JP2013100201A - Electronic component, conductive paste for aluminum electrode applied to the same, and glass composition for aluminum electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electronic component, the manufacturing yield, performance and reliability of which satisfy standards that can be used in a practical sense.SOLUTION: In a glass composition for the electrodes of the electronic component, the electronic component, in which an electrode having metal particles and a glass phase is formed on a silicon substrate, is characterized by being an oxide glass wherein: the glass phase in the electrode contains at least the oxides of vanadium, antimony and boron, and further contains at least one type of the oxides of phosphorus, tellurium, barium and tungsten; the content of the phosphorus is <10 mass% in terms of oxide; and the content of lead in the glass is ≤1,000 ppm.

Description

  The present invention relates to a conductive paste for aluminum electrodes formed on a silicon substrate, a glass composition for aluminum electrodes contained therein, and an electronic component manufactured using the conductive paste for aluminum electrodes.

  In an electronic component such as a solar battery cell using a silicon substrate having a pn junction, a silver electrode or an aluminum electrode is formed. These electrodes are formed on a silicon substrate or the like by applying, drying and baking a conductive paste containing a large number of silver and aluminum metal particles. Usually, this conductive paste is mainly composed of the metal particles, and is composed of glass particles, a binder resin, a solvent, and the like. At the time of electrode firing, by heating above the softening point of the glass particles in the conductive paste, the glass particles soften and flow to form electrodes, and firmly adhere to the substrate and the like.

  As this glass particle, a low melting glass mainly composed of lead oxide that softens and flows at low temperature has been conventionally used. However, the lead contained in the glass is a hazardous substance regulated by the RoHS Directive, etc., so as to reduce the impact on the environment, that is, to preserve the ecosystem, solar cells and plasma display panels In electronic parts such as these, lead-free low-melting glass has been applied to form electrodes. For example, Patent Document 1 proposes a lead-free low-melting glass containing bismuth oxide and silicon oxide in a silver electrode or an aluminum electrode formed in a solar battery cell. Patent Document 2 proposes a low-melting glass containing bismuth oxide and boron oxide.

  In particular, the conductive paste mainly composed of metal particles such as aluminum particles and aluminum alloy particles cannot be fired densely by the oxide film on the surface of the metal particles, and there is a problem in reducing the resistance. Regarding this point, Patent Document 3 proposes a technique for improving the sinterability of metal particles and reducing the resistance by adding particles of vanadium or vanadium oxide to the conductive paste. Patent Document 4 also proposes a technique for improving oxidation resistance and reducing resistance by adding carbon, germanium, tin, a metal hydride compound, a metal phosphide compound, and the like.

  On the other hand, as represented by solar cells and the like, in the electronic components that are strongly required to reduce the power generation cost, the electrodes of Patent Documents 1 to 4 are all in the production yield, performance and reliability of the electronic components. The improvement was not considered enough.

JP 2008-543080 A JP 2006-332032 A JP 7-73731 A Japanese Patent Laid-Open No. 5-298997

  In an electronic component such as a solar battery cell using a silicon substrate having a pn junction, a silver electrode is often applied to the n-type semiconductor side and an aluminum electrode is applied to the p-type semiconductor side. When conventional low melting glass mainly composed of lead oxide is used for these electrodes, the power generation efficiency of the solar battery cell, that is, the conversion efficiency is high. However, when the lead-free low-melting glass proposed in Patent Documents 1 and 2 is used for the electrode, there is a problem that the conversion efficiency is lowered.

  In addition, there is a problem that the amount of warpage of the solar battery cell increases and the manufacturing yield decreases. This is considered that the glass used for the electrode is influenced by the sintered state of the electrode, the interface state with the silicon substrate, and the like. In addition, regarding the reliability such as the lifetime, it is difficult to improve the conventional low melting point glass mainly composed of lead oxide and the materials and methods proposed in Patent Documents 1 to 4. In particular, in an aluminum electrode, it is gradually corroded by moisture, and aluminum hydroxide is generated to deteriorate the electrode performance.

  Therefore, in view of the above problems, the object of the present invention is a level in which the production yield, performance and reliability can be practically used in electronic parts such as solar cells using a silicon substrate having a pn junction in consideration of environmental conservation. Is to satisfy. Moreover, it is providing the electroconductive paste for aluminum electrodes which satisfy | fills the level which can be used practically about manufacture yield, performance, and reliability, and the glass composition for aluminum electrodes applied to it.

  In order to achieve the above object, the present invention provides an electronic component in which an electrode having metal particles and a glass phase is formed on a silicon substrate, and the glass phase in the electrode is at least vanadium (V), antimony (Sb) and an oxide of boron (B), and further including at least one of oxides of phosphorus (P), tellurium (Te), barium (Ba) and tungsten (W), and the content of phosphorus Is less than 10% by mass in terms of oxide, and the lead (Pb) content in the glass is 1000 ppm or less, a conductive paste for aluminum electrodes, and a glass composition for aluminum electrodes I will provide a.

  According to the present invention, it contains oxides of vanadium, antimony and boron, and further contains at least one of oxides of phosphorus, tellurium, barium and tungsten, and the phosphorus content is 10% by mass in terms of oxide. By applying an oxide glass whose lead content in the glass is less than 1000 ppm to the electrode, it is possible to provide electronic parts that satisfy practically usable levels in terms of production yield, performance, and reliability, and conductivity for aluminum electrodes. It is possible to provide a conductive paste and a glass composition for an aluminum electrode.

It is a typical DTA curve obtained by differential thermal analysis (DTA) of a glass composition. It is a plane schematic diagram which shows an example of the light-receiving surface of a typical photovoltaic cell. It is a plane schematic diagram which shows one example of the back surface of a typical photovoltaic cell. It is a cross-sectional schematic diagram in the AA 'line in FIG. FIG. 4B is an enlarged schematic cross-sectional view of a portion I in FIG. 4A. It is a graph which shows the relationship between the glass content contained in an aluminum electrode, the curvature amount of a photovoltaic cell, and conversion efficiency. It is a graph which shows the relationship between the glass content contained in an aluminum electrode, and the specific resistance of the electrode. It is a cross-sectional schematic diagram which shows one example of a typical plasma display panel. It is a cross-sectional schematic diagram which shows the structural example of the multilayer wiring board (5 layers) of LTCC.

