JP2013062231A - Manufacturing method of electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laser sealing method capable of obtaining long-term reliability without providing a material which adsorbs a gas component into an organic EL device or the like.SOLUTION: A method for manufacturing an electronic device via laser sealing comprises the steps of: (1) preparing a glass substrate; (2) manufacturing a sealing material paste by mixing a sealing material containing a glass powder and a vehicle containing an organic binder; (3) forming a coating layer by coating the glass substrate with the sealing material paste; (4) obtaining a glass substrate with a sealing material layer by firing the coating layer; (5) overlaying the glass substrate with a sealing material layer and a glass substrate on which no sealing material layer is formed via the sealing material layer; and (6) airtightly sealing the glass substrate with the sealing material layer and the glass substrate on which no sealing material layer is formed by irradiating the glass substrates with a laser beam so that a laser sealing temperature becomes a firing temperature or lower.

Description

  The present invention relates to a method for manufacturing an electronic device, and more particularly to a method for manufacturing an organic EL device by laser sealing (sealing treatment with laser light).

  In recent years, organic EL displays have attracted attention as flat display panels. Since the organic EL display can be driven by a direct current voltage, the driving circuit can be simplified, and there are advantages such as a liquid crystal display that does not depend on the viewing angle, is bright because of self-emission, and has a high response speed. Currently, organic EL displays are mainly used in small portable devices such as mobile phones, but in the future, application to ultra-thin televisions is expected. Note that the organic EL display is mainly driven by disposing an active element such as a thin film transistor (TFT) in each pixel in the same manner as a liquid crystal display.

  The organic EL display is composed of two glass substrates, a negative electrode such as metal, an organic light emitting layer, a positive electrode such as ITO, and an adhesive material. Conventionally, an organic resin adhesive material such as an epoxy resin having a low temperature curability or an ultraviolet curable resin has been used as the adhesive material. However, organic resin adhesive materials cannot completely block gas intrusion. For this reason, when an organic resin adhesive material is used, the airtightness inside the organic EL display cannot be maintained, and as a result, the organic light emitting layer having low water resistance is easily deteriorated, and the organic EL display There is a problem that the display characteristics of the display deteriorate with time. In addition, the organic resin-based adhesive material has an advantage that the glass substrates can be bonded to each other at a low temperature. However, since the water resistance is low, when the organic EL display is used for a long time, the reliability of the display is likely to be lowered. .

  On the other hand, the sealing material containing glass powder is excellent in water resistance as compared with the organic resin-based adhesive material, and is suitable for ensuring airtightness inside the organic EL display.

  However, since glass powder generally has a softening point of 300 ° C. or higher, application to an organic EL display has been difficult. Specifically, when glass substrates are sealed with the above-mentioned sealing material, the entire organic EL display is put into an electric furnace and baked at a temperature equal to or higher than the softening point of the glass powder to soften and flow the glass powder. It was necessary to let them. However, since the active element used in the organic EL display has only heat resistance of about 120 to 130 ° C., sealing the glass substrates by this method damages the active element due to heat, and the organic EL display. Display characteristics will deteriorate. In addition, since the organic light emitting material also has poor heat resistance, sealing the glass substrates by this method damages the organic light emitting material due to heat and degrades the display characteristics of the organic EL display.

  In view of such circumstances, in recent years, laser sealing has been studied as a method for sealing an organic EL display. According to laser sealing, since only the portion to be sealed can be locally heated, it is possible to seal the glass substrates together while preventing thermal degradation of the active element or the like.

JP 2008-166197 A

  Laser sealing is performed by the following processes, for example. First, the sealing material and the vehicle are mixed to produce a sealing material paste. Here, the vehicle is generally composed of an organic binder and a solvent. Next, the sealing material paste is applied in a frame shape along the outer peripheral edge of the glass substrate by a screen printing machine, a dispenser, or the like to form an application layer on the glass substrate. Subsequently, the coating layer is baked to form a sealing material layer on the glass substrate, and the sealing material layer and the glass substrate are fixed. Further, after the obtained glass substrate with the sealing material layer and the glass substrate on which the organic EL element or the like is formed are overlaid, laser light is irradiated along the sealing material layer to laser the glass substrates together. Seal.

  By the way, when the coating layer is baked, the organic binder in the vehicle is removed by incineration.

On the other hand, the sealing material itself contains a small amount of gas components such as CO ₂ and H ₂ O. However, these gas components are difficult to remove completely only by firing the coating layer. In the case of laser sealing, CO ₂ gas and H ₂ O gas are released to the outside. When these emitted gases come into contact with the organic EL element, the deterioration of the organic EL element is promoted, and the long-term reliability of the organic EL device is lowered. In order to suppress this problem, there is a method of providing a material that adsorbs a gas component inside the organic EL device, but this method may increase the cost.

  Therefore, the present invention creates a method in which the gas component is not easily released from the sealing material layer at the time of laser sealing, without providing a material that adsorbs the gas component inside the organic EL device, etc. A technical issue is to improve long-term reliability of organic EL devices and the like.

  As a result of intensive studies, the present inventors have found that the above technical problem can be solved by regulating the laser sealing temperature to be equal to or lower than the firing temperature of the coating layer, and propose the present invention. That is, the method for manufacturing an electronic device according to the present invention includes: (1) a step of preparing a glass substrate; (2) a sealing material containing glass powder; and an organic binder. A step of producing a sealing material paste by mixing a vehicle containing the coating material; (3) a step of applying the sealing material paste to the glass substrate to form a coating layer; and (4) a step of forming the coating layer. A step of baking to obtain a glass substrate with a sealing material layer; and (5) a glass substrate with a sealing material layer, and a glass substrate on which the sealing material layer is not formed via the sealing material layer; And (6) the glass substrate with the sealing material layer and the glass on which the sealing material layer is not formed by irradiating the laser beam so that the laser sealing temperature is equal to or lower than the firing temperature. Airtight with the board Characterized in that it comprises the step of. Here, when “baking the coating layer”, the step of removing the organic binder contained in the coating layer by incineration (debinding step) and the step of sintering the coating layer (sintering step) may be separated at the same time. You may go. The “glass substrate on which the sealing material layer is not formed” is usually a glass substrate on which an element of an electronic device is formed. “Laser sealing temperature” refers to a value obtained by measuring the temperature of the sealing material layer with a radiation thermometer during laser sealing. “Baking temperature” refers to the highest temperature in the step (4) in which the coating layer is baked, and the step of burning and removing the organic binder contained in the coating layer and the step of sintering the coating layer are separated. Refers to the highest temperature of any process.

