WO2013190981A1

WO2013190981A1 - Sealed container, electronic device, and solar cell module

Info

Publication number: WO2013190981A1
Application number: PCT/JP2013/065311
Authority: WO
Inventors: 正藤枝; 内藤　孝; 拓也青柳; 沢井　裕一
Original assignee: 株式会社日立製作所
Priority date: 2012-06-22
Filing date: 2013-06-03
Publication date: 2013-12-27
Also published as: JP2014007214A; JP5935120B2

Abstract

This invention has a glass member (4a), a metal member (5a), and a transition metal oxide glass (3) that fuses onto both the glass member (4a) and the metal member (5a). The transition metal oxide glass (3) is an n-type semiconductor. This invention is formed by bonding the glass member (4a) and the metal member (5a) using the transition metal oxide glass (3). The transition metal oxide glass (3) has transition metal ions having different valences, and the number of transition metal ions having higher valences is greater than the number of transition metal ions having lower valences. The transition metal oxide glass (3) contains vanadium, at least one of tellurium and phosphorus, and at least one of silver, iron, tungsten, copper, an alkali metal, and an alkali earth metal. The transition metal oxide glass (3) contains vanadium oxide, tellurium oxide, phosphorus oxide, and iron oxide, and the total mass thereof is no less than 75 mass% in relation to the mass of the transition metal oxide glass.

Description

Sealed container, electronic device and solar cell module

The present invention relates to a sealed container, and more particularly, to an electronic device using the sealed container, in particular, a solar cell module.

In a solar cell module, a plurality of solar cells are provided in a sealed container, and the solar cells are shielded and protected from the outside air. Further, in a display incorporating an organic light emitting diode (OLED), it has been proposed to seal the outer peripheral portion of two glass plates sandwiching the organic light emitting diode with a glass hermetic seal (for example, Patent Document 1). reference). The hermetic seal is softened with a laser to bond the two glass plates. For this hermetic seal, a V ₂ O ₅ —P ₂ O ₅ low melting point glass is used. Patent Document 2 proposes pre-sintering the V ₂ O ₅ —P ₂ O ₅ low melting point glass in an atmosphere that is less oxidizable than air.

Japanese Patent No. 4540669 JP 2008-527656 Gazette

Since electronic devices, particularly solar cell modules, are used for a long period of time, airtightness of sealed containers is not perfect, and moisture, atmospheric gases and raindrops in the air may permeate over a long period of time. it is conceivable that. In this case, it is thought that an internal photovoltaic cell and the electrical connection part which connects them deteriorate. In order to improve the hermeticity of the sealed container, it is indispensable to improve the sealing performance of the hermetic seal. However, the hermetic seal of Patent Document 1 is combined with the metal copper conductor, but the electronic device, in particular, the solar cell module. It was unsuitable for sealing (sealing) by adhesion between a glass member and a metal member used in a sealed container.

Therefore, the problem to be solved by the present invention is to provide a sealed container capable of hermetically sealing an internal space even when used for bonding a glass member and a metal member. Moreover, the subject which this invention tends to solve is providing the electronic device using this sealed container, especially a solar cell module.

In order to solve the above problems, the present invention includes a glass member, a metal member, and a transition metal oxide glass that is fused to both the glass member and the metal member, and the transition metal oxide glass. Is an n-type semiconductor, and is a sealed container formed by bonding the glass member and the metal member with the transition metal oxide glass. Moreover, this invention is an electronic device using this sealed container, especially a solar cell module.

According to the present invention, it is possible to provide a sealed container capable of hermetically sealing an internal space even when used for bonding a glass member and a metal member. Moreover, an electronic device using this sealed container, in particular, a solar cell module can be provided. Problems, configurations, and effects other than those described above will become apparent from the following description of embodiments.

It is a longitudinal cross-sectional view of the principal part of the solar cell module which concerns on the 1st Embodiment of this invention. It is an example of the DTA curve obtained by the differential thermal analysis (DTA) of a transition metal oxide glass. It is an example of the thermal expansion curve of transition metal oxide glass. It is a perspective view in the middle of manufacture of the sealed container which concerns on Example 2 of this invention. It is a longitudinal cross-sectional view in the middle of manufacture of the sealed container which concerns on Example 2 of this invention. It is an example of the transmittance | permeability curve of the transition metal oxide glass apply | coated and baked. It is a top view of the sealed container which concerns on Example 4 of this invention. FIG. 7B is a cross-sectional view taken along the line AA in FIG. 7A. It is a longitudinal cross-sectional view of the principal part of the solar cell module which concerns on the 2nd Embodiment of this invention. It is an assembly perspective view of the solar cell module which concerns on the 2nd Embodiment of this invention. It is a longitudinal cross-sectional view of the principal part of the solar cell module which concerns on the 3rd Embodiment of this invention. It is a longitudinal cross-sectional view of the principal part of the solar cell module which concerns on the 4th Embodiment of this invention.

Next, embodiments (examples) of the present invention will be described in detail with reference to the drawings as appropriate. In each figure, common portions are denoted by the same reference numerals, and redundant description is omitted. In addition, the present invention is not limited to each of the plurality of embodiments (examples) taken up here, and may be combined as appropriate.

(First embodiment)
In FIG. 1, the longitudinal cross-sectional view of the principal part of the solar cell module 1 which concerns on the 1st Embodiment of this invention is shown. In the solar cell module 1, it is necessary to protect the internal solar cells 6 from the outside air. A transparent transparent glass substrate (glass member (plate material)) 4 a that serves as a support plate of the solar cell module 1 and transmits sunlight is disposed on the light receiving surface side of the solar cell 6. A transparent sealing resin 11 enclosing a plurality of solar cells 6 is disposed below the transparent glass substrate 4a. The transparent sealing resin 11 is fused to the transparent glass substrate 4a. A back sheet 14 is disposed below the transparent sealing resin 11. The solar cell 6 is sandwiched between the transparent glass substrate 4a and the back sheet 14. As the transparent sealing resin 11, an ethylene-vinyl acetate copolymer (EVA), polyvinyl butyral (PVB), or the like can be used. The back sheet 14 is a sheet material having a multilayer structure of at least three layers. In the intermediate layer of the multilayer structure, an aluminum foil (metal member, sheet material) 5a is used for the purpose of moisture prevention and prevention of atmospheric gas intrusion. For the

insulating layers

12 and 13 on both sides of the aluminum foil 5a, a fluororesin film, a low hydrolysis type polyester film, a moisture-proof coating film, or the like can be used. The transparent sealing resin 11 is fused to the back sheet 14. In the periphery of the back sheet 14, the insulating layer 12 is omitted, and the transition metal oxide glass (sealing material) 3 is fused to the aluminum foil (metal member) 5a. The transition metal oxide glass (sealing material) 3 is fused to the peripheral edge of the transparent glass substrate 4a. The transparent glass substrate 4a and the aluminum foil 5a are disposed to face each other, and the transition metal oxide glass 3 is provided between the outer peripheral portions thereof. The transition metal oxide glass (sealing material) 3 bonds the transparent glass substrate 4a and the aluminum foil (metal member) 5a, and seals the gap generated between the transparent glass substrate 4a and the aluminum foil 5a. Thereby, the sealed container 2 formed by bonding the transparent glass substrate 4a and the aluminum foil 5a (back sheet 14) with the transition metal oxide glass 3 can be configured. In the sealed container 2, a plurality of solar cells 6 wrapped with a transparent sealing resin 11 are arranged. The plurality of solar cells 6 are connected to each other by lead wires (wiring) 7. Lead wires (wirings) 7 between the solar cells 6 are also arranged in the sealed container 2. This prevents moisture in the air and atmospheric gas from entering the inside of the sealed container 2, so that the solar battery cell 6 and the lead wire (wiring) 7 between them do not deteriorate and output over a long period of time. Reduction is suppressed. In FIG. 1, the insulating layer 12 at the peripheral edge of the back sheet 14 is omitted. However, if the insulation between the solar battery cell 6 and the outside can be sufficiently secured by the transparent sealing resin 11, the entire insulating layer 12 is provided. And the insulating layer 13 may be omitted.

