TW201139567A - Composition for forming p-type diffusion layer, method for forming p-type diffusion layer, and method for producing photovoltaic cell element - Google Patents

Abstract

The composition for forming a p-type diffusion layer contains an acceptor element-containing glass powder which has softening temperature of from 300 DEG C to 950 DEG C and a dispersion medium. A p-type diffusion layer and a photovoltaic cell element having a p-type diffusion layer are prepared by applying the composition for forming a p-type diffusion layer, followed by a thermal diffusion treatment.

Description

[Technical Field] The present invention relates to a composition for forming a P-type diffusion layer of a solar cell element, a method for producing a P-type diffusion layer, and a solar cell device. In a more detailed manner, the present invention relates to a p-type capable of reducing internal stress of a shi-shi substrate as a semiconductor substrate, suppressing damage of crystal grain bcmndary, suppressing growth of crystal defects, and suppressing warpage. Diffusion layer formation technology. [Prior Art] The manufacturing steps of the prior 矽 solar cell element will be described. First, in order to promote the efficiency of the optical confinement effect, it is required to form a p-type slab substrate with a texture structure, and then in a mixed gas atmosphere of oxygenated phosphorus (POCI3), nitrogen, and oxygen. 800 ° C to 90 (TC is processed for several tens of minutes to form an n-type diffusion layer in the same manner. In the prior method, since the diffusion of phosphorus is performed by using a mixed gas, not only the n-type diffusion layer is formed on the surface but also An n-type diffusion layer is also formed on the side surface and the back surface. For these reasons, side etching (also etching) is required to perform the n-type diffusion layer for removing the side surface. In addition, the n-type diffusion layer on the back side needs to be converted into germanium. a type of diffusion layer, thus printing an aluminum paste on the back side, and then calcining (sintering) it to make the n-type diffusion + type layer while obtaining an ohmic contact. Ρ However, the aluminum layer formed of the aluminum paste has low conductivity. In order to reduce the sheet resistance, the aluminum layer usually formed on the entire back surface is required to have a thickness of about ΐΏμΐΏ~2〇μιη after calcining at 201139567. Furthermore, if the number of turns of the aluminum layer is 'the thermal expansion coefficient of the crucible is greater than the thermal expansion of the aluminum, the difference k is large. Therefore, this difference causes a large internal stress in the 2 soil plates during the cooling process, and constitutes a crystal grain. The damage of the boundary, the growth of ~ crystal defects and the cause of Wei Qu. In order to solve this problem, there is a method of reducing the amount of coating of the paste composition and thinning the surface electrode layer. However, when the coating amount of the paste composition is reduced, the amount of the axis diffused from the surface of the p-type conductor substrate to the inside becomes insufficient. As a result, the desired back surface field (BSF) effect (the effect of generating the carrier (earth) ((4) (10) efficiencyn efficiency) is improved by the presence of the enamel layer), and thus the solar cell is generated. The problem of declining characteristics. Therefore, for example, Japanese Laid-Open Patent Publication No. 2-3-223813 proposes a paste composition which is contained in a powder, an organic medium, and a coefficient of thermal expansion which is smaller than the melting temperature and softening. The high-purity inorganic compound powder of any temperature and decomposition temperature towel. However, when the paste composition described in Japanese Laid-Open Patent Publication No. 2003-223813 is used, there is a case where warpage cannot be sufficiently suppressed. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the invention is to provide a method for manufacturing a solar cell element using a germanium substrate, which can suppress internal stress and warpage of the substrate in the germanium substrate. A composition for forming a p-type diffusion layer, a method for producing a p-type diffusion layer, and a method for producing a solar cell element are formed. 201139567^ozoopif The method for solving the above problems is as follows. &lt;1&gt; A composition for forming a P-type diffusion layer comprising a receptor element and having a softening temperature of 30 (rc to 95 (r glass powder/end, and dispersion medium. &lt;2&gt; as above &lt;1&gt; The composition for forming a p-type diffusion layer, wherein the acceptor element is at least one selected from the group consisting of B (boron), A1 (aluminum), and Ga (gallium). &lt;3&gt;&lt;1&gt; Or a composition for forming a p-type diffusion layer according to <2>, wherein the glass powder containing the above-mentioned acceptor element comprises: at least one selected from the group consisting of ruthenium 3, Al 2 〇 3 and Ga 2 〇 3 containing an acceptor element a substance, and at least one glass component selected from the group consisting of SiO 2 , K 20 , Na 20 , Li 2 〇, Ba 〇, sr 〇, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 , Ce 〇 2 and Mo03. The composition of the p-type diffusion layer according to any one of the above-mentioned items, wherein the glass powder has a crystallization temperature of 1050 ° C or more. <5> A method of producing a p-type diffusion layer, comprising: forming a p-type diffusion layer as described in any one of the above &lt;1&gt;~&lt;4&gt; The step of forming a product and the step of performing a thermal diffusion treatment. <6> A method for producing a solar cell element, comprising: coating the semiconductor substrate as described above in &lt;1 &gt;~&lt;4&gt; a step of forming a composition of a p-type diffusion layer, a step of performing a thermal diffusion treatment to form a p-type diffusion layer, and a step of forming an electrode on the formed p-type diffusion layer. 6 201139567 J〇z 〇uplf [Effects of the Invention] According to the present invention, it is possible to provide a method for suppressing internal stress and substrate warpage in a ruthenium substrate in a manufacturing step of a solar cell element using a ruthenium substrate.

A composition for forming a p-type diffusion layer and a p-type diffusion layer, a method for producing a P-type diffusion layer, and a method for producing a solar cell element. The above and other objects, features, and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] First, a composition for forming a P-type diffusion layer of the present invention will be described, and a method for producing a p-type diffusion layer and a solar cell element using a composition for forming a P-type diffusion layer will be described. Furthermore, in the present specification, the term "process" means not only an independent step but also a case where it cannot be clearly distinguished from other steps, and if the step can achieve the intended effect, then Also included in 2 terms. In addition, in this book, "~" means that the value of _ is the minimum value and the maximum __, respectively. Further, in the case of till, when the amount of each component in the composition is referred to, when a plurality of substances corresponding to the respective components are present in the composition, the corpse indicates that there are more than one in the group money. The composition of the material is formed by a composition that forms a p-type diffusion layer. The alizarin and the softening temperature are only known as "lang powder", and the disperse is paid. (4) considering the coating property, etc., 201139567 38286pif may also contain other additives as needed. Here, the composition of the so-called P-type diffusion layer means that the receptor 7C is contained and can be thermally diffused by thermal diffusion treatment (calcination) by, for example, coating on a ruthenium substrate. A material that forms a 卩-type diffusion layer. By using the composition for forming a p-type diffusion layer of the present invention, the step of forming the 〆-type diffusion layer and the step of forming the ohmic contact can be separated, thereby expanding the selection of the electrode material for forming the ohmic contact, and further expanding A choice of electrode construction. For example, when a low-resistance material such as silver is used for the electrode, a low resistance can be achieved with a thin film thickness. Further, the electrode does not need to be formed on the entire surface, and the comb-shaped electrode may be partially formed in a shape such as a comb shape. By forming the electrode into a partial shape such as a film or a comb shape as described above, it is possible to suppress the internal stress in the substrate and the occurrence of warpage of the substrate on both sides, and to form a diffusion layer on one side. Therefore, if the composition for forming a P-type diffusion layer of the present invention is applied, the (10) force generated in the substrate and the generation of the substrate-curvature generated in the method employed in the prior method are suppressed. The previously widely used method is: printing paste 'There is then a method of making it an ohmic contact while making the n-type diffusion layer into a p+ type diffusion layer. Further, since the acceptor component in the glass powder is hardly sublimated during calcination, it is suppressed that the p-type diffusion layer is formed outside the desired region due to the generation of volatile gas. The glass powder containing the acceptor element of the present invention will be described in detail. The term "receptor element" means an element which can form a p-type diffusion layer by doping it in a slate substrate. The element of the group 13 can be used as the acceptor element, for example, 8 201139567 jo^oupif, exemplified by B (boron), A1 (aluminum), and Ga (gallium). Examples of the acceptor element-containing substance for introducing the acceptor element into the glass powder include B2〇3, Ah〇3, and Ga2〇3, and preferably selected from the group consisting of B2〇3, Al2〇3, and Ga203. At least one of them. Further, the glass powder containing the acceptor element may be adjusted in accordance with the ratio of the component of the composition, thereby controlling the melting temperature, the softening temperature, the glass transition temperature, the chemical durability, and the like. It is preferable to further contain the glass component substance described below. Examples of the glass component material include SiO 2 , K 20 , Na 20 , and Li 20 .

BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, Zr02, Mo03, La203, Ce02, Nb205, Ta205, Y2〇3, Ti〇2

Zr〇2, Ge02, Te〇2, Lu2〇3, etc., preferably selected from the group consisting of si〇2, K20, Na20, Li2〇, BaO, SrO, CaO, MgO, BeO, ZnO,

At least one of PbO, CdO, SnO, Zr02, Ce02, and Mo03. Specific examples of the glass powder containing the acceptor element include both the above-mentioned acceptor element-containing substance and the above-mentioned glass component substance, and examples thereof include a B2〇rSi〇2 system (a glass component substance containing a receptor element) In the order of the following, the following B2〇rZn〇 system, B2〇3_pb〇 system, B2〇rCe〇2 system, Βζ〇3 individual system, etc., including b2〇3 as a substance containing an acceptor element, A12〇 A system containing, for example, A% as a substance containing an acceptor element, and a system such as a Ga2〇rSi〇2 system containing Ga2〇3 as a system containing a substance of an acceptor element. Further, it may be a glass powder containing (F) containing an acceptor element which is double-turned, such as an Al2CVB2〇3 system or a Ga2〇3_B2〇3 system. In the above, a glass containing one component or a composite glass containing two components 201139567 ^C/6〇pif is exemplified, but may also be a system such as B2〇rSi〇2-Na20 system or B2〇rSi〇2-Ce〇2 system. Similarly, a glass powder containing three or more substances. The content ratio of the glass component in the glass powder is preferably set in consideration of the melting temperature, the softening temperature, the glass transition temperature, the crystallization temperature, and the chemical durability. In general, it is preferably 〇1% by mass or more and 95%. The mass% or less is more preferably 5% by mass or more to 9% by mass or less. Specifically, when it is a B2〇3_Ce〇2 system glass, the content ratio of Ce〇2 is preferably 1% by mass or more and 5% by mass or less, more preferably 3 times or more to 40% by mass; g;% or less . By this content ratio, the P-type diffusion layer can be formed more uniformly. Further, the softening temperature of the glass powder is important from the viewpoint of obtaining a uniform p-type diffusion layer by diffusing the acceptor element more efficiently into the ruthenium substrate during the thermal diffusion treatment described later. In the present invention, the softening degree of the glass powder is from 300 ° C to 95 (TC, preferably 35 〇. (: ~ 90 〇ΐ, more preferably 37 (ΤΓ)

~85〇t, and thus better. c~8〇(rCe is more preferably 37〇C When the softening temperature of the glass powder is less than 3〇 (rc, the composition of the component is easily crystallized during thermal diffusion treatment at high temperature, and the step of removing the thermal expansion component is removed (4) In the presence of miscellaneous counts, the acceptor element is easily volatilized due to a decrease in melting point, and the thermal diffusion treatment tends to form an undesired portion to form a diffusion layer. In addition, the softening temperature of the last is more than 9 When there is a tendency, there is a tendency as follows;

