WO2013115101A1 - Electronic component, production method therefor, and sealing material paste used therein - Google Patents

Description

Electronic component, method for producing the same, and sealing material paste used therefor

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

There is an electronic component in which an organic element or an organic material is embedded between two transparent substrates. In this electronic component, in order to protect the organic element and the organic material from moisture, moisture and the like, the outer peripheral portion of the two transparent substrates is joined with a resin sealing material, and a desiccant is further incorporated into the electronic component. It has been installed. However, since bonding with resin has insufficient gas barrier properties (air tightness), water molecules are gradually permeated and sufficient reliability has not been obtained. On the other hand, a sealing material using low melting point glass enables bonding with high gas barrier properties (air tightness), but requires a bonding temperature significantly higher than that of a resin sealing material. At this bonding temperature, the heat resistance of the organic element and organic material incorporated in the electronic component is exceeded.

Therefore, a laser seal that can be locally heated has been devised. The sealing material uses low melting point glass which enables airtight bonding. It is important that the low melting glass be heated by absorbing the laser light used and softened and flow. Since such a method can heat only the outer peripheral portion of the two transparent substrates, high gas barrier properties (airtightness) can be achieved without causing thermal damage to the organic element or organic material incorporated in the electronic component. Enables glass bonding).

In a display or the like incorporating an organic light emitting diode (OLED), a glass substrate obtained by temporarily sintering a sealing material on the outer peripheral portion is combined with a glass substrate on which the other OLED is formed, and a laser is irradiated over the glass substrate. And softening and flowing the low melting glass in the sealing material to bond the two glass substrates. Patent Document 1 proposes a sealing material capable of joining the outer peripheral portion with a laser in an OLED display. This sealing material is a V ₂ O ₅ -P ₂ O ₅ -Sb ₂ O ₃ -based low melting glass that can be heated by laser, and a lithium alumino silicate (β-eucryptite) for reducing the thermal expansion coefficient. Containing filler particles. Further, the low-melting glass, K ₂ comprises _{O, Fe 2 O 3, ZnO} , one of _{TiO 2, Al 2 O 3,} B 2 O 3, WO 3, having a transition point T _g of the less than 350 ° C. . Patent Document 2 also proposes a glass package to which the same sealing material as in Patent Document 1 is applied. The low melting point glass contained in the sealing material is also similar to that of Patent Document 1. By pre-baking the outer peripheral portion of the glass substrate in a low oxidation atmosphere having an oxygen content smaller than that of air, it is possible to prevent the trivalent or tetravalent vanadium ion from changing to pentavalent. As a result, it is possible to prevent the deterioration of the softening flowability due to the laser irradiation and the deterioration of the moisture resistance and the water resistance of the bonding portion after the laser sealing.

Patent No. 4540669 Japanese Patent Application Publication No. 2008-527656

_{V 2 O 5 -P 2 O 5} -Sb 2 O 3 based low-melting glass contained in the above-mentioned sealing material susceptible to devitrification (crystallization). When the low melting point glass is devitrified, the softening fluidity and the adhesiveness by the laser irradiation are reduced, so that it is necessary to take time for temporary baking at a lower temperature. By increasing the laser output, it is possible to improve the softening flowability and adhesion, but there is a possibility that the organic element and the organic material incorporated in the electronic component may be thermally damaged. Moreover, in order to ensure moisture resistance and water resistance after joining by a laser, it was necessary to perform temporary baking before laser sealing in a low oxygen atmosphere.

Therefore, 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 the devitrification of the glass bonding layer.

In order to solve the above-mentioned subject, the present invention is an electronic component which has an organic member between two sheets of transparent substrates, and joins the perimeter part of the two sheets of transparent substrates with a sealing material containing low melting glass. The low melting point glass contains vanadium oxide (V ₂ O ₅ ), tellurium oxide (TeO ₂ ), phosphorus oxide (P ₂ O ₅ ) and iron oxide (Fe ₂ O ₃ ), and the following oxide conversion V ₂ O ₅ + TeO ₂ + P ₂ O ₅ + Fe ₂ O ₃ 7575% by mass, and V ₂ O ₅ > TeO ₂ > P ₂ O ₅ FeFe ₂ O ₃ (% by mass).

The present invention is also a sealing material paste containing low melting point glass, a resin binder and a solvent, wherein the low melting point glass is vanadium oxide (V ₂ O ₅ ), tellurium oxide (TeO ₂ ), phosphorus oxide (P ₂ ) ₂ O ₅ ) and iron oxide (Fe ₂ O ₃ ), and V ₂ O ₅ + TeO ₂ + P ₂ O ₅ + Fe ₂ O ₃ 7575 mass% in terms of the following oxide conversion, V ₂ O ₅ > TeO ₂ > P ₂ O ₅ 5Fe 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 a schematic top view of the electronic component as an example. It is a schematic sectional drawing of the sealing part along IB-IB shown to FIG. 1A. It is a schematic top view of the electronic component as an example. FIG. 3 is a schematic cross-sectional view of the sealing portion along IIB-IIB shown in FIG. 2A. It is a schematic top view which shows an example of the manufacturing method of the electronic component shown by FIG. 1A, 1B. FIG. 3B is a schematic cross-sectional view along IIIB-IIIB shown in FIG. 3A. It is a schematic top view which shows an example of the manufacturing method of the electronic component shown by FIG. 1A and 1B. FIG. 4B is a schematic cross-sectional view along IVB-IVB shown in FIG. 4A. It is a schematic sectional drawing which shows an example of the manufacturing method of the electronic component shown by FIG. 1A. It is a schematic perspective view which shows an example of the manufacturing method of the electronic component shown by FIG. 2A, 2B. It is a schematic sectional drawing which shows an example of the manufacturing method of the electronic component shown by FIG. 2A, 2B. It is a graph which shows an example of the DTA curve obtained by differential thermal analysis (DTA) of a typical low melting glass. It is a graph which shows an example of the thermal expansion curve of a typical low melting glass. It is the schematic which shows the laser irradiation experiment to a glass compacting body. It is the schematic which shows the state which apply | coated the glass paste for laser sealing. It is a schematic sectional drawing showing a laser irradiation state. It is a graph which shows an example of the transmittance | permeability curve of typical low melting glass.

