TW201003938A - Method and apparatus for manufacturing solar battery, and solar battery - Google Patents

Abstract

A method for manufacturing a solar battery, includes: forming, on a silicon substrate whose conductivity type is p-type or n-type, an anti-reflective film including a dopant whose conductivity type is different from that of the silicon substrate; and diffusing the dopant included in the anti-reflective film into the silicon substrate by heat-treating the anti-reflective film.

Description

201003938 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a manufacturer of a solar cell, a manufacturing device for a solar cell, and a solar cell. More specifically, the present invention relates to a laminated structure including a diffusion layer and an anti-reflection film by using a film forming process on a germanium substrate, and the battery characteristics are improved, and the manufacturing time can be shortened. And a method for manufacturing a solar cell having a reduced manufacturing cost, a solar cell manufacturing device, and a solar cell. [Prior Art] As a solar cell of the lanthanide system, it is known that a single crystal enamel solar cell using a single crystal yttrium, a polycrystalline solar cell using a polycrystalline slab layer, and an amorphous ruthenium using an amorphous ruthenium Battery, etc. The single crystal germanium solar cell has a structure in which a diffusion layer, an antireflection film, and a surface electrode are sequentially formed on the surface side of the p-type single crystal germanium substrate, and a BSF layer and a back surface are sequentially formed on the back side of the germanium substrate. electrode. The diffusion layer is a layer in which phosphorus (p) as an n-type dopant is diffused in the pulverized single crystal. Further, the antireflection film contains tantalum nitride (Si3N4). A texture structure for anti-reflection is formed on the surface of the single crystal substrate of the 5 hai. Further, the diffusion layer is obtained by diffusing the disk (P) on the surface of the above-mentioned substrate, and as a method of diffusing the disk (P), a method of diffusing the gas by a method of gas diffusion is used. This method is disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Since impurities are left on the surface of the diffusion layer, the surface of the diffusion layer is washed with hydrofluoric acid or the like in order to remove the impurities. In the manufacturing process of the solar cell, it is necessary to temporarily remove the substrate into the atmospheric gas environment for cleaning after the device used in the diffusion step, and then advance the cleaned substrate into the vacuum device for forming the anti-reflection film. The method of forming a surface electrode by a horse can be carried out by a so-called piercing process, which is disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei 5-259488, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. In the process of 'When the silver paste coated on the anti-reflection film is fired, the silver electrode formed by the shape of the image is passed through the anti-reflection film to bring the silver electrode into contact with the diffusion layer. In the method for manufacturing a solar cell of the ray solar cell, after the impurity on the surface of the layer such as fluoric acid or the like is used for cleaning, the antireflection film is allowed to diffuse (4)^, so that the interface between the diffusion layer and the antireflection film is generated by the mash The defects caused, etc. ^°果', there is a problem that it is difficult to further improve the battery characteristics. In the case of manufacturing (4) solar cells, the film is cleaned on the surface of the diffusion layer. After the step, the antireflection film is formed on the diffusion layer, and so there is a need to prepare a device dedicated to each step 139952.doc 201003938, so there is a shortening of the manufacturing steps and a reduction in the number of steps, since In the case of the step replacement device, the preparation time is prolonged, and it is difficult to solve the manufacturing time. In this case, the current manufacturing method is difficult to reduce the manufacturing time, reduce the number of steps, and reduce the manufacturing cost. The invention is completed to solve the above problems, and its purpose is to provide -

The manufacturing method of the solar cell, the manufacturing apparatus of the solar cell, and the solar cell can improve the battery characteristics, and it is not necessary to prepare a device dedicated to each step, and the manufacturing time can be shortened, the number of steps can be reduced, and the manufacturing cost can be reduced. It is not necessary to form a diffusion layer on the substrate in advance, and the anti-reflection film N is formed by forming a film by using a dopant, thereby shortening the manufacturing time and reducing the number of steps, and simultaneously performing dopant diffusion. The wear of the surface electrode can shorten the manufacturing time and reduce the number of steps. Alternatively, it is an object of the present invention to provide a method for producing a solar cell, a solar cell manufacturing apparatus, and a solar cell which do not require a cleaning step in the atmosphere after the diffusion step. As a result of earnest research on materials and solar cells, the inventors have found that forming an antireflection film containing a dopant on the substrate right, and then subjecting the antireflection film to heat treatment, can be performed during the heat treatment. The inclusions contained in the anti-reflection film diffuse into the shixi substrate to form a diffusion layer, and no impurities are generated at the interface between the diffusion layer and the anti-reflection film, and it is found that a film formation process can be used for the anti-reflection film. The film formation and heat treatment of the reflective film complete the present invention. 139952.doc 201003938 That is, the method for manufacturing a solar cell according to the first aspect of the present invention is to form an anti-dictionant having a conductivity type different from that of the above-mentioned germanium substrate on a p-type or n-type germanium substrate having a conductivity type. In the reflective film (antireflection film forming step), the upper anti-reflection film is heat-treated to diffuse the dopant contained in the anti-reflection film into the germanium substrate (heat treatment step). In the method of manufacturing a solar cell according to the first aspect of the present invention, after the antireflection film (the antireflection film forming step) is formed, a surface electrode is formed on the antireflection film (surface electrode forming step). When the dopant contained in the anti-reflection film is diffused into the substrate (heat treatment step), the surface electrode is formed by heating the anti-reflection film and the surface electrode of the surface electrode. The Shishi substrate is turned on, and the dopant is diffused into the germanium substrate. In the method for producing a solar cell according to the first aspect of the present invention, it is preferable that when the back surface electrode (back surface electrode formation/de) is formed on the back surface of the stone substrate, the anti-reflection is formed. a film forming step of forming an anti-reflection film containing an n-type dopant on a surface of the above-mentioned dream substrate having a conductivity type, and causing the above-mentioned dopant contained in the anti-reflection film to be in the above-mentioned stone substrate During the diffusion (heat treatment step), the 抗V is formed by heating the anti-reflection film and the back surface electrode to form the earth plate ′, and the dopant is diffused into the stone substrate, and one of the aluminum is formed. Divided into the above-mentioned germanium substrate. In the method for fabricating a battery of the first aspect of the present invention, it is preferred that the dopant is diffused into the germanium substrate on the slabs of the anti-reflective film. At the time (heat treatment step), the maximum value of the enthalpy, and ra庳' enthusiasm is 600. (: above and 120,000. 〇 ' ' 加 加 加 加 加 加 加 加 、 、 、 、 、 、 、 、 、 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 139 Preferably, before the forming the anti-reflection film, the ruthenium substrate is exposed to the plasma in a vacuum (plasma treatment step), after exposing the ruthenium substrate to the plasma, The anti-reflection film is formed in a state in which the substrate is kept in a vacuum.

