JP2013236092A - Conductive composition and method for manufacturing solar battery using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive composition arranged so that an appropriate electrical performance of an electrode arranged by use of it, and the adhesion with a substrate can be ensured.SOLUTION: The conductive composition comprises: silver powder; lead-free glass powder containing BiO, BO, ZnO and alkaline earth metal oxide at a predetermined ratio; and a vehicle made of an organic material. The conductive composition forms an electrode 13 piercing a silicon nitride layer 11 and electrically connected with an n-type semiconductor layer 12. The glass powder has a basicity of 0.3 to 0.8, and a glass transition point of 300-450°C. The alkaline earth metal oxide includes one or more oxides selected from a group consisting of MgO, BaO, CaO, and SrO. The glass powder includes, as a minor component, one or more oxides selected from a group consisting of SiO, AlO, ZrO, and NiO, which accounts for more than 0 to 2 mol%.

Description

  The present invention mainly relates to a conductive composition for forming an electrode of a solar cell. More specifically, the present invention relates to a conductive composition for forming an electrode through a silicon nitride layer of a solar cell and a solar cell using the same.

  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 power generation solar cells 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 a silicon nitride layer in a linear or comb-like shape using a method such as screen printing. To do. In this conductive composition, silver powder and glass powder are contained. By baking this, the glass powder is first softened and flows to the interface between the electrode and the substrate. Next, the glass and the silicon nitride layer react to remove the silicon nitride film. Furthermore, conduction can be obtained by contact between the n-type semiconductor layer appearing at the interface and silver after the removal. And as a thing for making such an electrode, in order to reduce an environmental load, the composition which is Pb free and maintains electrical performance is also proposed (for example, refer patent document 1).

JP 2006-332032 A (specifications [0014] and [0015])

  Here, in the formation of the electrode referred to as “fire-through”, if a silicon nitride layer remains between the electrode obtained by firing the paste-like conductive composition and the n-type semiconductor layer, the electrode and the n-type are formed. There arises a problem that conduction with the semiconductor layer is not ensured. In addition, if the electrode obtained by firing the paste-like conductive composition penetrates the silicon nitride layer and also penetrates the n-type semiconductor layer, there is a problem that it does not operate as a solar cell. . As an index indicating the reactivity between silicon nitride and glass, an index called basicity of glass is known. Further, the glass in the paste needs to flow and reach the substrate interface during firing, and an index called a glass transition point Tg is known as an index indicating the fluidity of the glass during firing. Therefore, in order to realize “fire-through”, a paste containing glass having an appropriate range of basicity and glass transition point Tg is required. However, in the composition in Patent Document 1, the basicity is expected to be low, and after firing, the silicon nitride film remains and it is expected that conduction between the electrode and the n-type semiconductor cannot be obtained.

An object of the present invention is to obtain a conductive paste capable of realizing good “fire-through” by containing a glass having a basicity and a glass transition point Tg within an appropriate range. It is in providing the manufacturing method of a battery.

As shown in FIG. 1, the first aspect of the present invention is a silver powder, a lead-free glass powder containing Bi ₂ O ₃ , B ₂ O ₃ , ZnO and an alkaline earth metal oxide, and a vehicle made of organic matter. the by baking of including conductive composition is a conductive composition for forming an electrode 13 for conducting the n-type semiconductor layer 12 formed below the silicon nitride layer 11 through the silicon nitride layer 11 .
Its distinctive point, ratio der 10 mol% to 50 mol% of a glass powder of an alkaline earth metal oxide is, the basicity of the glass powder is not more 0.3 to 0.8, glass The transition point is 300 ° C. to 450 ° C., the ratio of Bi ₂ O _{3 in} the glass powder is 10 mol% or more and 65 mol% or less, and the ratio of B ₂ O _{3 in} the glass powder is 20 mol% or more and 50 mol%. 1 and a ratio of ZnO in the glass powder of 0.1 mol% or more and 50 mol% or less, and the alkaline earth metal oxide is selected from the group consisting of MgO, BaO, CaO, SrO Or 2 or more, and 1 or 2 or more selected from the group consisting of SiO ₂ , Al ₂ O ₃ , ZrO ₂ , and NiO as a trace component of the glass powder, more than 0 mol% and 2 mol% or less And In the present specification, the lead-free glass refers to a glass containing 2 mol% or less of PbO as a trace component.

