TW201105599A - Glass member with sealing material layer attached thereto, electronic device produced using same, and process for producing same - Google Patents

Abstract

In order to inhibit a transparent conductive film from cracking or peeling off the glass substrate constituted of soda-lime glass while preventing the glass substrate from suffering cracking, breaking, etc. during laser sealing, a glass substrate (3) constituted of soda-lime glass has a surface (3a) including a sealing region and has a transparent conductive film (FTO film) (8) formed on the surface (3a). The sealing region has, disposed thereon, a sealing material layer (6) constituted of a burnt layer of a glass material for sealing which comprises a sealing glass, a low-expansion filler, and a laser-light-absorbing material. The sealing material layer (6) has a coefficient of thermal expansion a1, which is equal to or greater than the larger of the coefficient of thermal expansion a2 of the transparent conductive film (8) and a half of the coefficient of thermal expansion a3 of the glass substrate (3) and which is equal to or less than the smaller of 2 times the coefficient of thermal expansion a2 and the coefficient of thermal expansion a3.

Description

201105599 VI. Description of the Invention: [Technical Field, Privet Field to which the Sun and the Moon belong] 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. Background of the Invention A solar cell such as a dye-sensitized solar cell is reviewed for the application of a glass package in which a battery element (photoelectric conversion element) is sealed by two glass substrates (see Patent Document). For a flat-panel display device (FPD) such as an organic EL display (Organic EL display), a plasma display panel (PDp), or a liquid crystal display device (LCD), there are used display elements such as light-emitting elements. The glass substrate and the glass substrate for sealing are arranged to face each other, and the display element is sealed by a glass package in which the two glass substrates are sealed (see Patent Documents 2 and 3). A sealing material which seals between two glass substrates has a tendency to be applied to a sealing glass excellent in moisture resistance. Since the sealing temperature by the sealing glass is 400 to 600. (: The left and right, when the firing is performed using a heating furnace, the characteristics of the electronic device portion such as the dye-sensitized solar cell element or the 0EL element containing the electrolyte are deteriorated. Here, attempts are made to set the periphery of the two glass substrates. A sealing material layer containing a laser absorbing material is disposed between the sealing regions, and then irradiated with laser light to heat and melt to form a sealing layer (see Patent Documents 1 to 3). 201105599 Sealing by laser irradiation ( The laser seal can suppress the thermal influence on the electronic component portion, but on the contrary, it may cause cracking or cracking of the surface substrate, and may even cause difficulty in peeling off the conductive film formed on the surface of the glass substrate. When a laser seal is used, first, a sealing glass material containing a laser absorbing material is baked in a sealing region of a glass substrate to form a frame-shaped sealing material layer. Next, a glass substrate having a sealing material layer is separated. After the sealing material layer is laminated with another glass substrate, laser light is irradiated from one of the glass substrate sides to heat the sealing material layer. When it is melted, the electronic component portion is placed between the glass substrates. It is known to use a glass package for a glass material for laser sealing, especially when the glass substrate is a soda lime glass having a large thermal expansion coefficient. When the light is irradiated, the glass substrate is likely to be cracked or broken, and the glass substrate and the sealing layer are likely to be peeled off. In this case, Patent Document 1 discloses that the difference in thermal expansion coefficient between the glass substrate and the glass substrate is ι〇Μ〇 -7 η: the following glass material for sealing and a glass panel using the same. However, a transparent conductive film is formed on the surface of the glass substrate as a wiring layer for pulling the electrode of the electronic component portion outside the glass panel. It is known that the glass material for sealing which has a difference in thermal expansion coefficient between the glass substrate and the glass substrate is used to suppress cracking and cracking of the glass substrate during laser irradiation, and peeling between the glass substrate and the sealing layer. However, after the laser sealing, the transparent conductive film on the surface of the substrate is liable to be peeled off, which may impair the airtightness of the glass panel. When other system-based transparent conductive films using fluorine-doped tin oxide (FTO) film, laser sealing after peeling easily occurs transparent conductive film electrically case. 4201105599 CITATION LIST Patent Literature

