WO2011132778A1 - p型拡散層形成組成物、p型拡散層の製造方法、及び太陽電池素子の製造方法 - Google Patents
p型拡散層形成組成物、p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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- WO2011132778A1 WO2011132778A1 PCT/JP2011/059970 JP2011059970W WO2011132778A1 WO 2011132778 A1 WO2011132778 A1 WO 2011132778A1 JP 2011059970 W JP2011059970 W JP 2011059970W WO 2011132778 A1 WO2011132778 A1 WO 2011132778A1
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- Prior art keywords
- diffusion layer
- type diffusion
- forming composition
- layer forming
- ether
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Classifications
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- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- 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
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
-
- 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
- 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
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
-
- 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 a solar cell element p-type diffusion layer forming composition, a p-type diffusion layer manufacturing method, and a solar cell element manufacturing method. More specifically, the present invention relates to the internal stress of a silicon substrate as a semiconductor substrate. The present invention relates to a technique for forming a p-type diffusion layer that can be reduced to suppress damage at crystal grain boundaries, suppress crystal defect growth, and suppress warpage.
- 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.
- a few tens of minutes is performed to form an n-type diffusion layer uniformly on the substrate.
- n-type diffusion layers are formed not only on the surface but also on the side surface and the back surface. Therefore, side etching is performed to remove the n-type diffusion layer on the side surface.
- the back surface of the n-type diffusion layer must be converted into the p + -type diffusion layer, an aluminum paste is printed on the back, by firing this, the n-type diffusion layer at the same time as the p + -type diffusion layer , Got ohmic contact.
- the aluminum layer formed from the aluminum paste has low electrical conductivity, and in order to reduce the sheet resistance, the aluminum layer generally formed on the entire back surface must have a thickness of about 10 to 20 ⁇ m after firing. Furthermore, when a thick aluminum layer is formed in this way, the thermal expansion coefficient differs greatly between silicon and aluminum, so that a large internal stress is generated in the silicon substrate during the firing and cooling process, resulting in damage to the grain boundaries, In some cases, defects increased and warped.
- the present invention has been made in view of the above-described conventional problems, and in the manufacturing process of a solar cell element using a silicon substrate, the p-type diffusion is performed while suppressing the occurrence of internal stress and warpage of the substrate in the silicon substrate.
- ⁇ 2> The p-type diffusion layer forming composition according to ⁇ 1>, wherein the acceptor element is at least one selected from B (boron), Al (aluminum), and Ga (gallium).
- the glass powder containing the acceptor element is at least one acceptor element-containing material selected from B 2 O 3 , Al 2 O 3, and Ga 2 O 3 , and SiO 2 , K 2 O, and Na 2 O. And at least one glass component material selected from Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, Tl 2 O, SnO, ZrO 2 , and MoO 3.
- the lifetime killer element is at least selected from Fe (iron), Cu (copper), Ni (nickel), Mn (manganese), Cr (chromium), W (tungsten), and Au (gold)
- the p-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 3>, which is one kind.
- a method for producing a p-type diffusion layer comprising: a step of applying the p-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 4>, and a step of performing a thermal diffusion treatment.
- ⁇ 6> A step of applying the p-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 4> above on a semiconductor substrate and a thermal diffusion treatment to form a p-type diffusion layer
- the manufacturing method of the solar cell element which has a process and the process of forming an electrode on the formed said p-type diffused layer.
- the present invention it becomes possible to form a p-type diffusion layer while suppressing internal stress in the silicon substrate and warping of the substrate in the manufacturing process of the solar cell element using the silicon substrate.
- the lifetime of the carrier in the formed substrate is not greatly reduced.
- the p-type diffusion layer forming composition of the present invention will be described, and then a p-type diffusion layer using the p-type diffusion layer forming composition and a method for producing a solar cell element 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 p-type diffusion layer forming composition of the present invention comprises at least an acceptor element and a total amount of lifetime killer elements of 1000 ppm or less (hereinafter sometimes simply referred to as “glass powder”), a dispersion medium, In addition, other additives may be added as necessary in consideration of applicability and the like.