  The amount of gas released is inversely proportional to the viscosity of the sealing material. Increasing the firing temperature of the coating layer decreases the viscosity of the sealing material and increases the amount of gas released. However, the gas released here has no risk of deteriorating the organic EL element. Further, when the laser sealing temperature is lowered, the viscosity of the sealing material is increased and the amount of gas released is reduced. Therefore, if the laser sealing temperature is regulated to be equal to or lower than the firing temperature, it is possible to significantly suppress the amount of gas released during laser sealing. As a method for regulating the laser sealing temperature below the firing temperature, there is a method of increasing the firing temperature or lowering the laser sealing temperature. In the former method, it is effective to select a glass system having high thermal stability. In the case of the latter method, it is effective to optimize the laser light irradiation conditions, and it is also effective to optimize the content of the absorbing component of the laser light in the sealing material.

  Secondly, in the method for manufacturing an electronic device of the present invention, the laser sealing temperature is preferably 500 ° C. or lower. In this way, the amount of released gas is reduced during laser sealing.

Third, in the method for producing an electronic device of the present invention, it is preferable that the sealing material contains 97.5 to 100% by mass of an inorganic powder containing glass powder and 0 to 2.5% by mass of a pigment. . In this way, since the hermeticity inside the organic EL display can be secured by laser sealing, it is possible to prevent the situation where H ₂ O, O ₂ or the like that deteriorates the organic light emitting layer enters the organic EL display, and as a result The long-term reliability of the organic EL display can be improved.

  When the content of the inorganic powder is less than 97.5% by mass, the softening fluidity of the sealing material becomes poor during laser sealing, and it becomes difficult to increase the sealing strength. If the pigment content is regulated to 0.05% by mass or more, the laser light can be efficiently converted into heat energy, so that only the portion to be sealed is easily heated locally, resulting in an active element or the like. It is easy to laser seal glass substrates together while preventing thermal degradation of the glass substrates. On the other hand, if the pigment content is regulated to 2.5% by mass or less, the temperature of the sealing material layer may be unduly raised during laser sealing, thereby preventing a situation where the amount of released gas increases. It becomes possible. Furthermore, it becomes easy to prevent the situation where the glass is devitrified.

Fourth, in the method for producing an electronic device of the present invention, the glass powder contains SnO 35 to 70% and P ₂ O ₅ 10 to 30% as a glass composition in the following oxide equivalent mol%. Is preferred. If it does in this way, since the softening point of glass powder falls, the softening point of sealing material also falls. As a result, laser sealing can be completed in a short time, and the sealing strength can be increased during laser sealing. Here, “the following oxide conversion” means, for example, in the case of tin oxide, even if it is tetravalent tin oxide (SnO ₂ ), it is converted into divalent tin oxide (SnO), and “SnO” Means notation.

Fifth, in the method for producing an electronic device of the present invention, the glass powder has a glass composition as mol% in terms of the following oxide, Bi ₂ O ₃ 20 to 60%, B ₂ O ₃ 10 to 35%, It is preferable to contain 5 to 40% of ZnO and 5 to 30% of CuO + Fe ₂ O ₃ . If it does in this way, since the softening point of glass powder falls, the softening point of sealing material also falls. And in laser sealing, the energy of the irradiated laser beam can be directly absorbed and converted into heat efficiently, and the reaction between the sealing material and the glass substrate can be promoted. As a result, laser sealing can be completed in a short time, and the sealing strength can be increased during laser sealing.

Sixth, in the method of manufacturing an electronic device according to the present invention, the pigment may be C (carbon), Co ₃ O ₄ , CuO, Cr ₂ O ₃ , Fe ₂ O ₃ , MnO ₂ , SnO, or Ti _n O _{2n−. 1} (n is an integer), preferably one or more selected from spinel complex oxides.

  Seventhly, in the method for manufacturing an electronic device of the present invention, it is preferable that the inorganic powder further contains 0.1 to 60% by volume of a refractory filler.

  Eighth, in the method for manufacturing an electronic device of the present invention, it is preferable that the electronic device is an organic EL device. Here, the “organic EL device” includes an organic EL display, organic EL lighting, and the like.

  Ninthly, in the method for manufacturing an electronic device of the present invention, it is preferable that the organic binder is an aliphatic polyolefin carbonate.

10thly, it is preferable that the manufacturing method of the electronic device of this invention performs the baking of the said coating layer in inert atmosphere. Here, the “inert atmosphere” includes a neutral gas atmosphere such as an N ₂ gas atmosphere and an Ar gas atmosphere, and a reduced pressure atmosphere such as a vacuum atmosphere.

  Eleventh, an electronic device of the present invention is manufactured by the above-described method for manufacturing an electronic device.

It is a schematic diagram which shows the softening point Ts of the sealing material when it measures with a macro type | mold DTA apparatus.

  The method for producing an electronic device of the present invention includes a step of preparing a sealing material paste by mixing a sealing material containing glass powder and a vehicle containing an organic binder. As a method of mixing the sealing material and the vehicle, a method of mixing with a kneading apparatus such as a roll mill, a bead mill, or a ball mill is preferable in terms of homogeneity. Here, the roll mill is an apparatus for crushing aggregated particles represented by three rolls and an apparatus for applying the apparatus, and the bead mill is a medium stirring mill using driven beads as a medium. The ball mill includes not only a narrowly defined ball mill that works to break up the agglomerated particles by rolling ceramic balls in a container, but also a vibrating ball mill, a medium planetary mill, and the like.

  The method for manufacturing an electronic device of the present invention includes a step of applying a sealing material paste to a glass substrate to form a coating layer. As a method for applying the sealing material paste, printing by a screen printer and application by a dispenser are preferable. If it does in this way, an application layer can be formed efficiently.

The method for producing an electronic device of the present invention includes a step of firing the coating layer to obtain a glass substrate with a sealing material layer. The firing atmosphere is preferably an inert atmosphere, and particularly preferably an N ₂ atmosphere. In this way, glass powder, particularly _SnO-P 2 _{O 5} based glass powder becomes difficult to alteration.

  The firing temperature is preferably 460 ° C. or higher, 470 ° C. or higher, particularly 480 ° C. or higher. In this way, since the gas contained in the sealing material itself is released before laser sealing, the amount of emitted gas is reduced during laser sealing.

