JP5567785B2 - Conductive composition and method for producing solar cell using the same - Google Patents

Description

The present invention mainly relates to a conductive composition for forming an electrode of a solar cell. More particularly, a method for manufacturing a solar cell using the conductive composition Mono及 Bisore for forming the electrodes through the silicon nitride layer of the solar cell.

  Conventionally, what has a p-type semiconductor substrate as a solar cell is known. A pn junction is created in the solar cell, and radiation of an appropriate wavelength toward the pn junction serves as a source of external energy that generates hole-electron pairs in the solar cell. And due to the potential difference present at the pn junction, the holes and electrons cross this junction in the opposite direction, thereby causing a current flow that can deliver power to the external circuit. Yes. And most solar cells having such a configuration take the form of a metallized silicon wafer, i.e. a silicon wafer provided with conductive metal contacts.

  Here, most solar cells for power generation currently used on the earth are silicon solar cells. In this solar cell, a p-type semiconductor substrate is used, an n-type semiconductor layer is formed on the upper surface of the p-type semiconductor substrate to form a pn junction, and a silicon nitride layer is formed on the n-type semiconductor layer as an antireflection coating. Furthermore, it forms. An electrode that penetrates the silicon nitride layer and is electrically connected to the n-type semiconductor layer is formed on the silicon nitride layer. Here, the process for producing such silicon solar cells is generally aimed at maximizing simplification and minimizing manufacturing costs to enable mass production. Yes. For this reason, the electrode is formed by a procedure called “fire-through”.

  A specific procedure called “fire-through” for forming this electrode is to first print a paste-like conductive composition on the silicon nitride layer in a linear or comb-like shape using a method such as screen printing. To do. This conductive composition contains silver powder, and the silver is infiltrated into the silicon nitride layer by baking the paste. Next, an electrode obtained by firing the paste penetrates the silicon nitride layer and is brought into conduction with the n-type semiconductor layer under the silicon nitride layer. And the conductive paste containing boron is proposed as a thing for making such an electrode (for example, refer patent document 1).

JP 2006-93433 A (specification [0014], FIG. 3)

  However, in the formation of the electrode called “fire-through”, if a silicon nitride layer remains between the electrode obtained by firing the slurry-like conductive composition and the n-type semiconductor layer, the adhesion of the electrode There is a problem that cannot be secured. On the other hand, when the silver in the paste-like conductive composition that penetrates into the silicon nitride layer during firing further penetrates into the n-type semiconductor layer under the silicon nitride layer, the electrode directly conducts with the p-type semiconductor substrate. As a result, there arises a problem that sufficient conductivity between the electrode and the n-type semiconductor layer cannot be obtained. For this reason, in order to increase the performance of the solar cell, it is necessary to ensure appropriate electrical conductivity between the electrode penetrating the silicon nitride layer and the n-type semiconductor layer.

An object of the present invention is to provide a method of manufacturing a solar cell using the conductive composition Mono及 Bisore capable of ensuring adhesion of an appropriate electrical performance and substrate of the resulting electrode by firing .

As shown in FIG. 1, the first aspect of the present invention is printed on a silicon nitride layer formed on an n-type semiconductor layer on the upper surface of a p-type semiconductor substrate and is 1 to 30 at a temperature of 700 to 975 ° C. It is a conductive composition for forming an electrode that penetrates the silicon nitride layer and is electrically connected to the n-type semiconductor layer by baking for a minute .

The characteristic point is that a solvent in which α-terpineol and butyl carbitol acetate are mixed, an ethyl cellulose resin, and a vehicle in which a dicarboxylic acid dispersant is mixed are prepared, and silver powder, PbO—SiO ₂ —B ₂ O ₃ are mixed. The basicity of the main component is 0.5 or more and 0.8 or less, the glass transition point is 300 ° C. to 450 ° C., and trace components such as Fe ₂ O ₃ , TiO ₂ , SiO ₂ , Al ₂ O ₃ , A glass powder containing one or two or more oxides selected from the group consisting of ZrO ₂ and NiO in an amount of more than 0 mol% and not more than 5 mol% in a composition of the silver powder of 70 mass% or more and 95 to be less than mass%, and the glass powder to contain 10 parts by mass 1 part by mass or more with respect to the silver powder 100 parts by weight, were mixed in the vehicle, this obtained by kneading the mixture When A.

