TW201034846A - Glass member with seal-bonding material layer and method for producing same, and electronic device and method for manufacturing same - Google Patents

Abstract

Seal-bonding properties and reliability of an electronic device are improved by increasing bonding strength to a glass substrate with good reproducibility during laser seal-bonding. A glass substrate (3) has a sealing region. The sealing region is provided with a seal-bonding material layer (5) that is a fired layer of a seal-bonding glass material containing a seal-bonding glass, a low expansion filler and a laser absorbent. The seal-bonding glass contains, on a mass basis, 20-68% of SnO, 0.5-5% of SnO2 and 20-40% of P2O5. The seal-bonding material layer (5) has a residual carbon content of 20-1,000 ppm on a mass basis. The glass substrate (3) and a glass substrate (2) having an element formation region that is provided with an electronic element are stacked together, and the seal-bonding material layer (5) is melted by irradiation of laser light (6), so that the substrates (2, 3) are seal-bonded with each other.

Description

201034846 VI. Description of the Invention: [Technical Field] The present invention relates to a glass member having a sealing material layer, a method of manufacturing the same, an electronic device, and a method of manufacturing the same.

L·. J Background of the invention, such as an organic EL display | § (Organic Electro-Luminescence Display: OELD), a plasma display panel (PDP), a liquid crystal display device (LCD), etc. The glass substrate of the element for the light-emitting element and the glass substrate for sealing are disposed to face each other, and the light-emitting element is sealed by a glass package in which the two glass substrates are sealed (see Patent Document 1). In addition, a Dye-sensitized Solar Cell such as a dye-sensitized solar cell is also reviewed for the application of a glass package in which a solar cell element (photoelectric conversion element) is sealed by using two glass substrates. Refer to Patent Document 2). A sealing material for sealing between two glass substrates is used, for example, a sealing resin or a sealing glass. Since an organic EL (OEL) element or the like is easily deteriorated by moisture, a sealing glass excellent in moisture resistance or the like is used. Because the sealing temperature applied by the sealing glass is 400 to 600. (: The right and left, when the heat treatment is performed using a normal baking furnace, the characteristics of the electronic component such as the OEL element are deteriorated. Therefore, there is an attempt to arrange a laser between the sealing regions provided in the peripheral portion of the two glass substrates. The glass material layer for sealing of the absorbing material is irradiated with laser light, and the sealing glass material layer is heated by 201034846 to be dazzled, melted, and sealed (see Patent Documents 1 and 2). The seal (laser seal) suppresses the thermal influence on the electronic component portion. However, on the other hand, in the case of the conventional sealing glass (glass dielectric), it is difficult to sufficiently increase the bonding strength between the sealing layer and the glass substrate. The situation will be a cause of lowering the reliability of electronic devices such as FPDs, solar cells, etc. The sealing glass for laser sealing (glass medium) is such as pb-based glass powder, Sn0-P205-based glass powder, Bi2〇3_B2〇 Review of the use of the 3 series of glass powder (see Patent Document 3) and V205-based glass powder (see Patent Document 1), etc. Among these, SnO-P2〇5-based glass powder system It is a preferred material for a glass medium for laser sealing from the viewpoint that the softening point is low and the influence on the environment and the human body is small. However, it is conventionally known that only SnO-P2〇5 for heating by a baking furnace is used. The glass medium is used as a glass medium for laser sealing, and the bonding strength between the sealing layer and the glass substrate cannot be sufficiently improved. For example, Patent Document 4 describes that SnO-P2〇5 which is suitable for heating in a baking furnace is described. It is a glass medium, but it is composed of such a SnO-P2〇5-based glass, and it is difficult to sufficiently improve the adhesion strength to the glass substrate by laser heat treatment. This case is considered to be due to heating and laser heating in a firing furnace. The smelting conditions of the glass medium to be subjected to the singularity and the like are different. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1 Patent Application Patent Publication No. 2006-524419 Patent Document 2: Patent Publication No. 2008-115057 3: Japanese Patent Laid-Open Publication No. Hei 2 〇〇 〇 〇 〇 〇 2010 2010 34 34 34 34 34 34 34 34 34 34 34 34 34 34 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The object of the present invention is to provide a reproducible glass, a glass member having a sealing material layer and a method for producing the same, and a method for producing the same, and a method for producing the same. An electronic device capable of improving sealing reliability and mechanical reliability by improving the bonding strength between the rhing layer and the glass substrate, and a method of manufacturing the same. The method for solving the problem is a glass member having a sealing material layer according to an aspect of the present invention. Having a substrate and a sealing material layer having a sealing region; the dense riding layer is disposed on the sealing region of the glass plate and comprising a sealing glass, a low expansion filler, and a laser The sealing material is composed of a fired layer of a glass material for sealing; wherein the sealing glass contains: 20 to 68% of Sn 〇, 〇 5 to 5% of % 〇 2 and 2 〇 to 4 〇 % by mass ratio.残留 'And the material seal (4) layer of residual carbon in proportion to the ratio, in the range of 20 ~ 1000 ppm. A method of manufacturing a glass member having a sealing material layer according to an aspect of the present invention includes the steps of: preparing a glass substrate having a sealing region; and sealing glass, a low expansion filler material on the sealing region of the glass substrate And a step of applying a coating of a glass material for sealing a laser absorbing material, wherein the sealing glass comprises: 2 〇 to 68% of SnO, 0.5 to 5% of Sn02, and 20 to 40% by mass.卩2〇5; and the coating layer of the paste 5 201034846 is fired to form a sealing material layer having a residual carbon amount in a range of 20 to 1000 ppm by mass. An electronic device according to another 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 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 sealing layer is the first surface of the first glass substrate The sealing region and the second sealing region of the second glass substrate are formed to be sealed while a gap is formed in the element forming region, and the sealing layer is made of a sealing glass or a low expansion filler. And the 'refining and fixing layer of the glass material for sealing the laser absorbing material; wherein the sealing glass according to the mass ratio' contains: 20 to 68% of SnO, 〇.5 to 5% of Sn02 and 20 to 40% P2〇5, and the amount of residual carbon in the sealing layer is in the range of 20 to 1000 ppm by mass. A method of manufacturing an electronic device according to another aspect of the present invention, comprising: a step of preparing a first glass substrate, the first glass substrate having: an element formation region having an electronic component; and a periphery of the component formation region a first sealing region on the side; a step of preparing a second glass substrate including a second sealing region and a sealing material layer, wherein the second sealing region corresponds to the first sealing region of the first glass substrate; and the sealing material layer It 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 a laser absorbing material, and the residual carbon amount is in a range of 20 to 1000 ppm in terms of mass ratio. The sealing glass contains: 20 to 68% of SnO, 0.5 to 5% of Sn02, and 20 to 40% of P205 according to the mass ratio of 201034846; in the case where a gap is formed in the element forming region, the a step of laminating the first glass substrate and the second glass substrate in a sealing material layer; and irradiating the sealing material layer with laser light through the second glass substrate; The sealing material layer is melted to form the sealing step of the sealing layer between the first glass substrate and the second glass substrate step. EFFECT OF THE INVENTION According to the glass member having a sealing material layer and a method of manufacturing the same according to the aspect of the invention, when laser sealing, reproducibility improves the adhesion strength between the glass substrate and the sealing layer. Therefore, according to the electronic device of the present invention and the method of manufacturing the same, the sealing reliability and mechanical reliability of the electronic device 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. 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 a first glass substrate used in the manufacturing steps of the electronic device shown in Fig. 2. Fig. 4 is a cross-sectional view taken along line A-A in Fig. 3. Fig. 5 is a plan view showing a second glass substrate used in the manufacturing steps of the electronic device shown in Fig. 2. Fig. 6 is a cross-sectional view taken along line A-A in Fig. 5. 7 201034846 L square package method; j used to implement the invention

