JP5500079B2 - Glass member with sealing material layer and manufacturing method thereof, and electronic device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a glass member with a sealing material layer and a manufacturing method thereof, and an electronic device and a manufacturing method thereof.

  Flat-type display devices (FPD) such as organic electro-luminescence display (OELD), plasma display panel (PDP), liquid crystal display device (LCD), etc. are used for sealing glass substrates for elements on which light emitting elements are formed and for sealing It has a structure in which a light emitting element is sealed with a glass package in which a glass substrate is opposed to each other and these two glass substrates are sealed (see Patent Document 1). Further, in solar cells such as dye-sensitized solar cells, it has been studied to apply a glass package in which solar cell elements (photoelectric conversion elements) are sealed with two glass substrates (see Patent Document 2). ).

  Sealing resin or sealing glass is used as a sealing material for sealing between two glass substrates. Since organic EL (OEL) elements and the like are easily deteriorated by moisture, application of sealing glass excellent in moisture resistance and the like is being promoted. Since the sealing temperature by the sealing glass is about 400 to 600 ° C., the characteristics of the electronic element portion such as the OEL element are deteriorated when heat treatment is performed using a normal baking furnace. Therefore, a sealing glass material layer including a laser absorbing material is disposed between the sealing regions provided in the peripheral portions of the two glass substrates, and the sealing glass material layer is heated and melted by irradiating the laser beam thereto. Attempts have been made to seal (see Patent Documents 1 and 2).

Sealing by laser irradiation (laser sealing) can suppress the thermal influence on the electronic element part, while the conventional sealing glass (glass frit) can sufficiently increase the adhesive strength between the sealing layer and the glass substrate. This is difficult, and this is a factor that reduces the reliability of electronic devices such as FPDs and solar cells. As sealing glass (glass frit) for laser sealing, PbO glass powder, SnO—P ₂ O ₅ glass powder, Bi ₂ O ₃ —B ₂ O ₃ glass powder (see Patent Document 3), and V _{The use of 2} O ₅ glass powder (see Patent Document 1) has been studied. Among these, SnO—P ₂ O ₅ glass powder has a low softening point and has little influence on the environment and human body, and is therefore a material suitable for a glass frit for laser sealing.

However, simply applying the SnO—P ₂ O ₅ glass frit for heating by a conventional firing furnace to the glass frit for laser sealing cannot sufficiently increase the adhesive strength between the sealing layer and the glass substrate. Patent Document 4 describes SnO—P ₂ O ₅ glass frit applied to heating in a firing furnace, but the SnO—P ₂ O ₅ glass composition has an adhesive strength with a glass substrate by laser heat treatment. It is difficult to raise This is considered to be based on the difference in the melting condition of the glass frit between the heating by the baking furnace and the laser heating.

JP-T-2006-524419 JP 2008-115057 A JP 2008-059802 A JP 2003-146691 A

  An object of the present invention is to provide a glass member with a sealing material layer and a method for producing the same, which can increase the adhesive strength between the glass substrate and the sealing layer at the time of laser sealing with good reproducibility, and further the sealing layer and the glass substrate. It is an object of the present invention to provide an electronic device and a method for manufacturing the same that can improve the sealing reliability, the mechanical reliability, and the like by increasing the adhesive strength.

A glass member with a sealing material layer according to an aspect of the present invention is provided on a glass substrate having a sealing region, the sealing region of the glass substrate, a sealing glass, a low expansion filler, and a laser absorber. And a sealing material layer composed of a fired layer of a sealing glass material containing 20 to 68% SnO, 0.5 to 5% SnO ₂ and 20 to 40% by mass ratio. P ₂ O ₅ and the amount of residual carbon in the sealing material layer is in the range of 20 to 1000 ppm by mass.

The manufacturing method of the glass member with the sealing material layer which concerns on the aspect of this invention is the process of preparing the glass substrate which has a sealing area | region, and the SnO of 20-68% by mass ratio in the said sealing area | region of the said glass substrate. Applying a paste of a sealing glass material containing a sealing glass containing 0.5 to 5% SnO ₂ and 20 to 40% P ₂ O ₅ , a low expansion filler and a laser absorber; And firing the paste coating layer to form a sealing material layer having a residual carbon content in the range of 20 to 1000 ppm by mass.

An electronic device according to another aspect of the present invention includes a first glass substrate having an element formation region including an electronic element, and a first sealing region provided on an outer peripheral side of the element formation region, A second glass substrate having a second sealing region corresponding to the first sealing region of the first glass substrate; the first sealing region of the first glass substrate; and the second glass. Sealing formed between the second sealing region of the substrate so as to be sealed while providing a gap on the element forming region, and containing sealing glass, a low expansion filler, and a laser absorbing material A sealing layer made of a melt-fixed layer of a glass material, and the sealing glass is 20 to 68% SnO, 0.5 to 5% SnO ₂ and 20 to 40% P ₂ O _{5 by} mass ratio. And the amount of residual carbon in the sealing layer is 20 to 1000 ppm by mass It is characterized by a range.

An electronic device manufacturing method according to another aspect of the present invention includes a first glass substrate having an element formation region including an electronic element and a first sealing region provided on an outer peripheral side of the element formation region. A step of preparing, a second sealing region corresponding to the first sealing region of the first glass substrate, and a second sealing region formed on the second sealing region, and having a mass ratio of 20 to 68%. Comprising a fired layer of a sealing glass material comprising a sealing glass containing SnO, 0.5-5% SnO ₂ and 20-40% P ₂ O ₅ , a low expansion filler and a laser absorber, and A step of preparing a second glass substrate having a sealing material layer having a residual carbon content in a range of 20 to 1000 ppm by mass, and forming the gap on the element formation region, The first glass substrate and the second glass substrate through A step of laminating and irradiating the sealing material layer with a laser beam through the second glass substrate to melt the sealing material layer between the first glass substrate and the second glass substrate. And a step of forming a sealing layer to be sealed.

  According to the glass member with a sealing material layer and the manufacturing method thereof according to the aspect of the present invention, the adhesive strength between the glass substrate and the sealing layer can be improved with good reproducibility at the time of laser sealing. Therefore, according to the electronic device and the manufacturing method thereof according to the aspect of the present invention, it is possible to improve the sealing reliability and mechanical reliability of the electronic device.