In the conductive composition described in the first aspect, the basicity of the glass powder containing PbO—SiO ₂ —B ₂ O ₃ as a main component is 0.5 or more. The silicon nitride layer 11 can be reliably penetrated, and the adhesion of the obtained electrode can be ensured. Moreover, since the basicity is 0.8 or less, it is possible to avoid a situation in which the electrode obtained by baking directly conducts with the p-type semiconductor substrate beyond the n-type semiconductor layer 12, and the obtained electrode Sufficient conductivity of the n-type semiconductor layer 12 can be obtained.

As shown in FIGS. 1 and 2, the second aspect of the present invention is the step of performing etching treatment with acid or alkali on the p-type semiconductor substrate 14 to remove slice damage of the p-type semiconductor substrate 14; A step of performing a texture etching process on the p-type semiconductor substrate 14 to form a texture structure on the upper surface of the p-type semiconductor substrate 14, and thermally diffusing an n-type dopant on the upper surface of the p-type semiconductor substrate 14, A step of forming an n-type semiconductor layer 12 on the upper surface of the p-type semiconductor substrate 14, a step of forming a silicon nitride layer 11 on the n-type semiconductor layer 12, and a first viewpoint on the silicon nitride layer 11. A step of printing the conductive composition in a linear or comb shape, a step of printing an Al paste 17 on the lower surface of the p-type semiconductor substrate 14, and the printed conductive composition and Al page. The p-type semiconductor substrate 14 having the gate 17 is baked at a temperature of 700 to 975 ° C. for 1 to 30 minutes, thereby forming the electrode 13 penetrating the silicon nitride layer 11 and conducting to the n-type semiconductor layer 12. , P <+> layer 16, Al-Si alloy layer 19, and the process of forming the aluminum back surface electrode 18, and the manufacturing method of a solar cell.

In the method described in the second aspect, the electrode 13 is electrically connected to the n-type semiconductor layer 12 without passing through the silicon nitride layer 11 using the conductive composition based on the first aspect under the firing conditions. In addition, there is no direct conduction with the p-type semiconductor substrate 14.

According to the third aspect, an n-type semiconductor layer 12 is formed on the upper surface of a p-type semiconductor substrate 14, a silicon nitride layer 11 is formed on the n-type semiconductor layer 12, and a conductive property is formed on the silicon nitride layer 11. Production of a solar cell that forms a linear or comb-like electrode that passes through the silicon nitride layer 11 and is electrically connected to the n-type semiconductor layer 12 by printing the composition in a linear or comb-like shape and then baking the composition. a method, wherein the conductive composition is a combination formed product is obtained according to the process described first aspect.

In the method for manufacturing a solar cell described in the third aspect , appropriate electrical conductivity between the electrode 13 penetrating the silicon nitride layer 11 and the n-type semiconductor layer 12 is ensured, and the performance of the solar cell is increased. it can.

Conductive composition for forming an electrode of the present invention, a vehicle obtained by mixing the dispersant with α- terpineol and solvent and ethyl cellulose resin mixed with butyl carbitol acetate was prepared, and the following silver powder and below the glass powder After mixing with the vehicle, this mixture is kneaded and manufactured. The manufacturing method is such that the ratio of silver powder in the composition is 70 mass% or more and 95 mass% or less, and the glass powder is 100 mass parts of silver powder. On the other hand, it is contained in an amount of 1 to 10 parts by mass, and 1 or 2 selected from the group consisting of Fe ₂ O ₃ , TiO ₂ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO as a trace component of the glass powder. The basicity of the glass powder mainly containing PbO—SiO ₂ —B ₂ O ₃ is 0.5 or more and 0.8 or less, and the glass oxide contains more than 0 mol% and 5 mol% or less. Roll Since it is a requirement that the transition point is 300 ° C. to 450 ° C., the silicon nitride layer in the solar cell can be surely penetrated by firing, and the obtained electrode is secured and the obtained electrode is secured. It is possible to avoid a situation where the semiconductor layer directly conducts with the p-type semiconductor substrate beyond the n-type semiconductor layer, and sufficient conductivity between the electrode and the n-type semiconductor layer can be obtained. And in the manufacturing method of a solar cell provided with the linear or comb-like electrode formed by baking of such an electroconductive composition, appropriate electroconductivity with the electrode which penetrates a silicon nitride layer, and an n-type semiconductor layer Is ensured and the performance of the solar cell can be increased.