In order to soften the 'glass powder to maintain the granular shape, the glass component is uniformly covered in the microplate under the microscopic state, and the shape of the p-type diffusion layer becomes uneven, and the sheet resistance value rises. Happening. . The softening temperature of the baby-faced powder can be determined by a well-known differential thermal analysis peak, and more preferably 1200 ° C to =: r, the '__:== precipitation crystallization temperature can be known by the known difference The heat separation device (DTA) is easily measured based on the peak of the heat generation. Examples of the shape of the glassy haze include a substantially spherical shape, a plate shape, and a scale shape, and the coating properties or uniform diffusibility of the group c substrate forming the n-type diffusion layer are obtained. Request, flat, or plate shape. The particle size of the glass powder is particularly limited, and it is preferably less than (10). When a glass powder having a particle diameter of I or less is used, it is easy to smash the S 5 千 千 千 更 film of the particle size of the powder. Furthermore, the teaching path is more ideally 1〇=lower. = lower down = =, glass powder, but preferably _μΐη or more. Further, there is no particular limitation on the lower limit. At the location of the glass miscellaneous county, the average particle diameter can be determined by laser scattering dlffracti〇n meth〇d } ^ ^ ^ ^ ( ^ 11 201139567 ^ oxoupif size distribution ) The glass powder containing the acceptor element is produced by the following procedure: First, the raw material is weighed and filled into the crucible. The material of the crucible is platinum, platinum-ruthenium, rhodium, aluminum oxide, quartz. Carbon, etc. can be suitably selected in consideration of the melting temperature, the environment, and the reactivity with the smelting material, etc. Next, the molten metal is heated by a temperature corresponding to the glass composition in an electric furnace. The mixture is stirred so that the melt becomes uniform. Then, the obtained melt flows out onto a graphite plate, a platinum plate, a platinum-ruthenium alloy plate, a zirconia plate, or the like to vitrify the melt. A powdery form is formed, and 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-containing powder containing the acceptor element in the composition for forming the P-type diffusion layer is considered to be coatability. The content of the glass powder in the composition forming the p-type diffusion layer is preferably 0.1% by mass or more and 95% by mass or less, and more preferably 1% by mass or more and 90% or more. The mass % or less is more preferably i 5 mass % or more and 8 mass % or less, particularly preferably 2 mass % or more to 8 mass % / 0 or less. Next, the dispersion medium will be described. A medium for dispersing the above glass powder in the composition. Specifically, a binder or a solvent is used as a dispersion medium. As the binder, for example, polyvinyl alcohol, polypropylene decylamine, and polystyrene can be suitably selected. Class, polyethylene η ratio slightly. Ding g, polyethylene oxide (polyethylene oxide), polysulfonic acid, acrylamide, acid, 12 201139567 cellulose ethers, cellulose derivatives, carboxymethyl Cellulose, hydroxyethyl cellulose, ethyl cellulose, gelatin, starch and starch derivatives, sodium alginate, xaiUhan, guar and guar gum; i biological, scleroglucan, gum tragacanth (tragacanth) or dextrin imitation organism, (mercapto) propylene glycol, (mercapto) acrylic vinegar resin (such as (meth) acrylate resin, (mercapto) decyl methacrylate resin And the like, a butadiene resin, a styrene resin, a copolymer of the above, a bismuth-oxygen resin, etc. These may be used alone or in combination of two or more. The molecular weight of the binder is not particularly limited, and is preferable. In view of the desired viscosity as a composition, it is suitably adjusted. Examples of the solvent include acetone, mercaptoethyl ketone, methyl propyl ketone, decyl isopropyl ketone, and decyl butyl ketone. Ketone, mercaptoisobutyl ketone, methyl-n-pentyl ketone, methyl n-hexyl ketone, diethyl ketone, dipropyl ketone, mono-isobutyl ketone, trimethyl fluorenone, cyclohexyl a ketone solvent such as ketone, cyclopentanone, decylcyclohexane, 2,4-pentanedione or acetonylacetone; diethyl ether, methyl ethyl ether, methyl n-propyl ether, diisopropyl ether, tetrahydrofuran , methyltetrahydrofuran, dioxane, dimethyl dioxane, ethylene glycol dioxime ether, ethylene glycol monoethyl bromide - 正丙谜, ethylene glycol dibutyl hydrazine, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol decyl ethyl ether, diethylene glycol methyl-n-propyl ether, two Glycol fluorenyl-n-butyl ether, diethylene glycol di-n-propyl ether, mono-glycol di-n-butyl ether, diethylene glycol methyl-n-hexyl ether, triethylene glycol dioxime ether, diethylene glycol Diethyl ether, triethylene glycol decyl ethyl ether, triethylene glycol methyl-n-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol decyl-n-hexyl ether, tetraethylene glycol dif Ether, tetraethylene glycol diethyl ether, tetra-diethylene glycol methyl 13 201139567 oo^oopif ethyl ether, tetraethylene glycol decyl-n-butyl ether, diethylene glycol di-n-butyl ether, tetraethylene Alcohol-n-hexyl ether, tetraethylene glycol di-n-butyl ether, propylene glycol diterpenoid scale, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol dibutyl ether, dipropylene glycol dioxime ether, dipropylene glycol diethyl ether, two Propylene glycol decyl ethyl ether, dipropanol methyl-n-butyl bond, dipropylene glycol di-n-propyl propylene, dipropylene glycol di-n-butyl-, dipropylene glycol methyl-n-hexyl, tripropylene glycol diterpene ether, tripropylene glycol Diethyl ether, tripropyl Glycol decyl ethyl ether, tripropylene glycol sulfhydryl, n-butyl ketone, tripropylene glycol di-n-butyl ether, tripropylene glycol decyl-n-hexyl sulphate, tetrapropylene glycol dioxane, tetrapropylene glycol di-ethyl sulfonate, tetra-dipropylene glycol hydrazine Base ethyl ketone, tetrapropanediol decyl-n-butyl, monopropanol-n-butane, tetrapropylene glycol sulfhydryl-n-hexyl, tetrapropanol-n-butyric acid, etc.; Acetate, vinegar acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxyl acetate Butyl ester, decyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 2-(2-butoxyethoxy)ethyl acetate, benzyl acetate, cyclohexyl acetate, Nonylcyclohexyl acetate, decyl acetate, decyl acetate, ethyl acetate, ethylene glycol ruthenium acetate, diethylene glycol monoethylene glycol, diethylene glycol acetate _ n-butyl ether, Acetate-propanol acetate test, dipropylene glycol acetate, ethylene glycol diacetate, ethoxy triethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate Diethyl oxalate, di-n-butyl oxalate, methyl lactate, milk Sx, ethyl sulphate, n-butyl lactic acid, n-amyl lactate, ethylene glycol phthalate, ethylene glycol ethyl propionate, Ethylene glycol oxime ether acetate, ethylene glycol ethyl ether acetate, monoethylene glycol f ether acetate, diethylene glycol ethylene acetate, diethylene glycol-n-butyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol diethyl ether acetate 201139567 joz^oupif ester, propylene glycol propyl ether acetate vinegar,