  When the step of removing the organic binder by incineration is separately provided, it is preferable to fire at a temperature higher than the glass transition point of the glass powder and lower than the glass transition point of the sealing material. If it does in this way, it will become possible to promote decomposition volatilization of an organic binder. The time for maintaining the temperature higher than the glass transition point of the glass powder and lower than the glass transition point of the sealing material is preferably 1 minute or more, particularly preferably 5 minutes or more, and preferably 2 hours or less, particularly preferably 1 hour or less. If the holding time is too short, the organic binder may be sufficiently decomposed and volatilized. On the other hand, when the holding time is too long, the production efficiency of the glass substrate with a sealing material layer is lowered.

  In the method for producing an electronic device of the present invention, it is preferable to continuously perform the step of removing the organic binder by incineration and the step of sintering the coating layer, and it is more preferable to perform both steps simultaneously. In this way, the production efficiency of the glass substrate with a sealing material layer is improved.

  In the method for producing an electronic device of the present invention, sealing is performed by irradiating a laser beam so that the laser sealing temperature is equal to or lower than the firing temperature (preferably 10 ° C. or less, particularly 20 ° C. or less from the firing temperature). A step of hermetically sealing the glass substrate with the material layer and the glass substrate on which the sealing material layer is not formed; In this way, since only the portion to be sealed can be locally heated, it is possible to prevent thermal degradation of the elements of the electronic device and to improve the long-term reliability of the electronic device.

  The laser sealing temperature is preferably 500 ° C. or lower, 490 ° C. or lower, 480 ° C. or lower, 470 ° C. or lower, particularly 460 ° C. or lower. In this way, the amount of released gas is reduced during laser sealing.

Various lasers can be used for laser sealing. In particular, a semiconductor laser, a YAG laser, a CO ₂ laser, an excimer laser, an infrared laser, and the like are preferable in terms of easy handling.

The atmosphere for laser sealing is preferably an inert atmosphere, and particularly preferably an N ₂ atmosphere. In this way, the glass powder during the laser sealing, particularly SnO-P ₂ O ₅ based glass powder becomes difficult to alteration.

  Next, in the electronic device manufacturing method of the present invention, a suitable material configuration will be described below.

  In the sealing material which concerns on this invention, it is preferable to contain 97.5-100 mass% of inorganic powders containing glass powder, and 0-2.5 mass% of pigments, and inorganic powder 99-99. It is more preferable to contain 95 mass% and the pigment 0.05-1 mass%. In particular, the content of the inorganic powder is preferably 99.5 to 99.9% by mass. When the content of the inorganic powder is less than 97.5% by mass, the softening fluidity of the sealing material becomes poor during laser sealing, and it becomes difficult to increase the sealing strength. The pigment content is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass. If the pigment content is too small, it becomes difficult to convert laser light into heat energy. On the other hand, when the content of the pigment is too large, the sealing material is excessively heated during laser sealing, and the thermal degradation of the organic EL element proceeds, and the sealing material absorbs too much laser light. In the laser sealing, the temperature of the sealing material layer is unreasonably raised, and as a result, there is a possibility that the amount of released gas increases. Furthermore, the glass is easily devitrified, and the sealing strength is easily lowered.

As the glass powder according to the present invention, various glass systems can be used. From the viewpoint of thermal stability and water resistance, Bi ₂ O ₃ —B ₂ O ₃ glass, SnO—P ₂ O ₅ glass V ₂ O ₅ glass is preferred. In particular, SnO—P ₂ O ₅ glass is suitable from the viewpoint of low melting point characteristics. From the viewpoint of sealing strength, Bi ₂ O ₃ —B ₂ O ₃ based glass is suitable. Here, “to glass” refers to a glass containing an explicit component as an essential component and a total amount of 20 mol% or more.

The glass powder according to the present invention is preferably a SnO-containing glass powder, and the SnO-containing glass powder contains SnO 35 to 70% and P ₂ O ₅ 10 to 30% as a glass composition in mol% in terms of the following oxides. It is preferable to do. The reason for limiting the glass composition range as described above will be described below. In the description of the glass composition range, “%” indicates mol% unless otherwise specified.

  SnO is a component that lowers the melting point of glass. The SnO content is preferably 35 to 70%, 40 to 70%, and particularly preferably 50 to 68%. If the SnO content is 50% or more, the glass is softened and fluidized easily during laser sealing. If the content of SnO is less than 35%, the viscosity of the glass becomes too high, and it becomes difficult to perform laser sealing with a desired laser output. On the other hand, if the SnO content is more than 70%, vitrification becomes difficult.

P ₂ O ₅ is a glass-forming oxide and is a component that enhances thermal stability. The content of P ₂ O ₅ is preferably 10 to 30%, 15 to 27%, particularly preferably 15 to 25%. If the content of P ₂ O ₅ is less than 10%, the thermal stability tends to be lowered. On the other hand, when the content of P ₂ O ₅ is more than 30%, the weather resistance is lowered, and it is difficult to ensure long-term reliability of an organic EL device or the like.

  In addition to the above components, the following components can be added.

  ZnO is an intermediate oxide and a component that stabilizes the glass. The content of ZnO is preferably 0 to 30%, 1 to 20%, and particularly preferably 1 to 15%. If the ZnO content is more than 30%, the thermal stability tends to decrease.

B ₂ O ₃ is a glass-forming oxide, a component that stabilizes the glass, and a component that improves weather resistance. The content of B ₂ O ₃ is preferably 0 to 25%, 1 to 20%, particularly preferably 2 to 15%. When the content of B ₂ O ₃ is more than 25%, the viscosity of the glass becomes too high, and it becomes difficult to perform laser sealing with a desired laser output.

Al ₂ O ₃ is an intermediate oxide, a component that stabilizes the glass, and a component that lowers the thermal expansion coefficient. The content of Al ₂ O ₃ is preferably 0 to 10%, 0.1 to 10%, particularly preferably 0.5 to 5%. When the content of Al ₂ O ₃ is more than 10%, the softening point of the glass powder is unreasonably raised and it becomes difficult to perform laser sealing with a desired laser output.

SiO ₂ is a glass-forming oxide and is a component that stabilizes the glass. The content of SiO ₂ is preferably 0 to 15%, particularly preferably 0 to 5%. When the content of SiO ₂ is more than 15%, the softening point of the glass powder is unreasonably raised, and it becomes difficult to perform laser sealing with a desired laser output.