It is sectional drawing of the solar cell using the electroconductive composition of this invention embodiment. It is sectional drawing corresponding to FIG. 1 which shows the state before baking of the solar cell.

  Next, an embodiment for carrying out the present invention will be described with reference to the drawings.

As shown in FIG. 1, the conductive composition of the present invention has an electrode 13 that penetrates the silicon nitride layer 11 in the solar cell 10 and is electrically connected to the n-type semiconductor layer 12 formed under the silicon nitride layer 11. It is for forming. The conductive composition includes silver powder, glass powder mainly composed of PbO—SiO ₂ —B ₂ O ₃ , and a vehicle made of organic matter. Here, the ratio in the composition of silver powder is 70 mass% or more and 95 mass% or less. This is because when the silver powder is less than 70% by mass, the electric resistance of the electrode 13 after firing becomes high and there is a risk of deteriorating the characteristics of the solar cell 10, and when it exceeds 95% by mass, the coatability is increased. This is because of a tendency to decrease. Here, the ratio of the silver powder in the composition is more preferably 80% by mass or more and 90% by mass or less. Further, the silver powder has an average particle diameter of 0.1 to 2.0 μm obtained by a laser diffraction scattering method from the viewpoint of the coating property and the uniformity of the coating film. Is preferable, and it is still more preferable that it is 0.5-1.0 micrometer.

The glass powder contains PbO—SiO ₂ —B ₂ O ₃ as a main component, and is contained in an amount of 1 to 10 parts by mass with respect to 100 parts by mass of the silver powder. This glass powder is added in order to improve the adhesion in the electrode 13 after firing, and when the glass powder is less than 1 part by mass with respect to 100 parts by mass of the silver powder, the electrode 13 after firing. If the glass powder exceeds 10 parts by mass with respect to 100 parts by mass of silver powder, segregation of the glass may occur. The glass powder is more preferably 3 parts by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the silver powder.

  The basicity of the glass powder is 0.5 or more and 0.8 or less. This `` basicity '' was proposed by Kenji Morinaga et al., For example, his book `` K. Morinaga, H. Yoshida And H. Takebe: J. Am Cerm. Soc., 77, 3113 (1994) ''. The basicity of the glass powder is defined using the following formula. This excerpt is shown below.

"Coupling force between M _i -O oxide M _i O cation - given by the following equation as an oxygen ion attraction between A _i.

A _i = Z _i · Z ₀₂₋ / (r _i + r ₀₂₋ ) ² = Z _i · 2 / (r _i +1.40) ²
Z _i : valence of cation, oxygen ion is 2
R _i : cation radius (Å), oxygen ion is 1.40Å
The A _i of the inverse B _i a (1 / A _i) a single-component oxide M _i O oxygen donating ability.

B _i ≡1 / A _i
When the _{B i B CaO = 1, B} SiO2 = to 0 and the normalized, B _i of each single component oxides - index is given. When the _Bi -index of each component is expanded to a multi-component system by the cation fraction, the B-index (= basicity) of a glass oxide melt having an arbitrary composition can be calculated. B = Σn _i・ B _i
n _i : Cation fraction The basicity defined in this way represents the oxygen donating ability as described above, and the larger the value, the easier it is to donate oxygen and the easier transfer of oxygen with other metal oxides. . "
As is clear from the description of the above-mentioned book by Kenji Morinaga, “basicity” can be said to represent the degree of dissolution in the glass melt, and the basicity of the glass powder obtained by the above formula is 0.5. If it is above, the silicon nitride layer 11 in the solar cell 10 can be reliably penetrated by baking, and the adhesiveness of the obtained electrode can be ensured. On the other hand, when the basicity of the glass powder is 0.8 or less, the electrode obtained by firing is obtained by avoiding a situation where the electrode is directly connected to the p-type semiconductor substrate beyond the n-type semiconductor layer 12. Sufficient conductivity between the electrode and the n-type semiconductor layer 12 can be obtained.