It is sectional drawing which shows the structure of the electronic device by embodiment of this invention. It is sectional drawing which shows the manufacturing process of the electronic device by embodiment of this invention. It is a top view which shows the 1st glass substrate used in the manufacturing process of the electronic device shown in FIG. It is sectional drawing along the AA line of FIG. It is a top view which shows the 2nd glass substrate used at the manufacturing process of the electronic device shown in FIG. It is sectional drawing along the AA line of FIG.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing a configuration of an electronic device according to an embodiment of the present invention, FIG. 2 is a diagram showing a manufacturing process of the electronic device, and FIGS. 3 to 6 are diagrams showing a configuration of a glass substrate used therefor. An electronic device 1 shown in FIG. 1 constitutes a lighting device using a light emitting element such as an FPD such as an OELD, PDP, or LCD, or an OEL element, or a solar cell such as a dye-sensitized solar cell.

The electronic device 1 includes a first glass substrate (element glass substrate) 2 having an element formation region 2 a including an electronic element, and a second glass substrate (sealing glass substrate) 3. The first and second glass substrates 2 and 3 are made of, for example, non-alkali glass or soda lime glass. The alkali-free glass has a thermal expansion coefficient of about 35 to 40 × 10 ⁻⁷ / ° C. Soda lime glass has a thermal expansion coefficient of about 85 to 90 × 10 ⁻⁷ / ° C.

  In the element formation region 2a of the first glass substrate 2, an electronic element corresponding to the electronic device 1, for example, an OEL element for OELD or OEL illumination, a plasma light emitting element for PDP, a liquid crystal display element for LCD, In the case of a solar cell, a dye-sensitized photoelectric conversion unit and the like are formed. Electronic elements such as light emitting elements such as OEL elements and solar cell elements such as dye-sensitized photoelectric conversion units have various known structures, and are not limited to these element structures. The electronic device of the present invention is preferably an organic EL (OEL) device or a solar cell device.

As shown in FIGS. 3 and 4, the first glass substrate 2 has a first sealing region 2 b provided on the outer peripheral side of the element formation region 2 a. The first sealing region 2b is set so as to surround the element formation region 2a. As shown in FIG. 5, the second glass substrate 3 has a second sealing region 3a. The second sealing region 3a corresponds to the first sealing region 2b.
That is, when the first glass substrate 2 and the second glass substrate 3 are disposed to face each other, the first sealing region 2b and the second sealing region 3a are set to face each other, which will be described later. Thus, it becomes the formation region of the sealing layer 4 (the formation region of the sealing material layer 5 for the second glass substrate 3).

  The first glass substrate 2 and the second glass substrate 3 are disposed to face each other so as to form a gap on the element formation region 2a. The space between the first glass substrate 2 and the second glass substrate 3 is sealed with a sealing layer 4. That is, the sealing layer 4 is sealed between the sealing region 2b of the first glass substrate 2 and the sealing region 3a of the second glass substrate 3 while providing a gap on the element formation region 2a. Is formed. The electronic element formed in the element formation region 2 a is hermetically sealed with a glass panel constituted by the first glass substrate 2, the second glass substrate 3, and the sealing layer 4.

  The sealing layer 4 is a melt obtained by melting the sealing material layer 5 formed on the sealing region 3 a of the second glass substrate 3 with the laser beam 6 and fixing the sealing material layer 5 to the sealing region 2 b of the first glass substrate 2. It consists of a fixed layer. That is, the frame-shaped sealing material layer 5 is formed in the sealing region 3a of the second glass substrate 3 used for manufacturing the electronic device 1 as shown in FIGS. The sealing material layer 5 formed in the sealing region 3a of the second glass substrate 3 is sealed with the heat of the laser light 6 as shown in FIGS. 2 (c) and 2 (d). The sealing layer 4 that seals the space (element arrangement space) between the first glass substrate 2 and the second glass substrate 3 is formed by melting and fixing to the region 2b.

The sealing material layer 5 is a fired layer of a sealing glass material containing sealing glass (glass frit), a laser absorber, and a low expansion filler. The glass material for sealing is obtained by blending a laser absorbing material and a low expansion filler into sealing glass as a main component. The glass material for sealing may contain additives other than these as required. The sealing glass as the main component of the glass material for sealing contains tin having a composition of 20 to 68% SnO, 0.5 to 5% SnO ₂ and 20 to 40% P ₂ O ₅ by mass ratio. Phosphoric acid (SnO—P ₂ O ₅ based) glass is used. As will be described later, the content of the sealing glass as the main component of the sealing glass material depends on the blending amount of the laser absorber and the low expansion filler, but is 40 to 90 volumes with respect to the sealing glass material. %, Preferably 45 to 80% by volume. The sealing glass (glass frit) is preferably in the form of powder, and the maximum particle size is preferably 100 μm or less, more preferably 50 μm or less.

  The sealing glass (glass frit) for laser sealing is preferably such that the glass itself does not absorb the laser (transparent glass) in order to control the melting temperature of the glass. By controlling the melting temperature with the type and amount of the laser absorbing material added to the sealing glass, the laser sealing step can be performed with high reliability. The sealing glass (glass frit) preferably has a lower melting temperature in order to suppress thermal shock to the glass substrates 2 and 3. Furthermore, it is preferable not to contain lead, vanadium or the like in consideration of the influence on the environment and the human body. Tin-phosphate glass frit meets these requirements.

  In the sealing glass (tin-phosphate glass frit) used in this embodiment, SnO is a component for lowering the melting point of the glass, and is contained in the sealing glass in a range of 20 to 68% by mass. If the SnO content is less than 20% by mass, the softening temperature of the glass becomes high, and sealing at low temperatures becomes difficult. Furthermore, in order to soften the glass, it is necessary to increase the output of the laser beam 6, and as a result, cracks and the like are likely to occur in the glass substrates 2 and 3. If the SnO content exceeds 68 mass%, it will not vitrify. The SnO content is more preferably in the range of 30 to 65% by mass.

SnO ₂ is a component for stabilizing the glass, and is contained in the sealing glass in a range of 0.5 to 5% by mass. If the content of SnO ₂ is less than 0.5% by mass, the stability of the glass is lowered and devitrification is likely to occur, and devitrified substances are easily mixed during glass production. Further, SnO ₂ separates and precipitates in the glass that has been softened and melted during the laser heating, and the fluidity is impaired and the hermeticity tends to be lowered. When the content of SnO ₂ exceeds 5% by mass, SnO ₂ is likely to precipitate from the melting during glass production, and a stable glass cannot be obtained. In consideration of the stability and fluidity of the glass, the SnO ₂ content is more preferably in the range of 1 to 3.5% by mass.

P ₂ O ₅ is a component for forming a glass skeleton, and is contained in the sealing glass in a range of 20 to 40% by mass. When the content of P ₂ O ₅ is less than 20% by mass, it does not vitrify. The content of P ₂ O ₅ is likely to cause deterioration of weather resistance is phosphate glass inherent disadvantages exceeds 40 mass%. In consideration of the stability and weather resistance of the glass, the content of P ₂ O ₅ is more preferably in the range of 25 to 40% by mass.