Patent Document 1: Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-524419. Patent Document 3: Japanese Patent Laid-Open Publication No. Hei. The purpose of the present invention is to provide a glass member having a sealing material layer, and when the sealing between the two glass substrates is sealed by a laser, it is possible to prevent occurrence of cracks and breakage of the glass substrate formed of the (four) glass, and An electronic device capable of suppressing cracking of a transparent conductive film_film or peeling from a glass plate and providing a glass member having a layer (4) and (4), a high gas and a vacuum thereof, and a method of manufacturing the same. The second means for solving the problem is to have a sealing material layer, the member is provided with a domain material layer, and the (4) substrate has a surface provided with a sealing region, and is composed of sodium glass; the sealing material layer is formed on ^ The filling material and the mine are composed of a fired layer containing a sealing glass, a low expansion = a sealing glass material for i; the upper glass plate contains (4) _ zone _ the above surface 'formation of doping oxidation _ The coefficient of thermal expansion of the handle layer is one in one, and the core is in the other - ίί Ui "Τ'" y , which is the thermal expansion coefficient α 3 of the above transparent conductive film - value and Μ 5 201105599 Any one of the values of 0.5 times the value of the other value is smaller than any one of the value of the thermal expansion coefficient ^ 2 of the transparent conductive film and the value of the thermal expansion coefficient 3 of the glass substrate. The electronic device according to the aspect of the invention includes the first glass substrate, the second glass substrate, the electronic component portion, and the sealing layer, wherein the first glass substrate includes a surface on which the first sealing region is provided; 2 the glass substrate is provided to correspond to the first sealing region a surface of the second sealing region, wherein the surface is disposed to face the surface of the first glass substrate; the electronic component is disposed between the first glass substrate and the second glass substrate; The layer is formed between the first sealing region of the first glass substrate and the second sealing region of the second glass substrate, and is sealed with a sealing glass and a low expansion filling method. The first and second glass substrates are made of soda lime glass, and the first glass substrate contains the first sealing region, and the first and second glass substrates are made of a molten solid layer. The surface and the at least one of the surface of the second glass substrate including the second sealing region are formed by forming a transparent conductive film made of fluorine-doped tin oxide; the thermal expansion coefficient of the sealing layer is at least The other value is lower than the value of the thermal expansion coefficient "2" of the transparent conductive crucible and the thermal expansion coefficient of the glass substrate 〇: 3 times. Any one of the larger values is a value smaller than the value of the thermal expansion coefficient of the transparent conductive crucible and the value of the thermal expansion coefficient of the glass substrate. The manufacturing method of the electronic device according to the aspect of the invention includes the following step 6 201105599. The first glass substrate is provided. The first glass substrate includes a surface on which the first sealing region is provided, and is made of soda lime glass. a second glass substrate including a surface provided with a second sealing region corresponding to the first sealing region and made of soda lime glass; and the first sealing region of the second glass substrate or a sealing material layer is formed in the second sealing region of the second glass substrate, and the sealing material layer is composed of a fired layer of a sealing glass material containing a sealing glass, a low expansion filler, and a laser absorbing material; The surface of the first glass substrate is opposed to the surface of the second glass substrate, and the first glass substrate is integrated with the second glass substrate via the sealing material layer. Then, irradiating the sealing material layer with the laser light through the first glass substrate or the second glass substrate to melt the sealing material layer to form a sealing layer, the sealing layer being formed on the first glass substrate and the first (2) sealing the electronic component portion provided between the glass substrates, wherein the first glass substrate includes the surface of the first sealing region, and the second glass substrate includes the surface of the second sealing region And forming a transparent conductive film made of fluorine poly-doped tin oxide; the thermal expansion coefficient α 1 of the sealing material layer is greater than or equal to or lower than another value, and the value is higher than that of the transparent conductive film a value larger than a value of a thermal expansion coefficient α2 and a value of 〇·5 times the thermal expansion coefficient α 3 of the glass substrate, and the other value is twice the thermal expansion coefficient of the transparent conductive film, and the aforementioned A value smaller than any one of the values of the thermal expansion coefficient α3 of the glass substrate. Advantageous Effects of Invention According to the aspect of the present invention, a glass member having a sealing material layer and an electron I using the 201105599 D-series glass member and a manufacturing method thereof can prevent cracking of a glass substrate composed of soda lime glass during laser sealing. Defects such as breakage occur, and cracking of the transparent conductive film (FTO film) and peeling from the glass substrate can be suppressed. Therefore, the electronic device and the method of manufacturing the same according to the present invention can improve airtightness and reliability. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an electronic device according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing an example of the configuration of an electronic component in the electronic device shown in Fig. 1. 3(a) to 3(d) are cross-sectional views showing the steps of manufacturing the electronic device according to the embodiment of the present invention. Fig. 4 is a plan view showing the first glass substrate used in the manufacturing steps of the electronic device shown in Fig. 3. Fig. 5 is a plan view along the line A-A in Fig. 4. Fig. 6 is a plan view showing a second glass substrate used in the manufacturing steps of the electronic device shown in Fig. 3. Fig. 7 is a front view of the line A-A along the sixth drawing. Fig. 8 is an enlarged cross-sectional view showing a part of the manufacturing steps of the electronic device shown in Fig. 2. Fig. 9 is an enlarged cross-sectional view showing a part of the electronic device shown in Fig. 1. [Embodiment] Embodiments for carrying out the invention 8 201105599 Hereinafter, embodiments for carrying out the invention will be described. Fig. 1 is a view showing an electronic device according to an embodiment of the present invention, and Fig. 2 is a view showing an example of a configuration of an electronic component in the electronic device shown in Fig. 1, and Fig. 3 is an electron according to an embodiment of the present invention. FIG. 4 to FIG. 7 are diagrams showing the configuration of the first and second glass substrates, and FIG. 8 is an enlarged view of a part of the manufacturing steps of the electronic device, FIG. An enlarged view of the sealing portion of the electronic device is shown. The electronic device 1 shown in Fig. 1 is a solar cell such as a dye-sensitized solar cell, or an illumination device (such as OEL illumination) using a light-emitting element such as a FLD or a 0EL element such as a 〇ELD, a PDP or an LCD. By. The electronic device 1 includes a first glass substrate 2 and a second glass substrate 3. The first and second glass substrates 2 and 3 are made of soda lime glass. The soda lime glass system can use various known compositions. The soda lime glass constituting the first and second glass substrates 2 and 3 has a thermal expansion coefficient in the range of, for example, 80 to 90 (X1 〇 force). The electronic component portion 4 corresponding to the electronic device 设有 is provided between the front surface 2a of the first glass substrate 2 and the surface 3a of the second glass substrate 3 opposed thereto. The electronic component unit 4 includes a dye-sensitized solar cell element (dye-sensitized photoelectric conversion element), for example, a solar cell, and an OEL element if it is OELD or 〇EL illumination. The slurry light-emitting element is provided with a liquid crystal display element if it is an LCD. The electronic component unit 4 having a solar cell element such as a dye-sensitized solar cell element or a light-emitting element such as an OEL element has various known structures. The electronic device 1 of this embodiment is not limited to the element configuration of the electronic component portion 4. An example of the structure of the dye-sensitized solar power 201105599 pool element 40 of the electronic component unit 4 is shown in Fig. 2 . In the dye-sensitized solar cell element 4 shown in Fig. 2, a semiconductor electrode (photoelectrode/anode) 42 having a sensitizing dye is provided on the surface 2a of the first glass substrate 2 via a transparent conductive film 41. On the surface 3a of the second glass substrate 3 facing the front surface 2a of the second glass substrate 2, a counter electrode (cathode) 44 is provided via a transparent conductive film 43. The transparent conductive films 41 and 43 are made of a fluorine-doped tin oxide (FT〇) film. The semiconductor electrode 42 is made of a metal oxide such as titanium oxide, cerium oxide, cerium oxide, cerium oxide, tin oxide or zinc oxide. The semiconductor electrode is composed of a porous film of a metal oxide, and a sensitizing dye is adsorbed inside. As the sensitizing dye, for example, a metal complex dye such as a ruthenium complex dye or a hungry complex dye; an organic dye such as a cyanine dye, a merocyanine dye or a triphenyl decane dye can be used. The counter electrode 44 is composed of a film such as platinum, gold, silver or the like. Then, the electrolyte 45' is sealed between the first glass substrate 2 and the second glass substrate 3, and the dye-sensitized solar cell elements 4' are formed by the respective constituent elements. In the dye-sensitized solar cell element 40 shown in Fig. 2, element films such as wiring films or electrode electrodes for forming an element structure are formed on the respective surfaces 2a, 3a of the first and second glass substrates 2, 3, but The configuration of the electronic component portion 4 is not limited to this. For example, it is applied to an OEL element such as OELD or OEL illumination, and the first glass substrate 2 is used as a glass substrate for an element, and a component structure is formed on the surface. The second glass substrate 3 is used as the first glass substrate 3 A sealing member (a glass substrate for sealing) of the element on the surface of the glass substrate 2. The element film constituting the electronic component unit 4 or the element structure constituting the above is formed on at least one of the surfaces 2a and 3a of the first and second glass substrates 2 and 3, 201105599. As shown in FIGS. 4 and 5, the first element forming region formed by at least a part (4A) of the electronic component portion 4 is formed on the surface 2a of the second glass substrate 2 used for the manufacture of the electronic device 1. On the outer circumference of 2A, the old seal area 2B is set. The first sealing region 2B is provided to surround the second element forming region 2A. On the front surface 3a of the second glass substrate 3, as shown in Figs. 6 and 7, a second element forming region 3A corresponding to the first element forming region 2A and one corresponding to the first sealing region 2B are provided. The second sealing region 3B. In the dye-sensitized solar cell element 4A shown in Fig. 2, when the element film or the like is formed on the surface 3a of the second glass substrate 3, the electronic element portion 4 is formed in the second element forming region 3A. Part (4B). When the first glass substrate 2 is used as the glass substrate for the element, the second element forming region 3A of the surface 3a of the second glass substrate 3 becomes the opposing region of the first element forming region 2A. . Further, the second and second sealing regions 2B and 3B serve as a region in which the sealing layer is formed (the second sealing region 3B is a region in which the sealing material layer is formed). The first glass substrate 2 and the second glass substrate 3 are arranged to have a predetermined gap in accordance with the surfaces 2a and 3a formed by the structures 4A and 4B of the electronic component unit 4. The gap between the first glass substrate 2 and the second glass substrate 3 is sealed by the sealing layer 5. In other words, the sealing layer 5 is formed between the sealing region 2B of the first glass substrate 2 and the sealing region 3B of the second glass substrate 3 so as to be sealed by the electronic component portion 4. The electronic component unit 4 is hermetically sealed by a glass panel composed of the first glass substrate 2, the second glass substrate 3, and the sealing layer 5. The sealing layer 5 has a thickness ranging, for example, from 1 〇 to 10 pm. When the electronic component unit 4 uses the dye-sensitized solar cell element 4 or the like, the electronic component unit 4 is disposed in the entire gap between the first glass substrate 2 and the second glass substrate 3. Further, when the electronic component unit 4 is a 〇EL device or the like, a partial space remains between the first glass substrate 2 and the second glass substrate 3. This space can also be kept in its original state, and it can be filled with a transparent resin or the like. The transparent resin can be bonded to the glass substrates 2 and 3, or can be in contact with only the glass substrates 2 and 3. In the sealing layer 5, the sealing material layer 6 formed in the sealing region 3B of the second glass substrate 3 is melted by the laser light, and the splicing and fixing layer is fixed to the sealing region 2B of the second glass substrate 2 Constitute. In other words, the sealing region 3B of the second glass substrate 3 used in the production of the electronic device 1 is formed with a frame-shaped sealing material layer 6 as shown in Figs. 7 and 7 . The sealing material layer 6 formed in the sealing region 3 of the second glass substrate 3 is melted and fixed to the sealing region 2 of the first glass substrate 2 by the heat of the laser light to form the first glass substrate 2 and the first glass substrate 2 2 A sealing layer 5 sealed between glass substrates 3. The sealing material layer 6 is a fired layer of a sealing glass material containing a sealing glass, a low expansion filler, and a laser absorbent. The sealing glass material is blended into 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 other than these as needed. As the sealing glass (glass frit), for example, a low melting glass such as tin-phosphate glass, bismuth glass, vanadium glass or lead glass can be used. Among these factors, it is preferable to use tin-phosphoric acid when considering the sealing properties (adhesiveness) and reliability (adhesion reliability and airtightness) of the glass substrates 2 and 3, and the influence on the environment and the human body. 12 201105599 Sealing glass made of glass or bismuth glass. The tin-acid-breaking glass (glass frit) preferably has a % 〇 of 2 〇 68 68%, a % 〇 2 of 2 摩尔%, and a % of 2 () 〜 4 () 莫% (basic) The composition of the total of 6 χ is (10) mole %). It is a component that makes the glass look low. If the needle no content is not fine %, the glass viscosity will be improved, resulting in an excessively high sealing temperature. On the other hand, if it exceeds 68 mol%, it will not be vitrified. For example, 〇 2 is a component for making the glass stable. When the content of Sn〇2 is less than 0_5 mol%, the Sn 〇 2 is separated and precipitated in the glass which has been softened and smelted 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 easily precipitated from the melting of the low glazing glass. PA is a component for forming a glass skeleton. If the amount of (10) is less than 20 mol%, it will not be vitrified. On the other hand, if the content exceeds 40 mTorr/〇, there is a possibility that the weather resistance of the phosphate glass is deteriorated. Here, the ratio of SnO to Sn〇2 (% by mole) in the glass frit can be obtained as follows. First, the glass frit (low-melting glass powder) was subjected to acid decomposition, and the total amount of Sn atoms contained in the glass frit was measured by ICP emission spectrometry. Next, since Sn2+(SnO) is obtained by deuterium titration using an acid decomposition product, Sn4+(Sn02) can be obtained by subtracting the amount of Sn2+ obtained here from the total amount of Sn atoms. 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, a component that forms a glass skeleton such as SiO 2 or ZnO, B 2 〇 3, Al 2 〇 3, W03, and Mo03. , Nb205, Ti02, 13 201105599

ZrO2, Li20, Na20, Κ2〇, Cs2〇, MgO, CaO, SrO, BaO, etc., which are components which stabilize the glass, are regarded as optional components. However, if the content of the optional component is too large, the glass will be destabilized and devitrification will occur, and the glass transition point and softening point will increase. Therefore, the total content of the optional components is preferably set at 3〇% by mass or less. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is substantially 100% by mass. The silk-based glass (gas medium) preferably contains 7 〇 to 9 〇% by mass of Bi203, 1 to 20% by mass of ZnO, and 2 to 12% by mass. /. The composition of β2〇3 (basically the total amount is set to 100% by mass). The other 2〇3 series belong to the composition of the glass mesh. If the content of Bi2〇3 is less than 70% by mass, the softening point of the low-melting glass is increased, resulting in difficulty in sealing at a low temperature. When the content of Bi2〇3 exceeds 90% by mass, it is difficult to vitrify and the coefficient of thermal expansion tends to be too high.