A lead wire (wiring) 7 connected to the solar battery cell 6 and drawn out from the solar battery cell 6 is led out to the outside through a lead-out hole formed in the transparent sealing resin 11 and the back sheet 14. The lead-out hole is covered and sealed with silicon resin (silicone) 8 from the outside. The lead wire (wiring) 7 exposed to the outside is connected to the output cable 10 in the terminal box 9. It is preferable to use aluminum or an aluminum alloy for the lead wire (wiring) 7 and the aluminum foil (metal member) 5a, and the transition metal oxide glass 3 can be firmly fused. However, the present invention is not limited to this, and a metal or alloy other than aluminum may be used for the metal member (aluminum foil) 5a.

The transition metal oxide glass 3 is an n-type semiconductor in order to firmly adhere to the aluminum foil (metal member) 5a. The transition metal oxide glass 3 having an n-type semiconductor polarity is obtained by ringing a natural oxide layer formed on the surface of an aluminum foil (metal member) 5a so that the natural oxide layer is removed and the aluminum foil (metal Member) can be firmly bonded to 5a. The transition metal oxide glass 3 has transition metal ions having different valences. The number of expensive transition metal ions is larger than the number of low-valent transition metal ions. The ratio of the number of expensive transition metal ions to the number of low-valent transition metal ions is greater than one. Specifically, vanadium ions can be used as transition metal ions. An expensive number of vanadium ions can be converted to a pentavalent vanadium ion (V ⁺⁵ ), and a low number of vanadium ions can be converted to a tetravalent vanadium ion (V ⁺⁴ ). Then, the ratio to the number (concentration) of [V ^+5], 4 valent number of the vanadium ions (V ⁺⁴⁾ (Concentration) [V ^+4] pentavalent vanadium ions (V ⁺⁵⁾ ([V ^{+ 5} ] / [V ^{+ 4} ]) is greater than 1 ([V ^{+ 5} ] / [V ^{+ 4} ]> 1). In addition, the valence of the vanadium ion in the transition metal oxide glass 3 can be measured by the oxidation-reduction titration method according to JIS-G1221. Vanadium ions can be not only pentavalent and tetravalent but also trivalent (V ⁺³ ). Therefore, in order to make the transition metal oxide glass 3 into an n-type semiconductor, the number of tetravalent vanadium ions (V ⁺⁴ ) of the number (concentration) [V ⁺⁵ ] of pentavalent vanadium ions (V ⁺⁵ ) The ratio ([V ⁺⁵ ] / [V ⁺⁴ ]) to the number (concentration) [V ⁺⁴ ] is made larger than 1 ([V ⁺⁵ ] / [V ⁺⁴ ]> 1), not only 4 the ratio to the number (density) [V ^+3] number of valence of vanadium ions (V ⁺⁴⁾ (concentration) of [V ^+4], 3-valent vanadium ions ^{^{(V +3) ([V +4}} ] / [V ⁺³ ]) may be greater than 1 ([V ⁺⁴ ] / [V ⁺³ ]> 1).

The ratio ([V ⁺⁵ ] / [V ⁺⁴ ] and [V ⁺⁴ ] / [V ⁺³ ]) can be adjusted by the additive element, and the ratio ([V ⁺⁵ ] / [V ⁺⁴ ] and [V ⁺⁴ ] / [V ⁺³ ]) to be greater than 1, copper, silver, alkali metal (which has the effect of suppressing the reduction of vanadium pentoxide (V ₂ O ₅ )) For example, at least one element of potassium) and alkaline earth metal (for example, strontium and barium) may be added.

As described above, vanadium, which is a transition metal, becomes an oxide in the form of trivalent, tetravalent, and pentavalent ions. As the transition between these ion states occurs, the oxide layer (natural oxide) on the surface of the aluminum foil (metal member) 5a can be reduced, so that the transition metal oxide glass 3 is firmly bonded to the metal. can do. The fact that the semiconductor polarity of the transition metal oxide glass 3 is n-type increases the number of ions having a large valence. Raise your valence and give your opponent an electron to reduce your opponent. When it is n-type, the number of ions of transition metal that can increase its valence is small, and at first glance, it is considered difficult to reduce the metal to be joined. However, a reducing power sufficient to reduce the native oxide on the metal surfaces to be joined was obtained, and the transition metal oxide glass 3 adhered firmly to the metal. As described above, in the present invention, the semiconductor polarity of the transition metal oxide is made to be n-type, thereby enabling strong adhesion to the metal.

In addition to tellurium and phosphorus, which are vitrification components, elements having a relatively large ionic radius, such as barium and tungsten, and iron are added to significantly increase the moisture or atmospheric permeability of the transition metal oxide glass 3. Can be reduced.

Since the transition metal oxide glass 3 has a high absorption rate of light having a wavelength of 1100 nm or less, the transition metal oxide glass 3 can be heated by being irradiated with laser light having a wavelength of 1100 nm or less, and can be softened and flown and fused (laser sealing). . The transition metal oxide glass 3 is fused to the transparent glass substrate 4a and the aluminum foil 5a by irradiating the transition metal oxide glass 3 from the transparent glass substrate 4a side through which the laser light is transmitted. Can do. Note that the wavelength range of the laser light is desirably 400 to 1100 nm. In the wavelength range of less than 400 nm, the entire surface of the transparent glass substrate 4a may be heated. If the wavelength exceeds 1100 nm, the absorption of the transition metal oxide glass 3 is reduced, and it does not show good softening fluidity, and if there is a portion containing moisture, it may be heated and have an adverse effect. is there. On the contrary, in the wavelength range of 400 to 1100 nm, the transition metal oxide glass 3 can be heated without heating the entire surface of the transparent glass substrate 4a. The resin 11 can be sealed in the sealed container 2.

The glass transition point of the transition metal oxide glass 3 is 320 ° C. or lower, and its softening point is 380 ° C. or lower. Here, the transition point and the softening point are characteristic temperatures by differential thermal analysis (DTA), the transition point is the starting temperature of the first endothermic peak, and the softening point is the second endothermic peak temperature. When the transition point exceeds 320 ° C., a large residual strain may be generated in the laser sealing with rapid heating and rapid cooling. On the other hand, if the softening point exceeds 380 ° C., it becomes difficult to soften and flow easily during laser irradiation. According to the transition metal oxide glass 3, the laser sealing does not generate a large residual strain, and can be easily softened and flowed during laser irradiation.

