WO2011132779A1 - n型拡散層形成組成物、n型拡散層の製造方法、及び太陽電池素子の製造方法 - Google Patents
n型拡散層形成組成物、n型拡散層の製造方法、及び太陽電池素子の製造方法 Download PDFInfo
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- WO2011132779A1 WO2011132779A1 PCT/JP2011/059971 JP2011059971W WO2011132779A1 WO 2011132779 A1 WO2011132779 A1 WO 2011132779A1 JP 2011059971 W JP2011059971 W JP 2011059971W WO 2011132779 A1 WO2011132779 A1 WO 2011132779A1
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- Prior art keywords
- diffusion layer
- type diffusion
- forming composition
- layer forming
- glass powder
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
- H01L21/2251—Diffusion into or out of group IV semiconductors
- H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
- H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/2225—Diffusion sources
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an n-type diffusion layer forming composition for a solar cell element, a method for producing an n-type diffusion layer, and a method for producing a solar cell element, and more specifically, a specific portion of a silicon substrate that is a semiconductor substrate.
- the present invention relates to a technique that makes it possible to form an n-type diffusion layer.
- a p-type silicon substrate having a textured structure is prepared so as to promote the light confinement effect and achieve high efficiency.
- a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen and oxygen is used at 800 to 900 ° C.
- the n-type diffusion layer is uniformly formed by performing several tens of minutes.
- n-type diffusion layers are formed not only on the surface but also on the side surface and the back surface. Therefore, a side etching process for removing the side n-type diffusion layer is necessary.
- the n-type diffusion layer on the back surface needs to be converted into a p + -type diffusion layer.
- An aluminum paste is applied on the n-type diffusion layer on the back surface, and the p + -type diffusion is performed from the n-type diffusion layer by the diffusion of aluminum. Was converted into a layer.
- n-type diffusion layer in the gas phase reaction using phosphorus oxychloride, not only one surface (usually the light receiving surface, the surface) that originally requires the n-type diffusion layer but also the other surface ( An n-type diffusion layer is also formed on the non-light-receiving surface, back surface) and side surfaces. Further, even in the method of applying a solution containing phosphate and thermally diffusing, an n-type diffusion layer is formed on the surface other than the surface as in the gas phase reaction method. Therefore, in order to have a pn junction structure as an element, it is necessary to perform etching on the side surface and convert the n-type diffusion layer to the p-type diffusion layer on the back surface. In general, an aluminum paste which is a Group 13 element is applied to the back surface and fired to convert the n-type diffusion layer into a p-type diffusion layer.
- the present invention has been made in view of the above-described conventional problems, and an n-type diffusion layer is formed in a specific portion without forming an unnecessary n-type diffusion layer in a manufacturing process of a solar cell element using a silicon substrate. It is an object to provide an n-type diffusion layer forming composition capable of forming a solar cell element having a low surface resistance, a method for manufacturing an n-type diffusion layer, and a method for manufacturing a solar cell element .
- a glass powder containing a donor element and a dispersion medium, the glass powder containing a donor element-containing substance and a glass component substance, and a content ratio of the donor element-containing substance in the glass powder is The n type diffused layer formation composition which is 1 mass% or more and 80 mass% or less.
- composition for forming an n-type diffusion layer according to ⁇ 1> wherein the donor element is at least one selected from P (phosphorus) and Sb (antimony).
- the glass powder containing the donor element includes at least one donor element-containing material selected from P 2 O 3 , P 2 O 5 and Sb 2 O 3 , and SiO 2 , K 2 O, and Na 2 O. Or at least one glass component material selected from Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 and MoO 3. 2> The composition for forming an n-type diffusion layer according to 2>.
- ⁇ 4> The above-mentioned ⁇ 1>-, further comprising at least one metal selected from Ag (silver), Si (silicon), Cu (copper), Fe (iron), Zn (zinc), and Mn (manganese)
- a method for producing an n-type diffusion layer comprising: a step of applying the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 5>, and a step of performing a thermal diffusion treatment.
- ⁇ 7> A step of applying the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 5> on a semiconductor substrate and a thermal diffusion treatment to form an n-type diffusion layer
- the manufacturing method of the solar cell element which has the process to form and the process of forming an electrode on the formed said n type diffused layer.
- n-type diffusion layer in a specific portion without forming an unnecessary n-type diffusion layer in a manufacturing process of a solar cell element using a silicon substrate. Moreover, by setting it as the range of the content rate of the donor element containing material of this invention, a surface resistance value falls and it becomes possible to improve the performance as a solar cell element.
- FIG. 2A It is sectional drawing which shows notionally an example of the manufacturing process of the solar cell element of this invention. It is the top view which looked at the solar cell element from the surface. It is a perspective view which expands and shows a part of FIG. 2A.
- the n-type diffusion layer forming composition of the present invention will be described, and then the n-type diffusion layer and solar cell element manufacturing method using the n-type diffusion layer forming composition will be described.
- the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used if the intended action of the process is achieved. included.
- “to” indicates a range including numerical values described before and after that as a minimum value and a maximum value, respectively.
- the amount of each component in the composition in the present specification when there are a plurality of substances corresponding to each component in the composition, the plurality of the components present in the composition unless otherwise specified. It means the total amount of substance.
- the n-type diffusion layer forming composition of the present invention contains a glass powder containing at least a donor element (hereinafter sometimes simply referred to as “glass powder”) and a dispersion medium, and further considers coating properties and the like. Other additives may be contained as necessary.
- the n-type diffusion layer forming composition refers to a material that contains a donor element and can form an n-type diffusion layer by thermally diffusing the donor element after being applied to a silicon substrate.
- the composition for forming an n-type diffusion layer of the present invention is applied, the side etching step that is essential in the gas phase reaction method that has been widely employed is not required, and the process is simplified.
- the step of converting the n-type diffusion layer formed on the back surface into the p + -type diffusion layer is not necessary. Therefore, the method for forming the p + -type diffusion layer on the back surface and the material, shape, and thickness of the back electrode are not limited, and the choice of manufacturing method, material, and shape to be applied is widened. Although details will be described later, generation of internal stress in the silicon substrate due to the thickness of the back electrode is suppressed, and warpage of the silicon substrate is also suppressed.
- the glass powder contained in the n-type diffusion layer forming composition of the present invention is melted by firing to form a glass layer on the n-type diffusion layer.
