TW201043586A - Glass member with sealing material layer, electronic device using same, and manufacturing method thereof - Google Patents

Abstract

The purpose of the present invention is to suppress cracking and breaking of a glass substrate and to suppress separation of a thin film that is formed on the surface of the glass substrate, when the glass substrate is subjected to local heat sealing such as laser sealing. Specifically, a glass substrate (3) has a sealing region. The sealing region is provided with a sealing material layer (5) which is composed of a fired layer of a sealing glass material that contains a sealing glass, a low expansion filler and an electromagnetic wave absorbing material. The sealing material layer (5) contains 10-30% by volume of air bubbles, while containing 50-200 ppm by mass of carbon. The glass substrate (3) and a glass substrate (2), which has an element formation region that is provided with an electronic element, are laminated, and then the space between the glass substrates (2, 3) is sealed by melting the sealing material layer (5) by irradiating the sealing material layer (5) with an electromagnetic wave (6) such as laser light.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass member having a sealing material layer and an electronic device using the same and a method of manufacturing the same. L. BACKGROUND OF THE INVENTION A flat panel display device (FPD) such as an organic electro-luminescence display (OELD), a plasma display panel (pDP), or a liquid crystal display device (LCD) has the following structure: light is formed A glass package in which the glass substrate and the sealing glass substrate are disposed in a direction in which the glass substrate is sealed with the two glass substrates, and the display element is sealed (see Patent Document 1). In addition, a solar cell such as a dye-sensitized solar cell has been examined for the application of a glass package in which a solar cell element is sealed by two glass substrates (see Patent Document 2). A sealing material for sealing between two glass substrates is a sealing resin or a sealing glass. Since an organic EL (OEL) element or the like is easily deteriorated by moisture, it is recommended to use a sealing glass excellent in moisture resistance and the like. Since the sealing temperature by the sealing glass is about 400 to 600 °C, when the heat treatment is performed using a baking furnace, the characteristics of the electronic component such as the OEL element are deteriorated. Therefore, there is an attempt to arrange a layer of sealing glass material containing a laser absorbing material between the sealing regions provided in the peripheral portions of the two glass substrates, and then irradiate the laser light to locally heat and melt the sealing glass material layer. 201043586 Sealed and sealed (refer to Patent Documents 1, 2). The seal (laser seal) applied by laser irradiation can suppress the thermal influence on the electronic component portion, but on the other hand, the glass substrate may be cracked or broken during sealing, which may cause A wiring layer (conductive film) formed on the surface of the glass substrate is likely to be peeled off. When a laser seal is applied, first, a sealing glass material containing a laser absorbing material is fired in a sealing region of a sealing glass substrate to form a frame-like sealing glass material layer. Then, the glass substrate for sealing and the glass substrate for the element are laminated via a glass material layer for sealing, and then the laser light is irradiated from the side of the glass substrate for sealing, and the glass material layer for sealing is heated and melted to seal the glass substrate. . The laser light is irradiated while scanning along the glass material layer for frame sealing. The irradiated portion of the glass material layer for sealing is locally heated and swelled, and is rapidly cooled and solidified from the point of completion of the laser light irradiation. At this time, the glass material layer for sealing is melted and solidified with a decrease in film thickness of about 30 to 50%. Since the film thickness of the glass material layer for sealing is locally generated continuously in the irradiated portion of the laser light, the wiring layer formed on the surface of the glass substrate or the like is applied in a pattern of peeling force. As a result, problems such as peeling of the wiring layer and the like, and deterioration of airtightness derived from this phenomenon occur. Further, a stress based on the film thickness portion reduced by the sealing glass material layer is applied to the glass substrate. Since the stress is applied to the local portion abruptly, the glass substrate is liable to be cracked or broken. According to this, when the partial heat sealing such as a laser seal is applied to the sealing between the two glass substrates, the film thickness of the sealing glass material layer at the time of melting and solidification is reduced by 201043586, and the wiring layer formed on the surface thereof may be included. Inside, there are various doubts about various adverse conditions on the glass substrate. In other words, the decrease in the thickness of the glass material layer for sealing causes the occurrence of cracking and breakage of the glass substrate itself, and peeling of the film formed on the surface of the glass substrate or the like. These conditions will cause the airtightness and reliability of FPDs such as OELD, PDP, LCD, etc., or solar cells to decrease. Ο Ο 技术 技术 文献 Ο 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 It is to provide a glass member having a sealing material layer which can improve the sealing property between the glass substrates by suppressing the occurrence of cracks and breakage of the glass substrate when local heating is used for sealing between the two glass substrates. And the reliability thereof; the t-making method of the glass member having the sealing material layer, and the improved airtightness and reliability thereof, and the method for manufacturing the same, which are used by further The structure of the sealing material layer, the improvement of the money record and its reliability. The means used to solve the problem. a glass member having a layer of a sealing material, characterized by having a glass substrate and a sealing wire