- one i ^ V alcohol B: acetic acid vinegar, γ-butane vinegar, γ machine "two doses, di-n-propanol, isopropanol, / butyl: monobutanol first butanol, n-pentanol, isoamyl alcohol , 2_methetin, flute hexanol, 2-methylpentanol, first hexanol, 2-ethylbutanol, second heptanol, n-second octanol, n-nonanol, n-nonanol, Second, alcohol, ethylene glycol, propylene glycol, two = methyl decyl alcohol, diol, triethylene glycol, tripropylene glycol and other alcohol-based solvents. Two::, dipropylene glycol, ethylene glycol monophenyl ether , diethanol (tetra), ethyl ether, diethylene glycol mono-butter, diethylene glycol monomethyl: diethylene glycol monotriethylene glycol, tetraethylene glycol mono-n-butyl ether, propylene di-n-hexyl ether, ethoxy Methyl ether, dipropylene glycol monoethyl ether, tripropylene-, early methyl ether, dipropylene glycol single agent; (X-Xue thin, σ-monool monomethyl scale and other glycol monoterpene (allo-ocimene), lemon It is a linoleic solvent such as oleyl alcohol, terpineol, celery y, Luogui, t-decene, decene, and rosin. These may be used alone as a terpene solvent such as alkene or water. When formed into an n-type diffusion layer = two From the viewpoint of fabricity, 'preferably = when the object' is coated with 2-(2-butoxyethoxy)acetic acid of the substrate. ', diethylene glycol mono-positive test 15 201139567 The content ratio of the dispersion medium in the composition forming the p-type diffusion layer is determined in consideration of coatability and acceptor concentration. Considering the coatability, the viscosity of the composition forming the P-type diffusion layer is preferably 10 mPa. .S or more to 1,000,000 mPa.s or less, more preferably 5 〇 mPa.s or more to 500,000 mPa·s or less. Next, a method of manufacturing the P-type diffusion layer and the solar cell element of the present invention will be described. The tantalum substrate of the semiconductor substrate 10 is provided with an alkaline solution to remove the damaged layer' and the texture structure is obtained by characterization. In detail, the damage of the tantalum surface generated by slicing from the ingot is removed by using 2% by mass of caustic soda. Then, a mixture of 丨 mass% caustic soda f 10% by mass of isopropyl alcohol is used to form a texture structure. The solar cell element can promote optical confinement effect by forming a texture structure on the light-receiving surface (surface) side. Seeking to be more efficient. ^ In the mixed gas of oxygen (tetra) (8) cl3), nitrogen, and oxygen, the treatment is performed for several tens of minutes with Krc~WC, so that the n-type diffusion layer is formed in the same manner. At this time, the diffusion is spread in the Wei_ring On the side and back sides, the n-type diffusion layer is formed on the side surface and the back surface. Therefore, side etching is performed to remove the surface type diffusion layer on the side surface. Then, on the back surface of the p-type semiconductor substrate, that is, on the n-type diffusion layer of the surface Coating the above-mentioned p-type diffusion layer: the composition layer forming the p-type diffusion layer is formed too much. In the present invention, the cloth method is secret, such as printing, spinning, brushing: 201139567, fog method , scraper method, roll coater method, inkjet method, and the like. The coating amount of the composition forming the Ρ-type diffusion layer is not particularly limited. For example, the amount of the glass powder can be set to 001 g/nl g/m ', preferably 0.1 g/m2 to 1 〇 g/m2. Further, the composition of the composition forming the p-type diffusion layer is used to dry the enamel contained in the composition after coating. In this case, at 8 〇t: ~3 〇 (at a temperature of about rc = 1 minute to 1G minutes when heating the plate) #使肖赖机料 ^ minutes ~ 3G minutes or so. The dry and miscellaneous pieces depend on the formation The solvent composition of the composition of the bribes is not specifically determined in the present invention. The semi-conductive plate coated with the composition for forming the p-type diffusion layer is subjected to the above-mentioned composition at ΐ 120 to 120 ° C. Thermal diffusion treatment. By the thermal expansion, the receptor is diffused into the semiconductor substrate, and (4) the p+ diffusion/thermal diffusion treatment can be used to prepare a known continuous furnace or batch batch. In addition, the furnace environment during diffusion treatment The heat treatment time may be appropriately adjusted depending on the acceptor rhythm content of the composition forming the p-type diffusion layer or the softening temperature of the glass powder, for example. It can be set to i minutes to 6G minutes, and more minutes to 30 minutes. * Since a glass layer is formed on the surface of the formed P + -type diffusion layer, the glass layer is removed by etch. (4) Application of dipping a method in hydrogen acid or the like, a method of immersing in caustic soda, etc. In addition, in the previous manufacturing method, the aluminum paste was printed on the back side and then 201139567, which was used to make the n-dragon layer (4) p+ type expansion while obtaining ohmic contact. However, the aluminum formed by the aluminum paste The reduced thickness of the layer &gt; 1 resistance 'is usually formed in the entire f_|g layer after calcination: it needs to have a thickness of about 10 μm to 20 μπη. Further, if a thick layer is formed as described above, The coefficient of thermal expansion of the eve differs greatly from the coefficient of thermal expansion of the singularity. Therefore, in the process of calcination and cooling, a large internal stress is generated in the ruthenium substrate _, which causes the warpage. ^The internal stress exists for crystallization. The problem that the crystal grain boundary causes damage and power loss increases. In addition, it is easy to cause the warpage of the solar cell element in the module process or the connection with a copper wire called a tab wire. In recent years, due to the improvement of the slicing technology, the thickness of the tantalum substrate is becoming thinner, and the solar cell element tends to be more easily broken. However, According to the manufacturing method of the present invention, after the n-type diffusion layer is converted into the p + -type diffusion layer by the composition for forming a P-type diffusion layer of the present invention, an electrode is additionally provided on the p + -type diffusion layer. The material is not limited to aluminum. For example, Ag (silver) or Cu (copper) can be applied, and the thickness of the electrode on the back surface can be formed thinner than the previous thickness, and it is not necessary to form the entire surface. It can reduce the internal stress and warpage in the tantalum substrate generated during the calcination and cold parts. θ forms an anti-reflection film on the n-type diffusion layer formed above. The anti-reflection film is a well-known technique. For example, when the antireflection film is tantalum nitride, it is formed by a plasma Vapor Deposition (CVD) method using a mixed gas of SiH4 and cesium 3 as a raw material. 18 201139567 Jdzoopif At this point, hydrogen diffuses in the crystal and does not participate in the bonding of the helium atom, that is, the dangling bond and hydrogen bonding, and the defect is purified (hydrogen purification). More specifically, the mixed gas flow rate ratio NH3/SiH4 is 〇〇5 to 1.0, and the pressure to be reacted is 〇.1 T〇rr~2 Torr, and the temperature at the time of film formation is 30 (TC to 550 t, so that the plasma is made The discharge frequency is formed under the condition of 1 〇〇 kHz or more. On the anti-reflection film of the surface (light-receiving surface), the surface electrode age paste is printed and screened by screen printing, and (4) is a surface electrode. The metal paste for a surface electrode contains metal particles and glass particles as essentials, and optionally contains a resin binder, other additives, etc. Then, a back electrode is formed on the P + -type diffusion layer on the back surface as described above. In the invention, the material f or the formation method of the back surface electrode is not particularly limited. For example, a paste for a back surface electrode containing a metal such as ingot, silver or copper may be applied and dried to form a back surface electrode. For the connection between the solar cell elements in the process, a silver paste for forming a silver electrode may be provided on a part of the back surface. The electrode is calcined to form a solar cell element. If it is 60 〇t: ～900 ° C _ job a few seconds The age bell, the surface side, is melted as glass particles contained in the anti-reflective electric metal cap of the insulating film, and a part of the surface of the crucible is also melted, and metal particles (for example, silver particles) in the paste form a contact portion with the crucible substrate. And solidified. Thereby, the formed surface electrode and the germanium substrate are turned on. This is called fire-through. The shape of the surface electrode is described. The surface electrode is composed of a bus bar electrode and the bus bar The finger electrodes are formed by electrodes. 19 201139567 Such a surface electrode can be formed by, for example, screen printing of the above metal paste, plating of an electrode material, vapor deposition of an electrode material by electron beam heating in a high vacuum, or the like. It is known that the surface electrode including the bus bar electrode and the finger electrode is generally used as an electrode on the light-receiving surface side, and a known method of forming the bus bar electrode and the finger electrode on the light-receiving surface side can be applied. In the method of manufacturing a P-type diffusion layer and a solar cell element, 'in order to form a diffusion layer on a germanium substrate as a P-type semiconductor substrate, use Gasified phosphorus (POC13), a mixed gas of nitrogen and oxygen, but a composition forming an n-type diffusion layer may be used to form an n-type layer. In the composition forming the n-type diffusion layer, p (phosphorus) or yttrium is contained. (锑) Element of Group 15 is used as a donor element. In the method of forming a composition of an n-type diffusion layer for the formation of an n-type diffusion layer, first, the light-receiving surface of the surface of the p-type plate is used. Coating the composition forming the n-type diffusion layer, coating the composition of the present invention to form the p-type diffusion layer on the back surface, and then performing thermal diffusion treatment at 60 (rc ~ 12 〇〇t). By the thermal diffusion treatment, The donor element is diffused to form a n-type diffusion layer on the surface of the p-type; the substrate is diffused to form an n-type diffusion layer on the back surface. In addition to this step, by the above method Steps to make solar cell components. The entire contents of the application of the present application, which is hereby incorporated by reference in its entirety in its entirety in its entirety in the the the the the the the the the the the (4) ^ Say 1 book records the number of documents, special shots, and techniques, and the extent of the documents and patents, and the technical specifications. 201139567 ^ozoopif is quoted in this manual. [Examples] Hereinafter, examples of the invention will be more specifically described, but the invention is not limited by the examples. Further, as long as there is no special description in advance, the reagents are all used in the chemical. In addition, "%" means %) unless there is no explanation in advance. [Example 1] A B203-Ce02 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 4.9 μm was used (B2〇3: 39 6%, using an automatic milk spider kneading device).