  Moreover, the glass transition point of the glass powder is 300 to 450 ° C., and preferably 300 to 400 ° C. By setting the glass transition point to 300 ° C. to 450 ° C., the glass softens during firing and flows to the interface between the electrode and the substrate, and the glass and the silicon nitride layer can react.

  The glass transition point Tg was measured as follows. Differential thermal balance TG-DTA2000s manufactured by Mac Science Co., Ltd. was used, and the temperature was raised to 900 ° C. at a heating rate of 10 ° C./min as measurement conditions. At this time, the graph which plotted the temperature difference with a reference material with respect to temperature was obtained. From the graph (DTA curve) thus obtained, the intersection of the tangent along the base line and the tangent along the curve from the first inflection point to the second inflection point was defined as the glass transition point Tg.

  The vehicle is for forming a viscous composition called a “paste” having hydrodynamic properties suitable for printing, and is required to be an organic substance. Examples of this vehicle include those obtained by dissolving ethyl cellulose, acrylic resin, alkyd resin, and the like in a solvent. Other examples include polymers including ethyl hydroxyethyl cellulose, wood rosin, a mixture of ethyl cellulose and a phenol resin, a polymethacrylate of a lower alcohol, and a monobutyl ether of ethylene glycol monoacetate. The vehicle appropriately contains a thickener, a stabilizer, or other general additives.

  Next, the manufacturing method of the solar cell using the electrically conductive composition of this invention is demonstrated.

  As shown in FIG. 2, first, a p-type semiconductor substrate 14 is prepared. When a Si substrate is used as this substrate, either a single crystal substrate or a polycrystalline substrate may be used. In this case, in order to remove the slice damage of the substrate 14 sliced to a desired thickness first, the surface is mixed with hydrofluoric acid (hydrofluoric acid) and nitric acid or an alkaline solution such as sodium hydroxide for about 10 to 20 μm. Etching is preferred. In the case of using a single crystal substrate, it is preferable to form a texture structure on the upper surface in order to suppress reflection on the upper surface. This texture structure can be formed by adding 3 to 10% isopropyl alcohol to an alkaline solution such as sodium hydroxide having a concentration of 1 to 5% and etching at around 80 ° C. for 30 to 60 minutes. Further, by forming an oxide film of several hundreds nm on the lower surface of the p-type semiconductor substrate 14 before performing the texture etching, only the light receiving surface can have a texture structure.

A p ⁺ layer 16 is formed on the lower surface of the p-type semiconductor substrate 14 by a conventionally known method. As shown in FIG. 2, when Al paste is used, the Al paste 17 is printed on the lower surface of the p-type semiconductor substrate 14 and then fired. The Al paste 17 is converted from the dried state to the aluminum back electrode 18 shown in FIG. 1 by firing. During firing, the boundary between the Al paste 17 on the back surface and the back surface of the p-type semiconductor substrate 14 forms an alloy state, and an Al—Si alloy layer 19 is formed at the boundary after firing. A p ⁺ layer 16 is formed on the Al-Si alloy layer 19 on the p-type semiconductor substrate 14 side.

As a method for forming the p ⁺ layer 16, the Al paste 17 is not necessarily used, and another method may be used. For example, the p ⁺ layer 16 may be formed on the lower surface of the p-type semiconductor substrate 14 by vapor phase diffusion of BBr ₃ at 700 to 1000 ° C. for several tens of minutes. When the p ⁺ layer 16 is formed by this method, it is necessary to previously form an oxide film or the like on the light receiving surface side so as not to diffuse to the light receiving surface side. Also, a method of spin-coating a chemical solution containing a boron compound on the p-type semiconductor substrate 14 and annealing at 700 to 1000 ° C. or a method of diffusing and forming the p ⁺ layer 16 by ion implantation may be used.