The sealing material is shaken, and the glass substrate has a sealing area; the sealing material layer is transferred to the surface of the sealing layer 5 201043586 of the glass substrate, and comprises a sealing surface, a low expansion filler and an electromagnetic wave absorbing material. The sealing material is composed of a fired layer of a glass material; wherein the front sealing material layer contains bubbles in a range of 10 to 30% by volume, and contains carbon in a range of 50 to 200 ppm by mass. A method for producing a glass member having a sealing material layer according to the present invention is characterized in that a sealing glass containing a sealing glass, a low expansion filler, and an electromagnetic wave absorbing material is formed on the sealing region of a glass substrate having a sealing region. After the glass material layer is fired, the sealing glass material layer is fired to form a sealing material containing bubbles in a range of 1 〇 to 3 〇% by volume, and containing carbon in a range of 50 to 200 ppm by mass. Floor. An electronic device according to an aspect of the present invention includes: a first glass substrate, a second glass substrate, and a sealing layer, wherein the first glass substrate includes: an element forming region having an electronic component; and the component Forming a first sealing region on the outer peripheral side of the region; the second glass substrate has a second sealing region corresponding to the first sealing region of the first glass substrate, and the surface having the second sealing region is configured to be a surface of the second glass substrate having the first sealing region facing the first sealing layer; the sealing layer is formed in the first sealing region and sealing the first glass substrate and the second glass substrate The second sealing region is composed of a molten fixing layer of a sealing glass material containing a sealing glass, a low-expansion filler, and an electromagnetic wave absorbing material, wherein the sealing layer contains 10 to 35% by volume. The range of bubbles, and the size of the aforementioned bubbles is 〇. 1~丨00 μηι range. In the method of manufacturing an electronic device according to the aspect of the invention, the first glass substrate is provided in the first glass substrate, wherein the first glass substrate includes an element formation region having an electronic component and an outer peripheral side of the component formation region. a first sealing region; wherein the second glass substrate has a second sealing region and a sealing material layer; the second sealing region corresponds to the first sealing region of the first glass substrate; The sealing material layer is formed on the second sealing region, and is composed of a fired layer of a sealing glass material containing a sealing glass, a low expansion filler, and an electromagnetic wave absorbing material, and contains 10 to 30°/by volume. a range of bubbles including carbon in a range of 50 to 200 ppm by mass; and a surface of the first glass substrate and the second glass substrate that has the first sealing region and a surface having the second sealing region In the opposing manner, a layer is formed through the sealing material layer, and then the first glass substrate or the second glass substrate is irradiated with electromagnetic waves on the sealing material layer to locally heat the sealing material layer. The sealing layer is formed by sealing between the first glass substrate and the second glass substrate. According to the aspect of the invention, the glass member having the sealing material layer and the method for producing the same have excellent reproducibility, and it is possible to suppress the occurrence of cracks and breakage of the glass-filled substrate when the sealing is performed by local heating. Therefore, according to the electronic device of the aspect of the invention and the method of manufacturing the same, the airtightness and reliability thereof can be improved. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the structure of an electronic device according to an embodiment of the present invention. 7 201043586 The second (a) to (d) drawings are cross-sectional views showing the steps of manufacturing the electronic device according to the embodiment of the present invention. Fig. 3 is a plan view showing the first glass substrate used in the manufacturing process of the electronic device shown in Fig. 2. Fig. 4 is a cross-sectional view taken along line a-A of Fig. 3. Fig. 5 is a plan view showing a second glass substrate used in the manufacturing process of the electronic device shown in Fig. 2. Fig. 6 is a cross-sectional view taken along line a-A of Fig. 5. Fig. 7 is an enlarged plan view showing the first and second glass substrates shown in Fig. 2 in an enlarged manner. Fig. 8 is a cross-sectional view showing an enlarged view of the electronic device shown in Fig. 1. I: EMBODIMENT OF THE INVENTION MODE FOR CARRYING OUT THE INVENTION Hereinafter, the mode for carrying out the invention will be described with reference to the drawings. Fig. 1 is a structural view of an electronic device according to an embodiment of the present invention, and Fig. 2 is a manufacturing step diagram of an electronic device, and Figs. 3 to 6 show first and second glasses used. Fig. 7 is a cross-sectional view showing a part of the first and second glass substrates in an enlarged manner, and Fig. 8 is a cross-sectional view showing a part of the electronic device in an enlarged manner. The electronic device 1 shown in Fig. 1 constitutes an illumination device using a light-emitting element such as an FPLD or an OEL element such as an OELD, a PDP, or an LCD, or a solar cell such as a dye-sensitized solar cell. The electronic device 1 includes a first glass substrate (glass substrate for a component) 2 and a second glass substrate (glass substrate for sealing) 3 . The first glass substrate (element 201043586 glass substrate) 2 is provided with an element formation region 2 & The first and second glass substrates 2 and 3 are made of, for example, alkali-free glass or soda lime glass. The alkali-free glass system has a thermal expansion coefficient of about 35 to 40 (x 10_VC ). The soda lime glass has a coefficient of thermal expansion of about 85 to 9 Torr (x1 〇 -7 / ° C). In the element forming region 2 & of the first glass substrate 2, an electronic component corresponding to the electronic device 1 is formed, for example, an OLED or 〇EL illumination is used to form an OEL element, and in the case of a PDP, a plasma light-emitting element is formed. In the case of an LCD, a liquid crystal display element is formed. If it is a solar cell, a dye-sensitized photoelectric conversion unit or the like is formed. Electronic components such as a light-emitting element such as an OEL element or a solar cell element such as a dye-sensitized photoelectric conversion unit are provided with various known structures, and are not limited to those of the element structure. As shown in FIG. 3 and FIG. 4, the first glass substrate 2 has the i-th sealing region 21 and the i-th sealing region 2b provided on the outer peripheral side of the element forming region 2a, and is set to surround the element forming region 2a. . The second glass substrate 3 has a second sealing region 3a as shown in Figs. 5 and 6. The second sealing region 3a corresponds to the first sealing region 2b. In other words, when the first glass substrate 2 and the second glass substrate 3 are disposed to face each other, the first sealing region 2b and the second sealing region 3a are set to face each other, and will be the sealing layer 4 as will be described later. The formation region (the formation region of the sealing material layer 5 in the case of the second glass substrate 3). The first glass substrate 2 and the second glass substrate 3 are disposed such that the surfaces having the sealing regions 2b and 3a face each other and are formed, for example, in the element forming region 2a. In the solar cell element or the like, there is also a case where no gap is formed in the element forming region 2a. The space between the first glass substrate 2 and the second glass 9 201043586 substrate 3 is sealed by the sealing layer 4 . In other words, the sealing layer 4 is formed so as to be sealed between the sealing region 2b of the first glass substrate 2 and the sealing region 3a of the second glass substrate 3 in the case where a gap is formed between the glass substrates 2 and 3. The electronic component formed in the element formation region 23 is hermetically sealed by a glass panel composed of the first glass substrate 2, the second glass substrate 3, and the sealing layer 4. The sealing layer 4 is composed of a fusion-fixing layer that melts and seals the sealing material layer 5 formed on the sealing region 3a of the second glass substrate 3 to the first glass substrate 2. The area 2b is formed. The sealing material layer 5 is melted by local heating using electromagnetic waves 6 such as laser light or infrared rays. That is, in the sealing region 3a of the second glass substrate 3 for producing the electronic device, as shown in Figs. 5 and 6, the frame-shaped sealing material layer 5 is formed. The sealing material layer 5 formed in the sealing region 3a of the second glass substrate 3 is melted and fixed to the sealing region 2b of the second glass substrate 2 by heat of electromagnetic waves 6 such as laser light or infrared rays. Will be the first! The sealing layer 4 hermetically sealed between the glass substrate 2 and the second glass substrate 3. As shown in Fig. 7, the first glass substrate 2 has a film 7 formed on a surface on which a sealing region 设有 is provided. The film 7 formed on the surface of the second glass substrate 2 functions as a wiring for pulling out the electrode of the electronic component formed on the element formation region to the outside of the glass panel, for example, and functions as a wiring. Representative examples of the thin film 7 include, for example, a tin-doped indium oxide (ITO) film, a fluorine-doped tin oxide (FT〇) film, or the like, and a transparent conductive film such as an ITO film or an FTO film. A separate film can also be laminated with other conductive films or insulating films. With ιτ〇膜 or 201043586

The film 7 may be formed of a laminated film of a pure bismuth metal film or the like. Thin film or insulating inorganic compound film, or. The film 7 is selected from a conductive film and an insulating film.

