JP2013157161A - Electronic component, manufacturing method of the same and seal material paste used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce thermal damages on an organic element and an organic material which are incorporated in an electronic component, and efficiently manufacture the electronic component to reduce devitrification of a glass bonding layer.SOLUTION: An electronic component includes an organic member between two transparent substrates and an outer periphery of the two transparent substrates is bonded by a seal material containing low-melting glass. The low-melting glass contains a vanadium oxide, a tellurium oxide, a phosphorus oxide and an iron oxide, which is represented as the following formulas in terms of oxide: VO+TeO+PO+FeO≥75 mass%, VO>TeO>PO≥FeO(mass%).

Description

  The present invention relates to an electronic component in which an organic element or an organic material is incorporated between two transparent substrates, and the outer peripheral portion thereof is bonded using a sealing material.

  In an electronic component in which an organic element or organic material is embedded between two transparent substrates, the outer periphery of the two transparent substrates is sealed with resin in order to protect the organic element or organic material from moisture, moisture, and the like. They are joined with a stop material, and a desiccant is installed inside the electronic component. However, the bonding with the resin has insufficient gas barrier properties (airtightness), and water molecules gradually permeated, and sufficient reliability has not been obtained. On the other hand, a sealing material using low-melting glass can be bonded with a high gas barrier property (air tightness), but the bonding temperature is significantly higher than that of a resin sealing material, and organic elements and It exceeds the heat resistance of organic materials.

  In view of this, laser sealing that can be locally heated has been devised. As the sealing material, low-melting glass capable of airtight bonding is used. It is important that this low-melting glass is heated by absorbing the laser light used and then softens and flows. By adopting such a method, only the outer peripheral portion of the two transparent substrates can be heated, so that the gas barrier property (airtightness) can be achieved without causing thermal damage to the organic elements and organic materials incorporated in the electronic component. High glass bonding is possible.

In a display or the like in which an organic light emitting diode (OLED) is built, a glass substrate on which an encapsulating material is pre-fired is combined with a glass substrate on which the other OLED is formed, and the laser is irradiated through the glass substrate. Thus, the low melting point glass in the sealing material is softened and fluidized to join the two glass substrates. In patent document 1, the sealing material which can join an outer peripheral part with a laser is proposed in an OLED display. This sealing material includes a V ₂ O ₅ —P ₂ O ₅ —Sb ₂ O ₃ low melting point glass that can be heated by a laser, and lithium aluminosilicate (β-eucryptite for reducing the thermal expansion coefficient). ) Filler particles. Further, this low melting point glass contains any of K ₂ O, Fe ₂ O ₃ , ZnO, TiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , and WO ₃ and has a transition point T _g of less than 350 ° C. It is. Patent Document 2 also proposes a glass package to which the same sealing material as Patent Document 1 is applied. The low-melting glass contained in the sealing material is also the same as that of Patent Document 1, and trivalent or tetravalent vanadium ions are formed by pre-baking on the outer peripheral portion of the glass substrate in a low-oxidation atmosphere in which the amount of oxygen is less than that of air. The change to pentavalent is prevented, thereby preventing the softening fluidity due to laser irradiation from being deteriorated and the moisture resistance and water resistance of the joint after laser sealing from being lowered.

Japanese Patent No. 4540669 Special table 2008-527656 gazette

In the sealing material described above, the V ₂ O ₅ —P ₂ O ₅ —Sb ₂ O ₃ -based low-melting glass contained therein is liable to be devitrified (crystallized). Therefore, it was necessary to perform preliminary firing at a lower temperature over time. By increasing the laser output, softening fluidity and adhesion can be improved, but this has sufficiently caused the possibility of thermal damage to organic elements and organic materials incorporated in electronic components. Moreover, in order to ensure the moisture resistance and water resistance after joining with a laser, it was necessary to perform temporary baking before laser sealing in a low oxygen atmosphere.

  Accordingly, an object of the present invention is to reduce thermal damage to an organic element or an organic material incorporated in an electronic component, efficiently manufacture the electronic component, and reduce devitrification of the glass bonding layer.

In order to solve the above-described problems, the present invention provides an electronic component having an organic member between two transparent substrates, and joining the outer peripheral portions of the two transparent substrates with a sealing material containing low-melting glass. The low-melting glass contains vanadium oxide, tellurium oxide, phosphorus oxide and iron oxide, V ₂ O ₅ + TeO ₂ + P ₂ O ₅ + Fe ₂ O ₃ ≧ 75% by mass in terms of the following oxide, V ₂ O ₅ > TeO ₂ > P ₂ O ₅ ≧ Fe ₂ O ₃ (mass%).

Further, the present invention is a sealing material paste comprising a low-melting glass, a resin binder, and a solvent, wherein the low-melting glass contains vanadium oxide, tellurium oxide, phosphorus oxide, and iron oxide, V ₂ O ₅ + TeO ₂ + P ₂ O ₅ + Fe ₂ O ₃ ≧ 75% by mass, and V ₂ O ₅ > TeO ₂ > P ₂ O ₅ ≧ Fe ₂ O ₃ (% by mass).

  ADVANTAGE OF THE INVENTION According to this invention, the thermal damage with respect to the organic element and organic material which are incorporated in an electronic component can be reduced, an electronic component can be manufactured efficiently, and the devitrification of a glass joining layer can be reduced.

It is an example of the upper surface schematic of an electronic component, and the cross-sectional schematic of the sealing part. It is an example of the upper surface schematic of an electronic component, and the cross-sectional schematic of the sealing part. It is an example of the manufacturing method schematic of the electronic component shown in FIG. It is an example of the manufacturing method schematic of the electronic component shown in FIG. It is an example of the manufacturing method schematic of the electronic component shown in FIG. It is an example of the manufacturing method schematic of the electronic component shown in FIG. It is an example of the manufacturing method schematic of the electronic component shown in FIG. It is an example of the DTA curve obtained by the differential thermal analysis (DTA) of typical low melting glass. It is an example of the thermal expansion curve of typical low melting glass. It is the schematic of the laser irradiation experiment to a glass compacting body. It is the state schematic which apply | coated the glass paste for laser sealing. It is a cross-sectional schematic diagram showing a laser irradiation state. It is an example of the transmittance | permeability curve of typical low melting glass.

  The present invention will be described below. FIG. 1 and FIG. 2 show a schematic top view of two types of electronic components according to an embodiment of the present invention and a schematic cross-sectional view of the sealed portion. FIG. 1 has one or more organic members 3 (organic elements or organic materials) between two transparent substrates 1 and 2, and the outer peripheral portion of the two transparent substrates 1 and 2 is made of low melting glass. It is an electronic component joined with a sealing material 5 included. FIG. 2 shows an electronic component in which the distance between the two transparent substrates 1 and 2 is large and is joined with sealing materials 5 and 5 ′ via spacers 6.