The following description will be made with reference to the drawings for carrying out the invention. 1 is a view showing a structure of an electronic device according to an embodiment of the present invention, FIG. 2 is a view showing a manufacturing step of an electron split, and FIGS. 3 to 6 are views showing a glass substrate used for the above-described electronic cracking. Constructed map. The electronic device 1 shown in Fig. 1 constitutes an illumination device using an FPI, such as an OELD, a PDP, or an LCD, an OEL element, a light-emitting element, 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 including an element formation region 2a having an electronic component. 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 has a thermal expansion coefficient of about 35 to 4 〇x1 (about T7/°C. The soda lime glass has 85 to 9 〇xl (a thermal expansion coefficient of about T7/°C is in the element formation region 2a of the first glass substrate 2). Forming an electronic component that cooperates with the electronic device 1. For example, if it belongs to OELD or OEL illumination, an OEL component is formed, if it belongs to a PDP, a plasma light-emitting component is formed, if it belongs to an LCD, a liquid crystal display component is formed, and if it belongs to a solar cell, a dye sensitive is formed. An electronic component such as a light-emitting element such as an OEL element or a solar cell element such as a dye-sensitized photoelectric conversion unit is provided with various known structures, and is not limited to the element structure. The electronic component is preferably an organic EL (OEL) element or a solar cell element. The first glass substrate 2 has a first sealing region provided on the outer peripheral side of the region 2a of the element shape 201034846 as shown in Figs. 3 and 4 . The first sealing region 2b is set to surround the element forming region 2a. The second glass substrate 3 has a second sealing region 3a as shown in Fig. 5. The second sealing region 3a corresponds to the first sealing region 2 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 opposed to each other, and the sealing layer 4 is formed as will be described later. The formation region (the formation region of the sealing material layer 5 in the second glass substrate 3). The first glass substrate 2 and the second glass substrate 3 are arranged to face each other so as to form a gap in the element formation region 2a. The space between the first glass substrate 2 and the second glass substrate 3 is sealed by the sealing layer 4. That is, the sealing layer 4 is a sealing region 2b of the first glass substrate 2 and a sealing region 3a of the second glass substrate 3. The sealing is performed by providing a gap in the element forming region 2a. The electronic component formed in the element forming region 2a is made of the first glass substrate 2, the second glass substrate 3, and the sealing layer. The glass panel is configured to be hermetically sealed. The sealant layer 4 is composed of a refining and fixing layer which is formed on the sealing region 3a of the second glass substrate 3 by the laser light 6. The sealing material layer 5 is melted and fixed to the first glass In the sealing region 3a of the second glass substrate 3 used for the production of the electronic device 1, as shown in Figs. 5 and 6, a frame-shaped sealing material layer 5 is formed. The sealing material layer 5 ′ formed in the sealing region % of the second glass substrate 3 is melt-fixed to the first glass substrate 2 as shown in the second (c) and (d) by the heat of the laser light 6 . The sealing region 2b' forms a sealing layer 4 that seals a space (component arrangement space) between the first glass substrate 2 and the second glass substrate 9 201034846. The sealing material layer 5 contains a sealing glass (glass medium). A glass material fire-extinguishing layer for sealing a laser absorbing material and a low-expansion filler. The sealing glass material is blended with the laser absorbing material and the low expansion filler in the sealing glass of the main component. The glass material for sealing may contain an additive material other than these as needed. The sealing glass of the main component of the sealing glass material may be a tin-phosphate type consisting of 20 to 68% of Sn, 〇5 to 5% of Sn02, and 20 to 40% of P2〇5. SnO-P2〇5 series) glass. The sealing glass content of the main component of the glass material for sealing is preferably 40 to 90 by volume with respect to the glass material for sealing, depending on the amount of the laser absorbing material and the low-expansion filler. /. More preferably 45 to 8 vol%. Further, the sealing glass (glass medium) is preferably in the form of a powder, and the maximum particle diameter is preferably 1 μm or less, more preferably 50 μm or less. In the sealing glass for laser sealing (face medium), in order to control the blooming temperature of the glass, it is preferred that the glass itself does not absorb the laser (which is a transparent glass). The laser sealing step is performed with good reliability by utilizing the type and amount of the laser absorbing material added to the sealing glass, and the like. The sealing glass (glass medium) is intended to suppress the impact on the glass substrates 2, 3, and the temperature is preferably lower. Moreover, the impact of financial considerations on the environment and the body is best not included in the hunger, hunger and so on. The Siwei Nuori medium is in line with this record. σ The sealing glass used in the present embodiment (SinO is a component that makes the gambling point, and is in the range of 20 to 68 in the sealing material. Full 2 () quality. / : 201034846 The softening temperature will become higher. 'The sealing at low temperatures tends to be difficult. Moreover, it is necessary to increase the output of the laser light 6 in order to soften the glass. As a result, the glass substrates 2, 3 are prone to occur. If the content of SnO exceeds 68% by mass, it will not be vitrified. The content of SnO is preferably in the range of 3 〇 to 65% by mass.

Sn〇2 is a component which stabilizes glass, and is contained in the sealing glass in the range of 0_5 to 5% by mass. When the content of sn 〇 2 is less than 5% by mass, the glass stability is lowered, devitrification is likely to occur, and the opaque substance is easily mixed in the glass production. Further, when the laser is heated, Sn02 is separated and precipitated in the glass which is softened and melted, and the fluidity is impaired, so that the airtightness is easily lowered. When the content of Sn 〇 2 exceeds 5% by mass, Sn 〇 2 is easily precipitated from the molten glass during production, and stable glass cannot be obtained. The Sn2 content is preferably in the range of 1 to 3.5% by mass in consideration of factors such as stability and fluidity of the glass. ΡΖ〇5 is a component for forming a glass skeleton and is contained in the range of 20 to 40% by mass in the sealing glass. If p2〇5 contains less than 2〇 mass. /. It will not be vitrified. If the content of P2〇5 exceeds 4〇 mass. /. There is a possibility that the weather resistance of the characteristic defects of the acid-filled glass is deteriorated. When the stability and weather resistance of the glass are considered, the P2〇5 content is preferably in the range of 25 to 40% by mass. Here, the mass ratio of SnO to Sn02 in the glass medium can be determined as follows. First, after the acid decomposition of the glass medium (low-melting glass powder), the total amount of Sn atoms contained in the glass medium is measured by ICP emission spectrometry, because Sn2+ (SnO) is carried out by the molybdenum titration method using the acid decomposition product. Therefore, Sn4+(Sn02) can be obtained by subtracting the amount of Sn2+ obtained here from the total amount of Sn atoms. 11 201034846 The glass-based glass formed by the above three components has a low transfer point and is suitable for a low-temperature sealing material ‘but may contain, for example, SiO 2 , ZnO, B 2 〇 3,