In ₂ O ₃ is a component that enhances thermal stability. The content of In ₂ O ₃ is preferably 0 to 5%. When the content of In ₂ O ₃ is more than 5%, the batch cost increases.

Ta ₂ O ₅ is a component that enhances thermal stability. The content of Ta ₂ O ₅ is preferably 0 to 5%. When the content of Ta ₂ O ₅ is more than 5%, the softening point of the glass powder is unreasonably raised and it becomes difficult to perform laser sealing with a desired laser output.

La ₂ O ₃ is a component that enhances thermal stability and is a component that enhances weather resistance. The content of La ₂ O ₃ is preferably 0 to 15%, 0 to 10%, particularly preferably 0 to 5%. When the content of La ₂ O ₃ is more than 15%, batch cost soars.

MoO ₃ is a component that enhances thermal stability. The content of MoO ₃ is preferably 0 to 5%. When the content of MoO ₃ is more than 5%, the softening point of the glass powder is unreasonably raised and it becomes difficult to perform laser sealing with a desired laser output.

WO ₃ is a component that enhances thermal stability. The content of WO ₃ is preferably 0 to 5%. When the content of WO ₃ is more than 5%, the softening point of the glass powder is unreasonably raised and it becomes difficult to perform laser sealing with a desired laser output.

Li ₂ O is a component that lowers the melting point of glass. The content of Li ₂ O is preferably 0 to 5%. When the content of Li ₂ O is more than 5%, the thermal stability tends to be lowered. Na ₂ O is a component that lowers the melting point of glass. The content of Na ₂ O is preferably 0 to 10%, particularly preferably 0 to 5%. When the content of Na 2 _O is greater than 10%, the thermal stability tends to decrease. K ₂ O is a component that lowers the melting point of glass. The content of K ₂ O is preferably 0 to 5%. When the content of K 2 _O is more than 5%, the thermal stability tends to decrease.

  MgO is a component that enhances thermal stability. The content of MgO is preferably 0 to 15%. When the content of MgO is more than 15%, the softening point of the glass powder rises unreasonably and it becomes difficult to perform laser sealing with a desired laser output.

  BaO is a component that enhances thermal stability. The content of BaO is preferably 0 to 10%. When there is more content of BaO than 10%, the component balance of a glass composition will be impaired and it will become easy to devitrify glass conversely.

F ₂ is a component that lowers the melting point of glass. The content of F ₂ is preferably 0 to 5%. When the content of F ₂ is more than 5%, the thermal stability tends to decrease.

In consideration of thermal stability and low melting point characteristics, In ₂ O ₃ , Ta ₂ O ₅ , La ₂ O ₃ , MoO ₃ , WO ₃ , Li ₂ O, Na ₂ O, K ₂ O, MgO, BaO, And the total amount of F ₂ is preferably 10% or less.

  In addition to the above components, other components (CaO, SrO, etc.) can be added, for example, up to 10%.

It is preferable that the SnO—P ₂ O ₅ glass powder according to the present invention does not substantially contain a transition metal oxide. In this way, it is possible to prevent the situation where the glass absorbs too much laser light and the temperature of the sealing material layer rises improperly during laser sealing, resulting in an increase in the amount of emitted gas. The thermal stability of is difficult to decrease. Here, “substantially no transition metal oxide” means that the content of the transition metal oxide in the glass composition is 3000 ppm (mass) or less, preferably less than 1000 ppm (mass).

Glass powder according to the present _{invention, Bi 2 O 3 -B 2 O} 3 based glass powder also _{preferably, Bi 2 O 3 -B 2 O} 3 based glass powder, a glass composition, in mole as% terms of oxide _{, Bi 2 O 3 20~60%,} B 2 O 3 10~35%, 5~40% ZnO, preferably contains _{CuO + Fe 2 O 3 5~30%} . The reason for limiting the glass composition range as described above will be described below. In the description of the glass composition range below,% indicates a mol% unless otherwise specified.

Bi ₂ O ₃ is a main component for lowering the softening point, and its content is 20 to 60%, preferably 25 to 55%, more preferably 30 to 55%. If the content of Bi ₂ O ₃ is less than 20%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light. On the other hand, when the content of Bi ₂ O ₃ is more than 60%, the glass becomes thermally unstable, and the glass is easily devitrified at the time of melting or laser sealing.

B ₂ O ₃ is a component that forms a glass network of bismuth-based glass, and its content is 10 to 35%, preferably 15 to 30%, and more preferably 15 to 28%. When the content of B ₂ O ₃ is less than 10%, the glass becomes thermally unstable, and the glass tends to be devitrified at the time of melting or laser sealing. On the other hand, if the content of B ₂ O ₃ is more than 35%, the softening point becomes too high and the glass is difficult to soften even when irradiated with laser light.

  ZnO is a component that suppresses devitrification at the time of melting or laser sealing and lowers the coefficient of thermal expansion, and its content is 5 to 40%, preferably 5 to 35%, more preferably 5 to 33. %. If the ZnO content is less than 5%, it is difficult to obtain the above effect. On the other hand, when the ZnO content is more than 40%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.

CuO + Fe ₂ O ₃ is a component having light absorption characteristics, and when irradiated with laser light having a predetermined emission center wavelength, CuO + Fe ₂ O ₃ is a component that easily absorbs the laser light and softens the glass. CuO + Fe ₂ O ₃ is a component that suppresses devitrification at the time of melting or laser sealing. The content of CuO + Fe ₂ O ₃ is 5 to 30%, preferably 7 to 25%, more preferably 10 to 20%. If the content of CuO + Fe ₂ O ₃ is less than 5%, the light absorption characteristics are poor, and the glass is difficult to soften even when irradiated with laser light. On the other hand, when the content of CuO + Fe ₂ O ₃ is more than 30%, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed.

  CuO is a component having light absorption characteristics, and when irradiated with laser light having a predetermined emission center wavelength, it is a component that absorbs laser light and softens the glass, and at the time of melting or laser sealing It is a component that suppresses devitrification. The content of CuO is preferably 0 to 25%, 5 to 25%, 10 to 25%, particularly 10 to 20%. When there is more content of CuO than 25%, the component balance in a glass composition will be impaired, and it will become easy to devitrify glass conversely. If the CuO content is regulated to 5% or more, the light absorption characteristics are improved, and the glass is easily softened during laser sealing.