Hereinafter, the present invention will be described. FIGS. 1A and 1B and FIGS. 2A and 2B show schematic top views of two types of electronic components according to an embodiment of the present invention and cross-sectional schematic views of the sealing portions thereof. The electronic component shown in FIGS. 1A and 1B has two transparent substrates 1 and 2 and one or more organic members 3 (organic elements or organic materials) between the transparent substrates 1 and 2. The outer peripheral portions of the transparent substrates 1 and 2 were bonded with a sealing material 5 containing low melting glass. The electronic component shown in FIGS. 2A and 2B has two transparent substrates 1 and 2 with a larger gap, and the transparent substrates 1 and 2 are joined by the sealing material 5 and 5A via the spacer 6.

In the present invention, the low melting point glass contained in the sealing material 5, 5A contains vanadium oxide, tellurium oxide, phosphorus oxide and iron oxide, and the following oxide conversion V ₂ O ₅ , TeO ₂ , P ₂ O ₅ And Fe ₂ O ₃ is at least 75% by mass, and V ₂ O ₅ > TeO ₂ > P ₂ O ₅ FeFe ₂ O ₃ (% by mass). The low melting point glass satisfying this condition is efficiently absorbed by the light of the wavelength, heated, and softened and flows easily, particularly by laser irradiation. That is, by using the low melting point glass and the laser, heating can be stopped only at a desired place, and the outer peripheral portions of the two transparent substrates 1 and 2 can be joined without thermally damaging the organic member 3.

As a wavelength of a laser to be used, it is effective in the range of 400 to 1100 nm in which the low melting glass efficiently absorbs light and transmits the transparent substrate. If the wavelength is less than 400 nm, the transparent substrate and the organic element and organic material in the inside may be heated and deteriorated. On the other hand, if the wavelength exceeds 1100 nm, the light absorption of this low melting glass decreases, and it does not show good softening and fluidity, and if there is a place containing moisture, this moisture is heated and has an adverse effect. Sometimes.

As the low melting point glass, it is important to contain the largest amount of V ₂ O _{5 in} terms of oxide. By this, the low melting glass efficiently absorbs light in the wavelength range of 400 to 1100 nm and is heated. At the same time, the softening point T _s of the low melting glass can be lowered, and the low melting glass can be easily softened and flowed by irradiating the low melting glass with a laser in the wavelength range of 400 to 1100 nm.

TeO ₂ and P ₂ O ₅ are important components for vitrification. If the sealing material is not glass, it can not soften and flow at low temperatures. Also, the sealing material can not be easily softened and flowed by laser irradiation. P ₂ O ₅ has a greater effect of vitrifying than TeO ₂ and is effective for reducing thermal expansion, but when P ₂ O ₅ has a content of TeO ₂ or more, it lowers the moisture resistance and water resistance, and softens. It raises the point T _s . However, when the content of TeO ₂ is increased, the thermal expansion coefficient tends to increase. If the thermal expansion coefficient becomes too large, heat shock by laser irradiation may be broken before softening and flowing the low melting glass.

Fe ₂ O ₃ is a component that acts particularly on P ₂ O ₅ to improve the moisture resistance and water resistance of the low melting glass. Further, Fe ₂ O ₃ is also a component that efficiently absorbs light in the wavelength range of 400 to 1100 nm as V ₂ O ₅ does. However, when the content of Fe ₂ O ₃ exceeds P ₂ O ₅ , the low melting point glass is crystallized by heating. This crystallization is a phenomenon that hinders the softening and fluidity of the low melting point glass and is not desirable.

The role and effect of each of V ₂ O ₅ , TeO ₂ , P ₂ O ₅ and Fe ₂ O _{3 described} above can be obtained by the total content of those being 75 mass% or more, and by laser irradiation A joint portion with high reliability (adhesion, adhesion, moisture resistance, water resistance, etc.) can be obtained.

A 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 , 5 to ₅ in terms of the following oxides. It is 15% by mass of Fe ₂ O ₃ .

The inclusion of WO ₃ , MoO ₃ , Ta ₂ O ₅ , ZnO, BaO, SrO is effective for preventing or suppressing crystallization. The inclusion of MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , BaO, SrO, Ag ₂ O, and K ₂ O is effective for improving the moisture resistance and the water resistance. Containing Nb ₂ O ₅ , Ta ₂ O ₅ and ZnO is effective for reducing the thermal expansion coefficient. The contents of MoO ₃ , Ag ₂ O, and K ₂ O are effective for lowering the softening point T _s . On the other hand, the components promoting crystallization are Nb ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ , Ag ₂ O, and K ₂ O. Component would raise the softening point T _s is _{Sb 2 O 3, Bi 2 O} 3, BaO, is SrO. The components that increase the thermal expansion coefficient are MoO ₃ , BaO, SrO, Ag ₂ O, and K ₂ O. The components that lower the moisture resistance and water resistance are MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , and ZnO. Therefore, the content 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 is short and long It is. It is necessary to determine the components to be contained and the content thereof with due consideration given to the characteristics of the base composition consisting of V ₂ O ₅ , TeO ₂ , P ₂ O ₅ and Fe ₂ O ₃ .

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 in terms of the following oxides It is preferable that the sum of one or more be 25% by mass or less. When the total content of these components exceeds 25% by mass, the softening point T _s may be increased, the thermal expansion coefficient may be increased, or the crystallization tendency may be increased. In addition, 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, and K ₂ O More preferably, the total is 0 to 20% by mass.

When V ₂ O ₅ is less than 35% by mass, the low melting point glass may become difficult to soften and flow easily even when the low melting point glass is irradiated with a laser having a wavelength in the range of 400 to 1100 nm. On the other hand, when V ₂ O ₅ exceeds 55% by mass, reliability such as moisture resistance and water resistance may be lowered. The TeO ₂ is less than 19 mass%, the or crystallization tendency of the low-melting glass becomes large, or the softening point T _s is increased, humidity resistance, reliability such as water resistance decreases. On the other hand, when the content of TeO ₂ exceeds 30% by mass, the softening point T _s of the low melting glass is easily lowered to a low temperature, but the thermal expansion coefficient becomes large, and breakage occurs before the low melting glass softens and flows due to heat shock by laser irradiation. There is something to do.