In the method for producing a solar cell according to the first aspect of the present invention, it is preferable that the antireflection film is formed by a plasma CVD (Chemical Vapor Deposition) method, and the same plasma CVD apparatus is used. The above-mentioned ruthenium substrate is exposed to a plasma in a vacuum (plasma treatment step), and the above-described anti-reflection film (anti-reflection film formation step) is formed by the above-described plasma CVD method. Further, a solar cell manufacturing apparatus according to a second aspect of the present invention includes: a film forming apparatus that forms an anti-reflection film containing the dopant on a substrate while introducing a gas containing a dopant; and an electrode forming apparatus An electrode is formed on the substrate; and a heating device that heats the substrate to diffuse the dopant into the substrate. In the apparatus for manufacturing a solar cell according to a second aspect of the present invention, it is preferable that the film forming apparatus includes a plasma generating unit that performs plasma treatment on the substrate. Preferably, the solar cell manufacturing apparatus according to the second aspect of the present invention includes a substrate transfer mechanism that transports the substrate in the order of the film forming apparatus, the electrode forming apparatus, and the heating apparatus. Further, the third sad solar cell of the present invention comprises: a germanium substrate which is of a P-type or an n-type conductivity type; and a diffusion layer which is laminated on the germanium substrate, 139952.doc 201003938 and contains a conductive type and the above-mentioned germanium a dopant different in the substrate; and an anti-reflection ruthenium formed on the diffusion layer and containing the dopant. Preferably, in the third solar cancer cell of the present invention, the dopant concentration of the diffusion layer is lower than the dopant concentration of the anti-reflection film. According to the method of manufacturing a solar cell of the present invention, since the above step is included, the heat treatment step can be used to form a region in the vicinity of the interface with the anti-reflection film in the substrate while heat-treating the anti-reflection film. Expansion. "Month and then" can use the film forming process to perform the diffusion step and the film forming step of the antireflection film. Therefore, it is not necessary to form a diffusion layer on the substrate in advance, and the manufacturing time can be shortened and the number of (4) numbers can be reduced, and the manufacturing cost can be achieved. Since the use of the film forming process is carried out, it is not necessary to prepare a device dedicated to each step, which can shorten the manufacturing time and reduce the number of steps, and can reduce the manufacturing cost. Moreover, there is a dry type (4). In the case of forming a texture or the like, it may be carried out by forming and heat-treating an antireflection film containing a dopant together with a continuous vacuum apparatus. 'Thus' and the previous method 'for example, including the cleaning in an atmospheric environment, etc. 'Repeating the vacuum-atmosphere method and the like, the exhaust time can be shortened, and the overall manufacturing time can be shortened and the number of steps can be reduced. Therefore, the substrate can be kept clean and the main treatment can be carried out in a vacuum. 'In the case where it is necessary to form a back surface electrode by sputtering, 139952.doc 201003938 field, back surface electric field), an injection layer, a back electrode, etc. by sputtering In the case of the surface electrode forming step of forming the surface electrode on the anti-reflection film after the anti-reflection film forming step, the doping-diffusion can be simultaneously performed. And the wear of the surface electrode can shorten the manufacturing time and reduce the number of steps. According to the manufacturing apparatus of the solar cell of the present invention, since the device is provided, a series of device groups can be used to carry the dopant. The film formation of the anti-reflection film, the heat treatment of the anti-reflection film, the diffusion of the dopant into the germanium substrate, and the electrode formation. Moreover, the manufacturing time can be shortened, the number of steps can be reduced, and the manufacturing cost can be reduced. When there is a step of forming a texture by dry etching, etc., it is also possible to carry out the steps using a continuous vacuum apparatus. Therefore, the exhaust time can be shortened compared to the prior apparatus, and the entire CJ body manufacturing time can be realized. Shortening and reduction in the number of steps. The main treatment can be carried out in a vacuum using a series of devices, so that the substrate can be kept clean. When the step of forming the back surface BSF injection layer by sputtering or the step of forming the back surface electrode by _, etc., the steps can be carried out in a vacuum using a series of devices. The best mode for manufacturing the solar cell of the present invention, the solar cell coating device, and the solar cell will be described. 139952.doc 201003938 Furthermore, the form is better understood to better understand the gist of the invention. The invention is not limited to the invention unless otherwise specified. Fig. 1 is a cross-sectional view showing a solar cell according to an embodiment of the present invention. In Fig. 1, reference numeral 1 is a stone substrate, and symbol 2 is a diffusion layer. (4) Membrane, the symbol 4 is the BSF layer, the symbol I is 5 as the lf-surface electrode, the symbol 6 is the second back private pole, and the 唬7 is the surface electrode. The substrate 1' can be suitably selected for use in a single crystal germanium to be diffused with boron (B), gallium, & A, , ) (A), indium (In), etc. Object