The Zn lanthanum is a component which lowers the coefficient of thermal expansion and the like. If the content of Zn〇 is >, at 1 mass/〇, vitrification tends to be difficult. If the content exceeds the mass %, the Anu will be reduced when it is formed, and the breakage is likely to occur. The It shape & 3 is a component which expands the glass skeleton and can be made into a glassy range. If the content of b2〇3 is less than 2% by mass, the vitrification tends to be difficult. Conversely, if the content exceeds 12% by mass, the softening point becomes too high, and even if the weight is heavy during sealing, it is difficult to seal the temperature. - The glass-based glass formed by bismuth has a low transfer point and is suitable for low-temperature sealing materials, and may also contain, for example, A1203, ceQ2, (10), Ag20, Moo; Nb2〇5, Ta2〇5, Ga2〇3, sb2〇 3, (10), 〇, κ2〇, 14 201105599

Optional components such as Cs20, CaO, SrO, BaO, W03, p205, SnOx (x system 1 or 2). However, if the content of the optional component is too much, the glass will be unstable and devitrified, and there will be a possibility that the glass transition point or the softening point will rise. Therefore, the total content of the optional components is preferably set at 3〇. quality. /〇 below. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is substantially 100% by mass. The glass material for sealing contains a low expansion filler. The low-expansion filler is preferably selected from the group consisting of: sulphur dioxide, oxidized, oxidized, sulphuric acid, rutile, phosphoric acid, sodium-calcium glass, and borosilicate glass. The zirconium phosphate-based compound is, for example, (ZrO)2P2〇7, NaZr2(P04)3, KZr2(P04)3, Ca〇. 5 Zr2 (P04)3 ,