  The inventor includes oxides of vanadium, antimony and boron, and further includes one or more of oxides of phosphorus, tellurium, barium and tungsten, and the phosphorus content is less than 10% by mass in terms of oxide. When an electrode containing oxide glass with a lead content in the glass of 1000 ppm or less is baked and formed on a silicon substrate, the production yield, performance and reliability of electronic components using the silicon substrate are practically used. It has been found that it is possible to meet the level that can be used. For example, in a solar cell using a silicon substrate having a pn junction, when the oxide glass is contained in the aluminum electrode formed on the back surface of the cell on the p-type semiconductor side and fired, the glass does not contain lead. An oxide glass having the same level as that of a conventional lead oxide glass can be provided.

  In addition, according to the present invention, it is possible to provide an aluminum electrode conductive paste that satisfies practically usable levels in terms of production yield, performance, and reliability, and an aluminum electrode glass composition applied thereto. For example, specifically, in a solar cell using a silicon substrate having a pn junction, by forming an aluminum electrode containing the oxide glass on the p-type semiconductor side, the amount of warpage of the solar cell, conversion efficiency, and Electrode water resistance and adhesion are improved in a balanced manner, and a practically useful solar cell can be provided.

  Moreover, the moisture resistance and water resistance of the aluminum electrode, which could not be achieved with the lead oxide glass, could be improved. The present invention is based on this discovery.

  The oxide glass of the present invention contains oxides of vanadium, antimony and boron, and further contains one or more of oxides of phosphorus, tellurium, barium and tungsten, and the phosphorus content is 10 mass in terms of oxide. It is characterized by being less than%. If the phosphorus content is 10% by mass or more, the glass crystallizes and the fluidity decreases.

The preferable composition range of the oxide glass of the present invention is as follows: V ₂ O ₅ is 20 to 50% by mass, Sb ₂ O ₃ is 10 to 50% by mass, and B ₂ O ₃ is 10 to 40% in terms of the following oxides. %, TeO ₂ is 0 to 20% by mass, BaO is 0 to 20% by mass, and WO ₃ is 0 to 20% by mass. _Further, the total amount of _{V 2 O 5, Sb 2 O} 3 and _B 2 _{O 3} is 70 to 95 mass%. In the present invention, “20 to 50 mass%” means “20 mass% or more and 50 mass% or less”.

When V ₂ O ₅ is less than 20% by mass, reliability such as moisture resistance and water resistance of the aluminum electrode is lowered. On the other hand, when V ₂ O ₅ exceeds 50% by mass, the amount of warpage of the solar battery cell is increased, which affects the production yield of the cell.

When the Sb ₂ O ₃ content is less than 10% by mass, the amount of warpage of the solar battery cell is increased.

When B ₂ O ₃ is less than 10% by mass, the amount of warpage of the solar battery cell becomes large, while when it exceeds 40% by mass, the adhesion of the aluminum electrode is lowered.

P ₂ O ₅ , TeO ₂ , BaO and WO ₃ are used to facilitate the production of glass composed of V ₂ O ₅ , Sb ₂ O ₃ and B ₂ O ₃ , or to suppress crystallization of the produced glass. contains. However, when P ₂ O ₅ is 10% by mass or more, the amount of warpage of the solar battery cell is increased, and when TeO ₂ exceeds 20% by mass, the conversion efficiency of the solar battery cell is reduced, BaO or WO ₃ When each exceeds 20 mass%, the adhesiveness of an aluminum electrode will fall. Furthermore, when the total amount of V ₂ O ₅ , Sb ₂ O ₃ and B ₂ O ₃ is less than 70% by mass, the amount of warpage of the solar battery cell is increased, the conversion efficiency is decreased, or the reliability is increased. There was a tendency to decrease. On the other hand, if it exceeds 95% by mass, vitrification is very difficult and it is difficult to make uniform glass.

As a glass composition for an aluminum electrode that satisfies a practically usable level for reducing the amount of warpage of a solar battery cell, improving conversion efficiency, and electrode water resistance and adhesion, the preferred composition range is V in terms of the following oxide. ₂ O ₅ is 20 to 50 wt%, _Sb 2 _{O 3} is 10 to 50 _mass%, B 2 _{O 3} is 10 to 40 wt%, TeO ₂ 0 to 20% by weight, BaO is 0 to 20 wt%, and WO ₃ is 0 to 20% by mass, and the total amount of V ₂ O ₅ , Sb ₂ O ₃ and B ₂ O ₃ is 70 to 95% by mass. _Further, it is preferred that the total amount of _{P 2 O 5, TeO 2,} BaO, and WO ₃ is 5 to 30 mass%. The content of P ₂ O ₅ is more preferably 5% by mass or less.

  Furthermore, it is preferable that the glass content in the electrode formed in the photovoltaic cell is 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the metal particles. When the amount is less than 0.2 parts by mass, the amount of warpage of the solar battery cell is increased, and reliability such as moisture resistance and water resistance is also lowered.

  On the other hand, when it exceeds 2.0 parts by mass, the cell conversion efficiency tends to decrease. However, when it develops to the electrode of electronic parts other than a photovoltaic cell, it can contain glass to 15 mass%. When it exceeds 15 mass%, the electrical resistance of the aluminum electrode has increased. Furthermore, the glass has a transition point of 400 ° C. or lower, and the better the softening fluidity at 600 ° C., the higher the reliability such as the adhesion of the aluminum electrode to the substrate and the moisture resistance, and when applied to solar cells. Showed a small amount of warpage and high conversion efficiency.

  Furthermore, the glass of the present invention does not contain harmful lead (lead content is 1000 ppm or less). For this reason, it becomes possible to provide an environmentally friendly electronic component, a conductive paste for aluminum electrodes, and a glass composition for aluminum electrodes.

  Hereinafter, this embodiment will be specifically described. However, the present invention is not limited to the embodiments described here, and may be combined as appropriate.

Example 1
Table 1 shows the glass system examined in this example, its main component oxide and its characteristics. In Table 1, G-01 to 05 are examples of glass, and G-06 to 12 are comparative examples of glass. The “presence / absence of hazardous substances” in Table 1 was determined based on whether or not hazardous substances regulated by the RoHS Directive or Joint Industry Guideline (JIG) were included. The “transition point” was measured by differential thermal analysis (DTA) using each glass powder. The analysis temperature rising condition of DTA was 5 ° C./min in the atmosphere.

FIG. 1 shows an example of a typical DTA curve of glass. The starting temperature of the first endothermic peak is the transition point T _g , the peak temperature is the yield point M _g , and the starting temperature of the exothermic peak is the crystallization temperature T _cry . T _g and M _g are defined by viscosity, and T _{g corresponds} to 10 ^13.3 poise and M _g corresponds to 10 ¹¹ poise.