The thermal expansion coefficient of the transition metal oxide glass 3 is a value between the thermal expansion coefficients of the transparent glass substrate 4 a and the back sheet 14. Thereby, both the thermal expansion coefficient difference of the transition metal oxide glass 3 and the transparent glass substrate 4a and the thermal expansion coefficient difference of the transition metal oxide glass 3 and the back sheet | seat 14 can be made small. And generation | occurrence | production of the crack by the heat shock at the time of laser irradiation can be suppressed. In order to adjust the thermal expansion coefficient of the transition metal oxide glass 3 to a value between the thermal expansion coefficients of the transparent glass substrate 4a and the back sheet 14, the thermal expansion coefficient of the transition metal oxide glass 3 is reduced. In order to reduce the thermal expansion coefficient of the transition metal oxide glass 3, filler particles having a thermal expansion coefficient smaller than the thermal expansion coefficient of the glass component of the transition metal oxide glass 3 are used as the glass component of the transition metal oxide glass 3. It is mixed and vitrified together. As the filler particles, one or more of zirconium phosphate tungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ), and silicon (Si) can be used. The effect of lowering the thermal expansion coefficient of the transition metal oxide glass 3 is larger in the order of niobium oxide, silicon, and zirconium tungstate phosphate. Silicon generates heat by absorbing laser light having a wavelength in the range of 400 to 1100 nm. Moreover, the heat conductivity of silicon is better than the other two filler particles and the glass component of the transition metal oxide glass 3. For this reason, silicon is particularly effective for the laser sealing. The filler particle content is 35 parts by volume or less with respect to the volume part of the glass component of the transition metal oxide glass 3. Thereby, the thermal expansion coefficient can be set to a value between the thermal expansion coefficients of the transparent glass substrate 4a and the back sheet 14 while maintaining the strong adhesion with the metal of the glass component of the transition metal oxide glass 3. .

Further, the composition of the glass component of the transition metal oxide glass 3 (the composition of the component excluding the filler particles) has the following characteristics. The glass component of the transition metal oxide glass 3 contains vanadium oxide, tellurium oxide, phosphorus oxide and iron oxide. The sum of the mass converted to V ₂ O ₅ , TeO ₂ , P ₂ O ₅ , and Fe ₂ O _{3 respectively} is 75% by mass or more based on the mass of the glass component of the transition metal oxide glass 3. ing. The mass of vanadium oxide converted as V ₂ O ₅ is larger than the mass of tellurium oxide converted as TeO ₂ . The mass of tellurium oxide converted to TeO ₂ is larger than the mass of phosphorus oxide converted to P ₂ O ₅ . The mass converted to phosphorus oxide as P ₂ O ₅ is greater than or equal to the mass converted to iron oxide as Fe ₂ O ₃ . The glass component of the transition metal oxide glass 3 contains vanadium oxide in an amount of 35 to 55% by mass in terms of V ₂ O ₅ . The glass component of the transition metal oxide glass 3 contains 19-30% by mass of tellurium oxide in terms of TeO ₂ . The glass component of the transition metal oxide glass 3 contains 7 to 20% by mass of phosphorus oxide in terms of P ₂ O ₅ . The glass component of the transition metal oxide glass 3 contains 5 to 15% by mass of iron oxide in terms of Fe ₂ O ₃ .

It is important for the transition metal oxide glass 3 to contain the largest amount of V ₂ O _{5 in} terms of oxide, 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. I will do. 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. Fe ₂ O ₃ is also a component that efficiently absorbs a wavelength range of 400 to 1100 nm, like V ₂ O ₅ . However, if 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 fluidity of the low-melting glass and is not preferable. 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 Ts 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. On the other hand, when it exceeds 15% by mass, crystallization may be accelerated.

The glass component of the transition metal oxide glass 3 is any one of tungsten oxide, molybdenum oxide, copper oxide, tantalum oxide, manganese oxide, antimony oxide, bismuth oxide, zinc oxide, barium oxide, strontium oxide, silver oxide and potassium oxide. It is good to include the above. These metal ions oxides may take a plurality of valences, of which _{_{WO 3, MoO 3, CuO,}} Ta 2 O 5, MnO 2, Sb 2 O 3, Bi 2 O 3, ZnO, BaO, SrO, Ag The sum of the masses converted as ₂ O and K ₂ O is 25% by mass or less with respect to the mass of the transition metal oxide glass 3. 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.

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 reducing the thermal expansion coefficient, MoO ₃ , Ag ₂ O, K for reducing the softening point Ts ₂ O content 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 Ts 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 the moisture resistance and water resistance are MoO ₃ Nb ₂ O ₅ , Ta ₂ O ₅ , 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 .

In Example 1, the composition of the glass component (low melting point glass) of the transition metal oxide glass 3 clarified in the first embodiment is examined. Tables 1 to 4 show, as examples, compositions that can be glass components of the transition metal oxide glass 3 and various characteristics for each composition. As compositions (examples) that can be glass components of the transition metal oxide glass 3, glass Nos. 64 compositions of G1 to G64 are shown. Table 5 shows a composition that cannot be a glass component of the transition metal oxide glass 3 and various characteristics for each composition as a comparative example. As a composition (comparative example) that cannot be a glass component of the transition metal oxide glass 3, glass No. 1 in Table 5 was used. 16 types of compositions from G65 to G80 are shown.

In examining the composition, first, glass No. 1 was used. Low melting glass having a composition of G1 to G80 was produced. As raw materials, from a reagent manufactured by High Purity Chemical Laboratory, vanadium oxide V ₂ O ₅ , tellurium oxide TeO ₂ , phosphorus oxide P ₂ O ₅ , iron oxide Fe ₂ O ₃ , tungsten oxide WO ₃ , molybdenum oxide MoO ₃ , Copper oxide CuO, 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, strontium carbonate SrCoS ₃ , barium carbonate BaCO ₃ , silver oxide Ag ₂ O and Potassium carbonate K ₂ CO ₃ was used. Using these reagents as raw materials, glass no. For each composition of G1 to G80, these reagents were weighed so that the composition was obtained and the total mass was 200 g. Next, Glass No. For each composition of G1 to G80, weighed reagents were blended and mixed, placed in a platinum crucible, heated in an electric furnace and melted. In the electric furnace, the temperature was raised to a melting temperature of 900 to 1000 ° C. at a heating rate of 5 to 10 ° C./min, and heated at the melting temperature for 2 hours. In order to make the composition distribution uniform, hot water was stirred during heating for 2 hours at the melting temperature. Thereafter, the molten hot water was allowed to flow out of a platinum crucible onto a stainless steel plate that had been heated to 150 to 200 ° C. in advance and quenched to prepare a low melting glass. In the above, glass no. A low melting glass (glass component) having a composition of G1 to G80 was completed.

Next, glass no. The characteristics of the glass components G1 to G80 (low melting point glass) were measured. First, the density was measured. The measurement results are shown in the density column of Tables 1 to 5.

Next, differential thermal analysis (DTA) was performed. In the differential thermal analysis (DTA), first, the produced glass No. Part of the glass components G1 to G80 (low melting point glass) was pulverized with a jet mill until the average particle size became 3 μm or less to form powder. Using the powder, differential thermal analysis (DTA) was performed to raise the temperature to 500 ° C. at a rate of 5 ° C./min. And the DTA curve as shown in FIG. 2 was acquired. From this DTA curve, the transition point T _g , the yield point M _g , the softening point T _s and the crystallization temperature T _cry were determined (measured). Note that alumina (Al ₂ O ₃ ) powder was used as a standard sample. As shown in FIG. 2, the transition point The T _g, the onset temperature of the first endothermic peak was determined by the tangent method. Yield point M _g is the peak temperature of the first endothermic peak was determined by the tangent method. The softening point T _s was determined as the peak temperature of the second endothermic peak and obtained by the tangential method. The crystallization temperature _Tcry was determined as the starting temperature of the exothermic peak due to crystallization and was determined by the tangential method.

