JP6336139B2 - Solar cell element and manufacturing method thereof - Google Patents

Description

Cross-reference of related applications

  This international application claims the priority of Japanese Patent Application No. 2015-018529 (filed on Feb. 2, 2015). The disclosure content of the above Japanese patent application is incorporated into this international application.

  The present invention relates to a solar cell element and a manufacturing method thereof.

  For example, as disclosed in International Publication No. 2009/157079, a PERC (Passivated Emitter and Rear Cell) structure has been studied as a highly efficient solar cell element using a crystalline silicon substrate. Currently, further improvement in photoelectric conversion efficiency is required for the solar cell elements as described above.

A solar cell element according to an aspect of the present invention includes a semiconductor substrate having a first surface and a second surface located on the opposite side of the first surface, and a passivation film disposed on the second surface of the semiconductor substrate. And a first electrode in contact with the semiconductor substrate in a state of penetrating the passivation film at a plurality of locations. The solar cell element includes a second electrode that is linearly disposed in contact with the semiconductor substrate in a state of penetrating the passivation film at a position that does not overlap the first electrode in plan view, and the second electrode A third electrode covering a part of the electrode, each of the passivation film and the first electrode, and in contact with each of the first electrode and the second electrode without passing through the passivation film ; It has. In the solar cell element, the first electrode and the third electrode are made of a material mainly composed of aluminum, and the electrical resistivity of the first electrode is smaller than the electrical resistivity of the third electrode.

A method for manufacturing a solar cell element according to an embodiment of the present invention is a method for manufacturing a solar cell element having the above-described configuration, and includes a conductive paste I mainly composed of aluminum, a conductive paste mainly composed of silver, After the first electrode and the second electrode are formed through the passivation film, the conductive paste II of the same material as the conductive paste I is formed at a temperature lower than that of the conductive paste I. Firing is performed to form the third electrode.

FIG. 1 is a plan view showing an external appearance of a first surface side of a solar cell element according to an embodiment of the present invention. FIG. 2 is a plan view showing an appearance of the second surface side of the solar cell element according to the embodiment of the present invention. FIG. 3 is a cross-sectional view showing a cross-sectional state taken along line X-X ′ of FIGS. 1 and 2. 4A (a) to 4 (e) are enlarged cross-sectional views illustrating a method for manufacturing a solar cell element according to an embodiment of the present invention. 4B (f) to (h) are enlarged cross-sectional views illustrating a method for manufacturing a solar cell element according to an embodiment of the present invention. FIG. 5 is a cross-sectional view showing another cross-sectional state of the solar cell element according to the embodiment of the present invention. FIG. 6 is a cross-sectional view showing a cross-sectional state of a solar cell element according to another embodiment. FIG. 7 is a cross-sectional view showing a cross-sectional state of a solar cell element according to another embodiment.

  Hereinafter, embodiments of a solar cell element and a manufacturing method thereof according to the present invention will be described in detail with reference to the drawings. In addition, drawing is shown typically and a part is abbreviate | omitted in sectional drawing etc.

<Solar cell element>
1-3 shows a solar cell element 10 according to the present embodiment. The solar cell element 10 has a first surface 10a located mainly on the front (front) side where light is incident, and a second surface 10b located on the opposite side (back side) of the first surface 10a.

  Similarly, the substrate 1, which is a semiconductor substrate used for the solar cell element 10, also has a first surface 1 a and a second surface 1 b located on the opposite side of the first surface. The substrate 1 is a first semiconductor layer 2 that is a one-conductivity type (for example, p-type) semiconductor region, and a reverse conductivity type (for example, n-type) semiconductor region that is provided on the first surface 1a side of the first semiconductor layer 2. And a second semiconductor layer 3.

  Hereinafter, a solar cell element using p-type silicon as the substrate 1 (or the first semiconductor layer 2) will be described as an example.

  The p-type polycrystalline or single crystal silicon substrate has a thickness of about 100 to 250 μm, for example. If the shape of the substrate 1 is, for example, a substantially rectangular shape with one side of about 150 to 200 mm in plan view, a solar cell module in which a large number of solar cell elements 10 having the substrate 1 are arranged can be easily produced. However, the planar shape and size of the substrate 1 are not limited. When the first semiconductor layer 2 is p-type, an impurity such as boron or gallium is contained in the silicon substrate as a dopant element.

  The second semiconductor layer 3 is provided on the first surface 10 a side in the first semiconductor layer 2. The second semiconductor layer 3 is a semiconductor layer having a conductivity type opposite to that of the first semiconductor layer 2 (n-type in the case of the present embodiment), and the second semiconductor layer 3 is formed between the first semiconductor layer 2 and the second semiconductor layer 3. A pn junction is formed between them. The second semiconductor layer 3 can be formed, for example, by containing an impurity such as phosphorus as a dopant element on the first surface 1a side of the substrate 1.

  As shown in FIG. 3, light reflection can be reduced by providing a fine uneven structure (texture) for reducing the reflectance of the irradiated light on the first surface 1 a side of the substrate 1. The height of the convex portion of the texture is about 0.1 to 10 μm, and the length between the tops of the adjacent convex portions is about 0.1 to 20 μm.

  Moreover, the solar cell element 10 includes an antireflection film 5 and a surface electrode 7 on the first surface 10a side. Further, a back electrode 8 and a passivation film 4 are provided on the second surface 10b side.

  The antireflection film 5 can improve the photoelectric conversion efficiency of the solar cell element 10 by reducing the reflectance of the light irradiated on the first surface 10 a of the solar cell element 10. The antireflection film 5 is made of, for example, an insulating film such as a silicon oxide, aluminum oxide, or silicon nitride layer, or a laminated film thereof. As the refractive index and thickness of the antireflection film 5, a refractive index and a thickness that can realize a low reflection condition with respect to light in a wavelength range that can be absorbed by the substrate 1 and contribute to power generation out of sunlight may be appropriately adopted. . For example, when the antireflection film 5 made of silicon nitride is formed by PECVD (Plasma Enhanced Chemical Vapor Deposition), the refractive index is about 1.8 to 2.5 and the thickness is about 60 to 120 nm. can do.