In the case of the second glass substrate 3, the surface of the second glass substrate 3 is also provided with a thin portion 7a. However, the form of the film 7 is not limited thereto, and at least one of the substrates 2 3 is provided with a film of the sealing region 2b. Depending on the structure of the element or the like, there may be a case where a thin surface is formed only on the surface of the second glass substrate 3 where the sealing portion is provided. Accordingly, in the seventh drawing, the film 7 having the surface of the (4) region 2b is provided on the first slab 2, and the vertebral ridge 7 is in the first and second glass 2b, 3a. The film 7 formed on the surface of the first glass substrate 2 is formed as a film 7 that pulls the electrode of the electron 7C member to the outside of the glass panel. The film 7 is traversed through the square of the sealing region 2b. to make. Therefore, as shown in Fig. 8, the sealing 曰4 is formed to the case where the portion is in contact with the film 7. When the film is formed into the surface of the second glass substrate 3, the sealing material layer $ is formed even if the sealing portions 4 to 4 are in contact with the film. Accordingly, when at least a part of the dense material layer 5 is in contact with the film 7, it becomes important to suppress peeling of the film 7 when the sealing layer 4 is formed. The sealing material layer 5 contains a sealing glass (glass medium), an electromagnetic wave absorbing material (a material that absorbs electromagnetic waves such as f-light or infrared rays to generate heat), and a fired layer of a glass material for inspection of a low-expansion 201043586 expanded filler. The sealing glass material is preferably formed to contain a low expansion filler before the thermal expansion coefficient thereof is integrated with the thermal expansion rates of the glass substrates 2 and 3. The sealing glass material is a combination of an electromagnetic wave absorbing material and a low expansion filler in a sealing glass as a main component. The glass material for sealing may contain an additive material other than these as needed. As the sealing glass (glass medium), for example, a low-melting point glass such as tin-phosphate glass, bismuth-based glass, hunth-glass or mis-glass is used. Among these, it is preferable to use tin-phosphoric acid in consideration of factors such as sealing property (adhesiveness) to the glass substrates 2 and 3, reliability (continuity reliability, airtightness), and influence on the environment and the human body. It is a sealing glass made of glass or bismuth glass. The glass transition point of the sealing glass is preferably 250 to 30 (TC, in this case, it is preferable to use tin-phosphate glass. The tin-phosphate glass (glass medium) preferably has 2 〇 to 68 mol% of Sn 〇 , 0.5 to 5 moles %2Sn 〇 2, and 20 to 40 moles. / ho 〆 basically, the total amount is set to 100 moles / /). Sn0 is a component for lowering the melting point of glass. If the content of SnO is less than 20 mol%, the viscosity of the glass will increase, and the sealing temperature will be excessively increased. If it exceeds 68 mol%, vitrification will not occur.

SnCb is a component used to stabilize glass. When the content of Sn 〇 2 is less than 0.5 mol%, Sn 〇 2 is separated and precipitated in the softened (four) glaze during the sealing operation, and the fluidity is impaired, resulting in a decrease in sealing workability. When the content of Sn 〇 2 exceeds 5 mol%, Sn 〇 2 is likely to be precipitated from the melting of the low melting point glass. ί>2〇5 is a component used to form a glass skeleton. 12 201043586 If the content of 卩2〇5 is less than 20 m. /. It will not be vitrified, and if it contains more than 40% by mole, there will be doubts that the specific defects of phosphate glass are deteriorating. The ratio of SnO and Sn〇2 (% by mole) in this 'glass medium' can be determined as follows. First, the glass medium (low-melting glass powder) was subjected to acid decomposition, and the total amount of Sn atoms contained in the glass medium was measured by ICP emission spectrometry. Then, since the Sn2+(SnO) system can determine the acid-decomposed substance by the enthalpy titration method, the Sn2+(Sn02) can be obtained by subtracting the amount of Sn2+ obtained here from the total amount of Sn atoms. . The glass-based glass formed of the above three components has a low transfer point and is suitable for a low-temperature sealing material, but may contain the following components as an optional component: a component forming a glass skeleton such as SiO 2 or ZnO, B203, or Al 2 〇 3 , W03, Mo〇3, Nb205, Ti〇2, Zr〇2, Li20 'Na20, κ20,

A component such as Cs20, MgO, CaO, SrO, or BaO that stabilizes the glass. However, if the content of the optional component is too large, there is a concern that the glass becomes unstable and devitrification occurs, or the glass transition point and the softening point rise. Therefore, the total content of the optional components is preferably set to be equal to or less than mol%. The glass composition in this case is adjusted so that the total amount of the basic component and the arbitrary component is substantially 100% by mass. The sealing glass material contains an electromagnetic wave absorbing material that functions as a laser absorbing material and an infrared absorbing material. The electromagnetic wave absorbing material uses at least one metal selected from Fe, Cr, Μ, Co, Ni, and Cu, or contains A compound such as an oxide of the foregoing metal. The content of the electromagnetic wave absorbing material is preferably in the range of 0.1 to 5% by volume based on the glass material for sealing. If the electromagnetic wave absorption 13 201043586 material content is less than 01 volume Q /. However, the sealing material layer 5 cannot be sufficiently melted by irradiating laser light or infrared rays. When the content of the electromagnetic wave absorbing material exceeds 10 M%, 局部 when irradiated with laser light or infrared rays, local heat is generated in the vicinity of the interface with the second glass substrate 3, and the second glass substrate 3 is broken. The fluidity at the time of melting of the glass material for sealing is deteriorated, and the adhesion to the first glass substrate 2 is lowered. The method and the sealing glass material further contain a low expansion filler. As the low-expansion filler, at least one selected from the group consisting of cerium oxide, aluminum oxide, zirconium dioxide cerium oxalate, cordierite, zirconium phosphate-based compound, soda lime glass, and borosilicate glass can be used. The disc acid-missing compound may, for example, be (ZrO)2P2〇7, NaZr2(P〇4)3, KZr2(P04)3, Ca〇.5Zr2(P〇4)3, Na〇.5Nb〇.5Zr1. 5(P〇4)3, K〇. 5Nb〇. 5Zri. 5 (P〇4)3,