  In the conductive composition of the first aspect, the ratio of the alkaline earth metal oxide in the glass powder is 10 mol% or more and 50 mol% or less, so that the glass powder is lead-free glass, The basicity of the glass powder can be increased. For this reason, the silicon nitride layer 11 in the solar cell 10 can be reliably penetrated by firing, and the adhesion of the obtained electrode can be ensured.

Moreover, although glass powder is lead-free glass, since the basicity of glass powder shall be 0.3 or more, the silicon nitride layer 11 in the solar cell 10 can be reliably penetrated by baking, and adhesion of the obtained electrode Sex can be secured. 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. And since the transition point of glass shall be 300 to 450 degreeC, glass will soften during baking and it will flow to an electrode and a board | substrate interface, and it will become possible for glass and a silicon nitride layer to react.

Moreover, the adhesiveness with respect to the n-type semiconductor layer 12 of the electrode 13 after baking can be improved.
A second aspect of the present invention is a method for producing a conductive composition according to the first aspect, wherein a solvent in which α-terpineol and butyl carbitol acetate are mixed, an ethyl cellulose resin, and a dispersant are mixed. In this method, the vehicle is prepared, the silver powder and the glass powder are mixed in the vehicle, and then the mixture is kneaded.

A third aspect of the present invention is a p-type semiconductor substrate 14, an n-type semiconductor layer 12 formed on the upper surface of the p-type semiconductor substrate 14, and a silicon nitride layer 11 formed on the n-type semiconductor layer 12. , a method for manufacturing a solar cell that to form a linear or comb-shaped electrodes 13 which conduct the first baking n-type semiconductor layer 12 through the silicon nitride layer 11 is formed by the conductive composition aspect It is.
In the solar cell of 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 can be increased.

As shown in FIGS. 1 and 2, the fourth 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 the 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, The step of forming the n-type semiconductor layer 12 on the upper surface of the p-type semiconductor substrate 14, the step of forming the silicon nitride layer 11 on the n-type semiconductor layer 12, and the conductivity of the first aspect on the silicon nitride layer 11. A step of printing the conductive composition in a linear or comb shape, a step of printing the Al paste 17 on the lower surface of the p-type semiconductor substrate 14, and the printed conductive composition and Al paste 1 The p-type semiconductor substrate 14 having a thickness of 700 to 975 ° C. is fired for 1 to 30 minutes to form an electrode 13 that penetrates the silicon nitride layer 11 and is electrically connected to the n-type semiconductor layer 12. And a step of forming a + layer 16, an Al—Si alloy layer 19, and an aluminum back electrode 18.

  In the conductive composition for forming the electrode according to the first aspect of the present invention, since the ratio of the alkaline earth metal oxide in the glass powder is 10 mol% or more and 50 mol% or less, the glass powder is lead-free glass. Nevertheless, the basicity of the glass powder can be increased. Further, when the basicity of the glass powder is set to 0.3 to 0.8 and the glass transition point is set to 300 ° C. to 450 ° C., the silicon nitride layer in the solar cell is surely penetrated by firing, and the obtained electrode 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.

In the manufacturing method of the third aspect of the solar cell of the present invention, order to form a linear or comb-shaped electrode by baking of such conductive compositions, electrodes and n-type semiconductor penetrating the silicon nitride layer Appropriate electrical conductivity with the layer is ensured and its performance can be increased.

In the manufacturing method according to the fourth aspect of the present invention, since the linear or comb-like electrode is formed using such a conductive composition, the silicon nitride layer in the solar battery cell is surely penetrated by firing. And ensuring the adhesion of the obtained electrode and avoiding a situation in which the obtained electrode is directly connected to the p-type semiconductor substrate beyond the n-type semiconductor layer. A solar cell having sufficient conductivity can be manufactured.