Na〇.5Nb〇.5Zr1.5(P〇4)3, K〇. sNb〇. 5Zr,.5(P04)3,

Ca〇.25Nb〇.5Zr1.5(P〇4)3 'NbZr(P04)3 'Zr2(W03 )(P04)2 ' and these composite compounds. The "low expansion filler" means a lower coefficient of thermal expansion of a sealing glass having a main component of a sealing glass material. The content of the low-expansion filler is appropriately set so that the thermal expansion coefficient of the sealing glass 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, and preferably contains 20 to 50% by volume based on the glass material for sealing. If the content of the low expansion filler is less than 20% by volume, the adjustment effect of the thermal expansion ratio of the sealing glass material cannot be sufficiently obtained. When the content of the low-expansion filler exceeds 5% by volume, the fluidity of the glass material for sealing may be lowered, and the adhesive strength may be lowered. The sealing glass material further contains a laser absorbing material. The laser absorbing material is a compound selected from the group consisting of Fe, Cr, Μη, Co, Ni, and Cu, and at least one metal or an oxide containing the above metal. The content of the laser absorbing material is preferably in the range of 0.1 to 10% by volume based on the glass material for sealing. If the content of the laser absorbing material is less than 0.1% by volume, the sealing material layer 6 cannot be sufficiently melted at the time of laser irradiation. When the content of the laser absorbing material exceeds 10% by volume, localized heat may be generated in the vicinity of the interface with the second glass substrate 3 during laser irradiation, and the second glass substrate 3 may be broken. Further, the fluidity at the time of melting of the sealing glass material is deteriorated, and the adhesion to the first glass substrate 2 may be lowered. On the surfaces 2a and 3a of the first and second glass substrates 2 and 3, as shown in Fig. 8, transparent conductive films 7 and 8 made of an FTO film are formed. The FTO film is formed by a PVD method such as a sputtering method or a laser ablation method, a CVD method, a spray pyrolysis method, or the like, and has a film thickness of, for example, a range of 0.1 to Ιμηι. The transparent conductive films 7, 8 made of such an FTO film have a function of pulling at least a part of the wiring of the electronic component portion 4 outside the glass panel, and thus are formed so as to straddle the sealing regions 2, 3, respectively. . Therefore, as shown in Fig. 9, at least a part of the sealing layer 5 is in contact with the transparent conductive films 7, 8. Accordingly, when at least a part of the sealing material layer 6 is in contact with the transparent conductive films 7, 8, it is important to suppress peeling of the transparent conductive films 7, 8 when the sealing layer 5 is formed. Further, when the dye-sensitized solar cell element 40 is used in the electronic component unit 4, the wiring is pulled out from only one side of the electronic component unit 4. In such a device configuration, the transparent conductive film formed on one of the surfaces 2a and 3a of the first and second glass substrates 2 is in contact with the sealing material layer 6 or the sealing layer 5. When the electronic component 16 201105599 is to use a light-emitting element such as an OEL element, the transparent conductive film 7 formed on the surface 2& of the second glass substrate 2 is generally in contact with the sealing material layer 6 or the sealing layer 5. Accordingly, the transparent conductive film is formed on the surfaces 2a and 3a including the sealing regions 2β and 3B including at least one of the first and second glass substrates 2. When the sealing material layer 6 is irradiated with laser light to be melted, the sealing material layer 6 is sequentially smelted from the portion irradiated by the laser light scanned along it, and is rapidly solidified as the laser light is irradiated. The film is fixed to the first glass substrate 2. At this time, the transparent conductive films 7, 8 are applied according to the difference in thermal expansion between the substrates 2 and 3, and the difference in the expansion between the (4) material layers 6, and the VU here constitutes the glass of the glass substrates 2, 3. The coefficient of thermal expansion is 8〇9〇Xl0 /C, and the representative thermal expansion coefficient of the FTO constituting the transparent conductive films 7 and 8 is 38%. In addition, the thermal expansion coefficient of the ft film is also equivalent. As described above, the thermal expansion coefficient of the transparent conductive films 7, 8 is smaller than the thermal expansion coefficient of the glass substrate (nano-glass) 2, 3, so that the sealing material layer 6 is heated and diffused, although in the transparent conductive film. 7, 8 and the glass substrate 2, 3 K stress 'but not causing mutual destruction or transparent conductive film 7, ^ from the X mesh is softening flow from the sealing material layer 6, thus in the transparent guide 8 and pin material layer $ Stress will occur between the *. In the irradiation of laser light, . During the cooling process of the bundle 'sealing material layer 6, the glass substrates 2, 3, the transparent conductive films 7, 8 and the sealing material layer 6 are shrunk. 7. When the sealing material layer 6 has a thermal expansion similar to that of the glass sheets 2, 3, according to the difference in thermal expansion between the glass substrate 2, 3 and the sealing material layer 6, and the transparent conductive film 17 201105599, compared to the transparent conductive film 7 The glass substrate 2, 3 and the sealing material layer 6 have a large amount of shrinkage. The electric films 7, 8 are strong, and the rutting is large, so that the transparent conductive film 7, 8_1 is thick and transparent. The membranes 7, 8 are fresh, and the heart will increase. ® is a transparent conductive center = the portion where the sealing material layer 6 is formed and the portion of the layer 6 is different, and thus the formation region of the transparent conductive film electrical film sealing material layer 6 is cracked, and in the transparent conductive film 7, 8 and the interface between the glass substrates 2, 3 will peel off. It is composed of a tin oxide: agglomerates (polycrystals), and has a form of gas or a tin oxide containing crystals at the grain boundaries of such crystal grains. The grain boundaries in the film cause light to scatter 'although the uniformity of light and the homogeneous pure shot contribute to the mechanical strength of the ft 〇 film. That is, the FT ruthenium film is liable to be cracked along the grain boundary inside. Therefore, when the transparent conductive film 7'8 is a FT film, the difference in thermal expansion between the glass substrates 2, 3 and the sealing material layer 6, and the transparent conductive films 7 and 8 is easily made in the transparent conductive film 7'8. Recording cracks and peeling caused by cracks in the grain boundaries. On the other hand, when the sealing material layer has a thermal expansion coefficient similar to that of the transparent conductive film (FT〇 film) 7, 8, the difference in thermal expansion between the glass substrate 2, 3, the sealing material layer 6, and the transparent conductive film 7, 8 The sealing material layer 6 and the transparent conductive films 7 and 8 apply tensile stress to both of the glass substrates 2 and 3. In particular, since the FTO film belongs to the uneven layer having the crystal grain boundary as described above, the stress of the sealing material layer 6 is transmitted to the glass substrate 2' 3 via the grain boundary, resulting in the glass substrate 2, 3 and the transparent conductive film 7, 8 The stress at the interface increases. Therefore, the 201105599 transparent conductive films 7, 8 are easily cracked along the formation region of the sealing material layer 6, and peeling occurs even at the interface between the transparent conductive films 7, 8 and the glass substrates 2, 3. In addition, when the first glass substrate 2 does not have the transparent conductive film 7 so as to face the second glass substrate 3 on which the sealing material layer 6 is formed, the first glass substrate 2 is subjected to the same tensile stress, so that the first glass substrate 2 is subjected to the same tensile stress. The first glass substrate 2 is likely to be cracked, broken, or the like. Further, when the difference in thermal expansion between the glass substrates 2, 3 and the sealing material layer 6 is large, the stress applied to the glass substrates 2, 3 increases regardless of the presence or absence of the transparent conductive films 7, 8, so the first and second The glass substrates 2 and 3 are prone to cracking and cracking. In the above-described matter, the thermal expansion coefficient α丨 of the sealing material layer 6 is adjusted to be one value or more and not more than the other value, which is a relatively transparent conductive film (FTO film) 7, 8 The value of the thermal expansion coefficient α2 (α2 value), the thermal expansion coefficient of the glass substrates 2, 3, and the value of 0.5 times the value of 3 (〇5α3 value), which is a value that is relatively transparent. The thermal expansion coefficient 〇 of the film films 7 and 8 is twice the value of 2 (2 〇: 2 value) and the value of the thermal expansion coefficient α 3 of the glass substrates 2 and 3 (α 3 value) is small. value. By using the sealing material layer 6 having such a thermal % expansion coefficient α and the sealing layer 5, it is possible to suppress problems such as cracking and cracking of the glass substrates 2 and 3 made of soda lime glass, and to suppress transparent conduction. The films (FT〇 films) 7, 8 are peeled off from the glass substrates 2, 3. If the thermal expansion coefficient α i of the sealing material layer 6 exceeds a value smaller than the value of 2α 2 and any value, the glass substrate 2, 3 and the sealing material layer 6 are compared with the amount of shrinkage of the transparent conductive films 7, 8. The amount of shrinkage becomes large, so that a strong compressive stress is generated to the transparent conductive films 7, 8 and, as a result, the transparent conductive films 7, 8 are susceptible to cracking. On the other hand, if the thermal expansion coefficient of the sealing material layer 6 is less than any of the values of α 2 and 0.5 α 3 , the stress applied to the interface between the glass substrates 2 and 3 and the transparent conductive films 7 and 8 is applied. This will become large, and according to this, the transparent conductive films 7, 8 are liable to be cracked. The sealing material layer 6 of the present embodiment reduces the thermal expansion difference between the glass substrate 2, 3 and the transparent conductive films 7, 8 by reducing the difference in thermal expansion between the glass substrates 2, 3 and the transparent conductive films 7, 8 respectively, and the transparent conductive film 7 is cooled during the cooling process of the sealing material layer 6. 8 and the stress generated at the interface between the glass substrates 2 and 3, thereby suppressing the cracking of the transparent conductive films 7, 8 and the separation from the glass substrates 2, 3. The sealing layer 5 based on such a sealing material layer 6 is effective when the thickness thereof is 1 G or more times the film thickness of the transparent conductive films 7, 8. Specifically, when the thickness of the sealing layer 5 is set to ΠΜ〇〇μ4 with respect to the transparent conductive films 7 and 8 having a film thickness of 0.1 to 1 mm, it is effective. The specific thermal expansion coefficient α of the sealing material layer 6 is within the above range and is preferably set to 43 to 72. 〇范 胀诚~ can be adjusted by using (10) the amount of expansion filler. :r, :r::_ is reduced by two: the force of the transparent conductive film 7 and 8 formed on the surface of the base is increased in the direction of peeling v ^ U (four) film material layer 6_ less _, ^, 3 will It is applied according to the possibility of sealing. There may be cracks and fractures of the k-forming glass substrates 2, 3, etc. 201105599 That is, the sealing material layer 6 is easy to swell during the smelting direction, and expands in the direction of the line width, and in the subsequent cooling process toward the line width direction. The flow of the material layer 6 does not return to its original state, resulting in the sealing material layer 6 as a whole shrinking toward the sealing material. Since the expansion and contraction of the sealing material layer 6 are partially:, the transparent conductive films 7, 8 are liable to be generated when the sealing material layer 6 is contracted. In this case, the content of the low-expansion filler (four)% or more is effective. Thereby, the sealing material layer can be appropriately suppressed, and the peeling of the transparent conductive films 7, 8 can be suppressed. If the content of the low-expansion filler is too large, the fluidity of the binder will be excessively lowered, so that the low-expansion filling :: is set to 50% by volume or less. Breaking well = particle shape of low expansion filler (4) (4) (4) Material: Pull::) is valid. Specifically, the 'low-expansion filler is preferably a particle having a particle diameter exceeding the thickness of the sealing material layer 6, and the film thickness T of the dense layer 6 is contained in the particle size of the pin material. particle. By making the circumference have a G.5T or more. The low-expansion filler is more suitable for H. : Product ^ Above H' by using a low-filler containing G.1 vol%. The film thickness of the particles having a particle diameter of 0.5 Å or more and 1 Å or less is reduced. Stretching, can inhibit the particle ratio of the sealing material layer 6 when it is melt-solidified: a crucible having a particle size below which has a size of 〇 〇.57 or more and having a particle size below the surface 21 201105599 filler The particle content is relatively reduced, resulting in a low filler particle distribution of the sealing material layer 6 which is not (4). At this time, (4) the coefficient of thermal expansion of the material will increase partially, resulting in the situation that the sealing layer 5 itself is easy to scoop. The electronic device 1 of the above embodiment is manufactured, for example, as follows. First, as shown in the 3rd, 6th, and (4th), the sealing material layer is formed in the sealing area of the plate 3, and when the glass base is formed, it will first have the shape 2 value of the stomach in the α 2 value plate Q 5 " A sealing material for a value which is larger than any of the 〇·5α3 values and which is smaller than any of the 2α2 value and the α 3 value.仃-mouth and the week are made into a dense carrier. The resin which is a binder component is dissolved in a solvent. The resin can be used, for example, methyl cellulose, ethyl cellulose, cellulose, oxygen, and material. Cellulose such as methyl quinone is a base - methyl methacrylate butyl vinegar, methyl acrylate acid 2 - ethyl vinegar, _ acid butyl ketone acid -2- vinegar An organic resin such as a dilute acid resin obtained by dispersing a dilute acid monomer. When the fiber is used, the solvent may be a solvent such as terpineol, butyl mecan/senior; when the propylene resin is used In the case, it is possible to use a solvent such as acetophenone, terpineol, butyl carbitol acetate st, etc. The viscosity of the Θethyl carbitol vinegar sealing material paste is as long as it fits on the slab 3 The coating can be reduced by the amount of the coating. The ratio of the solvent to the solvent or the ratio of the sealing glass material to the carrier can be adjusted. Or a disperse lining is added to the glass paste as a well-known additive. The preparation of the sealing material paste can be used with a stirring wing. A known method such as a rotary mixer or a ball mill or a ball mill.