Ca0 2 5 Nb〇.5Zr15(P〇4)3, NbZr(P04)3, Zr2(W〇3)(P〇4)2, and these composite compounds. The "low-expansion filler" means a lower thermal expansion coefficient of a sealing glass which is a main component of the glass material for sealing. The content of the low-expansion filler is appropriately set in such a manner that the thermal expansion coefficient of the glass material for sealing is close to the thermal expansion coefficients of the glass substrates 2 and 3. The low-expansion filler is also different depending on the thermal expansion coefficient of the sealing glass or the glass substrates 2 and 3, but it is preferably in the range of 丨 to 50% by volume with respect to the glass material for sealing. If the content of the low-expansion filler is less than 1% by volume, the effect of adjusting the thermal expansion coefficient of the glass material for sealing cannot be sufficiently obtained. On the other hand, if the content of the low-expansion filler exceeds 50% by volume, the fluidity of the glass material for sealing may be lowered, which may cause a decrease in the strength of the adhesive. 14 201043586 The content of the low-expansion filler is preferably in the range of 25 to 50% by volume. By setting the content of the low-expansion filler to 25% by volume or more, the fluidity of the sealing glass material can be appropriately controlled. In other words, when the sealing material layer 5 is heated and melted by laser light or infrared rays, the flow of the glass material for sealing in the line width direction (the surface direction of the glass substrates 2 and 3) is suppressed. Thereby, the film thickness reduction of the sealing material layer 5 can be suppressed. However, if the content of the low-expansion filler is too large, the fluidity of the glass material for sealing is excessively lowered. Therefore, the content of the low-expansion filler is preferably 50% by volume or less. The thermal expansion coefficient of the sealing glass material containing the sealing glass, the low-expansion filler, and the electromagnetic wave absorbing material is preferably 40 to 85 (χ 10_7/° C.), more preferably 45 to 75 (xl 〇 _7/.). . However, when the local heating of the sealing material layer 5 uses, for example, laser light, the sealing material layer 5 is sequentially irradiated from the portion of the laser light scanned along it (4), at the end of the irradiation of the laser light. The film is fixed to the first glass substrate 2 by rapid cooling. Accordingly, the refining and solidification of the sealing material layer 5 occurs locally continuously, and the film thickness of the sealing material layer 5 is reduced when the wire is melted, and the film formed on the surface of the glass substrate 2_ is formed. 7 The force applied in the peeling direction is applied to the glass substrates 2, 3 in accordance with the reduced film thickness portion of the sealing material layer 5. Since the stress is applied to the portion sharply, the glass substrates 2 and 3 may be cracked or broken. In this case, the sealing material layer 5 of the embodiment includes 10 to 30% by volume of the gas (the microbubbles which are present in the sealing material layer 5_ are generally considered to be heated by laser irradiation or infrared irradiation or the like). Meeting 15 201043586 Inflated, biting the soil as carbon will become carbonated bubbles and will grow together. Also, recognize bubbles and so on. By this, the amount of gas is increased or a new less is generated. Therefore, it is possible to suppress (4) the film thickness at the time of melting of the material layer 5 is reduced by the local smelting and solidification of the sealing material layer 5 of the film 7, and the application is alleviated. That is, the film 7 which is subjected to the stress applied to the glass substrates 2 and 3 is peeled off, and the release property is preferably prevented from being formed with the sealing layer 4, and if the sealing material is made of U and the glass plate 2'3 Broken material, etc. The sub-suppression effect is obtained by expanding the bubble volume expansion of the film m $ ‘’, , ##, or the infrared material, which is based on the gas reduction in _5. If the bubble is less than 1% by volume, it is not sufficient: and the volume of the layer 5 is expanded (that is, the film thickness is reduced by the melting of the sealing material layer 5), that is, the film thickness cannot be sufficiently obtained. increase,. On the other hand, if the proportion of the bubbles in the sealing material layer 5 exceeds 3 〇% by volume, the adhesion strength of the sealing layer 4 is lowered due to an excessive increase in the volume of the bubbles after the smelting and solidification. The size of the bubble in the sealing material layer 5 is preferably set to be the same as the size of the gas package. If the bubble is smaller than Ο. ίμιη, there will be a situation in which the bubble dispersion state becomes too dense, resulting in a thinning of the thickness of the glass layer between the bubble and the bubble. In this state, the adhesion strength of the sealing layer 4 is liable to lower. On the other hand, when the size of the bubble exceeds 50 μΓη', continuous bubbles are easily formed by irradiation with laser light or infrared rays, and there is a fear that the airtightness of the sealing layer 4 is lowered. At least a part of the air bubbles in the sealing material layer 5 grows due to volume expansion or conformation when heated by laser or heated by infrared rays. In order to promote the growth of such bubbles, the sealing material layer 5 contains an appropriate amount of carbon. It will react with oxygen in the glass component to become a trioxide gas during the addition. Accordingly, by generating a gas in the sealing material layer 5 during heating, the bubbles can be more effectively grown. On the premise that such an effect can be obtained, the amount of carbon in the sealing material layer 5 is in the range of 5 Å to 2 〇〇卯 m in terms of mass ratio. Ο