In the present invention, the low-melting glass contained in the sealing materials 5 and 5 ′ contains vanadium oxide, tellurium oxide, phosphorus oxide and iron oxide, and is converted into V ₂ O ₅ , TeO ₂ , P ₂ O in terms of the following oxides. ₅ and Fe ₂ O ₃ are 75% by mass or more, and V ₂ O ₅ > TeO ₂ > P ₂ O ₅ ≧ Fe ₂ O ₃ (% by mass). The low-melting glass satisfying this condition absorbs the wavelength efficiently by laser irradiation, and is heated and softened and flows easily. That is, by using the low melting point glass and the laser, it is possible to keep heating only at a desired place, and without causing the organic member 3 to be thermally damaged, the outer peripheral portions of the two transparent substrates 1 and 2 are formed. Can be joined.

  As the wavelength of the laser to be used, a range of 400 to 1100 nm in which the low melting point glass efficiently absorbs and transmits through the transparent substrate is effective. If the wavelength is less than 400 nm, the transparent substrate and the organic elements and organic materials inside the transparent substrate may be heated or deteriorated. On the other hand, if the wavelength exceeds 1100 nm, the absorption of the low-melting-point glass is reduced, and no good softening fluidity can be exhibited.

As the low melting point glass, it is important to contain the most V ₂ O _{5 in} terms of oxides, thereby efficiently absorbing the wavelength range of 400 to 1100 nm and heating. At the same time, the softening point T _s of the low-melting glass can be lowered, and it can be easily softened and flowed by irradiation with a laser having a wavelength range of 400 to 1100 nm.

TeO ₂ and P ₂ O ₅ are important components for vitrification. If it is not glass, it cannot soften and flow at low temperatures. Also, it cannot be softened and flowed easily by laser irradiation. P ₂ O ₅ has a greater effect of vitrification than TeO ₂ and is effective for lowering thermal expansion. However, when the content is higher than TeO ₂ , the moisture resistance and water resistance are lowered, and the softening point T _s is increased. Resulting in. However, on the other hand, if the content of TeO ₂ is increased, the thermal expansion coefficient tends to increase, and if it is too large, the low melting point glass is damaged before it softens and flows due to heat shock caused by laser irradiation. Sometimes.

Fe ₂ O ₃ is a component that acts on P ₂ O ₅ in particular to improve the moisture resistance and water resistance of the low-melting glass. Further, like V ₂ O ₅ , it is also a component that efficiently absorbs a wavelength range of 400 to 1100 nm. However, if the content exceeds P ₂ O ₅ , the low melting point glass will be crystallized by heating. This crystallization is a phenomenon that hinders the softening fluidity of the low-melting glass and is not preferable.

The roles and effects of V ₂ O ₅ , TeO ₂ , P ₂ O ₅ and Fe ₂ O _{3 described} above are based on the reliability of laser irradiation because the total content is 75% by mass or more. A joint having high adhesion (adhesion, adhesion, moisture resistance, water resistance, etc.) can be obtained.

The particularly effective composition range of the low melting point glass is 35 to 55% by mass of V ₂ O _5, 19 to 30% by mass of TeO ₂ , 7 to 20% by mass of P ₂ O _{5 in} terms of the following oxides, Fe ₂ O ₃ is 5-15 wt%.

In order to prevent or suppress crystallization, it contains WO ₃ , MoO ₃ , Ta ₂ O ₅ , ZnO, BaO, SrO, and in order to improve moisture resistance and water resistance, MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , BaO , SrO, Ag ₂ O, K ₂ O, Nb ₂ O ₅ , Ta ₂ O ₅ , ZnO for reduction of thermal expansion coefficient, MoO ₃ , Ag ₂ O for lowering the softening point T _s The inclusion of K ₂ O is effective. On the other hand, components that promote crystallization are Nb ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , Ag ₂ O, K ₂ O, and components that increase the softening point T _s are Sb _2. O ₃ , Bi ₂ O ₃ , BaO, SrO, components that increase the coefficient of thermal expansion are MoO ₃ , BaO, SrO, Ag ₂ O, K ₂ O, and components that decrease moisture resistance and water resistance are MoO 3 ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , and ZnO. For this reason, the inclusion of WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , ZnO, BaO, SrO, Ag ₂ O, K ₂ O has advantages and disadvantages. Therefore, it is necessary to determine the component to be contained and the content thereof with sufficient consideration of the characteristics of the base composition composed of V ₂ O ₅ , TeO ₂ , P ₂ O ₅ and Fe ₂ O ₃ .

Of the following oxide conversions, WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , ZnO, SrO, BaO, Ag ₂ O, K ₂ O The total of one or more types is preferably 25% by mass or less. When the total of these contents exceeds 25% by mass, the softening point T _s may increase, the thermal expansion coefficient may increase, or the crystallization tendency may increase. Also, one or more of WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , ZnO, SrO, BaO, Ag ₂ O, K ₂ O The total is more preferably 0 to 20% by mass.

If V ₂ O ₅ is less than 35% by mass, it may be difficult to soften and flow easily even when irradiated with a laser having a wavelength in the range of 400 to 1100 nm. On the other hand, when it exceeds 55% by mass, reliability such as moisture resistance and water resistance may be lowered. If TeO ₂ is less than 19% by mass, the crystallization tendency may increase, the softening point T _s may increase, or the reliability such as moisture resistance and water resistance may decrease. On the other hand, if it exceeds 30% by mass, the softening point T _s tends to be lowered, but the thermal expansion coefficient becomes large, and the low melting point glass may be broken before it softens and flows due to heat shock caused by laser irradiation.

When P ₂ O ₅ is less than 7% by mass, the tendency to crystallize increases, and it may become difficult to soften and flow by laser irradiation. On the other hand, if it exceeds 20% by mass, the softening point T _s increases, and it may be difficult to soften and flow easily even when irradiated with a laser. Further, reliability such as moisture resistance and water resistance may be lowered. When Fe ₂ O ₃ is less than 5% by mass, reliability such as moisture resistance and water resistance is lowered, while when it exceeds 15% by mass, crystallization may be accelerated.

The total of one or more of WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , ZnO, SrO, BaO, Ag ₂ O, K ₂ O If it exceeds 20% by mass, the softening point T _s may be increased, the thermal expansion coefficient may be increased, or the crystallization tendency may be increased depending on the contained component.

Furthermore, it is effective that the low melting point glass has a transition point _Tg of 320 ° C. or lower and a softening point T _s of 380 ° C. or lower. Although described in detail later, the transition point T _g and the softening point T _{s mentioned} here are characteristic temperatures by differential thermal analysis (DTA), and the transition point T _g is the start temperature of the first endothermic peak, the softening point T. _s is the second endothermic peak temperature. When transition point T _g exceeds 320 ° C., there is a large residual strain in the laser sealing with a rapid heating and quenching occurs. On the other hand, when the softening point T _s exceeds 380 ° C., it becomes difficult to soften and flow easily during laser irradiation. In addition, it is effective that the low-melting glass has a coefficient of thermal expansion at 30 to 250 ° C. of 100 × 10 ⁻⁷ / ° C. or less. If the thermal expansion coefficient exceeds 100 × 10 ⁻⁷ / ° C., cracks may occur due to heat shock during laser irradiation.