Al2〇3, W03, Μο〇3, Nb2〇5, Ti02, Zr〇2, Li2〇, Na2〇, K20 'Cs20, MgO, CaO, SrO 'BaO and other optional components. However, if the individual content of each component or the total content of any component is too large, the glass will be unstable, and the glass will be deficient in the production of glass, and even if the degree of transparency is not lost, the tendency of glass crystallization will still be If the glass is too strong, the glass will crystallize without being softened, and there is a possibility that the glass substrates 2 and 3 cannot be adhered to each other. From this point of view, the total content of the above optional components is preferably set to 15% by mass or less. In the optional component, the content of the component of the 'Si〇2-forming glass skeleton' is preferably set to 10 mass. /❶The following. Further, it is preferable to form a knife with 〇2 as necessary and to contain 0.1 to 5% by mass. Such as: ZnO, B2〇3, AI2O3, W〇3,

Mo〇3, Nb205, Ti〇2, Zr〇2, Li20, Na20, K20, Cs20,

MgO, CaO, SrO, BaO, and the like are components which stabilize the glass, and the respective contents are preferably set to 10% by mass or less. If the individual content of each component exceeds 1 〇 mass. /. There is a possibility that the lens will be devitrified at the time of glass production, and there is a possibility that the crystallization tendency of the glass tends to be strong. Among the above-mentioned arbitrary components, such as Zn〇, B203, Al2〇3, W03, and M0O3, in addition to glass stabilization, there is an effect of lowering the coefficient of thermal expansion of the glass. It is preferable to use ZnO as an essential component and to contain 2 to 6% by mass. Further, such as: Nb205, Ti02, Zr02, etc. have an effect of improving chemical durability. For example, Li2〇, Na20, K20, Cs2〇, etc. have the effect of lowering the softening point of the glass and further improving the fluidity. 12 201034846 For example: MgO, CaO 'SrO, BaO, etc. have the effect of adjusting the point-degree of breakage and adjusting the coefficient of thermal expansion. The content of each of the components is preferably as described above, and the total content of the optional components is preferably not more than 15% by mass, more preferably 10% by mass or less. The glass material for sealing contains a low expansion filler. Preferably, the low-expansion filler is selected from at least one group consisting of, for example, cerium oxide, aluminum oxide, zirconium oxide, cerium-zirconium cordierite, zirconium phosphate-based compound, soda-lime glass, and borosilicate glass. . Examples of the zirconium phosphate-based compound include (ZrO)2P2〇7 and ΑΖΓ2(ρ〇4)3 (α is selected from Na, and at least one selected from the group), NbZr2(P04)3, and Zr2 ( W 〇 3) (P 〇 4) 2, or these composite compounds. "Low expansion filler" means a material having a lower coefficient of thermal expansion than a sealing glass which is a main component of a sealing glass material. The content of the low-expansion filler is appropriately set depending on the thermal expansion coefficient of the sealing glass and the thermal expansion coefficient of the glass substrates 2 and 3. The low-expansion filler is different depending on the thermal expansion coefficient of the sealing glass and the glass substrates 2 and 3, but it is preferably contained in the range of 1 to 50% by volume based on the glass material for sealing. When the glass substrates 2 and 3 are formed of an alkali-free glass (coefficient of thermal expansion: 35 to 40×l (r7/°c)), it is preferred to add a large amount (for example, a range of 3 〇 to 5 〇 vol%) of a low-expansion filler. When the glass substrates 2 and 3 are made of sodium-sprayed glass (thermal expansion coefficient: 85 to 9 _ force. 〇, it is preferable to add a small amount (for example, a range of 15 to 40% by volume) of a low-expansion filler. Further, the low-expansion filler is preferably in the form of a powder, and the maximum particle diameter is preferably 1 μm or less, more preferably 50 μm or less. The glass material for sealing further contains a laser absorbing material. Laser suction 13 201034846 For example, a compound such as Fe, HCQ, NiACuti, or a metal containing an oxide of the foregoing metal is used. The content of the laser absorbing material is preferably set to 0. In the range of 10 vol. /.. If the content of the laser absorbing material is not i_%, the sealing layer (4) may not be sufficient when laser irradiation. If the laser absorbing material contains more than 10% by volume, in the ray When the irradiation is performed, there is a locality near the interface with the second glass substrate 3. In the case of the heat generation, the second glass substrate 3 is broken, and the flow of the It shape or the nine-faced surface material is reduced, which may cause a decrease in the adhesion to the first glass substrate 2. The amount of the laser absorbing material 3 is reduced. Preferably, X is in the range of 1 to 9 vol%. Further, the laser absorbing material is preferably in a powder form, and the maximum particle diameter is preferably 5 Å or less, more preferably 2 Å or less. The tin-phthalic acid-based glass medium used is a sealing material for low-temperature heating because of its transparency and low glass transition point. S, when the sealing material layer 5 is irradiated with the laser light 6 to form the sealing layer 4 In the case where the tin-phosphate glass medium (sealing glass) is simply used for the laser sealing, the bonding strength between the glass substrates 2, 3 and the sealing layer 4 cannot be sufficiently improved. This phenomenon is considered to be because the heating is performed by the firing furnace. In the case of using laser heating, the melting conditions of the glass medium may be different. The bonding strength between the glass substrate and the glass medium is based on the residual strain caused by the difference in thermal expansion, and the glass base. The reaction with the glassy medium is generally carried out by heating in a baking furnace, and the reaction layer is formed at the interface between the glass substrate and the glass medium (sealing layer) regardless of the type of the glass substrate and the glass medium. The use of chemical bonding can increase the adhesion strength by 201034846. In other words, the sealing step of heating by the firing furnace is used, because there is sufficient time for forming the reaction layer at the subsequent interface, so that sufficient bonding strength can be obtained. The sealing step of the radiation heating is performed by irradiating the laser beam 6 while scanning along the frame-shaped male and sealing material layers 5. The sealing material layer 5 is sequentially melted from the portion irradiated by the laser light 6. And will be quenched and solidified as the irradiation of the laser light 6 is completed. In this case, the formation time of the reaction layer cannot be sufficiently obtained in the laser sealing step. Therefore, the glass bead having a composition of three components such as SnO, Sn2, and he»5 can not sufficiently improve the bonding strength between the glass substrates 2, 3 and the sealing layer 4 when the laser is reached or sealed. In the sealing step using laser heating, in order to form a reaction layer on the interface between the glass substrates 2, 3 and the sealing layer 4, an appropriate amount of carbon is left in the sealing material layer (the fired layer of the sealing glass material) 5. It is valid. That is, the carbon remaining in the sealing material layer 5 formed using the tin-phosphate glass medium has a function as a reducing agent. Therefore, even if the laser seal is melted and cured in a localized glass medium for a short period of time, the tin oxide can be reduced by the residual carbon in the sealing material layer 5, thereby improving the glass substrates 2, 3, and the tin-phosphorus phosphate glass. Reactivity between media. In other words, at the time of laser irradiation, a part of tin oxide can be changed into metallic tin (Sn) by reducing tin oxide (particularly, SnO which is easily reduced) in a tin-scale acid glass medium by residual carbon. The metal tin (tetra) has a property of being easily diffused into the glass substrates 2, 3. Therefore, by presenting a proper amount of metal tin (Sn) in the sealing material layer 5 which is melted by the irradiation of the light 6 , even in the laser sealing step of performing the melt curing of the glass medium between the short time 15 201034846, the subsequent interface can be A reaction layer is formed. Therefore, the adhesion strength between the glass substrates 2, 3 and the tin-phosphate glass medium (sealing layer 4) can be improved at the time of laser sealing. The amount of carbon remaining in the sealing material layer 5 (the amount of residual carbon of the sealing material layer 5) is set in the range of 20 to 1 ppm by mass. If the residual carbon amount of the sealing material layer $ is less than 20 Ppm, the ability as a reducing agent is insufficient, and the reduction effect of the above tin oxide cannot be sufficiently obtained. That is, the metal tin cannot be sufficiently formed, and as a result, the adhesion strength between the south glass substrates 2, 3 and the sealing layer 4 cannot be sufficiently extracted. On the other hand, when the residual carbon amount of the sealing material layer 5 exceeds a1000 ppm, the amount of metal tin generated is excessive, and the electric resistance value of the glass is lowered, so that the insulating property of the sealing layer 4 cannot be ensured. This situation will become the cause of various adverse conditions. In other words, in the sealing region 2b of the first glass substrate 2, a wiring for pulling the electrode of the electronic component formed in the element forming region 2a to the outside is formed. Since the excess residual carbon lowers the insulating property of the sealing layer 4, there is a possibility that a defect such as a new route occurs between the wirings formed on the first glass substrate 2 depending on the sealing layer 4'. The effect of improving the adhesion strength between the glass substrates 2, 3 and the sealing layer 4, the insulation of the sealing layer 4, and the like, and the residual carbon amount of the sealing material layer 5 are preferably in the range of 30 to 50 ppm by mass. . Further, the method of controlling the amount of residual carbon in the sealing material layer 5 will be described later. The thickness T1 of the sealing material layer 5 is set to match the required gap between the first glass substrate 2 and the second glass substrate 3 (i.e., the thickness T2 of the sealing layer 4). The Ray·Electric Ten device 1 