If the content of P ₂ O ₅ is less than 7% by mass, the crystallization tendency of the low melting glass may be increased, and furthermore, the low melting glass may be difficult to soften and flow due to the laser irradiation. On the other hand, if P ₂ O ₅ exceeds 20% by mass, the softening point T _s of the low melting glass may rise, and the low melting glass may not easily soften and flow even when the laser is irradiated. Furthermore, this P ₂ O ₅ may lower the reliability of the low melting point glass such as moisture resistance and water resistance. The Fe ₂ O ₃ is less than 5 wt%, the moisture resistance of the low-melting glass, the reliability of the water resistance is lowered, whereas, Fe ₂ O ₃ crystallization of the low-melting glass exceeds 15 mass% is promoted May be

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 in total If it exceeds 20% by mass, the softening point T _s of the low melting point glass may increase, the thermal expansion coefficient may increase, or the crystallization tendency may increase depending on the components contained.

Furthermore, the transition point T _g is 320 ° C. or less and a softening point T _s of the low melting glass is effective at 380 ° C. or less. Although the details will be described later, the transition point T _g and the softening point T _{s referred to} here are characteristic temperatures by differential thermal analysis (DTA), and the transition point T _g is the onset 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 in the low-melting glass. Further, the softening point T _s is higher than 380 ° C., the low-melting glass becomes hard to easily soften flow during laser irradiation. Further, it is effective that the low melting point glass has a thermal expansion coefficient of 100 × 10 ⁻⁷ / ° C. or less at 30 to 250 ° C. When 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. 1A and 1B and FIGS. 2A and 2B, the sealing material 5 may further contain, for example, a filler for reducing the thermal expansion coefficient, in addition to the low melting point glass. . The filler is preferably at least one of zirconium phosphate tungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ), and silicon (Si). These fillers have a thermal expansion coefficient smaller than that of 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 should be reduced. Can.

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

However, when the content of the filler exceeds 35 parts by volume, the softening and fluidity of the low melting glass in the sealing material may be reduced, and the adhesion may be weakened at the time of laser irradiation.

Moreover, in the electronic component of the present invention shown in FIGS. 1A and 1B, the thickness of the bonding layer made of the sealing material 5 is preferably 20 μm or less. When the thickness of the bonding layer exceeds 20 μm, the low melting point glass contained in the sealing material 5 far from the transparent substrate side irradiated with the laser is hard to soften and flow, so the entire thickness direction of the sealing material 5 is good. It will not show softening flowability. Further, in the electronic component shown in FIGS. 2A and 2B, it is desirable that the two transparent substrates 1 and 2 be joined via the spacer 6 when the distance between the two transparent substrates 1 and 2 is large, particularly when the distance is 100 μm or more. The thickness of the bonding layer at that time is preferably 20 μm or less in the same manner as described above for both of the sealing materials 5 and 5A.

Furthermore, in the electronic component of the present invention shown in FIGS. 1A and 1B and FIGS. 2A and 2B, the transparent substrates 1 and 2 or the spacer 6 are made of glass or resin. Since they are transparent, they have low absorptivity for light of wavelengths of 400 to 1100 nm and high transmittance. For this reason, even when a laser having a wavelength in the range of 400 to 1100 nm is irradiated, the laser can be transmitted without being heated, and only the sealing material 5 or 5A of the desired portion can be irradiated. In the sealing material 5 or 5A irradiated with the laser, since the low melting point glass contained therein softens and flows, 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 laminated with a resin, etc. . The present invention is also applicable to the case where a low heat resistant element or material is applied to the inside of an electronic component, and is not limited to the above 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 a resin binder and a solvent, it becomes easy to apply to a substrate like screen printing. Since the sealing material paste is applied to a substrate and then dried to evaporate the resin binder and the solvent, no bubbles are generated at the time of firing, and the airtightness of the formed sealing material can be enhanced. As a particle size of this low melting glass, it is preferable that an average particle size is 3 micrometers or less. Further, as the resin binder, ethyl cellulose or nitrocellulose is preferable, and as the solvent, butyl carbitol acetate is preferable. Furthermore, this sealing material paste may contain filler particles. As a particle size of this filler particle, it is preferable that an average particle size is larger than the average particle size of the said low melting glass. Moreover, it is preferable that content of this filler particle | grain is 35 volume parts or less with respect to 100 volume parts of powder of this low melting glass. Adhesiveness may become weak as above-mentioned as content of a filler particle is 35 volume parts or more.

Next, the manufacturing method of the electronic component of the present invention will be described. A method of manufacturing the electronic component shown in FIGS. 1A and 1B is briefly shown in FIGS. 3A and 3B-5. As shown to FIG. 3A and 3B, the sealing material 5 containing low melting glass is formed in the outer peripheral part of the transparent substrate 1. FIG. In the formation method, first, the above-mentioned sealing material paste to be the sealing material 5 is applied to the outer peripheral portion of the transparent substrate 1 and dried. When a glass substrate is used as the transparent substrate 1, the low melting point glass contained in the sealing material 5 is softened and flowed by the firing furnace or the irradiation of the laser 7 in the wavelength range of 400 to 1100 nm to bake 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 can not be used. Therefore, the sealing material 5 is fired and formed on the outer peripheral portion of the transparent substrate 1 by irradiation of the laser 7.

Next, as shown in FIGS. 4A and 4B, the other transparent substrate 2 on which one or more organic members 3 are formed is manufactured. The transparent substrate 2 may be either a glass substrate or a resin substrate, but is preferably combined 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 as shown in FIG. 5 to align the two transparent substrates 1 and 2 Then, the organic member 3 is disposed in the internal space formed by the transparent substrates 1 and 2 and the sealing material 5. In the case where the transparent substrate 1 coated with the sealing material 5 is fired by laser irradiation, the organic member 3 may be formed on the transparent substrate 1 because it is difficult to heat other than the outer peripheral portion of the transparent substrate 1. The sealing material 5 is irradiated with a laser 7 in the wavelength range of 400 to 1100 nm through the transparent substrate. The laser 7 may be applied to the sealing material 5 from the outside of any transparent substrate, but since the sealing material 5 is previously formed on the transparent substrate 1, the laser from the outside of the transparent substrate 2 to the sealing material 5 When 7 is irradiated, sealing can be performed more efficiently. At that time, care must be taken not to irradiate the laser 7 to the organic member 3 incorporated in the electronic component. This is because there is a high possibility that the organic member 3 may be damaged or degraded by the irradiation of the laser 7. The sealing material 5 softens and flows the low melting point glass contained in the sealing material 5 by the irradiation of the laser 7 and bonds the outer peripheral portions of the two transparent substrates 1 and 2.