Here, the mass ratio of SnO and SnO ₂ in the glass frit can be determined as follows. First, after the glass frit (low melting point glass powder) is acid-decomposed, the total amount of Sn atoms contained in the glass frit is measured by ICP emission spectroscopic analysis. Next, since Sn ²⁺ (SnO) is obtained by acidimetric decomposition, the amount of Sn ²⁺ determined there is subtracted from the total amount of Sn atoms to obtain Sn ⁴⁺ (SnO ₂ ).

The glass formed of the above-mentioned three components has a low glass transition point and is suitable for a sealing material for low temperature. However, SiO ₂ , ZnO, B ₂ O ₃ , Al ₂ O ₃ , WO ₃ , MoO ₃ , Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, MgO, CaO, SrO, BaO and other optional components may be contained. However, if the individual content of each component or the total content of optional components is too large, the glass becomes unstable, causing devitrification during glass production, and even if no devitrification occurs. There is a possibility that the tendency becomes too strong, and the glass is crystallized without being softened and flowing during heating, and cannot be adhered to the glass substrates 2 and 3.

From such a point, it is preferable that the total content of the optional components described above is 15% by mass or less. Of the optional components, SiO ₂ is a component that forms a glass skeleton, and the content thereof is preferably 10% by mass or less. Further, it is desirable to contain 0.1 to 5% by mass of SiO ₂ as an essential component. ZnO, B ₂ O ₃ , Al ₂ O ₃ , WO ₃ , MoO ₃ , Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, MgO, CaO, SrO BaO and the like are components that stabilize the glass, and each individual content is preferably 10% by mass or less. If the individual content of each component exceeds 10% by mass, devitrification may occur during glass production, or the crystallization tendency of the glass may increase.

Among the optional components described above, ZnO, B ₂ O ₃ , Al ₂ O ₃ , WO ₃ , MoO _{3 and the} like have an effect of reducing the thermal expansion coefficient of the glass in addition to stabilizing the glass. Preferably, ZnO is an essential component and 2 to 6% by mass is preferably contained. Nb ₂ O ₅ , TiO ₂ , ZrO _{2 and the} like have an effect of improving chemical durability. Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, etc. have the effect of lowering the softening point of the glass and improving the fluidity.
MgO, CaO, SrO, BaO, etc. have the effect of adjusting the viscosity of the glass and adjusting the thermal expansion coefficient. As described above, the content of each of these components is preferably in a range where the total content of arbitrary components does not exceed 15% by mass, and more preferably 10% by mass or less.

The glass material for sealing contains a low expansion filler. As the low expansion filler, at least one selected from the group consisting of silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compound, soda lime glass and borosilicate glass is preferably used. As the zirconium phosphate compound, (ZrO) ₂ P ₂ O ₇ , AZr ₂ (PO ₄ ) ₃ (A is at least one selected from the group consisting of Na, K and Ca), NbZr ₂ (PO ₄ ) ₃ , Zr ₂ (WO ₃ ) (PO ₄ ) ₂ , or a composite compound thereof. The low expansion filler has a lower thermal expansion coefficient than the sealing glass which is the main component of the sealing glass material.

The content of the low expansion filler is appropriately set so that the thermal expansion coefficient of the sealing glass approaches the thermal expansion coefficient of the glass substrates 2 and 3. The low expansion filler is preferably contained in the range of 1 to 50% by volume with respect to the glass material for sealing, although it depends on the thermal expansion coefficient of the sealing glass and the glass substrates 2 and 3. When the glass substrates 2 and 3 are formed of alkali-free glass (thermal expansion coefficient: 35 to 40 × 10 ⁻⁷ / ° C.), a relatively large amount (for example, a range of 30 to 50% by volume) of a low expansion filler is used. It is preferable to add. When the glass substrates 2 and 3 are formed of soda lime glass (thermal expansion coefficient: 85 to 90 × 10 ⁻⁷ / ° C.), a relatively small amount (for example, a range of 15 to 40% by volume) of a low expansion filler is used. It is preferable to add. The low expansion filler is preferably in the form of powder, and the maximum particle size is preferably 100 μm or less, and more preferably 50 μm or less.

  The glass material for sealing further contains a laser absorber. As the laser absorber, a compound such as at least one metal selected from the group consisting of Fe, Cr, Mn, Co, Ni and Cu or an oxide containing the metal is used. The content of the laser absorber is preferably in the range of 0.1 to 10% by volume with respect to the sealing glass material. When the content of the laser absorber is less than 0.1% by volume, the sealing material layer 5 cannot be sufficiently melted at the time of laser irradiation. When the content of the laser absorbing material exceeds 10% by volume, the second glass substrate 3 is cracked or sealed due to local heat generation near the interface with the second glass substrate 3 during laser irradiation, or sealing. There is a possibility that the fluidity at the time of melting of the glass material is deteriorated and the adhesiveness with the first glass substrate 2 is lowered. The content of the laser absorber is more preferably in the range of 1 to 9% by volume. The laser absorbing material is preferably in the form of powder, and the maximum particle size thereof is preferably 50 μm or less, and more preferably 20 μm or less.

  As described above, the tin-phosphate glass frit used in this embodiment is suitable as a sealing material for low-temperature heating because it has characteristics such as being transparent and having a low glass transition point. However, in forming the sealing layer 4 by irradiating the sealing material layer 5 with the laser beam 6, the glass substrate 2 can be obtained simply by applying tin-phosphate glass frit (sealing glass) to laser sealing. 3 and the sealing layer 4 cannot be sufficiently increased. This is considered to be based on the difference in the melting condition of the glass frit between the heating by the baking furnace and the laser heating.

  The adhesive strength between the glass substrate and the glass frit is based on the residual strain due to the difference in thermal expansion between them and the interfacial reaction between the glass substrate and the glass frit. When heating by a general firing furnace is applied, a reaction layer is formed at the interface between the glass substrate and the glass frit (sealing layer) regardless of the type of glass substrate or glass frit, and adhesion is achieved by chemical bonding. Strength can be increased. In other words, since the sealing process to which heating by the baking furnace is applied has a time for forming the reaction layer at the bonding interface, it is possible to obtain sufficient bonding strength.