  The “softening fluidity” was evaluated by producing a green compact having a diameter of 10 mm and a thickness of 5 mm using each glass powder and heating the compact on a alumina substrate. The heating conditions were as follows: a green compact placed on an alumina substrate was placed in an electric furnace maintained at 600 ° C. in the atmosphere for 1 minute and then taken out. When the good fluidity was obtained by visual observation, “◯”, and the good fluidity was not obtained, but when it was soft, “△”, the compacted body was still softened If not, it was evaluated as “×”.

  In the glass shown in Table 1, the glass containing the hazardous substance was only G-12. This Pb—B—Si—O-based glass has been widely applied to various electrodes of electronic parts such as solar cells and plasma display panels. The transition point was as low as 320 ° C., and the fluidity at 600 ° C. was very good.

  As an alternative to the Pb—B—Si—O-based glass, G-11 is a Pb-free glass that has been widely studied and is beginning to be put into practical use. Although this Bi-B-Si-O-based glass does not contain harmful regulatory substances, the transition point was increased by 70 ° C. compared to G-12. Its softening fluidity was not as good as G-12 but was good.

  Glasses having a transition point higher than that of G-11 are V-Sb-BW-O G-04 having a transition point of 400 ° C and V-B-Zn-O-based G-10 having a transition point of 445 ° C. Yes, G-04 showed good fluidity, but G-10 remained soft and did not flow. Therefore, it was found that the transition point is preferably 400 ° C. or lower.

  V-Sb-BPO system G-01, V-Sb-B-Te-O system G-02, V-Sb-B-Ba-O system G having a transition point of 400 ° C. or lower -03, V-Sb-B-W-O system G-04, V-Sb-B-P-Ba-W-O system G-05, V-P-B-O system G-07, V-Te-PO-based G-08 and V-Te-Zn-Ba-O-based G-09 had good fluidity at 600 ° C. However, the V-Sb-BO-based G-06 had a transition point as low as 315 ° C., but did not soften and flow at 600 ° C. This was due to the significant occurrence of crystallization.

  On the other hand, the V-Sb-BO-based G-01 to 05 containing one or more of P, Te, Ba and W does not remarkably crystallize as G-06, and P, Te, Crystallization could be suppressed by the inclusion of Ba and W. For this reason, G-01 to 05 had good fluidity at 600 ° C.

  A conductive paste for an aluminum electrode was prepared using each glass shown in Table 1, and mounted on a solar battery cell to evaluate the amount of warpage, conversion efficiency and environmental conservation of the cell. A non-contact shape measuring device (manufactured by Kyoshin Denki Co., Ltd., model: KLS-2020) is used for evaluation of the amount of warpage of the cell, and a solar simulator (manufactured by Celic Co., Ltd., model: for model): XIL) was used. Moreover, the external appearance, adhesiveness, and water resistance of each formed aluminum electrode were also evaluated.

  The conductive paste for aluminum electrodes was produced for each glass of G-01 to 12 in Table 1. First, the glass was pulverized into particles of 3 μm or less by a stamp mill and a jet mill. As the aluminum particles, those having an average particle diameter of 3 μm prepared by an atomization method are used, and with respect to 100 parts by mass of the aluminum particles, 0.4 to 10 parts by mass of the glass particles of G-01 to 10, and G-11 and -12. In the glass particles, 0.7 parts by mass were mixed.

  The reason for changing the mixing amount of the glass particles is that the specific gravity of the glass of G-11 and -12 is about twice as large as that of the glass of G-01 to 10, and the glass content is desired to be approximately the same by volume. . A conductive paste for an aluminum electrode was prepared by adding 40 parts by mass of a solvent in which 2% by mass of a binder resin had been dissolved in advance to 100 parts by mass of these mixtures and kneading. Here, ethyl cellulose was used as the binder resin and α-terpineol was used as the solvent.

  The example applied to the photovoltaic cell as an electronic component according to the present invention using the produced conductive paste for an aluminum electrode will be described.

  FIG. 2 is a schematic plan view showing an example of a light receiving surface of a typical solar battery cell. 3 is a schematic plan view showing an example of the back surface thereof, FIG. 4A is a schematic cross-sectional view taken along the line AA ′ in FIG. 2, and FIG. 4B is an enlarged schematic cross-sectional view of the I portion in FIG. 4A. is there.

  As the semiconductor substrate 1 of the solar cell 10, a single crystal silicon substrate or a polycrystalline silicon substrate is usually used, and boron or the like is contained to form a p-type semiconductor. On the light receiving surface side, irregularities are formed by chemical etching or the like in order to suppress reflection of sunlight. The light receiving surface is doped with phosphorus or the like, and an n-type semiconductor layer 2 having a thickness of about 1 μm is formed. And the pn junction part is formed in the boundary with a p-type bulk part. Furthermore, an antireflection layer 3 such as silicon nitride is formed on the light receiving surface with a thickness of about 100 nm by vapor deposition or the like.

  Next, the formation of the light receiving surface electrode 4 formed on the light receiving surface, and the back electrode 5 and the output electrode 6 formed on the back surface will be described.

  Usually, the light-receiving surface electrode 4 and the output electrode 6 are formed using a conductive paste for silver electrodes containing silver particles and glass particles, and the back electrode 5 is formed by using aluminum containing aluminum particles and glass particles. Electrode paste for electrodes is used. Each conductive paste is applied on the antireflection layer 3 formed on the light receiving surface of the semiconductor substrate 1 or the back surface of the semiconductor substrate 1 by screen printing or the like.

  After the conductive paste is dried, it is baked at around 800 ° C. in the atmosphere to form each electrode. At that time, on the light receiving surface, the glass composition contained in the light receiving surface electrode 4 reacts with the antireflection layer 3 to electrically connect the light receiving surface electrode 4 and the n-type semiconductor layer 2.

  On the back surface, the aluminum component in the back electrode 5 reacts with the p-type semiconductor substrate 1 to form an aluminum-silicon alloy layer 8, and further, an aluminum diffusion layer (Back Surface) in which aluminum diffuses into the p-type semiconductor substrate 1. Field: BSF layer) 7 is formed. By forming this BSF layer 7, it is possible to prevent carriers generated inside the solar battery cell from recombining on the back surface, and to improve the performance of the solar battery cell. Further, the alloy layer 8 also has an effect of reflecting light incident on the solar battery cell 10 on the back surface and confining the light in the p-type semiconductor substrate 1, which is useful for improving the performance of the solar battery cell.