Type single crystal substrate, 3 ar/7 + t P n-type single crystal ♦ substrate with η-type dopants such as phosphorus (p), arsenic (As), and antimony (Sb) diffused Any kind of substrate. On the surface of the stone substrate 1, a texture structure (not shown) having minute irregularities is formed by texture characterization. If the flower is used in the 1% battery, the texture of the substrate 1 can be used to improve the power generation efficiency. As the dream substrate 1, it is also possible to form a textured substrate, and in the present embodiment, it is also possible to form a texture by dry etching for a certain type of field. For the ruthenium substrate 1, a polycrystalline ruthenium substrate can be preferably used in addition to the above single crystal substrate, and it can be appropriately selected and used depending on the application. In the case where the substrate 1 of the Shixi substrate is P but the k 4 & P i substrate, phosphorus (P), arsenic (As), antimony (Sb), etc. are used! ! The type of dopant 6i 1 ^ ^ is diffused to the vicinity of the surface of the ruthenium substrate 1 and the thinner layer is a diffusion layer 2 . - In the case where the substrate 1 is an n-type germanium substrate, the thickness obtained by diffusing a p-type dopant such as boron (B) or —) (Α1) steel (ηη) toward the vicinity of the surface of the germanium substrate i The thinner layer is the diffusion layer 2. 139952.doc •10-201003938+When a film comprising a multilayer film having a film having a high refractive index and a film having a low refractive index is used as the antireflection film 3, it is preferable as a material constituting the film; For example, tantalum nitride (SiNx), titanium oxide (Τι〇2), niobium oxide (Nb2〇5), fluorinated town (10), magnesium oxide (Mg〇), oxidation, having a refractive index of 1.〇~4·0, Shi Xi (Si〇2) and so on. Further, in the case where the antireflection film 3 includes a film of a single layer, for example, a film of a transparent material such as cerium nitride which is formed on the diffusion layer 2 by a CVD method is used. The film contains phosphorus (Ρ) in the case where the tantalum substrate 1 is a p-type tantalum substrate, and an n-type dopant such as Ashen or Sb. The film contains boron (Β) in the case where the tantalum substrate 1 is an n-type tantalum substrate, and a p-type dopant such as gallium (Ga) or aluminum (Α1). As the film, it is preferable to use tantalum nitride (SiNx) or titanium oxide (Ti〇2) in the case of performing the fire-through step. The diffusion layer 2 is a region obtained by diffusing the dopant contained in the anti-reflection film 3 to the surface of the stone substrate i by heat treatment against the reflection film 3. The dopant concentration of the diffusion layer 2 is determined in such a manner as to produce the pn junction required for the solar cell. For example, the dopant itch #1 of the diffusion layer 2 depends on the amount of diffusion from the anti-reflection film 3, and thus is lower than that of the diffusion-resistant anti-reflection film 3 There are many cases of substance concentration. Generally, the film-forming antireflection film has a dopant concentration for the film 3 set higher than that required for the diffusion layer 2. However, the present invention is not limited to this, and there is also a combination of 寻 矽 矽 矽 矽 矽 矽 矽 矽 矽 139 139 139 139 139 139 139 139 139 139 139 139 139 139 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The doped layer of the diffusion layer 4 is a layer having a thin thickness formed by diffusing an element such as a back electrode constituting the ruthenium substrate by heat treatment. For example, a back electrode including a back surface electrode is formed on the back surface of the p-type slate substrate, and heat treatment is performed to diffuse aluminum to the ruthenium substrate, thereby forming the ruthenium layer 4. The first back surface electrode 5, the second back surface electrode 6, and the surface electrode 7 are metal electrodes obtained by firing a paste containing a conductive metal such as silver or aluminum. The f 2 back electrode 6 is formed on the moon surface of the ruthenium substrate so as to have a stripe pattern, and is formed to traverse the center portion of the back surface of the ruthenium substrate 1. The first back surface electrode 5 is provided on both sides of the second back surface electrode 6, and is formed on the back surface of the ruthenium substrate 1 in a rectangular pattern. The surface electrode 7 is formed on the surface of the stone base. The surface electrode 8 has a configuration in which a plurality of (for example, five) f-shaped electrode sheets are formed in the longitudinal direction of the second back surface electrode 6. The surface electrode 7 is connected to the diffusion layer 2 by a fire-through process. The heat treatment step of forming the diffusion layer 2, the heat treatment step of forming the layer 4, and the step of heat-treating the surface electrode 7 by a fire-through process may be separately performed. On the other hand, if any two steps or all steps are performed at the same time, the number of steps can be reduced and the device can be reduced. Next, a method of manufacturing the solar cell of the present embodiment will be described based on the drawings. Fig. 2 is a view showing a mode of a manufacturing apparatus for a solar cell of the embodiment. In Fig. 2, the U-phase of the symbol U-phase introduces a dopant-containing gas into a substrate 139952.doc 12 201003938 A film forming apparatus for forming a film containing an antireflection film with a dopant. Reference numeral 12 is an electrode forming device for forming an electrode on a substrate. The symbol 丨3 is a heating device that heats the substrate to diffuse the dopant into the substrate. The film forming unit 11 is provided with a plasma processing unit 14 for exposing the substrate to the electric raft. In the film forming apparatus U, the electrode forming apparatus 12, and the heating apparatus 13, the substrate transport mechanism that transports the substrate is provided by means of the apparatuses.