The sealing material paste is applied to the sealing region 3B of the second glass substrate 3 to dry, and a coating layer of the sealing material paste is formed. The sealing material paste is applied to the second sealing region 3B by a printing method such as screen printing or gravure printing, or applied along the second sealing region 38 using a dispenser or the like. The coating layer of the sealing material paste is dried, for example, at a temperature of 12 Torr or more for 1 minute or longer. The drying step is carried out by removing the solvent in the coating layer. If there is a residual solvent in the coating layer, the subsequent sintering step may cause the binder component to be sufficiently decomposed and burned, resulting in the possibility of being removed. The coating layer of the above-mentioned sealing material paste is fired to form a sealing material layer 6. In the baking step, the coating layer is first heated to a temperature lower than the glass transition point of the sealing glass (glass frit) which is a main component of the sealing glass material, and the bonding component in the coating layer is removed, and then heated to a seal. The glass material for sealing is melted and baked on the glass substrate 3 at a temperature higher than the softening point of the glass (glass frit). In this case, the sealing material layer 6 composed of the fired layer of the sealing glass material is formed on the sealing region 3B of the second glass substrate 3. Next, the second glass substrate 2 manufactured separately from the second glass substrate 3 is prepared, and a solar cell such as a dye-sensitized solar cell or a solar cell such as 〇ELD or PDP is produced using the 荨 荨 glass substrate 2, 3'. An electronic device 1 such as an illumination device using an FPD or 23 201105599 OEL element is used for an LCD or the like. In other words, as shown in Fig. 3(b), the first glass substrate 2 and the second glass substrate 3 are laminated via the sealing material layer 6 so as to face each other between the surfaces 2a and 3a. A gap is formed between the second glass substrate 2 and the second glass substrate 3 in accordance with the thickness of the sealing material layer 6. Next, as shown in Fig. 3(c), the sealing material layer 6 is irradiated with the laser light 9 through the second glass substrate 3. The laser light 9 is irradiated through any of the second and second glass substrates 2, 3. The laser light 9 is irradiated while being scanned along the frame-shaped sealing material layer 6. Then, the irradiation of the laser light 9 is performed across the entire circumference of the sealing material layer 6, and as shown in Fig. 3(d), the sealing layer 5 for sealing the second glass substrate 2 and the second glass substrate 3 is formed. In this case, the electronic component portion 4 disposed between the second glass substrate 2 and the second glass substrate 3 is hermetically sealed by the glass panel including the second glass substrate 2, the second glass substrate 3, and the sealing layer 5. The sealed electronic device is produced. Further, the glass panel of the present embodiment is not limited to the constituent parts of the electronic device i, and can be applied to a sealed body of an electronic component or a glass member (such as a building material) such as a laminated glass. The laser light 9 is not particularly limited, and laser light from, for example, a semiconductor laser, a carbon dioxide gas laser, a quasi-molecular filament, a YAG laser, a HeNe Ray, or the like can be used. The output of the laser light 9 is matched with the thickness of the sealing material layer 6, etc., and is preferably set to a range of, for example, 2 to 15. If the laser transmission wire is 2 W, the sealing material layer 6 cannot be made (4). The energy of the ▼, on the other hand, the right more than 150 W. The glass substrates 2 and 3 are more prone to cracking and cracking, etc. The output of the laser light is better in the range of 5 to i 〇〇 w. 24 201105599 The electronic device according to the embodiment 丨And a manufacturing step thereof, which can suppress problems such as cracking and cracking of the glass substrates 2 and 3 composed of soda lime glass during laser sealing, and can suppress cracking of the transparent conductive film (FT〇 film) 7, 8 and The transparent conductive film (FT0 film) 7 and 8 can be prevented from being peeled off from the glass substrates 2 and 3. Therefore, the mechanical degree of the electronic device 1 can be improved, the hermetic sealing property, the reliability, and the like can be improved. The sealing layer 5 is a layer composed of a material for refining and fixing the glass material for sealing, and in the electronic device manufactured as described above, it belongs to a layer formed by melting the sealing material layer 6 and cooling it. A material formed by firing a glass material for sealing The material of the sealing material layer 6 is sealed, so that the change is considered to be substantially absent as a material even after the step of melting and then cooling, so that the coefficient of thermal expansion of the sealing layer 5 is equal to that of the sealing material layer 6 described above. Thermal expansion coefficient α i. EXAMPLES Next, the specific examples of the present invention and the evaluation results thereof will be described. In addition, the following description is not intended to limit the invention, but may be changed in the form of the subject matter of the present invention. The particle size 〇5〇 was measured using a laser diffraction/scattering particle size distribution measuring apparatus. (Example 1) Preparation with Sn055.7 mol%, %〇23.1 mol%, p2〇532 5 mol% , 211 〇 4.8 mol %, Α 12 〇 32 · 3 mol. /, 8 丨〇 21.6 mol% of the composition of the tin-filled glass frit (softening point: 406 t), used as a low expansion filler Average particle size (D50) 5 pm, maximum particle size (Dmax) 2 (^mw zirconium phosphate ((Zr〇) 2P2 〇 7) powder ' and a group of 25 201105599 and a maximum particle size (Dmax) of 7 μηι Emulsion material. The above tin-disc acid frit 5 4 parts by volume, 43% by volume of the acid-filled powder, and 3% by volume of the laser absorbing material were mixed to prepare a glass material for sealing (thermal expansion coefficient after firing: 44 χ 1 〇·7 wide c). 80% by mass of the glass material and the carrier 2% by mass were mixed to prepare a sealing material paste. The carrier was dissolved in butyl carbitol acetate (3% by mass of nitrocellulose as a binder component). And a mixed solvent of dibutyl phthalate (10% by mass) was prepared in an amount of 97 mass% in 〇. Next, the surface of the preparation was provided with a 17-inch bismuth film having a film thickness of 5.5, and a soda-lime glass. (Coefficient of thermal expansion: 82 < 1 〇 _7 /. The second glass substrate (size: 100x100x1 ·lmmt) of the crucible is formed in the sealing region of the glass substrate by the screen printing method (line width: 1 mm), and then 13 (rcx5 points) Drying was carried out under conditions, and the coating layer was fired under the conditions of 45 〇»c><1 ,, and a sealing material layer having a film thickness T of 32 μm was formed as a yttrium phosphate powder for a low expansion filler. It does not contain particles exceeding the film thickness ,, and contains particles having a volume of 2 vol%, which has a particle diameter of 〇5 or more and 1 Τ or less with respect to the film thickness τ. Here, the sealing material layer has: 0.5 times the thermal expansion coefficient α2 (38xl〇7/ C ) of the film and the thermal expansion coefficient α 3 (82 > i〇-7/〇c) of the sodium | bow glass (41 >< 10_7 /. Any larger value (41xl〇-YC) or higher, and 2 times the coefficient of thermal expansion of the FTO film (38x! 0-7/°c) (76χ丨ο·%), and Calcium glass has a coefficient of thermal expansion of the range of thermal expansion coefficient α 3 (82X1 〇 _7 / . (:), any value below (76X1 (T7/°C)), (44X1 o-7/.^). Above The second glass substrate of the sealing material layer and the first glass substrate (the composition of the same shape and the same shape as the second glass substrate) prepared in addition to the second glass substrate are not provided with F1O Lang on the surface. The substrate is laminated via a sealing material layer. Then, the second glass substrate is passed through the second glass substrate to the sealing material layer, and the wavelength of 94 〇 nm, the output 65, and the laser light (semiconductor laser) are irradiated at a cleaning broom speed. The sealing material layer is melted and rapidly solidified to form a sealing layer having a thickness of 30 μm, thereby sealing the second glass substrate and the second glass substrate. Accordingly, an electronic device for sealing the electronic component portion with a glass panel is provided. (Embodiment 2) Preparation has Sn059.3 Mohr, /, Sn〇2〇8 mol%, ρ2〇533 3 mol%, ΖηΟ6.0 mol%, Si〇2〇6 A tin-scale acid glass frit having a composition of mol% (softening point: 367. 〇' as an average particle diameter (D50) for a low expansion filler of 10 pm, a maximum particle diameter (Dmax) of zirconium phosphate (Zr 〇) must (6) powder, and have Fe2〇3-Cr2〇3_c〇2 a laser absorbing material having a composition of 3 Mn 、 and a maximum particle diameter (Dmax) of 7 pm. The above-mentioned tin-phosphate type glass frit 53% by volume, zirconium phosphate powder 44 vol/〇, and a laser absorbing material 3 vol% are mixed and produced. Glass material for sealing (thermal expansion coefficient after firing: 46 χ 1 〇 -7 / /. The sealing glass material 80 罝% is mixed with the carrier 2 〇 mass% to prepare a sealing material paste. The carrier is prepared by dissolving 3% by mass of the basalized cellulose used as the binder component in butyl carbitol hydrate (9 〇 mass%) and acid butyl ketone (1 mass% mixed solvent 97% by mass). Next, a second glass substrate having a film thickness of μ5 μmη and a soda lime glass (coefficient of thermal expansion: Μχίο-7/^) is prepared (size: 27 201105599 on the glass plate). In the sealing area, the sealing material paste is applied by screen printing (line width: 1 mm) and dried according to the conditions of 13 minutes. The coating layer is fired according to the condition of 45 (^1 () minutes. The sealing material layer having a film thickness τ of 62 Å is formed. The zirconium phosphate powder used as the low expansion filler does not contain particles exceeding the film thickness τ, and contains particles having a volume of ❶/. The particle diameter τ is a particle diameter of 〇2 or more and 1 τ or less. Here, the sealing material layer has a coefficient of thermal expansion in the FTO film (38xl (r/°c), and a coefficient of thermal expansion of the soda lime glass). (^(SZxlO-Vt) 0.5 times the value (41xktYC) of any larger value (41xl〇-7rc) or more, and in the FTO film The thermal expansion coefficient α 2 (38 >< 10 force. (: 2 times the value of (:)) (76x1 〇.7 / °c), and the thermal expansion coefficient α 3 (82X1 〇 -7 / it) of Sodium Any smaller value (76x10 7 /<>C) in the range of thermal expansion coefficient α丨(46><1〇-7/.(3;). The second glass substrate having the sealing material layer described above, A first glass substrate (a substrate made of soda lime glass having the same composition and the same shape as the second glass substrate and having no FTO film on the surface) prepared separately from the second glass substrate is laminated via a sealing material layer. Next, the sealing material layer is irradiated with a laser beam having a wavelength of 940 nm and output of 85 W through a second glass substrate, and the laser beam is irradiated at a scanning speed of 1 mm/s to melt and cure the sealing material layer. The first glass substrate and the second glass substrate are sealed. Accordingly, the electronic device in which the electronic component portion is sealed by the glass panel is provided for evaluation of characteristics described later. (Example 3) Preparation with Sn063.3 mol % 811〇22.5mol%, Ρ2〇528·8Mo 28 201105599 Ear%, 211〇4.9mol%, a] Glass (softening point: 366 ° C),

Tin-scale acid glass composed of Al2〇3〇·5 mol%

(Dmax) lOpm laser absorbing material.