  In addition, in a photovoltaic cell, as a paste for the back electrode, conventionally, aluminum particles and low-melting glass are used, and a harmful Pb—B—Si—O-based or lead-free Bi—B—Si—O-based glass is used. A conductive paste containing a composition is used, but both glasses have a problem that reliability such as moisture resistance and water resistance of an aluminum electrode for a back electrode cannot be improved. Further, both glasses have a problem that foreign matter and irregularities are generated on the aluminum electrode, thereby reducing the yield. For this reason, the appearance of a glass composition for an aluminum electrode that achieves a level at which the performance, safety (lead-free), reliability, and productivity of solar cells can be practically used has been demanded.

  On the other hand, in the V-Te-PO system and the V-Te-Zn-Ba-O system, the water resistance of the aluminum electrode can be improved and the foreign matter and irregularities on the electrode can be remarkably reduced. There is a problem that the amount of warpage increases and the conversion efficiency further decreases. In the VPBO system, conversion efficiency can be improved, but the amount of warpage has not been reduced.

A solar battery cell according to the electronic component of the present invention was produced. As the semiconductor substrate 1, a p-type single crystal silicon substrate was used. The size of this silicon substrate was 125 mm square and the thickness was 200 μm. Next, in order to improve the light incident efficiency, a strongly alkaline aqueous solution composed of 1% sodium hydroxide (sodium hydroxide: NaOH) and 10% isopropyl alcohol (CH ₃ CH (OH) CH ₃ ) is used to receive light from the semiconductor substrate 1. The surface was etched to form irregularities. A liquid containing phosphorus pentoxide (P ₂ O ₅ ) is applied to the light receiving surface and heat-treated at 900 ° C. for 30 minutes to diffuse phosphorus (P) into the semiconductor substrate 1 and n having a thickness of about 1 μm on the light receiving surface. A type semiconductor layer 2 was formed. After removing phosphorus pentoxide, a silicon nitride film was uniformly formed on the n-type semiconductor layer 2 as the antireflection layer 3 with a thickness of about 100 nm. This silicon nitride film can be formed by a plasma CVD method using a mixed gas of silane (SiH ₄ ) and ammonia (NH ₃ ) as a raw material.

  Next, in order to form the light-receiving surface electrode 4, a conductive paste for silver electrode containing silver particles and glass particles is applied on the antireflection layer 3 in a grid shape by screen printing and dried at 150 ° C. for 10 minutes. I let you. Silver particles having an average particle diameter of about 2 μm were used. As the glass particles, V-Ag-P-Te-O-based low melting glass having an average particle diameter of about 2 μm and containing no harmful lead was used. The output electrode 6 formed on the back surface of the semiconductor substrate 1 was also applied by the screen printing method and dried using the same conductive paste for silver electrode as described above.

  Subsequently, for the back electrode 5, a conductive paste for aluminum electrode containing aluminum particles and glass particles was similarly applied and dried. As the conductive paste for an aluminum electrode, the conductive paste for an aluminum electrode produced using the above-described Example Glass G-01 to 05 and Comparative Example Glass G-06 to 12, respectively, was used. By rapidly heating to 800 ° C. in the atmosphere using a tunnel furnace and holding for 30 seconds, the light-receiving surface electrode 4, the back electrode 5 and the output electrode 6 were simultaneously fired and formed, and the solar battery cell 10 was produced. The film thickness of the light-receiving surface electrode 4 and the output electrode 6 after firing was about 20 μm, and the film thickness of the back electrode was about 40 μm.

  As described above, the warpage amount and the conversion efficiency of the solar battery cell 10 produced by changing the conductive paste for the aluminum electrode for the back electrode 5 were measured. Moreover, the produced photovoltaic cell 10 was also evaluated from the viewpoint of environmental conservation (presence of harmful regulated substances). Further, the appearance, adhesion and water resistance of the aluminum electrode formed for the back electrode 5 were also evaluated. Table 2 shows the evaluation results of the produced solar cells.

  The “sledge amount” in Table 2 is harmful but is based on the use of the proven Pb—B—Si—O-based G-12. The case was evaluated as “◯”, the case of being slightly larger as “Δ”, and the case of being extremely larger as “X”. In addition, “◯” described in the “Conversion Efficiency” column indicates that the cell conversion efficiency is 18.0% or more, “Δ” is 17.5% or more, less than 18.0%, and “X” is less than 17.5%. did.

  Regarding “environmental conservation”, it was determined whether or not the manufactured solar cell 10 contains a hazardous substance, and “No” was indicated when no harmful substance was included, and “X” was indicated when it was included. . In the case of lead, if it was 1000 ppm or less, it was rated as “◯”. The appearance of the aluminum electrode was evaluated by visual observation as “◯” when no surface foreign matter or large irregularities were observed, “△” when slightly recognized, and “×” when clearly recognized. did. The “adhesion” of the aluminum electrode was evaluated by a peel test. In the peel test, when a commercially available cellophane tape is attached to an aluminum electrode and peeled off, the aluminum electrode does not peel off, "○", when slightly peeled off, "△", when peeled off Is marked with “×”.

  “Water resistance” is a saturation type pre-shear cooker test using a pressure cooker tester (manufactured by Hirayama Manufacturing Co., Ltd., model: PC-242HSR2) under conditions of a temperature of 120 ° C., a pressure of 202 kPa, a humidity of 100% and a test time of 5 hours. It was evaluated as “◯” when the aluminum electrode was hardly discolored in appearance, “Δ” when it was partially blackened, and “x” when it was blackened all over. In addition, the above evaluation results are comprehensively examined and judged, and “◯” for practically good solar cells, “△” for insufficient solar cells, “ “×”.

  In Table 2, a glass having a warpage amount and conversion efficiency equivalent to that of a solar battery cell in which an aluminum electrode using Comparative Example Pb-B-Si-O-based glass G-12 is mounted as a back electrode is shown in Example G-01. -05 and Comparative Example G-06. In Comparative Examples G-07 to 11 other than those, at least one of them was inferior to G-12. G-12 has good warpage and conversion efficiency, but has a problem in environmental conservation because it contains lead, which is a hazardous substance. There were also problems with the appearance and water resistance of the aluminum electrode.

  In Comparative Example G-06, the amount of warpage and conversion efficiency were good, but the appearance and water resistance as an aluminum electrode were insufficient, and there was a problem in adhesion. This is presumably because the glass of G-06 is remarkably crystallized and does not have good softening fluidity. Glasses having practically good appearance, adhesion and water resistance as aluminum electrodes were Examples G-01 to 05 and Comparative Examples G-07 to 09. In consideration of the environment, both the amount of warpage and the conversion efficiency of the solar battery cells are good, and the glass that is practically good in terms of appearance, adhesion and water resistance as an aluminum electrode is shown in Examples G-01 to 05.