If the amount of the disk in the sealing material layer 5 exceeds 2 〇〇 ppm, the amount of gas generated during laser heating or infrared heating becomes excessive, resulting in an increase in continuous bubbles and a decrease in airtightness of the sealing layer 4. Doubt. If the amount of carbon in the sealing material layer 5 is less than 5 〇 ppm, the amount of gas generated is sufficient to sufficiently increase the bubble volume in the sealing material layer 5. In this case, the difference in film thickness between the 4/7 which has been heated and the portion which is heated and melted becomes large, and the crack of the glass substrate 2, 3 is caused by the film thickness of the film. The crushing and peeling of the sealing layer 4, and the peeling of the film 7 and the like. As the sealing layer 4 of the refining and solidifying body of the sealing material layer 5, it is preferable that the volume ratio of the bubbles is set to be in the range of 5 to 35%. In particular, it is preferred that the proportion of the bubble volume is larger than that of the sealing material layer 5 before sealing. The bubble of the sealing layer 4 is large] (long axis) k is set to G 丨 刚 刚 ^ ^ ^ ^ ^ ^ 抑 抑 抑 抑 封 封 封 封 封 封 封 封 封 封 封 封 封 封 封 封 封 封 封 封 封Therefore, it is easy to cause the breakage of the fracture layer 4 of the surface substrates 2, 3 or (4), the proportion of the bubbles in the peeling layer 4 of the film 7 is large, and when the size of the bubble is large, the sealing layer 4 = strength and airtightness become Easy to lower. The contact of the domain 4 17 201043586 The thickness of the sealing layer 4, 2, with respect to the thickness of the sealing material layer 5 is preferably 0.9 Τ or more and Ι.ΙΤρχ. Further, the volume V2 of the sealing layer 4 is preferably in a range of more than 1 and 1.15 V or less with respect to the volume of the sealing material layer 5. By satisfying such a condition, it is possible to suppress the breakage of the glass substrates 2, 3, the breakage and peeling of the sealing layer 4, and the peeling of the sealing layer 4 due to the reduction in film thickness when the sealing material layer 5 is condensed by resilience. Peeling and other situations. The thickness of the sealing layer 4 is preferably more than the above. The volume V2 of the sealing layer 4 is preferably 1.02 V or more. The sealing material layer 5 is formed on the sealing region 3a of the second glass substrate 3 as follows. First, the sealing material paste is prepared by mixing a sealing glass material with a vehicle. The carrier is obtained by dissolving a resin belonging to a binder component in a solvent. As the carrier resin, for example, cellulose-based resins such as mercapto cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, and nitrocellulose can be used; Ethyl acrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, etc. An organic resin such as an acrylic resin obtained by polymerization. As a solvent, in the case of a cellulose-based resin, a solvent such as terpineol, butyl carbitol acetate-hydrazine or ethyl carbitol acetate can be used. In the case of an acrylic resin, it is used as a solvent. , butyl carbitol acetate, ethyl carbitol alcohol ester and other solvents. The viscosity of the sealing material paste may be any combination of the resin (bonding component) 18 201043586 in the carrier and the solvent, or the sealing glass material and the carrier, as long as it can match the corresponding viscosity of the device applied to the glass substrate 3. The proportion is adjusted. A well-known additive of a glass paste such as an antifoaming agent or a dispersing agent can be added to the sealing material paste. The preparation of the sealing material paste can be applied by a known method such as a rotary mixer or a roller mill having a mixing wing, a ball mill or the like. Α α A sealing material paste is applied onto the sealing area % of the second glass substrate 3, and dried to form a coating layer of the sealing material paste. The sealing material paste is applied by a printing method such as plate printing or gravure printing, applied to the second sealing region, or coated in the second sealing region 3 by using a dispenser or the like. The coating layer which is lean in the sealing material is dried at a temperature of, for example, 12 Gt or more (four minutes) or more. The drying step is carried out in order to remove the solvent in the coating layer. A solvent remains in the cloth layer, and in the subsequent firing step, there is a fear that the binder component cannot be sufficiently decomposed and burned. The coating layer of the above-mentioned sealing material paste is fired to form a sealing material layer 5. In the baking step, the coating layer is first heated to a temperature lower than the glass transition point of the sealing glass (glass medium) which is a main component of the sealing glass material, and after the binder component in the coating layer is decomposed and burned, it is heated to Sealing glass (recommended by softening the temperature above the softening point, and smelting the sealing glass material), the gas generated by the decomposition and combustion of the bonding component (hereinafter referred to as "decomposition") is used to foam the glaze, and The foamed melt is burned on the glass plate to form a sealing material layer 5 composed of a fired layer of the glass frit material for sealing. The formation of the sealing material layer 5 is in the future. After the heat transfer to the glass transition of the sealing glass, the binder component is decomposed and burned, 19 201043586 can be controlled in the sealing material layer 5 by adjusting the temperature rise rate when heating to a temperature higher than the softening point of the sealing glass. The amount of bubbles and the size of the bubbles. Usually, a dense sealing material layer 5 can be obtained, and the temperature increase rate from the softening point of the sealing glass to the firing temperature is set to 丨~(7) The gas is decomposed, and the temperature increase rate in such a temperature range is set to 20 to 70. The 〇/min range 'will cause the decomposition gas to remain, and the sealing material layer 5 in which a moderately sized bubble exists in a desired range can be obtained. Moreover, if the temperature increase rate is accelerated within the range, the bubble amount will increase and a smaller bubble will be obtained, and if the temperature increase rate becomes slower, the bubble amount will decrease and a larger bubble will be obtained. Further, the 'sealing material layer 5' In the forming step, the amount of carbon of the sealing material layer 5 can be controlled by using a method such as (丨), (2), etc.: (丨) adding an organic substance or carbon or the like as a carbon source to the sealing glass (or a sealing glass material) In the case, the carbon derived from the carbon source is contained in the glass material for sealing; (2) a part of the carbon derived from the bonding component (organic resin) or the organic solvent derived from the sealing material paste remains (2) The method is preferable because it is not necessary to add a special step to control the amount of carbon. Further, even if the method is other than the above, the amount of carbon in the sealing material layer 5 can be made 5 to 2 in terms of mass ratio. 〇〇ρρηι range In the method of the above (1), for example, when the glass is pulverized, an organic substance such as an alcohol is added as a carbon source. This method also has a function of a pulverization aid because of an alcohol, and the like, The pulverization efficiency is not limited to organic substances, and may be carbon such as carbon black or graphite. Even if the amount of carbon added to the sealing glass or the carbon source such as carbon is set to one, Since the stone is changed according to the firing conditions, the correlation between the carbon source added and the carbon source added after firing is determined in advance. Then, the sealing material layer 5 is controlled accordingly. In addition, the amount of carbon source added may be constant, and the firing conditions (temperature, time) may be changed to control the carbon amount. (2) The method is to add a carbon source to the sealing glass, and A method of leaving a part of carbon of a binder component (organic resin) or an organic solvent derived from a carrier used for paste formation. In this case, the composition of the carrier, the composition ratio of the sealing glass material to the carrier when the paste is formed, the firing conditions, and the temperature from the temperature range in which the resin is burned or decomposed to the temperature at which the sealing glass is softened The rate of temperature rise and hold time within the range become important. The carrier used in the production of the related sealing material paste is not particularly limited in the case of the method (1), but in the case of the method (2), it is preferred to use a cellulose resin (especially nitrocellulose) in terpineol. It is obtained by dissolving in an organic solvent such as butyl carbitol acetate or ethyl carbitol acetate. (2) The carrier used in the method is preferably such that 15 to 5 mass% of nitrocellulose is selected from 95 to >. 5 mass% selected from the group consisting of pine, kikabitol acetate vinegar and decyl carbitol. Acetic acid® is prepared by dissolving any one of organic solvents or two or more kinds of mixed solvents. Further, in the case of the paste of the glass material for sealing, it is preferable to use 7 to 90% by mass of the sealing glass material and 10 to 30% by mass of the carrier to make a sealing material paste for 6 weeks. The controllability of the residual carbon amount of the sealing material layer 5 can be improved by using such a carrier and sealing the paste. In the baking step of the sealing material paste coating layer, generally, in order to reduce the glass material for sealing, the resin component can be completely decomposed, burned, and the conditional body can be δ' by the temperature at which the resin is decomposed and burned. And the temperature range of the temperature at which the sealing glass is softened and flowed is slowed down by 21 201043586, and the temperature rise rate is maintained for about 1 to 15 hours, which promotes decomposition and combustion of the resin. When the method of (2) is applied, an appropriate amount of carbon can be left in the sealing material layer 5 by controlling the decomposition and combustion steps of the resin. As described above, the resin component in the carrier is preferably nitrocellulose. The nitrocellulose is decomposed and burned at a temperature in the range of 200 to 250 tons. For example, the tin-scale acid glass medium softens the flow at a temperature of 26 〇 to 4 〇 (rc range. Therefore, 200 to 40 (the temperature range of TC is important. If the above-mentioned carbon-containing sealing material layer 5 can be controlled by It is obtained at a temperature increase rate of 2 to 400 ° C. Specifically, it is preferably heated at a temperature of 1 to 25 ° C/min in a temperature range of 200 to 40 (when the temperature is increased by a batch furnace or the like). In order to maintain the temperature in the furnace at 200 to 40 (in the TC temperature range, it is preferable to set the holding time to less than 50 minutes. Next, as shown in the second (a), the second glass is used. The substrate 3 (which has the sealing material layer 5) and the first glass substrate 2 (having the element forming region 2a' and the device forming region 2a having separately fabricated electronic components) are fabricated such as OELD, PDP, and LCD. An electronic device 1 such as an illumination device using an FPD or an OEL element or a solar cell such as a dye-sensitized solar cell, that is, as shown in the second (b), the first glass substrate 2 and the second glass are used. The surface of the substrate 'with the element forming region 2a is opposite to the surface on which the sealing material layer 5 is provided. In the element formation region 2a of the first glass substrate 2, a gap is formed by the thickness of the sealing material layer 5. Next, as shown in the second (c), the second glass substrate 3 is transmitted (or the first The glass substrate 2) irradiates the sealing material layer 5 with electromagnetic waves such as laser light or infrared rays. When laser light 6 is used as the electromagnetic wave 6, the laser light is irradiated along the side of the frame-shaped sealing material 22 201043586. There is no particular limitation, and laser light from a semiconductor laser, a tannic acid gas laser, a pseudo-molecular laser, a YAG laser 'HNe laser, etc. can be used. The output of the laser light is matched with the thickness of the sealing material layer 5, and the like. As appropriate, it is preferable to apply the heating temperature (processing temperature) of the sealing material layer 5 to the range of 500 to 800 ° C (for example, an output in the range of 25 to 85 W). If the heating temperature of the sealing material layer 5 is less than 500 ° c, there is a concern that the bubble cannot be sufficiently grown when the sealing material layer 5 is melted. Further, if the heating temperature of the sealing material layer 5 exceeds 800 ° C, it is easy to cause turtles on the glass substrates 2 and 3 when heated. Crack, broken, etc. The sealing material layer 5 is sequentially melted from the portion irradiated by the laser light scanned along the same, and is solidified and solidified on the first glass substrate 2 at the end of the laser light irradiation. Then, the sealing material layer is spread over the sealing material layer. The entire circumference of 5 is irradiated with laser light to form a sealing layer 4 for sealing the second glass substrate 2 and the second glass substrate 3 as shown in Fig. 2(d). Since the sealing material layer 5 is bubbled during melting When the film thickness is reduced and the film thickness is reduced, it is possible to suppress the breakage of the glass substrates 2 and 3, the breakage and peeling of the sealing layer 4, and the peeling of the film 7. In this case, the first glass substrate 2 is used. 2 The glass panel composed of the glass substrate 3 and the sealing layer 4 is formed into an electronic skirt which (4) the sub- 7L member is hermetically sealed in the component 侃 region h. The reliability of the electronic device h = the hermetic sealing property caused by the sealing layer 4, and the bonding strength between the glass substrate 'and the sealing layer 4, and the like. According to the present embodiment, since the airtightness and the adhesion strength can be improved by 23 201043586, the electronic device 1 excellent in the degree can be obtained. In addition, the glass panel to be hermetically sealed in (4) is not limited to the electronic device's rhyme that can be applied to t sub-components or glass members (such as building materials) such as double-layer vacuum glass. EXAMPLES Next, specific examples of the present invention and evaluation results thereof will be described. In addition, the following description is not intended to limit the invention, and may be changed in the form of the invention. (Example 1) Preparation of Imol/〇 indicates: SnO (; 55.7%;), SnOW.l%), P2〇5 (32.5%), ZnO (4.8〇/.), Al2〇3 (2.3 %), si〇2 (1,6%) tin-phosphate glass medium (glass transition point = 28〇t), bismuth ruthenate ((Zr0)2P207) powder as low expansion filler, and Fe2〇 3_Cr2〇3_c〇2〇3_Mn〇-based laser absorbing material (average particle diameter=2μηι). Further, 4% by mass of nitrocellulose as a binder component was dissolved in 96 mass. /. A carrier is prepared from a solvent composed of butyl carbitol acetate. Next, 51% by volume of the above-mentioned tin-filled glass medium, 45.2% by volume of the acid-recording powder, and 3 _8 of the laser absorbing material were used. A glass material (coefficient of thermal expansion: 45 x 10 7 / ° C) for sealing was prepared by mixing. A sealing material paste was prepared by mixing 84% by mass of the sealing glass material with 16% by mass of the carrier. Next, the sealing material paste was applied by screen printing method in the outer peripheral region of the second glass substrate (size: 9〇x9〇x〇.7mmt) composed of alkali-free glass (thermal expansion coefficient: 38xl (T7/°C)). After coating (line width: 500 μm), it was dried according to 12 (TC x 10 minutes. The film was formed on the surface of the second glass substrate. 24 201043586 The coating layer of the dried sealing material paste was applied. The heating rate i 5 /min is raised to 250 ° C, and is maintained at this temperature for 5 minutes, and the binder (nitrocellulose) is decomposed and burned (hereinafter referred to as "debonding agent treatment"), and then heated. The temperature was raised to 350 ° C / min at a rate of 15 ° C / min. (:, from 350 ° C (softening point) at a temperature increase rate of 50 ° C / min to 43 (rc, and maintained at this temperature for 1 而 minutes to complete the firing. This proceeds to form a layer of sealing material having a film thickness of "paw".