Further, in the electronic component shown in FIGS. 1 and 2, the present invention may include a filler in the sealing material 5 in addition to the low-melting glass, for example, in order to reduce the thermal expansion coefficient. One or more of zirconium tungstate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ), and silicon (Si) are preferable. These fillers have a smaller coefficient of thermal expansion than the present low-melting glass, and also have good wettability and adhesion to the present low-melting glass, so that the thermal expansion coefficient as the sealing material 5 can be reduced. it can.

The effect of lowering the thermal expansion coefficient of the sealing material 5 is Zr ₂ (WO ₄ ) (PO ₄ ) ₂ having the largest effect, followed by Si, and then Nb ₂ O ₅ . However, since Si absorbs a laser having a wavelength in the range of 400 to 1100 nm and can generate heat, and heat conduction is better than the other two fillers and low melting point glass, it is particularly effective for laser sealing. The filler content in the sealing material is preferably 35 parts by volume or less with respect to 100 parts by volume of the low-melting glass.

  However, if it exceeds 35 parts by volume, the softening fluidity of the low-melting glass in the sealing material is lowered, and the adhesiveness may be weakened during laser irradiation.

  In the electronic component of the present invention shown in FIG. 1, the thickness of the bonding layer made of the sealing material 5 is preferably 20 μm or less. If the thickness exceeds 20 μm, the low melting point glass contained in the sealing material 5 far from the laser-irradiated transparent substrate side is difficult to soften and flow, and therefore exhibits an overall good softening fluidity in the thickness direction of the sealing material 5. It will disappear. In addition, in the electronic component shown in FIG. 2, it is desirable that the distance between the two transparent substrates 1 and 2 is large, particularly when the distance is 100 μm or more, to be joined via the spacer 6. In this case, the thickness of the bonding layer is preferably 20 μm or less for both the sealing materials 5 and 5 ′ as described above.

  Furthermore, in the electronic component of the present invention shown in FIGS. 1 and 2, the transparent substrates 1 and 2 or the spacer 6 are made of glass or resin. Since these are transparent, they have a low absorptance at wavelengths of 400 to 1100 nm and a high transmittance. For this reason, even if a laser having a wavelength in the range of 400 to 1100 nm is irradiated, the laser is transmitted almost without being heated, and only a desired portion of the sealing material 5 or 5 'can be irradiated. Since the sealing material 5 or 5 'irradiated with the laser softens and flows the low melting point glass contained therein, the outer peripheral portions of the transparent substrates 1 and 2 can be joined.

  As described above, the present invention is effectively applied to a display incorporating an organic light emitting diode, a dye-sensitized solar cell incorporating an organic dye, a solar cell incorporating a photoelectric conversion element and bonded with a resin, and the like. It is. The present invention can also be applied to the case where an element or material having low heat resistance is applied inside the electronic component, and is not limited to the electronic component.

  Moreover, this invention is the sealing material paste containing the powder of the said low melting glass, a resin binder, and a solvent. By including the resin binder and the solvent, it becomes easy to apply to the substrate as in screen printing. Since the sealing material paste is applied to the substrate and then dried to volatilize the resin binder and the solvent, bubbles are not generated during firing, and the airtightness of the formed sealing material can be improved. As the particle size of the low-melting glass, the average particle size is preferably 3 μm or less. The resin binder is preferably ethyl cellulose or nitrocellulose, and the solvent is preferably butyl carbitol acetate. Further, the sealing material paste may contain filler particles. The filler particles preferably have an average particle size larger than the average particle size of the low-melting glass. Moreover, it is preferable that content of this filler particle is 35 volume parts or less with respect to 100 volume parts of powder of this low melting glass. When it is 35 parts by volume or more, the adhesiveness may be weakened as described above.

  Next, the manufacturing method of the electronic component of this invention is demonstrated. A method for manufacturing the electronic component shown in FIG. 1 is briefly shown in FIGS. As shown in FIG. 3, a sealing material 5 including a low melting point glass is formed on the outer peripheral portion of the transparent substrate 1. In the formation method, first, the sealing material paste to be the sealing material 5 is applied to the outer peripheral portion of the transparent substrate 1 and dried. When using a glass substrate for the transparent substrate 1, the low-melting glass contained in the sealing material 5 is softened and flowed by firing with a firing furnace or laser 7 in the wavelength range of 400 to 1100 nm, and fired to the transparent substrate 1. Form. When a resin substrate is used for the transparent substrate 1, the heat resistance of the resin is low and a firing furnace cannot be used. Therefore, the sealing material 5 is fired and formed on the outer peripheral portion of the transparent substrate 1 by irradiation with the laser 7.

  Next, as shown in FIG. 4, another transparent substrate 2 on which one or more organic members 3 are formed is produced. The transparent substrate 2 may be either a glass substrate or a resin substrate, but is preferably matched with the material of the transparent substrate 1. The surface of the transparent substrate 1 on which the sealing material 5 is formed and the surface of the transparent substrate 2 on which the organic member 3 is formed are opposed to each other as shown in FIG. The organic member 3 is disposed in an internal space formed by the transparent substrates 1 and 2 and the sealing material 5. In addition, when baking the transparent substrate 1 which apply | coated the sealing material 5 by laser irradiation, since it is hard to heat except the outer peripheral part of the transparent substrate 1, you may form the organic member 3 in the transparent substrate 1. FIG. A sealing material 5 is irradiated with a laser 7 in a wavelength range of 400 to 1100 nm through a transparent substrate. The laser 7 may irradiate the sealing material 5 from the outside of any transparent substrate. However, since the sealing material 5 is formed on the transparent substrate 1 in advance, the sealing material 5 is irradiated from the outside of the transparent substrate 2. Then, it can seal more efficiently. At that time, care must be taken not to irradiate the organic member 3 incorporated in the electronic component with the laser 7. This is because there is a possibility that the organic member 3 is damaged or deteriorated by the irradiation of the laser 7. The sealing material 5 softens and flows the low-melting glass contained in the sealing material 5 by irradiation with the laser 7, and joins the outer peripheral portions of the two transparent substrates 1 and 2.