Moreover, the manufacturing method of the electronic component shown to FIG. 2A, 2B is simply shown to FIG. 6 and FIG. As shown in FIG. 6, the sealing materials 5 and 5A are formed on at least the bonding surface of the spacer 6. The above-mentioned sealing material paste to be the sealing materials 5 and 5A is applied to the bonding surface where the spacer 6 is to be bonded to at least the transparent substrate, and dried. When the glass spacer 6 is used, it is contained in the sealing materials 5 and 5A by irradiating from both sides of the transparent substrates 1 and 2 with a baking furnace or lasers 7 and 7A in the wavelength range of 400 to 1100 nm. The low melting point glass is softened to flow and fired to form the spacer 6. In the case of using the spacer 6 made of resin, since the heat resistance of the resin is low and the firing furnace can not be used, the sealing material 5 is fired and formed on the spacer 6 by the irradiation of the laser 7 and 7A.

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

From the above, the electronic component of the present invention, the method for producing the same, and the sealing material paste used therefor efficiently produce the electronic component without causing thermal damage to the organic element and the organic material incorporated in the electronic component. In addition, it is possible to obtain a glass bonding layer which is excellent in adhesiveness, gas barrier property (air tightness), moisture resistance and water resistance.

Hereinafter, the present invention will be described in more detail using examples. However, the present invention is not limited to the description of the embodiments taken here, and may be combined as appropriate.

In this example, the composition and characteristics of the low melting point 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 point glasses shown in Tables 1 to 5, as a raw material, reagents V ₂ O ₅ , TeO ₂ , P ₂ O ₅ , Fe ₂ O ₃ , WO ₃ , MoO ₃ , Nb made by High-Purity Chemical Laboratory make 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 200 g in total, placed in a platinum crucible, and heated to 900 to 1000 ° C. at a heating rate of 5 to 10 ° C./min in an electric furnace to melt. The raw material was held for 2 hours while stirring to obtain a uniform glass at this temperature. Thereafter, the crucible was taken out, and the raw material was poured on a stainless steel plate preheated to 150 to 200 ° C. to produce a low melting point glass.

The produced low melting glass was crushed by a jet mill until the average particle size became 3 μm or less. The powder is subjected to differential thermal analysis (DTA) up to 500 ° C. at a heating rate of 5 ° C./min to obtain a transition point (T _g ), a deformation point (M _g ), a softening point (T _s ) and crystals. The _{crystallization} temperature ( _Tcry ) was measured. An 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 start temperature of the first endothermic peak, M _g is the peak temperature, T _s is the second endothermic peak temperature, and T _cry is the start temperature of the exothermic peak due to crystallization. The characteristic temperature of the glass is defined by the viscosity, and T _g , M _g and T _s are said to be temperatures at which the viscosity corresponds to 10 ^13.3 poise, 10 ^11.0 poise and 10 ^7.65 poise, respectively. To glass is softened flow at low temperatures, as much as possible, it is necessary to lower temperature of T _s. Further, in order to mitigate the thermal residual strain, as much as possible, it is preferable to cold the T _{g. Tcry} is the temperature at which the glass starts to crystallize. Crystallization, for inhibiting the softening fluidity of the glass, as much as possible, it is preferable that the T _cry to the high temperature side than T _s.

The produced low melting point glass was subjected to thermal strain removal in a temperature range of T _g to M _g and processed into a 4 × 4 × 20 mm prism. Using this, the thermal expansion coefficient of 30 to 250 ° C., transition temperature _TG and deformation temperature _AT were measured with a thermal expansion meter. The heating rate was 5 ° C./min. Further, as a standard sample, a cylindrical quartz glass of φ5 × 20 mm was used. FIG. 9 shows a thermal expansion curve of a typical low melting point glass. In FIG. 9, the amount of elongation of quartz glass as a standard sample is subtracted. The thermal expansion coefficient was calculated from the gradient of the amount of elongation in the temperature range of 30 to 250.degree. T _G is a temperature at which elongation starts significantly, and A _T is a temperature at which deformation occurs due to load. T _G was measured slightly higher than T _g of the above DTA. A _T was between M _g and T _s of the above DTA.

In the moisture resistance test of the produced low melting glass, what carried out the mirror surface process of the surface of the said sample for thermal expansion evaluation was used. The evaluation of the moisture resistance is carried out for 10 days under the conditions of a temperature of 85 ° C. and a humidity of 85%, "○" when the gloss of the mirror-finished glass surface is maintained, and "Δ" when the gloss decreases. When the glass collapsed, it was evaluated as "x".

The softness and fluidity of the produced low melting point glass is obtained by compacting the glass powder crushed by the jet mill with a hand press (1 ton / cm ² ) with a hand press (1 ton / cm ² ) and irradiating the glass compact with a variety of lasers over the transparent substrate. Evaluated by. The outline of the laser irradiation experiment to the glass compacting body is shown in FIG. The size of the glass green compact 8 was φ10 × 2 mm. The glass compacting body 8 was placed on the transparent substrate 1, and the laser 7 was irradiated toward the central portion of the glass compacting body 8 from the back side. A slide glass was used for the transparent substrate 1. For the laser 7, a semiconductor laser with a wavelength of 405 nm, a double wave of a YAG laser with a wavelength of 532 nm, a semiconductor laser with a wavelength of 630 nm, a semiconductor laser with a wavelength of 805 nm, and a YAG laser with a wavelength of 1064 nm are used. The evaluation of the softness and fluidity was “o” when the laser-irradiated part of the glass green compact 8 flowed, but it flowed, “●” when cracks frequently occurred, and “Δ” when softened. Although it softened, when the crack occurred frequently, it was set as "x" when neither flow nor softening was possible. In addition, the softness | flexibility 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 the optical microscope through the transparent substrate 1. FIG.