The characteristic temperature of glass (transition point T _g , yield point M _g , softening point T _s ) is defined by the viscosity, and the transition point T _g , yield point M _g , and softening point T _s have a viscosity of 10 ^13.3 poise respectively. , 10 ^11.0 poise and 10 ^7.65 poise. In order to soften and flow glass (low melting point glass) at a low temperature, it is necessary to lower the softening point T _s as much as possible. Further, in order to mitigate the thermal residual strain, as much as possible, it is preferable to lower temperature the transition point T _g. The crystallization temperature _Tcry is a temperature at which glass (low melting point glass) starts to crystallize. Since crystallization hinders the softening fluidity of the glass, it is desirable to make the crystallization temperature T _cry higher than the softening point T _{s as} much as possible.

Next, thermal expansion characteristics were measured. In the measurement of thermal expansion characteristics, first, the produced glass No. Glass component G1 ~ G80 part (low-melting glass), respectively, were annealed at a temperature within the temperature range of transition point T _g ~ sag M _g, to remove thermal strain. It was processed into a prismatic shape of 4 mm in length and 20 mm in height. Using this prism was measured and the thermal expansion coefficient at 30 ~ 250 ° C. The thermal dilatometer, the transition temperature T _G of thermal expansion characteristic temperature deformation temperature A _T. In the thermal dilatometer, a cylindrical quartz glass having a diameter of 5 mm and a height of 20 mm was used as a standard sample. In the thermal dilatometer, the temperature rising rate of the prism and the standard sample was 5 ° C./min, and the temperature was raised until the deformation temperature _AT could be confirmed. And by this temperature rise, the thermal expansion curve as shown in FIG. 3 was acquired. Note that the amount of elongation on the vertical axis of the thermal expansion curve in FIG. 3 is the amount of elongation obtained by subtracting the amount of elongation of quartz glass, which is a standard sample. The thermal expansion coefficient was calculated from the gradient of elongation with respect to temperature in the temperature range of 30 to 250 ° C. of the thermal expansion curve. The transition temperature _TG of the thermal expansion characteristic temperature was determined as a temperature at which a significant increase in the gradient of elongation begins, and was determined by the tangential method. The deformation temperature _AT is a temperature at which deformation occurs due to a load, and was determined as a peak temperature of elongation. Transition temperature T _G was determined to slightly higher than the transition point T _g of the said differential thermal analysis. Deformation temperature A _T is a M _g yield point of the differential thermal analysis was measured as a temperature between the softening point T _s.

Next, the produced glass No. A moisture resistance test was conducted on glass components G1 to G80 (low melting point glass). In the moisture resistance test, first, the same prism as that used in the measurement of thermal expansion characteristics was prepared, and the surface of the prism was mirror-finished. Then, as a moisture resistance test, an accelerated test was performed in which the sample was left for 10 days in an environment of a temperature of 85 ° C. and a humidity of 85%. The evaluation standard of moisture resistance is “◯” when the gloss of the mirror-finished glass surface is maintained, “△” when the gloss is lost, and “×” when the glass collapses. "

Next, the produced glass No. The softening fluidity of the glass components G1 to G80 (low melting point glass) was evaluated. In the evaluation of the softening fluidity, first, in the same manner as in the differential thermal analysis (DTA), a part of the low melting point glass was powdered. And this powder was compacted by a hand press (1 ton / cm ² ) to produce a glass compact. The glass compact was formed into a disk shape having a diameter of 10 mm and a height of 2 mm. This glass powder compact was placed on a white glass substrate, and various laser beams were transmitted through the white glass substrate from the white glass substrate side to irradiate the glass compact. As various laser beams, a laser beam having a wavelength of 405 nm by a semiconductor laser, a laser beam having a wavelength of 532 nm by a YAG laser, a laser beam having a wavelength of 630 nm by a semiconductor laser, a laser beam having a wavelength of 805 nm by a semiconductor laser, A laser beam having a wavelength of 1064 nm by a YAG laser was used. The evaluation criteria for the softening fluidity is “◯” when the laser irradiation part of the glass compact has flowed, “●” when it has flowed but many cracks occur, and “△” when softened. ”And“ ▲ ”when softened but frequently cracked, and“ X ”when neither fluid nor softened. The state of softening flow and the occurrence of cracks in the laser-irradiated part of the green compact were evaluated by observing with an optical microscope through a white glass substrate.

Glass Nos. Shown in Tables 1 to 4 G1 to G64 (Examples) and glass Nos. Shown in Table 5 The compositions of G65 to G80 (comparative examples) are compared with the various characteristics measured above. From this, glass no. Low melting point glasses having compositions of G1 to G64 (Examples) are glass Nos. Of Comparative Examples. G67,69,73 ~ 76 and 78-80 low softening point T _s than the low melting glass composition, for the softening point T _s is lower and 380 ° C. or less, has good softening fluidity.

Glass No. Low melting point glasses having compositions of G1 to G64 (Examples) are glass Nos. Of Comparative Examples. G69,74 ~ 76 and 78-80 the low-melting transition point T _g is lower than the glass compositions of, for transition low T _g and 320 ° C. or less, not observed cracks in the heat shock by laser irradiation.

Glass No. Low melting point glasses having compositions of G1 to G64 (Examples) are glass Nos. Of Comparative Examples. Since the thermal expansion coefficient is smaller than that of the low melting point glass having the composition of G68, 70 to 73, 77 and 78, and the thermal expansion coefficient is relatively small as 100 × 10 ⁻⁷ / ° C. or less, cracks caused by heat shock due to laser irradiation can not see.

Also, glass no. Low melting point glasses having compositions of G1 to G64 (Examples) are glass Nos. Of Comparative Examples. The moisture resistance is better than that of low melting glass having a composition of G65 to 68, 70 to 74, 76, 78 and 80.

Glass No. Low melting point glasses having compositions of G1 to G64 (Examples) are glass Nos. Of Comparative Examples. The softening fluidity by laser irradiation is better than the low melting glass having the composition of G67, 69, 73 to 76, and 78 to 80, and like the low melting glass having the composition of Comparative Examples 68, 70 to 73, 77, and 78. There is no occurrence of cracks. Glass No. The low melting point glass having the composition of G1 to G64 (Example) absorbs laser light having a wavelength in the range of about 400 to about 1100 nm efficiently, is heated, and has a low softening point T _s of 380 ° C. or less, which is good Soft fluidity. Furthermore, the transition point T _g is 320 ° C. or less and low thermal expansion coefficient is small as 100 × 10 ^-7 / ℃ less, cracks in the heat shock does not occur due to laser irradiation.