  Also, a method of manufacturing the electronic component shown in FIG. 2 is simply shown in FIGS. As shown in FIG. 6, sealing materials 5 and 5 ′ are formed on at least the joint surface of the spacer 6. The sealing material paste to be the sealing materials 5 and 5 'is applied to at least the joint surface where the spacer 6 is joined to the transparent substrate and dried. In the case where the glass spacer 6 is used, the sealing materials 5 and 5 ′ are irradiated by irradiation from both outer sides of the transparent substrates 1 and 2 with a firing furnace or lasers 7 and 7 ′ having a wavelength range of 400 to 1100 nm. The contained low melting point glass is softened and fluidized and fired and formed on the spacer 6. When the resin spacer 6 is used, since the heat resistance of the resin is low and a firing furnace cannot be used, the sealing material 5 is fired and formed on the spacer 6 by irradiation with the lasers 7 and 7 '.

  As shown in FIG. 7, the spacer 6 on which the sealing materials 5 and 5 'are formed is installed and fixed on the outer peripheral portion where the transparent substrate 1 and the other transparent substrate 2 on which one or more organic members 3 are formed face each other. , Lasers 7 and 7 'in the wavelength range of 400 to 1100 nm are applied to the sealing materials 5 and 5' through the transparent substrate. At that time, care must be taken not to irradiate the organic member 3 incorporated in the electronic component with the lasers 7 and 7 'as described above. The sealing materials 5 and 5 ′ soften and flow the low melting point glass contained in the sealing materials 5 and 5 ′ by the irradiation of the lasers 7 and 7 ′, and join the outer peripheral portions of the two transparent substrates 1 and 2 To do. The transparent substrates 1 and 2 may be either a glass substrate or a resin substrate as long as the reflectance in the wavelength range of 400 to 1100 nm is low and the transmittance is high.

  As described above, the electronic component of the present invention, the manufacturing method thereof, and the sealing material paste used therefor efficiently manufacture the electronic component without thermally damaging the organic element or the organic material incorporated in the electronic component. In addition, a glass bonding layer having good adhesion, gas barrier properties (air tightness), moisture resistance and water resistance can be obtained.

  Hereinafter, it demonstrates in detail using an Example. However, the present invention is not limited to the description of the embodiments taken up here, and may be combined as appropriate.

In this example, the composition and characteristics of the low-melting glass contained in the sealing material were examined. Examples are shown in Tables 1 to 4 and Comparative Examples are shown in Table 5. For the preparation of the low-melting glass shown in Tables 1 to 5, reagents V ₂ O ₅ , TeO ₂ , P ₂ O ₅ , Fe ₂ O ₃ , WO ₃ , MoO ₃ , Nb manufactured by High Purity Chemical Laboratory are used as raw materials. ₂ O ₅ , Ta ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , ZnO, SrCO ₃ , BaCO ₃ , Ag ₂ O and K ₂ CO ₃ were used. Using these raw materials, a predetermined amount was blended and mixed so as to be a total of 200 g, put into a platinum crucible, heated to 900 to 1000 ° C. at a heating rate of 5 to 10 ° C./min in an electric furnace, and melted. In order to obtain a uniform glass at this temperature, it was held for 2 hours with stirring. Thereafter, the crucible was taken out and poured onto a stainless steel plate heated to 150 to 200 ° C. in advance to produce a low melting point glass.

The produced low melting point glass was pulverized with a jet mill until the average particle size became 3 μm or less. By performing differential thermal analysis (DTA) up to 500 ° C. using the powder at a rate of temperature increase of 5 ° C./min, the transition point (T _g ), yield point (M _g ), softening point (T _s ) and crystal The _{crystallization} temperature (T _cry ) was measured. Note that alumina (Al ₂ O ₃ ) powder was used as a standard sample. FIG. 8 shows a DTA curve of a typical low melting point glass. As shown in FIG. 8, T _g is the first endothermic peak start temperature, _Mg is the peak temperature, T _s is the second endothermic peak temperature, and T _cry is the exothermic peak start temperature due to crystallization. The characteristic temperature of the glass is defined by the viscosity, T _g, M _g and T _s is said temperature corresponding to the viscosity of each 10 ^13.3 poise, 10 ^11.0 poise and 10 ^7.65 poise. In order to soften and flow glass at a low temperature, it is necessary to reduce the temperature of T _s as much as possible. Further, in order to mitigate the thermal residual strain, as much as possible, it is preferable to cold the T _g. T _cry is the temperature at which the glass begins to crystallize. Since crystallization hinders the softening fluidity of the glass, it is desirable to make T _cry higher than T _{s as} much as possible.

The low-melting glasses prepared to remove thermal strain in a temperature range of T _g ~M _g, was processed into a prism of 4 × 4 × 20mm. Using this, a thermal expansion coefficient of 30 to 250 ° C., a transition temperature _TG and a deformation temperature _AT were measured with a thermal dilatometer. The rate of temperature increase was 5 ° C./min. Further, as a standard sample, a cylindrical quartz glass having a diameter of 5 × 20 mm was used. FIG. 9 shows a thermal expansion curve of a low-melting glass which is a surface. In FIG. 9, the elongation amount of quartz glass which is a standard sample is subtracted. The thermal expansion coefficient was calculated from the gradient of elongation in the temperature range of 30 to 250 ° C. _TG is a temperature at which elongation starts remarkably, and _AT is a temperature at which deformation occurs due to a load. T _G was determined to slightly higher than the T _g of the DTA. A _T was between M _g ~T _s of the DTA.

  For the moisture resistance test of the produced low melting point glass, the surface of the sample for thermal expansion evaluation was mirror-finished. Evaluation of moisture resistance was carried out for 10 days under conditions of a temperature of 85 ° C. and a humidity of 85%. When the gloss of the mirror-finished glass surface was maintained, “◯”, and when the gloss decreased, “△ “If the glass broke down, it was evaluated as“ x ”.

The softening fluidity of the produced low melting point glass is that the glass powder crushed by the jet mill is compacted by hand press (1 ton / cm ² ), and the glass compact is irradiated with various lasers through a transparent substrate. Was evaluated by The outline of the laser irradiation experiment to the glass compacting body is shown in FIG. The size of the glass compact 8 was φ10 × 2 mm. The glass powder compact 8 was placed on the transparent substrate 1 and irradiated with a laser 7 from the back side toward the center of the glass powder compact 8. A slide glass was used for the transparent substrate 1. As the laser 7, a semiconductor laser having a wavelength of 405 nm, a double wave of a YAG laser of 532 nm, a semiconductor laser of 630 nm, a semiconductor laser of 805 nm, and a YAG laser of 1064 nm were used. The softening fluidity is evaluated as “◯” when the laser irradiation portion of the glass compact 8 has flowed, “●” when it has flowed but many cracks occur, and “△” when softening. When the cracks occurred frequently, “ΔΔ” was indicated, and when neither flow nor softening was indicated, “X” was assigned. In addition, the softening fluidity | liquidity of the laser irradiation part of the glass compacting body 8, and the generation | occurrence | production state of a crack were determined by observing with an optical microscope through the transparent substrate 1. FIG.