As can be seen from Examples G1 to G4 shown in Tables 1 to 4 and Comparative Examples G 65 to 80 shown in Table 5, the low melting point glasses of Examples G1 to G 64 are Comparative Examples G67, 69, 73 to 76 and 78. The softening point T _s is lower than the low melting point glass of ̃80, and the thermal expansion coefficient is smaller than that of the low melting point glasses of Comparative Examples G68, 70 to 73, 77 and 78. Further, Comparative Examples G65 to 68, 70 to 74, 76, Moisture resistance was better than the low melting point glasses of 78 and 80. In addition, the low melting point glass of Example G1 to 64 has better softening flowability by laser irradiation than the low melting point glass of Comparative Examples G67, 69, 73 to 76, and 78 to 80, and Comparative Examples 68, 70 to 72. Even when the softening and fluidity was good as in the low melting point glass of No. 77 and No. 77, cracks did not occur frequently.

The low melting glass of Example G1 to V64 contains vanadium oxide, tellurium oxide, phosphorus oxide and iron oxide, and the total 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 FeFe ₂ O ₃ (% by mass). Furthermore, the glass component 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. It may be WO ₃ + MoO ₃ + Nb ₂ O ₅ + Ta ₂ O ₅ + Ta ₂ O ₅ + MnO ₂ + Sb ₂ O ₃ + Bi ₂ O ₃ + ZnO 2 + BaO + SrO + Ag ₂ O + K ₂ O ≦ 25 mass% in terms of the following oxide. A particularly effective composition range is that 35 to 55% by mass of V ₂ O _5, 19 to 30% by mass of TeO ₂ and P ₂ O _{5 in} terms of the following oxides are satisfied while satisfying the above conditions. 7 to 20% by mass, 5 to 15% by mass of Fe ₂ O ₃ , and WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , MnO ₂ , Sb ₂ O ₃ , Bi ₂ O ₃ And the total of one or more of ZnO, SrO, BaO, Ag ₂ O and K ₂ O was 0 to 20% by mass.

In addition, the low melting glass of Example G1 to 64 efficiently absorbs a laser having a wavelength in the range of 400 to 1100 nm and is heated, and further, since the softening point T _s is as low as 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 performed using the low melting glass of Example G19 shown in Table 2 and a slide glass as a transparent substrate. A sealing material paste was produced using a G19 low melting point glass powder ground to an average particle size of 3 μm or less by a jet mill, a resin binder, and a solvent. The resin binder was nitrocellulose, and the solvent was butyl carbitol acetate. Using the sealing material paste, the sealing material paste was applied to the outer peripheral portion of the transparent substrate by screen printing as shown in FIG. 11, and after drying, the sealing material paste was fired at 380 ° C. for 30 minutes in the air. . The line width of the sealing material 5 formed on the transparent substrate 1 was 1.5 mm, and the thickness of the fired film was adjusted to about 5, 10, 20, and 30 μm by changing the application amount. As shown in FIG. 12, the transparent substrate 2 is installed opposite to each other, and the laser 7 is irradiated while moving at a speed of 8 mm / sec from the direction of the transparent substrate 1 to the sealing material 5. The parts were joined. The laser 7 used was the four types of lasers used in Example 1. All samples were able to be joined and the airtightness (gas barrier property) and adhesiveness were evaluated. The evaluation results are shown in Table 6.

The gas tightness (gas barrier property) was evaluated by carrying out a helium leak test, “o” when not leaking, and “x” when leaked. Also, the adhesiveness was evaluated as a peeling test, and when the transparent substrate and the sealing material were broken, it was evaluated as “○”, and when it was easily peeled from the interface between the transparent substrate and the sealing material, it was evaluated as “×”. . In the case of the fired film thickness of 20 μm or less, the airtightness and adhesiveness were good regardless of which laser was used. However, with the fired film thickness of 30 μm, depending on the laser used, there were cases where good air tightness and adhesiveness could not be obtained. The wavelengths of 532 nm and 1064 nm use YAG lasers, and YAG lasers are considered to have obtained good airtightness and adhesiveness because they have higher power than other semiconductor lasers. Since the semiconductor laser is very inexpensive compared to the YAG laser, it is better than the semiconductor laser can 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 sides of the transparent substrates 1 and 2, good airtightness and adhesiveness were obtained even with a 30 μm-baked film thickness. That is, when the thickness of the adhesive layer is large, there is a good possibility that it can be coped with by such a method.

The transmittance curve of the coating film which baked the low melting glass of Example G19 in FIG. 13 is shown. In the wavelength range of 300 to 2000 nm, the smaller the wavelength, the lower the transmittance, and the larger the fired film thickness, the lower the transmittance. It goes without saying that the low melting point glasses of the other examples shown in Tables 1 to 4 have similar transmittance curves, so that the same effect 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 is lower in heat resistance than the low melting point glass of G19, a semiconductor laser with a wavelength of 805 nm was used when firing on a transparent substrate in advance. Using this laser, a fired film of G19 was obtained with almost no heating of the polycarbonate. Subsequently, as shown in FIG. 12, various lasers were irradiated to bond the outer peripheral portions of the polycarbonates which are the transparent substrates 1 and 2, and the adhesion was evaluated in the same manner as described above. The same results as in the case of using slide glass for the transparent substrates 1 and 2 were obtained.

In this example, a glass substrate having a thermal expansion coefficient of 50 × 10 ⁻⁷ / ° C. was used as the transparent substrate. Example G43 shown in Table 3 was used for the low melting glass contained in the sealing material. Further, as a filler, zirconium phosphate tungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ) and silicon (Si) were used as a filler. And the same laser sealing experiment as Example 2 was implemented.