paste. The carrier is prepared by dissolving 3% by mass of cellulose as a binder component in butyl carbitol acetate (9% by mass) and dibutyl phthalate (97% by mass of a mixed solvent of ruthenium). The second glass substrate (size: lOOxlOOxl.lmmt) consisting of a film thickness 05|in^FT film and a soda lime glass (coefficient of thermal expansion: 82 < 1 〇 force. 〇) 'In the sealing region of the glass substrate, the sealing material paste was applied by screen printing (line width: lmrn), and then dried at i30 ° C x 5 minutes. By coating the coating layer 45 (rcxl0) The sealing material layer having a film thickness T of 65 μm is formed by firing in a sub-condition. The zirconium phosphate powder used as the low-expansion filler does not contain particles exceeding the film thickness, and contains particles in a range of 5 vol%. It has a particle diameter of Τ5Τ or more and 1Τ or less with respect to the film thickness τ. Here, the 'sealing material layer has a coefficient of thermal expansion 〇: 2 (38X10_7/°C) and sodium with a film of ?? 0.5 times the coefficient of thermal expansion of calcium glass α 3 (82X10_7/°C) (41χ10·7/°〇 A larger value (41 ><1〇_7/. 〇 above, and at 29 201105599 FT 〇 film thermal expansion coefficient α 2 (38 < 10-7 /. 〇 2 times value (76xHT7 / ° C ), and the thermal expansion coefficient ai (52xl〇-Yc) of any of the smaller values (76Xl0 / C) of the thermal expansion coefficient α 3 (8 2 X10 -7 plant C ) of the Nylon glass. The second glass substrate of the sealing material layer and the first glass substrate prepared separately from the second glass substrate (consisting of the same shape and the same shape as the second glass substrate, and having a film thickness 〇·5μηι on the surface) The substrate of the FTO film is laminated via a sealing material layer. Then, the second glass substrate is passed through the second glass substrate to the sealing material layer, and a laser beam (semiconductor laser) having a wavelength of 94 〇 nm and output of 72 W is scanned at 5 mm / s. The first glass substrate and the second glass substrate are sealed by melting the sealing material layer and cooling the film, thereby providing an electronic device in which the electronic component portion is sealed by the glass panel. For evaluation (Scheme 4) In the above Example 3, 'except for using tin/phosphoric acid frit 75 The glass material for sealing (the coefficient of thermal expansion after firing: 72 x 1 〇 · 7 / ° C) obtained by mixing 22 vol% of zirconium phosphate, zirconium phosphate powder, and 3 vol% of a laser absorbing material In the same manner as in the third embodiment, the sealing material layer is formed, and the first glass substrate and the second glass substrate are sealed. Accordingly, the electronic device in which the electronic component portion is sealed by the glass panel is provided for evaluation of characteristics to be described later. Here, the sealing material layer has a coefficient of thermal expansion (38xl 〇 -7 / ° C) in the FTO film and a coefficient of thermal expansion of the soda lime glass < 2 3 (82 >< 1 〇 -7 /. Any one of the larger values (41xl〇_7/°c) above the 0.5x value (41xl〇_7/°C) and twice the thermal expansion coefficient α 2 of the FTO film (38xl〇·7 Factory C) Value (76χ1(Τ7Λ:), 30 201105599) The coefficient of thermal expansion α in the range below the thermal expansion coefficient α 3 (82χ 1 (T7/°C) value of the soda lime glass (76xlO'7/°C) 72(72><1〇-7/°〇). (Comparative Example 1) In the above-mentioned Example 3, 52% by volume of a tin-scale acid-based glass frit, 455% by volume of a barium phosphate powder, and a sealing glass material (the same thermal expansion coefficient after firing: 37×1 (T7/t) other than the laser absorbing material 3 vol% of the laser absorbing material was formed, and the sealing material layer was formed in the same manner as in Example 3, and 1. The glass substrate and the second glass substrate are sealed. Accordingly, the electronic device in which the electronic component portion is sealed by the glass panel is provided for evaluation of characteristics to be described later. Here, the coefficient of thermal expansion of the sealing material layer α ι (37χ 1〇- 7/. ( ) is twice the thermal expansion coefficient α 2 (38 x 丨 0-7/°c) of the FTO film (76χ〖〇-7Γ(:), and the coefficient of thermal expansion of the soda lime glass a /82 χ 1 〇-7 / °C) Any of the values - the smaller value (76 > < 10 force. 〇 below, but belongs to the thermal expansion coefficient of the FTO film ^ (38x10 7 / ° C) and the thermal expansion coefficient of Naoma glass 3 (82xi 〇-7/〇c) is a smaller value than any of the larger values (41X10-YC) of the 5-fold value (41xl〇-VC). (Comparative Example 2) In the above-described Embodiment 3, A sealing glass material obtained by mixing 83% by volume of a tin-phosphate-based sloping filler, 14 parts by volume of a phosphoric acid powder, and 3 vol% of a laser absorbing material (thermal expansion coefficient after firing: 8) χΐ〇- In the same manner as in the third embodiment, the sealing material layer is formed in the same manner as in the third embodiment, and the third glass substrate and the second glass substrate are sealed. Thus, the electronic device is sealed by the glass panel. 31 201105599 The thermal expansion coefficient of the 'sealing material layer' is the coefficient of thermal expansion of the FTO film α <3 8 X1 〇_7/t:) and the coefficient of thermal expansion of soda lime glass a 3 (82xlO_7/°C) 55 times value (41><1〇-7/. 〇中任—larger value (41X10 7/C) or more, but belongs to the thermal expansion coefficient α 2 of the FTO film. (38 χ 10·7 / ° 〇 2 times the value (76 >< 10,. The coefficient of thermal expansion of yttrium and soda lime glass ύ: 3 (82 < 10·7 / ° 〇 value any smaller value (76xl (TVC) is also a larger value. (Example 5) Preparation with Bi2铋382.9% by mass, B2035.6% by mass, Zn01〇.7% by mass, CeOO.2% by mass, a12O30.5% by mass, Fe2〇3〇.a4% of the composition of the bismuth-based glass frit (softening point: 419). 〇, a cordierite powder having an average particle diameter (D50) of 15 pm, a maximum particle diameter (Dmax) of 45 pm, and a composition having Fe2〇3-Cr2〇3_C〇2〇3-MnO as a low-expansion filler, and the largest particle a laser absorbing material of (Dmax) l (^m), which is prepared by mixing 55 vol% of the above-mentioned glass frit, 43 vol% of cordierite powder, and 2 vol% of a laser absorbing material, thereby producing a glass material for sealing (burning) The thermal expansion coefficient after the formation: 46 χ 1 〇 -7 Λ:). The sealing glass material 8 〇 篁 % is mixed with the carrier 2 G mass % to prepare a sealing material paste. The carrier is used as a bonding component for the ethyl fiber. 5% by mass/〇, dissolved in 95% by mass of a mixed solvent of butyl carbitol acetate (89% by mass) and terpineol (11% by mass) Secondly, 'the second glass substrate (size: 100x100x1.lmmt) consisting of a thick film and prepared by a sodium dance glass with a thermal expansion coefficient: 86><1〇-7/. In the sealing region of the glass substrate, the sealing material 32 201105599 paste was applied by screen printing (line width: 1 mm), and then dried according to 13 (TCx5 knife condition). 45〇£>Cx1 is subjected to firing to form a sealing material layer having a film thickness of 6511111. The cordierite powder used as a low-expansion filler does not contain particles exceeding the film thickness τ, and contains 3 volumes. Particles in the % range 'This position has a particle diameter above and below 1 T with respect to the film thickness. Here, the sealing material layer has a coefficient of thermal expansion in the FTO film (38 x 107 / ° C), and soda calcium The coefficient of thermal expansion of the glass is α3 (0.5 χ1〇.7Γ(7) 0.5 times the value (43><1〇-7/. Any of the larger values (43xl〇-7/〇c)), and the thermal expansion of the FTO film The coefficient α 2 (38χ^/^^2 times value (76xl〇_7/t>c), and the coefficient of thermal expansion α /86χ 10_7/(:) of the soda lime glass a thermal expansion coefficient of a smaller value (76x10_7/° C.) or less; ι (46χ1〇-7/^). The second glass substrate having the sealing material layer and the first glass substrate separately prepared separately (The substrate made of soda lime glass having the same composition and the same shape as the second glass substrate and having no FT0 film on its surface) is laminated via a sealing material layer. Next, the sealing material layer is irradiated with a laser light having a wavelength of 808 nm and output 85 W (semiconductor laser) through the second glass substrate, and the sealing material layer is melted and quenched and solidified. The first glass substrate and the second glass substrate are sealed. According to this, the electronic device in which the electronic component unit is sealed by the glass panel is provided for evaluation of characteristics to be described later. (Example 6) An bismuth-based glass frit having a composition of Bi20383.1% by mass, 82035.66% by mass, Ζη〇ι〇$% by mass, and 八12〇3〇.5% by mass (softening point: 418. ^74 33) 201105599 Volume ° / 〇, cordierite powder 24% by volume, and laser absorbing material 2 volume 0 / 〇, mixed to form a sealing glass material (thermal expansion coefficient after firing: 7 0 X1 (T7 / °C) The sealing glass material was mixed with 8 % by mass of the glass material to prepare a sealing material paste. The carrier was dissolved in butyl carbitol acetic acid by 5 mass % of ethyl cellulose as a binder component. A mixed solvent of ester (89% by mass) and terpineol (11% by mass) was prepared in an amount of 95% by mass. Next, an FTO film having a film thickness of 0.5 μm was prepared on the surface, and the soda lime glass (thermal expansion) was prepared. Coefficient: 86\1〇-7/. The second glass substrate composed of 〇 (size: l〇〇xlO〇xl.lmmt) 'In the sealing region of the glass substrate, the sealing material paste was applied by screen printing method After the cloth (line width: 1mm), it is dried according to the conditions of 1301x5 minutes. By coating the coating layer according to 45 (rCxl In the condition of firing, a sealing material layer having a film thickness T of 65 μm is formed. The cordierite powder used as the low expansion filler does not contain particles exceeding the film thickness τ, and contains particles in the range of 3 vol%, and the particles have The particle size τ is a particle diameter of 5 □ or more and 1 Τ or less. Here, the sealing material layer has a coefficient of thermal expansion (38×10 7/° C.) in the FT 〇 film and a thermal expansion coefficient α 3 of the soda lime glass. (0.8χ丨〇·7/β(:) 0.5 times value (43><1〇_7/. Any one of the larger values (43><1〇-7/. The FTO film has a thermal expansion coefficient α 2 (38χ1〇-7/^) twice the value (76xl〇-7/〇c), and the soda lime glass has a thermal expansion coefficient α 3 (86xl〇-7/°c). Any one of the smaller values (76 x 10·7/1) or less in the range of thermal expansion coefficient α丨(70X1 (T7/t). The second glass substrate having the sealing material layer described above and the other prepared separately from the second glass substrate 1 glass substrate (a substrate made of soda-lime glass having the same composition and the same shape as the second glass substrate, and having an FTO film having a film thickness of 5 μm on the surface), 34 201105599, which is laminated via a sealing material layer Then, the sealing material layer is irradiated with a laser beam having a wavelength of 808 nm and outputting 85 W through a scanning wavelength of 808 nm through the second glass substrate, and the sealing material layer is melted and solidified by cooling. In this way, the first glass substrate and the second glass substrate are sealed. Accordingly, the electronic device in which the electronic component portion is sealed by the glass panel is provided for evaluation of characteristics to be described later. (Comparative Example 3) In the above-mentioned Example 5, a sealing glass material obtained by mixing the volume of the glass frit, the volume of the cordierite powder by 51% by volume, and the volume of the laser absorbing material by 2% by volume was used. (The thermal expansion coefficient after firing: 34×丨〇-7/〇c) The same as in Example 5, the sealing material layer was formed, and the first glass substrate and the second glass substrate were sealed. Accordingly, the electronic device 'sealed by the electronic component portion with the glass panel' is provided for evaluation of characteristics to be described later. Here, the coefficient of thermal expansion of the sealing material layer is α J34X 1 〇.7/. (]) is the thermal expansion coefficient α 2 of the FTO film (38 >< 10 '7 /. 