Thus, the glass No. According to the low melting point glass having the composition of G1 to G64 (Examples), excellent characteristics were obtained in the various characteristics described above. These glass Nos. From the compositions of G1 to G64 (Examples), a compositional composition common to these can be derived. The common composition is the glass No. The low melting point glass having the composition of G1 to G64 (Example) contains vanadium oxide, tellurium oxide, phosphorus oxide and iron oxide, and V ₂ O ₅ , TeO ₂ , P ₂ O ₅ and Fe _{2 in} terms of the following oxides. The total of O ₃ is 75% by mass or more and has a relationship of 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, copper 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 + CuO + Ta ₂ O ₅ + MnO ₂ + Sb ₂ O ₃ + Bi ₂ O ₃ + ZnO + BaO + SrO + Ag ₂ O + K ₂ O ≦ 25% by mass in terms of the following oxides. A particularly effective composition range is that V ₂ O ₅ is 35 to 55% by mass, TeO ₂ is 19 to 30% by mass, and P ₂ O ₅ is 7% in terms of the following oxides after satisfying the above-described composition conditions. ˜20 mass%, Fe ₂ O ₃ 5˜15 mass%, 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, The total of one or more of BaO, Ag ₂ O, and K ₂ O is 0 to 20% by mass.

In Example 2, the glass No. shown in Table 2 was used. The transition metal oxide glass 3 which uses the low melting glass of the composition of G19 as a glass component is produced. Using this transition metal oxide glass 3, a sealed container 2 is produced, and the hermeticity (gas barrier property) of the sealed container 2 and the adhesiveness of the transition metal oxide glass 3 are evaluated. In this evaluation, first, a glass No. The low melting glass having the composition of G19 was pulverized by a jet mill into a powder having an average particle size of 3 μm or less. And the sealing material paste was produced using this powder, the resin binder, and the solvent. Nitrocellulose was used as the resin binder, and butyl carbitol acetate was used as the solvent. If it is a sealing material paste, it can be apply | coated to a desired shape, The transition metal oxide glass 3 of a desired shape can be formed by baking this.

In FIG. 4, the perspective view in the middle of manufacture of the sealed container 2 which concerns on Example 2 of this invention is shown. A slide glass (white plate glass) was prepared as the transparent glass substrate 4a. As shown in FIG. 4, the said sealing material paste used as the transition metal oxide glass 3 was apply | coated to the outer peripheral part of the transparent glass substrate 4a in the frame shape with the screen printing method. Next, the solvent was removed by heating in the atmosphere at a temperature of 150 to 200 ° C. for 30 minutes. Next, Glass No. The temperature should be lower than the softening point T _s (355 ° C.) of the low melting point glass having the composition of G19. Specifically, the resin binder was removed by heating in the atmosphere at a temperature of 320 ° C. for 30 minutes. Thereby, the transition metal oxide glass 3 was able to be formed (baked) on the transparent glass substrate 4a. The line width W of the transition metal oxide glass 3 was 1.5 mm. Moreover, about the baking film thickness T of the transition metal oxide glass 3, in order to produce four different sealed containers 2 of about 5, 10, 20, and 30 μm, four types with different coating amounts are produced. As will be described later, since each of the four types was irradiated with five types of laser beams having different wavelengths used in Example 1, 20 types of sealed containers 2 were finally produced.

FIG. 5 shows a longitudinal sectional view of the sealed container 2 according to the second embodiment of the present invention in the middle of manufacture. In Example 2, instead of the aluminum foil (sheet material) of the back sheet 14 of the first embodiment, an aluminum substrate (plate material) is used as the metal member 5a. The aluminum substrate (metal member) 5a was disposed so as to face the transparent glass substrate 4a with the transition metal oxide glass 3 interposed therebetween. Laser light 15 was applied to the transition metal oxide glass 3 from the transparent glass substrate 4a side. The laser beam 15 was irradiated while moving along the transition metal oxide glass 3 at a speed of 8 mm / second, and was irradiated over the entire circumference of the frame shape of the transition metal oxide glass 3. Thereby, the transition metal oxide glass 3 was fused to the transparent glass substrate 4a and the aluminum substrate 5a. The transparent glass substrate 4a and the aluminum substrate 5a were bonded via the transition metal oxide glass 3. As the laser beam 15, five types of laser beams with different wavelengths used in Example 1 were irradiated.

Table 6 shows the evaluation results of the hermeticity (gas barrier property) of the sealed container 2 and the adhesiveness of the transition metal oxide glass 3. These evaluation results are shown for each fired film thickness of the transition metal oxide glass 3 and for each wavelength of irradiated laser light (irradiation laser wavelength). As an evaluation of the hermeticity (gas barrier property) of the sealed container 2, a helium leak test was performed. For the helium leak test, a port capable of depressurizing the inside of the sealed container 2 was formed in the aluminum substrate 5a although not shown. As an evaluation criterion, “◯” was set when no leak was detected, and “X” was set when a leak was detected.

In addition, a peel test was performed as an evaluation of the adhesion of the transition metal oxide glass 3. In the peeling test, a commercially available cellophane tape was attached to the aluminum substrate 5a with the transparent glass substrate 4a fixed to the base and pulled as it was. As an evaluation standard, when the transparent glass substrate 4a itself or the transition metal oxide glass 3 itself is broken, it is “◯”, and it is peeled off at the interface between the transition metal oxide glass 3 and the transparent glass substrate 4a or the aluminum substrate 5a. In this case, “x” was used. When the fired film thickness was 20 μm or less (less than 30 μm), the airtightness and adhesiveness were good regardless of the wavelength of the laser beam 15 used. However, when the fired film thickness is 30 μm, depending on the wavelength of the laser beam 15 to be used, there are cases where good airtightness and adhesiveness can be obtained or not. Specifically, when the fired film thickness was 30 μm, good hermeticity and adhesiveness were obtained by using the laser light 15 having wavelengths of 532 nm and 1064 nm. Further, when the fired film thickness was 30 μm, good hermeticity was obtained by using the laser beam 15 having a wavelength of 805 nm.

In FIG. The transmittance | permeability curve of the transition metal oxide glass 3 of the film | membrane shape which has a glass component of the composition of G19, apply | coated and baked is shown. In the wavelength region of 300 to 2000 nm, the shorter the wavelength, the lower the transmittance. Moreover, the transmittance | permeability fell, so that the baking film thickness was large. When the fired film thickness is large, the transmittance decreases, as shown in FIG. 5, when the laser beam 15 enters the transition metal oxide glass 3 from the transparent glass substrate 4 a side, the transition metal oxide glass 3. When the laser beam 15 is absorbed in the transition metal oxide glass 3 in the vicinity of the aluminum substrate 5a, the intensity of the laser beam 15 is attenuated and it is difficult to generate heat up to a temperature necessary for fusion to the aluminum substrate 5a. Conceivable. Therefore, when the fired film thickness is large, in addition to the incidence of the laser beam 15 from the transparent glass substrate 4a side, the laser beam 15 is emitted from the aluminum substrate 5a side or from the side surface of the transition metal oxide glass 3. Irradiation is sufficient.