  As shown in FIG. 1, the surface electrode 7 is an electrode provided on the first surface 1 a side of the substrate 1. The surface electrode 7 has several (for example, three in FIG. 1) bus bar electrodes 7a and a plurality of linear finger electrodes 7b.

  The bus bar electrode 7 a is an electrode for taking out electricity obtained by photoelectric conversion to the outside of the solar cell element 10 on the first surface 1 a of the substrate 1. The bus bar electrode 7a has a width of about 1 to 3 mm, for example. At least a part of the bus bar electrode 7a is electrically connected so as to cross the finger electrode 7b substantially perpendicularly.

  The finger electrode 7b is an electrode for collecting carriers generated by light incident on the substrate 1 and transmitting the collected carriers to the bus bar electrode 7a. The finger electrodes 7b have a plurality of linear shapes, have a width of about 30 to 200 μm, for example, and are provided with an interval of about 1 to 3 mm. In addition, you may provide the sub finger electrode 7c of the shape similar to the finger electrode 7b in the peripheral part of the board | substrate 1, and may electrically connect the finger electrodes 7b.

  The surface electrode 7 can be formed by, for example, applying a conductive paste containing silver as a main component into a desired shape by screen printing or the like and then baking it. Here, the main component indicates that the ratio of the total component is 50% or more, and the same applies to the following description. The thickness of the surface electrode 7 formed by firing the conductive paste is about 10 to 40 μm.

  The passivation film 4 is formed on substantially the entire surface of the substrate 1 on the second surface 1b side. As a result, the defect position causing the carrier recombination at the interface between the substrate 1 and the passivation film 4 can be reduced and the recombination of minority carriers can be reduced. The passivation film 4 is made of, for example, an insulating film such as silicon oxide, aluminum oxide, or silicon nitride layer, or a laminated film thereof. The thickness of the passivation film 4 is about 10 to 200 nm. If the first semiconductor layer 2 is a p-type layer as in this embodiment, a film having a negative fixed charge, such as an aluminum oxide layer formed by an ALD (Atomic Layer Deposition) method, is used as the passivation film 4. Good. In the passivation film 4 having a negative fixed charge, electrons which are minority carriers move away from the interface between the substrate 1 and the passivation film 4 due to the electric field effect, so that recombination of minority carriers is reduced. In order to obtain the same effect, if the second semiconductor layer 3 is an n-type layer, a film having a positive fixed charge such as silicon nitride formed by PECVD or the like is used as the antireflection film 5. Good.

  The back electrode 8 is an electrode provided on the second surface 1b side of the substrate 1, and includes a first electrode 8a, a second electrode 8b, and a third electrode 8c, as shown in FIGS.

  The first electrode 8a penetrates the passivation film 4 at many places. One end of the first electrode 8 a abuts on the second surface 1 b of the substrate 1, and carriers can be collected on the second surface 1 b of the substrate 1. The other end of the first electrode 8a is in contact with the third electrode 8c. The shape of the first electrode 8a may be a dot (dot) shape or a belt shape (linear shape). The diameter (or width) of the first electrode 8a is about 60 to 500 μm. Moreover, when the 1st electrode 8a consists of a several electrode area | region, the pitch of adjacent electrode areas should just be about 0.3-2 mm.

  The second electrode 8 b is an electrode for taking out electricity obtained by photoelectric conversion to the outside of the solar cell element 10 on the second surface 1 b of the substrate 1. The second electrode 8b is linearly disposed on the passivation film 4 at a position that does not overlap the first electrode 8a in plan view. Alternatively, the second electrode 8b is linearly disposed on the substrate 1 in a state where the second electrode 8b does not overlap the first electrode 8a in plan view and penetrates the passivation film 4. The thickness of the 2nd electrode 8b is about 10-30 micrometers, and the width | variety is about 1-7 mm. A plurality of second electrodes 8b are formed and arranged in a straight line. Moreover, the 2nd electrode 8b contains the silver which can be soldered as a main component so that the tab copper foil which is a ribbon-shaped connection conductor can be connected easily in a solar cell module manufacturing process. The second electrode 8b can be formed by, for example, applying a conductive paste containing silver as a main component in a desired shape by screen printing or the like, and then baking it. The shape of the second electrode 8b may be a shape that conducts with the third electrode 8c. For example, it is possible to form a protrusion on the rectangular electrode body shown in FIG. 2 and to cover the protrusion with the third electrode 8c.

  The third electrode 8c is in contact with each of the first electrode 8a and the second electrode 8b and electrically connects them. The third electrode 8c covers a part of the second electrode 8b, the passivation film 4, and the first electrode 8a. The third electrode 8c can transmit the electricity collected by the first electrode 8a to the second electrode 8b. For this reason, the third electrode 8c is formed on substantially the entire surface excluding a part of the region where the second electrode 8b of the second surface 1b of the substrate 1 is formed, for example, so as to cover all the first electrodes 8a. The thickness of the third electrode 8c is about 15 to 50 μm.

In the solar cell element 10 of this embodiment, the electrical resistivity of the first electrode 8a is smaller than the electrical resistivity of the third electrode 8c. For example, when the first electrode 8a and the third electrode 8c are formed by applying a conductive paste mainly composed of aluminum by screen printing, the electrical resistivity of the first electrode 8a is 10 to 24 × 10 ^{− 8} is about [Omega] m, the electrical resistivity of the third electrode 8c is 38 to 75 × ^{10 -8} [Omega] m approximately. By reducing the electrical resistivity of the first electrode 8a in contact with the substrate 1, the number of the first electrodes 8a (or the contact area between the first electrode 8a and the second surface 1b) can be reduced, and the passivation film 4 The area can be increased. Thereby, the photoelectric conversion efficiency of the solar cell element 10 can be improved.