On the other hand, the sealing step to which laser heating is applied is performed by irradiating the laser beam 6 while scanning along the frame-shaped sealing material layer 5. The sealing material layer 5 is melted in order from the portion irradiated with the laser beam 6 and is rapidly cooled and solidified when the irradiation of the laser beam 6 is completed. Thus, the reaction layer formation time cannot be sufficiently obtained in the laser sealing step. For this reason, only the glass frit having a three-component composition of SnO, SnO ₂ and P ₂ O ₅ cannot sufficiently increase the adhesive strength between the glass substrates 2 and 3 and the sealing layer 4 during laser sealing.

  In the sealing step to which laser heating is applied, in order to form a reaction layer at the adhesive interface between the glass substrates 2 and 3 and the sealing layer 4, the sealing material layer (firing layer for sealing glass material) 5 It is effective to leave an appropriate amount of carbon. That is, the carbon remaining in the sealing material layer 5 formed using the tin-phosphate glass frit functions as a reducing agent. For this reason, even in laser sealing in which local melting and solidification of the glass frit is performed in a short time, by reducing tin oxide with residual carbon in the sealing material layer 5, the glass substrates 2 and 3 and tin-phosphorus are reduced. The reactivity with the acid glass frit can be improved.

  That is, tin oxide (particularly SnO that is easily reduced) in the tin-phosphate glass frit is reduced with residual carbon during laser irradiation, so that a part of tin oxide becomes metal tin (Sn). Metal tin (Sn) has the property of easily diffusing into the glass substrates 2 and 3. Therefore, even in the laser sealing step in which the glass frit is melted and solidified in a short time by allowing an appropriate amount of metallic tin (Sn) to be present in the sealing material layer 5 melted by irradiation with the laser beam 6, A reaction layer can be formed at the adhesive interface. Therefore, it is possible to increase the adhesive strength between the glass substrates 2 and 3 and the tin-phosphate glass frit (sealing layer 4) at the time of laser sealing.

  The amount of carbon remaining in the sealing material layer 5 (the amount of residual carbon in the sealing material layer 5) is set to a range of 20 to 1000 ppm by mass ratio. If the residual carbon content of the sealing material layer 5 is less than 20 ppm, the ability as a reducing agent is insufficient, and the above-described reduction effect of tin oxide cannot be obtained sufficiently. That is, metal tin cannot be generated sufficiently, and as a result, the adhesive strength between the glass substrates 2 and 3 and the sealing layer 4 cannot be sufficiently increased. On the other hand, if the residual carbon content of the sealing material layer 5 exceeds 1000 ppm, the amount of metal tin produced becomes excessive, the glass resistance value is lowered, and the insulating property of the sealing layer 4 cannot be maintained. This causes various inconveniences.

  That is, in the sealing region 2b of the first glass substrate 2, a wiring for leading out the electrode of the electronic element formed in the element forming region 2a is formed. Excessive residual carbon lowers the insulating properties of the sealing layer 4, so that there is a possibility that inconvenience such as a short circuit may occur between the wirings formed on the first glass substrate 2 based on the sealing layer 4. Considering the effect of improving the adhesive strength between the glass substrates 2 and 3 and the sealing layer 4 and maintaining the insulation of the sealing layer 4, the residual carbon content of the sealing material layer 5 is 30 to 500 ppm by mass. It is more preferable to set the range. A method for controlling the amount of carbon remaining in the sealing material layer 5 will be described later.

  The thickness T1 of the sealing material layer 5 is set according to the required gap between the first glass substrate 2 and the second glass substrate 3, that is, the thickness T2 of the sealing layer 4. The electronic device 1 and the manufacturing process thereof according to this embodiment are particularly effective when the thickness T1 of the sealing material layer 5 is 10 μm or more. Further, the thickness T1 of the sealing material layer 5 is more preferably 10 to 100 μm. Even when the sealing material layer 5 having such a thickness T1 is sealed by irradiating the laser beam 6, according to this embodiment, the adhesive strength between the glass substrates 2, 3 and the sealing layer 4, It is possible to improve the hermetic sealing property of the glass panel.

The residual carbon in the sealing material layer 5 is not limited to the case where tin-phosphate glass frit is used, but glass frit having other composition (sealing glass), for example, bismuth (Bi ₂ O ₃ —B _2). This is also effective in the case of using (O ₃ system) glass frit. That is, even when the sealing material layer is formed using a glass frit containing 70 to 90% Bi ₂ O ₃ , 1 to 20% ZnO, and 2 to 12% B ₂ O ₃ by mass ratio, By leaving an appropriate amount of carbon, an effect similar to that obtained when a tin-phosphate glass frit is used can be expected.

  The sealing material layer 5 made of the sealing glass material as described above is formed on the sealing region 3a of the second glass substrate 3 as follows, for example. First, a sealing glass paste containing a sealing glass (tin-phosphate glass frit), a laser absorbing material, and a low expansion filler is mixed with a vehicle to prepare a sealing material paste.

  Examples of the vehicle include those obtained by dissolving a resin such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, and nitrocellulose in a solvent such as terpineol, butyl carbitol acetate, ethyl carbitol acetate, or methyl ( What melt | dissolved acrylic resins, such as a meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl methacrylate, in solvents, such as methyl ethyl ketone, terpineol, butyl carbitol acetate, and ethyl carbitol acetate. Used.

  The viscosity of the sealing material paste may be adjusted to the viscosity corresponding to the apparatus applied to the glass substrate 3, and can be adjusted by the ratio of the resin (binder component) and the solvent or the ratio of the sealing glass material and the vehicle. A known additive may be added to the sealing material paste as a glass paste such as an antifoaming agent or a dispersing agent. A known method using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill or the like can be applied to the preparation of the sealing material paste.

  A sealing material paste is applied to the sealing region 3a of the second glass substrate 3, and this is dried to form an application layer of the sealing material paste. The sealing material paste is applied onto the second sealing region 3a by applying a printing method such as screen printing or gravure printing, or is applied along the second sealing region 3a using a dispenser or the like. To do. The coating layer of the sealing material paste is dried, for example, at a temperature of 120 ° C. or more for 10 minutes or more. A drying process is implemented in order to remove the solvent in an application layer. If the solvent remains in the coating layer, the binder component may not be sufficiently removed in the subsequent firing step.

  The coating layer of the sealing material paste described above is fired to form the sealing material layer 5. In the firing step, first, the coating layer is heated to a temperature not higher than the glass transition point of sealing glass (glass frit), which is the main component of the sealing glass material, and the binder component in the coating layer is removed. The glass material for sealing is heated to a temperature equal to or higher than the softening point of the glass frit, and the glass material for sealing is melted and baked on the glass substrate 3. Thus, the sealing material layer 5 which consists of a baking layer of the glass material for sealing is formed. It is preferable to perform the baking process of the coating layer of sealing material paste in the temperature range of 200-500 degreeC, and it is more preferable to carry out in the temperature range of 230-430 degreeC.