(Modification of Example 2)
In the modification of Example 2, instead of the transparent glass substrate (slide glass) 4a of Example 2, a transparent resin substrate (resin member) was used. As an example, the transparent resin substrate is made of polycarbonate. Resin members such as polycarbonate are made of glass no. Since the heat resistance is lower than that of the low melting point glass having the composition of G19, the transition metal oxide glass 3 at 320 ° C. in Example 2 cannot be fired. Accordingly, the transition metal oxide glass 3 on the transparent resin substrate (polycarbonate) is baked by irradiating the transition metal oxide glass 3 with a laser beam 15 having a wavelength of 805 nm that is not absorbed by the polycarbonate from the transparent resin substrate side. went. The laser beam 15 was irradiated while moving at a predetermined speed along the transition metal oxide glass 3, and was irradiated over the entire circumference of the frame shape of the transition metal oxide glass 3. Thereby, the transition metal oxide glass 3 was baked. According to this, the temperature of the transparent resin substrate (polycarbonate) hardly increased. After that, similarly to Example 2, the transition metal oxide glass 3 was irradiated with laser light 15 having five kinds of wavelengths from the transparent resin substrate (polycarbonate) side to complete the sealed container 2. The evaluation results of the hermeticity (gas barrier property) of the sealed container 2 and the adhesiveness of the transition metal oxide glass 3 were the same as the evaluation results of Example 2.

Also in the present Example 3, the transition metal oxide glass 3 is produced similarly to Example 2, and the sealed container 2 is produced using this transition metal oxide glass 3. The airtightness (gas barrier property) of the sealed container 2 and the adhesiveness of the transition metal oxide glass 3 are evaluated. In Example 3, a glass substrate having a thermal expansion coefficient of 50 × 10 ⁻⁷ / ° C. was used as the transparent glass substrate 4a. Further, the glass component of the transition metal oxide glass 3 was changed to the glass No. 2 of Example 2. In place of the composition of G19, glass No. The composition was G43. Furthermore, in order to lower the thermal expansion coefficient of the transition metal oxide glass 3, filler particles were added. As filler particles, three types of zirconium phosphate tungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ), and silicon (Si) were used. The average particle size of the filler particles was about 5 μm.

In this evaluation, the glass No. The low melting point glass having the composition of G43 was pulverized by a jet mill into a powder having an average particle size of 3 μm or less. Next, using this powder, one of the three types of filler particles, a resin binder, and a solvent, three types of sealing material pastes having different types of filler particles were produced. Moreover, the content of the filler particles in the sealing material paste was changed to four types of 15, 25, 35, and 45 parts by volume with respect to 100 parts by volume of the powder. Therefore, finally, 12 types of sealing material paste (transition metal oxide glass 3) and 12 types of sealed containers 2 were produced correspondingly.

Glass No. used The density of low-melting glass composition of G43 is ^{_{3.53g / cm 3, Zr 2 (}} WO 4) (PO 4) 2 densities 3.80g / cm ^3, Nb ₂ density of O ₅ is 4.57g / cm ^3, Si The density of was 2.33 g / cm ³ . Further, ethyl cellulose was used as the resin binder, and butyl carbitol acetate was used as the solvent. As shown in FIG. 4, each of the 12 types of sealing material pastes was applied to the outer peripheral portion of the transparent glass substrate 4 a by screen printing. Next, the solvent was dried. Next, the resin binder was removed by heating in the atmosphere at a temperature of 400 ° C. for 30 minutes. Thereby, the transition metal oxide glass 3 was able to be formed (baked) on the transparent glass substrate 4a. The line width W of the transition metal oxide glass 3 was about 1.5 mm, and the film thickness T was about 20 μm.

Next, as shown in FIG. 5, an aluminum substrate (metal member) 5a was placed so as to face the transparent glass substrate 4a with the transition metal oxide glass 3 interposed therebetween. Next, the transition metal oxide glass 3 was irradiated with laser light 15 having a wavelength of 805 nm from the transparent glass substrate 4a side. The laser beam 15 was irradiated while moving along the transition metal oxide glass 3 at a speed of 8 mm / second, and was irradiated over the entire circumference of the frame shape of the transition metal oxide glass 3. As a result, the transition metal oxide glass 3 was fused to the transparent glass substrate 4a and the aluminum substrate 5a over the entire circumference. The transparent glass substrate 4a and the aluminum substrate 5a were bonded via the transition metal oxide glass 3. Thereby, the sealed container 2 was completed.

Table 7 shows the evaluation results of the hermeticity (gas barrier property) of the sealed container 2 and the adhesiveness of the transition metal oxide glass 3. These evaluation results are shown for each type and volume part of the filler particles. The evaluation method and evaluation criteria for airtightness (gas barrier property) and adhesiveness were the same as those in Example 2. From this, regardless of the type of filler particles, when the content was 35 parts by volume or less (less than 45 parts by volume), good airtightness and adhesiveness were obtained. Further, when the filler particle content was 45 parts by volume, good airtightness was obtained, but the adhesiveness deteriorated. This is because if there are too many filler particles, the area of the glass component in the transition metal oxide glass 3 fused to the transparent glass substrate 4a and the aluminum substrate 5a becomes small.

From the above, in order to bond the transparent glass substrate 4a and the aluminum substrate 5a in an airtight and strong manner, the content of the filler particles is set to 35 parts by volume or less (45 parts with the glass component in the transition metal oxide glass 3 being 100 parts by volume (45 (Less than volume part) is considered preferable. In Example 3, wettability (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), Nb ₂ O ₅ , and Si are selected as filler particles and the glass component in the transition metal oxide glass 3. However, the present invention is not limited to these, and β-eucryptite, cordierite, zirconium phosphate, zirconium silicate, and the like having a small thermal expansion coefficient are also applicable.

Based on the results of Examples 1 to 3, the solar cell module 1 according to the first embodiment was completed.

In the sealed container 2 of Example 2, as shown in FIG. 5, the height of the inner space of the sealed container 2 is equal to the fired film thickness of the transition metal oxide glass 3. As shown in Table 6, if the irradiation condition of the laser beam 15 is constant, the fired film thickness has an upper limit value that can ensure good airtightness and adhesiveness. And the height of the internal space of the sealed container 2 will also be restrict | limited to this upper limit. In the fourth embodiment, therefore, the sealed container 2 in which the height of the internal space of the sealed container 2 is not limited to the upper limit value will be described.

FIG. 7A shows a plan view of the sealed container 2 according to Example 4 of the present invention, and FIG. 7B shows a cross-sectional view taken along the line AA in FIG. 7A. A spacer (glass member) 4b is sandwiched between the transparent glass substrate 4a and the aluminum substrate 5a. As the spacer (glass member) 4b, similarly to the transparent glass substrate 4a, a glass member such as white plate glass having a high laser beam transmittance, or a resin member such as polycarbonate can be used. The transparent glass substrate 4a may be replaced with a resin member such as polycarbonate having a high laser light transmittance.

A plurality of glass members of a transparent glass substrate (plate material, glass member) 4a and spacers (frame material, glass member) 4b are bonded with a transition metal oxide glass 3a. Similarly, the aluminum substrate (plate, metal member) 5a and the spacer (glass member) 4b are bonded with a transition metal oxide glass 3b. The spacer (glass member) 4b and the transition

metal oxide glasses

3a and 3b have a frame shape and overlap each other. According to this, the height of the internal space of the sealed container 2 can be changed by changing the height of the spacer (glass member) 4b without changing the fired film thickness of the transition

metal oxide glasses

3a and 3b. . In the following description, the sealed container 2 manufactured by actually changing the height of the spacer (glass member) 4b in four ways will be described.