- a glass layer is formed on the n-type diffusion layer in the conventional gas phase reaction method and the method of applying a phosphate-containing solution, and thus the glass layer produced in the present invention is the same as the conventional method. Further, it can be removed by etching. Therefore, the n-type diffusion layer forming composition of the present invention does not generate unnecessary products and does not increase the number of steps as compared with the conventional method.
- the donor component in the glass powder is difficult to volatilize even during firing, the formation of an n-type diffusion layer not only on the surface but also on the back surface and side surfaces due to the generation of volatilized gas is suppressed. For this reason, for example, it is considered that the donor component is not easily volatilized because it is bonded to the element in the glass powder or is taken into the glass.
- the n-type diffusion layer forming composition of the present invention can form an n-type diffusion layer having a desired concentration at a desired site, a selective region having a high n-type dopant concentration is formed. It becomes possible to form. On the other hand, it is generally difficult to form a selective region having a high n-type dopant concentration by a gas phase reaction method, which is a general method of an n-type diffusion layer, or a method using a phosphate-containing solution. .
- a donor element is an element that can form an n-type diffusion layer by doping into a silicon substrate.
- a Group 15 element can be used, and examples thereof include P (phosphorus), Sb (antimony), Bi (bismuth), and As (arsenic). From the viewpoints of safety, ease of vitrification, etc., P or Sb is preferred.
- Examples of the donor element-containing material used for introducing the donor element into the glass powder include P 2 O 3 , P 2 O 5 , Sb 2 O 3 , Bi 2 O 3 and As 2 O 3 , and P 2 O 3 It is preferable to use at least one selected from P 2 O 5 and Sb 2 O 3 .
- the glass powder containing a donor element can control a melting temperature, a softening temperature, a glass transition point, chemical durability, etc. by adjusting a component ratio as needed. Furthermore, it is preferable to contain the glass component substance described below.
- glass component materials include SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, V 2 O 5 , SnO, ZrO 2 , MoO 3 , Examples include La 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , Y 2 O 3 , TiO 2 , ZrO 2 , GeO 2 , TeO 2, and Lu 2 O 3.
- SiO 2 , K 2 O, Na 2 It is preferable to use at least one selected from O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 , and MoO 3 .
- the glass powder containing a donor element include a system containing both the donor element-containing substance and the glass component substance, and a P 2 O 5 -SiO 2 system (in order of donor element-containing substance-glass component substance). in described, the same applies hereinafter), P 2 O 5 -K 2 O based, P 2 O 5 -Na 2 O-based, P 2 O 5 -Li 2 O system, P 2 O 5 -BaO-based, P 2 O 5 - SrO-based, P 2 O 5 -CaO-based, P 2 O 5 -MgO-based, P 2 O 5 -BeO based, P 2 O 5 -ZnO-based, P 2 O 5 -CdO based, P 2 O 5 -PbO system , P 2 O 5 —SnO system, P 2 O 5 —GeO 2 system, P 2 O 5 —TeO 2 system, etc., a system containing P 2 O 5 as a donor element-containing
- a glass powder containing two or more kinds of donor element-containing substances such as a P 2 O 5 —Sb 2 O 3 system and a P 2 O 5 —As 2 O 3 system, may be used.
- a composite glass containing two components has been exemplified, but a glass powder containing three or more components such as P 2 O 5 —SiO 2 —CaO may be used.
- the content ratio of the donor element-containing substance in the glass powder is 1% by mass in consideration of the doping concentration of the donor element into the silicon substrate, the melting temperature, softening temperature, glass transition point, and chemical durability of the glass powder. More than 80 mass%.
- the content ratio of the donor element-containing substance in the glass powder is less than 1% by mass, the doping concentration of the donor element into the silicon substrate is too low, and the n-type diffusion layer is not sufficiently formed.
- the content ratio of the donor element-containing material such as P 2 O 5 is larger than 80% by mass, the donor element-containing material absorbs moisture in the glass powder.
- the donor element-containing material is P 2 O 5
- phosphorus An acid (H 3 PO 4 ) is formed.
- moisture-absorbing substances such as H 3 PO 4 are volatilized during the thermal diffusion treatment, so that the diffusion of the donor element such as P (phosphorus) extends to the side surface and the back surface as well as the surface and other than the desired part.
- an n-type diffusion layer is also formed on the side surface and the back surface.
- the content ratio of the donor element-containing substance in the glass powder is preferably 2% by mass to 75% by mass, and more preferably 10% by mass to 70% by mass.
- the content ratio of the donor element-containing material in the glass powder is 30% by mass or more and 70% by mass. % Or less is more preferable.
- the content ratio of the glass component substance in the glass powder is preferably set in consideration of the melting temperature, the softening temperature, the glass transition point, and the chemical durability, and is generally 20% by mass to 99% by mass. It is preferably 25% by mass or more and 98% by mass or less, and more preferably 30% by mass or more and 90% by mass or less.
- the content ratio of SiO 2 is preferably 20% by mass or more and 99% by mass or less, and 30% by mass or more and 90% by mass or less. It is more preferable.
- the softening temperature of the glass powder is preferably 200 ° C. to 1000 ° C., more preferably 300 ° C. to 900 ° C., from the viewpoints of diffusibility and dripping during the diffusion treatment.
- the softening temperature of the glass powder can be easily measured from its endothermic peak using a known differential thermal analyzer (DTA).
- DTA differential thermal analyzer
- the shape of the glass powder examples include a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like. From the viewpoint of the application property to the substrate and the uniform diffusibility when it is an n-type diffusion layer forming composition, It is desirable to have a substantially spherical shape, a flat shape, or a plate shape.
- the particle size of the glass powder is desirably 100 ⁇ m or less. When glass powder having a particle size of 100 ⁇ m or less is used, a smooth coating film is easily obtained. Furthermore, the particle size of the glass powder is more desirably 50 ⁇ m or less. The lower limit is not particularly limited, but is preferably 0.01 ⁇ m or more.
- the particle diameter of glass represents an average particle diameter, and can be measured by a laser scattering diffraction particle size distribution measuring apparatus or the like.
- the glass powder containing a donor element is produced by the following procedure. First, weigh the ingredients and fill the crucible. Examples of the material for the crucible include platinum, platinum-rhodium, iridium, alumina, quartz, carbon, and the like, and are appropriately selected in consideration of the melting temperature, atmosphere, reactivity with the molten material, and the like. Next, it heats with the temperature according to a glass composition with an electric furnace, and is set as a melt. At this time, it is desirable to stir the melt uniformly. Subsequently, the obtained melt is poured onto a graphite plate, a platinum plate, a platinum-rhodium alloy plate, a zirconia plate or the like to vitrify the melt. Finally, the glass is crushed into powder. A known method such as a jet mill, a bead mill, or a ball mill can be applied to the pulverization.