The inside of the film forming apparatus 11 is maintained in a vacuum state, and the forming apparatus 丨j is used in a state where the inside is set to a special pressure. The inside of the electrode forming device 12 and the heating device 13 are maintained at atmospheric pressure, and the electrode forming device 12 and the heating device 13 are used at this atmospheric pressure. Therefore, the film forming apparatus u and the electrode forming apparatus can also be loaded with an interlocking chamber (not shown). In the transport path of the substrate, the (4) 1 of the dry silking of the texture may be applied to the upstream side of the film forming apparatus (when the illustration is omitted, the film forming apparatus 11 erodes the column w + ^ ^ , The substrate is transported between the etching apparatuses while maintaining the true state. The mounting method is too long, and the method of manufacturing the anode battery according to Fig. 3 will be described. Depending on the application, it can be selected from the single crystal on the surface of the ruthenium substrate 21 or the η-type conductivity of the ruthenium base + as shown in Fig. 3 (a), the p-type or n-type conductivity type is cleaned in the slurry (electrical Slurry treatment) As a p-type or n-electricity % substrate 21, the choice of the earth-glass enamel substrate is also selected. The surface is formed with a texture structure (not shown). I39952.doc • J3· 201003938 The second substrate is placed on the electro-converging film forming the anti-reflection film to decompress the inside of the plasma CVD device, and then the argon gas is introduced into the plasma CVD device. Plasma is generated on one side. Thereby, the substrate is exposed to the plasma to clean the substrate. It is also possible to carry out a plasma treatment by disposing a dedicated device in the device shown in Fig. 2. Further, in the case of monthly washing, a texture structure is formed on the surface of the substrate, so that the step of dry etching in vacuum can also be performed. Moreover, after the dry etching, the stone material is formed on the substrate while maintaining the vacuum gas atmosphere, thereby eliminating the man-hours for temporarily taking the substrate out to the atmosphere for cleaning. As shown in Fig. 3(b) On the surface of the ruthenium substrate 2 1 , an anti-reflection film 22 containing a dopant different from the ruthenium substrate 21 is formed into a film. The anti-reflection film 22 is heated toward the ruthenium substrate 2 1 . For example, when the Si Xi substrate 21 is a p-type tantalum substrate, the anti-reflection film 22 containing an n-type dopant such as phosphorus (P), Kun (As), or bismuth (sb) is formed into a film. In the case where the substrate 21 is an n-type germanium substrate, the anti-reflection film 22 containing a p-type dopant such as boron (b), recording (Ga) or indium (Α1) is formed into a film. A p-type germanium substrate is used as the germanium substrate 21, and an antireflection film containing phosphorus (P)-containing tantalum nitride (SiNx) is used by a CVD method. In the case of being deposited on the substrate, SiH4 gas, NH3 gas, PH3 gas diluted with H2, and N2 gas as a carrier gas are introduced into the film forming apparatus 11, and film formation is performed by plasma CVD. .doc -14· 201003938 The resistance value of the tantalum nitride (SiNx) doped with phosphorus (p) is 10% lower than that of the case where phosphorus (P) is not doped. In the screen printing method, a silver surface electrode 7 of a specific shape is formed on the anti-reflection film 22 as shown in Fig. 3(c). Then, a special shape is formed on the back surface of the ruthenium substrate 21 by screen printing. The first back surface electrode 5 and the second back surface electrode 6 (Fig. 3(d)). The material of the first back surface electrode 5 is preferably aluminum, and the material of the second back surface electrode 6 is preferably silver. Then, the stone substrate 21 on which the antireflection film 22, the surface electrode 7, the first surface electrode 5, and the second surface electrode 6 are formed is heat-treated (Fig. 3(e)). The heat treatment condition is: the gas atmosphere is In a reducing gas atmosphere or an inert gas atmosphere, the temperature is 600. (: above and 120 (rc or less, the time is !min or more and 120 minutes or less. The dopant contained in the anti-reflection film 22 by the heat treatment) The diffusion layer 2 is formed on the upper portion (surface side) of the stone substrate 2 1 . Further, the aluminum contained in the second back surface electrode 5 is directed toward the ruthenium substrate 21 by the heat treatment. Diffusion, so that the layer 4 is formed on the lower portion (back side) of the ruthenium substrate 21. Further, the surface electrode 7 is connected through the anti-reflection film 盥矽 board 21 by the fire. The anti-reflection 臈 2 2 is treated by the heat treatment. The anti-reflection film having a reduced dopant concentration is obtained by the solar cell of the present embodiment. I39952.doc -15- 201003938 The solar cell according to the present embodiment is a P-type (or n-type NMOS substrate). 1 The upper layer contains η-type (or ρ-type) dopants Since the diffusion layer 2 and the anti-reflection film 3 containing the n-type (or p-type) dopant are no longer defective in the interface between the diffusion layer 2 and the anti-reflection film 3 due to impurities, etc., further According to the method for manufacturing a solar cell of the present embodiment, the anti-reflection film 22 containing a dopant having a conductivity type different from the ruthenium substrate 21 is formed on the surface of the ruthenium substrate 21, and then the film formation is performed. The substrate gate of the anti-reflection film 22 is subjected to heat treatment to diffuse the dopant contained in the anti-reflection film 22 into the germanium substrate 2. Therefore, it is not necessary to clean the diffusion layer, and the diffusion process can be performed using a film formation process. Film-forming step of the anti-reflection film - Further, since the film formation process such as the CVD method is used, it is not necessary to prepare a device dedicated to each step, thereby shortening the manufacturing time and reducing the number of steps, and reducing the manufacturing cost. In the present embodiment, the poles 7 and the first back electrodes 5 and ' are heat-treated after the anti-reflection film 22, the surface electric power, and the second back surface electrode 6 are formed, but may be formed separately from the anti-reflection film. After the surface electrode is formed and after the surface electrode is formed, heat treatment may be performed, and any of them may be concentrated. Further, if the heat treatment is concentrated as described above, the heat treatment step and the cooling period may be shortened, so that the heat treatment step can be shortened. Apparatus for shortening heat treatment in the steps (Examples) Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the examples. 139952.doc -16- 201003938 (Example 1) A p-type single crystal germanium substrate having a thickness of 220 μm and 156 mm square formed on the surface by a texture is engraved on the surface, and a tantalum nitride (SiNx) containing phosphorus (P) is formed by a cvd method. The antireflection film is formed into a film. The film formation conditions were a substrate temperature of 300 t, a flow rate of SiH 4 gas of 1 〇〇 seem, a flow of NH 3 gas a: 80 seem, and a vop/ of only 2 dilutions. The flow rate of the Ph3 gas is 1500 sccm, the flow rate of the n2 gas as the carrier gas is 1000 seem, and the power is 1 〇〇〇 w.