First, the sealing material paste is glass no. The low melting point glass powder having the composition of G43, Si filler particles, nitrocellulose, and butyl carbitol acetate were used. The Si filler particles were 10 parts by volume with respect to 100 parts by volume of the powder. This sealing material paste was applied to the upper and lower surfaces of the spacer 4b. Next, the solvent was removed by heating at 150 to 200 ° C. for 30 minutes in the atmosphere. Next, provisional baking was performed by removing the binder by heating at 340 ° C. for 30 minutes in the atmosphere to complete the transition

metal oxide glasses

3a and 3b. The fired film thickness of each of the transition

metal oxide glasses

3a and 3b was 15 μm. Note that the spacer 4b was prepared by changing the width to 3 mm and changing the thickness in four ways of 70, 320, 500, and 1000 μm, respectively. These laminates were sandwiched between the transparent glass substrate 4a and the aluminum substrate 5a, respectively, and installed on the outer periphery thereof. Next, the transition

metal oxide glasses

3a and 3b were irradiated with laser light having a wavelength of 630 nm from the transparent glass substrate 4a side. The laser light passes through the transparent glass substrate 4a and irradiates the transition metal oxide glass 3b, and further passes through the transition metal oxide glass 3b and the spacer 4b to irradiate the transition metal oxide glass 3a. That is, the spacer 4b functions as a waveguide of laser light that transmits the laser light without being attenuated. The moving speed of the laser beam was 8 mm / second. The sealed container 2 was completed by the above. The airtightness (gas barrier property) of the sealed container 2 and the adhesiveness of the transition metal oxide glass 3 were evaluated in the same manner as in Example 2. Good airtightness and adhesiveness were obtained regardless of the thickness of the spacer 4b. It has been found that when the distance between the transparent glass substrate 4a and the aluminum substrate 5a is large, it is effective to use the spacer 4b. As the material of the spacer 4b, in addition to the white plate glass having high laser light transmittance, it is also possible to apply silicon or iron oxide which has a high laser absorption rate and generates heat.

(Second Embodiment)
In FIG. 8, the longitudinal cross-sectional view of the principal part of the solar cell module 1 which concerns on the 2nd Embodiment of this invention is shown. The solar cell module 1 of the second embodiment is completed based on the results of Examples 1 to 3 and the results of Example 4. The solar cell module 1 of the second embodiment is different from the solar cell module 1 of the first embodiment in that the spacer 4b described in Example 4 is used. Thereby, the effect similar to the effect obtained in Example 4 can be acquired. Thus, by providing the height of the spacer 4b according to the height of the solar cell (electronic component) 6, the sealed container 2 that is not limited to the height of the solar cell (electronic component) 6 is provided. Can do. Further, in the second embodiment, unlike the first embodiment, the lead wire (wiring) 7 drawn out from the solar battery cell 6 penetrates through the transition metal oxide glass 3a and is drawn out to the outside. Yes. A transparent glass substrate (glass member) 4 a and a spacer (glass member) 4 b are disposed around the transition metal oxide glass 3 a, and the transition metal oxide glass 3 a is fused to the lead wire (wiring, metal member) 7. The sealed container 2 is sealed by being attached to the transparent glass substrate (glass member) 4a and the spacer (glass member) 4b.

FIG. 9 shows an assembled perspective view of the solar cell module 1 according to the second embodiment of the present invention. Next, the manufacturing process of the solar cell module 1 will be described. First, a plurality of solar battery cells 6 are arranged in a row while performing connection soldering for each solar battery cell 6 using a lead wire (for example, a ribbon wire of a solder-plated copper base material) 7 with an automatic wiring device. A string cell 16 connected to is formed. These are connected in parallel and arranged in parallel (in three rows in the example of FIG. 9), and a plurality of solar cells 6 are arranged in a matrix. Next, a transparent glass substrate 4a is prepared, a transparent sealing resin (EVA sheet) 11b is arranged on the transparent glass substrate 4a, a matrix-like solar battery cell 6 is arranged thereon, and further transparent thereon. Sealing resin (EVA sheet) 11a is disposed. In addition, when using the backsheet 14 with the transparent sealing resin 11a (when the insulating layer 12 of the backsheet 14 also serves as the transparent sealing resin 11a), the transparent sealing resin 11a is omitted. Can do. Then, on the outer peripheral part of the transparent glass substrate 4a, on the upper and lower surfaces of the spacer 4b produced by the method described in Example 4, the transition

metal oxide glasses

3a and 3b were temporarily baked, and on that, The back sheet 14 with the peripheral aluminum foil 5a exposed is disposed. The exposed aluminum foil 5a is placed on and in contact with the transition metal oxide glass 3b. Next, the lead wire (wiring) 7 is taken out, and in the lamination apparatus, the transparent glass substrate 4a to the back sheet 14 are pressure-bonded and integrated in a vacuum at a temperature near the EVA crosslinking temperature. Thereby, the transparent sealing resins 11 a and 11 b integrally wrap the solar battery cell 6 and seal the solar battery cell 6. Next, as described in Example 4, laser light was irradiated from the transparent glass substrate 4a side, and the outer peripheral portion of the solar cell module 1 was joined (sealed). It is also possible to improve the lamination apparatus so that laser irradiation can be performed during lamination, and to perform lamination and laser irradiation simultaneously. Further, the transparent sealing resin (EVA sheet) may be omitted, and in this case, the lamination step can be omitted.

(Third embodiment)
In FIG. 10, the longitudinal cross-sectional view of the principal part of the solar cell module 1 which concerns on the 3rd Embodiment of this invention is shown. The solar cell module 1 of the third embodiment is different from the solar cell module 1 of the second embodiment in that a composite transparent substrate 18 is used instead of the transparent glass substrate 4a. The composite transparent substrate 18 has a transparent resin substrate 17 such as polycarbonate, and the surface thereof is covered with the same transition metal oxide glass 3c as the transition

metal oxide glasses

3a and 3b. As described in the modification of Example 2, the transition

metal oxide glasses

3a and 3c are firmly fused to the transparent resin substrate 17 such as polycarbonate. By covering the transparent resin substrate 17 with the transition metal oxide glass 3c, airtightness can be improved, and deterioration of the transparent resin substrate 17 with time and generation of scratches can be prevented. And the solar cell module 1 can be reduced in weight significantly by using the composite transparent substrate 18 instead of the transparent glass substrate 4a. The transition metal oxide glass 3c is coated on the transparent resin substrate 17 by applying the sealing material paste on the transparent resin substrate 17, and the softening point T _s temperature of the glass component of the transition metal oxide glass 3c. This can be done by heating and baking. The structure for drawing out the lead wire (wiring) 7 is the same as that in the first embodiment.

(Fourth embodiment)
In FIG. 11, the longitudinal cross-sectional view of the principal part of the solar cell module 1 which concerns on the 4th Embodiment of this invention is shown. The solar cell module 1 of the fourth embodiment is different from the solar cell module 1 of the second embodiment in that an aluminum frame (metal frame material) 19 is used. The aluminum frame 19 is provided on the outer peripheral portion of the solar cell module 1. The cross-sectional shape of the aluminum frame 19 is a U-shape, and is inserted so as to cover the outer peripheral portions of the transparent glass substrate 4 a and the back sheet 14. A transition metal oxide glass (sealing material) 3 is provided inside the U-shape of the aluminum frame 19 and is fused to the aluminum frame 19. The transition metal oxide glass (sealing material) 3 is fused to the transparent glass substrate 4a, the spacer 4b, and the aluminum foil 5a. Also by this, the sealed container 2 can be made airtight. Further, the aluminum frame 19 can increase the strength of the solar cell module 1. An aluminum frame may be used for the conventional solar cell module 1, and the aluminum frame can be used as it is as the aluminum frame 19 of the fourth embodiment. Note that the laser beam 15 is applied to the aluminum frame 19 for the fusion. Thereby, the aluminium frame 19 is heated and the heat is transferred to the transition metal oxide glass 3 to raise the temperature.