  On the other hand, if the electrical resistivity of the third electrode 8c occupying a wide area of the back electrode 8 is made larger than the electrical resistivity of the first electrode 8a, the following effects can be expected. In a solar cell module including a large number of solar cell elements 10, for example, when a part of the light receiving surface is shaded, the shaded solar cell element functions as a diode. For this reason, a large reverse bias current may flow through the solar cell element 10 in a shaded area. At this time, if a large reverse bias current flows for a long time, the semiconductor junction (pn junction) of the solar cell element 10 tends to deteriorate. Therefore, in the present embodiment, the electrical resistivity of the third electrode 8c is made approximately 1.5 to 7 times larger than the electrical resistivity of the first electrode 8a, thereby increasing the electrical resistivity of the entire back electrode 8. . For this reason, even if a reverse bias current flows through the pn junction part of the solar cell element 10 constituting the solar cell module for a long time, the reverse electrode current having a large electrical resistivity as a whole makes the reverse bias current small and hardly flows. can do. For this reason, a pn junction part becomes difficult to deteriorate and can provide the solar cell element 10 and solar cell module with high reliability. The electrical resistivity can be easily measured by using a sheet resistance measuring instrument, a step meter, a microprobe, etc., and calculated from the sheet resistance and thickness of the electrode. Can do.

Further, the BSF layer 13 can be formed on the substrate 1 by forming the first electrode 8a with a conductive paste containing aluminum. For example, after applying a conductive paste containing aluminum, the conductive paste is baked at a predetermined temperature profile having a maximum temperature equal to or higher than the melting point of aluminum. As a result, the first electrode 8 a is formed, and interdiffusion occurs between the aluminum in the conductive paste and the substrate 1, and the BSF in which the aluminum diffuses in the substrate 1 at a higher concentration than the first semiconductor layer 2. Layer 13 is formed. Since aluminum can be a p-type dopant, the concentration of the dopant contained in the BSF layer 13 is higher than the concentration of the dopant contained in the first semiconductor layer 2. Thus, in the BSF layer 13, the dopant element is present at a concentration higher than the concentration of the dopant element that is doped to make the first semiconductor layer 2 have one conductivity type. The BSF layer 13 has a role of forming an internal electric field on the second surface 1b side of the substrate 1 and reducing a decrease in photoelectric conversion efficiency due to minority carrier recombination in the vicinity of the surface of the second surface 1b of the substrate 1. doing. The BSF layer 13 can be formed, for example, by diffusing a dopant element such as boron or aluminum on the second surface 1b side of the substrate 1. The concentrations of the dopant elements contained in the first semiconductor layer 2 and the BSF layer 13 are about 5 × 10 ¹⁵ to 1 × 10 ¹⁷ atoms / cm ³ and 1 × 10 ^{18 to} 5 × 10 ²¹ atoms / cm ³ , respectively. Can do.

  As described above, the solar cell element 10 of the present embodiment is disposed on the substrate 1 having the first surface 1a and the second surface 1b located on the opposite side of the first surface 1a, and the back surface of the substrate 1. A passivation film 4 and a back electrode 8 disposed on the back surface of the substrate 1 are provided. The back electrode 8 includes a first electrode 8a, a second electrode 8b, and a third electrode 8c. The first electrode 8 a penetrates the passivation film 4 at a number of locations and is in contact with the substrate 1. The second electrode 8b is linearly disposed on the substrate 1 so as not to overlap the first electrode 8a in plan view, on the passivation film 4 or through the passivation film 4. In particular, the third electrode 8c covers a part of the periphery of the second electrode 8b and the like, the passivation film 4 and the first electrode 8a, and the first electrode 8a and the second electrode 8b. It touches. Thereby, even if a part of 3rd electrode 8c peels, a carrier is. The second electrode 8b can be reached through another portion of the third electrode 8c provided in a planar shape. For this reason, it is possible to provide the solar cell element 10 in which the photoelectric conversion efficiency is unlikely to decrease.

<Method for producing solar cell element>
Next, each process of the manufacturing method of the solar cell element 10 is demonstrated in detail.

  First, as shown in FIG. 4A (a), a substrate 1 is prepared. The substrate 1 may be, for example, single crystal silicon or polycrystalline silicon. The substrate 1 is produced by, for example, an existing CZ method or a casting method. Hereinafter, an example in which a p-type polycrystalline silicon substrate is used as the substrate 1 will be described. For example, an ingot of polycrystalline silicon is produced by a casting method. The electrical resistivity of the ingot may be about 1 to 5 Ω · cm, for example. For example, boron may be added as the dopant element. Next, the ingot is sliced using a wire saw device to obtain a large number of substrates 1. The substrate 1 has, for example, a square shape with a side of about 160 mm square and a thickness of about 200 μm. Thereafter, in order to remove the mechanical damage layer and the contamination layer on the cut surface of the substrate 1, the surface of the substrate 1 may be etched by a very small amount with an aqueous solution such as NaOH, KOH, hydrofluoric acid, or hydrofluoric nitric acid.

  Further, as shown in FIG. 4A (b), a texture may be formed on the first surface 1a of the substrate 1 in order to reduce light reflection. As a texture forming method, a wet etching method using an alkali solution such as NaOH or an acid solution such as hydrofluoric acid, or a dry etching method using an RIE (Reactive Ion Etching) method or the like can be used.