  These glasses contain vanadium (V), antimony (Sb) and boron (B), and at least one of oxides of phosphorus (P), tellurium (Te), barium (Ba) and tungsten (W). The oxide glass containing the above and having a phosphorus content of less than 10% by mass. Moreover, the transition point of these glasses was 400 degrees C or less, and had favorable fluidity | liquidity at 600 degreeC. Furthermore, these glasses do not contain harmful regulatory substances such as lead (lead content is 1000 ppm or less) and are sufficiently considered for the environment. The conductive paste for electrodes to which this glass is applied, and Even in an electronic component having an electrode formed of this conductive paste, the influence on the environmental load can be reduced.

  The RoHS regulation and joint industry guidelines stipulate that the lead content of electronic components is 1000 ppm or less. For this reason, each material constituting the electronic component should not contain intentionally harmful lead. However, lead may be mixed as an impurity, and it is preferable that each material constituting the electronic component is set to 1000 ppm or less as in the electronic component.

  The electrode glass according to the present invention contains vanadium (V), antimony (Sb), and boron (B), and among oxides of phosphorus (P), tellurium (Te), barium (Ba), and tungsten (W). Oxide glass containing at least one kind, developed on the premise of reducing the impact of environmental load, using conventional Pb-B-Si-O-based glass and Bi-B-Si-O-based glass It was found that the manufacturing yield, performance and reliability of the electronic parts satisfy the practically usable level at the same time.

  In the present embodiment, an example in which the present invention is applied to an aluminum electrode for the back surface of a solar battery cell using a silicon substrate has been described, but it is needless to say that any electrode other than an aluminum electrode can be applied as long as the electrode is formed on a silicon substrate. It can also be applied to electronic components other than solar cells.

(Example 2)
In Example 1, an oxide containing vanadium (V), antimony (Sb) and boron (B), and further containing one or more of phosphorus (P), tellurium (Te), barium (Ba) and tungsten (W). By applying oxide glass with a phosphorous content of less than 10% by mass to the electrodes, all of the production yield, performance and reliability of the electronic components must be satisfied at the same time, so that they can be used practically. I understood. Specifically, in a solar cell using a silicon substrate having a pn junction, an aluminum electrode including the oxide glass is formed on the p-type semiconductor side, thereby reducing the amount of warpage of the solar cell and the conversion efficiency. It was found that the improvement, the electrode water resistance and the adhesiveness all satisfy practically usable levels.

In this example, the composition of the oxide glass was examined in detail. Table 3 shows the composition and characteristics of the prepared glass. The glass preparation method of GA-01-24 shown in Table 3 is demonstrated. As the glass raw material, V ₂ O ₅ , Sb ₂ O ₃ , B ₂ O ₃ , P ₂ O ₅ , TeO ₂ , BaCO ₃ and WO ₃ were used, and each 200 to 300 g was blended and mixed. Place it in a platinum crucible, heat to 900-1000 ° C at a heating rate of 10 ° C / min in an electric furnace, hold it for 2 hours with stirring, and then pour it into a stainless steel plate to make GA-01-24 glasses, respectively. did. The produced glass was pulverized by a stamp mill and a jet mill until the average particle diameter became 2 μm or less, and each glass particle was obtained. The transition point and softening fluidity of the produced glass were evaluated in the same manner as in Example 1. The transition points of the produced glasses GA-01 to 24 were 400 ° C. or lower for any glass, and the softening fluidity at 600 ° C. was good.

  A conductive paste for an aluminum electrode was produced in the same manner as in Example 1 using glass particles of GA-01 to 24. However, aluminum alloy particles slightly containing magnesium (Mg) and zinc (Zn) were used for the aluminum particles. The method of making the particles was based on the atomization method as in Example 1. Nitrocellulose was used as the binder resin, and butyl carbitol acetate was used as the solvent. For comparison, in the same manner as in Example 1, for the aluminum electrodes each including Bi-B-Si-O-based glass G-11 and harmful Pb-B-Si-O-based glass G-12 shown in Table 1 Conductive paste was also produced and compared with the case of using GA-01-24.

  Using the produced conductive paste for aluminum electrodes, the solar cells shown in FIGS. 2 to 4 were produced and evaluated in the same manner as in Example 1. However, the semiconductor substrate 1 was a p-type polycrystalline silicon substrate having a 150 mm square and a thickness of 200 μm.

  Table 4 shows the evaluation results of the produced solar battery cells. In evaluating the “conversion efficiency” in Table 4, in this example, a polycrystalline silicon substrate having a cell conversion efficiency lower than that of a single crystal silicon substrate was used as the semiconductor substrate 1, so that it is very high as a polycrystalline silicon substrate. When the conversion efficiency was 16.0% or more, “◯”, 15.5% or more, less than 16.0%, “Δ”, and less than 15.5%, “X”. Other evaluations were performed in the same manner as in Example 1. However, in the “Comprehensive Evaluation”, “◎” for an excellent solar cell that showed good characteristics in any item, “○” for a solar cell superior in the past without any practical problem, It was evaluated as “Δ” for insufficient solar cells and “×” for practically problematic solar cells.

From the evaluation results of the solar cells in Table 4, preferable glass compositions for aluminum electrodes include vanadium (V), antimony (Sb), and boron (B), and also phosphorus (P), tellurium (Te), and barium. Good results were obtained over the entire composition of oxide glass containing one or more of (Ba) and tungsten (W) and having a phosphorus content of less than 10% by mass. In particular, it has been found that excellent solar cells can be obtained when GA-01 to 13 glass is used. The glass composition ranges in terms of the following oxides: V ₂ O ₅ is 20 to 50% by mass, Sb ₂ O ₃ is 10 to 50% by mass, B ₂ O ₃ is 10 to 40% by mass, and TeO ₂ is 0 to 0%. 20 mass%, BaO is 0 to 20 mass%, and WO ₃ is 0 to 20 mass%, and the total amount of V ₂ O ₅ , Sb ₂ O ₃ and B ₂ O ₃ is 70 to 95 mass%. It was.

  It goes without saying that the glass composition for an aluminum electrode having the above composition range can be effectively applied not only to solar cells but also to all electronic parts using a silicon substrate. Although it is particularly effective for aluminum electrodes, it can also be used for other than aluminum electrodes.