First, a low melting point glass powder of G43 ground to an average particle size of 3 μm or less by a jet mill, and a filler of Zr ₂ (WO ₄ ) (PO ₄ ) ₂ , Nb ₂ O ₅ or Si having an average particle size of about 5 μm. The sealing material paste was produced using particles, a resin binder, and a solvent. In addition, the content of the filler particles was 15, 25, 35, and 45 parts by volume with respect to 100 parts by volume of the G43 low melting glass, respectively. 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 a resin binder, and butyl carbitol acetate was used as a solvent. The sealing material paste was applied to the outer peripheral portion of the transparent substrate by screen printing as shown in FIG. 11, dried, and fired at 400 ° C. for 30 minutes in the air. 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 installed opposite to each other, and the semiconductor laser 7 having a wavelength of 805 nm is moved from the direction of the transparent substrate 1 to the sealing material 5 while moving at a speed of 8 mm / sec. The outer peripheral parts of 1 and 2 were joined. The air tightness (gas barrier property) and adhesion were evaluated in the same manner as in Example 2. The evaluation results are shown in Table 7.

When the difference in thermal expansion between the glass substrate and the low melting point glass G43 used for the transparent substrates 1 and 2 is large as in this embodiment, the filler is contained in the sealing material 5 so that the thermal expansion coefficient of the sealing material 5 is obtained. As a result, the occurrence of cracks can be prevented and good adhesion and airtightness can be obtained. In this example, a filler of Zr ₂ (WO ₄ ) (PO ₄ ) ₂ , Nb ₂ O ₅ or Si is contained. The inclusion of the filler resulted in good air tightness and adhesion. When the content of the filler is 45 parts by volume, the content of the low melting point glass G43 for bonding the transparent substrates 1 and 2 is decreased, and although the adhesion is inferior as compared with the other examples, it is good. Airtightness was maintained.

As mentioned above, in order to join the transparent substrates 1 and 2 airtightly and firmly with a laser, as for content of the filler particle contained in the sealing material 5, 35 volume parts or less are preferable with respect to 100 volume parts of low melting glass. it is conceivable that. In this example, Zr ₂ (WO ₄ ) (PO ₄ ) ₂ , Nb ₂ O ₅ and Si having good wettability with the present low melting point glass as filler particles were selected and examined. The filler particles are not limited to these, and β-eucryptite having a small thermal expansion coefficient, cordierite, zirconium phosphate, zirconium silicate and the like can also be used.

If the distance between the transparent substrates 1 and 2 is 100 μm or more, a crack is generated in the sealing material 5 even if the laser is irradiated from both sides in the manufacturing method shown in Example 2, The softening flowability of the low melting point glass was insufficient, and good air tightness and adhesion could not be obtained. Therefore, in the present embodiment, as shown in FIGS. 2A and 2B, the transparent substrates 1 and 2 are bonded via the spacer 6. The transparent substrates 1 and 2 were joined to the transparent substrates 1 and 2 and the spacer 6 by the manufacturing method shown to FIG. 6 and FIG. 7 using the white plate glass with high transmittance | permeability. 100 parts by volume of the low melting point glass powder of G43 and 10 parts by volume of Zr ₂ (WO ₄ ) (PO ₄ ) ₂ filler particles shown in Table 3 as in Example 3 for the sealing materials 5 and 5A, and ethylcellulose and butylcarbi The sealing material paste was applied to the spacer 6 as shown in FIG. 6 using a sealing material paste consisting of tol acetate, and after drying, the sealing material paste was fired at 400 ° C. in the air for 20 minutes. The fired film thickness was 15 μm each. The width of the spacer 6 was fixed at 3 mm, and the thickness was 70, 320, 500, and 1000 μm, respectively. The thicknesses of the sealing materials 5 and 5A are respectively 100, 350, 530, and 1030 μm. As shown in FIG. 7, they were placed on the outer circumferences of the four sides, and both sides of the transparent substrates 1 and 2 were irradiated with semiconductor lasers 7 and 7A having a wavelength of 630 nm for bonding. The feed rate of the laser was 8 mm / sec. The adhesion was evaluated in the same manner as in Example 2. It was found that good adhesion was obtained regardless of the thickness of the spacer 6, and it was effective to use the spacer 6 when the distance between the transparent substrates 1 and 2 was large.

In this example, a display including a large number of organic light emitting diodes (OLEDs) was fabricated and evaluated. This OLED display has the structure shown in FIGS. 1A and 1B. Since the OLED which is the built-in organic element 3 is easily deteriorated by moisture and oxygen, it is very difficult to airtightly and firmly bond the outer peripheral portions of the transparent substrates 1 and 2 with the sealing material 5 containing the low melting point glass. It is valid. In this example, non-alkali glass used for a liquid crystal display was used for the transparent substrates 1 and 2. 100 parts by volume of low melting point glass powder of G55 shown in Table 4 and 20 parts by volume of Zr ₂ (WO ₄ ) (PO ₄ ) ₂ filler particles shown in Table 4, 10 parts by volume of Si filler particles, and ethyl cellulose The sealing material paste is applied to the outer peripheral portion of the transparent substrate 1 as shown in FIGS. 3A and 3B using a sealing material paste made of butyl carbitol acetate, and after drying, the sealing material for 30 minutes at 400 ° C. in the air. The paste was fired to form a sealing material 5. 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 FIGS. 4A and 4B. The transparent substrate 2 and the transparent substrate 1 were made to face each other as shown in FIG. 5, and the laser 7 was irradiated toward the sealing material 5 from the direction of the transparent substrate 1. The laser 7 used the semiconductor laser with a wavelength of 805 nm, moved the outer peripheral portion at a speed of 8 mm / sec, and bonded the outer peripheral portions of the transparent substrates 1 and 2.

As a result of conducting a lighting test of the OLED display immediately after preparation, it was confirmed that the lighting did not occur. Also, the adhesion of the joint was good. Next, the display was subjected to a high temperature and high humidity test under the conditions of 85 ° C. and 85% Rh for 10 days, 25 days and 50 days, and a lighting test was performed. A resin bonded OLED display was also included as a comparison. The resin bonding layer had a width of 3 mm and a thickness of 10 μm. In the 10-day high-temperature and high-humidity test, although both OLED displays turned on without any problem, the display joined with the resin was greatly deteriorated by lighting after 25 days. This is because moisture and oxygen were introduced into the inside of the display from the resin junction and the OLED was degraded. On the other hand, according to the present invention, no deterioration was found in the lighting of the OLED even in a 50-day high-temperature and high-humidity test, and good results were obtained. This is a result suggesting that good airtightness is maintained. Further, as a result of evaluating the adhesion of the joint after the high temperature and high humidity test, a large decrease as in the resin joint was not observed, and it 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. Further, it goes without saying that the invention can also be applied to electronic parts such as lighting fixtures on which the OLED is mounted.