On the other hand, an n-type semiconductor layer 12 is formed on the upper surface of the p-type semiconductor substrate 14. The n-type semiconductor layer 12 can be formed by thermal diffusion of phosphorus (P) or the like. In this case, phosphorus oxychloride (POCl ₃ ) is generally used as a phosphorus diffusion source. For example, after the semiconductor layer 12 is formed on the entire surface of the p-type semiconductor substrate 14 and the upper surface thereof is protected with a resist or the like, it is removed from most surfaces by etching so that the n-type semiconductor layer 12 remains only on the upper surface. Next, the n-type semiconductor layer 12 can be formed on the upper surface of the p-type semiconductor substrate 14 by removing the resist using an organic solvent or the like. The n-type semiconductor layer 12 preferably has a sheet resistivity of about several tens of ohms per square centimeter and a thickness of about 0.3 to 0.5 μm.

  Next, the silicon nitride layer 11 as an antireflection coating is formed on the n-type semiconductor layer 12. The silicon nitride layer 11 is formed on the n-type semiconductor layer 12 by a process such as plasma enhanced chemical vapor deposition (CVD) to a thickness of about 700 to 900 mm.

  Then, using the conductive composition described above, an electrode 13 that penetrates the silicon nitride layer 11 and is electrically connected to the n-type semiconductor layer 12 formed thereunder is formed by a procedure called “fire-through”. Specifically, as shown in FIG. 2, the paste 21 made of the conductive composition described above is printed on the silicon nitride layer 11 in a linear or comb shape. Screen printing is preferable for printing the paste 21, but other printing methods may be used. Thereafter, firing is performed in an infrared furnace having a temperature range of about 700 to 975 ° C. for 1 to 30 minutes, preferably for several minutes to several tens of minutes. By this baking, silver in the paste 21 penetrates into the silicon nitride layer 11, and as shown in FIG. 1, the electrode 13 obtained by baking passes through the silicon nitride layer 11 and below the silicon nitride layer 11. Conductive with the n-type semiconductor layer 12. Thus, the electrode 13 obtained by firing can ensure the appropriate electrical performance and adhesion between the n-type semiconductor layer 12.

  Thus, the p-type semiconductor substrate 14, the n-type semiconductor layer 12 formed on the upper surface of the p-type semiconductor substrate 14, the silicon nitride layer 11 formed on the n-type semiconductor layer 12, and the A solar cell 10 including a linear or comb-like electrode 13 that penetrates the silicon nitride layer 11 and is electrically connected to the n-type semiconductor layer 12 is obtained.

  In the solar cell 10 configured as described above, as a result of ensuring appropriate electrical conductivity between the electrode 13 penetrating the silicon nitride layer 11 and the n-type semiconductor layer 12, the performance can be increased.

  Next, examples of the present invention will be described in detail together with comparative examples.

<Example 1>
A conductive paste was prepared as follows.

  First, 13 parts by mass of a solvent in which α-terpineol and butyl carbitol acetate were mixed at a ratio of 2: 1 was mixed with 1.5 parts by mass of an ethyl cellulose resin and 0.5 part by mass of a dicarboxylic acid-based dispersant as a dispersant. Got the vehicle.

Next, 82.5 parts by mass of Ag powder having an average particle size of 0.8 μm as the conductive powder, 0.5% basicity as the lead-based glass frit, and an average particle size of 0.4 ° C. having a glass transition point of 400 ° C. After mixing 2.5 parts by mass of 5 μm PbO—SiO ₂ —B ₂ O ₃ with 15 parts by mass of the vehicle, the mixture is kneaded with three rolls to obtain a conductive paste in which Ag powder and glass powder are dispersed. It was. The glass powder used at this time contained a total of 0.2 mol% of Fe ₂ O ₃ , TiO ₂ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO as trace components.

  Next, a substrate with an electrode was produced as follows using the paste.