(Example 3)
In this example, the effect of the content of the glass composition for an aluminum electrode of the present invention in the aluminum electrode on the amount of warpage and conversion efficiency of the solar battery cell was examined in detail. For this glass, GA-06 in Example 2 shown in Table 3 and Table 4 was used. The glass content of GA-06 was examined in the range of 0 to 5 parts by mass with respect to 100 parts by mass of aluminum particles (0, 0.2, 0.4, 0.7, 1.0, 1.5, 2 0.0, 2.5, 3.0, 3.5, 4.0 and 5.0 parts by weight).

  Twelve types of conductive pastes for aluminum electrodes were produced in the same manner as in Example 2 except that the glass content was changed. Using the produced conductive paste for aluminum electrode as the back electrode, the solar cells shown in FIGS. 2 to 4 were produced in the same manner as in Example 2, and the amount of warpage and the conversion efficiency were measured.

  FIG. 5 shows the relationship between the glass content contained in the aluminum electrode, the amount of warpage of the solar battery cells, and the conversion efficiency. When glass was not contained in the aluminum electrode as the back electrode, the amount of warpage of the solar battery cell was large and the conversion efficiency was low. When only 0.2 part by mass of GA-06 glass was contained, the amount of warpage and the conversion efficiency were improved at once. It was found that the amount of warpage is small and the conversion efficiency is high in GA-06 glass in the range of 0.2 to 2.0 parts by mass, and good solar cells can be obtained. However, when it exceeded 2.0 mass%, both deteriorated.

  As mentioned above, it turned out that the range of 0.2-2.0 mass parts is preferable for the glass content in the aluminum electrode applied as a back surface electrode of a photovoltaic cell. Needless to say, this is not limited to solar cells but can be effectively applied to all electronic components using a silicon substrate. Although it is particularly effective for aluminum electrodes, it goes without saying that it can be used for other than aluminum electrodes.

Example 4
In this example, the influence of the glass content in the aluminum electrode on the specific resistance of the electrode was examined. As the aluminum particles, aluminum alloy particles containing 10% by mass of silver were used. These particles were produced by the atomization method as in Example 1. As the glass, GA-07 in Example 2 shown in Tables 3 and 4 was used. The glass content of GA-07 was examined in the range of 0 to 25 parts by mass with respect to 100 parts by mass of aluminum alloy particles (0, 0.2, 2.0, 5.0, 10.0, 15.0, 20.0 and 25.0 parts by mass). In the same manner as in Example 3, eight types of conductive pastes for aluminum electrodes were produced by changing the glass content. However, ethyl cellulose was used instead of nitrocellulose as the binder resin. The solvent is butyl carbitol acetate.

  The produced conductive paste for aluminum electrodes was applied to a single crystal silicon substrate by a screen printing method and dried at 150 ° C. for 10 minutes. Then, it put into the electric furnace, heated to 600 degreeC with the temperature increase rate of 10 degree-C / min in air | atmosphere, held for 10 minutes, and cooled the furnace. The film thickness of the aluminum electrode was about 20 μm. The specific resistance of the aluminum electrode formed on the silicon substrate was measured by the four probe method.

FIG. 6 shows the relationship between the glass content contained in the aluminum electrode and the specific resistance of the electrode. As shown in FIG. 6, when glass was not included in the aluminum electrode, the specific resistance was high (on the order of 10 ⁻⁴ Ωcm). When only 0.2 parts by mass of GA-07 glass was contained, the specific resistance decreased at a stretch.

The GA-07 glass achieved a specific resistance of the order of 10 ⁻⁵ Ωcm in the range of 0.2 to 15.0 parts by mass. When the content was 20 parts by mass or more, the specific resistance of the aluminum electrode was increased again (on the order of 10 ⁻⁴ Ωcm). From this, when the aluminum electrode is simply used as a wiring or applied to an electronic component not using a silicon substrate, the glass content in the electrode is preferably in the range of 0.2 to 15.0 parts by mass. I understood. In this example, the aluminum electrode was examined, but it goes without saying that it can also be used for an aluminum electrode and other electrodes.

(Example 5)
In this embodiment, an example applied to an electrode of a plasma display panel (PDP) will be described. FIG. 7 is a schematic cross-sectional view showing an example of a plasma display panel. Hereinafter, a description will be given with reference to FIG.

  First, a general plasma display panel will be described. In the plasma display panel 11, the front plate 12 and the back plate 13 are arranged to face each other with a gap of 100 to 150 μm, and the gap between each substrate (the front plate 12 and the back plate 13) is maintained by the partition 14. The peripheral portions of the front plate 12 and the back plate 13 are hermetically sealed with a sealing material 15, and the inside of the panel is filled with a rare gas.

  A display electrode 20 is formed on the front plate 12, a dielectric layer 23 is formed on the display electrode 20, and a protective layer 25 (for example, MgO) for protecting the display electrode 20 and the like from discharge on the dielectric layer 23. Vapor deposition film) is formed. An address electrode 21 is formed on the back plate 13, a dielectric layer 24 is formed on the address electrode 21, and a partition wall 14 for configuring the cell 16 is provided on the dielectric layer 24. The partition wall 14 is made of a structure obtained by sintering a material containing at least a glass composition and a filler at 500 to 600 ° C., and is usually a stripe-like or box-like structure. The address electrodes 21 on the back plate 13 are formed so as to be orthogonal to the display electrodes 20 on the front plate 12.

  A minute space (cell 16) delimited by the barrier ribs 14 is filled with a phosphor. The phosphor in the cell 16 is formed by filling the cell 16 with a phosphor paste and baking it at 450 to 500 ° C. One pixel is composed of three color cells, a cell filled with the red phosphor 17, a cell filled with the green phosphor 18, and a cell filled with the blue phosphor 19. Each pixel emits various colors according to signals applied to the display electrode 20 and the address electrode 21.

  The sealing material 15 is applied in advance to the peripheral edge of either the front plate 12 or the back plate 13 by a dispenser method, a printing method, or the like. The applied sealing material 15 may be temporarily fired simultaneously with the firing of the phosphors 17 to 19. This is because, by pre-baking the applied sealing material, air bubbles in the glass sealing portion can be remarkably reduced, and a highly reliable (that is, highly airtight) glass sealing portion is obtained.

  Sealing of the front plate 12 and the back plate 13 is performed by placing the front plate 12 and the back plate 13 separately produced so as to face each other while accurately aligning them and heating to 420 to 500 ° C. At this time, the gas inside the cell 16 is exhausted while heating, and a rare gas is sealed instead, thereby completing a plasma display panel as an electronic component. Note that the sealing material 15 may be in direct contact with the display electrode 20 or the address electrode 21 during temporary firing of the sealing material or glass sealing, but the electrode wiring material and the sealing material do not chemically react. It is important to be configured as described above.