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, the best mode 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 contains silver powder, lead-free glass powder, and a vehicle made of organic matter. Here, the ratio of the silver powder in the composition is preferably 70% by mass or more and 95% by 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 75% 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 0.5-1.5 micrometers.

  The lead-free glass powder 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 2 parts by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the silver powder. The reason why the glass powder is limited to lead-free glass is to reduce the burden on the environment.

The lead-free glass powder contains Bi ₂ O ₃ , B ₂ O ₃ , ZnO and an alkaline earth metal oxide. The reason why the alkaline earth metal oxide is included is to increase the basicity of the glass powder. Here, the ratio of Bi ₂ O ₃ in the lead-free glass powder is 10 mol% or more and 65 mol% or less, the ratio of B ₂ O ₃ in the lead-free glass powder is 20 mol% or more and 50 mol% or less, and the ratio of ZnO in the Pb-free glass powder is Ru der 50 mol% or less than 0.1 mol%.

On the other hand, it is a requirement that the ratio of the alkaline earth metal oxide in the lead-free glass powder is 10 mol% or more and 50 mol% or less. Thereby, although the glass powder is lead-free glass, the basicity of the glass powder can be increased. For this reason, the silicon nitride layer 11 in the solar cell 10 can be reliably penetrated by firing, and the adhesion of the obtained electrode can be ensured. The basicity of the glass powder is Ru der 0.3 to 0.8.
Here, `` 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). ) ”Defines the basicity of the glass powder 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 above description, “basicity” can be said to represent the degree of dissolution in the glass melt, and if the basicity of the glass powder obtained by the above formula is 0.3 or more, By firing, the silicon nitride layer 11 in the solar cell 10 can be reliably penetrated, and the adhesion 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. The reason why such a range of basicity is required is that it is lead-free glass. The basicity is more preferably 0.3 or more and less than 0.8. The glass transition point of the glass powder is Ru 300 ° C. to 450 ° C. der. 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. Using a differential thermal balance (TG-DTA2000S, manufactured by Mac Science Co., Ltd.), a glass powder as a sample and a reference material were set on the differential thermal balance, and the room temperature was 10 ° C./min as a measurement condition. To 900 ° C. At this time, a curve (DTA curve) in which the temperature difference between the glass powder as a sample and the reference material was plotted against temperature was obtained. From the 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 may or may not contain thickeners, stabilizers, or other common additives.

Next, the manufacturing procedure of the solar cell using the conductive composition of the present invention will be described.
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% of IPA to an alkaline solution such as 1 to 5% sodium hydroxide 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 appropriate method. In the figure, an Al paste is used. As shown in FIG. 2, 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. Then, 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. Alternatively, a method of spin-coating a chemical solution containing a boron compound on the p-type semiconductor substrate 14 and then 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 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 can be 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 for several minutes to several tens of minutes in an infrared furnace having a temperature range of about 700 to 975 ° C. 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 penetrates 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, a vehicle in which 90 parts by mass of a solvent in which α-terpineol and butyl carbitol acetate were mixed at a ratio of 2: 1, 10 parts by mass of an ethyl cellulose resin and 40 parts by mass of a dicarboxylic acid-based dispersant as a dispersant was obtained. .
Next, 82.5% by mass of an Ag powder having an average particle size of 0.8 μm, an average particle size of 0.7 μm, a composition of Bi ₂ O ₃ : 45 mol%, B ₂ O ₃ : 25 mol%, ZnO : 5 mol%, BaO: 25 mol%, basicity of 0.530, glass transition point of 368 ° C. glass powder 2.5% by mass, and the above vehicle 15% by mass, A conductive paste was obtained by kneading with a three-roll mill. In addition, the qualitative and quantitative analysis of the glass powder used at this time was performed by the following method. First, in order to perform a qualitative analysis of the main component, a glass powder was placed on a lithium tetraborate green compact and pressed to prepare a green compact with a sample, and then a wavelength dispersive trend X-ray analyzer (ZSX-Primus II) Measurement was performed using a type RIGAKU). Furthermore, in order to analyze trace components, the same amount of carbon powder and glass powder were weighed and mixed, and then measured using a DC arc solid-state emission analyzer (manufactured by AURORA ThermoJararush).