- the p-type diffusion layer forming composition contains an acceptor element.
- the p-type diffusion layer is formed by thermally diffusing the acceptor element by applying thermal diffusion treatment (baking) after being applied to a silicon substrate. A material that can be used.
- the p + -type diffusion layer forming step and the ohmic contact forming step can be separated, and the choice of electrode material for forming the ohmic contact is widened.
- the options also expand. For example, if a low resistance material such as silver is used for the electrode, a low resistance can be achieved with a thin film thickness.
- the electrodes need not be formed on the entire surface, and may be partially formed like a comb shape. As described above, by forming a partial shape such as a thin film or a comb shape, it is possible to form a p-type diffusion layer while suppressing the occurrence of internal stress in the silicon substrate and warping of the substrate.
- the p-type diffusion layer forming composition of the present invention is applied, a conventionally widely employed method, that is, printing an aluminum paste and firing it to turn the n-type diffusion layer into a p + -type diffusion layer.
- a conventionally widely employed method that is, printing an aluminum paste and firing it to turn the n-type diffusion layer into a p + -type diffusion layer.
- the internal stress in the substrate and the warpage of the substrate that are generated by the method of obtaining the ohmic contact are suppressed.
- the acceptor component in the glass powder is not easily volatilized even during firing, the formation of a p-type diffusion layer other than the desired region due to the generation of the volatilizing gas is suppressed. The reason for this is considered that the acceptor component is bonded to an element in the glass powder or is taken into the glass, so that it is difficult to volatilize.
- the lifetime killer elements in the glass powder contained in the p-type diffusion layer forming crude composition of the present invention is 1000 ppm or less, the lifetime of carriers in the substrate on which the p-type diffusion layer is formed. Does not drop significantly. Details of the lifetime killer element will be described later.
- An acceptor element is an element that can form a p-type diffusion layer by doping into a silicon substrate.
- a Group 13 element can be used, and examples thereof include B (boron), Al (aluminum), and Ga (gallium).
- acceptor element-containing material used for introducing the acceptor element into the glass powder examples include B 2 O 3 , Al 2 O 3 , and Ga 2 O 3 , and B 2 O 3 , Al 2 O 3, and Ga 2 O. It is preferable to use at least one selected from 3 .
- the glass powder can control the melting temperature, softening point, glass transition point, chemical durability, and the like by adjusting the component ratio as necessary. Furthermore, it is preferable to contain the components 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, Tl 2 O, V 2 O 5 , SnO, and ZrO 2.
- the glass powder containing an acceptor element include a system containing both the acceptor element-containing substance and the glass component substance, and a B 2 O 3 —SiO 2 system (in order of acceptor element-containing substance—glass component substance). And the same applies hereinafter), B 2 O 3 —ZnO system, B 2 O 3 —PbO system, B 2 O 3 single system, etc., a system containing B 2 O 3 as an acceptor element-containing substance, Al 2 O 3 —SiO 2 system and the like systems containing for Al 2 O 3 acceptor element-containing materials, glass powders such as systems containing Ga 2 O 3 as the acceptor element-containing material of Ga 2 O 3 -SiO 2 system, and the like.
- a glass powder containing two or more kinds of acceptor element-containing materials such as Al 2 O 3 —B 2 O 3 series, Ga 2 O 3 —B 2 O 3 series, etc. may be used.
- a one-component glass or a composite glass containing two components is exemplified, but three or more components such as B 2 O 3 —SiO 2 —Na 2 O, B 2 O 3 —SiO 2 —CeO 2 and the like are exemplified. Glass powder containing a substance may be used.
- the total amount of elements (lifetime killer elements) that reduce the lifetime of the carrier in the glass powder is 1000 ppm or less, preferably 500 ppm or less, more preferably 100 pm or less, and even more preferably 50 ppm or less.
- the lifetime killer element include Fe, Cu, Ni, Mn, Cr, W, and Au.
- the amount of these elements can be analyzed with an ICP mass spectrometer, an ICP emission spectrometer, or an atomic absorption spectrometer.
- the lifetime of the carrier can be measured by the microwave photoconductive decay method ( ⁇ -PCD method).