The surface of a 25 mm square, 0.6 mm thick p-type polycrystalline Si substrate was etched with an aqueous solution of sodium hydroxide containing isopropyl alcohol to form a texture having irregularities of 2 to 3 μm. Next, after applying a phosphorus compound (POCl ₃ ) to one of the substrates, the n-type Si layer having a thickness of about 0.4 μm was formed by heating at 800 ° C. for several minutes. Subsequently, a silicon nitride film having a thickness of 0.07 μm was formed by plasma CVD. Thereafter, the conductive paste is formed on a silicon nitride film on the substrate surface by using a screen plate having an emulsion thickness of 30 μm and having a comb-shaped pattern in which six patterns each having a line width of 100 μm and a length of 17 mm are arranged with a space width of 2 mm. Screen printing was performed to form a printed pattern having a width of about 120 μm and a thickness of about 25 μm, and then dried at 150 ° C. for 10 minutes in a belt-type drying furnace. Further, on the back surface of the substrate, an Al paste was screen printed using a screen plate having a 20 mm square solid pattern and an emulsion thickness of 30 μm to form a printing pattern of about 20 mm square and a thickness of about 20 μm. Then, it was dried at 150 ° C. for 10 minutes in a belt type drying furnace. Furthermore, using an infrared lamp heating furnace, the temperature was raised from room temperature to 800 ° C. in 15 seconds in 15 seconds, and then cooled to room temperature in 15 seconds. A solar cell substrate on which an electrode was formed was obtained. A solar cell substrate using the paste containing the glass powder having a basicity of 0.5 and a glass transition point of 400 ° C. was designated as Example 1.

<Example 2>
Example 1 except that the basicity of the lead-based glass frit in the conductive paste is 0.6 and the glass transition point is PbO—SiO ₂ —B ₂ O ₃ having an average particle diameter of 0.5 μm and 360 ° C. Similarly, a conductive paste was prepared, and then a solar cell substrate with a comb-shaped electrode formed on the front surface and an Al electrode formed on the back surface was obtained under the same conditions and procedures as in Example 1. A solar cell substrate using the paste containing the glass powder having a basicity of 0.6 and a glass transition point of 360 ° C. was designated as Example 2.

<Example 3>
Example 1 except that the basicity of the lead-based glass frit in the conductive paste is 0.7 and the glass transition point is PbO—SiO ₂ —B ₂ O ₃ having an average particle size of 0.5 μm and a glass transition point of 340 ° C. Similarly, a conductive paste was prepared, and then a solar cell substrate with a comb-shaped electrode formed on the front surface and an Al electrode formed on the back surface was obtained under the same conditions and procedures as in Example 1. A solar cell substrate using a paste containing glass powder having a basicity of 0.7 and a glass transition point of 340 ° C. was designated as Example 3.

<Example 4>
Example 1 except that the basicity of the lead-based glass frit in the conductive paste is 0.8, and the glass transition point is PbO—SiO ₂ —B ₂ O ₃ having an average particle size of 0.5 μm and a glass transition point of 320 ° C. Similarly, a conductive paste was prepared, and then a solar cell substrate with a comb-shaped electrode formed on the front surface and an Al electrode formed on the back surface was obtained under the same conditions and procedures as in Example 1. Thus, a solar cell substrate using a paste containing glass powder having a basicity of 0.8 and a glass transition point of 320 ° C. was defined as Example 4.

<Comparative Example 1>
Example 1 except that the basicity of the lead-based glass frit in the conductive paste is 0.4 and the glass transition point is PbO—SiO ₂ —B ₂ O ₃ having an average particle diameter of 0.5 μm and a glass transition point of 620 ° C. Similarly, a conductive paste was prepared, and then a solar cell substrate with a comb-shaped electrode formed on the front surface and an Al electrode formed on the back surface was obtained under the same conditions and procedures as in Example 1. Thus, the solar cell substrate using the paste containing the glass powder having a basicity of 0.4 and a glass transition point of 620 ° C. was defined as Comparative Example 1.

<Comparative example 2>
Example 1 except that the basicity of the lead-based glass frit in the conductive paste is 0.9 and the glass transition point is 290 ° C. and PbO—SiO ₂ —B ₂ O ₃ having an average particle size of 0.5 μm. Similarly, a conductive paste was prepared, and then a solar cell substrate with a comb-shaped electrode formed on the front surface and an Al electrode formed on the back surface was obtained under the same conditions and procedures as in Example 1. Thus, the solar cell substrate using the paste containing the glass powder having a basicity of 0.9 and a glass transition point of 290 ° C. was defined as Comparative Example 2.