Next, as shown in FIG. 4A (c), an n-type second semiconductor layer 3 is formed on the first surface 1a of the textured substrate 1. The second semiconductor layer 3 is a coating thermal diffusion method in which paste-like P ₂ O ₅ is applied to the surface of the substrate 1 and thermally diffused, and a gas phase using gaseous POCl ₃ (phosphorus oxychloride) as a diffusion source. It is formed by a thermal diffusion method or the like. The second semiconductor layer 3 is formed to have a thickness of about 0.1 to 2 μm and a sheet resistance value of about 40 to 200Ω / □. For example, in the vapor phase thermal diffusion method, the substrate 1 is heat-treated for about 5 to 30 minutes at a temperature of about 600 to 800 ° C. in an atmosphere having a diffusion gas composed of POCl ₃ or the like, and then a phosphosilicate glass (hereinafter referred to as PSG). ) On the surface of the substrate 1. Thereafter, the substrate 1 is heat-treated for about 10 to 40 minutes at a high temperature of about 800 to 900 ° C. in an inert gas atmosphere such as argon or nitrogen. As a result, phosphorus diffuses from the PSG to the substrate 1, and the second semiconductor layer 3 is formed on the first surface 1 a side of the substrate 1.

  In the step of forming the second semiconductor layer 3, when the second semiconductor layer 3 is also formed on the second surface 1b side, only the second semiconductor layer 3 formed on the second surface 1b side is etched. Remove. Thereby, the p-type first semiconductor layer 2 is exposed on the second surface 1b side. For example, the second semiconductor layer 3 formed on the second surface 1b side is removed by immersing only the second surface 1b side of the substrate 1 in a hydrofluoric acid solution. Thereafter, PSG adhering to the first surface 1a side of the substrate 1 when the second semiconductor layer 3 is formed is removed by etching. At this time, the second semiconductor layer 3 formed on the side surface of the substrate 1 may also be removed.

  Next, as a passivation film formation step, a passivation film 4 made of, for example, aluminum oxide is formed on the second surface 1b of the first semiconductor layer 2 as shown in FIG. 4A (d). As a method for forming the passivation film 4, for example, an ALD method, a PECVD method, or the like can be used. However, the passivation effect can be increased by using the ALD method excellent in the coverage of the surface of the substrate 1.

  In the step of forming the passivation film 4 by the ALD method, first, the substrate 1 on which the second semiconductor layer 3 is formed is placed in the chamber of the film forming apparatus. Then, in a state where the substrate 1 is heated in a temperature range of 100 ° C. to 250 ° C., a plurality of series of steps of supplying the aluminum source gas, removing the aluminum source exhaust, supplying the oxidizing gas, and removing the oxidizing agent are performed. Repeat once. Thereby, the passivation film 4 made of aluminum oxide can be formed. As the aluminum raw material, for example, trimethylaluminum (TMA), triethylaluminum (TEA), or the like can be used. Moreover, water, ozone gas, etc. can be used as an oxidizing agent, for example. By using the ALD method, the passivation film 4 is also formed on the entire periphery including the first surface 1 a of the first semiconductor layer 2 and the side surface of the substrate 1. In this case, after applying an acid-resistant resist to the passivation film 4 on the second surface 1b, the unnecessary passivation film 4 may be removed by etching with hydrofluoric acid (HF) or the like.

Next, as shown in FIG. 4A (e), as the antireflection film forming step, an antireflection film 5 made of, for example, a silicon nitride film is formed on the first surface 1a side of the substrate 1. The antireflection film 5 is formed using, for example, PECVD method or sputtering method. When the PECVD method is used, the substrate 1 is heated in advance at a temperature higher than the temperature during film formation. Thereafter, a mixed gas of silane (SiH ₄ ) and ammonia (NH ₃ ) is supplied to the heated substrate 1 after being diluted with nitrogen (N ₂ ). And the antireflection film 5 is formed by making the reaction pressure in a chamber into 50-200 Pa and making it plasma by glow discharge decomposition. The film forming temperature at this time is about 350 to 650 ° C. Further, a frequency of 10 to 500 kHz is used as the frequency of the high frequency power source necessary for glow discharge. The gas flow rate supplied to the chamber is appropriately determined depending on the size of the chamber. The flow rate of the gas supplied to the chamber is, for example, in the range of 150 to 6000 sccm. The flow rate ratio B / A between the flow rate A of silane and the flow rate B of ammonia may be 0.5 to 15.

  Next, as shown in FIGS. 4B (f) to (h), as an electrode forming step, the front surface electrode 7 (bus bar electrode 7a and finger electrode 7b, sub finger electrode 7c) and the back surface electrode 8 (first electrode 8a, The second electrode 8b and the third electrode 8c) are formed as follows.

  First, as shown in FIG. 4B (f), the surface electrode 7 is formed using the first paste 16. The first paste 16 is, for example, a metal powder containing silver as a main component (for example, a main metal component is composed of only silver powder having a particle size of about 0.05 to 20 μm, preferably about 0.1 to 5 μm, and has a silver content. About 65 to 85% by mass of the total mass of the conductive paste). The first paste 16 further includes an organic vehicle (for example, about 5 to 15% by mass of the total mass of the conductive paste) and a glass frit (for example, about 0.05 to 10% by mass of the total mass of the conductive paste, About 40 to 60 atomic% of lead, about 20 to 40 atomic% of silicon, about 1 to 5 atomic% of phosphorus, and about 7 to 15 atomic% of boron. First, the first paste 16 is applied to the first surface 1a of the substrate 1 using screen printing. After this application, the solvent is evaporated and dried at a predetermined temperature.

  Further, the second electrode 8b, which is the back electrode 8, is formed using a conductive powder (second paste 17) containing a metal powder composed solely of silver as a main component, an organic vehicle, glass frit, and the like. The component of the second paste 17 may be the same as that of the first paste 16. As a coating method of the second paste 17, for example, a screen printing method or the like can be used. After this application, the solvent is evaporated and dried at a predetermined temperature.