- the content ratio of the glass component substance in the glass powder is preferably set as appropriate in consideration of the melting temperature, the softening temperature, the glass transition temperature, and the chemical durability, and is generally 0.1% by mass to 95% by mass. It is preferable that it is 0.5 mass% or more and 90 mass% or less.
- 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 during the diffusion treatment and dripping.
- the softening temperature of the glass powder can be 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 application property to a substrate and uniform diffusibility when an n-type diffusion layer forming composition is used. It is desirable to have a substantially spherical shape, flat shape, or plate shape.
- the particle size of the glass powder is desirably 50 ⁇ m or less. When glass powder having a particle size of 50 ⁇ m or less is used, a smooth coating film is easily obtained. Further, the particle size of the glass powder is more preferably 10 ⁇ 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 an acceptor 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 zirconia substrate, a carbon substrate 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 acceptor element in the p-type diffusion layer forming composition is determined in consideration of applicability, acceptor element diffusibility, and the like. Generally, the content ratio of the glass powder in the p-type diffusion layer forming composition is preferably 0.1% by mass or more and 95% by mass or less, and more preferably 1% by mass or more and 90% 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 dimethylaminoethyl (meth) acrylate polymer, polyvinyl alcohol, polyacrylamides, polyvinylamides, polyvinylpyrrolidone, poly (meth) acrylic acids, polyethylene oxides, polysulfonic acid, acrylamide alkyl sulfonic acid, and cellulose ether.
- Cellulose derivatives carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, gelatin, starch and starch derivatives, sodium alginate, xanthan, gua and gua derivatives, scleroglucan and scleroglucan derivatives, tragacanth and tragacanth derivatives, dextrin and dextrin derivatives, Acrylic resin, acrylic ester resin, butadiene resin, styrene resin, and these Polymer, and can appropriately select such as silicon dioxide. 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,
- Solvent methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec -Butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol 2-ethylbutanol, sec-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec- Heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexan
- ⁇ -terpineol diethylene glycol mono-n-butyl ether, and 2- (2-butoxyethoxy) ethyl acetate are preferred as the solvent from the viewpoint of applicability to the substrate.
- the content ratio of the dispersion medium in the p-type diffusion layer forming composition is determined in consideration of applicability and acceptor concentration.
- the viscosity of the p-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 total amount of lifetime killer elements in the glass powder is 1000 ppm or less
- the total amount of lifetime killer elements in the p-type diffusion layer forming crude composition is approximately 1100 ppm or less. Therefore, the total amount of lifetime killer elements in the p-type diffusion layer forming crude composition is preferably 500 ppm or less, and more preferably 100 ppm or less.
- an alkaline solution is applied to a silicon substrate which is a p-type semiconductor substrate to remove a damaged layer, and a texture structure is obtained by etching. Specifically, the damaged layer on the silicon surface generated when slicing from the ingot is removed with 20% by mass caustic soda. Next, etching is performed with a mixed solution of 1% by mass caustic soda and 10% by mass isopropyl alcohol to form a texture structure.
- a texture structure on the light receiving surface (surface) side, a light confinement effect is promoted, and high efficiency is achieved.
- the p-type diffusion layer-forming composition layer is formed by applying the p-type diffusion layer-forming composition onto the n-type diffusion layer on the back surface of the p-type semiconductor substrate, that is, the surface opposite to 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 semiconductor substrate coated with the p-type diffusion layer forming composition is subjected to thermal diffusion treatment at 600 to 1200 ° C.
- thermal diffusion treatment By this thermal diffusion treatment, the acceptor element diffuses into the semiconductor substrate, and a p + -type diffusion layer 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 acceptor element contained in the p-type diffusion layer forming composition. For example, it can be 1 minute to 60 minutes, and more preferably 5 minutes to 30 minutes.
- the glass layer 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.
- an aluminum paste is printed on the back surface, and this is baked to change the n-type diffusion layer into a p + -type diffusion layer, and at the same time, an ohmic contact is obtained.
- an aluminum layer formed from an aluminum paste has a low conductivity, and in order to reduce sheet resistance, an aluminum layer generally formed on the entire back surface must have a thickness of about 10 to 20 ⁇ m after firing.