  Next, in order to perform quantitative analysis on the elements detected by qualitative analysis, 1 g of sample was dissolved in a mixed acid of 10 ml of concentrated nitric acid and 3 ml of 50% aqueous hydrofluoric acid to prepare a sample for analysis (pressure oxidation) Decomposition), and measurement was performed using an inductively coupled plasma (ICP) emission spectrometer (manufactured by SPS3100 SII Nanotechnology).

As a result, 1.9 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected in total in the glass powder as trace components in addition to the main component, but PbO was not detected.

Next, an electrode-attached substrate was produced as follows.
Fabricate a substrate in which a phosphorous-doped n layer is formed on one side of a 20 mm square, 0.2 mm thick n-type Si wafer by 0.4 μm, and a 0.07 μm thick silicon nitride film is formed on the n layer by plasma CVD. did. On the substrate, the conductive paste was screen-printed using a screen plate having a mesh size of 325 and an emulsion thickness of 30 μm having a pattern of a line width of 100 μm and a space width of 2 mm, and a width of about 120 μm. A printed pattern having a thickness of about 25 μm was formed. Further, using a screen plate having a solid pattern of 20 mm on the back surface of the substrate and a mesh plate of # 325 and an emulsion thickness of 15 μm, aluminum paste was screen-printed to form a back electrode pattern having a thickness of 10 μm. Then, it dried for 10 minutes at 150 degreeC with the belt-type drying furnace. Further, using an infrared lamp heating furnace, the temperature was raised from room temperature to 800 ° C. in 15 seconds in 15 seconds, then cooled to room temperature in 15 seconds, and the printed pattern was baked to obtain a substrate with electrodes. This substrate with electrodes was designated as Example 1.

<Example 2>
The composition of the glass powder is Bi ₂ O ₃ : 60 mol%, B ₂ O ₃ : 25 mol%, ZnO: 5 mol%, BaO: 10 mol%, the basicity is 0.443, and the glass transition point is 334. A conductive paste was prepared in the same manner as in Example 1 except that one having a temperature of 0 ° C. was used, and a substrate with electrodes was prepared in the same procedure as in Example 1 using the paste. This substrate with electrodes was designated as Example 2. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, 1.7 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected in total in addition to the main components in the glass powder, but PbO was not detected.

<Example 3>
The composition of the glass powder is Bi ₂ O ₃ : 15 mol%, B ₂ O ₃ : 25 mol%, ZnO: 5 mol%, BaO: 55 mol%, basicity is 0.758, and glass transition point is 437. A conductive paste was prepared in the same manner as in Example 1 except that one having a temperature of 0 ° C. was used, and a substrate with electrodes was prepared in the same procedure as in Example 1 using the paste. This substrate with electrodes was designated as Example 3. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, 1.9 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected in total in addition to the main components in the glass powder, but PbO was not detected. It was included.

<Example 4>
The composition of the glass powder is Bi ₂ O ₃ : 40 mol%, B ₂ O ₃ : 45 mol%, ZnO: 5 mol%, BaO: 10 mol%, the basicity is 0.338, and the glass transition point is 416. A conductive paste was prepared in the same manner as in Example 1 except that one having a temperature of 0 ° C. was used, and a substrate with electrodes was prepared in the same procedure as in Example 1 using the paste. This substrate with electrodes was designated as Example 4. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, 1.5 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected as trace components in addition to the main component in the glass powder, but PbO was not detected.

<Example 5>
The composition of the glass powder is Bi ₂ O ₃ : 45 mol%, B ₂ O ₃ : 25 mol%, ZnO: 5 mol%, SrO: 25 mol%, the basicity is 0.487, and the glass transition point is 379. A conductive paste was prepared in the same manner as in Example 1 except that one having a temperature of 0 ° C. was used, and a substrate with electrodes was prepared in the same procedure as in Example 1 using the paste. This substrate with electrodes was designated as Example 4. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, 1.7 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected in total in addition to the main components in the glass powder, but PbO was not detected.