Ce〇2 . 10%, BaO · 10.4% ' Mo03 ·· 10%, Zn〇: 30%) at the end of 20 g with ethyl cellulose 0.3 g, 2-(2-butoxyethoxy)acetate 7 g of vinegar was mixed and pasteified to prepare a composition for forming a p-type diffusion layer. The thermal analysis device (TG-DTA, DTG60H type 'measurement conditions: heating rate 2〇°c/min, air flow rate 1 〇〇ml/min) manufactured by Shimadzu Corporation (share) was used for the above B2〇3_Ce〇2 system glass powder. As a result of the thermal analysis, the softening temperature was 600 °C. Further, the crystallization temperature is 1100 ° C or more, which exceeds the measurement range of the thermal analysis apparatus. Further, the shape of the glass particles was observed and judged using a TM-1000 scanning electron microscope manufactured by Hitachi High-Technologies Co., Ltd. The average particle diameter of the glass was calculated using a LS 13 320 laser scattering particle size distribution measuring apparatus (measuring wavelength: 632 nm) manufactured by Beckman Coulter Co., Ltd. Next, the prepared paste (forming a composition of the P-type diffusion layer 21 201139567 ^ozoopif l) is applied to the surface of the P-type ruthenium substrate (hereinafter, "back") by screen printing, and is brewed. Drying on a hot plate for 5 minutes: followed by: said: set to face. (3) Wei riding 1G minutes thermal diffusion treatment ^

In order to remove the glass layer, the substrate was immersed in 1% hydrofluoric acid for 5 minutes, and then washed with running water. Thereafter, drying is carried out. The surface of the side on which the composition on which the p-type diffusion layer is formed is 45 Ω/□, and B (boron) is diffused to form a 〆-type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the p + -type diffusion layer was not substantially formed. On the other hand, the warpage of the substrate was not generated on the substrate. The results are shown in Table i. Further, the sheet resistance was measured by a four-probe method using a L〇resta-EP MCP_T360 type low resistivity meter manufactured by Mitsubishi Chemical Corporation. [Example 2] A p-type diffusion layer was formed in the same manner as in Example j except that the thermal diffusion treatment time was set to 15 minutes. The sheet surface coated on the side of the composition on which the p-type diffusion layer was formed had a sheet resistance of 35 Ω/α, and B (boron) was diffused to form a Ρ+-type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the Ρ+ type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur on the substrate. [Example 3] A p-type diffusion layer was formed in the same manner as in Example 1 except that the thermal diffusion treatment time was set to 3 Torr. The surface resistance of the surface coated with the side on which the composition of the p-type diffusion layer was formed was 2 〇 ω / port, and β (boron) was diffused to form 22 201139567 oozoopif into a P + -type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the P + -type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur on the substrate. [Example 4] The glass powder was set to a Β203-Ζη0 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (b2〇3: 40%, ZnO: 40%, Ce02: 10% 'MgO: 5%) A composition forming a p-type diffusion layer was prepared in the same manner as in Example 1 except that 'CaO: 5%), and the p-type diffusion layer was formed using the composition forming the P-type diffusion layer. Further, the softening temperature of the glass powder was 580 °C. Further, the crystallization temperature is above the measurement range of the thermal analyzer. The sheet resistance of the surface coated with the side on which the composition of the p-type diffusion layer was formed was 48 Ω / 〇] Β (boron) diffused to form a p + -type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the p + -type diffusion layer was not substantially formed. In addition, no slight curvature of the substrate was produced on the substrate. [Example 5] The glass powder was set to a B203-SiO 2 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3·2 μηη (Β2〇3: 30%, Si〇2: 50%,

Ce02 : 10%, Zn〇: 10%) 'Aside from this, a composition for forming a p-type diffusion layer was prepared in the same manner as in Example i, and a composition for forming a p-type diffusion layer was used to form a p-type diffusion layer. . Further, the glass wool powder had a softening temperature of 680 °C. Further, the crystallization temperature was 110 Torr to 1, and the measurement range of the superheat analyzer was exceeded. 23 201139567 JOZOOpif The sheet resistance of the surface coated with the side on which the p-type diffusion layer is formed is 52 Ω/□, and B (boron) is diffused to form a P+ type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the ytterbium-type diffusion layer was not substantially formed. In addition, no warpage of the substrate occurred on the substrate. [Example 6] A p-type diffusion layer was formed in the same manner as in Example 5 except that the thermal diffusion treatment time was set to 30 minutes. The sheet surface on the side coated with the composition on which the p-type diffusion layer was formed had a sheet resistance of 33 Ω/□, and Β (boron) was diffused to form a Ρ-type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the ruthenium-type diffusion layer was not applied was too large to be measured, and it was judged that the ruthenium-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur on the substrate. [Example 7] The glass powder was set to a B2OrPbO system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (Β2〇3: 3〇〇/., Pb〇: 50%,

A composition for forming a P-type diffusion layer was prepared in the same manner as in the example except for ZnO: 20%), and a p-type diffusion layer was formed using the composition for forming a p-type diffusion layer. Further, the softening temperature of the glass powder was 34 Å. Hey. Further, the crystallization temperature is ll 〇〇 ° C or more, which exceeds the measurement range of the thermal analysis apparatus. The sheet resistance of the surface coated with the side on which the composition of the P-type diffusion layer was formed was 17 Ω/α, and Β (boron) was diffused to form a P + -type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the p + -type diffusion layer was not substantially formed. In addition, 面 24 201139567 no surface curvature of the substrate was produced on the substrate. [Example 8] The glass powder was set to a B2〇rSl〇2 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (b2〇3: 3〇%, called: 1〇%, 鄕, Zn〇) : Muscle, (5): 1 ()%), except that a composition for forming a P-type diffusion layer was prepared in the same manner as in Example 1, and the P-type diffusion-forming composition was used to form a p-type diffusion layer. Furthermore, the softening temperature of the glass powder is 3 thieves. In addition, the crystallization temperature is drawn. (: The above 'beyond the measurement range of the thermal analyzer. The sheet resistance of the surface coated with the side on which the p-type diffusion layer is formed is 25 Ω/α, and the Β (side) diffuses to form a diffusion layer. The sheet resistance of the portion to which the composition for forming the p-type diffusion layer was applied was too large to be measured, and it was judged that the diffusion layer was not substantially formed. Further, the surface curvature of the substrate was not produced on the Shih-hs substrate. [Example 9] The glass powder was set to a B203_SiO 2 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (β 2 〇 3 : 3 〇〇 / 0, SiO 2 : 10%,

A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1 except that PbO. 30%, ZnO: 20%, NaO: 10%), and the composition for forming a P-type diffusion layer was used to form. P-type diffusion layer. Further, the softening temperature of the glass powder was 390 °C. Further, the crystallization temperature is ii 〇〇 t: the above is beyond the measurement range of the thermal analysis apparatus. The sheet resistance of the surface coated with the side on which the composition of the p-type diffusion layer was formed was 31 Ω/□, and B (boron) was diffused to form a p + -type diffusion layer. On the other hand, in 25 201139567, the sheet resistance of the portion of the filament which was not coated with the p-type diffusion layer was too large to be measured, and it was judged that the p + -type diffusion layer was not substantially formed. In addition, no distortion of the substrate occurred on the Shi Xi substrate. [Example 10] The glass powder was set to a Β203_Ζη0 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (b2〇3: 3〇%, Zn〇: 4〇%,