- the thermal expansion coefficient differs greatly between silicon and aluminum, so that a large internal stress is generated in the silicon substrate during the firing and cooling process, causing warpage. This internal stress has a problem that the crystal grain boundary is damaged and the power loss increases.
- the warpage easily damages the solar cell element in the transportation of the solar cell element in the module process and the connection with a copper wire called a tab wire.
- the thickness of the silicon substrate has been reduced due to the improvement of the slice processing technique, and the solar cell element tends to be easily broken.
- the material used for the back electrode is not limited to aluminum.
- Ag (silver) or Cu (copper) can be applied, and the thickness of the back electrode can be made thinner than the conventional one. Further, it is not necessary to form the entire surface. Therefore, it is possible to reduce internal stress and warpage in the silicon substrate that occur during the firing and cooling processes.
- An antireflection film is formed on the n-type diffusion layer formed as described above.
- the antireflection film is formed by applying a known technique.
- the antireflection film 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. At this time, 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 to 2 Torr
- the temperature during film formation is 300 to 550 ° C.
- the surface electrode is formed by applying a surface electrode metal paste on the surface (light receiving surface) of the antireflection film by screen printing and drying.
- the metal paste for a surface electrode contains metal particles and glass particles as essential components, and includes a resin binder and other additives as necessary.
- a back electrode is also formed on the p + -type diffusion layer on the back surface.
- the material and forming method of the back electrode are not particularly limited.
- a back electrode paste containing a metal such as aluminum, silver, or copper may be applied and dried to form the back electrode.
- a silver paste for forming a silver electrode may be partially provided on the back surface for connection between cells in the module process.
- the above electrode is fired to complete the solar cell element.
- the antireflective film which is an insulating film, is melted by the glass particles contained in the electrode metal paste on the surface side, and part of the silicon surface is also melted.
- the metal particles (for example, silver particles) form a contact portion with the silicon substrate and solidify. Thereby, the formed surface electrode and the silicon substrate are electrically connected. This is called fire-through.
- the surface electrode includes a bus bar electrode and a finger electrode that intersects the bus bar electrode.
- a surface electrode can be formed 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.
- a surface electrode composed of a bus bar electrode and a finger electrode is generally used as an electrode on the light receiving surface side and is well known, and known forming means for the bus bar electrode and the finger electrode on the light receiving surface side can be applied.
- a mixed gas of phosphorus oxychloride (POCl 3 ), nitrogen and oxygen is used to form an n-type diffusion layer on a silicon substrate which is a p-type semiconductor substrate.
- the n-type layer may be formed using the n-type diffusion layer forming composition.
- the n-type diffusion layer forming composition contains a Group 15 element such as P (phosphorus) or Sb (antimony) as a donor element.
- the n-type diffusion layer forming composition is applied to the light-receiving surface which is the surface of the p-type semiconductor substrate, and the p-type of the present invention is applied to the back surface.
- the diffusion layer forming composition is applied and subjected to thermal diffusion treatment at 600 to 1200 ° C.
- the donor element diffuses into the p-type semiconductor substrate on the front surface to form an n-type diffusion layer, and the acceptor element diffuses on the back surface to form a p + -type diffusion layer.
- a solar cell element is produced by the same steps as those described above.
- the “carrier lifetime” shown below corresponds to the carrier lifetime of an n-type silicon substrate in which a B 2 O 3 -containing coating solution is applied to an n-type silicon substrate and thermally diffused to form a p-type diffusion layer.
- the lime time of the carrier of the n-type silicon substrate having the p-type diffusion layer produced in the example or the comparative example is shown as a relative value.
- the carrier lifetime is 70% or more from the practical point of view.
- Example 1 20 g of SiO 2 —B 2 O 3 glass (SiO 2 : 50 mol%, B 2 O 3 : 50 mol%, lifetime killer element 980 ppm) powder having a substantially spherical particle shape and an average particle diameter of 3.3 ⁇ m and 3 g of ethyl cellulose Then, 77 g of 2- (2-butoxyethoxy) ethyl acetate was mixed using an automatic mortar kneader to make a paste to prepare a p-type diffusion layer forming composition.