- the content ratio of the glass powder containing the donor element in the n-type diffusion layer forming composition is determined in consideration of the coating property, the diffusibility of the donor element, and the like.
- the content ratio of the glass powder in the n-type diffusion layer forming composition is preferably 0.1% by mass or more and 95% by mass or less, more preferably 1% by mass or more and 90% by mass or less, The content is more preferably 1.5% by mass or more and 85% by mass or less, and particularly preferably 2% by mass or more and 80% by mass or less.
- the dispersion medium is a medium in which the glass powder is dispersed in the composition. Specifically, a binder, a solvent, or the like is employed as the dispersion medium.
- binder examples include polyvinyl alcohol, polyacrylamides, polyvinylamides, polyvinylpyrrolidone, polyethylene oxides, polysulfonic acid, acrylamide alkylsulfonic acid, cellulose ethers, cellulose derivatives, carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, gelatin, starch And starch derivatives, sodium alginates, xanthan, gua and gua derivatives, scleroglucan and scleroglucan derivatives, tragacanth and tragacanth derivatives, dextrin and dextrin derivatives, (meth) acrylic acid resins, (meth) acrylic acid ester resins (e.g.
- Alkyl (meth) acrylate resins Alkyl (meth) acrylate resins, dimethylaminoethyl (meth) acrylate resins, etc.), butadiene Fat, styrene resins, copolymers thereof, Additional be appropriately selected siloxane resin. These are used singly or in combination of two or more.
- the molecular weight of the binder is not particularly limited, and it is desirable to adjust appropriately in view of the desired viscosity as the composition.
- the solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, Ketone solvents such as diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone; diethyl ether, methyl ethyl ether, methyl -N-propyl ether, di-iso-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane,
- n-type diffusion layer forming composition ⁇ -terpineol, diethylene glycol mono-n-butyl ether, and 2- (2-butoxyethoxy) ethyl acetate are preferred from the viewpoint of applicability to the substrate.
- the content ratio of the dispersion medium in the n-type diffusion layer forming composition is determined in consideration of applicability and donor concentration.
- the viscosity of the n-type diffusion layer forming composition is preferably 10 mPa ⁇ S or more and 1000000 mPa ⁇ S or less, more preferably 50 mPa ⁇ S or more and 500000 mPa ⁇ S or less in consideration of applicability.
- the n-type diffusion layer forming composition may contain other additives.
- other additives include metals that easily react with the glass powder.
- the n-type diffusion layer forming composition is applied on a semiconductor substrate and heat-treated at a high temperature to form an n-type diffusion layer. At that time, glass is formed on the surface. This glass is removed by dipping in an acid such as hydrofluoric acid, but some glass is difficult to remove depending on the type of glass. In that case, the glass can be easily removed after the acid cleaning by adding a metal such as Ag, Mn, Cu, Fe, Zn, or Si, which is easily crystallized with glass. Among these, it is preferable to use at least one selected from Ag, Si, Cu, Fe, Zn and Mn, and more preferable to use at least one selected from Ag, Si and Zn. It is particularly preferable to use it.
- the content ratio of the metal is desirably adjusted as appropriate depending on the type of glass and the type of the metal, and is generally 0.01% by mass or more and 10% by mass or less with respect to the glass powder.
- FIG. 1 is a schematic cross-sectional view conceptually showing an example of the manufacturing process of the solar cell element of the present invention.
- common constituent elements are denoted by the same reference numerals.
- an alkaline solution is applied to a silicon substrate which is a p-type semiconductor substrate 10 to remove a damaged layer, and a texture structure is obtained by etching.
- a texture structure is obtained by etching.
- the damaged layer on the silicon surface generated when slicing from the ingot is removed with 20% by mass caustic soda.
- etching is performed with a mixed solution of 1% by mass caustic soda and 10% by mass isopropyl alcohol to form a texture structure (the description of the texture structure is omitted in the figure).
- a texture structure on the light receiving surface (surface) side, a light confinement effect is promoted, and high efficiency is achieved.
- the n-type diffusion layer forming composition layer 11 is formed by applying the n-type diffusion layer forming composition to the surface of the p-type semiconductor substrate 10, that is, the surface that becomes the light receiving surface.
- the coating method is not limited, and examples thereof include a printing method, a spin method, a brush coating, a spray method, a doctor blade method, a roll coater method, and an ink jet method.
- the glass powder amount can be 0.01 g / m 2 to 100 g / m 2, and preferably 0.1 g / m 2 to 10 g / m 2 .
- a drying step for volatilizing the solvent contained in the composition may be provided after coating.
- drying is performed at a temperature of about 80 to 300 ° C. for about 1 to 10 minutes when using a hot plate and about 10 to 30 minutes when using a dryer or the like.
- the drying conditions depend on the solvent composition of the n-type diffusion layer forming composition, and are not particularly limited to the above conditions in the present invention.
- the manufacturing method of the p + -type diffusion layer (high concentration electric field layer) 14 on the back surface is limited to a method by conversion from an n-type diffusion layer to a p-type diffusion layer with aluminum. Therefore, any conventionally known method can be adopted, and the options of the manufacturing method are expanded. Therefore, for example, the high-concentration electric field layer 14 can be formed by applying the composition 13 containing a Group 13 element such as B (boron).
- composition 13 containing a Group 13 element such as B (boron) for example, a glass powder containing an acceptor element is used instead of a glass powder containing a donor element, and the same as the composition for forming an n-type diffusion layer.
- a p-type diffusion layer forming composition constituted as described above can be given.
- the acceptor element may be an element belonging to Group 13, and examples thereof include B (boron), Al (aluminum), and Ga (gallium).
- the glass powder containing acceptor element preferably comprises at least one selected from B 2 O 3, Al 2 O 3 and Ga 2 O 3.
- the method for applying the p-type diffusion layer forming composition to the back surface of the silicon substrate is the same as the method for applying the n-type diffusion layer forming composition described above on the silicon substrate.
- the high-concentration electric field layer 14 can be formed on the back surface by subjecting the p-type diffusion layer forming composition applied to the back surface to a thermal diffusion treatment similar to the thermal diffusion treatment in the n-type diffusion layer forming composition described later. .