  In order to light (emit light) the cell 16 of the plasma display panel, a voltage is applied between the display electrode 20 and the address electrode 21 of the cell 16 to be lighted to perform an address discharge in the cell 16 and plasma the rare gas. Excited to a state and accumulates wall charges in the cell. Next, by applying a certain voltage to the display electrode pair, display discharge occurs only in the cell where the wall charges are accumulated, and ultraviolet rays 22 are generated. Then, the phosphors 17 to 19 are caused to emit light using the ultraviolet rays 22 so that image information is displayed.

  Here, as the display electrode 20 and the address electrode 21, a silver thick film electrode wiring has been conventionally used in consideration of good electrical properties and oxidation resistance during manufacture. The display electrodes 20 and the address electrodes 21 can be formed by a sputtering method, but a printing method is advantageous for reducing the manufacturing cost. The dielectric layers 23 and 24 are usually formed by a printing method. Further, the display electrode 20, the address electrode 21, and the dielectric layers 23 and 24 formed by a printing method are generally baked in a temperature range of 550 to 620 ° C. in an oxidizing atmosphere.

  As described above, the silver thick electrode wiring has a problem that silver easily causes a migration phenomenon and a problem that a material cost is high. In order to solve these problems, it is preferable to change the electrode wiring of the silver thick film to the electrode wiring of the aluminum thick film or the aluminum alloy thick film. However, in order to change to the electrode wiring of the aluminum thick film or the aluminum alloy thick film, the specific resistance of the electrode wiring is low, the electrode wiring and the dielectric layer do not chemically react, and the vicinity of the formed electrode wiring It is necessary to satisfy the conditions such as that voids (bubbles etc.) are generated in the metal and the electric pressure resistance is not lowered.

  The aluminum alloy particles (Al-10% by mass Ag) used in Example 4 were prepared as metal particles to be included in the conductive paste for an aluminum electrode. Further, a binder resin and a solvent are further added and mixed to the powder mixed so that the glass particles of glass GA-07 used in Example 4 are 10 parts by mass when the aluminum alloy particles are 100 parts by mass. A conductive paste for an aluminum electrode was prepared by smelting. At this time, ethyl cellulose was used as the binder resin, and α-terpineol was used as the solvent.

  A plasma display panel according to the present invention was produced. First, the aluminum electrode conductive paste was applied to the entire surface of the front plate 12 and the back plate 13 by a screen printing method and dried at 150 ° C. in the atmosphere. Excess portions of the coating film were removed by photolithography to pattern the electrode wiring, and then baked in the atmosphere at 600 ° C. for 10 minutes to form the display electrodes 20 and the address electrodes 21.

  Next, the dielectric layers 23 and 24 were applied and fired at 560 ° C. for 30 minutes in the atmosphere. The front plate 12 and the back plate 13 produced as described above were arranged to face each other, and the outer edge portion was sealed with glass to produce a plasma display panel having a structure as shown in FIG.

  The electrode wiring (display electrode 20 and address electrode 21) formed using the conductive paste for aluminum electrode according to the present invention includes the interface between the display electrode 20 and the dielectric layer 23, the address electrode 21 and the dielectric layer 24. No generation of voids was observed at the interface, and a plasma display panel with a good appearance could be produced.

  Then, lighting experiment of the produced plasma display panel was conducted. The specific resistance of the display electrode 20 and the address electrode 21 did not increase. In addition, the panel could be turned on without deteriorating the electrical pressure resistance.

  Furthermore, no migration phenomenon as in the case of silver-thick electrode wiring occurred, and no other problems were found. From the above, it was confirmed that the conductive paste for aluminum electrodes of the present invention can be applied as an electrode wiring of a plasma display panel. Moreover, since it can be an alternative to expensive silver thick electrode wiring, it can greatly contribute to cost reduction.

(Example 6)
In this embodiment, an example in which the electronic component according to the present invention is applied to an electrode of a multilayer wiring board will be described. FIG. 8 is a schematic cross-sectional view showing a structural example before firing a multilayer wiring board (5 layers) of LTCC (Low Temperature Co-fired Ceramics). As shown in FIG. 8, the multilayer wiring board 30 is a wiring board on which wiring (conductive paste 31 for wiring) is formed three-dimensionally.

  Hereinafter, a description will be given with reference to FIG. The production of the multilayer wiring board is usually performed by the following procedure. First, a green sheet 32 containing glass powder, ceramic powder, and a binder is prepared, and a through hole 33 is opened at a desired position. The conductive paste 31 for wiring is applied to a desired wiring pattern by a printing method on the green sheet 32 having the through holes 33 opened, and the through holes 33 are also filled. If necessary, the conductive paste 31 for wiring is also applied to the back surface of the green sheet 32 by a printing method. When applying to the back surface of the green sheet 32, it is performed after drying the conductive paste 31 for wiring applied to the front surface.

  A plurality of green sheets 32 having a predetermined wiring pattern are stacked and integrally fired to produce an LTCC multilayer wiring board. In general, the firing condition is a temperature of about 900 ° C. in the atmosphere. As the conductive paste for wiring, silver conductive paste is usually used in consideration of good electrical properties and oxidation resistance during production.

  Studies are also being conducted on the use of inexpensive copper conductive paste that is advantageous for mitigating the migration phenomenon. However, since firing is performed in a nitrogen atmosphere for the purpose of preventing oxidation of copper particles, the conductive paste 31 and the binder in the green sheet 32 are not successfully removed (debindered), and a dense multilayer wiring board is obtained. It was difficult.

  In addition, in the conventional conductive paste using copper, the glass phase is easy to soften and flow in the portion where the green sheet 32 and the conductive paste 31 are in contact with each other during baking, and the copper particles are oxidized, and the specific resistance of the electrode wiring is reduced. There was an increasing problem. Furthermore, a void may be generated at the interface due to a chemical reaction with the glass phase.

  A multilayer wiring board according to the present invention was produced. As the conductive paste 31 for wiring, the conductive paste for aluminum electrode examined in Example 5 was used, and a multilayer wiring laminate as shown in FIG. For 30 minutes.