- the lifetime killer element in the glass powder was analyzed for content and type of element by a high frequency inductively coupled plasma emission spectroscopic analyzer and a high frequency inductively coupled plasma mass spectrometer. The same applies to the following embodiments.
- the glass powder contained Fe, Cu, and Ni as lifetime killer elements.
- 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 prepared paste (p-type diffusion layer forming composition) was applied to the surface of the n-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 to remove the glass layer, washed with running water, and then dried.
- the sheet resistance of the surface on which the p-type diffusion layer forming composition was applied was 80 ⁇ / ⁇ , and B (boron) was diffused to form a p-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the p-type diffusion layer was not substantially formed.
- the lifetime of the carrier was 74%. Further, no warpage of the substrate occurred.
- Example 2 Other than replacing the used glass powder with SiO 2 —B 2 O 3 glass powder (SiO 2 : 50 mol%, B 2 O 3 : 50 mol%, lifetime killer element 530 ppm, substantially spherical, average particle diameter 3.8 ⁇ m) Formed a p-type diffusion layer in the same manner as in Example 1.
- the glass powder contained Fe, Cu, and Ni as lifetime killer elements.
- the sheet resistance of the surface on which the p-type diffusion layer forming composition was applied was 82 ⁇ / ⁇ , and B (boron) was diffused to form a p-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the p-type diffusion layer was not substantially formed.
- the lifetime of the carrier was 82%. Further, no warpage of the substrate occurred.
- Example 3 Other than replacing the used glass powder with SiO 2 —B 2 O 3 glass powder (SiO 2 : 50 mol%, B 2 O 3 : 50 mol%, lifetime killer element 470 ppm, substantially spherical, average particle diameter 3.3 ⁇ m) Formed a p-type diffusion layer in the same manner as in Example 1.
- the glass powder contained Fe, Cu, and Ni as lifetime killer elements.
- the sheet resistance of the surface on which the p-type diffusion layer forming composition was applied was 78 ⁇ / ⁇ , and B (boron) was diffused to form a p-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the p-type diffusion layer was not substantially formed.
- the lifetime of the carrier was 87%. Further, no warpage of the substrate occurred.
- Example 4 The glass powder used was changed to SiO 2 —B 2 O 3 glass powder (SiO 2 : 50 mol%, B 2 O 3 : 50 mol%, lifetime killer element 120 ppm, substantially spherical, average particle diameter 3.7 ⁇ m). Formed a p-type diffusion layer in the same manner as in Example 1.
- the glass powder contained Fe, Cu, and Ni as lifetime killer elements.
- the sheet resistance on the surface coated with the p-type diffusion layer forming composition was 81 ⁇ / ⁇ , and B (boron) was diffused to form a p-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the p-type diffusion layer was not substantially formed.
- the lifetime of the carrier was 91%. Further, no warpage of the substrate occurred.
- Example 5 Other than replacing the used glass powder with SiO 2 —B 2 O 3 glass powder (SiO 2 : 50 mol%, B 2 O 3 : 50 mol%, lifetime killer element 85 ppm, substantially spherical, average particle diameter 3.5 ⁇ m) Formed a p-type diffusion layer in the same manner as in Example 1.
- the glass powder contained Fe, Cu, and Ni as lifetime killer elements.
- the sheet resistance of the surface on which the p-type diffusion layer forming composition was applied was 80 ⁇ / ⁇ , and B (boron) was diffused to form a p-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the p-type diffusion layer was not substantially formed.
- the lifetime of the carrier was 95%. Further, no warpage of the substrate occurred.
- Example 6 Except that the glass powder used was SiO 2 —B 2 O 3 glass powder (SiO 2 : 50 mol%, B 2 O 3 : 50 mol%, lifetime killer element 20 ppm, substantially spherical, average particle diameter 3.2 ⁇ m) A p-type diffusion layer was formed in the same manner as in Example 1.
- the glass powder contained Fe, Cu, and Ni as lifetime killer elements.