A composition forming a p-type diffusion layer was prepared in the same manner as in Example i except that CaO: 20% 'Al2〇3: 10%), and the composition forming the p-type diffusion layer was used to form p-type diffusion. Floor. Further, the softening temperature of the glass powder was 505 C. Further, the crystallization temperature was 11 〇〇〇c or more, which exceeded the measurement range of the thermal analyzer. The sheet resistance of the surface coated with the side on which the composition of the p-type diffusion layer was formed was 43 Ω/□' B (boron) diffused to form a p + -type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the P-type diffusion layer was not applied was too large to be measured, and it was judged that the p + -type diffusion layer was not substantially formed. In addition, no surface curvature of the substrate was produced on the Shi Xi substrate. [Example 11] The glass powder was set to a B203-SiO 2 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (B2〇3: 50%, Si02: 10%,

A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1 except that ZnO · 30% ' CaO : 10) ' and the thermal diffusion treatment time was set to 2 〇 minutes, and p-type diffusion was formed using the same. The composition of the layer forms a P-type diffusion layer. Further, the softening temperature of the glass powder was 69 ° C. Further, the crystallization temperature is 1100 ° C or more, which exceeds the measurement range of the thermal analysis apparatus. 26 201139567 JO^-OUpif The sheet resistance of the surface coated with the side on which the p-type diffusion layer is formed is 56 Ω/□'B (boron) diffuses to form a p+ type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the p + -type diffusion layer was not substantially formed. In addition, no distortion of the substrate occurred on the substrate. [Example 12] The glass powder was set to a B203-SiO 2 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (b2〇3: 22%, Si〇2: 58%,

CaO: 2G%), in addition to this, a P-type diffusion layer tester was prepared in the same manner as in the example i side, and a P-type diffusion layer was formed using the composition forming the p-type diffusion layer. Further, the glass powder has a softening temperature of 85 (rc. Further, the 'crystallization temperature is 110 (TC or more, which exceeds the measurement range of the thermal analyzer. The sheet resistance of the surface coated with the side of the composition forming the p-type diffusion layer) The ytterbium-type diffusion layer was formed by diffusion of 78 Ω/ο' Β (boron). On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that it was substantially not formed. The p+ type diffusion layer was not formed on the shixi substrate. [Example 13] The glass powder was set to a B2〇rSi〇2 system having a substantially spherical shape and an average particle diameter of 3·2 哗. Glass (β2〇3 · 25%, Si〇2 : 6〇%,

CaO · 15%) 'Other than this' The group forming the P-type diffusion layer was prepared in the same manner as in Example i, and the composition of the p-type diffusion layer was formed to form a p-type diffusion layer. Furthermore, the softening temperature of the glass powder is dip. 27 201139567 In addition, the crystallization temperature is ll 〇〇 °C or more, which exceeds the measurement range of the thermal analyzer. The sheet resistance of the surface coated on the side of the composition on which the P-type diffusion layer was formed was 82 Ω/□'B (boron) diffused to form a p+-type diffusion layer. On the other hand, the sheet resistance of the portion to which the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the ruthenium-type diffusion layer was not substantially formed. In addition, no warpage of the substrate was produced on the substrate. [Example 14] The glass powder was set to a B203-SiO 2 system glass (b2〇3: 2〇%, Si〇2: 65; 〇' having a particle shape of a substantially spherical shape and an average particle diameter of 3_2 μηη.

CaO: 1〇〇/0, aI2〇3: 5%), except that a composition for forming a p-type diffusion layer was prepared in the same manner as in the example, and the composition forming the p-type diffusion layer was used to form P-type diffusion layer. Further, the glass powder has a softening temperature of 94 (TC. Further, the crystallization temperature is 11 〇〇〇c or more, which exceeds the measurement range of the thermal analyzer. ... the surface coated with the side of the composition forming the p-type diffusion layer The sheet resistance is 96 Ω/ci'B (boron) diffuses to form a 〆-type diffusion layer. On the other hand, the sheet resistance of the portion where the composition forming the p-type diffusion layer is not applied is too large to be measured, and it is judged as The P + -type diffusion layer was not formed in the permeation. The distortion of the substrate did not occur on the substrate. [Comparative Example 1] The glass powder was set to a B203-SiO 2 having a substantially spherical shape and an average particle diameter of 3.2 μηη. System glass (B2〇3: 10%, Si〇2: 2〇%,

PbO: 40% 'NaO: 30%), except that a composition for forming a p-type diffusion layer was prepared in the same manner as in Example}, in the manner of the following example, and a thermal diffusion treatment was carried out using a :: product. Furthermore, the glass "last"::: forms a p+ type diffusion layer on the surface of the composition coated with the (four) remaining layer. In addition, the sheet has a sheet resistance D. However, the portion 3' sheet resistance to which the composition for forming the p-type diffusion layer was not applied was 7 G Ω / 〇 ' p + type diffusion layer was formed to an unnecessary portion. Further, warpage of the substrate did not occur on the substrate. [Comparative Example 2] The glass powder was set to a B20rSi02 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (β2〇3 ··5%, Si〇2 ··93〇/〇,

Na〇 : 2%) In addition, a composition for forming a p-type diffusion layer was prepared in the same manner as in Example i, and the composition for forming the p-type diffusion layer was subjected to thermal diffusion treatment. Further, the softening temperature of the glass powder was 1,100. The upper side exceeds the measurement range of the thermal analysis device. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was too large to be measured. It was judged that the p + -type diffusion layer was not substantially formed. Further, the button of the substrate was not produced on the stone substrate. 29 201139567t ^ ^ ^ Λ A.

[Table 1] Glass powder glass powder softening point (°C) Example 1 B2〇3-Ce〇2 system 600 Example 2 B2〇3-Ce〇2 system 600 Example 3 B203-Ce02 Lanthanide 600 Example 4 Β203-Ζη0 system 580 Example 5 B203-Si02 Lanthanide 680 Example 6 B203-Si02 System 680 Example 7 B203-Pb0 System 340 Example 8 B203-Si02 System 370 Example 9 B2〇3_Si〇2 System 390 Example 10 Β203-Ζη0 System 505 Example 11 B203- Si02 system 690 Example 12 B203-SiO 2 system 850 Example 13 B203-SiO 2 system 880 Example 14 B203-SiO 2 system 940 Comparative Example 1 B203-SiO 2 system 240 Comparative Example 2 B203-SiO 2 system &gt; 1100

As described above, by using the composition for forming a p-type diffusion layer of the present invention, the p-type diffusion layer can be uniformly formed without causing warpage of the ruthenium substrate. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. [Simple description of the diagram] None. [Main component symbol description] None. 30

Claims (1)