The thickness of the obtained antireflection film was 70 nm. Then, in the region where the second back surface electrode was formed on the back surface of the substrate, a silver paste having a thickness of 20 μm was applied by a screen printing method, followed by 15 Å. Dry and dry for 10 minutes. Then, the surface of the ruthenium substrate is 篦 + + + + + + + 之 1 1 者 者 + + 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The sputum was also poorly distributed, and then dried at 1 50 ° C for 10 minutes.

Further, in a region where the surface electrode is formed on the surface of the substrate, a silver paste having a thickness of 20 is applied by a screen printing method, and then the "four" plate is subjected to "4" minutes by "drying" for four minutes. The heat treatment is performed to form the n-type diffusion layer in the ruthenium substrate by diffusing the dopant/dye contained in the anti-reflection film into the ruthenium substrate. Further, the aluminum of the first back electrode is turned toward the back surface of the ruthenium substrate. Forming a depth of about 10 _ dina layer. 1 ~ 矽 substrate, and then the surface electrode is passed through a film containing phosphorus (ρ) doped nitrite (smx) anti-reflection 139952.doc 17 201003938 and is conductive with the diffusion layer. The solar cell obtained in this manner can obtain the same light conversion efficiency as the solar cell in which the diffusion layer is formed by the prior method. (Embodiment 2) The thickness of the textured structure is formed on the surface by texture etching. 22〇μηι, 156 mm square η 刮 曰 曰 苴 苴 , ,