  Further, the first electrode 8 a is formed using the third paste (conductive paste I) 18. The third paste 18 is a metal powder containing aluminum as a main component (for example, the main metal component is composed only of aluminum powder having a particle size of about 0.05 to 20 μm, preferably about 0.1 to 5 μm, and the aluminum content is About 65 to 80% by mass of the total mass of the conductive paste). The third paste 18 further includes an organic vehicle (for example, about 5 to 15% by mass of the total mass of the conductive paste) and a glass frit (for example, about 0.05 to 10 atomic% of the total mass of the conductive paste, About 40 to 60 atomic% of lead, about 20 to 40 atomic% of silicon, about 1 to 5 atomic% of phosphorus, and about 7 to 15 atomic% of boron. The third paste 18 is applied in a dotted or linear manner at a predetermined position on the second surface 1b at a position away from the already applied second paste 17. As a coating method, a screen printing method or the like can be used. After this application, the solvent may be evaporated and dried at a predetermined temperature.

Thereafter, the substrate 1 on which the first paste 16, the second paste 17 and the third paste 18 are applied has a maximum temperature of about 750 to 950 ° C. in the baking furnace, and the maximum temperature is about several tens of seconds to several tens of minutes. The first firing is performed while maintaining. As a result, each conductive paste is sintered, and the first electrode 8a and the second electrode 8b of the front electrode 7 and the back electrode 8 are formed as shown in FIG. 4B (g). During the first firing, the first paste 16 fires through the antireflection film 5 and is connected to the n-type second semiconductor layer 3 on the first surface 1 a of the substrate 1 to form the surface electrode 7. The third paste 18 also fires through the passivation film 4 and is connected to the p-type first semiconductor layer 2 on the second surface 1b to form the first electrode 8a. Along with the formation of the first electrode 8a, the BSF layer 13 is also formed. Further, the second paste 17 is baked to form the second electrode 8b. At this time, the second paste 17 may be formed on the passivation film 4 without fire-through the passivation film 4 as shown in FIG. Alternatively, as shown in FIG. 5, the passivation film 4 may be formed on the first semiconductor layer 2 by fire-through. For example, the presence or absence of fire-through can be adjusted by appropriately selecting the glass frit component in the second paste 17. For example, when the passivation film 4 is fire-through, it is possible to use a SiO ₂ —BiO ₃ —PbO-based glass frit for the glass frit. On the other hand, when the passivation film 4 is not fire-through, it is possible to use B ₂ O ₃ —SiO ₂ —ZnO glass frit for the glass frit.

  Next, as shown in FIG. 4B (h), the third electrode 8 c is formed using a fourth paste (conductive paste II) 19. The fourth paste 19 has a metal powder containing aluminum as a main component (for example, about 65 to 80% by mass of the total mass of the conductive paste). The fourth paste 19 further contains an organic vehicle (for example, about 5 to 15% by mass of the total mass of the conductive paste) and glass frit (for example, about 5 to 25% by mass of the total mass of the conductive paste). The composition of the glass frit is about 0.05 to 10 mass% of the total mass of the conductive paste, the components are about 40 to 60 atomic% of lead, silicon is about 20 to 40 atomic%, phosphorus is about 1 to 5 atomic%, About 7 to 15 atomic% of boron). The fourth paste 19 is applied onto the second surface 1b so as to come into contact with the already formed first electrode 8a and the end of the second electrode 8b. At this time, by applying to almost the entire surface of the second surface 1b where the second electrode 8b is not formed, it is possible to contact the end of the second electrode 8b without strict alignment. As the coating method, a screen printing method or the like can be used. After this application, the solvent may be evaporated and dried at a predetermined temperature.

  Thereafter, the substrate 1 on which the fourth paste 19 has been applied is subjected to the second baking in a baking furnace for several tens of seconds to several tens of minutes under a temperature condition lower than the first baking condition of 600 to 700 ° C. Do. As a result, the third electrode 8 c is formed on the second surface 1 b side of the substrate 1. Here, when the third electrode 8c is made of the same material as the first electrode 8a, the firing temperature of the fourth paste 19 for forming the third electrode 8c is equal to the third paste for forming the first electrode 8a. Lower than the firing temperature of 18. For this reason, the third electrode 8c is less likely to be denser than the first electrode 8a, and the third electrode 8c has a higher electrical resistivity than the first electrode 8a.

  Further, since the first electrode 8a is formed at a high firing temperature, the contact between the metal particles in the electrode is good, and the porosity in the electrode is lowered, so that the first electrode 8a can be dense. For this reason, the electrical resistivity of the first electrode 8a decreases, and the contact resistance with the substrate 1 can decrease. On the other hand, since the third electrode 8c formed with a large area is formed at a low firing temperature, the porosity can be increased and the thermal contraction in the hole portion can be reduced. For this reason, at the time of manufacture of the solar cell element 10, the curvature by the difference with the thermal expansion coefficient of the board | substrate 1 grade | etc., And the 3rd electrode 8c cannot generate | occur | produce easily.

  As described above, when the conductive paste containing aluminum having substantially the same component is used, the peak temperature of the first firing is set higher than the peak temperature of the second firing. Thereby, the electrical resistivity of the first electrode 8a can be made smaller than the electrical resistivity of the third electrode 8c.

  In addition, this invention is not limited to the said form, Many corrections and changes can be added within the scope of the present invention. For example, the electrode forming step is performed after the surface electrode 7 (bus bar electrode 7a and finger electrode 7b, subfinger electrode 6c) having similar components and the second electrode 8b of the back electrode 8 are formed. Firing for forming the three electrodes 8c and the first electrode 8a may be performed separately.

<Modification 1>
As shown in FIG. 6, in the embodiment according to the first modification, a first silicon oxide film 11 thinner than the passivation film 4 is interposed between the passivation film 4 and the substrate 1 on the second surface 10 b side. Yes. Since other configurations are the same as those of the above-described embodiment, description thereof is omitted.

  By providing the first silicon oxide film 11, dangling bonds derived from crystal defects on the surface of the substrate 1 can be effectively terminated, and the photoelectric conversion efficiency of the solar cell element can be further improved.

For the first silicon oxide film 11, it is desirable to use an ALD method excellent in coverage. Examples of the source gas by the ALD method include N, N, N ′, N ′, tetraethylsilanediamine <H ₂ Si [N (C ₂ H ₅ ) ₂ ] ₂ > gas, ozone (O ₃ ), water vapor, and the like. Can be used to form a film.