In this example, a dye-sensitized solar cell incorporating an organic dye was produced 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 to form nano-sized particles. It reaches the electrode while diffusing in the particle. On the other hand, at the counter electrode, electrons are injected into the electrolyte to reduce iodine (I). Power can be generated by this. Dye-sensitized solar cells are effective for cost reduction because they do not use non-vacuum, low-temperature processes and silicon, but there are major problems in reliability. Sealing technology is the key to improving its reliability. Since an organic dye or an electrolyte having low heat resistance is used, sealing needs to be performed at a low temperature equal to or lower than the heat resistance temperature, and resin sealing is generally used. However, resin sealing has a big problem that long-term reliability can not be secured.

The present invention was applied to sealing of a dye-sensitized solar cell in the same manner as in Example 5. For the transparent substrates 1 and 2, white sheet glass with high transmittance was used. The formation of the sealing material 5 on the transparent substrate 1 was performed using the same sealing material paste and the same baking conditions as in Example 4. A cell containing a large number of organic dyes and the like was formed or placed in the transparent substrate 2 side, and the peripheral portions of the transparent substrates 1 and 2 were joined by laser irradiation in the same manner as in Example 5. The transparent substrates 1 and 2 were able to be joined firmly by the sealing material 5, and adhesiveness was favorable. Moreover, there was no problem even in the same high temperature and high humidity test as in Example 5, and good airtightness was maintained. Moreover, the adhesion after the high temperature and high humidity test was also good. Furthermore, no corrosion of the joint due to iodine (I) was observed. However, the electrode was corroded by iodine (I). From this, in addition to the sealing of the dye-sensitized solar cell, the low melting glass according to the present invention can be expanded to the coating of an electrode.

From the above, it has been found that the present invention can be effectively applied to dye-sensitized solar cells. Further, it goes without saying that the invention can be applied not only to dye-sensitized solar cells but also to electronic components such as organic solar cells.

In this example, a large number of photoelectric conversion elements were incorporated, and a solar cell bonded with a resin was manufactured and evaluated. As a photoelectric conversion element, a double-sided light receiving cell using a single crystal silicon substrate was used. Also, these cells are connected in series by tab lines. Conventionally, an EVA sheet is pasted between two transparent substrates, and the end is fixed by an aluminum frame and a resin sealing material. In general, white sheet glass with high transmittance is applied to the transparent substrate. Most of the solar cell's subsequent accidents are caused by the water that penetrates inside. EVA sheets do not have high gas barrier properties (airtightness), and moisture permeates over many years gradually, and the tab wires connecting between cells with the moisture and the connections, and the cells The formed electrode may be corroded and broken. For this reason, it is very important to ensure that the water does not penetrate, in order to ensure the long-term reliability of the solar cell.

In this example, the white sheet glass was used for the transparent substrate, and an EVA sheet was used for the resin to be bonded. Since the thickness of the double-sided light receiving cell used was about 250 μm including the electrode part on both sides and the bonding layer made of EVA sheet was about 250 μm on both sides of the cell, it was decided to join through the spacer as shown in FIGS. . Since the distance between the transparent substrates 1 and 2 is about 500 μm, a white sheet glass having a width of 3.5 mm and a thickness of 470 μm was used as the spacer 6. The sealing material paste was prepared using the low melting point glass powder of G55 shown in Table 4, Si filler particles, ethyl cellulose and butyl carbitol acetate. 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 was applied to the outer peripheral portion of the transparent substrate 1 and one side of the spacer 6 with a width of 3 mm by screen printing, and dried. After drying, the sealing material paste was fired at 400 ° C. in the atmosphere for 30 minutes to form the sealing material 5 on the transparent substrate 1 and the sealing material 5A on the spacer. The fired film thickness at that time was 15 μm respectively. The spacer 6 on which the sealing material 5A was formed was placed on the transparent substrate 2 and was weighted and heated at 400 ° C. in the atmosphere for 30 minutes to bond the spacer 6 and the transparent substrate 2 with the sealing material 5A. At that time, in order to secure the airtightness of the corners, the low melting point glass paste of G55 was applied to the joint of the spacers 6 and simultaneously fired. Between the transparent substrates 1 and 2 produced as described above, several double-sided light receiving cells connected by tab wires were set so that the sealing material 5 and the spacer 6 face each other, and they were bonded by an EVA sheet. Next, the semiconductor laser with a wavelength of 805 nm was moved from the transparent substrate 1 side at a speed of 8 mm / sec, and the transparent substrates 1 and 2 were bonded with the sealing material 5 and 5A via the spacer 6. The airtightness and adhesion of the sealing materials 5 and 5A were both good. It goes without saying that long-term reliability can be ensured as compared with a resin sealing material.

Although this embodiment has been described with respect to a solar cell using a double-sided light receiving Si cell and an EVA sheet, the present invention can be applied to general solar cells in which a cell and a transparent substrate are adhered and fixed using a resin. For example, it can be applied to thin film solar cells.

The OLED display, the dye-sensitized solar cell, and the Si solar cell to which the present invention is applied have been described above. On the other hand, the present invention is not limited to the above, and can be applied to low heat resistant organic elements and electronic components in general containing an organic material, and the reliability of the electronic components can be remarkably improved.