<Comparison test and evaluation>
The front and back electrodes of the substrates with electrodes in Examples 1 to 4 and Comparative Examples 1 and 2 were connected by an I / V tester, and series resistance values were measured. Regarding the evaluation, the DC resistance value calculated from the I / V curve is lower than the reference value, and the case where the I / V curve shows the diode characteristic is passed, and the DC resistance value calculated from the I / V curve is the reference value. The case where it was higher and the IV curve did not show diode characteristics was rejected. The evaluation results are shown in Table 1 together with the glass composition.

表１及び表２から明らかなように、実施例１〜４にあっては、Ｉ・Ｖ曲線から算出される直流抵抗値が基準値より低く、かつＩ・Ｖ曲線がダイオード特性を示している。これに対して、比較例１〜２では、Ｉ・Ｖ曲線から算出される直流抵抗値が基準値より高く、かつＩ・Ｖ曲線がダイオード特性を示さないことが判る。

As is clear from Tables 1 and 2, in Examples 1 to 4, the DC resistance value calculated from the I / V curve is lower than the reference value, and the I / V curve shows the diode characteristics. . On the other hand, in Comparative Examples 1 and 2, it can be seen that the DC resistance value calculated from the IV curve is higher than the reference value, and the IV curve does not show diode characteristics.

  Therefore, by using a conductive composition in which the basicity of the glass powder is 0.5 to 0.8 and the glass transition point is 300 to 450 ° C., relatively high power generation efficiency in the solar cell substrate is obtained. It can be seen that the present invention is effectively established.

DESCRIPTION OF SYMBOLS 10 Solar cell 11 Silicon nitride layer 12 N type semiconductor layer 13 Electrode 14 P type semiconductor substrate

Claims (3)

Printed on the silicon nitride layer formed on the n-type semiconductor layer on the upper surface of the p-type semiconductor substrate, and baked at a temperature of 700 to 975 ° C. for 1 to 30 minutes, thereby penetrating the silicon nitride layer and the n a conductive composition for forming an electrode for conduction type semiconductor layer,
A vehicle in which a solvent in which α-terpineol and butyl carbitol acetate are mixed, an ethyl cellulose resin, and a dicarboxylic acid-based dispersant are prepared,
Silver powder _{and, PbO-SiO 2 -B 2 O} 3 Fe 2 as basicity be less than 0.5 and not more than 0.8 A 300 ° C. to 450 ° C. is glass transition point trace as major components A glass powder containing 0 mol% or more and 5 mol% or less of one or more oxides selected from the group consisting of O ₃ , TiO ₂ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO, The vehicle so that the ratio of the silver powder in the composition is 70% by mass or more and 95% by mass or less, and the glass powder is contained in an amount of 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the silver powder. A conductive composition obtained by kneading the mixture after mixing . performing an etching treatment with acid or alkali on the p-type semiconductor substrate to remove slice damage of the p-type semiconductor substrate;
Applying a texture etching process to the p-type semiconductor substrate to form a texture structure on the upper surface of the p-type semiconductor substrate;
Forming an n-type semiconductor layer on the upper surface of the p-type semiconductor substrate by thermally diffusing an n-type dopant on the upper surface of the p-type semiconductor substrate;
Forming a silicon nitride layer on the n-type semiconductor layer;
Printing the conductive composition according to claim 1 in a linear or comb-like pattern on the silicon nitride layer;
Printing an Al paste on the lower surface of the p-type semiconductor substrate;
An electrode that is electrically connected to the n-type semiconductor layer through the silicon nitride layer by baking the p-type semiconductor substrate having the printed conductive composition and Al paste at a temperature of 700 to 975 ° C. for 1 to 30 minutes. And a step of forming a p ⁺ layer, an Al—Si alloy layer, and an aluminum back electrode. An n-type semiconductor layer is formed on the upper surface of the p-type semiconductor substrate, a silicon nitride layer is formed on the n-type semiconductor layer, and a conductive composition is printed linearly or comb-toothed on the silicon nitride layer. Thereafter, baking is performed to form a linear or comb-like electrode that penetrates the silicon nitride layer and is electrically connected to the n-type semiconductor layer.
Method of manufacturing a solar cell, wherein the conductive composition is a set formed of claim 1, wherein.

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