As can be seen from Examples G1 to 64 shown in Tables 1 to 4 and Comparative Examples G65 to 80 shown in Table 5, the low melting point glasses of Examples G1 to 64 are Comparative Examples G67, 69, 73 to 76, and 78. The softening point T _s is lower than that of the low melting point glass of ˜80, and the thermal expansion coefficient is lower than those of the low melting point glasses of Comparative Examples G68, 70 to 73, 77 and 78, and Comparative Examples G65 to 68, 70 to 74,76, The moisture resistance was better than the low melting glass of 78 and 80. Further, the low melting point glass of Examples G1 to 64 has better softening fluidity by laser irradiation than the low melting point glasses of Comparative Examples G67, 69, 73 to 76 and 78 to 80, and Comparative Examples 68 and 70 to 72. No cracks occurred frequently even if the softening fluidity was good as in the low melting point glass No. 77 and No. 77.

The low melting point glass of Examples G1 to 64 contains vanadium oxide, tellurium oxide, phosphorus oxide and iron oxide, and is the sum of V ₂ O ₅ , TeO ₂ , P ₂ O ₅ and Fe ₂ O ₃ in terms of the following oxides. Was 75% by mass or more and V ₂ O ₅ > TeO ₂ > P ₂ O ₅ ≧ Fe ₂ O ₃ (% by mass). Further, as a glass component, any one or more of tungsten oxide, molybdenum oxide, niobium oxide, tantalum oxide, manganese oxide, antimony oxide, bismuth oxide, zinc oxide, barium oxide, strontium oxide, silver oxide and potassium oxide are included. However, WO ₃ + MoO ₃ + Nb ₂ O ₅ + Ta ₂ O ₅ + MnO ₂ + Sb ₂ O ₃ + Bi ₂ O ₃ + ZnO + BaO + SrO + Ag ₂ O + K ₂ O ≦ 25 mass% in terms of the following oxides. A particularly effective composition range satisfies the above conditions, and V ₂ O ₅ is 35 to 55 mass%, TeO ₂ is 19 to 30 mass%, and P ₂ O ₅ is 7 to 20 mass in terms of the following oxides. %, Fe ₂ O ₃ is 5 to 15 wt%, and _{WO 3, MoO 3, Nb 2} O 5, Ta 2 O 5, MnO 2, Sb 2 O 3, Bi 2 O 3, ZnO, SrO, BaO, Ag The total of one or more of ₂ O and K ₂ O was 0 to 20% by mass.

In addition, the low melting point glass of Examples G1 to 64 efficiently absorbs and heats a laser having a wavelength in the range of 400 to 1100 nm, and has a low softening point T _s of 380 ° C. or less. Indicated. Furthermore, the transition point T _g is 320 ° C. or less and low thermal expansion coefficient is relatively small as 100 × 10 ^-7 / ℃ less, cracks in the heat shock by laser irradiation was small.

  In this example, a laser sealing experiment was conducted using the low melting point glass of Example G19 shown in Table 2 and a slide glass as the transparent substrate. A sealing material paste was prepared using a low melting point glass powder of G19 pulverized with a jet mill to an average particle size of 3 μm or less, a resin binder, and a solvent. Nitrocellulose was used as the resin binder, and butyl carbitol acetate was used as the solvent. Using this sealing material paste, it was applied to the outer peripheral portion of the transparent substrate by screen printing as shown in FIG. 11, dried, and then baked in the atmosphere at 380 ° C. for 30 minutes. The line width of the sealing material 5 formed on the transparent substrate 1 was set to 1.5 mm, and the coating amount was adjusted so that the fired film thicknesses were about 5, 10, 20, and 30 μm, respectively. As shown in FIG. 12, the transparent substrate 2 is placed oppositely, the laser 7 is irradiated from the direction of the transparent substrate 1 to the sealing material 5 while moving at a speed of 8 mm / second, and the outer periphery of the transparent substrates 1 and 2. The parts were joined. As the laser 7, the four types of lasers used in Example 1 were used. All samples could be joined and evaluated for airtightness (gas barrier property) and adhesion. The evaluation results are shown in Table 6.

  The airtightness (gas barrier property) was evaluated by performing a helium leak test and evaluating “◯” when no leak occurred and “×” when leaking. In addition, the adhesion was evaluated as “◯” when a peel test was performed and the transparent substrate or the sealing material was damaged, and “X” when easily peeled from the interface between the transparent substrate and the sealing material. . When the fired film thickness was 20 μm or less, airtightness and adhesiveness were good regardless of which laser was used. However, when the fired film thickness is 30 μm, good airtightness and adhesiveness may not be obtained depending on the laser used. Since YAG lasers are used at wavelengths of 532 nm and 1064 nm, and higher power than other semiconductor lasers, it is considered that good airtightness and adhesiveness were obtained. Since the semiconductor laser is very cheap compared to the YAG laser, the semiconductor laser can never be used for laser sealing, and the thickness of the bonding layer is preferably 20 μm or less.

  However, when laser was irradiated from both surfaces of the transparent substrates 1 and 2, good airtightness and adhesiveness were obtained even when the fired film thickness was 30 μm. That is, when the thickness of the adhesive layer is large, there is a possibility that it can be handled by such a method.

  The transmittance | permeability curve of the coating film which baked the low melting glass of Example G19 in FIG. 13 is shown. In the wavelength region of 300 to 2000 nm, the transmittance decreased as the wavelength decreased, and the transmittance decreased as the fired film thickness increased. Needless to say, the low melting point glasses of the other examples shown in Tables 1 to 4 have similar transmittance curves, so that similar effects can be obtained.

  Next, a laser sealing experiment was conducted in the same manner as described above using polycarbonate as the transparent substrate. Since polycarbonate has lower heat resistance than G19 low-melting glass, a semiconductor laser having a wavelength of 805 nm was used when firing on a transparent substrate in advance. When this laser was used, a fired coating film of G19 was obtained with little heating of the polycarbonate. Subsequently, as shown in FIG. 12, various kinds of lasers were irradiated to join the outer peripheral portions of the polycarbonates 1 and 2, and the adhesion was evaluated in the same manner as described above. The same result as that obtained when the slide glass was used for the transparent substrates 1 and 2 was obtained.

In this example, a glass substrate having a thermal expansion coefficient of 50 × 10 ⁻⁷ / ° C. on the transparent substrate, Example G43 shown in Table 3 on the low melting point glass contained in the sealing material, and phosphorus as a filler in the sealing material A laser sealing experiment similar to that in Example 2 was performed using zirconium tungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ), and silicon (Si).