  Here, the thickness of the first silicon oxide film 11 is made thinner than that of the passivation film 4. As a result, the negative fixed charge of aluminum oxide forming the passivation film 4 becomes superior to the positive fixed charge of the first silicon oxide film 11. Then, it is possible to make it difficult to lower the passivation effect of the passivation film 4.

  The film thickness of the first silicon oxide film 11 is desirably less than half the film thickness of the passivation film 4. For example, when the thickness of the passivation film 4 is about 50 nm, the thickness of the first silicon oxide film 11 is about 20 nm. Thus, the film thickness of the first silicon oxide film 11 is preferably less than half the film thickness of the passivation film 4. As a result, even when the second silicon oxide film 12 described later is formed in addition to the first silicon oxide film 11, the negative fixed charge of the aluminum oxide forming the passivation film 4 becomes positive in the first silicon oxide film 11. It becomes dominant compared to the fixed charge. For this reason, it is possible to make it difficult to lower the passivation effect of the passivation film 4.

<Modification 2>
In the embodiment according to the modified example 2, as shown in FIG. 7, the second silicon oxide film 12 thinner than the passivation film 4 is interposed between the passivation film 4 and the third electrode 8c. Since other configurations are the same as those of the above-described embodiment, description thereof is omitted.

  By providing the second silicon oxide film 12, aluminum or the like can be made difficult to diffuse into the passivation film 4 when the third electrode 8c is formed. Thereby, the passivation effect of the passivation film 4 can be further improved.

  For the second silicon oxide film 12, it is desirable to use an ALD method that is excellent in coverage as in the case of the first silicon oxide film 11.

  Further, the film thickness of the second silicon oxide film 12 is desirably less than half the film thickness of the passivation film 4 as described above. For example, when the thickness of the passivation film 4 is about 50 nm, the thickness of the second silicon oxide film 12 is desirably about 20 nm.

<Modification 3>
In the embodiment according to the third modification, the metal component of the conductive paste (third paste 18) for forming the first electrode 8a mainly contains aluminum and further contains silver. Since other configurations are the same as those of the above-described embodiment, description thereof is omitted.

  When the third paste 18 uses a main metal component made only of aluminum, it is considered that an oxide film is formed on the surface of the first electrode 8a during firing of the first electrode 8a. At this time, the contact resistance in the connection part of the 1st electrode 8a and the 3rd electrode 8c increases, and the photoelectric conversion efficiency of the solar cell element 10 may fall. On the other hand, by adding silver to the third paste 18, it becomes difficult to form a surface oxide film in firing, and the contact resistance at the connection portion between the first electrode 8 a and the third electrode 8 c can be reduced. it can.

  Furthermore, as for the metal component of the 3rd paste 18, it is desirable that the mass% of silver is larger than the mass% of aluminum. The presence of aluminum makes it possible to form a good BSF layer 13, and the presence of silver makes it difficult to form an oxide film on the surface of the first electrode 8a.

  Furthermore, as a result of tests repeatedly conducted by the inventors, it is more preferable that silver in the metal component is about 70 to 99.5% by mass and aluminum is about 0.5 to 30% by mass. Thereby, a good BSF layer 13 can be formed, and the oxide film formation on the surface of the first electrode 8a can be further reduced.

  In addition, the 3rd paste 18 which concerns on the modification 3 is the same as that of embodiment mentioned above except the composition of a metal component.

<Modification 4>
In the embodiment according to the modified example 4, the metal component of the conductive paste (second paste 17) for forming the second electrode 8b includes silver as a main component, and further includes aluminum. Other configurations are the same as those in the above-described embodiment.

  Aluminum is added to the second paste 17 in addition to silver. Thereby, a BSF layer can be formed also in the 1st semiconductor layer 2 of the board | substrate 1 directly under the 2nd electrode 8b with the baking of the 2nd paste 17. FIG. And the recombination of the minority carrier of a BSF layer part can be reduced, and the further improvement in photoelectric conversion efficiency can be aimed at.

  In addition, the 2nd paste 17 which concerns on the modification 4 is the same as that of embodiment mentioned above except the composition of a metal component.

  Moreover, it is more desirable that the silver in the metal component is about 85 to 99.5% by mass and the aluminum is about 0.5 to 15% by mass as a result of the tests repeatedly performed by the inventors. As a result, a good BSF layer 13 can be formed on the first semiconductor layer 2 of the substrate 1 immediately below the second electrode 8b, and soldering to the second electrode 8b is also possible.

  Further, the conductivity for forming the conductive paste (third paste 18) and the second electrode 8b for forming the first electrode 8a, as shown in <Modification 3> and <Modification 4> above. The paste may be made of the same material. Accordingly, the third paste 18 and the second paste 17 can be simultaneously printed by the screen printing method, and the number of steps in the manufacturing process of the solar cell element 10 can be reduced.

  As the substrate 1, a polycrystalline silicon substrate doped with boron and having a square side of about 156 mm and a thickness of about 200 μm in plan view was prepared. The substrate 1 was obtained by subjecting an ingot produced by a casting method to processing such as slicing using a wire saw device. Further, the surface layer portion of the substrate 1 having a thickness of about 10 μm was etched using an aqueous sodium hydroxide solution to remove the damaged layer on the surface layer portion of the substrate 1. Then, the surface of the substrate 1 was cleaned. The following processing was performed on the substrate 1 thus prepared.

  As shown in FIG. 4A (b), a fine texture was formed on the first main surface 7a side of the substrate 1 by using the RIE method.