By the step of forming the above-mentioned sealing material layer, bubbles having a size (long axis) of 5 to 1 〇 μη are present in the sealing material layer at a volume ratio of 15%. The volume ratio and size of the bubbles were measured by SEM observation of the cross section of the sealing material layer, and the carbon content of the post-sealing material layer was 200 ppm. The amount of carbon in the sealing material layer is a value measured by carbon sulphur (4) EMIA_32GV (trade name, manufactured by Horiba, Ltd.). Other embodiments are the same. The second glass substrate having the upper (four) seal (four) layer and the first glass substrate having the element formation region (a glass substrate having the same shape as the second glass substrate and having the same shape as the red glass FT (10)) . Then, the ribs are irradiated with the wavelength of _nm and the laser beam of the output shoulder at the scanning speed (four) through the second glass substrate, and the sealing material layer is melted and quenched and solidified, and the first glass substrate and the second glass substrate are given. seal. The force α temperature when the sealing material layer was subjected to f-irradiation was measured by a light-emitting thermometer. Film thickness τ of the sealing layer (smoothing and solidifying layer of the sealing material layer) Thickness of the film thickness of the pair of sealing material layers Τι (Τ2/Τι), M2 volume ratio and size (long axis), sealing layer The ratio of the volume ν2 to the volume of the Misha material layer 25 201043586 (V2/Vi) was determined by wearing a sealing layer by SEM. As a result, the film thickness L of the sealing layer was 58 μm, the thickness ratio (τ2/τ〇 system (9) 2, the volume ratio (V2/Vl) was ι·08, the bubble volume ratio was 2〇%, and the bubble size (long axis) was Further, the volume ratio is a value obtained by the ratio of the load-bearing area of the sealing material layer to the sealing layer. This electronic coating is provided for evaluation of characteristics described later (Examples 2 to 5) except for the sealing material layer. The time for debonding treatment (hereinafter referred to as "debonding agent time"), the laser light output to (4) the material layer, and the processing temperature of the sealing material layer are changed to the conditions shown in Table 1, except for the conditions shown in Table 1. The sealing material layer forming step for the second glass substrate and the laser sealing step for the first glass substrate and the second glass substrate are carried out as in the first embodiment. The carbon amount of the material layer, the sealing material layer and the sealing layer are also sealed. The film thickness Τ, τ2, film thickness ratio αντ,), volume ratio and size (long axis) of the bubble, and volume ratio (V2/Vl) were measured as in Example 1. The measurement results are shown in Table 1. Such an electronic device is provided for evaluation of characteristics described later. (Example 6) 78 parts by volume of a tin-phosphate type glass medium having the same composition as in Example 1, 2% by volume of cordierite powder, and 2% by volume of a laser absorbent material were mixed to obtain a glass material for sealing. (The coefficient of thermal expansion: 72 < 1 〇 _7 / 〇. The sealing glass material 84 mass 0 / 〇 was mixed with the carrier 16% by mass to prepare the dense material θ. Next, in the sodium gin glass ( Thermal expansion coefficient: 87><1〇-7/.〇) The outer peripheral region of the second glass substrate (size: looxiooxi.immt) having the FTO film formed, and the sealing material paste was applied by screen printing (line) After the width: 26 201043586 500 μηι), the drying step, the debonding agent step, and the firing step were carried out under the same conditions as in Example 将. The second glass substrate having the above-mentioned sealing material layer and the first glass substrate having the element forming region were used. (Glass substrate with FTO film composed of soda-lime glass having the same composition and shape as the second glass substrate) is laminated. Then, the second glass substrate is passed through, and the laser light having a wavelength of, for example, a claw is outputted at 25 W. Mm / s scanning speed to the sealing material layer In the row irradiation, the first glass substrate and the second glass substrate are U-sealed by laminating and sealing the sealing material layer. The carbon amount of the sealing material layer, the thickness of the sealing material layer and the sealing layer T1, D, 2, film thickness ratio (τντο, volume ratio and size of the bubble (long axis), volume ratio CVWO ' was measured as in Example i. The measurement results are shown in Table 2. This electronic device is provided to be described later. (Comparative Example 1 to 2) Using a glass material (glass transition point = 36q (7), a glass material for sealing (thermal expansion coefficient = 72 x 10 force, C), as in Example 6, the second aspect was carried out. a sealing material layer forming step of the glass substrate and a laser sealing step of the first glass substrate and the second glass substrate. The step of forming the sealing material layer is performed by heating the temperature to a temperature of 5 t:/min to 2 耽, and After the temperature is maintained for 5 minutes for debonding treatment, the temperature is raised to π-temperature, and the temperature is maintained for 1 minute. The amount of carbon in the sealing material layer, the thickness of the material layer and the thickness of the (four) layer. 1, [, film thickness ratio The volume ratio and size (long axis) and volume ratio (Μ) of the bubble are shown in Table 2. The electronic device was supplied to the characteristic evaluation described later, and the column 1 was an example in which a glass substrate having no T0 。 was used. 27 201043586 (Comparative Examples 3 to 4) The formation of the sealing material layer for the second glass substrate, and the first glass substrate and the first embodiment were carried out in the same manner as in Example 1 except that the steps of forming the sealing material layer were changed as follows. 2 Laser sealing of the glass substrate. The sealing material layer is formed by first heating the dried sealing material paste coating layer to 250 at a heating rate of 5 ° C / min. (: At this temperature, the shovel (Comparative Example 3) and 60 minutes (Comparative Example 4) were held at this temperature to carry out the debonding agent treatment, and then the temperature was raised to 430 at a temperature increase rate of 5 ° C/min. The temperature remains 1 于