First, a low melting point glass powder of G43 pulverized by a jet mill to an average particle size of 3 μm or less, and a Zr ₂ (WO ₄ ) (PO ₄ ) ₂ , Nb ₂ O ₅ or Si filler having an average particle size of about 5 μm. A sealing material paste was prepared using particles, a resin binder, and a solvent. The filler particle content was 15, 25, 35, and 45 parts by volume with respect to 100 parts by volume of the low melting point glass of G43. The density of the low-melting glass G43 used was _{^{3.53g / cm 3, Zr 2 (}} WO 4) (PO 4) 2 of the density 3.80g / cm ^3, Nb ₂ density of O ₅ is 4.57 g / cm ³ The density of Si was 2.33 g / cm ³ . Further, ethyl cellulose was used as the resin binder, and butyl carbitol acetate was used as the solvent. Using this sealing material paste, it was applied to the outer peripheral portion of the transparent substrate by screen printing as shown in FIG. 11, dried, and then fired in the atmosphere at 400 ° C. for 30 minutes. The sealing material 5 formed on the transparent substrate 1 had a line width of 1.5 mm and a film thickness of about 10 μm.

  As shown in FIG. 12, the transparent substrate 2 is placed oppositely, and the semiconductor laser 7 having a wavelength of 805 nm is irradiated from the direction of the transparent substrate 1 to the sealing material 5 while moving at a speed of 8 mm / second. The outer peripheries of 1 and 2 were joined. In the same manner as in Example 2, airtightness (gas barrier property) and adhesiveness were evaluated. The evaluation results are shown in Table 7.

When the difference in thermal expansion between the glass substrate used for the transparent substrates 1 and 2 and the low melting point glass G43 is large as in this embodiment, the thermal expansion coefficient of the sealing material 5 is obtained by containing a filler in the sealing material 5 Therefore, generation of cracks can be prevented, and good adhesiveness and airtightness can be obtained. In this example, a filler of Zr ₂ (WO ₄ ) (PO ₄ ) ₂ , Nb ₂ O ₅ or Si was contained. Good hermeticity and adhesiveness were obtained by the inclusion of the filler. When the content of the filler is 45 parts by volume, the content of the low-melting glass G43 for joining the transparent substrates 1 and 2 is reduced, so the adhesiveness is inferior compared with other examples, but good. Airtightness was maintained.

From the above, in order to airtightly and firmly join the transparent substrates 1 and 2 with the laser, the content of the filler particles contained in the sealing material 5 is preferably 35 parts by volume or less with respect to 100 parts by volume of the low-melting glass. it is conceivable that. In this example, Zr ₂ (WO ₄ ) (PO ₄ ) ₂ , Nb ₂ O ₅ and Si, which have good wettability with the low melting point glass, were selected and examined as filler particles. In addition, β-eucryptite, cordierite, zirconium phosphate, zirconium silicate and the like having a small thermal expansion coefficient can also be used.

If the distance between the transparent substrates 1 and 2 is 100 μm or more, the manufacturing method shown in Example 2 may cause cracks in the sealing material 5 even if the laser is irradiated from both sides, and may be included in the sealing material 5. The softening fluidity of the low melting point glass was insufficient, and good airtightness and adhesiveness could not be obtained. Therefore, in this embodiment, as shown in FIG. 2, the transparent substrates 1 and 2 are joined via the spacer 6. The transparent substrates 1 and 2 and the spacer 6 were made of white glass having high transmittance, and the transparent substrates 1 and 2 were joined by the manufacturing method shown in FIGS. 100 parts by volume of the low melting point glass powder of G43 shown in Table 3 and 10 parts by volume of Zr ₂ (WO ₄ ) (PO ₄ ) ₂ filler particles as shown in Table 3 in the same manner as in Example 3 and the sealing materials 5 and 5 ′, ethyl cellulose and butyl Using a sealing material paste made of carbitol acetate, it was applied to the spacer 6 as shown in FIG. 6, dried and then fired in the atmosphere at 400 ° C. for 20 minutes. The fired film thickness was 15 μm. The width of the spacer 6 was fixed to 3 mm, and the thickness was set to 70, 320, 500, and 1000 μm, respectively. When the thicknesses of the sealing materials 5 and 5 ′ are added, they are 100, 350, 530, and 1030 μm, respectively. As shown in FIG. 7, these were respectively installed on the outer periphery of the four sides and joined by irradiating semiconductor lasers 7 and 7 'having a wavelength of 630 nm from both surfaces of the transparent substrates 1 and 2. The laser feed rate was 8 mm / second. The adhesion was evaluated in the same manner as in Example 2. It has been found that good adhesiveness is obtained regardless of the thickness of the spacer 6 and that it is effective to use the spacer 6 when the distance between the transparent substrates 1 and 2 is large.

In this example, a display having a large number of organic light emitting diodes (OLEDs) built therein was manufactured and evaluated. This OLED display has the structure shown in FIG. Since the OLED which is the built-in organic element 3 is easily deteriorated by moisture and oxygen, it is very difficult to hermetically and firmly join the outer peripheral portions of the transparent substrates 1 and 2 with the sealing material 5 including the low melting point glass. It is valid. In this embodiment, non-alkali glass used for a liquid crystal display is used for the transparent substrates 1 and 2. On the outer periphery of the transparent substrate 1, 100 parts by volume of the low melting glass powder of G55 shown in Table 4, 20 parts by volume of Zr ₂ (WO ₄ ) (PO ₄ ) ₂ filler particles, 10 parts by volume of Si filler particles, ethyl cellulose and Using a sealing material paste made of butyl carbitol acetate, as shown in FIG. 3, it is applied to the outer periphery of the transparent substrate 1, dried and then fired in the atmosphere at 400 ° C. for 30 minutes to form the sealing material 5. did. The formed sealing material had a width of 2.5 mm and a fired film thickness of 10 μm. On the other hand, a large number of OLEDs corresponding to the number of pixels were formed on the transparent substrate 2 as shown in FIG. The transparent substrate 2 and the transparent substrate 1 were opposed to each other as shown in FIG. 5, and the laser 7 was irradiated from the direction of the transparent substrate 1 toward the sealing material 5. As the laser 7, a semiconductor laser having a wavelength of 805 nm was used, the outer peripheral portion was moved at a speed of 8 mm / second, and the outer peripheral portions of the transparent substrates 1 and 2 were bonded.

  As a result of conducting a lighting test of the OLED display immediately after the production, it was confirmed that the OLED display was lit without problems. Moreover, the adhesiveness of the joint was also good. Next, this display was subjected to a high temperature and high humidity test under conditions of 85 ° C.-85% Rh-10 days, 25 days and 50 days, and a lighting test was performed. For comparison, an OLED display bonded with resin was also included. The resin bonding layer had a width of 3 mm and a thickness of 10 μm. In the high temperature and high humidity test for 10 days, both OLED displays lighted without any problem, but the display joined with the resin was greatly deteriorated by lighting after 25 days. This is because moisture and oxygen are introduced into the display from the resin joint and the OLED deteriorates. On the other hand, in the present invention, even in a high temperature and high humidity test for 50 days, no deterioration was observed in the lighting of the OLED, and the test result was good. This is a result suggesting that good airtightness is maintained. Furthermore, as a result of evaluating the adhesiveness of the joint after the high-temperature and high-humidity test, there was no significant decrease as if it was joined with a resin, which was almost the same as before the test.