- the sheet resistance of the surface on which the p-type diffusion layer forming composition was applied was 85 ⁇ / ⁇ , and B (boron) was diffused to form a p-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the p-type diffusion layer was not substantially formed.
- the lifetime of the carrier was 98%. Further, no warpage of the substrate occurred.
- Example 7 Except that the glass powder used was SiO 2 —B 2 O 3 glass powder (SiO 2 : 50 mol%, B 2 O 3 : 50 mol%, lifetime killer element 8 ppm, substantially spherical, average particle diameter 3.5 ⁇ m) A p-type diffusion layer was formed in the same manner as in Example 1.
- the glass powder contained Fe, Cu, and Ni as lifetime killer elements.
- the sheet resistance on the surface coated with the p-type diffusion layer forming composition was 81 ⁇ / ⁇ , and B (boron) was diffused to form a p-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more, which was not measurable, and it was determined that the p-type diffusion layer was not substantially formed.
- the lifetime of the carrier was 100%. Further, no warpage of the substrate occurred.
- the prepared paste (p-type diffusion layer forming composition) 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 to remove the glass layer, washed with running water, and then dried.
- the sheet resistance of the surface on which the p-type diffusion layer forming composition was applied was 80 ⁇ / ⁇ , and B (boron) was diffused to form a p-type diffusion layer.
- the sheet resistance on the back surface was 1000000 ⁇ / ⁇ or more and could not be measured, and no p-type diffusion layer was formed. However, the career lifetime was as low as 68%.
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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、基板に一様に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を行う。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、裏面にアルミペーストを印刷し、これを焼成して、n型拡散層をp+型拡散層にするのと同時に、オーミックコンタクトを得ている。
本発明は、以上の従来の問題点に鑑みなされたものであり、シリコン基板を用いた太陽電池素子の製造工程において、シリコン基板中の内部応力、基板の反りの発生を抑制しつつp型拡散層を形成することが可能なp型拡散層形成組成物であって、これにより得られたp型拡散層を有する基板においてキャリアのライフタイムが大きく低下しないp型拡散層形成組成物、p型拡散層の製造方法、及び太陽電池素子の製造方法の提供を課題とする。
<1> アクセプタ元素を含みライフタイムキラー元素の総量が1000ppm以下であるガラス粉末と、分散媒と、を含有するp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およ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、p型拡散層形成組成物とはアクセプタ元素を含有し、例えば、シリコン基板に塗布した後に熱拡散処理(焼成)することでこのアクセプタ元素を熱拡散させてp型拡散層を形成することが可能な材料をいう。本発明のp型拡散層形成組成物を用いることで、p+型拡散層形成工程とオーミックコンタクト形成工程とを分離でき、オーミックコンタクト形成のための電極材の選択肢が広がるとともに、電極の構造の選択肢も広がる。例えば銀等の低抵抗材を電極に用いれば薄い膜厚で低抵抗が達成できる。また、電極も全面に形成する必要はなく、櫛型等の形状のように部分的に形成してもよい。以上のように薄膜あるいは櫛型形状等の部分的形状にすることで、シリコン基板中の内部応力、基板の反りの発生を抑えながらp型拡散層を形成することが可能となる。
さらにガラス粉末中のアクセプタ成分は焼成中でも揮散しにくいため、揮散ガスの発生によって所望の領域以外にまでp型拡散層が形成されるということが抑制される。この理由として、アクセプタ成分がガラス粉末中の元素と結合しているか、又はガラス中に取り込まれているため、揮散しにくいものと考えられる。
アクセプタ元素とは、シリコン基板中にドーピングさせることによってp型拡散層を形成することが可能な元素である。アクセプタ元素としては第13族の元素が使用でき、例えばB(ほう素)、Al(アルミニウム)及びGa(ガリウム)等が挙げられる。
ガラス成分物質としては、SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、V2O5、SnO、ZrO2、MoO3、La2O3、Nb2O5、Ta2O5、Y2O3、TiO2、GeO2、TeO2及びLu2O3等が挙げられ、SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、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。
また、Al2O3-B2O3系、Ga2O3-B2O3系等のように、2種類以上のアクセプタ元素含有物質を含むガラス粉末でもよい。
上記では1成分ガラスあるいは2成分を含む複合ガラスを例示したが、B2O3-SiO2-Na2O系、B2O3-SiO2-CeO2系等のように、3成分以上の物質を含むガラス粉末でもよい。
ライフタイムキラー元素として、Fe、Cu,Ni、Mn、Cr、W及びAuが挙げられる。これらの元素量はICP質量分析装置、ICP発光分析装置、原子吸光分析装置で分析できる。また、キャリアのライフタイムはマイクロ波光導電減衰法(μ-PCD法)により測定できる。
ガラス粉末の粒径は、50μm以下であることが望ましい。50μm以下の粒径を有するガラス粉末を用いた場合には、平滑な塗膜が得られやすい。更に、ガラス粉末の粒径は10μm以下であることがより望ましい。なお、下限は特に制限されないが、0.01μm以上であることが好ましい。