  In the step of forming the sealing material layer 5 as described above, (1) an organic substance or carbon is used as a carbon source in the sealing glass (or sealing glass material), and a part of the carbon derived from the carbon source remains. (2) by applying a method such as leaving a part of carbon derived from the binder component (organic resin) or the organic solvent in the sealing material paste, the residual carbon amount of the sealing material layer 5 is reduced. Control. In addition, even if it is a method other than these, if it is a method which can make the residual carbon amount of the sealing material layer 5 into the range of 20-1000 ppm by mass ratio, it is applicable.

  Regarding the method (1) described above, for example, an organic substance such as alcohol is added as a carbon source when the glass is crushed. In this method, alcohol or the like also acts as a grinding aid, so that the glass grinding efficiency can be increased. The carbon source added to the sealing glass is not limited to an organic substance, and may be carbon such as carbon black or graphite. Even if the addition amount of carbon sources such as organic substances and carbon to the sealing glass is constant, the amount of residual carbon varies depending on the firing conditions, so the correlation between how much the pre-added carbon source remains after firing is calculated. deep. Based on this, the residual carbon amount of the sealing material layer 5 is controlled. Further, the amount of residual carbon may be controlled by making the addition amount of the carbon source constant and changing the firing conditions (temperature, time).

  The method (2) is a method in which a carbon source derived from a binder component (organic resin) or an organic solvent used for forming a paste is left without adding a carbon source to the sealing glass. In this case, the composition of the vehicle, the composition ratio between the sealing glass material and the vehicle when making the paste, the firing conditions, particularly the temperature rise rate in the temperature range from the temperature range where the resin burns and decomposes to the softening of the sealing glass And retention time is important. The vehicle used for producing the sealing material paste is not particularly limited when the method (1) is applied. However, when the method (2) is applied, nitrocellulose is replaced with terpineol, butyl carbitol acetate, ethyl. It is preferable to use those dissolved in an organic solvent such as carbitol acetate.

  The vehicle used in the method (2) is 0.5 to 5% by mass of nitrocellulose, any one organic solvent selected from the group consisting of terpineol, butyl carbitol acetate and ethyl carbitol acetate, or two kinds It is preferable that the solvent is dissolved in 95 to 99.5% by mass of the above mixed solvent. Furthermore, regarding pasting of the sealing glass material, it is preferable to prepare a sealing material paste by mixing 85 to 93% by mass of the sealing glass material with 7 to 15% by mass of the vehicle. By using such a vehicle or sealing material paste, the controllability of the residual carbon amount of the sealing material layer 5 is improved.

  With respect to the baking process of the sealing material paste coating layer, generally, conditions that can completely burn and decompose the resin component are applied so as not to reduce the glass material for sealing. Specifically, the resin is burned by slowing the rate of temperature rise in the temperature range below the temperature at which the sealing glass softens and flows above the temperature at which the resin burns and decomposes, or by holding for about 1 to 15 hours, It promotes decomposition. When the method (2) is applied, an appropriate amount of carbon is left in the sealing material layer 5 by controlling the combustion and decomposition processes of the resin.

  As described above, nitrocellulose is preferred as the resin component in the vehicle. Nitrocellulose burns and decomposes at temperatures in the range of 200-250 ° C. The temperature at which the sealing glass of this embodiment softens and flows is in the range of 260 to 450 ° C. For this reason, the temperature range of 200-450 degreeC becomes important. The sealing material layer 5 having residual carbon as described above can be obtained by controlling the temperature rising rate of 200 to 450 ° C. Specifically, it is preferable to raise the temperature range of 200 to 450 ° C. at a rate of 10 to 35 ° C./min. When firing in a batch furnace or the like, when keeping in the temperature range of 200 to 450 ° C. to make the furnace temperature uniform, the holding time is preferably less than 20 minutes. By applying such conditions, the amount of residual carbon in the sealing material layer 5 can be controlled within a desired range.

  Next, as shown to Fig.2 (a), the 2nd glass substrate 3 which has the sealing material layer 5, and the 1st glass substrate 2 which has the element formation area 2a provided with the electronic device produced separately from it, Is used to manufacture an electronic device 1 such as an OELD, PDP, LCD or other FPD, an illumination device using an OEL element, or a solar cell such as a dye-sensitized solar cell. That is, as shown in FIG. 2B, the first glass substrate 2 and the second glass substrate 3 are arranged such that the surface having the element formation region 2a and the surface having the sealing material layer 5 face each other. Laminate. A gap is formed on the element formation region 2 a of the first glass substrate 2 based on the thickness of the sealing material layer 5.

  Next, as shown in FIG. 2C, the sealing material layer 5 is irradiated with laser light 6 through the second glass substrate 3. The laser beam 6 is irradiated while scanning along the frame-shaped sealing material layer 5. The laser beam 6 is not particularly limited, and a laser beam from a semiconductor laser, a carbon dioxide gas laser, an excimer laser, a YAG laser, a HeNe laser, or the like is used. The output of the laser beam 6 is appropriately set according to the thickness of the sealing material layer 5 and the like, but is preferably in the range of 2 to 150 W, for example. If the laser output is less than 2 W, the sealing material layer 5 may not be melted, and if it exceeds 150 W, cracks and cracks are likely to occur in the glass substrates 2 and 3. The output of the laser beam is more preferably in the range of 5 to 100W.

  The sealing material layer 5 is melted in order from the portion irradiated with the laser beam 6 scanned along the sealing material layer 5, and is rapidly cooled and solidified and fixed to the first glass substrate 2 when the irradiation of the laser beam 6 is completed. Then, by irradiating the entire circumference of the sealing material layer 5 with the laser beam 6, as shown in FIG. 2 (d), a seal that seals between the first glass substrate 2 and the second glass substrate 3 is sealed. The wearing layer 4 is formed. Since the sealing material layer 5 using the sealing glass (tin-phosphate glass frit) improves the reactivity with the glass substrate 2 based on the residual carbon, the laser beam 6 can be irradiated in a short time. Also in the melting and solidifying step (sealing step), the adhesion between the glass substrate 2 and the sealing glass is improved. Therefore, the adhesive strength between the glass substrates 2 and 3 and the sealing layer 4 can be increased.

  In this way, an electronic device 1 in which an electronic element formed in the element formation region 2a is hermetically sealed with a glass panel constituted by the first glass substrate 2, the second glass substrate 3, and the sealing layer 4 is formed. Make it. The glass panel whose inside is hermetically sealed is not limited to the electronic device 1 but can also be applied to a sealing body (package) of an electronic component or a glass member (building material or the like) such as vacuum pair glass. .