- the thermal diffusion treatment of the p-type diffusion layer forming composition is preferably performed simultaneously with the thermal diffusion treatment of the n-type diffusion layer forming composition.
- the semiconductor substrate 10 on which the n-type diffusion layer forming composition layer 11 is formed is subjected to thermal diffusion treatment at 600 ° C. to 1200 ° C.
- thermal diffusion treatment As shown in FIG. 1C, the donor element diffuses into the semiconductor substrate, and the n-type diffusion layer 12 is formed.
- a known continuous furnace, batch furnace, or the like can be applied to the thermal diffusion treatment. Further, the furnace atmosphere during the thermal diffusion treatment can be appropriately adjusted to air, oxygen, nitrogen or the like.
- the thermal diffusion treatment time can be appropriately selected according to the content of the donor element contained in the n-type diffusion layer forming composition. For example, it can be 1 minute to 60 minutes, and more preferably 2 minutes to 30 minutes.
- a glass layer such as phosphate glass is formed on the surface of the formed n-type diffusion layer 12, this phosphate glass is removed by etching.
- etching a known method such as a method of immersing in an acid such as hydrofluoric acid or a method of immersing in an alkali such as caustic soda can be applied.
- n-type diffusion layer 12 In the method for forming an n-type diffusion layer of the present invention in which the n-type diffusion layer 12 is formed using the n-type diffusion layer forming composition 11 of the present invention shown in FIGS. Only the n-type diffusion layer 12 is formed, and unnecessary n-type diffusion layers are not formed on the back surface and side surfaces. Therefore, in the conventional method of forming an n-type diffusion layer by a gas phase reaction method, a side etching process for removing an unnecessary n-type diffusion layer formed on a side surface is essential. According to the manufacturing method of the invention, the side etching process is not required, and the process is simplified.
- n-type diffusion layer formed on the back surface it is necessary to convert an unnecessary n-type diffusion layer formed on the back surface into a p-type diffusion layer.
- a group 13 element is added to the n-type diffusion layer on the back surface.
- a method is adopted in which an aluminum paste is applied and baked to diffuse aluminum into the n-type diffusion layer and convert it into a p-type diffusion layer.
- an aluminum amount of a certain amount or more is required in order to sufficiently convert to the p-type diffusion layer and to form a high concentration electric field layer of p + layer. Therefore, the aluminum layer is formed thick. There was a need.
- the manufacturing method of the present invention since an unnecessary n-type diffusion layer is not formed on the back surface, it is not necessary to perform conversion from the n-type diffusion layer to the p-type diffusion layer, and the necessity of increasing the thickness of the aluminum layer is eliminated. . As a result, generation of internal stress and warpage in the silicon substrate can be suppressed. As a result, it is possible to suppress an increase in power loss and damage to the solar cell element.
- the manufacturing method of the p + -type diffusion layer (high concentration electric field layer) 14 on the back surface is limited to a method by conversion from an n-type diffusion layer to a p-type diffusion layer with aluminum. Therefore, any conventionally known method can be adopted, and the options of the manufacturing method are expanded.
- a p-type diffusion layer forming composition configured in the same manner as the n-type diffusion layer forming composition is formed on the back surface (n).
- the p + -type diffusion layer (high-concentration electric field layer) 14 is preferably formed on the back surface by applying to the surface opposite to the surface on which the mold diffusion layer forming composition is applied and baking.
- the material used for the back surface electrode 20 is not limited to Group 13 aluminum, and for example, Ag (silver), Cu (copper), or the like can be applied. In addition, it can be formed thinner than the conventional one.
- an antireflection film 16 is formed on the n-type diffusion layer 12.
- the antireflection film 16 is formed by applying a known technique.
- the antireflection film 16 is a silicon nitride film, it is formed by a plasma CVD method using a mixed gas of SiH 4 and NH 3 as a raw material.
- hydrogen diffuses into the crystal, and orbits that do not contribute to the bonding of silicon atoms, that is, dangling bonds and hydrogen are combined to inactivate defects (hydrogen passivation).
- the mixed gas flow ratio NH 3 / SiH 4 is 0.05 to 1.0
- the reaction chamber pressure is 0.1 Torr to 2 Torr
- the temperature during film formation is 300 ° C. to 550 ° C.
- a surface electrode metal paste is printed, applied and dried by a screen printing method on the antireflection film 16 on the surface (light receiving surface) to form the surface electrode 18.
- the metal paste for a surface electrode contains (1) metal particles and (2) glass particles as essential components, and includes (3) a resin binder and (4) other additives as necessary.
- the back electrode 20 is also formed on the high-concentration electric field layer 14 on the back surface.
- the material and forming method of the back electrode 20 are not particularly limited.
- the back electrode 20 may be formed by applying and drying a back electrode paste containing a metal such as aluminum, silver, or copper.
- a silver paste for forming a silver electrode may be partially provided on the back surface for connection between solar cell elements in the module process.
- the electrode is fired to complete the solar cell element.
- the antireflection film 16 that is an insulating film is melted by the glass particles contained in the electrode metal paste on the surface side, and the surface of the silicon 10 is also partially melted.
- Metal particles (for example, silver particles) in the paste form a contact portion with the silicon substrate 10 and solidify. Thereby, the formed surface electrode 18 and the silicon substrate 10 are electrically connected. This is called fire-through.
- FIG. 2A is a plan view of a solar cell element in which the surface electrode 18 includes a bus bar electrode 30 and a finger electrode 32 intersecting with the bus bar electrode 30 as viewed from the surface.
- FIG. 2B is a perspective view showing a part of FIG.
- Such a surface electrode 18 can be formed, for example, by means such as screen printing of the above-described metal paste, plating of the electrode material, or vapor deposition of the electrode material by electron beam heating in a high vacuum.
- the surface electrode 18 composed of the bus bar electrode 30 and the finger electrode 32 is generally used as an electrode on the light receiving surface side and is well known, and it is possible to apply known forming means for the bus bar electrode and finger electrode on the light receiving surface side. it can.
- the solar cell element in which the n-type diffusion layer is formed on the front surface, the p + -type diffusion layer is formed on the back surface, and the front surface electrode and the back surface electrode are further provided on the respective layers has been described.
- a layer formation composition it is also possible to produce a back contact type solar cell element.
- the back contact type solar cell element has all electrodes provided on the back surface to increase the area of the light receiving surface. That is, in the back contact type solar cell element, it is necessary to form both the n-type diffusion region and the p + -type diffusion region on the back surface to form a pn junction structure.
