photolithography. did. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD, indium tin oxide was formed by sputtering and photolithography was used. A pixel electrode was formed by etching. Next, a polyimide resin liquid was applied on the second main surface of the glass substrate on which the pixel electrode was formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. The obtained glass laminate is referred to as a glass laminate X1.
Next, a chromium film was formed by sputtering on the second main surface of the glass substrate in the other glass laminate A1, and a light-shielding layer was formed by etching using photolithography. Next, a color resist was further applied by a die coating method to the second main surface side of the glass substrate provided with the light shielding layer, and a color filter layer was formed by a photolithography method and thermal curing. Next, an indium tin oxide film was further formed on the second main surface side of the glass substrate by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid was applied to the second main surface of the glass substrate provided with the counter electrode by a die coating method, and columnar spacers were formed by a photolithography method and heat curing. Next, a polyimide resin solution was applied on the second main surface of the glass substrate on which the columnar spacers were formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. Next, after the sealing resin liquid is drawn in a frame shape on the second main surface side of the glass substrate by the dispenser method, and the liquid crystal is dropped in the frame by the dispenser method, the above-described glass laminate X1 is used. The 2nd main surface side of the glass substrate of a sheet of glass laminated body was bonded together, and the laminated body which has an LCD panel by ultraviolet curing and thermosetting was obtained. Hereinafter, the laminate having the LCD panel is referred to as a laminate X2 with a panel.
Next, LCD panel B (corresponding to an electronic device) composed of a substrate on which a TFT array is formed and a substrate on which a color filter is formed is peeled off from the laminate X2 with a panel in the same manner as in Example 1 and the substrate with the inorganic layer is peeled off. Got.
When an IC driver was connected to the manufactured LCD panel B and driven under normal temperature and normal pressure, no display unevenness was observed in the driving region.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on August 1, 2014 (Japanese Patent Application No. 2014-157570) and a Japanese patent application filed on April 27, 2015 (Japanese Patent Application No. 2015-090550). Is incorporated herein by reference.

DESCRIPTION OF SYMBOLS 10,11 Glass laminated body 12 Support substrate 14 Inorganic layer 16 Support substrate 18 with an inorganic layer Glass substrate 20 Electronic device member 22 Laminated body 24 with electronic device member 24 Electronic device 26 Fragile layer

Claims (24)