<Example 6>
As a glass powder, the composition is Bi ₂ O ₃ : 45 mol%, B ₂ O ₃ : 25 mol%, ZnO: 5 mol%, CaO: 25 mol%, basicity is 0.447, and glass transition point is 362. A conductive paste was prepared in the same manner as in Example 1 except that one having a temperature of 0 ° C. was used, and a substrate with electrodes was prepared in the same procedure as in Example 1 using the paste. This substrate with electrodes was designated as Example 4. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, 1.6 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected in total in addition to the main components in the glass powder, but PbO was not detected.

<Example 7>
As a glass powder, the composition is Bi ₂ O ₃ : 45 mol%, B ₂ O ₃ : 25 mol%, ZnO: 5 mol%, MgO: 25 mol%, basicity is 0.394, and glass transition point is 351. A conductive paste was prepared in the same manner as in Example 1 except that one having a temperature of 0 ° C. was used, and a substrate with electrodes was prepared in the same procedure as in Example 1 using the paste. This substrate with electrodes was designated as Example 4. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, 1.9 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected in total in addition to the main components in the glass powder, but PbO was not detected.

<Comparative Example 1>
As glass powder, the composition is Bi ₂ O ₃ : 75 mol%, B ₂ O ₃ : 20 mol%, ZnO: 2.5 mol%, BaO: 2.5 mol%, basicity is 0.428, glass A conductive paste was prepared in the same manner as in Example 1 except that one having a transition point of 290 ° C. was used, and a substrate with an electrode was prepared by the same procedure as in Example 1 using the paste. This substrate with electrodes was designated as Comparative Example 1. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, 1.6 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected in total in addition to the main components in the glass powder, but PbO was not detected.

<Comparative example 2>
The composition of the glass powder is Bi ₂ O ₃ : 40 mol%, B ₂ O ₃ : 50 mol%, ZnO: 5 mol%, BaO: 5 mol%, basicity is 0.289, and glass transition point is 425. A conductive paste was prepared in the same manner as in Example 1 except that one having a temperature of 0 ° C. was used, and a substrate with electrodes was prepared in the same procedure as in Example 1 using the paste. This substrate with electrodes was designated as Comparative Example 2. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, 1.6 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected in total in addition to the main components in the glass powder, but PbO was not detected.

<Comparative Example 3>
The composition of the glass powder is Bi ₂ O ₃ : 5 mol%, B ₂ O ₃ : 30 mol%, ZnO: 60 mol%, BaO: 5 mol%, the basicity is 0.429, and the glass transition point is 485. A conductive paste was prepared in the same manner as in Example 1 except that one having a temperature of 0 ° C. was used, and a substrate with electrodes was prepared in the same procedure as in Example 1 using the paste. This substrate with electrodes was designated as Comparative Example 3. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, a total of 1.8 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected as minor components in addition to the main component in the glass powder, but PbO was not detected.

<Comparative example 4>
As glass powder, the composition is Bi ₂ O ₃ : 2.5 mol%, B ₂ O ₃ : 25 mol%, ZnO: 2.5 mol%, BaO: 70 mol%, basicity is 0.901, glass A conductive paste was prepared in the same manner as in Example 1 except that one having a transition point of 466 ° C. was used, and a substrate with electrodes was prepared by using the paste in the same procedure as in Example 1. This substrate with electrodes was designated as Comparative Example 4. In addition, the analysis similar to Example 1 was performed about the glass powder used at this time. As a result, a total of 1.4 mol% of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO were detected as minor components in addition to the main component in the glass powder, but PbO was not detected.

<Comparison test and evaluation>
The front and back electrodes of the substrates with electrodes in Examples 1 to 7 and Comparative Examples 1 to 4 were connected by an I / V tester, and series resistance values were measured. For 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 standard. The case where the value was higher than the value and the I / V curve did not show the diode characteristics was regarded as unacceptable. The evaluation results are shown in Table 1 together with the glass composition.