and the manufacturing steps thereof according to the present embodiment are particularly effective in the case where the thickness T1 of the sealing material layer 201034846 is set to 1 〇μηι or more. Further, it is more preferable to set the thickness Τ1 of the sealing material layer 5 to 10 to ΙΟΟμιη. When the sealing material layer 5 having such a thickness τι is irradiated with the laser light 6 and sealed, according to the present embodiment, the bonding strength between the glass substrates 2, 3 and the sealing layer 4 can be improved, and the glass panel can be lifted. Hermetic sealing and so on. Further, in the case where the residual carbon in the sealing material layer 5 is not limited to the case of using a tin-phosphate glass medium, a case where a glass medium (sealing glass) of another composition (for example, a bismuth system (BisOrBiO3 type) glass medium) is used is also used. effective. That is, when using a mass ratio, it contains 70 to 90% of Bi203, 1-2% of ZnO, and 2 to 12 °/. In the case where the glass medium is formed into a sealing material layer, the same effect as in the case of using a tin-filled glass medium can be expected by leaving an appropriate amount of carbon. The sealing material layer 5 composed of the above-mentioned sealing glass material is formed on the sealing region 3& of the second glass substrate 3 as will be described later. First, a sealing glass material containing your sealed glass (tin-phosphate glass medium), a laser absorbing material, and a low-expansion filler is mixed with a vehide to prepare a sealing material paste. The carrier can be used, for example, to dissolve, for example, methyl cellulose, ethyl cellulose, m-methyl cellulose, oxyethyl cellulose m-vitamin, propyl cellulose, cellulose material m, such as pine oil. In a solvent such as alcohol, butyl carbitol acetate vinegar or ethyl carbitol acetate vinegar, or for example, such as methyl (meth) propionate, methyl (meth) acrylate, (methyl) Acrylic acid, such as butyl acrylate or 2-hydroxyethyl methacrylate, is dissolved in, for example, methyl ethyl ketone, terpineol, butyl carbitol acetate, phenanthrene + bisphenol Among solvents such as acetate. 17 201034846 ^The sealing material __ degree system can be adjusted as long as the corresponding viscosity on the glass substrate 3 is matched with the ratio of the ratio of the binder to the solvent and the ratio of the glass material for sealing to the cutting (four). In the sealing material, it is also possible to add a known additive to the glass paste, such as _, 分 (4). The sealing material _ can be prepared by using a rotary mixer, a feeder, a ball with a wing. In the second glass substrate 3, the sealing material paste is applied in the sealing region, and the coating layer of the sealing material paste is formed. The sealing material paste is used, for example, screen printing. Printing methods such as gravure printing are applied to the second sealing region 3a or applied along the second sealing region using a dispenser or the like. The coating layer of the sealing material paste is applied at a temperature of, for example, 12 Torr or more. It takes 10 minutes or more to dry. The drying step is difficult to remove the solvent in the coating layer. If there is solvent remaining in the coating layer, there is a possibility that the binder component may not be sufficiently removed in the subsequent baking step. The above sealing material The coating layer of the paste is fired to form the sealing material layer 5. The baking step is first to heat the coating layer to a temperature below the glass transition point of the sealing glass (glass medium) which is the main component of the sealing glass material. After removing the binder component in the coating layer, it is heated to a temperature equal to or higher than the softening point of the sealing glass (glass medium), and the sealing glass material is melted and melted onto the glass substrate 3. Thus, a seal is formed. The sealing material layer 5 is formed by using a fired layer of a glass material. The coating layer baking step of the sealing material paste is preferably carried out according to a temperature range of 200 to 500 ° C, more preferably 230 to 430 ° C. The temperature range is implemented. In the step of forming the sealing material layer 5, the following method is employed: 18 201034846 (1) Organic matter or carbon is used as a carbon source and is present in the sealing glass (or sealed) In the glass material, a part of the carbon derived from the carbon source remains; a method of leaving the binder component (organic resin) in the sealing material paste or a part of the carbon derived from the organic solvent, and the sealing material layer 5 Residue In addition, the method of the above-mentioned (1) can be applied to the method in which the amount of residual carbon in the sealing material layer 5 can be in the range of 20 to 1000 ppm by mass. In the method of pulverizing glass, for example, an organic substance such as an alcohol is added as a carbon source. This method is because the alcohol or the like also functions as a pulverization aid, so that the pulverization efficiency of the glass can also be improved. The carbon source added to the carbon source is not limited to organic matter, and may be carbon such as carbon black or graphite. Even if the amount of carbon source such as organic matter or carbon is set to be constant with respect to the sealing glass, the amount of residual carbon remains. In accordance with the firing conditions, the relevant information on the extent to which the added carbon source remains after firing is determined in advance, and the residual carbon content of the sealing material layer 5 is controlled based on this data. In addition, the amount of carbon source added can be set to a certain value, and the firing conditions (temperature, time) can be changed to control the amount of residual carbon. The method of (2) is a method in which a carbon source is not added to the sealing glass, and a part of carbon derived from a binder component (organic resin) or an organic solvent used for gelatinization is left. In this case, the composition of the carrier, the composition ratio of the sealing glass material to the carrier at the time of gelatinization, and the firing conditions, particularly in the temperature range from the burning and decomposition of the resin to the softening of the sealing glass, the temperature rising rate And holding time are important matters. Regarding the carrier used in the production of the sealed paste, the method using the method (1) is not 19, 201034846, and the limitation is particularly limited to the case of the branch of the bismuth (2). For example, it is used in organic solvents such as terpineol, carbamide, and ethyl carbitol acetate. (2) The method of (4) carrier, preferably 0.5 to 5 mass% of deuterated cellulose 'dissolved in a group consisting of pine _, τ carbamide and ethyl carbitol acetate vinegar - an organic solvent, or two or more kinds of mixed refrigerants 95 to 99.5 mass%. Further, as for the gelatinization of the glass material for sealing, it is preferred to carry out the β-β-β I-forming material paste with 85 to 93% by mass of the material and 7 to 15% by mass of the carrier. By using such a carrier or a sealing material paste, the residual carbon amount controllability of the sealing material layer 5 can be improved. The coating layer baking step of the sealing material paste is generally carried out in such a manner that the resin component is completely burned and decomposed in a manner that does not reduce the &' sealing glass material. Specifically, in the temperature region in which the resin is burned or decomposed to a temperature higher than the degree of softening and flowing of the sealing glass, the temperature increase rate is slowed, and the enthalpy is maintained for about 15 hours, thereby promoting the combustion of the resin. ,break down. In the case of the method of (2), an appropriate amount of carbon remains in the sealing material layer 5 by controlling the combustion and decomposition steps of the resin. As described above, the resin component in the carrier is preferably nitrocellulose. Nitrocellulose is burned and decomposed at a temperature in the range of 200 to 250 °C. The temperature at which the sealing glass of the present embodiment softens and flows is 260 to 450. (: range. Therefore, 200 to 450. (: The temperature range is important. The sealing material layer 5 having residual carbon as described above can be obtained by controlling the temperature increase rate of 200 to 450 ° C. Specifically, Preferably, it is in the range of 200 to 450. (: The temperature is raised in the temperature range according to 20 201034846 10 to 35 ° C / min. When the batch furnace or the like is used for firing, the temperature in the furnace is uniform, while remaining in the furnace 200 to 45 (in the case of the TC temperature range, it is preferable to set the holding time to less than 2 minutes. By using such a condition, the residual carbon amount of the sealing material layer 5 can be controlled within a desired range. As shown in Fig. 2(a), the second glass substrate 3 (having a sealing material layer 5) and the first glass substrate 2 (having an element forming region 2a having the element forming region) are used. An electronic device manufactured separately, for example, an illuminating device using FPD or OEL elements such as 0ELD, PDP, LCD, or an electronic device such as a solar cell such as a dye-sensitized solar cell is as shown in Fig. 2(b) It is shown that the second glass substrate 2 and the second glass substrate 3 have several pieces. One surface of the region 2a is laminated with respect to one surface having the sealing material layer 5. The gap is formed in the element forming region 2a of the first glass substrate 2 in accordance with the thickness of the sealing material layer 5. As shown in Fig. 2(c), the sealing material layer 5 is irradiated with the laser beam 6 through the second glass substrate 3. The laser beam 6 is irradiated while being Q-scanned along the frame-shaped sealing material layer 5. The laser beam 6 is not particularly limited. Laser light from, for example, semiconductor laser, carbon dioxide gas laser, excimer laser, YAG laser, HeNe laser, etc. can be used. The output of the laser light 6 is appropriately set in accordance with the thickness of the sealing material layer 5, etc. It is set to, for example, 2 to 15 〇w. If the laser output is less than 2 W, there is a possibility that the sealing material layer 5 cannot be melted. On the other hand, if it exceeds 15 〇w, the glass substrates 2 and 3 are easy. Cracks, breaks, etc. occur. The output of the laser