Fe ₂ O ₃ is a component having light absorption characteristics. When irradiated with laser light having a predetermined emission center wavelength, Fe ₂ O ₃ is a component that absorbs the laser light and softens the glass, and at the time of melting or laser. It is a component that suppresses devitrification at the time of sealing. The content of Fe ₂ O ₃ is preferably 0 to 10%, 0.1 to 10%, 0.2 to 10%, particularly 0.5 to 10%. When the content of Fe ₂ O ₃ is more than 10%, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed. If the content of Fe ₂ O ₃ is regulated to 0.1% or more, the light absorption characteristics are improved, and the glass is easily softened during laser sealing.

Fe ions in iron oxide exist in the state of Fe ²⁺ or Fe ³⁺ . In the present invention, Fe ions in iron oxide are not limited to either Fe ²⁺ or Fe ³⁺ , and may be any. Therefore, in the present invention, even Fe ²⁺ is handled after being converted to Fe ₂ O ₃ . In particular, when an infrared laser is used as the irradiation light, since Fe ²⁺ has an absorption peak in the infrared region, the ratio of Fe ²⁺ is preferably large. For example, the ratio of Fe ²⁺ / Fe ^{3+ in} iron oxide is 0. It is preferable to regulate to 0.03 or more (preferably 0.08 or more).

  In addition to the above components, for example, the following components may be added.

SiO ₂ is a component that improves water resistance. The content of SiO ₂ is preferably 0 to 10%, in particular 0 to 3%. If the content of SiO ₂ is more than 10%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light.

Al ₂ O ₃ is a component that improves water resistance. The content of Al ₂ O ₃ is preferably 0 to 5%, particularly 0 to 2%. When the content of Al ₂ O ₃ is more than 5%, the softening point becomes too high and the glass is difficult to soften even when irradiated with laser light.

  MgO + CaO + SrO + BaO (total amount of MgO, CaO, SrO and BaO) is a component that suppresses devitrification at the time of melting or laser sealing, and the content of MgO + CaO + SrO + BaO is preferably 0 to 20%, particularly 0 to 15%. It is. If the content of MgO + CaO + SrO + BaO is more than 20%, the softening point becomes too high and the glass is difficult to soften even when irradiated with laser light.

  MgO, CaO and SrO are components that suppress devitrification during melting or laser sealing. The content of each component is preferably 0 to 5%, particularly 0 to 2%. When the content of each component is more than 5%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light.

  BaO is a component that suppresses devitrification during melting or laser sealing. The content of BaO is preferably 0 to 15%, in particular 0 to 10%. When the content of BaO is more than 15%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light.

CeO ₂ and Sb ₂ O ₃ are components that suppress devitrification during melting or laser sealing. The content of each component is preferably 0 to 5%, 0 to 2%, particularly 0 to 1%. When there is more content of each component than 5%, the component balance in a glass composition will be impaired, and conversely, it will become easy to devitrify glass. From the viewpoint of enhancing the thermal stability, it is preferable to add a small amount of Sb ₂ O ₃ , and specifically, it is preferable to add 0.05% or more of Sb ₂ O ₃ .

WO ₃ is a component that suppresses devitrification at the time of melting or laser sealing. The content of WO ₃ is preferably 0 to 10%, in particular 0 to 2%. When the content of WO ₃ is more than 10%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.

In ₂ O ₃ + Ga ₂ O ₃ (total amount of In ₂ O ₃ and Ga ₂ O ₃ ) is a component that suppresses devitrification during melting or laser sealing. The content of In ₂ O ₃ + Ga ₂ O ₃ is preferably 0 to 5%, particularly 0 to 3%. If the content of In ₂ O ₃ + Ga ₂ O ₃ is more than 5%, the batch cost increases. In addition, the content of In ₂ O ₃ is more preferably 0 to 1%, and the content of Ga ₂ O ₃ is more preferably 0 to 0.5%.

  The oxides of Li, Na, K, and Cs are components that lower the softening point. However, since they have an action of promoting devitrification at the time of melting, the total amount is preferably regulated to less than 1%.

P ₂ O ₅ is a component that suppresses devitrification at the time of melting. However, if the content of P ₂ O ₅ is more than 1%, the glass tends to undergo phase separation during melting.

_{La 2 O 3, Y 2 O} 3 and _Gd 2 _{O 3} is a component to suppress phase separation during melting, when these total amount is more than 3%, the softening point becomes too high, the laser beam Even when irradiated, the glass becomes difficult to soften.

NiO, V ₂ O ₅ , CoO, MoO ₃ , TiO _2, and MnO ₂ are components having light absorption characteristics. When irradiated with laser light having a predetermined emission center wavelength, the laser light is absorbed and glass is absorbed. It is a component that facilitates softening. The content of each component is preferably 0 to 7%, particularly 0 to 3%. If the content of each component is more than 7%, the glass tends to be devitrified during laser sealing.

  PbO is a component that lowers the softening point, but it is a component that is concerned about environmental effects. Therefore, the content of PbO is preferably less than 0.1%.

  Even if it is a component other than the above, you may add to 5%, for example in the range which does not impair a glass characteristic.

  The glass powder according to the present invention preferably contains substantially no PbO from the environmental viewpoint. Here, “substantially no PbO” refers to the case where the content of PbO in the glass composition is 1000 ppm (mass) or less.

The average particle diameter D50 of the glass powder is preferably less than 15 μm, 0.5 to 10 μm, particularly 1 to ₅ μm. When regulating the average particle diameter D ₅₀ of the glass powder to less than 15 [mu] m, liable to narrow the gap between the two glass substrates, the heat of this case, the time required for the laser sealing is reduced, the glass substrate and the sealing material Even if there is a difference in expansion coefficient, cracks and the like are less likely to occur at the interface between the glass substrate and the sealing material layer. Here, the “average particle diameter D ₅₀ ” refers to a value measured by the laser diffraction method. In the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle. The particle size is 50% (hereinafter the same).

The 99% particle size D ₉₉ of the glass powder is preferably 30 μm or less, 20 μm or less, and particularly preferably 10 μm or less. When regulating the 99% particle size D ₉₉ of the glass powder to 30μm or less, it tends to narrow the gap between the two glass substrates, in this case, the time required for the laser sealing is reduced, the glass substrate and the sealing material Even if there is a difference in thermal expansion coefficient, cracks and the like are hardly generated at the interface between the glass substrate and the sealing material layer. Here, “99% particle size D ₉₉ ” refers to a value measured by the laser diffraction method, and in the cumulative particle size distribution curve on the volume basis when measured by the laser diffraction method, the cumulative amount is accumulated from the smaller particle. The particle size is 99% (the same applies hereinafter).