J W Shi. The amount of carbon in the sealing material layer 'the thickness of the sealing material layer and the sealing layer, the ratio of the thickness of the sealing layer 2, the film thickness (τντο, the volume ratio and size of the bubble (long axis), the volume & (WVO, as shown in Table 2) This electronic device was supplied to the characteristic evaluation described later. Next, the appearance of the glass panels of Examples 1 to 6 and Comparative Examples 1 to 4 was used to estimate whether or not the glass substrate was cracked, whether the sealing layer was cracked, and whether FTO was present or not. The appearance is measured and evaluated by an optical microscope. Moreover, the airtightness of each glass panel is measured. The airtightness is measured by a helium leak test. The results of the measurements and evaluation are shown in Table 1. Table 2 shows the manufacturing conditions of the glass panel in combination with Table 1 and Table 2. 28 201043586 [Table i]

Example 1 Example 2 Example 3 Example 4 Example 5 Glass material for sealing Glass dielectric material Tin-ruthenium-based glass transition point (°c) 280 280 280 280 280 Formulation ratio (% by volume) 51 51 51 51 51 Low expansion filler material Zirconium phosphate compounding ratio (% by volume) 45.2 45.2 45.2 45.2 45.2 Average particle size of laser material (μηι) 2 2 2 2 2 Formulation ratio (% by volume) 3.8 3.8 3.8 3.8 3.8 Thermal expansion coefficient (χ1χ( Τ7/°〇45 45 45 45 45 Glass substrate material with FTO glass thickness (mm) 0.7 0.7 0.7 0.7 0.7 firing step debonding agent time (min) 5 5 5 5 30 firing temperature rc) 430 430 430 430 430 Sealing material layer thickness μ(μηι) 57 57 57 57 57 Bubble volume ratio (%) 15 15 15 15 15 Bubble size (μΐΏ) 5-10 5-10 5-10 5-10 5-20 Carbon content ( Ppm) 200 200 200 200 100 Laser wavelength (nm) 940 940 940 940 940 Output (W) 36 38 40 42 36 Scanning speed (mm/s) 10 10 10 10 10 Processing temperature (°c) 650 690 720 750 650 Sealing layer thickness Τ2 (μιη) 58 58 59 59 58 Thickness ratio (T/TD 1.02 1.02 1.04 1.04 1.02 by volume ratio (Vz /VO 1.08 1.10 1.12 1.14 1,03 Bubble volume ratio (%) 20 23 24 28 18 Bubble size (μηι) 15-20 15-25 15-30 15-30 15-25 Evaluation results Appearance substrate cracks without or without No seal layer cracks, no or no, no FTO film peeling, no, no, no, no, no, no, no, no, no air, no air tightness, there are some 29 201043586 [Table 2]

Example 6 Comparative Example ί | Comparative Example 2 Comparative Example 3 | Comparative Example 4 Glass Material Tin - Phosphate Glass Oxide Glass Tin - Moth Painting 1 Series Glass Media Glass Transfer Point (°C) 280 360 360 280 280 For sealing Formulation ratio (% by volume) 78 73.5 73.5 51 51 Glass low expansion material cordierite __ Phosphorus S Chu Zircon material filling ratio (% by volume) 20 24.5 24.5 45.2 45.2 Laser average particle size (μιη) 2 2 2 2 2 Material mix ratio (% by volume) 2 2 2 3.8 3.8 Thermal expansion coefficient (χ10_7/°〇72 Ί2 72 45 45 Glass-based shuttle material soda-lime glass* FTO-free alkali-free glass plate thickness (mm) 1.1 1.1 1.1 0.7 0.7 firing debonding agent time (min) 5 5 5 30 60 ------- step firing temperature (°c) 430 460 460 430 430 thickness ΤΚμίΏ) 55 15 15 57 57 sealed bubble volume ratio (%) 20 0.1 0.1 5 5 Material layer bubble size (μηι) 3-7 0.1 under 0.1 less than 2-5 2-5 carbon (ppm) 200 35 35 35 40 wavelength (nm) 940 940 940 940 940 laser light output ( W) 25 72 70 36 36 — Scanning speed (mm/s) 5 5 5 10 10 Processing temperature (°c) 570 600 570 650 650 --- -- Thickness Τ 2 (μΐΏ) 52 10.2 11 50 50 — Thickness ratio (τ/Π) 0.95 0.68 0.73 0.88 0.88 ------- Sealing layer volume ratio (Vj/Vj) 1.07 1 1 1 - 1 —·— -- Bubble volume ratio (%) 27 0.1 0.1 5 5 ------ Bubble size (um) 5-10 0.01 ] 0.01 2-5 2-5 ------- No cracks in the substrate - ----- No~~~----^ Sealing layer cracks without or without _____- No--- Evaluation results Appearance FTO film is not separated - There is a '-- Then good or bad 〇XXXX ~--- Airtightness is present or not - None - None ------------- J *: Example 6 and Comparative Example 2 have FTO film 'Comparative Example 1 does not have FT〇犋. It is known from Tables 1 and 2 that the glass sheets obtained in Example 6 did not have cracking of the glass substrate and the sealing layer, and the F10 film was not formed, and the airtightness was excellent. The reason is that the bubbles are grown by the melting step of the sealing material layer, and the film thickness of the sealing material layer is suppressed from being reduced. On the other hand, in the comparative example using a glass substrate not provided with an FTO film, a crack occurred in the glass substrate, and a comparative example 2 to 4 'FTO film having a glass substrate provided with an FT film was used. In the case of peeling, the sealing state and airtightness of the sealing layer are impaired. INDUSTRIAL APPLICABILITY A glass member having a sealing material layer of the present invention can be used as a glass substrate used in manufacturing a flat-panel display device or a solar cell panel, and the flat-panel display device or solar cell panel has A structure in which a display element or a solar cell element is sealed between two glass substrates arranged in opposite directions. Further, the electronic device of the present invention has the flat-panel display device or the solar cell panel of the above configuration. In addition, the entire contents of the specification, the scope of the application, the drawings, and the abstract of the Japanese Patent Application No. 2009-113282, filed on May 8, 2009, are hereby incorporated by reference in its entirety herein in BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the structure of an electronic device according to an embodiment of the present invention. 2(a) to 2(d) are cross-sectional views showing the steps of manufacturing the electronic device according to the embodiment of the present invention. Fig. 3 is a plan view showing the first glass substrate used in the manufacturing process of the electronic device shown in Fig. 2. Fig. 4 is a cross-sectional view taken along line A-A of Fig. 3. 31 201043586 Fig. 5 is a plan view showing a second glass substrate used in the manufacturing process of the electronic device shown in Fig. 2. Fig. 6 is a cross-sectional view taken along line A-A of Fig. 5. Fig. 7 is a cross-sectional view showing the first and second glass substrates shown in Fig. 2 in an enlarged manner. Fig. 8 is a cross-sectional view showing an enlarged view of the electronic device shown in Fig. 1. [Description of main component symbols] 1...electronic device 3a...second sealing region 2...first glass substrate 4...sealing layer 2a...element forming region 5...sealing material layer 2b. ..1st sealing area 6...electromagnetic wave 3...second glass substrate 7...film 32