201139567 VII. Application for Patent Park: 1. A composition for forming a P-type diffusion layer, comprising: a glass powder containing an acceptor element and having a softening temperature of 30 (rc~^(^^; and a dispersion medium. The composition for forming a p-type diffusion layer according to the first aspect of the invention, wherein the above-mentioned acceptor element is at least one selected from the group consisting of B (boron), A1 (aluminum), and Ga (gallium). The composition for forming a p-type diffusion layer according to the above item, wherein the glass powder containing the above-mentioned acceptor element comprises: at least one substance containing an acceptor element selected from the group consisting of Β2〇3, Α12〇3, and Ga203; At least one glass component material from SiO 2 , K 2 〇, Na 20 , Li 2 〇, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, ZrO 2 , Ce02 and Mo03. The composition for forming a p-type diffusion layer, wherein the crystallization temperature of the glass powder is 1〇5〇°c or more. 5_ a method for producing a p-type diffusion layer, comprising: coating as claimed in the patent scope Formation of P type according to any one of items 1 to 4 a step of forming a composition of the diffusion layer; and a step of performing a thermal diffusion treatment. 6. A method of manufacturing a solar cell element, comprising: coating on a semiconductor substrate as in any one of claims 1 to 4 of the patent application scope The step of forming a composition of the p-type diffusion layer; 31 201139567 w»OZ.O\jpif performing a thermal diffusion treatment to form a P-type diffusion layer; and forming an electrode on the formed P-type diffusion layer 32 201139567 ^oz-oupif IV. Designated representative map: (1) The representative representative of the case is: No. (2) The symbol of the symbol of the representative figure is simple: None. 5. If there is a chemical formula in this case, please reveal The chemical formula that best shows the characteristics of the invention: None. 3 201139567 . 38286pifl ' is the Chinese version of the 100114096 No-line correction page Revision date: 1 year 7 . Month 15 曰. List: B (boron), A1 (aluminum) And Ga (gallium), etc. As a substance containing an acceptor element for introducing an acceptor element into a glass powder, B2〇3, Al2〇3, and Ga2〇3' are preferably used. 3, Al2〇 At least one of 3 and Ga 203. Further, the glass powder containing the acceptor element may adjust the component ratio as needed, thereby controlling the melting temperature, the softening temperature, the glass transition temperature, the chemical durability, etc. It is preferable to further include the following Glass component substance ❹ As the glass component, Si〇2, K2O, Na20, Li2〇, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, SnO, Zr02, M〇03, La203, Ce02, Nb205, Ta205, Y2〇3, Ti〇2, Zr02, Ge02, Te02 and Lu203, etc., preferably selected from the group consisting of SiO2, κ20, Na20, Li20, BaO, SrO, CaO, MgO, BeO, ZnO, PbO At least one of CdO, SnO, Zr02, Ce02, and Mo03. Specific examples of the glass powder containing the acceptor element include a substance including the above-mentioned acceptor element-containing substance and the above-mentioned glass component substance, and examples thereof include a B2〇rSi〇2 system (containing an acceptor element). The material _ broken glass component substance is described in the following order, the Β203-Ζη0 system, the BaCVPbO system, the B2〇rCe02 system, the B2〇3 single system, etc., which contains ruthenium as a substance containing an acceptor element, A12〇3_si〇 2 system or the like 'Al2〇3 is a system containing a substance of an acceptor element, and a Ga2〇3_Si〇2 system or the like contains a glass powder such as Ga2〇3 as a system containing a substance of an acceptor element. Further, it may be a glass powder containing two or more kinds of substances containing an acceptor element, such as the A12〇3_b2〇3 system and the Ga2CVB2〇3 system. 201139567 &lt;r 38286pifl &gt; For the Dirty Gang No. 6 Chinese manual, there is no sizing correction page correction period: July 15th, 100th, in the above, exemplified a glass containing one component or a composite glass containing two components, but It may be a glass powder containing three or more components, such as a B2〇3_Si〇2_Na2〇 system or a BA-SiCVCeO2 system. The content ratio of the glass component in the glass powder is preferably set in consideration of the melting temperature, the softening temperature, the glass transition temperature, the crystallization temperature, and the chemical durability. In general, it is preferably 〇1% by mass or more and 95%. The mass% or less is more preferably 0.5% by mass or more and 9% by mass or less. Specifically, when it is a BaCVCeO2 system glass, the content ratio of Ce〇2 is preferably from i% by mass or more to 5% by mass or less, more preferably from 3 mass% to more than 4% by mass. By this content ratio, the P-type diffusion layer can be formed more uniformly. Further, the softening temperature of the glass frit is more important in the viewpoint of obtaining a p-type diffusion layer of a uniform sentence by diffusing the acceptor element more efficiently into the slab substrate during the thermal diffusion treatment to be described later. In the present invention, the softening temperature of the glass powder is 1.00 (: ~ 950. (:, preferably 3 thief ~ 9 〇〇. 〇, more preferably 3 ～ 850 ° C ' and further preferably 40 (TC~800 ° C. ^When the softening temperature of the glass powder is less than 300 ° C, the heat expansion treatment at a high temperature is easy to crystallize the daytime glass component, and in the etching removal step of the glass component after the heat diffusion treatment, There is a tendency that the etching removability is lowered, and there is a tendency that the acceptor element is easily volatilized due to a decrease in melting point, and a P-type diffusion layer is likely to be formed in an unnecessary portion during thermal diffusion treatment. In addition, when the glassy powder is softened When the temperature exceeds 950 ° C, there is a tendency that the glass is hard to soften during the thermal diffusion treatment, and the glass powder maintains a granular shape, so that the glass component is not uniformly covered on the substrate under the microscopic state, the receptor element 201139567 38286pifl Correction date: July 15th, 1st, the 100th No. 100114096 Chinese manual, no line correction page spreads, and the formation of the p-type diffusion layer becomes a case where the sheet resistance value rises. ·? It can be easily determined from the basin peak by a well-known differential thermal analysis (Otafferenta Thermal Analyzer, Dta). *,,, (10) In addition, in the present invention, the daily temperature of the glass powder is relatively high. 'More preferably, it is t or more, and more preferably.. The crystallization temperature is 105 (TC or more, thermal diffusion 2 = crystallization is suppressed. Thereby, the glass after thermal diffusion treatment becomes == = In the step, the residual of the crystallized compound is suppressed, and the glass component is further increased. The crystallization temperature of the glass powder can be measured by the analysing device (grandfather) according to the peak of the sensory peak.", the knife is in the shape of the powder. In addition, the coating property or the feather diffusing property of the composition which is formed into a p-type diffusion layer, which is formed into a substantially spherical shape, a flat shape, a plate shape, a scale shape, or the like, is exemplified. The particle diameter of the glass powder is not limited to, and is not limited to, preferably 100 μm or less. When a glass powder having a particle diameter of 1 μm or less is used, it is easy to obtain. More flat glass powder The particle size of the final glass = 7 is more preferably 10 tons or less. Further, the lower limit is not particularly limited, but is preferably 0.01 μm or more. / The glass particle diameter indicates an average particle diameter. The measurement is performed by a laser scattering diffraction method particle size distribution (particie 11 201139567 38286pifl revision date: July 15, 100, the 100114096 Chinese manual no-line correction page size distribution) measuring device or the like. The glass powder containing the acceptor element was produced by the following procedure. First, weigh the ingredients and fill them into the hanging pot. The material of the trouble may be