  The inorganic powder according to the present invention preferably further contains a refractory filler. In this way, the thermal expansion coefficient of the sealing material can be reduced, and the mechanical strength of the sealing material can be increased. The mixing ratio of the glass powder and the refractory filler in the inorganic powder is 40 to 100%: 0 to 60%, 40 to 99.9%: 0.1 to 60%, 45 to 90%: 10 to 55 in volume%. %, 50 to 80%: 20 to 50%, 50 to 70%: 30 to 50%, and particularly preferably 50 to 65%: 35 to 50%. When the content of the refractory filler is more than 60% by volume, the ratio of the glass powder is relatively reduced, and the efficiency of laser sealing is likely to be lowered. In addition, it becomes difficult to receive the effect by a refractory filler as content of a refractory filler is less than 0.1 volume%.

Zircon, zirconia, tin oxide, quartz, β-spodumene, cordierite, mullite, quartz glass, β-eucryptite, β-quartz, zirconium phosphate, zirconium phosphate tungstate, zirconium tungstate as refractory filler NbZr (PO ₄ ) _{3 and} other compounds having a basic structure of [AB ₂ (MO ₄ ) ₃ ],
A: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc. B: Zr, Ti, Sn, Nb, Al, Sc, Y etc. M: P, Si, W, Mo etc. Alternatively, these solid solutions can be used.

The 99% particle size D ₉₉ of the refractory filler is preferably 20 μm or less, 15 μm or less, and particularly preferably 10 μm or less. If the 99% particle size D ₉₉ of the refractory filler is larger than 20 μm, a portion having a thickness of 30 μm or more is likely to occur in the sealed portion, and therefore the gap between the glass substrates becomes non-uniform in the organic EL display. It becomes difficult to make the organic EL display thinner. Moreover, when regulating the 99% particle size D ₉₉ of the refractory filler to 20μm or less, tends to narrow the gap between the two glass substrates, in this case, the time required for the laser sealing is reduced, the glass substrate and the sealing Even if there is a difference in the thermal expansion coefficients of the adhesive materials, cracks and the like are hardly generated at the interface between the glass substrate and the sealing material layer.

In the sealing material according to the present invention, the pigment is preferably an inorganic pigment. Carbon, Co ₃ O ₄ , CuO, Cr ₂ O ₃ , Fe ₂ O ₃ , MnO ₂ , SnO, TinO _2n-1 (n is an integer) One or more selected from spinel complex oxides are more preferable, and carbon is particularly preferable. These pigments are excellent in color developability and have good absorption of laser light. Further, when Bi ₂ O ₃ —B ₂ O ₃ glass is used as the glass powder, the pigment is an oxide pigment containing one or more of Cu, Cr, Fe, and Mn from the viewpoint of compatibility. preferable.

Although various materials can be used as carbon, amorphous carbon and graphite are particularly preferable. These carbon has a property of easily processing the average particle diameter _{D 50} of the primary particles in the 1 to 100 nm. In addition, when SnO is contained in the glass composition of glass powder, if carbon is added as a pigment, the effect which suppresses the oxidation of SnO at the time of baking can also be anticipated.

  The pigment preferably contains substantially no Cr-based oxide from the environmental viewpoint. Here, “substantially free of Cr-based oxide” refers to a case where the content of Cr-based oxide in the pigment is 1000 ppm (mass) or less.

The average particle diameter D50 of the primary particles of the pigment is preferably 1 to 100 nm, 3 to 70 nm, 5 to 60 nm, and particularly preferably 10 to ₅₀ nm. If the primary particles of the pigment are too small, the pigments tend to aggregate together, making it difficult to uniformly disperse the pigment in the sealing material, and the glass powder may not locally soften and flow during laser sealing. Occurs. Further, even if the primary particles of the pigment are too large, it is difficult to uniformly disperse the pigment in the sealing material, and there is a possibility that the glass powder does not soften and flow locally during laser sealing.

  In the sealing material according to the present invention, the softening point is preferably 500 ° C. or lower, 460 ° C. or lower, 450 ° C. or lower, 420 ° C. or lower, and particularly preferably 400 ° C. or lower. When the softening point is higher than 500 ° C., the efficiency of laser sealing tends to decrease. The lower limit of the softening point is not particularly limited, but it is preferable to limit the softening point to 300 ° C. or higher in consideration of thermal stability. Here, the “softening point” refers to a value measured with a macro-type differential thermal analysis (DTA) apparatus in a nitrogen atmosphere, DTA starts measurement from room temperature, and the rate of temperature rise is 10 ° C./min. . In addition, the softening point measured with the macro type | mold DTA apparatus points out the temperature (Ts) of the 4th bending point shown in FIG.

Currently, an active matrix drive in which an active element such as a TFT is arranged and driven in each pixel is adopted as an organic EL display as a drive method. In this case, non-alkali glass (for example, OA-10G manufactured by Nippon Electric Glass Co., Ltd.) is used for the glass substrate. The thermal expansion coefficient of the alkali-free glass is usually 40 × 10 ⁻⁷ / ° C. or less. On the other hand, the thermal expansion coefficient of the sealing material is often 76 to 90 × 10 ⁻⁷ / ° C. Therefore, in order to prevent stress fracture of the sealing portion, it is necessary to strictly match the thermal expansion coefficient of the sealing material with the thermal expansion coefficient of the alkali-free glass. Therefore, when a low expansion refractory filler, particularly NbZr (PO ₄ ) ₃ , zirconium phosphate and cordierite, is added to the sealing material, the thermal expansion coefficient of the sealing material can be significantly reduced. In the sealing material according to the present invention, the thermal expansion coefficient is 85 × 10 ⁻⁷ / ° C. or less, 75 × 10 ⁻⁷ / ° C. or less, 65 × 10 ⁻⁷ / ° C. or less, 55 × 10 ⁻⁷ / ° C. or less, particularly It is preferably 49 × 10 ⁻⁷ / ° C. or less. If it does in this way, a residual stress will become small and it will become easy to prevent the stress destruction of a sealing part. Here, the “thermal expansion coefficient” refers to an average value measured by a push rod type thermal expansion coefficient measurement (TMA) apparatus. For example, when using SnO—P ₂ O ₅ glass powder, a temperature of 30 to 250 ° C. The average value measured in the range refers to the average value measured in the temperature range of 30 to 300 ° C. when Bi ₂ O ₃ —B ₂ O ₃ glass powder is used.