1. A support substrate with an inorganic layer comprising a support substrate and an inorganic layer disposed on the support substrate;
   A glass substrate that is detachably laminated on the inorganic layer,
   The inorganic layer is a metal oxide layer containing two or more metal elements;
   The metal element is a first metal element having the highest electronegativity among the metal elements, and a second metal element having a value of 1.65 or less and a second metal element having an electronegativity smaller than that of the first metal element. The glass laminated body containing the above.
2. The glass laminate according to claim 1, wherein the first metal element is a trivalent metal element.
3. The glass laminate according to claim 1 or 2, wherein the first metal element is In, Al, Bi, Fe, Mn, Cr, Co, Sc, Y, or Ga.
4. The glass laminate according to any one of claims 1 to 3, wherein the first metal element is In.
5. The second metal element includes at least one selected from the group consisting of Ce, Zr, Mn, Ta, Hf, Be, Nb, La, Sc, Y, V, Ti, and a lanthanoid other than Ce. The glass laminate according to any one of claims 1 to 4.
6. The glass laminate according to any one of claims 1 to 5, wherein the second metal element contains at least one of Ce and Zr.
7. The glass laminate according to any one of claims 1 to 6, wherein the inorganic layer has an average thickness of 10 to 100 nm.
8. It has a support substrate, an inorganic layer, a fragile layer, and a glass substrate in this order,
   The inorganic layer includes two or more kinds of metal elements (excluding boron element), and the metal elements include the metal element A having the highest electronegativity among the metal elements and the metal elements. Among them, at least the metal element B having the smallest electronegativity is included,
   The fragile layer includes the metal element A and the metal element B,
   The atomic ratio of the metal element B and the metal element A in the fragile layer to the atomic ratio X (the metal element B / the metal element A) of the metal element B and the metal element A in the inorganic layer A glass laminate in which a ratio of Y (the metal element B / the metal element A) (atomic ratio Y / atomic ratio X) is more than 1.05 and less than 9.0.
9. The glass laminate according to claim 8, wherein a peel strength when peeling the glass substrate is 2.0 N / 25 mm or less.
10. The metal element A is In, Al, Bi, Fe, Mn, Cr, Co, Sc, Y or Ga;
    The glass laminate according to claim 8 or 9, wherein the inorganic layer contains an oxide of the metal element A.
11. The glass laminate according to any one of claims 8 to 10, wherein the metal element A is In, and the inorganic layer contains In ₂ O ₃ .
12. 12. The metal element B according to claim 8, wherein the metal element B is a metal element having an electronegativity of 1.65 or less (excluding metal elements of Groups 1 and 2 of the periodic table). The glass laminate according to 1.
13. The glass laminate according to any one of claims 8 to 12, wherein the metal element B is a lanthanoid other than Ce, Zr, Mn, Ta, Hf, Nb, La, Sc, Y, V, Ti, or Ce. body.
14. The glass laminate according to any one of claims 8 to 13, wherein the metal element B is Ce or Zr.
15. The glass laminate according to any one of claims 1 to 14, wherein the support substrate is a glass substrate.
16. Forming a member for an electronic device on the surface of the glass substrate in the glass laminate according to any one of claims 1 to 7 to obtain a laminate with the member for an electronic device;
    Separating the support substrate with an inorganic layer contained in the glass laminate from the laminate with the electronic device member, and obtaining an electronic device having the glass substrate and the electronic device member. Production method.
17. A support substrate and an inorganic layer disposed on the support substrate;
    The inorganic layer is a metal oxide layer containing two or more metal elements;
    The metal element is a first metal element having the highest electronegativity among the metal elements, and a second metal element having a value of 1.65 or less and a second metal element having an electronegativity smaller than that of the first metal element. Including
    The support substrate with an inorganic layer used in order to laminate | stack a glass substrate on the said inorganic layer, and to manufacture a glass laminated body.
18. The support substrate with an inorganic layer according to claim 17, wherein the first metal element is a trivalent metal element.
19. The support substrate with an inorganic layer according to claim 17 or 18, wherein the first metal element is In, Al, Bi, Fe, Mn, Cr, Co, Sc, Y, or Ga.
20. The support substrate with an inorganic layer according to any one of claims 17 to 19, wherein the first metal element is In.
21. The second metal element includes at least one selected from the group consisting of Ce, Zr, Mn, Ta, Hf, Be, Nb, La, Sc, Y, V, Ti, and a lanthanoid other than Ce. The support substrate with an inorganic layer according to any one of claims 17 to 20.
22. The support substrate with an inorganic layer according to any one of claims 17 to 21, wherein the second metal element contains at least one of Ce and Zr.
23. A glass substrate is manufactured by laminating a support substrate and a support substrate with an inorganic layer including an inorganic layer disposed on the support substrate, and a glass substrate so that the inorganic layer and the glass substrate are in contact with each other. Process,
    Heating the glass laminate at a temperature of 400 ° C. or higher;
    Peeling and collecting the support substrate with an inorganic layer from the heated glass laminate; and
    Performing a surface treatment on the surface of the inorganic layer of the recovered support substrate with the inorganic layer,
    The inorganic layer is a metal oxide layer containing two or more kinds of metal elements, and the metal element has a first metal element having the highest electronegativity among the metal elements, and is more electrically than the first metal element. The manufacturing method of the support substrate with an inorganic layer containing the 2nd metal element 5at% or more whose negative degree is small and whose value is 1.65 or less.
24. The method for producing a support substrate with an inorganic layer according to claim 23, wherein the surface treatment is an oxidation treatment or a polishing treatment.

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