light is preferably in the range of 5 to 100 W. The sealing material layer 5 is sequentially melted from the portion irradiated by the laser light 6 scanned along it, if the irradiation of the laser light 6 ends , it will be cured quickly, and 21 2010 34846 is fixed to the first glass substrate 2. Then, by irradiating the laser light 6 around the entire sealing material layer 5, the second glass substrate 2 and the second glass substrate are formed as shown in Fig. 2(d). Three sealing layers 4 are sealed. Since the sealing material layer 5 using a sealing glass (tin-phosphate glass medium) enhances reactivity with the glass substrate 2 in accordance with residual carbon, even when irradiated with laser light 6 In the short-time melt-solidification step (sealing step), the adhesion between the glass substrate 2 and the sealing glass can be improved. Therefore, the bonding strength between the glass substrates 2 and 3 and the sealing layer 4 can be improved. In this case, an electronic device in which the electronic components formed on the element forming region are hermetically sealed by using the glass panel composed of the first glass substrate 2, the second glass substrate 3, and the sealing layer 4 is used. Further, the glass panel which is hermetically sealed inside is not limited to the electronic device, and can be applied to, for example, the (four) body (difficult) of the electronic department, or the glass element (building material, etc.). The reliability of the electronic device 1 depends on, for example, the hermetic sealing property by the sealing layer*, or the bonding strength between the glass substrates 2, 3 and the sealing layer 4, and the like. According to the present embodiment, an electronic device excellent in reliability can be obtained because the hermetic sealing property and the adhesion strength can be improved! . Here, the paraffin that is layered in the sealing material remains even after the laser seal. Therefore, the sealing layer 4' formed by using the residual amount in the mass ratio of 20 to 1 is the same as the sealing material layer 5 even if the form of carbon is changed. Therefore, according to the sealing layer 4 in which the residual carbon amount is in the range of 2 〇 to 1 〇〇〇, the electronic device (4) can be improved in sealing reliability and mechanical reliability. 22 201034846 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 modifications may be made in the form of the spirit of the invention. (Example 1) Preparation by mass ratio, containing: SnO: 55.7%, Sn02: 3.1%, P2〇5: 32.5%, ZnO: 4·80/〇, Al2〇3: 2.3%, SiO 2 : 1.6% Tin-phosphate glass medium, strontium phosphate ((Zr0)2P207) powder as a low expansion filler, and mass ratio: Fe203: 35%, 0203: 35%, Co203: 20%, MnO: 10% The composition of the laser absorber. In addition, 4% by mass of nitrocellulose as a binder component was dissolved in 96% by mass of a solvent composed of butyl carbitol acetate to prepare a carrier. A tin-phosphate glass medium was produced as follows. First, the glass is dissolved in a manner to achieve the above composition ratio to obtain cullet. Next, the cullet was pulverized using an oxidized Ming ball mill. At this time, the pulverization aid added 2 cc of ethanol to the glass lkg. Next, classification was carried out by means of a gas current classifier with a maximum particle diameter of 8 μm to obtain a target tin-acid-based glass medium. Then, 56 parts by volume of the tin-phosphate glass medium, 42% by volume of zirconium phosphate powder, and 2% by volume of the laser absorbing material were mixed to obtain a glass material for sealing (thermal expansion coefficient: 47 x 10 7 / ° C). The sealing glass material 80% by mass and 20% by mass of the carrier were mixed to prepare a sealing material paste. Then, the sealing material 23 201034846 paste was applied by screen printing in the outer peripheral region of the second glass substrate (size: 90×90×〇.7 mmt) composed of the non-experimental glass (thermal expansion coefficient: 38 χ 10·7 /° () ( Line width: 500 μm) After drying, drying was carried out under conditions of 120 ° 匸Χίο. The dried sealing material paste was applied to the layer, and the temperature was raised to 2.5 at a temperature increase rate of 〇/min. (:, at this temperature After the debonding agent treatment was carried out for 4 minutes, the temperature was raised by 5° (2/πΰη was heated to 430 ° C, and the temperature was maintained for 10 minutes to be fired. Thus, the film thickness was formed into (9) The amount of residual carbon in the sealing material layer is 200 ppm. The amount of residual carbon in the sealing material layer is a value measured using a carbon and sulfur analyzer EMIA_32〇v (trade name, manufactured by Horiba, Ltd.). In the same manner, the second glass substrate having the above-mentioned sealing material layer and the second glass substrate having the element forming region (the region where the OEL element has been formed) (the alkali-free composition of the same shape and the same shape as the second glass substrate) Glass house The substrate (the substrate) is laminated, and then the laser material (semiconductor laser) having a wavelength of 94 〇 nm and outputting 25 W is irradiated at a scanning speed of 1 〇//s through the second glass substrate to the sealing material layer, thereby sealing. The material layer (4) was cooled and solidified, and the first glass substrate and the second glass substrate were sealed. The amount of residual carbon in the sealing layer was measured in the same manner as the sealing material layer, and it was confirmed that the sealing material layer remained. The amount of carbon is equal. In the latter, the electronic device for sealing the element forming region by the glass panel is examined. (Examples 2 to 4) In addition to the composition of the tin-disc glass medium, low expansion filling The type of the material, the type of the laser absorbing material, and the ratio of the blending materials are changed to the conditions shown in Table ,, and the rest are the same as the modulating sealing material paste of the embodiment. In addition to using the sealing material paste, the sealing material will be sealed. The material layer _ carbon retention control method was changed to 24 201034846 except for the method shown below, and the formation of the sealing material layer for the second glass substrate, the first glass substrate and the second glass were carried out as in the first embodiment. Laser sealing of the board. In the evaluation of the characteristics described later, an electronic device that seals the element forming region by the glass panel in this manner is provided. The residual carbon amount of the sealing material layer is 45 〇 ppm in Example 2, and Examples 3 is 70 ppm, and Example 4 is 850 ppm. The residual carbon amount is measured as in Example 1. In Example 2, the residual carbon amount of the sealing material layer was controlled as follows. When tin-phosphate glass was used The medium, the low-expansion filler, and the laser absorbing material are mixed to form a glass material for sealing, and blended into a blackening agent as a reducing agent. The blending amount of carbon black is set to 5 for the sealing glass material. 〇〇PPm. A coating layer for forming a sealing material paste as in Example 1 except for using such a sealing glass material (dried by rcxi〇min). The dried (4) paste coating layer is heated to 230 at a heating rate of 8 ° C / min, held at this temperature for (9) minutes, and then de-bonded, and then heated to a heating rate of 8 t / min to 43〇t, and baked at this temperature for 10 minutes. In Example 3, the residual carbon amount of the sealing material layer was controlled as follows. A coating layer of a sealing material paste is formed as in the embodiment. The sealing material paste was prepared by mixing 84% by mass of the sealing glass material with the carrier 丄6 f amount%. The coating layer was dried at 120 ° C x 1 min. In addition, ethanol was not used in the pulverization of cullet. The dried sealing material paste was coated with >#, heated to a temperature of 25 ° C / min to 43 ° C, and kept at this temperature for 1 G minutes * baking. In Example 4, residual carbon amount control was carried out in accordance with the conditions as in the examples. At this time, the blending amount of carbon black was set to 1000 ppm in the glass material for sealing relative to 25 201034846. In Examples 2 to 4, the residual carbon amount of the sealing layer was the same as that of the sealing material layer. (Examples 5 to 6) The tin-filled glass medium, the low-expansion filler, and the laser absorbing material shown in Table 1 were prepared and mixed by the composition ratios shown in Table 1, respectively. Glass material for sealing. The sealing glass material 82% by mass was mixed with 18% by mass of the carrier of Example 1, to prepare a sealing material paste. Then, in the outer peripheral region of the second glass substrate (size: 10〇xl〇〇x〇.55mmt) composed of soda lime glass (thermal expansion coefficient: 87xi〇_7/°c), each sealing material paste was used in the screen. After the printing method was applied (line width: 5 〇〇 gm), it was dried by 120 ° C for 10 minutes. Each of the coating layers (after drying) of the above-mentioned sealing material paste was subjected to baking to form a sealing material layer having a film thickness T1 of 60 μm. Regarding the method of controlling the residual carbon amount of the sealing material layer, Example 5 is as in Example 3, and Example 6 is as in Example 1. The residual carbon content of the sealing material layer of Example 5 was 100 ppm, and Example 6 was 150 ppm. Next, a second glass substrate having a sealing material layer and a second glass substrate having a device forming region (a region in which an OEL element has been formed) (a substrate made of soda lime glass having the same composition and shape as the second glass substrate) ) Implementing a layer. Next, the laser light (semiconductor laser) having a wavelength of 940 nm and outputting 40 W is irradiated to the sealing material layer through the second glass substrate to a sealing speed of 5 mm/s, and the sealing material layer is melted and rapidly solidified. 1 The glass substrate and the second glass substrate are sealed. The residual amount of the layer is the same as that of the sealing material layer. In the characteristic evaluation sheet described later, an electronic device that seals the element forming region by using the glass panel 2010 20108 glazing panel is provided. (Comparative Example 1) A tin-phosphate glass medium having the same composition as in Example 1 was used. The glass material for sealing was prepared and sealed as in Example 1.