2 times the value of 〇 (76xUrV ° c ), and the coefficient of thermal expansion α 3 (86 χ 1 〇Ί ) of the soda lime glass The lower value—smaller value (below 76x 1(T7/°C)' but belongs to the thermal expansion coefficient α 2 of the FTO film (38><10·7/°〇 and the coefficient of thermal expansion of the sodium-fed glass〇; 3( 〇5 times value of 86xi〇-7/°c) (43xl (T7/°C)) (43><1〇_7/. 〇 is also a smaller value. (Comparative Example 4) A glass material for sealing obtained by mixing 81% by volume of an enamel-based glass frit having the same composition as in Example 5, 17% by volume of cordierite powder, and 2% by volume of a laser absorbing material (thermal expansion after firing) The sealing material layer was formed in the same manner as in Example 6 except that the coefficient: 82 <1 〇 _7 / 〇), and the first glass 35 201105599 glass substrate and the second glass substrate were sealed. The electronic device for sealing the electronic component portion of the glass panel is provided for the characteristic flatness described later, and the thermal expansion coefficient α of the sealing material layer (8 kwxio / 〇 is the thermal expansion coefficient α 2 of the FTO film (38 x 10_7 /. (: The hot face of the Sodium Dance Glass is the largest value (43 ><1〇-7/. 〇 above' but belongs to the thermal expansion coefficient 较(38 Niang) of the FTO film twice (76 reading) ), and the smaller value of the thermal expansion (four) number a 3 (86xl (T7/°C) value of the _glass is larger than the white value. (Comparative Example 5) Example 5 is a glass material for sealing obtained by mixing a % by volume of a silk-based glass frit of the same composition, 5% by volume of a cordierite powder, and 2% by volume of a laser absorbing material (thermal expansion coefficient after firing: In the same manner as in Example 6, except that l〇lx1〇-V>c), a sealing material layer was formed, and the second glass substrate and the second glass substrate were sealed. Accordingly, the electronic component portion was coated with a glass panel. The sealed electronic device is provided for the evaluation of the characteristics described later. Here, the thermal expansion coefficient ai of the sealing material layer (101x10-7/<>>c) is the thermal expansion coefficient a 2 of the FT〇 film (3 8 X1 (T7/) °C) is higher than the larger value (43xur7/°C) of any of the 5 times value (43xl0-Vc) of the coefficient of thermal expansion of a soda lime glass (3xixi-Vc), but belongs to the FT〇 film. Thermal expansion coefficient 〇 2 (38X l (r7/°C) double value (76xl0_7 wide C), and soda lime glass thermal expansion coefficient α 3 (86x 10 force. (:) value any of the smaller values (76χ 1 〇·7Λ:) It is still larger than the value of the thermal expansion coefficient α 3 (86xl (T7/°C) of Nahe glass. Next, regarding the appearance of the glass panels of Examples 1 to 6 and Comparative Examples 1 to 5, 36 201105599, the substrate fracture at the end of the laser light irradiation, the FT film crack and the peeling were evaluated. The appearance was observed and evaluated by a light microscope. i. The airtightness of each glass panel was measured. The airtightness is measured by a helium leak test. The results of (4), (4) and "the manufacturing conditions of the panel are all = 7 and Table 2. In addition, "the thermal expansion coefficient (2 1" is a thermal expansion coefficient of the glass material for sealing after sealing (that is, the material of the sealing material 经) which is described in the position of the sealing glass material. [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Sealing glass composition ratio (mol%) SnO 55.7 59.3 63.3 63.3 63.3 63.3 Sn02 3.1 0.8 2.5 2.5 2.5 2.5 P2〇5 32.5 33.3 28.8 28.8 28.8 28.8 ZnO 4.8 6 , 0 4.9 4.9 4.9 4.9 AI2O3 2.3 - 0.5 0.5 0.5 0.5 Si02 1.6 0.6 - - - - Softening point (°c) 406 367 366 366 366 366 Low expansion filler phosphoric acid • Zirconium laser absorbing material Fe-Cr-Co-Mn -0 Glass material ratio for sealing (% by volume) Sealing glass 54 53 63 75 52 83 Low expansion filler 43 44 34 22 45 14 Laser absorbing material 3 3 3 3 3 3 Thermal expansion coefficient α, (xlO'VC) 44 46 52 72 37 81 Sodium-lime glass for the first glass substrate (coefficient of thermal expansion a 3=82x10_7/°C) Whether or not the FTO film is present (thermal expansion coefficient of FTO film α 2=38x 10.Vt) Line width of firing step (mm ) 1 1 1 1 1 1 Drying temperature (°c) 130 130 130 130 130 130 firing temperature (°c) 450 450 450 450 450 450 The second glass substrate material soda lime glass (thermal expansion coefficient α3=82χ10·7/°FTO film presence or absence of any sealing step laser wavelength (nm) 940 940 940 940 940 940 laser output (w) 65 85 72 72 72 72 Scanning speed (mm/s) 5 10 5 5 5 5 Sealing film thickness (μπι) 30 60 60 60 60 60 37 201105599 αComparative 〇: Larger value of 2 and 0.5 (1 41 41 41 41 41 41 Small value of 2α2 and α3 (2) 76 76 76 76 76 76 Relationship between value 1 and <^ and value 2 4|<44<76 41<46<76 41<52<;7641<72<7641>37<7641<81>76 substrate cracking all-or-nothing--one--evaluation of FTO film cracking with no or no results FTO film peeling without or without There are 1-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- 5.6 5.6 5.6 5.6 5.6 ZnO 10.7 10.8 10.7 10.7 10.7 CeO 0.2 — 0.2 0.2 0.2 Al2〇3 0.5 0.5 0.5 0.5 0.5 Fe203 0.1 — 0.1 0.1 0.1 Softening point 419 419 418 419 419 419 Low expansion filler cordierite laser absorbing material Fe-Cr-Co-Mn-0 Sealing sloping ratio (% by volume) Sealing glass 55 74 47 $1 93 Low expansion filler 43 24 51 17 5 Laser absorbing material 2 2 2 2 2 Thermal expansion coefficient α! (xlO'7/°C) 46 70 34 82 101 1st glazing iR - material soda lime glass (thermal expansion coefficient a3=86xl (T7/ °C) Whether or not the FTO film is present (FTO film thermal expansion coefficient a 2=38x 10_7/°C) Burning step line width (mm) 1 1 1 1 Drying temperature (°c) 130 130 130 130 130 firing temperature ( °c) 450 450 450 450 450 2nd glass substrate material soda lime glass (coefficient of thermal expansion α 3=86x 1 (T7/°C) FTO film with or without sealing step '''''' (nm) 808 808 808 808 808 Laser output (W) 85 85 85 85 85 Scanning speed (mm/s) 10 10 10 10 10 Sealing film thickness (μηι) 60 60 60 60 60 〇: Compare -1 α The larger value of 2 and 〇.5α 3 (1) 43 43 43 43 43 2〇; 2 and the smaller value of 3 (2) 76 76 76 76 76 ^ and α, and the relationship between value 43 < 46 <;7643<70<7643>34< 76 43<82>76 43<101>76 38 201105599 Evaluation results: The substrate cracked without (unbonded) There was FTO film cracking without (unbonded) There was FTO film peeling without (unbonded) No gas It is known from Tables 1 and 2 that the glass panels obtained in Examples 1 to 5 belong to the FTO film without cracking and peeling, and are excellent in both appearance and airtightness. With respect to these examples, Comparative Example 1 was cracked in the FTO film, and Comparative Example 2 was cracked and peeled off in the FTO film, and airtightness could not be obtained. In Comparative Example 3, the sealing material layer could not be bonded to the glass substrate. In Comparative Example 4, FTO film cracking occurred and cracking occurred in the second glass substrate. In Comparative Example 5, the FTO film was cracked and peeled off, and the first glass substrate was cracked, and airtightness could not be obtained. . INDUSTRIAL APPLICABILITY A glass member having a sealing material layer of the present invention can be effectively used for manufacturing a solar cell having a structure in which a solar cell element or a display element is sealed between two glass substrates arranged in opposite directions. A glass substrate used for a panel or a flat panel display device. Further, the electronic device of the present invention has the solar cell panel and the flat panel display device of the above configuration. In addition, the specification, patent application scope, drawings and abstracts of the patent application No. 2009-128679 filed on May 28, 2009 are hereby incorporated herein by reference in . BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an electronic device according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing an example of an electronic component unit 39 in the electronic device of Fig. 1 . The third (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. 4 is a plan view showing the first glass substrate used in the manufacturing steps of the electronic device shown in Fig. 3. Fig. 5 is a cross-sectional view taken along line A-A of Fig. 4. Fig. 6 is a plan view showing a second glass substrate used in the manufacturing steps of the electronic device shown in Fig. 3. Fig. 7 is a cross-sectional view taken along line A-A of Fig. 6. Fig. 8 is an enlarged cross-sectional view showing a part of the manufacturing steps of the electronic device shown in Fig. 2. Fig. 9 is an enlarged cross-sectional view showing a part of the electronic device shown in Fig. 1. [Description of main component symbols] 1...electronic device 5...sealing layer 2...first glass substrate 6...sealing material layer 2a...surface 7,8...transparent conductive film (FTO film) 2A ...first element forming region 9...laser light 2B...first sealing region 40...dye-sensitized solar cell element 3...second glass substrate 41...transparent conductive film 3a. .. surface 42. semiconductor electrode (photoelectrode/anode) 3A... second element forming region 43...transparent conductive film 3B...second sealing region 44···counter electrode (cathode) 4. .. electronic component part 45...electrolyte 40