  In addition to glass powder, refractory filler, and pigment, glass beads or the like may be added as a spacer in the sealing material.

  The sealing material paste according to the present invention includes a sealing material, a vehicle, and the like. The vehicle usually contains a resin binder and a solvent. If necessary, a surfactant, a thickener and the like may be added to the vehicle.

As the organic binder, aliphatic polyolefin carbonates, particularly polyethylene carbonate and polypropylene carbonate are preferred. These organic binders have properties that make it difficult to alter glass powder, particularly SnO—P ₂ O ₅ glass powder, when the organic binder is removed by incineration.

  Solvents include N, N'-dimethylformamide, ethylene glycol, dimethyl sulfoxide, dimethyl carbonate, propylene carbonate, butyrolactone, caprolactone, N-methyl-2-pyrrolidone, phenyl diglycol (PhDG), dibutyl phthalate (DBP) It is preferable that 1 type, or 2 or more types chosen from benzyl glycol (BzG), benzyl diglycol (BzDG), and phenyl glycol (PhG) are included. These solvents have properties that make it difficult to alter the glass powder. In particular, among these solvents, one or two selected from propylene carbonate, phenyl diglycol (PhDG), dibutyl phthalate (DBP), benzyl glycol (BzG), benzyl diglycol (BzDEG), and phenyl glycol (PhG). The above is preferable. These solvents have a boiling point of 240 ° C. or higher. For this reason, when these solvents are used, it becomes easy to suppress the volatilization of the solvent when applying the sealing material paste using a screen printer or the like, and as a result, the sealing material paste is stabilized for a long period of time. Can be used. Furthermore, phenyl diglycol (PhDG), dibutyl phthalate (DBP), benzyl glycol (BzG), benzyl diglycol (BzDEG), and phenyl glycol (PhG) have high affinity with pigments. For this reason, even if the addition amount of these solvents is small, the situation where a pigment separates in the sealing material paste can be suppressed.

  Hereinafter, based on an Example, this invention is demonstrated in detail. The following examples are merely illustrative. The present invention is not limited to the following examples.

  Table 1 shows Examples (Sample Nos. 1 to 3) and Comparative Examples (Sample Nos. 4 and 5) of the present invention. Table 2 shows examples (samples Nos. 6 to 8) and comparative examples (samples Nos. 9 and 10) of the present invention.

SnO—P ₂ O ₅ glass powder was prepared as follows. First, after preparing the raw materials so as to have a predetermined glass composition (mol%, SnO 59%, P ₂ O ₅ 20%, ZnO 5%, B ₂ O ₃ 15%, Al ₂ O ₃ 1%), This prepared raw material was put in an alumina crucible and melted in a nitrogen atmosphere at 900 ° C. for 1 to 2 hours. Next, the obtained molten glass was formed into a film shape with a water-cooled roller. Subsequently, the obtained glass film was pulverized with a ball mill and then air-classified to obtain glass powder. This glass powder has a glass transition point of 301 ° C., a softening point of 385 ° C., a density of 3.88 g / cm ³ , an average particle size D ₅₀ of 1.5 μm, a 90% particle size D ₉₀ of 3.5 μm, and 99%. The particle size D ₉₉ was 5.7 μm.

In the following manner _to prepare a Bi ₂ O 3 _-B 2 _{O 3} based glass powder. First, in a predetermined glass composition (in mol%, Bi ₂ O ₃ 37%, B ₂ O ₃ 26%, ZnO 17.5%, CuO 14%, BaO 5% Fe ₂ O ₃ 0.5%) After the raw materials were prepared, the prepared raw materials were put in a platinum crucible and melted at 1000 ° C. in an air atmosphere for 1 to 2 hours. Next, the obtained molten glass was formed into a film shape with a water-cooled roller. Subsequently, the obtained glass film was pulverized with a ball mill and then air-classified to obtain glass powder. This glass powder has a glass transition point of 360 ° C., a softening point of 435 ° C., a density of 6.96 g / cm ³ , an average particle size D ₅₀ of 1.1 μm, a 90% particle size D ₉₀ of 2.1 μm, and 99%. The particle size D ₉₉ was 2.9 μm.

  The glass transition point is a value measured with a push rod TMA apparatus. In addition, as a measurement sample, the glass powder was sintered precisely and then processed into a predetermined shape.

The softening point is a value measured with a macro DTA apparatus. The measurement was performed under a nitrogen atmosphere when using SnO—P ₂ O ₅ glass powder, and under an air atmosphere when using Bi ₂ O ₃ —B ₂ O ₃ glass powder. Moreover, the measurement was started from room temperature at a heating rate of 10 ° C./min.

Sample No. In 1-5, zirconium phosphate was used as a refractory filler. Zirconium phosphate had a density of 3.80 g / cm ³ , an average particle diameter D ₅₀ of 1.6 μm, a 90% particle diameter D ₉₀ of 3.3 μm, and a 99% particle diameter D ₉₉ of 5.1 μm.

Sample No. For cords 6 to 10, cordierite was used as a refractory filler. Cordierite had a density of 2.63 g / cm ³ , an average particle size D ₅₀ of 0.9 μm, a 90% particle size D ₉₀ of 1.8 μm, and a 99% particle size D ₉₉ of 2.3 μm.

Ketjen black (graphite) was used as the pigment. The average particle diameter _{D 50} of the primary particles of the pigment was 20 nm.

The average particle diameter D ₅₀ , 90% particle diameter D ₉₀ , and 99% particle diameter D ₉₉ are values measured with a laser diffraction particle size distribution meter.

Sample No. In 1-5, a mixture of _SnO-P 2 _{O 5} based glass powder 60 vol% and 40 vol% refractory filler described above to prepare an inorganic powder. Next, 99.75% by mass of inorganic powder and 0.25% by mass of pigment were mixed to produce a sealing material. This sealing material had a glass transition point of 363 ° C., a softening point of 430 ° C., and a density of 3.85 g / cm ³ .

Sample No. In 6-10, a mixture of _Bi 2 _O 3 _-B 2 _{O 3} based glass powder 75 vol% and 25 vol% refractory filler described above to prepare a sealing material (inorganic powder). This sealing material had a glass transition point of 370 ° C., a softening point of 450 ° C., and a density of 5.88 g / cm ³ .