The formation of the sealing material layer for the second glass substrate, W, and the laser sealing of the first glass substrate and the second glass substrate. The method for controlling the amount of the sealing material layer is the same as in the second embodiment, and is used in the lacquer m.

A method of blending carbon black into the material. However, the blending amount of carbon black was set to 1500 ppm with respect to the glass material for sealing. In the evaluation of the characteristics described later, an electron penetration (Fig. 2) in which the element forming region was sealed by the glass panel was provided in a barren manner (Comparative Example 2), and V205 was prepared by mass ratio: 44.3%, Sb2〇3: 35 p/P2〇5: I9.7%, Al2〇3: 0.5%, Ti〇2: 〇.4% composed of lanthanide glass. A glass medium and a lead phosphate powder as a low expansion filler. Further, 4% by mass of nitrocellulose as a binder component was dissolved in 96% by mass of diethylene glycol monobutyl ether acetate to prepare a carrier. The lanthanide glass medium is 90 volumes. /. The glass material for sealing was prepared by mixing with the cordierite powder in an amount of 1% by volume. The coefficient of thermal expansion was 74 χ 1 〇 · 7 Γ (:). The cerium sealing glass material was 73% by mass and the carrier 27 mass was used. Then, a sealing material paste was prepared. Then, the sealing material paste was applied by a screen printing method in the outer peripheral region of the second glass substrate composed of the same alkali-free glass as in Example ( (line width w: 500 μm) After that, drying was carried out under the conditions of 12 〇txl 〇 minutes. The coating layer was fired under conditions of 450 〇C x 10 minutes to form a sealing material layer having a film thickness T1 of 60 μm. 27 201034846 Then 'will have a sealing material The second glass substrate of the layer and the W-th glass substrate having the element formation region (the region in which the OLED element is formed) (the glass substrate having the same shape as the first '1) are laminated. Then, the second transmission is performed. The glass substrate is irradiated with laser light having a wavelength of 940 nm and output (... (semiconductor laser) at a scanning speed of 5 mm/s. By melting the sealing material layer and quenching it, the glacial substrate is immersed. The second glass substrate is sealed. In the characteristic evaluation described later, an electronic device that seals the element formation region by the glass panel is provided. Next, the appearance of the glass panels of Examples 1 to 6 and Comparative Examples 2 to 2 is described. The glass substrate was evaluated for cracks. The appearance was observed by an optical microscope and evaluated. The airtightness of each glass panel was measured. The airtightness was evaluated using a helium leak tester. In addition, Example 1 was used. The bonding strength between the sealing layer and the glass substrate and the resistance value of the sealing layer performed by the glass material for sealing used in ～6 and Comparative Examples 1 to 2 were measured as follows. The measurement and evaluation results are as follows. Table 1 and Table 2. The manufacturing conditions of the glass panel are collectively described in Table 1 and Table 2. The method of measuring the adhesion strength of the glass substrate by the sealing glass material is as follows. First, at the first glass substrate end of 30 mm in width In the vicinity of the portion, a sealing material layer having a thickness of 60 μm and a line width of 1 mm was formed using a sealing material paste of each example. The paste coating layer was fired under appropriate conditions. Then, the second glass substrate is placed on the sealing material layer. The second glass substrate is in a different state from the first glass substrate (the first and second glass substrates are in a straight line around the sealing material layer). In the arrangement of the state of the arrangement, the 28 201034846 and the like are subjected to pressurization using a load of 1 〇 kg while irradiating a laser beam having a wavelength of 940 nm at a scanning speed of 10 mm/s on the sealing material layer to perform sealing. The output of the laser light is applied. A value suitable for each material is set. One of the glass substrates of the sample for measuring the strength of the subsequent strength formed by the above is fixed by a jig, and a portion of 20 mm is applied at a speed of 1 mm/min from the sealing layer of the other glass substrate. When the pressure is applied and the sealing layer is broken, the load is evaluated as "adhesion strength". The method for measuring the resistance value of the sealing layer is as follows. First, a glass substrate A in which two 1T tantalum conductive films were formed at intervals of 4 ^ was prepared. Further, a glass substrate B having a film thickness of 60 μm, a width of 1 mm, and a length of 30 mm of a sealing material layer (a sealing material layer formed using each of the sealing material pastes) was separately prepared. Next, the glass substrate A and the glass substrate B are stacked so as to straddle the two layers of the sealing material layer on the electric film. From the side of the glass substrate B toward the sealing material layer, laser light having a wavelength of 940 nm was irradiated and irradiated at a scanning speed of i 〇 mm/s. With respect to the sample for measuring the resistance value formed in this manner, an electrode is connected to two conductive films, and a minute current meter having a bias voltage of 1 〇〇 is used to measure a minute current, and a resistance value is obtained. . In the case where the resistance value between the two ITO conductive films of the glass substrate a before the laser sealing of the reference sample was measured in the nitrogen atmosphere, the measurement was 2·〇χ1〇12 Ω. Regarding the resistance value obtained from each example, the case where the measured value is 2 〇xl 〇 or more is rated as "good (〇)", and the case where the measured value is less than 2·〇Χΐ〇1 Ω is rated as " Bad (X)" and recorded in Tables 1 and 2. 29 201034846 [Table 1] Example 1 Example 2 Example 3 Example 4 Sealed glass (% by mass) SnO 55/7 55.7 67.8 61.2 Sn02 3.1 3.1 2.4 1.2 P2〇5 32.5 32.5 29.8 31.8 ZnO 4.8 4.8 — 5.8 ai2o3 2.3 2.3 — Si02 1.6 1.6 Low expansion filler zirconium phosphate zirconium phosphate (1) Cerium oxide + (2) Cordierite zirconium phosphate laser absorption material Fe-Cr-Co-Mn-0 Fe-Cr-Co-Mn-O Fe- Mn-Cu-Al-0 Fe-Cr-Co-Mn-O Glass material for sealing (% by volume) Sealing glass 56 56 49 51.5 Low expansion filler 42 42 (1)40+0)10 46.0 Laser absorbing material 2 2 1 2.5 Residual carbon in the sealing material layer (mass ppm) 200 450 70 850 Glass substrate without glass evaluation results Air tightness 〇〇〇〇 Next strength (g) 150 120 130 140 Resistance value 〇〇〇〇 Substrate crack 〇〇〇〇30 201034846 [Table 2] Example 5 Example 6 Comparative Example 1 Comparative Example 2 SnO 59.3 63.3 55.7 — Sn〇2 0.8 2.5 3.1 — P2〇5 33.3 28.8 32.5 — ZnO 6.0 4.9 4.8 — Sealed glass (quality %) Al2〇3 — 0.5 2.3 0.5 Si02 0.6 — 1.6 — V205 — — — 44.3 Sb2〇 3 — — — 35.1 P2〇5 — — — 19.7 Ti〇2 — — — 0.4 Low Expansion Filler Oxidized Cordierite Zirconium Zirconium Phosphate Laser Absorbing Material Fe-Cr-Co-Mn-0 Fe-Mn-Cu- Al-0 Fe-Cr-Co-Mn-0 — Glass material for sealing (% by volume) Sealing glass 70 78.5 56 90 Low expansion filler 28 20.0 42 10 Laser absorber 2 1.5 2 — Residual carbon in the sealing material layer Amount (mass 15pm) 100 150 1200 — Glass substrate soda lime glass, alkali-free glass, airtightness, evaluation, strength (g) 180 200 180 20, the following results, resistance value 〇〇X 〇 substrate crack 〇〇〇〇