  The reliability of the electronic device 1 depends on the hermetic sealing property by the sealing layer 4 and the adhesive strength between the glass substrates 2 and 3 and the sealing layer 4. According to this embodiment, since the hermetic sealing property and the adhesive strength can be increased, it is possible to obtain the electronic device 1 having excellent reliability. Here, the carbon in the sealing material layer 5 remains even after laser sealing. For this reason, the sealing layer 4 formed by using the sealing material layer 5 having a residual carbon amount in the range of 20 to 1000 ppm by mass ratio has a residual carbon amount itself that is the sealing material, even if the carbon form is changed. Equivalent to layer 5. Therefore, according to the sealing layer 4 having a residual carbon content in the range of 20 to 1000 ppm by mass ratio, it is possible to improve the sealing reliability and mechanical reliability of the electronic device 1.

  Next, specific examples of the present invention and evaluation results thereof will be described. In addition, the following description does not limit this invention, The modification | change in the form along the meaning of this invention is possible.

Example 1
Tin having a composition of SnO 55.7%, SnO ₂ 3.1%, P ₂ O ₅ 32.5%, ZnO 4.8%, Al ₂ O ₃ 2.3%, SiO ₂ 1.6% by mass ratio Phosphate glass frit, zirconium phosphate ((ZrO) ₂ P ₂ O ₇ ) powder as low expansion filler, Fe ₂ O ₃ 35%, Cr ₂ O ₃ 35%, Co ₂ O ₃ 20% by mass ratio, A laser absorber having a composition of 10% MnO was prepared. Further, 4% by mass of nitrocellulose as a binder component was dissolved in 96% by mass of a solvent made of butyl carbitol acetate to prepare a vehicle.

  The tin-phosphate glass frit is manufactured as follows. First, glass cullet was prepared by melting glass so as to have the above component ratio. Next, the glass cullet was pulverized with an alumina ball mill. At this time, 2 cc of ethanol was added to 1 kg of glass as a grinding aid. Next, it classified so that the maximum particle size might be set to 8 micrometers with an airflow classifier, and the target tin-phosphate glass frit was obtained.

Next, a glass material (thermal expansion coefficient: 47 × 10 ⁻⁷ / s) that is sealed by mixing 56 volume% of the tin-phosphate glass frit, 42 volume% of zirconium phosphate powder, and 2 volume% of the laser absorber. ° C). A sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of vehicle. Next, a sealing material paste is applied to the outer peripheral region of the second glass substrate (dimension: 90 × 90 × 0.7 mmt) made of alkali-free glass (thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C.) by screen printing. After coating (line width: 500 μm), drying was performed at 120 ° C. for 10 minutes.

  The coating layer of the sealing material paste after drying is heated to 250 ° C. at a temperature rising rate of 5 ° C./min, held at this temperature for 40 minutes, and subjected to binder removal treatment, and then 430 ° C. at a temperature rising rate of 5 ° C./min. The mixture was heated up to 10 minutes and held at this temperature for 10 minutes for firing. In this way, a sealing material layer having a film thickness T1 of 60 μm was formed. The residual carbon content of the sealing material layer was 200 ppm. The residual carbon content of the sealing material layer is a value measured using a carbon / sulfur analyzer EMIA-320V (trade name, manufactured by HORIBA, Ltd.). The same applies to the other embodiments.

  The second glass substrate having the sealing material layer described above and a first glass substrate having an element formation region (region in which an OEL element is formed) (consisting of an alkali-free glass having the same composition and shape as the second glass substrate). Substrate). Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 25 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer. Thus, the first glass substrate and the second glass substrate were sealed. In addition, when the residual carbon amount of the sealing layer was measured in the same manner as the sealing material layer, it was confirmed that it was equivalent to the residual carbon amount of the sealing material layer. Thus, the electronic device which sealed the element formation area with the glass panel was used for the characteristic evaluation mentioned later.

(Examples 2 to 4)
A sealing material paste was prepared in the same manner as in Example 1 except that the composition of the tin-phosphate glass frit, the type of the low expansion filler and the laser absorber, and the mixing ratio thereof were changed to the conditions shown in Table 1. did. While using these sealing material pastes and changing the control method of the residual carbon amount of the sealing material layer to the method shown below, the sealing material layer for the second glass substrate was changed in the same manner as in Example 1. Formation and laser sealing of the first glass substrate and the second glass substrate were performed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later. Regarding the residual carbon content of the sealing material layer, Example 2 was 450 ppm, Example 3 was 70 ppm, and Example 4 was 850 ppm. The amount of residual carbon was measured in the same manner as in Example 1.

  In Example 2, the amount of residual carbon in the sealing material layer was controlled as follows. When producing a glass material for sealing by mixing a tin-phosphate glass frit, a low expansion filler and a laser absorber, carbon black was blended as a reducing agent. The compounding quantity of carbon black was 500 ppm with respect to the glass material for sealing. A coating layer of the sealing material paste (dried at 120 ° C. × 10 minutes) was formed in the same manner as in Example 1 except that such a sealing glass material was used. The coating layer of the sealing material paste after drying is heated to 230 ° C. at a temperature rising rate of 8 ° C./min, held at this temperature for 60 minutes, and subjected to binder removal treatment, and then 430 ° C. at a temperature rising rate of 8 ° C./min. The mixture was heated up to 10 minutes and held at this temperature for 10 minutes for firing.

  In Example 3, the residual carbon content of the sealing material layer was controlled as follows. In the same manner as in Example 1, a coating layer of the sealing material paste was formed. The sealing material paste was prepared by mixing 84% by mass of the sealing glass material with 16% by mass of the vehicle. The coating layer was dried under the conditions of 120 ° C. × 10 minutes. Note that ethanol was not used during the pulverization of the glass cullet. The coating layer of the sealing material paste after drying was heated to 430 ° C. at a temperature increase rate of 25 ° C./min, held at this temperature for 10 minutes, and fired. In Example 4, the amount of residual carbon was controlled under the same conditions as in Example 2. Under the present circumstances, the compounding quantity of carbon black was 1000 ppm with respect to the glass material for sealing. In Examples 2 to 4, the residual carbon content of the sealing layer was equivalent to that of the sealing material layer.

(Examples 5-6)
A tin-phosphate glass frit, a low expansion filler, and a laser absorber shown in Table 1 were prepared, and these were mixed at a composition ratio shown in Table 1 to prepare glass materials for sealing. A sealing material paste was prepared by mixing 82% by mass of these sealing glass materials with 18% by mass of the same vehicle as in Example 1. Next, a sealing material paste is applied to each outer peripheral region of a second glass substrate (dimensions: 100 × 100 × 0.55 mmt) made of soda lime glass (thermal expansion coefficient: 87 × 10 ⁻⁷ / ° C.) by screen printing. (Line width: 500 μm) and then dried under conditions of 120 ° C. × 10 minutes.