On the substrate, the anti-reflection film containing the side (B) is formed by pE_cvD (PlaSma-Enhanced Chemical Vap〇r Dep〇siu〇n, electric auxiliary product # ' The film formation condition is that the substrate temperature is 3〇〇. The flow rate of the gas is 7〇<-, the flow rate of the Li 3 gas is 8Q coffee, and the flow rate of the B2H6 gas by the & dilution is 15 ( () sccm, as the carrier gas & gas flow rate is 1000 seem, the power is 1 〇〇〇 w. The thickness of the obtained anti-reflection film is 7 〇 nm. Then, on the back side of the financial substrate 'by Shen Shuai (10) eurrent, DC) magnetron sputtering method to make a film of 〇.5 μιη with phosphorus (p) doped on the back of the film, coated by the screen printing J method a 20 μm thick silver paste, followed by drying at 15 (rc for 1 min.), then forming a surface electrode on the surface of the crucible substrate, applying a 2G (four) thickness silver paste by screen printing, Then, dry for 15 minutes (four minutes). Then, heat treatment of the ruthenium substrate for 3 minutes by 75 (TC), thereby making the anti-reflection film The impurity diffuses into the germanium substrate, and a P-type diffusion layer is formed in the substrate. 139952.doc 18 201003938 Further, the surface electrode passes through an anti-reflection film containing boron (B) doped tantalum nitride (SiNx). Contact with the diffusion layer. In the solar cell obtained in this manner, the light conversion efficiency equivalent to that of the solar cell in which the diffusion layer was formed by the prior method can be obtained. (Example 3) A textured structure is formed on the surface by texture etching. On a 矽-type single crystal germanium substrate having a thickness of 22 pm and 156 mm square, a nitrogen containing phosphorus (p) is contained by a CVD (Catalytic Chemical Vapor Deposition 'catalytic chemical vapor deposition) method. The anti-reflection film of bismuth (SiNx) is formed into a film. The film formation conditions are a substrate temperature of 300 ° C, a flow rate of SiH 4 gas is 1 〇〇 sccm, and a flow rate of NH 3 gas is 8 〇 sccm, diluted by & ν 〇 The flow rate of the gas of ι%ρ氐 is 1500 sccm, and the flow rate of the gas as the carrier gas is 1000 seem' The power is 1 〇〇〇w. The thickness of the obtained anti-reflection film is 70 nm. Then, on the back of the ruthenium substrate The area where the second back electrode is formed, Applying a silver paste of 20 μηι thickness by screen printing, followed by 15 〇. Drying for 10 minutes. Then, forming the area of the back electrode on the back surface of the ruthenium substrate, by screen printing Applying a 20 μηι thickness aluminum paste, and then drying it for 15 minutes at 15 。. Further, in the region where the surface electrode is formed on the surface of the ruthenium substrate, a thickness of 20 μm is applied by screen printing. The silver paste is then dried at 15 〇 for 1 〇. λ 139952.doc •19- 201003938 Then the substrate was heat treated at 75 〇t for 3 minutes. Thereby, the dopant contained in the anti-reflection film is diffused into the germanium substrate, and an n-type diffusion layer is formed in the germanium substrate. Further, aluminum of the first back electrode is diffused into the substrate, and a BSF layer having a depth of about 10 μm is formed on the back surface of the substrate. Further, the surface electrode is conducted through the antireflection film containing phosphorus (germanium) doped tantalum nitride (SiNx) to be electrically connected to the diffusion layer. In the solar cell obtained in this manner, the light conversion efficiency equivalent to that of the solar cell in which the diffusion layer was formed by the prior method can be obtained. (Example 4) On a p-type single crystal germanium substrate having a thickness of 22 μm and 156 mm square formed on the surface by texture etching, by using germanium (Si) containing phosphorus (p) A DC magnetron sputtering method for forming a target is used to form an antireflection film containing tantalum nitride (SiNx) containing phosphorus (p). The film formation conditions were a substrate temperature of 100 ° C, a flow rate of Ar gas of 50 seem, a flow rate of NH 3 gas of 50 seem, and a sputtering power of 3 W/cm 2 . The thickness of the obtained antireflection film was 70 nm. Then, in a region where the second back surface electrode was formed on the back surface of the substrate, a silver paste having a thickness of 20 μm was applied by a screen printing method, followed by 15 Å. Dry and dry for 10 minutes. Then, in a region where the first back surface electrode was formed on the back surface of the substrate, a thickness of 20 μm was applied by a screen printing method, and then dried at 1 for 10 minutes. Further, in the