  From the above, it has been found that the present invention can be effectively applied to an OLED display. Moreover, it cannot be overemphasized that it can expand also to electronic components, such as a lighting fixture in which OLED is mounted.

In this example, a dye-sensitized solar cell containing an organic dye was prepared and evaluated. In general, in this solar cell, organic dye molecules are formed on the surface of a large number of titania (TiO ₂ ) nanoparticles, and when the dye is irradiated with light, excited electrons are injected into TiO ₂ , It reaches the electrode while diffusing inside the particles. On the other hand, at the counter electrode, electrons are injected into the electrolyte and iodine (I) is reduced. This can generate electricity. Dye-sensitized solar cells are effective in reducing costs because they do not use non-vacuum, low-temperature processes and silicon, but have a significant problem with reliability. Sealing technology is the key to improving the reliability. Since organic dyes and electric fields with low heat resistance are used, sealing must be performed at a temperature lower than their heat resistance temperature, and sealing with resin is generally used. However, resin sealing has a major problem that long-term reliability cannot be ensured.

  The present invention was applied to sealing a dye-sensitized solar cell in the same manner as in Example 5. For the transparent substrates 1 and 2, white plate glass having high transmittance was used. The formation of the sealing material 5 on the transparent substrate 1 was performed using the same baking conditions as those of the same sealing material paste as in Example 4. A cell containing a large number of organic dyes or the like was formed or installed on the transparent substrate 2, and the outer peripheral portions of the transparent substrates 1 and 2 were joined by laser irradiation in the same manner as in Example 5. It was able to join firmly and adhesiveness was favorable. Moreover, the high temperature and high humidity test similar to that in Example 5 had no problem and good airtightness was maintained. Moreover, the adhesion after the high temperature and high humidity test was also good. Further, corrosion due to iodine (I) at the joint was not observed. However, the electrode was corroded by iodine (I). From this, besides the sealing of the dye-sensitized solar cell, the low-melting glass according to the present invention can be applied to the covering of the electrode.

  From the above, it was found that the present invention can be effectively applied to a dye-sensitized solar cell. Moreover, it cannot be overemphasized that it can expand | deploy not only to a dye-sensitized solar cell but to electronic components, such as an organic solar cell.

  In this example, a large number of photoelectric conversion elements were built in and a solar cell bonded with a resin was manufactured and evaluated. A double-sided light receiving cell using a single crystal silicon substrate was used as the photoelectric conversion element. These cells are connected in series by tab wires. Conventionally, an EVA sheet is bonded between two transparent substrates, and ends are fixed with an aluminum frame and a resin sealing material. In general, a white plate glass having a high transmittance is applied to the transparent substrate. Most of the subsequent accidents of solar cells are caused by water penetrating inside. EVA sheet does not have high gas barrier properties (airtightness), and moisture gradually permeates over a long period of time. The formed electrode may be corroded and disconnected. For this reason, it is very important to prevent moisture from penetrating in order to ensure the long-term reliability of the solar cell.

In this example, the white plate glass was used as the transparent substrate, and the EVA sheet was used as the resin to be bonded. Since the thickness of the double-sided light-receiving cell used was about 250 μm including the electrodes on both sides and the EVA sheet was attached to the both sides of the cell with a thickness of about 250 μm, it was decided to join via spacers as shown in FIG. Since the distance between the transparent substrates 1 and 2 is about 500 μm, the spacer 6 is white plate glass having a width of 3.5 mm and a thickness of 470 μm. As the sealing material paste, G55 low melting point glass powder, Si filler particles, ethyl cellulose and butyl carbitol acetate shown in Table 4 were used. The content of the Si filler particles was 15 parts by volume with respect to 100 parts by volume of the low melting point glass of G55. First, a sealing material paste having a width of 3 mm was applied to the outer peripheral portion of the transparent substrate 1 and one surface of the spacer 6 by a screen printing method, and dried. After drying, baking was performed in the atmosphere at 400 ° C. for 30 minutes to form the sealing material 5 on the transparent substrate 1 and the sealing material 5 ′ on the spacer. The fired film thicknesses at that time were each 15 μm. The spacer 6 on which the sealing material 5 'is formed is placed on the transparent substrate 2, and the spacer 6 and the transparent substrate 2 are bonded with the sealing material 5' by applying weight and heating in the atmosphere at 400 ° C for 30 minutes. .
At that time, in order to ensure the airtightness of the corners, the low melting point glass paste of G55 was applied to the joint between the spacers 6 and fired at the same time. Between the transparent substrates 1 and 2 produced as described above, several double-sided light-receiving cells connected by tab wires were placed so that the sealing material 5 and the spacer 6 faced each other, and they were bonded together using an EVA sheet. Next, the outer peripheral portion of a semiconductor laser having a wavelength of 805 nm was moved from the transparent substrate 1 side at a speed of 8 mm / second, and the transparent substrates 1 and 2 were joined with the sealing materials 5 and 5 ′ via the spacers 6. Both airtightness and adhesiveness were good. Needless to say, long-term reliability can be ensured as compared with a resin sealing material.

  In this embodiment, the solar cell using the double-sided light receiving Si cell and the EVA sheet has been described. However, the present invention can be applied to all types of solar cells in which cells and transparent substrates are bonded and fixed using a resin. For example, it can be applied to a thin film solar cell.

  As described above, the OLED display, the dye-sensitized solar cell, and the Si solar cell to which the present invention is applied have been described. However, the present invention is not limited to these, and is generally applied to an electronic component having an organic element or organic material with low heat resistance. It can be applied, and the reliability of the electronic component can be remarkably improved.

DESCRIPTION OF SYMBOLS 1, 2 Transparent substrate 3 Organic member 5 Sealing material 6 Spacer 7, 7 'Laser 8 Glass compacting body

Claims (25)