Next, phosphorus is diffused on the substrate 1 by vapor phase thermal diffusion using phosphorus oxychloride (POCl ₃ ) as a diffusion source to form an n-type semiconductor layer having a sheet resistance of about 60 to 100Ω / □, A pn junction was formed. The n-type semiconductor layer formed on the side surface of the substrate 1 and the second main surface 7b side was removed with a hydrofluoric acid solution. Thereafter, the remaining PSG was removed with a hydrofluoric acid solution. As a result, an n-type second semiconductor layer 3 was formed on the p-type first semiconductor layer 2 of the substrate 1 as shown in FIG. 4A (c).

Next, as shown in FIG. 4A (d), a passivation film 4 made of aluminum oxide was formed on the entire surface of the substrate 1 by an ALD method to a thickness of about 15 nm. In forming the passivation film 4, the substrate 1 was held upright in the chamber of the ALD apparatus, and the temperature of the substrate 1 was maintained at about 200 ° C. under reduced pressure. Trimethylaluminum (TMA) was used as a source gas, and N ₂ , He, and H ₂ were used as a carrier gas and a purge gas. Ozone was used as the oxidizing gas.

  The passivation film 4 includes a supply process (P1), a diffusion process (gas sealing process) (P2), an exhaust process (P3), an oxidizing gas supply process (P4), a diffusion process (gas sealing process) (P5) and The steps P1 to P6 of the exhaust step (P6) were repeated a plurality of times. The time required for each step per cycle of P1 to P6 is P1: about 1 second, P2: about 3 seconds, P3: about 5 seconds, P4: about 1 second, P5: about 2 seconds, P6: about 3 Seconds. And the film-forming time (cycle number) was determined from the film-forming speed calculated beforehand.

Thereafter, as shown in FIG. 4A (e), antireflection made of a silicon nitride film having a refractive index of 1.9 to 2.1 and a film thickness of about 70 to 90 nm is formed on the first surface 1a of the substrate 1 by PECVD. A film 5 was formed. This is because the inside of the chamber of the PECVD apparatus is set to about 500 ° C., a mixed gas of silane (SiH ₄ ) and ammonia (NH ₃ ) is diluted with nitrogen (N ₂ ), and is plasmatized by glow discharge decomposition to form silicon nitride. Was deposited.

  Then, on the first surface 1a side of the substrate 1, a conductive paste (silver paste) mainly composed of silver and made of glass frit, an organic vehicle, or the like is formed on the first surface side electrode (first bus bar electrode) as shown in FIG. 8 and the first collector electrode 9) were applied and dried. Also on the second main surface 7b side, the silver paste was applied to the pattern of the second bus bar electrode 10 as shown in FIG. 2 (b) and dried. Further, an electrode conductive paste (aluminum paste) mainly composed of aluminum on the second main surface 7b side and made of glass frit, an organic vehicle, or the like is a pattern of the second collector electrode 11 as shown in FIG. And then dried.

  Next, the substrate 1 coated with silver paste and aluminum paste and dried was fired at a peak temperature (about 750 ° C.) for about 10 minutes to form a first surface side electrode and a second surface side electrode. The first bus bar electrode 8 had a width of about 1.7 mm and a thickness of about 11 μm. The first current collecting electrode 9 had a width of about 0.05 mm and a thickness of about 11 μm. The second bus bar electrode 10 had a width of about 3.5 mm and a thickness of about 10 μm. The thickness of the 2nd current collection electrode 11 was about 33 micrometers. In this way, a solar cell element was produced.

Next, as shown in FIG.6 (d), the 1st paste 16 for formation of the surface electrode 7 (the bus-bar electrode 7a and the finger electrode 7b, the sub finger electrode 7c) is formed in the 1st surface 1a of the board | substrate 1. It applied to the pattern as shown in FIG. 1 using the screen printing method. As the first paste 16, a paste containing about 80% by mass of silver, about 14% by mass of SiO ₂ —Bi ₂ O ₃ —PbO-based glass frit and about 6% by mass of an organic vehicle was used. The organic vehicle used ethyl cellulose as the binder and diethylene glycol monobutyl ether acetate as the organic solvent. The paste film thickness immediately after printing the first paste 16 was about 18 μm. After this application, the first paste 16 was dried at a temperature of about 140 ° C. for about 3 minutes to evaporate the solvent.

  Moreover, the 2nd paste 17 for forming the 2nd electrode 8b of the back surface electrode 8 was apply | coated to the pattern as shown in FIG. 2 using the screen printing method. The second paste 17 used was the same component as the first paste 16. The paste film thickness immediately after printing of the second paste 17 was about 17 μm. After this application, the second paste 17 was dried at a temperature of about 140 ° C. for about 3 minutes to evaporate the solvent.

  Thereafter, a third paste 18 for forming the first electrode 8a of the back electrode 8 was applied using a screen printing method. As the third conductive paste 18, an aluminum powder having an average particle size of about 0.1 to 5 μm and having an aluminum content of about 75 mass% of the total mass of the third paste was used. Furthermore, in the third paste, glass frit (about 5 atomic% of the total mass of the conductive paste, components are about 50 atomic% of lead, about 30 atomic% of silicon, about 2 atomic% of phosphorus, and about 10 atomic% of boron) And an organic vehicle (about 10% by mass of the total mass of the conductive paste) was used.

  The paste film thickness immediately after printing the second paste 17 was about 28 to 34 μm.

  Thereafter, first baking was performed on the substrate 1 on which the first paste 16, the second paste 17, and the third paste 18 were applied. In the first firing, the maximum temperature is a temperature I (600 ° C.), a temperature II (650 ° C.), a temperature III (700 ° C.), a temperature IV (750 ° C.), and a temperature V (800 ° C.). The temperature VI (850 ° C.), the temperature VII (900 ° C.), the temperature VIII (950 ° C.), and the temperature IX (1000 ° C.) were maintained for about 20 seconds. When the maximum temperature was less than 600 ° C. (temperature I) such as 550 ° C., the temperature was too low, and the first firing could not be performed.

  Next, as shown in FIG. 4B (h), a fourth paste 19 for forming the third electrode of the back current collector 8 was applied using a screen printing method. The fourth paste 19 had the same components as the third paste 18. The paste film thickness immediately after printing the fourth paste 19 was about 31 to 42 μm.