- the n-type diffusion layer forming composition of the present invention can form an n-type diffusion site only at a specific site, and therefore can be suitably applied to the production of a back contact type solar cell element.
- Example 1 20 g of P 2 O 5 —SiO 2 glass (P 2 O 5 content: 10%) powder having a substantially spherical particle shape, an average particle diameter of 3.5 ⁇ m, and a softening temperature of 490 ° C., and 0.3 g of ethyl cellulose, Then, 7 g of 2- (2-butoxyethoxy) ethyl acetate was mixed using an automatic mortar kneader to make a paste, thereby preparing an n-type diffusion layer forming composition.
- the glass particle shape was determined by observing with a TM-1000 scanning electron microscope manufactured by Hitachi High-Technologies Corporation.
- the average particle size of the glass was calculated using a LS 13 320 type laser scattering diffraction particle size distribution analyzer (measurement wavelength: 632 nm) manufactured by Beckman Coulter, Inc.
- the softening point of the glass was obtained from a differential heat (DTA) curve using a DTG-60H type differential heat / thermogravimetric simultaneous measuring device manufactured by Shimadzu Corporation.
- the prepared paste was applied to the surface of the p-type silicon substrate by screen printing and dried on a hot plate at 150 ° C. for 5 minutes. Subsequently, thermal diffusion treatment was performed for 10 minutes in an electric furnace set at 1000 ° C., and then the substrate was immersed in hydrofluoric acid for 5 minutes in order to remove the glass layer, and washed with running water. There was some deposit on the surface, but it could be easily removed by rubbing with a waste cloth. Thereafter, drying was performed.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 80 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- the sheet resistance was measured by a four-probe method using a Loresta-EP MCP-T360 type low resistivity meter manufactured by Mitsubishi Chemical Corporation.
- Example 2 An n-type diffusion layer was formed in the same manner as in Example 1 except that the thermal diffusion treatment time was 20 minutes.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 62 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- Example 3 An n-type diffusion layer was formed in the same manner as in Example 1 except that the thermal diffusion treatment time was 30 minutes.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 54 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- Example 4 Except that the glass powder was replaced with P 2 O 5 —SiO 2 glass powder (P 2 O 5 content: 30%) having a substantially spherical particle shape, an average particle diameter of 3.5 ⁇ m, and a softening temperature of 543 ° C. Then, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 55 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- Example 5 Except that the glass powder was replaced with P 2 O 5 —SiO 2 glass powder (P 2 O 5 content: 50%) having a substantially spherical particle shape, an average particle diameter of 3.5 ⁇ m, and a softening temperature of 587 ° C. Then, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 43 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- Example 6 The glass powder was replaced with P 2 O 5 —SiO 2 glass powder (P 2 O 5 content: 60%) having a substantially spherical particle shape, an average particle diameter of 3.5 ⁇ m, and a softening temperature of 612 ° C. Then, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 40 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer. On the other hand, the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- Example 7 Except that the glass powder was replaced with P 2 O 5 —SiO 2 glass powder (P 2 O 5 content: 70%) having a substantially spherical particle shape, an average particle diameter of 3.5 ⁇ m, and a softening temperature of 633 ° C. Then, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 41 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- Example 8 Except for replacing the glass powder with P 2 O 5 —ZnO glass powder (P 2 O 5 content: 10%) having a substantially spherical particle shape, an average particle diameter of 3.5 ⁇ m, and a softening temperature of 495 ° C., An n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 67 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- Example 9 Except for replacing the glass powder with P 2 O 5 —CaO glass powder (P 2 O 5 content: 40%) having a substantially spherical particle shape, an average particle diameter of 3.5 ⁇ m, and a softening temperature of 591 ° C., An n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and an n-type diffusion layer was formed using this composition.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 22 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- Example 10 19.7 g of P 2 O 5 —SiO 2 glass (P 2 O 5 content: 10%) powder having a substantially spherical particle shape, an average particle diameter of 3.5 ⁇ m, and a softening temperature of 527 ° C., and 0 Ag .3 g, 0.3 g of ethyl cellulose, and 7 g of 2- (2-butoxyethoxy) ethyl acetate were mixed using an automatic mortar kneader to prepare a paste, thereby preparing an n-type diffusion layer forming composition. Thereafter, the same operation as in Example 1 was performed. As a result, the substrate after cleaning had no glass deposits and was easily removed.
- the sheet resistance of the surface was 72 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance of the back surface was not measurable at 1000000 ⁇ / ⁇ , and it was determined that the n-type diffusion layer was not substantially formed.
- Example 1 The glass powder was replaced with P 2 O 5 —SiO 2 glass powder (P 2 O 5 content: 0.5%) having a substantially spherical particle shape, an average particle diameter of 3.5 ⁇ m, and a softening temperature of 467 ° C. Except for the above, an n-type diffusion layer forming composition was prepared in the same manner as in Example 1, and a thermal diffusion treatment was performed in the same manner as in Example 1 using this composition. The sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
- n-type diffusion layer forming composition was prepared by mixing 20 g of ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) powder, 3 g of ethyl cellulose, and 7 g of 2- (2-butoxyethoxy) ethyl acetate to prepare a paste.
- the prepared paste was applied to the surface of the p-type silicon substrate by screen printing and dried on a hot plate at 150 ° C. for 5 minutes.
- a thermal diffusion treatment was performed for 10 minutes in an electric furnace set at 1000 ° C., and then the substrate was immersed in hydrofluoric acid for 5 minutes to remove the glass layer, washed with running water, and dried.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 14 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 50 ⁇ / ⁇ , and an n-type diffusion layer was also formed on the back surface.
- n-type diffusion layer forming composition was prepared by mixing 1 g of ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) powder with 7 g of pure water, 0.7 g of polyvinyl alcohol and 1.5 g of isopropyl alcohol. .
- the prepared solution was applied to the surface of the p-type silicon substrate by a spin coater (2000 rpm, 30 sec) and dried on a hot plate at 150 ° C. for 5 minutes.
- a thermal diffusion treatment was performed for 10 minutes in an electric furnace set at 1000 ° C., and then the substrate was immersed in hydrofluoric acid for 5 minutes to remove the glass layer, washed with running water, and dried.
- the sheet resistance of the surface on which the n-type diffusion layer forming composition was applied was 10 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
- the sheet resistance on the back surface was 100 ⁇ / ⁇ , and an n-type diffusion layer was also formed on the back surface.