表１から明らかなように、実施例１〜７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、且つ、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１〜４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、且つ、Ｉ・Ｖ曲線がダイオード特性を示さないことが判る。
よって、無鉛ガラス粉末である場合には、アルカリ土類金属酸化物のガラス粉末中の比率が１０モル％以上５０モル％以下であって、その塩基度が０．３〜０．８である導電性組成物を用いることにより、太陽電池における窒化ケイ素層を貫通する電極とｎ型半導体層との適切な導通性を確保できることが判る。

As is clear from Table 1, in Examples 1 to 7, 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 to 4, 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, in the case of lead-free glass powder, the ratio of the alkaline earth metal oxide in the glass powder is 10 mol% or more and 50 mol% or less, and the basicity is 0.3 to 0.8. It can be seen that by using the conductive composition, appropriate electrical conductivity between the electrode penetrating the silicon nitride layer in the solar cell and the n-type semiconductor layer can be secured.

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

Claims (4)

Through a silver powder, a lead-free glass powder containing _{Bi 2 O 3, B 2 O} 3, ZnO and alkaline earth metal oxides, by baking of a vehicle made of an organic substance including electrically conductive composition, a silicon nitride layer in the conductive composition for forming the electrodes of the solar cell to be electrically connected to the n-type semiconductor layer which is formed under the silicon nitride layer and,
Ri ratio der 10 mol% to 50 mol% of the glass powder of the alkaline earth metal oxide,
The basicity of the glass powder is 0.3 or more and 0.8 or less, and the glass transition point is 300 ° C. to 450 ° C.,
The ratio of Bi ₂ O _{3 in} the glass powder is from 10 mol% to 65 mol%, the ratio of B ₂ O _{3 in} the glass powder is from 20 mol% to 50 mol%, and The ratio of ZnO in the glass powder is 0.1 mol% or more and 50 mol% or less,
The alkaline earth metal oxide includes one or more selected from the group consisting of MgO, BaO, CaO, and SrO,
The conductive composition comprising 1 or 2 or more selected from the group consisting of SiO ₂ , Al ₂ O ₃ , ZrO ₂ and NiO as a trace component of the glass powder in excess of 0 mol% and 2 mol% or less. object. A method for producing a conductive composition according to claim 1, comprising:
The vehicle is prepared by mixing a solvent in which α-terpineol and butyl carbitol acetate are mixed, an ethyl cellulose resin, and a dispersant, and the silver powder and the glass powder are mixed into the vehicle, and then the mixture is kneaded. A method for producing a conductive composition. and p-type semiconductor base plate, and the n-type semiconductor layer formed on the upper surface of the p-type semiconductor base plate, a silicon nitride layer formed on the n-type semiconductor layer, the conductive composition of claim 1 Symbol placement straight or method of manufacturing a solar cell that to form a comb-shaped electrodes which are formed conducting with the n-type semiconductor layer through the silicon nitride layer by baking of the object. subjected to p-type semiconductor base etching treatment with an acid or alkali plate, and removing the slices damage of the p-type semiconductor base plate,
And textured etching the p-type semiconductor base plate, forming a texture structure on the upper surface of the p-type semiconductor base plate,
By thermally diffusing an n-type dopant on the upper surface of the p-type semiconductor base plate, forming an n-type semiconductor layer on the upper surface of the p-type semiconductor base plate,
Forming a silicon nitride layer on the n-type semiconductor layer,
A step of printing a conductive composition of claim 1 Symbol placement in a straight line or a comb shape on the silicon nitride layer,
The lower surface of the p-type semiconductor base plate, and a step of printing the Al paste,
By firing the p-type semiconductor base plate having the printed conductive composition and Al paste, to form a conductive electrode conducting with the n-type semiconductor layer through the silicon nitride layer, p ⁺ layer , Al-Si alloy layer, the manufacturing method of the solar cell and a step of forming an aluminum back surface electrodes.

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