  Thereafter, second baking was performed on the substrate 1 on which the fourth paste 19 was applied. In the second baking, the maximum temperature is a temperature A (600 ° C.), a temperature B (650 ° C.), a temperature C (700 ° C.), a temperature D (750 ° C.), and a temperature E (800 ° C.). The temperature F (850 ° C.), the temperature G (900 ° C.), and the temperature H (950 ° C.) were maintained for about 20 seconds. In addition, when the maximum temperature was less than 600 ° C. (temperature A) such as 550 ° C., the second firing could not be performed because the temperature was too low.

  The temperatures I to VIII and A to H are median and have a range of plus or minus 10 ° C. For example, when the temperature is 700 ° C., the temperature is in the range of 690 to 710 ° C.

  Under the above firing conditions, three solar cell elements were produced.

Based on JIS C 8913, the photoelectric conversion efficiency was measured under the conditions of irradiation of AM (Air Mass) 1.5 and 100 mW / cm ² , and the average was calculated for the solar cell element produced as described above.

  The results are shown in Table 1. Table 1 shows the standard value of the photoelectric conversion efficiency when the first firing condition and the second firing condition are combined. This standard value is indicated by an index with the average value of the measurement results of all the solar cell elements as 100. However, a horizontal bar indicates a case where the conductive paste was not fired well and the photoelectric conversion efficiency could not be measured due to electrode peeling or oxidation. Further, the firing results performed at temperatures E to H are the same as those at temperature D, and are omitted.

  From Table 1, it is preferable if the maximum temperature of the first firing is 750 ° C. or more and 950 ° C. or less (temperatures IV to VIII) and the maximum temperature of the second firing is 600 ° C. or more and 700 ° C. or less (temperatures AC). It was found that firing was possible. In order to increase the photoelectric conversion efficiency, the maximum temperature of the first baking is 750 ° C. to 900 ° C. (temperature IV to VII), and the maximum temperature of the second baking is 650 ° C. to 700 ° C. (temperature B To C).

  Next, in Table 1, in the case of conditions where temperature can be suitably baked and the highest temperature of the first baking and the highest temperature of the second baking are the lowest, respectively, temperature IV (750 ° C.) − Temperature A (600 ° C.) The electrical resistivity of the first electrode 8a and the third electrode 8c was determined for each of the highest temperature VIII (950 ° C.) and the temperature C (700 ° C.). For electrical resistivity, the sheet resistance value and thickness of each of the first electrode 8a and the third electrode 8c were measured using a four-probe type sheet resistor, a stylus profilometer, a microprobe, and the like. And the electrical resistivity of each solar cell element was computed from the measured sheet resistance value and thickness. The results are shown in Table 2.

When the first electrode 8a and the third electrode 8c can be suitably fired from Table 2, the electrical resistivity of the first electrode 8a is in the range of 10-24 × 10 ⁻⁸ Ωm, and the electrical resistance of the third electrode 8c The rate was found to be in the range of 38 to 75 × 10 ⁻⁸ Ωm. Moreover, it confirmed that the electrical resistivity of the 1st electrode 8a electrode was smaller than the electrical resistivity of the 3rd electrode 8c.

1: Substrate (semiconductor substrate)
1a: First surface 1b: Second surface 2: First semiconductor layer (p-type semiconductor layer)
3: Second semiconductor layer (n-type semiconductor layer)
4: Passivation film 5: Antireflection film 7: Front electrode 7a: Bus bar electrode 7b: Finger electrode 7c: Sub finger electrode 8: Back electrode 8a: First electrode 8b: Second electrode 8c: Third electrode 10: Solar cell element 10a: First surface 10b: Second surface 11: First silicon oxide film 12: Second silicon oxide film 13: BSF layer 16: First paste 17: Second paste 18: Third paste (conductive paste I)
19: Fourth paste (conductive paste II)

Claims (9)

A semiconductor substrate having a first surface and a second surface located on the opposite side of the first surface;
A passivation film disposed on the second surface of the semiconductor substrate;
A first electrode in contact with the semiconductor substrate in a state of penetrating the passivation film at a plurality of locations;
A second electrode disposed in a straight line in contact with the semiconductor substrate in a state of penetrating the passivation film at a position not overlapping the first electrode in plan view;
The third electrode covers a part of the second electrode, the passivation film, and the first electrode, and is in contact with each of the first electrode and the second electrode without penetrating the passivation film . An electrode,
The first electrode and the third electrode are made of a material mainly composed of aluminum,
The solar cell element in which the electrical resistivity of the first electrode is smaller than the electrical resistivity of the third electrode.   The solar cell element according to claim 1, further comprising an antireflection film disposed on the first surface of the semiconductor substrate.   3. The solar cell element according to claim 1, wherein the second surface of the semiconductor substrate includes p-type silicon, and the passivation film is made of a material mainly composed of aluminum oxide.   4. The solar cell element according to claim 3, wherein a first silicon oxide film thinner than the passivation film is interposed between the passivation film and the semiconductor substrate.   5. The solar cell element according to claim 3, further comprising a second silicon oxide film disposed between the passivation film and the third electrode, wherein the second silicon oxide film is thinner than the passivation film. Made of a material the second electrode is composed mainly of silver, a solar cell element according to any one of claims 1 to 5. The solar cell element according to claim 6 , wherein the second electrode contains aluminum. The solar cell element according to any one of claims 1 to 7 , wherein the first electrode contains silver. A method of manufacturing a solar cell device according to any one of claims 1 to 8, and the conductive paste I mainly containing aluminum, by firing a conductive paste mainly composed of silver, wherein the passivation After forming the first electrode and the second electrode penetrating the film, the conductive paste II made of the same material as the conductive paste I is baked at a temperature lower than that of the conductive paste I, and the third electrode The manufacturing method of the solar cell element which forms.

Images