The fourth embodiment is different from the second embodiment in that the lead wire (wiring) 7 drawn out from the solar battery cell 6 is sealed not with the silicon resin 8 but with the transition metal oxide. This is that the same transition metal oxide glass 3d as the physical glass 3 is used. Accordingly, the insulating layer 13 around the lead-out hole formed in the back sheet 14 is omitted, and the transition metal oxide glass 3d is fused to the exposed aluminum foil 5a. The transition metal oxide glass 3d is also fused to a lead wire (wiring) 7 drawn out to the outside. Also by this, the sealed container 2 is sealed.

The present invention is not limited to the first to fourth embodiments and Examples 1 to 4 described above, and includes various modifications. For example, the first to fourth embodiments and Examples 1 to 4 described above have been described in detail for easy understanding of the present invention, and are not necessarily limited to those having all the configurations described above. is not. Further, a part of the configuration of an embodiment (example) can be replaced with the configuration of another embodiment (example), and another embodiment (example) can be replaced with the configuration of an embodiment (example). It is also possible to add the configuration of the embodiment. Moreover, it is also possible to add, delete, and replace other configurations for a part of the configuration of each embodiment (example). That is, 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 together 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. In addition, this embodiment (example) can be applied to all types of solar cells in which cells are bonded and fixed to a transparent substrate. For example, it can be applied to thin film solar cells, organic solar cells, and dye-sensitized solar cells. As described above, the present invention can be applied to OLED displays, dye-sensitized solar cells, Si solar cells, plasma display panels, ceramic mounting substrates, and electronic components generally incorporating low heat resistance organic elements and organic materials. The reliability of the electronic parts can be significantly improved.

1 Electronic device (solar cell module)
2 Sealed

container

3, 3a, 3b, 3d Transition metal oxide glass (sealing material)
3, 3c Transition metal oxide glass (coating layer)
4a Glass member (plate material, transparent glass substrate)
4b Glass member (frame material, spacer, white plate glass)
5a Metal member (plate material (aluminum substrate) or sheet material (backsheet metal (aluminum) layer, aluminum foil))
5b Metal member (wiring)
6 Electronic components (solar cells)
7 Lead wire (wiring)
8 Silicone resin
9 Terminal box 10

Output cable

11, 11a, 11b Transparent sealing resin (EVA sheet)
12, 13 Insulating layer of back sheet 14 Back sheet 15 Laser light 16 String cell 17 Transparent resin substrate 18 Composite transparent substrate 19 Aluminum frame (metal frame material)

Claims

A glass member or a resin member;
A metal member;
A transition metal oxide glass fused to both the glass member or the resin member and the metal member;
The transition metal oxide glass is an n-type semiconductor,
A sealed container formed by adhering the glass member or the resin member and the metal member with the transition metal oxide glass.
The transition metal oxide glass has transition metal ions having different valences,
2. The sealed container according to claim 1, wherein the number of expensive transition metal ions is larger than the number of low-valent transition metal ions.
The transition metal oxide glass includes vanadium, includes at least one of tellurium and phosphorus, and includes at least one of silver, iron, tungsten, copper, an alkali metal, and an alkaline earth metal. The sealed container according to claim 1 or 2.
The transition metal oxide glass includes vanadium oxide, tellurium oxide, phosphorus oxide and iron oxide,
The sum of the mass converted to V 2 O 5 , TeO 2 , P 2 O 5 , and Fe 2 O 3 , respectively, is 75% by mass or more with respect to the mass of the transition metal oxide glass. The sealed container according to any one of claims 1 to 3.
The transition metal oxide glass includes vanadium oxide, tellurium oxide, phosphorus oxide and iron oxide,
The mass obtained by converting vanadium oxide as V 2 O 5 is larger than the mass obtained by converting tellurium oxide as TeO 2 .
The mass of tellurium oxide converted as TeO 2 is larger than the mass of phosphorus oxide converted as P 2 O 5 ,
Mass obtained by converting the phosphorus oxide as P 2 O 5 is a sealed container according to any one of claims 1 to 4, characterized in that the iron oxide is at least mass calculated as Fe 2 O 3.
The transition metal oxide glass is
Containing vanadium oxide in terms of V 2 O 5 , 35 to 55% by mass,
Containing 19-30% by mass of tellurium oxide in terms of TeO 2 ;
Phosphorus oxide, converted as P 2 O 5 , contains 7 to 20% by mass,
6. The sealed container according to claim 1, wherein iron oxide is contained in an amount of 5 to 15% by mass in terms of Fe 2 O 3 .
The transition metal oxide glass is
Including one or more of tungsten oxide, molybdenum oxide, copper oxide, tantalum oxide, manganese oxide, antimony oxide, bismuth oxide, zinc oxide, barium oxide, strontium oxide, silver oxide and potassium oxide,
The sum of the masses converted to WO 3 , MoO 3 , CuO, Ta 2 O 5 , MnO 2 , Sb 2 O 3 , Bi 2 O 3 , ZnO, BaO, SrO, Ag 2 O, and K 2 O, respectively, is The sealed container according to any one of claims 1 to 6, wherein the content is 25% by mass or less based on the mass of the transition metal oxide glass.
The glass member or the resin member is plate-shaped,
The metal member is plate-shaped or sheet-shaped,
The said glass member or the said resin member, and the said metal member are arrange | positioned facing each other, The said transition metal oxide glass is provided in those outer peripheral parts, The any one of Claim 1 thru | or 7 characterized by the above-mentioned. Item 2. The sealed container according to item 1.
It has a plurality of the glass member or the resin member,
The sealed container according to any one of claims 1 to 8, wherein the glass member or the resin member is bonded with the transition metal oxide glass.
A spacer that is glass or resin is provided between the glass member or the resin member and the metal member,
The glass member or the resin member and the spacer are bonded with the transition metal oxide glass,
The metal member and the spacer are bonded with the transition metal oxide glass,
The sealed container according to claim 8 or 9, wherein the spacer is provided on an outer peripheral portion of the glass member or the resin member and the metal member.
The glass member or the resin member, the metal member and a metal frame member disposed on the outer periphery of the spacer,
The sealed container according to claim 10, wherein the glass member or the resin member, the metal member, and the spacer are bonded to the metal frame member by the transition metal oxide glass.
The said glass member or the said resin member, and the said metal member are adhere | attached and formed by the said transition metal oxide glass softened and flowed by laser irradiation, The any one of Claim 1 thru | or 11 characterized by the above-mentioned. Item 2. The sealed container according to item 1.
The sealed container according to any one of claims 1 to 12, wherein a material of the metal member is aluminum or an aluminum alloy.
A sealed container according to any one of claims 1 to 13,
An electronic component that houses the sealed container,
The metal member has wiring drawn out from the electronic component to the outside,
The electronic device, wherein the wiring and the glass member, the resin member, or the metal member other than the wiring are sealed with the transition metal oxide glass.
A sealed container according to any one of claims 1 to 13,
A solar cell module comprising a plurality of solar cells for housing the sealed container.