platinum, platinum-ruthenium, rhodium, alumina, quartz, carbon, etc., and may be appropriately selected in consideration of the melting temperature, the environment, and the reactivity with the molten material. ~(7)1 Secondly, the electric furnace is heated by a temperature corresponding to the glass composition to form a melt. At this time, it is preferable to agitate the squares and lines in which the melt becomes uniform. &quot; Then, the obtained solution is allowed to flow out onto a graphite plate, a nameplate, a face-gold alloy plate, a zirconia plate or the like to vitrify the melt. ° Finally, the glass is pulverized to form a powder. The pulverization can be applied to a known method such as a jet bead mill or a ball mill. The content ratio of the glass powder containing the acceptor element in the red-formed material forming the Ρ-type diffusion layer is determined in consideration of coatability, diffusibility of the acceptor element, and the like. In general, the composition content ratio of the p-type diffusion layer is preferably _ mass% or more to 95 mass% == ! The quality is as high as 9 G mass% or less, and more preferably 1 to 8 mass% or less, particularly preferably Once more than $10/〇, the dispersion medium is from up to 8Q_. The incorporation of 4 bis refers to dispersing the above-mentioned glass powder in the composition, using a spotting agent or a solvent or the like as a dispersion medium. As a binder, for example, a sickle-like shape; I sheet amines, polyethylene amines, d-vinyl alcohol, polypropylene (p〇lyethylene oxlde ^ ^ ^ ^ ^ ^ 頬, poly-% acid, acrylamide) Alkyl sulfonic acid, 12 201139567 38286pifl JOZ-OOpiIl is no correction for Chinese coffee book No. 100114096 曰 Corrected flood season: July 15, 100 = propylene glycol propyl acetate, dipropylene glycol methyl acetate乙B_'γγ, γ-valerolactone, etc. ^ - Ν-methylpyrrolidone, its 々 々 丨, acetonitrile, N NW each di-based such as _, Ν-butyl decylamine , Ν Ν-dimethyl meth, 1 f per hexyl sulfonamide, hydrazine, hydrazine dimethyl hydrazine; methanol, ethanol, n-propanol, isopropanol 4 dibutanol, the first: r Dingsa TL, Wu Butanol, Dijon &amp; butyl, n-pentanol, isoamyl alcohol, 2-methylbutanol, flute-pentanol, third pentanol, 3_methyl A TP3^ Alcohol, 2-ethylbutane di-, n-hexanol, 22, alcohol, "n-nonanol, n-nonanol, di-, di-, ethyl alcohol, tripropylene glycol and other alcohol-based solvents; Dimethyl = ethyl hydrazine, ethylene glycol monophenyl, Ethylene glycol single nail shout: alcohol] ether, diethylene glycol single _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Base guanidine, dipropylene glycol mono (10), butyl propylene glycol, dipropylene glycol single agent (10) thin, bismuth; alcohol Ullo-oclmene), holding rare earth &amp; bellerolene 一种 one, or a combination of two or more 4 Cloth dispersing, when forming a product, the coating of the substrate is called butoxy single-positive top, 15 201139567 38286pifl is the 100114096 Chinese manual without a sizing correction page. Correction period: 100 years July 15 曰 formation P The content ratio of the dispersion medium in the composition of the type of diffusion layer is determined in consideration of coatability and acceptor concentration. X Considering the coatability, the viscosity of the composition forming the P-type diffusion layer is preferably 10 mPa·s or more. It is more than 1,000,000 mPa.S or less, more preferably 5 〇mpa s or more to 500,000 mPa.S or less. Next, a method of manufacturing the P-type diffusion layer and the solar cell element of the present invention will be described. ° For a stone as a p-type semiconductor substrate The substrate is given an experimental solution to damage the layer and obtain a grain by etching. In particular, the taxis use '20% by mass of caustic soda to remove 4 damaged layers from the surface. Then, use a mixture of =% by mass (four) to form a texture to promote the optical ship effect. High efficiency. The formation of the text, the culture and the science can be followed by 'in the case of oxygenated phosphorus (p〇cl), 氦 备 备 u, _. . ~900. . The treatment of tens of minutes of milk from: also reaches the side and back, the two sides of n, and also formed on the side, back. Because of the phenotype diffusion layer and ❹m. 4 The above-mentioned opposite substance is coated on the n-type diffusion layer on the surface of the back disk side of the side surface of the semiconductor substrate, and the composition of the p-type diffusion is formed. There is no limitation in the method. For example, in this U, the application of the coating method, the brush coating, and the spraying 16 201139567 38286pifl The correction date: July 15, 100 is the 100114096 Chinese manual without the sizing correction page on the substrate. Produce the enchantment of the substrate. [Example 8] The glass powder was set to a B203-SiO 2 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (B2〇3: 30%, SiO 2 : 10%, PbO · 40% ' ZnO : 10%) 'CaO: 1%%), except that a composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and the composition for forming a P-type diffusion layer was used to form a p-type diffusion layer. Further, the glass Q powder had a softening temperature of 370 ° C. Further, the crystallization temperature is ll 〇〇 ° C or more, which exceeds the measurement range of the thermal analyzer. The sheet resistance of the surface coated with the side on which the composition of the p-type diffusion layer was formed was 25 Ω/□' B (collar) to form a p + -type diffusion layer. On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the p + -type diffusion layer was not substantially formed. In addition, no surface curvature of the substrate was produced on the Shi Xi substrate. [Example 9] The glass powder was set to a B2〇3-Si〇J-based glass having a particle shape of a substantially spherical shape and an average particle diameter of 〇3.2 μm (b2〇3: 30%, Si〇2: 10%, PbO: A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1 except that 30% 'ZnO: 20% 'NaO: 10%), and the composition for forming a p-type diffusion layer was used to form a P-type. Diffusion layer. Further, the softening temperature of the glass powder was 390 °C. Further, the crystallization temperature is ii 〇〇 ° c or more and exceeds the measurement range of the thermal analysis apparatus. The sheet resistance of the surface coated with the side on which the composition of the p-type diffusion layer was formed was 31 Ω/□' B (bad) diffusion to form a p + -type diffusion layer. On the other hand, 25 201139567 38286pifl · The sheet resistance of the part of the composition of the p-type diffusion layer is too large for the first leg of the employee's article, if there is no scribe line correction page, the date of the modification is July 15 曰 uncoated. However, it was judged that the p+ type diffusion layer was not formed substantially. In addition, the embossing of the substrate is not generated on the substrate. [Example 10] A glass powder was set to a B2〇3_Zn〇 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μm (b2〇3: 3〇%, Zn〇: 4〇%, CaO: 20% ' Al2〇3: 10%) 'Aside from this, a composition for forming a P-type diffusion layer was prepared in the same manner as in Example 1, and a composition for forming a diffusion layer of 1) was used to form a diffusion layer of the type]. Further, the softening temperature of the glass powder was 505. (: The other 'crystallization temperature is cc or more, which exceeds the measurement range of the 孰 analyzer. The surface resistance of the surface coated with the opening of the composition of the p-type diffusion layer is 43 Ω/□, B ( On the other hand, the sheet resistance of the portion where the composition for forming the p-type diffusion layer was not applied was too large to be measured, and it was judged that the p + -type diffusion layer was not substantially formed. No warpage of the substrate occurred on the substrate. [Example 11] The glass powder was set to a BaCVSiO2 system glass having a particle shape of a substantially spherical shape and an average particle diameter of 3.2 μη (B2〇3: 50%, Si〇2: 10%, A composition forming a p-type diffusion layer was prepared in the same manner as in Example 1 except that ZnO. 30%, CaO. 10%) was set to 2 〇 minutes, and a p-type was formed using the same method as in Example 1. The composition of the diffusion layer forms a p-type diffusion layer. Further, the glass powder has a softening temperature of 69 (rc. Further, the crystallization temperature is 110 (TC or more, which exceeds the measurement range of the thermal analyzer.