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Abstract
Description
まず、光閉じ込め効果を促して高効率化を図るよう、テクスチャー構造を形成したp型シリコン基板を準備し、続いてオキシ塩化リン(POCl3)、窒素、酸素の混合ガス雰囲気において800~900℃で数十分の処理を行って一様にn型拡散層を形成する。この従来の方法では、混合ガスを用いてリンの拡散を行うため、表面のみならず、側面、裏面にもn型拡散層が形成される。そのため、側面のn型拡散層を除去するためのサイドエッチング工程が必要であった。また、裏面のn型拡散層はp+型拡散層へ変換する必要があり、裏面のn型拡散層の上にアルミニウムペーストを付与して、アルミニウムの拡散に
よってn型拡散層からp+型拡散層に変換させていた。
行い、裏面においてはn型拡散層をp型拡散層へ変換しなければならない。一般には、裏面に第13族元素であるアルミニウムのペーストを塗布、焼成し、n型拡散層をp型拡散層へ変換している。
<1> ドナー元素を含むガラス粉末と、分散媒と、を含有し、前記ガラス粉末がドナー元素含有物質とガラス成分物質とを含有し、前記ガラス粉末中の前記ドナー元素含有物質の含有比率が、1質量%以上80質量%以下であるn型拡散層形成組成物。
尚、本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。また、本明細書において「~」は、その前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示すものとする。さらに本明細書において組成物中の各成分の量について言及する場合、組成物中に各成分に該当する物質が複数存在する場合には、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
ここで、n型拡散層形成組成物とは、ドナー元素を含有し、シリコン基板に塗布した後にこのドナー元素を熱拡散することでn型拡散層を形成することが可能な材料をいう。本発明のn型拡散層形成組成物を用いることで、所望の部位にのみn型拡散層が形成され、裏面や側面には不要なn型拡散層が形成されない。
ドナー元素とは、シリコン基板中にドーピングさせることによってn型拡散層を形成することが可能な元素である。ドナー元素としては第15族の元素が使用でき、例えばP(リン)、Sb(アンチモン)、Bi(ビスマス)及びAs(ヒ素)等が挙げられる。安全性、ガラス化の容易さ等の観点から、P又はSbが好適である。
ガラス成分物質としては、SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、V2O5、SnO、ZrO2、MoO3、La2O3、Nb2O5、Ta2O5、Y2O3、TiO2、ZrO2、GeO2、TeO2及びLu2O3等が挙げられ、SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2、及びMoO3から選択される少なくとも1種を用いることが、好ましい。
なお、P2O5-Sb2O3系、P2O5-As2O3系等のように、2種類以上のドナー元素含有物質を含むガラス粉末でもよい。
上記では2成分を含む複合ガラスを例示したが、P2O5-SiO2-CaO等のように、3成分以上の物質を含むガラス粉末でもよい。
なお、ガラス粉末の軟化温度は公知の示差熱分析装置(DTA)によって、その吸熱ピークから容易に測定することができる。
ここで、ガラスの粒径は、平均粒子径を表し、レーザー散乱回折法粒度分布測定装置等により測定することができる。
最初に原料を秤量し、るつぼに充填する。るつぼの材質としては白金、白金―ロジウム、イリジウム、アルミナ、石英、炭素等が挙げられるが、溶融温度、雰囲気、溶融物質との反応性等を考慮して適宜選ばれる。
次に、電気炉でガラス組成に応じた温度で加熱し融液とする。このとき融液が均一となるよう攪拌することが望ましい。
続いて得られた融液をグラファイト板、白金板、白金-ロジウム合金板、ジルコニア板等の上に流し出して融液をガラス化する。
最後にガラスを粉砕し粉末状とする。粉砕にはジェットミル、ビーズミル、ボールミル等公知の方法が適用できる。
分散媒とは、組成物中において上記ガラス粉末を分散させる媒体である。具体的に分散媒としては、バインダーや溶剤などが採用される。
n型拡散層形成組成物とした場合、基板への塗布性の観点から、α-テルピネオール、ジエチレングリコールモノ-n-ブチルエーテル、酢酸2-(2-ブトキシエトキシ)エチルが好ましい。
n型拡散層形成組成物の粘度は、塗布性を考慮して、10mPa・S以上1000000mPa・S以下であることが好ましく、50mPa・S以上500000mPa・S以下であることがより好ましい。
n型拡散層形成組成物は、半導体基板上に塗布され、高温で熱処理されることでn型拡散層を形成するが、その際に表面にガラスが形成される。このガラスは、ふっ酸等の酸に浸漬して除去されるが、ガラスの種類によっては除去し難いものがある。その場合に、ガラスと結晶化しやすいAg、Mn、Cu、Fe、Zn、Si等の金属を添加しておくことにより、酸洗浄後に容易にガラスを除去することができる。これらのなかでも、Ag、Si、Cu、Fe、Zn及びMnから選択される少なくとも1種を用いることが好ましく、Ag、Si及びZnから選択される少なくとも1種を用いることがより好ましく、Agを用いることが特に好ましい。
詳細には、インゴットからスライスした際に発生するシリコン表面のダメージ層を20質量%苛性ソーダで除去する。次いで1質量%苛性ソーダと10質量%イソプロピルアルコールの混合液によりエッチングを行い、テクスチャー構造を形成する(図中ではテクスチャー構造の記載を省略する)。太陽電池素子は、受光面(表面)側にテクスチャー構造を形成することにより、光閉じ込め効果が促され、高効率化が図られる。
上記n型拡散層形成組成物の塗布量としては特に制限はない。例えば、ガラス粉末量として0.01g/m2~100g/m2とすることができ、0.1g/m2~10g/m2であることが好ましい。
さらにp型拡散層形成組成物をシリコン基板の裏面に付与する方法は、既述のn型拡散層形成組成物をシリコン基板上に塗布する方法と同様である。
裏面に付与されたp型拡散層形成組成物を、後述するn型拡散層形成組成物における熱拡散処理と同様に熱拡散処理することで、裏面に高濃度電界層14を形成することができる。尚、p型拡散層形成組成物の熱拡散処理は、n型拡散層形成組成物の熱拡散処理と同時に行なうことが好ましい。
熱拡散処理時間は、n型拡散層形成組成物に含まれるドナー元素の含有率などに応じて適宜選択することができる。例えば、1分間~60分間とすることができ、2分間~30分間であることがより好ましい。
したがって、従来広く採用されている気相反応法によりn型拡散層を形成する方法では、側面に形成された不要なn型拡散層を除去するためのサイドエッチング工程が必須であったが、本発明の製造方法によれば、サイドエッチング工程が不要となり、工程が簡易化される。
この内部応力は、結晶の結晶粒界に損傷を与え、電力損失が大きくなるという課題があった。また、反りは、モジュール工程における太陽電池素子の搬送や、タブ線と呼ばれる導線との接続において、太陽電池素子を破損させ易くしていた。近年では、スライス加工技術の向上から、シリコン基板の厚みが薄型化されつつあり、更に太陽電池素子が割れ易い傾向にある。
例えば、ドナー元素を含むガラス粉末の代わりにアクセプタ元素を含むガラス粉末を用いて、n型拡散層形成組成物と同様にして構成されるp型拡散層形成組成物を、シリコン基板の裏面(n型拡散層形成組成物を塗布した面とは反対側の面)に塗布し、焼成処理することで、裏面にp+型拡散層(高濃度電界層)14を形成することが好ましい。