Claims (1)

201105599 VII. Shenqing Patent Range: 1. A glass member having a sealing material layer, comprising: a glass substrate having a surface provided with a sealing region and composed of soda lime glass; and a sealing material layer formed on The sealing region of the glass substrate is composed of a fired layer of a sealing glass material containing a sealing glass, a low-expansion filler, and a laser absorbing material. The glass substrate includes the sealing region described above. On the surface, a transparent conductive film made of fluorine-doped tin oxide is formed; the thermal expansion coefficient of the sealing material layer is greater than or equal to one value and below another value, which is a thermal expansion coefficient α 2 of the transparent conductive film. The value is a value larger than any one of 0.5 times the thermal expansion coefficient α 3 of the glass substrate, and the other value is twice the value of the thermal expansion coefficient α 2 of the transparent conductive film, and the _substrate A value smaller than any of the values of the thermal expansion coefficient α 3 . 2. The glass member having a sealing material layer according to the invention of claim i, wherein the sealing glass material contains the low expansion filler in the range of 2 G to 5 (% by volume), and is in appeasement product. /. The aforementioned laser absorbing material in the range. 3. The glass member having a sealing material layer according to claim 1 or 2, wherein the (10) expansion filler material contains particles having a particle diameter exceeding a thickness of the sealing material layer, and is contained in 〇1 to 99% by volume. The particles in the range have a thickness τ with respect to the above-mentioned sealing material layer, and are in the range of 41 201105599 0.5T or more and less than IT. 4. The glass member having a sealing material layer according to any one of the preceding claims, wherein the low-expansion filler material is derived from bismuth bismuth oxide, zirconia, bismuth citrate , cordierite, phosphoric acid-missing compound: at least one of the soda-lime glass and the borosilicate glass, wherein the glass member of the invention is in the form of a glass member of any one of claims 1 to 4, wherein the aforementioned laser The absorbent material is composed of a compound containing at least one metal selected from the group consisting of h, ' a Mn, Co, Ni, and Cu, or a compound containing a former or a second genus. A glass member having a sealing material layer of tin-phosphoric acid or a glass member according to any one of claims 1 to 5, wherein the sealed glass bottle is made of silk glass. 7. An electronic device comprising: a first glass substrate having a surface on which a first sealing region is provided; and a second glass substrate provided with a second sealing region corresponding to the second sealing region; The surface 'and the surface layer are disposed to face the surface of the first glass substrate; the electronic component portion ' is disposed between the first glass substrate and the second glass substrate; and the sealing layer is The gas that seals the electronic component portion is formed between the first sealing region of the first glass substrate and the second sealing region of the second glass substrate, and includes a sealed glass, a low expansion filler, and The first and second glass substrates are made of soda lime glass, and the first glass substrate includes the aforementioned first glass substrate. Forming at least one of the surface of the first sealing region and the surface of the second glass substrate including the second sealing region to form a transparent portion made of fluorine-doped tin oxide The thermal expansion coefficient I of the sealing layer is greater than or equal to or lower than another value, and the value is 0.5 times the value of the thermal expansion coefficient α2 of the transparent conductive film and 0.5 times the thermal expansion coefficient α 3 of the glass substrate. Any one of the larger values is a value smaller than the value of the thermal expansion coefficient α 2 of the transparent conductive film and the value of the thermal expansion coefficient α 3 of the glass substrate. [8] The electronic device of claim 7, wherein the electronic component is provided with a solar cell component. 9. A method of manufacturing an electronic device comprising the steps of: preparing a first glass substrate having a surface on which a first sealing region is provided and comprising a nanoglass; and preparing a second glass The second glass substrate is provided with a surface provided with a second sealing region corresponding to the first sealing region, and is made of soda lime glass, and the first sealing region of the first glass substrate or the first 2 forming a sealing material layer in the second sealing region of the glass substrate, the sealing material layer being composed of a fired layer of a sealing glass material containing a sealing glass, a low expansion filler, and a laser absorbing material; The surface of the glass substrate is in a state of being opposed to the surface of the second glass 43 201105599 substrate, and the first glass substrate is laminated with the second glass substrate via the sealing material layer. Irradiating the sealing material layer by the first glass substrate or the second glass substrate to melt the sealing material layer to form a sealing layer, the sealing layer The electronic component portion provided between the first glass substrate and the second glass substrate is sealed; wherein the first glass substrate includes the surface of the first sealing region and the second glass a transparent conductive film made of fluorine-doped tin oxide is formed on at least one of the surface of the substrate including the second sealing region; and the thermal expansion coefficient α of the sealing material layer is one value or more and not more than another value. The value is a value larger than a value of a thermal expansion coefficient α 2 of the transparent conductive film and a value 0.5 times a thermal expansion coefficient α 3 of the glass substrate, and the other value is larger than that of the transparent conductive conductive material. A value twice the thermal expansion coefficient α2 and a value smaller than any of the values of the thermal expansion coefficient 〇; 3 of the glass substrate. 10. The method of manufacturing an electronic device according to claim 9, wherein the sealing glass material comprises: the low-expansion filler in a range of 20 to 50% by volume, and the volume in (1) 丨 to (7) ^/^ The aforementioned laser absorbing material within the range. The method of manufacturing an electronic device according to claim 9 or claim 1, wherein the low-expansion filler is not contained in a particle having a particle diameter exceeding a thickness of the sealing material layer, and is contained in a range of 〇丨 to column vol% In the inner layer 44 201105599, the particles have a particle diameter in the range of 0.5 T or more and 1 Torr or less with respect to the thickness Τ of the sealing material layer. The method of manufacturing an electronic device according to any one of claims 9 to 11, wherein the electronic component unit is provided with a solar cell element. 45