  The glass transition point is a value measured with a push rod TMA apparatus. In addition, as a measurement sample, after sealing the sealing material densely, what was processed into the predetermined shape was used.

The softening point is a value measured with a macro DTA apparatus. The measurement was performed under a nitrogen atmosphere when using SnO—P ₂ O ₅ glass powder, and under an air atmosphere when using Bi ₂ O ₃ —B ₂ O ₃ glass powder. Moreover, the measurement was started from room temperature at a heating rate of 10 ° C./min.

  A sealing material paste was prepared as follows. First, the sealing material and the vehicle were kneaded so as to have a viscosity of about 70 Pa · s (25 ° C., Shear rate: 4), and then kneaded with a three-roll mill until uniform, thereby forming a paste. Polyethylene carbonate (MW: 129000) was used as the resin component in the vehicle, and propylene carbonate was used as the solvent component. A vehicle in which 25% by mass of polyethylene carbonate was dissolved in propylene carbonate was used. Next, the sealing material paste has a thickness of about 10 μm and a width of about 30 μm on the periphery (□ 33 mm) of a 40 mm long × 50 mm wide × 0.5 mm thick glass substrate (OA-10G manufactured by Nippon Electric Glass Co., Ltd.). After printing with a screen printer so as to be about 0.6 mm, the sample was dried for 15 minutes at 85 ° C. in an air atmosphere. Nos. 1 to 5 were baked under the conditions described in the table under a nitrogen atmosphere (however, the temperature was raised from room temperature to 10 ° C./min, and the temperature was lowered to room temperature at 10 ° C./min). The resin component was removed by incineration, and a sealing material layer was formed on the glass substrate. Sample No. No. 6 to 10 were fired under the conditions described in the table under the air atmosphere (however, the temperature was raised from room temperature to 10 ° C./min, and the temperature was lowered to room temperature at 10 ° C./min). The resin component was removed by incineration, and a sealing material layer was formed on the glass substrate.

  Subsequently, a glass substrate (manufactured by Nippon Electric Glass Co., Ltd.) having a length of 50 mm, a width of 50 mm, and a thickness of 0.5 mm obtained by vacuum-depositing a Ca film (film thickness: about 100 nm) in advance on the sealing material layer on a central portion □ 30 mm OA-10G) is arranged so as to overlap in a nitrogen atmosphere, and then irradiated with laser light having a wavelength of 808 nm under the conditions described in the table along the sealing material layer from the glass substrate side on which the sealing material layer is formed. By doing so, the sealing material layer was softened and fluidized, and the glass substrates were hermetically sealed.

  At the time of laser light irradiation, the temperature of the sealing material layer was measured with a radiation thermometer to measure the laser sealing temperature.

Airtightness was evaluated as follows. The sample after laser sealing was put into a dryer set at a temperature of 85 ° C. and a humidity of 85% for 1000 hours, and the alteration of the Ca film was observed. A case where no white spot was observed in the Ca film was evaluated as “◯”, and a case where a white spot was observed in the Ca film was evaluated as “×”. The Ca film is colorless and transparent, but when the Ca film comes into contact with moisture, it becomes white Ca (OH) ₂ . Therefore, it is possible to evaluate the airtightness in the sample by observing the change of the Ca film.

As apparent from Tables 1 and 2, Sample No. In 1-3 and 6-8, white spots were not observed in the Ca film in the evaluation of airtightness. On the other hand, sample No. In 4, 5, 9, and 10, several white spots of about 0.5 mm were observed in the Ca film in the evaluation of airtightness. This fact is because the laser sealing temperature is higher than the firing temperature, so during laser sealing, H ₂ O gas is generated from within the sealing material layer and reacts with the Ca film to produce Ca (OH) _2. This is probably due to the fact that

  The method for producing an electronic device of the present invention is suitable as a method for producing a solar cell such as a dye-sensitized solar cell, a lithium ion secondary battery, and a MEMS package in addition to the organic EL device.

Claims (11)

In a method of manufacturing an electronic device by laser sealing,
(1) preparing a glass substrate;
(2) mixing a sealing material containing glass powder and a vehicle containing an organic binder to produce a sealing material paste;
(3) applying the sealing material paste to the glass substrate to form an application layer;
(4) firing the coating layer to obtain a glass substrate with a sealing material layer;
(5) Overlaying the glass substrate with the sealing material layer and the glass substrate on which the sealing material layer is not formed, through the sealing material layer;
(6) Laser sealing is performed so that the laser sealing temperature is equal to or lower than the firing temperature, and the glass substrate with the sealing material layer and the glass substrate on which the sealing material layer is not formed are hermetically sealed. And a method for manufacturing the electronic device.   The method for manufacturing an electronic device according to claim 1, wherein the laser sealing temperature is 500 ° C. or lower.   The said sealing material contains the inorganic powder 97.5-100 mass% containing a glass powder, and the pigment 0-2.5 mass%, The manufacture of the electronic device of Claim 1 or 2 characterized by the above-mentioned. Method. Said glass powder is a glass composition including, in mol% terms of oxide, SnO 35 to _70%, any one of claims 1 to 3, characterized in that it contains _P 2 O 5 10 to 30% The manufacturing method of the electronic device of description. Said glass powder is a glass composition including, in mol% terms of _{oxide, Bi 2 O 3 20~60%,} B 2 O 3 10~35%, 5~40% ZnO, CuO + Fe 2 O 3 5~30% The manufacturing method of the electronic device as described in any one of Claims 1-3 characterized by the above-mentioned. The pigment is, C _{(carbon), Co 3 O 4, CuO} , Cr 2 O 3, Fe 2 O 3, MnO 2, SnO, Ti n O 2n-1 ( n is an integer), selected from the spinel composite oxide The method for manufacturing an electronic device according to claim 1, wherein the electronic device is one type or two or more types.   The said inorganic powder contains 0.1-60 volume% of refractory fillers further, The manufacturing method of the electronic device as described in any one of Claims 1-6 characterized by the above-mentioned.   The said electronic device is an organic EL device, The manufacturing method of the electronic device as described in any one of Claims 1-7 characterized by the above-mentioned.   The method for producing an electronic device according to any one of claims 1 to 8, wherein the organic binder is an aliphatic polyolefin carbonate.   The method for manufacturing an electronic device according to claim 1, wherein the coating layer is fired in an inert atmosphere.   An electronic device produced by the method for producing an electronic device according to claim 1.