As is apparent from Tables 1 and 2, the glass panels obtained in accordance with Examples 1 to 6 were excellent in appearance and airtightness, and good adhesion strength was obtained. On the other hand, in the glass panel of Comparative Example 1 in which the amount of the sealing material layer was more than 10,000 ppm, it was found that although the strength was good, the insulating property of the sealing layer was lowered. In this case, the wiring formed on the glass substrate is likely to have a problem such as a short circuit 31 201034846. Moreover, the conventional glass panel of Comparative Example 2 using a bismuth-based glass medium is a bonding strength, and the reliability of the glass panel (electronic device) is poor. 0 Industrial Applicability The present invention can be utilized, for example, in a layer having a sealing material. A glass member, and an electronic device such as an organic EL display (four), an electric display panel, (9) a display device such as a display device, or a dye-sensitized solar cell. In addition, the entire contents of the specification, application scope, drawings, and information of the patent application for the application of the patent application filed on December 19, 2, 2011, are included in this case. This book _^ book reveals. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the structure of an electronic device. Fig. 1 is a view showing 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 a first glass substrate used in the manufacturing steps of the electronic device shown in Fig. 2. Fig. 4 is a cross-sectional view taken along line A-A in Fig. 3. Fig. 5 is a plan view showing the second glass substrate used in the steps of the electronic device shown in Fig. 2 and the raw water brewing step. Fig. 6 is a cross-sectional view taken along line A-A in Fig. 5. [Description of main component symbols] 32 201034846 1···electronic device 3a...second sealing region 2··first glass substrate 4...sealing layer 2a...element forming region 5...sealing material layer 2b...first sealing region 6... Laser light 3···2nd glass substrate T1, T2...thickness