  When the specific resistance of the electrode wiring was measured on the produced multilayer wiring board, a value as designed was obtained. Next, cross-section observation of the produced multilayer wiring board was performed. As a result, the produced multilayer wiring board was fired sufficiently densely. Therefore, it seems that the specific resistance is also a value as designed. This was thought to be because the binder removal was completed almost completely during the lifting process. It was also confirmed that no voids were generated near the interface due to the chemical reaction between the glass phase and the electrode wiring. From the above, it was confirmed that the conductive paste for aluminum electrodes of the present invention can be applied as electrode wiring of a multilayer wiring board. Moreover, since it can be an alternative to expensive silver thick electrode wiring, it can greatly contribute to cost reduction.

DESCRIPTION OF SYMBOLS 1 ... p-type semiconductor substrate, 2 ... n-type semiconductor layer, 3 ... Antireflection layer, 4 ... Light-receiving surface electrode, 5 ... Back electrode, 6 ... Output electrode, 7 ... BSF layer, 8 ... Alloy layer, 10 ... Solar cell Cell: 11 ... Plasma display panel, 12 ... Front plate, 13 ... Back plate, 14 ... Partition wall, 15 ... Sealing material, 16 ... Cell, 17 ... Red phosphor, 18 ... Green phosphor, 19 ... Blue phosphor, DESCRIPTION OF SYMBOLS 20 ... Display electrode, 21 ... Address electrode, 22 ... Ultraviolet, 23, 24 ... Dielectric layer, 25 ... Protective layer, 30 ... Multi-layer wiring board, 31 ... Conductive paste for wiring, 32 ... Green sheet, 33 ... Through-hole .

Claims (19)

  An electrode having metal particles and a glass phase formed on a silicon substrate, wherein the glass phase in the electrode contains at least oxides of vanadium, antimony, and boron, and further includes phosphorus, tellurium, and barium And an oxide glass containing one or more of the oxides of Tangten, wherein the phosphorus content is less than 10% by mass in terms of oxide, and the lead content in the glass is 1000 ppm or less. Features electronic components. 2. The electronic component according to claim 1, wherein the glass phase in the electrode is 20 to 50 mass% of V ₂ O _{5, 10} to 50 mass% of Sb ₂ O ₃ , and B _{2 in} terms of the following oxides. 10 to 40% by mass of O _3, 0 to 20% by mass of TeO ₂ , 0 to 20% by mass of BaO, and 0 to 20% by mass of WO ₃ , and V ₂ O ₅ , Sb ₂ O ₃ and B An electronic component, wherein the total amount of ₂ O ₃ is 70 to 95% by mass. 3. The electronic component according to claim 1, wherein the P ₂ O ₅ content is 5% by mass or less. 4. The electronic component according to claim 1, wherein a total amount of the P ₂ O ₅ , TeO ₂ , BaO, and WO ₃ is 5 to 30% by mass.   5. The electronic component according to claim 1, wherein the metal particles in the electrode are aluminum or an aluminum alloy.   6. The electronic component according to claim 1, wherein the silicon substrate has a pn junction, and the electrode is formed on the p-type semiconductor surface.   The electronic component according to claim 1, wherein the glass phase in the electrode is contained at a ratio of 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the metal particles. An electronic component characterized by that.   The electronic component according to claim 1, wherein the electronic component is a solar battery cell.   Metal particles made of aluminum or an aluminum alloy and glass particles are conductive paste for an aluminum electrode dispersed in a solvent in which a binder resin is dissolved, and the glass particles include at least vanadium, antimony, and boron oxides, Furthermore, it contains one or more of oxides of phosphorus, tellurium, barium and tungsten, the phosphorus content is less than 10% by mass in terms of oxide, and the lead content in the glass is 1000 ppm or less. A conductive paste for aluminum electrodes characterized by The conductive paste for an aluminum electrode according to claim 9, wherein the glass phase in the electrode is 20 to 50% by mass of V ₂ O _{5 and 10} to 50% by mass of Sb ₂ O _{3 in} terms of the following oxides. %, B ₂ O ₃ is 10 to 40% by mass, TeO ₂ is 0 to 20% by mass, BaO is 0 to 20% by mass, and WO ₃ is 0 to 20% by mass, and V ₂ O ₅ and Sb ₂ A conductive paste for an aluminum electrode, wherein the total amount of O ₃ and B ₂ O ₃ is 70 to 95% by mass. The conductive paste for aluminum electrodes according to claim 9 or 10, wherein the amount of P ₂ O ₅ is 5% by mass or less. The aluminum electrode conductive paste according to any one of claims 9 to 11, wherein the total amount of the P ₂ O ₅ , TeO ₂ , BaO and WO ₃ is 5 to 30% by mass. Conductive paste for electrodes.   The conductive paste for an aluminum electrode according to any one of claims 9 to 12, wherein the glass particles are contained at a ratio of 0.2 to 15.0 parts by mass with respect to 100 parts by mass of the metal particles. A conductive paste for an aluminum electrode, characterized in that   The conductive paste for an aluminum electrode according to any one of claims 9 to 13, wherein the glass particles are contained at a ratio of 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the metal particles. A conductive paste for an aluminum electrode, characterized in that   The aluminum electrode conductive paste according to any one of claims 9 to 14, wherein the binder resin is ethyl cellulose or nitrocellulose, and the solvent is α-terpineol or butyl carbitol acetate. Conductive paste for electrodes.   A glass composition contained in an aluminum electrode, wherein the glass composition contains at least an oxide of vanadium, antimony, or boron, and further contains at least one oxide of phosphorus, tellurium, barium, and tungsten, The aluminum content is less than 10% by mass in terms of oxide, the lead content in the glass is 1000 ppm or less, the transition point is 400 ° C. or less, and it flows at 600 ° C. Glass composition. A aluminum electrode glass composition according to claim 16, wherein the glass phase in the electrodes in the following in terms of _oxide, V 2 _{O 5} is 20 to 50 wt%, _Sb 2 _{O 3} is 10 to 50 _wt%, B 2 _{O 3} is 10 to 40 wt%, TeO ₂ 0 to 20 wt%, a BaO is 0 to 20 wt%, and WO ₃ 0 to 20 wt%, yet _V 2 _O 5, The glass composition for an aluminum electrode, wherein the total amount of Sb ₂ O ₃ and B ₂ O ₃ is 70 to 95% by mass. The glass composition for an aluminum electrode according to claim 16 or 17, wherein the amount of P ₂ O ₅ is 5% by mass or less. The glass composition for an aluminum electrode according to any one of claims 16 to 18, wherein a total amount of the P ₂ O ₅ , TeO ₂ , BaO and WO ₃ is 5 to 30% by mass. A glass composition for an aluminum electrode.

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