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ジルコニア基板やカーボン基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。
p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)エチルが好ましい溶剤として挙げられる。
p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。
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。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p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。
熱拡散処理時間は、p型拡散層形成組成物に含まれるアクセプタ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、5分間~30分間であることがより好ましい。
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、タブ線と呼ばれる銅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。
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0.1~2Torr、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。
このような表面電極は、例えば、上述の金属ペーストのスクリーン印刷、又は電極材料のメッキ、高真空中における電子ビーム加熱による電極材料の蒸着などの手段により形成することができる。バスバー電極とフィンガー電極とからなる表面電極は受光面側の電極として一般的に用いられていて周知であり、受光面側のバスバー電極及びフィンガー電極の公知の形成手段を適用することができる。
n型拡散層の形成にn型拡散層形成組成物を用いる方法では、まず、p型半導体基板の表面である受光面にn型拡散層形成組成物を塗布し、裏面に本発明のp型拡散層形成組成物を塗布し、600~1200℃で熱拡散処理する。この熱拡散処理により、表面ではp型半導体基板中へドナー元素が拡散してn型拡散層が形成され、裏面ではアクセプタ元素が拡散してp+型拡散層が形成される。この工程以外は上記方法と同様の工程により、太陽電池素子が作製される。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、およ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3.3μmのSiO2-B2O3系ガラス(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素980ppm)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77gとを自動乳鉢混練装置を用いて混合してペースト化し、p型拡散層形成組成物を調製した。
使用したガラス粉末をSiO2-B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素530ppm、略球状、平均粒子径3.8μm)に代えた以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p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82Ω/□であり、B(ほう素)が拡散しp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、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは82%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2-B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素470ppm、略球状、平均粒子径3.3μm)に代えた以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p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78Ω/□であり、B(ほう素)が拡散しp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、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは87%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2-B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素120ppm、略球状、平均粒子径3.7μm)に代えた以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p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81Ω/□であり、B(ほう素)が拡散しp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、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは91%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2-B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素85ppm、略球状、平均粒子径3.5μm)に代えた以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p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80Ω/□であり、B(ほう素)が拡散しp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、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは95%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2-B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素20ppm、略球状、平均粒子径3.2μm)とした以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p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85Ω/□であり、B(ほう素)が拡散しp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、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは98%であった。更に、基板の反りは発生していなかった。
使用したガラス粉末をSiO2-B2O3系ガラス粉末(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素8ppm、略球状、平均粒子径3.5μm)とした以外は実施例1と同様にp型拡散層形成を行った。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
p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81Ω/□であり、B(ほう素)が拡散しp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、p型拡散層は実質的に形成されていないと判断された。また、キャリアのライフタイムは100%であった。更に、基板の反りは発生していなかった。