Claims (1)

201034846 VII. Patent application scope: 1. 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 of the glass substrate, and It is composed of a fired layer of a sealing glass material containing a sealing glass, a low-expansion filler, and a laser absorbing material, wherein 'the sealing glass contains: sn0, 〇.5~ of 20 to 68 〇/〇 according to the mass ratio. 5% of _2 and 20 to 40% of p2〇5, and the amount of residual carbon in the aforementioned sealing material layer is in the range of 2 (M _ppm by mass ratio. 2. Sealed as in the patent application range W) a glass member of a material layer, wherein the low-expansion filler is composed of cerium oxide, aluminum oxide, zirconium dioxide, cerium lanthanum silicate, cordierite, lanthanum phosphate compound, glass, and silicate glass. The first low-expansion filler is formed in the glass material for sealing. '% by volume 3. ^ Patent application No. 1 or 2 of the glass member having a sealed (four) layer' wherein the laser absorbing material is selected from at least a group consisting of ^& Ni and Cu The gold Mn-Co compound is composed of the above-mentioned laser absorbing material in the range of % of the sealing glass material. The 3-shaped (1) carcass is as claimed in the item (1) of the patent application, and the glass member having the sealing material layer, wherein the sealing glass ZnO, R Γ > λ. ^ is advanced from SiO 2 , 2 3 'Al 2 〇 3, WO"_3,2〇5, Ti〇2, 34 4. 201034846 Zr02, Li2〇, he 2〇, Κ2〇, Cs20, MgO, CaO, SrO and BaO are at least selected from the group. The mass ratio meter has a content range of 15% or less. 5. A method for producing a glass member having a sealing material layer, comprising: a step of preparing a glass substrate having a sealing region; and the aforementioned sealing of the glass substrate as described a step of applying a paste of a sealing glass material containing a sealing glass, a low-expansion filler, and a laser absorbing material, and the sealing glass contains .20 to 68% of SnO and strontium by mass ratio. 5 to 5% of Sn02 and 20 to 40% of P2〇5; and the coating layer of the paste is fired to form a residual carbon amount in a range of 20 to 1 〇〇〇ppm. Step of sealing the material layer. 6. If the patent application scope is 5 A method for producing a glass member having a sealing material layer, wherein a sealing glass containing at least one of an organic substance and a hindrance is used as a carbon source, and in the baking step of the coating layer, A part of the carbon of the source of the slave is left in the layer of the sealing material. 7. The method for producing a glass member having a sealing material layer according to claim 5 or 6, wherein the low expansion filler is from the second oxidation At least one type of composition is selected from the group consisting of Shi Xi, Oxidation, Dioxin, Oxalic Acid, Cordierite, Acidic Cone, Sodium Calcium Glass and Boric Acid Glass, and the aforementioned sealing glass The method of manufacturing a glass member having a sealing material layer according to any one of claims 5 to 7 wherein the material comprises the above-mentioned low-expansion filler. It is composed of a metal selected from the group consisting of Fe Cr, Mn, Co, Ni, and Cu, or a compound containing the above metal, and the sealing glass material is contained in the range of 0.1 to 10% by volume. The method of manufacturing a glass member having a sealing material layer according to any one of claims 5 to 8, wherein the sealing glass system is further from SiO 2 , Zno, B 2 〇 3, and Al 2 . At least 丨3, W〇3, M〇〇3, Nb2 〇5, Ti02, ΖΚ2, Li20, Na20, K2〇, Cs2〇, Mg〇, Ca〇, SrO, and BaO According to the mass ratio, the content range is below 15%. 10. An electronic device comprising: a first glass substrate having an element forming region having an electronic component; and a second sealing region provided on an outer peripheral side of the element forming region; and a second glass substrate; a second sealing region corresponding to the first sealing region of the first glass substrate; and a sealing layer that is the second sealing region of the first glass substrate and the second sealing region of the second glass substrate The sealing layer is formed by providing a gap in the element forming region, and the sealing layer is fused by a sealing glass material including a sealing glass, a low expansion filler, and a laser absorbing material. The sealing layer is composed of: 2 to 68% of SnO, 55 to 5% of Sn 2 and 20 to 40 by mass ratio. /. The amount of residual carbon in the sealing layer in the above-mentioned sealing layer is in the range of 20 to 1 〇〇〇 ppm. 36 201034846 11. As claimed in the patent scope (4) slave electronic device, the towel, the aforementioned sealing glass system further advances from Si〇2, Zn0, b2〇3, Ai2〇3, w〇, Mo〇3 Nb2 05, Ti〇 2. At least a selected species of Zr〇2, Li2〇, Na2Ο, κ2〇, Cs2 O, MgO, CaO, SrO, and BaO is included, and the content ranges from 15% or less in terms of mass ratio. 12. The electronic device of claim 10, wherein the electronic component is an organic EL component or a solar cell component. 13. A method of manufacturing an electronic device, comprising: a step of preparing a first glass substrate, the second glass substrate having: an element formation region having an electronic component; and an outer peripheral side of the component formation region a first sealing region; a step of preparing a second glass substrate including a second sealing region and a sealing material layer, wherein the second sealing region corresponds to the first sealing region of the first glass substrate; and the sealing material layer is formed on The second sealing region is formed of a fired layer of a sealing glass material containing a sealing glass, a low-expansion filler, and a laser absorbing material, and the residual carbon amount is in the range of 20 to 1000 ppm. The sealing glass contains: 20 to 68% of SnO, 0.5 to 5% of Sn02, and 20 to 40 Å/〇 of P205 by mass ratio; in the case where a gap is formed in the element forming region, the sealing material is interposed a step of laminating the first glass substrate and the second glass substrate; and irradiating the sealing material layer with laser light through the second glass substrate to cause the aforementioned Sealing material layer is melted to form the sealing step of the sealing layer between the first glass 37201034846 glass substrate and the second glass substrate step. 14. The method of manufacturing an electronic device according to claim 13, wherein the sealing glass system further comprises from SiO 2 , Zn 0 , B 203 , Al 2 〇 3 , W 03 , Mo 〇 3 , Nb 205 , Ti 〇 2 , Zr 〇 2 At least one selected from the group consisting of Li20, Na20, K20, Cs20, MgO, CaO, SrO, and BaO, and the content range is 15% or less in terms of mass ratio. 15. The method of manufacturing an electronic device according to claim 13 or claim 14, wherein the electronic component is an organic EL device or a solar cell device. 38