Claims (1)

201043586 VII 1. Patent application scope: A glass member having a sealing material layer, comprising: a glass substrate having a sealing region; and a sealing material layer disposed on the sealing region (4) of the glass substrate - and having 3 a sintered layer of a sealing material for a male, a glass-sealed, a low-expansion filler, and an electromagnetic wave absorbing material; wherein the sealing material layer contains bubbles in a range of 1 〇 to 3 〇% by volume, and It contains a range of 5G to fine ppm depending on the mass ratio. 2. The glass member having the sealing material layer of the item i, wherein the size of the bubble is in the range of 〇. 3. The glass member having a sealing material layer according to the patent application No. 13 Ge 2, wherein the low-expansion filler material is derived from oxidizing, oxidizing, zirconium dioxide, strontium ruthenate, cordierite, zirconium phosphate Choose at least the compound, soda lime glass and shed stone acid glass! Material composed of the foregoing The glass material for sealing contains the above-mentioned low-expansion filler in the range of the volume ratio. 4. The glass member having a sealing material layer according to any one of the above-mentioned items of claim 1, wherein the electromagnetic wave absorbing material is selected from the group consisting of Fe, cr, ^^, (^, at least metal or containing The above-mentioned metal compound is composed of a compound of the above-mentioned metal, and the glass material for sealing contains the electromagnetic wave absorbing material in the range of 〇·1 to 1% by volume. The glass member of the sealing material layer, the sealing glass is made of tin-phosphate glass structure 33 201043586. 6. A method for manufacturing a glass member having a sealing material layer, characterized in that the glass has a sealing area A sealing glass material layer containing a sealing glass, a low-expansion filler, and an electromagnetic wave absorbing material is formed on the sealing region of the substrate. Then, the sealing glass material layer is fired to form a volume ratio of 10 to 30. a bubble of a range of %, and a layer of a sealing material containing carbon in a range of 50 to 200 ppm by mass. 7. An electronic device characterized by having: a first glass The plate plate has an element forming region having an electronic component and a first sealing region provided on an outer peripheral side of the element forming region, and a second glass substrate having a first sealing region corresponding to the first glass substrate. a sealing region, wherein a surface of the second sealing region is disposed to face a surface of the first glass substrate having the ith sealing region; and a sealing layer is formed by the second glass substrate and the first surface (2) A method of sealing between glass substrates is formed between the first sealing region and the second sealing region, and is provided by a molten fixing layer of a sealing glass material containing a sealing glass, a low expansion filler, and an electromagnetic wave absorbing material. The above-mentioned sealing layer contains air bubbles in a range of 1 〇 to 35 〇 / 依 in terms of volume ratio, and the size of the aforementioned air bubbles is called a claw range. 8. The electronic device according to claim 7 At least one of the first glass substrate and the second glass substrate has a conductive film formed on a surface having the sealing region and A film of at least i 34 201043586 selected from the insulating film. 9. A method of producing an electronic device, comprising: preparing a first glass substrate, wherein the first glass substrate has an element formation region having an electronic component, and a first sealing region provided on an outer peripheral side of the element forming region; and a second glass substrate having a second sealing region and a sealing material layer; wherein the second sealing region corresponds to the first glass substrate The first sealing region is formed on the second sealing region, and is composed of a firing layer of a sealing glass material containing a sealing glass, a low-expansion filler, and an electromagnetic wave absorbing material, and The air bubble is contained in a range of 10 to 30% by volume, and contains carbon in a range of 50 to 200 ppm by mass; _ the first glass substrate and the second glass substrate have a first sealing region The surface is opposed to the surface having the second sealing region, and is laminated via the sealing material layer; and then passes through the first glass In the plate or the second glass substrate, electromagnetic waves are irradiated onto the sealing material layer to perform localized heating, and the sealing material layer is melted to form a seal for sealing the first glass substrate and the second glass substrate. Floor. 10. The method of manufacturing an electronic device according to claim 9, wherein the bubble size present in the sealing material layer is in the range of 0.1 to 50 μm. 11. The method of manufacturing an electronic device according to claim 9 or claim 10, wherein the sealing layer comprises a gas 35 201043586 bubble in a range of 10 to 35% by volume, and the size of the bubble is in the range of 0.1 to ΙΟΟ μηη. The method of manufacturing an electronic device according to any one of claims 9 to 11, wherein the sealing material layer has a thickness of 密封2, and the sealing layer has a thickness of Τ2 The layer has a film thickness Τ2 of 0.9 Å or more and a range of Ι.ΙΤρΧ. 13. The method of manufacturing an electronic device according to any one of claims 9 to 12, wherein the sealing layer is formed when the volume of the sealing material layer is 乂, and the volume of the sealing layer is V2. It has a volume ν2 of more than 1\^ and ι.Μνρχ. The method of manufacturing an electronic device according to any one of claims 9 to 13, wherein at least one of the first glass substrate and the second glass substrate has a surface formed on a surface having the sealing region At least one selected from the group consisting of a conductive film and an insulating film. The method of manufacturing an electronic device according to any one of claims 9 to 14, wherein the laser light is irradiated onto the sealing material layer to be melted. 36