また後述するように、裏面の表面電極20に用いる材料は第13族のアルミニウムに限定されず、例えばAg(銀)やCu(銅)などを適用することができ、裏面の表面電極20の厚さも従来のものよりも薄く形成することが可能となる。
より具体的には、上記混合ガス流量比NH3/SiH4が0.05~1.0、反応室の圧力が0.1Torr~2Torr、成膜時の温度が300℃~550℃、プラズマの放電のための周波数が100kHz以上の条件下で形成される。
バックコンタクト型の太陽電池素子は、電極を全て裏面に設けて受光面の面積を大きくするものである。つまりバックコンタクト型の太陽電池素子では、裏面にn型拡散部位及びp+型拡散部位の両方を形成しpn接合構造とする必要がある。本発明のn型拡散層形成組成物は、特定の部位にのみn型拡散部位を形成することが可能であり、よってバックコンタクト型の太陽電池素子の製造に好適に適用することができる。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が490℃のP2O5-SiO2系ガラス(P2O5含有量:10%)粉末20gと、エチルセルロース0.3gと、酢酸2-(2-ブトキシエトキシ)エチル7gとを自動乳鉢混練装置を用いて混合してペースト化し、n型拡散層形成組成物を調製した。
熱拡散処理時間を20分とした以外は実施例1と同様にn型拡散層形成を行った。n型拡散層形成組成物を塗布した側の表面のシート抵抗は62Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
裏面のシート抵抗は1000000Ω/□以上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
熱拡散処理の時間を30分とした以外は実施例1と同様にn型拡散層形成を行った。n型拡散層形成組成物を塗布した側の表面のシート抵抗は54Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
他方、裏面のシート抵抗は1000000Ω/□以上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
ガラス粉末を粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が543℃のP2O5-SiO2系ガラス粉末(P2O5含有量:30%)に代えた以外は、実施例1と同様にしてn型拡散層形成組成物を調製し、これを用いてn型拡散層形成を行った。n型拡散層形成組成物を塗布した側の表面のシート抵抗は55Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
他方、裏面のシート抵抗は1000000Ω/□以上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
ガラス粉末を粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が587℃のP2O5-SiO2系ガラス粉末(P2O5含有量:50%)に代えた以外は、実施例1と同様にしてn型拡散層形成組成物を調製し、これを用いてn型拡散層形成を行った。n型拡散層形成組成物を塗布した側の表面のシート抵抗は43Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
他方、裏面のシート抵抗は1000000Ω/□以上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
ガラス粉末を粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が612℃のP2O5-SiO2系ガラス粉末(P2O5含有量:60%)に代えた以外は、実施例1と同様にしてn型拡散層形成組成物を調製し、これを用いてn型拡散層形成を行った。n型拡散層形成組成物を塗布した側の表面のシート抵抗は40Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
他方、裏面のシート抵抗は1000000Ω/□以上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
ガラス粉末を粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が633℃のP2O5-SiO2系ガラス粉末(P2O5含有量:70%)に代えた以外は、実施例1と同様にしてn型拡散層形成組成物を調製し、これを用いてn型拡散層形成を行った。n型拡散層形成組成物を塗布した側の表面のシート抵抗は41Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
他方、裏面のシート抵抗は1000000Ω/□以上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
ガラス粉末を粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が495℃のP2O5-ZnO系ガラス粉末(P2O5含有量:10%)に代えた以外は、実施例1と同様にしてn型拡散層形成組成物を調製し、これを用いてn型拡散層形成を行った。n型拡散層形成組成物を塗布した側の表面のシート抵抗は67Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
他方、裏面のシート抵抗は1000000Ω/□以上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
ガラス粉末を粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が591℃のP2O5-CaO系ガラス粉末(P2O5含有量:40%)に代えた以外は、実施例1と同様にしてn型拡散層形成組成物を調製し、これを用いてn型拡散層形成を行った。n型拡散層形成組成物を塗布した側の表面のシート抵抗は22Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
他方、裏面のシート抵抗は1000000Ω/□以上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が527℃のP2O5-SiO2系ガラス(P2O5含有量:10%)粉末19.7gと、Agを0.3gと、エチルセルロース0.3gと、酢酸2-(2-ブトキシエトキシ)エチル7gとを自動乳鉢混練装置を用いて混合してペースト化し、n型拡散層形成組成物を調製した。その後、実施例1と同様な操作を実施した。
その結果、洗浄後の基板にはガラスの付着物が無く、容易に除去されていた。また、表面のシート抵抗は72Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
他方、裏面のシート抵抗は1000000Ω/□上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
ガラス粉末を粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が467℃のP2O5-SiO2系ガラス粉末(P2O5含有量:0.5%)に代えた以外は、実施例1と同様にしてn型拡散層形成組成物を調製し、これを用いて実施例1と同様にして熱拡散処理を行った。
n型拡散層形成組成物を塗布した側の表面のシート抵抗は1000000Ω/□以上で測定不能であり、n型拡散層は実質的に形成されていないと判断された。
ガラス粉末を粒子形状が略球状で、平均粒子径が3.5μm、軟化温度が711℃のP2O5-SiO2系ガラス粉末(P2O5含有量:85%)に代えた以外は、実施例1と同様にしてn型拡散層形成組成物を調製し、これを用いて実施例1と同様にして熱拡散処理を行った。