region where the surface electrode was formed on the surface of the substrate, a silver paste of 20 μm thickness was applied by screen printing method of 139952.doc • 20-201003938, and then dried for 15 minutes by 15 generations. Then, take 750. (The heat treatment was performed for the ruthenium substrate for 3 minutes. Thereby, the dopant contained in the anti-reflection film was diffused into the ruthenium substrate, and an n-type diffusion layer was formed in the ruthenium substrate. The aluminum of the electrode diffuses into the germanium substrate, and a BSF layer having a depth of about 丨〇μηη is formed on the back surface of the germanium substrate. Further, the surface electrode passes through the pit-reflecting film containing phosphorus-doped tantalum nitride (SiN〇) and diffused The solar cell obtained in this manner can obtain the same light conversion efficiency as the solar cell in which the diffusion layer is formed by the prior method. (Example 5) The thickness of the textured structure is formed on the surface by texture etching. On the 156 mm square-type single crystal germanium substrate, an antireflection film containing phosphorus (P)-containing tantalum nitride (SiNx) was formed by pE_CVD. The film formation condition was that the substrate temperature was 3 °. C, the flow rate of SiH4 gas is 丨〇〇seem, the flow rate of helium gas is 80 sccm, the flow rate of i ν〇ι% gas diluted by & is 1 500 seem, and the flow rate of gas as carrier gas is 1000 seem ' Power is 1〇〇〇w. Obtained The thickness of the reflective film is 70 nm. Then, for the ruthenium substrate having the anti-reflection film, laser annealing is performed using a YAG (yttriUm aluminum garnet) laser having an output of 100 W twice the harmonics. The dopant contained in the anti-reflection film is diffused into the crucible substrate. 139952.doc 21 201003938 The condition of the laser annealing is an energy density of 3 〇〇 mJ/cm 2 and an irradiation time of 30 minutes. An n-type diffusion layer having a small thickness is formed in the vicinity of the interface between the substrate and the anti-reflection film. Then, a region where the second back electrode is formed on the back surface of the substrate is coated with 20 μm by screen printing. a silver paste of thickness, followed by drying for 10 minutes at wl 5 。t. ' Then, the second electrode of the back surface of the back surface of the substrate is coated with a 20 μm thick aluminum paste by screen printing, and thereafter 15 干燥 It was dried for 1 minute. Further, a silver paste having a thickness of 20 μm was applied by a screen printing method in a region where the surface electrode was formed on the surface of the substrate, followed by drying at 〇 〇. The first back electrode and the second back surface are formed The extreme pole 0 and the surface electricity are then 750. (: The heat treatment is performed for the Shishi substrate for 3 seconds. Thus, a bribe layer having a depth of about ι〇_ is formed on the back surface of the Shishi substrate. Meanwhile, the surface electrode is worn. The anti-reflection film containing phosphorus (germanium) doped with cerium (siNx) is electrically connected to the diffusion layer. The solar cell obtained in this manner has the same light conversion efficiency as the solar cell which has formed the diffusion layer by the prior method. (Example 6) On the p-type polycrystalline germanium substrate with a thickness of 2 〇〇 952 952 〇〇 〇〇 〇〇 〇〇 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 952 An antireflection film containing phosphorus (P)-containing cerium nitride (SiNx) was formed into a film by a CVD method. The film formation conditions are the substrate temperature of 300 ° C, the flow rate of SiH 4 gas is 1 〇〇 seem, the flow rate of NH 3 gas is 80 seem, and the flow rate of 1 vol % PH3 gas diluted by h 2 is 1 500 seem ' as the carrier gas n2 The gas flow rate is 1000 seem and the power is 1 〇〇〇W. The thickness of the obtained antireflection film was 70 nm. Then, a silver paste having a thickness of 20 μm was applied by a screen printing method to the region where the second back electrode was formed on the back surface of the substrate, and then dried for 15 minutes at 15 Torr. Then, in a region where the i-th back electrode was formed on the back surface of the substrate, an aluminum paste having a thickness of 20 μm was applied by a screen printing method, and thereafter dried at 15 〇 1 for 10 minutes. Further, in the region where the surface electrode was formed on the surface of the substrate, a silver paste having a thickness of μη was applied, followed by coating for 15 minutes by TC dry 10 screen printing method, and then 750 °C at 750 °C. (: The tantalum substrate was heat-treated for 3 seconds.