  By baking the application layer (after drying) of the sealing material paste described above, a sealing material layer having a film thickness T1 of 60 μm was formed. Regarding the method for controlling the amount of residual carbon in the sealing material layer, Example 5 was the same as Example 3, and Example 6 was the same as 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 first glass substrate having a second glass substrate having a sealing material layer and an element formation region (region where an OEL element is formed) (soda lime glass having the same composition and shape as the second glass substrate) Substrate). Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 40 W through the second glass substrate at a scanning speed of 5 mm / s to melt and rapidly solidify the sealing material layer. Thus, the first glass substrate and the second glass substrate were sealed. The residual carbon content of the sealing layer was equivalent to that of the sealing material layer. Thus, the electronic device which sealed the element formation area with the glass panel was used for the characteristic evaluation mentioned later.

(Comparative Example 1)
Using a tin-phosphate glass frit having the same composition as in Example 1, the production of a sealing glass material, the preparation of a sealing material paste, and the sealing material layer on the second glass substrate in the same manner as in Example 1. Formation and laser sealing of the first glass substrate and the second glass substrate were performed. As for the method for controlling the residual carbon content of the sealing material layer, a method of blending carbon black into the glass material for sealing was applied in the same manner as in Example 2. However, the compounding quantity of carbon black was 1500 ppm with respect to the glass material for sealing. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Comparative Example 2)
Vanadium having a composition of 44.3% V ₂ O ₅ , 35.1% Sb ₂ O ₃ , 19.7% P ₂ O ₅ , 0.5% Al ₂ O ₃ , 0.4% TiO _{2 by} mass ratio. Zirconium phosphate powder was prepared as a system glass frit and a low expansion filler. Further, 4% by mass of nitrocellulose as a binder component was dissolved in 96% by mass of butyl diglycol acetate to prepare a vehicle.

A glass material for sealing (thermal expansion coefficient: 74 × 10 ⁻⁷ / ° C.) was prepared by mixing 90% by volume of vanadium glass frit and 10% by volume of cordierite powder. A sealing material paste was prepared by mixing 73% by mass of the sealing glass material with 27% by mass of the vehicle. Next, the sealing material paste was applied by screen printing to the outer peripheral region of the second glass substrate made of alkali-free glass similar to that in Example 1 (line width W: 500 μm), and then the condition of 120 ° C. × 10 minutes. And dried. By baking this coating layer under the conditions of 450 ° C. × 10 minutes, a sealing material layer having a film thickness T1 of 60 μm was formed.

  Next, a first glass substrate having a second glass substrate having a sealing material layer and an element formation region (region where an OEL element is formed) (soda lime glass having the same composition and shape as the second glass substrate) Substrate). Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 40 W through the second glass substrate at a scanning speed of 5 mm / s to melt and rapidly solidify the sealing material layer. Thus, the first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the element formation region was sealed with the glass panel was subjected to the characteristic evaluation described later.

  Next, regarding the appearance of the glass panels of Examples 1 to 6 and Comparative Examples 1 and 2, the presence or absence of cracks in the glass substrate was evaluated. The appearance was evaluated by observing with an optical microscope. Moreover, the airtightness of each glass panel was measured. The airtightness was evaluated by applying a helium leak test. Furthermore, the adhesive strength with the glass substrate of the sealing layer by the glass material for sealing used in Examples 1-6 and Comparative Examples 1-2, and the resistance value of the sealing layer were measured as follows. These measurement / evaluation results are shown in Tables 1 and 2. Tables 1 and 2 also show the manufacturing conditions of the glass panel.

  The measuring method of the adhesive strength of the glass substrate by the glass material for sealing is as follows. First, a sealing material layer having a thickness of 60 μm and a line width of 1 mm is formed in the vicinity of the end of the first glass substrate having a width of 30 mm using the sealing material paste of each example. The paste coating layer is fired under conditions suitable for each. Then, the edge part of a 2nd glass substrate is arrange | positioned on a sealing material layer. The second glass substrate is disposed so as to alternate with the first glass substrate (the first and second glass substrates are arranged in a straight line with the sealing material layer as the center). Sealing is performed by irradiating the sealing material layer with laser light having a wavelength of 940 nm at a scanning speed of 10 mm / s while pressurizing them with a load of 10 kg. The output of the laser beam is a value suitable for each material. One glass substrate of the adhesive strength measurement sample thus formed is fixed with a jig, and a 20 mm portion from the sealing layer of the other glass substrate is pressed at a speed of 1 mm / min, and the sealing layer is broken. The load at that time is defined as the adhesive strength.

  The measuring method of the resistance value of the sealing layer is as follows. First, a glass substrate A on which two ITO conductive films are formed at intervals of 4.3 mm is prepared. Separately, a glass substrate B on which a sealing material layer (sealing material layer formed using the sealing material paste of each example) having a film thickness of 60 μm, a width of 1 mm, and a length of 30 mm is prepared. Next, the glass substrate A and the glass substrate B are overlaid so that the sealing material layer crosses over the two ITO conductive films. Sealing is performed by irradiating the sealing material layer from the glass substrate B side with laser light having a wavelength of 940 nm at a scanning speed of 10 mm / s.

For the resistance value measurement sample thus formed, electrodes are connected to two ITO conductive films, and a minute current is measured with a minute ammeter with a bias voltage of 100 V to obtain a resistance value. The measurement is performed in a nitrogen atmosphere. When the resistance value between the two ITO conductive films of the glass substrate A before laser sealing as a reference sample was measured, it was 2.0 × 10 ¹² Ω. Regarding the resistance value according to each example, Table 1 and Table 1 indicate that the measured value is 2.0 × 10 ¹¹ Ω or more as good (◯), and the measured value is less than 2.0 × 10 ¹¹ Ω as defective (×). It is shown in 2.

  As is clear from Tables 1 and 2, it can be seen that the glass panels according to Examples 1 to 6 are both excellent in appearance and airtightness and have better adhesive strength. On the other hand, although the adhesive strength is favorable in the glass panel of Comparative Example 1 in which the residual carbon content of the sealing material layer exceeds 1000 ppm, it can be seen that the insulating property of the sealing layer is lowered. In this case, there is a high possibility that inconvenience such as a short circuit occurs in the wiring formed on the glass substrate. Furthermore, the glass panel of the comparative example 2 using the conventional vanadium-type glass frit had low adhesive strength, and was inferior to the reliability of a glass panel (electronic device).