n型拡散層形成組成物を塗布した側の表面のシート抵抗は36Ω/□であり、P(リン)が拡散しn型拡散層が形成されていた。
しかしながら、裏面のシート抵抗が255Ω/□であり、裏面にもn型拡散層が形成されていた。
リン酸二水素アンモニウム(NH4H2PO4)粉末20gとエチルセルロース3g、酢酸2-(2-ブトキシエトキシ)エチル7gを混合してペースト化し、n型拡散層形成組成物を調製した。
次に、調製したペーストをスクリーン印刷によってp型シリコン基板表面に塗布し、150℃のホットプレート上で5分間乾燥させた。続いて、1000℃に設定した電気炉で10分間熱拡散処理を行い、その後ガラス層を除去するため基板をふっ酸に5分間浸漬し、流水洗浄、乾燥を行った。
リン酸二水素アンモニウム(NH4H2PO4)粉末1gと純水7g、ポリビニルアルコール0.7g、イソプロピルアルコール1.5gを混合して溶液を調製し、n型拡散層形成組成物を調製した。
次に、調製した溶液をスピンコータ(2000rpm、30sec)によってp型シリコン基板表面に塗布し、150℃のホットプレート上で5分間乾燥させた。続いて、1000℃に設定した電気炉で10分間熱拡散処理を行い、その後ガラス層を除去するため基板をふっ酸に5分間浸漬し、流水洗浄、乾燥を行った。
12 n型拡散層
14 高濃度電界層
16 反射防止膜
18 表面電極
20 裏面電極(電極層)
30 バスバー電極
32 フィンガー電極
Claims (7)
- ドナー元素を含むガラス粉末と、分散媒と、を含有し、前記ガラス粉末がドナー元素含有物質とガラス成分物質とを含有し、前記ガラス粉末中の前記ドナー元素含有物質の含有比率が、1質量%以上80質量%以下であるn型拡散層形成組成物。
- 前記ドナー元素が、P(リン)及びSb(アンチモン)から選択される少なくとも1種である請求項1に記載のn型拡散層形成組成物。
- 前記ドナー元素を含むガラス粉末が、P2O3、P2O5及びSb2O3から選択される少なくとも1種のドナー元素含有物質と、SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2及びMoO3から選択される少なくとも1種のガラス成分物質と、を含有する請求項1又は請求項2に記載のn型拡散層形成組成物。
- 更にAg(銀)、Si(ケイ素)、Cu(銅)、Fe(鉄)、Zn(亜鉛)及びMn(マンガン)から選択される少なくとも1種の金属を含む請求項1~請求項3のいずれか1項に記載のn型拡散層形成組成物。
- 前記金属が、Ag(銀)である請求項4に記載のn型拡散層形成組成物。
- 請求項1~請求項5のいずれか1項に記載のn型拡散層形成組成物を塗布する工程と、
熱拡散処理を施す工程と、
を有するn型拡散層の製造方法。 - 半導体基板上に、請求項1~請求項5のいずれか1項に記載のn型拡散層形成組成物を塗布する工程と、
熱拡散処理を施して、n型拡散層を形成する工程と、
形成された前記n型拡散層上に電極を形成する工程と、
を有する太陽電池素子の製造方法。
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WO2013005738A1 (ja) * | 2011-07-05 | 2013-01-10 | 日立化成工業株式会社 | n型拡散層形成組成物、n型拡散層の製造方法及び太陽電池素子の製造方法 |
WO2013129002A1 (ja) * | 2012-02-29 | 2013-09-06 | 日立化成株式会社 | n型拡散層形成組成物、n型拡散層の製造方法、及び太陽電池セルの製造方法 |
JP2014179360A (ja) * | 2013-03-13 | 2014-09-25 | Hitachi Chemical Co Ltd | n型拡散層形成組成物、n型拡散層を有する半導体基板の製造方法、及び太陽電池素子の製造方法 |
JP2015050357A (ja) * | 2013-09-02 | 2015-03-16 | 日立化成株式会社 | p型拡散層を有するシリコン基板の製造方法、太陽電池素子の製造方法及び太陽電池素子 |
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KR20140092489A (ko) * | 2012-12-29 | 2014-07-24 | 제일모직주식회사 | 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극 |
CN107146757A (zh) * | 2016-08-26 | 2017-09-08 | 扬州杰盈汽车芯片有限公司 | 一种喷雾式晶圆附磷工艺 |
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- 2011-04-22 TW TW103135127A patent/TW201508821A/zh unknown
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WO2013005738A1 (ja) * | 2011-07-05 | 2013-01-10 | 日立化成工業株式会社 | n型拡散層形成組成物、n型拡散層の製造方法及び太陽電池素子の製造方法 |
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WO2013129002A1 (ja) * | 2012-02-29 | 2013-09-06 | 日立化成株式会社 | n型拡散層形成組成物、n型拡散層の製造方法、及び太陽電池セルの製造方法 |
JP5610100B2 (ja) * | 2012-02-29 | 2014-10-22 | 日立化成株式会社 | n型拡散層形成組成物、n型拡散層の製造方法、及び太陽電池セルの製造方法 |
JP2014220510A (ja) * | 2012-02-29 | 2014-11-20 | 日立化成株式会社 | n型拡散層形成組成物、n型拡散層の製造方法、及び太陽電池セルの製造方法 |
JP2014179360A (ja) * | 2013-03-13 | 2014-09-25 | Hitachi Chemical Co Ltd | n型拡散層形成組成物、n型拡散層を有する半導体基板の製造方法、及び太陽電池素子の製造方法 |
JP2015050357A (ja) * | 2013-09-02 | 2015-03-16 | 日立化成株式会社 | p型拡散層を有するシリコン基板の製造方法、太陽電池素子の製造方法及び太陽電池素子 |
Also Published As
Publication number | Publication date |
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JP5958485B2 (ja) | 2016-08-02 |
TWI499070B (zh) | 2015-09-01 |
KR20130066614A (ko) | 2013-06-20 |
JP5626339B2 (ja) | 2014-11-19 |
TW201508821A (zh) | 2015-03-01 |
TW201201400A (en) | 2012-01-01 |
KR20140129375A (ko) | 2014-11-06 |
CN102844841B (zh) | 2016-06-15 |
KR101484833B1 (ko) | 2015-01-21 |
JPWO2011132779A1 (ja) | 2013-07-18 |
JP2014170939A (ja) | 2014-09-18 |
CN102844841A (zh) | 2012-12-26 |
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