An electronic component having an organic member between two transparent substrates and having an outer peripheral portion of the two transparent substrates joined with a sealing material containing low-melting glass, wherein the low-melting glass is vanadium oxide, oxidized It contains tellurium, phosphorus oxide and iron oxide, V ₂ O ₅ + TeO ₂ + P ₂ O ₅ + Fe ₂ O ₃ ≧ 75% by mass in terms of the following oxide, and V ₂ O ₅ > TeO ₂ > P ₂ O ₅ ≧ Electronic component which is Fe ₂ O ₃ (mass%). The low melting point glass is 35 to 55% by mass of V ₂ O _{5 in} terms of the following oxide, 19 to 30% by mass of TeO ₂ , 7 to 17% by mass of P ₂ O _{5, and 5} to 15% by mass of Fe ₂ O _3. The electronic component according to claim 1, wherein the electronic component is%. The low melting point glass further contains at least one of tungsten oxide, molybdenum oxide, niobium oxide, tantalum oxide, manganese oxide, antimony oxide, bismuth oxide, zinc oxide, barium oxide, strontium oxide, silver oxide and potassium oxide, and 1 of WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , ZnO, SrO, BaO, Ag ₂ O, K ₂ O 3. The electronic component according to claim 1, wherein the total of the seeds or more is 25% by mass or less. Of the following oxide conversions, WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , ZnO, SrO, BaO, Ag ₂ O, K ₂ O The electronic component according to claim 3, wherein the total of one or more types is 20 mass% or less.   The electronic component according to any one of claims 1 to 4, wherein the low melting point glass softens and flows when irradiated with a laser having a wavelength range of 400 to 1100 nm.   The electronic component according to any one of claims 1 to 5, wherein the low melting point glass has a transition point of 320 ° C or lower and a softening point of 380 ° C or lower. The electronic component according to claim 1, wherein the low-melting glass has a thermal expansion coefficient of 30 to 250 ° C. of 100 × 10 ⁻⁷ / ° C. or less. The sealing material includes a filler, and the filler is at least one of zirconium tungstate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ), and silicon (Si). The electronic component according to claim 1.   The electronic component according to claim 8, wherein a content of the filler is 35 parts by volume or less with respect to 100 parts by volume of the low-melting glass.   The electronic component according to claim 1, wherein a thickness of the sealing material that joins the outer peripheral portions of the two transparent substrates is 20 μm or less.   The distance between the two transparent substrates is 100 μm or more, and the outer peripheral portion of the two transparent substrates is bonded with the sealing material via a spacer, and each of the two transparent substrates is bonded to the spacer. The electronic component according to claim 1, wherein the sealing material has a thickness of 20 μm or less.   The electronic component according to claim 11, wherein the transparent substrate and the spacer are made of glass.   The electronic component according to claim 11, wherein the transparent substrate and the spacer are made of resin. The electronic component according to claim 1, wherein the organic member is any one of an organic light emitting diode, an organic dye, and a photoelectric conversion element. A sealing material paste containing a low-melting glass, a resin binder, and a solvent, wherein the low-melting glass contains vanadium oxide, tellurium oxide, phosphorus oxide, and iron oxide, and is converted to V ₂ O ₅ + TeO _{2 in} terms of the following oxides. A sealing material paste in which + P ₂ O ₅ + Fe ₂ O ₃ ≧ 75 mass% and V ₂ O ₅ > TeO ₂ > P ₂ O ₅ ≧ Fe ₂ O ₃ (mass%). The low melting point glass is 35 to 55% by mass of V ₂ O _{5 in} terms of the following oxide, 19 to 30% by mass of TeO ₂ , 7 to 17% by mass of P ₂ O _{5, and 5} to 15% by mass of Fe ₂ O _3. The sealing material paste according to claim 15, which is%. The low-melting glass further contains one or more of tungsten oxide, molybdenum oxide, niobium oxide, tantalum oxide, manganese oxide, antimony oxide, bismuth oxide, zinc oxide, barium oxide, strontium oxide, silver oxide and potassium oxide, and 1 of WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , ZnO, SrO, BaO, Ag ₂ O, K ₂ O The sealing material paste according to claim 15 or 16, wherein the total of the seeds or more is 25% by mass or less.   The sealing material paste according to any one of claims 15 to 17, wherein the low melting point glass has a transition point of 320 ° C or lower and a softening point of 380 ° C or lower. 19. The sealing material paste according to claim 15, wherein the low-melting glass has a thermal expansion coefficient of 30 to 250 ° C. of 100 × 10 ⁻⁷ / ° C. or less. Further, a filler is contained, and the filler is at least one of zirconium tungstate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ), and silicon (Si). The sealing material paste according to any one of 15 to 19.   21. The sealing material paste according to claim 20, wherein the filler content is 35 parts by volume or less with respect to 100 parts by volume of the low-melting glass powder. In the manufacturing method of an electronic component having an organic member between two transparent substrates, and joining the outer peripheral portion of the two transparent substrates with a sealing material containing low-melting glass,
A step of applying the sealing material paste according to any one of claims 15 to 21 to an outer peripheral portion of the transparent substrate made of glass, and a drying furnace after drying the sealing material paste or in a wavelength range of 400 to 1100 nm The step of baking by laser irradiation to form a sealing material, the surface of the glass transparent substrate on which the sealing material is formed, and the other transparent substrate made of glass or resin are opposed to each other. A step of fixing the transparent substrate, a step of irradiating the sealing material with a laser having a wavelength range of 400 to 1100 nm through the transparent substrate, and a step of softening and flowing the low-melting glass. A manufacturing method for electronic parts. In the manufacturing method of an electronic component having an organic member between two transparent substrates, and joining the outer peripheral portion of the two transparent substrates with a sealing material containing low-melting glass,
A step of applying the sealing material paste according to any one of claims 15 to 21 to an outer peripheral portion of a resin-made transparent substrate; and a laser irradiation in a wavelength range of 400 to 1100 nm after the sealing material paste is dried. The step of baking and forming the sealing material, the surface of the resin transparent substrate on which the sealing material is formed, and the other transparent substrate made of glass or resin are opposed to each other, and the two transparent An electron comprising: a step of fixing a substrate; a step of irradiating a laser having a wavelength range of 400 to 1100 nm to the sealing material through the transparent substrate; and a step of softening and flowing the low melting point glass. How to make parts. In the manufacturing method of an electronic component having an organic member between two transparent substrates, and joining the outer peripheral portion of the two transparent substrates with a sealing material containing low-melting glass,
A step of applying the sealing material paste according to any one of claims 15 to 21 to at least a bonding surface of a rod-shaped glass spacer; and a laser having a wavelength in a wavelength range of 400 to 1100 nm after drying the sealing material paste Firing the material to form a sealing material, fixing the glass spacer between the transparent substrate made of glass and the other glass or resin transparent substrate, 400 A method for producing an electronic component, comprising: a step of irradiating the sealing material with a laser having a wavelength range of ˜1100 nm through the transparent substrate; and a step of softening and flowing the low melting point glass. In the manufacturing method of an electronic component having an organic member between two transparent substrates, and joining the outer peripheral portion of the two transparent substrates with a sealing material containing low-melting glass,
A step of applying the sealing material paste according to any one of claims 15 to 21 to at least a joint surface of a rod-shaped resin spacer, and irradiation of a laser having a wavelength range of 400 to 1100 nm after the sealing material paste is dried. Baking, forming a sealing material, fixing the resin spacer between the transparent substrate made of resin and the other glass or resin transparent substrate, and 400-1100 nm A process for irradiating the sealing material with a laser in a wavelength range through the transparent substrate, and softening and flowing the low melting point glass.