INDUSTRIAL APPLICATION This invention can be utilized for manufacture of electronic devices, such as a glass member with a sealing material layer, flat type display apparatuses, such as an organic electroluminescent display, a plasma display panel, and a liquid crystal display device, or a dye-sensitized solar cell.
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2008-323422 filed on Dec. 19, 2008 are cited here as disclosure of the specification of the present invention. Incorporated.

  DESCRIPTION OF SYMBOLS 1 ... Electronic device, 2 ... 1st glass substrate, 2a ... Element formation area, 2b ... 1st sealing area, 3 ... 2nd glass substrate, 3a ... 2nd sealing area, 4 ... Sealing layer 5 ... Sealing material layer, 6 ... Laser beam.

Claims (15)

A glass substrate having a sealing region;
Provided on the sealing region of the glass substrate, comprising a sealing material layer composed of a fired layer of a sealing glass material containing a sealing glass, a low expansion filler and a laser absorber,
The sealing glass contains 20 to 68% SnO, 0.5 to 5% SnO ₂ and 20 to 40% P ₂ O ₅ by mass ratio, and the amount of residual carbon in the sealing material layer is mass. A glass member with a sealing material layer, characterized by being in a range of 20 to 1000 ppm in proportion.   The low expansion filler is made of at least one selected from the group consisting of silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compound, soda lime glass and borosilicate glass, and the sealing glass material is The glass member with a sealing material layer according to claim 1, wherein the low expansion filler is contained in an amount of 1 to 50% by volume.   The laser absorber is made of at least one metal selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu, or a compound containing the metal, and the glass material for sealing has the laser absorber of 0. It contains in 1-10 volume% of range, The glass member with the sealing material layer of Claim 1 or Claim 2 characterized by the above-mentioned. The sealing glass further includes SiO ₂ , ZnO, B ₂ O ₃ , Al ₂ O ₃ , WO ₃ , MoO ₃ , Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , Li ₂ O, Na ₂ O, K ₂ O. 4. The method according to claim 1, comprising at least one selected from the group consisting of Cs ₂ O, MgO, CaO, SrO, and BaO in a mass ratio of 15% or less. 5. Glass member with a sealing material layer. Preparing a glass substrate having a sealing region;
A sealing glass containing 20 to 68% SnO, 0.5 to 5% SnO ₂ and 20 to 40% P ₂ O ₅ by mass ratio in the sealing region of the glass substrate; and a low expansion filler Applying a paste of a sealing glass material containing a laser absorber;
Baking the coating layer of the paste, and forming a sealing material layer having a residual carbon content in the range of 20 to 1000 ppm by mass, and a method for producing a glass member with a sealing material layer .   The sealing glass containing at least one of an organic substance and carbon as a carbon source is used, and a part of carbon derived from the carbon source is left in the sealing material layer in the firing step of the coating layer. The manufacturing method of the glass member with a sealing material layer of Claim 5 to do.   The low expansion filler is made of at least one selected from the group consisting of silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compound, soda lime glass and borosilicate glass, and the sealing glass material is The said low expansion filler is contained in 1-50 volume%, The manufacturing method of the glass member with a sealing material layer of Claim 5 or Claim 6 characterized by the above-mentioned.   The laser absorber is made of at least one metal selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu, or a compound containing the metal, and the glass material for sealing has the laser absorber of 0. It contains in 1-10 volume%, The manufacturing method of the glass member with a sealing material layer of any one of Claim 5 thru | or 7 characterized by the above-mentioned. The sealing glass further includes SiO ₂ , ZnO, B ₂ O ₃ , Al ₂ O ₃ , WO ₃ , MoO ₃ , Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , Li ₂ O, Na ₂ O, K ₂ O. 9. The method according to claim 5, comprising at least one selected from the group consisting of Cs ₂ O, MgO, CaO, SrO and BaO in a mass ratio of 15% or less. The manufacturing method of the glass member with a sealing material layer. A first glass substrate having an element formation region including an electronic element, and a first sealing region provided on an outer peripheral side of the element formation region;
A second glass substrate having a second sealing region corresponding to the first sealing region of the first glass substrate;
Formed so as to seal between the first sealing region of the first glass substrate and the second sealing region of the second glass substrate while providing a gap on the element formation region. A sealing layer comprising a sealing glass, a low-expansion filler and a laser-absorbing material, and a sealing layer composed of a melt-fixed layer of a sealing glass material,
The sealing glass contains 20 to 68% SnO, 0.5 to 5% SnO ₂ and 20 to 40% P ₂ O ₅ by mass ratio, and the amount of residual carbon in the sealing layer is mass ratio. An electronic device having a range of 20 to 1000 ppm. The sealing glass further includes SiO ₂ , ZnO, B ₂ O ₃ , Al ₂ O ₃ , WO ₃ , MoO ₃ , Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , Li ₂ O, Na ₂ O, K ₂ O. The electronic device according to claim 10, comprising at least one selected from the group consisting of Cs ₂ O, MgO, CaO, SrO, and BaO in a mass ratio of 15% or less.   12. The electronic device according to claim 10, wherein the electronic element is an organic EL element or a solar cell element. Preparing a first glass substrate having an element formation region including an electronic element and a first sealing region provided on an outer peripheral side of the element formation region;
A second sealing region corresponding to the first sealing region of the first glass substrate, and 20% to 68% SnO, 0.5% by mass, formed on the second sealing region, 0.5 It consists of a fired layer of a sealing glass material containing a sealing glass containing ˜5% SnO ₂ and 20-40% P ₂ O ₅ , a low expansion filler, and a laser absorber, and the residual carbon content is mass Preparing a second glass substrate having a sealing material layer in a range of 20 to 1000 ppm in proportion;
Laminating the first glass substrate and the second glass substrate through the sealing material layer while forming a gap on the element formation region;
Sealing that seals a gap between the first glass substrate and the second glass substrate by irradiating the sealing material layer with laser light through the second glass substrate to melt the sealing material layer. And a step of forming a layer. The sealing glass further includes SiO ₂ , ZnO, B ₂ O ₃ , Al ₂ O ₃ , WO ₃ , MoO ₃ , Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , Li ₂ O, Na ₂ O, K ₂ O. 14. The method of manufacturing an electronic device according to claim 13, comprising at least one selected from the group consisting of Cs ₂ O, MgO, CaO, SrO and BaO in a mass ratio of 15% or less.   15. The method of manufacturing an electronic device according to claim 13, wherein the electronic element is an organic EL element or a solar cell element.

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