A P-type diffusion layer is formed in the stone substrate.

The pole is electrically connected to the diffusion layer through an anti-reflection film containing -(P)-doped nitridite (siNx).

139952.doc -23· 201003938 (Comparative example) A p-type single crystal, 151 mm square p-shaped single crystal, earth ant (surface coated) formed on the surface of the surface recording surface by texture characterization The cloth contains a coating of phosphorus (P), and then a heat treatment of 90 (rc) is applied to form a diffusion layer having a thickness of about 〇5 near the surface of the substrate.

Then, the diffusion layer was subjected to S, 1 □ / month / none using hydrofluoric acid, and further washed with ultrapure water. Then, the anti-reflection film containing Nitrogen Fossil (SiNx) was formed on the δ-Heil diffusion layer by the CVE) method. The film formation conditions are as follows: the substrate temperature is: Cm' with a flow rate of 3 gas of 30, and the flow of n2 gas as a carrier gas is 600 seem, and the power is 3 〇〇 w. The thickness of the obtained antireflection film was 7 〇 nm. Then, in the region on the back surface of the ruthenium substrate where the electrode of the first battlefield 2 electrode was formed, a 20 μΓ thick thickness of the giant pavilion was applied by <silver f, followed by I 50 by screen printing. (: Drying for 1 minute. Then, in the area of the back surface of the enamel substrate, the surface of the electrode of the 丄 乂 丄 , , , , , , , , 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 15 (TC is dried for 10 minutes. Further, 'the surface of the surface of the surface of the surface of the substrate is formed by coating the silver paste of 20 (four) thickness by the printing method, and then drying for 15 minutes in the 15th generation. a back electrode, a second back electrode, and a surface electrode. Then, the ruthenium substrate is heat-treated at 75 (TC) for 3 seconds. Thereby, a depth of about 1 〇 is formed on the back surface of the ruthenium substrate. 139952.doc 201003938 Layer. At the same time, the surface electrode is electrically connected to the diffusion layer through an anti-reflection film containing nitrogen cut. The photoelectric conversion efficiency of the solar cell obtained in this way is 12 to 17 〇 / 〇. When the cleaning is insufficient or the substrate is not kept in a clean state after cleaning, there is a case where the photoelectric conversion efficiency is lowered, and there is a case where the quality is unstable. According to the above results, the sun of the embodiment is known. Battery and ratio Compared with the solar cell of the example, the same output and photoelectric conversion efficiency can be obtained. Further, in the solar cell of the embodiment 6, since the antireflection film and the diffusion layer can be formed by the film formation process, the comparative example is not required. The cleaning step can shorten the manufacturing time, reduce the number of steps, and reduce the manufacturing cost. As described in detail above, the present invention is suitable for improving the battery characteristics of a solar cell, without preparing a device dedicated to each step, It is possible to reduce the number of steps, the method of manufacturing a solar cell, and the manufacturing method of a solar cell, and the solar cell, which are reduced in the number of steps. Fig. 1 is a cross-sectional view showing a solar cell according to an embodiment of the present invention, and (a) (e) is a cross-sectional view showing a method of fabricating the present invention. Battery manufacturing 139952.doc •25· 201003938 [Main component symbol description] 1 夕 substrate 2 diffusion layer 3 anti-reflection film 4 BSF layer 5 first back electrode 6 second Back electrode 7 Surface electrode 11 Film forming device 12 Electrode forming device 13 Heating device 14 Plasma generating portion 15 Substrate conveying mechanism 21 Hard substrate 22 Antireflection film 139952.doc -26-

Claims (1)

201003938 VII. Patent application scope: 1. A method for manufacturing a solar cell, characterized in that: anti-reflection is formed on a germanium substrate having a conductivity type of p-type or n-type, and a dopant containing a conductivity type different from the germanium substrate is formed. a film; heat-treating the anti-reflection film to diffuse a dopant contained in the anti-reflection film into the germanium substrate. 2. The method of manufacturing a solar cell according to claim 1, wherein after forming the anti-reflection film, forming a surface electrode on the anti-reflection film; and causing the dopant contained in the anti-reflection film to be in the ruthenium substrate At the time of diffusion, the surface electrode and the substrate are electrically connected by heating the surface substrate on which the antireflection film and the surface electrode are formed, and the dopant is diffused into the ruthenium substrate. 3. The method of manufacturing a solar cell according to claim 1 or 2, wherein a back electrode containing aluminum is formed on a back surface of the germanium substrate; and iJ is a surface of the germanium substrate having a conductivity type of p type when the antireflection film is formed. Forming an anti-reflection film containing an n-type dopant; and forceing the dopant contained in the anti-reflection film to diffuse into the stone substrate; 'forming the anti-reflection film by heating and the back surface The substrate 'is diffused into the germanium substrate, and the portion of the above-mentioned @ is diffused into the dream substrate. The method for producing a solar cell according to Item 1 or 2, wherein, when the dopant contained in the anti-reflection film is diffused toward the germanium substrate, the highest heating temperature is 60 CTC or more and 1200 t is I39952.doc 201003938 The lower 'heating time is 1 minute or more and 120 minutes or less. 5. The method of manufacturing a solar cell according to claim 1 or 2, wherein the ruthenium substrate is exposed to a plasma under vacuum before forming the anti-reflection film; after exposing the ruthenium substrate to the plasma, The anti-reflection film is formed in a state where the crucible substrate is held in a vacuum. 6. The method of manufacturing a solar cell according to claim 5, wherein the anti-reflection film is formed by a plasma CVD method; using the same plasma CVD device, exposing the ruthenium substrate to ruthenium in a vacuum, moxibustion, borrowing The antireflection film is formed by the above plasma CVD method. A solar cell manufacturing apparatus, comprising: a film forming apparatus that introduces a gas containing a dopant on a surface of a film, and forms an antireflection film containing the dopant on a substrate; An electrode is formed on the substrate; and a heating device that heats the substrate to diffuse the dopant into the substrate. 8. The apparatus for manufacturing a solar cell according to claim 7, wherein the film formation unit comprises a plasma generating portion that performs plasma treatment on the substrate. 9. The solar cell manufacturing apparatus according to claim 7 or 8, wherein the substrate transfer apparatus is configured to transport the substrate in the order of the film forming apparatus, the electrode forming apparatus, and the heating apparatus. 10. A solar cell characterized by comprising: a germanium substrate, which is a conductive type? Type or n-type; i39952.doc 201003938 diffusion layer, which is laminated on the above-mentioned germanium substrate, a contains different dopants of the conductive fish-based substrate; and /, an anti-reflective film is formed on the diffusion layer The above-mentioned doping 11. The solar cell of claim 1, wherein the diffusion layer of the diffusion layer is lower than the dopant concentration of the anti-reflection film. 139952.doc