粒子形状が略球状で、平均粒子径が3.3μmのSiO2-B2O3系ガラス(SiO2:50mol%、B2O3:50mol%、ライフタイムキラー元素1180ppm)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77gを混合してペースト化し、p型拡散層形成組成物を調製した。ガラス粉末中には、ライフタイムキラー元素として、Fe、Cu、Niが含まれていた。
Claims (6)
- アクセプタ元素を含み、ライフタイムキラー元素の総量が1000ppm以下であるガラス粉末と、分散媒と、を含有するp型拡散層形成組成物。
- 前記アクセプタ元素が、B(ほう素)、Al(アルミニウム)及びGa(ガリウム)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p型拡散層形成組成物。 - 前記アクセプタ元素を含むガラス粉末が、B2O3、Al2O3及びGa2O3から選択される少なくとも1種のアクセプタ元素含有物質と、SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、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p型拡散層形成組成物。
- 前記ライフタイムキラー元素が、Fe(鉄)、Cu(銅)、Ni(ニッケル)、Mn(マンガン)、Cr(クロム)、W(タングステン)及びAu(金)から選択される少なくとも1種である請求項1~請求項3のいずれか1項に記載のp型拡散層形成物。
- 請求項1~請求項4のいずれか1項に記載のp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p型拡散層の製造方法。
- 半導体基板上に、請求項1~請求項4のいずれか1項に記載のp型拡散層形成組成を塗布する工程と、
熱拡散処理を施してp型拡散層を形成する工程と、
形成された前記p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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EP11772109.2A EP2562793B1 (en) | 2010-04-23 | 2011-04-22 | METHOD FOR PRODUCING p-TYPE DIFFUSION LAYER, AND METHOD FOR PRODUCING SOLAR CELL ELEMENT |
KR1020127028224A KR101868163B1 (ko) | 2010-04-23 | 2011-04-22 | p 형 확산층 형성 조성물, p 형 확산층의 제조 방법, 및 태양 전지 소자의 제조 방법 |
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US13/642,526 US20130071968A1 (en) | 2010-04-23 | 2011-04-22 | Composition for forming p-type diffusion layer, method of forming p-type diffusion layer, and method of producing photovoltaic cell |
US14/076,212 US9520529B2 (en) | 2010-04-23 | 2013-11-09 | Composition for forming P-type diffusion layer, method of forming P-type diffusion layer, and method of producing photovoltaic cell |
US14/678,766 US20150214418A1 (en) | 2010-04-23 | 2015-04-03 | Composition for forming p-type diffusion layer, method of forming p-type diffusion layer, and method of producing photovoltaic cell |
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2011
- 2011-04-22 EP EP15168121.0A patent/EP2930740A1/en not_active Withdrawn
- 2011-04-22 CN CN201180020188.0A patent/CN102859659B/zh not_active Expired - Fee Related
- 2011-04-22 TW TW103124862A patent/TWI548102B/zh active
- 2011-04-22 JP JP2012511720A patent/JP5573946B2/ja not_active Expired - Fee Related
- 2011-04-22 KR KR1020127028224A patent/KR101868163B1/ko active IP Right Grant
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- 2011-04-22 WO PCT/JP2011/059970 patent/WO2011132778A1/ja active Application Filing
- 2011-04-22 EP EP11772109.2A patent/EP2562793B1/en not_active Not-in-force
- 2011-04-22 US US13/642,526 patent/US20130071968A1/en not_active Abandoned
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2013
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2014
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2015
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Also Published As
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CN102859659A (zh) | 2013-01-02 |
TW201138128A (en) | 2011-11-01 |
US20130071968A1 (en) | 2013-03-21 |
TW201448237A (zh) | 2014-12-16 |
TWI548102B (zh) | 2016-09-01 |
EP2562793A4 (en) | 2013-09-11 |
CN102859659B (zh) | 2017-07-28 |
JP2014099660A (ja) | 2014-05-29 |
KR101868163B1 (ko) | 2018-06-15 |
US20150214418A1 (en) | 2015-07-30 |
TWI495118B (zh) | 2015-08-01 |
JPWO2011132778A1 (ja) | 2013-07-18 |
KR20130098142A (ko) | 2013-09-04 |
US9520529B2 (en) | 2016-12-13 |
JP5573946B2 (ja) | 2014-08-20 |
EP2562793A1 (en) | 2013-02-27 |
EP2562793B1 (en) | 2017-08-30 |
US20140065761A1 (en) | 2014-03-06 |
EP2930740A1 (en) | 2015-10-14 |
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