1, 2 Transparent substrate 3 Organic member 5, 5A Sealing material 6 Spacer 7, 7A Laser 8 Glass powder compact

Claims (25)

It is an electronic component which has an organic member between two transparent substrates, and the outer peripheral part of the two transparent substrates is joined by a sealing material containing low melting glass, wherein the low melting glass is vanadium oxide (V ₂ O ₅ ), tellurium oxide (TeO ₂ ), phosphorus oxide (P ₂ O ₅ ) and iron oxide (Fe ₂ O ₃ ), and converted to the following oxide: V ₂ O ₅ + TeO ₂ + P ₂ O ₅ + Fe ₂ O is ₃ ≧ 75 wt%, the electronic component is a _{V 2 O 5> TeO 2>} P 2 O 5 ≧ Fe 2 O 3 ( wt%). Wherein the low melting point glass is V ₂ O ₅ is 35-55 wt% in the following in terms of oxide, a TeO ₂ is 19-30% by weight, a P ₂ O ₅ is 7 to 17 mass%, Fe ₂ The electronic component according to claim 1, wherein O ₃ is 5 to 15% by mass. The low melting point glass further includes tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), manganese oxide (MnO ₂ ), antimony oxide (Sb ₂₎ O ₃ ), bismuth oxide (Bi ₂ O ₃ ), zinc oxide (ZnO), barium oxide (BaO), strontium oxide (SrO), silver oxide (Ag ₂ O) or potassium oxide (K ₂ O) Containing one or more kinds, 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, in the following oxide conversion The electronic component according to claim 1, wherein the sum of one or more of K ₂ O is 25% by mass or less. The low melting point glass is 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, in terms of the following oxides. The electronic component according to claim 3, wherein the sum of one or more of K ₂ O is 20% by mass or less. The electronic component according to claim 1, wherein the low melting point glass softens and flows by irradiating a laser in a wavelength range of 400 to 1100 nm. The electronic component according to claim 1, wherein the transition point of the low melting glass is 320 ° C or less and the softening point is 380 ° C or less. The electronic component according to claim 1, wherein a thermal expansion coefficient at 30 to 250 ° C of the low melting glass is 100 × 10 ^-7 / ° C or less. The sealing material contains a filler, and the filler is at least one of zirconium phosphate tungstate (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 the 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 bonding 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 through the spacer, and bonding each of the two transparent substrates to the spacer The electronic component according to claim 1, wherein a thickness of the sealing material is 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 comprising a low melting glass, a resin binder, and a solvent, wherein the low melting glass is vanadium oxide (V ₂ O ₅ ), tellurium oxide (TeO ₂ ), phosphorus oxide (P ₂ O ₅ ), and oxidation. It contains iron (Fe ₂ O ₃ ), and in the following oxide conversion, V ₂ O ₅ + TeO ₂ + P ₂ O ₅ + Fe ₂ O ₃ 7575 mass%, and V ₂ O ₅ > TeO ₂ > P ₂ O ₅ ≧ Fe ₂ O ₃ (wt%) in a sealing material paste. The low melting point glass has 35 to 55% by mass of V ₂ O ₅ , 19 to 30% by mass of TeO ₂ , 7 to 17% by mass of P ₂ O _{5 and} 5 to 15% of Fe ₂ O _{3 in} terms of the following oxides. The sealing material paste according to claim 15, which is mass%. The low melting point glass further includes tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), manganese oxide (MnO ₂ ), antimony oxide (Sb ₂₎ O ₃ ), bismuth oxide (Bi ₂ O ₃ ), zinc oxide (ZnO), barium oxide (BaO), strontium oxide (SrO), silver oxide (Ag ₂ O) or potassium oxide (K ₂ O) Containing one or more kinds, 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, in the following oxide conversion The sealing material paste according to claim 15, wherein the sum of one or more of K ₂ O is 25% by mass or less. The sealing material paste according to claim 15, wherein the transition point of the low melting glass is 320 ° C or less and the softening point is 380 ° C or less. The sealing material paste according to claim 15, wherein a thermal expansion coefficient at 30 to 250 ° C of the low melting glass is 100 × 10 ^-7 / ° C or less. The film may further contain a filler, and the filler is one or more of zirconium phosphate tungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ), and silicon (Si). The sealing material paste as described in. The sealing material paste according to claim 20, wherein the content of the filler is 35 parts by volume or less with respect to 100 parts by volume of the low melting point glass powder. In a method of manufacturing an electronic component, comprising an organic member between two transparent substrates, and bonding the periphery of the two transparent substrates with a sealing material containing low melting point glass,
A step of applying the sealing material paste according to claim 15 to the outer peripheral portion of the transparent substrate made of glass, and firing the sealing material paste after firing by firing in a firing furnace or irradiation of a laser in a wavelength range of 400 to 1100 nm. And forming a sealing material, the transparent substrate made of glass and the other transparent substrate made of glass or resin being opposed to each other to form two transparent substrates A method of fixing an electronic component, and fixing the laser light in a wavelength range of 400 to 1100 nm to the sealing material through the transparent substrate to soften and flow the low melting glass. In a method of manufacturing an electronic component, comprising an organic member between two transparent substrates, and bonding the periphery of the two transparent substrates with a sealing material containing low melting point glass,
A step of applying the sealing material paste according to claim 15 on the outer peripheral portion of a transparent substrate made of resin, and baking the sealing material paste after drying by irradiation of a laser in a wavelength range of 400 to 1100 nm A step of forming a material, and a step of fixing two transparent substrates by opposing the surface of the transparent resin substrate on which the sealing material is formed and the other transparent substrate made of glass or resin And irradiating the sealing material over the transparent substrate with a laser in a wavelength range of 400 to 1100 nm to soften and flow the low melting glass. In a method of manufacturing an electronic component, comprising an organic member between two transparent substrates, and bonding the periphery of the two transparent substrates with a sealing material containing low melting point glass,
A step of applying the sealing material paste according to claim 15 to at least a bonding surface of a rod-like glass spacer, and drying the sealing material paste after firing by firing in a firing furnace or laser irradiation in a wavelength range of 400 to 1100 nm. A step of forming a sealing material, a step of fixing the glass spacer between the outer periphery of the transparent substrate made of glass and the transparent substrate made of another glass or resin, and a wavelength range of 400 to 1100 nm And irradiating the sealing material over the transparent substrate to soften and flow the low-melting glass. In a method of manufacturing an electronic component, comprising an organic member between two transparent substrates, and bonding the periphery of the two transparent substrates with a sealing material containing low melting point glass,
A step of applying the sealing material paste according to claim 15 on at least a bonding surface of a rod-like resin spacer, and baking the sealing material paste after drying by irradiation of a laser in a wavelength range of 400 to 1100 nm A step of forming a material, a step of fixing the resin spacer between the outer periphery of the transparent substrate made of resin and the transparent substrate made of another glass or resin, and a laser in a wavelength range of 400 to 1100 nm And irradiating the sealing material over the transparent substrate to soften and flow the low melting glass.

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